1-Nitro-2,2-diaminoethylene derivatives.

The present invention relates to new 1-nitro-2,2-diaminoethylene derivatives, processes and intermediates for their preparation, pesticides containing these compounds and their use in pest control.

The 1-nitro-2,2-diamino-ethylene derivatives according to the invention correspond to the formula I.<chemistry id="chem0001" num="0001"><img file="EP0302833A2_D0001.tif" /></chemistry> wherein X chlorine, fluorine, halogen-substituted or unsubstituted C₁-C₅-alkyl, halogen-substituted or unsubstituted C₁-C₅ alkoxy, halogen-substituted or unsubstituted C₁-C₅ alkylthio, halogen-substituted or unsubstituted alkylsulphinyl, halogen-substituted or unsubstituted alkylsulphonyl, also nitro, cyano, thiocyanato, C₃-C₅-haloalkenyl, C₃-C₅-haloalkynyl, Hydroxy, C₁-C₅-alkoxycarbonyl, amino, di-C₁-C₄-alkylamino, C₁-C₅-alkylcarbonyl, C₁-C₅-alkylcarbonylamino or C₁-C₅-alkylcarbonyloxy, n the numbers 0-4, R₁ is hydrogen, C₁-C₅-alkyl, C₃-C₇-cycloalkyl, R₂ is hydrogen, C₁-C₅-alkyl, C₃-C₇-cycloalkyl, R₃ is hydrogen, C₁-C₅-alkyl, C₃-C₇-cycloalkyl, benzyl or pyridinylmethyl, or R₂ and R₃ together with the nitrogen atom connecting them pyrrolidinyl or piperazinyl mean, wherein no more than one of the radicals R₁, R₂ and R₃ is hydrogen, including the cis and trans isomers and including the salts of the compounds of formula I.

The alkyls and alkyl-containing radicals which are suitable as substituents, such as alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, can be straight-chain or branched. Examples of such alkyls are methyl, ethyl, propyl, cyclopropyl, isopropyl, butyl, i-butyl, sec-butyl, tert-butyl or pentyl, and their isomers.

The halogens which are suitable as substituents are both fluorine and chlorine and bromine and iodine, with fluorine and chlorine being preferred.

The halogen-substituted C₁-C₅-alkyls which can be considered as substituents can be straight-chain or branched and can only be partially or perhalogenated, the definitions given above applying to the halogens and the alkyls. Suitable examples of such substituents include methyl, mono- to trisubstituted by fluorine, chlorine and / or bromine, such as CHF₂ or CF₃; the one to five times substituted by fluorine, chlorine and / or bromine ethyl such as CH₂CF∋, CF₂CF₃, CF₂CCl₃, CF₂CHCl₂, CF₂CHF₂, CF₂CFCl₂, CF₂CHBr₂, CF₂CHClF, CF₂CHBrF or CClFCHClF; the one to seven times substituted by fluorine, chlorine and / or bromine, propyl or isopropyl such as CH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃ or CH (CF₃) ₂; the butyl or fluorine, chlorine and / or bromine substituted butyl or one of its isomers such as CF (CF₃) CHFCF₃ or CH₂ (CF₂) ₂CF₃.

The pyridinylmethyl radical in the compounds of the formula I is any of the three isomers α, β and γ of the formula:<chemistry id="chem0002" num="0002"><img file="EP0302833A2_D0002.tif" /></chemistry> into consideration.

Depending on the steric arrangement of the substituents bonded to the ethylene carbon atoms, the compounds of the formula I can be present as one of the cis and trans isomers or as a mixture thereof.

If one of the radicals R₁, R₂ and R₃ is hydrogen, the enamines according to the invention can also be present in the tautomeric imine form.

The compounds of formula I can also be in the form of acid addition salts. Both organic and inorganic acids are suitable for the formation of such salts. Examples of such acids include hydrochloric acid, hydrobromic acid, nitric acid, various phosphoric acids, sulfuric acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, maleic acid, fumaric acid, lactic acid, tartaric acid or salicylic acid.

The following connecting groups of the formula I are preferred in the context of the present invention.<ul id="ul0001" list-style="none"><li>1. Those 1-nitro-2,2-diamino-ethylene derivatives in which X is chlorine or fluorine.</li><li>2nd Those 1-nitro-2,2-diamino-ethylene derivatives in which X chlorine, n the numbers 0-2, R₁ is hydrogen, methyl, ethyl or cyclopropyl, R₂ is hydrogen or methyl, R₃ is hydrogen, C₁-C₅ alkyl, benzyl or pyridinylmethyl, or R₂ and R₃ together with the nitrogen atom connecting them represent the pyrrolidinyl or piperazinyl radical, mean.</li><li>2.1 Of these compounds are those of Formula Ia<chemistry id="chem0003" num="0003"><img file="EP0302833A2_D0003.tif" /></chemistry> preferably in which X₁ and X₂ are independently hydrogen or chlorine and R₁ is hydrogen, methyl or ethyl.</li><li>2.1.1. Of this group, those in which n = 0 are to be emphasized. The following individual connections are to be emphasized from the latter group:<chemistry id="chem0004" num="0004"><img file="EP0302833A2_D0004.tif" /></chemistry></li><li>2.1.2 Of the compounds of the formula Ia defined under 2.1, those in which X 1 and X 2 are chlorine are also preferred. Of this group is in particular the compound of the formula<chemistry id="chem0005" num="0005"><img file="EP0302833A2_D0005.tif" /></chemistry> prefers.</li></ul>

Finally, of the compounds defined under number 2, those of the formula Ic<chemistry id="chem0006" num="0006"><img file="EP0302833A2_D0006.tif" /></chemistry> prefers.

