CS215464B1

CS215464B1 - New esters of thiophosphoric acid and their preparation

Info

Publication number: CS215464B1
Application number: CS877280A
Authority: CS
Inventors: Vaclav Konecny
Original assignee: Vaclav Konecny
Priority date: 1980-12-12
Filing date: 1980-12-12
Publication date: 1982-08-27

Abstract

Estery kyseliny tiofosforečnej všeobecného váprca V v ktorom R1 znamená alkyls 1 až 4 atómami uhlíka, R2 znamená alkoxy, N-alkylamido, N,N-dialkylamido, kde alkyl vždy obsahuje 1 až 4 atomyuhlíka, fenyl, 2-alkexyetoxy s 1 až 4 atómami uhlíka v alkoxyskupine. Sposob přípravy zlúčenín V reakciou zlúčeniny vzorca VI H0 - S s esterom kyseliny chlórtiofosforečnej všeobecného vzorca VII v ktorom R1 a R2 majú úž uvedený význam v prostředí organického riedidla, ako je aceton, metylketón, butylacetát, dimetylformamid, pri teplote 25 až 100 °C.General calcium thiophosphoric acid esters V in which R 1 means alkyl with 1 to 4 carbon atoms, R 2 means alkoxy, N-alkylamido, N,N-dialkylamido, where alkyl always contains 1 to 4 carbon atoms, phenyl, 2-alkoxyethoxy with 1 to 4 carbon atoms in the alkoxy group. Method of preparation of compounds V by reaction of compound of formula VI H0 - S with ester of chlorothiophosphoric acid of general formula VII in which R1 and R2 have the previously mentioned meaning in the environment of an organic diluent such as acetone, methyl ketone, butyl acetate, dimethylformamide, at a temperature of 25 to 100 °C.

Description

Czechoslovak Socialist Republics (19)

DESCRIPTION OF THE INVENTION

TO CERTIFICATE 215464 (11) (Bl)

(51) Int. Cl.3C 07 F 9/18 (22) Entries 12 12 80 (21) (PV 8772-80) (40) Published 30 10 81

INVITATION OFFICE AND DISCOVERY (45)

Published 01 01 85 (75) · ;. «

Author of the invention KONEČNÝ VÁCLAV RNDr. CSc., BRATISLAVA (54) New esters of thiophosphoric acid and their method of preparation

Thiophosphoric Acid Esters V R 2 '

Wherein R 1 and R 2 are as defined above in an organic diluent environment such as acetone, methyl ketone, butyl acetate, dimethylformamide, temperature 25 to 100 ° C. V 1 in which R 1 is alkyl of 1 to 4 carbon atoms, R 2 is alkoxy, N-alkylamido, N, N-dialkylamide, wherein alkyl is always 1 to 4 carbon atoms, phenyl, 2-alkexyetoxy of 1 to 4 atoms carbonyl alkoxy.

A method of preparing compounds V by reacting a compound of formula VI

H0 - S

with a chlorothiophosphoric acid ester of formula VII iPo

215464 215464

The present invention provides novel thiophosphoric acid esters and processes for their preparation. The compounds of the present invention may be used as insecticides.

From the literature, esters of thio-dithiophosphoric acid of the general formulas I-IV / HO /, P - S - N - OOOH * 'H hs / 0 / ir / 1 / are known.

/ BO / jP - S - H - 50J - RJ / 11 / CO - CH,

Where R is alkyl, aryl, R 1 is alkyl, phenyl, R 2 is alkyl prepared by the action of N-chloramide; resp. N-chlorimide with thio-dithiophosphoric acid alkaline phosphate (Ger. Pat.1.068.252).

New thiophosphoric acid esters of the formula V ^-CO 'X * have now been found in which R1 is alkyl of 1 to 4 carbon atoms, R2 is alkoxy, N-alkylamido, N, N-dialkylamido, where alkyl is always it contains 1 to 4 carbon atoms, phenyl, 2-alkoxyethoxy having 1 to 4 carbon atoms alkoxy, 2-chloroethoxy.

At the same time, a method of preparing a general formula V by reaction of a compound of formula VI is determined

with a chlorothiophosphoric ester of formula VII and an ICO.

P - Cl in which R 1 and R 2 are as defined above in an organic diluent environment such as acetone, methyl ethyl ketone, dioxane, butyl acetate, dimethylformamide and the like, at a temperature of 25 to 100 ° C.

The following examples illustrate but do not limit the invention. and 2 h at 70-80 ° C. After cooling, the reaction mixture was poured into ice water and stirred vigorously. The precipitated crystalline solid was collected by filtration, the crude product was purified by recrystallization, mp = 123-125 ° C.

