CS217685B1

CS217685B1 - New O- (2-chloroethyl) -O-isobutyl-O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) thiophosphate and its preparation

Info

Publication number: CS217685B1
Application number: CS841580A
Authority: CS
Inventors: Vaclav Konecny; Jozefina Wolfshoerndlova
Original assignee: Vaclav Konecny; Jozefina Wolfshoerndlova
Priority date: 1980-12-03
Filing date: 1980-12-03
Publication date: 1983-01-28

Abstract

Nový 0-(2-chlóretyl)0-izobutyl 0-(l-metyl- -5-metoxy-6-oxo-lH-pyridazín-4-yl)tiofosfát vzorca II, Cl-CHgC^O í-o4h9o ného organického riedidla, ako je metylketón, aceton, nitril kyseliny octovej, octan butylnatý, dioxan, toluén, pri teplote 40 až 110 °C. Sposob přípravy zlúčeniny vzorca II reakciou 0-(2-chlóretyl)0-(l-metyl-5-metoxy-6~ -oxo-lH-pyridazín-4-yl)chlórtiofosfátu vzorca Sposob přípravy zlúčeniny vzorca II reakciou 0-(2-chlóretyl)0-izobutylchlórtiofosfátu vzorca III C1-CHoCH5C) 2 2 P - Cl i-c4H9o ^'s so sol’ou l-metyl-5-metoxy-6-oxo-lH-pyridazín-4-olu vzorca IV, s izobutylalkoholom alebo s butylátom alkalickým pri teplote 0 až 60 °C. Sposob přípravy zlúčenín vzorca II reakciou 0-izobutyl-0-(l-metyl-5-metoxy-6-oxo- -lH-pyridazín-4-yl)chlórtiofosfátu vzorca VI '4 9 M = alkalický kov, najma sodík, draslík, ďalej tetraetylamónium, v prostředí vod -CHs 2-chlóretanolom pri teplote 0 až 60 °C.A new O-(2-Chloroethyl)O-isobutyl O-(1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl)thiophosphate of formula II, Cl-CHgC^O í-o4h9o in an organic solvent such as methyl ketone, acetone, acetic acid nitrile, butyl acetate, dioxane, toluene, at a temperature of 40 to 110 °C. Method of preparation of compound of formula II by reaction of 0-(2-chloroethyl)0-(1-methyl-5-methoxy-6~ -oxo-1H-pyridazin-4-yl)chlorothiophosphate of formula Method of preparation of compound of formula II by reaction of 0-(2-chloroethyl)0-isobutylchlorothiophosphate of formula III C1-CHoCH5C) 2 2 P - Cl i-c4H9o ^'s with salt 1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-ol of formula IV, with isobutyl alcohol or with alkaline butylate at a temperature of 0 to 60 °C. Method of preparation of compounds of formula II by reaction of 0-isobutyl-0-(1-methyl-5-methoxy-6-oxo--1H-pyridazin-4-yl)chlorothiophosphate of formula VI '4 9 M = alkali metal, especially sodium, potassium, further tetraethylammonium, in an environment of water -CHs with 2-chloroethanol at a temperature of 0 to 60 °C.

Description

Czechoslovak SocialistREPUBLIC (19) DESCRIPTION OF THE INVENTION FOR COPYRIGHT CERTIFICATE 217685 (11) (B1) É (22) Enrolled 03 12 80 (21) (PV 8415-80) (51) Int. Cl.3 C 07 F 9/18 OFFICE AND DISCOVERY OFFICE (40) Published 30 04 82 (45) Published 16 07 84

Author of the invention KONEČNÝ VÁCLAV RNDr. CSc., BRATISLAVA, WOLFSH0RNDLOVAJOZEFlNA ing., PEZINOK (54) New O- (2-chloroethyl) -O-isobutyl-O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) thiophosphate and a method for its preparation

New O- (2-chloroethyl) O-isobutyl O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) thiophosphate Formula II

Cl-CH 2 Cl 2 O 4 -O 4h 9

organic diluent such as methyl ketone, acetone, acetic acid nitrile, butyl acetate, dioxane, toluene, at 40-110 ° C.

A process for preparing the compound of formula II by reacting O- (2-chloroethyl) O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) chlorothiophosphate of the formula

A process for the preparation of the compound of formula II by reacting O- (2-chloroethyl) O-isobutylchlorothiophosphate of formula III with C1-CHoCH5C1 2 P-Cl-4H9O3 with a salt of 1-methyl-5-methoxy-6-oxo- 1 H-pyridazin-4-ol of formula IV,

with isobutyl alcohol or alkali butylate at 0 to 60 ° C.

A method for preparing compounds of formula II by reacting O-isobutyl-O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) chlorothiophosphate of formula VI

'4 9 M = alkali metal, in particular sodium, potassium, straight tetraethylammonium, in the water-

-CH- with 2-chloroethanol at 0 to 60 ° C. 217685 * 'λ - - ......., -. -i ... Á 9

The present invention provides novel O- (2-chloroethyl) O-isobutyl O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) thiophosphate as well as a method for its preparation. The compound of the invention may be used as a pesticide. Among the literature known are pesticides of the various pyridazin-4-yl esters of the organophosphoric acids of the general formula I,

wherein R 1 and R 2 are the same butborate alkyl, alkoxy, alkylamido, dimethylamino, R 3 is halo, alkoxy, alkylthio, R 4 is alkyl, cycloalkyl, aryl (Pestra, Sci. 10, 227-238 (1979); