SU1351515A3 - Method of producing ether chlorides of ethylthiophosphonic acid - Google Patents

Abstract

The invention relates to phosphonic acid esters, in particular, to a method for the preparation of ethyl chloroformate esters of ethyl ethyl phosphate acid (1) the common form {CHly-CH2-P (0) (SR) Cl, where a) R -CCCH,) or K-C (CH3), - CHjCHj, which can be used as intermediates for the preparation of diesters of thiophysulfonic acids (II), exhibiting insecticidal activity. The goal is to develop an accessible method for obtaining new compounds of the indicated class. Compounds 1 are prepared from ethylphosphonic acid dichloride and the corresponding thiol in toluene in the presence of triethylamine. Compound II is obtained by the interaction of compound I and ethylene Na or phenol in toluene or acetone in the presence of triethylamine in a nitrogen atmosphere at 18-20 C. A 1% solution in acetone or compound II exhibits a high insecticidal effect: the mortality of Diabrotica undecimpunctata 80- 100%, with no phytoxicity. 1 tab. JV with JV

Description

SR

, 2 -CH g - °

- CH,

11351515

The invention relates to the chemistry of organophosphorus compounds with a C-P in the mouth, and specifically to a process for the preparation of ethyl thio-osonic acid ethyl esters of the general formula

 C1 C, H5-Rich

ABOUT

where R is -C (CH3) 3 or-C (CHj) which can be used as intermediates for the preparation of thiophosphonic acid diesters exhibiting insecticidal activity.

The aim of the invention is to develop an affordable method for the preparation of ethyl thiophosphonic acid ester chlorides, which are used to produce effective insecticides. ;

Approximately 1, the acid chloride. S-tert-butyl-ethyl-thiophosphonic acid

BUT

15

with a

x

Cahs-p

, C1

 S

about

-C-CH-i

I

SN

25

18 g (0.2 mol) of 2-methyl-2-propanethiol are added to a solution of 32.0 g (0.22 mol) of ethylphosphonic acid dichloride in 200 ml of toluene. With stirring and dropwise, 22 g (0.22 mol) of triethylamine is added and the reaction temperature is maintained at 30-35 ° C while adding

amine; the mixture continues to stir until the next day at room temperature. The amine hydrochloride is filtered off and the toluene solution is concentrated under vacuum. 200 MMP hexane is added and the solution is filtered again.

The solvents are removed by distillation under vacuum and the residual liquid is distilled, the product (25 ° C in 72.5% yield) is distilled at 72-73 ° C at 0.7 mm Hg. The structure was confirmed by H1-1P spectroscopy in CDCTj with tetramethylsilane as an internal standard.

A singlet at 1.7 ppm (S-tert-.-Butyl), two triplets at 1.2 and 1.5 ppm (CHj), a multiplet at 2.4 ppm

(CH)

CoHs-PC СССНз ГСН СНз

 °

,

15

Examples of the use of the compounds obtained for the synthesis of biologically active compounds.

Example T. Preparation of o-ethyl S-tert-butyl ethyl thiophosphonate.

To a solution of 8.0 g (0.048 mol) of S-tert-butyl-methylthiophosphonic acid chloride prepared in Example 1 in 50 MP of toluene was added a solution of sodium ethylate (0.04 mol) in 40 ml of standard. The addition is carried out dropwise with stirring, and the reaction is carried out under a nitrogen atmosphere. Stirring is continued until the next day at room temperature, then about 80% of the solvents are removed under vacuum. 100 ml of toluene are added and the sodium chloride formed during the reaction is filtered off. The toluene is removed under vacuum and the residual liquid is distilled. Product (5.8 g, yield 69.6%)

25

Jq

distilled at 69-72 ° C under a vacuum of 0.2 mm Hg.

PMR analysis of this compound confirms the indicated structure.

In a similar way, compounds of the general formula

I

ABOUT

.OKi SR,

Jq

35

the value of the radicals and the boiling point of which are listed in Table. one. -..

Table 1

45

50

Example 6. Obtaining o-phenyl-S-tert-butyl ethyl thiophosphate.

To a solution of 5.0 g (0.025 mol) of the acid S-tert-butyl-ethylphosphonic acid obtained in Example 1z and 2.35 g (0.025 mol) of phenol in

31

20 ml of acetone was added 2.5 g (0.025 mol) of triethylamine.

The mixture is kept under a nitrogen atmosphere with stirring at room temperature.

The reaction mixture is added with 100 m of toluene and washed once with 5% sodium hydroxide solution and twice with water. The solution was dried over anhydrous sodium sulfate and the solvent was removed by distillation in vacuo. The residual liquid is exposed to high vacuum (0.2 mm Hg) for 15 minutes. A target product is obtained, the structure of which is confirmed by PMR spectrometry in CDCIg with tetramethylsilane as an internal standard.

