JPH05140075A - 2-(2-chloro-4-substituted-methylphenoxy)ethyl carbamic acid derivative, its production, its intermediate and noxious life controlling agent containing the derivative as active component - Google Patents

Abstract

PURPOSE:To provide a new compound useful as an agent for controlling noxious life such as hemipterous vermin and lepidopterous vermin. CONSTITUTION:The compound of formula I (R<1> is 1-ethylpropyl or isobutoxy; R<2> is methyl or ethyl), e.g. 2-[2-chloro-4-(2-ethylbutyl)phenoxy]ethylcarbamic acid ethyl ester. The compound of formula I can be produced by reacting an amine compound of formula II with a carboxylic acid compound of formula III (L<1> is halogen) in a solvent (e.g. THF) in the presence of a base (e.g. triethylamine).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel 2- (2-chloro-4-substituted-methylphenoxy) ethylcarbamic acid derivative, a process for producing the same, an intermediate thereof and a pest control agent containing the same as an active ingredient. ..

[0002]

2. Description of the Related Art The fact that certain carbamic acid derivatives have a pest controlling effect has hitherto been disclosed in, for example, JP-A-54-54.
It is described in Japanese Patent No. 151929.

[0003]

However, these compounds are not always sufficient as active ingredients of pest control agents.

[0004]

SUMMARY OF THE INVENTION In view of the above situation, the present inventors have conducted diligent studies to find a compound having a better pest control effect, and as a result, the following general formula
It was found that the 2- (2-chloro-4-substituted methylphenoxy) ethylcarbamic acid derivative represented by Chemical formula 8 (hereinafter referred to as the compound of the present invention) has an extremely high juvenile hormone-like activity, and the present invention is completed. That is, the present invention provides a compound represented by the general formula

[0005]

[Chemical 8]

[In the formula, R ¹ represents a 1-ethylpropyl group or an isobutoxy group, and R ² represents a methyl group or an ethyl group. ] A 2- (2-chloro-4-substituted methylphenoxy) ethylcarbamic acid derivative represented by the above, a method for producing the same, an intermediate thereof and a pest control agent containing the same as an active ingredient.

The compounds according to the invention have an excellent juvenile hormone-like activity against insects, which is markedly different from most conventional insecticides. That is, it exhibits effects such as inhibition of adult transformation, egg hatching, and adult sterilization. As a result, the compound of the present invention includes various pests, including pests that have developed resistance to existing insecticides, that is, agricultural, forestry and horticultural pests,
It mainly acts as a growth regulator, a sterilizing agent, an ovicide or a growth inhibitor against stored grain pests and sanitary pests, and exhibits a high control effect.

The compound of the present invention represented by the general formula:
For example, it can be manufactured by the following method.

(Production Method A) General Formula 9

[0010]

[Chemical 9]

[In the formula, R ¹ has the same meaning as described above. ]
With an amine compound represented by the general formula:

[0012]

[Chemical 10]

[Wherein R ² has the same meaning as described above, L 2
¹ represents a halogen atom. ] It can manufacture by making it react with the carboxylic acid type compound shown by these. In the production method A, the reaction is preferably carried out in the presence of a suitable base in a solvent that does not influence the reaction.

Examples of usable bases include alkali carbonates such as potassium carbonate or organic bases such as triethylamine and pyridine. If necessary, a catalyst such as ammonium salt (eg, triethylbenzylammonium chloride) may be added to the reaction system.

Examples of usable solvents include ketones such as acetone and methyl ethyl ketone, hydrocarbons such as benzene, hexane and toluene, ethers such as diethyl ether, isopropyl ether, tetrahydrofuran and dioxane, dichloromethane, chloroform, 1, and the like.
Examples thereof include halogenated hydrocarbons such as 2-dichloroethane and chlorobenzene, acetonitrile, nitromethane and dimethyl sulfoxide. If necessary, a mixed solvent of these solvents or a mixed solvent with water can also be used.

The reaction temperature is usually in the range of -20 ° C to the boiling point of the solvent used in the reaction, but it is -5 ° C.
More preferred is a temperature from to the boiling point of the solvent used in the reaction.

The molar ratio of the raw materials can be set arbitrarily, but it is advantageous to carry out the reaction at an equimolar ratio or a ratio close thereto.

The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to obtain the desired compound of the present invention. If necessary, it can be purified by usual operations such as chromatography, distillation and recrystallization.

(Production Method B) General Formula 11

[0020]

[Chemical 11]

[In the formula, R ¹ has the same meaning as described above. ]
And an isocyanate compound represented by the general formula R ² —O
H [in the formula, R ² represents the same meaning as described above. ] It can manufacture by making it react with the alcoholic compound shown by these. In the production method B, the reaction is preferably carried out in the presence of a suitable catalyst, if necessary, in a solvent that does not influence the reaction.

Examples of usable catalysts include organic bases such as triethylamine, pyridine and sodium acetate, aluminum chloride, hydrogen chloride or boron trifluoride ether complex (BF _3. (C ₂ H ₅ ).
₂ O) and the like.

