LT3959B - Oxadiazine derivatives - Google Patents

Abstract

The compounds, (which have the formulae given below),<IMAGE>where A means a residual which has none or one to four substitutes, is aromatic or non aromatic, monocyclic or bi-cyclic, heterocyclic. One or two substitutes of A can be chosen from the group, consisting of a halogen-C1-C3-alkyl, cyclopropyl, halogen cyclopropyl, C2-C3-alkenyl, C2-C3-alkynyl, halogen-C2-C3-alkenyl, halogen-C2-C3-alkynyl, halogen-C1-C3-alkoxy, C1-C3-alkyltio, halogen-C1-C3-alkylthio, allyloxy, propargyloxy, allylthio, propargylthio, halogenallyloxy, halogenalylthio, cyanogens and nitrogen, from one to four substitutes of A can be chosen from group, consisting of C1-C3-alkyl, C1-C3-alkoxy and halogen. R means C1-C6-alkyl, phenyl-C1-C4-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl or C2-C6-alkynyl. X means N-NO2 or N-CN. If there is a need, tautomers can be used either free or in the form of salts, as agrochemical biologically active components, and they are produced by the method, described in the patent.

Description

The invention relates to compounds of the following formula

^N ^ R

X (wherein A represents an unsubstituted or mono- to four-substituted, aromatic or non-aromatic, monocyclic or dicyclic, heterocyclic residue, wherein one to two A substituents may be selected from the group consisting of halo-C 1 -C 3 alkyl) , cyclopropyl, halogenciklopropilo C ₂ -C ₃ alkenyl, C ₂ -C 3 alkynyl, halo-C ₂ -C ₃ alkenyl, halo-C ₂ -C ₃ alkynyl, halo-Ci-C3-alkoxy, Ci-C _3- alkylthio, halo-C 1 -C ₃ -alkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, and one to four A substituents may be selected from the group consisting of C ₁ -C ₃ alkyl, CrCs- alkoxy and halogen; R represents hydrogen, C ₁ -C ₆ alkyl, phenyl-C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, and X represents N-NO ₂ or N-CN, in free or salt form, if appropriate, tautomers of these compounds in free or salt form of these compounds and tautomers of the method of preparation, the pest control agents, the biologically active substances of which are selected from these compounds and tautomers, as appropriate, in free form or in the form of agrochemically used salts, the methods of obtaining and using these agents, the plant seeds treated with the agents; intermediates, in free or salt form, the tautomers of these intermediates in free or salt form, where appropriate, and the process for the preparation and utilization of these intermediates.

Known pest control agents as biologically active agents against arthropods containing certain oxadiazine derivatives are described in U.S. Pat. 3059027, C 07 D 273/04, and also FR no. 1450485, C 07 D 273/04 in the patent specifications.

However, the biological properties of these known compounds in the field of pest control are not entirely satisfactory, and there is a need to propose other compounds having anti-pest properties, particularly suitable for insect control, and this object is solved by the present invention.

The compounds of formula I may be present in the form of tautomers. For example, if R represents hydrogen, then the compounds of formula I may have the 3-H-4-iminoperhydro-1,3,5-oxadiazine partial structure in equilibrium with 4-amino-1,2,5,6-tetrahydro-1,3, Partial structure of 5-oxadiazine. As used herein, the compounds of Formula I are understood to include the corresponding tautomers, even if not specifically mentioned in each case.

Compounds of formula I having at least one base center may form e.g. conjugated salts. They are formed, for example, with strong inorganic acids such as mineral acids, such as perchloric acid, sulfuric acid, nitric acid, nitric acid, phosphoric acid or hydrohalic acid, and with such strong organic acids as, where appropriate, halogen substituted Cr C ₄ -alkanoic acids such as acetic acid as required with unsaturated dicarboxylic acids such as oxalic, malonic, succinic, maleic, fumaric or phthalic acids such as hydroxycarbonic acids such as ascorbic, lactic , malic, tartaric, citric, or benzoic acids, or with organic sulfonic acids, as appropriate, e.g. with halogen substituted CrC4-alkane or aryl sulfonic acids, e.g. methane or p-toluenesulfonic acid. In addition, compounds of formula I having at least one acidic group may form salts with bases. Suitable base salts are, for example, metal salts such as alkali and alkaline earth salts, such as sodium, potassium or magnesium salts, or salts with ammonia or organic amine, such as morpholine, piperidine, pyrrolidine, and short carbon chains. mono-, di-, or trialkylamine, e.g. ethyl, diethyl, triethyl or dimethylpropylamine, or with a short-chain mono-, di- or trihydroxyalkylamine, such as mono-, di- or triethanolamine. Depending on the circumstances, the corresponding internal salts may be formed. Agrochemically useful salts are preferred within the scope of the invention, but salts having disadvantages in agrochemical application, e.g. bees or fish toxic salts which are used, for example, in the isolation or purification of free compounds of the formula I or their agrochemically used salts. Because of the elastic bond between the compounds of Formula I in the free form and their salts, hereinafter referred to as the free compounds of the formula I and their salts, where appropriate, are understood to mean the corresponding salts and the free compounds of the formula I. The same applies to tautomers of the compounds of the formula I and their salts. As a general rule, the free form shall take precedence.

The general terms used above and below have the following meanings unless otherwise specified.

As heterocyclic residues A of the ring backbone, heteroatoms A refer to all elements of the periodic system which can form at least two covalent bonds.

Halogen, per se as a group, and as a structural element of other groups and compounds such as haloalkyl, haloalkylthio, haloalkoxy, haloencyclopropyl, haloalkenyl, haloallyloxy and haloallylthio, is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine. first fluorine or chlorine, most chlorine.

Carbon-containing groups and compounds, unless otherwise indicated, have from 1 to 6 carbon atoms, usually from 1 to 3, most preferably from 1 to 2 carbon atoms.

Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, most commonly cyclopropyl.

Alkyl, in itself, as a group, as well as a structural member of other groups and compounds such as phenylalkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, is, respectively, the number of carbon atoms in the group or compound in question or straight chain, ie methyl, ethyl, propyl, butyl, pentyl or hexyl, or branched, e.g. isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl or isohexyl.

Alkenyl, haloalkenyl, alkynyl and haloalkynyl are straight-chain or branched and have two or more often one unsaturated carbon-carbon bond (s), respectively. The double or triple bonds of these substituents are usually separated from the rest of the compound of formula I by a saturated carbon atom. Examples include allyl, metal, but-2-enyl, but-3-enyl, propargyl, but-2-ynyl and but-3-ynyl.

Carbon-containing groups and halogen-substituted compounds such as haloalkyl, haloalkylthio, haloalkoxy, haloencyclopropyl, haloalkenyl, haloalkynyl, haloallyloxy, and haloallylthio may be partially halogenated or overhalogenated, and in the case of multiple halogenation, the halogen substituents may be the same. Examples of haloalkyls, in themselves as a group, as well as a structural member of other groups and compounds such as haloalkylthio and haloalkoxy, are one to three methyl, fluoro, chloro and / or bromo substituents such as CHF ₂ or CF ₃ ; one to five ethyl substituted by fluorine, chlorine and / or bromine, such as CH ₂ CF ₃ , CF ₂ CF ₃ , CF ₂ CCl ₃ , CF ₂ CHCl ₂ , CF ₂ CHF ₂ , CF ₂ CFCl _2i CF ₂ CHBr ₂ , CF ₂ CHCIF, CH ₂ CHBrF or CCIFCHCIF; one to seven 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 one to nine butyl or one of its isomers of fluorine, chlorine and / or bromine, as

CF (CF ₃ ) CHFCF ₃ , CF ₂ (CF ₂ ) ₂ CF _3, or CH ₂ (CF ₂ ) ₂ CF ₃ . Examples of haloalkenyls include 2,2-difluoroethen-1-yl, 2,2-dichloroethen-1-yl, 2-chloroprop-1-en-3-yl, 2,3-dichloroprop-1-en-3-yl and 2,3 -dibromprop-1-en-3-yl. Examples of haloalkynyls include 2-chloroprop-1-in-3-yl, 2,3-dichloroprop-1-in-3-yl and 2,3-dibromoprop-1-in-3-yl. Examples of halogenocyclopropyls are 2chlorocyclopropyl, 2,2-difluorocyclopropyl and 2-chloro-2-fluorocyclopropyl. Examples of haloalyloxy include 2-chloroprop-1-en-3-yloxy, 2,3-dichloroprop-1-en-3-yloxy and 2,3-dibromoprop-1-en-3-yloxy. Examples of haloallylthio are

2-chloroprop-1-en-3-ylthio, 2,3-dichloroprop-1-en-3-ylthio, and 2,3-dibromoprop-1-en-3-ylthio.