Compounds of the general formula are obtained in a similar manner.

CoHg-Px

X o

the value of the radicals in the table. 2

ORi SR

which

table 2

o-methyl-phenyl

p-chloro-phenyl

Phenyl

m-trifluoromethylphenyl

p-Fluoro-phenyl

p-chloro-phenyl

o-chloro-phenyl

Phenyl

tert-vutil

Tert-Amin

tert-aghsh

- V

The test of diesters of ethylphosphoic acid for insecticidal activity was carried out with respect to Diabrotica (Corn rootworm) and beech surveyors (Southern armuwoun).

0

Characteristic intensity with respect to Diabrotica. (CRW).

The test compound is used in the form of a 1% solution in acetone or ethanol. The basic solution is then diluted with an aqueous solution of tween-20 to the desired concentration (i.e. 100; 10; 1; 0.1; 0.005 ppm), 2 ml of this solution is pipetted into a 9-cm Petri dish containing for a layer of filter paper. The larvae of the second stage of development of water in the cup, which is then closed. 5 After two days (48 h), the number of dead and dead larvae is counted.

Insecticidal activity is from the very beginning the contact action 0 and the effect due to evaporation and very little due to ingestion. The results are presented in table. 3

The intensity is typical for SpodopCera 5 eridanica (AW) beech surveyors.

A basic 1% solution of the test compound is prepared in acetone, then diluted to the desired concentration with an aqueous solution containing 500 ppm. Tween - 20. Lima (Lima bean) bean leaves are immersed in the solution and transferred to Petri dishes (XOx x 15 mm) containing two layers of moistened 2 MP of filter paper water. 5 Each Petri dish contains one leaf and. remains open to. dry the solution on the sheet. 5 larvae are placed on a sheet in the third stage of development of beech dredmers (Spodo-0 ptera Eridania) in a Petri dish.

The insects are harvested for 72 hours, after which the mortality is calculated. The results are presented in Table. 3

Table3

50

55

95

75

100

100

100 100

100

100

90

Comparative trials. soil resistance (Diabrotica undecim - punctata SC.I.).

Fertile land was treated with compounds to obtain samples of different concentrations. The soil was kept at room temperature in shaded glass vessels and. Diabrotica larvae were infected at regular intervals.

The compounds are dissolved in acetone and introduced into moist soil to obtain the required concentrations. Each sample was thoroughly mixed and decomposed so that excess solvent could evaporate. Thereafter, the soil is placed in dark glass jars and stored at room temperature.

VNIIPI Order 5301/59 Circulation 348 Subscription Proizv.-poly. pr-tie, Uzhgorod, st. Project, 4

When tested, about 20 g of treated, moist soil (moisture 23%) is placed in a glass vial containing one sprouted corn and 2.5 ml of distilled water. Carried out four treatments. Py-seven-day larvae D..U. added to each bubble. Bubbles

they are closed with air permeable plugs and kept at 25 ° C for four days, after which the mortality rate of the larvae has been established.

As a result, when the concentration in the soil is twenty parts per thousand, the compound according to Example 9 of the present invention causes 100% mortality of the larvae On the day the compound is introduced into the soil, as well as 14 days after the introduction. Under the same conditions, the known compounds 0-chlorophenyl-S-ethylthiophosphonate and 0-methylthiophenyl-S-ethyl ethylthiof.phosphonate provide

respectively, 45 and 85% of the larvae die on the day of application to the soil and become completely ineffective after 14 days. These results show the excellent insecticidal activity of dysphers.

Znithphosphonic acid, which can be used to fight against many types of insect parasites, such as Coleoptera (especially Diabrotica sp.) and Lepidoptera (especially beech surveyor). In addition, the phytotoxicity of the treated plants was not observed in these tests.

P-rmula of the invention

The method of obtaining ether chlorohydride of ethylthiophosphonic acid of the general formula

45

SpN.-R II o

-С1 SR

50

whereCS (CH3) s or-C (CH,) 2-CH2-CH3 j

 that is, ethylphosphonic acid dichloride-anhydride is reacted with the corresponding thiol in toluene in the presence of triethylamine at 30-35 ° C.

Claims (1)

Claim Method for producing ethyl thiophosphonic acid ester chlorides of general formula C ₂ H ₅ —P < ^Cl • Il SR 0 where R is —C (CH ₃ ) ₃ or —C (CH ₃ ) ₂ —CH ₂ —CH ₃ ,. consisting in the fact that dichlorohydride 5 ° ethylphosphonic acid is reacted with the corresponding thiol in toluene in the presence of. triethylamine at 30-35 C. VNIIIPI Order 5301/59 Circulation 348 'Subscription Custom polygr. ave, city of Uzhgorod, st. Project, 4