JPH027308B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides N-(benzamidosulfenyl)-
This invention relates to N-methyl carbamate, its production method, and insecticides and acaricides containing the compound. N-(benzamidosulfenyl)-N of the present invention
-Methyl carbamate has the following formula: (In the formula, R ₁ represents an alkyl group having 1 to 10 carbon atoms, R ₂ represents an alkyl group having 1 to 3 carbon atoms or an allyl group, R ₃ represents a methyl group,
_-CONH2 or -CON( _CH3 ) ₂ , and _X1 , _X2 and _X3 are each a hydrogen atom, a halogen atom, a C1-C4 alkyl group or a C1-4 haloalkyl group represents. ). In the above definition, the halogen atom represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom. Suitable alkyl groups for R ₁ , R ₂ , X ₁ , X ₂ and X ₃ can be straight-chain or branched alkyl groups. Examples of such groups include: methyl, trifluoromethyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec- and tertiary-butyl, n-pentyl,
Mention may be made of n-hexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups and isomers thereof. In the formula, R ₁ represents a methyl group, R ₂ represents an alkyl group having 1 to 3 carbon atoms,
Compounds in which R ₃ represents a methyl group or -CON(CH ₃ ) ₂ and X ₁ , X ₂ and X ₃ each represent a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group are preferable. However, particularly preferred compounds are those of the formula in which R ₁ represents a methyl group and R ₂ represents a C 1 -C 3 alkyl group;
R ₃ represents a methyl group or -CON(CH ₃ ) ₂ , and X ₁
and X ₂ each represent a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group, and
This is a compound in which X ₃ represents a hydrogen atom. The compound represented by the formula can be obtained by a method known per se as follows. In the above formula, R ₁ , R ₂ , R ₃ ,
X ₁ , X ₂ and X ₃ have the meanings defined in the formula and X represents a halogen atom, in particular a fluorine atom or a chlorine atom. These methods are carried out at a reaction temperature of -50° to 130°C, preferably -10° to 100°C, under normal pressure or slightly elevated pressure, and in the presence of a solvent or diluent inert to the reactants. conduct. Bases suitable for these processes are in particular trialkylamines, pyridines and dialkylanilines as tertiary amine agents, and hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline earth metals, and also Mention may be made of alkali metal alcoholates such as potassium tert-butylate and sodium methylate. Examples of suitable solvents or diluents are ethers and ethereal compounds such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran; aliphatic and aromatic hydrocarbons, especially benzene, toluene and xylene; and ketones such as acetone, methyl ethyl ketone and cyclohexanone. . The starting materials of the formula are novel compounds and also constitute an object of the present invention. The starting materials of the formula are known and can be prepared by methods analogous to known methods. The compounds of the formula are suitable for controlling plant and animal pests. These compounds also have fungicidal and phytoregulatory properties. In particular, compounds of the formula include insects of the following orders: Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Thrips. Orders: Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera,
Suitable for controlling mites and ticks of the order Hymenoptera and Acarina. In particular, the compounds of the formula are effective against insects that damage plants (such as Spodoptera littoralis and Heliothis virescens) in cultivation areas of ornamental and useful plants, especially in cotton cultivation areas, and in vegetable gardens. Insects that damage plants [e.g. Leptinotarsa decemlineata]
