RU2774755C2 - Pesticides - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: present invention relates to a compound of the formula I, where A¹ is CR^A; A² is N or CR^B; A³ is CR^B1; W is O, S(=O)_m or NR⁶; R^A, R^B and R^B1, independently of each other, are H, halogen; Q is -C(R⁴R⁵)-O-, -S(=O)_m-C(R⁷R⁸)-, -N(R²)-C(R⁹R¹⁰)-, -N(R²)-C(=O)- or -C(R¹⁷)=C(R¹⁸)-; where Ar is attached on either side to Q; m is 0, 1 or 2; R² is H, C₁-C₆-alkyl; R⁴, R⁵, R⁷, R⁸, R⁹, R¹⁰, R¹⁷, R¹⁸ are the same or different and are H, C₁-C₆-alkyl; R⁶ is H, C₁-C₆-alkyl unsubstituted or substituted with halogen, or -CH₂-phenyl; Ar is phenyl or 5- or 6-element hetaryl, which is unsubstituted or substituted with R^Ar, where R^Ar is C₁-C₆-alkyl, C₁-C₆-alkoxy, where alkyl, alkoxy substituents are substituted or unsubstituted with halogen, R¹ is a substituent of the formula Y-Z-T-R¹¹ or Y-Z-T-R¹²; where Y is -CR^ya=N-, where N is attached to Z; -NR^yc-C(=O)-, where C(=O) is attached to Z; or Z is a simple bond; -NR^zc-C(=S)-, where C(=S) is attached to T; -N=C(S-R^za)-, where T is attached to a carbon atom; -O-C(=O)-, where T is attached to a carbon atom; or T is O, N or N-R^T; R¹¹ is phenyl, hetaryl, carbonyl-hetaryl, hetaryl-C₁-C₄-alkyl or hetaryloxy-C₁-C₄-alkyl, where phenyl rings are not substituted or substituted with R_g, and where hetaryl is 5- or 6-element monocyclic hetaryl, which contains one oxygen atom and one sulfur atom in the ring; R¹² is a radical of the formula A¹, where # is a point of attachment to T; R¹²¹, R¹²², R¹²³ are C₁-C₆-alkoxy; R¹²⁴ is C₁-C₆-alkyl; and where R^ya is H; R^yc, R^zc are H; R^T is H; R^za is C₁-C₆-alkyl; R^g is C₁-C₆-alkyl. A pesticide composition containing pesticide-effective amount of a compound of the formula (I), a method for destroying or controlling invertebrate pests, a method for protecting cultivated plants and the use of a compound of the formula (I) are also proposed.

EFFECT: proposed compound shows high pesticide activity, and it can be used to protect cultivated plants from attack or infection by invertebrate pests.

6 cl, 3 tbl, 37 ex

Description

Invertebrate pests, such as insects, arachnids and nematodes, destroy cultivated and harvested crops and attack wooden dwellings and outbuildings, thereby causing significant economic losses in food supply and damage to property. Accordingly, there is a need for new means of controlling invertebrate pests.

For example, from patent publication WO 2016/156076 carbamoylated and thiocarbamoylated oxime derivatives are known that have found application as pesticides, from patent publication WO 2016/116445 derivatives of semicarbazones and thiosemicarbazones are known that have found application as pesticides.

Due to the ability of target pests to acquire resistance to pesticidal active agents, there is a need to identify additional compounds for the control of invertebrate pests such as insects, arachnids and nematodes. In addition, there is a need for new compounds having high pesticidal activity and exhibiting a broad spectrum of activity against a wide variety of invertebrate pests, especially against difficult-to-control insects, arachnids and nematodes.

Therefore, the aim of the present invention is to identify and create compounds that exhibit high pesticidal activity and have a wide spectrum of activity against invertebrate pests.

It has been found that these objectives can be achieved with substituted bicyclic compounds of formula I as shown and described below, including their stereoisomers, their salts, in particular their agriculturally or veterinarily acceptable salts, their tautomers and their N-oxides.

In one aspect, the present invention relates to compounds of formula I,

where

A ¹ is N or CR ^A ;

A ² is N or CR ^B ;

A ³ is N or CR ^B1 ;

W is O, S(=O) _m or NR ⁶ ;

R ^A , R ^{B and} R ^B1 are independently H, halogen, N ₃ , OH, CN, NO ₂ , -SCN, -SF ₅ , C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy , C ₂ -C ₆ -alkenyl, tri-C ₁ -C ₆ -alkylsilyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl, C ₁ -C ₆ -alkoxy -C ₁ -C ₄ -alkoxy, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkoxy, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkyl-C ₃ -C ₆ -cycloalkoxy, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted by halogen, C(=O)-OR ^a , NR ^b R ^c ,

OC ₁ -C ₆ -alkylene-NR ^b R ^c , C ₁ -C ₆ -alkylene-CN, NH-C ₁ -C ₆ -alkylene-NR ^b R ^c , C(=O)-NR ^b R ^c , C (=O)-R ^d , SO ₂ NR ^b R ^c , or S(=O) _m R ^e , phenyl, phenoxy, phenylcarbonyl, phenylthio, or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted by R ^f ;

Q is -C(R ⁴ R ⁵ )-O-, -C(=O)-O-, -S(=O) _m -C(R ⁷ R ⁸ )-, -N(R ² )-S (=O) _m- ,

-N(R ² )-C(R ⁹ R ¹⁰ )-, -C(=O)-C(R ¹⁹ R ²⁰ )-, -N(R ² )-C(=O)-, -C(R ¹³ R ¹⁴ )-C(R ¹⁵ R ¹⁶ )- or

-C(R ¹⁷ )=C(R ¹⁸ )-; where Ar is attached on either side to Q;

m is 0, 1 or 2;

R ² is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy-C ₁ -C ₄ alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₄ -alkyl, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted with halogen, C(=O)-OR ^a , C ₁ -C ₆ -alkylene-NR ^b R ^c , C ₁ -C ₆ -alkylene-CN,

C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c , S(=O) _m R ^e , phenyl or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted R ^f ;

R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ are the same or different and are H, halogen, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₄ -alkyl, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted by halogen , C(=O)-OR ^a , C ₁ -C ₆ -alkylene-NR ^b R ^c ,

C(=O)-OR ^a , C ₁ -C ₆ -alkylene-NR ^b R ^c , C ₁ -C ₆ -alkylene-CN, C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c , S(=O) _m R ^e , phenyl or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted by R ^f ;

R ⁶ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy-C ₁ -C ₄ alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₄ -alkyl, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted with halogen, C(=O)-OR ^a , C ₁ -C ₆ -alkylene-NR ^b R ^c , C ₁ -C ₆ -alkylene-CN,

C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c , S(=O) _m R ^e , phenyl, -CH ₂ -C(=O)-OR ^a or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted with R ^f ;

Ar is phenyl or a 5- or 6-membered hetaryl which is unsubstituted or substituted with R ^Ar where

R ^Ar is halogen, N ₃ , OH, CN, NO ₂ , -SCN, -SF ₅ , C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₂ -C ₆ alkenyl, tri-C ₁ -C ₆ -alkylsilyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkoxy, C ₃ - C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkoxy, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₄ -alkyl, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted with halogen,

C(=O)-OR ^a , NR ^b R ^c , C ₁ -C ₆ -alkylene-NR ^b R ^c , OC ₁ -C ₆ -alkylene-NR ^b R ^c , C ₁ -C ₆ -alkylene-CN, NH-C ₁ -C ₆ -alkylene-NR ^b R ^c , C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c or S(=O) _m R ^e , phenyl, phenoxy, phenylcarbonyl, phenylthio or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted with R ^f ;

R ¹ is a substituent of the formula YZTR ¹¹ or YZTR ¹² ; where

Y is -CR ^ya =N-, where N is attached to Z;

-NR ^yc -C(=O)-, where C(=O) is attached to Z; or

-NR ^yc -C(=S)-, where C(=S) is attached to Z;

Z is a single bond;

-NR ^zc -C(=O)-, where C(=O) is attached to T;

-NR ^zc -C(=S)-, where C(=S) is attached to T;

-N=C(SR ^za )-, where T is attached to a carbon atom;

-O-C(=O)-, where T is attached to a carbon atom, or

-NR ^zc -C(SR ^za )=, where T is attached to a carbon atom;

T is O, N or NR ^T ;

R ¹¹ is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy-C ₁ -C ₄ alkyl, C ₃ -C ₆ - cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkyl-C ₃ -C ₆ -cycloalkoxy, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted halogen, C ₁ -C ₆ -alkylene-NR ^b R ^c , C ₁ -C ₆ -alkylene-CN, C (=O) -NR ^b R ^c , C (=O) -R ^d , aryl, aryl- carbonyl, aryl-C ₁ -C ₄ -alkyl, aryloxy-C ₁ -C ₄ -alkyl,

hetaryl, carbonyl-hetaryl, hetaryl-C ₁ -C ₄ -alkyl or hetaryloxy-C ₁ -C ₄ -alkyl, where the phenyl rings are unsubstituted or substituted with R ^g and where hetaryl is a 5- or 6-membered monocyclic hetaryl or 8- , 9- or 10-membered bicyclic hetaryl;

R ¹² is a radical of formula A ¹ ;

where # denotes the point of attachment to T;

R ¹²¹ , R ¹²² , R ¹²³ are the same or different and are H, halogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy -C ₁ -C ₄ -alkyl, C ₁ -C ₆ -alkoxy, C ₂ -C ₆ -alkenyloxy, C ₂ -C ₆ -alkynyloxy, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkoxy, C ₁ -C ₆ -alkylcarbonyloxy, C ₁ -C ₆ -alkenyl-carbonyloxy, C ₃ -C ₆ -cycloalkylcarbonyloxy, where alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy and cycloalkyl substituents are substituted or unsubstituted by halogen or NR ^b R ^c or one of R ¹²¹ , R ¹²² , R ¹²³ may also be oxo;

R ¹²⁴ is H, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl, C ₁ -C ₆ -alkoxy or C ₂ -C ₆ -alkenyloxy, where alkyl, alkoxy , alkenyl and alkenyloxy substituents are substituted or unsubstituted with halogen;

and where

R ^ya is H, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -alkyl-C ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -alkyl-C ₃ -C ₆ -cycloalkoxy, where alkyl, alkoxy , alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted with halogen,

C(=O)-OR ^a , C ₁ -C ₆ -alkylene-NR ^b R ^c , C ₁ -C ₆ -alkylene-CN, C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c , S(=O) _m R ^e , phenyl or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted by R ^f ;

R ^yc , R ^zc are the same or different and are H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₄ alkyl-C ₁ -C ₆ -alkoxy, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -alkyl-C ₃ -C ₆ -cycloalkyl or C ₁ -C ₄ -alkyl-C ₃ -C ₆ -cycloalkoxy, where alkyl, alkoxy, alkenyl , alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted with halogen;

R ^T is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₄ alkyl-C ₁ -C ₆ alkoxy, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₄ -alkyl, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted with halogen,

C(=O)-OR ^a , C ₁ -C ₆ -alkylene-NR ^b R ^c , C ₁ -C ₆ -alkylene-CN, C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c , S(=O) _m R ^e , phenyl or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted by R ^f ;

R ^zc together with R ^T , if present, may form a C ₁ -C ₆ alkylene or a linear C ₂ -C ₆ alkenylene group, where CH ₂ is a substituent for a linear C ₁ -C ₆ alkylene and a linear C ₂ -C ₆ -alkenylene can be replaced by carbonyl or C=NR' and/or where 1 or 2 CH ₂ substituents can be replaced by O or S and/or where linear C ₁ -C ₆ -alkylene and linear C ₂ -C ₆ -alkenylene can be unsubstituted or substituted with R ^h ;

R ^za is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₂ -C ₆ alkenyl, tri-C ₁ -C ₆ alkylsilyl, C ₂ -C ₆ alkynyl, C ₁ -C ₄ -alkyl-C ₁ -C ₆ -alkoxy, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -alkyl-C ₃ -C ₆ -cycloalkoxy, C ₁ -C ₄ -alkyl-C ₃ -C ₆ -cycloalkyl, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted by halogen, C ₁ -C ₆ -alkylene-NR ^b R ^c , C ₁ -C ₆ -alkylene-CN, (=O) -NR ^b R ^c , C(=O)-R ^d , phenyl, phenylcarbonyl or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted with R ^f ;

R ^za together with R ^T , if present, may form a C ₁ -C ₆ alkylene or linear C ₂ -C ₆ alkenylene group, where CH ₂ is a substituent for linear C ₁ -C ₆ alkylene and linear C ₂ -C ₆ -alkenylene can be replaced by carbonyl or C=NR' and/or where 1 or 2 CH ₂ substituents can be replaced by O or S and/or where linear C ₁ -C ₆ -alkylene and linear C ₂ -C ₆ -alkenylene can be unsubstituted or substituted with R ^h ;

R ^a , R ^b and R ^c are the same or different and are H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₄ -alkyl, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted by halogen, C ₁ -C ₆ -alkylene-CN, phenyl or -CH ₂ -phenyl,

where the phenyl rings are unsubstituted or substituted with R ^f ;

R ^d is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy-C ₁ -C ₄ alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₄ -alkyl, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted with halogen, phenyl or -CH ₂ -phenyl,

where the phenyl rings are unsubstituted or substituted with R ^f ;

R ^e represents C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, where alkyl, cycloalkyl substituents are substituted or unsubstituted with halogen, phenyl and - CH ₂ -phenyl,

where the phenyl rings are unsubstituted or substituted with R ^f ;

R ^f is halogen, N ₃ , OH, CN, NO ₂ , -SCN, -SF ₅ , C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₂ -C ₆ alkenyl, tri-C ₁ -C ₆ -alkylsilyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkoxy, C ₃ - C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkoxy, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₄ -alkyl, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted by halogen, C(=O)-OR ^a , NR ^b R ^c , C ₁ -C ₆ -alkylene-NR ^b R ^c , -C ₁ -C ₆ -alkylene- NR ^b R ^c , C ₁ -C ₆ -alkylene-CN, NH-C ₁ -C ₆ -alkylene-NR ^b R ^c , C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c or S(=O) _m R ^e ;

R ^g is halogen, N ₃ , OH, CN, NO ₂ , -CN, -SF ₅ , C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, C ₂ -C ₆ -alkenyl, tri-C ₁ -C ₆ -alkylsilyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkoxy, C ₃ - C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkoxy, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₄ -alkyl, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted by halogen, C(=O)-OR ^a , NR ^b R ^c , C ₁ -C ₆ -alkylene-NR ^b R ^c , -C ₁ -C ₆ -alkylene- NR ^b R ^c , C ₁ -C ₆ -alkylene-CN, NH-C ₁ -C ₆ -alkylene-NR ^b R ^c , C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c or S(=O) _m R ^e ;

R ^h is halogen, OH, C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl or CN;

with the proviso that when Z is a single bond, R ^T is different from H;

and their N-oxides, stereoisomers, tautomers, and agriculturally or veterinarily acceptable salts.

In addition, the present invention also relates to processes and intermediates for the preparation of compounds of formula I and active compound combinations which contain them. In addition, the present invention relates to agricultural or veterinary compositions containing compounds of formula I, and the use of compounds of formula I or compositions that contain them, for the destruction or control of invertebrate pests and/or for the protection of crops, plants, plant propagation material and/or cultivated plants from attack and/or infestation by invertebrate pests. The present invention also relates to methods of using compounds of formula I. In addition, the present invention relates to seeds containing compounds of formula I, where the compounds of formula I include N-oxides, stereoisomers, tautomers and their agriculturally or veterinarily acceptable salts.

General technique:

With appropriate modification of the starting compounds, the compounds of formula I can be obtained in accordance with the methods given in the schemes below.

Compounds of formula (I) can be prepared by organic chemistry methods, for example, using the methods described in this document further after schemes 1-26 and in the description of the synthesis of examples. In schemes 1 - 26, the radicals Ar, A ¹ , A ² , A ³ and R ¹ , R ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ^ya , R ^zc , R ^yc , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are as defined for formula (1), unless otherwise indicated.

Compounds of formula (I) wherein Z is a single bond or -NR ^zc -C(=S)- or -NR ^zc -C(=O)- and T is O, N or NR ^T are compounds of formula (Ia ) and can be obtained by analogy with the methods described in WO 2011/017504 or WO 2015/007682, or the methods described in Scheme 1.

Scheme 1:

In one embodiment of Scheme 1, an aldehyde or ketone of formula (II) is reacted with a compound of formula (E1) where Z is -NR ^zc -C(=S)- or -NR ^zc -C (=O)- and T is N, in the presence or absence of a solvent. Suitable solvents are polar protic solvents. If the reaction is carried out in the absence of a solvent, the compound of formula (E1) also usually acts as a solvent. The compounds of formula (E1) are commercially available or can be prepared using organic reactions similar to the method described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March.

According to another embodiment of Scheme 1, an aldehyde or ketone of formula (II) is first reacted with a hydrazine of formula R ^zc NHNH ₂ , and then reacted with an isocyanate of formula R ¹¹ -NCO or isothiocyanate R ¹¹ -NCS to obtain a compound of formula (Ia), where Z is -N(R ^zc )-C(=O) or

-N(R ^zc )-C(=S) and T is N.

According to another embodiment of Scheme 1, the aldehyde or ketone of formula (II) is first reacted with hydroxylamine, followed by reaction with an R ¹² -L compound, where L is a suitable leaving group such as halogen or activated OH. Thus, a compound of formula (Ia) is obtained, where Z is a single bond and T is O.

In another embodiment of the above reaction, an aldehyde or ketone of formula (II) is first reacted with hydroxylamine, followed by reaction with an isocyanate of formula R ¹¹ -NCO or isothiocyanate R ¹¹ -NCS to give a compound of formula (Ia) wherein Z is -OC(=O)- or

-OC(=S)- and T is N.

Compounds of formula (Ib) wherein Z is -NR ^zc -C(=S)- or -NR ^zc -C(=O)- wherein C(=S) or C(=O) is attached to T and T is O, N or NR ^T , can be obtained by analogy with the method described in Synthesis, 2010, 2990-296, or as shown in Scheme 2.

Scheme 2:

According to the method shown in Scheme 2, the isocyanate of formula (IIIa) is subjected to reaction with the compound of formula (E2) in accordance with the methods of isocyanate chemistry. The isocyanate of formula (IIIa) can be obtained, for example, using the Lossen rearrangement of the corresponding hydroxamic acid (IVa). Hydroxamic acid (IVa) is reacted with 1-propanephosphonic acid cyclic anhydride (T3P) in the presence of a base. The base is preferably N-methylmorpholine. An isocyanate of formula (IIIa) can be prepared by a Curtius rearrangement of the corresponding azide of formula (IVb), for example in analogy to the method described in WO 2014/204622.

To convert compounds of formula (Ia) and (Ib) where R ^yz or R ^zc is H to compounds (I) where R ^yz or R ^zc is different from H, compounds of formula (Ia) and (Ib) where R ^yz or R ^zc is H can be reacted with compounds of the formulas R ^yz -Lg or R ^zc -Lg, where R ^yz or R ^zc is different from H and Lg is a leaving group such as a bromine, chlorine or iodine atom or tosylate, mesylate or triflate to give compounds of formula (Ia) and (Ib) wherein R ^yz or R ^zc is different from H. The reaction is conveniently carried out in the presence of a base such as sodium hydride or potassium hydride, conveniently in a polar aprotic solvent, such as N,N-dimethylformamide, tetrahydrofuran, dioxane, acetonitrile, dimethyl sulfoxide or pyridine, or a mixture of these solvents, at a temperature in the range of 0 °C to 100 °C.

Compounds of formula (Ic) can be prepared from compounds of formula (IIc) using the reactions shown below.

Scheme 3:

R ^11/12 corresponds to the radicals R ¹¹ or R ¹² respectively. The reaction shown above can be carried out by analogy with conventional methods for the preparation of carbamates. In a first embodiment, an amine of formula (IIc) is converted to either an isocyanate or a p-nitrophenyl carbamate after treatment with an alcohol of formula R ¹¹ -OH or R ¹² -OH, respectively, in the presence of an organic or inorganic base. In another embodiment, a compound of formula (IIc) is reacted with a chloroformate of formula R ^{11/12 -OC} (=O)-Cl. Chloroformate is obtained from alcohols R ¹¹ / ¹² -OH by treatment with phosgene or triphosgene in the presence of a base, such as pyridine. Compounds of formula (Ic) where Z is -N(R ^zc )-C(=O)- or -N(R ^zc )-C(=S)- can be prepared in analogy to the methods described in WO 2013 /009791, or by analogy with the methods described in US 2012/0202687.

Compounds of formula (IIb) and (IIc) can be prepared from compounds of formula (IIa) using the reactions shown below.

Scheme 4:

In the above reactions, -Hal represents a bromine, chlorine or iodine atom or tosylate, mesylate or triflate. The reaction step (i) can be carried out in analogy to the method described in WO 2015/051341. Reaction step (ii) can be carried out in analogy to the method described in European Journal of Medicinal Chemistry, 49, 310-323, 2012. Compounds of formula (IIc) (step (iii) of the above reaction) can be prepared by reacting compounds of formula ( IIa) with ammonia or amines of the formula R ^yc NH ₂ in the presence of a metal catalyst or its salts, preferably copper or its salts, as described in Chem. Commun., 2009, 3035-3037.

Compounds of formula (IIa-1) and (IIa-2) wherein Q is -N(R ² )-C(=O)- or OC(=O) and W is N(R ⁶ ) can be prepared using the reactions shown below.

Scheme 5:

In the above reactions, -Hal represents a bromine, chlorine or iodine atom or a tosylate, mesylate or triflate, preferably bromine. Compounds of formula (IIa-1) can be prepared from conventional intermediates of formula (IIg-2) by forming an amide by reacting compounds of formula (IIg-2) with Ar-NH ₂ in the presence of a suitable condensing agent such as HATU and a base, such as DIPEA. Compounds of formula (IIa-2) can be prepared from conventional intermediates of formula (IIg-2) by esterification by reacting a compound of formula (IIg-2) with ArOH in the presence of an acid. Steps (vi) and (vii) can be carried out in a manner similar to that described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March.

Compounds of formula (IIg-2) can be prepared from compounds of formula (IIg) in two steps. Step (iv) can be carried out by reacting compounds of formula (IIg) with alkyl halides in the presence of suitable bases such as potassium carbonate, as described in WO 2011/050245. Step (v) includes hydrolysis of the ester with a suitable base such as LiOH, NaOH as mentioned in WO 2011/050245.

Compounds of formula (IIg) are commercially available and can also be prepared from compounds of formula (IId) using the reactions shown below. Compounds of formula (IId) are commercially available.

Scheme 6:

In the above reactions, -Hal' represents a bromine, chlorine, fluorine or iodine atom, preferably fluorine or chlorine. -Hal is a bromine, chlorine or iodine atom or a tosylate, mesylate or triflate, preferably bromine. Compounds of formula (IIe) can be prepared from compounds of formula (IId) via a 4-step sequence. Step (viii) involves reduction of the ester to an aldehyde using DIBAL as the reducing agent as described in Tetrahedron Letters, 48(29), 5061-5064, 2007. Step (ix) involves cyclization by boiling with hydrazine in DMF as described in Journal of Organic Chemistry, 71(21), 8166-8172, 2006. Step (x) involves introducing a formyl group at position 3 according to the methods described in WO 2016/057834. Step (xi) involves N-alkylation using the appropriate alkyl halides with suitable bases such as potassium carbonate as described in WO 2011/050245. Compounds of formula (IIf) can be prepared by oxidation of compounds of formula (IIe) using KMnO ₄ and compounds of formula (IIh) can be prepared by reduction of compounds of formula (IIe) using NaBH as described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March. Compounds of formula (IIg) can be prepared from compounds of formula (IIe) by esterification in analogy to the method described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March.

Compounds of formula (IIa-3) wherein Q is -C(R ¹⁹ R ²⁰ )-C(=O)- and W is N(R ⁶ ) can be prepared from compounds of formula (IIf) according to the reactions below.

Scheme 7:

In the above reactions, -Hal represents a bromine, chlorine or iodine atom, preferably bromine. Compounds of formula (IIa-3) can be prepared from compounds of formula (IIf) in analogy to the methods described in Organic Letters 2016, 18(23), 6026-6029.

Compounds of formula (IIa-4), (IIa-5) and (IIa-6) can be obtained from compounds of formula (IIi) in the following way.

Scheme 8:

In the reactions above, -Hal' may be fluorine, chlorine, bromine or iodine, preferably chlorine or bromine, and -Hal may be chlorine, bromine or iodine, preferably bromine. Compounds of formula (IIa-4), (IIa-5) and (IIa-6) can be prepared from compounds of formula (IIi) by reaction with compounds of formula Ar-OH or Ar-NHR ² or Ar-SH by heating in a polar protic or aprotic solvent in acidic, basic or neutral media as described in WO 2010/129053, WO 2007/146824 or Chemical Communications, 2014, 50, 1465. Compounds of formula (IIi) can be prepared from compounds of formula (IIh) using methods similar to those described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March.

Compounds of formula (IIa-7) and (IIa-8) can be prepared by the reactions below.

Scheme 9:

In the above scheme, -Hal is fluorine, chlorine, bromine or iodine, preferably bromine. Step (xx) includes hydrolysis of the ester with a suitable base such as LiOH, NaOH as mentioned in WO 2011/050245. Step (xxi) involves the formation of an amide by reacting compounds of formula (IIk) with Ar-NH ₂ in the presence of a suitable condensing agent such as HATU and a base such as DIPEA. Step (xxii) involves esterification by reacting a compound of formula (IIk) with ArOH in the presence of an acid. Steps (xxi) and (xxii) can be carried out in analogy to the method as described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March.

Compounds of formula (IIj) are commercially available and can also be prepared from compounds of formula (IId) using the reactions shown below. Compounds of formula (IId) are commercially available.

Scheme 10:

In the above reactions -Hal represents fluorine, chlorine, bromine or iodine, preferably bromine, and -Hal' represents fluorine, chlorine, bromine or iodine, preferably fluorine. In the scheme above, step (xxiii) involves converting the ester to methyl ketone using organic reactions in a manner similar to that mentioned in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March. Step (xxiv) involves the formation of an oxime by refluxing the ketone with NH ₂ OH•HCl in a protic solvent such as MeOH, similar to the method described in Medicinal Chemistry Research, 25 (3), 449-455, 2016. Step (xxv) includes a base-catalyzed cyclization similar to the method described in WO 2015/042397. Step (xxvi) involves the oxidation of the SeO ₂ methyl group to an aldehyde as described in European Journal of Medicinal Chemistry, 84, 42-50, 2014. Steps (xxvii) and (xxviii) involve oxidation and reduction similar to the methods described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March. Step (xxix) involves converting oxime to thioxime using a Lawesson reagent as described in Phosphorus, Sulfur and Silicon and the Related Elements, 184(9), 2408-2426, 2009. Steps (xxx), (xxxi), (xxxii) and (xxxiii) can be carried out similarly to steps (xxv), (xxvi), (xxvii) and (xxviii). Compounds of formula (IIj) can be prepared from compounds of formula (IIk-1) and (IIk-2) by esterification in analogy to the method described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March.

Compounds of formula (IIa-9) where W is S or O can be prepared from compounds of formula (IIk) by the reactions below.

Scheme 11:

Compounds of formula (IIa-9) can be prepared from compounds of formula (IIk) in analogy to the methods described in Organic Letters 2016, 18(23), 6026-6029.

Compounds of formula (IIa-10), (IIa-11) and (IIa-12) where W is S or O can be prepared from compounds of formula (IIm) by the reactions below.

Scheme 12:

In the above reaction, Hal' may be fluorine, chlorine, bromine or iodine, preferably chlorine or bromine. Hal may be chlorine, bromine or iodine, preferably bromine or tosylate, mesylate or triflate. Compounds of formula (IIa-10), (IIa-11) and (IIa-12) can be prepared from compounds of formula (IIn) by reaction with compounds of formula Ar-OH or Ar-NHR ² or Ar-SH by heating in a polar protic or aprotic solvent in acidic, basic or neutral media as described in WO 2010/129053, WO 2007/146824 or Chemical Communications, 2014, 50, 1465. Compounds of formula (IIn) can be prepared from compounds of formula (IIm) using organic reactions similar to the method described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March. Compounds of formula (IIa-12) can also be oxidized using mCPBA to produce compounds with various sulfur oxidation states as described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March.

Compounds of formula (IIa-13) and (IIa-14) wherein W is N(R ⁶ ) or O or S can be prepared from compounds of formula (IIe), (IIl-1) and (IIl-2) by the reactions below.

Scheme 13:

In the above reaction, -Hal is chlorine or bromine, preferably bromine. Compounds of formula (IIa-13) and (IIa-14) where W is N(R ⁶ ) or O or S can be prepared from compounds of formula (IIe), (IIl-1) and (IIl-2) with using a Wittig reaction using a phosphorus ylide and bases such as K ^t BuO in THF followed by hydrogenation in a manner known in organic chemistry such as using hydrogen gas and a suitable metal catalyst as described in March's Advanced Organic Chemistry 6th edition, Michael B Smith and Jerry March.

Compounds of formula (IIa-15) can be prepared from commercially available compounds of formula (IId) by the reactions below.

Scheme 14:

In the above reaction, -Hal' represents chlorine, fluorine, bromine or iodine, preferably fluorine and chlorine, and -Hal represents chlorine, bromine or iodine, preferably bromine. Compounds of formula (IIo) can be prepared from (IId) by reacting it with substituted hydrazines in protic solvents such as EtOH and microwave irradiation as described in WO 2010/054279. Compounds of formula (IIa-15) can be obtained from (IIo) by esterification in analogy to the method described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March.

Compounds of formula (IIa-16) and (IIa-17) can be prepared from compounds of formula (IIo) and (IIp) by the reactions below.

Scheme 16:

In the above reaction, -Hal is chlorine, bromine or iodine, preferably bromine. Compounds of formula (IIa-16) and (IIa-17) can be prepared by heating compounds of formula Ar-C(R ⁴ R ⁵ )-Lg and Ar-C(R ⁷ R ⁸ )-Lg (wherein Lg may be bromine , chlorine, tosylate, mesylate) in a polar protic or aprotic solvent with compounds of formula (IIo) and (IIp) in acidic, basic or neutral media similar to the methods described in WO 2010/129053, WO 2007/146824 or Chemical Communications, 2014, 50, 1465. Step (xlvi) involves converting a hydroxyl group to a thiol group using Lawesson's reagent. Compounds of formula (IIa-17) can be further oxidized using mCPBA to produce compounds with different oxidation states of sulfur in a manner similar to that described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March.

Compounds of formula (IIa-18), (IIa-19) and (IIa-20) can be prepared by the reactions below.

Scheme 17:

In the above reaction, -Hal is chlorine, bromine or iodine, preferably bromine, and -Hal' is chlorine, fluorine, bromine or iodine, preferably fluorine or chlorine. Compounds of formula (IIa-18), (IIa-19) and (IIa-20) can be prepared from commercially available compounds of formula (IIq) in two steps. By reacting compounds (IIq) with substituted hydrazines in protic solvents such as EtOH and microwave irradiation as described in WO 2010/054279, compounds of formula (IIr) can be obtained. Compounds of formula (IIa-18) can be prepared by heating compounds of formula Ar-C(R ⁹ R ¹⁰ )-Lg (wherein Lg may be bromine, chlorine, tosylate, mesylate) with compounds of formula (IIr) in polar protic or aprotic solvent in an acidic, basic or neutral medium similar to the methods described in WO 2010/129053, WO 2007/0146824 or Chemical Communications, 2014, 50, 1465, as shown in step (xlix). Compounds of formula (IIa-9) can be prepared from compounds of formula (IIr) using an amide coupling reaction similar to the methods described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March, as shown in step (l). Compounds of formula (IIa-20) can be prepared from compounds of formula (IIr) by treatment with an appropriate Ar-SO ₃ Cl in the presence of bases such as pyridine and condensing agents such as DMAP, as described in Chemistry - A European Journal, 20 (1), 317-322, 2014 (stage(li)).

Compounds of formula (IIa-21) (IIa-22) and (IIa-23) can be prepared by the reactions below.

Scheme 18:

In the above reaction Hal' is chlorine, bromine or iodine, preferably bromine. Compounds of formula (IIa-21) and (IIa-23) can be prepared by heating compounds of formula Ar-C(R ⁴ R ⁵ )-Lg and Ar-C(R ⁷ R ⁸ )-Lg (wherein Lg may be bromine , chlorine, tosylate, mesylate) with compounds of formula (IIs) and (IIt) in a polar protic or aprotic solvent in acidic, basic or neutral media as described in WO 2010/129053, WO 2007/146824 or Chemical Communications, 2014, 50 , 1465, as shown in steps (lii) and (liv). Compounds of formula (IIa-22) can be prepared from compounds of formula (IIs) by esterification as described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March, as shown in step (li). Step (liii) involves converting a hydroxyl group to a thiol group using Lawesson's reagent. Compounds of formula (IIa-23) can be further oxidized using mCPBA to produce compounds with different oxidation states of sulfur in a manner similar to that described by March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March.

Compounds of formula (IIs) are commercially available or can be prepared from commercially available compounds of formula (IId') by the reactions below.

Scheme 19:

In the above reaction, -Hal is chlorine, bromine or iodine, preferably bromine. Suitable reaction conditions for carrying out the above reaction steps are described in Organic Process Research & Development, 2016, 20, 233-241.

Compounds of formula (IIa-24), (IIa-25) and (IIa-26) can be prepared by the reactions below.

Scheme 20:

In the above reaction, -Hal is chlorine, bromine or iodine, preferably bromine. Compounds of formula (IIa-25) can be prepared by heating compounds of formula Ar-C(R ⁹ R ¹⁰ )-Lg (wherein Lg may be bromine, chlorine, tosylate, mesylate) with compounds of formula (IIu) in polar protic or aprotic solvent in an acidic, basic or neutral medium as described in WO 2010/129053, WO 2007/146824 or Chemical Communications, 2014, 50, 1465, as shown in step (lviii). Compounds of formula (IIa-24) can be prepared from compounds of formula (IIu) using an amide coupling reaction similar to the methods described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March, as shown in step (lvii). Compounds of formula (IIa-26) can be prepared from compounds of formula (IIu) by treatment with an appropriate Ar-SO ₃ Cl in the presence of bases such as pyridine and condensing agents such as DMAP, as described in Chemistry - A European Journal, 20 (1), 317-322, 2014 (stage (lix)).

Compounds of formula (IIu) are commercially available or can be prepared from commercially available compounds of formula (IId) by the reactions below.

Scheme 21:

In the above reaction, -Hal is chlorine, bromine or iodine, preferably bromine, and -Hal' is chlorine, fluorine, bromine or iodine, preferably fluorine or chlorine. Compounds of formula (IIu) can be prepared from commercially available compounds of formula (IId). Step (lx) includes recovery using NaBH ₄ as described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March. Step (lxi) involves converting alcohols to nitriles by treating the alcohols with tert-butyl hypochlorite in the presence of (2,2,6,6-tetramethylpiperidin-1-yl)oxidanil (TEMPO) as described in Synthesis, 2013, 45, 2155-2164. Step (lxii) involves the one-pot cyclization of ortho-substituted benzonitriles to 3-amino-1,2-benzisoxazoles as described in Tetrahedron Letters, Vol. 37, no. 17, 2885-2886, 1996.

Compounds of formula (IIa-27), (IIa-28) and (IIa-29) can be prepared by the reactions below.

Scheme 22:

In the above reaction, -Hal is chlorine, bromine or iodine, preferably bromine. Compounds of formula (IIa-28) and (IIa-29) can be prepared by heating compounds of formula Ar-C(R ⁴ R ⁵ )-Lg and Ar-C(R ⁷ R ⁸ )-Lg (wherein Lg may be bromine , chlorine, tosylate, mesylate) with compounds of formula (IIv) and (IIw) in a polar protic or aprotic solvent in an acidic, basic or neutral medium, as described in WO 2010/129053, WO 2007/146824 or Chemical Communications, 2014, 50 , 1465 as shown in steps (lxiv) and (lxvi). Compounds of formula (IIa-27) can be prepared from compounds of formula (IIv) by esterification in analogy to the method described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March, as shown in step (lxiii). Step (lxv) involves converting a hydroxyl group to a thiol group using Lavesson's reagent. Compounds of formula (IIa-29) can be further oxidized using mCPBA to produce compounds with different oxidation states of sulfur in a manner similar to that described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March.

Compounds of formula (IIv) are commercially available or can be prepared from commercially available compounds of formula (IId) by the reactions below.

Scheme 23:

In the above reaction, -Hal is chlorine, bromine or iodine, preferably bromine, and -Hal' is chlorine, fluorine, bromine or iodine, preferably fluorine or chlorine. Compounds of formula (IIv) can be prepared from commercially available compounds of formula (IId). Step (lxvii) includes recovery using NaBH ₄ as described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March. Step (lxviii) involves converting alcohols to nitriles by treatment with tert-butyl hypochlorite in the presence of (2,2,6,6-tetramethylpiperidin-1-yl)oxidanil (TEMPO) as described in Synthesis, 2013, 45, 2155-2164. Steps (lxix) and (lxx) involve sequential Na ₂ S selective halogen replacement followed by oxidative cyclization as described in Journal of Medicinal Chemistry, 2016, 59, 9906-9918.

Compounds of formula (IIa-30), (IIa-31) and (IIa-32) can be prepared by the reactions below.

Scheme 24:

In the above reaction, -Hal is chlorine, bromine or iodine, preferably bromine. Compounds of formula (IIa-31) can be prepared by heating compounds of formula Ar-C(R ⁹ R ¹⁰ )-Lg (wherein Lg is bromine, chlorine, tosylate or mesylate) with compounds of formula (IIx) in polar protic or aprotic solvents in acidic, basic or neutral media as described in WO 2010/129053, WO 2007/146824 or Chemical Communications, 2014, 50, 1465 as shown in step (lxxii). Compounds of formula (IIa-30) can be prepared from compounds of formula (IIx) using an amide coupling reaction similar to the methods described in March's Advanced Organic Chemistry 6th edition, Michael B. Smith and Jerry March, as shown in step (lxxi). Compounds of formula (IIa-32) can be prepared from compounds of formula (IIx) by treatment with an appropriate Ar-SO ₃ Cl in the presence of bases such as pyridine and condensing agents such as DMAP, as described in Chemistry - A European Journal, 20 (1), 317-322, 2014 (stage(lxxiii)).

Compounds of formula (IIx) can be prepared from compounds of formula (IIv) by the reactions below.

Scheme 25:

In the above reaction, -Hal is chlorine, bromine or iodine, preferably bromine. Step (lxxiv) includes halogenation as described in European Journal of Medicinal Chemistry, 123 (2016) 332-353. Step (lxxv) includes amination as described in Chemistry A European Journal, 2015, 21, 3701 - 3707.

Compounds of formula (IIa-33) can be prepared by the reactions below.

Scheme 26:

In the above reaction, -Hal is chlorine, bromine or iodine, preferably bromine. Compounds of formula (IIa-33) can be prepared from compounds of formula (IIp), (IIt) and (IIw) using suitable reaction conditions as described in Chemistry Select, 3, 490-494, 2016 (step (lxxvi)), EP1992/524634 (stage (lxxvii)), Chemistry - A European Journal, 20(1), 317-322, 2014 (stage (lxxviii)).

Individual compounds of formula I can also be obtained by modification of other compounds of formula I or their intermediates.

If the synthesis provides mixtures of isomers, separation is generally not required because in some cases individual isomers may interconvert during processing for use or in use (eg, by exposure to light, acids or bases). Such transformations can also occur after use, for example, in the processing of plants in the treated plant or in harmful fungi to be controlled.

The skilled person will readily appreciate that the advantages for substituents, also in particular those shown in the tables below for the respective substituents given in this document in connection with compounds I, apply accordingly to the intermediates. Thus, the substituents in each case, independently of one another, or more preferably in combination, have the meanings defined herein.

Unless otherwise indicated, the term "compound(s) according to the invention" or "compound(s) of the invention" or "compound(s) of formula (I)" refers to compounds of formula I.

The term "compound(s) according to the invention" or "compounds of formula I" includes the compound(s) as defined herein, as well as their stereoisomer, salt, tautomer, or N-oxide. The term "compound(s) of the present invention" should be understood as equivalent to the term "compound(s) of the invention" and therefore also includes its stereoisomer, salt, tautomer or N-oxide.

The term "composition(s) according to the invention" or "composition(s) of the present invention" embraces composition(s) containing at least one compound of formula I according to the invention, as defined above. The compositions of the invention are preferably agricultural or veterinary compositions.

