JPH01319467A - Benzoisothiazole based compound, production thereof and insecticide containing the same - Google Patents

Abstract

NEW MATERIAL:A benzoisothiazole based compound expressed by formula I (R is alkyl) or salt thereof. EXAMPLE:3-Acetylamino-4-difluoromethoxybenzoisothiazole-1,1-dioxide. USE:Useful as an insecticide exhibiting high insecticidal activity and excellent exterminating activity, especially to a sucking insect pest such as aphid as well as excellent systemic transition properties. PREPARATION:A compound expressed by formula II is reacted with an oxidant such as m-chloroperbenzoic acid or hydrogen peroxide at -30-+120 deg.C, especially 0-40 deg.C in a solvent such as methylene chloride to afford the compound expressed by formula I. The compound expressed by formula II is synthesized as shown in the reaction formula.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to novel benzisothiazole compounds, methods for producing them, and insecticides containing them.

(Prior art) Benziisothiazole compounds are described in various publications and are known. For example, JP-A-59-108703
No. 61-189278, 3-acetylamino-4-methoxybenziisothiazole-1,1
-dioxide is disclosed. However, this compound has a methoxy group at the 4-position, and the benzisothiazole compound of the present invention has a difluoromethoxy group at the 4-position, and both compounds are different in that the substituent at the 4-position is different. Different.

(Disclosure of the Invention) The present inventors conducted various studies on benzisothiazole compounds, and found that 3-alkylcarbonylamino-4-difluoromethoxybenzisothiazole-1
, 1-dioxide has been found to exhibit high insecticidal activity, particularly excellent extermination activity against sweat-absorbing pests such as aphids, and to have excellent systemic transferability.

The present invention relates to a benzisothiazole compound represented by the general formula (wherein R is an alkyl group) or a salt thereof.

Further, the salt is a salt formed from a benzisothiazole compound of general formula (+) and a basic substance.

In the above-mentioned - Shipman (1), the alkyl group represented by R includes those having 1 to 4 carbon atoms, such as methyl group, ethyl group, propyl group, and butyl group; It also includes structural isomers of chains or branched fatty chains.

Since the benzisothiazole compound represented by the above-mentioned -Funenin (1) has a tautomer represented by the following general formula (bi), the present invention provides the benziisothiazole compound represented by the general formula (1) and -Funenin ( b) Both tautomers are targeted.

■) (Bi) (R is as mentioned above) In addition, tautomers such as the relationship between -Funenin (1) and -Funenin (B) are as follows: -Funenin (■), (In) ( IV) and (V) also exist.

The compound represented by -Funenin (+) can be produced by the following production method.

([1) (In the formula, R is as described above) Examples of the oxidizing agent used in the reaction include organic peroxide-hydrogen peroxide such as m-4-day perbenzoic acid and perbenzoic acid. It will be done. Also, this reaction is usually -30 to +1
The reaction temperature is 20°C, preferably 0 to 40°C, in the presence of a solvent, and the reaction time is usually 2 to 24 hours. Examples of the solvent include halogenated hydrocarbons such as methylene chloride and chloroform; carboxylic acids such as acetic acid and propionic acid; and the like.

The compound represented by -Funenin (n) can be produced, for example, by the following production method.

(V) (rV) (III)
(II) (In the formula, R is as described above) [Demethylation step] Examples of the sodium salt of alkylthiol include those in which the alkyl group has 1 to 4 carbon atoms, such as the sodium salt of ethanethiol. Examples of the aprotic polar solvent include dimethylformamide and hexamethylphosphoric triamide.

Moreover, this reaction is carried out at 40-140'C, preferably at 60-140'C.
It is carried out at 100°C and the reaction time is 1 to 3 hours.

[Difluoromethylation step]

Examples of basic substances include alkali metal hydrides such as potassium carbonate, sodium hydroxide, and sodium hydride, hydroxides, and carbonates, and examples of aprotic polar solvents include dimethylformamide and dioxane. . This reaction is carried out at 30-140°C, preferably at 5°C.
It is carried out at 0-110°C and the reaction time is 0.3-2 hours.

[Alkyl carbonylation step]

Basic substances include sodium hydride, triethylamine, 1.8-diazabicyclo-[5°4.0)-7-
Examples of the solvent include ethers such as diethyl ether and tetrahydrofuran; halogenated hydrocarbons such as chloroform and methylene chloride; and aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. Can be mentioned.

