KR0150400B1 - Substituted 2,4-diamimo-5-cyanopyrimidine and the process for preparation thereof - Google Patents

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Description

Substituted 2,4-diamino-5-cyano pyrimidine and process for preparing these compounds

The present invention relates to novel substituted 2,4-diamino-5-cyano pyrimidines and their salts and the middle aged, the preparation of these compounds and the use of the compounds for pest and external parasite control. This novel compound is a compound of formula (I):

Wherein R ₁ is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl, and R ₂ is hydrogen, C ₁ -C ₁₀ alkyl or C ₃ -C ₆ cyclo Alkyl or a radical selected from the group consisting of — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ and — (CH ₂ ) ₅ ) in combination R ₁ and R ₂ ; R ₃ is hydrogen or a —CO—R ₅ or —SO ₂ —R ₆ radical; R ₄ is -NH ₂ , -NH-CO-R ₅ , -NH-SO ₂ -R ₆ , Or a radical selected from the group consisting of —NH—CH═NR ₁₀ ; R ₅ is hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₆ cycloalkyl, C ₁ -C ₆ alkoxy, perhalogenated C ₁ -C ₃ alkyl or Radical; R ₆ is C ₁ -C ₆ alkyl; R ₇ is hydrogen or C ₁ -C ₆ alkyl; R ₈ and R ₉ are each independently hydrogen or C ₁ -C ₆ alkyl, or R ₈ and R ₉ collectively represent-(CH ₂ ) ₃ )-,-(CH ₂ ) ₄ -and-(CH ₂ ) ₅ A radical selected from the group consisting of; R ₁₀ is a -SO ₂ -R ₁₃ radical or Radical; R ₁₁ and R ₁₂ are each independently hydrogen or C ₁ -C ₆ alkyl, or R ₁₁ and R ₁₂ collectively represent-(CH ₂ ) ₃ )-,-(CH ₂ ) ₄ )-and-(CH ₂ ) _A radical selected from the group consisting of ₅ ; R ₁₃ is C ₁ -C ₁₀ alkyl, up to 10 halogen atoms C ₁ -C ₁₀ alkyl, or C ₃ -C ₆ cycloalkyl; R ₁₄ and R ₁₅ are each independently C ₁ -C ₁₀ alkyl; And X and Y are each independently oxygen or sulfur.

Within the scope of the present invention, halogen atoms and halogen substituents mean fluorine, chlorine, bromine or iodine, with fluorine and chlorine being preferred.

Preferred compounds of formula (I) because of advantageous properties are those in which R ₁ is hydrogen or C ₁ -C ₄ alkyl and R ₂ is C ₁ -C ₄ alkyl or C ₃ -C ₆ cycloalkyl, or R ₁ and R ₂ Together are-(CH ₂ ) ₄ )-or-(CH ₂ ) ₅ -radical, R ₃ is hydrogen, R ₄ is -NH ₂ or -NH-CO-R ₅ radical, and R ₅ is C _1- Compounds and salts thereof as well as C ₄ alkyl or perhalogenated C ₁ -C ₃ alkyl, R ₁ is hydrogen, methyl or ethyl, R ₂ is C ₁ -C ₄ alkyl or cyclopropyl, R ₃ is hydrogen, General formula (I) compounds and salts thereof, wherein R ₄ is a -NH ₂ or -NH-CO-R ₅ radical, and R ₅ is C ₁ -C ₃ alkyl. Because of excellent pesticide activity, particularly preferred compounds of formula (I) are those in which R ₁ is hydrogen, methyl or ethyl, R ₂ is cyclopropyl, R ₃ is hydrogen, and R ₄ is —NH ₂ or —NH—CO -C ₂ H ₅ radicals, and salts thereof.

Salts of the compounds of formula (I) mean physiologically acceptable addition salts of inorganic or organic acids. Examples of the inorganic acid include hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, phosphorous acid and nitric acid. Examples of organic acids include trifluoroacetic acid, trichloroacetic acid, formic acid, oxalic acid, succinic acid, maleic acid, lactic acid, glycolic acid, aconitic acid, citric acid, benzoic acid, benzenesulfonic acid and methanesulfonic acid.

The compound of formula (I) may be reacted with a) reacting a compound of formula (II) with ammonia, or b) reacting a compound of formula (III) with an amine of a compound of formula (IV) And the resulting general formula (I) compound (compound Ia) wherein R ₃ is hydrogen and R ₄ is -NH ₂ radical, in a known manner, R ₃ is -CO-R ₅ or -SO ₂ -R ₆ and Or R ₄ is-NH-CO-R ₅ , -NH-SO ₂ -R ₆ , Or by converting the general formula (I) compound having -NH-CH = NR ₁₀ and converting the generated general formula (I) compound into a salt thereof, if necessary.