Depending on the substitution scheme, the compounds according to the invention may have one or more centers of chirality, in which case they exist as mixtures of enantiomers or diastereomers. The invention provides both individual pure enantiomers or pure diastereomers of the compounds according to the invention and mixtures thereof, as well as the use of pure enantiomers or pure diastereomers of the compounds according to the invention or mixtures thereof. Suitable compounds according to the invention also include all possible geometric stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may occur in the case of an alkene, a carbon-nitrogen double bond, or an amide group. The term "stereoisomer(s)" includes both optical isomers and enantiomers or diastereomers, the latter due to more than one center of chirality in the molecule, as well as geometric isomers (cis/trans isomers). The present invention relates to all possible stereoisomers of the compounds of formula I, that is to say to single enantiomers or diastereomers, as well as mixtures thereof.

The compounds of the invention may be amorphous or may exist in one or more different crystalline forms (polymorphs) which may have different macroscopic properties such as stability or exhibit different biological properties such as activity. The present invention relates to amorphous and crystalline compounds according to the invention, mixtures of different crystalline forms of the respective compounds according to the invention, as well as their amorphous or crystalline salts.

The term "tautomers" embraces isomers which are derivatives of compounds of formula I which are formed by displacement of an H atom, including at least one H atom located on a nitrogen, oxygen or sulfur atom. Examples of tautomeric forms are keto-enol forms, imine-enamine forms, urea-isourea forms, thiourea-isothiourea forms, (thio)amide-(thio)imidate forms, and the like.

The term "stereoisomers" includes both optical isomers and enantiomers or diastereomers, the latter due to more than one center of chirality in the molecule, as well as geometric isomers (cis/trans isomers).

Depending on the substitution scheme, the compounds of formula I may have one or more centers of chirality, in which case they exist as mixtures of enantiomers or diastereomers. One of the centers of chirality is the carbon atom of the isothiazoline ring, which carries the radical R ¹ . The invention provides both pure enantiomers or diastereomers and mixtures thereof, as well as the use according to the invention of pure enantiomers or diastereomers of compound I or mixtures thereof. Suitable compounds of formula I also include all possible geometric stereoisomers (cis/trans isomers) and mixtures thereof.

The term N-oxides refers to form I compounds in which at least one nitrogen atom is present in an oxidized form (as NO). More specifically, it refers to any compound of the present invention that contains at least one tertiary nitrogen atom oxidized to an N-oxide substituent.

N-oxides of compounds I can be prepared by oxidizing, for example, the ring nitrogen of the N-heterocycle, for example, the pyridine or pyrimidine ring present in Ar or R ¹¹ , or the imino nitrogen present in the central tricyclic ring, using a suitable oxidizing agent such as peroxycarboxylic acid or other peroxides. The person skilled in the art knows when and at what positions in the compounds of the present invention, N-oxides can be obtained.

Salts of compounds of formula I are preferably agriculturally and veterinarily acceptable salts. They can be prepared in a conventional manner, for example by reacting a compound with an acid anion in case the compound of formula I has a basic functionality, or by reacting an acidic compound of formula I with a suitable base.

Suitable agriculturally and veterinarily acceptable salts are in particular salts of those cations or acid addition salts of those acids whose cations and anions are known and suitable in the art for the formation of salts for agricultural and veterinary use, respectively, and do not have any undesirable effect on the effect of the compounds according to this invention. Suitable cations are in particular alkali metal ions, preferably lithium, sodium and potassium, alkaline earth metals, preferably calcium, magnesium and barium, and transition metals, preferably manganese, copper, zinc and iron, as well as ammonium (NH ₄ ⁺ ) and substituted ammonium, in which one to four hydrogen atoms are replaced by C ₁ -C ₄ -alkyl, C ₁ -C ₄ -hydroxyalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, hydroxy-C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, phenyl or -CH ₂ -phenyl. Examples of substituted ammonium ions are methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2(2-hydroxyethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, in addition, phosphonium ions , sulfonium ions, preferably tri-(C ₁ -C ₄ -alkyl)sulfone, and sulfoxonium ions, preferably tri-(C ₁ -C ₄ -alkyl)sulfoxonium. Suitable veterinarily acceptable acid addition salts, for example those formed by compounds of formula I containing a basic nitrogen atom, for example an amino group, are salts of inorganic acids, for example hydrochlorides, sulfates, phosphates and nitrates, and salts of organic acids, for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methanesulfuric acid, methanesulfonic acid and succinic acid.

Suitable acid addition salt anions are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and anions of C ₁ -C ₄ alkanoic acids, preferably formate , acetate, propionate and butyrate. They can be obtained by reacting a compound of formula I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

The term spineless pest, as used herein, covers animal populations such as insects, arachnids and nematodes that can infect plants, thereby causing significant damage to the plants they infect, as well as ectoparasites that can infect animals, in in particular, warm-blooded animals such as, for example, mammals or birds or other higher animals such as reptiles, amphibians or fish, thereby causing significant damage to infected animals.

The term "plant propagation material" means all generative parts of a plant such as seeds and vegetative plant material such as cuttings and tubers (eg potatoes) that can be used to propagate a plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which should be replanted after germination or after emerging from the soil. Plant propagation materials can be treated prophylactically with a plant protection agent either before planting or after transplanting. Said young plants may also be protected prior to transplantation by total or partial dip or flood treatment.

The term "plants" embraces any type of plant, including "modified plants" and in particular "cultivated plants".

The term "modified plants" refers to any of the wild-type species or related species or related genera of the cultivated plant.

The term "growing plants" includes plants that have been modified by breeding, mutagenesis, or genetic engineering, including, but not limited to, agricultural biotech products that are on the market or under development (see http://www.bio.org/speeches/ pubs/er/agri_products.asp).

Genetically modified plants are plants whose genetic material has been so modified by recombinant DNA techniques that it cannot be obtained under natural conditions by crossing, mutation or natural recombination. Typically, one or more genes are integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include, but are not limited to, targeted post-translational modification of protein(s), oligo- or polypeptides, for example by glycosylation or polymer addition, such as prenylated, acetylated, farnesylated fragments of PEG fragments.

Plants that have been modified by crossing, mutagenesis or genetic engineering, such as those that have been rendered resistant to treatment with specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4-D; bleaching herbicides such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors or phytoendesaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonylurea or imidazolinones; enolpyruvylshikimate 3-phosphate synthase (EPSP) inhibitors such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACC) inhibitors; or oxynil (ie bromoxynil or ioxynil) herbicides, as a result of conventional methods of crossing or genetic engineering; in addition, plants that have been conferred resistance to certain classes of herbicides through several genetic modifications, such as resistance to both glyphosate and glufosinate, or both glyphosate and another class of herbicides, such as ALS inhibitors, HPPD inhibitors, auxin herbicides or ACCase inhibitors. These herbicide tolerance technologies are, for example, described in Pest Management Science 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005, 269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Science 57, 2009, 108; Australian Journal of Agricultural Research 58, 2007, 708; Science 316, 2007, 1185; and in the literature cited therein. Some cultivated plants have acquired herbicide resistance through mutagenesis and conventional breeding methods, such as Clearfield® rape (canola, BASF SE, Germany) is resistant to imidazolinones, such as imazamox, or ExpressSun® sunflower (DuPont, USA) is resistant to sulfonylurea such as tribenuron. Genetic engineering techniques have been used to provide crop plants such as soybeans, cotton, corn, beets, and rapeseed with resistance to herbicides such as glyphosate, imidazolinones, and glufosinate, some of which are under development or available under brand names or trade names. brands RoundupReady® (glyphosate-resistant, Monsanto, USA), Cultivance® (imidazolinone-resistant, BASF SE, Germany) and LibertyLink® (glufosinate-resistant, Bayer CropScience, Germany).

In addition, also included are plants which, by application of recombinant DNA techniques, are capable of synthesizing one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, especially from Bacillus thuringiensis, such as δ-endotoxins, e.g., CryIA(b), CryIA (c) CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins (VIPs), eg VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacterial colonized nematodes, eg Photorhabdus spp. or Xenorhabdus spp.; toxins that are produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins that are produced by fungi such as Streptomycetes toxins, plant lectins such as pea or barley lectin; agglutinins; proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIPs) such as ricin, maize RIP, abrin, luffin, saporin, or bryodin; steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid IDP glycosyl transferase, cholesterol oxidase, ecdysone or HMG-CoA reductase inhibitors; ion channel blockers such as sodium or calcium channel blockers; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases and glucanases. In the context of the present invention, said insecticidal proteins or toxins should be clearly understood to include pretoxins, fusion proteins, truncated or otherwise modified proteins. Fusion proteins are distinguished by a novel combination of protein domains (see, for example, WO 02/015701). Additional examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed in, for example, EP-A 374753, WO 93/007278, WO 95/34656, EP-A 427529, EP-A 451878, WO 03/18810 and WO 03/52073. Methods for obtaining such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. These insecticidal proteins found in genetically modified plants confer resistance to pests from all taxonomic groups of arthropods, especially beetles (Coeloptera), dipterans (Diptera) and butterflies (Lepidoptera), as well as nematodes (Nematoda) in plants that produce these proteins. . Genetically modified plants capable of synthesizing one or more insecticidal proteins are, for example, the plants described in the publications mentioned above, some of which are commercially available, such as YieldGard® (maize cultivars producing Cry1Ab toxin), YieldGard® Plus ( corn cultivars producing Cry1Ab and Cry3Bb1 toxins), Starlink® (corn cultivars producing Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1, Cry35Ab1 and phosphinothricin-N-acetyltransferase [PAT] enzyme) NuCOTN® 33B (cotton cultivars, producing Cry1Ac toxin), Bollgard® I (cotton cultivars producing Cry1Ac toxin), Bollgard® II (cotton cultivars producing Cry1Ac and Cry2Ab2 toxins) VIPCOT® (cotton cultivars producing VIP toxin) NewLeaf® (potato cultivars producing Cry3A toxin ) Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (e.g. Agrisure® CB) and Bt176 from S yngenta Seeds SAS, France (corn cultivars producing Cry1Ab toxin and PAT enzyme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified type of Cry3A toxin, cf. WO 03/018810), MON 863 from Monsanto Europe SA, Belgium (corn cultivars producing Cry3Bb1 toxin), IPC 531 from Monsanto Europe SA, Belgium (cotton cultivars producing a modified type of Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium ( maize cultivars producing Cry1F toxin and PAT enzyme).

In addition, also included are plants which, by the use of recombinant DNA techniques, are capable of synthesizing one or more proteins to increase the resistance of such plants to, or tolerance to, bacterial, viral or fungal pathogens. Examples of such proteins are so-called "pathogenesis-related proteins" (PR proteins, see e.g. EP-A 392225), plant disease resistance genes (e.g. potato cultivars expressing resistance genes active against Phytophthora infestans, derived from the Mexican wild potato, Solanum bulbocastanum) or T4-lysozyme (eg potato cultivars capable of synthesizing such proteins with increased resistance against bacteria such as Erwinia amylovora). Methods for obtaining such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

Also included are plants that, due to the use of recombinant DNA techniques, are capable of synthesizing one or more proteins to increase productivity (e.g., biomass production, grain yield, starch content, oil content, or protein content), drought tolerance, soil salinity, or other limiting growth of environmental factors or tolerance of pests and fungal, bacterial or viral pathogens of such plants.

In addition, plants are included which, due to the use of recombinant DNA techniques, contain a modified amount of ingredients or new ingredients, in particular to improve human or animal nutrition, for example, oilseeds producing long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids. health promoting acids (eg Nexera® rapeseed, Dow AgroSciences, Canada).

In addition, plants are included which, due to the use of recombinant DNA techniques, contain a modified amount of ingredients or new ingredients, in particular to improve the production of raw materials, for example, potatoes that produce increased amounts of amylopectin (for example, Amflora® potatoes, BASF SE, Germany ).

The organic substituents mentioned in the above variable definitions are - like the term halogen - collective terms for separate lists of individual members. The prefix C _n -C _m indicates in each case the possible number of carbon atoms in the group.

The term halogen means in each case F, Br, Cl or I, in particular F, Cl or Br.

The term "alkyl", as used herein, and in alkyl substituents alkoxy, alkylthio, and the like, refers to saturated straight or branched hydrocarbon radicals containing 1-2 ("C ₁ -C ₂ -alkyl"), 1 - 3 ("C ₁ -C ₃ -alkyl"), 1 - 4 ("C ₁ -C ₄ -alkyl") or 1 - 6 ("C ₁ -C ₆ -alkyl") carbon atoms.

C ₁ -C ₂ -alkyl represents CH ₃ or C ₂ H ₅ . C ₁ -C ₃ -alkyl is additionally propyl and isopropyl. C ₁ -C ₄ alkyl is optionally butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1,1-dimethylethyl (tert-butyl). C ₁ -C ₆ -alkyl is additionally also, for example, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl.

The term "haloalkyl" as used herein, which is also expressed as "alkyl, partially or fully halogenated", straight or branched alkyl groups containing 1-2 ("C ₁ -C ₂ -haloalkyl"), 1-3 ( "C ₁ -C ₃ -haloalkyl"), 1 - 4 ("C ₁ -C ₄ -haloalkyl") or 1 - 6 ("C ₁ -C ₆ -haloalkyl") carbon atoms (as mentioned above), where some or all hydrogen atoms in these groups are replaced by halogen atoms, as mentioned above: in particular, C ₁ -C ₂ -haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1- chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2- dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl. C ₁ -C ₃ haloalkyl is additionally, for example, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1,1-difluoropropyl, 2,2-difluoropropyl, 1,2-difluoropropyl, 3,3-difluoropropyl, 3 ,3,3-trifluoropropyl, heptafluoropropyl, 1,1,1-trifluoroprop-2-yl, 3-chloropropyl and the like. Examples for C ₁ -C ₄ haloalkyl are, in addition to those mentioned for C ₁ -C ₃ haloalkyl, 4-chlorobutyl and the like.

The term "alkylene" (or alkadiyl) as used herein means in each case an alkyl radical as defined above, where one hydrogen atom at any position of the carbon chain is replaced by one additional bonding site, thus forming a bivalent substituent. Alkylene preferably has 1 to 6 carbon atoms (C ₁ -C ₆ alkylene), 2 to 6 carbon atoms (C ₂ -C ₆ alkylene), in particular 1 to 4 carbon atoms (C ₁ -C ₄ alkylene) or 2-4 carbon atoms (C ₂ -C ₄ -alkylene). Examples of alkylene are methylene (CH ₂ ), 1,1-ethanediyl, 1,2-ethanediyl, 1,3-propanediyl, 1,2-propanediyl, 2,2-propanediyl, 1,4-butanediyl, 1,2-butanediyl , 1,3-butanediyl, 2,3-butanediyl, 2,2-butanediyl, 1,5-pentadiyl, 2,2-dimethylpropan-1,3-diyl, 1,3-dimethyl-1,3-propanediyl, 1 ,6-hexanediyl and the like.

The term "alkenyl", as used herein, refers to monounsaturated straight or branched hydrocarbon radicals containing 2-3 ("C ₂ -C ₃ -alkenyl"), 2-4 ("C ₂ -C ₄ -alkenyl") or 2-6 ("C ₂ -C ₆ -alkenyl) carbon atoms and a double bond in any position, for example, C ₂ -C ₃ -alkenyl, such as ethenyl, 1-propenyl, 2-propenyl or 1-methylethenyl; C ₂ -C ₄ -alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-utenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl , 1-methyl-2-propenyl or 2-methyl-2-propenyl, C ₂ -C ₆ -alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-utenyl, 2-butenyl, 3 -butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl , 1-ethyl-1-butenyl, 2-ethyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenium l, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2- methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl- 3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1- dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3- dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3- dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1- ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-pro foam and the like.

The term "alkynyl" as used herein refers to straight or branched hydrocarbon groups containing 2-3 ("C ₂ -C ₃ alkynyl"), 2-4 ("C ₂ -C ₄ alkynyl"), or 2-6 ("C ₂ -C ₆ -alkynyl") carbon atoms and one or two triple bonds in any position, for example, C ₂ -C ₃ -alkynyl, such as ethynyl, 1-propynyl or 2-propynyl; C ₂ -C ₄ alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl and the like, C ₂ -C ₆ alkynyl , such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1 -methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1 -hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl , 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl , 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1 -ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl and the like.

The term "cycloalkyl", as used herein, refers to mono- or bi- or polycyclic saturated hydrocarbon radicals containing, in particular, 3-6 ("C ₃ -C ₆ -cycloalkyl") or 3-5 ("C ₃ -C ₅ -cycloalkyl") or 3 - 4 ("C ₃ -C ₄ -cycloalkyl") carbon atoms. Examples of monocyclic radicals containing 3 to 4 carbon atoms include cyclopropyl and cyclobutyl. Examples of monocyclic radicals containing 3 to 5 carbon atoms include cyclopropyl, cyclobutyl and cyclopentyl. Examples of monocyclic radicals containing 3 to 6 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of monocyclic radicals containing 3 to 8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of bicyclic radicals containing 7 or 8 carbon atoms include bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl, and bicyclo[3.2.1]octyl. Preferably the term cycloalkyl means a monocyclic saturated hydrocarbon radical.

The term "cycloalkoxy" as used herein refers to a cycloalkyl radical, in particular a monocyclic cycloalkyl radical as defined above, containing in particular 3-6 ("C ₃ -C ₆ -cycloalkoxy"), or 3- 5 ("C ₃ -C ₅ -cycloalkoxy"), or 3 - 4 ("C ₃ -C ₄ -cycloalkoxy") carbon atoms, which are attached through an oxygen atom to the rest of the molecule.

The term "cycloalkyl-C ₁ -C ₄ -alkyl" refers to C ₃ -C ₈ -cycloalkyl ("C ₃ -C ₈ -cycloalkyl-C ₁ -C ₄ -alkyl"), preferably C ₃ -C ₆ -cycloalkyl ( "C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl"), more preferably C ₃ -C ₄ -cycloalkyl ("C ₃ -C ₄ -cycloalkyl-C ₁ -C ₄ -alkyl"), as defined above (preferably a monocyclic cycloalkyl group) attached to the rest of the molecule via a C ₁ -C ₄ alkyl group as defined above. Examples of C ₃ -C ₄ -cycloalkyl-C ₁ -C ₄ -alkyl are cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl and cyclobutylpropyl. Examples of C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, in addition to those mentioned for C ₃ -C ₄ -cycloalkyl-C ₁ -C ₄ -alkyl, are cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl and cyclohexylpropyl.

The term "C ₁ -C ₂ -alkoxy" means a C ₁ -C ₂ -alkyl group, as defined above, attached through an oxygen atom. The term "C ₁ -C ₃ -alkoxy" means a C ₁ -C ₃ -alkyl group, as defined above, attached through an oxygen atom. The term "C ₁ -C ₄ -alkoxy" means a C ₁ -C ₄ -alkyl group, as defined above, attached through an oxygen atom. The term "C ₁ -C ₆ -alkoxy" means a C ₁ -C ₆ -alkyl group, as defined above, attached through an oxygen atom. The term "C ₁ -C ₁₀ -alkoxy" means a C ₁ -C ₁₀ -alkyl group, as defined above, attached through an oxygen atom. C ₁ -C ₂ -alkoxy means OCH ₃ or OC ₂ H ₅ .

C ₁ -C ₃ -alkoxy is additionally, for example, n-propoxy and 1-methylethoxy (isopropoxy). C ₁ -C ₄ -alkoxy is additionally, for example, butoxy, 1-methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1,1-dimethylethoxy (tert-butoxy). C ₁ -C ₆ -alkoxy is additionally, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy , 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3.3 -dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy. C ₁ -C ₈ -alkoxy is additionally, for example, heptyloxy, octyloxy, 2-ethylhexyloxy and their positional isomers. C ₁ -C ₁₀ -alkoxy is additionally, for example, nonyloxy, decyloxy and their positional isomers.

The term "C ₁ -C ₂ haloalkoxy" means a C ₁ -C ₂ haloalkyl group as defined above attached via an oxygen atom. The term "C ₁ -C ₃ haloalkoxy" means a C ₁ -C ₃ haloalkyl group as defined above attached via an oxygen atom. The term "C ₁ -C ₄ haloalkoxy" means a C ₁ -C ₄ haloalkyl group as defined above attached via an oxygen atom. The term "C ₁ -C ₆ haloalkoxy" means a C ₁ -C ₆ haloalkyl group as defined above attached via an oxygen atom. C ₁ -C ₂ -haloalkoxy means, for example, OCH ₂ F, OCHF ₂ , OCF ₃ , OCH ₂ Cl, OCHCl ₂ , OCCl ₃ , chlorofluoromethoxy, dichlorofluoromethoxy, chlordifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2, 2-trichloroethoxy or OC ₂ F ₅ . C ₁ -C ₃ haloalkoxy is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy , 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH ₂ -C ₂ F ₅ , OCF ₂ -C ₂ F ₅ , 1-(CH ₂ F) -2-fluoroethoxy, 1 -(CH ₂ Cl)-2-chloroethoxy or 1-(CH ₂ Br)-2-bromoethoxy. C ₁ -C ₄ haloalkoxy is additionally, for example, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy. C ₁ -C ₆ haloalkoxy is additionally, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-bromopentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy.

The term "C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl", as used herein, refers to straight or branched alkyl containing 1 to 4 carbon atoms, as defined above, where one hydrogen atom is replaced by C ₁ -C ₆ alkoxy group as defined above. Examples are methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, n-butoxymethyl, sec-butoxymethyl, isobutoxymethyl, t-butoxymethyl, 1-methoxyethyl, 1-ethoxyethyl, 1-propoxyethyl, 1-isopropoxyethyl, 1-n-butoxyethyl, 1-sec- butoxyethyl, 1-isobutoxyethyl, 1-tert-butoxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-n-butoxyethyl, 2-sec-butoxyethyl, 2-isobutoxyethyl, 2-tert-butoxyethyl , 1-methoxypropyl, 1-ethoxypropyl, 1-propoxypropyl, 1-isopropoxypropyl, 1-n-butoxypropyl, 1-sec-butoxypropyl, 1-isobutoxypropyl, 1-tert-butoxypropyl, 2-methoxypropyl, 2-ethoxypropyl, 2-propoxypropyl , 2-isopropoxypropyl, 2-n-butoxypropyl, 2-sec-butoxypropyl, 2-isobutoxypropyl, 2-tert-butoxypropyl, 3-methoxypropyl, 3-ethoxypropyl, 3-propoxypropyl, 3-isopropoxypropyl, 3-n-butoxypropyl, 3 -sec-butoxypropyl, 3-isobutoxypropyl, 3-t-butoxypropyl and the like.

The term "alkoxyalkoxy", as used herein, refers to an alkoxyalkyl radical, in particular a C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl radical, as defined above, attached via an oxygen atom to the rest of the molecule. Their examples are OCH ₂ -OCH ₃ , OCH ₂ -OC ₂ H ₅ , n-propoxymethoxy, OCH ₂ -OCH(CH ₃ ) ₂ , n-butoxymethoxy, (1-methylpropoxy)methoxy, (2-methylpropoxy)methoxy, OCH ₂ -OC(CH ₃ ) ₃ , 2-(methoxy)ethoxy, 2-(ethoxy)ethoxy, 2-(n-propoxy)ethoxy, 2-(1-methylethoxy)ethoxy, 2-(n-butoxy)ethoxy, 2-(1-methylpropoxy)ethoxy, 2-(2-methylpropoxy)ethoxy, 2-(1,1-dimethylethoxy)ethoxy and the like.

The "oxo" substituent replaces CH ₂ with a C(=O) group.

The term "aryl" refers to phenyl and bi- or polycyclic carbocycles having at least one fused phenylene ring attached to the rest of the molecule. Examples of bi or polycyclic carbocycles having at least one phenylene ring are naphthyl, tetrahydronaphthyl, indanyl, indenyl, anthracenyl, fluorenyl and the like.

The term "aryl-C ₁ -C ₄ -alkyl" refers to C ₁ -C ₄ -alkyl, as defined above, where one hydrogen atom may be replaced by an aryl radical, in particular a phenyl radical. Specific examples of aryl-C ₁ -C ₄ -alkyl are -CH ₂ -phenyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl, 3-phenyl-1-propyl and 2-phenyl-2-propyl.

The term "aryloxy-C ₁ -C ₄ -alkyl" refers to C ₁ -C ₄ -alkyl, as defined above, where one hydrogen atom may be replaced by an aryloxy radical, in particular a phenoxy radical. Specific examples of aryloxy-C ₁ -C ₄ -alkyl are phenoxymethyl, 1-phenoxyethyl, 2-phenoxyethyl, 1-phenoxypropyl, 2-phenoxypropyl, 3-phenoxy-1-propyl and 2-phenoxy-2-propyl.

The term "aryl-C ₁ -C ₄ -carbonyl" refers to aryl, as defined above, in particular, the phenyl radical, which is attached through a carbonyl to the rest of the molecule. Specific examples of arylcarbonyl are benzoyl, 1-naphthoyl and 2-naphthoyl.

The term "hetaryl" refers to aromatic heterocycles containing 5 or 6 ring atoms (5- or 6-membered hetaryl) and being monocyclic, or 8, 9 or 10 ring atoms and being bicyclic. Hetaryl will typically contain at least one ring atom selected from O, S and N, in the case of N, may be an imino nitrogen or an amino nitrogen which carries a hydrogen or a radical other than hydrogen. Hetaryl may contain 1, 2, 3 or 4 additional nitrogen atoms as ring members and is an imino nitrogen. Examples of 5- or 6-membered hetaryl are 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5 -pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 1,3,4-triazol-1-yl , 1,3,4-triazol-2-yl, 1,3,4-oxadiazolyl-2-yl, 1,3,4-thiadiazolyl-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3 -pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl and 1,3,5-triazin-2-yl. Examples of 8-, 9- or 10-membered hetaryl are, for example, quinolinyl, isoquinolinyl, cinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzothienyl, benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzimidazolyl, imidazo[1,2 -a]pyridin-2-yl, thieno[3,2-b]pyridin-5-yl, imidazo[2,1-b]-thiazol-6-yl and 1,2,4-triazolo[1,5- a]pyridin-2-yl.

Examples of N-attached 5-, 6-, 7- or 8-membered saturated heterocycles are pyrrolidin-1-yl, pyrazolidin-1-yl, imidazolidin-1-yl, oxazolidin-3-yl, isoxazolidin-2-yl, thiazolidin- 3-yl, isothiazolidin-2-yl, piperidin-1-yl, piperazin-1-yl, morpholin-4-yl, thiomorpholin-4-yl, 1-oxothiomorpholin-4-yl, 1,1-dioxothiomorpholin-4- silt, azepan-1-yl and the like.

The term "hetaryl-C ₁ -C ₄ -alkyl" refers to C ₁ -C ₄ -alkyl, as defined above, where one hydrogen atom is replaced by a hetaryl radical, in particular a pyridyl radical. Specific examples of hetaryl-C ₁ -C ₄ -alkyl are 2-pyridylmethyl, 3-pyridylmethyl, 4-pyridylmethyl, 1-(2-pyridyl)ethyl, 2-(2-pyridyl)ethyl, 1-(3-pyridyl)ethyl , 2-(3-pyridyl)ethyl, 1-(4-pyridyl)ethyl, 2-(4-pyridyl)ethyl and the like.

The term "hetaryloxy-C ₁ -C ₄ -alkyl" refers to C ₁ -C ₄ -alkyl, as defined above, where one hydrogen atom is replaced by a hetaryloxy radical, in particular a pyridyloxy radical. Specific examples of hetaryloxy-C ₁ -C ₄ -alkyl are 2-pyridyloxymethyl, 3-pyridyloxymethyl, 4-pyridyloxymethyl, 1 (2-pyridyloxy)ethyl, 2-(2-pyridyloxy)ethyl, 1-(3-pyridyloxy)ethyl, 2-(3-pyridyloxy)ethyl, 1-(4-pyridyloxy)ethyl, 2-(4-pyridyloxy)ethyl and the like.

The term "hetaryl-C ₁ -C ₄ -carbonyl" refers to hetaryl, as defined above, in particular, to a C-linked hetaryl radical, for example, 2-, 3- or 4-pyridyl, 2- or 3-thienyl, 2 - or 3-furyl, 1-, 2- or 3-pyrrolyl, 2- or 4-pyrimidinyl, pyridazinyl, 1-, 3- or 4-pyrazolyl, 1-, 2- or 4-imidazolyl, which is attached via carbonyl to the rest of the molecule.

The term "substituted", unless otherwise indicated, refers to substituted with 1, 2, or as many substituents as possible. If there is more than one substituent as defined in the compounds of formula I, they are independently the same or different unless otherwise indicated.

With respect to variables, embodiments of the compounds of formula I are as follows.

In one preferred embodiment, W is O.

In another preferred embodiment, W is NR ⁶ .

In another preferred embodiment, W is S(=O) _m .

In one preferred embodiment, A ¹ is CR ^A .

In another preferred embodiment, A ¹ is N.

In one preferred embodiment, A ² is CR ^B .

In another preferred embodiment, A ² is N.

In one preferred embodiment, A ³ is CR ^B1 .

In another preferred embodiment, A ³ is N.

In one preferred embodiment, W is O, A ¹ is CR ^A , A ² is CR ^B , and A ³ is N.

In another preferred embodiment, W is O, A ¹ is CR ^A , A ² is CR ^B , and A ³ is CR ^B1 .

In another preferred embodiment, W is O, A ¹ is N, A ² is N, and A ³ is R ^B1 .

In another preferred embodiment, W is O, A ¹ is CR ^A , A ² is N, and A ³ is R ^B1 .

In another preferred embodiment, W is O, A ¹ is N, A ² is CR ^B , and A ³ is R ^B1 .

In another preferred embodiment, W is O, A ¹ is CR ^A , A ² is N, and A ³ is N.

In another preferred embodiment, W is N, A ¹ is CR ^A , A ² is CR ^B , and A ³ is N.

In another preferred embodiment, W is N, A ¹ is CR ^A , A ² is CR ^B , and A ³ is CR ^B1 .

In another preferred embodiment, W is N, A ¹ is N, A ² is N, and A ³ is CR ^B1 .

In another preferred embodiment, W is N, A ¹ is CR ^A , A ² is N, and A ³ is R ^B1 .

In another preferred embodiment, W is N, A ¹ is N, A ² is CR ^B , and A ³ is R ^B1 .

In another preferred embodiment, W is N, A ¹ is CR ^A , A ² is N, and A ³ is N.

In another preferred embodiment, W is S(=O) _m , A ¹ is CR ^A , A ² is CR ^B and A ³ is N.

In another preferred embodiment, W is S(=O) _m , A ¹ is CR ^A , A ² is CR ^B and A ³ is CR ^B1 .

In another preferred embodiment, W is S(=O) _m ,

A ¹ is N, A ² is N and A ³ is R ^B1 .

In another preferred embodiment, W is S(=O) _m ,

A ¹ is CR ^A , A ² is N and A ³ is R ^B1 .

In another preferred embodiment, W is S(=O) _m ,

A ¹ is N, A ² is CR ^B and A ³ is R ^B1 .

In another preferred embodiment, W is S(=O) _m ,

A ¹ is CR ^A , A ² is N and A ³ is N.

In one preferred embodiment, R ^A is H, halogen, OH, CN, NO ₂ , -SCN, -SF ₅ , C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ haloalkoxy, C ₂ -C ₆ alkenyl or tri-C ₁ -C ₆ alkylsilyl.

In a more preferred embodiment, R ^A is H, halogen, OH, CN, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₂ -C ₆ -alkenyl or tri-C ₁ -C ₆ -alkylsilyl.

In the most preferred embodiment, R ^A is H, Cl, Br, F, OH, CN, CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , isopropyl, cyclopropyl, allyl and propargyl, CH ₂ F, CHF ₂ , CF ₃ , OCH ₃ , OC ₂ H ₅ , OCH ₂ F, OCHF ₂ , OCF ₃ , OCH ₂ CH ₂ CF ₃ , OCH ₂ CF ₂ CHF ₂ or OCH ₂ CF ₂ CF ₃ .

In one preferred embodiment, R ^B is H, halogen, OH, CN, NO ₂ , -SCN, -SF ₅ , C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ haloalkoxy, C ₂ -C ₆ alkenyl or tri-C ₁ -C ₆ alkylsilyl.

In a more preferred embodiment R ^B is H, halogen, OH, CN, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₂ -C ₆ -alkenyl or tri-C ₁ -C ₆ -alkylsilyl.

In the most preferred embodiment, R ^B is H, Cl, Br, F, OH, CN, CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , isopropyl, cyclopropyl, allyl and propargyl, CH ₂ F, CHF ₂ , CF ₃ , OCH ₃ , OC ₂ H ₅ , OCH ₂ F, OCHF ₂ , OCF ₃ , OCH ₂ CH ₂ CF ₃ , OCH ₂ CF ₂ CHF ₂ or OCH ₂ CF ₂ CF ₃ .

In one preferred embodiment, R ^B1 is H, halogen, OH, CN, NO ₂ , -SCN, -SF ₅ , C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ - alkoxy, C ₁ -C ₆ haloalkoxy, C ₂ -C ₆ alkenyl or tri-C ₁ -C ₆ alkylsilyl.

In a more preferred embodiment, R ^B1 is H, halogen, OH, CN, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₂ -C ₆ -alkenyl or tri-C ₁ -C ₆ -alkylsilyl.

In the most preferred embodiment, R ^B1 is H, Cl, Br, F, OH, CN, CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , isopropyl, cyclopropyl, allyl and propargyl, CH ₂ F, CHF ₂ , CF ₃ , OCH ₃ , OC ₂ H ₅ , OCH ₂ F, OCHF ₂ , OCF ₃ , OCH ₂ CH ₂ CF ₃ , OCH ₂ CF ₂ CHF ₂ or OCH ₂ CF ₂ CF ₃ .

In one preferred embodiment, Q is

-C(R ⁴ R ⁵ )-O-, where C is attached to Ar.

In another preferred embodiment, Q is -C(R ⁴ R ⁵ )-O-, where O is attached to Ar.

In another preferred embodiment, Q is -C(=O)-O-, where C is attached to Ar.

In another preferred embodiment, Q is -C(=O)-O-, where O is attached to Ar.

In another preferred embodiment, Q is

-S(=O) _m -C(R ⁷ R ⁸ )-, where S is attached to Ar.

In another preferred embodiment, Q is

-S(=O) _m -C(R ⁷ R ⁸ )- , where C is attached to Ar.

In another preferred embodiment, Q is

-N(R ² )-S(=O) _m -, where N is attached to Ar.

In another preferred embodiment, Q is

-N(R ² )-S(=O) _m -, where S is attached to Ar.

In another preferred embodiment, Q is

-N(R ² )-C(R ⁹ R ¹⁰ )-, where N is attached to Ar.

In another preferred embodiment, Q is

-N(R ² )-C(R ⁹ R ¹⁰ )-, where C is attached to Ar.

In another preferred embodiment, Q is

-C(=O)-C(R ¹⁹ R ²⁰ )-, where C(=O) is attached to Ar.

In another preferred embodiment, Q is

-C(=O)-C(R ¹⁹ R ²⁰ )-, where C(R ¹⁹ R ²⁰ ) is attached to Ar.

In another preferred embodiment, Q is

-N(R ² )-C(=O)-, where N is attached to Ar.

In another preferred embodiment, Q is

-N(R ² )-C(=O)-, where C is attached to Ar.

In another preferred embodiment, Q is

-C(R ¹³ R ¹⁴ )-C(R ¹⁵ R ¹⁶ )-.

In another preferred embodiment, Q is -C(R ¹⁷ )=C(R ¹⁸ )-.

In one preferred embodiment, R ⁶ is H,

C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₄ -alkyl, where alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted by halogen,

C(=O)-OR ^a , C ₁ -C ₆ -alkylene-NR ^b R ^c , C ₁ -C ₆ -alkylene-CN, C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c , S(=O) _m R ^e , phenyl or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted by R ^f ;

In another preferred embodiment, R ⁶ is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy-C ₁ -C ₄ alkyl , C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₄ -alkyl, where alkyl, alkoxy, alkenyl, alkynyl, the cycloalkyl and cycloalkoxy substituents are substituted or unsubstituted with halogen,

In another preferred embodiment, R ⁶ is C(=O)-OR ^a , C ₁ -C ₆ alkylene-NR ^b R ^c , C ₁ -C ₆ alkylene-CN, C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c , S(=O) _m R ^e , phenyl or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted by R ^f ;

In another preferred embodiment, R ⁶ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, -CH ₂ -C(=O)-OR ^a or -CH ₂ -phenyl;

In another preferred embodiment, R ⁶ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, or -CH ₂ -phenyl;

In another preferred embodiment, R ⁶ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, or -CH ₂ -C(=O)-OR ^a ;

In another preferred embodiment, R ⁶ is H or C ₁ -C ₆ alkyl;

In another preferred embodiment, R ⁶ is H;

In another preferred embodiment, R ⁶ is C ₁ -C ₆ alkyl;

In one preferred embodiment, R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ are the same or different and are H, halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkylalkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -halocycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkoxy-C ₁ -C ₄ -alkyl, C(=O)-OR ^a , C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c , S(=O) _m R ^e , phenyl or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted with R ^f ;

In a more preferred embodiment, R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ are the same or different and are H, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkylalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, C(=O)-OR ^a , C( =O)-NR ^b R ^c , C(=O)-R ^d , phenyl or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted by R ^f ;

In the most preferred embodiment, R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ are the same or different and are H, halogen, C ₁ -C ₆ alkyl or C ₁ -C ₆ haloalkyl;

In one preferred embodiment, Ar is phenyl which is unsubstituted or substituted with R ^Ar .

In another preferred embodiment, Ar is a 5- or 6-membered hetaryl that is unsubstituted or substituted with R ^Ar .

In a more preferred embodiment, Ar is phenyl, pyrimidinyl, pyridazinyl, or pyridyl which is unsubstituted or substituted with R ^Ar .

In one preferred embodiment, R ^Ar is halo, OH, CN, NO ₂ , SCN, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ -haloalkoxy or SR ^e .

In a more preferred embodiment R ^Ar is F, Cl , Br, OH, CN, NO ₂ , SCN, CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , isopropyl, CH ₂ F, CHF ₂ , CF ₃ , CH ₂ CF ₃ , CF ₂ CHF ₂ , C ₂ F ₅ , CH ₂ CH ₂ CF ₃ , CH ₂ CF ₂ CHF ₂ , CH ₂ CF ₂ CF ₃ , OCH ₃ , OC ₂ H ₅ , n-propyloxy, isopropyloxy , OCH ₂ F, OCHF ₂ , OCF ₃ , OCH ₂ CF ₃ , OCF ₂ CHF ₂ , OC ₂ F ₅ , OCH ₂ CH ₂ CF ₃ , OCH ₂ CF ₂ CHF ₂ , OCH ₂ CF ₂ CF ₃ , or SR ^e , where R ^e represents C ₁ -C ₆ -alkyl, in particular C ₁ -C ₃ -alkyl, such as CH ₃ ,C ₂ H ₅ , n-C ₃ H ₇ or isopropyl or C ₁ -C ₆ - haloalkyl, in particular fluorinated C ₁ -C ₃ -alkyl, such as CH ₂ F, CHF ₂ , CF ₃ , CH ₂ CF ₃ , CF ₂ CHF ₂ , C ₂ F ₅ , CH ₂ CH ₂ CF ₃ , CH ₂ CF ₂ CHF ₂ or CH ₂ CF ₂ CF ₃ .

Particularly preferred Ar are shown in Table A below.

Table A:

Ar-1

Ar-2

Ar-3

Ar-4

Ar-5

Ar-6

Ar-7

Ar-8

Ar-9

Ar-10

Ar-11

Ar-12

Ar-13

Ar-14

Ar-15

Ar-16

Particularly preferably Ar is selected from Ar-1 - Ar-16;

also particularly preferably Ar is selected from Ar-1 to Ar-13;

In one preferred embodiment, R ¹ is

^YZTR11 .

In another preferred embodiment, R ¹ is YZTR ¹² .

In one preferred embodiment, Y is -CR ^ya =N-, where N is attached to Z.

In another preferred embodiment, Y is -NR ^yc -C(=S)-, where C(=S) is attached to Z.

In another preferred embodiment, Y is -NR ^yc -C(=O)-, where C(=O) is attached to Z.

In one preferred embodiment, Z is a single bond;

-NR ^zc -C(=O)-, where C(=O) is attached to T;

-NR ^zc -C(=S)-, where C(=S) is attached to T;

-N=C(SR ^za )-, where T is attached to a carbon atom; or

-NR ^zc -C(SR ^za )=, where T is attached to a carbon atom;

In another preferred embodiment, Z is -NR ^zc -C(=S)-, where C(=S) is attached to T.

