KR100447361B1 - Inhibitors and methods of inhibiting harmful fungi - Google Patents

Abstract

a) at least one p-hydroxyaniline derivative of the general formula (I)

b) at least one amide compound of the general formula II

Composition for inhibiting harmful fungi, which is contained in a solid or liquid carrier, and

A method of inhibiting harmful fungi using compositions of this type is described.

<Formula I>

<Formula II>

A-CO-NR ⁸ -R ⁹

Wherein the substituents have the meanings mentioned in the detailed description.

Description

Inhibitors and methods of inhibiting harmful fungi

The present invention relates to inhibitory compositions of harmful fungi and methods of inhibiting harmful fungi using such forms of compositions.

The p-hydroxyaniline derivatives of formula I below are known to be used as active compounds in bactericidal compositions.

[Formula I]

Thus, compounds of formula I are disclosed in European Patent Application No. 0 339 481, European Patent Application No. 0 653 418 and German Patent Application Nos. 195 04 599.8 and 195 40 970.1.

European Patent Application 545 099 discloses an analide compound of the formula

Wherein A is a phenyl substituted at the 2-position by methyl, trifluoromethyl, chlorine, bromine or iodine, or a constant aromatic which may be unsubstituted or substituted by methyl, chlorine, or trifluoromethyl or Is a non-aromatic heterocyclic group, R is a constant aliphatic or cycloaliphatic group which may be unsubstituted or substituted by halogen, or unsubstituted or C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C _1- C ₄ -alkylthio, or phenyl substituted by halogen. These compounds can be used to inhibit Botrytis.

European patent application 589 391 discloses an analogue compound of the same formula wherein A is a ring group of the formula:

Wherein R ¹ is hydrogen or C ₁ -C ₄ -alkyl, R ² is halogen, or C ₁ -C ₄ -alkyl, and R ³ is C ₁ -C ₄ -alkyl or C ₁ -C ₄ -halo Alkyl, n is 1 or 2 and R has essentially the meanings indicated above. These compounds can also be used for the treatment of filamentous fungi.

WO 93/11117 discloses compounds of the general formula

Wherein Q is C ₁ -C ₃ -alkyl, C ₂ -C ₃ -alkenyl, C ₂ -C ₃ -alkynyl,-(CH ₂ ) _m CH = or-(CH ₂ ) _m -X- (CH ₂ ) _m- ,

n is 0 or 1,

m is each independently 0, 1, 2, or 3,

Each X is independently O or S,

R ¹ is a constant alicyclic group,

R ² is hydrogen, fluorinated methyl, methyl, ethyl, C ₂ -C ₆ -alkenyl, C ₃ -C ₆ -cycloalkyl, phenyl, alkylthioalkyl, alkoxyalkyl, haloalkylthioalkyl, haloalkoxyalkyl or hydride Oxyalkyl,

R ³ is halomethyl, halomethoxy, methyl, ethyl, halogen, cyano, methylthio, nitro, aminocarbonyl or aminocarbonylmethyl,

R ⁴ is hydrogen, halogen or methyl,

R ⁵ , R ⁶ and R ⁷ are each independently of each other hydrogen, halogen, cyano, C ₁ -C ₆ -alkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -alkynyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₃ -C ₄ -cycloalkyl and halomethoxy. These compounds are bactericidally active but alone are wide enough and do not have a satisfactory spectrum of action.

However, it is known that when the active compounds are used alone, their action can only be observed temporarily, ie after a certain time, the regrowth of the fungus.

It is an object of the present invention to increase the action of the composition to inhibit harmful fungi.

We have found that this object is achieved when the indicated types of compounds are used in combination.

Therefore, the present invention

a) at least one p-hydroxyaniline derivative of the general formula (I)

b) at least one amide compound of the general formula II

The present invention relates to a composition for inhibiting harmful fungi, which is contained in a solid or liquid carrier.

<Formula I>

[Formula II]

A- CO- NR ⁸ -R ⁹

Where

R ¹ may be hydrogen, some or all of which may be halogenated and / or an alkoxy group, a haloalkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkenyl group (the cyclo group is partially 1, 2 or 3 halogen atoms, an alkyl group and / Or an alkoxy group, which may carry one or two of the alkyls, some or all of which may be halogenated and / or substituents of nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy and alkylthio Aryl which may carry one, two or three of them,

Some or all may be halogenated and / or alkyl groups, haloalkyl groups, alkoxy groups, haloalkoxy groups and aryl (some or all may be halogenated and / or nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy and alkyl Cycloalkyl or cycloalkenyl, which may involve one, two, three, four or five of the substituents of thio)

Some or all may be halogenated and / or alkyl groups, haloalkyl groups, alkoxy groups, haloalkoxy groups and aryl (some or all may be halogenated and / or nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy and alkyl C ₆ -C ₁₅ -bicycloalkyl group or C which may involve one, two, three, four or five of the substituents of thio) _{Is a 7-} C ₁₅ -bicycloalkenyl group

R ² and R ³ are independently of each other halogen, alkyl, haloalkyl, alkoxy or haloalkoxy,

Z is H or R ^4- (CO)-,

R ⁴ may be part or all halogenated and / or alkoxy, haloalkoxy, alkylthio, cycloalkyl, cycloalkenyl or aryl (aromatic group is nitro group, cyano group, halogen group, alkyl group, haloalkyl group, alkoxy group, halo Alkyl group or alkenyl group which may carry one of alkoxy group and alkylthio group)

A cycloalkyl group or cycloalkenyl group which may carry one, two or three of halogen, alkyl, haloalkyl and alkoxy groups,

Aryl which may be partially or fully halogenated and / or may carry one, two or three of nitro groups, cyano groups, alkyl groups, haloalkyl groups, alkoxy groups, haloalkoxy groups and alkylthio groups,

