JPH0473427B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel N-substituted-S-substituted-aminothiol compounds and methods for their production. Nitromethylene heterocyclic compounds are known to have interesting levels of insecticidal activity - for example the following compounds: See British Patent No. 1513951, which is particularly exemplified. Hitherto, N-substituted derivatives of compound A and their analogs have been synthesized by converting heterocyclic compound A or its analogs into derivatives - for example, GB 1513951, page 555.
See line 61. However, attempts to synthesize certain N-acyl derivatives by direct acylation of Compound A and its analogs have failed to yield the desired derivatives. Furthermore, the synthesis of Compound A involves the use of hazardous intermediates, and therefore a route to N-acyl derivatives that avoids Compound A was desired. Applicants have discovered a new process for the preparation of N-substituted derivatives of Compound A and its analogs which avoids the need to use the heterocyclic intermediate Compound A. This new process, claimed in a pending application, uses new N-substituted-S-substituted-aminothiols as starting materials. These N-substituted-S-substituted-aminothiols are novel compounds and form the subject of the present invention. The aminothiols are easy to obtain and economically synthesized. Surprisingly, some of the compounds also have insecticidal activity in their own right. Therefore, the present invention provides the general formula: [In the formula, n is 2, 3 or 4, Hal is a halogen atom, and R is optionally substituted formyl, alkanoyl, alkenoyl,
Alkynoyl, aroyl, carbamoyl, oxaroyl, alkoxycarbonyl, aryloxycarbonyl, alkylthiocarbonyl, arylthiocarbonyl, alkylthio-thiocarbonyl, arylthio-thiocarbonyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, alkylamino Sulfonyl, arylaminosulfonyl, alkylaminosulfinyl, arylaminosulfinyl, and the formula: (wherein each R° is independently an optionally substituted alkyl or aryl group, each X is independently an oxygen or sulfur atom, and each y is independently 0 or 1) is an acyl group selected from the group consisting of the phosphorus-containing acyl groups of the following). In the general formula, preferably n=2 or 3, more preferably n=3. The halogen atom is preferably chlorine, fluorine or bromine. If the acyl group R contains an alkyl, alkenyl or alkynyl group, each group preferably contains up to 30, more preferably up to 20 carbon atoms; but often the carbon content is up to 8 or up to 4. can be. If the acyl group R contains an aryl group, this preferably represents a phenyl group. Optional substituents which may be present in the acyl group are preferably fluorine, chlorine, bromine and iodine; nitro; cyano; alkyl, alkoxy, alkylthio, alkenyl and alkynyl of up to 6 carbon atoms; and optionally fluorine, chlorine, Bromine, iodine, C
Aryl, aryloxy and arylthio optionally substituted with one or more groups selected from (1-4)-alkyl, nitro and cyano, preferably selected from phenyl, phenoxy and phenylthio. Particular examples of aminothiols according to the invention are those in the general formula where n=3, Hal is chlorine and R is one of the following acyl groups: aroyl (e.g. benzoyl), alkanoyl (e.g. 2 to 11 haloalkanoyl (e.g. containing 2 to 11 carbon atoms and 1 to 5 chlorine, fluorine or bromine atoms), arylsulfonyl (e.g. phenylsulfonyl), alkylsulfonyl (e.g. C _1-10 (alkylsulfonyl), (alkyl-O) ₂ P(O)- (e.g. each alkyl group contains 1 to 4 carbon atoms), (alkyl-O) ₂ P(S)- (e.g. each alkyl group contains 1 to 4 carbon atoms) containing 1 to 4 carbon atoms), (phenyl-O) ₂ P(O)-, alkoxycarbonyl (e.g. containing 2 to 11 carbon atoms), alkylthiocarbonyl (e.g. containing 2 to 11 carbon atoms) ), and dialkylcarbamoyl (e.g., each alkyl group contains 1 to 4 carbon atoms), where each of the above acyl groups is one or more selected from methyl, nitro, chlorine fluorine, and bromine substituents. It can carry the above substituents. The present invention relates to aminothiols having the following general formula: R-NH-( _CH2 ) _o -SH () in which R and n have the meanings given above; and aminothiols having the general formula: (wherein Hal is a halogen atom) in the presence of a base preferably selected from alkali metal or alkaline earth metal or ammonium hydroxides, carbonates, bicarbonates or persalts. Below, N-substituted- of the general formula including reacting in the presence of an inert solvent
Includes a method for producing an S-substituted aminothiol. Conveniently the base is an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. A suitable solvent such as a tertiary alcohol such as t-