Phenylalkyl is an alkyl group attached to a compound of formula I which is substituted by phenyl, wherein the alkyl group is usually straight chain and the phenyl group is attached to the alkylated group at a position higher than α, most preferably at position ω; examples are benzyl, 2-phenylethyl and 4-phenylbutyl. Preferred embodiments within the scope of the invention are as follows:

(1) A compound of formula I wherein

A represents an unsubstituted or mono- to four-substituted, aromatic or non-aromatic, monocyclic or dicyclic, heterocyclic residue, wherein one to two A substituents may be selected from the group consisting of halo-C ₁ -C ₃ -alkyl, cyclopropyl, halogenocyclopropyl, C ₂ -C ₃ alkenyl, C ₂ -C ₃ alkynyl, halogen-C ₂ -C ₃ alkenyl, halogen-C ₂ -C ₃ alkynyl, halo-C ₁ -C ₃ alkoxy, C ₁ -C ₃ -alkylthio, halo-C ₁ -C ₃ -alkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, and one to four A substituents may be selected from the group consisting of C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy and halogen;

R represents hydrogen, C ₁ -C ₆ alkyl, phenyl-C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl; and X represents N-NO ₂ or N-CN;

(2) A compound of formula I wherein the A-ring backbone is composed of a ring having 5 or 6 members, to which another ring having 5 or 6 members may be attached, in particular a ring having 5 members or more often 6 members;

(3) A compound of formula I wherein the ring ring A is unsaturated, especially having a double bond or more typically 2 to 4, preferably conjugated double bonds, preferably a compound having 2, most often conjugated double bonds, especially having an aromatic character;

(4) The compound of formula I wherein the ring A backbone has from 1 to 4, in particular from 1 to 3, in particular 1 or 2 heteroatoms, with 1 heteroatom being particularly preferred;

(5) The compound of formula I, wherein ring A is selected from the group consisting of ring rings

N.

Y

wherein E, respectively, is C ₁ -C ₃ -alkyl, Y, respectively, is hydrogen, C ₁ -C ₃ -alkyl or cyclopropyl, and E or Y, respectively, are not a substitute for A but are attached to the A-ring backbone;

(6) The compound of Formula I wherein the ring A backbone has 1, 2 or 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, the heteroatoms in the ring backbone having at most one atom being an oxygen atom and the ring backbone at least one of the heteroatoms in the backbone is a sulfur atom, especially having 1, 2 or 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, the heteroatoms in the parent ring backbone having at most one being an oxygen or sulfur atom, usually at least one nitrogen atom.

(7) a compound of Formula I, wherein A is attached to the remainder of the compound of Formula I via its ring C atom;

(8) A compound of the formula I wherein A is unsubstituted or substituted with one or two substituents selected from the group consisting of halogen, C ₁ -C ₃ alkyl, halo-C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy and halogen -C 1 -C ₃ -alkoxy, in most cases unsubstituted or mono- or di-substituted with halo and C ₁ -C ₃ -alkyl;

(9) A compound of formula I wherein ring A is a pyridyl, 1-oxydopyridine or thiazolyl group, most commonly ring A is a pyrid-3-yl, 1-oxide-3pyridine or thiazol-5-yl group, most preferably A is pyrid-3-yl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-C ₁ -C ₃ alkylpyrid-5-yl, 1-oxide-3-pyridine, 2-halo-1-oxide A -5-pyridine, 2,3-dihalo-1-oxide-5-pyridine or 2-halo-thiazol-5-yl group, in particular A is pyrid-3-yl, 2-halopyrid-5-yl, 2-halo-1 oxide-5pyridine or 2-halogenothiazol-5-yl, most commonly A is 2-chloropyrid-5-yl, 2-methylpyrid-5-yl, 1-oxide-3-pyridine, 2chloro-1-oxide-5-pyridine , 2,3-dichloro-1-oxido-5-pyridine or 2-chlorothiazol-5-yl, in particular pyrid-3-yl, 2-chloropyrid-5-yl, 2-chloro-1-oxide-5-pyridine or the 2-chlorothiazol-5-yl group, most preferably A is 2-chloropyrid-5-yl or the most common 2-chlorothiazol-5-yl group.

(10) A compound of Formula I wherein R is C ₁ -C ₆ alkyl, phenyl-C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₃ -C ₄ alkenyl or C ₃ -C ₄ alkynyl;

primarily CrCe-alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₄ -alkenyl or C ₃ -C ₄ alkynyl, usually CrCe-alkyl, phenyl-CRC ₄ -alkyl, C ₃ -C ₄ alkenyl, or C ₃ -C ₄ -alkynyl, most CRC ₄ alkyl, usually methyl.

(11) A compound of Formula 1 wherein X is N-NO ₂ ;

(12) A compound of the formula I, wherein A represents, at one or more substituents selected from the group consisting of halogen and C 1 -C ₃ alkyl, pyridyl, bonded through its C ring atom to the remainder of the compound of formula I -oxido-pyridine or thiazolyl group, R represents C 1 -C 6 -alkyl, phenyl-C 1 -C ₄ -alkyl, C ₃ -C 6 -cycloalkyl, C ₃ -C ₄ -alkenyl or C ₃ -C ₄ -alkynyl and X represents N-NO ₂ or N-CN;

(13) A compound of formula I wherein A represents 2-chloropyrid-5-yl, 2-methylpyrid-5-yl, 1-oxide-3-pyridine, 2-chloro-1-oxide-5-pyridine, 2,3- a di-chloro-1-oxide-5-pyridine or 2-chlorothiazol-5-yl group, R represents C 1 -C ₄ alkyl and X represents N-NO ₂ ;

(14) A compound of formula I wherein A represents a 2-chlorothiazol-5-yl or 2-chloropyrid-5-yl group, R represents a C 1 -C ₄ alkyl and X represents N-NO ₂ .

Particular preference is given to the compounds of formula I listed in Examples H3 and H4 according to the invention.

The compounds of the following names are preferred according to the invention:

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-pyridinomethyl) -perhydro-1,3,5-oxadiazine,

d) 5- (2-Chloro-1-oxido-5-peridiniomethyl) -3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine; and

e) 3-methyl-5- (2-methylpyrid-5-ylmethyl) -4-nitroimino-perhydro-1,3,5-oxadiazine.

A further object of the invention is a process for the preparation of compounds of the formula I or, where appropriate, their tautomers, in free or salt form, for example by:

(a) A compound of the formula below

X which is known or may be obtained by analogy with the corresponding known compounds and wherein A, R and X are the same as in formula I, or a tautomer thereof and / or a salt thereof, reacting usually in the presence of a base or another acidic catalyst, with formaldehyde or paraformaldehyde or

b) obtaining a compound of the formula I wherein R is not hydrogen or, where appropriate, a tautomer and / or salt thereof, for example a) or c), to obtain a compound of the formula I wherein R is hydrogen, or a tautomer thereof; or the salt reacts, usually in the presence of a base, with a compound of the formula below

Y-R (III), which is known or may be obtained by analogy with the corresponding known compounds, and wherein R is the same as hydrogen, as in formula I, and Y represents a leaving group, or

c) a compound of the formula below

O

X wherein R and X are the same as in formula I, or a tautomer and / or salt thereof is reacted in the presence of a base with a compound of the formula below

A-CH ₂ -Y (V) which is known or may be obtained by analogy with the corresponding known compounds and wherein A is the same as in formula I and Y represents a leaving group or, if necessary, a tautomer thereof and / or the salt and / or, if desired, the compound of formula I or its tautomer obtained according to the method of preparation or otherwise is converted into the other compound of formula I or its tautomer in free or salt form, as appropriate. isolating the mixture and the desired isomer and / or converting the free compound of formula I or a tautomer thereof into a salt or a salt of a compound of formula I or a tautomer thereof into a free compound of formula I or a tautomer thereof; or to another salt.

Similarly, the same applies to the starting materials listed above and below, their tautomers and / or salts, and the tautomers and / or salts of the compounds of formula I above.

The reactions described above and below are carried out in a conventional manner, e.g. in the absence or usually in the presence of a suitable solvent or diluent or mixture thereof, and may be carried out, if necessary, at room temperature or heating, e.g. boiling point of the reaction mixture, usually from about -20 ° C to about + 150 ° C, and if necessary in a sealed container under pressure, inert atmosphere and / or anhydrous medium. Particularly favorable reaction conditions can be seen in the examples.

The starting materials listed above and below, which are used for the preparation of the compounds of the formula I or their tautomers, respectively in free or salt form, are known or may be obtained by known methods, e.g.

(a) Option:

Suitable bases for facilitating the reaction include, for example, alkali or alkaline earth metal hydroxides, hydrates, amides, alkanolates, acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines, alkylenediamines, as appropriate, N-alkylated, as appropriate, unsaturated, cycloalkylamines, , heterocyclyls, ammonium hydroxide as well as carbocyclic amines. Exemplary bases include sodium hydroxide, hydride, amide, methanolate, acetate, carbonate, potassium tert-butanolate, hydroxide, carbonate, hydride, lithium diisopropylamide, potassium (trimethylsilyl) amide, calcium hydride, triethylamine, diisopropylamine, , cyclohexylamine, N-cyclohexyl-N, N-dimethylamine, N, N-diethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide, and 1,5-diazabicyclo / 5.4.0 / undek-5-en (DBU).

Suitable acidic catalysts for facilitating the reaction include, for example, the catalytic amounts of acids previously mentioned as suitable for the formation of conjugated salts with the compounds of formula I.

The reaction partners can simply react with each other, i.e. without the addition of a solvent or diluent, e.g. in the melt. However, it is usually useful to add an inert solvent or diluent or a mixture thereof. Examples of such solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, hexane, cyclohexane, hexane, cyclohexane, , trichloroethane or tetrachloroethane; esters such as acetic acid or ethyl ester; ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxy diethyl ether, tetrahydrofuran or dioxane; ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides such as Ν, Ν-dimethylformamide, N, N-diethylformamide, Ν, Ν-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles such as acetonitrile or propionitrile; and sulfoxides such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, the solvents or diluents may be present in excess of a base such as triethylamine, pyridine, N-methylmorpholine or N, N-diethylaniline. If the reaction is carried out in the presence of an acid catalyst, the solvents or diluents may include excess acids, such as strong organic carboxylic acids, such as, for example, halogen-substituted C ₁ -C ₄ alkanoic acids, e.g. formic acid, acetic acid. or propanoic acid.

The reaction is most preferably carried out at a temperature in the range of about 0 ° C to about + 180 ° C, with a temperature range of about + 10 ° C to about 130 ° C being preferred, in most cases between room temperature and the boiling point of the reaction mixture.

Depending on the circumstances, the water formed during the reaction may be removed using a water separator, by acetic acid distillation, and using a suitable molecular sieve.

(b) Option:

Compounds of formula III Y is a leaving group eg., Hydroxy, C _r C ₈ alkoxy, halo-Ci-C ₈ alkoxy, CrCe alkanoyloxy, mercapto, CRC ₈ alkylthio, halo-Ci-C ₈ alkylthio CRC ₈ -alkansulfoniloksi , halo-C _r C ₈ alkanesulfonyloxy, benzolsulfoniloksi, toluenesulfonyloxy and halogen.

Suitable bases for facilitating the release of HY are, for example, from the type of base shown in variant a).

Reaction partners can simply react with each other, i.e. without the addition of a solvent or diluent, such as in a melt. However, it is usually useful to add an inert solvent or diluent or a mixture thereof. Examples of such solvents or diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, hexane, cyclohexane, hexane, cyclohexane, , trichloroethane or tetrachloroethane; esters as acetic acid ethyl ester: ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxy diethyl ether, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol; amides such as Ν, Ν-dimethylformamide, N, N-diethylformamide, Ν, Ν-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; nitriles such as acetonitrile or propionitrile; and sulfoxides such as dimethylsiloxide. If the reaction is carried out in the presence of a base, the solvents or diluents may be present in excess of the base such as triethylamine, pyridine, N-methylmorpholine or N, N-diethylaniline.

The reaction is most preferably carried out at a temperature in the range of about 0 ° C to about + 180 ° G, with a temperature range of about + 10 ° C to about 130 ° C being preferred, in most cases between room temperature and the boiling point of the reaction mixture.

(c) Option:

Suitable leaving groups Y in the compounds of formula V are, for example, those of variant b).

Suitable bases facilitating the degradation of HY are, for example, those of variant (a).

Reaction partners can simply react with each other, i.e. without the addition of a solvent or diluent, such as in a melt. However, it is usually useful to add an inert solvent or diluent or a mixture thereof. Suitable solvents or diluents are, for example, those of variant (b).

The reaction is most preferably carried out over a temperature range of about -20 ° C to about + 180 ° C, with a preferred range of about + 10 ° C to + 100 ° C, in most cases between room temperature and the boiling point of the reaction mixture.

Many of the compounds of formula IV and their tautomers used as starting materials in process (c), according to the circumstances, in the free or salt form are novel and are also an object of the invention. Particular preference is given within the scope of the invention to the compounds of formula IV listed in Examples H1 and H2 and their tautomers.

Another object of the invention is the free or salt form of the compounds of formula IV or their tautomers, as appropriate, e.g.

d) a compound of the formula below

H H

X which is known or may be obtained by analogy with known compounds and wherein R and X are the same as in formula I or the tautomer and / or salt thereof reacts with formaldehyde or paraformaldehyde, e.g. (a) in a variant for the reaction of a compound of formula II or a tautomer and / or salt thereof with formaldehyde or paraformaldehyde, respectively; or

e) reacting a compound of formula IV wherein R is not hydrogen or a tautomer and / or salt thereof, with a compound of formula IV wherein R is hydrogen, or a tautomer and / or salt thereof, obtained according to variant d).

YR (III), which is known or may be obtained by analogy with known compounds, and wherein R, except hydrogen, is the same as in formula I and Y is a leaving group, e.g. variant describes the reaction of the compound of formula I or, where appropriate, its tautomer and / or salt with a compound of formula III and / or, if desired, a compound of formula IV or its tautomer obtained according to the process or otherwise, respectively in free or salt form is transferred to another compound of formula IV or a tautomer thereof, the mixture of isomers obtained by the preparation is separated and isolated, and / or the compound of formula IV or its tautomer obtained according to a method of preparation or otherwise is converted into a salt or another method. the resulting salt of a compound of formula IV or a tautomer thereof is converted into the free compound of formula IV or its tautomer, or another salt.

The compound of formula I or IV obtained by the process or otherwise can be converted in a known manner into another compound of formula I or IV wherein one or more substituents of the parent compound of formula I or IV are conventionally substituted by one or more other substituents according to the invention. For example:

In a compound of formula -1, which is unsubstituted A, substituents may be introduced into A; or

- In the compound of formula I which is substituted with A, the A substituents may be replaced by other substituents.

Depending on the circumstances, depending on the appropriate reaction conditions and starting materials, it is possible to replace only one substituent in one reaction step with another substituent according to the invention, or at the same reaction step several substituents may be substituted for other substituents according to the invention.

The compounds of formula I or IV may be prepared in a known manner. Thus, for example, conjugated salts of the compounds of formula I or IV are obtained by treatment with a suitable acid or ion-exchange reagent, and salts with bases are obtained by treatment with a suitable base or ion-exchange reagent.

Salts of the compounds of formula I or IV may be converted in the conventional manner into the free compounds of formula I or IV, conjugated salts, e.g., by treatment with a suitable base medium or a suitable ion exchange reagent, and salts with bases, e.g. reagent.