Also, this reaction is carried out at -20 to +60°C, preferably at O to 4°C.
The reaction time is 0.3 to 2 hours.

Next, specific production examples of the compound represented by the above-mentioned - formation (+) will be described.

Synthesis Example 1 Synthesis of 3-acetylamino-4-difluoromethoxybenziisothiazole-1゜■-dioxide (Compound 1 below) Suspend 2.8 g of sodium hydride (60% Nujol mixture) in 50 ml of dimethylformamide. Ethanethiol 5- was added dropwise to the solution under water cooling. After 0 dropwise addition, stirring was continued until the generation of hydrogen gas was completed, and 5 g of 3-amino-4-methoxybenziisothiazole was added to the solution. Solution 10- was gradually added dropwise.

After the completion of the dropwise addition, the reaction solution was heated to 80°C and reacted for 2 hours. After the completion of the reaction, the solvent was distilled off under reduced pressure. To the resulting residue, 50ml of water was added, and then concentrated hydrochloric acid was added dropwise. The pH of the solution was adjusted to 6.

Next, ethyl acetate was added for extraction, and the organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. 2.3 g of thiazole (melting point 88-92°C) was obtained.

(2) After dissolving 1.1 g of 3-amino-4-hydroxy-benzisothiazole obtained in step (1) in 90 d of dimethylformamide along with 1.8 g of potassium carbonate, the solution was heated to 100'C. After that, chlorodifluoromethane gas was introduced into this solution while stirring for 30 minutes. After the reaction was completed, the reaction solution was poured into 300 g of ice water, and then ethyl acetate was added to perform extraction. organic layer,
After washing with saturated brine and drying over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane-1/3) to obtain 3-amino-4. 0.8 g of -difluoromethoxybenziisothiazole (melting point 36-42°C) was obtained.

(3) Add 0.3 g of sodium hydride (60% Nujol mixture) to 1.4 g of 3-amino-4-difluoromethoxybenziisothiazole obtained in step (2) in tetrahydrofuran i8H (10 ml) under water cooling. Gradually drop it, and after the generation of hydrogen gas is completed, acetyl chloride 0
．． 6g of tetrahydrofuran (5Id)? 8 liquid was gradually added dropwise at the same temperature. After the dropwise addition was completed, stirring was continued for 30 minutes while gradually returning the solution temperature to room temperature.
'8 solution was poured into 50 m2 of ice water, and ethyl acetate was added to perform extraction. The organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to give 3-acetylamino-4-difluoromethoxybenziisothiazole (melting point 123-124°C). 85g was obtained.

(4) 3-acetylamino- obtained in the above step (3)
4-difluoromethoxybenziisothiazole 0.8g
methylene chloride? 1.5 g of m-chloroperbenzoic acid was gradually added to 10 d of liquid 8 at room temperature, and then the reaction solution was
Furthermore, after the completion of the reaction, which was stirred at room temperature for 12 hours, the solvent was distilled off under reduced pressure.
/2) to obtain the target product, 3-acetylamino-
4-difluoromethoxybenziisothiazole-1,1
0.5 g of -dioxide (melting point 179-180°C) was obtained.

Next, representative examples of the compounds represented by the above-mentioned -formation (1) are listed in Table 1.

The compounds of the present invention represented by -formation (+) above in Table 1 exhibit excellent activity as active ingredients of insecticides, particularly against green peach aphid, cotton aphid, radish aphid, potato aphid, bean aphid, snow willow aphid, It is highly effective in exterminating sweat-absorbing pests such as aphids such as the barley beetle. Furthermore, the compound of the present invention has excellent permeability and transferability, and an excellent pesticidal effect can also be obtained by treating soil with the compound of the present invention.

When using the compound of the present invention as an active ingredient of an insecticide, it can be used in combination with an agricultural chemical adjuvant in the form of an emulsion, a powder, a granule, a wettable powder, a liquid, an aerosol, a paste, or a suspension. It can be formulated into various forms such as agents. The mixing ratio of these ingredients is usually 0.5 to 90 parts by weight of the active ingredient and 10 to 99.5 parts by weight of the pesticide auxiliary. When actually using these preparations, either use them as is or
Alternatively, it can be used after being diluted to a predetermined concentration with a diluent such as water.