Examples of usable solvents include hydrocarbons such as benzene, toluene and hexane, diethyl ether, diisopropyl ether, tetrahydrofuran,
Ethers such as dioxane, polar solvents such as N, N-dimethylformamide, dimethylsulfoxide and hexamethylphosphoric triamide, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane and chlorobenzene, acetonitrile or nitromethane, etc. Can be raised. If necessary, a mixed solvent of these solvents can also be used. The reaction temperature can usually range from -20 ° C to the boiling point of the solvent used in the reaction, but is more preferably from -5 ° C to the boiling point of the solvent used in the reaction.

The molar ratio of the raw materials can be set arbitrarily, but it is advantageous to carry out the reaction at an equimolar ratio or a ratio close thereto.

After completion of the reaction, the reaction solution can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to obtain the desired compound of the present invention. If necessary, it can be purified by usual operations such as chromatography, distillation and recrystallization.

(Production Method C) General Formula 12

[0027]

[Chemical 12]

[Wherein R ¹ has the same meaning as described above, and M 1
¹ represents an alkali metal atom or a hydrogen atom. ] And a phenolic compound represented by the general formula:

[0029]

[Chemical 13]

[Wherein R ² has the same meaning as described above, and L 2
² represents a halogen atom, a methanesulfonyloxy group or a toluenesulfonyloxy group. ] It can manufacture by making it react with the carboxylic acid type compound shown by these. In the production method C, the reaction is preferably carried out in the presence of a suitable base in an inert solvent. However,
When M ₁ is an alkali metal atom, the presence of a base is not always necessary.

Examples of usable solvents include methanol, ethanol, propanol, isopropanol,
Lower alcohols such as tertiary butyl alcohol, ketones such as acetone and methyl ethyl ketone, hydrocarbons such as hexane, benzene and toluene, ethers such as diethyl ether, isopropyl ether, tetrahydrofuran and dioxane, N, N-dimethylformamide, Dimethyl sulfoxide, hexamethylphosphoric triamide and other polar solvents, dichloromethane, chloroform, 1,
Examples thereof include halogenated hydrocarbons such as 2-dichloroethane and chlorobenzene, acetonitrile, nitromethane and water. If necessary, a mixed solvent of these solvents can also be used.

Examples of usable bases include caustic alkalis such as caustic potash, caustic soda, alkali carbonates such as potassium carbonate, alkali metals such as sodium metal, hydrides of alkali metals such as sodium hydride, sodium methoxide and sodium ethoxide. Examples thereof include organic bases such as side, triethylamine and pyridine. If necessary, a catalyst such as ammonium salt (eg, triethylbenzylammonium chloride) may be added to the reaction system.

The reaction temperature may range from -20 ° C to the boiling point of the solvent used in the reaction, but is -5 ° C.
The range from to the boiling point of the solvent used in the reaction is more desirable.

The molar ratio of the raw material and the base to be used in the reaction can be set arbitrarily, but it is advantageous to carry out the reaction in an equimolar ratio or a ratio close thereto.

The reaction solution after completion of the reaction can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to obtain the desired compound of the present invention. If necessary, it can be purified by usual operations such as chromatography, distillation and recrystallization.

A compound represented by the following general formula:
A carboxylic acid compound represented by the formula: R ² —OH [wherein R ² has the same meaning as described above. ] The alcohol-based compound represented by and the carboxylic acid-based compound represented by the general formula 13 are commercially available compounds, or commercially available compounds such as those described in J. Prakt. Chem.,
It can be adjusted by known techniques described in 21 , 124 (1880) and the like and ordinary methods in accordance therewith. The amine compound represented by the general formula 9, the isocyanate compound represented by the general formula 11, and the phenolic compound represented by the general formula 12 as raw materials of the compound of the present invention are
For example, the conventional method shown below (reaction formula 14
And the reaction formula 15) and the like.

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[Wherein R ¹ has the same meaning as described above, and M 1
¹ 'represents an alkali metal atom. ] In addition, the general formula 1
6

[0040]

[Chemical 16]

[In the formula, R ¹ has the same meaning as described above. ]
The phenolic compound represented by [corresponding to the case where M ¹ represents a hydrogen atom among the phenolic compounds represented by the general formula 12] can be produced, for example, by a usual method shown below. General formula 17

[0042]

[Chemical 17]

[In the formula, R ¹ has the same meaning as described above. ]
The phenol derivative represented by the general formula 16 can be synthesized by reacting the phenol derivative represented by the above with a chlorinating agent in the presence of a solvent.