In another preferred embodiment, Z is -NR ^zc -C(=O)-, where C(=O) is attached to T.

In another preferred embodiment, Z is -N=C(SR ^za )-, where T is attached to a carbon atom.

In another preferred embodiment, Z is

-NR ^zc -C(SR ^za )=, where T is attached to a carbon atom.

In another preferred embodiment, Z is -O-C(=O)-, where T is attached to a carbon atom;

In another preferred embodiment, Z is a single bond.

In one preferred embodiment, T is O.

In another preferred embodiment, T is NR ^T .

In another preferred embodiment, T is N.

In one preferred embodiment, R ^ya is H, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy which is unsubstituted or substituted with halogen, phenyl, or -CH ₂ -phenyl where the phenyl rings are unsubstituted or substituted with R ^f .

In a more preferred embodiment, R ^ya is H, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy which is unsubstituted or substituted with halogen, or phenyl which is unsubstituted or substituted by R ^f .

In the most preferred embodiment, R ^ya is H, F, Cl, Br, CH ₃ , C ₂ H ₅ , n-C ₃ H ₇ , isopropyl, CH ₂ F, CHF ₂ , CF ₃ , CH ₂ CF ₃ , CF ₂ CHF ₂ , C ₂ F ₅ , CH ₂ CH ₂ CF ₃ , CH ₂ CF ₂ CHF ₂ , CH ₂ CF ₂ CF ₃ , OCH ₃ , OC ₂ H ₅ , n-propyloxy, isopropyloxy, OCH ₂ F, OCHF ₂ , OCF ₃ , OCH ₂ CF ₃ , OCF ₂ CHF ₂ , OC ₂ F ₅ , OCH ₂ CH ₂ CF ₃ , OCH ₂ CF ₂ CHF ₂ , OCH ₂ CF ₂ CF ₃ , or phenyl which is unsubstituted or substituted with R ^f .

In a further most preferred embodiment, R ^ya is H or CH ₃ ;

In one embodiment, R ^yc , R ^zc are H, C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, which are unsubstituted or substituted with halogen, phenyl or -CH ₂ -phenyl, where the rings are unsubstituted or substituted R ^f .

In a more preferred embodiment, R ^yc and R ^zc are H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, or phenyl which is unsubstituted or substituted with R ^f .

In the most preferred embodiment, R ^yc and R ^zc are H, CH ₃ ,C ₂ H ₅ , n-C ₃ H ₇ , isopropyl, CH ₂ F, CHF ₂ , CF ₃ , CH ₂ CF ₃ , CF ₂ CHF ₂ , C ₂ F ₅ , CH ₂ CH ₂ CF ₃ , CH ₂ CF ₂ CHF ₂ , CH ₂ CF ₂ CF ₃ , or phenyl which is unsubstituted or substituted with R ^f .

In a further most preferred embodiment, R ^{yc and} R ^zc are H or CH ₃ ;

In one preferred embodiment, R ^T is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₄ alkyl-C ₁ -C ₆ - alkoxy which is unsubstituted or substituted by halogen, C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c , S(=O) _m R ^e , phenyl or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted with R ^f .

In a more preferred embodiment, R ^T is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₄ alkyl-C ₁ -C ₆ alkoxy , which is unsubstituted or substituted with halogen.

In the most preferred embodiment, R ^T is H or C ₁ -C ₆ alkyl.

In another preferred embodiment, R ^zc together with R ^T , if present, form a C ₁ -C ₆ alkylene or a linear C ₂ -C ₆ alkenylene group, wherein CH ₂ is a substituent for linear C ₁ -C ₆ alkylene and linear C ₂ -C ₆ -alkenylene can be replaced by carbonyl or C=NR' and/or where 1 or 2 CH ₂ substituents can be replaced by O or S and/or where linear C ₁ -C ₆ -alkylene and linear C ₂ -C ₆ -alkenylene may be unsubstituted or substituted with R ^h .

In a more preferred embodiment, R ^zc together with R ^T , if present, form a C ₁ -C ₆ alkylene or a linear C ₂ -C ₆ alkenylene group, wherein CH ₂ is a substituent for linear C ₁ -C ₆ alkylene and linear C ₂ -C ₆ -alkenylene is replaced by a carbonyl group.

In another more preferred embodiment, R ^zc together with R ^T , if present, form a C ₁ -C ₆ alkylene or a linear C ₂ -C ₆ alkenylene group, wherein CH ₂ is a substituent of a linear C ₁ -C ₆ alkylene and a linear C ₂ -C ₆ -alkenylene is replaced by C=NR' and where 1 or 2 CH ₂ substituents can be replaced by O or S and/or where linear C ₁ -C ₆ -alkylene and linear C ₂ -C ₆ -alkenylene can be unsubstituted or substituted R ^h .

In another more preferred embodiment, R ^zc together with R ^T , if present, form a C ₁ -C ₆ -alkylene or a linear C ₂ -C ₆ -alkenylene group, where 1 or 2 CH ₂ Deputy linear C ₁ -C ₆ - alkylene and linear C ₂ -C ₆ -alkenylene are replaced by O or S and/or where linear C ₁ -C ₆ -alkylene and linear C ₂ -C ₆ -alkenylene may be unsubstituted or substituted with R ^h .

In one preferred embodiment, R ^za is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkylene-NR ^b R ^c , C ₁ -C ₆ -C(= O)-R ^d , phenyl, phenylcarbonyl or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted with R ^f ;

In a more preferred embodiment, R ^za is H, C ₁ -C ₆ alkyl or C ₁ -C ₆ haloalkyl;

In the most preferred embodiment, R ^za is H, C ₁ -C ₆ alkyl.

In another preferred embodiment, R ^za together with R ^T , if present, form a C ₁ -C ₆ alkylene or a linear C ₂ -C ₆ alkenylene group, wherein CH ₂ is a substituent for linear C ₁ -C ₆ alkylene and linear C ₂ -C ₆ -alkenylene can be replaced by carbonyl or C=NR' and/or where 1 or 2 CH ₂ substituents can be replaced by O or S and/or where linear C ₁ -C ₆ -alkylene and linear C ₂ -C ₆ -alkenylene may be unsubstituted or substituted with R ^h ;

In a more preferred embodiment, R ^za together with R ^T , if present, form a C ₁ -C ₆ alkylene or a linear C ₂ -C ₆ alkenylene group, wherein CH ₂ is a substituent for linear C ₁ -C ₆ alkylene and linear C ₂ -C ₆ -alkenylene is replaced by a carbonyl group.

In another more preferred embodiment, R ^za together with R ^T , if present, form a C ₁ -C ₆ alkylene or a linear C ₂ -C ₆ alkenylene group, wherein CH ₂ is a substituent of a linear C ₁ -C ₆ alkylene and a linear C ₂ -C ₆ -alkenylene is replaced by C=NR' and where 1 or 2 CH ₂ substituents can be replaced by O or S and/or where linear C ₁ -C ₆ -alkylene and linear C ₂ -C ₆ -alkenylene can be unsubstituted or substituted R ^h .

In another more preferred embodiment, R ^za together with R ^T , if present, form a C ₁ -C ₆ alkylene or a linear C ₂ -C ₆ alkenylene group, where 1 or 2 CH ₂ substituents of the linear C ₁ -C ₆ - alkylene and linear C ₂ -C ₆ -alkenylene are replaced by O or S and/or where linear C ₁ -C ₆ -alkylene and linear C ₂ -C ₆ -alkenylene may be unsubstituted or substituted with R ^h .

In a preferred embodiment, R ^a , R ^b and R ^c are H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl which is unsubstituted or substituted with halogen, C ₁ - C ₆ -alkylene-CN, phenyl or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted with R ^f ;

In a more preferred embodiment, R ^a , R ^b and R ^c are H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl which is unsubstituted or substituted with halogen, phenyl, or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted with R ^f .

In a preferred embodiment, R ^d is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl which is unsubstituted or substituted with halogen, phenyl, or -CH ₂ -phenyl, where phenyl rings are unsubstituted or substituted with R ^f .

In a more preferred embodiment, R ^d is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, or phenyl which is unsubstituted or substituted with R ^f .

In one preferred embodiment, R ^e is C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ halocycloalkyl, phenyl, or -CH ₂ -phenyl, where the phenyl rings are unsubstituted or substituted with R ^f .

In a more preferred embodiment, R ^e is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, or phenyl, unsubstituted or substituted with R ^f .

In one preferred embodiment, R ^f is halogen, N ₃ , OH, CN, NO ₂ , -SCN, -SF ₅ , C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkoxy, which is unsubstituted or substituted by halogen, C(=O)-OR ^a , NR ^b R ^c , C ₁ -C ₆ -alkylene-NR ^b R ^c , C ₁ -C ₆ -alkylene-CN, C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c , or S (=O) _m R ^e .

In a more preferred embodiment, R ^f is halogen, N ₃ , OH, CN, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkoxy, which is unsubstituted or substituted by halogen,
C(=O)-OR ^a , NR ^b R ^c , C ₁ -C ₆ -alkylene-NR ^b R ^c , C ₁ -C ₆ -alkylene-CN, C(=O)-NR ^b R ^c , C( =O)-R ^d , SO ₂ NR ^b R ^c or S(=O) _m R ^e .

In a preferred embodiment, R ^g is halogen, N ₃ , OH, CN, NO ₂ , -SCN, -SF ₅ , C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₂ -C ₆ alkenyl , C ₂ -C ₆ alkynyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkoxy, which is unsubstituted or substituted by halogen, C(=O)-OR ^a , NR ^b R ^c , C ₁ -C ₆ -alkylene-NR ^b R ^c , NH-C ₁ -C ₆ -alkylene-NR ^b R ^c ,

C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c or S(=O) _m R ^e .

In a more preferred embodiment, R ^g is halogen, N ₃ , OH, CN, NO ₂ , C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, C ₂ -C ₆ alkenyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkoxy, which is unsubstituted or substituted by halogen,
C(=O)-OR ^a , NR ^b R ^c , C ₁ -C ₆ -alkylene-NR ^b R ^c , C(=O)-NR ^b R ^c , C(=O)-R ^d , SO ₂ NR ^b R ^c or S(=O) _m R ^e .

In one implementation, m is 0.

In another implementation, m is 1.

In another implementation, m is 2.

означает присоединение к 9-членному гетарилу, In a more preferred embodiment, R ¹ is defined by the formulas Y-1 - Y-9 where

means attachment to a 9-membered hetaryl,

D is R ¹¹ or R ¹² and where R ^T , R ¹¹ , R ¹² , R ^ya , R ^yc , R ^za and R ^zc are as defined for compounds of formula I.

означает присоединение к 9-членному гетарилу, In a more preferred embodiment, R ¹ is defined by the formulas Y-1 - Y-8 where

means attachment to a 9-membered hetaryl,

D is R ¹¹ or R ¹² and where R ^T , R ¹¹ , R ¹² , R ^ya , R ^yc , R ^za and R ^zc are as defined for compounds of formula I.

означает присоединение к 9-членному гетарилу и R¹¹, R¹²,R^T, R^ya, R^za и R^zc являются такими, как определено для соединений формулы I.In another more preferred embodiment, R ¹ is defined by the formulas YZT-1 - YZT-9, where

means attachment to a 9-membered hetaryl and R ¹¹ , R ¹² , R ^T , R ^ya , R ^za and R ^zc are as defined for compounds of formula I.

означает присоединение к 9-членному гетарилу и R¹¹, R¹²,R^T, R^ya, R^za и R^zc являются такими, как определено для соединений формулы I.In another more preferred embodiment, R ¹ is defined by the formulas YZT-1 - YZT-8, where

means attachment to a 9-membered hetaryl and R ¹¹ , R ¹² , R ^T , R ^ya , R ^za and R ^zc are as defined for compounds of formula I.

означает присоединение к 9-членному гетарилу, D представляет собой R¹¹ или R¹². In the most preferred embodiment, R ¹ is defined by the formulas Y-1A - Y-9A, where

means attachment to a 9-membered hetaryl, D is R ¹¹ or R ¹² .

означает присоединение к 9-членному гетарилу, D представляет собой R¹¹ или R¹². In the most preferred embodiment, R ¹ is defined by the formulas Y-1A - Y-8B, where

means attachment to a 9-membered hetaryl, D is R ¹¹ or R ¹² .

In one preferred embodiment, R ¹¹ is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₆ alkoxy-C ₁ -C ₄ alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkyl-C ₃ -C ₆ -cycloalkoxy, which is unsubstituted or substituted by halogen, aryl, arylcarbonyl , aryl-C ₁ -C ₄ -alkyl, aryloxy-C ₁ -C ₄ -alkyl, hetaryl, carbonylhetaryl, C ₁ -C ₄ -alkylhetaryl and C ₁ -C ₄ -alkylhetaryloxy, where the aryl or hetaryl rings are unsubstituted or substituted with R ^g and where hetaryl is a 5- or 6-membered monocyclic hetaryl or an 8-, 9- or 10-membered bicyclic hetaryl.

In a more preferred embodiment, R ¹¹ is C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₃ -C ₆ cycloalkyl which is unsubstituted or substituted with halogen, aryl, arylcarbonyl, aryl-C ₁ -C ₄ -alkyl, aryloxy-C ₁ -C ₄ -alkyl, hetaryl, carbonylhetaryl, C ₁ -C ₄ -alkylhetaryl and C ₁ -C ₄ -alkylhetaryloxy, where the rings are unsubstituted or substituted by R ^g and where hetaryl is a 5- or 6-membered monocyclic hetaryl or an 8-, 9- or 10-membered bicyclic hetaryl.

In the most preferred embodiment, R ¹¹ is aryl, aryl-C ₁ -C ₄ -alkyl, hetaryl or hetaryl-C ₁ -C ₄ -alkyl, where the rings are unsubstituted or substituted with R ^g and where hetaryl in hetaryl or hetaryl-C ₁ -C ₄ -alkyl is preferably a 5- or 6-membered monocyclic hetaryl such as pyridyl, pyrimidinyl, pyridazinyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, isoxazolyl or isothiazolyl which is unsubstituted or substituted with R ^g .

Examples of particularly preferred R ¹¹ radicals are the radicals R ¹¹ -1 - R ¹¹ -29,

shown in Table A-1 below.

Table A-1.

R ^11-1

R ^11-2

R ^11-3

^R11-4

^R11-5

^R11-6

^R11-7

R ^11-8

^R11-9

R ^11-10

R ^11-11

R ^11-12

R ^11-13

R ^11-14

R ^11-15

R ^11-16

R ^11-17

R ^11-18

R ^11-19

R ^11-20

R ^11-21

R ^11-22

^R11-23

^R11-24

^R11-25

^R11-26

^R11-27

^R11-28

^R11-29

In one embodiment, R ¹² is a radical of formula (A ¹ ),

where # denotes the point of attachment to T and where R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ are as defined above, and where R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ independently of each other and especially in combination preferably have the following values:

R ¹²¹ is C ₁ -C ₄ -alkoxy, in particular OCH ₃ , OC ₂ H ₅ ;

R ¹²² is C ₁ -C ₄ alkoxy such as OCH ₃ , OC ₂ H ₅ , n-propoxy or isopropoxy or C ₃ -C ₄ alkenyloxy such as allyloxy, where R ¹²² is preferably OCH ₃ , OC ₂ H ₅ or N-propoxy;

R ¹²³ is OH, C ₁ -C ₄ -alkoxy, such as OCH ₃ , OC ₂ H ₅ , or C ₃ -C ₄ -alkenyloxy, such as allyloxy, where R ¹²³ preferably means OCH ₃ , OC ₂ H ₅ ;

R ¹²⁴ is C ₁ -C ₄ -alkyl, such as CH ₃ or C ₂ H ₅ or C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, such as methoxymethyl, ethoxymethyl, 2-methoxyethyl or 2- ethoxyethyl, where R ¹²⁴ is preferably methyl.

In a more preferred embodiment, R ¹² is in particular a radical of formula (A ¹¹ ), for example (A ¹¹ -a) or (A ¹¹ -b)

where # denotes the point of attachment to T and where R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ are as defined above, and where R ¹²¹ , R ¹²² , R ¹²³ and R ¹²⁴ independently of each other and especially in combination preferably have the following values:

R ¹²¹ is C ₁ -C ₄ -alkoxy, in particular OCH ₃ or OC ₂ H ₅ ;

R ¹²² is C ₁ -C ₄ alkoxy such as OCH ₃ , OC ₂ H ₅ , n-propoxy or isopropoxy or C ₃ -C ₄ alkenyloxy such as allyloxy, where R ¹²² is preferably OCH ₃ , OC ₂ H ₅ or n-propoxy;

R ¹²³ is OH, C ₁ -C ₄ alkoxy such as OCH ₃ or OC ₂ H ₅ or

C ₃ -C ₄ -alkenyloxy, such as allyloxy, where R ¹²³ preferably means OCH ₃ or OC ₂ H ₅ ;

R ¹²⁴ is C ₁ -C ₄ -alkyl, such as CH ₃ or C ₂ H ₅ or C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkyl, such as methoxymethyl, ethoxymethyl, 2-methoxyethyl or

2-ethoxyethyl, where R ¹²⁴ is preferably methyl.

Separate examples of R ¹² radicals are the following radicals A ¹¹ -1, A ¹¹ -1a, A ¹¹ -1b, A ¹¹ -2, A ¹¹ -2a, A ¹¹ -2b, A ¹¹ -3, A ¹¹ -3a and A ¹¹ -3b:

In more preferred embodiments, compounds of formula I are selected from compounds of formula I.A - I.V.

where Ar is phenyl or a 5- or 6-membered hetaryl substituted with R ^Ar ;

R ^Ar is halogen, OH, CN, NO ₂ , SCN, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, or

SR ^e , where alkyl and alkoxy are unsubstituted or substituted with halogen;

R ² is H, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, C ₁ -C ₄ alkyl-C ₁ -C ₆ alkoxy, or C ₃ -C ₆ -cycloalkyl, which is unsubstituted or substituted with halogen, and phenyl, which is unsubstituted or substituted with R ^f ;

Q is -C(R ⁴ R ⁵ )-O-, -C(=O)-O-, -S(=O) _m -C(R ⁷ R ⁸ )-, -N(R ² )-S (=O) _m- ,

-N(R ² )-C(R ⁹ R ¹⁰ )-, -C(=O)-C(R ¹⁹ R ²⁰ )-, -N(R ² )-C(=O)-, -C(R ¹³ R ¹⁴ )-C(R ¹⁵ R ¹⁶ )- or

-C(R ¹⁷ )=C(R ¹⁸ )-; where Ar is attached on either side to Q;

R ^A is H, halogen, OH, CN, NO ₂ , -SCN, -SF ₅ , C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy or C ₂ -C ₆ alkenyl;

R ^B is H, halogen, OH, CN, NO ₂ , -SCN, -SF ₅ , C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy or C ₂ -C ₆ alkenyl;

R ^B1 is H, halogen, OH, CN, NO ₂ , -SCN, -SF ₅ , C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy or C ₂ -C ₆ alkenyl;

and R ¹ is YZTR ¹¹ or YZTR ¹² as defined in Formula I.

More preferred compounds of formula I are compounds of formula I.1 - I.24, where R ¹ is selected from Y-1A, Y-1B, Y-2A, Y-2B, Y-3A, Y-3B, Y-3C, Y -3D, Y-4A, Y-4B, Y-4C, Y-4D, Y-5A, Y-5B, Y-6A, Y-6B, Y-7A, Y-7B, Y-8A, and Y- 8B; where D is R ¹¹ or R ¹² and other variables are as defined herein.

Also more preferred are compounds of formula I, where

A ¹ is CR ^A ;

A ² is N or CR ^B ;

A ³ is CR ^B1 ;

W is O, S(=O) _m or NR ⁶ ;

R^A, R^Band R^B1are independently H or halogen;

Q is -C(R ⁴ R ⁵ )-O-, -S(=O) _m -C(R ⁷ R ⁸ )-, -N(R ² )-C(R ⁹ R ¹⁰ )-, -N (R ² )-C(=O)- or -C(R ¹⁷ )=C(R ¹⁸ )-; where Ar is attached on either side to Q;

m is 0, 1 or 2;

R ² represents H or C ₁ -C ₆ -alkyl;

R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹⁷ , R ¹⁸ are the same or different H or C ₁ -C ₆ alkyl;

R ⁶ is H, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl or -CH ₂ -phenyl;

Ar is Ar-2, Ar-3, Ar-10, Ar-13 or Ar-14;

R ¹ is Y-1A, Y-3C, Y-5A, Y-6A, Y-7A, Y-8A or Y-9A;

D is R ¹¹ or R ¹² ;

R ¹¹ is R ¹¹ -1 or R ¹¹ -10;

R ¹² is A ¹¹ -1b or A ¹¹ -3b;

Also more preferred is a compound of formula I wherein

A ¹ is CR ^A ;

A ² is N or CR ^B ;

A ³ is CR ^B1 ;

W is O, S, NH, N-CH ₃ , N-CH(CH ₃ ) ₂ , N-CH ₂ (C ₆ H ₅ ), N-CH ₂ CHF ₂ or NC ₂ H ₅ ;

R ^A , R ^{B and} R ^B1 are independently H or halogen, preferably H or F;

Q is -CH ₂ -O-, -CH=CH-, -CH(CH ₃ )-O-, -S(=O) ₂ -CH ₂ -, -S-CH ₂ -, -S-CH( C ₄ H ₉ )-, -NH-CH ₂ -, -NH-C(=O)- or -N(CH ₃ )-C(=O)-; where Ar is attached on either side to Q;

Ar is Ar-2, Ar-3, Ar-10, Ar-13 or Ar-14

R ¹ is Y-1A, Y-3C, Y-5A, Y-6A, Y-7A, Y-8A or Y-9A

D is R ¹¹ or R ¹² ;

R ¹¹ is R ¹¹ -1 and R ¹¹ -10

R ¹² is A ¹¹ -1b and A ¹¹ -3b.

Also more preferred is a compound of formula I wherein

A ¹ is N or CR ^A ;

A ² is N or CR ^B ;

A ³ is CR ^B1

W is NR ⁶ ;

R ^A , R ^{B and} R ^B1 independently of each other represent H, halogen, C ₁ -C ₆ -alkyl or S(=O) _m R ^e , where C ₁ -C ₆ -alkyl is unsubstituted or substituted with halogen;

Q is -OC(R ⁴ R ⁵ )-, -N(R ² )-C(R ⁹ R ¹⁰ )-, -N(R ² )-C(=O)- or

-C(R ¹⁷ )=C(R ¹⁸ );

m is 0, 1 or 2;

R ² represents H or C ₁ -C ₆ -alkyl;

R ⁴ , R ⁵ , R ⁹ , R ¹⁰ , R ¹⁷ , R ¹⁸ are the same or different and are H and C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy-C ₁ -C ₄ -alkyl, where alkyl, alkoxy substituents are substituted or unsubstituted with halogen;

R ⁶ is H, C ₁ -C ₆ -alkyl, where alkyl is unsubstituted or substituted with halogen or -CH ₂ -C(=O)-OR ^a ;

Ar is Ar-1, Ar-2, Ar-3, Ar-4, Ar-10, Ar-12, Ar-13, Ar-14, Ar-15 or Ar-16;

R ¹ is Y-1A, Y-5A, Y-6A, Y-7A or Y-8A;

D is R ¹¹ or R ¹² ;

R ¹¹ is R ¹¹ -1, R ¹¹ -10 or R ¹¹ -29;

R ¹² is A ¹¹ -1b, A ¹¹ -2b or A ¹¹ -3b.

Also more preferred is a compound of formula I wherein

A ¹ is N or CR ^A ;

A ² is N or CR ^B ;

A ³ is CR ^B1 ;

W is NR ⁶ ;

R ^A , R ^{B and} R ^B1 independently of each other represent H, halogen or C ₁ -C ₆ -alkyl, where alkyl is unsubstituted or substituted with halogen;

Q is -OC(R ⁴ R ⁵ )-, -N(R ² )-C(R ⁹ R ¹⁰ )- or -N(R ² )-C(=O)-;

m is 0, 1 or 2;

R ² represents H or C ₁ -C ₆ -alkyl;

R ⁴ , R ⁵ , R ⁹ , R ¹⁰ are the same or different and are H or

C ₁ -C ₆ -alkyl, where alkyl is unsubstituted or substituted with halogen;

R ⁶ is C ₁ -C ₆ alkyl;

Ar is Ar-2;

R ¹ is Y-1A, Y-5A, Y-6A or Y-7A;

D is R ¹¹ or R ¹² ;

R ¹¹ is R ¹¹ -1;

R ¹² is A ¹¹ -1b or A ¹¹ -3b;

more preferred compounds of formula I are compounds of formula I.1 - I.24, where

Ar is Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , Ar ⁷ , Ar ⁸ , Ar ⁹ , Ar ¹⁰ , Ar ¹¹ or Ar ¹² ;

A ¹ is N, CH or CH ₃ ;

A ² is N, CH or CH ₃ ;

A ³ is N, CH or CH ₃ ;

W is N, O or S;

R ¹ is Y-1A, Y-1B, Y-2A, Y-2B, Y-3A, Y-3B, Y-3C, Y-3D, Y-4A, Y-4B, Y-4C, Y- 4D, Y-5A, Y-5B, Y-6A, Y-6B, Y-7A, Y-7B, Y-8A or Y-8B; where D represents R ¹¹ or R ¹² ;

R ¹¹ is R ¹¹ -1, R ¹¹ -2, R ¹¹ -3, R ¹¹ -5, R ¹¹ -6, R ¹¹ -7, R ¹¹ -8, R ¹¹ -9, R ¹¹ -10, R 11-11, R ^11-12 , R ^11-13 , R ^11-14 , R ^11-15 , R ^11-16 , R ^11-17 , R ^11-18 , R ^11-19 , ^{R 11-20} , R ^11-21 , R ^11-22 , R 11-23, R ^11-25 , R ^11-26 , R ^11-27 , R ^11-28 or ^{R 11-29} ;

R ¹² is (A ¹¹ -1), (A ¹¹ -2) or (A ¹¹ -3).

As used herein, the term "compound(s) of the present invention" or "compound(s) of the invention" refers to compound(s) of formula (I) as defined above, which is also referred to as "compound(s) of formula I ", or "compound(s) I", or "formula I compound(s)", and includes its salts, tautomers, stereoisomers and N-oxides.

The present invention also relates to a mixture of at least one compound of the present invention with at least one component for mixing, as defined in this document. Preferred are binary mixtures of one compound of this invention as component I with one component to mix, as defined herein, as component II. Preferred weight ratios of such binary mixtures are from 5000:1 to 1:5000, preferably from 1000:1 to 1:1000, more preferably from 100:1 to 1:100, particularly preferably from 10:1 to 1:10. In such binary mixtures, components I and II may be used in equal amounts, or an excess of component I or an excess of component II may be used.

The mixing components may be selected from pesticides, insecticides, nematicides, acaricides, fungicides, herbicides, plant growth regulators, fertilizers. Preferred mixing partners are insecticides, nematicides and fungicides.

The following is a list of M pesticides, grouped and numbered according to the Insecticide Resistance Research Committee (IRAC) Mode of Action Classification, that can be used in combination with the compounds of the present invention and result in a potential synergistic effect intended to illustrate possible combinations. , but in no way limiting the scope of the claims of this invention:

M.1 Acetylcholinesterase (AChE) inhibitors from class M.1A carbamates, e.g. , oxamyl, pirimicarb, propoxur, thiodicarb, thiophanox, trimetacarb, XMC, xylicarb and triazimate; or from class M.1B organophosphates, e.g. acephate, azamethifos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, koumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfotone, EPN, ethion, etoprofos, famfur, fenamiphos, fenitrothion, fenthion, fostiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, metidathione, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phentoate, phorate, fosalon, phosmet, phosphamidon, phoxim, pyrimifos-methyl, profenofos, propetamphos, prothiophos, pyraclophos, pyridafenthion, quinalphos, sulfotep, tebupyrimphos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon and vamidothione;

M.2. GABA-gated chloride channel antagonists such as: M.2A cyclodiene organochlorine compounds such as endosulfan or chlordane; or M.2B fiprols (phenylpyrazoles) such as ethiprole, fipronil, flufiprol, pyrafluprole and pyriprole;

M.3 Sodium channel modulators from class M.3A pyrethroids, e.g. acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin , lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyfenotrin, deltamethrin, empentrin, esfenvalerate, etofenprox, fenpropatrin, fenvalerate, flucitrinate, flumethrin, tau-fluvalinate, halfenprox , heptafluthrin, imiprothrin, meperlfluthrin, methofluthrin, momftorthrin, permethrin, phenothrin, pralletrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthrin, tetramethrin, tralometrin and transfluthrin; or M.3B sodium channel modulators such as DDT or methoxychlor;

M.4 Nicotinacetylcholine receptor (nAChR) agonists of the M.4A class of neonicotinoids, eg acetamiprid, clothianidin, cycloxapride, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or compounds M.4A.2: (2E-)-1-[(6-chloropyridin-3-yl)methyl]-N'-nitro-2-pentylidenehydrazinecarboximidamide; or M4.A.3: 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5-propoxy-1,2,3,5,6,7-hexahydroimidazo[1, 2-a]pyridine; or from class M.4B nicotine;

M.5 Allosteric nicotinic acetylcholine receptor activators from the class of spinosyns, eg spinosad or spinetoram;

M.6 Chloride channel activators of the avermectins and milbemycins, eg abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;

M.7 Juvenile hormone mimetics such as M.7A juvenile hormone analogues such as hydroprene, kinoprene and methoprene; or others such as M.7B fenoxycarb or M.7C pyriproxyfen;

M.8 substituted non-specific (multi-site) inhibitors, eg M.8A alkyl halides such as methyl bromide and other alkyl halides or M.8B chloropicrin or M.8C sulfuryl fluoride or M.8D borax or M.8E potassium antimonyl tartrate;

M.9 Selective feeding blockers for Homoptera, eg M.9B pymetrozine or M.9C flonicamid;

M.10 Mite growth inhibitors, eg M.10A clofentezin, hexythiazox and difluvidazine or M.10B ethoxazole;

M.11 Microbial disruptors of insect midgut membranes, eg bacillus thuringiensis or bacillus sphaericus and insecticidal proteins produced by bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis or Bt proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1;

M.12 Mitochondrial ATP synthase inhibitors, eg M.12A diafenthiuron or M.12B organotin mitocides such as azocyclotin, cyhexatin or fenbutatino acid or M.12C propargyte or M.12D tetradifon;

M.13 Uncoupler of oxidative phosphorylation by breaking the proton gradient, eg chlorfenapyr, DNOC or sulfuramide;

M.14 Nicotinacetylcholine receptor (nAChR) channel blockers, eg nereistoxin analogs such as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;

M.15 Type 0 chitin biosynthesis inhibitors, such as benzoylureas, such as, for example, bistrifluorone, chlorfluaziron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron or triflumuron;

M.16 Type 1 chitin biosynthesis inhibitors, such as burofezin;

M.17 Moulting disruptors, Diptera, such as cyromazine;

M.18 Ecdysone receptor agonists such as diacylhydrazines, eg methoxyfenoside, tebufenoside, halofenoside, fufenoside or chromafenoside;

M.19 Octoramine receptor agonists, such as amitraz;

M.20 Mitochondrial complex III electron transport inhibitors, eg M.20A hydramethylnon or M.20B acechinocyl or M.20C fluacripyrim;

M.21 Mitochondrial complex I electron transport inhibitors, eg M.21A METI acaricides and insecticides such as phenazakhine, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad or M.21B rotenone;

M.22 Voltage-dependent sodium channel blockers, e.g. M.22A indoxacarb or M.22B meteflumizone or M.22B.1: 2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]- N-[4-(difluoromethoxy)phenyl]hydrazinecarboxamide or M.22B.2: N-(3-chloro-2-methylphenyl)-2-[(4-chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl] methylene]hydrazinecarboxamide;

M.23 Acetyl CoA carboxylase inhibitors such as tetronic and tetramic acid derivatives, eg spirodiclofen, spiromesifen or spirotetramat;

M.24 Mitochondrial complex IV electron transport inhibitors, eg M.24A phosphine such as aluminum phosphide, calcium phosphide, phosphine or zinc phosphide or M.24B cyanide;

M.25 Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives, eg cyenopyraphene or cyflumethophen;

M.28 Ryanodine receptor modulators of the diamide class, such as flubendiamide, chloranthraliniprole (Rynaxypyr®), cyantraliniprole (Cyazypyr®), tetraniliprole or phthalamide compounds M.28.1: (R)-3-chloro-N1-{2-methyl- 4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamide and M.28.2: (S)-3-chloro-N1- {2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamide or compound M.28.3: 3-bromo- N-{2-bromo-4-chloro-6-[(1-cyclopropylethyl)carbamoyl]phenyl}-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide (ISO proposed name: cyclaniliprol) or compound M.28.4: methyl-2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino) benzoyl]-1,2-dimethylhydrazinecarboxylate; or a compound selected from M.28.5a) - M.28.5d) and M.28.5h) - M.28.5l): M.28.5a) N-[4,6-dichloro-2-[(diethyl-lambda -4-sulfanylidene)carbamoyl]phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5b) N-[4-chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-6-methylphenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole -3-carboxamide; M.28.5c) N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-methylphenyl]-2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carboxamide; M.28.5d) N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]phenyl]-2-(3-chloro-2-pyridyl)-5-( trifluoromethyl)pyrazole-3-carboxamide; M.28.5h) N-[4,6-dibromo-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole- 3-carboxamide; M.28.5i) N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2- pyridinyl)-1H-pyrazole-5-carboxamide; M.28.5j) 3-chloro-1-(3-chloro-2-pyridinyl)-N-[2,4-dichloro-6-[[(1-cyano-1-methylethyl)amino]carbonyl]phenyl]- 1H-pyrazole-5-carboxamide; M.28.5k) 3-bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-1-(3,5-dichloro-2-pyridyl)-1H-pyrazole-5-carboxamide; M.28.5l) N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy )-1H-pyrazole-5-carboxamide; or

M.28.6: cyhalodiamide; or

M.29. insecticidally active compounds with an unknown or unclear mode of action, such as afidopyrofene, afoxolaner, azadiractin, amidoflumet, benzoximate, biphenazate, broflanilide, bromopropylate, quinomethionate, cryolite, dichlormesothiasis, dicofol, flufenerim, flomethoquin, fluensulfone, fluhexafon, flupyradifuron, flupyramin, fluralaner, methoxadiazon, piperonyl butoxide, piflubumide, pyridalil, pyrifluquinasone, sulfoxaflor, thioxazafen, triflumesopyrim, or compounds

M.29.3: 11-(4-Chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-izadispiro[4.2.4.2]-tetradec-11-en-10-one or compound

M.29.4: 3-(4'-Fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2-one or compound

M.29.5: 1-[2-Fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1H-1,2,4-triazole-5- amine or compounds based on bacillus firmus (Votivo, I-1582); or

compound selected from M.29.6, where compound M.29.6a) - M.29.6k): M.29.6a) (E/Z)-N-[1-[(6-chloro-3-pyridyl)methyl] -2-pyridylidene]-2,2,2-trifluoroacetamide; M.29.6b) (E/Z)-N-[1-[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoroacetamide; M.29.6c) (E/Z)-2,2,2-trifluoro-N-[1-[(6-fluoro-3-pyridyl)methyl]-2-pyridylidene]acetamide; M.29.6d) (E/Z)-N-[1-[(6-bromo-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoroacetamide; M.29.6e) (E/Z)-N-[1-[1-(6-chloro-3-pyridyl)ethyl]-2-pyridylidene]-2,2,2-trifluoroacetamide; M.29.6f) (E/Z)-N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoroacetamide; M.29.6g) (E/Z)-2-chloro-N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoroacetamide; M.29.6h) (E/Z)-N-[1-[(2-chloropyridin-5-yl)methyl]-2-pyridylidene]-2,2,2-trifluoroacetamide; M.29.6i) (E/Z)-N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,3,3,3-pentafluoropropanamide.); M.29.6j) N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluorothioacetamide; or M.29.6k) N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-N'-isopropylacetamidine; or connections

M.29.8: fluazaindolizine; or connections

M.29.9.a): 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1-oxothietan-3-yl) benzamide; or M.29.9.b): fluxametamide; or

M.29.10: 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1H-pyrazole; or

compound selected from M.29.11, where compound M.29.11b) - M.29.11p): M.29.11.b) 3-(benzoylmethylamino)-N-[2-bromo-4-[1,2,2, 3,3,3-hexafluoro-1-(trifluoromethyl)propyl]-6-(trifluoromethyl)phenyl]-2-fluorobenzamide; M.29.11.c) 3-(benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl ]benzamide; M.29.11.d) N-[3-[[[2-iodo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl] phenyl]-N-methyl-benzamide; M.29.11.e) N-[3-[[[2-bromo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl ]-2-fluorophenyl]-4-fluoro-N-methylbenzamide; M.29.11.f) 4-fluoro-N-[2-fluoro-3-[[[2-iodo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-( trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methylbenzamide; M.29.11.g) 3-fluoro-N-[2-fluoro-3-[[[2-iodo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-( trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methylbenzamide; M.29.11.h) 2-chloro-N-[3-[[[2-iodo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl] amino]carbonyl]phenyl]-3-pyridinecarboxamide; M.29.11.i) 4-cyano-N-[2-cyano-5-[[2,6-dibromo-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl ]phenyl]carbamoyl]phenyl]-2-methylbenzamide; M.29.11.j) 4-cyano-3-[(4-cyano-2-methylbenzoyl)amino]-N-[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro -1-(trifluoromethyl)propyl]phenyl]-2-fluorobenzamide; M.29.11.k) N-[5-[[2-chloro-6-cyano-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]- 2-cyanophenyl]-4-cyano-2-methylbenzamide; M.29.11.l) N-[5-[[2-bromo-6-chloro-4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2- cyanophenyl]-4-cyano-2-methyl-benzamide; M.29.11.m) N-[5-[[2-bromo-6-chloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]- 2-cyanophenyl]-4-cyano-2-methylbenzamide; M.29.11.n) 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl ]phenyl]-carbamoyl]phenyl]-2-methylbenzamide; M.29.11.o) 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl ]phenyl]-2-methylbenzamide; M.29.11.p) N-[5-[[2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano -phenyl]-4-cyano-2-methylbenzamide; or

compound selected from M.29.12, where compound M.29.12a) - M.29.12m): M.29.12.a) 2-(1,3-dioxan-2-yl)-6-[2-(3- pyridinyl)-5-thiazolyl]pyridine; M.29.12.b) 2-[6-[2-(5-fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]pyridine; M.29.12.c) 2-[6-[2-(3-pyridinyl)-5-thiazolyl]-2-pyridinyl]pyridine; M.29.12.d) N-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; M.29.12.e) N-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; M.29.12.f) N-ethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthiopropanamide; M.29.12.g) N-methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthiopropanamide; M.29.12.h) N,2-dimethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthiopropanamide; M.29.12.i) N-ethyl-2-methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthiopropanamide; M.29.12.j) N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-2-methyl-3-methylthiopropanamide; M.29.12.k) N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N,2-dimethyl-3-methylthiopropanamide; M.29.12.l) N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-methyl-3-methylthiopropanamide; M.29.12.m) N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylthio-propanamide; or connections

M.29.14a) 1-[(6-chloro-3-pyridinyl)methyl]-1,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitroimidazo[1,2- a] pyridine; or M.29.14b) 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine -5-ol; or connections

M.29.16a) 1-isopropyl-N,5-dimethyl-N-pyridazin-4-ylpyrazole-4-carboxamide; or M.29.16b) 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-ylpyrazole-4-carboxamide; M.29.16c) N,5-dimethyl-N-pyridazin-4-yl-1-(2,2,2-trifluoro-1-methyl-ethyl)pyrazole-4-carboxamide; M.29.16d) 1-[1-(1-cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-ylpyrazole-4-carboxamide; M.29.16e) N-ethyl-1-(2-fluoro-1-methylpropyl)-5-methyl-N-pyridazin-4-ylpyrazole-4-carboxamide; M.29.16f) 1-(1,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-ylpyrazole-4-carboxamide; M.29.16g) 1-[1-(1-cyanocyclopropyl)-ethyl]-N,5-dimethyl-N-pyridazin-4-ylpyrazole-4-carboxamide; M.29.16h) N-methyl-1-(2-fluoro-1-methylpropyl]-5-methyl-N-pyridazin-4-ylpyrazole-4-carboxamide; M.29.16i) 1-(4,4-difluorocyclohexyl) )-N-ethyl-5-methyl-N-pyridazin-4-ylpyrazole-4-carboxamide; or M.29.16j) 1-(4,4-difluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-ylpyrazole-4-carboxamide, or

M.29.17 a compound selected from compounds M.29.17a) to M.29.17j): M.29.17a) N-(1-methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.29.17b) N-cyclopropyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.29.17c) N-cyclohexyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.29.17d) 2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H-indazole-4-carboxamide; M.29.17e) 2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H-indazole-5-carboxamide; M.29.17f) methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]-hydrazinecarboxylate; M.29.17g) N-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide; M.29.17h) N-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide; M.29.17i) 2-(3-pyridinyl)-N-(2-pyrimidinylmethyl)-2H-indazole-5-carboxamide; M.29.17j) N-[(5-methyl-2-pyrazinyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide, or

M.29.18 a compound selected from M.29.18a) to M.29.18d): M.29.18a) N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-N-ethyl- 3-(3,3,3-trifluoropropylsulfanyl)propanamide; M.29.18b) N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropylsulfinyl)propanamide; M.29.18c) N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-3-[(2,2-difluorocyclopropyl)methylsulfanyl]-N-ethylpropanamide; M.29.18d) N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-3-[(2,2-difluorocyclopropyl)methylsulfinyl]-N-ethylpropanamide; or connection

M.29.19 sarolaner or compound

M.29.20 Lotirunner.