OR ⁵ or NR ⁶ R ⁷ ,

R ⁵ may be partially or fully halogenated and / or alkoxy group, haloalkoxy group, alkylthio group, cycloalkyl group, cycloalkenyl group or aryl group (aromatic group nitro group, cyano group, halogen group, alkyl group, haloalkyl group, alkoxy Alkyl group or alkenyl group, which may be accompanied by one, two or three of the group, haloalkoxy group and alkylthio group, or

A cycloalkyl group or a cycloalkenyl group which may carry one, two or three of a halogen group, an alkyl group, a haloalkyl group and an alkoxy group or

Aryl which may be partially or fully halogenated and / or may carry one, two or three of nitro groups, cyano groups, alkyl groups, haloalkyl groups, alkoxy groups, haloalkoxy groups and alkylthio groups,

R ⁶ may be partially or completely halogenated and / or alkylthio group, cycloalkyl group, cycloalkenyl group or aryl group (aromatic group is nitro group, cyano group, halogen group, alkyl group, haloalkyl group, alkoxy group, haloalkoxy group and Alkyl group or alkenyl group, which may carry one of two, three, or three of the alkylthio groups, or

Cycloalkyl or cycloalkenyl groups which may carry one, two or three of halogen, alkyl, haloalkyl and alkoxy groups,

Some or all are aryl groups which may be halogenated and / or may carry one, two or three of nitro groups, cyano groups, alkyl groups, haloalkyl groups, alkoxy groups, haloalkoxy groups and alkylthio groups,

R ⁷ is hydrogen or alkyl,

A is suitably aryl which may have one, two or three substituents independently selected from each other from alkyl, halogen, CHF ₂ , CF ₃ , alkoxy, haloalkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl Aromatic or non-aromatic, 5- or 6-membered heterocycle having 1 to 3 heteroatoms selected from the group or O, N and S,

R ⁸ is hydrogen, alkyl or alkoxy,

R ⁹ is suitably independently of each other one, two or three selected from phenyl, alkenyl, alkynyl, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy and cycloalkenyloxy Having a substituent of, and may be additionally substituted with one or more halogen atoms,

Aliphatic and cycloaliphatic groups may be partially or wholly halogenated, and / or cycloaliphatic groups are substituted with one, two or three alkyl groups, and phenyl groups are partially one to five halogen atoms and / or alkyl, haloalkyl, alkoxy, A hetero atom having 1 to 3 substituents independently selected from haloalkoxy, alkylthio and haloalkylthio, suitably with an amide phenyl group substituted by one or more alkyl groups and / or selected from O and S A phenyl group or a cycloalkyl group fused to a saturated 5-membered ring which may have

In the present invention, halogen is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.

The term "alkyl" includes straight and branched alkyl groups. In this case, they are preferably straight or branched C ₁ -C ₁₂ -alkyl groups, in particular C ₁ -C ₈ -alkyl groups, more preferably C ₁ -C ₆ -alkyl groups and particularly preferably C ₁ -C ₄ Or a C ₁ -C ₃ -alkyl group. Examples of alkyl groups include, in particular, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1 , 2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 1-ethylpentyl, 2- Alkyl such as ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl.

Haloalkyl is an alkyl group as defined above which is partially or wholly halogenated by one or more halogen atoms, in particular fluorine or chlorine. It preferably has one, two or three halogen atoms, with difluoromethane or trifluoromethyl groups being particularly preferred.

The above descriptions about alkyl groups and haloalkyl groups apply equally to alkyl groups and haloalkyl groups such as alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl and alkylsulfonyl.

Alkyl groups include straight chain and branched alkenyl groups. In this case, they are preferably straight or branched C ₂ -C ₁₂ -alkenyl groups and in particular C ₂ -C ₆ -alkenyl groups. Examples of alkenyl groups include 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4- Pentenyl, 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-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4- Hexenyl, 5-hexenyl, 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-2-butenyl, 1 , 2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2 -Butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2- Methyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl, especially 2-prop Phenyl, 2-butenyl, 3-methyl-2-butenyl and 3-methyl-2-pentenyl.

Alkyl groups may be halogenated by some or all of one or more halogen atoms, in particular fluorine and chlorine. Preferably it has 1, 2, or 3 halogen atoms.

Alkynyl groups include straight or branched alkynyl groups. In this case, they are preferably straight or branched C ₂ -C ₁₂ -alkynyl groups and especially C ₂ -C ₆ -alkynyl groups. Examples of alkynyl groups are 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3- Butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1,1-dimethyl-2-propenyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl , 4-alkynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl -4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,2-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2- Dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1 -Methyl-2-propenyl.

The above description of alkenyl groups and their halogen substituents and alkenyl groups applies equally to alkenyloxy and alkynyloxy.

The cycloalkyl group is preferably a C ₃ -C ₇ -cycloalkyl group such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. When the cycloalkyl group is substituted, it preferably has 1, 2 or 3 C ₁ -C ₄ -alkyl groups as substituents.

Cycloalkenyl is preferably a C ₄ -C ₇ -cycloalkenyl group such as cyclobutenyl, cyclopentenyl or cyclohexenyl. When the cycloalkenyl group is substituted, it preferably has 1, 2 or 3 C ₁ -C ₄ -alkyl groups as substituents.

The cycloalkoxy group is preferably a C ₅ -C ₆ -cycloalkoxy group, such as cyclopentyloxy or cyclohexyloxy. When the cycloalkoxy group is substituted, it preferably has 1, 2 or 3 C ₁ -C ₄ -alkyl groups as substituents.