As the chlorinating agent in the above reaction, chlorine, t-butyl hypochlorite, sulfuryl chloride or the like can be used. If necessary, a solvent can be used, and examples of the solvent that can be used include dichloromethane, dichloroethane, carbon tetrachloride, benzene, acetic acid and the like. It goes without saying that the solvent used here is properly used according to the type of chlorinating agent. The reaction temperature may range from −78 ° C. to the boiling point of the solvent or chlorinating agent (sulfuryl chloride etc.) used in the reaction, but from −20 ° C. to the solvent or chlorinating agent (sulfuryl chloride) used in the reaction. Etc.) up to the boiling point range is desirable.
The molar ratio of the raw material and the chlorinating agent to be used for the reaction can be set arbitrarily, but it is advantageous to carry out the reaction at an equimolar ratio or a ratio close thereto.

After completion of the reaction, the reaction solution can be subjected to usual post-treatments such as extraction with an organic solvent and concentration to obtain the desired compound.

If necessary, chromatography, distillation,
It can also be purified by a usual operation such as recrystallization.

The phenol derivative represented by the general formula 17 may be a commercially available phenol derivative or can be produced from a commercially available compound by a known method.

Examples of pests on which the compound of the present invention is effective include the followings.

Hemiptera pests Planthoppers such as brown planthoppers, sedgeown planthoppers, and leafhoppers, leafhoppers, leafhoppers, leafhoppers, leafhoppers, leafhoppers, leafhoppers, etc. Aphids, stink bugs, whiteflies of tobacco, whiteflies such as whitefly, whitefly, scale insects, gum beetles, psyllids, etc.

Lepidopteran pests Plutella xylostella (Nikameichu), Pseudococcidae, Plutella xylostella, Spodoptera litura, Spodoptera litura, Spodoptera litura, Pseudomonas aeruginosa, etc.
Agrothis spp., Heliothis spp. ( Heliothis spp.) Such as leaf moths, hornworms, leaf moths, hemlock moths, hemlock moths, mosquitoes, cabbage moths and tamanaga moths
p.), diamondback moth, moth, moth, etc.

Diptera Pests Musca such as Culex pipiens, Culex pipiens, Aedes albopictus such as Aedes aegypti, Aedes albopictus, Anopheles mosquito such as Aedes albopictus, Musca, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, Musca domestica, flesh fly Drosophila, such as onion flies, gall midges, fruit flies, fruit flies, fruit flies,
Butterfly flies, flies, gnats, sand flies, etc.

Coleoptera pests Western corn rootworms, Southern corn rootworms, and other corn rootworms, Rana buoy buoy, scarab beetles such as Himekonega, weevil, Weevil weevil, Weevil weevil and other weevils, Beetle, etc. Beetle beetles, Chrysomelidae beetle, Chrysomelidae and other leaf beetles, Shibushi beetles, Epilachna spp. Such as Nijuyahochitentou, Flat beetle beetles, Nagasinushi beetles, Cerambycidae, etc.

Pests of the Lepidoptera, German cockroaches, Black cockroaches, American cockroaches, Black cockroaches, Cockroaches, etc.

Pests of the order Thysanoptera, Thrips palmi, Thrips thrips, Thrips thrips, etc.

Hymenoptera pests Ants, bees such as turnips, etc.

Orthoptera insect pests such as moss, grasshopper, etc.

Insect pests Human fleas, etc.

Lice pests Human lice, lice, etc.

Isopterous pests Effective against Yamato termites, house termites and the like.
Further, among them, it is more suitable for the control of hemiptera pests, and particularly, it exhibits a superior effect on planthoppers and leafhoppers that damage rice crops, and exhibits an excellent control effect.

By adding other insecticides and / or acaricides, the pest control of the compound of the present invention can be applied practically to a wider variety of pests and a wider variety of use situations. Suitable additives include, for example, fenitrothion [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothioate], phenthion [O, O-dimethyl O- [3-methyl-4- (methylthio) phenyl]. Phosphorothioate], diazinon [O, O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-ylphosphorothioate], chlorpyrifos [O, O-diethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate] ], Acephate [O, S-dimethylacetylphosphoramidothioate], methidathion [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazole-3-]
Ilmethyl O, O-dimethyl phosphorodithioate], ethyl thiomethone [O, O-diethyl S-2-
Ethylthioethyl phosphorodithioate], DDVP
[2,2-dichlorovinyl dimethyl phosphate], sulprophos [O-ethyl O-4- (methylthio) phenyl S-propyl phosphorodithioate], cyanophos [O-4-cyanophenyl O, O-dimethyl phosphorothioate], salicione [2-methoxy-4H-
1,3,2-benzodioxaphosphinin-2-sulfide], dimethoate [O, O-dimethyl-S- (N-
Methylcarbamoylmethyl) dithiophosphate], fentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl 2,2,2-trichloro- 1-hydroxyethylphosphonate], azinphos-methyl [S-3,4-dihydro-4-oxo-1,
2,3-benzotriazin-3-ylmethyl O, O-
Dimethylphosphorodithioate], monocrotophos [dimethyl (E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate], and other organic phosphorus compounds,

