SI9300673A - Oxadiazine derivatives - Google Patents

Abstract

Compounds of formula (I) wherein A is unsubstituted or once or four times substituted, aromatic but non-aromatic, monocyclic or bicyclic, heterocyclic a residue where one to two substituents may be present of A is selected from the group consisting of halogen C1-C3 alkyl, cycloproptl, halogencyclopropyl, C2-C3- alkenyl, C2-C3-alkynyl, halogen-C2-C3-alkenyl, halogen-C2-C3-alkynyl, halogen-C1-C3-alkoxy, C1-C3-alkylthio, halogen-C1-C3-alkylthio, allyloxy, propargyloxy, allythio, propargylthio, halogenallyloxy, halogenallythio, cyano and nitro, and one to four substituents of A from a group consisting of C1-C3-alkyl, C1-C3-alkoxy and halogens; R is hydrogen, C1-C6-alkyl, phenyl-C1-C4-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl or C2-C6-alkynyl; and X is N-NO2 or N-CN, or as the case may be their tautomers, in each case in free form or form salts can be used as agrochemical active substances and we can prepare them in a familiar way.

Description

CIBA-GEIGY AG

OXADIAZINE DERIVATIVES

The present invention relates to compounds of formula

Γ ° Ί

X where

A represents an unsubstituted or one to four times substituted, aromatic or non-aromatic, monocyclic or bicyclic, heterocyclic radical, wherein one to two substituents of A may be selected from the group consisting of halogen-C 1 -C 4 alkyl, cyclopropyl, halogencyclopropyl, C ₂ -C ₃ -alkenyl, C ₂ -C ₃ -alkynyl, halogen-C ₂ C ₃ -alkenyl, halogen-C ₂ -C ₃ -alkynyl, halogen-C ₁ -C ₄ alkoxy, C ₁ -C ₆ -alkylthio, halogen C - C ₃ -alkylthio, allyloxy, propargyloxy, allylthio, propargylthio, halogenallyloxy, halogenallythio, cyano and nitro, and one to four substituents of A from the group consisting of C 1 -C 6 alkyl, C 1 -C 4 alkoxy and halogen;

R represents hydrogen, C, -C ₆ -alkyl, phenyl-Cj-C ^ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₂ -C ₆ -alkenyl, or C _<C alkynyl; and X represents N-NO ₂ or N-CN, in free or salt form, optionally tautomers, in free or salt form of these compounds, a process for the preparation and use of these compounds and tautomers, pest control agents, of which they are active the substance is selected from these compounds and tautomers, in each case in the free form or in the form of an agrochemical salt, for the processes for the preparation and use of these agents, for the plant seed material treated therewith, for the pest control process, in the free form or in the form of salts, for the preparation of these compounds, optionally tautomers, in the free or salt form, of these intermediates, and of a process for the preparation and use of these intermediates.

Certain oxadiazine derivatives have been proposed in the literature as arthropodacid-active agents in pest control agents. The biological properties of these known compounds, however, cannot be fully satisfied in the field of pest control, which is why there is a need to have further compounds with pest control properties, especially for insect control, and this task of the invention is solved by the preparation of the present compounds I.

Compounds I may partially exist as tautomers. If e.g. R is hydrogen, the corresponding compounds I may exist as such with a 3-H-4-imino-perhydro-1,3,5-oxadiazine moiety in equilibrium with the corresponding tautomers having 4-amino-1,2,5,6tetrahydro -l, 3,5-Oxadiazine Partial Structure. Accordingly, compounds I, above and below, as appropriate, are also to be understood as corresponding tautomers, even when the latter are not specifically mentioned in each case.

Compounds I having at least one basic center may form e.g. acid addition salts. We form these, e.g. with strong inorganic acids, such as mineral acids, e.g. perchloric acid, sulfuric acid, nitric acid, nitric acid, phosphoric acid or hydrohalic acid, with strong organic carboxylic acids, as in the present case, e.g. with halogen substituted C1-C6-alkanecarboxylic acids, e.g. acetic acid, as optionally unsaturated dicarboxylic acids, e.g. oxalic, malonic, succinic, maleic, fumaric or phthalic acids, such as hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or as benzoic acid, or with organic sulfonic acids, such as, for example, e.g. with halogen substituted C1-C4 alkane or aryl-sulfonic acids, e.g. methane or p-toluenesulfonic acid. Furthermore, compounds I with at least one acid group may form with salt bases. Suitable salts with bases are e.g. metal salts, such as alkali metal or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or organic amines, such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethylpropyl-amine, or mono-, di- or trihydroxy-lower alkylamine, e.g. mono-, di- or triethanolamine. Furthermore, suitable internal salts may be formed as appropriate. Agrochemically useful salts are preferred in the invention; it also covers salts for agrochemical applications that have drawbacks, e.g. are toxic to bees or fish that can be e.g. used for insulation or. purification of free compounds I or their agrochemical salts. Due to the narrow relationship between the free form compounds and the salts thereof, we understand the free compounds I and above described below. their salts in a reasonable and expedient manner, in the given case, of the corresponding salts, respectively. free compounds I. Appropriate for tautomers of compounds I and their salts. In general, free form is preferred.

The general terms used previously and hereinafter have the following meanings, unless otherwise derogated.

As heteroatoms in the ring-base framework of heterocyclic residue A, all elements of the periodic system capable of forming at least two covalent bonds are considered.

Halogen - as a group by itself, as well as a structural element of other groups and compounds, such as halogenalkyl, halogenalkylthio, halogenalkoxy, halogencyclopropyl, halogenalkenyl, halogenalkynyl, halogenallyloxy and halogenallythio, - is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, especially fluorine or chlorine, especially chlorine.

Carbon-containing groups and compounds contain, unless otherwise defined, 1 to and with 6, preferably 1 to and with 3, in particular 1 or 2 carbon atoms.

Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferably cyclopropyl.

Alkyl - as a group in its own right, as well as a structural element of other groups and compounds, such as phenylalkyl, halogenalkyl, alkoxy, halogenalkoxy, alkylthio and halogenalkylthio - is, in each case, taking into account, on a case by case basis, the number of carbon atoms in the corresponding group or compounds, but not branched, i.e. methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.

Alkenyl, halogenalkenyl, alkynyl and halogenalkynyl are unbranched or branched and each contain two or preferably one unsaturated carbon-carbon bond (s). The double or triple bonds of these substituents are preferably separated by at least one saturated carbon atom from the rest of compound I. Examples include allyl, methylyl, but-2-enyl, but-3-enyl, propargyl, but-2-inyl and but-3-inyl.

Halogen substituted groups and compounds containing carbon, such as halogenalkyl, halogenalkylthio, halogenalkoxy, halogencyclopropyl, halogenalkenyl, halogenalkynyl, halogenallyloxy and halogenallylthio, may be partially halogenated or perhalogenated, and may be halogenated in the case of multiple halogenation. Examples of halogenalkyl - as a group alone, as well as a structural element of other groups and compounds such as halogenalkylthio and halogenalkoxy - are one to three times fluorine, chlorine and / or bromine substituted methyl, such as CHF ₂ or CF ₃ ; five times with flora, chlorine and / or bromine substituted ethyl, such as CH ₂ CF ₃ ; CF ₂ CC1 ₃ , CF ₂ CHC1 ₂ , CF ₂ CHF ₂ , CF ₂ CFC1 ₂ , CF ₂ CHBr ₂ , CF ₂ CHC1F, CF ₂ CHBrF or CC1FCHC1F; one to seven times with fluorine, chlorine and / or bromine substituted propyl or isopropyl, such as CH ₂ CHBrCH ₂ Br, CF ₂ CHFCF ₃ , CH ₂ CF ₂ CF ₃ , CF ₂ CF ₂ , CF ₃ or CH (CF ₃ ) ₂ ; and once to nine times fluorine, chlorine and / or bromine substituted butyl or one of its isomers, such as CF (CF ₃ ) CHFCF ₃ , CF ₂ (CF ₂ ) ₂ CF ₃ or CH ₂ (CF ₂ ) ₂ CF ₃ . Examples of halogenalkenyl are 2,2-difluoroten-1-yl, 2,2-dichlorethen-1-yl, 2-chloroprop-len-3-yl, 2,3-dichloroprop-1-en-3-yl and 2, 3-dibromprop-1-en-3-yl. Examples of halogenalkynyl are 2-chloroprop-1-yn-3-yl, 2,3-dichloroprop-1-yn-3-yl and 2,3-dibromoprop-1-yn-3-yl. Examples of halogencyclopropyl are 2-chlorocyclopropyl, 2,2-difluorocyclopropyl and 2-chloro-2-fluorocyclopropyl. Examples of halogenallyloxy are 2-chloroprop-1-en-3-yloxy, 2,3-dichloropropen-3-yloxy, and 2,3-dibromoprop-1-en-3-yloxy. Examples of halogenallylthio are 2-chloro-prop-en-3-ylthio, 2,3-dichloroprop-1-en-3-ylthio and 2,3-dibromoprop-1-en-3-ylthio.

