JPS6061561A - Novel aminothiol - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel N-substituted-S-substituted-aminothiol compounds and methods for their preparation.

Nitromethylene heterocyclic compounds are known to have interesting levels of insecticidal activity - for example the following compounds are particularly exemplified in British Patent No. 1. Ta/3. See Tata/No. Specification. Traditionally, N-substituted derivatives of compound A and their analogs have been synthesized by converting the heterocyclic compound A or its analogs into derivatives - see, for example, British Patent No. 1J/3. See Tata/No. Specification, Page T, JJ-Otsu/Line. 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 that avoids the need to use the heterocyclic intermediate Compound A. This new process, claimed in a pending application, uses as starting material a novel N-substituted-
Using S-substituted-aminothiols.

These N-substituted-8-substituted-aminothiols are novel compounds and form the subject of the present invention. The aminothiols are easy to obtain and can be synthesized economically. Surprisingly, some of the compounds also have insecticidal activity in their own right.

Accordingly, the present invention relates to the following general formula: %() where n is 2, 3 or ≠, Hat is a halodane atom, and R is an optionally substituted compound derived from an organic acid. is a good acyl group).

Aminothiols of general formula l are preferably n=, 2 or F
i3, preferably n=3. The halogen atom is preferably chlorine, fluorine or bromine.

The optionally substituted group represented by R is derived from an organic acid. Is the organic acid mono- or polycal d? It can be a carbamic acid, a substituted carbamic acid or a carbonic acid or a mono- or di-thio analog thereof; It can be a sulfonic acid, a sulfinic acid, an aminosulfonic acid or an aminosulfinic acid; or it can be a phosphorus-containing acid. Specific examples of suitable acyl groups derived from nucleic acids are the following optionally substituted groups: formylalkanoylalkenoylalkynoylaroylcarbamoyloxaroylalkoxyl? Nylaryloxycargenylalkylthiocarvinylarylthiocarbnylalkylthiocar? - ruthiothiocarbonylalkylsulfonylarylsulfonylalkylsulfinylarylsulfinylalkylaminesulfonylaryllaminosulfonylalkylaminosulfinylarylaminosulfonyl compound.

Formula (wherein each Ro is independently an optionally substituted alkyl or aryl group, sb, each X is independently an oxygen or sulfur atom, sb, and each y is independently 0)
or/is a phosphorus-containing acyl group.

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 g″1Illll or ≠ 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, alkylthiomialkenyl and alkynyl of up to 2 carbon atoms; and optionally fluorine, chlorine, aryl, aryloxy and arylthio optionally substituted with /l or more groups selected from bromine, iodine, C(/-≠)-alkyl, nitro and cyano;
Preferably selected from phenyl, phenoxy and phenylthio.

Particular examples of aminothiols according to the invention are those of the general formula W = 3, Hal is chlorine, and R is one of the following acyl groups: nialyl (e.g. benzoyl), alkanoyl (e.g. 2 to 77 A carbon atom can be replaced by haloalkanoyl (e.g. containing from 77 carbon atoms and/or ! chlorine, fluorine or bromine atoms), arylsulfonyl (e.g. evaphenylsulfonyl), alkylsulfonyl (e.g. C1-1°alkylsulfonyl) , (Alkyl-0)2P(0)- (e.g. each alkyl group contains 7 to ≠ carbon atoms), (Alkyl-0)2P(S)- (e.g. each alkyl group contains / to ≠ carbon atoms) (phenyl-o)2p(o)-, alkylsulfonyl (e.g. containing from 71 carbon atoms), alkylthiocarvinyl (e.g. containing from 2 to 77 carbon atoms), and dialkylcarbamoyl (e.g. each alkyl group is /
or ≠ carbon atoms), where each of the above acyl groups can carry methyl, nitro, chlorine or more substituents.

The present invention provides an aminothiol having the following general formula: %(%) (in which R and n have the above-mentioned meanings) and a halonitroethylene having the general formula: (wherein Hal is a halodane atom), General formula comprising reacting in the presence of a base preferably selected from alkali metal or alkaline earth metal or ammonium hydroxides, carbonates, bicarbonates or acetates in the presence of an inert solvent. The present invention includes a method for producing an N-substituted-S-substituted aminothiol of I. Conveniently the base is an alkali metal hydroxide such as potassium hydroxide or potassium hydroxide.