Commercially available M compounds of the above list can be found in The Pesticide Manual, 16th Edition, C. MacBean, British Crop Protection Council (2013) among other publications. The online version of the Pesticide Manual is updated regularly and is available at http://bcpcdata.com/pesticide-manual.html.

Another online pesticide database with generic ISO names is http://www.alanwood.net/pesticides.

M.4 neonicotinoid cycloxapride known from WO 2010/069266 and WO 2011/069456, neonicotinoid M.4A.2, which is sometimes also called guadipyr, known from WO 2013/003977, and neonicotinoid M.4A.3 (approved as paichongding in China), known from WO 2007/101369. The metaflumizone analog M.22B.1 is described in CN10171577 and the analog M.22B.2 in CN 102126994. The phthalamides M.28.1 and M.28.2 are both known from WO 2007/101540. Anthranilamide M.28.3 is described in WO2005/077934. The hydrazide compound M.28.4 is described in WO 2007/043677. Anthranilamides M.28.5a) - M.28.5d) and M.28.5h) are described in WO 2007/006670, WO 2013/024009 and WO 2013/024010, anthranilamide M.28.5i) is described in WO 2011/085575, M. 28.5j) in WO 2008/134969, M.28.5k) in US 2011/046186 and M.28.5l) in WO 2012/034403. The diamide compound M.28.6 can be found in WO 2012/034472. The spiroketal-substituted cyclic ketoenol derivative M.29.3 is known from WO 2006/089633 and the biphenyl-substituted spirocyclic ketoenol derivative M.29.4 from WO 2008/067911. Triazoylphenyl sulfide M.29.5 is described in WO 2006/043635 and biological control agents based on bacillus firmus are described in WO 2009/124707. Compounds M.29.6a) - M.29.6i), referred to as M.29.6, are described in WO 2012/029672 and M.29.6j) and M.29.6k) in WO 2013/129688. Nematocide M.29.8 is known from WO 2013/055584. Isoxazoline M.29.9.a) is described in WO 2013/050317. Isoxazoline M.29.9.b) is described in WO 2014/126208. An analog of the pyridalyl type M.29.10 is known from WO 2010/060379. Broflanilide carboxamides and M.29.11.b) - M.29.11.h) are described in WO 2010/018714 and carboxamides M.29.11i) - M.29.11.p) in WO 2010/127926. Pyridylthiazoles M.29.12.a) - M.29.12.c) are known from WO 2010/006713, M.29.12.d) and M.29.12.e) are known from WO 2012/000896, M.29.12.f) - M. 29.12.m) from WO 2010/129497. Compounds M.29.14a) and M.29.14b) are known from WO 2007/101369. Pyrazoles M.29.16.a) - M.29.16h) are described in WO 2010/034737, WO 2012/084670 and WO 2012/143317, respectively, and pyrazoles M.29.16i) and M.29.16j) are described in US 61/ 891437. Pyridinilindazoles M.29.17a) - M.29.17.j) are described in WO 2015/038503. Pyridylpyrazoles M.29.18a) - M.29.18d) are described in US 2014/0213448. Isoxazoline M.29.19 is described in WO 2014/036056. Isoxazoline M.29.20 is known from WO 2014/090918.

Listed below are the fungicides in combination with which the compounds of the present invention may be used without limiting the scope of the present invention:

A) Respiratory inhibitors

- Inhibitors of complex III at the Q _o site (e.g. strobilurins): azoxystrobin (A.1.1), coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), phenaminestrobin (A.1.6), phenoxystrobin/fluphenoxystrobin (A.1.7), flucoxastrobin (A.1.8), kresoxim-methyl (A.1.9), mandestrobin (A.1.10), methominostrobin (A.1.11), orysastrobin (A.1.12) ), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1.17), 2-(2-(3-(2,6- dichlorophenyl)-1-methylallylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methylacetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb/chlordincarb (A.1.20), famoxadone (A.1.21), fenamidone (A.1.21), methyl-N-[2-[(1,4-dimethyl-5-phenylpyrazol-3-yl)oxymethyl]phenyl]-N-methoxycarbamate (A.1.22), 1-[3-chloro- 2-[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1.23), 1-[3-bromo-2-[ [1-(4-Chlorophenyl)pyrazol-3-yl]oxymethyl]phenyl]-4-methyltetrazol-5-one (A.1.24), 1-[2-[[1-(4-chloro phenyl)pyrazol-3-yl]oxymethyl]-3-methylphenyl]-4-methyl-tetrazol-5-one (A.1.25), 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl ]hydroxymethyl]-3-fluorophenyl]-4-methyltetrazol-5-one (A.1.26), 1-[2-[[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxymethyl]-3-fluoro -phenyl]-4-methyltetrazol-5-one (A.1.27), 1-[2-[[4-(4-chlorophenyl)thiazol-2-yl]oxymethyl]-3-methylphenyl]-4-methyltetrazol-5 -one (A.1.28), 1-[3-chloro-2-[[4-(p-tolyl)thiazol-2-yl]oxymethyl]phenyl]-4-methyltetrazol-5-one (A.1.29), 1-[3-cyclopropyl-2-[[2-methyl-4-(1-methyl-pyrazol-3-yl)phenoxy]methyl]phenyl]-4-methyltetrazol-5-one (A.1.30), 1- [3-(difluoromethoxy)-2-[[2-methyl-4-(1-methylpyrazol-3-yl)phenoxy]methyl]phenyl]-4-methyl-tetrazol-5-one (A.1.31), 1- methyl-4-[3-methyl-2-[[2-methyl-4-(1-methylpyrazol-3-yl)phenoxy]methyl]phenyl]tetrazol-5-one (A.1.32), 1-methyl-4 -[3-methyl-2-[[1-[3-(trifluoromethyl)phenyl]-ethylideneamino]oxymethyl]phenyl]tetrazol-5-one (A.1.33), (Z,2E)-5-[1-( 2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethylpent-3-enamide (A.1.34), (Z,2E)-5-[1-(4-chlorophenyl)pyrazole -3-yl]oxy-2-methoxy imino-N,3-dimethylpent-3-enamide (A.1.35), (Z,2E)-5-[1-(4-chloro-2-fluorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N ,3-dimethylpent-3-enamide (A.1.36),

-inhibitors of complex III at the Q _i site: cyazofamide (A.2.1), amisulbrom (A.2.2), [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxypyridine- 2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate (A.2.3), [(3S,6S,7R,8R)-8-benzyl -3-[[3-(acetoxymethoxy)-4-methoxypyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate (A.2.4) , [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxypyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonane -7-yl] 2-methylpropanoate (A.2.5), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxypyridine -2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate (A.2.6); (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1, 5-dioxonan-7-yl 2-methylpropanoate (A.2.7), (3S,6S,7R,8R)-8-benzyl-3-[3-[(isobutyryloxy)methoxy]-4-methoxypicolinamido]-6-methyl -4,9-dioxo-1,5-dioxonan-7-yl isobutyrate (A.2.8);

complex II inhibitors (e.g. carboxamides): benodanil (A.3.1), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6) ), fluopyram (A.3.7), flutolanil (A.3.8), fluxapiroxade (A.3.9), furametpyr (A.3.10), isofetamide (A.3.11), isopyrazam (A.3.12), mepronil (A.3.13) , oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), trifluzamide (A.3.18), N-(4'-trifluoromethylthiobiphenyl -2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide (A.3.19), N-(2-(1,3,3-trimethylbutyl)phenyl)-1,3-dimethyl -5-fluoro-1H-pyrazole-4-carboxamide (A.3.20), 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A .3.21), 3-(trifluoromethyl)-1-methyl-N-(1,1,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.22), 1,3-dimethyl-N-(1 ,1,3-trimethylindan-4-yl)pyrazol-4-carboxamide (A.3.23), 3-(trifluoromethyl)-1,5-dimethyl-N-(1,1,3-trimethylindan-4-yl)pyrazole -4-carboxamide (A.3.24), 1,3,5-trimethyl-N-(1,1,3-trimethylindan-4-yl)pyr zol-4-carboxamide (A.3.25), N-(7-fluoro-1,1,3-trimethylindan-4-yl)-1,3-dimethylpyrazole-4-carboxamide (A.3.26), N-[2 -(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methylpyrazole-4-carboxamide (A.3.27);

- other respiration inhibitors (e.g. complex I, uncoupling agents): diflumetorim (A.4.1), (5,8-difluoroquinozolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridine- 2-yloxy)phenyl]ethyl}amine (A.4.2); nitrophenyl derivatives: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometallic compounds: fentin salts such as fentin acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); amethoctradine (A.4.11); and silthiopham (A.4.12);

B) Sterol biosynthesis inhibitors (IHD fungicides)

C14 demethylase inhibitors (IDM fungicides): triazoles: aconazole (B.1.1), bitertanol (B.1.2), bromuconazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B. 1.6), diniconazole-M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole (B .1.13), imibenconazole (B.1.14), ipconazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazol (B.1.20), penconazole (B. 1.21), propiconazole (B.1.22), prothioconazole (B.1.23), simeconazole (B.1.24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1.27), triadimenol (B.1.28 ), triticonazole (B.1.29), uniconazole (B.1.30), 1-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiranylmethyl]-5-thiocyanato -1H-[1,2,4]triazolo (B.1.31), 2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H -[1,2,4]triazol-3-thiol (B.1.32), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1,2,4-triazol-1-yl )pentan-2-ol (B.1.33), 1-[4-(4-chlorophe noxy)-2-(trifluoromethyl)phenyl]-1-cyclopropyl-2-(1,2,4-triazol-1-yl)ethanol (B.1.34), 2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)butan-2-ol (B.1.35), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1,2,4-triazol-1-yl)butan-2-ol (B.1.36), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1- (1,2,4-triazol-1-yl)butan-2-ol (B.1.37), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2, 4-triazol-1-yl)propan-2-ol (B.1.38), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-3-methyl-1-(1,2,4-triazole -1-yl)butan-2-ol (B.1.39), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl) pentan-2-ol (B.1.40), 2-[4-(4-fluorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1,2,4-triazol-1-yl)propan-2-ol (B.1.41), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1,2,4-triazol-1-yl)pent-3-yn-2-ol (B. 1.51); imidazoles: imazalil (B.1.42), pefurazoate (B.1.43), prochloraz (B.1.44), triflumizole (B.1.45); pyridines, pyridines and piperazines: fenrimol (B.1.46), nuarimol (B.1.47), pyrifenox (B.1.48), triforin (B.1.49), [3-(4-chloro-2-fluorophenyl)-5-( 2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1.50);

-Delta14 reductase inhibitors: aldimorph (B.2.1), dodemorph (B.2.2), dodemorph acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidine (B.2.6), piperalin (B.2.7), spiroxamine (B.2.8);

-3-ketoreductase inhibitors: fenhexamide (B.3.1);

C) Nucleic acid synthesis inhibitors

-phenylamides or acylamino acid fungicides: benalaxyl (C.1.1), benalaxyl-M (C.1.2), chiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (mefenoxam, C.1.5), ofurac (C .1.6), oxadixyl (C.1.7);

-others: hymexazole (C.2.1), octilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p- tolylmethoxy)pyridine-4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyridine-4-amine (C.2.7);

D) Inhibitors of cell division and cytoskeleton

tubulin inhibitors such as benzimidazoles, thiophanates: benomyl (D1.1), carbendazim (D1.2), fuberidazole (D1.3), thiabendazole (D1.4), thiophanate-methyl (D1.5); triazolopyridines: 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-[1,2,4]triazolo[1,5-a]pyridine (D1.6 );

- other cell division inhibitors: diethofenocarb (D2.1), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriophenone ( D2.7);

E) Inhibitors of amino acid and protein synthesis

- methionine synthesis inhibitors (anilino-pyridines): cyprodinil (E.1.1), mepanipyrim (E.1.2), pyrimethanil (E.1.3);

-protein synthesis inhibitors: blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hydrochloride hydrate (E.2.3), mildomycin (E.2.4), streptomycin (E.2.5), oxytetracycline (E.2.6) ), polyoxin (E.2.7), validamycin A (E.2.8);

F) Signal Transmission Inhibitors

- MAP/histidine kinase inhibitors: fluorimide (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vinclozoline (F.1.4), fenpiclonil (F.1.5), fludioxonil (F.1.6);

- G protein inhibitors: quinoxifene (F.2.1);

G) Inhibitors of lipid and membrane synthesis

-Phospholipid biosynthesis inhibitors: edifenphos (G.1.1), iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1.4);

-lipid peroxidation: diclorane (G.2.1), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chlorneb (G.2.6), etridiasol ( G.2.7);

-phospholipid biosynthesis and cell wall growth: dimethomorph (G.3.1), flumorph (G.3.2), mandipropamide (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7) and N-(1-(1-(4-cyanophenyl)ethanesulfonyl)but-2-yl)carbamic acid 4-fluorophenyl ester (G.3.8);

- compounds affecting the permeability of cell membranes and fatty acids: propamocarb (G.4.1);

-fatty acid amide hydrolase inhibitors: oxathiapiproline (G.5.1), 2-{3-[2-(1-{[3,5-bis(difluoromethyl-1H-pyrazol-1-yl]acetyl}piperidin-4-yl )-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenylmethanesulfonate (G.5.2), 2-{3-[2-(1-{[3 ,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl) 1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl }-3-chlorophenylmethanesulfonate (G.5.3);

H) Multisite inhibitors

- inorganic active substances: Bordeaux mixture (H.1.1), copper acetate (H.1.2), copper hydroxide (H.1.3), copper oxychloride (H.1.4), basic copper sulfate (H.1.5), sulfur (H. 1.6);

-thio- and dithiocarbamates: ferbam (H.2.1), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram ( H.2.7), zineb (H.2.8), ziram (H.2.9);

-organochlorine compounds (e.g. phthalimides, sulfonamides, chloronitriles): anilazine (H.3.1), chlorthalonil (H.3.2), captofol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid ( H.3.6), dichlorophene (H.3.7), hexachlorobenzene (H.3.8), pentachlorophenol (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.11), N-(4-chloro- 2-nitro-phenyl)-N-ethyl-4-methylbenzenesulfonamide (H.3.12);

-guanides and others: guanidine (H.4.1), dodine (H.4.2), dodine free base (H.4.3), guasatin (H.4.4), guasatin acetate (H.4.5), iminoctadine (H.4.6) , iminoctadine triacetate (H.4.7), iminoctadine tris(albesilate) (H.4.8), dithianone (H.4.9), 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3- c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone (H.4.10);

I) Cell wall synthesis inhibitors

- glucan synthesis inhibitors: validamycin (I.1.1), polyoxin B (I.1.2);

melanin synthesis inhibitors: pyrochilon (I.2.1), tricyclazole (I.2.2), carpropamide (I.2.3), dicyclomet (I.2.4), phenoxanil (I.2.5);

J) Crop protection inducers

acibenzolar-S-methyl (J.1.1), probenazole (J.1.2), isothianil (J.1.3), thiadinyl (J.1.4), prohexadione-calcium (J.1.5); phosphonates: fosetyl (J.1.6), fosetyl aluminum (J.1.7), phosphoric acid and its salts (J.1.8), potassium or sodium bicarbonate (J.1.9);

K) Unknown mode of action

bronopol (K.1.1), quinomethionate (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclomesin (K.1.7), diphenzoquat (K.1.8), diphenzoquat methyl sulfate (K.1.9), diphenylamine (K.1.10), phenpyrizamine (K.1.11), flumetover (K.1.12), flusulfamide (K.1.13), fluthianil (K.1.14) , metasulfocarb (K.1.15), nitrapyrine (K.1.16), nitrothalisopropyl (K.1.18), oxathiapiproline (K.1.19), tolprocarb (K.1.20), oxincopper (K.1.21), proquinazid (K .1.22), tebufloquine (K.1.23), tecloftalam (K.1.24), triazoxide (K.1.25), 2-butoxy-6-iodo-3-propylchromen-4-one (K.1.26), 2-[3 ,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro -1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone (K.1.27), 2-[3,5-bis(difluoromethyl)-1H-pyrazole -1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol- 3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone (K.1.28), 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5- dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone (K.1.29), N-(cyclopropylmethoxyimino-(6-difluoromethoxy-2,3- difluorophenyl)methyl)-2-phenylacetamide (K.1.30), N'-(4-(4-chloro-3-trifluoromethylphenoxy)-2,5-dimethylphenyl)-N-ethyl-N-methylformamidine (K.1.31 ), N'-(4-(4-fluoro-3-trifluoromethylphenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methylformamidine (K.1.32), N'-(2-methyl-5- trifluoromethyl-4-(3-trimethylsilanylpropoxy)phenyl)-N-ethyl-N-methylformamidine (K.1.33), N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanylpropoxy)phenyl)-N-ethyl -N-methylformamidine (K.1.34), methoxyacetic acid 6-tert-butyl-8-fluoro-2,3-dimethylquinolin-4-yl ester (K.1.35), 3-[5-(4-methylphenyl) -2,3-dimethylisoxazolidin-3-yl]pyridine (K.1.36), 3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine (pyrisoxazole) (K.1.37), amide N-(6-methoxypyridin-3-yl)cyclopropanecarboxylic acid (K.1.38), 5-chloro-1-(4,6-dimethoxypyridin-2-yl)-2-methyl-1H-benzoimidazole (K.1.39), 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxyphenyl)isoxazol-5-yl]-2-prop-2-i loxiacetamide, ethyl (Z)-3-amino-2-cyano-3-phenylprop-2-enoate (K.1.40), picarbutrazox (K.1.41), pentyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)phenylmethylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.42), 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6 -fluorophenyl]propan-2-ol (K.1.43), 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol (K.1.44 ), 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline (K.1.45), 3-(4,4-difluoro-3,3-dimethyl -3,4-dihydroisoquinolin-1-yl)quinoline (K.1.46), 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline (K.1.47 ), 9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-1,4-benzoxazepine (K.1.48).

Fungicides described by common names, their preparation and their activity against harmful fungi, for example, are known (see: http://www.alanwood.net/pesticides/); these substances are commercially available.

Fungicides are described by IUPAC nomenclature, their preparation and their pesticidal activity are also known (see Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; EP- A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP -A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; de 102005009458; US 3.296,272; US 3.325.503; Wo 98/46608; Wo 99/14187; Wo 99/24413; Wo 99/27783; Wo 00/29404; Wo 00/29404; 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO 02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624; WO 11/028657; WO2012/168188; WO 2007/006601; /77514; O 13/024010 and WO 13/047441, WO 13/162072, WO 13/092224, WO 11/135833).

Biopesticides

Suitable mixing partners for the compounds of the present invention are also biopesticides.

Biopesticides have been defined as a form of pesticides based on microorganisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds such as metabolites, proteins, or extracts from biological or other natural sources) (US Environmental Protection Agency : http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two main classes, microbial and biochemical pesticides:

(1) Microbial pesticides are composed of bacteria, fungi, or viruses (and often include metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classified as microbial pesticides even though they are multicellular.

(2) Biochemical pesticides are natural substances, or structurally similar to them and functionally identical to natural substances and extracts from biological sources, that control pests or provide other means of protecting crops, as defined below, but are characterized by a non-toxic mode of action (for example, growth regulation or development, attractants, repellents, or protective activators (eg, causing resistance), they are relatively non-toxic to mammals.

Biopesticides for use against crop diseases have already proven themselves in various crops. For example, biopesticides already play an important role in the fight against mould. Advantages include: no soaking time before harvest, the ability to use under moderate to severe disease pressure, and the ability to use a mixture or variable program with other registered pesticides.

The main use of biopesticides is in the field of seed treatment and soil modification. Seed treatments with biopesticides, for example, are used to control fungal pathogens that are found in the soil, causing seed rot, blight, root rot and white rot. They can also be used to control internal fungal pathogens in seeds, as well as fungal pathogens that are found on the surface of seeds. Many biopesticide products also show the ability to stimulate host defenses and other physiological processes that can make treated crops more resistant to various biotic and abiotic stresses or can regulate plant growth. Many biopesticide products also demonstrate the ability to promote plant health, plant growth, and/or activity to increase yields.

The following list of biopesticides in combination with which the compounds of the present invention are used may be intended to illustrate possible combinations, but not limit them:

L) Biopesticides

L1) Microbial pesticides with fungicidal, bactericidal, virucidal activity and/or plant strength activators: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenulate (also called Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibacillus alvei, Paenibacillus polymyxa, Pantoea vagans, Penicillium bilaiae, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas, Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum , T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, squash yellow mosaic virus (avirulent strain);

L2) Biochemical pesticides with fungicidal, bactericidal, virucidal activity and/or plant strength activators: Harpin protein, Reynoutria sachalinensis extract;

L3) Microbial pesticides with insecticidal, acaricidal, molluscicidal and/or nematocidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bassiana, B. brongniartii, Burkholderia spp., Chromobacterium subtsugae, Cydia pomonella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV), Flavobacterium spp. Helicoverpa zea (HzSNPV), Heterorhabditisbacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, Metarhizium anisopliae, Metarhizium anisopliae var. anisopliae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis non-cleopolyhedrovirus (SpliNPV), Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces galbus, S. microflavus;

L4) Biochemical pesticides with insecticidal, acaricidal, molluscicidal, pheromone and/or nematocidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-2, 4-ethyldecadienoate (pear ether), (Z,Z,E)-7,11,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanyl senecioate, cis-jasmone, 2-methyl 1-butanol, methyl eugenol, methyl jasmonate, (E, Z)-2,13-octadecadien-1-ol, (E,Z)-2,13-octadecadien-1-ol acetate, (E,Z)-3,13-octadecadien-1-ol, R-1- octen-3-ol, pentathermanone, (E,Z,Z)-3,8,11-tetradecatrienyl acetate, (Z,E) 9,12-tetradecadien-1-yl acetate, Z-7-tetradecen-2-one, Z -9-tetradecen-1-yl acetate, Z-11-tetradecenal, Z-11-tetradecen-1-ol, Chenopodium ambrosiodes extract, Neem tree seed oil, Quillaia tree extract;

L5) Microbial pesticides to reduce plant stress, to regulate plant growth, to promote plant growth and/or promote yield increase: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhizobium leguminosarum bv. phaseoli, R. l. bv. trifolii, R.l. bv. viciae, R. tropici, Sinorhizobium meliloti.

The biopesticides of L1) and/or L2) may also exhibit insecticidal, acaricidal, molluscicidal, pheromone, nematocidal activity, reduce plant stress, regulate plant growth, promote plant growth and/or promote yield increase. The biopesticides of L3) and/or L4) can exhibit fungicidal, bactericidal, virocidal activity, activate plant defenses, reduce plant stress, regulate plant growth, promote plant growth and/or promote yield increase. The biopesticides of L5) may also exhibit fungicidal, bactericidal, virocidal, plant defense activating, insecticidal, acaricidal, molluscicidal, pheromone and/or nematocidal activity.

Many of these biopesticides have been deposited under the deposit numbers indicated in this document (prefixes such as ATCC or DSM refer to the abbreviation of the respective culture collection, see for example: http://www.wfcc.info/ccinfo /collection/by_acronym/), they are mentioned in the literature, registered and/or commercially available: mixtures with Aureobasidium pullulans DSM 14940 and DSM 14941 isolated in 1989 in Konstanz, Germany, Germany (for example, blastospores in BlossomProtect® from bio -ferm GmbH, Austria), Azospirillum brasilense Sp245, first isolated in the wheat region of Southern Brazil (Passo Fundo), at least until 1980 (BR 11005; e.g. GELFIX® Gramíneas from BASF Agricultural Specialties Ltd., Brazil), A. brasilense strains Ab-V5 and Ab-V6 (e.g. in AzoMax from Novozymes BioAg Produtos papra Agricultura Ltda., Quattro Barras, Brazil or Simbiose-Maíz® from Simbiose-Agro, Brazil; Plant Soil 331, 413-425, 2010), Bacillus amyloliquefaciens strain AP-188 (NRRL B-50615 and B-50331; US 8,445,255); B. amyloliquefaciens spp. plantarum D747 isolated from air in Kikugawa-shi, Japan (US 20130236522 A1; FERM BP-8234; e.g. Double Nickel™ 55 WDG from Certis LLC, USA), B. amyloliquefaciens spp. plantarum FZB24 isolated from soil in Brandenburg, Germany (also called SB3615; DSM 96-2; J. Plant Dis. Prot. 105, 181-197, 1998; e.g. Taegro® from Novozyme Biologicals, Inc., USA), B amyloliquefaciens ssp. plantarum FZB42 isolated from soil in Brandenburg, Germany (DSM 23117; J. Plant Dis. Prot. 105, 181-197, 1998; e.g. RhizoVital® 42 from AbiTEP GmbH, Germany), B. amyloliquefaciensssp. plantarum MBI600 isolated from horse beans at Sutton Bonington, Nottinghamshire, UK, up to at least 1988 (also called 1430; NRRL B-50595; US 2012/0149571 A1; e.g. Integral® from BASF Corp., USA), B amyloliquefaciens spp. plantarum QST-713 isolated from a 1995 peach orchard in California, USA (NRRL B-21661; e.g. Serenade® MAX from Bayer Crop Science LP, USA), B. amyloliquefaciens spp. plantarum TJ1000 isolated 1992 in South Dakota, USA (also called 1BE; ATCC BAA-390; CA 2471555 A1; e.g. QuickRoots™ from TJ Technologies, Watertown, SD, USA), B. firmus CNCM I-1582, variant of the parental strain EIP-N1 (CNCM I-1556) isolated from the soil of the central plains of Israel (WO 2009/126473, US 6,406,690; e.g. Votivo® from Bayer CropScience LP, USA), B. pumilus GHA 180 isolated from the rhizosphere of apple trees in Mexico City (IDAC 260707-01; e.g. PRO-MIX® BX from Premier Horticulture, Quebec, Canada), B. pumilus INR-7, also referred to as BU-F22 and BU-F33, isolated until at least 1993 from cucumber infested with Erwinia tracheiphila (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumilus QST 2808 isolated from soil collected in Pohnpei, Federated States of Micronesia in 1998 (NRRL B-30087; e.g. Sonata ® or Ballad® Plus from Bayer Crop Science LP, USA), B. simplex ABU 288 (NRRL B-50304; US 8,445,255), B. subtilis FB17, also called UD 1022 or UD10-22, isolated from red beet orniches in North America (ATCC PTA-11857; System. Appl. microbiol. 27, 372-379, 2004; US 2010/0260735; WO 2011/109395); B. thuringiensis sp. aizawai ABTS-1857, isolated from soil sampled in the Ephraim Valley, Wisconsin, USA, in 1987 (also called ABG-6346; ATCC SD-1372; e.g., XenTari® from BioFa AG, Munsingen, Germany), B. t . ssp. kurstaki ABTS-351, identical to HD-1, isolated in 1967 from a diseased black larva of a pink bollworm in Brownsville, Texas, USA (ATCC SD-1275; e.g., Dipel® DF from Valent BioSciences, IL, USA), B. t. ssp. tenebrionis NB-176-1, mutant of strain NB-125, wild-type strain, isolated in 1982 from a dead pupa of the mealworm beetle (DSM 5480; EP 585 215 B1; e.g., Novodor® from Valent BioSciences, Switzerland), Beauveria bassiana GHA (ATCC 74250; e.g. BotaniGard® 22WGP from Laverlam Int. Corp., USA), B. bassiana JW-1 (ATCC 74040; e.g. Naturalis® from CBC (Europe) S.r.l., Italy), Bradyrhizobium elkanii strains SEMIA 5019 (also called 29W), isolated in Rio de Janeiro, Brazil, and SEMIA 587, isolated in 1967 in Rio Grande do Sul State, from a plot previously inoculated with a North American isolate, and used in commercial inoculants since 1968 ( Appl Environ Microbiol 73(8), 2635, 2007; e.g. GELFIX 5 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum532c isolated from a field in Wisconsin, USA (Nitragin 61A152; Can. J. Plant. Sci 70, 661-666, 1990; for example, in Rhizoflo®, Histick®, Hicoat® Super from BASF Agricultural Specialties Ltd., Canada), B. japonicum E-109 strain variant USDA 138 (INTA E109, SEMIA 5085; Eur. J. Soil Biol. 45, 28-35, 2009; Biol. fertil. Soils 47, 81-89, 2011); B. japonicum strains deposited with SEMIA known from Appl. Environ. microbiol. 73(8), 2635, 2007: SEMIA 5079 isolated from the soil of the Kerrados region, Brazil, Embrapa-Querrados, used in commercial inoculants since 1992 (CPAC 15; e.g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum SEMIA 5080, obtained in the laboratory of Embrapa-Querrados in Brazil and used in commercial inoculants since 1992, is a natural variant of SEMIA 586 (CB1809) that was isolated in the USA (CPAC 7; e.g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil); Burkholderia sp. A396 isolated from soil in Nikko, Japan in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio Innovations, Inc., USA), Coniothyrium minitans CON/M/91-08 isolated from rapeseed (WO 1996/021358; DSM 9660; e.g. Contans® WG, Intercept® WG from Bayer CropScience AG, Germany), harpin (alpha-beta) protein (Science 257, 85-88, 1992; e.g. Messenger™ or HARP-N- Tek from Plant Health Care plc, UK), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (J. Invertebrate Pathol. 107, 112-126, 2011; e.g. Helicovex® from Adermatt Biocontrol, Switzerland; Diplomata® from Koppert, Brazil; Vivus® Max from AgBiTech Pty Ltd., Queensland, Australia), Helicoverpa zea nucleopolyhedrovirus (HzSNPV) single capsid (e.g. Gemstar® from Certis LLC, USA), Helicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e.g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia), Heterorhabditisbacteriophora (e.g. Nemasys® G from BASF Agricultural Specialities Limited, UK), Isaria fumosorosea Apopka-97 isolated from mealybug on guinura in Apopka, Florida, USA (ATCC 20874; Biocontrol Science Technol. 22(7), 747-761, 2012; e.g. PFR-97™ or PreFeRal® from Certis LLC, USA), Metarhizium anisopliaevar. anisopliae F52, also called 275 or V275, isolated from apple seedlings in Austria (DSM 3884, ATCC 90448; e.g. Met52® Novozymes Biologicals BioAg Group, Canada), Metschnikowia fructicola 277 isolated from grapes in central Israel (US 6,994,849; NRRL Y-30752; eg formerly Shemer® from Agrogreen, Israel), Paecilomyces ilacinus 251 isolated from infected nematode eggs in the Philippines (AGAL 89/030550; WO1991/02051; Crop Protection 27, 352-361, 2008; eg BioAct® from Bayer CropScience AG, Germany and MeloCon® from Certis, USA), Pasteuria nishizawae Pn1 isolated from soybean fields in the mid-2000s. in Illinois, USA (ATCC SD-5833; Federal Register 76(22), 5808, February 2, 2011; e.g., Clariva™ PN from Syngenta Crop Protection, LLC, USA), Penicillium bilaiae (also called P. bilaii), strains ATCC 18309 (= ATCC 74319), ATCC 20851 and/or ATCC 22348 (= ATCC 74318), previously isolated from soil in Alberta, Canada (Fertilizer Res. 39, 97-103, 1994; Can. J. Plant Sci. 78( 1), 91-102, 1998; US 5,026,417, WO 1995/017806; e.g. Jump Start®, Provide® from Novozymes Biologicals BioAg Group, Canada), Reynoutria sachalinensis extract (EP 0307510 B1; e.g. Regalia® SC from Marrone BioInnovations , Davis, CA, USA or Milsana® from BioFa AG, Germany), Steinernema carpocapsae (e.g. Millenium® from BASF Agricultural Specialities Limited, UK), S. feltiae (e.g. Nemashield® from BioWorks, Inc., USA; Nemasys ® from BASF Agricultural Specialities Limited, UK), Streptomyces microflavus NRRL B-50550 (WO 2014/124369; Bayer CropScience, Germany), T. harzianum T-22, also called KRL-AG2 is being developed (ATCC 20847; BioControl 57, 687-696, 2012; for example, Plantshield® from BioWorks Inc., USA or SabrEx™ from Advanced Biological Marketing Inc., Van Wert, OH, USA).

According to the invention, the solid material (dry matter) of biopesticides (with the exception of oils such as Neem's oil) are considered as active components (for example, obtained after drying or evaporation of the extraction or suspension medium in the case of liquid formulations of microbial pesticides).

In accordance with the present invention, the weight ratios and percentages used in this document for a biological extract, such as a Quillai extract, are based on the total weight of the dry matter (solid material) content of the respective extract(s).

The total weight ratios of compositions containing at least one microbial pesticide in the form of viable microbial cells, including dormant forms, can be determined by using the number of CFU of the respective microorganism to calculate the total mass of the respective active ingredient according to the following equation, where 1 × 10 ¹⁰ CFU is equal to one gram the total weight of the respective active ingredient. A colony forming a unit is a measure of viable microbial cells, in particular fungal and bacterial cells. In addition, in this document, "CFU" can also mean the number of (juvenile) individual nematodes in the case of (entomopathogenic) nematode biopesticides, such as Steinernema feltiae.

When mixtures containing microbial pesticides are used for crop protection, application rates preferably range from about 1 x 10 ⁶ to 5 x 10 ¹⁵ (or more) cfu/ha, preferably from about 1 x 10 ⁸ to about 1 x 10 ¹³ cfu/ ha, even more preferably from about 1 x 10 ⁹ to about 1 x 10 ¹² CFU/ha. In the case of (entomopathogenic) nematodes as microbial pesticides (e.g. Steinernema feltiae), the application rate is preferably about 1 x 10 ⁵ to 1 x 10 ¹² (or more), more preferably 1 x 10 ⁸ to 1 x 10 ¹¹ , even more preferably 5 x 10 ⁸ to 1 x 10 ¹⁰ individuals (eg as eggs, young or any other live stage, preferably young infection stage) per ha.

When mixtures containing microbial pesticides are used for seed treatment, the application rate relative to plant propagation material ranges from about 1 x 10 ⁶ to 1 x 10 ¹² (or more) cfu/seed. Preferably the concentration is from about 1 x 10 ⁶ to about 1 x 10 ⁹ cfu/seed. With respect to microbial pesticides II, application rates for plant propagation material are also preferably about 1 x 10 ⁷ to 1 x 10 ¹⁴ (or more) cfu per 100 kg of seed, preferably 1 x 10 ⁹ to about 1 x 10 ¹² cfu per 100 kg of seeds.

The invention also relates to agrochemical compositions containing an auxiliary substance and at least one compound of the present invention or a mixture thereof.

The agrochemical composition contains a pesticidally effective amount of a compound of the present invention or a mixture thereof. The term "pesticidally effective amount" is defined below.

The compounds of the present invention, or mixtures thereof, can be formulated into conventional types of agrochemical compositions, for example, solutions, emulsions, suspensions, dusts, powders, pastes, granules, extrudates, capsules, and mixtures thereof. Examples of formulation types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, lozenges, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), extrudates (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal products (e.g. LN) as well as gel formulations for processing plant propagation material such as seeds (eg GF). These and other types of agrochemical compositions are defined in "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.

The compositions are prepared in a known manner as described in Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T & F Informa, London, 2005.

Examples of suitable excipients are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, binders, thickeners, wetting agents, repellents, attractants, nutritional stimulants, compatibilizers, bactericides, antifreezes, defoamers, colorants, tackifiers, and binders.

Suitable solvents and liquid carriers are water and organic solvents such as medium to high boiling point petroleum fractions, eg kerosene, diesel fuel; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, for example, toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, eg ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, for example cyclohexanone; esters, eg lactate, carbonates, fatty acid esters, gamma-butyrolactone; fatty acid; phosphonates; amines; amides, eg N-methylpyrrolidone, fatty acid dimethylamides; and their mixtures.

Suitable solid carriers or fillers are minerals, for example, silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, eg cellulose, starch; fertilizers, eg ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, vegetable products, eg cereal flour, cinchona flour, wood flour, nutshell flour and mixtures thereof.

Suitable surfactants are surface active compounds such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes and mixtures thereof. Such surfactants can be used as an emulsifier, dispersant, solubilizer, wetting agent, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are given in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. And North American Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, fatty acid and oil sulfonates, ethoxylated alkylphenol sulfonates, alkoxylated arylphenol sulfonates, condensed naphthalenes sulfonates, dodecyl and tridecylbenzene sulfonates, naphthalenes and alkylnaphthalenes sulfonates, sulfosuccinates or sulfosuccinates. Examples of sulfates are sulfates of fatty acids and oils, ethoxylated alkylphenols, alcohols, ethoxylated alcohols or fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohol or alkylphenol ethoxylates.

Suitable non-ionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. For alkoxylation, ethylene oxide and/or propylene oxide, preferably ethylene oxide, can be used. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are esters, glycerol esters or fatty acid monoglycerides. Examples of sugar-based surfactants are sorbitan, ethoxylated sorbitans, sucrose and glucose esters, or alkyl polyglycosides. Examples of polymeric surfactants are homo- or copolymers of vinyl pyrrolidone, vinyl alcohol or vinyl acetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups or long chain primary amine salts. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are those of the A-B or A-B-A type containing blocks of polyethylene oxide and polypropylene oxide, or of the ABC type containing alkanols, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid combination polymers. Examples of polybases are polyvinylamine or polyethyleneamines.

Suitable adjuvants are compounds having very little or even no pesticidal activity and improving the biological effectiveness of the compounds of the present invention relative to the target. Examples are surfactants, mineral or vegetable oils and other auxiliary agents. For more examples, see Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (eg xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates.

Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.

Suitable antifreezes are ethylene glycol, propylene glycol, urea and glycerin.

Suitable defoamers are silicones, long chain alcohols and salts of fatty acids.

Suitable dyes (eg red, blue or green) are pigments with low water solubility and water soluble dyes. Examples are inorganic dyes (eg iron oxide, titanium oxide, iron hexacyanoferate) and organic dyes (eg alizarin, azo and phthalocyanine dyes).

Suitable tackifiers or coupling agents are polyvinylpyrrolidone, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes and cellulose ethers.

Examples of types of compositions and their preparation are as follows:

i) Water soluble concentrates (SL, LS)

10-60% by weight of the compound I according to the invention and 5-15% by weight of a wetting agent (eg alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (eg alcohols) up to 100% by weight. The active substance dissolves when diluted with water.