In phenylalkyl, the rest of compound I is bound by an alkyl group substituted with a phenyl group, wherein the alkyl group is preferably unbranched and the phenyl group is preferably attached in a higher than the α-position, especially in the ω-position of the alkyl group; examples are benzyl, 2-phenylethyl and 4-phenylbutyl.

Preferred embodiments of the invention are:

(1) a compound of formula I wherein

A represents an unsubstituted or once or four times substituted, aromatic or non-aromatic, monocyclic or bicyclic, heterocyclic radical, wherein one to two substituents of A may be selected from the group consisting of halogen-C 1 -C ₃ alkyl, cyclopropyl, halogencyclopropyl, C ₂ -C ₃ -alkenyl, C ₂ -C ₃ -alkynyl, halogen-C ₂ -C ₃ -alkenyl, halogen-C ₂ -C ₃ -alkynyl, halogen-C ₁ -C ₃ -alkoxy, C 1 -C ₃ alkylthio, halogen -C 1 -C 4 -alkylthio, allyloxy, propargyloxy, allylthio, propargylthio, halogenallyloxy, halogenallythio, cyano and nitro, and one to four substituents of A from the group consisting of C-C ₃ -alkyl, C ₁ -C ₄ - alkoxy and halogen;

R represents hydrogen, C, -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₂ -C _fi -alkenyl or C ₂ -C ₆ -alkynyl; and X is N-NO ₂ or N-CN;

(2) a compound of formula I, wherein the ring-base frame A is from a ring of 5 or 6 ring members to which one further ring with 5 or 6 ring members can be anelated, especially from a ring with 5 or preferably 6 ring members ;

(3) a compound of formula I wherein the ring-base framework A is unsaturated, in particular contains one double bond or preferably 2 to 4, preferably conjugated double bonds, preferably contains 2, preferably conjugated double bonds, particularly expressing an aromatic character;

(4) a compound of formula I, wherein the ring-base framework A contains 1 to and s 4, especially 1 to and s 3, preferably 1 or 2, heteroatoms, especially preferably 1 heteroatom;

(5) a compound of formula I wherein the ring-base frame A is selected from the group consisting of ring-base frames o

<ζ

Tv 'tv θ' 'N', U \

N ^ N

S ^<iiiKx s ^X ^ S 'N'

N '

N_

А.

About ST

N N

ΛΛ

S 'O ^^ CT

N ^ A

N '

AA .N. AL

J ·.

^ A / AA '

Ν ^<? ^ ^Χχ Ν N ^ ^ Σ: A, j '"X".

Ί

N.

/ \ ϊΧ'Σ

N <?

J ·.

S 'Ό' S

S 'S ^<i? ^ ^Xx S

N

J ·

Ί ·,

N ^ A ZA; Z '

S 'S' s' N

JN

'Q U U Q

γ

Ο

Ν

Ο

Υ s

and

Y where E is each C 1 -C ₃ -alkyl, Y in each case hydrogen, C 1 -C 6 alkyl or cyclopropyl and E or. Y is not always present as a substituent of A, but is assigned to the ring base frame of A;

(6) a compound of formula I wherein the ring-base framework of A contains 1, 2 or 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, wherein at most one of the ring-base framework heteroatoms is , oxygen, and being at most one of the ring-base heteroatoms, a sulfur atom, in particular 1, 2, or 3 heteroatoms selected from the group consisting of oxygen, sulfur, and nitrogen, wherein at most one of the heteroatoms which is there are at least one sulfur atom in the ring-base framework, an oxygen or sulfur atom;

(7) a compound of formula I, wherein A is bonded via the C-atom of its ring-base framework to the rest of compound I;

(8) a compound of formula I wherein A is unsubstituted or once or twice substituted with substituents selected from the group consisting of halogen, C 1 -C ₃ -alkyl, halogen C-C-alkyl, C 1 -C ₄ alkoxy and halogen- C 1 -C 4 alkoxy, preferably unsubstituted or mono- or polysubstituted with substituents selected from the group consisting of halogen and C 1 -C 6 -alkyl;

(9) a compound of formula I wherein the ring-base framework A is pyridyl,

1- Oxidopyridinio- or thiazolyl group, preferably the ring-base framework A is pyrid-3-yl, 1-oxido-3-pyridinio- or thiazol-5-yl group, in particular A is pyrid-3-yl, 2-halogenpyrid -5-yl, 2,3-dihalogenpyrides-5-yl,

2- C ₁ -C ₃ -alkylpyrid-5-yl, 1-oxido-3-pyridinio-, 2-halogen-1-oxido-5-pyridinio-,

The 2,3-dihalogen-1-oxido-5-pyridinio- or 2-halogentiazol-5-yl group, in particular A, is pyrid-3-yl, 2-halogen-pyrid-5-yl, 2-halogen-1-oxido-5 -pyridinioally 2-halogentiazol-5-yl group, preferably A is 2-chlorpyrid-5-yl, 2-methylpyrid-5-yl, 1-oxido-3-pyridinio-,

The 2-chloro-1-oxido-5-pyridinio-, 2,3-dichloro-1-oxido-5-pyridinio- or 2-chlorothiazol-5-yl group, in particular A, is pyrid-3-yl, 2-chlorpyrid- 5-yl, 2-chloro-1-oxido-5-pyridinio-or

A 2-chlorothiazol-5-yl group, in particular A is a 2-chloropyrid-5-yl or preferably 2-chlorothiazol-5-yl group;

(10) a compound of formula I wherein RC is -C-alkyl, phenyl-C-C-alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C-alkenyl or CC-alkynyl, in particular C 1 -C 4 -alkyl , C ₃ -C ₆ -cycloalkyl, C ₃ -C ₄ -alkenyl or C ₃ -C ₄ -alkynyl, preferably C ₁ -C ₄ -alkyl, phenyl-C ₁ -C ₄ -alkyl, C ₃ -C ₄ -alkenyl, or C ₃ -C ₄ -alkynyl, especially C ₁ -C ₄ -alkyl, preferably methyl;

(11) a compound of formula I wherein X is N-NO ₂ ;

(12) a compound of formula I, wherein A represents, via the C atom of its ring-base framework, the rest of compound I bonded, unsubstituted or once or twice with substituents selected from the group consisting of halogen and C-C ₃ -alkyl, substituted, pyridyl, 1-oxidopyridinio- or thiazolyl group, R is a C-C ₆ alkyl, phenyl-C, -C-alkyl, C, -C-cycloalkyl, C, -C-alkenyl or C ., - C.-alkynyl and X is N-NO ₂ or N-CN;

(13) a compound of formula I, wherein A is 2-chlorpyrid-5-yl, 2-methylpyrid-5-yl, 1-oxido-3-pyridinio-, 2-chloro-1-oxido-5-pyridinio-, 2 , 3-dichloro-l-oxido-5-piridinioali 2-klortiazol-5-yl group, R is a C _x -C ₄ alkyl and x is N-NO _2;

(14) a compound of formula I, wherein A is 2-chlorothiazol-5-yl or 2-chloro-pyrid-5-yl, R is C-C-alkyl and X is N-NO ₂ .

Particularly preferred in the invention are the compounds of formula I listed in Examples H3 and H4.

Particularly preferred in the invention are (a) 5- (2-chloropyrid-5-ylmethyl) -3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine, (b) 5- (2-chlorothiazole-5 -ylmethyl) -3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine, (c) 3-methyl-4-nitroimino-5- (1-oxido-3-pyridiniomethyl) -perhydro-1,3 , 5-oxadiazine, (d) 5- (2-chloro-1-oxido-5-pyridiniomethyl) -3-methyl-4-nitroimino-perhydro-1,3,5oxadiazine and (e) 3-methyl-5- ( 2-methylpyrid-5-ylmethyl) -4-nitroimino-perhydro-1,3,5-oxadiazine.