Wherein R ₁ to R ₁₅ , X and Y are as defined above and n is 0, 1 or 2.

In the preparation a), the reaction of the sulfonyl compound (n = 2) of general formula (II) with ammonia is generally carried out in an organic solvent such as acetonitrile, tetrahydrofuran, dioxane or in a temperature range of 10 ° to 100 ° C, or Run in a solvent / water mixture. The same reaction conditions can be applied to preparation b) in which 2-chloro-4, 6-diamino-5-cyano pyrimidine of formula (III) is reacted with formula (IV) amine. When methylthio compound (n = 0) is used as starting material in formula a), the reaction with ammonia is preferably an autoclave at temperatures ranging from 100 ° to 170 ° C., typically at about 160 ° C., under elevated pressure. To run inside.

The conversion of a compound of formula (I) wherein R ₄ is —NH ₂ to a compound of which R ₄ has the other meanings referred to herein is the reaction of the amino group at the 6-position of the pyrimidine ring with a suitable known reactant already known. It can carry out by. Thus, for example, the 6-aminopyrimidine of formula (I) may be selected from Hal-CO-R ₅ , wherein Hal is a halogen atom, preferably a chlorine atom and R ₅ , R ₆ and R ₁₀ have a given meaning; The compound is reacted with a compound of the type Hal-SO ₂ -R ₆ , (R ₅ -CO) ₂ O or R ₆ O-CH = NR ₁₀ to give the general formula (I) compound, which is suitably substituted at the 6-position.

R ₄ is If it is necessary to prepare a compound of formula (I) which is a radical, the 6-NH ₂ group Reacts with an acetal of where R ₆ , R ₇ , R ₈ and R ₉ have the meaning given. Analogous formulations and suitable reactants give the general formula (I) compounds wherein R ₃ is —CO—R ₅ or —SO ₂ —R ₆ radicals from 4-aminopyrimidines of formula (I), wherein R ₃ is hydrogen. can do.

The acylation reactions described above can be carried out in an inert solvent or diluent at temperatures ranging from 0 ° to 120 ° C., preferably from 40 ° to 80 ° C., at atmospheric pressure in the presence of a base and at atmospheric pressure. Examples of suitable solvents and diluents include alkanes such as homologues thereof including isomers up to n-heptane and n-heptadecane; diethyl ether, dipropyl ether, dibutyl ether, dimethoxyethane, dioxane or tetrahydrofuran; Ethers such as; chlorinated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride or chlorobenzene; Aromatic hydrocarbons such as benzene, toluene or xylene. Other Inert Solvents and Diluents

Moreover, it can use suitably for the manufacturing method of this invention. Bases which can be suitably used in the present reaction include, for example, alkylamines such as triethylamine or diisopropylethylamine and pyridine or N-methylpyrrolidone.

Starting compounds of the general formula (II) are novel, and in particular, these compounds have excellent pesticide properties, in particular pesticidal properties, and constitute the object of the present invention. These compounds can be prepared as follows:

a) For example, a compound of formula II wherein n is o may be prepared according to the following scheme:

Formula (VI) salts prepared by the reaction of dimethyl N-cyanodithiocarboxyimidate and malonitrile of formula (V) used as starting materials in the above preparation are known (e.g. Rec. Trav. Ch. 90/1971, 463; J. Chem. Comm. 1974 /, 350). Formula (II) compounds wherein n is o can be obtained by cyclizing the formula (VI) salt with 5N HCl and then reacting the resulting formula (VI) pyrimidine with the corresponding formula (IV) amine. have.

b) In addition, general formula (II) compounds wherein n is o can be obtained as follows:

The sodium salt of the general formula (VIII), the urea of the general formula (IX) and the uracil of the general formula (X) shown in the above reaction scheme are known. (E.g. J. Chem. Soc., Chem. Comm. 1974, 350; Helv. Chim. Act. 1985, 1155). The preparation of novel substituted pyrimidines of formulas (XI) and (XII) can be carried out by known methods. The reaction of general formula (XII) with ammonia produces a compound of general formula (II) wherein n is o.

c) Starting compounds of the general formula (II) wherein n is 1 or 2 can be prepared by the originally known process wherein n oxidizes o to the general formula (II) compound. (E.g., The Chemistry of Heterocyclic Compounds, Vol. 16: Pyrimidines, Intersc. Publ. Inc., N.Y. 1959).