BPMC (2-sec-butylphenylmethylcarbamate), benfuracarb [ethyl N-
[2,3-Dihydro-2,2-dimethylbenzofuran-
7-yloxycarbonyl (methyl) aminothio] -N
-Isopropyl-β-alaninate], propoxur [2-isopropoxyphenyl N-methylcarbamate], carbosulfan [2,3-dihydro-2,2-
Dimethyl-7-benzo [b] furanyl N-dibutylaminothio-N-methylcarbamate], carbaryl [1
-Naphthyl-N-methylcarbamate], mesomel [S
-Methyl-N-[(methylcarbamoyl) oxy] thioacetimidate], ethiophencarb [2- (ethylthiomethyl) phenylmethylcarbamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyloxy ], Carbamate compounds such as oxamyl [N, N-dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide],

Etofenprox [2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether], fenvalerate [(RS) -α-
Cyano-3-phenoxybenzyl (RS) -2- (4-
Chlorophenyl) -3-methylbutyrate], esfenvalerate [(S) -α-cyano-3-phenoxybenzyl (S) -2- (4-chlorophenyl) -3-methylbutyrate], fenpropatorin [( RS) -α-
Cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS) -α-cyano-3-phenoxybenzyl (1RS, 3RS)-(1RS, 3RS) -3 −
(2,2-Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl (1RS, 3RS)-(1RS, 3R
S) -3- (2,2-Dichlorovinyl) -2,2-methylcyclopropanecarboxylate], cyhalothrin [(RS) -α-cyano-3-phenoxybenzyl (Z)-(1RS, 3RS) -3 -(2-chloro-3,
3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S) -α-cyano-m-phenoxybenzyl (1
R, 3R) -3 (2,2-dibromovinyl) -2-dimethylcyclopropanecarboxylate], cycloprothrin [(RS) -α-cyano-3-phenoxybenzyl (RS) -2,2-dichloro-] 1- (4-ethoxyphenyl) cyclopropanecarboxylate] and the like,

Thiadiazine derivatives such as buprofezin (2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-triadiazan-4-one), imidacloprid [1- (6-chloro-3-pyridyl] Methyl) -N-nitroimidazolidine-2-ylideneamine] and the like, nitroimidazolidine derivatives, cartap [S, S '-(2-dimethylaminotrimethylene) bis (thiocarbamate)], thiocyclam [N, N-dimethyl-1,2,2,2]. 3-trithian-5-ylamine], bensultap [S, S′-2-dimethylaminotrimethylene di (benzenethiosulfonate)] and other nereistoxin derivatives, endosulfan [6,7,8,
9,10,10-hexachloro-1,5,5a, 6
9,9a-hexahydro-6,9-methano-2,4,3
-Benzodioxathiepine oxide], γ-BHC
Chlorinated hydrocarbon compounds such as [1,2,3,4,5,6-hexachlorocyclohexane], chlorfluablone [1- (3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridine) -2-yloxy) phenyl] -3- (2,6-difluorobenzoyl) urea], teflubenzuron [1- (3,5-dichloro-
2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea], flufenoxuron [1-
Benzoylphenylurea compounds such as [4- (2-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl] -3- (2,6-difluorobenzoyl) urea], amitraz [N, N '[( Methylimino)
Dimethylidine] di-2,4-xylidine], chlorodiform [N '-(4-chloro-2-methylphenyl)-
N, N-dimethylmethanimidamide] and the like formamidine derivatives and the like.

When the compound of the present invention is used as an active ingredient of a pest control agent, it may be used as it is without adding any components of the book, but it is usually a solid carrier, liquid carrier, gaseous carrier or bait. Etc., and if necessary, add surfactants and other auxiliaries for formulation, oils, emulsions, wettable powders, flowable agents such as water-suspending agents / emulsifiers, granules, powders,
It is used as a formulation for aerosol, self-combustion type smoke agent / chemical reaction type smoke agent / heated smoke agent such as porous ceramic plate smoke agent, ULV agent and poison bait.

These formulations usually contain the compound of the present invention as an active ingredient in an amount of 0.001% to 95% by weight.
Examples of solid carriers used for formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talc, ceramics, and other inorganic minerals (sericite, quartz, Sulfur, activated carbon, calcium carbonate, hydrated silica, etc.),
Examples thereof include fine powders or granules of chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium salt, etc.), and examples of liquid carriers include water, alcohols (methanol, ethanol, etc.), ketones (acetone, Methyl ethyl ketone, etc.),
Aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, light oil, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile) , Isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, tetrachloride) Carbon, etc.), dimethyl sulfoxide, soybean oil, vegetable oil such as cottonseed oil, etc.,
Examples of the gaseous carrier, that is, the propellant include CFC gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas and the like.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and their polyoxyethylenated products, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohols. Examples include derivatives.

Examples of auxiliaries for preparation such as sticking agents and dispersants include casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers. (Polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, etc.) and the like, and examples of the stabilizer include PAP (isopropyl acid phosphate) and BH.
T (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil , Surfactants, fatty acids or esters thereof, and the like.