The cycloalkenyloxy group is preferably a C ₅ -C ₆ -cycloalkenyloxy group such as cyclopentenyloxy or cyclohexenyloxy. When the cycloalkenyloxy group is substituted, it preferably has 1, 2 or 3 C ₁ -C ₄ -alkyl groups as substituents.

Bicycloalkyl is preferably decalinyl, indanyl, hydrindanyl, boryl, pinanyl, caranyl, norbornyl and bicyclo [2.2.2] octanyl.

Bicycloalkenyl may have one or two double bonds, preferably indenyl, pineneyl, norbornenyl and norbornadienyl.

Aryl is preferably phenyl.

Hetaryl is preferably a 5-membered or 6-membered aromatic heterocycle having one, two or three heteroatoms independently selected from N, O and S. In this case, in particular, pyridinyl, pyrimidinyl, thiazolyl, pyrazolyl, oxazolyl, isoxazolyl, isothiazolyl, imidazolyl, pyrrolyl, furanyl, thienyl or triazolyl.

Heterocyclyl is preferably a 5- or 6-membered, saturated or unsaturated heterocycle having one, two or three heteroatoms independently selected from N, O and S. In this case, especially the dihydro, tetrahydro and hexahydro derivatives mentioned under the "hetaryl" geometry. Pyrrolidinyl, tetrahydrofuranyl, imidazolidinyl, pyrazolidinyl, oxazolidinyl, isoxoxazolidinyl, thiazolidinyl, isothiazolidinyl, piperidinyl or morpholinyl are preferred.

When A in formula II is a phenyl group, it may have one, two or three of the aforementioned substituents at any desired position. Preferably these substituents are independently selected from each other from alkyl, difluoromethyl, trifluoromethyl and halogen, in particular chlorine, bromine and iodine. Especially preferably, the phenyl group has one substituent in the 2-position.

When A is a 5-membered heterocycle, it is a furyl, thiazolyl, pyrazolyl, imidazolyl, oxazolyl, thienyl, triazolyl or thiadiazolyl group or their corresponding dihydro or tetrahydro derivatives. Thiazolyl group or pyrazolyl group is preferable.

In the case where A is a 6-membered heterocycle, a pyridyl group or a group of the following formula is preferable in this case.

Wherein one of the X and Y groups is O, S, or NR ²⁰ (R ²⁰ is H or alkyl), and the other is CH ₂ , S, SO, SO ₂ or NR ²⁰ . The dashed line means suitably double bonds may be present.

In particular, preferably the 6-membered aromatic heterocycle is a pyridyl group, in particular a 3-pyridyl group or a group of the following formula.

Wherein X is CH ₂ , S, SO, SO ₂ .

The aforementioned heterocyclic groups may suitably have one, two or three of the abovementioned substituents, which substituents are preferably independently selected from alkyl, halogen, difluoromethyl or trifluoromethyl do.

Especially preferably, A is a group of the following formula.

Wherein R ¹⁰ , R ¹¹ , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are independently of each other hydrogen, alkyl, in particular methyl, halogen, in particular chlorine, CHF ₂ or CF ₃ .

The R ⁸ group of formula II is preferably a hydrogen atom.

The R ⁹ group of formula II is preferably a phenyl group.

Preferably, the general formula R ⁹ groups have one or more substituents, particularly preferably in the 2-position. Preferably the substituent (or substituents) is selected from alkyl, cycloalkyl, cycloalkenyl, halogen or phenyl.

Substituents for the R ⁹ group may be substituted in order. Aliphatic or cycloaliphatic substituents can in this case be partially or fully halogenated, in particular fluorinated or chlorinated. Preferably they have one, two or three fluorine or chlorine atoms. If the substituent of the R ⁹ group is a phenyl group, it may be substituted by one to three halogen atoms, especially chlorine atoms and / or groups preferably selected from alkyl and alkoxy. The phenyl group is particularly preferably substituted at the p-position with a halogen atom, ie a particularly preferred substituent of the R ⁹ group is a p-halosubstituted phenyl group. R ⁹ groups may also be fused to saturated 5-membered rings, some of which may have from 1 to 3 alkyl substituents. R ⁹ is then, for example, indanyl, thiindanil or oxindanil. In particular, indanyl or 2-oxininyl bonded to the nitrogen atom via the 4-position is preferred.

According to a preferred embodiment, the composition of the present invention contains a compound of formula I wherein Z is hydrogen as p-hydroxyaniline derivative.

According to another preferred embodiment, the composition of the present invention contains a compound of general formula (I).

Wherein Z is hydrogen,

R ¹ may be partially or fully halogenated and / or may contain an alkoxy group, a haloalkoxy group, a cycloalkyl group, a cycloalkenyl group (the cyclo group may partially carry one, two or three halogen atoms and / or alkyl groups) Aryl which may carry one or two of them, some or all may be halogenated and / or carry one, two or three of the substituents of alkyl and haloalkyl,

Some or all may be halogenated and / or alkyl groups, haloalkyl groups, aryl groups (some or all may be halogenated and / or may involve one, two, or three of the substituents of alkyl and haloalkyl) Cycloalkyl group or cycloalkenyl group which may accompany one kind, two kinds, three kinds, four kinds or five kinds of

C ₆ -C ₁₅ -bicycloalkyl or C ₇ -C ₁₅ -which may be halogenated in part or in whole and / or may involve one, two, three, four or five of the alkyl or haloalkyl groups. Bicycloalkenyl,

R ² and R ³ are independently of each other halogen, alkyl and haloalkyl.

According to a particularly preferred embodiment, the composition of the present invention contains a composition of general formula (I).

In the formula,

Z is hydrogen,

R ¹ is alkyl which may be partially or fully halogenated and / or may be halogenated in part or all and / or may be accompanied by aryl and / or alkyl;

Cycloalkyl groups or cycloalkenyl groups, some or all of which may be halogenated and may carry one, two, three, four or five alkyl groups,

Some or all are bicycloalkyl groups or bicycloalkenyl groups which may be halogenated and / or may carry one, two, three, four or five alkyl groups,

R ² and R ³ independently of one another are halogen (in particular fluorine or chlorine), or alkyl.

According to a particularly preferred embodiment, the composition of the present invention contains a compound of formula I as shown in Table I. 1 as p-hydroxyaniline derivative.

Table I.1

*) (A) = European Patent Application No. 653 417

(B) = European Patent Application No. 653 418

(C) = German Patent Application No. 195 04 599.8

(D) = German Patent Application No. 195 40 970.1

According to a particular embodiment, the composition of the present invention contains a compound of general formula I as shown in Table I. 2 below.

Table I.2

According to a more preferred embodiment, the composition of the present invention is a amide compound, wherein A, independently of each other, has one, two or three substituents selected from alkyl, halogen, difluoromethyl and trifluoromethyl groups, It contains a compound of formula II which is a phenyl, pyridyl, dihydropyranyl, dihydroxythiinyl, dihydroxythiinyl oxide, dihydroxythiinyl dioxide, furyl, thiazolyl, pyrazolyl or oxazolyl groups.

According to a more preferred embodiment,

A is a pyridin-3-yl group unsubstituted or substituted in the 2-position by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl or methylsulfonyl,

A phenyl group in which the 2-position is substituted or unsubstituted with methyl, trifluoromethyl, chlorine, bromine or iodine,

2-methyl-5,6-dihydropyran-3-yl group,

2-methyl-5,6-dihydro-1,4-oxathiin-3-yl or their 4,4-dioxide or 4-oxide group,

2-methylfuran-3-yl group in which the 4-position and / or 5-position is substituted or unsubstituted with methyl,

A thiazol-5-yl group unsubstituted or substituted in the 2-position and / or 4-position with methyl, chlorine, difluoromethyl or trifluoromethyl,

Thiazol-4-yl, unsubstituted or substituted in the 2-position and / or 5-position with methyl, chlorine, difluoromethyl or trifluoromethyl,

1-methylpyrazol-4-yl, unsubstituted or substituted in the 3-position and / or 5-position with methyl, chlorine, difluoromethyl or trifluoromethyl, or

2-position and / or 4-position is an oxazol-5-yl group substituted or unsubstituted by methyl or chlorine.

According to a more preferred embodiment, the composition of the present invention contains, as an amide compound, a compound of formula II wherein R ⁹ is a phenyl group substituted or unsubstituted by one, two or three substituents.

According to a more preferred embodiment, the composition of the present invention is an amide compound, wherein R ⁹ in the 2-position,

C ₃ -C ₆ -alkyl group, C ₅ -C ₆ -cycloalkenyl group, C ₅ -C ₆ -cycloalkoxy group, which may be substituted by _one , two or three C ₁ -C ₄ -alkyl groups, C ₅ -C ₆ -cycloalkenyloxy group,

A C ₁ -C ₄ -alkyl group, a C ₁ -C ₄ -haloalkyl group, a C ₁ -C ₄ -alkoxy group, a C ₁ -C ₄ -haloalkoxy group substituted by 1 to 5 halogen atoms and / or independently of each other , C ₁ -C ₄ - alkylthio and C ₁ -C ₄ - substituted phenyl group 1 to 3 selected from haloalkylthio,

Indanyl or oxindanil substituted or unsubstituted by 1,2 or 3 C ₁ -C ₄ -alkyl groups

It contains the compound of general formula II which is a phenyl group which has either.

According to a more preferred embodiment, the composition of the present invention contains a compound of the general formula (IIa) as an amide compound.

[Formula IIa]

In the formula, A

ego,

X is methylene, sulfur, sulfinyl or sulfonyl (SO ₂ ),

R ¹⁰ is methyl, difluoromethyl, trifluoromethyl, chlorine, bromine or iodine,

R ¹¹ is trifluoromethyl or chlorine,

R ¹² is hydrogen or methyl,

R ¹³ is methyl, difluoromethyl, trifluoromethyl or chlorine,

R ¹⁴ is hydrogen, methyl or chlorine,

R ¹⁵ is methyl, difluoromethyl or trifluoromethyl,

R ¹⁶ is hydrogen, methyl, difluoromethyl, trifluoromethyl or chlorine,

R ¹⁷ is C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or halogen.

According to a particularly preferred embodiment, the composition contains a compound of the general formula IIb as amide compound.

Formula IIb]

Wherein R ¹⁸ is halogen,

R ¹⁹ is phenyl substituted with halogen.

Usable amide compounds are mentioned in European Patent Applications 545 099 and 589 301, the references of which are hereby made entirely.

The preparation of amide compounds of general formula II is disclosed, for example, in European Patent Application No. 545 099 or 589 301 and can also be prepared in a similar manner.

To show synergy, active compounds I and II are usually used in a weight ratio of 20: 1 to 1:20, preferably 10: 1 to 1: 5, especially 3: 1 to 1: 1.

The invention also encompasses treatment of fungi, their habitats or substances, plants, seeds, soils, surfaces or spaces to be protected from fungal attack with the above-described compositions, which may use the active compounds simultaneously, together or separately Or may be added continuously.

The compositions of the present invention can be used by spraying, spraying, spraying, spraying or spraying, for example in the form of direct sprayable solutions, powders, suspensions, even in high rates of aqueous, oily, or other suspensions. Or in the form of dispersions, emulsions, oil dispersions, pastes, powder spreading compositions, scattering compositions, and granules. These forms of use will depend on the intended use, but in all cases the active compounds of the invention should be as finely dispersed as possible.

In general, plants are sprayed or sprayed with the active compound and the seeds of the plant are treated with the active compound.