The compounds of the formula I according to the invention can be prepared by stepwise reaction of the nitromethylene derivatives of the formula II<chemistry id="chem0007" num="0007"><img file="EP0302833A2_D0007.tif" /></chemistry> in which L₁ and L₂ leaving groups, such as alkylthio, alkylsulfinyl or chlorine, are prepared with appropriately substituted amines.

The compound of formula II, wherein L₁ and L₂ have the meaning given above, either<ul id="ul0002" list-style="none"><li>a) first with the equivalent amount of a pyridinylmethylamine of the formula III<chemistry id="chem0008" num="0008"><img file="EP0302833A2_D0008.tif" /></chemistry> wherein R₁ has the meaning given under formula I, for 1-nitro-2-pyridinylmethylamino-ethylene derivative of the formula IV<chemistry id="chem0009" num="0009"><img file="EP0302833A2_D0009.tif" /></chemistry> wherein R₁, X and n, or L₁ have the meaning given under the formula I or II, implemented and then the compound IV with an amine of formula V.<chemistry id="chem0010" num="0010"><img file="EP0302833A2_D0010.tif" /></chemistry> wherein R₂ and R₃ have the meaning given under formula I, converted to 1-nitro-2,2-diamino-ethylene derivative of the formula I, or</li><li>b) a nitroethylene derivative of the formula II is first converted into the 1-nitro-2-amino-ethylene derivative of the formula VI with the equivalent amount of an amine of the formula V,<chemistry id="chem0011" num="0011"><img file="EP0302833A2_D0011.tif" /></chemistry> wherein R₂ and R₃, or L₁ have the meaning given under formula II or V, implemented and then this compound is reacted with a pyridinylmethylamine of the formula III to the 1-nitro-2,2-diamino-ethylene derivative of the formula I and this is isolated .</li></ul>

According to a preferred embodiment of the production process, the respective intermediate of formula IV or formula VI is processed further without isolation.

The intermediates of formula IV are new, have strong insecticidal properties and are also an object of the present invention. The compounds of the formula IV can be prepared in the first stage of the process described above and then isolated in substance.

The process for the preparation of the compounds of the formula I via the new intermediates of the formula IV is likewise an object of the present invention, just as the process leading to the compounds of the formula I via the known intermediates of the formula VI, and the process for the preparation of the compound of the Formula IV.

Suitable solvents in the preparation of the intermediates IV and VI and the end product I are aprotic, polar solvents, such as acetonitrile, dimethylformamide, dimethyl sulfoxide, etc., and aromatic solvents, such as benzene or toluene, furthermore chlorinated hydrocarbons, tetrahydrofuran, or ethers and alcohols .

The reactions take place in the temperature range between 0 ° and the boiling point of the reaction mixture, under atmospheric or, if appropriate, under reduced pressure.

The addition of salts, which act as buffers, such as disodium hydrophosphate, can favor the course of the reaction.

The starting products of the formula II are known and, like the intermediates of the formula VI, can be prepared by known methods.

Of the compounds of formula II, in which L₁ and L₂ are lower alkylthio or benzylthio, are known intermediates in preparative organic chemistry and are commercially available.

Those compounds of formula II in which L₁ and L₂ are chlorine can be prepared according to EP-A 135 803 from the known 1-nitro-2-trichloroethane by HCl elimination.

Those compounds of formula II in which L₁ is an alkylthio radical and L₂ is an alkylsulfinyl radical are described in US Pat. No. 4,028,375.

The intermediate products of formula VI, as well as their production are in the Gazetta Chimica Italiana <u style="single">111</u> 217 (1981) and in Arch. Pharm. (2) 161-167 (1986).

The compounds of the formula<chemistry id="chem0012" num="0012"><img file="EP0302833A2_D0012.tif" /></chemistry> in which R₄ represents an aryl or heteroaryl radical which is optionally substituted, R₅ represents straight-chain, branched or cyclic alkyl or alkenyl, which is optionally substituted by alkoxy or cycloalkyl, or represents an optionally substituted aryl or heteroaryl radical, X₅ represents optionally alkyl-substituted methylene or a chemical bond, where R₅ is not aryl if X₅ represents a single bond, are known as circulatory drugs, in particular as antihypertensive agents from DE-OS 32 32 462.

EP-A 154 178 describes 1-pyridinylalkyl-2-nitromethylidene-1,3-diazacycloalkanes which are insecticidal, miticidal and nematicidal, the heterocycle having 5-7 members. This publication relates to compounds which have the formula<chemistry id="chem0013" num="0013"><img file="EP0302833A2_D0013.tif" /></chemistry> correspond, where m is 2, 3 or 4 and n is 0, 1, 2 or 3.