Examples of base materials for self-burning smoke agents include nitrates, nitrites, guanidine salts, potassium chlorate,
Combustion exothermic agents such as nitrocellulose, ethyl cellulose, wood flour, thermal decomposition stimulants such as alkali metal salts, alkaline earth metal salts, dichromates and chromates, oxygen supply agents such as potassium nitrate, melamine, wheat starch, etc. Examples include a combustion-supporting agent, a filler such as diatomaceous earth, and a binder such as a synthetic paste. As the base material of the chemical reaction type smoke agent, for example, alkali metal sulfide, polysulfide, hydrosulfide, hydrous salt,
Exothermic agents such as calcium oxide, carbonaceous substances, iron carbide, catalysts such as activated clay, azodicarbonamide, benzenesulfonylhydrazine, dinitrosopentamethylenetetramine, organic foaming agents such as polystyrene and polyurethane, natural fiber pieces, synthetic fibers Examples include fillers such as pieces.

Examples of base materials for poison baits include bait ingredients such as grain flour, vegetable essential oils, sugars and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, and capsicum. Examples include edible foods such as powdered foods, cheese flavor, and onion flavor.

Formulations of flowable agents (suspension in water or emulsions in water) generally contain 1 to 75% of the compound in an amount of 0.5 to 15%.
% Dispersant, 0.1-10% suspension aid (eg, protective colloid or compound that imparts thixotropic properties), 0-
Fine in water containing 1.0% of suitable auxiliaries (eg antifoaming agents, rust preventives, stabilizers, spreading agents, penetration aids, antifreeze agents, antibacterial agents, anti-smudge agents, etc.) It is obtained by dispersing in. It is also possible to use an oil in which the compound is hardly dissolved in place of water to prepare a suspension in oil. Examples of the protective colony include gelatin, casein, gums, cellulose ether, polyvinyl alcohol and the like. Examples of the compound that imparts thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, polyacrylic acid, and the like.

The thus obtained preparation is used as it is or after diluted with water or the like. Also other pesticides,
It can be used simultaneously with or without mixing with nematicides, acaricides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil improvers, animal feeds and the like.

When the compound of the present invention is used as an agricultural pest control agent, its application amount is usually 0.001 g to 500 g per 10 ares, preferably 0.1.
It is from g to 500 g. When emulsions, wettable powders, flowables, etc. are diluted with water, the application concentration is usually 0.
It is 0001ppm-1000ppm, and granules, powders, etc. are applied as they are without any dilution. When used as a pest control agent for epidemics, emulsions, wettable powders, flowable agents, etc. are usually diluted with water to a concentration of 0.0001 ppm to 10,000 ppm and applied, and an oil agent, an aerosol, a smoke agent, an ULV agent, For poison bait, apply as it is.

The application amount and application concentration depend on the kind of formulation, application time, application place, application method, type of pest, degree of damage, etc., and increase without regard to the above range, It can be reduced.

[0074]

EXAMPLES The present invention will be described in more detail below with reference to production examples, formulation examples and test examples, but the present invention is not limited to these examples. First, production examples of the compound of the present invention will be shown.

Production Example 1 Production of compound (1) by (Production method A) 2- [2-chloro-4- (2-ethylbutyl) phenoxy] ethylamine 0.50 g and ethyl chloroformate 0.2
To a solution prepared by dissolving 1 g in 20 ml of acetone, potassium carbonate
0.27 g was added, and the mixture was heated under reflux for 24 hours with stirring.
After concentrating the reaction solution, the residue was poured into 50 ml of water and extracted twice with 100 ml of ethyl acetate. After drying and concentrating the ethyl acetate solution, the residue was chromatographed on silica gel.
0.39 g of-[2-chloro-4- (2-ethylbutyl) phenoxy] ethylcarbamic acid ethyl ester was obtained. The compound number is (1). Income rate: 61%
n ^24.8 _D 1.5122

[0076] Production Example 2 Production of 2- (Process A) with compound (2) (2-chloro-4-isobutoxy-methylphenoxy) ethylamine 0.40g and ethyl chloroformate _0.1
To a solution prepared by dissolving 7 g in 20 ml of acetone, potassium carbonate
0.22 g was added, and the mixture was heated under reflux for 24 hours with stirring.
After concentrating the reaction solution, the residue was poured into 50 ml of water and extracted twice with 100 ml of ethyl acetate. After drying and concentrating the ethyl acetate solution, the residue was chromatographed on silica gel.
-(2-chloro-4-isobutoxymethylphenoxy)
0.34 g of ethyl ethyl ethylcarbamate was obtained. The compound number is (2). Yield: 67% n ^24.8 _D 1.5089