Starting compounds of the general formula (III) such as, for example, 2-chloro-4, 6-diamino-5-cyanopyrimidine can be obtained from Chem. Ber. Known in 1968, 1244, the compounds of formula (VII) may be oxidized to form sulfones and reacted with ammonia to produce the following reaction schemes in which -SO ₂ CH ₃ is replaced by -NH ₂ :

2,4,6-triamino-5-nitropyrimidine pesticides, in particular pesticides, which are amino groups which may be substituted, are already known from EP 0084, 758. The compounds of formulas (I) and (II) are structurally different from known compound materials in containing cyano groups in the 5-position.

Surprisingly, it has been found that the compounds of formulas (I) and (II) and salts thereof have excellent pesticide properties that are acceptable by plants and low toxicity to warm-blooded animals. They are particularly suitable for controlling pests and representative pests of the species Acarina, which invade plants and animals.

In particular, the general formula (I) and (II) compounds are Lepidoptera, Coleoptera, Homoptera, Hepoptera, Diptera, Tisantoptera (Thysanoptera), Orthoptera, Anoplura, Siphonaptera, Silomapta, Mallophaga, Thysanura, Isoptera, Psocoptera And pests of the tree Hymenoptera; And a representative pest control of Acarina tree with the Ixodidae, the Argasidae, the Tetranychidae and the Deermanyssidae.

In addition to acting on flies and mosquito larvae, such as, for example, Musca domestica, the compounds of the present invention can be used for ornamental plants and useful crops, in particular cotton (e.g., Spodoptera littoralis and Heliotisviruses) And also suitable for controlling plant infestation erosion pests in fruits and vegetables (e.g., flutella xylostelma, Lasperesia pomonella, leptinotarsa desemrineata and epirakna baribestis). Do. Compounds of formulas (I) and (II) are also effective against rice pests. The compounds of general formulas (I) and (II) also have a significant scattering action and in particular larval eradication against pests, in particular larvae of harmful eroding pests. When adult insect pests ingest the active compound with food, it can be observed that spawning and / or hatching rates are reduced in many pests, especially choloteera such as, for example, Antonomus grandis. Compounds of formulas (I) and (II) are used for the control of external parasites such as Lucilia sericata in livestock and productive livestock, for example by treating animals, cowsheds, barn stalls and the like. May also be used.

When herbivores are treated with the compounds of the invention by methods such as, for example, wet dips, swelling or spray races, the surprising sticking of the active ingredients is an example of the skin and fur of the animal. For example, it provides a lasting toxic effect on external parasites such as harmful diphthera. This prevents the active ingredient administered to the skin or hair of a productive livestock from being washed away too quickly by rainwater loaded on the animal.

A particular advantage of the compounds of the present invention is that they can be orally administered to productive livestock. In this method of administration, the active ingredient exhibits effective and sustained pesticidal activity, especially in the excretion secreted from the digestive tract. Thus, the diphtheria larvae hatched from the deposited eggs are immediately lethal, so that it is possible to control infection by harmful pests such as diphtheria, especially before the outbreak occurs near animals such as barns, hedges and pastures. A particularly important aspect of this particular dosage form is that the compound of formula (I) is physiologically harmless to warm-blooded animals because of its structural properties. This method of selectively controlling the spread of pests is more effective and at the same time more economical than conventional methods of large-scale treatment of barns and fences.

Good pesticide activity of the compounds of general formulas (I) and (II) corresponds to a mortality of at least 50-60% against these pests.

The activity of the compounds of the present invention and compositions containing them is substantially extended and adapted to the surrounding environment by the addition of other insecticides and / or tick repellents. Examples of suitable additives include organophosphate compounds, nitro phenols and derivatives thereof, formamidine, urea, carbamate, pyrethroids, chlorinated hydrocarbons, and Bacillus serenosis agents.

The compounds of the present invention are used in a round, or preferably with adjuvant commonly used in the formulation art, and also known methods are emulsifiable concentrates, direct sprayable or dilutable solutions, diluents, wettable powders, water solubles, dusting agents. , Granules, and capsules, for example, in polymeric materials. Along with the nature of the composition, the method of administration, such as spraying, atomizing, spraying, spraying or pouring, is selected according to the intended purpose and the surrounding environment.