The compounds of formula I or IV may be converted in a known manner into other salts of formula I or IV, by conjugation of salts, for example by treatment with other inorganic acids such as hydrochloric acid, or by treatment with a suitable metal salt such as sodium, barium. either the silver salt or by treatment with an acid such as silver acetate in a suitable solvent in which the inorganic salt formed, such as silver chloride, is insoluble and thereby precipitates in the reaction mixture.

Depending on the process or reaction conditions, compounds of formula I or IV with salt-forming properties in free form or in salt form may be obtained.

The compounds of formula I or IV and their tautomers, as appropriate, in free or salt form, may be present in the possible isomeric form or as a mixture thereof, e.g., depending on number, absolute and relative configuration of asymmetric carbon atoms in the molecule and / or non-aromatic double bonds in the configuration molecule, as pure isomers such as antipodes and / or diastereomers, as mixtures of eanantiomers, e.g., racemates, mixtures of diastereomers or mixtures of racemates; the invention includes both pure isomers and all possible mixtures of isomers; and, accordingly, this is to be understood unless the stereomeric units are mentioned in each individual case.

The diastereomeric mixtures and the racemate mixtures may be separated into pure diastereomers or racemates, depending on the physico-chemical properties of the components, either in free form or in the salt form, depending on the starting materials and method of preparation or otherwise obtained. by fractional crystallization, distillation and / or chromatography.

Accordingly, the resulting mixtures of enantiomers, such as racemates, can be divided into optical antipodes by known methods, for example, by recrystallization from an optically active solvent, chromatography on chiral adsorbents, such as high pressure liquid chromatography (HPLC) on acetylcellulose, enzymes, by the formation of linking compounds, e.g. by using chiral chargers where only one enantiomer is complexed, or by conversion to diastereomeric salts, e.g., by reaction of a basic final racemate with an optically active carboxylic acid such as camphor, tartaric or malic acid. , or with a sulfuric acid such as camphor sulfuric acid and separating the resulting mixture of diastereomers, e.g. due to their different solubility, by fractional crystallization into diastereomers from which the desired enantiomer can be isolated, using a suitable, e.g. one.

In addition to the appropriate separation of mixtures of isomers, the pure diastereomers, e.g., enantiomers, of the invention may also be obtained by methods known in the art of diastereoselective or enantioselective synthesis, e.g., wherein the adducts of the invention are carried out by appropriately adapted stereochemistry.

If the individual components have different biological activities, it is useful to synthesize or separate a biologically active isomer, e.g., an enantiomer or diastereomer, or a mixture of isomers, e.g., an enantiomer or diastereomer.

The compounds of formula I or IV, in free or salt form, may also be obtained in the form of their hydrates and / or in other forms containing a solvent which has been used, if necessary, to crystallize a compound in solid form.

The present invention relates to all embodiments of the process wherein at any stage of the process the parent compound is used or the intermediate is obtained or the derivative or salt and / or racemate or antipode of the compound is used and especially if they are formed. under reaction conditions.

A preferred object of the invention is the preparation of H1-H4 in the preparation of examples.

The starting materials and intermediates used in the preparation of the compound of the formula I or its salt according to the invention, in the free or salt form, respectively, which are novel and their preparation, their use as starting or intermediates in the preparation of the compound of the formula I it relates to a compound of formula IV.

The compounds of the formula I according to the invention, which are favorably transmitted by warm-blooded fish, fish and plants, are already valuable as preventive or curative biologically active substances with a broad biocidal spectrum, even in small application concentrations. The biologically active substances according to the invention are effective for all or individual stages of the development of animal pests such as insects, from normally sensitive to resistant forms. The insecticidal activity of the biologically active substances according to the invention may occur directly, i. for killing pests when death occurs immediately or after some time, such as hatching, or indirectly, for example, by reduced egg laying or nutrition, where good activity corresponds to at least 5060% killing / mortality rates.

Examples of such animal pests include, for example, the Lepidoptera lineage

Aderis spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseoia fusca, Chadra cautella, Carposina nippon. , Chor / stoneura spp., Ctysia ambiguella, Cnaphatocrocis spp., Cnephasia spp., Cochytis spp., Coleophora spp., Crocidolomia binotalis, Cryptophiebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp. , Eucosma spp., Eupoeci / ia ambiguella, Euproctis spp., Euxoa spp .; ., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sęxta, Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Pano / is flammea, Pectinophora gossypiella, Phthorimaea operculella, Pieris sp. xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp., Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichop / usia ni \ r Yponomeuta spp.

for example from Coleoptera row

Agriotes spp., Anthonomus spp., Atomaria iinearis, Chaetocnema tibialis, Cosmopolites spp., CurcuHo spp., Dermestes spp., Diabrotica spp., Epi / achna spp., Eremnus spp., Leptinotarsa decemtineata, Lissorhop. , Orycaephiius spp., Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Triboiium spp. and Trogoderma spp;

for example from the Orthoptera row

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Peri planeteta spp. and Schistocerca spp., for example from the Isoptera line

Reticulitermes spp .;

for example from the Psocoptera row

Liposcetis spp., For example from the order Anoplura

Haematopinus spp., Linognathus spp., Pediculus spp., Pemhigus spp. and

Phylloxera spp., For example, from Mallophaga

Damaiinea spp. and Trichodectes spp. \ for example from the order Thysanoptera

Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips taken, Thrips tabaci \ r Scirtothrips aurantir, for example from the order Heteroptera

Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp., Leptocorise spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergellasinguiaris, Scotinopharaspp. and Triatoma spp. \ for example from Homoptera

Aieurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp., Aspidiotus spp., Bemisia tabaci, Ceroptaster spp. spp., Laode, phax spp., Lecanium corni, Lepidosaphes spp., Macrosiphus spp., Myzus spp., Nephotettix spp., Nitaparvata spp., Paratoria spp., Pemphigus spp., Planococcus spp., Pseudau / acaspis spp. Pseudococcus spp., Psyiia spp., Puivinaria aethiopica, Ouadraspidiotus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus spp., Schizaphis spp., Sitobion spp., Triaieurodes vaporariorum, Trioza erytreae

Acromyrmex, Atta spp., Cephus spp., Diprionidae, Diprionidae, GUpinia poiytoma, Hopiocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Soienosis spp. and Vespaspp. ·, for example, from the Diptera line

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cutereba spp., Dacus spp., Drosophaha melanogaster, Fannia spp., Gastrophilus spp., Giosophila spp. , Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseoiia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Phagoietis pomonella, Sciara spp., Stom. spp., Tannia spp. and Tipuiaspp. ', for example from the order Siphonaptera

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

Lepsima saccharina.

The biologically active substances according to the invention can be combated in particular in the gardens and forests of plants, especially agricultural useful and ornamental plants, or on plants, such as fruits, flowers, leaves, stems, tubers or roots, of these types of pests, e.g. reducing or destroying them, and subsequent plant parts are partially protected against these pests.

Of the target crops, cereals such as wheat, barley, rye, oats, rice, maize or millet are the main focus; beet as sugar or fodder beet; fruits, such as seed fruits, stone fruits, and berries, such as apples, pears, plums, peaches, almonds, cherries, or berries, such as strawberries, raspberries, or blackberries; legumes such as beans, lentils, peas, soya; oil fruits such as rape, mustard, poppy, oil, sunflower, coconut, castor, cocoa or peanut; cucumbers, such as pumpkins, cucumbers or melons; fibrous plants such as cotton, flax, hemp, grapefruit or tangerine; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or paprika; Laurel leaves, such as avocado, cinnamon or camphor; as well as tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, grapes, hops, natural rubber plants, banana plants and ornamental plants.

The biologically active substances according to the invention are particularly useful in combating Aphis craccivora, Bemisia tabaci, Diabrotica balteata, Heliothis virescens, Myzus persicae, Nephotettix cincticeps and NUparvata lugens in vegetable, corn, fruit, rice and soy crops.

Other uses of the materials according to the invention are the storage of stockpiles of materials and, especially in the hygiene sector, the protection of domestic and useful animals against the specified pest species.

Therefore, the present invention also relates to pest control means selected from the intended purpose and the present conditions, such as emulsifiable concentrates, suspension concentrates, directly sprayed or diluted solutions, pastes, diluted emulsions, spray powders; soluble powders, dispersible powders, enveloping powders, pollinating agents, granules or capsules in polymeric materials containing at least one biologically active substance according to the invention.