Production Example 3 Production of Compound (3) of the Present Invention by (Production Method B) 2- [2-chloro-4- (2-ethylbutyl) phenoxy] ethylisocyanate (0.60 g) and a few drops of pyridine were dissolved in 10 ml of methanol. The reaction was heated to reflux. After 1 hour, the reaction mixture was concentrated and the residue was subjected to silica gel chromatography to give 2- [2-chloro-4- (2
-Ethylbutyl) phenoxy] ethylcarbamic acid methyl ester 0.35 g was obtained. The compound number is (3)
And Yield: 53% n ^23.5 _D 1.5127

Production Example 4 Production of Compound (4) of the Present Invention by Production Process C 2-chloro-4-isobutoxymethylphenol 0.30
g and 20 ml of N, N-dimethylformamide were placed in a reaction vessel, 0.20 g of 2-chloroethylcarbamic acid methyl ester and 0.41 g of potassium carbonate were added with stirring, and the mixture was heated at 50 ° C. for 7 hours. The reaction solution was poured into 100 g of ice water and extracted twice with 100 ml of ethyl acetate. The ethyl acetate solution was dried and concentrated, and the residue was subjected to silica gel chromatography to give 2- (2-chloro-4-isobutoxymethylphenoxy) ethylcarbamic acid methyl ester.
0.51 g was obtained. The compound number is (4). Yield: 33% n ^23.9 _D 1.5092

Next, an example of producing an intermediate will be shown. Intermediate Production Example Production of Intermediate Compound (5) 2-chloro-4- (2-ethylbutyl) phenol 2.
00 g, chloroacetonitrile 0.71 g, dimethylformamide 150 ml and potassium carbonate 1.56 g are put into a reaction vessel and stirred. After stirring at an internal temperature of 70 to 80 ° C. for 5 hours in an oil bath, the reaction solution is cooled to room temperature. The reaction solution is poured into water, extracted twice with 100 ml of ethyl acetate, and then the ethyl acetate solution is washed twice with 200 ml of water. The ethyl acetate solution is dried over magnesium sulfate, filtered, and concentrated to give 2-chloro-4- (2-ethylbutyl) phenoxy] acetonitrile as a crude product. 2.00 g of this crude product and 200 ml of tetrahydrofuran are placed in a reaction vessel and cooled to 0 ° C. While stirring and maintaining the internal temperature at 0 to 5 ° C, borane tetrahydrofuran complex (1.0 MT
Slowly add 120 ml of HF solution). After finishing the dropping
Allow to warm to room temperature and stir overnight. The reaction solution was poured into 300 ml of water, tetrahydrofuran was removed under reduced pressure, and the reaction product was extracted with 100 ml of ethyl acetate three times under salting out.
Further, it is washed with 200 ml each of a 5% hydrochloric acid aqueous solution, water and a 10% caustic soda aqueous solution. The ethyl acetate solution is dried over magnesium sulfate, filtered, and concentrated to give 2-chloro-4- (2-ethylbutyl) phenoxy] ethylamine. The compound number is (5).

Intermediate Production Example Production of Intermediate Compound (6) 2-chloro-4-isobutoxymethylphenol 3.00
g, 1.05 g of chloroacetonitrile, 150 ml of dimethylformamide and 2.32 g of potassium carbonate are placed in a reaction vessel and stirred. After stirring at an internal temperature of 70 to 80 ° C. for 5 hours in an oil bath, the reaction solution is cooled to room temperature. The reaction solution is poured into water, extracted twice with 100 ml of ethyl acetate, and then the ethyl acetate solution is washed twice with 200 ml of water. The ethyl acetate solution is dried over magnesium sulfate, filtered, and concentrated to give 2-chloro-4-isobutoxymethylphenoxy] acetonitrile as a crude product. 3.00 g of this crude product and 200 ml of tetrahydrofuran are placed in a reaction vessel and cooled to 0 ° C. While stirring and maintaining the internal temperature at 0 to 5 ° C, borane tetrahydrofuran complex (1.0 MTH
(F solution) (177 ml) is slowly added dropwise. After the dropping is completed, the temperature is raised to room temperature and the mixture is stirred overnight. The reaction solution was poured into 300 ml of water, and tetrahydrofuran was removed under reduced pressure, and then the reaction product was extracted with 100 ml of ethyl acetate three times under salting out, and further 200 ml of 5% hydrochloric acid aqueous solution, water and 10% caustic soda aqueous solution, respectively. Wash. The ethyl acetate solution is dried over magnesium sulfate, filtered, and concentrated to give 2-chloro-4-isobutoxymethylphenoxy] ethylamine. The compound number is (6).

Formulation examples are shown below. The parts are parts by weight, and the compounds of the present invention are represented by the same compound numbers as above.

Formulation Example 1 Emulsion 10 parts of each of the compounds (1) to (4) of the present invention were dissolved in 35 parts of xylene and 35 parts of dimethylformamide, and polyoxyethylene styryl phenyl ether 14 was added thereto.
Parts and 6 parts of calcium dodecylbenzene sulfonate are added and well mixed with stirring to obtain 10% emulsions of each.