The auxiliary agents mentioned here include carriers, emulsifiers, layering agents, dispersants, spreading agents, penetrants, lubricants, thickeners, stabilizers, etc., which may be added as appropriate. Bye. 1
! ! The carrier is divided into solid carriers and liquid carriers, and solid carriers include starch, activated carbon, soybean flour, wheat flour, wood flour, and a! , t5) Animal and plant products such as milk, talc,
Examples include SEL physical powders such as kaolin, bentonite, calcium carbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, and sulfur powder. Liquid carriers include water, alcohols such as methyl alcohol and ethylene glycol, acetone, and methyl ethyl ketone. Ketones such as dioxane, ethers such as tetrahydrofuran, aliphatic hydrocarbons such as kerosene and kerosene, xylene, trimethylbenzene, tetramethylhenzene,
Aromatic hydrocarbons such as cyclohexane and solvent naphtha, halogenated hydrocarbons such as chloroform and chlorobenzene, acid amides such as dimethylformamide,
Examples include esters such as acetic acid ethyl ester and glycerin ester of fatty acids, nitriles such as acetonitrile, and sulfur-containing compounds such as dimethyl sulfoxide.

In addition, other agricultural chemicals such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides,
It can be mixed or used in combination with plant growth regulators, etc., and in this case may exhibit even more (extraordinary) effects.

For example, insecticides, acaricides, or nematicides,
〇-(4-fromo210lophenyl), 0-ethyl
S-propyl phosphorothioate, 2,2-dichlorovinyl dimethyl d; sulfate, ethyl 3-methyl-4-(methylthio)phenyl isopropyl phosphoroamidate, 0.0-dimethyl 0-4-nitrom
-Tolyl phosphorothioate, 0-ethyl 0-4-
2I Lophenyl Phenylphosphonothioate, 02
0-Diethyl 0-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate, 0.0-dimethyl O-(3,5,6-)lichloro-2-pyridyl)
Organic phosphate ester compounds such as phosphorothioate, 0.3-dimethyl acetyl phosphoramidothioate, o-(2,4-dichlorophenyl) 〇-ethyl S-propyl phosphorodithioate; l-naphthyl methyl carbamate, 2-isopropoxyphenyl methyl carbamate, 2-methyl-2-(methylthio)propionaldehyde 〇-methylcarbamoyloxime, 2,3-dihydro-2,2-dimethylbenzofuran-7-ylmethylcarbamate, dimethyl N,
N'-(thiobis((methylimino)carbonyloxy)]bisethanimidothioate, S-methyl N
-(methylcarbamoyloxy)thioacetimizo-1
・,N,N-dimethyl-2-methylrubamoyl quinimino-2-(methylthio)acetamide, 2-(ethylthiomethyl)phenyl methylcarbamate, 2-dimethylamino-5,6-dimethylpyrimidine-4 -yl dimethylcarbamate, S,S' -Carbamate compounds such as 2-dimethylaminotrimethylenebis(thiocarbamate); 2.2.2-trichloro-1,
Predominantly chlorinated compounds such as 1-bis(4-chlorophenyl)ethanol and 4-chlorophenyl-2,4,5-trichlorophenylsulfone; organometallic compounds such as tricyclohexyltine hydroxide; (R3)-
α-cyano-3-phenoxybenzyl (R5)-2-
(4-chlorophenyl)-3-methylbutyrate, 3-
Phenoxybenzyl (In2)-cis, trans-3-
(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate, (R3) -α-cyano-
3-phenoxybenzyl (In2) -cis, trans-3-(2,2-dichlorovinyl)-2゜2-dimethylcyclopropanecarboxylate, (S)-α-cyano-3-phenoxybenzyl (IR)- cis-3-(
2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate, (R3)-α-cyano-3-
Phenoxyhensyl (In2)-cis, trans-3
-(2-chloro-3,3,34-lifluoropropenyl)
2,2-dimethylcyclopropanecarboxylate, 4
-Methyl-2,3,5,6-tetrafluorobenzyl-3-(2-chloro-3,3゜3-trifluoro-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylic acid Pyrethroid compounds such as 1-(4-
chlorophenyl)-3-(2,6-difluorobenzoyl)urea, 1-(3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenyl)-3-(2, Benzoylurea compounds such as 6-difluorobenzoyl)urea, 1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea; 2-tert-butylimino-3 -isopropyl-5-phenyl-3,4
゜5.6-Tetrahydro-2H-1,3,5-thiadiazin-4-one, trans-(4-chlorophenyl)-
N-cyclohexyl-4-methyl-2-oxothiazolidinone-3-carboxamide, N-methylbis(2,4
Compounds such as -xylyliminomethyl)amine; isopropyl (2E.