In such compositions, the biologically active agent may be used in its pure form, namely in the form of a solid biologically active agent, e.g., as a special size grain, or most commonly with at least one formulation aid such as a diluent, e.g. surfactant compound (tenside).

Among the solvents which may be mentioned, for example, partially hydrogenated aromatic hydrocarbons, preferred C ₈ -C ₁₂ alkyl benzene fractions, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons such as paraffins or cyclohexane, such as ethanol, propanol or butanol, glycols as well as their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, isophorone or diacetane alcohol, such as strongly polar solvents, N-methylpyrrolidone-2, dimethylsulfoxide or N, N-dimethylformamide, water, where appropriate, epoxidized vegetable oils such as rapeseed, castor, coconut or soybean oils, as appropriate, and silicone oils.

Natural rock flour such as calcite, talc, kaolin, montmorillonite, or atapulgite are commonly used as solid carriers, such as pollen and dispersible powders. High dispersion silica or high dispersion absorbent polymerizates may be added to improve physical properties. The granular adsorbent granulate carriers include porous pumice stone, brick rubble, sepiolite or concrete, and non-adsorbent carrier calcite or sand. In addition, many granular materials of inorganic or organic origin can be used, particularly dolomite or crushed plant residues.

Of the surfactant compounds, depending on the formulation of the biologically active agent, nonionic, cationic and / or anionic surfactants or mixtures of surfactants having good emulsifying, dispersing and coating properties are to be mentioned; the following surfactants are to be considered as examples only; many other surfactants used in formulations and in accordance with the invention are described in the accompanying literature.

Of the non-ionic surfactants, the polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated and unsaturated fatty acids and alkylphenols, which may have from 3 to 30 glycol ether groups and from 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue and 6 to 18 carbon, atoms in the alkyl residue of an alkylphenol. Further suitable are water-soluble containing from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups, polyethylene oxide adducts with polypropylene glycol, ethylenediamine polypropylene glycol and alkylpolypropylene glycol having from 1 to 10 carbon atoms in the alkyl chain. The listed compounds usually have from 1 to 5 ethylene glycol units per propylene glycol unit. Examples include noninfenolpolyethoxyethanol, castor oil polyglycol ether, polypropylene polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. The fatty acid esters of polyoxyethylene sorbitan are mentioned below as polyoxyethylene sorbitan trioleate.

In the case of cationic surfactants, we are dealing, in particular, with quaternary ammonium salts which are substituted with at least one 822 C-alkyl residue and, alternatively, low molecular weight, optionally halogenated alkyl, benzyl or hydroxyalkyl residues. The salts are usually in the form of halides, methylsulphates or ethylsulphates. Examples are stearyl-trimethyl-ammonium chloride and benzyl-di- (2-chloroethyl) ethylammonium bromide.

Suitable anionic surfactants can be both water-soluble soaps and synthetic surfactants. As for the soaps of higher fatty acids (C ₁₀ -C22) alkali, alkaline earth metals and, if necessary, ammonium, substituted salt as oleic or stearic acid, or of natural fatty acid mixtures which can be obtained from nuts or thallium oil, sodium or potassium salts; the methyl-taurine salts of fatty acids should be further mentioned. However, synthetic surfactants, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates, are more commonly used. The fatty sulfonates are generally in the form of the alkali, alkaline earth metal or optionally substituted ammonium salts, and generally have an alkyl moiety of from 8 to 22 C-atoms wherein alkyl has an alkyl moiety of the acyl moiety; by way of example, sodium or calcium salts of lignin sulphonic acid, sulfuric acid dodecyl ester or a mixture of fatty alcohol sulphates of natural fatty acids. They also include sulphonic acid salts of sulfuric acid esters and fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives usually contain 2 sulfuric acid groups and a fatty acid residue of 8 to 22 C-atoms. Alkylarylsulfonates are, for example, sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid-formaldehyde condensation product. Phosphates, as the salts or phospholipids of the phosphoric acid ester of p-nonylphenol- (4-14) -ethylene oxide adduct, respectively, are mentioned below.

The compositions generally contain from 0.1 to 99%, in particular from 0.1 to 95%, of the biologically active substance and from 1 to 99.9%, in particular of from 5 to 99%.

99.9% of the at least one solid or liquid excipient, and in general from 0 to 25%, in particular 0.1 to 20%, may comprise tenside (in each case,% by weight). Concentrated medium is the preferred product for sale, whereas the end user will typically use a dilute medium with a significantly lower concentration of the biologically active substance. The composition of the priority measures shall be in particular the following (% = percentage by weight):

Emulsifiable concentrates:

Biologically active substance: 1 to 90%, in particular 5 to 20% Tenside: 1 to 30%, in particular 10 to 20%

Solvent: 5 to 98%, in particular 70 to 85%

Pollination measures:

Biologically active substance: 0.1 to 10%, in particular 0.1 to 1% Solid carrier: 99.9 to 90%, in particular 99.9 to 99%

Suspension concentrates:

Biologically active substance: 5 to 75%, in particular, 10 to 50% Water: 94 to 24%, in particular 88 to 30%

Tenside: 1 to 40%, in particular 2 to 30%

Coating powder:

Biologically active substance: 0.5 to 90%, in particular, 1 to 80% Tenside: 0.5 to 20%, in particular 1 to 15%

Solid carrier: 5 to 99%, in particular 15 to 98%

Granules:

Biologically active substance: 0.5 to 30%, in particular 3 to 15%

Solid carrier: 99.5 to 70%, in particular 97 to 85%

The addition of other biologically active insecticidal agents can significantly extend or adapt the action of the present invention to appropriate conditions. Additives that may be added to the biologically active substance include, for example, the following classes of biologically active substances: organophosphorus compounds, nitrophenols and their derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and preparations of Bacillus thuringiensis.

The compositions according to the invention may also contain other solid or liquid excipients such as stabilizers, such as epoxidized vegetable oils (e.g. epoxidized coconut, rapeseed or soybean oil), foam extinguishers such as silicone oil, if necessary. , preservatives, viscosity regulators, binders and / or adhesives, as well as fertilizers or other biologically active substances for specific effects, such as acaricides, bactericides, fungicides, nematocides, molluscicides or selective herbicides.

The means according to the invention can be obtained in a known manner in the absence of excipients, e.g. by grinding, sieving and / or pressing a solid biologically active substance or a mixture of biologically active substances, e.g. ., by mixing and / or grinding the biologically active substance or a mixture thereof with the excipient (s). The present invention also relates to a process for the preparation of an agent according to the invention and to the use of a compound of formula I for the preparation of such an agent.

Ways of using this tool, i.e. methods of controlling the above types of pests, selected according to the intended purposes and appropriate conditions, such as spraying, aerosol spraying, pollination, application, dressing, spray application or simple application, and the use of means for combating said pests are further objects of the present invention. Typical application concentrations are between 0.1 and 1000 m.d., preferably 0.1 to 500 m.d., biologically active substance. In general, the rate of application per hectare is between 1 and 2000 g of active substance per hectare, in particular between 10 and 1000 g / ha, with a preference of between 20 and 600 g / ha.

The preferred application in the field of plant protection is applied to the leaves of the plant (application on leaves), where the frequency of application and the amount used are controlled depending on the pest infestation. However, the biologically active substance can also reach the plant through the roots (systemic action), in which case the plant location is moistened with a liquid medium, or the biologically active substance in solid form is introduced into the plant location, e.g., in the form of granules ( application to the ground). In the case of aqueous rice crops, such granules can be dosed into a flooded rice field.

The means according to the invention are also suitable for the protection of plant seeds, such as fruit, tuber or cereal seed or seedlings for protection against animal pests. In this case, the seeds can be treated with this agent before sowing, eg the seeds can be treated before sowing. The biologically active substances according to the invention may also be applied to a coating of seeds, in which case the seeds may be either in a micrometer liquid medium or coated with a solid medium. The tool can also be applied at the seed placement site, eg in seedbeds.

These methods of treating plant seeds and the seeds so treated are further objects of the invention.

The following examples illustrate the invention. However, they do not limit the invention. Temperatures are given in degrees Celsius.