Butyl alcohol, ethers such as diethyl ether, tetrahydrofuran and dimethoxyethane, ketones such as acetone, nitrogen-containing solvents such as dimethylformamide, hydrocarbons such as benzene, xylene and toluene, and sulfur-containing solvents such as dimethyl sulfoxide may be used. Although the reaction can proceed at room temperature, it is generally -
It may be carried out at temperatures of 30° to +50°C, suitably -20° to +30°C. The molar ratio of aminothiol to halonitroethylene can range from 1:4 to 2:1. However, it is generally preferred to have an excess of halonitroethylene, thus preferred molar ratios are within the range of 1:1 to 1:4. Better results are achieved when a mixture of base and aminothiol (preferably in equimolar proportions) is added to the halonitroethylene (preferably present in molar excess). N-substituted-aminothiols of the formula may be prepared by N-acylation of the corresponding unsubstituted aminothiol. Compounds of the formula can be converted to the corresponding pesticide-active heterocyclic compounds by reaction with a base in the presence of an inert solvent: It can be converted into Preferred bases are alkali metal or alkaline earth metal hydrides and alkoxides and alkali metal amides. Suitable solvents include alcohols, ethers, ketones, nitrogen-containing solvents,
Contains hydrocarbons and sulfur-containing solvents. The reaction may be carried out at a temperature of -30° to +50°C, conveniently at room temperature. The molar ratio of base to amide can be, for example, from 1:2 to 2:1, preferably from 1:1 to 2:1. Some of the N-substituted-S-substituted-aminothiols according to the invention also exhibit pesticidal activity, especially against harmful insects. They are armyworms (Spodoptera
It exhibits activity against pests such as P. littoralis. Accordingly, the present invention includes pesticide compositions comprising an N-substituted-S-substituted-aminothiol compound of the general formula together with a carrier. Any suitable carrier or carrier mixture commonly used in the formulation of pesticides may be used. The invention is further illustrated in the following examples. Example 1 Preparation of N-acetyl-S-(1-chloro-2-nitroethenyl)-3-aminopropanethenitol. To N-acetyl-3-aminopropanethiol (400mg) in methanol (5ml) was added sodium hydroxide (120mg) in methanol (5ml) over 10 minutes. This mixture was then added to 1,1-dichloro-2-nitroethene (950mg) in methanol (5ml) at 0°C over 20 minutes. This was stirred for an additional 20 minutes and then poured into 2% HCl saturated with NaCl and extracted with methylene chloride. The product was purified on a silica gel column.
Yield 400 mg; oil. Example 2 N-phenylsulfonyl-S-(1-chloro-
Production of 3-aminopropanethenyl)-2-nitroethenyl Hydrochloride of 3-amino-propanethenyl (5
g) was added sodium methoxide (1 g Na; 25 ml methanol) and the mixture was allowed to cool.
Solvent was removed. Methylene chloride (60ml) to the product
and triethylamine (6g) and to it phenylsulfonyl chloride (7g) in methylene chloride (40ml) was added dropwise over 30 minutes at 0°C. After 20 minutes at room temperature, the product was washed with 2% HCl and triturated with diethyl ether. Yield of disulfide, bis-(N-phenylsulfonyl-3-aminopropyl)-disulfide, 6.2 g. The disulfide (3.1 g) was treated with triphenylphosphine (2.5 g) in water (2.5 g), methanol (50 ml) and 10 drops of 10% HCl and 11
Refluxed for an hour. Most of the solvent was removed and the resulting product was taken up in methylene chloride and washed with water. The product was purified on a silica gel column. Yield of N-phenylsulfonyl-3-aminopropanethiol: 1.6 g. Analysis: Calculated: C46.8; H5.6; N6.1% Measured: C46.8; H5.8; N5.9% N-phenylsulfonyl-3-aminopropanethiol ( 231 mg) of sodium hydroxide (80 mg) in methanol (3 ml).
was added over 5 minutes and the mixture was then diluted with 1,1-dichloro-2-
Nitroethene (284 mg) was added dropwise over 20 minutes at 0°C. The reaction mixture was kept at 0° C. for 30 minutes and then poured into 2% HCl saturated with NaCl and extracted with methylene chloride. The product was generated on a silica gel column. Yield 93 mg; melting point 105-106°C. Analysis: Calculated value: C39.2; H3.9; N8.3% Measured value: C39.6; H3.8; N8.2% Example 3 N-benzoyl-S-(2-nitro-1-chloroethenyl)- Preparation of 3-aminopropanethiol N-benzoyl-3- in methanol (12 ml)
Aminopropanethiol (780 mg) under nitrogen at 0°C.
Sodium hydroxide (160 mg) in methanol (6 ml) was added dropwise. This mixture was then poured under nitrogen at 0.
1,1-dichloro- in methanol (20 ml) at °C.
Added dropwise to 2-nitroethene (1.2g) over 20 minutes. The reaction mixture was poured into 2% HCl saturated with NaCl and extracted with methylene chloride. The product was purified using a silica gel column. Yield 252
mg. Analysis: Calculated value: C47.9; H4.3; N9.3% Measured value: C48.3; H4.3; N9.3% Example 4-11 By a method similar to that described in Examples 1 to 3, Compounds of the formulas detailed in the table were prepared.