II) Dispersible concentrates (DC)

5-25% by weight of the compound I according to the invention and 1-10% by weight of a dispersant (eg polyvinylpyrrolidone) are dissolved in an organic solvent (eg cyclohexanone) up to 100% by weight. Dilution with water results in a dispersion.

iii) Emulsifiable concentrates (EC)

15-70% by weight of the compound I according to the invention and 5-10% by weight of emulsifiers (eg calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in a water-immiscible organic solvent (eg an aromatic hydrocarbon) up to 100% by weight. Dilution with water results in an emulsion.

iv) Emulsions (EW, EO, ES)

5-40% by weight of the compound I according to the invention and 1-10% by weight of emulsifiers (eg calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40% by weight of a water-immiscible organic solvent (eg an aromatic hydrocarbon). This mixture is introduced into water up to 100 wt.% using an emulsifying device and converted into a homogeneous emulsion. Dilution with water results in an emulsion.

v) Suspensions (SC, OD, FS)

In a ball mill with a stirrer, 20-60 wt.% of the compound I according to the invention is ground with the addition of 2-10 wt.% of dispersants and wetting agents (for example, sodium lignosulfonate and ethoxylated alcohol), 0.1-2 wt.% of a thickener (for example, xanthan gum) and water up to 100 wt.% to obtain a thin suspension of the active substance. Dilution with water results in a stable suspension of the active substance. For an FS type composition, up to 40% by weight of a binding agent (eg polyvinyl alcohol) is added.

vi) Water-dispersible granules and water-soluble granules (WG, SG)

50-80 wt.% of the compound I according to the invention is finely ground with the addition of dispersants and wetting agents (for example, sodium lignosulfonate and ethoxylated alcohol) to 100 wt.% and water-dispersible granules or water-soluble granules are obtained using technical devices (for example, extruder, spray column, fluidized bed). Dilution with water results in a stable dispersion or solution of the active substance.

vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)

50-80 wt.% of compound I according to the invention is ground in a rotor-stator mill with the addition of 1-5 wt.% dispersants (for example, sodium lignosulfonate), 1-3 wt.% wetting agents (for example, ethoxylated alcohol) and a solid carrier ( eg silica gel) up to 100% by weight. Dilution with water results in a stable dispersion or solution of the active substance.

viii) Gel (GW, GF)

In a ball mill with a stirrer, 5-25 wt.% of the compound I according to the invention is crushed with the addition of 3-10 wt.% of dispersants (for example, sodium lignosulfonate), 1-5 wt.% of a thickener (for example, carboxymethyl cellulose) and water to 100 wt. % to obtain a thin suspension of the active substance. Dilution with water results in a stable suspension of the active substance.

ix) Microemulsions (ME)

5-20 wt.% of the compound I according to the invention is added to 5-30 wt.% of a mixture of organic solvents (for example, fatty acid dimethylamide and cyclohexanone), 10-25 wt.% of a mixture of surfactants (for example, ethoxylated alcohol and arylphenol ethoxylate ) and water up to 100 wt.%. This mixture is stirred for 1 hour to obtain a spontaneously thermodynamically stable microemulsion.

x) Microcapsules (CS)

An oil phase containing 5-50 wt. % of the compound I according to the invention, 0-40 wt. - or triacrylate) are dispersed in an aqueous solution of a protective colloid (eg polyvinyl alcohol). Initiate radical polymerization using a radical initiator, which leads to the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase containing 5-50 wt. % of a compound of formula I according to the invention, 0-40 wt. , dispersed in an aqueous solution of a protective colloid (for example, polyvinyl alcohol). The addition of a polyamine (eg hexamethylenediamine) results in the formation of polyurea microcapsules. The amount of monomers is up to 1-10 wt.%. The wt % values refer to the entire CS composition.

xi) Dust-like powders (DP, DS)

1-10 wt.% of the compound I according to the invention is finely ground and mixed well with a solid carrier (for example, finely divided kaolin) up to 100 wt.%.

xii) Wood pellets (GR, FG)

0.5-30 wt.% of the compound I according to the invention is finely ground and mixed with a solid carrier (eg silicate) up to 100 wt.%. Granulation is carried out by extrusion, spray drying or fluid bed.

xiii) Ultra Low Volume (UL) Liquids

1-50 wt.% of the compound I according to the invention is dissolved in an organic solvent (eg aromatic hydrocarbon) up to 100 wt.%.

Composition types i) - xi) may optionally contain additional auxiliary agents, such as 0.1-1 wt.% bactericides, 5-15 wt.% antifreeze, 0.1-1 wt.% defoamers and 0.1-1 wt. .% dyes.

Agrochemical compositions usually contain from 0.01 to 95%, preferably from 0.1 to 90% and most preferably from 0.5 to 75% by weight of the active substance. The active substances are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

Various types of oils, wetting agents, excipients, fertilizers or trace elements and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, protective agents). These agents can be mixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user applies the composition of the present invention, typically with a pre-dosing device, backpack sprayer, spray tank, spray aircraft, or irrigation system. As a rule, the agrochemical composition is diluted with water, buffer and/or additional auxiliary agents to the desired concentration and thus a ready-to-use spray liquid or agrochemical composition according to the invention is obtained. As a rule, from 20 to 2000 liters, preferably from 50 to 400 liters of ready-to-use spray liquid is applied per hectare of agriculturally useful area.

According to one embodiment, the individual components of the composition of this invention, such as parts of the complex or parts of a binary or ternary mixture, can be mixed by the user himself in a spray tank and, if necessary, additional auxiliary agents can be added.

In a further embodiment, the individual components of the composition of the present invention, or partially premixed components, e.g., components containing the compounds of the present invention and/or components to be blended as defined above, may be self-mixed by the user in a spray tank and, if desired, may be added additional support agents.

In a further embodiment, the individual components of the composition according to the invention, or partially premixed components, e.g. components containing compounds of the present invention and/or components to be mixed as defined above, may be applied simultaneously (e.g. after tank mixing) or sequentially.

The compounds of the present invention are useful in protecting crops, plants, plant propagation materials such as seeds or soils or waters in which plants grow from attack or infestation by animal pests. Thus, the present invention also relates to a method for protecting plants, including contacting crops, plants, plant propagation materials such as seeds, or soils or waters in which plants grow, which are to be protected from attack or infestation by animal pests, with a pesticidally effective the amount of the compound of the present invention.

The compounds of the present invention are also suitable for use in the eradication or control of animal pests. Thus, the invention also relates to a method for the destruction or control of animal pests, including contacting animal pests, their habitat, breeding or feeding area, or crops, plants, plant propagation materials such as seeds, or soils, territories, material or environment in which animal pests grow or can grow, with a pesticidally effective amount of a compound of the present invention.

The compounds of the present invention are effective both by contact and by ingestion. In addition, the compounds of the present invention can be used at any stage of development such as egg, larva, pupa and adult.

The compounds of the present invention can be used as such or in the form of compositions containing them, as defined above. In addition, the compounds of the present invention can be used together with components for mixing, as defined above, or in the form of compositions containing the above mixtures, as defined above. The components of this mixture can be applied simultaneously, together or separately, or in succession, i.e. immediately after each other, and thus create an "in situ" mixture at the right place, for example, on a plant, the sequence in the case of a separate application, as a rule, does not affect result of control measures.

Application can be carried out both before and after infestation of crops, plants, plant propagation materials such as seeds, soils or territories, material or environments by pests.

Suitable application methods include tillage, seed treatment, furrow application and foliar application, among others. Soil treatment methods include soaking the soil, drip irrigation (drip application to the soil), dipping roots, tubers or bulbs, or spraying into the soil. Seed treatment technologies include seed dressing, seed coating, seed pollination, seed soaking, and seed granulation. Furrow application typically includes the steps of forming a furrow in the area to be treated, seeding the furrow with seeds, applying the pesticidal active compound to the furrow, and closing the furrow. Foliar application refers to the application of a pesticidally active compound to the leaves of a plant, for example using spray equipment. For foliar application, it may be advantageous to modify pest behavior by using pheromones in combination with the compounds of the present invention. Appropriate pheromones for particular crops and pests are known to those skilled in the art and are publicly available from pheromone and semi-chemical databases such as http://www.pherobase.com.

As used herein, the term "contact" includes both direct contact (applying compounds/compositions directly to an animal or plant pest - typically the leaves, stem, or roots of a plant) and indirect contact (applying compounds/compositions to a pest site). , that is, the environment, breeding area, plant, seed, soil, area, material or environment in which the pest grows or may grow, the pest of animals or plants).

The term "animal pest" includes arthropods, gastropods and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects. Insects that are of particular importance to crops are commonly referred to as crop pests.

The term "crop" refers to both growing and harvested crops.

The term "plant" includes cereals such as durum and other wheats, rye, barley, triticale, oats, rice or corn (fodder corn and sweet/sweet corn as well as field corn) beets such as sugar beet or fodder beet ; fruits such as stone fruits, hard fruits or soft fruits, for example apples, pears, plums, peaches, nectarines, almonds, cherries, papaya, strawberries, raspberries, blackberries or gooseberries; legumes such as beans, lentils, peas, alfalfa or soybeans; oil plants such as rapeseed (oilseed rape), oil turnip, mustard, olives, sunflower, coconut, cocoa beans, castor plants, oil palm, peanuts or soybeans; pumpkins such as squash, gourd, cucumber or melon; cellular plants such as cotton, linen, hemp or jute; citrus fruits such as oranges, lemons, grapefruits or tangerines; vegetables such as eggplant, spinach, lettuce (eg iceberg lettuce), chicory, cabbage, asparagus, cabbage, carrots, onions, garlic, leeks, tomatoes, potatoes, pumpkin or bell peppers; bay plants such as avocado, cinnamon or camphor; energy and commodity plants such as corn, soybean, rapeseed, sugarcane or oil palm; tobacco; nuts such as walnuts; pistachios; coffee; tea; banana; grapes (table and juice grapes, wine grapes) hops; sweet leaf (also called stevia); natural rubber plants or ornamental and woodland plants such as flowers (carnation, petunia, geranium/pelargonium, violets and balsam), shrubs, deciduous trees (eg poplar) or evergreens such as conifers; eucalyptus; turf; lawn; grass, such as fodder grass for animals or for ornamental purposes. Preferred plants include potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or sugarcane; fruit; grape; ornamental plants; or vegetables such as cucumbers, tomatoes, beans or squash.

The term "plant" is understood to mean wild-type plants and plants that have been modified by conventional breeding, or mutagenesis, or genetic engineering, or a combination thereof.

Plants that have been modified by mutagenesis or genetic engineering are of particular commercial importance and include alfalfa, rape (e.g. oilseed rape), beans, cloves, chicory, cotton, eggplant, eucalyptus, flax, lentils, corn, melon, papaya, petunia, plums, poplars, potatoes, rice, soybeans, squash, sugar beets, sugar cane, sunflowers, bell peppers, tobacco, tomatoes and cereals (e.g. wheat), in particular corn, soybeans, cotton, wheat and rice. In plants that have been modified by mutagenesis or genetic engineering, one or more genes have been mutagenized or integrated into the plant's genetic material. One or more mutagenized or integrated genes are preferably selected from pat, epsps, cry1Ab, bar, cry1Fa2, cry1Ac, cry34Ab1, cry35AB1, cry3A, cryF, cry1F, mcry3a, cry2Ab2, cry3Bb1, cry1A.105, dfr, barnase, vip3Aa20, barstar, als, bxn, bp40, asn1 and ppo5. Mutagenesis or integration of one or more genes is carried out in order to improve certain properties of the plant. Such properties, also known as traits, include abiotic stress resistance, altered growth/yield, disease resistance, herbicide resistance, insect resistance, modified product quality, and dust control. Of these properties, resistance to herbicides, for example resistance to imidazolinones, resistance to glyphosate or resistance to glufosinate, is of particular importance. Some plants have acquired herbicide resistance by mutagenesis, eg Clearfield® oilseed rape has acquired resistance to imidazolinones, eg imazamox. Alternatively, genetic engineering methods have been used to produce plants such as soybeans, cotton, corn, beets and oilseed rape resistant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the tradenames RoundupReady® (glyphosate) and LibertyLink® (glufosinate). In addition, resistance to insects, in particular resistance to Lepidoptera and resistance to Coleoptera, is important. Insect resistance is usually achieved by modifying plants by integrating the cry and/or vip genes, which have been isolated from Bacillus thuringiensis (Bt) and encode the corresponding Bt toxins. Genetically modified insect resistant plants are commercially available under trade names including WideStrike®, Bollgard®, Agrisure®, Herculex®, YieldGard®, Genuity® and Intacta®. Plants can be modified by mutagenesis or genetic engineering for a single property (single trait) or for a combination of properties (collective traits). A collection trait, for example, is a combination of herbicide resistance and insect resistance, and is of increasing importance. In general, all relevant modified plants for a single or collective trait, as well as detailed information on mutagenization or integrated gene and related phenomena are posted on the websites of the organization "International Service for Collecting Data on the Use of Biotechnology in Agriculture (ISAAA)" (http ://www.isaaa.org/gmapprovaldatabase) and Center for Environmental Risk Assessment (CERA) (http://cera-gmc.org/GMCropDatabase).

Surprisingly, it has been found that the pesticidal activity of the compounds of the present invention can be enhanced by the insecticidal trait of the modified plant. In addition, the compounds of the present invention have been found to be useful for preventing insects from becoming resistant to an insecticidal trait or for controlling pests that have already acquired resistance to the insecticidal trait of a modified plant. In addition, the compounds of the present invention are suitable for controlling pests against which the insecticidal trait is not effective, so that complementary insecticidal activity can be advantageously used.

The term "plant propagation material" means all generative parts of plants, such as seeds and vegetative plant material, such as cuttings and tubers (eg potatoes), which can be used to propagate a plant. This term includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other plant parts. Seedlings and young plants that should be transplanted after germination or after emerging from the soil may also be included. These plant propagation materials can be treated prophylactically with a plant protection agent either at the time of planting or after transplanting.

The term "seed" includes seeds and sprouts of plants of all kinds, including, but not limited to, natural seeds, seed pieces, root shoots, corms, bulbs, fruits, tubers, grains, cuttings, cut shoots, etc., and means preferably natural seeds.

In general, "pesticidally effective amount" means the amount of an active ingredient required to achieve an observable effect on growth, including necrosis, death, inhibition, prevention and removal, killing, or otherwise reducing the occurrence and activity of the target organism. A pesticidally effective amount may vary for different compounds/compositions used in the invention The pesticidally effective amount of the compositions will also vary depending on the prevailing conditions such as the desired pesticidal effect and duration, weather conditions, target species, location, method of application, and the like.

In tillage, furrow application or application to a pest habitat or nest, the amount of active ingredient is from 0.0001 to 500 g per 100 m ² , preferably from 0.001 to 20 g per 100 m ² .

For use in crop treatment, for example by foliar application, the rate of application of the active ingredients of this invention may be in the range of 0.0001 to 4000 g per hectare, for example 1 g to 2 kg per hectare or 1 g to 750 g per hectare, preferably 1 g to 100 g per hectare, more preferably 10 g to 50 g per hectare, e.g. 10 to 20 g per hectare, 20 to 30 g per hectare, 30 to 40 g per hectare or 40 to 50 grams per hectare.

The compounds of the present invention are particularly suitable for use in seed treatment to protect the seed from insect pests, in particular soil pests, and the roots of germinated seeds and shoots from soil pests and leaf insects. The present invention also relates to a method for protecting seeds from insects, in particular from ground insects, and the roots of germinated seeds and shoots from insects, in particular from ground and leaf insects, where said method includes treating the seeds before sowing and/or after infection with the compound of the present invention. More preferable is the protection of the roots and shoots of seedlings. More preferable is the protection of seedling shoots from biting and sucking insects and nematodes.

The term "seed treatment" includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed pollination, seed soaking, seed granulation, and furrow application methods. Preferably, seed treatment with the active compound is carried out by spraying or pollinating the seeds before sowing the plants and before the plants emerge.

The present invention also includes coated seeds or seeds containing the active compound. The term "coated and/or containing" generally means that the active ingredient is preferably on the surface of the propagation product upon application, although more or less of the ingredient may penetrate the propagation product, depending on the method of application. When said propagation product is (re)planted, it can absorb the active ingredient.

Suitable seeds are cereals, root vegetables, oilseeds, vegetables, spices, ornamental crops, durum and other wheat, barley, oats, rye, corn (feed corn and sweet/sweet corn, and field corn), soybeans, oilseeds , Cruciferous, Cotton, Sunflower, Banana, Rice, Oilseed Rape, Oilseed Turnip, Sugar Beet, Fodder Beet, Eggplant, Potato, Grass, Lawn Grass, Sod, Forage Grass, Tomato, Leek, Pumpkin/Squash, Cabbage, Lettuce iceberg, pepper, cucumber, melon, Brassica spp., melon, beans and peas, garlic, onions, carrots, nodule plants such as potatoes, sugar cane, tobacco, grapes, petunias, geraniums/pelargoniums, violets and balsam.

In addition, the active compound can also be used to treat seeds of plants that have been modified by mutagenesis or genetic engineering and which, for example, tolerate the action of herbicides or fungicides or insecticides. Such modified plants have been described in detail above.

Conventional seed treatment compositions include, for example, flowable FS concentrates, LS solutions, suspoemulsions (SE), DS dry treatment powders, WS water-dispersible slurry treatment powders, SS water-soluble powders, and ES and EC emulsions, and GF gel formulations. These compositions can be applied to seeds diluted or undiluted. Application to seeds is carried out before sowing or directly on the seeds, or after pre-germination. Preferably, the compositions are applied in such a way as not to cause germination.

The concentrations of the active substance in the ready-to-use compositions, which can be obtained after dilution by two to ten times, are preferably from 0.01 to 60 wt.%, more preferably from 0.1 to 40 wt.%.

In a preferred embodiment, the FS composition is used for seed treatment. Typically, the FS composition may contain 1-800 g/l active ingredient, 1-200 g/l surfactant, 0-200 g/l antifreeze, 0-400 g/l binder, 0-200 g/l pigment and up to 1 liter of solvent, preferably water.

Particularly preferred FS compositions of the compounds of the present invention for seed treatment typically contain from 0.1 to 80 wt.% (1-800 g/l) active ingredient, from 0.1 to 20 wt.% (1-200 g/l) not less than one surfactant, e.g. 0.05 to 5 wt.% humectant and 0.5 to 15 wt.% dispersant, up to 20 wt.%, for example, 5 to 20 wt.% antifreeze, from 0 up to 15 wt.%, for example, from 1 to 15 wt.% of a pigment and / or dye, from 0 to 40 wt.%, for example, from 1 to 40 wt.% of a binding agent (adhesive / adhesive agent), optionally, up to 5 wt.%, for example, from 0.1 to 5 wt.% of a thickener, optionally from 0.1 to 2 wt.% of an antifoam agent, and optionally a preservative such as a biocide, an antioxidant, etc., for example , in an amount of from 0.01 to 1 wt.%, as well as a filler/diluent up to 100 wt.%.

In seed treatment, the rates of application of the compounds of this invention are usually from 0.1 g to 10 kg per 100 kg of seeds, preferably from 1 g to 5 kg per 100 kg of seeds, more preferably from 1 g to 1000 g per 100 kg of seeds and, in in particular from 1 g to 200 g per 100 kg of seeds, for example from 1 g to 100 g or from 5 g to 100 g per 100 kg of seeds.

In addition, the invention also relates to seeds containing the compound of the present invention or its agriculturally acceptable salt, as defined herein. The amount of a compound of the present invention or an agriculturally acceptable salt thereof will generally range from 0.1 g to 10 kg per 100 kg of seeds, preferably from 1 g to 5 kg per 100 kg of seeds, in particular from 1 g to 1000 g per 100 kg seeds. For specific crops, such as lettuce, the rate may be higher.

The invention also concerns a composition containing seeds and a compound of the present invention, or an agriculturally acceptable salt thereof, as defined herein. The amount of a compound of the present invention or an agriculturally acceptable salt thereof will generally range from 0.1 g to 10 kg per 100 kg of seeds, preferably from 1 g to 5 kg per 100 kg of seeds, in particular from 1 g to 1000 g per 100 kg seeds. For specific crops, such as lettuce, the rate may be higher.

The compounds of the present invention can be used to improve plant health. In addition, the present invention also relates to a method for improving plant health by treating a plant, plant propagation material and/or the place where the plant grows or is to be grown with an effective and non-phytotoxic amount of a compound of the present invention.

As used herein, "effective and non-phytotoxic amount" means that the compound is used in an amount that produces the desired effect, but does not cause any phytotoxic symptoms on the treated plant or on the plant grown from the treated sprout or treated soil.

The terms "plant" and "plant propagation material" are defined above.

"Plant health" should be understood as the state of a plant and/or its products, which is determined by individual aspects or in combination with each other, such as yield (for example, increased biomass and/or increased content of valuable ingredients), quality (for example, improved content or composition of certain ingredients or shelf life), plant vigor (e.g. improved plant growth and/or greener leaves ("greening effect"), resistance to abiotic (e.g. drought) and/or biotic stress (e.g. disease), and production efficiency (e.g. collection efficiency, manufacturability).

The above indicators of plant health may be interdependent and may arise from each other. Each indicator is defined in this field and can be determined by methods known to a person skilled in the art.

The compounds of this invention are also suitable for use against non-agricultural insect pests. For use against said non-agricultural insect pests, the compounds of the present invention can be used as bait compositions, gels, general insect sprays, aerosols, ultra-low volume application compositions and nets (impregnated or surface applied). In addition, cleaning and shearing methods can be applied.

As used herein, the term "non-agricultural pest" refers to pests that are particularly relevant to targets other than the target crop, such as ants, termites, wasps, flies, mites, mosquitoes, crickets, or cockroaches.

The bait may be a liquid, solid or semi-solid formulation (eg gel). The bait used in the composition is a product that is attractive enough to induce insects such as ants, termites, wasps, flies, mosquitoes, crickets, etc. or cockroaches to consume it. Attractiveness can be controlled using feeding stimulants or sex pheromones. Food stimulants are selected, for example, but not exclusively, from animal and/or vegetable proteins (meat, fish or blood meal, insect parts, egg yolk), from fats and oils of animal and/or vegetable origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, glucose, starch, pectin, or even molasses or honey. Fresh or rotten parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more specific to insects. Specific pheromones are described in the literature (eg http://www.pherobase.com) and known to those skilled in the art.

For use in bait compositions, a typical active ingredient content is from 0.001 wt.% to 15 wt.%, preferably from 0.001 wt.% to 5 wt.% active compound.

Compositions of the compounds of the present invention, such as aerosols (eg, in spray cans), oily sprays, or pump sprays, are particularly suitable for the lay user to control pests such as flies, fleas, mites, mosquitoes, or cockroaches. Aerosol formulations preferably consist of the active compound, solvents, in addition auxiliary substances such as emulsifiers, perfume oils, if appropriate, stabilizers, and, if necessary, propellants.

Oil spray formulations differ from aerosol formulations in that propellants are not used.

For use in spray formulations, the active ingredient content is from 0.001 to 80% by weight, preferably from 0.01 to 50% by weight, and most preferably from 0.01 to 15% by weight.

The compounds of the present invention and their respective compositions can also be used in mosquito and smoke coils, smoke cartridges, vaporizers or long-acting vaporizers, as well as moth papers, moth pads or other vaporization systems that do not rely on heat.

Methods for controlling infectious diseases transmitted by insects (for example, malaria, dengue and yellow fever, lymphatic filariasis and leishmaniasis), using the compounds of the present invention and their respective compositions, also include surface treatment of houses and buildings, spraying air and impregnating curtains, tents, things clothes, bed nets, tsetse fly traps and the like. Insecticide compositions for application to fibres, textiles, knitwear, nonwovens, meshes or foils and tarpaulins preferably comprise a mixture comprising an insecticide, optionally a repellent and at least one binder.

The compounds of the present invention and their compositions can be used to protect woody materials such as trees, fence boards, sleepers, frames, art artifacts, etc., and buildings, as well as building materials, furniture, leathers, fibers, vinyl products, electrical wires and cables, etc., from ants and/or termites, and to control ants and termites that cause damage to crops or humans (for example, when pests enter homes and public places).

Typical application rates in the protection of materials are, for example, 0.001 g to 2000 g or 0.01 g to 1000 g active compound per m ² treated material, preferably 0.1 g to 50 g per m ² .

Insecticide compositions for use in impregnating materials typically contain 0.001 to 95% by weight, preferably 0.1 to 45% by weight and more preferably 1 to 25% by weight of at least one repellent and/or insecticide. The compounds of the present invention are particularly useful in the effective control of animal pests such as arthropods, gastropods and nematodes, including but not limited to:

Lepidoptera insects, eg Achroia grisella, Acleris spp., such as A. fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. such as A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. such as A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A. subterranea; Alabama argillacea, Aleurodicus dispersus, Alsophila pometaria, Ampelophaga rubiginosa, Amyelois transitella, Anacampsis sarcitella, Anagasta kuehniella, Anarsia lineatella, Anisota senatoria, Antheraea pernyi, Anticarsia (=Thermesia) spp., such as A. gemmatalis; Apamea spp., Aproaerema modicella, Archips spp. such as A. argyrospila, A. fuscocupreanus, A. rosana, A. xyloseanus; Argyresthia conjugella, Argyroploce spp., Argyrotaenia spp. such as A. velutinana; Athetis mindara, Austroasca viridigrisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. such as C. murinana, C. podana; Cactoblastis cactorum, Cadra cautella, Calingo braziliensis, Caloptilis theivora, Capua reticulana, Carposina spp. such as C. niponensis, C. sasakii; Cephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp. such as C. indicus, C. suppressalis, C. partellus; Choreutis pariana, Choristoneura spp. such as C. conflictana, C. fumiferana, C. longicellana, C. murinana, C. occidentalis, C. rosaceana; Chrysodeixis (=Pseudoplusia) spp. such as C. eriosoma, C. includens; Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Cochylis hospes, Coleophora spp., Colias eurytheme, Conopomorpha spp., Conotrachelus spp., Copitarsia spp. =Epinotia) aporema, Cydalima (=Diaphania) perspectalis, Cydia (=Carpocapsa) spp. such as C. pomonella, C. latiferreana; Dalaca noctuides, Datana integerrima, Dasychira pinicola, Dendrolimus spp. such as D. pini, D. spectabilis, D. sibiricus; Desmia funeralis, Diaphania spp. such as D. nitidalis, D. hyalinata; Diatraea grandiosella, Diatraea saccharalis, Diphthera festiva, Earias spp. such as E. insulana, E. vittella; Ecdytolopha aurantianu, Egira (=Xylomyges) curialis, Elasmopalpus lignosellus, Eldana saccharina, Endopiza viteana, Ennomos subsignaria, Eoreuma loftini, Ephestia spp. such as E. cautella, E. elutella, E. kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp., such as F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. such as G. funebrana, G. molesta, G. inopinata; Halysidota spp., Harrisina americana, Hedylepta spp., Helicoverpa spp. such as H. armigera (=Heliothis armigera) , H. zea (=Heliothis zea); Heliothis spp. such as H. assulta, H. subflexa, H. virescens; Hellula spp. such as H. undalis, H. rogatalis; Helocoverpa gelotopoeon, Hemileuca oliviae, Herpetogramma licarsisalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homoeosoma electellum, Homona magnanima, Hypena scabra, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Kakivoria flavofasciata, Keiferia lycopersicella, Lambdina fiscellaria fiscellaria, Lambdina fiscellaria lugubrosa,Lamprosema indicata, Laspeyresia molesta, Leguminivora glycinivorella, Lerodea eufala, Leucinodes orbonalis, Leucoma salicis, Leucoptera spp. such as L. cochella, L. scitella; Leuminivora lycinivorella, Lithocolletis blancardella, Lithophane antennata, Llattia octo (=Amyna axis), Lobesia botrana, Lophocampa spp., Loxagrotis albicosta, Loxostege spp., such as L. sticticalis, L. cereralis; Lymantria spp. such as L. dispar, L. monacha; Lyonetia clerkella, Lyonetia prunifoliella, Malacosoma spp. such as M. americanum, M. californicum, M. constrictum, M. neustria; Mamestra spp. such as M. brassicae, M. configurata; Mamstra brassicae, Manduca spp. such as M. quinquemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mocis spp. such as M. lapites, M. repanda; Mocis latipes, Monochroa fragariae, Mythimna separata, Nemapogon cloacella, Neoleucinodes elegantalis, Nepytia spp., Nymphula spp., Oiketicus spp., Omiodes indicata, Omphisa anastomosalis, Operophtera brumata, Orgyia pseudotsugata, Oria spp., Orthaga thyrisalis, Ostrinia spp., such as O. nubilalis; Oulema oryzae, Paleacrita vernata, Panolis flammea, Parnara spp., Papaipema nebris, Papilio cresphontes, Paramyelois transitella, Paranthrene regalis, Paysandisia archon, Pectinophora spp. such as P. gossypiella; Peridroma saucia, Perileucoptera spp., such as P. cochella; Phalera bucephala, Phryganidia californica, Phthorimaea spp. such as P. operculella; Phyllocnistis citrella, Phyllonorycter spp. such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathypena scabra, Platynota spp. such as P. flavedana, P. idaeusalis, P. stultana; Platyptilia carduidactyla, Plebejus argus, Plodia interpunctella, Plusia spp, Plutella maculipennis, Plutella xylostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus lepigone, Pseudaletia spp., such as P. sequax, P. unipuncta; Pyrausta nubilalis, Rachiplusia nu, Richia albicosta, Rhizobius ventralis, Rhyacionia frustrana, Sabulodes aegrotata, Schizura concinna, Schoenobius spp., Schreckensteinia festaliella, Scirpophaga spp. such as S. incertulas, S. innotata; Scotia segetum, Sesamia spp. such as S. inferens, Seudyra subflava, Sitotroga cerealella, Sparganothis pilleriana, Spilonota lechriaspis, S. ocellana, Spodoptera (=Lamphygma) spp. such as S. cosmoides, S. eridania, S. exigua , S. frugiperda, S. latisfascia, S. littoralis, S. litura, S. omithogalli; Stigmella spp., Stomopteryx subsecivella, Strymon bazochii, Sylepta derogata, Synanthedon spp. such as S. exitiosa, Tecia solanivora, Telehin licus, Thaumatopoea pityocampa, Thaumatotibia (=Cryptophlebia) leucotreta, Thaumetopoea pityocampa, Thecla spp., Theresimima ampelophaga spp, Tildenia inconspicuella, Tinea spp. such as T. cloacella, T. pellionella; Tineola bisselliella, Tortrix spp. such as T. viridana; Trichophaga tapetzella, Trichoplusia spp. such as T. ni; Tuta (=Scrobipalpula) absoluta, Udea spp. such as U. rubigalis, U. rubigalis; Virachola spp., Yponomeuta padella and Zeiraphera canadensis;

Insects from the order Coleoptera (Coleoptera), for example, Acalymma vittatum, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus spp., such as A. anxius, A. planipennis, A. sinuatus; Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimallus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala corpulenta, Anomala rufocuprea, Anoplophora spp. such as A. glabripennis; Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogonia spp., Atthous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp., Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B. rufimanus; Byctiscus betulae, Callidiellum rufipenne, Callopistria floridensis, Callosobruchus chinensis, Cameraria ohridella, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp. such as C. assimilis, C. napi; Chaetocnema tibialis, Cleonus mendicus, Conoderus spp. such as C. vespertinus; Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryptorhynchus lapathi, Ctenicera spp. such as C. destructor; Curculio spp., Cylindrocopturus spp., Cyclocephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp., such as D. undecimpunctata, D. speciosa, D. longicornis, D. semipunctata, D. virgifera; Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp. such as E. varivestis, E. vigintioctomaculata; Epitrix spp. such as E. hirtipennis, E. similaris; Eutheola humilis, Eutinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera spp. such as H. brunneipennis, H. postica; Hypomeces squamosus, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp. such as L. bilineata, L. melanopus; Leptinotarsa spp. such as L. decemlineata; Leptispa pygmaea, Limonius californicus, Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp. such as L. bruneus; Liogenys fuscus, Macrodactylus spp. such as M. subspinosus; Maladera matrida, Megaplatypus mutates, Megascelis spp., Melanotus communis, Meligethes spp. such as M. aeneus; Melolontha spp. such as M. hippocastani, M. melolontha; Metamasius hemipterus, Microtheca spp., Migdolus spp. such as M. fryanus, Monochamus spp. such as M. alternatus; Naupactus xanthographus, Niptus hololeucus, Oberia brevis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Otiorrhynchus sulcatus, Oulema melanopus, Oulema oryzae, Oxycetonia juconda, P. cochleariae; Phoracantha recurva, Phyllobius pyri, Phyllopertha horticola, Phyllophaga spp. such as P. helleri; Phyllotreta spp. such as P. chrysocephala, P. nemorum, P. striolata, P. vittula; Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psacothea hilaris, Psylliodes chrysocephala, Prostephanus truncates, Psylliodes spp., Ptinus spp., Pulga saltona, Rhizopertha dominica, Rhynchophorus spp., such as R. billineatus, R. ferrugineus, R. palmarum , R. phoenicis, R. vulneratus; Saperda candida, Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp. such as S. granaria, S. oryzae, S. zeamais; Sphenophorus spp. such as S. levis; Stegobium paniceum, Sternechus spp. such as S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. such as T. castaneum; Trogoderma spp., Tychius spp., Xylotrechus spp. such as X. pyrrhoderus; and, Zabrus spp. such as Z. tenebrioides;

Insects from the Diptera order, for example Aedes spp., such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bactrocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chrysomyia spp. such as C. bezziana, C. hominivorax, C. macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as C. hominivorax; Contarinia spp. such as C. sorghicola; Cordylobia anthropophaga, Culex spp. such as C. nigripalpus, C. pipiens, C. quinquefasciatus, C. tarsalis, C. tritaeniorhynchus; Culicoides furens, Culiseta inornata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Dasineura oxycoccana, Delia spp., such as D. antique, D. coarctata, D. platura, D. radicum; Dermatobia hominis, Drosophila spp. such as D. suzukii, Fannia spp. such as F. canicularis; gastraphilus spp. such as G. intestinalis; Geomyza tipunctata, Glossina spp. such as G. fuscipes, G. morsitans, G. palpalis, G. tachinoides; Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp. such as H. platura; Hypoderma spp. such as H. lineata; Hyppobosca spp., Hydrellia philippina, Leptoconops torrens, Liriomyza spp. such as L. sativae, L. trifolii; Lucilia spp. such as L. caprina, L. cuprina, L. sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as M. destructor; Musca spp. such as M. autumnalis, M. domestica; Muscina stabulans, Oestrus spp. such as O. ovis; Opomyza florum, Oscinella spp. such as O. frit; Orseolia oryzae, Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp. such as P. antiqua, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis spp. such as R. cerasi, R. cingulate, R. indifferens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp. such as S. haemorrhoidalis; Simulium vittatum, Sitodiplosis mosellana, Stomoxys spp. such as S. calcitrans; Tabanus spp. such as T. atratus, T. bovinus, T. lineola, T. similis; Tannia spp., Thecodiplosis japonensis, Tipula oleracea, Tipula paludosa and Wohlfahrtia spp;

Fringed-winged insects (Thysanoptera), e.g. Baliothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp., such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp. such as S. citri, S. dorsalis, S. perseae; Stenchaetothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp. such as T. imagines, T. hawaiiensis, T. oryzae, T. palmi, T. parvispinus, T. tabaci;

Insects of the order Hemiptera, eg Acizzia jamatonica, Acrosternum spp., such as A. hilare; Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsugae, Adelphocoris spp. such as A. rapidus, A. superbus; Aeneolamia spp., Agonoscena spp., Aulacorthum solani, Aleurocanthus woglumi, Aleurodes spp., Aleurodicus disperses, Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp. such as A. craccivora, A. fabae, A. forbesi, A. gossypii, A. grossulariae, A. maidiradicis, A. pomi, A. sambuci, A. schneideri, A. spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacaspis yasumatsui, Aulacorthum solani, Bactericera cockerelli (Paratrioza cockerelli), Bemisia spp. such as B. argentifolii, B. tabaci (Aleurodes tabaci); Blissus spp. such as B. leucopterus; Brachycaudus spp. such as B. cardui, B. helichrysi, B. persicae, B. prunicola; Brachycolus spp., Brachycorynella asparagi, Brevicoryne brassicae, Cacopsylla spp. such as C. fulguralis, C. pyricola (Psylla piri); Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horni, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp. , Cimex spp. such as C. hemipterus, C. lectularius; Coccomytilus halli, Coccus spp. such as C. hesperidum, C. pseudomagnoliarum; Corythucha arcuata, Creontiades dilutus, Cryptomyzus ribis, Chrysomphalus aonidum, Cryptomyzus ribis, Ctenarytaina spatulata, Cyrtopeltis notatus, Dalbulus spp., Dasynus piperis, Dialeurodes spp., such as D. citrifolii; Dalbulus maidis, Diaphorina spp. such as D. citri; Diaspis spp. such as D. bromeliae; Dichelops furcatus, Diconocoris hewetti, Doralis spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp., such as D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Empoasca spp. such as E. fabae, E. solana; Epidiaspis leperii, Eriosoma spp. such as E. lanigerum, E. pyricola; Erythroneura spp., Eurygaster spp. such as E. integriceps; Euscelis bilobatus, Euschistus spp. such as E. heros, E. impictiventris, E. servus; Fiorinia theae, Geococcus coffeae, Glycaspis brimblecombei, Halyomorpha spp. such as H. halys; Heliopeltis spp., Homalodisca vitripennis (=H. coagulata), Horcias nobilellus, Hyalopterus pruni, Hyperomyzus lactucae, Icerya spp. such as I. purchase; Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L. ulmi; Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp. such as L. hesperus, L. lineolaris, L. pratensis; Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus, Macrosiphum spp. such as M. rosae, M. avenae, M. euphorbiae; Macrosteles quadrilineatus, Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Melanocallis (=Tinocallis) caryaefoliae, Metcafiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzocallis coryli, Murgantia spp., such as M. ascalonicus, M. cerasi, M. nicotianae, M. persicae, M. varians; Nasonovia ribis-nigri, Neotoxoptera formosana, Neomegalotomus spp, Nephotettix spp. such as N. malyanus, N. nigropictus, N. parvus, N. virescens; Nezara spp. such as N. viridula; Nilaparvata lugens, Nysius huttoni, Oebalus spp. such as O. pugnax; Oncometopia spp., Orthezia praelonga, Oxycaraenus hyalinipennis, Parabemisia myricae, Parlatoria spp., Parthenolecanium spp., such as P. corni, P. persicae; Pemphigus spp. such as P. bursarius, P. populivenae; Peregrinus maidis, Perkinsiella saccharicida, Phenacoccus spp. such as P. aceris, P. gossypii; Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp. such as P. devastatrix, Piesma quadrata, Piezodorus spp. such as P. guildinii; Pinnaspis aspidistrae, Planococcus spp. such as P. citri, P. ficus; Prosapia bicincta, Protopulvinaria pyriformis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. such as P. comstocki; Psylla spp. such as P. mali; Pteromalus spp., Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp., such as R. pseudobrassicas, R. insertum, R. maidis, R. padi; Sagatodes spp., Sahlbergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mali, Scaptocoris spp., Scaphoides titanus, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea Spissistilus festinus (=Stictocephala festina), Stephanitis nashi, Stephanitis pyrioides, Stephanitis takeyai, Tenalaphara malayensis, Tetraleurodes perseae, Therioaphis maculate, Thyanta spp. such as T. accerra, T. perditor; Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeurodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as U. citri, U. yanonensis; and Viteus vitifolii,

Hymenoptera insects, e.g. Acanthomyops interjectus, Athalia rosae, Atta spp., such as A. capiguara, A. cephalotes, A. cephalotes, A. laevigata, A. robusta, A. sexdens, A. texana, Bombus spp., Brachymyrmex spp., Camponotus spp. such as C. floridanus, C. pennsylvanicus, C. modoc; Cardiocondyla nuda, Chalibion sp, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Dorymyrmex spp., Dryocosmus kuriphilus, Formica spp., Hoplocampa spp., such as H. minuta, H. testudinea; Iridomyrmex humilis, Lasius spp., such as L. niger, Linepithema humile, Liometopum spp., Leptocybe invasa, Monomorium spp., such as M. pharaonis, Monomorium, Nylandria fulva, Pachycondyla chinensis, Paratrechina longicornis, Paravespula spp., such as P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp. such as P. megacephala; Pogonomyrmex spp. such as P. barbatus, P. californicus, Polistes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex cyaneus, Solenopsis spp. such as S. geminata, S. invicta, S. molesta, S. richteri, S. xyloni, Sphecius speciosus, Sphex spp., Tapinoma spp., such as T. melanocephalum, T. sessile; Tetramorium spp. such as T. caespitum, T. bicarinatum, Vespa spp. such as V. crabro; Vespula spp. such as V. squamosal; Wasmannia auropunctata, Xylocopa sp.