Suitable for controlling plant-destructive insects such as the green peach aphid (Myzus persicae) and the peach aphid (Myzus persicae). In this connection, it should be emphasized that the compound represented by the formula and especially against insects of the family Aphididae (e.g. Aphis fabae, Aphis craccivora and Myzus persicae), as well as a strong and pronounced penetrative action as well as contact action. It is to show. The compounds of the formula also have a very effective action against flies such as the house fly (Musca domestica) and against mosquito larvae. In addition, the compounds of the formula have broad-spectrum ovicidal and ovicidal larvicidal action and are also effective against exoparasitic mites and ticks of the families Ixodidae, Argasidae and Dermanyssidae, for example. It has a useful action against plant-pathogenic nematodes as well as against plant-pathogenic nematodes. The compounds of the formula can be used in neat form or preferably with the auxiliaries customary in formulation technology and can thus be used as emulsion concentrates, directly sprayable or dilutable solutions, diluted They can be formulated by known methods into dosage forms such as emulsions, wettable powders, soluble powders, powders or granules, and microencapsulations, for example in polymeric substances. The application method may be, for example, spraying, spraying, dusting, scattering or pouring, depending on the situation at the time, such as the purpose of application and the nature of the composition. The formulations, i.e. compositions containing the compound of the formula (active ingredient) and optionally solid or liquid auxiliaries, can be prepared in a known manner, e.g. by combining the active ingredient with fillers such as solvents or solid carriers, and optionally with surfactants. (tensides) by homogeneous mixing and/or grinding. Suitable solvents include aromatic hydrocarbons, preferably those having 8 to 12 carbon atoms, such as xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and these. Ethers and esters such as ethanol, ethylene glycol, monomethyl or monoethyl ether of ethylene glycol, ketones such as cyclohexanone, strong polar solvents such as N-
Mention may be made of methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut or soybean oil; or water. Solid carriers used, for example, for dusts and dispersible powders, usually include natural mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly dispersed silicic acids or highly dispersed absorbent polymers can also be used to improve the physical properties.
Suitable granular adsorptive carriers are porous carriers such as pumice, crushed brick, sepiolite or bentonite, and non-adsorptive carriers are materials such as calcite or sand. Furthermore, most pre-granulated materials of inorganic or organic nature can be used, such as especially dolomite or powdered plant residues. Suitable surfactants include nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient represented by the above formula to be incorporated. It will be done. In this case, the term "surfactant" is also understood to mean mixtures of surfactants. Suitable anionic surfactants include water-soluble soaps and water-soluble synthetic surfactants. Suitable soaps include alkali metals, alkaline earth metals, higher fatty acids having 10 to 22 carbon atoms,
or optionally substituted ammonium salts, such as the sodium or potassium salts of oleic acid or stearic acid or the sodium or potassium salts of natural fatty acid mixtures obtained, for example, from coconut oil or tallow. The soap also includes fatty acid methyltaurine salts. However, more often so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfuric esters, sulfonated benzimidazole derivatives or alkylaryl sulfonates. Fatty sulfonates or fatty sulfates are
It is usually in the form of an alkali metal salt, an alkaline earth metal salt or an optionally substituted ammonium salt, and contains an alkyl group having 8 to 22 carbon atoms, including the alkyl group or the alkyl moiety in an acyl group. It means. Examples include the sodium or calcium salts of lignosulfonic acid, dodecyl sulfate or fatty alcohol sulfate mixtures obtained from natural fatty acids. This class of surfactants also includes salts of sulfuric esters and sulfonates of fatty alcohol/ethylene oxide adducts. Sulfonated benzimidazole derivatives, preferably having two sulfonic acid groups and one C8-C22 fatty acid group. Alkylarylsulfonates include, for example, the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid/formaldehyde condensation products. Suitable synthetic surfactants also include the corresponding phosphate salts, such as the phosphoric acid ester of the adduct of 4 to 14 moles of ethylene oxide and p-nonylphenol. Nonionic surfactants are preferably aliphatic or cycloaliphatic alcohols or polyglycol ether derivatives of saturated or unsaturated fatty acids and alkylphenols. The ether derivatives contain 3 to 30 glycol ether groups and 8 to 8 carbon atoms in the (aliphatic) hydrocarbon group.
20 as well as 6 to 18 carbon atoms in the alkyl portion of the alkylphenol. Other suitable nonionic surfactants include polypropylene glycols with 1 to 10 carbon atoms in the alkyl chain, ethylene diamine propylene glycol and ethylene glycol ether groups with alkyl polypropylene glycols having 1 to 10 carbon atoms.
250 and 10 propylene glycol ether groups
Examples include water-soluble polyethylene oxide adducts containing from 1 to 100 polyethylene oxide adducts. These compounds usually have 1 to 5 ethylene glycol units per propylene glycol unit. Representative examples of nonionic surfactants include nonylphenol polyethoxyethanol, castor oil polyglycol ether, polypropylene/polyoxyethylene adduct, tributylphenoloxypolyethoxyethanol, polyethylene glycol, and octylphenoxyethoxyethanol. Can be mentioned. Suitable nonionic surfactants also include fatty acid esters of polyoxyethylene sorbitan and polyoxyethylene sorbitan trioleate. The cationic surfactant has at least one alkyl group having 8 to 22 carbon atoms as an N substituent, and optionally a halogenated lower alkyl group, benzyl group, or lower alkyl hydroxide group as another substituent. A quaternary ammonium salt having the following is preferred. The above ammonium salts are in the form of halides, methyl sulfates or ethyl sulfates,
For example, stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide is preferred. Surfactants commonly used in compounding techniques are described in the following literature: “Mc Cutcheon's Detergents Detergents and Emulsifiers Annual.
and Emulsifiers Annual)”, MC Publishing Corporation (MC Publishing
Corp.), Ringewood, New Jersey 1979 edition. The insecticide and acaricide of the present invention usually contains 0.1 to 99% of the compound represented by the formula, preferably 0.1 to 99%.
95%, solid or liquid auxiliaries 1 to 99.9% and surfactants 0 to 25%, preferably 0.1 to 25%
Contains %. Commercial formulations are preferably concentrated compositions, but
The end user generally dilutes it before use. The formulations according to the invention can also contain other additives, such as stabilizers, antifoams, viscosity regulators, binders, adhesives and fertilizers or other active ingredients for obtaining special effects. Formulation example Formulation example of a liquid active ingredient represented by the formula (in the examples, [%] represents [% by weight]).