Formula (I) or (II) Compounds (Active Ingredients) Formulations, eg compositions, formulations or mixtures, containing combinations of light other pesticides or tick repellents and, if necessary, solid liquid adjuvant, are for example active The components are prepared by known methods such as mixing and / or grinding uniformly with a solvent, a solid carrier and optionally a cooperative agent such as a surfactant compound (surfactant).

Suitable solvents include, for example, aromatic hydrocarbons containing preferably 8 to 12 carbon atoms, such as xylene mixtures or substituted naphthalenes; Phthalates such as dibutyl phthalate or dioctylphthalate; Aliphatic hydrocarbons such as cyclohexane or paraffin; Alcohols and glycols such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether and ethers and esters thereof; Ketones such as cyclohexanone; Strong polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide; And vegetable oils such as epoxidized coconut oil or soy bean oil or epoxidized vegetable oils; Or water.

Solid carriers used in, for example, dusting agents and dispersible powders are natural mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly disperse silicic acid or highly disperse absorbent polymers may also be added to improve physical properties. Suitable granular adsorption carriers are, for example, porous such as pumice, broken bricks, sepiolite or bentonite; Suitable non-absorbent carriers are also materials such as calcite or sand. In addition, many inorganic or organic pregranular materials, for example dolomite or ground plant residues, can also be used.

Depending on the nature of the active ingredient to be formulated or its combination with other pesticides or mite repellents, suitable surfactant compounds are nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. The term surfactant is meant to encompass a mixture of surfactants.

Suitable anionic surfactants can be both water soluble soaps and water soluble synthetic surfactant compounds.

Suitable soaps are, for example, alkali metal salts of higher fatty acids (C ₁₀ -C ₂₂ ), alkalis such as sodium or potassium salts of oleic or stearic acid, sodium or potassium salts of natural fatty acid mixtures obtained from coconut or animal oils. Earth metal salts or unsubstituted or substituted ammonium salts. More suitable surfactants are also modified and circular phospholipids with fatty acid methyltaurine salts.

However, so-called synthetic surfactants are often used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkyl aryl sulfonates.

Fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain C ₈ -C ₂₂ alkyl radicals comprising alkyl moieties of acyl radicals, for example lignosulfonic acid Sodium salt or calcium salt of a dodecyl sulfate, or fatty alcohol sulfate mixture obtained from natural fatty acids. These compounds also include salts of sulfated and sulfonated fatty alcohol / ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain one sulfonic acid group and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylaryl sulfonates are dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or sodium salts, calcium salts or triethanol amine salts of naphthalenesulfonic acid and formaldehyde condensates. Also suitable are the corresponding phosphates such as, for example, the phosphate ester salts of adducts of p-nonylphenol with 4 to 14 moles of ethylene oxide.

The nonionic surfactants are preferably polyglycol ether derivatives of aliphatic or substituted alcohols, or saturated or unsaturated fatty acids and alkylphenols, which derivatives contain 3 to 30 and 8 to 20 glycol ether groups in the (aliphatic) hydrocarbon moiety. And the alkyl residues of the four carbon atoms and the alkylphenols contain from 6 to 18 carbon atoms.

More suitable nonionic surfactants are water soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycols containing 1 to 10 carbon atoms in the alkyl chain, which are 20 to 250 Ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of nonionic surfactants include nonylphenolpolyethoxyethanol, castor oil polyglycol ether, polypropylene / polyethylene oxide adduct, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol Can be mentioned. For example, fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate are also suitable as nonionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts containing at least one C ₈ -C ₂₂ alkyl radical as an N-substituent, an unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radical as another substituent. . This salt is preferably in the form of a halide such as, for example, stearyltrimethylammonium chloride or benzyldi (Z-chloroethyl) ethylammonium bromide, methylsulfate or ethylsulfate.

Surfactants commonly used in the field of formulations are described, for example, in McCutcheon's Detergents and Emulsifiers Annual, Mc Publishing Corp., Ridgewood, New Jersey, 1979; Dr. Helmut Stache, Tensid Taschenbuch (Handbook of Surfactants), Carl Hanser Verlag, Munich / Vienna 1981.

Agrochemical compositions typically comprise from 0.1 to 99%, preferably from 0.1 to 95%, from 1 to 99.9% of a solid or liquid adjuvant, from 0 to 25% of a surfactant or active agent or combination thereof with other pesticides or acaricides, Preferably it is contained 0.1 to 20%.