Examples of receipt

Example H1

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

O

^ΗΓ Υ ^Ν -ΟΗ ₃ n-No ₂ or 3-methyl-4-nitroamino-1,2,3,6-tetrahydro-1,3,5-oxadiazine

O ^Ν γ ^ οκ _;

N (H) -NO ₂

To 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 added 30.5 g of paraformaldehyde at room temperature, refluxed for 16 hours and then evaporated in vacuo. The residue is purified by chromatography on a column of silica gel; dichloromethane / methanol (95: 5) / to give the title compound, m.p. 137-139 ° C.

Example H2

Analogously to the description of Example H1 it is also possible to obtain

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

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

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

3-cyclopropyl-4-nitroimino-perhydro-1,3,5-oxadiazine, or 3-cyclopropyl-4nitroamino-1,2,3,6-tetrahydro-1,3,5-oxadiazine, 3-allyl-4-nitroiminoperhydro -1,3,5-oxadiazine, or 3-allyl-4-nitroamino-1,2,3,6-tetrahydro-1,3,5-oxadiazine (resin),

4-nitroimino-3-propargyl-perhydro-1,3,5-oxadiazine, or 4-nitroamino-3-propargyl-1,2,3,6-tetrahydro-1,3,5-oxadiazine (melting point: 102104 ° C) ,

4-cyanoimino-3-methyl-perhydro-1,3,5-oxadiazine, or 4-cyanoamino-3-methyl-1,2,3,6-tetrahydro-1,3,5-oxadiazine (melting point: 121122 ° C) ,

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

4-cyanoimino-3-cyclopropyl-perhydro-1,3,5-oxadiazine, or 4-cyanoamino-3-cyclopropyl-1,2,3,6-tetrahydro-1,3,5-oxadiazine; and

4-nitroimino-3- (2-phenylethyl) -perhydro-1,3,5-oxadiazine, or 4-nitroamino-3- (2-phenylethyl) -1,2,3,6-tetrahydro-1,3,5- oxadiazine (melting point: 123-125 ° C).

Example H3

5- (2-Chloropyrid-5-ylmethyl) -3-methyl-4-nitroiminoperhydro-1,3,5-oxadiazine (Table 1, Compound # 1.2).

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 Ν, Ν-dimethylformamide is added for 4 hours. warm at 50 ° C, filter, evaporate the filtrate in vacuo on a rotary evaporator and purify the residue by chromatography (silica gel; dichloromethane / methanol (95: 5)). This gives the title compound, m.p. 116-118 ° C.

Example H4

Other compounds of Tables 1 and 2 can be obtained in an analogous manner as described in Examples H1-H3. The "Physical Data" column of these tables gives the melting points of the respective compounds.

Sample recipes (% = percentage by weight)

Example F1

Emulsion concentrates a) b) c) Biologically active substance no. 1.2 25% 40% 50% Ca-dodecylbenzenesulfonate 5% 8% 6% Castor oil-polyethylene glycol ether (36 mol EO) 5% - -

Tributylphenol-polyethylene glycol

ether (30 mol EO) - 12% 4% Cyclohexanone - 15% 20% A mixture of xylenes 65% 25% 20%

table

N-NO ₂

R

Compound A R

No.

1.1 ^N CH ₃

1.5

Physical data

116-118 ° C

132-134 ° C

210 ° C (decomposition)

188-191 ° C

The compound

No.

A

R

Physical data

1.6

1.7

1.8

1.9

1.10

1.11

1.12

1.13

199 ° C (decomposition)

141-144 ° C

Resin

Compound A

No.

R Physical data

1.14

1.15

1.16 θ ′ N

nC ₄ H ₉ Resin

Alil

Resin

Propargii 103-108 ° C nC ₄ H ₉ 71-73 ° C

Mp 176 ° C

CH ₂ CH ₂ -C ₆ H ₅ Resin

CH2CH2-C6H5 Resin

Table 2 0 n ^ N ^ / N— R Y N-CN The compound A R Physical data No.

2.1

2.2

2.3

N

Cl N

CH ₃

CH ₃ 108-109 ° C

CH ₃ 92-93 ° C

2.6

Compound A

No.

R Physical data

Dilution of such concentrates with water may result in emulsions of any desired concentration.

Example F2

Solutions

Biologically active substance no. 1.3 Polyethylene glycol monomethyl ether Polyethylene glycol (mol. Wt. 400)

a) b) c) d)

80% 10% 5% 95%

20% 70%

41 N-methyl-2-pyrrolidone 20% - Epoxidized coconut oil 1% 5% Gasoline (boiling point limits 160-190 ° C) 94% -

The solutions are suitable for use in the form of small droplets.

Example F3 Granules a) b) c) d) Biologically active substance no. 1.2 5% 10% 8% 21% Kaolin 94% - 79% 54% High degree of variance silicic acid 1% - 13% 7% Atapulgitas - 90% - 18%

The biologically active substance is dissolved in dichloroethane, sprayed on a carrier and then the solvent is evaporated off under vacuum.

Example F4

Pollination measures a) b)

Biologically active substance no. 1.2 2% 5%

High dispersion silica 1% 5%

Talin 97% Kaolin - 90%

The mixing of carrier materials and biologically active material results in a ready-to-use pollinator.

Example F5

Spray powder a) b) c) Biologically active substance no. 1.2 25% 50% 75% Na-lignin sulfonate 5% 5% - Na-lauryl sulfate 3% - 5% Na-diisobutylnaphthalenesulfonate - 6% 10% Octylphenol-polyethylene glycol ether (7-8 mol EC) - 2% - High dispersion silica 5% 10% 10% Kaolin 62% 27%

The biologically active substance is mixed with additives and well ground in a suitable mill. This produces a sprayable powder which can be diluted with water to any desired concentration of suspension.

Example F6

Emulsion concentrate

Biologically active substance no. 1.3

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

Ga-dodecylbenzenesulfonate

Castor oil-polyglycol ether (36 mol EO)

Cyclohexanone

A mixture of xylenes

When diluting this concentrate with water, emulsions of the desired concentration may be present.

10%

3%

3%

4%

30%

50% made any

Example F7

Pollination measures

a) b)

Biologically active substance no. 1.2 5% 8%

Talk

Kaolin

95%

92%

Mixing the biologically active agent with the carrier and grinding it in a suitable mill results in ready-to-use pollinator.

Example F8

Extruded granulate

Biologically active substance no. 1.3 10%

Na lignin sulphonate 2%

Carboxymethylcellulose 1%

Kaolin 87%

The biologically active substance is mixed with the additives, ground and moistened with water. This mixture is extruded, granulated and then air-dried.

F9 jealousy

Coating granulate

Biologically active substance no. 1.2 3%

Polyethylene glycol (mol. Wt. 200) 3%

Kaolin

94%

In the mixer, the finely divided biologically active substance is applied evenly over the polyethylene glycol-moistened kaolin. This results in a dust-free envelope granulate.

Example F10

Suspension concentrate

Biologically active substance no. 1.3 40% Ethylene glycol 10% Nonylphenol-polyethylene glycol ether (15 mol ΞΟ) 6% Na-lignin sulfonate 10% Carboxymethylcellulose 1% 37% aqueous solution of formaldehyde 0.2% Silicone oil, 75% aqueous in the form of an emulsion 0.8% Water 32%

The finely divided biologically active substance is mixed with additives. This gives a suspension concentrate from which any concentration can be made by dilution with water.

Biological samples (% = percentage by weight, unless otherwise specified)

Example B1

Effect against Anthonomus grandis

Young cotton plants are sprayed with an aqueous spray emulsion solution containing 400 ppm. biologically active substances. When the spray mixture dries, the plants are housed with 10 adult Anthonomus grandis individuals and placed in a plastic container. Results are evaluated after 3 days. By comparing the number of dead beetles with the damage caused by beetles in treated and untreated plants, a percentage reduction in population and a percentage reduction in damage (effect%) are found.

and Table 2 showed good performance in this test. Compounds no. 1.2, 1.3, and 2.3 with an effect greater than 80%.