Any 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.

The reaction may proceed at room temperature, but generally it is between =30° and -50°C, suitably 1: -, l! 00 to +
It can be carried out at a temperature of 30°C.

The molar ratio of aminothiol ■ and halonitroethylene ■ is /
:l/L to 2:/. However, it is generally preferred to have an excess of halonitroethylene, such that the preferred molar ratio is within the range /:/ to /:≠. A mixture of base and aminothiol H (preferably in equimolar proportions) is added to halonitroethylene III (preferably t
Good results are achieved when L<u present in molar excess).

N-substituted aminothiols of formula (1) can be prepared by N-acylation of the corresponding unsubstituted aminothiols.

Compounds of formula I are converted to the corresponding pesticide-active heterocyclic compounds by reaction with base in the presence of an inert solvent. 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, hydrocarbons and sulfur-containing solvents. The reaction is carried out at a temperature of 13°C to 10°C, conveniently at room temperature. For example, the molar ratio of base and amide is /
:2 or 2:/, preferably /:/ or 2:/
can be.

The N-substituted-S-S-substituted-aminothiols according to the invention also exhibit agricultural and forestry activity, particularly against harmful insects.
That l-1 is 8i. dnn master. Eyes ÷ ÷ xya11-
Shows activity against pests such as.

Accordingly, the present invention includes agrochemical compositions comprising an N-substituted-8-substituted-aminothiol compound of general formula I 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/Preparation of N-ySef-S-(/-chloro-!-nitroethenyl)-3-aminopropanethiol N-acetyl-3-aminopropanethiol (4'00 m!?) in methanol (3 ml') ) in methanol (3me) to sulfurium hydroxide (/20 m
9) Added over rough 0 minutes. This mixture was then added to /,/-dichloro-2-nitroethene (93; Omg) in methanol (5 Inl) at 0°C over 20 minutes. This was stirred for a further 20 minutes and then N
Saturated with aCl. 2%) TCI and extracted with methylene chloride. The product was purified on a silica dull column. Yield IA 00 m9: oil.

Example 2 N-phenylsulfonyl-8-CI-chloro-2-
Preparation of 3-amino-zolo-5-thiol hydrochloride (5 g) with sodium methoxide (N87 g; methanol 2j'd)
was added and the mixture was allowed to cool.

Solvent was removed. To the product was added methylene chloride (0-) and triethylamine (ty>) and to it was added phenylsulfonyl chloride (7g) in methylene chloride (4tOrnl) dropwise over 30 minutes at 0°C.2g at room temperature. After minutes the product was washed with 2 T HCl and triturated with diethyl ether.Disulfide, bis-(N-phenylsulfonyl-3-aminopropyl)-
Yield of disulfide B, 211° The disulfide (3,/9> was treated with water (2, Jl), methanol CjOd> and 70 drops of 70 tif (triphenylphosphine C2511 in C1), set to 17
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-aminogulononothiol/, JF.

Analysis: Calculated value = Cl1 - Otsuza;
N-phenylsulfonyl-3-amitsunoroba/thiol (23/m9) in methanol (Jml)
) of sodium hydroxide (♂0) in methanol was added over 5 minutes, and the mixture was then mixed with /,/-dichloro-2-nitroethene (,2,!i') in methanol (2).
tl-m9) over 20 minutes at 0°C. The reaction mixture was kept at 0° C. for 30 minutes and then saturated with NaCl. Poured into 2% HCl and extracted with methylene chloride. The product was purified on a silica dull column. Yield: 3 rng; melting point: 10! -1g℃.

Analysis - Calculated value ", C39,2", H3,9: N and 3% Measured value: C39, O; H3, g; N and 2 Example 3 N-benzoyl-5-(j-nitro-/-chloro ethynyl)-
Production of 3-aminozolopanthiol Methanol (/,
To N~benzoyl-3-aminopro-yanthiol (7♂oIv) in 2me) was added dropwise sodium hydroxide (/θlψ) in methanol at 0°C under nitrogen.