Similar, also insecticidally active 1-pyridinylmethyl-2-nitromethylidene-azacycloalkanes and 1-pyridinylmethyl-2-nitromethylidene-1,3-diazacycloalkanes have also been described in EP-A 192 060.

In contrast to the compounds described in these publications, in which the 2-position ethylene carbon atom is defined as a member of a heterocycle, the corresponding rest of the compounds according to the invention is not ring-shaped.

Other, also insecticidally active, nitroethylene derivatives are known from the "Advances in Pesticide Science", Part 2, Pergamon Press, 1979, pp. 206-217. However, these compounds do not contain pyridinylmethyl.

The aim of the present invention was to provide further active substances for pest control.

Surprisingly, it has been found that the compounds of the formula I according to the invention and the intermediates of the formula IV are valuable active compounds in pest control, while being well tolerated by warm-blooded animals and plants. For example, the compounds of the formulas I and IV are suitable for controlling pests on animals and plants. Such pests belong mainly to the trunk of the arthropods, such as, in particular, insects of the orders Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera or Hymenoptera and Arachniden of the order Acarina, for example Mites and ticks. Every stage of development of the pests can be controlled, ie both the adults, pupae and nymphs, and especially the larvae and eggs. Larvae and eggs of phytopathogenic insect pests and mites in ornamental and useful plants, such as fruit and vegetable plants, and especially in cotton plants, can be effectively combated. If compounds of the formulas I and IV are taken up by adults, their effect can be seen in the immediate killing of the pests or else in reduced egg deposition and / or hatching rate. The latter phenomenon can be observed especially in coleopteras. Ectoparasites, such as, for example, mites and ticks, and dipteras, such as, for example, Lucilia sericata, are particularly suitable for controlling animal parasitic pests, in particular on domestic and farm animals.

The good pesticidal activity of the compounds of the formulas I and IV according to the invention corresponds to a mortality rate of at least 50-60% of the pests mentioned.

The compounds of the formulas I and IV are used in unchanged form or, preferably, together with auxiliaries which are customary and inert in plants and are compatible with plants and can therefore be used, for example, to prepare emulsion concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules , encapsulations in, for example, polymeric substances can also be processed in a known manner. The application methods, such as spraying, atomizing, dusting, scattering or pouring, as well as the means are chosen in accordance with the intended goals and the given conditions.

The formulation, ie the active ingredient of the formulas I and / or IV, or combinations of these active ingredients with other insecticides or acaricides, and, if appropriate, compositions, preparations or compositions comprising a solid or liquid additive are prepared in a known manner, for example by intimate mixing and / or grinding the active ingredients with extenders, such as with solvents, solid carriers, and optionally surface-active compounds (surfactants).

Possible solvents are: Aromatic hydrocarbons, preferably the fractions C₈ to C₁₂, such as Xylene mixtures or substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane, paraffins, alcohols and glycols, and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones, strongly polarehexanone, such as cyclohexanone such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils, such as epoxidized coconut oil or soybean oil, or water.

Natural rock flours, such as calcite, talc, kaolin, montmorillonite or attapulgite, are generally used as solid carriers, for example for dusts and dispersible powders. To improve the physical properties, highly disperse silicas or highly disperse absorbent polymers can also be added. Porous types such as pumice, broken brick, sepiolite or bentonite come as granular, adsorptive granule carriers, and non-sorptive carrier materials, for example Calcite or sand in question. In addition, a large number of granulated materials of inorganic or organic nature, such as in particular dolomite or comminuted plant residues, can be used.

Depending on the nature of the active ingredient of the formula I or IV to be formulated or the combinations of these active ingredients with other insecticides or acaricides, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. Surfactants are also to be understood as mixtures of surfactants.

Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

Suitable soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), such as the Na or K salts or oleic or stearic acid, or of natural fatty acid mixtures, for example from coconut or tall oil can be won. Also to be mentioned as surfactants are the fatty acid methyl taurine salts and modified and unmodified phospholipids.

However, so-called synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are generally present as alkali, alkaline earth or optionally substituted ammonium salts and generally have an alkyl radical with 8 to 22 carbon atoms, alkyl also including the alkyl part of acyl radicals, for example the Na or Ca Salt of lignin sulfonic acid, dodecylsulfuric acid ester or a fatty alcohol sulfate mixture made from natural fatty acids. This subheading also includes the salts of sulfuric acid esters and sulfonic acids from fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid residue with about 8-22 carbon atoms. Alkylarylsulfonates are, for example, the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonic acid / formaldehyde condensation product. Corresponding phosphates, such as, for example, also come Salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide adduct, in question.

Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols. Other suitable nonionic surfactants are the water-soluble 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups containing polyethylene oxide adducts with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol with 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, castor oil thioxilate, polypropylene / polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable.

The cationic surfactants are primarily quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N substituents and have low, optionally halogenated alkyl, benzyl or low hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, for example stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) ethylammonium bromide.

The surfactants commonly used in formulation technology are described, inter alia, in the following publications: "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood, New Jersey, 1979; Dr. Helmut Stache "Tensid Taschenbuch", Carl Hanser Verlag Munich / Vienna 1981.

The pesticidal preparations generally contain 0.1 to 99%, in particular 0.1 to 95%, active ingredient of the formula I or IV or combinations of these active ingredients with other insecticides or acaricides, 1 to 99.9% of a solid or liquid additive and 0 to 25%, in particular 0.1 to 20%, of a surfactant. While concentrated agents are preferred as a commercial product, the end user generally uses diluted preparations which have significantly lower active substance concentrations.

The agents can also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.

1. Production of intermediate and end products

1.1 Intermediates of formula IV

Example 1.1.1:

Preparation of the intermediate 2- (N-methyl-N-pyridin-3-yl-methyl-amino) -2-methylthio-1-nitro-ethylene

<chemistry id="chem0014" num="0014"><img file="EP0302833A2_D0014.tif" /></chemistry>

26 g (0.156 mol) of 1-nitro-2,2-dimethylthioethylene are dissolved in 80 ml of toluene. 18.3 g (0.15 mol) of N-methyl-N-pyridin-3-yl-methylamine are added dropwise to this solution at 70 ° C. for 30 minutes and the solution is stirred at the same temperature for one hour.

After evaporation of the solvent, the evaporation residue in solution (ethylene acetate / methanol = 97/3) is purified by column chromatography over silica gel. The 2- (N-methyl-N-pyridin-3-yl-methyl-amino) -2-methylthio-1-nitro-ethylene (product no. 1.1, table 1) is isolated after evaporation of the solvent in vacuo as a thick oil .

The following connections can be made in an analogous manner:<tables id="tabl0001" num="0001"><img file="EP0302833A2_D0015.tif" /></tables>

Example 1.2.1:

Preparation of the intermediate 2- (N-butyl-N-methyl-amino) -2-methylthio-1-nitro-ethylene.

The toluene solution of 8.26 g (0.05 mol) of 1-nitro-2,2-di (methyl-thio) ethylene and 5.25 g (0.06 mol) of Nn-butyl-N-methylamine are used during Heated under reflux for 2 hours. After evaporation of the toluene in vacuo, 10.2 g of 2- (N-butyl-N-methylamino) -2-methylthio-1-nitroethylene are isolated as oil as the distillation residue (<maths id="math0001" num=""><img file="EP0302833A2_D0016.tif" /></maths> = 1.584). (Product No. 2.1, Table 2.)

The following connections can be made in an analogous manner:<tables id="tabl0002" num="0002"><img file="EP0302833A2_D0017.tif" /></tables>

1.3 end products

Example 1.3.1:

Preparation of the end product 2-butylamino-2- (N-methyl-N-pyridin-3-yl-methyl-amino) -1-nitro-ethylene.

<chemistry id="chem0015" num="0015"><img file="EP0302833A2_D0018.tif" /></chemistry>

6 g of 2- (N-methyl-N-pyridin-3-yl-methyl-amino) -2-methylthio-1-nitro-ethylene, 2.19 g of n-butylamine in 20 ml of acetonitrile as solvent are at 70 ° C kept. After evaporation of the solvent in vacuo, the evaporation residue is dissolved in dichloromethane and column chromatographed on silica gel. The product is eluted with dichloromethane / methanol = 95/5. After evaporation of the solvent, the 2-butylamino-2- (N-methyl-N-pyridin-3-yl-methylamino) -1-nitroethylene is isolated as an oil, (<maths id="math0002" num=""><img file="EP0302833A2_D0019.tif" /></maths> = 1.618). (Product No. 3.1, Table 3.)

Example 1.3.2:

Preparation of 2- (Nn-butyl-N-methylamino) -2- (pyridin-3-ylmethylamino) -1-nitroethylene.

5.2 g of 2- (Nn-butyl-N-methylamino) -2-methylthio-1-nitroethylene, 2.84 g of pyridin-3-ylmethylamine, 3.69 g of disodium hydrophosphate in 30 ml of ethanol are used for 1 hour heated under reflux for a long time. After filtering the salt, the solvent is evaporated from the solution in vacuo and the evaporation residue in ethyl acetate / methanol = 95/5 is chromatographed on a column filled with silica gel. The product is eluted with ethyl acetate / methanol 85/15; After evaporation of the solvent, 3.7 g of 2- (Nn-butyl-N-methylamino) -2- (pyridin-3-ylmethylamino) -1-nitroethylene are isolated as a viscous oil (product 3.2, Table 3).

The NMR spectrum and the elementary analysis are in agreement with the structure mentioned.

Example 1.3.3:

Preparation of the end product 2-methylamino-2- (N-methyl-N-pyridin-3-yl-methyl-amino) -1-nitro-ethylene.

5.0 g of 2- (N-methyl-N-pyridin-3-yl-methylamino) -2-methylthio-1-nitroethylene and 2.07 g of 33% methylamine solution in ethanol are added with 3.12 g of disodium hydrophosphate and 25 ml of ethanol heated under reflux for 1 hour. After filtering off the salts, the filtrate in vac. evaporated and the evaporation residue in ethyl acetate / methanol = 95/5 to 85/5 column chromatographed on silica gel. After evaporation of the solvents, the product is isolated as a viscous oil (product 3.3, table 3).