Commercial products are preferably formulated in concentrates, while the end consumer usually uses a practically low concentration of dilute formulation.

The composition may also contain other ingredients such as stabilizers, antifoams, viscosity modifiers, binders, tackifiers, as well as fertilizers or other active ingredients to achieve special effects.

Example 1

a) Preparation of Starting Compound: 2-cyclopropylamino-4-amino-5-cyano-6-methylthiopyrimidine

i) While cooling with ice water, 650 ml of concentrated hydrochloric acid is added dropwise to a solution in which 93 g of 2-cyano-3-cyano amino-3-methylthioacrylonitrile and sodium salt are dissolved in 425 ml of water. The batch is then stirred for about 12 hours at room temperature. The precipitate is separated by filtration and treated with aqueous sodium carbonate solution. 20 g of the resulting 2-chloro-4-amino-5-cyano-6-methylthiopyrimidine (melting point 268 ° C) was stirred in 250 ml of acetonitrile to prepare a suspension, and the mixture was subjected to cyclo in this suspension with vigorous stirring at reflux temperature. 11.4 g of propylamine is added dropwise. The batch is further stirred for 12 hours and then water is added. The precipitate is separated by filtration to give the title compound of the following general formula having a melting point of 215 ° -218 ° C. (Compound 3.1)

ii) 20 g of N, N-diethylaniline are slowly added dropwise to a mixture of 18.3 g of 5-cyano-6-methylthiouracil and 80 ml of phosphoroxy chloride. The batch is then refluxed for 1.5 hours and then concentrated by evaporation. The residue is mixed with 200 ml of ice water, stirred, collected by filtration and washed with water. After drying, the crude product is chromatographed through a silica gel column (eluted with a 6: 3: 1 mixture of toluene / chloroform / ethyl acetate). 22 g of 2,4-dichloro-5-cyano-6-methylthiopyrimidine (melting point 118 ° -120 ° C) was dissolved in 200 ml of acetonitrile and 11.4 g of cyclopropylamine added to 40 ml of acetonitrile at -10 ° C. Add solution. The reaction mixture is stirred at room temperature for 2 hours and then poured into 2 liters of ice water. The precipitate is filtered by suction. Thus obtained 26.1 g of 2-cyclopropylamino-4-chloro-5-cyano-6-methylthiopyrimidine having the melting point of 139 ° -141 ° C is stirred in 100 ml of acetonitrile.

Then, 300 ml of 30% aqueous ammonia solution is added to the suspension, which is stirred at room temperature for about 10 hours and then at reflux for 5 hours. The solid residue obtained from the cooled batch is filtered by suction and washed with water. Recrystallization from 150 ml of methyl cellosolve affords the title compound of the general formula indicated in i) with a melting point of 215 ° -218 ° C.

b) preparation of 2-cyclopropylamino-4,6-diamino-5-cyanopyrimidine

33.7 g of 2-cyclopropylamino-4-amino-5-cyano-6-methylthiopyrimidine prepared according to a) is reacted with 150 g of ammonia for 15-20 hours in an autoclave at 150 ° C. The reaction product was repeatedly stirred in water and then separated by filtration to give the title compound of the general formula having a melting point of 249 ° -251 ° C. (Compound No. 1.1).

Example 2

a) Preparation of the starting compound: 2-diethylamino-4-amino-5-cyano-6-methylsulfonylpyrimidine

Into the reaction vessel is charged 47.5 g of 2-diethylamino-4-amino-5-cyano-6-methylthiopyrimidine in 650 ml of methylene chloride. Without cooling, 88.7 g of 3-chloroperbenzoic acid is added to this batch. The reaction mixture is stirred for 2 hours and then filtered. The filtrate is concentrated by evaporation and the residue is suspended in diethyl ether and filtered by suction to give the title compound of the following general formula having a melting point of 170 ° -172 ° C. (Compound No. 3.2).

b) preparation of 2-diethylamino-4,6-diamino-5-cyanopyrimidine

26.9 g of 2-diethylamino-4-amino-5-cyano-6-methylsulfonylpyrimidine prepared according to a) is added to 300 ml of a 30% aqueous ammonia solution and 100 ml of acetonitrile. This batch is then stored under reflux for 12 hours, cooled, and the precipitate is separated by filtration. The precipitate is stirred in water and filtered by suction to give the title compound of the following general formula having a melting point of 222 ° -224 ° C. (Compound 1.2)