Orthoptera insects, e.g. Acheta domesticus, Calliptamus italicus, Chortoicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp., such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. such as L. migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M. spretus; Nomadacris septemfasciata, Oedaleus senegalensis, Scapteriscus spp., Schistocerca spp. such as S. americana, S. gregaria, Stemopelmatus spp., Tachycines asynamorus and Zonozerus variegatus;

Pests from the class Arachnida, for example mites, for example from the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma spp. (e.g. A. americanum, A. variegatum, A. maculatum), Argas spp., such as A. persicu), Boophilus spp., such as B. annulatus, B. decoloratus, B. microplus, Dermacentor spp., such such as D. silvarum, D. andersoni, D. variabilis, Hyalomma spp., such as H. truncatum, Ixodes spp., such as I. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacificus, Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, O. hermsi, O. turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. such as P. ovis, Rhipicephalus spp. such as R. sanguineus, R appendiculatus, Rhipicephalus evertsi, Rhizoglyphus spp., Sarcoptes spp., such as S. scabiei; and from the family Eriophyidae including Aceria spp. such as A. sheldoni, A. anthocoptes, Acallitus spp., Aculops spp. such as A. lycopersici, A. pelekassi; Aculus spp. such as A. schlechtendali; Colomerus vitis, Epitrimerus pyri, Phyllocoptruta oleivora; Eriophytes ribis and Eriophyes spp. such as Eriophyes sheldoni; from the family Tarsonemidae, including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Stenotarsonemus spp. Steneotarsonemus spinki; from the family Tenuipalpidae including Brevipalpus spp. such as B. phoenicis; from the family Tetranychidae, including Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Petrobia latens, Tetranychus spp., such as T. cinnabarinus, T. evansi, T. kanzawai, T, pacificus, T. phaseulus, T. Telarius and T . urticae; Bryobia praetiosa; Panonychus spp. such as P. ulmi, P. citri; Metatetranychus spp. And Oligonychus spp. such as O. pratensis, O. perseae, Vasates lycopersici; Raoiella indica, from the Carpoglyphidae family, including Carpoglyphus spp.; Penthaleidae spp. such as Halotydeus destructor; from the family Demodicidae such as Demodex spp.; from the family Trombicidea, including Trombicula spp.; from the family Macronyssidae, including Ornothonyssus spp.; from the Pyemotidae family, including Pyemotes tritici; Tyrophagus putrescentiae; from the family Acaridae, including Acarus siro; from the family Araneida including Latrodectus mactans, Tegenaria agrestis, Chiracanthium sp, Lycosa sp Achaearanea tepidariorum and Loxosceles reclusa;

Nematoda type pests, eg plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp., such as M. hapla, M. incognita, M. javanica; cyst nematodes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H. avenae, H. glycines, H. schachtii, H. trifolii; nematodes Seed gall, Anguina spp.; stem and leaf nematodes, Aphelenchoides spp. such as A. besseyi; stinging nematodes, Belonolaimus spp., such as B. longicaudatus; pine nematodes, Bursaphelenchus spp. such as B. lignicolus, B. xylophilus; ring nematodes, Criconema spp., Criconemella spp. such as C. xenoplax and C. ornata; and, Criconemoides spp. such as Criconemoides informis; Mesocriconema spp.; stem and tuber nematodes, Ditylenchus spp. such as D. destructor, D. dipsaci; awl-nosed nematodes, Dolichodorus spp.; Spiral nematodes, Heliocotylenchus multicinctus; sheatoid and shell nematodes, Hemicycliophora spp. and Hemicriconemoides spp.; Hirshmanniella spp.; lanceolate nematodes, Hoploaimus spp.; fake root growth nematodes, Nacobbusspp.; needle nematodes, Longidorusspp., such as L. elongatus; wounding nematodes, Pratylenchusspp., such as P. brachyurus, P. neglectus, P. penetrans, P. curvitatus, P. goodeyi; earth nematodes, Radopholusspp., such as R. similis; Rhadopholus spp.; Rhodopholus spp.; kidney nematodes, Rotylenchus spp. such as R. robustus, R. reniformis; Scutellonema spp.; bristly root nematodes, Trichodorus spp., such as T. obtusus, T. primitivus; Paratrichodorus spp. such as P. minor; stunted nematodes, Tylenchorhynchus spp., such as T. claytoni, T. dubius; citrus nematodes, Tylenchulus spp., such as T. semipenetrans; Dagger nematodes, Xiphinema spp.; and other plant parasites of the nematode species;

Termite insects (Isoptera), eg Calotermes flavicollis, Coptotermes spp., such as C. formosanus, C. gestroi, C. acinaciformis; Cornitermes cumulans, Cryptotermes spp. such as C. brevis, C. cavifrons; Globitermes sulfureus, Heterotermes spp. such as H. aureus, H. longiceps, H. tenuis; Leucotermes flavipes, Odontotermes spp., Incisitermes spp., such as I. minor, I. Snyder; Marginitermes hubbardi, Mastotermes spp. such as M. darwiniensis Neocapritermes spp. such as N. opacus, N. parvus; Neotermes spp., Procornitermes spp., Zootermopsis spp. such as Z. angusticollis, Z. nevadensis, Reticulitermes spp. such as R. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. santonensis, R. virginicus; Termes natalensis,

Insects from the order of cockroaches (Blattaria), for example Blatta spp., such as B. orientalis, B. lateralis; Blattella spp. such as B. asahinae, B. germanica; Leucophaea maderae, Panchlora nivea, Periplaneta spp. such as P. americana, P. australasiae, P. brunnea, P. fuligginosa, P. japonica; Supella longipalpa, Parcoblatta pennsylvanica, Eurycotis floridana, Pycnoscelus surinamensis,

Flea (Siphonoptera) insects, e.g. Cediopsylla simples, Ceratophyllus spp., Ctenocephalides spp., such as C. felis, C. canis, Xenopsylla cheopis, Pulex irritans, Trichodectes canis, Tunga penetrans and Nosopsyllus fasciatus,

Insects of the bristletail order (Thysanura), such as Lepisma saccharina, Ctenolepisma urbana and Thermobia domestica,

Pests from the class Chilopoda, eg Geophilus spp., Scutigera spp., such as Scutigera coleoptrata;

Pests from the Diplopoda class, e.g. Blaniulus guttulatus, Julus spp., Narceus spp.,

Pests from the class Symphyla (Symphyla), for example, Scutigerella immaculata,

Leather-winged insects (Dermaptera), such as Forficula auricularia,

Springtail insects (Collembola), e.g. Onychiurus spp., such as Onychiurus armatus,

Pests from the isopod order (Isopoda), for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber,

Insects of the order louse (Phthiraptera), for example, Damalinia spp., Pediculus spp., such as Pediculus humanus capitis, Pediculus humanus corporis, Pediculus humanus humanus; Pthirus pubis, Haematopinus spp. such as Haematopinus eurysternus, Haematopinus suis; Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp.,

Examples of other pest species that can be controlled by the compounds of formula (I) include: from the sub-kingdom Mollusca, class Bivalves, eg Dreissena spp.; class gastropods, e.g. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, Succinea spp.; Helminth class, e.g. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascarislubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculusmedinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp. such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora lispp, Stronyloides ., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.

The compounds of the present invention are suitable for use in the treatment or protection of animals from infestation or infestation with parasites. Therefore, the present invention also relates to the use of the compounds of the present invention for the manufacture of a medicament for the treatment or protection of animals from infestation or infestation by parasites. In addition, the present invention relates to a method of treating or protecting animals from infestation and infestation by parasites, including oral, topical or parenteral administration or use in animals of a parasiticide effective amount of a compound of the present invention.

The present invention also relates to the non-therapeutic use of the compounds of the present invention for the treatment or protection of animals from infestation and infestation with parasites. In addition, the present invention relates to a non-therapeutic method of treating or protecting animals from infestation and infestation by parasites, including applying to the site of the lesion a parasitically effective amount of a compound of the present invention.

The compounds of the present invention are also useful in the eradication or control of parasites in and on animals. Furthermore, the present invention relates to a method for killing or controlling parasites in and on animals, which comprises contacting the parasites with a parasiticide effective amount of a compound of the present invention.

The present invention also relates to the non-therapeutic use of the compounds of the present invention for the control or destruction of parasites. In addition, the present invention relates to a non-therapeutic method for the destruction or control of parasites, including the application to the site of a parasiticide effective amount of a compound of the present invention.

The compounds of the present invention can be effective both through contact (through soil, glass, walls, bed net, carpet, blankets, or animal parts) and ingestion (eg, bait). In addition, the compounds of the present invention can be used at any stage of development.

The compounds of the present invention may be used as such or in the form of compositions containing the compounds of the present invention.

The compounds of the present invention can be used together with a mixing agent active against pathogenic parasites, as well as with synthetic coccidiosis compounds, polyester antibiotics such as Amprolium, Robenidine, Toltrazuril, Monensin, Salinomycin, Maduramycin, Lasalocid, Narasin or Semduramycin, or with other components for mixing as defined above, or in the form of compositions containing said mixtures.

The compounds of the present invention and compositions containing them can be applied orally, parenterally or topically, for example, dermally. The compounds of the present invention may be systemically or non-systemically effective.

The use may be prophylactic, therapeutic or non-therapeutic. In addition, the application can be carried out prophylactically in places where the occurrence of parasites is expected.

As used herein, the term "contact" includes both direct contact (application of the compounds/compositions directly to the parasite, including application directly to the animal, or excluding applications directly to the animal, such as application to the habitat in the latter case) and indirect contact (applying compounds/compositions to the site of the parasite). Contact with a parasite by treatment of its place of residence is an example of a non-therapeutic use of the compounds of the present invention.

The term "habitat" means a habitat, food supply, breeding site, territory, material or environment in which a parasite grows or may grow outside the animal.

As used herein, the term "parasites" includes endo and ectoparasites. In some embodiments of the present invention, endoparasites may be preferred. In other embodiments, ectoparasites may be preferred. Infestations of warm-blooded animals and fish include, but are not limited to, lice, lice, mites, nose grubs, bloodsuckers, biting flies, moss flies, flies, myasitic fly larvae, red mites, midges, mosquitoes, and fleas.

The compounds of the present invention are particularly useful in controlling parasites of the following orders and species, respectively:

fleas (Siphonaptera) such as Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans and Nosopsyllus fasciatus; cockroaches (Blattaria - Blattodea), for example Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae and Blatta orientalis; flies, mosquitoes (Diptera) e.g. , Chrysomya hominivorax Chrysomya macellaria intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus ar gentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola and Tabanus similis; lice (Phthiraptera) such as Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus; mites and parasitic mites (Parasitiformes): mites (Ixodida) e.g. eg Ornithonyssus bacoti and Dermanyssus gallinae; Actinidia (Prostigmata) and Ascaris-like (Astigmata), e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp. ., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp; bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus; lice, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.; lice (suborder Arnblycerina and Ischnocerina), for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp. and Felicola spp.; ascaris nematodes: straight worms and trichinosis (Trichosyringida), for example, Trichinellidae (Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp.; rabtiditis, eg Rhabditis spp., Strongyloides spp., Helicephalobus spp.; strongylides, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunostomum spp. (hookworm), Trichostrongylus spp., Haemonchus contortus, Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus, Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp., Aleurostrongylus abstrusus and Dioctophyma renale; intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (pinworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp. and Oxyuris equi; kamallanida, for example, Dracunculus medinensis (guinea guinea pig); Spirurids, eg Thelazia spp., Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp.a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi and Habronema spp.; spiny-headed worms (Acanthocephala) eg Acanthocephalus spp., Macracanthorhynchus hirudinaceus and Oncicola spp.; planaria (Plathelminthes): trematodes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria alata, Paragonimus spp. and Nanocyetes spp.; cercomeromorphs, in particular cestodes (helminths), for example, Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp. , Sirometra spp., Anoplocephala spp. and Hymenolepis spp.

As used herein, the term "animal" includes warm-blooded animals (including humans) and fish. Preferred are mammals such as cattle, sheep, wild boars, camels, deer, horses, pigs, birds, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, also fur animals such as mink, chinchillas and raccoons, birds such as chickens, geese, turkeys and ducks, fish such as freshwater and saltwater fish such as trout, carp and eel. Pets such as dogs or cats are especially preferred.

In a general sense, "parasiticidally effective amount" means the amount of active substance necessary to achieve a noticeable effect on growth, including the consequences of necrosis, death, inhibition, prevention and removal, elimination or reduction of the appearance and activity of the target organism. The parasiticidally effective amount may vary for different compounds/compositions used in the invention. The parasiticidally effective amount of the compositions will also vary depending on the prevailing conditions such as desired parasiticidal effect and duration, target species, method of application, etc.

In general, the compounds of this invention are advantageously administered in a total amount of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.

For oral administration to warm-blooded animals, the compounds of formula I may be formulated as animal feeds, animal feed premixes, animal feed concentrates, tablets, solutions, pastes, suspensions, lotions, gels, tablets, boluses and capsules. In addition, the compounds of formula I can be administered to animals as part of their drinking water. For oral administration, the selected dosage form should provide the animal with 0.01 mg/kg to 100 mg/kg animal body weight per day of the compound of formula I, preferably 0.5 mg/kg to 100 mg/kg animal body weight per day.

Alternatively, the compounds of formula I can be administered parenterally to animals, for example by intravascular, intramuscular, intravenous or subcutaneous injection. The compounds of formula I may be dispersed or dissolved in a physiologically acceptable vehicle for subcutaneous injection. Alternatively, compounds of formula I may be formed into an implant for subcutaneous administration. In addition, the compound of formula I may be administered transdermally to the animal. For parenteral administration, the selected dosage form should present to the animal from 0.01 mg/kg to 100 mg/kg body weight of the animal compound of formula I per day.

Compounds of formula I can also be applied topically to animals in the form of dipping liquids, dusts, powders, collars, medallions, sprays, shampoos, spot and pour formulations, as well as in the form of oil-in-water or water-in-oil ointments or emulsions. . For topical application, dipping liquids and sprays usually contain from 0.5 m.h. up to 5000 m.h. and preferably from 1 m.h. up to 3000 m.h. compounds of formula I. In addition, the compounds of formula I can be formulated as ear tags for animals, in particular tetrapods such as cattle and sheep.

Suitable compositions are:

- Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for application to the skin or body cavities, compositions for perfusion, gels;

- Emulsions and suspensions for oral or dermal administration; semi-solid compositions;

- Compositions in which the active compound is present in an ointment or in an oil-in-water or water-in-oil emulsion;

- Solid compositions such as powders, premixes or concentrates, granules, dragees, tablets, boluses, aerosol capsules and inhalers, products containing the active compound.

Compositions suitable for injection are prepared by dissolving the active ingredient in an appropriate solvent and optionally adding additional excipients such as acids, bases, buffer salts, preservatives and solubilizers. Appropriate excipients for injectable solutions are known in the art. The solutions are filtered and sterile packaged.

Oral solutions are administered directly. The concentrates are administered orally after pre-dilution to the applicable concentration. Oral solutions and concentrates are prepared in accordance with the state of the art and as described above for injectable solutions, and sterilization procedures are not required.

Solutions for application to the skin are impregnated, sprayed, rubbed, sprinkled or sprinkled. Solutions for application to the skin are prepared in accordance with the state of the art and as described above, and as described above for injection solutions, while sterilization procedures are not required.

The gels are applied or applied to the skin or injected into body cavities. Gels are prepared by treatment with solutions prepared as described for solutions for injection with sufficient thickener to obtain a clear material having an ointment-like consistency. Suitable thickeners are known in the art.

The pour-on compositions are poured or sprayed on limited areas of the skin, the active compound penetrates the skin and acts systemically. The pour-on formulations are prepared by dissolving, suspending or emulsifying the active substance in skin-friendly solvents or solvent mixtures. If necessary, other auxiliaries are added, such as dyes, bioabsorption agents, antioxidants, light stabilizers, adhesives. Such suitable excipients are known in the art.

Emulsions can be administered orally, dermally or by injection. Emulsions are water-in-oil or oil-in-water emulsions. They are obtained by dissolving the active compound in the hydrophobic or hydrophilic phase and homogenizing it with the solvent of the other phase using appropriate emulsifiers and, if necessary, other auxiliaries such as colorants, absorption aids, preservatives, antioxidants, light stabilizers, substances that increase viscosity. Suitable hydrophobic phases (oils), suitable hydrophilic phases, suitable emulsifiers and suitable additional emulsion auxiliaries are known in the art.

Suspensions can be administered orally or topically/dermally. They are obtained by suspending the active ingredient in a suspending agent, if appropriate, with the addition of other excipients such as wetting agents, coloring agents, bioabsorption aids, preservatives, antioxidants, light stabilizers. Suitable suspending agents and other suitable suspension auxiliaries, including wetting agents, are known in the art.

Semi-solid compositions can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only in their higher viscosity.

To obtain solid compositions, the active compound is mixed with suitable excipients, if appropriate, with the addition of excipients, and the desired form is obtained. Suitable excipients for this purpose are known in the art.

Compositions that can be used in the invention may contain, as a rule, from about 0.001 to 95 wt.% the compounds of this invention.

Ready-to-use formulations contain compounds active against parasites, preferably ectoparasites, in concentrations from 10 m.h. up to 80 wt.%, preferably from 0.1 to 65 wt.%, more preferably from 1 to 50 wt.%, most preferably from 5 to 40 wt.%.

Compositions which are diluted prior to use contain compounds active against ectoparasites at concentrations of 0.5 to 90% by weight, preferably 1 to 50% by weight.

In addition, the compositions contain compounds of formula I against endoparasites in concentrations from 10 m.h. up to 2 wt.%, preferably from 0.05 to 0.9 wt.%, particularly preferably from 0.005 to 0.25 wt.%.

Topical application can be carried out using molded articles containing the compound, such as collars, medallions, ear tags, bands for fixation on body parts, adhesive strips and foil.

It is generally advantageous to use solid compositions which release the compounds of the present invention in a total amount of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg. kg body weight of the treated animal for three weeks.

Examples:

Receiving examples:

With appropriate modification of the starting materials, the procedures described in the preparation examples below were used to obtain additional compounds of formula I. The compounds thus obtained are listed below in Table X along with physical data.

Compounds can be characterized, for example, using high performance liquid chromatography/mass spectrometry (HPLC/MS), ¹ H-NMR and/or their melting points.

Analytical HPLC/MS - Method 1: Agilent Eclipse Plus C18, 50 X 4.6 mm, ID 5 µm; Elution: A = 10 mM ammonium formate (0.1% formic acid), B = acetonitrile (0.1% formic acid), flow = 1.25 ml/min at 40 °C; Gradient: 10% B - 100% B - 1.5 min, hold for 1 min, 1 min - 100% B. Run time = 3.5 min.

Analytical HPLC/MS - Method 2: Kinetex XB C18 1.7 µm 50 x 2.1 mm; A = Water + 0.1% TFA, B = Acetonitrile, flow = 0.8 ml/min - 1.0 ml/min for 1.5 min at 60°C; Gradient: 5% B - 100% B - 1.5 min.

¹ H-NMR: Signals were characterized by chemical shifts (m.h., δ [delta]) relative to tetramethylsilane, respectively, CDCl ₃ for ¹³ C-NMR, by their multiplicity and their integral (given relative number of hydrogen atoms). The following abbreviations are used to characterize signal multiplicity: m=multiplet, r=heptet, k=quartet, t=triplet, d=doublet and s=singlet.

The following abbreviations were used: d for day(s), h for hour(s), min for minute(s), rt/room temperature 20-25°C, h _y for holding hour; DMSO for dimethyl sulfoxide, OAc for acetate, EtOAc for ethyl acetate, THF for tetrahydrofuran, t-BuOH for tert-butanol, dppfPdCl for [1,1′-bis(diphenylphosphino)ferrocene]-dichloropalladium(II), DIPEA for diisopropylethylamine, DCM for dichloromethane and DMAP for 4-dimethylaminopyridine

Example 1:

1-(2,6-dimethylphenyl)-3-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]indazol-6-yl]methyleneamino]thiourea (C-1 of Table X ):

Stage 1: Methyl 6-bromo-1-methylindazole-3-carboxylate:

To a solution of methyl 6-bromo-1H-indazole-3-carboxylate (1.3 g) in acetonitrile (20 ml) and DMF (3 ml) was added potassium carbonate (3.52 g) at room temperature. Then, methyl iodide (1.27 ml) was added to the reaction mixture at 0°C. The reaction mixture was stirred at room temperature for 16 hours. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was diluted with water (80 ml) and then extracted with ethyl acetate (50 ml x 3). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 5-30% ethyl acetate in heptane as mobile phase) to give the title compound (0.750 g). HPLC/MS (Method 1) : V _y : 1.876 min; MS: m/z = 269.10 (M+1). ¹ H NMR (300 MHz, Chloroform-d) δ 8.11 (d, J = 8.6 Hz, 1H), 7.68 (s, 1H), 7.44 (dd, J = 8.6, 1 .3 Hz, 1H), 7.28 (s, 1H), 4.16 (s, 3H), 4.06 (s, 3H).

Stage 2: (6-bromo-1-methyl-indazol-3-yl) methanol:

To a solution of Methyl 6-bromo-1-methylindazole-3-carboxylate (0.750 g) in 10 ml THF was added diisobutylaluminum hydride (8.36 ml) at -78°C. The reaction mixture was then stirred at room temperature for 16 hours. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was quenched with a saturated solution of NH ₄ Cl and 1N HCl solution. The aqueous layer was extracted with ethyl acetate (30 ml x 3). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 5-50% ethyl acetate in heptane as mobile phase) to give the title compound (0.500 g). HPLC/MS (Method 1) : V _y : 1.567 min; MS: m/z = 243.0 (M+1). ¹ H NMR (300 MHz, Chloroform-d) δ 7.67 (d, J = 8.5 Hz, 1H), 7.56 (s, 1H), 7.31 - 7.21 (m, 2H), 5.01 (s, 2H), 4.00 (s, 3H).

Stage 3: 6-bromo-3-(chloromethyl)-1-methylindazole:

To a solution of (6-bromo-1-methylindazol-3-yl)methanol (0.500 g) in THF (10 ml) was added phosphorus oxychloride (0.25 ml g) under an inert atmosphere. The reaction mixture was heated at 70°C for 3 hours. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 5-30% ethyl acetate in heptane as mobile phase) to give the title compound (0.450 g). HPLC/MS (Method 1) : V _y : 2.053 min; MS: m/z = 261.0 (M+1). ¹ H NMR (300 MHz, Chloroform-d) δ 7.77 (d, J = 8.6 Hz, 1H), 7.67 (s, 1H), 7.40 (dd, J = 8.6, 1 .3 Hz, 1H), 5.01 (s, 2H), 4.11 (s, 3H), 3.66 (t, J = 6.6 Hz, 4H), 3.53 (t, J = 6 .0 Hz, 8H), 1.95 (dt, J = 14.4, 6.6 Hz, 4H), 1.80 (dt, J = 12.7, 6.2 Hz, 4H), 1.71 (t, J = 2.8 Hz, 4H).

Stage 4: 6-bromo-1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]indazole:

To a solution of 4-(trifluoromethoxy)phenol (0.27 ml) in DMF (5 ml) was added potassium tert-butoxide (0.398 g). The reaction mixture was stirred for 10 min at room temperature. Then 6-bromo-3-(chloromethyl)-1-methyl-indazole (0.460 g) dissolved in 3 ml of DMF was added to the reaction mixture. The reaction mixture was stirred for 5 hours at room temperature. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was diluted with water (30 ml) and then extracted with ethyl acetate (30 ml x 3). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 5-30% ethyl acetate in heptane as mobile phase) to give the title compound (0.610 g). HPLC/MS (Method 1) : V _y : 2.347 min; MS: m/z = 403.0 (M+1). ¹ H NMR (300 MHz, Chloroform-d) δ 7.72 - 7.63 (m, 1H), 7.61 - 7.54 (m, 1H), 7.26 (s, 2H), 7.14 (d, J = 8.6 Hz, 2H), 7.03 (d, J = 9.2 Hz, 2H), 5.38 (s, 2H), 4.03 (s, 3H).

Stage 5: 1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]-6-vinylindazole:

Tributyl(vinyl)tin (0.52 ml) and chloride 1,1'-bis(diphenylphosphino)ferrocene]palladium (II) (0.066 g). The reaction mixture was heated at 110°C for 2 hours. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was diluted with water (20 ml) and extracted with ethyl acetate (30 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 0-30% ethyl acetate in heptane as mobile phase) to give the title compound (0.260 g). HPLC/MS (Method 1) : V _y : 2.382 min; MS: m/z = 349.2 (M+1). ¹ H NMR (300 MHz, Chloroform-d) δ 7.75 (d, J = 8.7 Hz, 1H), 7.36 - 7.27 (m, 2H), 7.14 (d, J = 8 .7 Hz, 2H), 7.09 - 7.00 (m, 2H), 6.89 - 6.77 (m, 1H), 5.86 (d, J = 17.5 Hz, 1H), 5 .43 - 5.30 (m, 3H), 4.07 (s, 3H).

Stage 6: 1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]indazole-6-carbaldehyde:

Osmium tetroxide (0.015 g) was added to a solution of 1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]-6-vinylindazole (0.341 g) in 1,4-dioxane (5 ml) and water (2 ml) at 0°C and stirred at the same temperature for 5 minutes. Sodium periodate (0.461 g) was then added. The reaction mixture was stirred for 3 hours at room temperature. The progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was quenched in an aqueous solution of sodium sulfite (20 ml), and then was extracted with ethyl acetate (30 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 5-50% ethyl acetate in heptane as mobile phase) to give the title compound (0.084 g). HPLC/MS (Method 1) : V _y : 2.075 min; MS: m/z = 351.25 (M+1). ¹ H NMR (300 MHz, Chloroform-d) δ 10.18 (s, 1H), 7.98 (d, J = 5.7 Hz, 2H), 7.73 (d, J = 8.7 Hz, 1H), 7.22 - 7.02 (m, 5H), 6.86 (dd, J = 13.5, 9.0 Hz, 1H), 5.46 (s, 2H), 4.19 (s , 3H), 3.73 (s, 5H), 3.59 (t, J = 6.6 Hz, 1H), 3.51 - 3.41 (m, 3H), 1.76 (dd, J = 64.8, 6.8 Hz, 13H), 1.42 - 1.24 (m, 5H), 0.94 (t, J = 7.3 Hz, 2H).

Step 7: 1-(2,6-dimethylphenyl)-3-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]-indazol-6-yl]methyleneamino]thiourea (C -1 Tables X):

A mixture of 1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]indazole-6-carbaldehyde (0.250 g) and 1-amino-3-(2,6-dimethylphenyl)thiourea (0.139 g) in EtOH (5 ml) was heated at 80 ^o C for 3 hours. The progress of the reaction was monitored by TLC. The reaction mixture was cooled and concentrated under reduced pressure. Then the reaction mass was diluted with water (15 ml) and was extracted with ethyl acetate (25 ml x 2). The combined organic solvent was dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluting with 0-5% methanol in dichloromethane as mobile phase) to give the title compound (0.160 g). HPLC/MS (Method 1) : V _y : 2.20 min; MS: m/z = 528.90 (M+1). ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 11.88 (s, 1H), 9.91 (s, 1H), 8.27 (s, 1H), 8.06 (s, 1H), 7 .86 (d, J = 17.2 Hz, 2H), 7.31 (d, J = 8.8 Hz, 2H), 7.23 - 7.10 (m, 5H), 5.45 (s, 2H), 4.10 (s, 3H), 2.21 (s, 6H).

Example 2:

(2Z)-3-(2,6-dimethylphenyl)-2-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]-indazol-6-yl]methylenehydrazono]thiazolidine- 4-one (C-2 of Table X):

To a solution of 1-(2,6-dimethylphenyl)-3-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]indazol-6-yl]methyleneamino]thiourea (0.160 g ) in ethanol (5.0 ml) NaOAc (0.100 g) and methyl bromoacetate (0.139 g) were added at room temperature. Then the reaction mixture was stirred at 28°C for 16 hours. The progress of the reaction was monitored by TLC. The reaction mixture was diluted with water (15 ml) and extracted with ethyl acetate (25 ml x 2). The combined organic solvent was dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 0-5% methanol in dichloromethane as mobile phase) to give the title compound (0.074 g). HPLC/MS (Method 1) : V _y : 2.33 min; MS: m/z = 568.3 (M+1). ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 8.45 (s, 1H), 7.89 (d, J = 8.3 Hz, 2H), 7.66 (d, J = 8.8 Hz , 1H), 7.42 - 7.13 (m, 8H), 5.45 (s, 2H), 4.29 (s, 2H), 4.06 (s, 3H), 2.12 (s, 6H).

Example 3:

1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]indazol-6-yl]methyleneamino]thiourea (C-3 of Table X):

A mixture of 1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]indazole-6-carbaldehyde (0.085 g) and 1-amino-3-(2-isopropylphenyl)thiourea (0.051 g) in EtOH (5 ml) heated at 80 ^° C. for 3 hours. The progress of the reaction was monitored by TLC. The reaction mixture was cooled and concentrated under reduced pressure. Then the reaction mixture was diluted with water (15 ml) and was extracted with ethyl acetate (25 ml x 2). The combined organic solvent was dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 10-50% EtOAc in heptane as mobile phase) to give the title compound (0.131 g). HPLC/MS (Method 1) : V _y : 2.31 min; MS: m/z = 542.3 (M+1). ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 11.91 (s, 1H), 10.02 (s, 1H), 8.28 (s, 1H), 8.03 (s, 1H), 8 .01 - 7.87 (m, 1H), 7.82 (d, J = 8.6 Hz, 1H), 7.42 - 7.13 (m, 8H), 5.45 (s, 2H), 4.09 (s, 3H), 3.20 - 3.07 (m, 1H), 1.20 (d, J = 6.9 Hz, 6H).

Example 4:

(2Z)-3-(2-isopropylphenyl)-2-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]-indazol-6-yl]methylenehydrazono]thiazolidine-4- he (C-4 of Table X):

To a solution of 1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]-indazol-6-yl]methyleneamino]thiourea (0.170 g, 0.314 mmol) in ethanol (5.0 mL) NaOAc (0.103 g, 1.256 mmol) and methyl bromoacetate (0.144 g, 0.942 mmol) were added at room temperature. Then the reaction mixture was stirred at 28°C for 16 hours. The progress of the reaction was monitored by TLC. The reaction mixture was diluted with water (15 ml) and extracted with ethyl acetate (25 ml x 2). The combined organic solvent was dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluting with 10-50% EtOAc in heptane as mobile phase) to give the title compound (0.183 g). HPLC/MS (Method 1) : V _y : 2.36 min; MS: m/z = 582.4 (M+1). ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 8.43 (s, 1H), 7.89 (d, J = 9.2 Hz, 2H), 7.67 (d, J = 8.8 Hz , 1H), 7.50 (k, J = 7.8, 7.2 Hz, 2H), 7.41 - 7.14 (m, 6H), 5.45 (s, 2H), 4.44 - 4.10 (m, 2H), 4.06 (s, 3H), 2.86 - 2.74 (m, 1H), 1.16 (dd, J = 9.0, 7.0 Hz, 7H) .

Example 5:

[(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyltetrahydropyran-2-yl] N-[1-methyl-3-[[4-(trifluoromethoxy)benzoyl]amino]indazole -6-yl]carbamate (C-5 of Table X):

Step 1 N-(6-bromo-1-methyl-indazol-3-yl)-4-(trifluoromethoxy)benzamide:

4- trifluoromethoxybenzoyl chloride (0.80 g) and allowed to slowly warm to room temperature and stirred for 16 hours. The reaction mixture was poured into water, extracted with EtOAc, and the organic layer was washed with brine, dried over MgSO ₄ , filtered and concentrated under reduced pressure. Purify by column chromatography using an EtOAc/cyclohexane gradient to give the title compound (1.38 g). ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.52 (s, 1H), 8.05 - 7.94 (m, 3H), 7.51 (d, J = 1.7 Hz, 1H), 7 .38 - 7.31 (m, 2H), 7.28 - 7.21 (m, 2H), 3.93 (s, 3H).

Step 2. Methyl 1-methyl-3-[[4-(trifluoromethoxy)benzoyl]amino]indazole-6-carboxylate:

Solution of N-(6-bromo-1-methyl-indazol-3-yl)-4-(trifluoromethoxy)benzamide (1.08 g), DIPEA (1.1 ml) and dppfPdCl ₂ (191 mg) in methanol at 60 °C in an atmosphere of CO (g) (1 atm) was stirred for 16 hours. The reaction mixture was poured into water and extracted with CH ₂ Cl ₂ and the organic layer was dried over MgSO ₄ , filtered and concentrated under reduced pressure and used without further purification (1.32 g). HPLC/MS (Method 2): _Vy =1.15 min, MS: m/z=394(M+).

Step 3. 1-methyl-3-[[4-(trifluoromethoxy)benzoyl]amino]indazole-6-carboxylic acid:

A suspension of 1-methyl-3-[[4-(trifluoromethoxy)benzoyl]amino]indazole-6-carboxylate (1.63 g) and LiOH.H ₂ O in THF/water (3:1, 60 ml) was stirred at room temperature for 16 hours. The reaction was then quenched with water. HCl (1 M) and the resulting precipitate was isolated by filtration, washed with ice water and then dried (0.95 g). ¹ H NMR (400 MHz, DMSO-d ₆ ) δ 13.12 (s, 1H), 11.07 (s, 1H), 8.28-8.16 (m, 3H), 7.84 (d, J = 8.6 Hz, 1H), 7.66 (dd, J = 8.6, 1.3 Hz, 1H), 7.59 - 7.52 (m, 2H), 4.10 (s, 3H ).

Step 4. 1-methyl-3-[[4-(trifluoromethoxy)benzoyl]amino]indazole-6-carbonyl azide:

A suspension of 1-methyl-3-[[4-(trifluoromethoxy)benzoyl]amino]indazole-6-carboxylate (0.45 g) in thionyl chloride (3 ml) and DMF (2 drops) was stirred and refluxed for 4 hours and at this time a solution was formed. The reaction mixture was concentrated under reduced pressure, dissolved in CH ₂ Cl ₂ and then concentrated. The crude solid (0.49 g) was suspended in acetone (4 ml) at 0° C. and a solution of NaN ₃ (0.19 g) in water (6.5 ml) was added slowly. During stirring for 16 hours, the reaction mixture was allowed to slowly warm to room temperature, the resulting precipitate (0.19 g after 2 steps) was isolated by filtration and washed with water.

Step 5 [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl] N-[1-methyl-3-[[4-(trifluoromethoxy) benzoyl]amino]indazol-6-yl]carbamate (C-5 of Table X):

A stirred solution of 1-methyl-3-[[4-(trifluoromethoxy)benzoyl]amino]indazole-6-carbonyl azide (0.140 g) in toluene (6 ml) was heated at 100°C for 2 hours and then cooled to room temperature and concentrated under reduced pressure. The resulting oil was dissolved in acetonitrile (6 ml), (3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-ol (0.11 g) and Cs ₂ CO ₃ ( 0.056 g) and the suspension was stirred at room temperature for 16 hours. The reaction mixture was poured into water and extracted with EtOAc, and the organic layer was dried over MgSO ₄ , filtered and concentrated under reduced pressure. Purify by column chromatography using an EtOAc/cyclohexane gradient to give the title compound (40 mg). ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.13 (s, 1H), 7.83 (d, J=8.5 Hz, 2H), 7.48-7.40 (m, 2H), 7 .25 (d, J = 8.4 Hz, 2H), 6.94 (dd, J = 8.8, 1.7 Hz, 1H), 6.24 (d, J = 2.0 Hz, 1H) , 4.09 (s, 3H), 3.71 (dq, J = 12.9, 5.1, 3.8 Hz, 1H), 3.70 (s, 1H), 3.61 - 3.46 (m, 11H), 3.22 (t, J = 9.4 Hz, 1H), 2.05 (s, 1H), 1.42 (s, 1H), 1.32 (d, J = 6, 2 Hz, 3H), 1.28 (dt, J = 19.0, 6.7 Hz, 1H).

Example 6:

[(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyltetrahydropyran-2-yl] N-[1-methyl-3-[[4-(trifluoromethoxy)phenyl]carbamoyl]indazole -6-yl]carbamate (C-6 of Table X):

Stage 1: Methyl 1-methyl-3-[[4-(trifluoromethoxy)phenyl]carbamoyl]indazole-6-carboxylate

A solution of methyl 3-bromo-1-methyl-indazole-6-carboxylate (0.90 g), 4-(trifluoromethoxy)aniline (0.89 g), DIPEA (1.4 ml) and Pd(dppf)Cl ₂ ( 0.24 g) in dimethylacetamide (60 ml) was heated at 80°C with stirring in an atmosphere of CO (g) (5 atm) for 19 hours. The reaction mixture was left to cool to room temperature, then was extracted with ethyl acetate with washing with water, dried over MgSO ₄ , filtered and concentrated under reduced pressure. Purify by silica gel chromatography using an ethyl acetate/cyclohexane gradient to give the title compound (0.65 g). HPLC/MS (Method 2): V _y : 1.32 min; MS: m/z = 394 (M+1).

Stage 2: 1-methyl-3-[[4-(trifluoromethoxy)phenyl]carbamoyl]indazole-6-carboxylic acid:

A solution of methyl 1-methyl-3-[[4-(trifluoromethoxy)phenyl]carbamoyl]indazole-6-carboxylate (0.83 g) and LiOH.H ₂ O (0.13 g) in THF (15 ml) and H ₂ O (5 ml) was stirred at room temperature for 16 hours. The reaction mixture was then poured onto an ice-cold solution of aq. HCl (1M) and the resulting precipitate was isolated by filtration, washing with cold water. The wet solid was dried by distillation with toluene (3x) and then precipitated with diisopropyl ether (0.40 g) and used without further purification.

Stage 3: 1-methyl-3-[[4-(trifluoromethoxy)phenyl]carbamoyl]indazole-6-carbonyl azide:

To a solution of 1-methyl-3-[[4-(trifluoromethoxy)phenyl]carbamoyl]indazole-6-carboxylic acid (0.40 g) in CH ₂ Cl ₂ at 0°C was added oxalyl chloride (0.11 ml), and then 1 drop of DMF. The reaction mixture was warmed to room temperature and stirred for 3 hours and then concentrated to dryness. The obtained crude oil was suspended in acetone (7 ml) and then added to a stirred solution of NaN ₃ (0.18 g) at 0°C. The reaction mixture was stirred for 16 hours at room temperature, then the resulting precipitate was isolated by filtration, washing with cold water, and dried to give the title compound (285 mg). HPLC/MS (Method 2): V _y : 1.33 min; MS: m/z = 405 (M+1).

Stage 4: [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyltetrahydropyran-2-yl] N-[1-methyl-3-[[4-(trifluoromethoxy)phenyl] carbamoyl]indazol-6-yl]carbamate (C-6 of Table X):

A suspension of 1-methyl-3-[[4-(trifluoromethoxy)phenyl]carbamoyl]indazole-6-carbonyl-azide (0.14 g) in toluene was heated at 80°C for 2 hours, cooled to room temperature, and then concentrated. The resulting crude oil was dissolved in CH ₃ CN (6 ml) at room temperature and then Cs ₂ CO ₃ (56 mg) and (3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyltetrahydropyran-2 was added -ol (0.11 g). After 16 hours the reaction mixture was concentrated and partitioned between ethyl acetate and aq. _NaHC03 . The organic layer was dried over MgSO ₄ , filtered and concentrated. Purify by silica gel chromatography using an ethyl acetate/cyclohexane gradient to give the title compound (70 mg). HPLC/MS (Method 2): V _y : 1.25 min; MS: m/z = 584 (M+1). ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.84 (s, 1H), 8.29 (d, J = 8.7 Hz, 1H), 8.10 - 8.04 (m, 1H), 7 .82 - 7.73 (m, 2H), 7.23 (d, J = 8.6 Hz, 2H), 6.99 (s, 1H), 6.92 (dd, J = 8.7, 1 .8 Hz, 1H), 6.23 (d, J = 2.0 Hz, 1H), 4.10 (s, 2H), 3.77 - 3.65 (m, 2H), 3.61 - 3 .47 (m, 8H), 3.22 (t, J = 9.4 Hz, 1H), 1.34 (d, J = 6.2 Hz, 2H).

Example 7:

6-[(E)-[(2-isopropylphenyl)carbamothioylhydrazono]methyl]-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (C-7 of Table X):

Stage 1: 6-bromo-1H-indazole-3-carbaldehyde:

A solution of 6-bromoindole (6 g) in acetone (200 ml) was cooled to 0° C. under an inert atmosphere. To the solution was added NaNO ₂ (16.89 g) in water (30 ml) and 2N aq. HCl (70 ml) dropwise at 0°C in an inert atmosphere. The reaction mixture was stirred at room temperature for 1 hour. The progress of the reaction was monitored by TLC. After completion of the reaction, the solvents were evaporated in vacuo and the precipitated product was filtered through filter paper. The product was washed with cold DCM (50 ml) and dried under reduced pressure to give the title compound (6.5 g). HPLC/MS (Method 1) : V _y : 1.699 min; MS: m/z = 225 (M-1).

Stage 2: 6-bromo-1-methyl-indazole-3-carbaldehyde:

To a solution of 6-bromo-1H-indazole-3-carbaldehyde (3 g) in dry THF (30 ml) was added methyl iodide (2.27 g) and K ₂ CO ₃ (2.76 g) under an inert atmosphere. The reaction mixture was stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (60 ml) and extracted with ethyl acetate (80 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 15-20% ethyl acetate in heptane as mobile phase) to give (2.1 g) the title compound. HPLC/MS (Method 1): V _y : 1.898 min; MS: m/z = 238.2 (M+1).