The formulations are prepared by increasing the amount of active compound using known methods, for example, solvents and / or carriers, using emulsifiers and dispersants if desired, and other organic solvents as auxiliary solvents when water is used as diluent. Can also be used. These suitable adjuvants are mainly:

Aromatics (e.g. xylenes), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone) amines (e.g. ethanolami, dimethyl Solvents such as formamide) and water;

Carriers such as basic natural minerals (eg kaolin, alumina, talc, lime) and basic synthetic minerals (eg highly dispersed silicic acid, silicates);

Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene-fatty alcohol-ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste solutions and methylcellulose.

Suitable surface-active substances are ammonium salts of alkyl- and alkylarylsulfonates, alkyl, lauryl ethers and fatty acid alkyl sulfates, alkali metals, alkaline earth metals of aromatic sulfonic acids or fatty acids, for example lignosulfonic acids, phenolsulfonic acids With naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid

Salts of sulfated hexa-, hepta- and octadecanol and also salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalenes and their derivatives with formaldehyde, polyoxyethylene octylphenyl ethers, ethoxylated iso Octyl-octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether, alkylaryl polyether alcohol, isotridecyl alcohol, fatty alcohol-ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene or polyoxypropylene Alkyl ethers, lauyl alcohol polyglycol ether acetates, sorbitol esters, lignin-sulfite waste liquors or methylcellosolves, naphthalenesulfonic acids or condensation products of naphthalene with phenols and formaldehyde.

Powders, sprays, and powder compositions can be prepared by mixing the active materials with a solid carrier or by abrasion of the bond.

Granules, such as coated, saturated and uniform granules, can be prepared by binding the active compound to a solid carrier. Solid carriers are mineral soils such as silicic acid, silica gel, silicates, talc, kaolin, limestone, lime, church clay, ocher, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, basic synthetic materials, ammonium sulfate, ammonium phosphate Fertilizers, such as ammonium nitrate, urea and cereal flours, bark, wood and nut husk flours, cellulose powders or other solid carriers.

Examples of preparations containing the active compound in a weight ratio of 1: 1:

I. A solution of 90 parts by weight of active compound and 10 parts by weight of N-methylpyrrolidone, suitable for use in the form of very small droplets;

II. 20 parts by weight of the active compound, 80 parts by weight of xylene, 10 parts by weight of an additional product of 8 to 10 moles of ethylene oxide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 1 caster oil, based on 1 mole of N-monoethanolamide of oleic phosphate. A mixture of 5 parts by weight of an addition product of 40 moles of ethylene oxide to moles; Fine dispersion of the solution in water gives a dispersion;

III. An aqueous dispersion of 20 parts by weight of the active compound, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, and 20 parts by weight of an additional product of 40 moles of ethylene oxide based on 1 mole caster oil;

IV. An aqueous dispersion of 20 parts by weight of active compound, 25 parts by weight of cyclohexanol, 65 parts by weight of mineral oil fraction having a boiling point of 210 to 280 degrees Celsius and 10 parts by weight of an additional product of 40 moles of ethylene oxide based on 1 mole of caster oil.

V. A mixture of 80 parts by weight of the active compound, 3 parts by weight of sodium salt of diisobutylnaphthalene-1-sulfonic acid, 10 parts by weight of sodium salt of lignosulfonic acid from sulfite waste and 7 parts by weight of powdered silica gel, ground in a hammer mill; Finely dispersing the mixture in water gives a dispersion mixture;

VI. 3 parts by weight of active compound, 97 parts by weight of finely divided kaolin, known mixtures; This powdered composition contains 3% by weight of active compound.

VII. 8 parts by weight of paraffin oil sprayed on the surface of silica gel, 30 parts by weight of active compound, 92 parts by weight of powdered silica gel; This preparation gives the active compound excellent adhesion.

VIII. A stable aqueous dispersion, which can be further diluted 40 parts by weight of active compound, 10 parts by weight of sodium salt of phenolsulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water.

IX. 20 parts by weight of active compound, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of sodium salt of phenolsulfonic acid-urea-formaldehyde condensate and 88 parts by weight of paraffin mineral oil .

The compositions of the present invention have excellent activity against a broad spectrum of fungi, in particular filamentous fungi of phytopathology. In certain cases, they exhibit systemic activity (ie, they can be absorbed by the treated plant without loss of activity and can be suitably carried in the plant) and can be used as leaf fungicides and soil fungicides.

They are used for various cereal plants such as wheat, rye, barley, oats, rice, corn, grass, cotton, beans, coffee, sugar cane, vines, fruits and ornamental plants and edible plants such as cucumbers, beans and gourds, And is particularly important for controlling various fungi on the seeds of these plants.

The compositions are used for treating fungi or seeds, wherein plants, minerals or soils can be protected from fungal attack with fungicidally active amounts of active compounds.

Used by fungi before or after infection of minerals, plants or seeds.

The compositions are particularly suitable for inhibiting the diseases of the following plants.

Erysipe graminis (grain mold) in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in gourds,

Grapes in apples Podosphaera leucotricha,

Uncinula necator on the vine,

Venturia inaequalis (scab) in apples,

Helminthosporium in cereals,

Septoria nodorum on wheat,

Strawberry, filamentous gray matter (Botrytis cinerea, gray form) on the vine;

Cecospora arachidicola in peanuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Fusarium and Verticillium species in various plants,

This Alternaria species from vegetables and fruits,

Monilinia in fruit,

Sclerotinia on Rape and Vegetables

It is preferable to use against filamentous fungi.

The composition is also used for the protection of substances against, for example, Paecilomyces variotii (wood preservation).

Generally the bactericidal composition contains 0.1 to 95, preferably 0.5 to 90% by weight of active compound.