Table: These concentrates can be diluted with water to obtain emulsions of the desired concentration.

[Table] Tell

Table: These solutions are suitable for application in microdroplets. (3) Granules (a) (b) Active ingredient 5% 10% Kaolin 94% - Highly dispersed silicic acid 1% - Attapulgite - 90% Dissolve the active ingredient in methylene chloride and spray the solution onto the surface of the carrier. and then evaporate the solvent under reduced pressure. (4) Powder (a) (b) Active ingredient 2% 5% Highly dispersed silicic acid 1% 5% Talc 97% - Kaolin - 90% For ready-to-use powder, add the active ingredient to the carrier and mix thoroughly. obtained by Examples of formulations of solid active ingredients represented by the formula (in examples, [%] represents [% by weight])

[Table] When the active ingredient is mixed homogeneously with the auxiliaries and the mixture is thoroughly milled in a suitable grinder, a wettable powder is obtained which, when diluted with water, gives a suspension of the desired concentration. (6) Active ingredients of emulsion concentrate 10% Octylphenol polyethylene glycol ether (contains 4 to 5 moles of ethylene oxide) 3% Calcium dodecylbenzenesulfonate 3% Castor oil polyglycol ether (contains 35 moles of ethylene oxide) 4% Cyclohexanone 30% Xylene mixture 50% These concentrates can be diluted with water to obtain the desired concentration of emulsion. (7) Powder (a) (b) Active ingredient 5% 8% Talc 95% - Kaolin - 92% A ready-to-use powder is produced by mixing the active ingredient with the carrier and milling this mixture in a suitable grinder. Obtained by grinding. (8) Granules by extrusion Active ingredients 10% Sodium lignosulfonate 2% Carboxymethyl cellulose 1% Kaolin 87% The active ingredients are mixed with the auxiliaries and ground and the mixture is then moistened with water. The mixture is pressed and then dried with a stream of air. (9) Coated granules Active ingredient 3% Polyethylene glycone 200 3% Kaolin 94% The pulverized active ingredient is applied uniformly to the kaolin moistened with polyethylene glycol in a mixer. In this way, dust-free coated granules are obtained. (10) Active ingredients of suspension concentrate 40% Ethylene glycol 10% Nonylphenol polyethylene glycol ether (containing 15 moles of ethylene oxide) 6% Sodium lignosulfonate 10% Carboxymethyl cellulose 1% 37% formaldehyde in water 0.2% 75% in the form of aqueous emulsion silicone oil
0.8% Water 32% When the finely ground active ingredient is intimately mixed with the auxiliaries,
A suspension concentrate can be obtained which can be diluted with water to give a suspension of the desired concentration. Example 1 (a) Production of N'-[N-(4-methylbenzoyl)-N-methylamide]-sulfenyl-N'-methylcarbamoyl fluoride 15.7 g of HF was mixed with 200 ml of toluene (in a polyethylene container) at -50°C. inside) I put it inside. Then 46.7 ml of N-methyl isocyanate was added dropwise at -50°C. Then heat the mixture at -30° to -50°C for 2
Stir for an hour and then dilute with toluene. −10
℃, 145 g of 4-methylbenzoylamide methylsulfenyl chloride were first added dropwise, and then 108.5 ml of triethylamine was added dropwise over 30 minutes. The reaction mixture was stirred at 20° C. for 18 hours and at 50° C. for 6 hours, then cooled and filtered with suction. The filtrate was concentrated. The crude product is recrystallized from methylene chloride/hexane (1:1) to give the following formula with a melting point of 66° to 67°C: A compound represented by was obtained. The following compounds were also synthesized in a similar manner. (b) Production of N'-[N-(4-methylbenzoyl)-N-methylamido-sulfenyl]-N'-methyl-carbamoyloxy-thioacetimidate 1-methylmercaptoacetal oxime
6.3 g and N′-[N-(4-methylbenzoyl)
15.4 g of -N-methylamide]-sulfenyl-N'-methylcarbamoyl fluoride were dissolved in 50 ml of methylene chloride. 11.05 g of triethylamine was added dropwise to this solution while stirring.
The reaction mixture was stirred at 20 °C for 16 h and then at 45 °C.
The mixture was stirred for 2 hours. The solvent is evaporated and the crude product is recrystallized from a 1:1 mixture of methylene chloride and hexane to give the following formula with a melting point of 118°-121°C: A compound represented by was obtained. The following compounds were also synthesized in a similar manner.

【table】

[Table] Biological Examples Example 2 Stomach poisoning insecticidal effect on Spodobra littoralis Compounds to be tested 12, 50, 100,
Solutions containing 200 or 400 ppm were sprayed. After drying of the coating, larvae of the species Spodobutella littoralis (L ₃ -instar) were attached to the plants.
Two plants were used for each test compound and test species. After 48 hours, the number of deaths was counted.
Tests were conducted at 28°C and 60% relative humidity. The test results are shown in the table below. The numbers in the table indicate the insecticidal rate (%). (- indicates that the insect killing rate is 80% or less.)

[Table] Example 3 Contact insecticidal action against green peach aphid (Myzus persicae) Before the start of the test, about 200 green peach aphids were attached to each bean plant [Vicia faba] grown in water. did. After 3 days, the treated plants were sprayed with a solution containing 400, 200 or 50 ppm of the compound to be tested until dripping from a distance of 30 cm. Two plants were used for each given concentration of test compound and the number of dead plants counted after 24 hours. The test results are shown in the table below. The numbers in the table indicate the insecticidal rate (%). (- indicates that the insect killing rate is 80% or less.)