Example 3

Preparation of 2-diethylamino-4-amino-5-cyano-6-isobutyrylaminopyrimidine

7 g of triethylamine is added to a solution to which 10.3 g of 2-diethylamino-4,6-diamino-5-cyanopyrimidine (prepared according to Example 2) is added in 90 ml of tetrahydrofuran. 8.5 g of isobutyryl anhydride is then added dropwise to this solution at 60 ° C. The reaction mixture is heated at reflux for 48 h, concentrated by evaporation and the residue is washed with diethyl ether to give the title compound of the general formula having a melting point of 151 ° -152 ° C. (Compound 1.3)

Example 4

Preparation of N, N-dimethyl-N '-(2-cyanopropylamino-4-amino-5-cyanopyrimidin-6-yl) formamidine

3.7 g of dimethylformamide diethyl acetal was added dropwise to a solution added with 3.8 g of 2-cyclopropylamino-4,6-diamino-5-cyanopyrimidine in 100 ml of dioxane at 45 ° -50 ° C. The reaction mixture is stirred at 45-50 ° C. for 8 hours. The solvent is distilled off and the crude product is recrystallized in ethanol to give the title compound of the following general formula having a melting point of 192 ° -195 ° C. (Compound 1.4)

Example 5

Preparation of Starting Compound: 2-Chloro-4,6-diamino-4-amino-5-cyano-6-methylthiopyrimidine

To a reaction vessel at 0 ° C., a suspension to which 750 ml of dioxane and 250 ml of water was added 50 g of finely powdered 2-chloro-4-amino-5-cyano-6-methylthiopyrimidine was charged. While stirring without cooling, a strong chlorine gas stream is passed through this suspension. After about 20 minutes a clear solution forms. After 30 minutes the chlorine introduction is stopped and the batch is stirred for 0.5 hours. The reaction mixture is concentrated by evaporation and the residue is suspended in 600 ml of ice water and the suspension is filtered. 46.4 g of residual 2-chloro-4-amino-5-cyano-6-methylsulfonylpyrimidine (decomposed at melting point 253 ° C.) is stirred in 25 g of 30% aqueous ammonia solution and 1000 ml of acetonitrile for 2 hours at room temperature. The batch is concentrated by evaporation, the residue is suspended in water and the suspension is filtered to give the title compound of the following general formula having a melting point of at least 260 ° C. (Compound 5.1)

The compounds of formula (I) are also prepared according to the methods described above:

Salts of the general formula (I) are prepared by reaction with each acid.

The compounds of formula (I) may be prepared as described above:

Intermediates of the following general formula (II) are prepared as described above:

Intermediates of the following general formula (II) may be prepared as described above:

Intermediates of the following general formula (IX) are prepared as described above.

Intermediates of the general formula (XI) may also be prepared as described above:

Example 6

Formulation of active ingredients or combinations of these ingredients with other pesticides or tick repellents according to Examples 1 to 3 (hereinafter, percentages are by weight)

1.wetting powder

a) b) c)

Active Ingredient or Combination 25% 50% 75%

Sodium Lignosulfonate 5% 5%-

Sodium Lauryl Sulfate 3%-5%

Sodium Diisobutylnaphthalenesulfonate-6% 10%

Octylphenol polyethylene glycol ether

(Ethylene oxide 7-8 mol)-2%-

Highly dispersed silicic acid 5% 10% 10%

Kaolin 62% 27%

The active ingredient or combination is thoroughly mixed with the adjuvant and the mixture is ground thoroughly in a suitable mill to give a wettable powder which can be a suspension of the required concentration when diluted with water.

2. Emulsifiable Concentrate

10% active ingredient or combination

Octylphenol polyethylene glycol ether 3%

(4-5 mol of ethylene oxide)

Calcium Dodecylbenzene Sulfonate 3%

Castor Oil Polyglycol Ether 4%

(36 mol of ethylene oxide)

Cyclohexanone 30%

Xylene Mixture 50%

Any concentration of emulsion required may be obtained by diluting this concentrate with water.

3. Spray

a) b)

Active Ingredient or Combination 5% 8%

Talc 95%-

Kaolin-92%

The active ingredient is mixed with the carrier and the mixture is ground in a suitable mill to obtain a ready-to-use spreading agent.

4. Extruded Granule

10% active ingredient or combination

Sodium lignosulfonate 2%

Carboxymethylcellulose 1%

Kaolin 87%

The active ingredient or combination is mixed and ground with the adjuvant, and the mixture is then wetted with water. The mixture is extruded and then dried in air stream.

