DE2323720C3 - Thiazoltriazolylthionophosphoric acid esters, their preparation and use - Google Patents

Description

wherein R ¹ and R ^{2 are} methyl, ethyl or isopropyl groups.

2. Use of the thionophosphoric acid ester according to claim 1 as an insecticide or acaricide.

720

ated thiophosphoryl halide with the corresponding 2-Hydroxy-5-methyl-6-halothiazolo [3,2-b] -s-thiazole in the presence of dimethylformamide or dimethyl sulfoxide as an inert solvent and an alkaline condensing agent. These thionophosphoric acid esters according to the main patent are suitable as insecticidal or acaricidal active ingredients.

It has now been found, according to the invention, that thionophosphoric acid esters within the meaning of the claim are also effective insecticides or acaricides and are superior to the esters known from DT-OS 1942015, having an analogous structure but unsubstituted in the 6-position. For example, the acute oral toxicity LD ₅₀ for mice for O, O-dialkyl-2- (5-ethyl-bbromothiazolo [3,2-b] -s-thiazolyl) -thionophosphate

200 mg / kg.

The invention is further illustrated by the following comparisons and examples.

The main patent relates to thiazolotriazolylthionophosphoric acid esters the formula

CH,

R ^: O

wherein R 'and R ^{2 are} methyl or ethyl and X is chlorine or bromine. These phosphoric acid esters are produced by reacting the correspondingly substituted

example 1

O, O-Dimethyl-2- (5-ethyl-6-bromothiazolo [3,2-b] -s-triazolyl) -thionophosphate was prepared by adding 3.1 g of 2-hydroxy-5-ethy! -b-bromothiazolo [3,2-b] -s-thiazole, I g Potassium carbonate and 2.1 g O.O-dimethylthionophosphorychloride, dissolved in 15 ecm dimethylformamide, held at 35 to 40 ° C. for 4 hours with stirring. The reaction mass was poured into water and made alkaline with a sodium hydroxide solution to remove it. Crystallize reaction product. This was filtered off, washed with water and dried. It was recrystallized from η-hexane. 3.35 g of white needles with a melting point of 55 to 50 C. are obtained.

Elemental analysis for C8HiiNjO3S2BrP:

Found C 25.63, H 2.75. N 11, S 17.21. Br 21./4, P 8.18;

calcd C 25.80, H 2.95, N 11.29, S 17.34, Br 21.50, P 8.33.

Example 2

3.1 g of 2-hydroxy 5-ethyl-6-bromothiazole (3,2-b -) - s-thiazole, 1 g of potassium carbonate and 2.32 g of Ο, Ο-diethylthionophosphoryl chloride, dissolved in 15 ecm of dimethylformamide, implemented by heating to 40 to 50 ⁰ C for 4 hours. After working up as in Example 1, 4 g of white crystals of O, O-diethyl 2- (5-ethyl-6-bromothiazolo [3,2-b] -s-thiazolyl) thionyl phosphate were obtained. Mp. 67 to 68 ⁰ C.

Elemental analysis for CioHisN303S2BrP:

Found C 29.79, H 3.91, N 10.27, S 16.00, Br 20.11, P 7.79;

calcd C 30.00, H 3.75, N 10.50, S 16.00, Br 20.00, P 7.75.

Example 3

3.1 g of 2-hydroxy-5-ethyl-6-bromo [3,2-b] -s-triazole, 1 g of potassium carbonate and 2.97 g of Ο, Ο-diisopropylthionophosphoryl chloride, dissolved in 15 ecm of dimethylformamide, were in 3 Reacted for hours with stirring at 40 to 45 ° C. After working up as in Example 1, 4.01 g of white needles Ο, Ο-diisopropyl 2- (5-ethyI-6-bromothiazolo [3,2-b] -s-thiazolyl) thionophosphate with a melting point of 50 to 51 ⁰ C.

Elemental analysis for Ci2Hi <»N3O3S2BrP:

Found C 33.70, C 4.71, N 9.82, S 15.00, Br 18.64, P 7.04;

calculated C 33.64, C 4.43, N 9.81, S 14.95, Br 18.69, P 7.24.

Comparative experiment 1

In this comparative experiment, the insecticidal effectiveness of the substance according to the invention is demonstrated Example 2 shown versus house flies.

Comparative solutions of the same concentration were formed in acetone and the effectiveness was determined.

20 houseflies (Musca domestica Linne) would be at the breast side 1 μΐ of the active ingredient in acetone solution treated and held at a temperature of 25 ⁰ C and a humidity of 65%. The dead flies were counted 24 and 48 hours after the treatment and the mortality was calculated. The results are shown in Table I below.

Table I. Compound active ingredient active ingredient

0 ^ g / 1 row 0 ^ 5 ng / 1 fly

after after after after

24h 48h 24h 48 mercenary

Comparison*)

phosphate.

100 100 30

70 70 0

40 10

Comparative experiment 2

Here, the insecticidal effectiveness of the substances according to the invention according to Examples 1 to 3 is against Cabbage worms identified ten armyworms (Leucaiiia separata Walker) bred over several generations were subjected to the investigations.

A corn leaf was immersed in an aqueous emulsion of the emulsifiable concentrate for 30 seconds and air-dried, and then placed on a 9 cm diameter filter paper in a dish. The worms were also introduced into these. After 1 or 3 days, the dead animals were counted and the mortality was determined.

Table II

Active ingredient active ingredient concentration

313 ppm 15.7 ppm 7.S ppm

1 day 3 days 1 day 3 days 1 day 3 days

2 3 Comparison*

·) O, ¹
phosphate

100 100

100 100

100 100

70 100

60 90 60 30th

100

100

100

80

50

60

50

90

100

90

Comparative experiment 3

It was found that the substances of Examples 1 and 2 have a very good activity against mites. to About 30 adult female desert spider mites (Tetranychus desertorum Banks) on the main leaves of French beans, the 7th up to 10 days old, applied. After one day, the damaged mites were removed from the plants

ίο removed, and the active ingredients to be examined were now sprayed on as an aqueous suspension of the emulsifiable concentrate and after the first and third day the dead mites counted and the mortality calculated. It was found that on one Concentration of 500 ppm after 3 days the effectiveness of the two substances according to the invention could be judged very much.

Comparative experiment 4

The insecticidal activity of the compound from Example 3 compared to the comparison compound was demonstrated Rice stem borer examined and 20 hatched larvae of the rice stem borer (Chilo suppressalis Walker) inoculjert on potted rice, height 30 to 40 cm, four per pot. One week after the inoculation 30 ecm of a certain concentrated solution were sprayed onto the hoop with the hatched larvae and the pots are kept at room temperature. A week later the rice was opened and the The dead reissing borer was counted and the mortality was determined from this.

Table III Active substance mortality (%)

3IJ ppm 15.6 ppm 7.8 ppm

comparison

100
100

91

84

Claims (1)

Claims: 23 1. Thiazoltriazolylthionophosphoric acid ester of the formula N N- R ¹ OS Jl i VII Λ Λ / Ρ —O N S Br / R ² O