As a further object of the invention is a process for the preparation of compounds of formula I or, optionally, their tautomers, in each case in free or salt form, e.g. characterized in that

a) a compound of formula

H H i i

X (Π), which is known or can be prepared analogously to the corresponding known compounds, and where A, R and X have the meanings given for formula I, or their tautomer and / or salt, is metabolised, preferably in the presence of a base or a further acid catalyst, by formaldehyde or paraformaldehyde or

b) for the preparation of a compound of formula I wherein R is other than hydrogen, or optionally its tautomer and / or salt, e.g. according to variant a) or c) a obtainable compound of formula I, wherein R is hydrogen, or a tautomer and / or salt thereof, is reacted, preferably in the presence of a base, with a compound of formula

Y-R (III), which is known or can be prepared analogously to the corresponding known compounds, and wherein R for the formula I has the meanings indicated with the exception of hydrogen and Y stands for the leaving group, or

c) a compound of formula

Γ °, ^h ^ ⁿ y ⁿ X (IV), where R and X for the formula I have the meanings given, or their tautomer and / or salt, is reacted, preferably in the presence of a base, with a compound of the formula a-ch ₂ -y ( V) which is known or can be prepared analogously to the corresponding known compounds, and wherein A has the indicated meaning of formula I and Y stands for the leaving group or optionally its tautomer and / or salt and / or, if desired, by the process of or the otherwise obtainable compound of formula I or its tautomer, in each case in free or salt form, is converted to another compound of formula I or its tautomer, by the process the resulting mixture of isomers is separated and the desired isomer is isolated and / or by process or otherwise a recoverable free compound of formula I or its tautomer is converted into a salt, or by a process or otherwise obtained salt of a compound of formula I or its tautomer is converted into a free compound of formula I or its tautomer or any other salt.

The starting materials referred to above and below, with respect to their tautomers and / or salts, are in an analogous manner as indicated above for tautomers and / or salts of compounds I.

The metabolites described above and below are carried out in a manner known per se, e.g. in the absence or usually in the presence of a suitable solvent or diluent, or a mixture thereof, where required to be operated under refrigeration, at room temperature or under heating, e.g. in the temperature range from about -80 ° C to the boiling point of the reaction mixture, preferably from about -20 ° C to about +150 ° C and, if necessary, in a sealed container, under pressure, in an inert gas atmosphere and / or under anhydrous conditions. Particularly preferred reaction conditions can be seen from the examples.

The starting materials described above and below, which can be used to prepare compounds I or optionally their tautomers, in each free or salt form, are known or can be prepared by known methods, e.g. according to the information below.

Variant a):

Suitable bases for facilitating metabolism are e.g. alkali- or earth-alkali-hydroxides, -hydrides, -amides, -alkanolates, -acetates, -carbonates, -dialkylamides or -alkylsilylamides, alkylamines, alkylenediamines, optionally N-alkylated, optionally unsaturated, cycloalkylamines, basic heterocycles hydroxides as well as carbocyclic amines. For example, sodium hydroxide, -hydride, -amide,

-methanolate, -acetate, -carbonate, potassium tert-butanolate, -hydroxide, -carbonate, -hydride, lithium diisopropylamide, potassium bis (trimethylsilyl) -amide, calcium hydride, triethylamine, diisopropyl-ethyl-amine, triethylenediamine, cyclohexylamine, cyclohexylamine N-cyclohexyl-N, N-dimethylamine, Ν, Ν-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine,

N-methylmorpholine, benzyl trimethylammonium hydroxide as well as 1,5-diazabicyclo [5.4.0] undec-5-ene (DBU).

Suitable acid catalysts for facilitating metabolism are e.g. those acids used in the catalytic amounts indicated above as being suitable for the formation of acid addition salts with compounds I.

The reaction partners can be metabolized as such, i.e. without the addition of solvent or diluent, e.g. in the melt. For the most part, the addition of an inert solvent or diluent or mixtures thereof is useful. Examples of such solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogens such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane trichloroethylene or tetrachloroethylene; esters such as acetic acid esters; ethers such as diethyl ether, dipropylether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethylether, dimethoxydiethylether, tetrahydrofuran or dioxane; ketones such as acetone, methylethylketone or methylisobutylketone; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerin; amides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethyl-phosphoric acid triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides such as dimethylsulfoxide. If the reaction is carried out in the presence of a base, they can also serve as solvents and diluents in excess of the base used, such as triethylamine, pyridine, N-methylmorpholine or Ν, diet-diethylaniline. If the reaction is carried out in the presence of an acid catalyst, they can also serve as solvents and thinners in excess of the acid used, e.g. strong organic carboxylic acids, such as, for example, e.g. with halogen substituted C 1 -C 4 -alkanecarboxylic acids, e.g. formic acid, acetic acid or propionic acid.

The reaction is preferably carried out in the temperature range from about 0 ° C to about + 180 ° C, preferably from about +10 ° C to about +130 ° C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.

In the reaction, the resulting reaction water can optionally be removed by means of a water separator, azeotropic distillation or the addition of a suitable molecular sieve.

Option b):

Suitable leaving groups Y in compounds III are e.g. hydroxy, C 1 -C 8 alkoxy, halogen C 1 -C 8 alkoxy, C 1 -C 6 alkanoyloxy, mercapto, C 1 -C 8 alkylthio, halogen C 1 -C 8 alkylthio, C 1 -C 8 alkanesulfonyloxy, halogen-C 1 -C 6 alkanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy and halogen.

Suitable bases for facilitating HY-cleavage are e.g. under variant a) of the specified species.

The reaction partners can be metabolized as such, i.e. without the addition of solvent or diluent, e.g. in the melt. Most often, the addition of an inert solvent or diluent or mixtures thereof is useful. Examples of such solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogens such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane, dichloromethane trichlorethane or tetrachlorethene; esters such as acetic acid esters; ethers such as diethyl ether, dipropylether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethylether, dimethoxydiethylether, tetrahydrofuran or dioxane; ketones such as acetone, methylethylketone or methylisobutylketone; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerin; amides such as N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone or hexamethyl-phosphoric acid triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides such as dimethylsulfoxide. If the reaction is carried out in the presence of a base, the excess used bases such as triethylamine, pyridine, N-methylmorpholine or Ν, diet-diethylaniline may also serve as solvents or diluents.

The reaction is preferably carried out in the temperature range from about 0 ° C to about + 180 ° C, preferably from about +10 ° C to about +130 ° C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.

Variant c):

Suitable leaving groups Y in compounds V are e.g. under variant b) of the specified species.

Suitable bases for facilitating HY-cleavage are e.g. under variant a) of the specified species.

The reaction partners can be metabolized as such, i.e. without the addition of solvent or diluent, e.g. in the melt. Most often, the addition of an inert solvent or diluent or mixtures thereof is useful. Suitable solvents and thinners are e.g. under variant b) of the specified species.

The reaction is preferably carried out in a temperature range from about -20 ° C to about + 180 ° C, preferably from about +10 ° C to about +100 ° C, in many cases in the range between room temperature and the reflux temperature of the reaction mixture.

In process variant c), compounds IV and their tautomers, in each free or salt form, are used as educts, and are novel and are also subject of the invention. Particularly preferred according to the invention are the compounds of formula IV and tautomers thereof in examples HI and H2.

As a further object of the invention is a process for the preparation of compounds of formula IV and their tautomers, in each case in free or salt form, e.g. characterized in that

d) a compound of formula

HH ^{Η Ν} γ% (VI),

X is known or can be prepared analogously to the corresponding known compounds, and wherein R and X have the meanings given for formula I, or the tautomer and / or salt thereof is reacted with formaldehyde or paraformaldehyde, e.g. in an analogous manner as described in variant a) for the appropriate metabolism of a compound of formula II or its tautomer and / or salt with formaldehyde or paraformaldehyde, or

e) to prepare a compound of formula IV, wherein R is other than hydrogen, or a tautomer and / or salt thereof, e.g. according to variant d) a obtainable compound of formula IV, wherein R is hydrogen, or a tautomer thereof and / or a salt of a compound of formula

Υ - R (III), which is known or can be prepared analogously to the corresponding known compounds, and wherein R for the formula I has the indicated meanings with the exception of hydrogen and Y stands for the leaving group, e.g. in an analogous manner as described in variant b) for the appropriate metabolism of a compound of formula I or, optionally, its tautomer and / or salt with a compound of formula III and / or, if desired, by a process or otherwise obtainable compound with Formula IV, or tautomer thereof, in each case in free or salt form, is converted to another compound of Formula IV or tautomer thereof, by the process, the resulting mixture of isomers is separated and the desired isomer is isolated and / or by the process or otherwise obtainable free compound of the formula IV or its tautomer is converted into a salt, or by a process or otherwise obtainable salt of a compound of formula IV or its tautomer, is converted into a free compound of formula IV or its tautomer or other salt.

By process or otherwise obtainable compound I or. IV can be converted in another known manner to another compound I or. IV such that one or more substituents of the starting compound I or. IV is in the usual way replaced by another (i) substituent (s) of the invention.

For example, you can:

- substituents are introduced into compound I with unsubstituted residue A into residue A; or

- in compounds I with substituted residue A, substituents of residue A are replaced by other substituents.