【table】

[Table] Example 12 Insecticidal activity The insecticidal activity of certain compounds of the present invention was determined in a patent application.
Evaluation was made using the method described in Example 34 of No. 59-25319. The compound of Example No. 1 killed all test insects in the test against the house fly (Musca domestica), and the compound of Example No. 2 killed all the test insects in the test against the armyworm (Spodoptera littoralis) and Aedesaegypti. did. Example 13 Preparation of N-phenylsulfonyl-2-nitromethylene-2H-1,3-thiazine N-phenylsulfonyl-S-(1-chloro-2-nitroethenyl) in t-butanol (5 ml)
-3-aminopropanethol (100mg) and t-
Potassium t-butoxide (35mg) in butanol (2ml) was added over 6 minutes. After 20 minutes at room temperature,
The reaction mixture was poured into 2% HCl saturated with NaCl,
And then extracted with methylene chloride. The product was purified on a silica gel column. Yield 54mg; melting point
107℃. Analysis: Calculated: C44.0; H4.0; N9.2 Measured: C44.0; H4.0; N9.3.

Claims (1)

[Claims] 1. General formula: [In the formula, n is 2, 3 or 4, Hal is a halogen atom, and R is optionally substituted formyl, alkanoyl, alkenoyl,
Alkynoyl, aroyl, carbamoyl, oxaroyl, alkoxycarbonyl, aryloxycarbonyl, alkylthiocarbonyl, arylthiocarbonyl, alkylthio-thiocarbonyl, arylthio-thiocarbonyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, alkylamino Sulfonyl, arylaminosulfonyl, alkylaminosulfinyl, arylaminosulfinyl, and the formula: (wherein each R° is independently an optionally substituted alkyl or aryl group, each X is independently an oxygen or sulfur atom, and each y is independently 0 or 1) is an acyl group selected from the group consisting of phosphorus-containing acyl groups of )] N-substituted-S-substituted-aminothiol. 2 n is 3, Hal is chlorine, and R
is aroyl, alkanoyl, haloalkanoyl,
arylsulfonyl, alkylsulfonyl, dialkyloxy-oxophosphorus, diphenoxy-oxophosphorus, dialkyloxythiophosphorus, dialkylcarbamoyl, alkoxycarbonyl or alkylthiocarbonyl,
2. A compound according to claim 1, wherein the R group is optionally substituted with one or more methyl, nitro, chlorine, fluorine or bromine substituents. 3 n is 3, and R is formyl, C(2
-5) alkanoyl or haloalkanoyl, benzoyl, halobenzoyl, phenylsulfonyl, halophenylsulfonyl, or dialkylcarbamoyl, dialkylaminosulfonyl, dialkoxythiophosphorus or dialkylcarbamoyl, in which each alkyl group has 1 to 4 carbon atoms; The compound according to claim 1, which is an alkoxyoxophosphorus. 4 General formula: [In the formula, n is 2, 3 or 4, Hal is a halogen atom, and R is optionally substituted formyl, alkanoyl, alkenoyl,
Alkynoyl, aroyl, carbamoyl, oxaroyl, alkoxycarbonyl, aryloxycarbonyl, alkylthiocarbonyl, arylthiocarbonyl, alkylthio-thiocarbonyl, arylthio-thiocarbonyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, alkylamino Sulfonyl, arylaminosulfonyl, alkylaminosulfinyl, arylaminosulfinyl, and the formula: (wherein each R° is independently an optionally substituted alkyl or aryl group, each X is independently an oxygen or sulfur atom, and each y is independently 0 or 1) is an acyl group selected from the group consisting of the phosphorus-containing acyl groups of the following formula: R-NH-(CH ₂ ) _o -SH ( ) (wherein R and n have the meanings given above) and an aminothiol having the general formula: (In the formula, Hal is a halogen atom) The above-mentioned production method is characterized in that the halonitroethylene of the following formula is reacted in the presence of a base and an inert solvent. 5 General formula as active ingredient: [In the formula, n is 2, 3 or 4, Hal is a halogen atom, and R is optionally substituted formyl, alkanoyl, alkenoyl,
Alkynoyl, aroyl, carbamoyl, oxaroyl, alkoxycarbonyl, aryloxycarbonyl, alkylthiocarbonyl, arylthiocarbonyl, alkylthio-thiocarbonyl, arylthio-thiocarbonyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, alkylamino Sulfonyl, arylaminosulfonyl, alkylaminosulfinyl, arylaminosulfinyl, and the formula: (wherein each R° is independently an optionally substituted alkyl or aryl group, each X is independently an oxygen or sulfur atom, and each y is independently 0 or 1) An insecticide composition comprising an N-substituted-S-substituted-aminothiol, which is an acyl group selected from the group consisting of phosphorus-containing acyl groups, together with a carrier.