5. Cloth granulation

3% active ingredient or combination

Polyethylene glycol (molecular weight 200) 3%

Kaolin 94%

In a mixer, the milled active ingredient or combination is administered to kaolin moistened with polyethylene glycol. In this way, a coated particle free of dust is obtained.

6. Suspension concentrate

40% active ingredient or combination

Ethylene Glycol 10%

Nonylphenol Polyethylene Glycol Ether 6%

(15 mol of ethylene oxide)

Sodium Lignosulfonate 10%

Carboxymethylcellulose 1%

37% formaldehyde aqueous solution 0.2%

0.8% silicone oil in 75% emulsion

32% of water

The finely divided active ingredient or combination is intimately mixed with the adjuvant and diluted with water to give a suspension concentrate which can yield suspensions of any concentration required.

7. Pour solution

30.00 g of active ingredient

Sodium Dioctylsulfosuccinate 3.00g

Benzyl Alcohol 35.46 g

Ethylene Glycol Monomethyl Ether 35.46g

103.92g = 100ml

With vigorous stirring, the active ingredient is dissolved in most of the two solvent mixtures. Then, sodium dioctylsulfosuccinate is dissolved in the resulting solution while heating, if necessary, and the remaining solvent mixture is added.

Example 7

Action on housefly

50 g of freshly prepared CMSA nutrient substrate for maggots are loaded into a number of beakers. Pipette a volume of acetone solution containing 1% by weight of each test compound into the nutrient substrate present in the beaker to bring the active ingredient concentration to 800 ppm. This substrate is mixed thoroughly and the acetone is then evaporated over 20 hours.

25 daily housefly maggots are then placed in each beaker containing a nutrient substrate treated with each active ingredient at a given concentration for testing. After the maggots are chrysalis, the chrysalis is shed from the substrate by shedding water and then the perforated stopper is deposited in a container.

Count each batch of washed pupa to determine the toxic effects of this test compound on maggot growth. After 10 days count the number of flies hatched from the pupa.

The general formulas (I) and (II) compounds according to Examples 1 to 3 show excellent activity in this test.

Example 8

Action on Lucilia sericata

1 ml of an aqueous solution of formulation containing 0.5% of the test compound at 50 ° C. is added to 9 ml of medium. Subsequently, about 30 freshly hatched Lucilia sericata larvae are added to this medium, and the insecticidal action is measured by evaluating mortality after 48 and 96 hours.

In this test, the compounds of the general formulas (I) and (II) according to Examples 1 to 3 show excellent activity against Lucilia cericata.

Example 9

Action on Lucilia cuprina

Freshly deposited flies (Lucilia cuprina) eggs are added in small numbers (30-50 tablets) each in a number of test tubes with 1 ml of test solution and 4 ml of nutrient medium mixed. After inoculation of the medium, the test tube is sealed with a cotton cap and then incubated for 4 days in an incubator at 30 ° C. Larvae of about 1 cm in length (stage 3) develop at the end of this 4 day period in the control untreated medium. If the substance is active, the larvae will die or almost die until the end of this period.

Repelling the larvae is also considered because it causes the larvae to leave the medium and consequently starve to death.

In this test, the compounds of the general formulas (I) and (II) according to Examples 1 to 3 are very effective against Lucilia Cuprina.

Example 10

Action on Aedes aegypti

A certain amount of a 1% solution of the test compound in acetone is pipetted and added to the surface of 150 ml water in a beaker to obtain a 800 ppm solution. After the acetone has evaporated, 30 to 40 biennial edes edge larvae are placed in a beaker containing the test compound. Lethality is measured after 1, 2 and 5 days.

In this test, the compounds of general formulas (I) and (II) according to Examples 1 to 3 show good activity against edes edge.

Example 11

Insecticidal action against erosive pests

An approximately 25 cm high cotton crop in the pot is sprayed with an aqueous emulsion containing 100, 200 and 400 ppm of each test compound. After the spray coating is dry, the cotton crops are infected with the Spodoptera littoraltis and Heliotis viresense larvae in the L-stage. This test is performed at 24 ° C. and 60% relative humidity. After 2 days the larval mortality is measured.

In this test, compounds 1.1 and 1.2 show 80-100% mortality against Sofodoterra larvae at 200 and 400 ppm concentrations, respectively. Compounds 1.1 and 1.2 exhibit 80-100% mortality against Heliotis larvae at concentrations of 100 ppm and 400 ppm, respectively.