In this case, depending on the choice of suitable reaction conditions and starting materials, it is possible to replace only one substituent with another substituent of the invention in one reaction step, or to replace several substituents with another substituent in the same reaction step of the invention.

The salts of compounds I and. IV can be prepared in a known manner. So we get e.g. the acid addition salts of compounds I and. IV by treatment with a suitable acid or a suitable ion-exchange reagent, and salts with bases by treatment with a suitable base or a suitable ion-exchange reagent.

The salts of compounds I and. IV can be converted in the usual way to free compounds I or. IV, acid addition salts e.g. by treatment with a suitable basic agent or with a suitable ion-exchange reagent and salts with bases e.g. by treatment with a suitable acid or a suitable ion-exchange reagent.

The salts of compounds I and. IV can be metabolised in a known manner to other salts of compound I or. IV, acid addition salts e.g. to other acid addition salts, e.g. by treating an inorganic acid salt such as hydrochloride with a suitable metal salt such as sodium, barium or silver salt, acids, e.g. with silver acetate, in a suitable solvent in which the inorganic salt formed is e.g. silver chloride, insoluble and thus eliminated from the reaction mixture.

Depending on the method of procedure, the reaction conditions can be obtained of compounds I or. IV, having free-form or salt-forming properties.

The compounds I or. IV, and in each case as appropriate, their tautomers, in each case in free or salt form, may exist in the form of one of the possible isomers or as a mixture thereof, e.g. according to the number, absolute and relative configuration of asymmetric carbon atoms in the molecule and / or depending on the configuration of non-aromatic double bonds appearing in the molecule, as pure isomers, as antipodes and / or diastereomers, or as isomeric mixtures, as enantiomeric mixtures, e.g. racemates, diastereomeric mixtures or racemic mixtures; the invention also relates to pure isomers, as well as to all possible isomeric mixtures, and it is appropriate to understand the above and below in each case, even when the stereochemical details are not specifically mentioned in each case.

By the process - depending on the choice of starting materials and method of operation - or otherwise obtainable diastereomeric mixtures and racemic mixtures of compounds I or IV, in free form or salt form, can be separated, by known physics, into pure diastereomers or racemates, e.g. by fractionation crystallization, distillation and / or chromatography.

Properly obtainable enantiomeric mixtures, such as racemates, can be separated into optical antipodes by known methods, e.g. by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, e.g. by high pressure liquid chromatography (HPLC) on acetylcellulose, using suitable microorganisms, by grafting with specific, mobilized enzymes, through the formation of clathrates, e.g. using chiral crown ethers where only one enantiomer is complexed, or by conversion to diastereomeric salts, e.g. by metabolizing the basic racemate of the final substance with an optically active acid such as a carboxylic acid, e.g. with caffeic, tartaric or malic acid, or sulfonic acid, e.g. caffeine sulfonic acid, and separating the mixture of diastereomers thus obtained, e.g. based on their different solubilities by fractionation crystallization, into diastereomers from which the desired enantiomers can be released by the action of a suitable e.g. basic agent.

Apart from the separation of the corresponding isomeric mixtures, the pure diastereomers and / or The enantiomers of the invention are also obtained by commonly known diastereoselective and / or diastereoselective methods. enantioselective syntheses, e.g. so that the process of the invention is carried out with educts of appropriately appropriate stereochemistry.

Preferably, each time is isolated or. biosoluble isomers are synthesized, e.g. enantiomers or diastereomers, or an isomeric mixture, e.g. enantiomeric mixture or diastereomeric mixture to the extent that the individual components have different biological efficacy.

The compounds I or. IV, in free or salt form, may also be obtained in the form of their hydrates and / or include other solvents, e.g. optionally useful for crystallization in solid form of existing compounds.

The invention relates to all such embodiments of the process from which a compound is obtained that can be obtained at any stage of the process as a starting or intermediate product, by which all or some of the missing steps are carried out, or by which the starting material is used in the form of a derivative or. salts and / or its racemates, respectively. antipodes, or in particular, are formed under reaction conditions.

In the process of the present invention, such starting materials and intermediates, in each case in the free or salt form, which lead to the compounds I or I, are preferably used. their salts, which are shown as particularly valuable inputs.

The invention particularly relates to the preparation procedures described in Examples HI to H4.

For the preparation of compounds I and / or the salts used starting materials and intermediates of the invention, in each case in free or new salt form, a process for their preparation and their use as starting materials and intermediates for the preparation of compounds I, are also the subject of the present invention; this is especially true of compounds IV.

Compounds I of the invention are, in the field of pest control, in the favorable transferability of warm-blooded animals, fish and plants, at low concentrations used, the active substance with a very favorable biocidal spectrum is preventively and / or curatively valuable. The active substances of the invention are effective against all or individual stages of development of normally sensitive but also resistant animal pests such as insects. The insecticidal action of the active substances of the invention can be directly demonstrated, that is, in the killing of a pest that occurs directly or only after some time, e.g. in levitation, or indirectly, e.g. in the reduction of egg deposition and / or hatching rates, where good functioning corresponds to a mortality rate (mortality) of at least 50 to 60%.

These animal pests include, for example:

from the order of Lepidoptera for example

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis. , Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparophesis castanea. spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis sppria, Lobocollethis spp. ., Malacosoma spp., Mamestra brassicae, Manduca sexta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Pieris spp., Pieris spp., Pieris spp., Pieris spp. Scirpophaga spp., S esamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp .;

from the order of Coleoptera for example

Agriotes spp., Anthonomus spp., Atomaria linearis, Choaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp., Leptinotarsa decemlineata, Lissorcappolthpp. Spp. spp., Otiorhynchus spp., Phlyctinus spp., Popiha spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and Trogoderma spp .;

from the Orthoptera order for example

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Periplaneta spp. and Schistocerca spp .; from the order Isoptera for example Reticulitermes spp .;

from the order of Psocoptera for example

Liposcelis spp .;

from the order of Anoplur for example

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp ·;

from the order of Mallophaga for example

Damalinea spp. and Trichodectes spp .;

from the order of Thysanoptera for example

Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palm trees, Thrips tabaci and Scirtothrips aurantii; from the order of Heteroptera for example

Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis, Scotinophara spp. and Triatoma spp .;

from the order of Homoptera for example

Aleurothrisux floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium, Chrysomphalus dictyospermi, Coccus hesperidum, Epoasiappa, Erposa, Erpura, Erpa, Erpura, Erposa, Erpura , Laodelphax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudoc, spp. ., Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri;

from the order of Hymenoptera for example

Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp .;

from the Diptera order for example

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex xpp., Cuterebra spp., Dacus spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Glossina spp., Glossina spp. ., Hyp20 pobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Somara spp., Somara spp. ., Tabanus spp., Tannia spp. and Tipula spp .; from the order of Siphonapter for example

Ceratophyllus spp. and Xenopsylla cheopis and from the order of Thysanura for example

Lepisma saccharina.

The active substances of the invention can be used to suppress in particular pests of the aforementioned type, which are found on plants, especially useful and ornamental plants in agriculture, horticulture and in the forest, or on parts of such plants as fruits, flowers, leaves, stems, tubers or roots, that is to say, to prune or destroy them, with some parts of the plant being protected against these pests.

Cereals, such as wheat, barley, rye, oats, rice, corn or sorghum, are particularly targeted as target crops; beets, such as sugar or fodder beets; fruits, e.g. baked, stone and berry fruits such as apples, pears, plums, peaches, almonds, cherries or strawberries, e.g. strawberries, raspberries or blackberries; leguminous vegetables, such as beans, lentils, peas or soybeans; oilseeds, such as rape, mustard, poppy, olive, sunflower, coconut, castor, cocoa or groundnuts; pumpkins, such as pumpkins, cucumbers or melons; fibrous plants such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, or peppers; laurels such as avocado, cinnamon or camphor; as well as tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, rubber and ornamental plants.

The active substances of the invention are particularly suitable for the control of Aphis craccivora, Bemisia tabaci, Diabrotica balteata, Heliothis virescens, Myzus persicae, Nephotettix cincticeps and Nilaparvata lugens on vegetable, maize, fruit, rice and soybean cultures.

Further areas of application of the active substances of the invention are the protection of supplies and warehouses and materials, as well as in the hygiene field, in particular the protection of pets and beneficial domestic animals from pests of the aforementioned type.

The invention therefore also relates to pest control agents selected according to the set goals and given ratios, such as emulsifiable concentrates, suspension concentrates, directly dispersible or dilutable solutions, lubricating pastes, diluted emulsions, spraying powders, soluble powders, dispersible powders, wettable powders, powders, granules or capsules in polymeric substances containing - at least one of the active substances of the invention.

The active substance is used in these agents in pure form, a solid active substance e.g. in a particular grain size, or preferably together with - at least - one of the excipients customary in formulation techniques such as fillers, e.g. solvents or solid carriers or such as surfactants.