Analysis for C18H10NO5PS3 Off: 9.46% P 29.39% S (mh = 327.24) Found: 8.98% P 28.91% SS structure of the compound was confirmed by IR spectroscopy. IR spectra in chloroform: vas (C = O) 1,754 cm -1 vs (C = O) 1,804 cm -1 in (P = S) 658 cm -1

By a similar procedure, compounds were prepared: 0,0-dielgd-O- (3,6-dmin-3,4,5,6-tetrahydrophthyrimidine) thiotosphate

mp = 88-90 ° C

Analysis for C 10 H 14 NO 5 PS 3: 8.72% P 27.07% S (mh = 355.30) Found: 8.62% P 27.28% SS structure of the compound was confirmed by IR spectroscopy. IR spectra in chloroform: va (C = O) 1756 cm @ -1 vs (C = O) 1805 cm @ -1 in (P = S) 656 cm @ -1 O-ethyl-O-iaopeopyl-O- (3,6 -dithiii-3,4,5,6-tetrahydro-phthalimide) thiofol

mp = 49-51 ° C

Analysis for

CnHieNOjPSj Off: 8.38% P 26.05% S (mh = 369.37) Find: 8.02% P 25.92% S 0-faop »opyl-0-BMzyi-0- (3.6 -dttft-3,4,5,6-tetrahydro-thiazide) -thiofoefut

mp = 60-63 ° C

Analysis for C 10 H 14 NO 5 PS 3 Off: 8.72% P 27.07% S

(mh = 355.37) Found: 8.53% P 27.36% S O-ethyl-O-ethyl-O- (3,6-dithin-3,4,5,6-tetrahydrofuran)

MfaMltfofoHt tt = 100-101 ° C

Analysis for

C9H12NO5PS3 Off: 9.05% P 28.20% S (mh = 341.30) Observe: 8.97% P 28.42% S-O-ethyl-N, N-cHn-ethyl-amide-O- (3 6-ditun-3,4,5,6-tetrahydrophthalimide) thiophosphate

Analysis for C10H15N2O4PS3: 8.75% P 27.15% S

(mh = 354.26) Found: 9.01% P 27.46% S O-ethyl-O- (3,6-dithen-3,4,5,6-tetrahydrophthalimide (phenylthiophosphonate

mp 113-116 ° C

Analysis for

C14N14NO4PS3 Off: 8.00% P 24.82% S (mh = 387.30) Observe: 8.14% P 24.89% S O-ethyl-N-isopropyemido-O- (3,6-dithiene -3,4,5,6-tetrahydrophthalimide) thiophosphate

mp = 73-75 ° C

Analysis for

CnH17N2O4PS3 Off: 8.41% P 26.09% S (mh = 368.27) Observe: 8.60% P 26.22% S Example 1 O, O-dimethyl-O- (3,6-diol) -3,4,5,6-tetrahydrophthalimide) thiophosphate, To 12 g of N-hydroxy-3,6-dithiene-3,4,5,6-tetrahydro-phthalimide (0.06 mol) in 80 ml of dimethylformamide and 8.6 g of potassium carbonate (0.06 mol) were added with stirring to 9.6 g of 0,0-dimethylchlorothiophosphate

(0.06 mol), the reaction mixture was stirred at 25 ° C for 2 h

Claims

215464 O-Ethyl-O- (2-methoxyethyl) -O- (3,6-di-3,4,5,6-tetrahydro-phthalimide) thiophosphate m.p. = 36-39 ° C Analysis for C 11 H 16 NO 6 PS 3 Off: 8.04% P 24.95% S (MW = 385.35) Observe: 8.11% P 25.12% S In the following table, the biological test results are Compound Konc. % of the activity of A. fa-bae T. ur-ticae O, O-dithhyl-O- (3,6-dithiene - 3,4,5,6-tetrahydrophthalimide) thiophosphate 0.1 100 0, O-diethyl-O- (3,6-dithiine-3, 4,5,6-tetrahydrophthalimide) thiophosphate 0.1 100 O-ethyl-O-isopropyl-O- (3,6-dithiin-3,4,5) , 6-tetrahydrophthalimide) thiophosphate 0.1 100 O-isopropyl-O-methyl-O- (3,6-dithine-3,4,5,6-tetrahydro-phthalimide) thiophosphate 0.1 100 O-ethyl-O- methyl O- (3,6-dithiene-3,4,5,6-tetrahydrophthalimide) thiophosphate 0.1 100 O-ethyl-N, N-dimethylamido-O- (3,6-dithiamine) 3,4,5,6-tetrahydrophthalimide) thiophosphate 0,1 100 O-ethyl-O- (3,6-dithiene-3,4,5,6-tetrahydrophthalimide) phenylthiophosphonate 0,1 100 O-ethyl -0- (3,6-dithiin-3,4,5,6-tetrahydrophthalimide (N-isopropylamidothiophosphate) 0,1 100 (-0- / 2-methoxyethyl) thiophosphate 0,1 100 - 0,0-dimethyl-0 - (3-methyl-4-nitrophenyl) thiophosphate (feni-trotion) Standard 0,1 100 100 SUBJECT

1. New thiophosphoric acid esters of the general formula V. "with

wherein R 1 is alkyl of 1 to 4 carbon atoms, R 2 is alkoxy, N-alkylamido, N, N-dialkylamide, wherein the alkyl radicals contain 1 to 4 carbon atoms, phenyl, 2-alkoxetoxy having 1 to 4 carbon atoms, alkoxy .

2. A process for preparing the compounds of claim 1, wherein the compound of formula (VI) is reacted

with a chlorothiophosphoric ester of formula VII

wherein R 1 and R 2 are as defined above in an organic diluent environment such as acetone, methyl ethyl ketone, butyl acetate, dimethylformamide, temperature 25 to 100 ° C. Price: 2,40 Kčs Printed by Moravské tiskařské závody, operation 12, Leninova 21, Olomouc