Example B2

Effect against Aphis craccivora

The pea seedlings are infected with Aphis craccivora, then sprayed with a spray solution containing 400 ppm. and then incubated at 20 ° C. After 3 and 6 days, the results were evaluated. By comparing the number of dead leaf lice on treated and untreated plants, a percentage reduction in population (% efficacy) is observed.

and Table 2 showed good performance in this test. Compounds no. 1.2.1.3.1.15, 2.2, and 2.3 with an effect greater than 80%.

Example B3

Effect against Bemisia tabaci

Sprouting beans were placed in gauze cages and housed in adult Bemisia tabaci individuals. After laying the eggs, all adult individuals were removed. After 10 days, the plants with the nymphs on them were sprayed with an aqueous spray emulsion solution containing 400 ppm. biologically active substances. A further 14 days later, the percentage of egg hatching was evaluated compared to the untreated controls.

and Table 2 showed good performance in this test. Compounds no. 1.2 and 1.3, with exposure above 80%.

Example B4

Effects on Ctenocephalides fe / is (systemic)

Twenty adult Ctenocephalides fe / is flea adult individuals are housed in a flat, round, gauze-covered cage. A container is placed on top of the cage, which is covered with a parafilm membrane from below. The vessel contains blood containing 5 m.d. biologically active substance and which is kept at a constant temperature of 37 ° C. Fleas take blood through the membrane. 24 and 48 hours after placement, the results are evaluated. By comparing the number of dead fleas in the treated blood with the number of dead fleas in the untreated blood, a percentage reduction in population (% efficacy) is observed. 24 hours after treatment, blood is replaced with new as well as treated blood.

and Table 2 showed good performance in this test. Compounds no. 1.2 and 1.3, with exposure above 80%.

Example B5

Effect against Diabrotica baiteata

The maize sprouts are sprayed with an aqueous spray emulsion solution containing 400 ppm. biologically active substances. Once the spray mixture has dried, the seedlings are housed in 10 second stage larvae of Diabrotica baiteata and placed in a plastic container. Results are evaluated after 6 days. By comparing the number of dead larvae on treated and untreated plants, a percentage reduction in population (% efficacy) is observed.

and Table 2 showed good performance in this test. Compounds no. 1.2,1.3,1.5 and 2.3 with an effect greater than 80%.

Example B6

Effect against Heliothis virescens

Young soy plants are sprayed with an aqueous spray emulsion solution containing 400 ppm. biologically active substances. After the spray mixture dries, the plants are housed in 10 first stage Heliothis virescens caterpillars and placed in a plastic container. Results are evaluated after 6 days. By comparing the number of dead caterpillars with the damage caused by caterpillars on treated and untreated plants, a percentage reduction in population and a percentage reduction in damage (% efficiency) are found.

and Table 2 showed good performance in this test. Compounds no. 1.2 and 1.3, with exposure above 80%.

Example B7

Effect against Heliothis virescens (ovi- / larvizid)

Heliothis virescens eggs placed on cotton are sprayed with an aqueous spray emulsion solution containing 400 ppm. biologically active substances. After 8 days, the rate of hatching from eggs and caterpillars was assessed relative to the untreated controls (% population decline).

and Table 2 showed good performance in this test.

Example B8

Effect against Myzus persicae

Pea seedlings were infected with Myzus persicae and subsequently sprayed with a spray solution containing 400 ppm. and then incubated at 20 ° C. After 3 and 6 days, the results were evaluated. By comparing the number of dead leaf lice on treated and untreated plants, a percentage reduction in population (% efficacy) was observed.

and Table 2 showed good performance in this test. Compounds no. 1.2 and 1.3, with exposure above 80%.

Example B9

Effects against Myzus persicae (systemic)

The pea seedlings were infected with Myzus persicae and then put into roots in a spray solution containing 400 ppm. and then incubated at 20 ° C. After 3 and 6 days, the results were evaluated. By comparing the number of dead leaf lice on treated and untreated plants, a percentage reduction in population (% efficacy) was observed.

and Table 2 showed good performance in this test. Compounds no. 1.2, 1.3, and 1.5 with an effect greater than 80%.

Example B10

Effects against Nephotettix cincticepts

Rice plants are sprayed with an aqueous spray emulsion solution containing 400 ppm. biologically active substances. Once the spray mixture dries, the plants are colonized by stage 2 and 3 larvae. After 21 days Results are evaluated. By comparing the number of live cicadas on treated and untreated plants, a percentage reduction in population (% efficacy) is observed.

and Table 2 showed good performance in this test. Compounds no. 1.2.1.3 and 1.5 with an effect greater than 80%.

Example B11

Effect against Nephotettix cincticepts (systemic)

The pots containing rice plants are placed in an aqueous emulsion solution containing 400 ppm. biologically active substances. The plants are then colonized by stage 2 and 3 larvae. Results are evaluated after 6 days. By comparing the number of cycads on treated and untreated plants, a percentage reduction in population (% efficacy) is observed.

and Table 2 showed good performance in this test. Compounds no. 1.3, 1.5, 1.13, and 1.15, with effects over 80%.

Example B12

Effect against Nitaparvata lugens

Rice plants treated with an aqueous spray emulsion solution containing 400 ppm. biologically active substances. When the spray mixture dries, the rice plants are colonized by stage 2 and stage 3 cicad larvae. Results are evaluated after 21 days. By comparing the number of live cicadas on treated and untreated plants, a percentage reduction in population (% efficacy) is observed.

and Table 2 showed good performance in this test. Compounds no. 1.2, 1.3, 1.5, 1.8, and 2.3, with exposure above 80%.

Example B13

Effect against Nitaparvata lugens (systemic)

Pots containing rice plants are placed in an aqueous emulsion solution containing 10 ppm. biologically active substances. The plants are then colonized by stage 2 and 3 larvae. Results are evaluated after 6 days. By comparing the number of cycads on treated and untreated plants, a percentage reduction in population (% efficacy) is observed.

Example B14

Effect against Blattella germanica

Add to the Petri dish an amount of acetone solution of the biologically active substance (0.1%) such that it corresponds to an application rate of 1 g / m ² . When the solvent has evaporated, 10 Blattella germanica nymphs (last stage of the nymph) are placed in a dish and exposed to the test substance for 2 hours. The nymphs are then anesthetized with CO ₂ , transferred to a new Petri dish and stored in the dark at 25 ° C and 70% humidity. After 48 hours, the insecticidal effect is determined by calculating the degree of murder.

and Table 2 showed good performance in this test. Compound no. 1.3 with an impact of over 80%.

Example B15

Effect against Lucilia cuprina

After 30-50 freshly placed Lucilia cuprina eggs are placed in tubes containing 4 ml of nutrient medium and 1 ml of test solution containing 16 ppm. biologically active substances. After the eggs have been added to the culture medium, the test tubes are capped with cotton swabs and incubated for 4 days at 30 ° C in an incubator. By this time, larvae about 1 cm in length develop in the untreated medium (stage 3). If the test substance is active, the larvae die or are clearly smaller by this time point. After 96 hours, the results are evaluated.

and Table 2 showed good performance in this test. Compound no. 1.3 with an impact of over 80%.

Example B16

Effect against Musca domestica

Treat the sugar lump with the test substance solution such that, after drying overnight, the test substance has a sugar concentration of 250 ppm. The treated piece is placed in an aluminum dish with a damp cotton swab and 10 adults of OP-resistant Musca domestica strain. This is covered with a Becher slide and incubated at 25 ° C. After 24 hours, the mortality rate is determined.

and Table 2 showed good performance in this test. Compound no. 1.3 with an impact of over 80%.