Suitable solvents may be, for example: optionally partially hydrogenated aromatic hydrocarbons, preferably fractions of C ₈ to C ₁₂ alkylbenzenes, such as xylenic mixtures, alkylated naphthalenes or tetrahydronaphthalenes, aliphatic or cycloaliphatic hydrocarbons, such as paraffin or cyclohexane, alcohols, ethanol, alcohols propanol or butanol, glycols as well as their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol mono-methyl- or ethyl-ether, ketones such as cyclohexanone, isophorone or diacetanol alcohol, strongly polar solvents, such as N-methylpyrrolid-2-pyrrolide dimethylsulfoxide or Ν, Ν-dimethylformamide, water, optionally epoxidized vegetable oils, as in the present case epoxidized rapeseed, castor, coconut or soybean oil and silicone oils.

As solids, e.g. for powders and dispersible powders, we generally use natural stone flours such as calcite, talc, kaolin, montmorillonite or atapulgite. Highly dispersed silica or highly dispersible absorbent polymerizates can also be added to improve the physical properties. As granular, adsorptive granulate carriers, porous types such as float, brick chippers, sepiolite or bentonite, and not sorptive carrier materials calcite or sand are considered. In addition, many of the granular materials of inorganic or organic nature, in particular dolomite or crushed plant residues, can be used.

Depending on the type of active substance to be formulated, surfactants are suitable, nonionic, cationic and / or anionic surfactants or surfactant compositions with good emulsifying, dispersing and wetting properties. The surfactants introduced below should only be considered as examples; Numerous further surfactants, useful in the formulation and according to the invention, are described in the proposed literature.

Non-ionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain from 3 to 30 glycol ether groups and from 8 to 20 carbon atoms in (aliphatic) hydrocarbons and up to 6 carbon atoms and up to 6 in the alkyl residue of alkylphenol. Also suitable are water-soluble, 20 to 250 ethylene glycol ether and 10 to 100 propylene glycol ether groups containing polyethylene oxide adducts on polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. These compounds typically contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples include nonylphenolpolyethoxyethanol, castor oil polyglycoleters, polypropylene polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters with polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are further preferred.

The cationic surfactants are mainly quaternary ammonium salts having at least one alkyl residue of 8 to 22 C atoms as substituents and lower, optionally halogenated, alkyl, benzyl, or lower hydroxyalkyl residues as further substituents. Salts preferably exist as halides, methylsulphates or ethylsulphates. Examples are stearyltrimethyl-ammonium chloride and benzyl-di- (2-chloroethyl) -ethyl-ammonium bromide.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surfactants. Suitable alkalis, alkaline earth alkalis and optionally substituted higher fatty acid ammonium salts (C ₂₂ C ₂₂ ), such as the oleic or stearic acid sodium or potassium salts, or mixtures of natural fatty acids which may be obtained e.g. of coconut oil or tallow oil; we should also mention the methyl-taurine salts of the fatty acid. However, synthetic surfactants, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates, are more commonly used. Fat sulphonates and -sulphates generally exist as alkali, alkaline earth or optionally substituted ammonium salts and generally have an alkyl residue of 8 to 22 C atoms, where alkyl also includes the alkyl portion of the acyl radical; as an example, the sodium or calcium salt of ligninsulfonic acid, the dodecyl sulfuric acid ester or a mixture of fatty alcohol sulphates made from natural fatty acids. Also included are sulfuric acid and sulfonic acid esters salts with fatty alcoholethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and one fatty residue having about 8 to 22 C atoms. Alkylarylsulfonates are e.g. sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or the condensation product of naphthalenesulfonic acid formaldehyde. Further suitable phosphates, such as phosphoric acid ester salts with p-nonylphenol- (4-14) -ethylene oxide adduct, or phospholipids, are also suitable.

The agents generally contain 0.1 to 99%, in particular 0.1 to 95% of the active substance and 1 to 99.9%, in particular 5 to 99.9%, of at least the solid or liquid excipients, where they can generally be 0 to 25%, in particular 0.1 to 20% of the surfactant (% means mass percentage). While concentrated products are more preferred as market products, as a rule end-user uses dilute agents containing significantly lower concentrations of the active substance. The priority means are composed in particular in the following ways (% = percentage by weight):

Emulsifiable concentrates:

active substance:

surfactant:

solvent:

Dusty:

active substance: solid carrier:

Suspension concentrates:

active substance:

water:

surfactant:

Wetting powders:

active substance: surfactant:

solid carrier material:

Granules:

active substance: solid active substance:

up to 90%, preferably 5 to 20% to 30%, preferably 10 to 20% 5 to 98%, preferably 70 to 85%

0.1 to 10%, preferably 0.1 to 1% 99.9 to 90%, preferably 99.9 to 99% to 75%, preferably 10 to 50% 94 to 24%, preferably 88 to 30% 1 to 40 %, preferably 2 to 30%

0.5 to 90%, preferably 1 to 80%, 0.5 to 20%, preferably 1 to 15%, 5 to 99%, preferably 15 to 98%

0.5 to 30%, preferably 3 to 15%, 99.5 to 70%, preferably 97 to 85%

The effect of the agents of the invention can be significantly expanded by the addition of other insecticidal active substances and adapted to the given conditions. For example, as an active substance, additives, for example, should be considered. representatives of the following classes of active substances: organic phosphorus compounds, nitrophenols and derivatives, formamidines, urea, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations. The agents of the invention may also contain further solid or liquid auxiliaries such as stabilizers, e.g. optionally epoxidized vegetable oils (e.g. epoxidized coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and / or adhesives, as well as fertilizers or other active substances to achieve special effects, e.g. acaricides, bactericides, fungicides, nematosides, molluscides, or selective herbicides.

The agents of the invention can be prepared in a known manner, in the absence of excipients, e.g. by grinding sieving and / or compressing a solid or a mixture of active substances, e.g. to a given grain size, and in the presence of at least one excipient, e.g. by vigorously mixing and / or grinding the active substance or mixture of the active substance with the excipient (s). These processes for the preparation of the agents of the invention and the use of compounds I for the preparation of these agents also form the object of the present invention.

Methods of application for agents, that is, procedures for controlling pests of the aforementioned type, which can be selected according to the set goals and given ratios, such as spraying, degreasing, spreading, spreading, disinfecting, spreading or watering, and the use of pest control agents of the said type are are further objects of the present invention. Typical concentrations of use are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm of the active substance. Consumption per hectare is generally 1 to 2000 g of active substance per hectare, in particular 10 to 1000 g / ha, preferably 20 to 600 g / ha.

A particularly advantageous process of application in the field of plant protection is the application to plant foliage (leaf application), where the application frequency and the amount consumed can be adjusted according to the attack with each pest. The active substance can also enter the plants through the root system (systemic action) by soaking the plant site with a liquid agent or introducing the active substance in solid form into the plant site, e.g. into the ground, e.g. in the form of granulate (floor application). In Indian rice crops, such granules can be further dosed to a flooded rice field.

The agents of the invention are also suitable for protecting plant seed material, e.g. seeds, such as fruits, tubers or grains, or plant cuttings,

IS against animal pests. The seed material can then be treated with an agent prior to crushing, e.g. disinfect before sowing. The active substances of the invention can also be applied to the seeds by coating the grains either by soaking them in a liquid medium or by coating them with a solid agent. The agent can also be used for the application of seed material at the site of application, e.g. when sowing in sowing furrows. These treatment processes for plant seed material and the plant seed material thus treated are further objects of the present invention.

The following examples serve to illustrate the invention. They do not limit the invention. Temperatures are given in degrees Celsius.

Examples of preparation

Example HI:

3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine

Γ ° Ί

HN. N

OH,

N-NO ₂ oz. 3-methyl-4-nitroamino-1,2,3,6-tetrahydro-1,3,5-oxadiazine

CH γ · 'CH,

N (H) -NO ₂

A mixture of 20 g of N-methyl-N'-nitro-guanidine, 17 g of triethylamine, 100 ml of dioxane and 100 ml of toluene was stirred at room temperature with 30.5 g of paraformaldehyde, heated under reflux for 16 hours and then evaporated in vacuo. The residue was purified by column chromatography [silica gel; dichloromethane / methanol (95: 5)] to give the title compound, which melted at 137 to 139 °.

