DE2262189C3 - Thionophosphoryl-thienyl- (2) -undfuryl- (2) -alpha-oximino-acetonitrile compounds and pesticides containing these compounds - Google Patents

Description

in the X chlorine, R methyl or ethyl and Z sulfur or in the X hydrogen, R ethyl and Z represents oxygen. > 5

2. Pesticides containing a compound according to claim 1 as an active ingredient in addition to the usual Thinners.

The subject matter of the invention is defined in the claims.

The compounds of the invention can conveniently be prepared in the following manner will:

HCl

CH ₂ O

KCN

acetone

N / A
Butyl-ONO

Il

CI-P (OR) ₂

CH ₂ Cl

CH ₂ CN

"-C = NOH

CN

^30th

35

40

45

-C = NOP (OR) ₂

CN

55

The compounds according to the invention have a strong inseclicidal and acaricidal activity relatively low toxicity to warm-blooded animals and, at the same time, low phytotoxicity. your Effect sets in quickly and lasts for a long time.

Insects that can be effectively controlled with the compounds according to the invention are those chewing insects, as well as certain larvae and caterpillars and also those insects which are harmful to their Have an effect below the surface of the earth. Numerous mites and ticks can also be infected with the Compounds according to the invention are effectively combated

The compounds according to the invention can be processed into pesticides in the customary manner. These are in the form of solutions. Emulsions, suspensions, emulsifiable concentrates. Spray powders. Pastes, soluble powders, dusts and granular preparations are used.

The pesticides according to the invention contain the compounds according to the invention for direct Application or for field use generally in meniicn of 0.00001 and 20 percent by weight, preferably from 0.0002 to 20 percent by weight, in particular from 0.01 to 2 percent by weight on the mix.

example 1
«-Oximino-2-fury! Acetonitrile

A cooled solution of 6.9 g (O ^ mol) Natriummctall in 200ml of ethanol is added dropwise at 10 C with 30.9 g (0.3 mol) of butyl nitrite and then with 32.1 g (0.3 mol) of 2-Furanacetonitril. The mixture is stirred for 1 hour at 10 ° C. and then for 3 hours at room temperature. The dark-colored mixture is then evaporated in vacuo. The sodium salt is then washed with ether and dissolved in water. The solution is acidified with concentrated hydrochloric acid (up to a pH of 3). The solid is filtered off, washed with water, dried and recrystallized from chloroform. 21 g of product with a melting point of 122 to 124 ° C. are obtained.

Ο, Ο-Diälhylthionophosphoryl-.i-oximino-2-furylacetonitrile

A mixture of 6.8 g (0.05 mol), / - Oximino ^ -furylacctonitril and 5.05 g (0.05 mol) Triethylamine in 200 ml of diethyl ether with stirring with a solution of 9.4 g (0.05 mol) of diethyl chlorothiophosphate in 25 ml of diethyl ether. The reaction mixture is stirred for 8 hours and then in succession washed with water, dilute sodium hydroxide solution and again with water. Then will the mixture dried over magnesium sulfate. The drying agent is filtered off and the product is evaporated the resulting filtrate in vacuo. A solid product is obtained, which after recrystallization from pentane provides a solid with a melting point of 46 to 48 ° C.

Example 2
<(- Oximino-5-chloro-2-thienylacetonitrile

A solution of 2.3 g (0.1 mol) of sodium metal in 50 ml of ethanol, which was ^{cooled to 0 °} C. in an ice bath, is added, while stirring, with 15.8 g (0.1 mol) of 5-chloro-2- thienylacetonitrile. When the addition is complete, 10.3 g (0.1 mol) of butyl nitrite are added. The reaction mixture is stirred for 1 hour at 0 ° C. and 3 hours at room temperature. The mixture is then evaporated to dryness in vacuo and the residue obtained is washed with ether. The sodium salt of the product is dissolved in water and the solution is acidified with concentrated hydrochloric acid ( The solid fraction is filtered off, washed with water, dried and recrystallized from chloroform. This gives the desired compound with a melting point of 174 to 176 ° C.

O.O-diethylthtoflophosphoryl-K-oxirnir.o-S-chloro-2-thicnylaccionhril

A solution of H.3g (0.06 mol) is carried Diethyl chlorothiophosphate dropwise with stirring into a solution of 11.16 g (0.06 mol) u-oximino-S-chloro-I-lhienylacetonitrile and 6.06 g (0.06 mol) of triethylamine in 200 ml of diethyl ether. One stirs that Mixture for 4 hours and then wash it successively with water, dilute sodium hydroxide solution and again with water. Then the solution is dried over magnesium sulfate, filtered and the filtrate is concentrated, until you get an oil. The oil will after standing brought to crystallization. Recrystallization from pentane gives a pure substance with a melting point of 46 bis 47 C.

Example 3

O ^ -Dirneihylthionophosphoryl-u-oximino-S-chloro-

2-thienylacetonitrile

A solution of 6.1 g (0.033 mol) is added ι-oximino-5-chloro-2-thienylacetonitrile and 3.4g (0.033 Moij triethylamine in 200 ml of diethyl ether with a solution of 5.2 g (0.033 mol) of dimethylchlorothiophosphate in 25 ml of diethyl ether. The mixture obtained is washed successively with water, diluted sodium hydroxide solution and again with water. The solution is dried over magnesium sulfate, filter it and concentrate the filtrate until an oil is obtained. The oil is then caused to crystallize. After recrystallization from pentane, a product of melting point 48 to 50 ° C. is obtained.

Claims (1)

Palent claims: 1. Thionophosphoryl-; hienyl- (2) - and -furyl- (2) - «-Oximinoaeetonitrile of the formula X- JC = NOP (OR) ₂ / \ ίο CN