The rate of use differs depending on the desired effect, between 0.02 and 3 kg of active compound per ha.

When treating seed, the amount of active compound is generally required to be 0.001 to 50 grams, preferably 0.01 to 10 grams per kilogram of seed.

Compositions of the invention in the form of use as fungicides may also contain other active compounds such as herbicides, insecticides, growth regulators, fungicides or fertilizers.

When mixed with fungicides, in the body in many cases an increase in the spectrum of action of fungi is obtained.

The following list of fungi that can be used with the compounds of the present invention is for the purpose of illustrating binding possibilities and does not limit:

sulfur,

Dithiocarbonate and derivatives thereof, such as dimethyldithiocarbamate of ferric iron, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediamine-bis- Dithiocarbamate, tetramethylthiuram disulfide, zinc ammonia complex (N, N-ethylene-bis-dithiocarbamate), zinc ammonia complex (N, N-propylene-bis-dithiocarbamate), Zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-propylene-bis (thiocarbamoyl) disulfide,

Nitro derivatives such as dinitro (1-methylheptyl) phenyl crotonate, 2-s-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-s-butyl-4,6 -Dinitrophenyl isopropyl carbonate, diisopropyl 5-nitroisopalate;

Heterocyclic materials such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl phthalimidophosphono Thioate, 5-amino-1-β- [bis (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole,

2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo-β-[4,5-b] quinoxaniline, methyl 1- (butylcarbamoyl)- 2-benzimidazole carbamate, 2-methoxycarbanoylamino benzimidazole, 2- (furi-2-yl) benzimidazole, 2- (thiazol-4-yl) benzimidazole, N- (1 , 1,2,2, -tetrachloroethylthio) tetrahydrophthalylimide, N-trichloromethylthiotetrahydrophthalimide, N-trichloromethylthioptalimide, N-dichlorofluoromethyl Thio-N ', N'-dimethyl-N-phenylsulfamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylbenzothiazole, 1,4 -Dichloro-2,5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, 2-thiopyridine-1-oxide, 8-hydroxyquinoline or cobalt thereof Salt, 2,3-dihydro-5-caranilideo-6-methyl-1,4-oxatiin, 2,3-dihydro-5-caranilideo-6-methyl-1 , 4-oxathiin-4,4-dioxide,

2-methyl-5,6-dihydro-4H-pyran-3-carboxanalide,

2-methyl-furan-3-carboxanalide,

2,5-dimethyl-furan-3-carboxanalide,

2,4,5-trimethyl-furan-3-carboxanalide,

2,5-dimethyl-furan-3-carboxylic acid cycloexylamide,

N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide,

2-methylbenzanalide,

2-iodobenzanalide,

N-formyl-N-morpholine-2,2,2-trichloroethyl acetate,

Piperazine-1,4-dilbis (1- (2,2,2-trichloroethyl)) formamide,

1- (3,4-dichloroanilino) -1-formylamido-2,2,2-trichloroethane,

2,6-dimethyl-N-tridecylmorpholine or salts thereof,

2,6-dimethyl-N-cyclododecylmorpholine or salt thereof,

N- [3- (p-t-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine,

N- [3- (p-t-butylphenyl) -2-methylpropyl] piperidine,

1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole,

1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole,

N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazole urea,

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone,

1- (4-chlorophenyl) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol,

α- (2-chlorophenyl)-α- (4-chlorophenyl) -5-pyrimidinmethanol,

5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,

Bis (p-chlorophenyl) -3-pyridinmethanol,

1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene,

1,2-bis (3-methoxycarbonyl-2-thioureido) benzene,

And various fungicides, for example,

Dodecylguanidine acetate,

3- [3- (3,5-dimethyl) -2-oxycyclohexyl-2-hydroxyethyl] glutamide, hexachlorobenzene,

DL-methyl-N- (2,6-dimethylphenyl) -N-2-furoyl alanate,

DL-methyl-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester,

N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyroacetone,

DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester,

5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine,

3- (3,5-dichlorophenyl) -5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,

3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin,

N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide,

2-cyano- [N-ethylaminocarbonyl-2-methoximino] acetamide

1- [2- (2,4-dichlorophenyl) pentyl] -1 H-1,2,4-triazole,

2,4-difluoro-α- (1H-1,2,4-triazolyl-ylmethyl) benzhydryl alcohol,

N- (3-chloro-2,6-dinitro-4-trifluoromethylphenyl) 5-trifluoromethyl-3-chloro-2-aminopyridine,

1-((bis (4-fluorophenyl) methylsilyl) methyl-1H-1,2,4-triazole,

[2- (4-chlorophenyl) ethyl] (1,1-dimethylethyl) 1H-1,2,4-triazole-1-ethanol, 1- [3- (2-chlorophenyl) -1- (4 -Fluorophenyl) oxirane-2-yl-methyl] -1-H-1,2,4-triazole, strobilurine

For example, methyl E-methoxyimino- [α- (o-toyloxy) -o-tolyl] acetate, methyl E-2- {2- [6- (2-cyanophenoxy) pyrimidine-4 -Yl-oxy] phenyl} -3-methoxyacrylate, methylE-methoxyimino- [α- (2,5-dimethyloxy) -o-tolyl] acetamide,

Anilinopyridine,

For example, N- (4,6-dimethylpyrimidin-2-yl) aniline,

N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline,

N- (4-methyl-6-cyclopropylpyrimidin-2-yl) aniline,

Phenylpyrrole,

For example, 4- (2,2-difluoro-1,3-benzodioxol-4-yl) -pyrrole-3-carbonitrile, cinnamid

For example,

3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acrylic acid morpholide.