Example H2:

In an analogous manner, as described in the case of HI, we can also prepare:

3-ethyl-4-nitroimino-perhydro-1,3,5-oxadiazine, resp. 3-ethyl-4-nitroamino-1,2,3,6-tetrahydro-1,3,5-oxadiazine,

4- nitroimino-3-propyl-perhydro-1,3,5-oxadiazine, resp. 4-nitroamino-3-propyl-1,2,3,6tetrahydro-1,3,5-oxadiazine (resin),

3-butyl-4-nitroimino-perhydro-1,3,5-oxadiazine, resp. 3-butyl-4-nitroamino-1,2,3,6tetrahydro-1,3,5-oxadiazine (melting point 80 - 82 °),

3-cyclopropyl-4-nitroimino-perhydro-1,3,5-oxadiazine, resp. 3-cyclopropyl-4-nitroamino 1,2,3,6-tetrahydro-1,3,5-oxadiazine,

3- allyl-4-nitroimino-perhydro-1, 3,5-oxadiazine, resp. 3-allyl-4-nitroamino-1,2,3,6-tetrahydro-1,3,5-oxadiazine (resin),

4- nitroimino-3-propargyl-perhydro-1,3,5-oxadiazine, resp. 4-nitroamino-3-propargyl 1,2,3,6-tetrahydro-1,3,5-oxadiazine (melting point: 102 - 104 °),

4-cyanoimino-3-methyl-perhydro-1,3,5-oxadiazine, resp. 4-cyanoamino-3-methyl-1,2,3,6tetrahydro-1,3,5-oxadiazine (melting point 121-122 °),

4-cyanoimino-3-ethyl-perhydro-1,3,5-oxadiazine, resp. 4-cyanoamino-3-ethyl-1,2,3,6-tetrahydro-1,3,5-oxadiazine,

4-cyanoimino-3-cyclopropyl-perhydro-1,3,5-oxadiazine resp. 4-cyanoamino-3-cyclopropyl-1,2,3,6-tetrahydro-1,3,5-oxadiazine and

4-Nitroimino-3- (2-phenylethyl) -perhydro-1,3,5-oxadiazine, resp.

4- nitroamino-3- (2-phenylethyl) -1,2,3,6-tetrahydro-1,3,5-oxadiazine (m.p .: 123-125 °).

Example H3:

5- (2-Chloropyrid-5-ylmethyl) -3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine (Table 1, compound no. 1.2)

Cl

A mixture of 1.44 g of 3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine, 2.2 g of 2-chloro-5-chloromethyl-pyridine, 3.7 g of potassium carbonate and 20 ml of N, N-dimethylformamide heated to 50 ° C for 4 hours, filtered, the filtrate on a rotary evaporator was evaporated in vacuo and the residue was chromatographed [silica gel; dichloromethane / methanol (95: 5)]. This gives the title compound, which melts at 116 to 118 °.

Example H4:

In the analogous manner as described in Examples HI to H3, the other compounds of Tables 1 and 2 can also be prepared. In the column, the physical data in these tables indicate the given temperatures at each time of the melting point of the compound in question.

Table 1

Λ

A / ^N \ / ^{N — R} n

N-NO,

Compound no

Physical data

1.1 σ ch ₃ 1.2 ch ₃ 1.3 ^Cl ch ₃ 1.4 σ ⁷ X 0 - X Cl + ch ₃ 1.5 ch ₃ 0- 1.6 ^cl xr Cl ch ₃ 1.7 ^cl Xr Cl N + ch ₃ 1.8 «, XX ch ₃ 1.9 c ₂ h ₅ 1.10 «U c ₂ h ₅

116-118 °

132-134 °

210 ° (decay)

188-191 °

199 ° (decay)

141-144 °

Compound no. A R Physical data

1.11 c, XX ^ 3 1.12 —D 1.13 «XX I1-C3H7 resin 1.14 «<R I1-C4H9 resin 1.15 alil resin 1.16 Xf propargyl 103-108 ' 1.17 x 11-C4H9 71-73 ° 1.18 ° x propargyl 176 ° 1.19 «XX CH ₂ CH ₂ -C ₆ H ₅ resin 1.20 «-S„ X resin

Table 2

² · ¹⁰ _C1 XX —o

Compound no.

Physical data

2.11

- ^ 1

Examples of preparations (% = percentage by weight)

Example Fl: Emulsion concentrates

Active substance no. 1.2

Ca-dodecylbenzenesulfonate Castor oil polyethylene glycol ether (36 mol EO)

Tributylphenolpolyethylene glycol ether (30 mol EO)

Cyclohexanone An xylene mixture

a) b) c)% 40% 50%% 8% 6%

5% 12% 4%% 20%% 25% 20%

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

Example F2: Solutions

a) b) c) d)

Active substance no. 1.3

Ethylene glycol monomethyl ether Polyethylene glycol MG 400 N-methyl-2-pyrrolidone Epoxidated coconut oil Gasoline (boiling range 160 -190 ° C)

80%

20%

10%

70%

20% 94%

95%

The solutions are suitable for use in very small droplets.

%

Example F3: Granules ^a ) b) ^c ) d) Active substance no. 1.2. 5% 10% 8% 21% Kaolin 94% - 79% 54% Highly dispersed silica 1% - 13% 7% Atapulgit - 90% - 18%

The active substance was dissolved in dichloromethane, sprayed onto the support and the solvent evaporated in vacuo immediately.

Example F4: Dust ^a ) b) Active substance no. 1.2 2% 5% Highly dispersed silica 1% 5% Talc 97% - Kaolin - 90%

Good mixing of the carrier materials with the active substance gives ready-to-use powders.

Example F5: Spray powder a) b) ^c ) Active substance no. 1.2 25% 50% 75% Na-ligninsulfonate 5% 5% - Na-laurylsulfate 3% - 5% Na-diisobutylnaphthalenesulfonate - 6% 10% Octylphenol polyethylene glycol ether (7 - 8 mol EO) - 2% - Highly dispersed silica 5% 10% 10% Kaolin 62% 27% -

The active substance is mixed with additives and ground well in a suitable mill. A spray powder is obtained which can be diluted with water to suspensions of any desired concentration.

Example F6: Emulsion concentrate

Active substance no. 1.3 10%

Octylphenol polyethylene glycol ether (4-5 mol EO) 3%

Ca-dodecylbenzenesulfonate 3%

Castor oil polyglycoleter (36 mol EO) 4%

Cyclohexanone 30%

Xylene mixture 50%

Emulsions of any concentration can be prepared from this concentrate by dilution with water.

Example F7: Dusty

Active substance no. 1.2

Talc

Kaolin

a) b)% 8%

95%

92%

Prepared powders are prepared by mixing the active substance with the carrier and grinding at a suitable mill.

Example F8: Extrusion granulate

Active substance no. 1.3 10%

Na-ligninsulfonate 2%

Carboxymethylcellulose 1%

Kaolin 87%

The active substance is mixed with additives, ground and moistened with water. This mixture is extruded, granulated and then dried in an air stream.

Example F9: Shell granulate

Active substance no. 1.2 Polyethylene glycol (MM 200) Kaolin

3%

3%

94%

The finely ground active substance in the mixer is uniformly applied to the polyethylene glycol moistened kaolin. In this way, a dust-free wrapping granulate is obtained.

Example F10: Suspension concentrate

Active substance no. 1.3

Ethylene glycol

Nonylphenol polyethylene glycol ether (15 mol EO)

Na-ligninsulfonate

Carboxymethylcellulose% aqueous formaldehyde solution

Silicone oil in the form of a 75% aqueous emulsion

Water

40%

10%

6%

10% 1%

0.2%

0,8%

32%

The finely ground active substance is well mixed with additives. A suspension concentrate is thus obtained from which a suspension of any desired concentration can be prepared by diluting with water.

Biological cases (% = percentage by mass, unless otherwise stated)

Example BI: Effect against Anthonomus grandis

Spray the young cotton plants with an aqueous emulsion sprayer containing 400 ppm of active substance. After drying the spray coating of the seedlings, populate with 10 adults of Anthonomus grandis and place in a plastic container. Three days later, an evaluation is performed. From the comparison of the number of dead beetles and the damage to swallows between treated and untreated plants, we determine the percentage reduction in population and the percentage reduction in damage to swallows (% effect).

The compounds of Tables 1 and 2 show a good effect in this test. In particular, compounds No.

1.2,1.3 and 2.3 effect with more than 80%.

Example B2: Action against Aphis craccivora

The pea seedlings were infected with Aphis craccivora, immediately sprayed with a sprinkler containing 400 ppm of active substance and then incubated at 20 ° C.

and 6 days later the evaluation is performed. From the comparison of the number of dead aphids on treated and untreated plants, we determine the percentage reduction in population (% effect).

The compounds of Tables 1 and 2 show a good effect in this test. In particular, compounds No. 1.2,1.3,1.15, 2.2 and 2.3 effect with more than 80%.

Example B3: Effect against Bemisia tabaci

Place low bean plants in gauze cages and populate with adult Bemisia tabaci. After egg laying, all adults are removed. 10 days later, the plants, with their nymphs sensitive, were sprayed with an aqueous emulsion sprinkler containing 400 ppm of active substance. After a further 14 days, evaluate the percentage of hatching of eggs compared to untreated controls.

The compounds of Tables 1 and 2 show a good effect in this test. In particular, they show compounds of no. 1.2 and 1.3 effect with more than 80%.

Example B4: Effect against Ctenocephalides felis (systemic)

Twenty adult lice of the species Ctenocephalides felis are placed in a flat, round, gauze-covered cage on both sides. Place a container on the cage, which is sealed with a parafilm membrane on the underside. The container contains blood containing 5 ppm of active substance and is continuously heated to 37 ° C. Lice feed on blood through the membrane. An evaluation is performed 24 and 48 hours after adjustment. From the comparison of the number of dead lice in the use of treated blood and in the use of untreated blood, we determine the percentage decrease in population (% effect). 24 hours after treatment, the blood is replaced by new, also treated blood.

The compounds of Tables 1 and 2 show a good effect in this test. In particular, they show compounds of no. 1.2 and 1.3 effect with more than 80%.

Example B5: Effect against Diabrotica balteata

Spray the seedlings of maize with an aqueous emulsion sprinkler containing 400 ppm of active substance. After drying the sprinkler liner, plant seedlings with 10 larvae of the second stage Diabrotica balteata and place in a plastic container. 6 days later, an evaluation is performed. From the comparison of the number of dead larvae between treated and untreated plants, we determine the percentage decrease in population (% of effect).

The compounds of Tables 1 and 2 show a good effect in this test. In particular, compounds No.

1.2,1.3,1.5 and 2.3 effect with more than 80%.

Example B6: Effect against Heliothis virescens

Young soybean plants are sprayed with an aqueous emulsion sprayer containing 400 ppm of active substance. After drying the spray coating, the plants are planted with 10 caterpillars of the first stage of Heliothis virescens and placed in a plastic container. 6 days later, an evaluation is performed. From the comparison of the number of dead caterpillars and the damage to planting between treated and untreated plants, we determine the percentage reduction in population and damage to planting (% effect).

The compounds of Tables 1 and 2 show a good effect in this test. In particular, they show compounds of no. 1.2 and 1.3 effect with more than 80%.

Example B7: Effect against Heliothis virescens (ovi / larvicide)

Heliothis virescens eggs deposited on cotton are sprayed with an aqueous emulsion sprayer containing 400 ppm of active substance. After 8 days, we evaluate the percentage of hatching eggs and the survival rates of the caterpillars compared to the untreated controls (% population reduction).

The compounds of Tables 1 and 2 show a good effect in this test

Example B8: Effect against Myzus persicae

The pea seedlings were infected with Myzus persicae, then sprayed immediately with a spray spray containing 400 ppm of active substance and then incubated at 20 °. 3 and 6 days later, the evaluation is performed. From the comparison of the number of dead aphids on treated and untreated plants, we determine the percentage reduction in population (% effect).

The compounds of Tables 1 and 2 show a good effect in this test. In particular, they show compounds of no. 1.2 and 1.3 effect with more than 80%.

Example B9: Effect against Mvzus persicae (systemic)

The pea seedlings were infected with Myzus persicae, immediately rooted in a spray broth containing 400 ppm of active substance and then incubated at 20 °. 3 and 6 days later, the evaluation is performed. From the comparison of the number of dead aphids on treated and untreated plants, we determine the percentage reduction in population (% effect).

The compounds of Tables 1 and 2 show a good effect in this test. In particular, compounds No.

1.2,1.3 and 1.5 effect with more than 80%.

Example B10: Effect against Nephotettix cincticeps

Spray the rice plants with an aqueous emulsion sprayer containing 400 ppm of active substance. After drying the spray coating, the plants are planted with stage 2 and 3 larvae. 21 days later, an evaluation is performed. From the comparison of the number of surviving dwarves on treated and untreated plants, we determine the percentage decrease in population (% of effect).

The compounds of Tables 1 and 2 show a good effect in this test. In particular, compounds No.

1.2,1.3 and 1.5 effect with more than 80%.

Example Bill: Effect against Nephotettix cincticeps (systemic)

Put the pots with the rice plants in an aqueous emulsion solution containing 400 ppm of active substance. The plants are then populated with stage 2 and 3 larvae. 6 days later, an evaluation is performed. From the comparison of the number of gills on treated and untreated plants, we determine the percentage decrease in population (% effect).

The compounds of Tables 1 and 2 show a good effect in this test. In particular, compounds No. 1.3,1.5,1.13 and 1.15 effect with more than 80%.

Example BI2: Effect against Nilaparvata lugens

The rice plants are treated with an aqueous emulsion sprayer containing 400 ppm of active substance. After drying the spray coating of the rice plant, it is populated with stage 2 and stage 3 larvae. 21 days later, an evaluation is performed. From the comparison of the number of surviving dwarves on treated and untreated plants, we determine the percentage decrease in population (% of effect).

The compounds of Tables 1 and 2 show a good effect in this test. In particular, compounds No.

1.2,1.3,1.5,1.8 and 2.3 effect with more than 80%.

Example B13: Effect against Nilaparvata lugens (systemic)

Put the pots with rice plants in an aqueous emulsion solution containing 10 ppm of active substance. The plants are then populated with stage 2 and 3 larvae. 6 days later, an evaluation is performed. From the comparison of the number of surviving dwarves on treated and untreated plants, we determine the percentage decrease in population (% of effect).

The compounds of Tables 1 and 2 show a good effect in this test. In particular, compounds No. 1.2,1.3,1.4, 1.5,1.13,1.15, 2.2 and 2.3 effect with more than 80%.

Example B14: Effect against Blattella germanica

Add as much acetone solution (0,1%) of the active substance into the petri dish that its amount corresponds to the amount consumed 1 g / m ² . When the solvent has evaporated, place 10 nymphs of Blattella germanica (the last stage of the nymph) in the vessel and expose the test compound for 2 hours. The nymphs are then narcotized with CO ₂ , transferred to fresh petri dishes and kept at 25 ° and about 70% air humidity in the dark. After 48 hours, the insecticidal effect is determined by determining the mortality rate.

The compounds of Tables 1 and 2 show a good effect in this test. In particular, compound no. 1.3. An effect of more than 80%.

Example B15: Effect against Lucilia cuprina

Place 30 to 50 freshly hatched Lucilia cuprina eggs in tubes in which 4 ml of nutrient medium was previously mixed with 1 ml of test solution containing 16 ppm of active substance. After sowing the culture medium, the tubes are closed with a cotton wool stopper, and in a hatcher at 30 °, we simmer for 4 days. Until now, approximately 1 cm long larvae develop in the untreated medium (stage 3). If the test substance is active, the larvae are either dead or clearly retarded by this point. The evaluation is performed after 96 hours.

The compounds of Tables 1 and 2 show a good effect in this test. In particular, compound no. 1.3. An effect of more than 80%.

Example B16: Effect against Musca domestica

The sugar cube is treated with so much test substance solution that, after drying overnight, the test substance concentration in the sugar is 250 ppm. Place the cubes thus treated in an aluminum cup with a moist cotton swab and 10 adults of the OP-resistant Musca domestica. Cover them with a glass beaker and incubate at 25 °. Mortality rates are determined after 24 hours.

The compounds of Tables 1 and 2 show a good effect in this test. In particular, compound no. 1.3. An effect of more than 80%.