Claims (30)

A compound of the formula below wherein A represents an unsubstituted or mono- to four-substituted, aromatic or non-aromatic, monocyclic or dicyclic, heterocyclic residue, and one to two A substituents may be selected from the group consisting of halogen-C 1 -C 3 -alkyl, cyclopropyloxy, halo-benzycyclopropyl, C 2 -C ₃ -alkenyl, C 2 -C 3 -alkynyl, halo-C 2 -C ₃ -alkenyl, halo-C 2 -C ₃ -alkynyl, halo-C ₁ -C 5 -alkoxy, C ₁ -C ₃ -alkylthio , halo-C ₁ -C ₃ alkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro, and one to four A substituents may be selected from the group consisting of C ₁ -C ₃ alkyl, C ₁ -C ₃ alkoxy and halogen; R represents hydrogen, C ₁ -C ₆ alkyl, phenyl-C ₁ -C ₄ alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl; and X represents N-NO ₂ or N-CN, or, where appropriate, a tautomer thereof, in free or salt form. Compound of formula I according to claim 1, characterized in that A is a ring backbone consisting of a ring with 5 or 6 members, to which another ring with 5 or 6 members, or, if necessary, a tautomer thereof, may be attached. Compound of formula I according to claim 1, characterized in that A is an unsaturated ring framework or, if necessary, a tautomer thereof. Compound of formula I according to claim 1, characterized in that A is a ring backbone having 1-4 heteroatoms or, if necessary, a tautomer thereof. 5. A compound of the formula I as claimed in claim 1, wherein A is an annular backbone selected from the group consisting of annular backbone E E E N N. wherein E is C ₁ -C ₃ alkyl, Y is hydrogen, C 1 -C ₃ alkyl or cyclopropyl, respectively, and E or Y, respectively, are not A substituents, but are assigned to A's ring backbone. 6. A compound of the formula I as claimed in claim 5, wherein A is a ring backbone having 1, 2 or 3 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen and at most one atom of the heteroatoms in the ring backbone is the oxygen atom and at least one atom of the heteroatoms in the ring backbone are a sulfur atom and, if necessary, its tautomer. 7. A compound of formula I according to claim 6, wherein A is attached to the remainder of the compound of formula I via its C-ring ring backbone. 8. A compound of the formula I as claimed in claim 7, wherein A is unsubstituted or has one or two substituents selected from the group consisting of halogen, C 1 -C ₃ -alkyl, halogen-C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy and halo-C ₁ -C ₃ -alkoxy, or, where appropriate, a tautomer thereof. Compound of formula I according to claim 8, characterized in that the ring A backbone is a pyridyl, 1-oxidopyridine or thiazolyl group or, if necessary, a tautomer thereof. Compound of formula I according to claim 1, characterized in that R is C ₁ -C ₆ -alkyl, phenyl-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₄ -alkenyl or C ₃ -C _{6 4-} alkynyl, or, where appropriate, its tautomer. A compound of formula 11.1 according to claim 1, wherein X is N-NO ₂ or, where appropriate, a tautomer thereof. 12. A compound of the formula I as claimed in claim 9, wherein A is fused, unsubstituted or substituted with one or two substituents selected from the group consisting of halogen and C1-C, through the ring atom of its C-ring backbone. _{A 3-} alkyl, pyridyl, 1-oxidopyridine or thiazolyl group, R represents C ₁ -C ₆ -alkyl, phenyl-C ₁ -C ₄ -alkyl, C ₈ -C ₆ -cycloalkyl, C 3 -C ₄ -alkenyl or C 3 -C ₄ -alkynyl and X represents NNO ₂ or N-CN or, where appropriate, its tautomer. 13. A compound of the formula I as claimed in claim 12, wherein A is 2-chloropyrid-5-yl, 2-methylpyrid-5-yl, 1-oxide-3-pyridine, 2-chloro-1-oxide-5-pyridine, 2 , 3-dichloro-1-oxido-5-pyridine or 2-chlorothiazol-5-yl, R represents C ₁ -C ₄ alkyl and X represents N-NO ₂ . A compound of formula 14.1 according to claim 13 wherein A represents a 2-chlorothiazol-5-yl or 2-chloropyrid-5-yl group, R represents a C ₁ -C ₄ alkyl and X represents N-NO ₂ . 15. A compound of formula I as claimed in claim 13, which is selected from the group consisting of: 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-pyridinomethyl) -perhydro-1,3,5-oxadiazine, d) 5- (2-chloro-1-oxido-5-peridiniomethyl) -3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazine; and e) 3-methyl-5- (2-methylperid-5-ylmethyl) -4-nitroimino-perhydro-1,3,5-oxadiazine. 16. A process for the preparation of a compound of formula I according to claim 1 or, where appropriate, a tautomer thereof, in free or salt form, wherein (a) A compound of the formula below X which is known or may be obtained by analogy with known compounds and wherein A, R and X are the same as in formula I, or a tautomer and / or a salt thereof, are reacted, usually in the presence of a base or another acidic catalyst, with formaldehyde or paraformaldehyde or b) for the preparation of a compound of formula I wherein R is not hydrogen or, if necessary, a tautomer and / or salt thereof, e.g. according to a) or c), a compound of formula I wherein R is hydrogen, or a tautomer thereof and / or a salt thereof is reacted, usually in the presence of a base, with a compound of the formula below Y-R (III), which is known or may be obtained by analogy with the corresponding known compounds, and wherein R has the same meaning except hydrogen and Y represents a terminal group, or c) a compound of the formula below H R X (IV) wherein R and X are the same as in formula I, or a tautomer and / or salt thereof is reacted in the presence of a base with a compound of the formula below A - CH ₂ -Y (V) which is known or may be obtained by analogy with the corresponding known compounds and wherein A is the same as in formula I and Y represents a terminal group or, where appropriate, its tautomer and / or a salt and / or, if desired, a compound of formula I or its tautomer obtained according to the method of preparation or otherwise, depending on the circumstances, is converted into another compound of the formula I or its tautomer in free or salt form isolating and isolating the desired isomer and / or converting the free compound of formula I or its tautomer obtained by the process or otherwise into a salt or converting the salt of the compound of formula I or its tautomer into a free compound of formula I or its tautomer or other salt. 17. A pest control agent, comprising at least one compound of the formula I as claimed in claim 1 or, if appropriate, a tautomer thereof, in free or agrochemical form as a biologically active substance in a salt form and optionally. The support material. Use of a measure according to claim 17 for killing insects. 19. A process for the preparation of a device according to claim 17 comprising at least one excipient, wherein the biologically active agent is mixed and / or ground with the excipient (s). Use of a compound of the formula I as claimed in claim 1 or, if appropriate, its tautomer, in free or agrochemically acceptable salt form, for preparing the agent of claim 17. Use of a measure according to claim 17 for controlling pests. Use according to claim 21, wherein the pests are insects. Use according to claim 21, characterized in that the agent according to claim 17 is used for the protection of plant seeds. 24. A pest control method, characterized in that the agent according to claim 17 is applied to the pests or to their living space. Use of the method of claim 24 for killing insects. A bud according to claim 24 for the protection of plant seeds, characterized in that it is a seed or a seeding site. 27. Plant seeds which have undergone treatment as described in point 26. 28. Compound of Formula below o X wherein R and X are the same as in formula I or its tautomer, as appropriate, in free or salt form. A process for the preparation of a compound of formula IV according to claim 28, optionally in free or salt form, as appropriate, wherein d) a compound of the formula below H H (VI), X which is known or may be obtained by analogy with known corresponding compounds and wherein R and X are the same as in formula I or the tautomer and / or salt thereof reacts with formaldehyde or paraformaldehyde, e.g. it is described in variant (a) for the appropriate reaction of a compound of formula II or a tautomer salt thereof with formaldehyde or paraformaldehyde, or e) For the preparation of a compound of formula IV wherein R is not hydrogen or a tautomer and / or salt thereof, a compound of formula IV wherein R is hydrogen or a tautomer and / or salt thereof obtained by, for example, variant d) reacts with the formula compound YR (UI), which is known or may be obtained by analogy with known compounds, and wherein R, except hydrogen, is the same as in formula I, and Y is a terminal group, e.g. variant describes the reaction of a compound of formula I, or a tautomer and / or salt thereof, as appropriate, with a compound of formula III, and / or, where appropriate, a compound of formula IV or a tautomer thereof in the form of a salt, is converted to another compound of formula IV or a tautomer thereof, the mixture of isomers obtained by the preparation is isolated and the desired isomer is isolated and / or the compound of formula IV or its tautomer obtained in another way or or another salt of a compound of formula IV or a tautomer thereof, is converted into the free compound of formula IV or a tautomer thereof, or a j another salt. Use of a compound of formula IV according to claim 28 or, where appropriate, a tautomer thereof, in free or salt form, to obtain a compound according to claim 1.