Stage 3: 6-bromo-1-methyl-indazole-3-carboxylic acid:

To a solution of 6-bromo-1-methyl-indazole-3-carbaldehyde (1 g) in CH ₃ CN (10 ml) and water (4 ml) was added KMnO ₄ (1.32 g) at room temperature. The reaction mixture was stirred for 12 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was poured into ice water and filtered through a pad of cellite. The cellite layer was washed with water and the pH of the filtrate was adjusted to ~3-4 using aq. 1N HCl solution. The precipitated product was filtered through filter paper and dried under reduced pressure to give (0.8 g) the title compound. HPLC/MS (Method 1) : V _y : 1.569 min; MS: m/z = 253 (M-1).

Stage 4: 6-bromo-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide:

To a solution of 6-bromo-1-methyl-indazole-3-carboxylic acid (0.8 g) in dry DCM (10 ml) was added 4-trifluoromethoxyaniline (0.61 g) and triethylamine (1.04 g) at 0° C in an inert atmosphere. The reaction mixture was stirred at room temperature for 5 minutes and then a solution of propylphosphonium anhydride (5.98 g, 50% in ethyl acetate) was added to the reaction mixture. The reaction mixture continued to stir for 12 hours at room temperature. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (50 ml) and extracted with ethyl acetate (60 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-25% ethyl acetate in heptane as mobile phase) to give (1.2 g) the title compound. HPLC/MS (Method 1) : V _y : 2.186 min; MS: m/z = 413.9 (M-1).

Stage 5: 1-methyl-N-[4-(trifluoromethoxy)phenyl]-6-vinylindazole-3-carboxamide:

A solution of 6-bromo-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (1 g) in dry toluene (10 ml) was washed with nitrogen for 10 minutes. Pd(dppf)Cl ₂ (0.106 g) was added to the solution and the nitrogen flush was continued for another 10 minutes. Tributylvinyltin (1.148 g) was then added to the solution. The reaction mixture was stirred for 3 hours at 110°C. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was allowed to cool to room temperature, then diluted with water (50 ml) and extracted with ethyl acetate (60 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-25% ethyl acetate in heptane as mobile phase) to give (0.450 g) the title compound. HPLC/MS (Method 1) : V _y : 2.196 min; MS: m/z = 362.15 (M+1).

Stage 6: 6-formyl-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide:

A solution of 1-methyl-N-[4-(trifluoromethoxy)phenyl]-6-vinylindazole-3-carboxamide (0.450 g) in 1,4-dioxane (5 ml) and water (2 ml) was cooled to 0°C in an inert atmosphere. OsO ₄ (0.005 g) and NaIO ₄ (0.584 g) were added to the stirred solution under an inert atmosphere. The reaction mixture was stirred at room temperature for 4 hours. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water (10 ml), quenched with water. sodium sulfite solution (10 ml) and extracted with ethyl acetate (20 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-22% ethyl acetate in heptane as mobile phase) to give (0.300 g) the title compound. HPLC/MS (Method 1) : V _y : 2.098 min; MS: m/z = 362.0 (M-1).

Step 7: 6-[(E)-[(2-isopropylphenyl)carbamothioylhydrazono]methyl]-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (C-7 of Table X):

1-amino-3-(2-isopropylphenyl)thiourea (0.173 g) was added to a solution of 6-formyl-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (0.3 g) in ethanol (3 ml) at room temperature under an inert atmosphere. The reaction mixture was stirred for 3 hours at 85°C. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was cooled to room temperature and the precipitated product was filtered through filter paper. The residue was washed with cold EtOH (2 ml), triturated with pentane (5 ml) and dried under reduced pressure to give (0.280 g) the title compound. HPLC/MS (Method 1) : V _y : 2.229 min; MS: m/z = 553.3 (M-1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 11.96 (s, 1H), 10.62 (s, 1H), 10.07 (s, 1H), 8.32 (s, 1H), 8 .22 - 8.15 (m, 2H), 8.09 (d, J = 8.6 Hz, 1H), 8.06 - 7.99 (m, 2H), 7.37 (t, J = 8 .8 Hz, 3H), 7.32 (ddd, J = 8.0, 6.0, 2.7 Hz, 1H), 7.29 - 7.20 (m, 2H), 4.25 (s, 3H), 3.16 (hept, J = 6.9 Hz, 1H), 1.21 (d, J = 6.9 Hz, 6H).

Example 8:

6-[(E)-[(Z)-[3-(2-isopropylphenyl)-4-oxothiazolidin-2-ylidene]hydrazono]methyl]-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole- 3-carboxamide (C-8 of Table X):

To a stirred solution of 6-[(E)-[(2-isopropylphenyl)carbamothioylhydrazono]-methyl]-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (0.24 g) in EtOH ( 5 ml) was added NaOAc (0.071 g) and methyl bromoacetate (0.099 g) at room temperature. The reaction mixture continued to stir at room temperature for 12 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (20 ml) and extracted with ethyl acetate (25 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-25% ethyl acetate in heptane as mobile phase) to give (0.2 g) the title compound. HPLC/MS (Method 1) : V _y : 2.325 min; MS: m/z=595.1 (M+1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 10.63 (s, 1H), 8.47 (s, 1H), 8.26 (d, J = 8.5 Hz, 1H), 8.06 - 7.98 (m, 3H), 7.83 (d, J = 8.5 Hz, 1H), 7.56 - 7.45 (m, 2H), 7.40 - 7.32 (m, 3H ), 7.29 (dd, J = 7.9, 1.2 Hz, 1H), 4.32 - 4.22 (m, 1H), 4.22 (s, 3H), 4.17 (d, J = 17.3 Hz, 1H), 2.81 (hept, J = 6.9 Hz, 1H), 1.16 (dd, J = 16.7, 6.8 Hz, 6H).

Example 9:

[(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenyl]carbamoyl]indazol-6-yl]methyleneamino]N-(2-isopropylphenyl)carbamate (C-9 of Table X):

Stage 1: 6-[(E)-hydroxyiminomethyl]-1-methyl-N-[4-(trifluoromethoxy)phenyl] indazole-3-carboxamide

Hydroxylamine hydrochloride (0.191 g) and sodium acetate (0.226 g) were added to a solution of 6-formyl-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (0.25 g) in EtOH (3 ml ) at room temperature in an inert atmosphere. The reaction mixture was stirred for 3 hours at 85°C. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was cooled to room temperature, diluted with water (25 ml) and extracted with ethyl acetate (30 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 25-30% ethyl acetate in heptane as mobile phase) to give (0.275 g) the title compound. HPLC/MS (Method 1) : V _y : 1.941 min; MS: m/z=379 (M+1).

Stage 2: [(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenyl]carbamoyl]indazol-6-yl]-methyleneamino]N-(2-isopropylphenyl)carbamate (C-9 of Table X) :

1-isocyanato-2-isopropylbenzene (0.143 g) and triethylamine (0.150 g) were added to a solution of 6-[(E)-hydroxyiminomethyl]-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide ( 0.28 g) in toluene (3 ml) at room temperature under an inert atmosphere. The reaction mixture was stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC. After completion, the reaction mass was diluted with water (25 ml) and was extracted with ethyl acetate (30 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified prep. TOP to give (0.170 g) the title compound. HPLC/MS (Method 1) : V _y : 2.250 min; MS: m/z = 538.2 (M-1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 10.66 (s, 1H), 9.36 (s, 1H), 8.81 (s, 1H), 8.30 (d, J = 8, 5 Hz, 1H), 8.25 (s, 1H), 8.06 - 7.99 (m, 2H), 7.90 (dd, J = 8.6, 1.2 Hz, 1H), 7, 41 - 7.34 (m, 3H), 7.38 - 7.20 (m, 2H), 4.27 (s, 3H), 3.23 (n, J = 6.9 Hz, 1H), 1 .20 (d, J = 6.8 Hz, 6H).

Example 10:1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)anilino]methyl]-indazol-6-yl]methyleneamino]thiourea (C-10 X tables):

Stage 1: 6-(1,3-dioxolan-2-yl)-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide:

Ethylene glycol (0.718 g) and p-toluenesulfonic acid ( 0.073 g) at room temperature in an inert atmosphere. The reaction mixture was stirred for 12 hours at 110°C. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was cooled to room temperature, diluted with water (20 ml), quenched with water. sodium bicarbonate solution (20 ml) and extracted with ethyl acetate (60 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-22% ethyl acetate in heptane as mobile phase) to give (1.1 g) the title compound. HPLC/MS (Method 1) : V _y : 2.038 min; MS: m/z = 408.15 (M+1).

Stage 2: N-[[6-(1,3-dioxolan-2-yl)-1-methylindazol-3-yl]methyl]-4-(trifluoromethoxy)-aniline:

To a stirred solution of 6-(1,3-dioxolan-2-yl)-1-methyl-N-[4-(trifluoromethoxy)-phenyl]indazole-3-carboxamide (0.5 g) in dry DCM (10 ml) DIBAL-H (0.610 g) was added at 0° C. under an inert atmosphere. The reaction mixture was stirred at room temperature for 2 hours. To the reaction mixture was again added (0.610 g) DIBAL-H. Then the reaction mixture was stirred for 12 hours at 45°C. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water (20 ml), quenched with water. 1N HCl solution and extracted with ethyl acetate (30 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 22-25% ethyl acetate in heptane as mobile phase) to give (0.25 g) the title compound. HPLC/MS (Method 1) : V _y : 2.022 min; MS: m/z = 394.1 (M+1).

Stage 3: 1-methyl-3-[[4-(trifluoromethoxy)anilino]methyl]indazole-6-carbaldehyde:

To a solution of N-[[6-(1,3-dioxolan-2-yl)-1-methylindazol-3-yl]methyl]-4-(trifluoromethoxy)-aniline (0.25 g) in acetone (3 ml) p-toluenesulfonic acid (0.012 g) was added and the reaction mixture was stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water (15 ml), quenched with water. sodium bicarbonate solution (10 ml) and extracted with ethyl acetate (30 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 25-30% ethyl acetate in heptane as mobile phase) to give (0.1 g) the title compound. HPLC/MS (Method 1) : V _y : 2.018 min; MS: m/z = 350.0 (M+1).

Stage 4: 1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)anilino]methyl]-indazol-6-yl]methyleneamino]thiourea (C-10 X tables):

1-amino-3-(2-isopropylphenyl)thiourea (0.06 g) was added to a solution of 1-methyl-3-[[4-(trifluoromethoxy)anilino]methyl]indazole-6-carbaldehyde (0.1 g) in EtOH (2 ml) at room temperature under an inert atmosphere. Then the reaction mixture was stirred for 3 hours at 85°C. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was cooled to room temperature and the precipitated product was filtered through filter paper. The residue was washed with cold EtOH (2 ml), triturated with pentane (5 ml) and dried under reduced pressure to give (0.07 g) the title compound. HPLC/MS (Method 1) : V _y : 2.217 min; MS: m/z=541.3 (M+1). ¹ H NMR (300 MHz, DMSO-d ₆ ) δ 11.88 (s, 1H), 9.99 (s, 1H), 8.25 (s, 1H), 7.94 (s, 1H), 7 .84 (s, 2H), 7.46 - 7.20 (m, 2H), 7.02 (d, J = 8.4 Hz, 2H), 6.71 (d, J = 8.9 Hz, 2H), 6.65 - 6.47 (m, 1H), 4.56 (d, J = 5.8 Hz, 2H), 4.039 (s, 3H), 3.13 (n, J = 7.0 Hz, 1H), 1.19 (d, J = 6.9 Hz, 6H).

Example 11:

(2Z)-3-(2-isopropylphenyl)-2-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)anilino]methyl]-indazol-6-yl]methylenehydrazono]thiazolidine-4- he (C-11 of Table X):

To a stirred solution of 1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)anilino]methyl]indazol-6-yl]methyleneamino]thiourea (0.170 g) in EtOH (4 ml) was added NaOAc (0.052 g) and methyl bromoacetate (0.072 g) at room temperature. The reaction mixture continued to stir at room temperature for 12 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (20 ml) and extracted into ethyl acetate (30 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-25% ethyl acetate in heptane as mobile phase) to give (0.065 g) the title compound. HPLC/MS (Method 1) : V _y : 2.240 min; MS: m/z=581.3 (M+1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.40 (s, 1H), 7.90 (d, J = 8.5 Hz, 1H), 7.84 (s, 1H), 7.59 (dd, J = 8.6, 1.2 Hz, 1H), 7.50 (dtd, J = 14.9, 7.9, 1.6 Hz, 2H), 7.34 (td, J = 7 .6, 1.7 Hz, 1H), 7.27 (dd, J = 7.9, 1.4 Hz, 1H), 7.03 (d, J = 8.6 Hz, 2H), 6.77 - 6.68 (m, 2H), 6.57 (s, 1H), 4.56 (s, 2H), 4.26 (d, J = 17.2 Hz, 1H), 4.20 - 4, 09 (m, 1H), 4.01 (s, 3H), 2.80 (p, J = 6.8 Hz, 1H), 1.15 (dd, J = 13.5, 6.8 Hz, 6H ).

Example 12:

1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[1-[4-(trifluoromethoxy)phenoxy]ethyl]indazol-6-yl]methyleneamino]thiourea (C-12 of Table X ):

Stage 1: 1-(6-bromo-1-methylindazol-3-yl)ethanol:

To a stirred solution of 6-bromo-1-methylindazole-3-carbaldehyde (1.5 g) in dry THF (15 mL) was added methylmagnesium bromide (0.823 g, 1M in THF) at 0° C. under an inert atmosphere. The reaction temperature was slowly raised to room temperature. The reaction mixture continued to stir at room temperature for 2 hours. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was quenched with water. ammonium chloride solution (25 ml) and extracted with ethyl acetate (30 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-22% ethyl acetate in heptane as mobile phase) to give (0.750 g) the title compound. HPLC/MS (Method 1) : V _y : 1.602 min; MS: m/z = 255.05 (M+1).

Stage 2: 6-bromo-1-methyl-3-[1-[4-(trifluoromethoxy)phenoxy]ethyl]indazole:

In a microwave bottle, 4-trifluoromethoxyphenol (0.168 g) and triphenylphosphine (0.217 g) were added to a solution of 1-(6-bromo-1-methylindazol-3-yl)ethanol (0.2 g) in dry THF (2 ml) in inert atmosphere and cooled to 0°C. The reaction mixture was stirred at 0° C. for 5 minutes, then DBAD (0.217 g) was added to the reaction mixture. The reaction mixture continued to stir at 42°C for 2 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (10 ml) and extracted with ethyl acetate (10 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-25% ethyl acetate in heptane as mobile phase) to give (0.2 g) the title compound. HPLC/MS (Method 1) : V _y : 2.400 min; MS: m/z=416.9 (M+1).

Stage 3: 1-methyl-3-[1-[4-(trifluoromethoxy)phenoxy]ethyl]-6-vinylindazole:

A solution of 6-bromo-1-methyl-3-[1-[4-(trifluoromethoxy)phenoxy]ethyl]indazole (0.2 g) in dry toluene (2 ml) was washed with nitrogen for 10 minutes. Pd(dppf)Cl ₂ (0.021 g) was added to the solution and the nitrogen flush was continued for another 10 minutes. Then, tributylvinyltin (0.229 g) was added to the solution, and the reaction mixture was heated at 110° C. for 3 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was cooled to room temperature, diluted with water (10 ml) and extracted with ethyl acetate (20 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-25% ethyl acetate in heptane as mobile phase) to give (0.150 g) the title compound. HPLC/MS (Method 1) : V _y : 2.287 min; MS: m/z = 363.15 (M+1).

Stage 4: 1-methyl-3-[1-[4-(trifluoromethoxy)phenoxy]ethyl]indazole-6-carbaldehyde:

To a stirred solution of 1-methyl-3-[1-[4-(trifluoromethoxy)phenoxy]ethyl]-6-vinyl-indazole (0.15 g) in 1,4-dioxane (2 ml) and water (1 ml) OsO ₄ (0.002 g) and NaIO ₄ (0.194 g) were added at 0° C. under an inert atmosphere. The reaction mixture was stirred at room temperature for 3 hours. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water (10 ml), quenched with water. sodium sulfite solution (10 ml) and extracted with ethyl acetate (20 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-22% ethyl acetate in heptane as mobile phase) to give (0.05 g) the title compound. HPLC/MS (Method 1) : V _y : 2.112 min; MS: m/z = 365.1 (M+1).

Step 5: 1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[1-[4-(trifluoromethoxy)phenoxy]ethyl]-indazol-6-yl]methyleneamino]thiourea (C -12 Tables X):

To a solution of 1-methyl-3-[1-[4-(trifluoromethoxy)phenoxy]ethyl]indazole-6-carbaldehyde (0.05 g) in EtOH (1 ml) was added 1-amino-3-(2-isopropylphenyl) thiourea (0.029 g) at room temperature under an inert atmosphere. Then the reaction mixture was stirred for 3 hours at 85°C. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was cooled to room temperature and the precipitated product was filtered through filter paper. The residue was washed with cold EtOH (2 ml), triturated with pentane (5 ml) and dried under reduced pressure to give (0.05 g) the title compound. HPLC/MS (Method 1) : V _y : 2.272 min; MS: m/z = 554.2 (M-1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 11.89 (s, 1H), 9.99 (s, 1H), 8.25 (s, 1H), 7.97 (s, 1H), 7 .89 - 7.78 (m, 2H), 7.37 (d, J = 7.7 Hz, 1H), 7.31 (dt, J = 8.1, 4.0 Hz, 1H), 7, 27 - 7.15 (m, 4H), 7.13 - 7.06 (m, 2H), 5.92 (k, J = 6.5 Hz, 1H), 4.05 (s, 3H), 3 .13 (n, J = 6.9 Hz, 1H), 1.76 (d, J = 6.5 Hz, 3H), 1.22 - 1.12 (m, 6H).

Example 13:

(2Z)-3-(2-isopropylphenyl)-2-[(E)-[1-methyl-3-[1-[4-(trifluoromethoxy)phenoxy]ethyl]-indazol-6-yl]methylenehydrazono]thiazolidine- 4-one (C-13 of Table X):

1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[1-[4-(trifluoromethoxy)phenoxy]ethyl]-indazol-6-yl]methyleneamino]thiourea mixture (0.320 g) , NaOAc (0.095 g) and methyl bromoacetate (0.132 g) in EtOH (6.0 ml) were stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (25 ml) and extracted with ethyl acetate (30 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-25% ethyl acetate in heptane as mobile phase) to give (0.15 g) the title compound. HPLC/MS (Method 1) : V _y : 2.342 min; MS: m/z = 596.25 (M+1), 1H NMR (500 MHz, DMSO-d ₆ ) δ 8.39 (s, 1H), 7.90 (d, J = 8.5 Hz, 1H ), 7.85 (s, 1H), 7.62 (d, J = 8.5 Hz, 1H), 7.49 (dt, J = 14.9, 7.8 Hz, 2H), 7.34 (t, J = 7.5 Hz, 1H), 7.30 - 7.19 (m, 3H), 7.09 (d, J = 8.7 Hz, 2H), 5.91 (k, J = 6.4 Hz, 1H), 4.26 (d, J = 17.3 Hz, 1H), 4.14 (d, J = 17.6 Hz, 1H), 4.02 (s, 3H), 2 .79 (n, J = 6.9 Hz, 1H), 1.75 (d, J = 6.5 Hz, 3H), 1.19 - 1.08 (m, 6H).

Example 14:

(2Z)-2-(2-isopropylphenyl)imino-3-[(E)-[1-methyl-3-[1-[4-(trifluoromethoxy)phenoxy]ethyl]-indazol-6-yl]methyleneamino]thiazolidine -4-one (C-14 of Table X):

Mixture of 1-methyl-3-[1-[4-(trifluoromethoxy)phenoxy]ethyl]indazole-6-carbaldehyde (0.2 g) and (2Z)-3-amino-2-(2-isopropylphenyl)iminothiazolidine-4 -one (0.137 g) in acetic acid (2 ml) was stirred at room temperature for 3 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (15 ml) and extracted with ethyl acetate (25 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 25-30% ethyl acetate in heptane as mobile phase) to give (0.075 g) the title compound. HPLC/MS (Method 1) : V _y : 2.399 min; MS: m/z = 596.25 (M+1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 9.28 (s, 1H), 8.17 (d, J = 1.2 Hz, 1H), 8.06 (d, J = 8.5 Hz , 1H), 7.81 (dd, J = 8.6, 1.3 Hz, 1H), 7.36 (dd, J = 7.7, 1.6 Hz, 1H), 7.32 - 7, 20 (m, 3H), 7.21 - 7.13 (m, 3H), 6.93 (dd, J = 7.7, 1.4 Hz, 1H), 6.01 (k, J = 6, 5 Hz, 1H), 4.21 (s, 2H), 4.15 (s, 3H), 3.05 (hept, J = 6.9 Hz, 1H), 1.83 (d, J = 6, 4 Hz, 3H), 1.19 (d, J = 6.9 Hz, 6H).

Example 15:

1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]pyrazolo-[4,3-c]pyridin-6-yl]methyleneamino] thiourea (C-15 of Table X):

Stage 1: 4,6-dichloro-N-methoxy-N-methylpyridine-3-carboxamide:

To a solution of 4,6-dichloropyridine-3-carboxylic acid (5.0 g) in DMF (100 ml) was added EDC.HCl (4.85 g), N-methylmorpholine (3.43 ml) and N,O-dimethylhydroxylamine (3.04 g) and the reaction mixture was stirred for 16 hours at room temperature. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (100 ml) and extracted with ethyl acetate (50 ml x 3). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 0-50% ethyl acetate in heptane as mobile phase) to give (5.7 g) the title compound as a solid. RX/MS (Method 1) : V _y : 1.59 min; MS: m/z = 235.0 (M+1).

Stage 2: 1-(4,6-dichloro-3-pyridyl)ethenone:

To a stirred solution of 4,6-dichloro-N-methoxy-N-methylpyridine-3-carboxamide (5.7 g) in THF (40 ml) was added methylmagnesium bromide (16.16 g) at 0°C. The reaction mass was stirred for 16 hours at room temperature. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with saturated ammonium chloride solution (100 ml) and extracted with ethyl acetate (50 ml X 3). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 0-50% ethyl acetate in heptane as mobile phase) to give (4.0 g) the title compound. HPLC/MS (Method 1) : V _y : 1.73 min; MS: m/z = 231.0 (M+1).

Stage 3: 6-chloro-1,3-dimethylpyrazolo[4,3-c]pyridine:

To a stirred solution of 1-(4,6-dichloro-3-pyridyl)ethanone (4.0 g) in methanol (25 ml) was added methylhydrazine (2.28 g) at 0°C. Then the reaction mixture was heated at 50°C for 2 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was concentrated under reduced pressure, diluted with water (100 ml) and extracted with ethyl acetate (30 ml X 3). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 0-20% ethyl acetate in heptane as mobile phase) to give (1.6 g) the title compound. HPLC/MS (Method 1) : V _y : 1.52 min; MS: m/z = 182.1 (M+1).

Stage 4: 3-(bromomethyl)-6-chloro-1-methylpyrazolo[4,3-c]pyridine:

To a stirred solution of 6-chloro-1,3-dimethylpyrazolo[4,3-c]pyridine (3.1 g) in CCl ₄ (25 ml) was added N-bromosuccinimide (3.66 g) and benzoyl peroxide (0.332 g) at room temperature. temperature. Then the reaction mixture was heated at 78°C for 16 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was concentrated under reduced pressure, diluted with water (100 ml) and extracted with ethyl acetate (30 ml x 3). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 0-20% ethyl acetate in heptane as mobile phase) to give (1.6 g) the title compound. HPLC/MS (Method 1) : V _y : 1.69 min; MS: m/z = 302.95 (M+1).

Stage 5: 6-chloro-1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]pyrazolo[4,3-c]pyridine:

To a stirred solution of 4-(trifluoromethoxy)phenol (0.342 ml) in DMF (5 ml) was added potassium tert-butoxide (0.323 g) at room temperature under an inert atmosphere. After 10 minutes, 3-(bromomethyl)-6-chloro-1-methylpyrazolo[4,3-c]pyridine (0.5 g) was added to the reaction mixture, and the reaction mixture was stirred at room temperature for 5 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (25 ml) and extracted with ethyl acetate (30 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-25% ethyl acetate in heptane as mobile phase) to give (0.470 g) the title compound. HPLC/MS (Method 1): V _y : 2.099 min; MS: m/z = 358 (M+1).

Stage 6: 1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]-6-vinylpyrazolo[4,3-c]-pyridine:

A stirred solution of 6-chloro-1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]-pyrazolo[4,3-c]pyridine (0.47 g) in dry 1,4-dioxane (5 ml) flushed with nitrogen for 10 minutes. Pd(dppf)Cl ₂ (0.058 g) was added to the solution and the nitrogen flush was continued for another 10 minutes. Tributylvinyltin (0.625 g) was added to the reaction mixture and heated at 110° C. for 12 hours with stirring. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was cooled to room temperature, diluted with water (30 ml) and extracted with ethyl acetate (40 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-25% ethyl acetate in heptane as mobile phase) to give (0.2 g) the title compound. HPLC/MS (Method 1) : V _y : 1.921 min; MS: m/z = 350.3 (M+1).

Stage 7: 1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]pyrazolo[4,3-c]pyridine-6-carbaldehyde:

To a stirred solution of 1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]-6-vinyl-pyrazolo[4,3-c]pyridine (0.2 g) in 1,4-dioxane (2 ml) OsO ₄ (0.003 g) and NaIO ₄ (0.268 g) were added at 0° C. under an inert atmosphere. The reaction mixture continued to stir at room temperature for 3 hours. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water (10 ml), quenched with water. sodium sulfite solution (10 ml) and extracted with ethyl acetate (20 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-22% ethyl acetate in heptane as mobile phase) to give (0.055 g) the title compound. HPLC/MS (Method 1) : V _y : 1.905 min; MS: m/z = 352.1 (M+1).

Stage 8: 1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]-pyrazolo[4,3-c]pyridin-6-yl ]methyleneamino]thiourea (C-15 of Table X):

A mixture of 1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]pyrazolo[4,3-c]pyridine-6-carbaldehyde (0.053 g) and 1-amino-3-(2-isopropylphenyl)thiourea (0.033 d) in EtOH (2 ml) was heated at 85°C for 3 hours in an inert atmosphere. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was cooled to room temperature and the precipitated product was filtered through filter paper. The residue was washed with cold EtOH (2 ml), triturated with pentane (5 ml) and dried under reduced pressure to give (0.045 g) the title compound. HPLC/MS (Method 1) : V _y : 2.115 min; MS: m/z = 541.25 (M-1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 14.46 (s, 1H), 12.06 (s, 1H), 10.26 (s, 1H), 10.03 (s, 1H), 9 .17 (s, 1H), 8.57 (s, 1H), 8.36 (s, 1H), 8.21 (d, J = 7.4 Hz, 1H), 7.55 (s, 1H) , 7.40 (d, J = 7.7 Hz, 1H), 7.34 (d, J = 8.8 Hz, 6H), 7.32-7.18 (m, 7H), 5.60 ( s, 1H), 5.54 (s, 2H), 4.15 (s, 2H), 4.09 (s, 3H), 3.38 (s, 1H), 3.32 (s, 7H), 3.19 - 3.08 (m, 1H), 2.58 (d, J = 18.8 Hz, 1H), 2.43 (s, 0H), 1.31 (d, J = 9.7 Hz , 1H), 1.19 (dd, J = 22.4, 6.8 Hz, 14H).

Example 16:

(2Z)-3-(2-isopropylphenyl)-2-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]-pyrazolo[4,3-c]pyridine-6- yl]methylenehydrazono]thiazolidin-4-one (C-16 of Table X):

1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[[4-(trifluoromethoxy)phenoxy]methyl]pyrazolo[4,3-c]pyridin-6-yl]methyleneamino mixture ]thiourea (0.045 g), NaOAc (0.014 g) and methyl bromoacetate (0.019 g) in EtOH (2 ml) was stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (15 ml) and extracted with ethyl acetate (20 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 25-30% ethyl acetate in heptane as mobile phase) to give (0.022 g) the title compound. HPLC/MS (Method 1) : V _y : 2.221 min; MS: m/z = 583.6 (M+1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 9.25 (s, 1H), 8.35 (s, 1H), 8.16 (s, 1H), 7.61-7.44 (m, 2H), 7.41 - 7.26 (m, 4H), 7.26 - 7.18 (m, 2H), 5.55 (s, 2H), 4.30 (d, J = 17.4 Hz , 1H), 4.19 (d, J = 17.4 Hz, 1H), 4.14 (s, 3H), 2.94 - 2.72 (m, 1H), 1.16 (dd, J = 13.6, 6.9 Hz, 6H).

Example 17:

4-fluoro-6-[[(2-isopropylphenyl)carbamothioylhydrazono]methyl]-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (C-17 of Table X):

Stage 1: ethyl 2-(4-bromo-2,6-difluorophenyl)-2-oxoacetate:

To a mixture of 1-bromo-3,5-difluorobenzene (1 g) in THF (5 ml) cooled to -78°C,

a solution of lithium bis(trimethylsilyl)amide (1.04 g) in THF was added. Diethyl oxalate (0.87 g) was then added and the mixture was stirred for 4 hours. Saturated ammonium chloride solution was added and the mixture was extracted with ethyl acetate, the extracts were washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate and evaporated under reduced pressure. The resulting solid was subjected to flash silica gel column chromatography using an ethyl acetate/heptane gradient as eluent to give the title compound (0.61 g). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.71 (d, J = 8.3 Hz, 2H), 4.29 (d, J = 7.1 Hz, 2H), 1.22 (t , J = 7.1 Hz, 3H).

Stage 2: ethyl 6-bromo-4-fluoro-1-methylindazole-3-carboxylate:

A mixture of ethyl 2-(4-bromo-2,6-difluorophenyl)-2-oxoacetate (0.1 g), methylhydrazine sulfate (0.10 g) and triethylamine (0.089 g) in N-methylpyrrolidone (3 ml) was heated at 80 °C for 1 hour. The mixture was diluted with water and extracted with ethyl acetate. The organic extracts were separated, washed with saturated sodium chloride solution, dried over anhydrous sodium sulfate and evaporated in vacuo. The resulting residue was subjected to flash silica gel column chromatography using an ethyl acetate/heptane gradient as eluent to give the title compound (0.07 g). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.00 (d, J = 1.1 Hz, 1H), 7.34 (dd, J = 10.1, 1.2 Hz, 1H), 4 .36 (k, J = 7.1 Hz, 2H), 4.14 (s, 3H), 1.34 (t, J = 7.1 Hz, 3H).

Stage 3: 6-bromo-4-fluoro-1-methylindazole-3-carboxylic acid:

Ethyl 6-bromo-4-fluoro-1-methylindazole-3-carboxylate (2.4 g) and lithium hydroxide (1.0 g) in a mixture of THF (15 ml) and water were stirred at room temperature for 3 hours. The reaction mixture was neutralized with 2M hydrochloric acid solution. The solid was filtered, washed with water and pentane and dried to give the title compound (2.16 g). ¹ H NMR (500 MHz, DMSO-d ₆ ); ¹ H NMR (500 MHz, DMSO-d6) δ 13.14 (s, 1H), 8.00 (s, 1H), 7.33 (d, J = 10.0 Hz, 1H), 4.13 ( s, 3H).

Stage 4: 6-bromo-4-fluoro-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide:

A mixture of 6-bromo-4-fluoro-1-methylindazole-3-carboxylic acid (0.06 g, 0.22 mmol), 4-(trifluoromethoxy)aniline (0.04 g), 1-[bis( dimethylamino)-methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium (0.167 g) and N,N-diisopropylethylamine (0.057 g) in DMF (3 ml) were stirred at room temperature for 16 hours. The mixture was poured into ice-water and the solid was filtered, washed with water and pentane and dried to give the title compound (0.07 g). HPLC/MS (Method 1): V _y : 2.22 min, m/z = 431.6 (M+1); ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 10.70 (s, 1H), 8.05 (s, 1H), 7.95 (d, J = 8.7 Hz, 2H), 7.36 (t, J = 8.1 Hz, 3H), 4.19 (s, 3H).

Stage 5: 4-fluoro-1-methyl-N-[4-(trifluoromethoxy)phenyl]-6-vinylindazole-3-carboxamide:

6-bromo-4-fluoro-N,1-dimethyl-N-[4-(trifluoromethoxy)phenylindazole-3-carboxamide (0.2 g), [1,1′-bis(diphenylphosphino)ferrocene]dichloropaladium (II) (0.017 g) and tri-n-butylvinyltin (0.220 g) in 1,4-dioxane (4 ml) were heated at 100°C for 3 hours. The mixture was filtered through Celite, then the filtrate was diluted with water and extracted with ethyl acetate. The organic extracts were dried over anhydrous sodium sulfate and evaporated under reduced pressure, and the resulting residue was subjected to flash column chromatography using an ethyl acetate/heptane gradient to give the title compound (0.1 g). HPLC/MS (Method 1): V _y : 2.18 min; m/z = 390.2 (M+1); ¹ H NMR (500 MHz, DMSO-d ₆ ): δ 10.64 (s, 1H), 7.96 (d, J = 8.6 Hz, 2H), 7.69 (s, 1H), 7, 36 (dd, J = 16.9, 10.2 Hz, 3H), 6.89 (dd, J = 17.6, 10.9 Hz, 1H), 6.09 (d, J = 17.6 Hz , 1H), 5.46 (d, J = 10.9 Hz, 1H), 4.20 (s, 3H).

Stage 6: 4-fluoro-6-formyl-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide:

A mixture of 4-fluoro-N,1-dimethyl-N-[4-(trifluoromethoxy)phenyl]-6-vinylindazole-3-carboxamide (0.1 g), osmium tetroxide (0.004 g) and sodium periodate (0.17 g ) in 1,4-dioxane (4 ml) and water (1 ml) was stirred at room temperature for 12 hours. Sodium sulfite solution (0.5%) was added and the mixture was extracted with ethyl acetate. The organic extracts were dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the resulting residue was subjected to silica gel flash column chromatography to give the title compound (0.07 g); HPLC/MS (Method 1): V _y : 1.961 min; m/z = 392.1 (M+1); ¹ H NMR (500 MHz, DMSO-d ₆ ): δ 10.77 (s, 1H), 10.14 (d, J = 2.1 Hz, 1H), 8.39 (d, J = 0.9 Hz, 1H), 8.01 - 7.92 (m, 2H), 7.47 (dd, J = 10.4, 1.0 Hz, 1H), 7.42 - 7.34 (m, 2H) , 4.32 (s, 3H).

Step 7: 4-fluoro-6-[[(2-isopropylphenyl)carbamothioylhydrazono]methyl]-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (C-17 of Table X):

A mixture of 4-fluoro-6-formyl-N,1-dimethyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (0.065 g) and 1-amino-3-(2-isopropylphenyl)thiourea (0.037 g ) in ethanol (3 ml) was heated at 80°C for 6 hours. The mixture was concentrated under reduced pressure, and the residue was subjected to flash silica gel column chromatography using a dichloromethane/methanol gradient as eluent to give the title compound (0.026 g). HPLC/MS (Method 1): V _y : 2.237 min; m/z=573.2 (M+1); ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 12.01 (s, 1H), 10.69 (s, 1H), 10.20 (s, 1H), 8.28 (s, 1H), 8 .10 (d, J = 12.1 Hz, 1H), 8.01 - 7.91 (m, 3H), 7.42 - 7.29 (m, 4H), 7.25 (td, J = 7 .5, 1.5 Hz, 1H), 7.19 (dd, J = 7.8, 1.4 Hz, 1H), 4.24 (s, 3H), 3.15 (hept, J = 7, 0 Hz, 1H), 1.21 (d, J = 6.9 Hz, 6H).

Example 18:

4-fluoro-6-[[(2-isopropylphenyl)carbamothioylhydrazono]methyl]-N,1-dimethyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (C-18 of Table X):

Stage 1: 6-bromo-4-fluoro-N,1-dimethyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide:

Sodium hydride was added to a stirred solution of 6-bromo-4-fluoro-1-methyl-N-[4-(trifluoromethoxy)phenyl]-indazole-3-carboxamide (0.3 g) in DMF (3 ml) at 0°C (0.02 g) and stirred for 15 minutes. Then methyl iodide (0.128 g) was added and the mixture was stirred at room temperature for 12 hours. Saturated ammonium chloride solution was added and the mixture was extracted with ethyl acetate. The organic extracts were dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was subjected to silica gel flash column chromatography to give the title compound (0.26 g). HPLC/MS (Method 1): V _y : 2.14 min; m/z = 447.3 (M+1); ¹ H NMR (500 MHz, CDCl ₃ ) δ 7.28 (d, J = 12.9 Hz, 2H), 7.19 (s, 1H), 7.05 (d, J = 8.2 Hz, 2H ), 6.96 (d, J = 9.4 Hz, 1H), 3.88 (s, 3H), 3.54 (s, 3H).

Stage 2: 4-fluoro-N,1-dimethyl-N-[4-(trifluoromethoxy)phenyl]-6-vinylindazole-3-carboxamide:

A mixture of 6-bromo-4-fluoro-N,1-dimethyl-N-[4-(trifluoromethoxy)phenylindazole-3-carboxamide (0.35 g), 1,1'-bis(diphenylphosphino)ferrocene]dichloropaladium (II) (0.03 g) and tri-n-butylvinyltin (0.37 g) in 1,4-dioxane (6 ml) were heated at 100°C for 3 hours. The reaction mixture was filtered through Celite, the filtrate was diluted with water and extracted with ethyl acetate. The organic extracts were dried over anhydrous sodium sulfate and evaporated under reduced pressure, and the resulting residue was subjected to flash silica gel column chromatography to give the title compound (0.27 g). RX/MS (Method 1): V _y : 2.09 min, m/z = 390.4 (M+1); ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 7.52 (s, 1H), 7.42 - 7.16 (m, 5H), 6.82 (dd, J = 17.5, 10.9 Hz, 1H), 6.02 (d, J = 17.6 Hz, 1H), 5.41 (d, J = 11.0 Hz, 1H), 3.91 (d, J = 18.0 Hz, 3H), 3.45 (s, 3H).

Stage 3: 4-fluoro-6-formyl-N,1-dimethyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide:

A mixture of 4-fluoro-N,1-dimethyl-N-[4-(trifluoromethoxy)phenyl]-6-vinylindazole-3-carboxamide (0.4 g), osmium tetroxide (0.013 g), sodium periodate (0.65 g ) in 1,4-dioxane (6 ml) and water (3 ml) was stirred at room temperature for 12 hours. Sodium sulfite solution (0.5%) was added and the mixture was extracted with ethyl acetate. The organic extracts were dried over anhydrous sodium sulfate and concentrated under reduced pressure, and the resulting residue was subjected to silica gel flash column chromatography to give the title compound (0.3 g). HPLC/MS (Method 1): V _y : 1.9 min; m/z = 396 (M+1); ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 10.07 (d, J = 2.1 Hz, 1H), 8.24 (s, 1H), 7.43 - 7.18 (m, 5H) , 4.12 - 3.99 (s, 3H), 3.47 (s, 3H).

Step 4: 4-fluoro-6-[[(2-isopropylphenyl)carbamothioylhydrazono]methyl]-N,1-dimethyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (C-18 of Table X):

A mixture of 4-fluoro-6-formyl-N,1-dimethyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (0.29 g) and 1-amino-3-(2-isopropylphenyl)thiourea ( 0.16 g) in THF (10 ml) was heated at 60°C for 2 hours. The mixture was evaporated in vacuo and the residue subjected to flash silica gel column chromatography using a dichloromethane/methanol gradient as eluent to give the desired compound (0.3 g). HPLC/MS (Method 1): _Vy : 2.15 min, m/z = 587.2 (M+1); ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 11.96 (s, 1H), 10.15 (s, 1H), 8.21 (s, 1H), 7.98 (d, J = 12, 1 Hz, 1H), 7.76 (s, 1H), 7.45 - 6.90 (m, 8H), 3.97 (s, 3H), 3.45 (s, 3H), 3.13 ( n, J = 6.8 Hz, 1H), 1.20 (d, J = 6.9 Hz, 6H).