The synergism of the compositions of the present invention is shown in the Examples, below, active compounds I used as compounds of the following formulas I.2.1, I.2.5, and I.2.7 It is described with reference to the amide compound used as the compound of II.1.

[Formula I.2.1]

[Formula I.2.5]

[Formula I.2.7]

[Formula II.1]

<Example 1>

Activity against Filamentous Gray Matter

After well developing 4-5 leaves, paprika seeds of various "Neusiedler Ideal Elite" were added dropwise with an aqueous suspension containing 80% active compound and 20% emulsifier in the dry matter. Spray until After spraying, the coating was dried and the plants were sprayed with a fungi suspension of Kondia gray white protein and placed in a room of high atmospheric humidity at 22 degrees Celsius to 24 degrees Celsius. After 5 days, the diseases grew extremely on the plants of the untreated control, so that the necrosis of the resulting leaves covered most of the leaves (100% onset).

Visually measuring the area of infected leaves (percent percentage) is converted to efficiency as% of untreated control. Efficiency 0 is the same as onset in the untreated control, efficiency 100 is 0% onset. The expected efficiency of the active compound binding is determined by Colby's formula (see SR Colby, "Calculating synergistic and antagonistic responses of herbicide combination :, weeds 15, pages 20 to 22 (1967)) and compared with the observed efficiency. The results are shown in Table 1 below.

The test results show that the observed efficiencies at all mixing ratios are higher than the efficiencies previously calculated by Colby's formula, ie a synergistic effect exists.

<Example 2>

Activity against Filamentous Gray Matter in Black Pepper Plants.

Slices of green pepper plants were sprayed until water was added by the aqueous active compound formulation containing 80% of the active compound and 20% of the emulsifier in the dry matter. After spraying, the coating was dried for 2 hours, and the fruit pieces were grafted with a spore suspension of filamentous gray white matter containing 1.7 × 10 ⁶ spores per ml of biodissolved solution of 2% strength. The grafted fruit pieces were then incubated in a humid room at 18 degrees Celsius for 4 days. The growth of filamentous fungi was then visually assessed on affected fruit pieces (100% incidence).

Visually measuring the area of infected leaves (percent percentage) is converted to efficiency as% of untreated control. Efficiency 0 is the same as onset in the untreated control, efficiency 100 is 0% onset. The expected efficiency for the active compound binding is determined by Colby's formula (see SR Colby, "Calculating synergistic and antagonistic responses of herbicide combination :, weeds 15, pages 20 to 22 (1967)) and compared with the observed efficiency. The results are shown in Table 2 below.

The test results show that the observed efficiencies at all mixing ratios are higher than the efficiencies previously calculated by Colby's formula, ie there is a synergistic effect.

Claims (15)

a) at least one p-hydroxyaniline derivative of formula (I) b) at least one amide compound of formula II A composition for inhibiting harmful fungi, which is contained in a solid or liquid carrier. <Formula I> <Formula II> A-CO-NR ⁸ -R ⁹ Where R ¹ may be hydrogen, some or all of which may be halogenated and / or an alkoxy group, a haloalkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkenyl group (cyclo group having 1, 2 or 3 halogen atoms, alkyl group and / or alkoxy Alkyl, which may carry one or two of them, may be halogenated and / or one of the substituents of nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy and alkylthio Aryl which may involve species, two or three species, Some or all may be halogenated and / or alkyl groups, haloalkyl groups, alkoxy groups, haloalkoxy groups and aryl (these may be some or all halogenated and / or nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy and Cycloalkyl or cycloalkenyl, which may involve one, two, three, four or five of the substituents of alkylthio) Some or all may be halogenated and / or alkyl groups, haloalkyl groups, alkoxy groups, haloalkoxy groups and aryl (these may be some or all halogenated and / or nitro, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy and C ₆ -C ₁₅ -bicycloalkyl group which may carry one, two, three, four or five of the substituents of alkylthio) C ₇ -C ₁₅ -bicycloalkenyl group R ² and R ³ are independently of each other halogen, alkyl, haloalkyl, alkoxy or haloalkoxy, Z is H or R ^4- (CO)-, R ⁴ may be part or all halogenated and / or alkoxy, haloalkoxy, alkylthio, cycloalkyl, cycloalkenyl or aryl (aromatic group is nitro group, cyano group, halogen group, alkyl group, haloalkyl group, alkoxy group, halo Alkyl group or alkenyl group which may carry one of alkoxy group and alkylthio group) A cycloalkyl group or cycloalkenyl group which may carry one, two or three of halogen, alkyl, haloalkyl and alkoxy groups, Aryl which may be partially or fully halogenated and / or may carry one, two or three of nitro groups, cyano groups, alkyl groups, haloalkyl groups, alkoxy groups, haloalkoxy groups and alkylthio groups, OR ⁵ or NR ⁶ R ⁷ , R ⁵ may be partially or fully halogenated and / or alkoxy group, haloalkoxy group, alkylthio group, cycloalkyl group, cycloalkenyl group or aryl group (aromatic group nitro group, cyano group, halogen group, alkyl group, haloalkyl group, alkoxy Alkyl group or alkenyl group, which may be accompanied by one, two or three of the group, haloalkoxy group and alkylthio group, or A cycloalkyl group or a cycloalkenyl group which may carry one, two or three of a halogen group, an alkyl group, a haloalkyl group and an alkoxy group or Aryl which may be partially or fully halogenated and / or may carry one, two or three of nitro groups, cyano groups, alkyl groups, haloalkyl groups, alkoxy groups, haloalkoxy groups and alkylthio groups, R ⁶ may be partially or completely halogenated and / or alkylthio group, cycloalkyl group, cycloalkenyl group or aryl group (aromatic group is nitro group, cyano group, halogen group, alkyl group, haloalkyl group, alkoxy group, haloalkoxy group and Alkyl group or alkenyl group, which may carry one of two, three, or three of the alkylthio groups, or Cycloalkyl or cycloalkenyl groups which may carry one, two or three of halogen, alkyl, haloalkyl and alkoxy groups, Some or all are aryl groups which may be halogenated and / or may carry one, two or three of nitro groups, cyano groups, alkyl groups, haloalkyl groups, alkoxy groups, haloalkoxy groups and alkylthio groups, R ⁷ is hydrogen or alkyl, A is pyridyl, thiazolyl, pyrazolyl or oxazolyl, which may have one, two or three substituents independently selected from alkyl, halogen, CHF ₂ , CF ₃ , and R ⁸ is hydrogen, alkyl or alkoxy, R ⁹ is 1 to 5 halogen atoms and / or independently of each other C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkoxy, C ₁ -C ₄ - it is phenyl substituted with 1 to 3 halo groups selected from alkylthio -alkylthio and C ₁ -C _4. The composition of claim 1 wherein Z in the compound of formula I is hydrogen. The compound of claim 2 wherein R ¹ may be partially or fully halogenated Alkoxy groups, haloalkoxy groups, cycloalkyl groups, cycloalkenyl groups (cyclo groups may in part carry one, two, or three halogen atoms and / or alkyl groups), aryl groups (some or all may be halogenated) And / or may carry one, two, or three of the substituents of alkyl and haloalkyl). Some or all may be halogenated and / or alkyl groups, haloalkyl groups, aryl groups (some or all may be halogenated and / or may involve one, two, or three of the substituents of alkyl and haloalkyl) Cycloalkyl group or cycloalkenyl group which may accompany one kind, two kinds, three kinds, four kinds or five kinds of C ₆ -C ₁₅ -bicycloalkyl or C ₇ -C ₁₅ -which may be halogenated in part or in whole and / or may involve one, two, three, four or five of the alkyl or haloalkyl groups. Bicycloalkenyl, R ² and R ³ are independently of each other halogen, alkyl and haloalkyl Phosphorus composition. The compound of claim 3 wherein R ¹ may be partially or fully halogenated, Some or all alkyl which may be halogenated and / or which may involve alkyl, Cycloalkyl groups or cycloalkenyl groups, some or all of which may be halogenated and may carry one, two, three, four or five alkyl groups, Some or all are bicycloalkyl groups or bicycloalkenyl groups which may be halogenated and / or may carry one, two, three, four or five alkyl groups, R ² and R ³ are each independently halogen, in particular fluorine or chlorine, or alkyl. The composition of claim 1, wherein the compound of formula I is a compound of the following table. The composition of claim 1, wherein the compound of formula I is a compound of the following table. 7. The method of claim 1, wherein A composition containing a compound of formula II as an amide compound. In the formula, group A Pyridin-3-yl groups unsubstituted or substituted with halogen, methyl, difluoromethyl or trifluoromethyl, A thiazol-5-yl group unsubstituted or substituted with methyl, chlorine, difluoromethyl or trifluoromethyl in the 2-position and / or 4-position, A thiazol-4-yl group unsubstituted or substituted with methyl, chlorine, difluoromethyl or trifluoromethyl, 2-- and / or 5-position, A 1-methylpyrazol-4-yl group unsubstituted or substituted with methyl, chlorine, difluoromethyl or trifluoromethyl in the 3-position and / or 5-position, or 2-position and / or 4-position is one of the oxazol-5-yl groups unsubstituted or substituted with methyl, chlorine. The composition according to any one of claims 1 to 6, which contains as an amide compound a compound of formula (IIa). <Formula IIa> Where A is ego, R ¹¹ is trifluoromethyl or chlorine, R ¹² is hydrogen or methyl, R ¹³ is methyl, difluoromethyl, trifluoromethyl or chlorine, R ¹⁴ is hydrogen, methyl or chlorine, R ¹⁵ is methyl, difluoromethyl or trifluoromethyl, R ¹⁶ is hydrogen, methyl, difluoromethyl, trifluoromethyl or chlorine, R ¹⁷ is C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or halogen. The composition according to any one of claims 1 to 6, which contains as an amide compound a compound of formula (IIb). <Formula IIb> Wherein R ¹⁸ is halogen, R ¹⁹ is phenyl substituted with halogen. A composition according to claim 9, which contains as an amide compound a compound of the formula: 8. A composition according to claim 7, which contains as a amide compound a compound of formula IIa. <Formula IIa> Where A is ego, R ¹¹ is trifluoromethyl or chlorine, R ¹² is hydrogen or methyl, R ¹³ is methyl, difluoromethyl, trifluoromethyl or chlorine, R ¹⁴ is hydrogen, methyl or chlorine, R ¹⁵ is methyl, difluoromethyl or trifluoromethyl, R ¹⁶ is hydrogen, methyl, difluoromethyl, trifluoromethyl or chlorine, R ¹⁷ is C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio or halogen. 8. A composition according to claim 7, which contains as a amide compound a compound of formula IIb. <Formula IIb> Wherein R18 is halogen, R ¹⁹ is phenyl substituted with halogen. A composition according to claim 8, which contains as a amide compound a compound of formula IIb. <Formula IIb> Wherein R ¹⁸ is halogen, R ¹⁹ is phenyl substituted with halogen. The composition according to claim 1, which is formulated in two parts, one part containing active compound I in a solid or liquid carrier and the other part containing an amide compound of formula II in a solid or liquid carrier. Treating a fungus, their habitat or a substance, plant, seed, soil, surface or space to be protected from attack by the composition of any one of claims 1 to 10 and 11 to 14, , A method for inhibiting harmful fungi, wherein the active compounds can be added simultaneously, together or separately, or continuously.