The following connections can be made in an analogous manner:<tables id="tabl0003" num="0003"><img file="EP0302833A2_D0020.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP0302833A2_D0021.tif" /></tables>

Example 2: Formulations of active compounds of the formulas I and IV according to the preparation examples 1.1.1. and 1.3.1 to 1.3.3

<tables id="tabl0005" num="0005"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><tbody valign="top"><row><entry namest="col1" nameend="col3" align="justify">(% = Weight percent)</entry></row></tbody></tgroup><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col3" align="left"><u style="single">2.1 Emulsion concentrates</u></entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">a)</entry><entry namest="col3" nameend="col3" align="center">b)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Active ingredient according to the preparation examples 1.1.1. and 1.3.1-1.3.3.</entry><entry namest="col2" nameend="col2" align="right">10 %</entry><entry namest="col3" nameend="col3" align="right">25 %</entry></row><row><entry namest="col1" nameend="col1" align="left">Ca-dodecylbenzenesulfonate</entry><entry namest="col2" nameend="col2" align="right">-</entry><entry namest="col3" nameend="col3" align="right">5 %</entry></row><row><entry namest="col1" nameend="col1" align="left">Castor oil-polyethylene glycol ether (36 mol AeO)</entry><entry namest="col2" nameend="col2" align="right">25 %</entry><entry namest="col3" nameend="col3" align="right">5 %</entry></row><row><entry namest="col1" nameend="col1" align="left">Tributylphenol polyethylene glycol ether (30 mol AeO)</entry><entry namest="col2" nameend="col2" align="right">-</entry><entry namest="col3" nameend="col3" align="right">-</entry></row><row><entry namest="col1" nameend="col1" align="left">Cyclohexanone</entry><entry namest="col2" nameend="col2" align="right">-</entry><entry namest="col3" nameend="col3" align="right">40 %</entry></row><row><entry namest="col1" nameend="col1" align="left">Butanol</entry><entry namest="col2" nameend="col2" align="right">15 %</entry><entry namest="col3" nameend="col3" align="right">-</entry></row><row><entry namest="col1" nameend="col1" align="left">Xylene mixture</entry><entry namest="col2" nameend="col2" align="right">-</entry><entry namest="col3" nameend="col3" align="right">25 %</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Ethyl acetate</entry><entry namest="col2" nameend="col2" align="right">50 %</entry><entry namest="col3" nameend="col3" align="right">-</entry></row></tbody></tgroup></table></tables>

Emulsions of any desired concentration can be prepared from such concentrates by dilution with water. <tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col3" align="left"><u style="single">2.2 solutions</u></entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">a)</entry><entry namest="col3" nameend="col3" align="left">b)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Active ingredient according to the preparation examples 1.1.1. and 1.3.1. until 1.3.3.</entry><entry namest="col2" nameend="col2" align="right">10 %</entry><entry namest="col3" nameend="col3" align="right">5 %</entry></row><row><entry namest="col1" nameend="col1" align="left">Polyethylene glycol (MG 400)</entry><entry namest="col2" nameend="col2" align="right">70 %</entry><entry namest="col3" nameend="col3" align="right">-</entry></row><row><entry namest="col1" nameend="col1" align="left">N-methyl-2-pyrrolidone</entry><entry namest="col2" nameend="col2" align="right">20 %</entry><entry namest="col3" nameend="col3" align="right">20 %</entry></row><row><entry namest="col1" nameend="col1" align="left">Epoxidized coconut oil</entry><entry namest="col2" nameend="col2" align="right">-</entry><entry namest="col3" nameend="col3" align="right">1 %</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Petrol (boiling limits 160-190 ° C)</entry><entry namest="col2" nameend="col2" align="right">-</entry><entry namest="col3" nameend="col3" align="right">74 %</entry></row></tbody></tgroup></table></tables>

The solutions are suitable for use in the form of tiny drops. <tables id="tabl0007" num="0007"><table frame="all"><tgroup cols="3" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="52.50mm" /><colspec colnum="2" colname="col2" colwidth="52.50mm" /><colspec colnum="3" colname="col3" colwidth="52.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col3" align="left"><u style="single">2.3 granules</u></entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">a)</entry><entry namest="col3" nameend="col3" align="center">b)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Active ingredient according to the preparation examples 1.1.1. and 1.3.1. until 1.3.3.</entry><entry namest="col2" nameend="col2" align="right">5 %</entry><entry namest="col3" nameend="col3" align="right">10 %</entry></row><row><entry namest="col1" nameend="col1" align="left">kaolin</entry><entry namest="col2" nameend="col2" align="right">94 %</entry><entry namest="col3" nameend="col3" align="right">-</entry></row><row><entry namest="col1" nameend="col1" align="left">Fumed silica</entry><entry namest="col2" nameend="col2" align="right">1 %</entry><entry namest="col3" nameend="col3" align="right">-</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Attapulgite</entry><entry namest="col2" nameend="col2" align="right">-</entry><entry namest="col3" nameend="col3" align="right">90 %</entry></row></tbody></tgroup></table></tables>

The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated off in vacuo.

2.4 Extruder granules

Active ingredient according to the preparation examples 1.1.1. and 1.3.1-1.3.3. 10% Na lignin sulfonate 2% Carboxymethyl cellulose 1% Kaolin 87%

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

2.5 coating granules

Active ingredient according to the preparation examples 1.1.1. and 1.3.1-1.3.3. 3% Polyethylene glycol (MG 200) 3% Kaolin 94%

The finely ground active ingredient is evenly applied in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.<tables id="tabl0008" num="0008"><table frame="all"><tgroup cols="5" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="31.50mm" /><colspec colnum="2" colname="col2" colwidth="31.50mm" /><colspec colnum="3" colname="col3" colwidth="31.50mm" /><colspec colnum="4" colname="col4" colwidth="31.50mm" /><colspec colnum="5" colname="col5" colwidth="31.50mm" /><thead valign="top"><row><entry namest="col1" nameend="col5" align="left"><u style="single">2.6 dusts</u></entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">a)</entry><entry namest="col3" nameend="col3" align="left">b)</entry><entry namest="col4" nameend="col4" align="left">c)</entry><entry namest="col5" nameend="col5" align="left">d)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Active ingredient according to the preparation examples 1.1.1. and 1.3.1.-1.3.3.</entry><entry namest="col2" nameend="col2" align="right">2 %</entry><entry namest="col3" nameend="col3" align="right">5 %</entry><entry namest="col4" nameend="col4" align="right">5 %</entry><entry namest="col5" nameend="col5" align="right">8 %</entry></row><row><entry namest="col1" nameend="col1" align="left">Fumed silica</entry><entry namest="col2" nameend="col2" align="right">1 %</entry><entry namest="col3" nameend="col3" align="right">5 %</entry><entry namest="col4" nameend="col4" align="right">-</entry><entry namest="col5" nameend="col5" align="right">-</entry></row><row><entry namest="col1" nameend="col1" align="left">talc</entry><entry namest="col2" nameend="col2" align="right">97 %</entry><entry namest="col3" nameend="col3" align="right">-</entry><entry namest="col4" nameend="col4" align="right">95 %</entry><entry namest="col5" nameend="col5" align="right">-</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">kaolin</entry><entry namest="col2" nameend="col2" align="right">-</entry><entry namest="col3" nameend="col3" align="right">90 %</entry><entry namest="col4" nameend="col4" align="right">-</entry><entry namest="col5" nameend="col5" align="right">92 %</entry></row></tbody></tgroup></table></tables>

Ready-to-use dusts are obtained by intimately mixing the excipients with the active ingredient and optionally grinding them in a suitable mill. <tables id="tabl0009" num="0009"><table frame="all"><tgroup cols="4" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="39.37mm" /><colspec colnum="2" colname="col2" colwidth="39.37mm" /><colspec colnum="3" colname="col3" colwidth="39.37mm" /><colspec colnum="4" colname="col4" colwidth="39.37mm" /><thead valign="top"><row><entry namest="col1" nameend="col4" align="left"><u style="single">2.7 wettable powder</u></entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="left">a)</entry><entry namest="col3" nameend="col3" align="left">b)</entry><entry namest="col4" nameend="col4" align="left">c)</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Active ingredient according to the preparation examples 1.1.1. and 1.3.1.-1.3.3.</entry><entry namest="col2" nameend="col2" align="right">20 %</entry><entry namest="col3" nameend="col3" align="right">50 %</entry><entry namest="col4" nameend="col4" align="right">75 %</entry></row><row><entry namest="col1" nameend="col1" align="left">Na lignin sulfonate</entry><entry namest="col2" nameend="col2" align="right">5 %</entry><entry namest="col3" nameend="col3" align="right">5 %</entry><entry namest="col4" nameend="col4" align="right">-</entry></row><row><entry namest="col1" nameend="col1" align="left">Na lauryl sulfate</entry><entry namest="col2" nameend="col2" align="right">3 %</entry><entry namest="col3" nameend="col3" align="right">-</entry><entry namest="col4" nameend="col4" align="right">5 %</entry></row><row><entry namest="col1" nameend="col1" align="left">Na diisobutylnaphthalenesulfonate</entry><entry namest="col2" nameend="col2" align="right">-</entry><entry namest="col3" nameend="col3" align="right">6 %</entry><entry namest="col4" nameend="col4" align="right">10 %</entry></row><row><entry namest="col1" nameend="col1" align="left">Octylphenol polyethylene glycol ether (7-8 mol AeO)</entry><entry namest="col2" nameend="col2" align="right">-</entry><entry namest="col3" nameend="col3" align="right">2 %</entry><entry namest="col4" nameend="col4" align="right">-</entry></row><row><entry namest="col1" nameend="col1" align="left">Fumed silica</entry><entry namest="col2" nameend="col2" align="right">5 %</entry><entry namest="col3" nameend="col3" align="right">10 %</entry><entry namest="col4" nameend="col4" align="right">10 %</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">kaolin</entry><entry namest="col2" nameend="col2" align="right">67 %</entry><entry namest="col3" nameend="col3" align="right">27 %</entry><entry namest="col4" nameend="col4" align="right">-</entry></row></tbody></tgroup></table></tables>

The active ingredient is mixed well with the additives and ground in a suitable mill. Spray powder is obtained which can be diluted with water to form suspensions of any desired concentration.

2.8 Suspension concentrate

Active ingredient according to the preparation examples 1.1.1. and 1.3.1.-1.3.3. 40% Ethylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol AeO) 6% Na lignin sulfonate 10% Carboxymethyl cellulose 1% 37% aqueous formaldehyde solution 0.2% Silicone oil in the form of a 75% aqueous emulsion 0.8% Water 32%

The finely ground active ingredient is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

Example 3.1:

Feeding poison and contact effects on Laodelphax striatellus and Nilaparvata lugens (nymphs);

The test is carried out on growing plants. To do this, 4 rice plants (stem thickness 8 mm) with a height of approx. 20 cm are planted in pots (diameter 8 cm).

The plants are sprayed on a turntable with 100 ml of an emulsion, prepared from the emulsion concentrate according to Example 2a) by adding water, containing 400 ppm of the respective active ingredient. After the spray coating has dried on, each plant is populated with 20 nymphs of the test animals in the third stage. In order to prevent the cicadas from escaping, a glass cylinder, which is open on both sides, is put over the populated plants and covered with a gauze cover. The nymphs are held on the treated plant for 10 days until the following developmental stage is reached. % Mortality is evaluated 1, 4 and 8 days after treatment.

Compounds Nos. 1.1, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7 and 3.8 show 80-100% activity in this test against Nilaparvate lugens.

Example 3.2:

Systemic effect on Nilaparvata lugens

Rice plants about 10 days old (approx. 10 cm high) are placed in a plastic beaker which contains 20 ml of an aqueous emulsion preparation of the active substance to be tested, which is prepared from the emulsion concentrate according to Example 2a) by adding water, in a concentration of 100 ppm contains and is closed with a perforated plastic lid. The root of the rice plant is pushed through a hole in the plastic lid into the aqueous test preparation. The hole was then sealed with cotton wool to hold the plant in place and eliminate the influence of the gas phase from the test preparation. Then the rice plant is populated with 20 nymphs from Nilaparvata lugens in the N 2 to N 3 stage and covered with a plastic cylinder. The test is carried out at 20 ° C and 60% relative humidity with an illumination period of 16 hours. After five days, the number of test animals killed is compared to untreated controls. This determines whether the active ingredient absorbed through the root kills the test animals on the upper parts of the plant.

Compounds Nos. 1.1, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7 and 3.8 show 80-100% activity (mortality) against Nilaparvata lugens in the above test.

3.3 Effect on Spodoptera littoralis (larvae)

Two cotton plants, about 15-20 cm high, grown in pots are treated with a sprayable preparation of the active substance to be tested. After the spray coating has dried on, the dripped plants are placed in a tin container of approximately 20 liters, which is covered with a glass plate. The moisture inside the covered vessel is regulated so that no condensed water forms. Direct light falling on the plants is avoided. Then the two plants are infested, with a total of:<ul id="ul0003" list-style="none"><li>a) 50 larvae of Spodoptera littoralis or Heliothis virescens of the first larval stage;</li><li>b) 20 larvae of Spodoptera littoralis or Heliothis virescens of the third larval stage;</li></ul> After 2 days, the evaluation against untreated controls is carried out on the number of larvae still living.

Compound No. 3.3 shows a mortality of 80-100% in a concentration of 400 ppm.

3.4 Effect on Heliothis virescens (eggs)

A cotton plant grown in a pot is treated with a sprayable liquid preparation of the active substance to be tested from a height of approx. 15-20 cm. After the spray coating has dried on, the potted plant is placed in a metal container of about 20 liters, which is covered with a glass plate. The moisture inside the covered vessel is regulated so that no condensed water forms. Direct light falling on the plant is avoided. The plant is then infested, with a total of two ice levels from Spodoptera littoralis or Heliothis virescens (2 leaves of a plant are enclosed in a plexiglass cylinder closed on both sides with gauze); two ice levels from Spodoptera or part of a cotton leaf with eggs from Heliothis placed thereon are added to the enclosed leaves.

After 4 days, the evaluation compared to untreated controls takes into account the hatching rate (number of larvae hatched from the eggs).

Compounds Nos. 3.3 and 3.6 show 100% mortality in a concentration of 400 ppm in the above test.

3.5. Contact effect on Myzus persicae

Approximately 4 to 5 day old pea seedlings (pisum sativum) soaked in water are colonized with approx. 200 individuals of the species Myzus persicae before the start of the experiment. The plants treated in this way are sprayed 24 hours later with an aqueous suspension containing up to 200 ppm of the compound to be tested until dripping wet. Two plants are used per test substance. The kill rate achieved is evaluated 24 and 72 hours after application. The test is carried out at 21-22 ° C and about 60% relative humidity.

Compounds Nos. 1.1, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7 and 3.8 show good effects in this test.

3.6 Contact effect on Aphis craccivora

4-5 day old pea seedlings (pisum sativum) grown in pots are populated with about 200 individuals of the species Aphis craccivora before the start of the experiment. The plants treated in this way are sprayed 24 hours later with an aqueous preparation containing the compound to be tested to the point of dripping wet. Two plants are used per test compound. The kill rate achieved is evaluated after a further 24 and 72 hours. The experiment is carried out at 21-22 ° C and a rel. Humidity of about 55% carried out.