Example 19 4-fluoro-6-[[(Z)-[3-(2-isopropylphenyl)-4-oxothiazolidin-2-ylidene]-hydrazono]methyl]-N,1-dimethyl-N-[4-( trifluoromethoxy)phenyl]indazole-3-carboxamide (C-19 of Table X):

4-Fluoro-6-[(E)-[(2-isopropylphenyl)carbamothioylhydrazono]methyl]-N,1-dimethyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide mixture (0.18 g) , sodium acetate (0.05 g) and methyl bromoacetate (0.187 g) in THF (4 ml) were heated at 40 °C for 6 hours. The mixture was diluted with water and extracted with ethyl acetate, the organic extracts were dried over sodium sulfate, concentrated under reduced pressure, and the residue was subjected to silica gel flash column chromatography to give the title compound (0.12 g). HPLC/MS (Method 1): V _y : 2.299 min; m/z = 627.4 (M+1) ⁺ ; ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.39 (d, J = 1.5 Hz, 1H), 7.75 (s, 1H), 7.49 (dtd, J = 15.0, 7.9, 1.6 Hz, 2H), 7.38 - 7.24 (m, 7H), 4.28 (d, J = 17.4 Hz, 1H), 4.16 (d, J = 17 .3 Hz, 1H), 3.94 (s, 3H), 3.45 (s, 3H), 2.79 (r, J = 6.8 Hz, 1H), 1.15 (dd, J = 10 .6, 6.8 Hz, 6H).

Example 20:

1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[(E)-2-[4-(trifluoromethoxy)phenyl]vinyl]-indazol-6-yl]methyleneamino]thiourea ( C-20 Table X):

Stage 1: 1H-indazol-6-ylmethanol:

To a stirred solution of methyl 1H-indazole-6-carboxylate (6 g) in THF (150 ml) was added a 1M solution of LiAlH ₄ in THF (34.7 ml) at 0°C. The reaction mixture was stirred at room temperature for 16 hours. The reaction mixture was quenched with NaOH solution and extracted with ethyl acetate. The crude product was filtered through celite and the organic layer was separated, washed with brine, dried over anhydrous Na ₂ SO ₄ and concentrated under reduced pressure to give the title compound (4.5 g). HPLC/MS (Method 1): V _y : 1.114 min; m/z = 149 (M+1).

Stage 2: 1H-indazole-6-carbaldehyde:

To a stirred solution of 1H-indazol-6-ylmethanol (1.5 g) in DCM (15 ml) and THF (15 ml) was added Dess-Martin periodinan (4.29 g) and stirred at room temperature for 16 hours. DCM was added and filtered through celite. The filtrate was evaporated in vacuo to give the title compound (1.3 g). HPLC/MS (Method 1): V _y : 1.290 min; m/z = 146 (M+1).

Stage 3: 3-iodo-1H-indazole-6-carbaldehyde:

To a stirred solution of 1H-indazole-6-carbaldehyde (2.4 g) in DMF (20 ml) was added K ₂ CO ₃ (5.6 g) and I ₂ (7.5 g). The reaction mixture was stirred at room temperature for 2 hours. Upon completion, the reaction mixture was diluted with sodium thiosulfate solution and stirred for 10 minutes, after which a solid precipitate formed. The solid was filtered and dried in vacuo to give the title compound (3.8 g). HPLC/MS (Method 1): V _y : 1.624 min; m/z = 271 (M-1).

Stage 4: 3-iodo-1-methyl-indazole-6-carbaldehyde:

To a stirred solution of 3-iodo-1H-indazole-6-carbaldehyde (3.2 g) in THF (50 ml) was added K ₂ CO ₃ (3.2 g) and MeI (2.5 g). The reaction mixture was stirred at room temperature for 16 hours. After completion, the reaction mixture was quenched with water, extracted with ethyl acetate, concentrated under reduced pressure, and the residue was subjected to silica gel flash column chromatography to give the title compound (1.2 g). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 10.16 (s, 1H), 8.37 (s, 1H), 7.80-7.47 (m, 2H), 4.18 (s, 3H).

Stage 5: 1-methyl-3-[(E)-2-[4-(trifluoromethoxy)phenyl]vinyl]indazole-6-carbaldehyde:

To a stirred solution of 3-iodo-1-methylindazole-6-carbaldehyde (0.15 g) in DMF (1 ml) was added 1-(trifluoromethoxy)-4-vinylbenzene (0.118 g) and DIPEA (0.141 g). The reaction mixture was washed with Ar for 10 minutes and Pd(OAc) ₂ (0.012 g) tri(o-tolyl)phosphine (0.048 g) was added. The reaction mixture was heated at 110°C for 24 hours. After completion, the reaction mixture was diluted with water and extracted with ethyl acetate, the organic extracts were dried over sodium sulfate, concentrated under reduced pressure, and the residue was subjected to silica gel flash column chromatography to give the title compound (0.04 g).

Step 6: 1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[(E)-2-[4-(trifluoromethoxy)phenyl]vinyl]indazol-6-yl]methyleneamino ]thiourea (C-20 of Table X):

A mixture of 1-methyl-3-[(E)-2-[4-(trifluoromethoxy)phenyl]vinyl]indazole-6-carbaldehyde (0.1 g) and 1-amino-3-(2-isopropylphenyl)thiourea (0 03 g) in EtOH (1 ml) was heated at 90°C for 2 hours. After 2 hours a solid precipitate formed. The solid was filtered, washed with cold EtOH and dried in vacuo to give the title compound (0.093 g). HPLC/MS (Method 1): V _y : 2.323 min; m/z = 538 (M+1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 10.02 (s, 1H), 8.29 (s, 1H), 8.17 (d, J = 8.6 Hz, 1H), 8.04 (s, 1H), 7.94 (d, J = 8.5 Hz, 1H), 7.90 - 7.81 (m, 2H), 7.58 (d, J = 16.6 Hz, 1H) , 7.53 (d, J = 16.6 Hz, 1H), 7.37 (m, J = 7.8, 3.9 Hz, 3H), 7.31 (s, 1H), 7.27 - 7.20 (m, 2H), 4.11 (s, 3H), 3.20 - 3.08 (m, 1H), 1.20 (d, J = 6.9 Hz, 6H).

Example 21:

(2Z)-3-(2-isopropylphenyl)-2-[(E)-[1-methyl-3-[(E)-2-[4-(trifluoromethoxy)phenyl]vinyl]-indazol-6-yl] methylenehydrazono]thiazolidin-4-one (C-21 of Table X):

1-(2-isopropylphenyl)-3-[(E)-[1-methyl-3-[(E)-2-[4-(trifluoromethoxy)phenyl]vinyl]-indazol-6-yl]methyleneamino]thiourea mixture (0.08 g), NaOAc (0.049 g) and methyl bromoacetate (0.046 g) in EtOH (5 ml) were heated at 40°C for 8 hours. After completion, the reaction mixture was diluted with water and extracted with ethyl acetate, the organic extracts were dried over sodium sulfate, concentrated under reduced pressure, and the residue was subjected to silica gel flash column chromatography to give the title compound (0.060 g). HPLC/MS (Method 1): V _y : 2.377 min; m/z = 578 (M+1). δ ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.46 (s, 1H), 8.25 (d, J = 8.6 Hz, 1H), 7.92 (s, 1H), 7, 90 - 7.83 (m, 2H), 7.73 (dd, J = 8.7, 1.2 Hz, 1H), 7.60 - 7.45 (m, 4H), 7.44 - 7, 32 (m, 3H), 7.28 (dd, J = 7.8, 1.4 Hz, 1H), 4.28 (d, J = 17.2 Hz, 1H), 4.16 (d, J = 17.3 Hz, 1H), 4.08 (s, 3H), 2.82 (r, J = 6.7 Hz, 1H), 1.17 (dd, J = 16.6, 6.8 Hz , 6H).

Example 22:

1-(2-isopropylphenyl)-3-[(E)-[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzothiazol-6-yl]methyleneamino]thiourea (C-22 of Table X) :

Stage 1: (6-bromo-1,2-benzothiazol-3-yl)methanol:

LiBH ₄ (0.069 g ). The reaction mixture was stirred at 0°C for 2 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (30 ml) and quenched with aq. 5% NaOH solution, extracted with ethyl acetate (40 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-22% ethyl acetate in heptane as mobile phase) to give (0.380 g) the title compound. HPLC/MS (Method 1) : V _y : 1.680 min; MS: m/z = 246 (M+1).

Stage 2: 6-bromo-3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzothiazole:

4-Trifluoromethoxyphenol (0.963 g) and triphenylphosphine ( 1.182 g). The reaction mixture continued to stir at 0° C. for 5 minutes and then DBAD (1.038 g) was added. Then the reaction mixture was stirred at 42°C for 2 hours in the microwave. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (50 ml) and extracted with ethyl acetate (60 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 8-10% ethyl acetate in heptane as mobile phase) to give (1 g) the title compound. HPLC/MS (Method 1) : V _y : 2.428 min; MS: m/z = 404 (M-1).

Step 3: 3-[[4-(trifluoromethoxy)phenoxy]methyl]-6-vinyl-1,2-benzothiazole:

A solution of 6-bromo-3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzothiazole (0.9 g) in dry toluene (10 ml) was washed with nitrogen for 10 minutes. Pd(dppf)Cl ₂ (0.098 g) was added to the solution and washing was continued for another 10 minutes. Tributylvinyltin (0.847 g) was added to the reaction mixture and heated at 110° C. for 3 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was cooled to room temperature, diluted with water (50 ml) and extracted with ethyl acetate (60 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 15-20% ethyl acetate in heptane as mobile phase) to give (0.660 g) the title compound. HPLC/MS (Method 1) : V _y : 2.391 min; MS: m/z = 352 (M+1).

Step 4: 3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzothiazole-6-carbaldehyde:

To a stirred solution of 3-[[4-(trifluoromethoxy)phenoxy]methyl]-6-vinyl-1,2-benzothiazole (0.660 g) in 1,4-dioxane (6 ml) and water (2 ml) under an inert atmosphere at 0°C was added OsO ₄ (0.007 g) and NaIO ₄ (0.880 g). The reaction mixture was stirred at room temperature for 3 hours. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water (20 ml), quenched with water. sodium sulfite solution (15 ml) and extracted with ethyl acetate (40 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-22% ethyl acetate in heptane as mobile phase) to give (0.170 g) the title compound. HPLC/MS (Method 1) : V _y : 2.108 min; MS: m/z = 354.4 (M+1).

Step 5: 1-(2-isopropylphenyl)-3-[(E)-[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzothiazol-6-yl]methyleneamino]thiourea (C-22 X tables):

A mixture of 3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzothiazole-6-carbaldehyde (0.17 g) and 1-amino-3-(2-isopropylphenyl)thiourea (0.101 g) in EtOH ( 2 ml) was heated at 85°C for 3 hours. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was cooled to room temperature, and the precipitated product was filtered through filter paper. The residue was washed with cold EtOH (2 ml), triturated with pentane (5 ml) and dried under reduced pressure to give (0.165 g) the title compound. HPLC/MS (Method 1) : V _y : 2.347 min; MS: m/z=545.1 (M+1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 11.97 (s, 1H), 10.12 (s, 1H), 8.63 (s, 1H), 8.31-8.19 (m, 3H), 7.41 - 7.29 (m, 4H), 7.28 - 7.15 (m, 4H), 5.63 (s, 2H), 3.14 (g, J = 6.9 Hz , 1H), 1.20 (d, J = 6.9 Hz, 6H).

Example 23: (2Z)-3-(2-isopropylphenyl)-2-[(E)-[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzothiazol-6-yl]methylenehydrazono]thiazolidine -4-one (C-23 of Table X):

1-(2-isopropylphenyl)-3-[(E)-[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzothiazol-6-yl]methyleneamino]thiourea mixture (0.115 g), NaOAc (0.035 g) and methyl bromoacetate (0.048 g) in EtOH (2.0 ml) were stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (15 ml) and extracted with ethyl acetate (20 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-25% ethyl acetate in heptane as mobile phase) to give (0.060 g) the title compound. HPLC/MS (Method 1) : V _y : 2.419 min; MS: m/z=585.2 (M+1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.50 (d, J = 7.1 Hz, 2H), 8.31 (d, J = 8.5 Hz, 1H), 7.95 (dd , J = 8.5, 1.3 Hz, 1H), 7.55 - 7.44 (m, 2H), 7.38 - 7.25 (m, 4H), 7.23 - 7.16 (m , 2H), 5.62 (s, 2H), 4.29 (d, J = 17.4 Hz, 1H), 4.17 (d, J = 17.3 Hz, 1H), 2.80 (d , J = 6.9 Hz, 1H), 1.16 (dd, J = 12.6, 6.8 Hz, 6H).

Example 24:

1-(2-isopropylphenyl)-3-[(E)-[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazol-6-yl]methyleneamino]thiourea (C-24 of Table X) :

Stage 1: (6-bromo-1,2-benzoxazol-3-yl)methanol:

LiBH ₄ (0.133 g ). The reaction mixture was stirred at 0°C for 2 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (20 ml), quenched with 5% NaOH solution and extracted with ethyl acetate (30 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 15-20% ethyl acetate in heptane as mobile phase) to give (0.8 g) the title compound. HPLC/MS (Method 1) : V _y : 1.587 min; MS: m/z = 229 (M+1).

Stage 2: 6-bromo-3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazole:

4-Trifluoromethoxyphenol (0.469 g) and triphenylphosphine ( 0.575 g). The reaction mixture was stirred at 0° C. for 5 minutes and then DBAD (0.505 g) was added. Then the reaction mixture was stirred at 35°C for 2 hours in a microwave. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (20 ml) and extracted with ethyl acetate (30 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 10-12% ethyl acetate in heptane as mobile phase) to give (1.5 g) the title compound. HPLC/MS (Method 1) : V _y : 2.296 min; MS: m/z=389 (M+1).

Stage 3: 3-[[4-(trifluoromethoxy)phenoxy]methyl]-6-vinyl-1,2-benzoxazole:

A solution of 6-bromo-3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazole (1.5 g) in dry toluene (15 ml) was washed with nitrogen for 10 minutes. Pd(dppf)Cl ₂ (0.170 g) was added to the solution and washing was continued for another 10 minutes. Tributylvinyltin (1.838 g) was added to the reaction mixture and heated at 105°C for 3 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was cooled to room temperature, diluted with water (40 ml) and extracted with ethyl acetate (50 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluting with 15-20% ethyl acetate in heptane as mobile phase) to give (1.4 g) the title compound. HPLC/MS (Method 1) : V _y : 1.929 min; MS: m/z = 332.1 (M+1).

Step 4: 3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazole-6-carbaldehyde:

To a stirred solution of 3-[[4-(trifluoromethoxy)phenoxy]methyl]-6-vinyl-1,2-benzoxazole (2 g) in 1,4-dioxane (16 ml) and water (4 ml) at 0°C OsO ₄ (0.030 g) and NaIO ₄ (2.795 g) were added under inert atmosphere. The reaction mixture was stirred at room temperature for 3 hours. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was diluted with water (50 ml), quenched with water. sodium sulfite solution (20 ml) and extracted with ethyl acetate (60 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 25-30% ethyl acetate in heptane as mobile phase) to give (0.6 g) the title compound, which was used without analysis.

Stage 5: 1-(2-isopropylphenyl)-3-[(E)-[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazol-6-yl]methyleneamino]thiourea (C-24 X tables):

A mixture of 3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazole-6-carbaldehyde (0.2 g) and 1-amino-3-(2-isopropylphenyl)thiourea (0.124 g) in EtOH ( 2 ml) was heated at 85°C for 3 hours. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was cooled to room temperature and the precipitated product was filtered through filter paper. The residue was washed with cold EtOH (2 ml), triturated with pentane (5 ml) and dried under reduced pressure to give (0.180 g) the title compound. HPLC/MS (Method 1) : V _y : 2.276 min; MS: m/z=529.3 (M+1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 11.99 (s, 1H), 10.19 (s, 1H), 8.44 (s, 1H), 8.27 (s, 1H), 8 .00 - 7.92 (m, 2H), 7.35 (dddd, J = 16.6, 15.0, 7.8, 1.6 Hz, 4H), 7.28 - 7.16 (m, 4H), 5.65 (s, 2H), 3.13 (r, J = 6.9 Hz, 1H), 1.19 (d, J = 6.9 Hz, 6H).

Example 25:

(2Z)-3-(2-isopropylphenyl)-2-[(E)-[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazol-6-yl]methylenehydrazono]thiazolidine-4- he (C-25 of Table X):

1-(2-isopropylphenyl)-3-[(E)-[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazol-6-yl]methyleneamino]thiourea mixture (0.125 g), NaOAc (0.029 g) and methyl bromoacetate (0.054 g) in EtOH (3 ml) were stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (15 ml) and extracted with ethyl acetate (20 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure. The crude product was purified by flash chromatography (eluted with 20-25% ethyl acetate in heptane as mobile phase) to give (0.11 g) the title compound. HPLC/MS (Method 1) : V _y : 2.335 min; MS: m/z = 569.3 (M+1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.56 (s, 1H), 8.11 - 8.05 (m, 2H), 7.93 (dd, J = 8.3, 1.1 Hz, 1H), 7.61 - 7.50 (m, 2H), 7.45 - 7.36 (m, 3H), 7.40 - 7.30 (m, 1H), 7.33 - 7, 24 (m, 2H), 5.71 (s, 2H), 4.35 (d, J = 17.3 Hz, 1H), 4.22 (d, J = 17.3 Hz, 1H), 2, 85 (r, J = 6.8 Hz, 1H), 1.21 (dd, J = 11.0, 6.8 Hz, 6H).

Example 26:

(E)-1-[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazol-6-yl]-N-[(2S,3R,4S,5S,6S)-3.4 ,5-trimethoxy-6-methyltetrahydropyran-2-yl]oxymethanimine (C-26 of Table X):

A mixture of 3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazole-6-carbaldehyde (0.15 g) and O-[(2S,3R,4S,5S,6S)-3.4, 5-trimethoxy-6-methyltetrahydropyran-2-yl]hydroxylamine (0.108 g) in EtOH (2 ml) was heated at 85° C. for 4 hours. The progress of the reaction was monitored by TLC. After completion, the reaction mixture was evaporated under reduced pressure and the crude product was purified by flash chromatography (eluted with 35-40% ethyl acetate in heptane as mobile phase) to give (0.045 g) the title compound. HPLC/MS (Method 1) : V _y : 2.179 min; MS: m/z = 539.25 (M-1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 8.60 (s, 1H), 8.02 (d, J = 8.4 Hz, 2H), 7.78 (dd, J = 8.2, 1.2 Hz, 1H), 7.38 - 7.31 (m, 2H), 7.27 - 7.19 (m, 2H), 5.66 (s, 2H), 5.56 (d, J = 2.1 Hz, 1H), 3.82 (dd, J = 3.2, 2.1 Hz, 1H), 3.60 - 3.50 (m, 1H), 3.47 - 3.36 ( m, 9H), 3.06 (t, J = 9.2 Hz, 1H), 1.17 (d, J = 6.2 Hz, 3H).

Example 27:

[(2S,3R,4S,5S,6S)-3,4,5-trimethoxy-6-methyltetrahydropyran-2-yl] N-[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2- benzoxazol-6-yl]carbamate (C-27 of Table X):

Stage 1: 3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazole-6-carboxylic acid:

_{KMnO 4} (0.328 g) and the reaction mixture was stirred at room temperature for 12 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was poured into ice water and filtered through a pad of cellite. The cellite layer was washed with water and the pH of the filtrate was adjusted to ~3-4 using aq. 1N HCl solution. The precipitated product was filtered through filter paper and dried under reduced pressure to give (0.360 g) the title compound. HPLC/MS (Method 1) : V _y : 1.947 min; MS: m/z = 352 (M-1).

Step 2: [[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazole-6-carbonyl]imino-lambda5-azanylidene]azanide:

Triethylamine (0.124 g) and ethyl chloroformate (0.143 g). The reaction mixture was stirred at room temperature for 2 hours and then NaN ₃ (0.068 g) in water (1 ml) was added and stirring continued at room temperature for 12 hours. The progress of the reaction was monitored by TLC. Upon completion, the reaction mixture was diluted with water (10 ml) and extracted with DCM (20 ml x 2). The combined organic extracts were dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure to give (0.3 g) the title compound which was used without analysis.

Step 3: [(2S,3R,4S,5S,6S)-3,4,5-trimethoxy-6-methyltetrahydropyran-2-yl]N-[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1 ,2-Benzoxazol-6-yl]carbamate (C-27 of Table X):

Mixture of [[3-[[4-(trifluoromethoxy)phenoxy]methyl]-1,2-benzoxazole-6-carbonyl]imino-lambda5-azanylidene]azanide (0.3 g) and (3R,4R,5S,6S) -3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-ol (0.164 g) in CH ₃ CN (3 ml) was heated at 85°C for 2 hours. The reaction mixture was then cooled to 0° C. and cesium carbonate (0.085 g) was added. The reaction mixture was further stirred for 12 hours at room temperature. The progress of the reaction was monitored by TLC. After completion, the solvent of the reaction mixture was concentrated under reduced pressure. The residue was purified by flash chromatography (eluted with 25-30% ethyl acetate in heptane as mobile phase) to give (0.026 g) the title compound. HPLC/MS (Method 1) : V _y : 2.127 min; MS: m/z = 557.3 (M+1). ¹ H NMR (500 MHz, DMSO-d ₆ ) δ 10.40 (s, 1H), 8.04 (s, 1H), 7.91 (d, J = 8.7 Hz, 1H), 7.47 (dd, J = 8.7, 1.6 Hz, 1H), 7.40 (d, J = 8.7 Hz, 2H), 7.27 (d, J = 9.1 Hz, 2H), 6 .06 (d, J = 2.1 Hz, 1H), 5.64 (s, 2H), 3.83 (t, J = 2.7 Hz, 1H), 3.69 (dt, J = 12, 4, 6.3 Hz, 1H), 3.57 (dd, J = 9.3, 3.2 Hz, 1H), 3.53 - 3.44 (m, 9H), 3.10-3.14 (t, 1H), 1.27 - 1.19 (m, 3H).

Example 64:

Synthesis of 6-[[[(2-isopropylanilino)methylsulfanylmethylene]hydrazono]methyl]-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (C-64 of Table X):

To a mixture of 6-[[(2-isopropylphenyl)carbamothioylhydrazono]methyl]-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (0.15 g) in ethanol (10 ml) was added sodium acetate (0.075 g) and methyl iodide (0.18 g). The mixture was heated at 68°C for 4 hours. The mixture was then cooled to room temperature, diluted with water and extracted with ethyl acetate. The ethyl acetate extracts were washed with brine, dried over anhydrous sodium sulfate and evaporated under reduced pressure. The resulting residue was purified by silica gel flash column chromatography using an ethyl acetate/heptane gradient as eluent to give the title compound (0.06 g). HPLC/MS (Method 1): V _y : 2.48 min; m/z = 569 (M+1); ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.85 (s, 1H), 8.61 (s, 1H), 8.40 (d, J = 8.5 Hz, 1H), 8.26 (s , 1H), 7.85 (dd, J = 8.5, 1.2 Hz, 1H), 7.81 - 7.74 (m, 2H), 7.72 (d, J = 4.4 Hz, 1H), 7.34 (m, 3H), 7.23 (m, 3H), 4.18 (s, 3H), 3.29 (m, 1H), 2.48 (s, 3H), 1, 29 (d, J = 6.9 Hz, 6H).

Example 65:

Synthesis of 6-[[[3-(2-isopropylphenyl)thiazolidin-2-ylidene]hydrazono]methyl]-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (C-65 of Table X) :

Carbonate potassium (0.1 g) and 1-bromo-2-chloroethane (0.12 g). The mixture was heated at 65°C for 3 hours. The mixture was cooled to room temperature, diluted with brine and extracted with ethyl acetate. The ethyl acetate extracts were washed with brine, dried over sodium sulfate and concentrated under reduced pressure, and the resulting residue was subjected to flash silica gel column chromatography to give the title compound (0.1 g). HPLC/MS (Method 1): V _y : 2.34 min; m/z = 581 (M+1); ¹ H NMR (300 MHz, CDCl ₃ ) δ 8.85 (s, 1H), 8.40 - 8.24 (m, 2H), 7.84 - 7.69 (m, 3H), 7.62 ( s, 1H), 7.45 - 7.38 (m, 1H), 7.38 - 7.30 (m, 1H), 7.30 - 7.20 (m, 4H), 4.14 (s, 3H), 4.11 - 4.00 (m, 1H), 4.00 - 3.85 (m, 1H), 3.45 - 3.26 (m, 2H), 3.12 (m, 1H) , 1.25 (dd, J = 15.0, 6.9 Hz, 6H).

Example 66:

Synthesis of 6-[[[3-(2-isopropylphenyl)-1,3-thiazinan-2-ylidene]hydrazono]methyl]-1-methyl-N-[4-(trifluoromethoxy)phenyl]indazole-3-carboxamide (C -66 Table X):

Potassium carbonate (0.2 g) and 1- bromine-3-chloropropane (0.103 g). The mixture was heated at 66°C for 12 hours. The reaction mixture was then cooled to room temperature, diluted with brine and extracted with ethyl acetate. The organic extracts were washed with brine, dried over sodium sulfate and concentrated under reduced pressure. The resulting residue was subjected to flash silica gel column chromatography using an ethyl acetate/heptane gradient as eluent to give the title compound (0.09 g). HPLC/MS (Method 1): V _y : 2.46 min; m/z = 595 (M+1); ¹ H NMR (500 MHz, CDCl ₃ ) δ 8.83 (s, 1H), 8.31 (d, J = 8.5 Hz, 1H), 8.14 (s, 1H), 7.79 - 7 .74 (m, 2H), 7.72 (dd, J = 8.5, 1.1 Hz, 1H), 7.59 (s, 1H), 7.39 (dd, J = 7.8, 1 .6 Hz, 1H), 7.33 (m, 1H), 7.29 - 7.24 (m, 1H), 7.23 (d, J = 8.6 Hz, 2H), 7.19 (dd , J = 7.7, 1.4 Hz, 1H), 4.12 (s, 3H), 3.84 - 3.62 (m, 1H), 3.54 (m, 1H), 3.11 ( m, 3H), 2.36 (m, 2H), 1.23 (d, J = 6.9 Hz, 6H).

Examples of the compound of formula I shown in Table X were prepared using a method similar to the above examples, or by modifying the examples mentioned above or their intermediates, or using a method similar to the methods mentioned in the general procedure.

Table X: No. Ar-Q

R ^one HPLC/MS AT _at
min C-1

528.9
(Method 1) 2.20 C-2

568.3
(Method1) 2.33 C-3

542.3
(Method 1) 2.31 C-4

582.4
(Method 1) 2.36 C-5

-- -- C-6

584
(Method 2) 1.25 C-7

553.3
(Method 1) 2.22 C-8

595.1
(Method 1) 2.32 C-9

538.2
(Method 1) 2.25 C-10

541.3
(Method 1) 2.21 C-11

581.3
(Method 1) 2.24 C-12

554.2
(Method 1) 2.27 C-13

596.2
(Method 1) 2.34 C-14

596.2
(Method 1) 2.39 C-15

541.2
(Method 1) 2.11 C-16

583.6
(Method 1) 2.22 C-17

573.2
(Method 1) 2.23 C-18

587.2
(Method 1) 2.15 C-19

627.4
(Method 1) 2.29 C-20

538
(Method 1) 2.32 C-21

578
(Method 1) 2.37 C-22

545.1
(Method 1) 2.34 C-23

585.2
(Method 1) 2.41 C-24

529.3
(Method 1) 2.27 C-25

569.3
(Method 1) 2.33 C-26

539.2
(Method 1) 2.17 C-27

557.3
(Method 1) 2.12 C-28

554.3
(Method 1) 2.26 C-29

590.3
(Method 1) 2.13 C-30

630.6
(Method 1) 2.11 C-31

602.5
(Method 1) 1.97 C-32

618.2
(Method 1) 1.93 C-33

556.2
(Method 1) 2.36 C-34

598.3
(Method 1) 2.4 C-35

570.3
(Method 1) 2.31 C-36

612
(Method 1) 2.65 C-37

528.3
(Method 1) 2.12 C-38

568.3
(Method 1) 2.16 C-39

592.3
(Method 1) 2.36 C-40

632.4
(Method 1) 2.43 C-41

554.3
(Method 1) 2.34 C-42

596.3
(Method 1) 2.38 C-43

567.2
(Method 1) 2.27 C-44

609.3
(Method 1) 2.32 C-45

603.2
(Method 1) 2.22 C-46

645.1
(Method 1) 2.32 C-47

631.3
(Method 1) 2.34 C-48

671.3
(Method 1) 2.39 C-49

671.1
(Method 1) 2.46 C-50

583.1
(Method 1) 2.40 C-51

623.1
(Method 1) 2.42 C-52

623.1
(Method 1) 2.46 C-53

528.1
(Method 1) 2.16 C-54

566.1
(Method 1) 2.20 C-55

611.2
(Method 2) 1.37 C-56

597.2
(Method 2) 1.26 C-57

570.2
(Method 2) 1.31 C-58

598.2
(Method 2) 1.41 C-59

586
(Method 2) 1.34 C-60

557.1
(Method 2) 1.36 C-61

585.2
(Method 2) 1.39 C-62

609.2
(Method 2) 1.48 C-63

663.1
(Method 2) 1.51 C-64

569.2
(Method 1) 2.48 C-65

595.6
(Method 1) 2.46 C-66

581.2
(Method 1) 2.37

Biological examples:

Example B1: Effect on yellow fever mosquito (Aedes aegypti)

To assess the control of the yellow fever mosquito (Aedes aegypti), the assay block consisted of 96-well microplates containing 200 µl of tap water per well and 5-15 freshly hatched A. aegypti larvae.

The active compounds were formulated using a solution containing 75% (v/v) water and 25% (v/v) DMSO. Different concentrations of the formulated compounds or mixtures were sprayed onto the insect diet at 2.5 μl using a custom designed micro-nebulizer with two repeats.

After application, microplates were incubated at 28 + 1°C, RH 80 + 5% for 2 days. Then visually assessed the mortality of larvae.

In this study, compounds C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-12, C-13, C-14, C- 15, C-19, C-25, C-30, C-38, C-39, C-40, C-41, C-42, C-43, C-44, C-46, C-51, C-57 and C-58 at 800 p.m. showed at least 75% mortality compared to untreated controls.

Example B2: Action on orchid thrips (dichromothrips corbetti)

The adult Dichromothrips corbetti used for the bioassay was obtained from a colony that is continuously maintained in the laboratory. For the purposes of the study, the test compound was diluted with 1:1 acetone:water (v:v), plus Kinetic® HV at a concentration of 0.01 v/v.

The activity of each compound against thrips was evaluated using the flower dip technique. All petals of individual intact orchid flowers were immersed in the treatment solution and allowed to dry in Petri dishes. The treated petals were placed in a separate sealed plastic container along with about 20 adult thrips. All the studied arenas were kept under continuous lighting and a temperature of about 28 °C during the entire period of the study. After 3 days, the number of live thrips on each petal was counted. The percentage of mortality was recorded 72 hours after treatment.

In this study, compounds C-1, C-2, C-3, C-4, C-6, C-12, C-13, C-14, C-15, C-19, C-28, C- 30, C-37, C-38, C-39, C-40, C-41, C-42, C-43, C-44, C-45, C-46, C-51, C-52 and C-56 at 500 m.h. showed at least 75% mortality compared to untreated controls.

Example B3: Action on the cotton weevil (Anthonomus grandis)

To assess the control of the cotton weevil (Anthonomus grandis), the assay unit consisted of 96-well microplates containing an insect diet and 5-10 A. grandis eggs.

Compounds were formulated using a solution containing 75% vol./about. water and 25% vol./about. DMSO. Different concentrations of the formulated compounds were sprayed into insect diets at 5 μl using a custom designed micro-nebulizer with two repeats.

After application, the microplates were incubated at a temperature of about 25 + 1 °C and a relative humidity of about 75 + 5% for 5 days. Then visually assessed the mortality of eggs and larvae.

In this study, compounds C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-12, C-15, C-17, C- 18, C-19, C-22, C-23, C-24, C-25, C-28, C-29, C-30, C-33, C-34, C-37, C-38, C-39, C-40, C-41, C-42, C-43, C-44, C-45, C-46, C-50, C-51, C-55, C-56, C- 57, C-58 and C-60 at 800 p.m. showed at least 75% mortality compared to untreated controls.

Example B4: Effect on silver whitefly (Bemisia argentifolii) (adults)

The active compounds were formulated using a Tecan liquid manipulator in 100% cyclohexanone as a 10,000 ppm solution, which was filled into tubes. Solution 10000 m.h. serially diluted in 100% cyclohexanone to give intermediate solutions. These served as stock solutions for which final dilutions were made with Tecan in 50% acetone : 50% water (v/v) in 5 or 10 ml glass bottles. The non-ionic surfactant (Kinetic®) was included in the solution in a volume of 0.01% (v/v). The bottles were then inserted into an automated electrostatic sprayer equipped with a plant/insect spray nozzle.

Cotton plants at the cotyledon stage (one plant per pot) were sprayed using an automated electrostatic plant sprayer equipped with a spray nozzle. The plants were dried in a sprayer fume hood and then removed from the sprayer. Each pot was placed in a plastic cup and about 10 to 12 adult whiteflies (about 3-5 days old) were introduced. Insects were collected using an aspirator and a non-toxic Tygon® tubing connected to a barrier pipette tip. The tip containing the collected insects was then gently inserted into the soil containing the plant to be treated, allowing the insects to crawl out of the tip to reach the leaves to feed. The cups were covered with a reusable shielding lid. The test plants were kept in a grow room at a temperature of approximately 25°C and a relative humidity of approximately 20-40% for 3 days, avoiding direct exposure to fluorescent light (24 hours photoperiod) to prevent heat trapping inside the dish. Mortality was assessed 3 days after treatment compared to untreated control plants.

In this study compounds C-3, C-6, C-12, C-13, C-14, C-28, C-39, C-40, C-42, C-55 and C-56 at 300 m .h. showed at least 75% mortality compared to untreated controls.

Example B5: Action on tobacco leaflet (Heliothis virescens)

To assess the control of the tobacco leafworm (Heliothis virescens), the assay unit consisted of 96-well microplates containing an insect diet and 15-25 H. virescens eggs.

Compounds were formulated using a solution containing 75% vol./about. water and 25% vol./about. DMSO. Various concentrations of the formulated compounds were sprayed onto the insect diet at 10 μl using a custom designed micro-nebulizer with two repeats.

After application, the microplates were incubated at a temperature of about 28 + 1 °C and a relative humidity of about 80 + 5% for 5 days. Then visually assessed the mortality of eggs and larvae.

In this study, compounds C-1, C-2, C-3, C-6, C-7, C-8, C-12, C-13, C-14, C-15, C-17, C- 18 C-19, C-22, C-23, C-24, C-25, C-29, C-30, C-33, C-34, C-37, C-38, C-39, C -40, C-41, C-42, C-43, C-44, C-45, C-46, C-47, C-50, C-51, C-55, C-56, C-57 , C-58 and C-61 at 800 m.h. showed at least 75% mortality compared to untreated controls.

Example B6: Action on cabbage moth (Plutella xylostella)

The active compound was dissolved at the desired concentration in a 1:1 (v:v) mixture of distilled water:acetone. A surfactant (Kinetic® HV) was added in an amount of 0.01% (v/v). The test solution was prepared on the day of use.

Cabbage leaves were immersed in the test solution and dried in air. The treated leaves were placed in Petri dishes lined with damp filter paper and ten third stage larvae were introduced. Mortality was assessed 72 hours after treatment. Nutritional damage was also recorded using a 0-100% scale.

In this study, compounds C-1, C-2, C-3, C-4, C-6, C-7, C-8, C-12, C-13, C-14, C-15, C- 18 C-19, C-22, C-23, C-24, C-25, C-28, C-30, C-34, C-37, C-38, C-39, C-40, C -41, C-42, C-43, C-44, C-45, C-46, C-50, C-51, C-52, C-55, C-56, C-57, C-58 , C-60 and C-61 at 500 m.h. showed at least 75% mortality compared to untreated controls.

Example B7: Action on the southern armyworm (Spodoptera eridania), 2nd stage larvae

The active compounds were formulated using a Tecan liquid manipulator in 100% cyclohexanone as a 10,000 ppm solution, which was filled into tubes. Solution 10000 m.h. serially diluted in 100% cyclohexanone to give intermediate solutions. These served as stock solutions for which final dilutions were made with Tecan in 50% acetone : 50% water (v/v) in 10 or 20 ml glass bottles. The non-ionic surfactant (Kinetic®) was included in the solution in a volume of 0.01% (v/v). The bottles were then inserted into an automated electrostatic sprayer equipped with a plant/insect spray nozzle.

Lima bean plants (cultivar Sieva) were grown 2 plants per pot and selected for treatment at the 1st true leaf stage. The test solutions were sprayed onto the leaves using an automated electrostatic sprayer equipped with a spray nozzle. Plants were dried in a sprayer fume hood and then removed from the sprayer. Each pot was placed in perforated plastic bags with a zipper. Approximately 10 - 11 cutworm larvae were placed in a bag and the bags closed with a zipper. The test plants were kept in a growth room at a temperature of about 25°C and a relative air humidity of about 20-40% for 4 days, avoiding direct exposure to fluorescent light (24-hour photoperiod) to prevent heat trapping inside the bags. Mortality and reduced feeding were assessed 4 days after treatment compared to untreated control plants.

In this study, compounds C-1, C-3, C-6, C-7, C-8, C-12, C-13, C-14, C-15, C-17, C-18, C- 19, C-22, C-23, C-38, C-39, C-40, C-42, C-43, C-44, C-45, C-46, C-51, C-55, C-57 and C-58 at 300 p.m. showed at least 75% mortality compared to untreated controls.

Claims (38)

1. Compound of formula I

where A ¹ represents CR ^A ; A ² is N or CR ^B ; A ³ is CR ^B1 ; W is O, S(=O) _m or NR ⁶ ; R ^A , R ^B and R ^B1 are independently H, halogen; Q is -C(R ⁴ R ⁵ )-O-, -S(=O) _m -C(R ⁷ R ⁸ )-, -N(R ² )-C(R ⁹ R ¹⁰ )-, -N (R ² )-C(=O)- or -C(R ¹⁷ )=C(R ¹⁸ )-; where Ar is attached on either side to Q; m is 0, 1 or 2; R ² represents H, C ₁ -C ₆ -alkyl; R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹⁷ , R ¹⁸ are the same or different and are H, C ₁ -C ₆ alkyl; R ⁶ is H, C ₁ -C ₆ -alkyl, unsubstituted or substituted with halogen, or -CH ₂ -phenyl; Ar is phenyl or a 5- or 6-membered hetaryl which is unsubstituted or substituted by R ^Ar where R ^Ar represents C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkoxy, where alkyl, alkoxy substituents are unsubstituted or substituted by halogen, R ¹ is a substituent of the formula YZTR ¹¹ or YZTR ¹² ; where Y is -CR ^ya =N-, where N is attached to Z; -NR ^yc -C(=O)–, where C(=O) is attached to Z; or Z is a single bond; -NR ^zc -C(=S)-, where C(=S) is attached to T; -N=C(SR ^za )-, where T is attached to a carbon atom; -O-C(=O)-, where T is attached to a carbon atom; or T is O, N or NR ^T ; R ¹¹ is phenyl, hetaryl, carbonyl-hetaryl, hetaryl-C ₁ -C ₄ -alkyl or hetaryloxy-C ₁ -C ₄ -alkyl, where the phenyl rings are unsubstituted or substituted by R ^g and where hetaryl is 5- or 6 -membered monocyclic hetaryl, which contains in the ring one oxygen atom and one sulfur atom; R ¹² is a radical of formula A ¹

where # denotes the point of attachment to T; R ¹²¹ , R ¹²² , R ¹²³ are C ₁ -C ₆ alkoxy; R ¹²⁴ is C ₁ -C ₆ alkyl; and where R ^ya represents H; R ^yc , R ^zc are H; ^RT is H; R ^za is C ₁ -C ₆ alkyl; R ^g is C ₁ -C ₆ alkyl. 2. A pesticidal composition comprising a pesticidally effective amount of a compound of formula (I) according to claim 1 and at least one inert liquid or solid carrier. 3. Pesticide composition according to claim 2, characterized in that it contains an additional active substance. 4. A method for the destruction or control of invertebrate pests, characterized in that the method includes bringing said pests or their food, environment or habitat into contact with a pesticidally effective amount of at least one compound of formula (I) according to p. 1. 5. A method for protecting cultivated plants from attack or infestation by invertebrate pests, characterized in that the method comprises bringing the plants or soil or water where the plants grow into contact with a pesticidally effective amount of at least one compound of formula (I) according to claim 5. one. 6. The use of a compound of formula (I) according to claim 1 for protecting cultivated plants from attack or infestation by invertebrate pests.