DD239797A1 - PROCESS FOR PREPARING NEW O-ALKYL-N-2,2-DICHLORVINYL- (THIO) PHOSPHORIC ACID OR BZW. -PHOSPHONSAEUREESTERAMIDEN - Google Patents

Abstract

The hitherto unknown title compounds are simple to prepare according to the invention by reacting O-alkyl-N- (1-hydroxy-2,2,2-trichloroethyl) - (thio) -phosphoric acid or -phosphonic acid ester amides or their chlorine substitution products, the O-alkyl- N- (1,2,2,2-tetrachloroethyl) - (thio) phosphoric acid or phosphonic acid ester amides, by reaction with zinc dust in the presence of acetic acid. The starting compounds are either known from the literature or readily accessible by analogy. The title compounds have insecticidal and acaricidal properties and are useful as pesticides.

Description

0 o

GCl ₃ -CH-NH-P-OR CCl ₃ -CH-NH-P-OR

OH X Cl X

II 'IH

wherein R and X have the abovementioned meanings, with zinc dust in the presence of acetic acid, optionally in an organic solvent, at a temperature between 10 and 8O ⁰ C for reaction.

2. The method according to point ^, characterized in that is used as the organic solvent diethyl ether, benzene, toluene or acetic acid.

3. The method according to item 1 and 2, characterized in that the zinc dust is optionally used in excess.

4. The method according to item 1 to 3, characterized in that the reaction between 20 and 3O ⁰ C is performed.

Field of application of the invention

The invention relates to a process for the preparation of hitherto unknown O-alkyl-N-2,2-dichlorovinyl (thio) phosphoric acid or -phosphonsäureesteramiden the general formula I,

Il

CCl ₀ β CH - NH - P - OR I

2 1

in the

R is methyl or ethyl and X is methyl, ethyl, methoxy, ethoxy or methylthio, which have insecticidal and acaricidal activity and are suitable as pesticides.

Characteristic of the known technical solutions

From DE-OS 2133200 and 2202855 is already known that O-alkyl-O ^ - have - dichlorvinyl-thiophosphorsäureesteramide insecticidal and acaricidal properties. These compounds can be prepared by successive action of alcohols and amines on 0-2,2-dichlorovinyl-thiophosphorsäureesterdichloride according to the scheme

S S

CCl ₀ = CH-O-PCl _{0 for} CCl ₀ = CH-OP-OR

^{2 2} (2) R « ₂ NH 2 J

hersteilen. In contrast, the isomeric title compounds are not accessible analogously.

Furthermore, it is known that the adducts formed by addition of carboxylic acid amides to chloral can be converted with zinc and acetic acid into N-2,2-dichlorovinylcarboxamides. The feasibility of this reaction, however, would be

limited to the use of N- (1-hydroxy-2,2,2-trichloroethyl) -carboxamides (Z.org.Chim., 1972, Chim. Atsetilena, 3.Tr.Vses.Konf., 1968, 79, published by Nauka, Moscow 1972; Z.obsc.Chim. 1974348).

Aim of the invention

The aim of the invention is to develop a process for the preparation of previously unknown 0-alkyl-N-2,2-dichlorovinyl (thio) phosphoric acid or -phosphonsäureesteramide.

Explanation of the essence of the invention

The object of the invention is achieved in that according to the invention 0-Alykl-N- (1-hydroxy-2,2,2-trichloroethyl) - · (thio) phosphoric acid or -phosphonsäureesteramide of formula II (variant A) or their chlorine substitution products, the 0-alkyl-N- (1,2,2,2-tetrachloroethyl) - (thio) phosphoric acid or phosphonic acid ester amides, of the formula IM (variant B),

0 0

It t

CCl ₀ -CH-NH-P-OR CCl ₀ -CH-NH-P-OR

3 ι I 3 ι ι

OH X Cl X

II ItI

wherein R and X have the abovementioned meanings, with zinc dust in the presence of acetic acid, optionally in an organic solvent, at a temperature between 10 and 80 ⁰ C for reaction brings.

The reaction is surprising in that amide bonds of the (thio) phosphoric acid or -phosphonsäureesteramide are generally much more sensitive to acid than that of the carboxylic acid amides. The process according to the invention is expediently carried out in the presence of organic solvents, such as diethyl ether, benzene, toluene or acetic acid.