This mixture was then mixed with methanol (20 ml) at 0°C under nitrogen.
) in /,/-dichloro-2-nitroethene (/,,2
g) was added dropwise over 20 minutes. The reaction mixture was diluted with NaCl
It was saturated. Pour into 2 ml of MCI and extract with methylene chloride.

The product was purified using a silica dull column. Yield, 2
j2■.

Analysis: Calculated value: Cl1t7.9''', Hll, 3
”, N9.3 CH measurement value: C'Alr, 3 ”, Ht,
3'', N9.3% Example≠-// Compounds of formula 9 were prepared as detailed in Table IK in a manner similar to that described in Examples/--3.

Example/2 Pesticide activity The pesticide activity of some of the compounds of the present invention was determined in a patent application filed in 1973.
It was evaluated using the method described in Example 3≠ of No. 25379.

Example: The compound negative/ is found in the house fly (Musc adome).
stlca) and killed all test insects in a test against 5podoptera.
1ittoralis and Ae. aegypti (Ae
All test insects were killed in the test against d e saegypti).

Example 73 Preparation of N-phenylsulfonyl-2-nitromethylene-,2H-/,3-thianone. Potassium t-butoxide (33; m) in t-butanol (2 ml) to mother antithiol (100 m9)
9) was added over 6 minutes. After 20 minutes at room temperature, the reaction mixture was poured into 2% CI saturated with NaCl and then extracted with methylene chloride.

The product was purified on a silica dull column. Yield j≠mg
; Melting point: 107°C.

Analysis: Calculated value: C'A11.0; HIl, o:N
9.2 Measured value: C4LIAO:H'AO;N9.3 Name of agent Kawahara 1) - Continuation of the first page of ears 281102'/330-4

Claims (6)

[Claims] (1) General formula: % formula % () (in the formula, n is 2, 3 or G, Hal is a halogen atom, and R is an optionally substituted acyl group derived from an organic acid) ) N-substituted-S-substituted-aminothiol. (2) Formyl, alkanoyl, alkenoyl, alkinoyl, aroyl, carbamoyl, oxaloyl, alkoxycarbonyl, aryloxycarbyl, alkylthiocarbinyl, arylthiocarbinyl, alkylthio-thiocarbyl, arylthio-, in which R may be optionally substituted thiocarbunyl, alkylsulfonyl, arylsulfonyl, alkylsulfinyl, arylsulfinyl, alkylaminosulfonyl, arylaminosulfonyl, alkylaminosulfinyl, arylaminosulfinyl, or formula = (wherein each Ro
are independently optionally substituted alkyl or aryl groups, each X is independently an oxygen or sulfur atom, and each y is independently θ or /)
2. The compound according to claim 1, wherein the compound is an acyl group selected from phosphorus-containing acyl groups. (3) n is 3, Hal is chlorine, and R is aroyl, alkanoyl, haloalkanoyl, arylsulfonyl, alkylsulfonyl, dialkyloxy-
oxophosphorus, diphenoxy-oxophosphorus,
-1 with dialkyloxythiophosphorus, dialkylcarbamoyl, alkoxycarbunyl or alkylthiocarvinyl, the R group optionally being substituted with/or more methyl, nitro, chlorine, fluorine or bromine substituents; Claim 1 or 2 characterized by
Compounds described in Section. (4) n is 3, Ashi, R is Polmyr, C(,2
-j) 7 # force/ilmata haloalkanoyl, benzoyl, halobenzoyl, phenylsulfonyl, halophenylsulfonyl, 1fc (ri each yl # # group 7
The compound according to claim 1, which is a sialgylcarbamoyl, dialkylaminosulfonyl, dialkoxythiophosphorus or dialkoxyoxophosphorus having 5:/≠ carbon atoms. (5) A method for producing a compound according to claim 1, which has the general formula: % formula %() (wherein R and n have the meanings specified in claim 1) The method for producing aminothiol and halonitroethylene of the general formula: (wherein mat is a herodane atom) in the presence of a base and an inert solvent. (6) An agrochemical composition containing an N-substituted-8-substituted-aminothiol according to any one of claims 1 to 5 as an active ingredient together with a carrier.