Formulation Example 2 Wettable Powder 20 parts of each of the compounds (1) to (4) of the present invention, 4 parts of sodium lauryl sulfate and 2 parts of calcium ligninsulfonate.
Part, 20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of silicon earth are added to the mixture and mixed by stirring with a juice mixer to obtain a 20% wettable powder.

Formulation Example 3 Granules To 5 parts of each of the compounds (1) to (4) of the present invention, 5 parts of sodium dodecylbenzenesulfonate, 30 parts of bentonite and 60 parts of clay are added, and they are sufficiently stirred and mixed. Then
An appropriate amount of water is added to these mixtures, the mixture is further stirred, granulated by a granulator, and dried by ventilation to obtain 5% granules.

Formulation Example 4 Dust formulation 0.3 parts of each of the compounds (1) to (4) of the present invention, 1 part of synthetic hydrous silicon oxide fine powder, trade name Dorilleth B as a flocculant
After thoroughly mixing 1 part (manufactured by Sankyo Co., Ltd.) and 7.7 parts of clay in a mortar, stir and mix with a juice mixer. 90 parts of cut clay is added to the obtained mixture and mixed in a bag to obtain each powder.

Formulation Example 5 Powders 0.3 parts of each of the compounds (1) to (4) of the present invention, 2 parts of fenitrothion as an organophosphorus compound, 3 parts of synthetic hydrous silicon oxide fine powder, trade name Doloreth B (as an aggregating agent) 1 part of Sankyosha Co., Ltd.) and 3.7 parts of clay are thoroughly mixed in a mortar and then mixed by stirring with a juice mixer. 90 parts of cut clay was added to the obtained mixture and mixed in a bag to obtain each powder.

Formulation Example 6 Powder 0.3 parts of each of the compounds (1) to (4) of the present invention, 2 parts of BPMC (O-sec-butylphenyl N-methylcarbamate) as a carbamate compound, synthetic hydrous silicon oxide fine powder 3 parts, 1 part of trade name Dorilles B (manufactured by Sankyosha Co., Ltd.) as a flocculant, and 3.7 parts of clay are mixed well in a mortar and then mixed with stirring with a juice mixer. 90 parts of cut clay was added to the obtained mixture and mixed in a bag to obtain each powder.

Formulation Example 7 Dust agent 1 part of each of the compounds (1) to (4) of the present invention was dissolved in an appropriate amount of acetone, and 5 parts of a synthetic hydrous silicon oxide fine powder, P
Add 0.3 parts AP and 93.7 parts clay, stir and mix with a juice mixer, and remove acetone by evaporation to remove 1% of each.
Get a powder.

Formulation Example 8 Flowable Agent 10 parts of each of the compounds (1) to (4) of the present invention is added to 40 parts of an aqueous solution containing 6 parts of polyvinyl alcohol, and the mixture is stirred with a mixer to obtain a dispersant. In this, xanthan gum
0.05 parts and aluminum magnesium silicate 0.1
40 parts of an aqueous solution containing 10 parts of propylene glycol and 10 parts of propylene glycol are added, and the mixture is gently stirred and mixed to obtain 10 parts of each.
% To give an emulsifier in water.

Formulation Example 9 Oil formulation 0.1 part of each of the compounds (1) to (4) of the present invention was mixed with 5 parts of xylene.
Parts and 5 parts of trichloroethane are dissolved and mixed with 89.9 parts of deodorized kerosene to obtain a 0.1% oil solution.

Formulation Example 10 Oily aerosol 0.1 parts of each of the compounds (1) to (4) of the present invention, 0.2 parts of tetramethrin, 0.1 part of d-phenothrin, 10 parts of trichloroethane and 59.6 parts of deodorized kerosene were mixed and dissolved. Then, after filling the aerosol container and attaching the valve portion, 30 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the valve portion to obtain an oil-based aerosol.

Formulation Example 11 Aqueous Aerosol 0.2 parts of each of the compounds (1) to (4) of the present invention, 0.2 part of d-allethrin, 0.2 part of d-phenothrin, 5 parts of xylene,
Aerosol container was filled with a mixture of 3.4 parts of deodorized kerosene and 1 part of emulsifier {Atmos 300 (registered trade name of Atlas Chemical Co.)} and pure 50 parts, and a valve part was attached and sprayed through the valve part. 40 parts of the agent (liquefied petroleum gas) is charged under pressure to obtain an aqueous aerosol.

Formulation Example 12 Heating and Smoke Agent 100 mg of each of the compounds (1) to (4) of the present invention was dissolved in an appropriate amount of acetone and impregnated into a porous ceramic plate of 4.0 cm × 4.0 cm and 1.2 cm in thickness. Obtain a heated smoker.

Next, it will be shown by test examples that the compound of the present invention is useful as an active ingredient of a pest controlling agent. The compounds of the present invention are shown by the same compound numbers as above, and the compounds used for comparison and control are shown by the compound numbers in Table 1.