[Table] Example 4 Systemic insecticidal action against the bean aphid (Aphis craccivora) The grown rooted bean plants are transplanted into pots with 600 cubic cm of soil, and then the compound to be tested
Solutions containing 200, 100, 50, 12 or 3ppm 50
ml was poured directly onto the clay pot. After 24 hours, insects of the pea aphid species were attached to the parts of the plants above the soil pot, and the plants were then placed in plastic cylinders to protect them from contact with the test component, which could occur directly or through the gas phase. I sat there. The number of deaths was counted 48 hours after the start of the test. Two plants, each in a separate bottle, were used per concentration of test component. Tests were conducted at 25°C and 70% relative humidity. The test results are shown in the table below. The numbers in the table indicate the insecticidal rate (%). (- indicates that the insect killing rate is 80% or less.)

【table】

【table】

Claims (1)

[Claims] Primary formula (): (In the formula, R ₁ represents an alkyl group having 1 to 10 carbon atoms, R ₂ represents an alkyl group having 1 to 3 carbon atoms or an allyl group, and R ₃ represents a methyl group, -CONH ₂ or -CON (CH ₃ ) ₂ and X ₁ , X ₂ and X ₃ each represent a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group or a C 1 -C 4 haloalkyl group. N-(Benzamidosulfenyl)-N-methylcarbamate. 2 In the formula, R ₁ represents a methyl group, and R ₂
represents an alkyl group having 1 to 3 carbon atoms,
Claim 1, wherein R ₃ represents a methyl group or -CON(CH ₃ ) ₂ , and X ₁ , X ₂ and X ₃ each represent a hydrogen atom, a chlorine atom, a methyl group or a trifluoromethyl group. compound. 3 In the formula, R ₁ represents a methyl group, and R ₂
represents an alkyl group having 1 to 3 carbon atoms, R ₃ represents a methyl group or -CON(CH ₃ ) ₂ , and X ₁ and X ₂ represent a hydrogen atom, a chlorine atom,
represents a methyl group or a trifluoromethyl group,
and the first claim representing X ₃ hydrogen atoms.
Compounds described in Section. Quaternary formula: The compound according to claim 3, which is represented by: 5th order formula: The compound according to claim 3, which is represented by: Sixth formula: A compound according to claim 3, which is represented by: 7 Formula: The compound according to claim 3, which is represented by: 8th formula: The compound according to claim 3, which is represented by: 9 Formula: The compound according to claim 3, which is represented by: 10th formula: The compound according to claim 3, which is represented by: 11 Formula: The compound according to claim 3, which is represented by: 12th equation: The compound according to claim 3, which is represented by: 13th formula: The compound according to claim 3, which is represented by: 14th formula: The compound according to claim 3, which is represented by: 15th formula: The compound according to claim 3, which is represented by: 16th formula: The compound according to claim 3, which is represented by: 17 Formula: The compound according to claim 3, which is represented by: 18 Formula: The compound according to claim 3, which is represented by: 19 Formula: (In the formula, R ₁ represents an alkyl group having 1 to 10 carbon atoms, X represents a halogen atom, and
X ₁ , X ₂ and X ₃ each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms. ) in the presence of a base, the following formula: (In the formula, R ₂ represents an alkyl group having 1 to 3 carbon atoms or an allyl group, and R ₃ represents a methyl group, -CONH ₂ or -CON(CH ₃ ) _2. )
The following formula consists of reacting with a compound represented by: A method for producing N-(benzamidosulfenyl)-N-methyl carbamate represented by the formula (wherein R ₁ , R ₂ , R ₃ , X ₁ , X ₂ and X ₃ have the above meanings). 20 As an active ingredient, the following formula: (In the formula, R ₁ represents an alkyl group having 1 to 10 carbon atoms, R ₂ represents an alkyl group having 1 to 3 carbon atoms or an allyl group, R ₃ represents a methyl group,
_-CONH2 or -CON( _CH3 ) ₂ , and _X1 , _X2 and _X3 are each a hydrogen atom, a halogen atom, a C1-C4 alkyl group or a C1-4 haloalkyl group represents. ) Insecticide containing N-(benzamidosulfenyl)-N-methyl carbamate,
Acaricide. 21. The insecticide and acaricide according to claim 20, which is applied to habitats of pests of animals and plants.