4E) -If-methoxy-3,7,11-trimethyl-
Compounds similar to femininity hormones such as 2,4-dodecagenoate; and other compounds include dinitro compounds, sulfur compounds, urea compounds, and triazine compounds. Furthermore, it can be mixed or used in combination with microbial pesticides such as BT agents and insect pathogenic virus agents.

For example, as a fungicide, S-benzyl 0゜0-diisopropyl phosphorothioate, 0-ethyl S, S
-diphenyl phosphorodithioate, aluminum
Staged phosphorus compounds such as ethyl hydrogen phosphonate; monochromatic chlorine compounds such as 4,5゜6.7-tetrachlorophuclide and tetrachloroisophthalonitrile; polymers of Manganese ethylene bis(dithiocarbamate) , zinc ethylene bis(dithiocarbamate) polymer, zinc and maneb complex, disinc acid bis(dimethyldithiocarbamate) ethylene bis(
dithiocarbamate compounds such as polymers of zinc propylene bis(dithiocarbamate); 3a,4,7,7a-tetrahydro-N=(
Trichloromethanesulfenyl)phthalimide, 3a.

4.7.7a-tetrahydro-N-(1,1,2゜2-
Tetrachloroethanesulfenyl)phthalimide, N-
N-halogenothioalkyl compounds such as ()dichloromethylsulfenyl)phthalimide; 3-(3,5-
dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide, (RS)-
3-(3゜5-dichlorophenyl)-5-methyl-5
-vinyl-1,3-oxazolidine-2,4-dione,
Dicarboximide compounds such as N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide; methyl 1-(butylcarbamoyl)benzimidazol-2-yl carbamate;
Benzimidazole compounds such as dimethyl 4.4-(0-phenylene)bis(3-thioallophanate); 1-(4-chlorophenoxy)-3,3-dimethyl-1-(IH,,1,2 ,4-)Riazol-1-yl)butanone, 1-(biphenyyl-4-yloxy)-
3,3-dimethyl-1-(IH-1゜2.4-triazol-1-yl)butan-2-ol, 1-(N-(
4-chloro-2-trifluoromethylphenyl)-2-
Propoxyacetimidoyl)imidazole, 1-(
2-(2,4-dichlorophenyl)-4-ethyl-1,
3-dioxolan-2-ylmethyl)-111-1,2
,4-triazole, 1-(2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolane-2
-ylmethyl)-1H-1,2,4-triazole,!
-(2-(2,4-dichlorophenyl)pentyl)-1
H-1,2,4) Azole compounds such as lyazole 2.4-dichloro-α-(pyrimidin-5-yl)benzhydryl alcohol, (±)-2,4”-difluoro-α-(IH Carbinol compounds such as -1,2,4-triazol-1-ylmethyl)benzhydryl alcohol; 3'-isopropoxy-〇-toluanilide, α,α,α-trifluoro-3゜-isopropoxy- Benzanilide compounds such as 0-trianilide: methyl N-(2-methoxyacetyl)-N-(2,
Acylalanine compounds such as 6-xylyl)-DL-alaninate; 3-chloro-N-(3-chloro-2,
6-sinitro 4-α,α,α-trifluorotrile)
= Viridinamine-based compounds such as 5-trifluoromethyl-2-viridinamine; Other compounds include piperazine-based compounds, morpholine-based compounds, anthraquinone-based compounds, quinoxaline-based compounds, crotonic acid-based compounds,
Examples include sulfenic acid compounds, urea compounds, and antibiotics.

The insecticide containing the compound of the present invention as an active ingredient is generally applied at a concentration of 1 to 20,000 ppm, preferably 20 to 2.
The concentration of these active ingredients, which is carried out at a concentration of 0,000 ppm, can be appropriately changed depending on the form of the preparation, the method of application, purpose, timing, location, pest outbreak status, etc. The application amount per unit area is about 0.1 to 5,000 g, preferably 10 to 1.0 g of the active ingredient compound per 10 a.
00g is used. However, in special cases it is also possible to depart from these ranges.

Various formulations containing the compound of the present invention or dilutions thereof can be applied by commonly used application methods, namely:
Spreading (e.g. scattering, spraying, misting, atomizing, scattering, water surface application, etc.), soil application (mixing, irrigation, etc.),
It can be carried out by surface application (coating, powder coating, coating, etc.). In addition, the so-called ultra-high concentration small amount spraying method (ultra
It can also be applied by low-volume).

In this way it is possible to contain 100% of the active ingredient.

Test Example 1 Green peach aphid insecticidal test cup (diameter 1
cm, height 4CI11) 3rd from the 4th to 5th leaf stage of planting
Alternatively, leave only the fourth leaf and apply adhesive (
Fujitan gel) was applied, and two adult green peach aphids were inoculated onto the eggplant leaves. After spawning larvae for 2 days, the adults were removed, and together with the eggplant leaves, they were immersed in a chemical solution adjusted to 800 ppm for about 10 seconds, air-dried, and then left in a constant temperature room with lighting at 26°C. After 5 days of treatment, survival was determined and the mortality rate was calculated using the formula below. Compound 1 had a mortality rate of 1.
It was 00%. Furthermore, exfoliation of the son-in-law was also considered as death.

Treated Insect Count Test Example 2 Green peach aphid and cotton aphid insecticidal test (foliar spraying treatment) A formulation containing the compound ai as an active ingredient was dispersed in water,
The concentration was adjusted to a specified level. Potted eggplant infested with green peach aphid and cotton aphid (5-6 leaves! II
I) to the predetermined concentration? The prepared chemical solution was applied to the leaves and leaves using a spray gun, and the plants were left to air dry in a greenhouse.

The number of insects was investigated before treatment and on the 4th and 8th day after treatment. The results are shown in Tables 2 and 3.

Table 2 Green peach aphid test results Table 3 Cotton aphid test results Test example 3 Cotton aphid insecticidal test (systemic transfer test) A formulation containing Compound No. 1 as the active ingredient is dispersed in water, and a prescribed amount of... Adjusted to Q degree. Potted eggplants (5 to 6 leaves) infested with cotton aphids were treated by soil irrigation with the chemical solution 4Qrnl adjusted to the predetermined concentration. The number of insects was investigated before the treatment and 2.8 and 144 days after the treatment. The results are shown in Table 4.

Table 4 Cotton aphid test results Next, formulation examples of the compounds of the present invention will be described below.

Formulation Example 1 (a) 20 parts by weight of compound r rainbow 1 (b)
72 parts by weight of N,N'-dimethylformamide (c) 8 parts by weight or more of polyo-4-soethylenealkyl phenyl ether are uniformly mixed and dissolved to form an emulsion.

Formulation Example 2 (a) Compound level 1 50 parts by weight (b) Tetramethyl-\benzene 38 parts by weight (c) Alkylbenzene sulfonate, polyoxene ethylene alkylphenol ether, and polyoxyethylene phenyl fluoride L
Kol ether emulsifier (product name Ageli Seal P)
-311, Kao Soap (manufactured by 1) 12 parts by weight or more are uniformly mixed and dissolved to form an emulsion.

Formulation example 3 (a) Compound level 1 5 parts by weight (I) Hentonite 45 kaolin (c) 50 parts by weight or more of kaolin are kneaded with a small amount of water, extruded into granules, and dried to form granules. .

Formulation Example 4 (a) Compound 1 0.50 parts by weight (b) Polyoxyethylene octylphenyl ether
0.15 parts by weight (c) 0.10 parts by weight of polyoxyethylene phosphoric acid ester (d) 99.25 parts by weight of granular carbonate (a) ~
(C) is mixed uniformly in advance, diluted with an appropriate amount of acetone, and then sprayed onto (D) to remove the acetone to form granules.

Formulation Example 5 (a) Compound 1 50 parts by weight (b) Silica 15 parts by weight (c) Fine clay 25 parts by weight (d) Naphthalenesulfonic acid soda formalin condensate
2 parts by weight (e) dialkyl sulfosakushi, ? ,
- 3 mFfi parts (f) Polyoxyethylene alkyl allyl ether sulfate 5 parts by weight or more are uniformly mixed and ground to prepare a wettable powder.

Patent applicant: Ishihara Sangyo Co., Ltd.

Claims (1)

[Claims] 1. A benzisothiazole compound or a salt thereof represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (in the formula, R is an alkyl group) . 2. Contains a benzisothiazole compound or its salt represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (in the formula, R is an alkyl group) as an active ingredient Insecticide. 3. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(II) (In the formula, R is an alkyl group) A general formula characterized by reacting a compound represented by the following with an oxidizing agent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I) (In the formula, R is as described above) A method for producing a benzisothiazole compound or its salt.