Example 12

Actions on Antonomomus grandis

Two cotton crops in six leaf stages in a pot are sprayed with a wettable emulsion solution containing 400 ppm of the test compound. After the spray coating is dry (about 1.5 hours), each crop is infected with 10 adult scarabs (Antonomos grandis). The gauze stopper prevents the movement of the scarab from the crop by pushing the treated crop infected with the test pest into a plastic cylinder. The treated crops are then stored at 25 ° C. and about 60% relative humidity. After 2, 3, 4 and 5 days, evaluation is made to determine the mortality (percent in the back) of the scarab as well as the anti-erosive action compared to the control untreated crop.

The general formulas (I) and (II) compounds according to Examples 1 to 3 show good activity in this test.

Example 13

Action on true mites

A) African True Mite (Amblyomma hebraeum)

50 pupa are counted in a test tube and soaked for 1 to 2 minutes in 2 ml of an emulsified solution prepared using a diluent to contain 400 ppm of the test compound. The test tube is then capped with a standard face and the face is placed at the level of the test tube capable of absorbing the emulsion. Evaluate after 1 week. Two experiments are conducted for each test compound.

B) Bophylus microplus (larvae: Boophilus microplus)

The test is conducted with 20 op-sensitive larvae and 20 op-resistant larvae using a diluent series similar to that used in Test A. In the test, the general formula (I) and the general formula (II) compounds according to Examples 1 to 3 may be used for the pupa of African mites and Buphylus microfluids. Very effective against larvae.

Example 14

Insecticidal: Nilaparvata Lugens

Spray the crop containing 400 ppm of test compound. After drying the spray coating, the crop is infected with the pupa of Niparfarta Rugens in stage N or N. Two crops per test compound and specimen are used. The mortality rate is assessed after 6 days. This test is performed at 26 ° C. and 60% relative humidity. In this test, 80-1 to 100% effect on the chrysalis of compound 1.1 niparavata rugens.

Example 15

Action on Soil (Diabrotica balteata)

Five corn seedlings 1 to 3 cm high and filter paper discs are immersed in an aqueous solution of test compound containing 4 parts by volume acetone. The impregnated filter paper discs are laid on the bottom of a 200 ml plastic beaker. Place the dry filter paper discs with corn seedlings and Diabrotica Valteata larvae at L- or L-stage on this first disc. The test is carried out at about 24 ° C, 40-60% relative humidity and under light. After 6 days, it is evaluated compared to the untreated control.

In this test, Compound 1.15 shows 80-100% mortality at 400 ppm concentration.

Example 16

Action on Nephotettix cincticeps

The test is carried out as a growing crop. For this purpose, rice crops, about 20 days old and about 15 cm high, are implanted in multiple pots (5.5 cm in diameter).

Crop in each pot is sprayed with 100 ml of acetone solution containing 400 ppm of this test compound on a rotating table. After the spray coating has dried, each crop is infected with 20 pupa of test organisms in the second or third stage. To prevent the cicada from running away, place each crop in a holding glass cylinder and seal it with a gauze stopper. Store the pupa for 5 days on the treated crop that must be re-sprayed at least once. This test is conducted at about 23 ° C. and 55% relative humidity. The crop is exposed to light for 16 hours a day.

In this test, compound 1.1 according to Example 1 has an effect of 80-100%.

Example 17

Insecticidal gastric toxicity against Flutella xylostella

The potted four-leaf Chinese cabbage crop (pot size: 10 cm diameter) is sprayed with an emulsified aqueous solution containing 3 to 400 ppm of test compound and dried on the crop.

After two days, the individually treated Chinese cabbage crops are infected with 10 fluteella xylostella larvae at the L-stage. The test is carried out at 24 ° C. and 60% relative humidity in dim light. After 2 and 5 days, larval mortality is assessed to determine mortality. Formula (I) compounds according to Examples 1-4 show 80-100% mortality in this test.

Claims (3)

A compound of formula (II) Wherein R ₁ is hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl and R ₂ is hydrogen, C ₁ -C ₁₀ alkyl or C ₃ -C ₆ Cycloalkyl or R ₁ and R ₂ taken together are a radical selected from the group consisting of — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ — and — (CH ₂ ) ₅ —, where n is 0, 1 Or two. A compound of formula (II) comprising preparing a compound of formula (XIII) by reacting the compound of formula (VII) with chlorine to react the compound of formula (XIII) with ammonia Manufacturing Method: A pesticide composition comprising as an active ingredient a compound of formula (II) as claimed in claim 1 and at least one adjuvant.