[0095]

[Table 1]

Test Example 1 Metamorphosis Inhibitory Action on Larvae of the Brown Planthopper The emulsion of the test compound obtained according to Formulation Example 1 was diluted with water to a predetermined concentration and applied to rice seedlings planted in polyethylene cups in 20 ml / 2 pots. Sprayed in proportion. After air-drying, 10 3rd instar larvae of brown planthopper were released per pot.
After a day, the rate of inhibition of emergence was calculated. As a result, the compounds (1), (2), (3) and (4) of the present invention inhibited 100% emergence at the test concentrations of 5 ppm and 50 ppb, respectively. on the other hand,
The control compound (A) inhibited the emergence only at 58% at the test concentration of 5 ppm, and at the test concentration of 50 ppb, almost no drug effect was observed.

Test Example 2 Proliferation Inhibitory Action against Brown Planthopper The emulsion of the test compound obtained according to Formulation Example 1 was diluted with water to a predetermined concentration, and the seedlings were planted in polyethylene cups at a ratio of 20 ml / 2 pot. It was sprayed with. After air-drying, 5 male and 5 female adult brown planthoppers were released per pot, and the eggs were laid for 3 days. Two weeks later, the number of surviving nymphs of the next generation was investigated to determine the growth inhibition rate. As a result, the compounds (1), (2), (3) and (4) of the present invention were tested at a concentration of 20 ppm.
It inhibited the emergence by 100%. On the other hand, the control compound (A) inhibited the emergence of only 38% at the test concentration of 20 ppm.

Test Example 3 Proliferation Inhibitory Action Against Brown Planthopper The emulsion of the test compound obtained according to Formulation Example 1 was diluted with water to a predetermined concentration, and the rice seedlings (length: about 20 cm) were planted in pots (1 / 5000a). ) Was sprayed at a rate of 40 ml / 2 pots. After air-drying, the pot was covered with a wire netting gage, and 10 male and 10 female adult brown planthoppers were released per pot and left in a greenhouse. After about 3 weeks, the number of surviving nymphs of the next generation was investigated to determine the growth inhibition rate. As a result, the compound of the present invention (1)
(2), (3) and (4) are 100 at the test concentration of 100 ppm.
% Inhibition of emergence.

[0099]

INDUSTRIAL APPLICABILITY The compounds of the present invention are hemiptera pests, lepidopteran pests, diptera pests, coleopteran pests, reticoptera pests, total pests pests, orthoptera pests, hymenoptera pests, hidden pests. It has an excellent control effect against eye pests, lice pests, and other pests such as Lepidoptera, and can be used for various purposes as a pest control agent.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroaki Fujimoto 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Koji Umeda 4-2-1 Takashi, Takarazuka-shi In Sumitomo Kagaku Kogyo Co., Ltd. (72) Inventor Norichu Matsuo 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd.

Claims (6)

[Claims] 1. A general formula: ## STR1 ## [In the formula, R ¹ represents a 1-ethylpropyl group or an isobutoxy group, and R ² represents a methyl group or an ethyl group. ]
2- (2-chloro-4-substituted methylphenoxy) ethylcarbamic acid derivative represented by 2. A general formula: ## STR2 ## [In the formula, R ¹ represents a 1-ethylpropyl group or an isobutoxy group. ] And an amine compound represented by the following general formula: [In the formula, R ² represents a methyl group or an ethyl group, and L ¹ represents a halogen atom. ] The carboxylic acid type compound shown by these is made to react, The 2- of Claim 1 characterized by the above-mentioned.
Process for producing (2-chloro-4-substituted methylphenoxy) ethylcarbamic acid derivative. 3. A general formula: ## STR4 ## [In the formula, R ¹ represents a 1-ethylpropyl group or an isobutoxy group. Isocyanate compounds and the general formula R ² -OH [represented by the formula], R ² represents a methyl group or an ethyl group. ] The alcoholic compound shown by these is made to react, The manufacturing method of the 2- (2-chloro-4- substituted methylphenoxy) ethylcarbamic acid derivative of Claim 1 characterized by the above-mentioned. 4. A general formula: ## STR5 ## [In the formula, R ¹ represents a 1-ethylpropyl group or an isobutoxy group, and M ₁ represents an alkali metal atom or a hydrogen atom. ] And a phenolic compound represented by the general formula: [In the formula, R ² represents a methyl group or an ethyl group, and L ² represents a halogen atom, a methanesulfonyloxy group or a toluenesulfonyloxy group. ] The carboxylic acid type compound shown by these is made to react, The manufacturing method of the 2- (2-chloro-4- substituted methylphenoxy) ethylcarbamic acid derivative of Claim 1 characterized by the above-mentioned. 5. A general formula: embedded image [In the formula, R ¹ represents a 1-ethylpropyl group or an isobutoxy group. ] The amine compound shown by these. 6. A pest control agent comprising the 2- (2-chloro-4-substituted methylphenoxy) ethylcarbamic acid derivative according to claim 1 as an active ingredient.