Suitable reaction temperatures are between +10 and + 8O ⁰ C, preferably between 20 and 30 ⁰ C. Since the reaction is exothermic, external cooling may be necessary. When using Il (variant A) at least equimolar amounts of acetic acid are necessary, in the case of III (variant B) suffice catalytic amounts.

The zinc dust is used in equimolar amounts or in excess of 100%; The resulting zinc chloride can be removed after completion of the reaction by simply shaking out with water.

The compounds I obtained after working up are obtained as oils, which usually crystallize rapidly and can be easily obtained by analysis.

The (thio) phosphoric acid or -phosphonsäureesteramide required as starting materials of the formula II or IM are z.T. in the literature (DD-WP 137839, DE-AS 1052984 and Z.obsc.Chim. 1968, 2778) or can be prepared analogously

become. ,

embodiments

example 1

0, S-dimethyl- _A N-2,2-dichlorovinyl) thiophosphoramide (variant A). ^;

To a solution of 28.9 g (0.1 mol) of OS-dimethyl-NO-hydroxy ^^ - trichlorethyD-thiophosphorsäureamid in 30 ml of acetic acid are added at 25 to 30 ⁰ C with stirring and cooling in portions 13.1 g (0.2 mol ) Zinc dust. The mixture is stirred for 30 minutes at this temperature, then 100 ml of diethyl ether, shaken three times with 20 ml of water, neutralized the ether phase with sodium bicarbonate solution, dried over magnesium sulfate and the solvent is distilled off. This leaves 10.5 g (44% of theory) of a slightly yellow oil, ng ⁵ = 1.5450. ³¹ P-NMR (acetone): δ = 29.7 ppm. ¹ H NMR (DMSO): CH δ = 6.54ppm (dd), Jhcnh ⁼ 12.0Hz, Jhcnp ⁼ 8.0Hz.

Example 2

0-ethyl-N- (2,2-dichlorovinyl) ethanephosphonic acid amide (variant B)

A solution of 30.3 g (0.1 mol) of 0-ethyl-N- (1,2,2,2-tetrachloroethyl) -ethanphosponsäureamid in 100 ml of diethyl ether is treated with 1 ml of acetic acid and then analogously to Example 1 with 9.8 g ( 0.15 mol) of zinc dust reacted at 20 to 25 ° C. The work-up is carried out as indicated in Example 1, but without further addition of solvent. This gives 17.8 g (77% of theory) of crystalline product; after recrystallization from benzene / hexane mp. 84 to 89 ° C. ³¹ P-NMR (acetone): δ = 31.0 ppm. ¹ H-NMR (DMSO): £ Η δ = 6.57ppm (dd), Jhcnh ⁼ 12.0Hz, Jhcnp ⁼ 7.8Hz.

Examples 3 to 9

Further analogously prepared compounds of the formula I are shown in Table 1.

Tab. 1: Illustrated compounds of the formula I.

R X variant Y. (%) Fp. (Χ) ö ³¹ P (ppm, acetone) CH ₃ OCH ₃ B 59 50-58 3.8 C2H5 OC ₂ H ₆ B 75 51-62 1.2 CH ₃ SCH ₃ A 44 oil 29.7 CH ₃ SCH ₃ B 91 35-42 29.3 C ₂ H ₅ SCH ₃ B 82 61-67 27.2 C2H5 C ₂ H ₅ B 77 84-89 31.0 CH ₃ CH ₃ B 59 oil 30.0

Claims (1)

Invention claim: 1. A process for preparing new O-alkyl-N-2,2-dichloro-vinyl- (thio) phosphoric acid or phosphonic acid ester amides of the general formula I, "τ CCl ₂ β CH - NH - P - OR * in the R is methyl or ethyl and X is methyl, ethyl, methoxy, ethoxy or methylthio, characterized in that O-alkyl-N, N-hydroxy-C 1-10 -trichloroethyl-thio-phosphonic acid or -phosphonic acid ester-amides of the formula II or their chlorine substitution products, O-alkyl- Nd ^^ - tetrachloroethylthiophosphoric acid or phosphonic acid ester amides of the formula III,