Compounds Nos. 1.1, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7 and 3.8 show good effects in this test.

3.7. Effect against soil insects (Diabrotica balteata)

There are 5 approximately one to three cm long maize seedlings and a rondelle of filter paper immersed in an aqueous preparation containing 0.2 to 12.5 ppm of the active ingredient to be tested. The wet filter paper disc is placed on the bottom of a 200 ml plastic cup, and then the 5 treated corn seedlings are added to the cup along with 10 larvae of Diabrotica balteata of the second to third larval stages. Two approaches are carried out for each active ingredient concentration. The cups filled with the larvae are kept for 6 days in daylight, a relative humidity of 40 to 60% and a temperature of 22 to 24 ° C. The percentage kill of the test animals is then determined.

Compounds No. 1.1, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7 and 3.8 show good effects in this test.

3.8 Insecticidal systemic effects: Aphis craccivora

Rooted bean plants are transplanted into pots containing 600 cc of soil. Then pour 50 ml of a preparation of the compounds to be tested (obtained from a 25% wettable powder) each in a concentration of 400 ppm directly on the earth in the pots.

After 24 hours, lice of the species Aphis craccivora are placed on the aerial parts of the plants and the plants are placed over them with a plastic cylinder in order to protect the lice from possible contact or gas effects of the test substance.

The killing achieved is evaluated 48 and 72 hours after the start of the test. Two plants, one in a separate pot, are used per test substance. The test is carried out at 25 ° C and 70% relative humidity.

Compounds Nos. 1.1, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, and 3.8 show good effects in the above test.

3.9 Insecticidal systemic effects: Myzus persicae

Rooted cabbages in the 4- to 5-leaf stage are transplanted into pots that contain 60 cc of soil. 50 ml of an aqueous formulation of the compound I to be tested (obtained from a 25% wettable powder) are then poured directly onto the earth in a concentration of 400 ppm.

After 24 hours, aphids of the species Myzus persicae are placed on the aerial plant parts of the treated plants and the plants are covered with plastic cylinders in order to protect the aphids from possible contact or gas effects of the test substance.

The% kill achieved is evaluated 48 hours after the start of the test. Two plants, one in separate pots, are used per test substance. The test is carried out at approx. 25 ° C and 60% relative humidity.

Compounds Nos. 1.1, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7 and 3.8 show good effects in the above test.

3.10 Insecticidal leaf penetration effect: Aphis craccivora

A suitable small branch of Vicia faba, which is severely infected with aphids from the species Aphis craccivora, is placed in a plastic cup of about 8 cm (diameter about 6 cm). The cup is covered with a plastic lid, which has a punched-out opening of 2 cm in diameter in the middle. A leaf of a Vicia faba plant is placed on the opening in the lid without separating this leaf from the potted plant. The sheet is then fixed with a second perforated lid on the cup over the opening of the first lid. From the bottom, ie through the opening of the first cover, the aphids in the cup now infect the top leaf of the forage plant. On top of the sheet, an aqueous preparation of the active ingredient to be tested is applied evenly in a concentration of 400 ppm using a brush. It is checked whether the test substance applied on one side to the top of the leaf of the fodder plant diffuses through the leaf on its underside in sufficient quantity to kill sucking aphids there.

The test is carried out at about 20 ° C and 60% relative humidity. Evaluation for% mortality is carried out 48 hours after drug application.

Compounds Nos. 1.1, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7 and 3.8 show good effects in the above test.

3.11 Insecticidal activity (systemic water): Aphis craccivora

Pea seedlings that had been infested with the aphids 24 hours before the start of the experiment are placed in 20 ml of an aqueous broth containing 400 ppm of the active ingredient to be tested. The aqueous broth is made from an emulsion concentrate or a wettable powder preparation of the active ingredient in question and is located in a vessel that is closed with a plastic lid with holes. The root of the infested pea plant is pushed into the broth through a hole in the plastic lid. The hole is then sealed with cotton wool in order to fix the plant and to eliminate any influence of the gas phase from the broth.

The test is carried out at 20 ° C and 60 ° C relative humidity. After two days, the number of test animals which are no longer absorbent is assessed in comparison with untreated controls. This determines whether the active ingredient absorbed through the root kills the aphids on the upper parts of the plant.

Compounds Nos. 1.1, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7 and 3.8 show a good systemic activity against insects of the species Aphis craccivora in the above experiment.

3.12 Effect against Nephotettix cincticeps (nymphs)

The test is carried out on growing plants. For this purpose, rice plants about 20 days old and about 15 cm high are planted in pots (diameter 5.5 cm).

The plants are sprayed on a turntable with 100 ml of an acetone solution containing 400 ppm of the active ingredient to be tested. After the spray coating has dried on, each plant is populated with 20 nymphs of the test animals in the second or third stage. In order to prevent the cicadas from escaping, a plexiglass cylinder is placed over each of the populated plants and covered with a gauze cover. The nymphs are held on the treated plant for 5 days, which must be watered at least once. The test is carried out at a temperature of approx. 23 ° C., at 55% relative atmospheric humidity and with an exposure period of 16 hours.

Compounds No. 1.1, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7 and 3.8 show good effects in this test.