Claims (30)

PATENT APPLICATIONS A compound of formula (I), characterized in that A represents an unsubstituted or once or four times substituted, aromatic or non-aromatic, monocyclic or bicyclic, heterocyclic radical, wherein one to two substituents of A may be selected from the group consisting of halogen-C ₁ -C ₃ alkyl, cyclopropyl, halogencyclopropyl, C ₂ -C ₃ -alkenyl, C ₂ -C ₃ -alkynyl, halogen-C ₂ -C ₃ -alkenyl, halogen-C ₂ -C ₃ -alkynyl, halogen-C 1 -C 6 alkoxy, C 1 -C ₃ alkylthio, halogen-C 4 -Cg-alkylthio, allyloxy, propargyloxy, allylthio, propargylthio, halogenallyloxy, halogenallythio, cyano and nitro, and one to four substituents of A from the group consisting of C1-C6-alkyl, C1-C8-alkoxy and halogen; R is hydrogen, C 1 -C 4 -alkyl, phenyl-C ₁ -C 1 -alkyl, C ₃ -C ₆ -cycloalkyl, C ₂ -C ₆ -alkenyl or CC-alkynyl; and X is N-NO ₂ or N-CN, or optionally its tautomer, in each case in free or salt form. Compound according to claim 1 of the formula I, characterized in that the ring-base frame A is made of a ring with 5 or 6 ring members, to which an additional ring with 5 or 6 ring members or, optionally, its tautomer. Compound according to claim 1 of the formula I, characterized in that the ring-base frame A is unsaturated or, optionally, its tautomer. A compound according to claim 1 of formula I, characterized in that the ring-base framework A contains 1 to 4 heteroatoms, or optionally a tautomer thereof. A compound according to claim 1 of the formula I, characterized in that the ring-base frame A is selected from the group consisting of ring-base frames Ν UK% Ν ^Χ % 'N οΡ ^ οΡ ^ οΡ ^' sP Ν. Ν ^ Ν Λ. ^ Tl N '^ ^X ' N <ί? Ο- S ^ (PS ^ S ^ <P ^ cP _O A _S J - «A '''Τι S Ο Ν O ^z OS ^ ^ NS ^ N UK ^X N JS '· *' n ^ -'- ' N. N J Λ / ' Υ Υ γ ο Υ Υ wherein E is each C 1 -C ₃ -alkyl, Y in each case hydrogen, C 1 -C 8 -alkyl or cyclopropyl, and E or. Y is not always present as a substituent of A, but is assigned to the ring base A, or optionally its tautomer. A compound according to claim 5 of formula I, characterized in that the ring-base framework A contains 1, 2 or 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, with at most one of the heteroatoms having are in the ringbase, the oxygen atom, and is at most one of the heteroatoms in the ringbase, the sulfur atom, or optionally its tautomer. A compound according to claim 6 of formula I, characterized in that A is bonded via the C atom of its ring base to the rest of compound I, or optionally its tautomer. A compound according to claim 7 of formula I, characterized in that A is unsubstituted or once or twice substituted with substituents selected from the group consisting of halogen, C 1 -C 6 alkyl, halogen-C 1 -C 6 alkyl, C C 1 -C 4 -alkoxy and halogen-C 1 -C 4 alkoxy, or optionally a tautomer thereof. A compound according to claim 8 of formula I, characterized in that the ring-base framework A is a pyridyl, 1-oxidopyridinio or thiazolyl group, or optionally a tautomer thereof. A compound according to claim 1 of formula I, characterized in that RC is -C 1 -alkyl, phenyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₄ -alkenyl or C ₃ -C _4- alkynyl, or optionally its tautomer. A compound according to claim 1 of formula I, wherein X is N-NO ₂ , or optionally a tautomer thereof. A compound according to claim 9 of formula I, characterized in that A represents via the C-atom of its ring-base framework bound, unsubstituted or once or twice with substituents selected from the group consisting of the group consisting of halogen and C-C-alkyl substituted, pyridyl, 1-oxidopyridinio- or thiazolyl group, R represents C ₁ -C ₆ alkyl, phenyl-C-C-alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ C ₄ -alkenyl or C ₃ -C ₄ -alkynyl and X is N-NO ₂ or N-CN, or optionally its tautomer. A compound according to claim 12 of formula I, wherein A is 2-chloropyrid-5-yl, 2-methylpyrid-5-yl, 1-oxido-3-pyridinio-, 2-chloro-1-oxido-5- pyridinio-, 2,3-dichloro-1-oxido-5-pyridinio- or 2-chlorothiazol-5-yl group, R is C 1 -C 4 alkyl and X is N-NO ₂ . A compound according to claim 13 of formula I, wherein A is a 2-chlorothiazol-5-yl or 2-chloropyrid-5-yl group, R is C 1 -C 6 -alkyl and X is N-NO ₂ . A compound according to claim 13 of formula I, selected from the group consisting of compounds (a) 5- (2-chloropyrid-5-ylmethyl) -3-methyl-4-nitroimino-perhydro-1, 3,5-oxadiazine, (b) 5- (2-chlorothiazol-5-ylmethyl) -3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine, (c) 3-methyl-4-nitroimino- 5- (1-Oxido-3-pyridiniomethyl) -perhydro-1,3,5-oxadiazine, (d) 5- (2-chloro-1-oxido-5-pyridiniomethyl) -3-methyl-4-nitroimino-perhydro -1, 3,5oxadiazine and (e) 3-methyl-5- (2-methylpyrid-5-ylmethyl) -4-nitroimino-perhydro-1,3,5-oxadiazine. 16. A process for the preparation of a compound according to claim 1 of formula I, or optionally its tautomer, in each case in free or salt form, characterized in that a) a compound of formula H H I I X (Π), which is known or can be prepared analogously to the corresponding known compounds, and wherein A, R and X have the meanings given for formula I, or their tautomer and / or salt, is metabolised, preferably in the presence of a base or further an acid catalyst, by formaldehyde or paraformaldehyde or b) for the preparation of a compound of formula I wherein R is other than hydrogen, or optionally its tautomer and / or salt, e.g. according to variant a) or c) a obtainable compound of formula I, wherein R is hydrogen, or a tautomer and / or salt thereof, is reacted, preferably in the presence of a base, with a compound of formula Y-R (III), which is known or can be prepared analogously to the corresponding known compounds, and wherein R for the formula I has the meanings indicated with the exception of hydrogen and Y stands for the leaving group, or c) a compound of formula X (IV), where R and X have the meanings given for formula I, or their tautomer and / or salt, is preferably reacted in the presence of a base with a compound of formula a-ch ₂ -y (V) which is known or can be prepared analogous to the corresponding known compounds and wherein A has the indicated meaning for formula I and Y stands for the leaving group or optionally its tautomer and / or salt, and / or, where desired, a process or otherwise obtainable compound of formula I, or its tautomer, in each case in free or salt form, is converted to another compound of formula I, or a tautomer thereof, by the process, the resulting mixture of isomers is separated and the desired isomers are isolated and / or by the process, or by any other method, the free compound of formula I or its the tautomer is converted into a salt, or by a process or otherwise obtained salt of a compound of formula I or its tautomer, is converted into a free compound of formula I or its tautomer, or into another salt. 17. A pest control product comprising at least one compound according to claim 1 of Formula I, or optionally a tautomer, in each case in free form or in the form of an agrochemical salt, and optionally at least one excipient, as the active substance. . 18. An insect repellent agent according to claim 17. A method for the preparation of at least one excipient-containing agent according to claim 17, characterized in that the active substance is well mixed with the excipient (s) and / or milled. Use of a compound of claim 1 of formula I, or optionally a tautomer thereof, in each free or agrochemical salt form, for the preparation of an agent of claim 17. Use of an agent according to claim 17 for pest control. Use according to claim 21 for the control of insects. Use according to claim 21 for the protection of plant seed material. 24. A pest control method, characterized in that the agent of claim 17 is applied to the pests or their habitat. 25. The method of claim 24 for controlling insects. 26. A method according to claim 24 for the protection of a plant seed material, characterized in that the seed material or the site of wear of the seed material is treated. Plant vegetable material, characterized in that it is treated according to the method described in claim 26. A compound of formula A ^Η ' ^Ν γ ^Ν Ή X (IV), wherein R and X are as defined in formula I, or a tautomer thereof, in each case in free or salt form. A process for the preparation of a compound according to claim 28 of formula IV, or optionally its tautomer, in each case in free or salt form, characterized in that d) a compound of formula H H (VI), X which is known or can be prepared analogously to the corresponding known compounds and wherein R and X have the meanings indicated for formula I, or the tautomer and / or salt thereof is reacted with formaldehyde or paraformaldehyde, e.g. in an analogous manner as described in variant a) for the appropriate metabolism of a compound of formula II or its tautomer and / or salt with formaldehyde or paraformaldehyde, or e) to prepare a compound of formula IV, wherein R is other than hydrogen, or a tautomer and / or salt thereof, e.g. according to variant d) a obtainable compound of formula IV, wherein R is hydrogen, or a tautomer thereof and / or a salt of a compound of formula Y-R (III), which is known or can be prepared analogously to the corresponding known compounds, and wherein R for the formula I has the meanings indicated with the exception of hydrogen, and Y stands for the leaving group, e.g. in an analogous manner as described in variant b) for the appropriate metabolism of a compound of formula I or, optionally, its tautomer and / or salt with a compound of formula III, and / or, where desired, by a process or by any other means obtainable a compound of formula IV or a tautomer thereof, in each case in free form or in salt form, is converted to another compound of formula IV or a tautomer thereof, by the process the resulting mixture of isomers is separated and the desired isomers are isolated and / or by the process or otherwise obtainable free a compound of formula IV or a tautomer thereof is converted into a salt, or a process or otherwise obtainable salt of a compound of formula IV or its tautomer is converted into a free compound of formula IV or its tautomer or other salt. Use of a compound of claim 28 of formula IV, or optionally its tautomer, in each case in free or salt form, for the preparation of a compound of claim 1.