DD255347A1 - METHOD OF PREPARING N- (1-AMINO-2,2-DICHLORETHYLIDENE) THIOPHOSPHORIC ACID O, S-DIMETHYL ETERIMIDES - Google Patents

Abstract

The invention relates to a process for the preparation of substituted thiophosphoric acid-O, S-dimethylesterimiden which have acaricidal and insecticidal effects. They are used as pesticides. These active substances are obtained by reacting tetrachloroethyl thiophosphorus acid amides according to the invention successively with trialkyl phosphite, triethylamine and ammonia or a primary or secondary amine at temperatures between 0 and 80 ° C., optionally in an organic solvent.

Description

R ¹ = R ^{2 is} hydrogen or methyl or R ^{1 is} hydrogen and R ^{2 is} a C ₁ - to C ₃ -alkyl group or R ¹ and R ^{2 are} part of a morpholino or piperidino ring, characterized in that N- (1, 2,2,2-tetrachloroethyl) -thiophosphoric acid-O, S-dimethy1esteramide of the formula II

J OMe · ι,

001, -CHCl-NH-P '

SMe

successively with a trialkyl phosphite, triethylamine and ammonia or a primary or secondary amine of the general formula II,

wherein R ¹ and R ^{2 have} the meanings given above, at a temperature between 0 and 80 ⁰ C implemented.

2. The method according to claim 1, characterized in that is used as Trialkylphosphit trimethyl phosphite or triethyl phosphite.

3. The method according to claim 1 and 2, characterized in that the reaction temperature is between 10 and 30 ⁰ C.

4. The method according to claim 1 to 3, characterized in that the reaction is carried out in the organic solvent.

5. Process according to Claims 1 to 4, characterized in that toluene, benzene, diaryl ether, tetrahydrofuran or halogenated hydrocarbons are used as the solvent.

Field of application of the invention

The invention relates to a process for the preparation of N- (1-amino-2,2-dichloroethylidene) -thiophosphoric acid O, S-dimethylesterimides of general formula I,

?, OMe N - P '/ ^N SMe

CHCl ₀ -C ₁ ι

^NO

R ¹ = R ^{2 is} hydrogen or methyl or

R ^{1 is} hydrogen and R ^{2 is} a C ₁ to C ₃ alkyl group or

R ¹ and R ^{2 represent} part of a morpholino or piperidino ring.

The thiophosphoric acid imides of the general formula I are novel compounds which are distinguished by acaricidal and insecticidal effects. They are used as pesticides in agriculture.

Characteristic of the known state of the art

It is already known that phosphorylated amidine derivatives of general formula A can be prepared by phosphorylation of suitable amidines with thiophosphoryl chlorides and subsequent hydrolysis and alkylation reactions (DE, OS 2758173).

1. Cl-P (OR) ₂

2. HO ₁ OH "9 OR Mu , NH-P '

^ * ^ JSXl 'SR

R ¹ = H, C ₁ - to C ₄ -alkyl or cyclopropyl

According to this known method, the title compounds are difficult to access because the corresponding dichloroacetamidines are unstable compounds (J.C.Grivas and A.Taurins, Can. J. Chem. 39, 761 [1961]).

Object of the invention

The aim of the invention is to develop a technically easy to carry out process for the preparation of N- (1-amino-2,2-dichloroethylidene) -thiophosphorsäure-0, S-dimethylesterimiden.

Explanation of the essence of the invention

It has now been found that N- (1-amino-2,2-dichloroethylidene) -thiophosphorsäure-0, S-dimethylesterimide of the general formula I is obtained, if the already known in accordance with DD-PS 137839 thiophosphoric acid amides, chloral and an inorganic acid chloride readily accessible Nd ^^^ - TetrachlorethylJ-thiophosphorsäure OS dimethylesteramide of the formula II

MeO 2

P-NH-CHCl-CCl

y o Il

MeS

successively with a trialkyl phosphite, triethylamine and ammonia or a primary or secondary amine formula

HN

in which R ¹ and R ^{2 have} the meanings given above, at a temperature between 0 and 80 ⁰ C implemented.

As is known from DD-PS 239796 that the reaction of Thiophosphorsäureesteramids of formula II with an amine and triethylamine to N- (amidomethylidene) -thiphosphorsäureesterimiden, you have to call the newly discovered reaction as extremely surprising and unpredictable, since the implementation of a If the compound of the formula II is allowed to react beforehand with a trialkyl phosphite, the course is completely different.

The coproducts formed are triethylamine hydrochloride and dialkyl phosphite, which can be separated by filtration, distillation and extraction with an organic solvent and water.

As trialkyl phosphite, trimethyl phosphite or triethyl phosphite can be used.

Preferably, the reaction should be carried out in the temperature range between 10 and 30 ° C. It can be done in an organic solvent. Suitable solvents are, in particular, benzene, toluene, diaryl ether, tetrahydrofuran or halogenated hydrocarbons.

The N- (1-amino-2,2-dichloroethylidene) -thiophosphoric acid O, S-dimethyl ester imides of the general formula I prepared by the process according to the invention are obtained as oils or crystallizing oils which are used without further purification as pesticides in agriculture can.

embodiments example 1

1.49 g (0.012 mol) of trimethyl phosphite or 1.99 g (0.012 mol) of triethyl phosphite are added dropwise with stirring to a suspension of 3.08 g (0.01 mol) of thiophosphoric acid amide of the formlline 5 ml of benzene and 5 ml of diethyl ether. The mixture is stirred for 1.5 hours at room temperature, added dropwise with further stirring 1.21 g (0.012 mol) of triethylamine and after 1 hour 0.47 g (0.015 mol) of methylamine dissolved in 1 ml of diethyl ether to. After two hours, taken up in 10 ml of diethyl ether and washed three times with 3 ml of water. After removal of the solvent, 2.40 g (92%) of oily crude product are obtained.

By column chromatography, 2.30 g (87%) of a crystalline solid can be isolated from it for analysis. NR ¹ R ² = NHMe, m.p. 76 to 78 ° C; ³¹ P-NMR (acetone); δ = 26.7 ppm. The following compounds of the formula I were prepared in an analogous manner, as indicated in Example 1:

example

NR ¹ R ²

yield n ⁸ _D or ³¹ P NMR (%) Mp. (Ppm) 72 84-85 ⁰ C 33.2 88 1.5340 26.5 68 1.5210 26.4 85 68-74 ⁰ C 26.5 86 1.5460 24.6

2 NH ₂ 3 NHEt 4 NHN-Pr 5 NHi Pr 6 NMe ₂

1.5554

1.5475

25.2

25.7

Claims (1)

1. A process for preparing N- (1-amino-2,2-dichloroethylidene) -thiophosphoric acid O, S-dimethylesterimides of general formula I, OMe // SMe CHCl ₉ -C
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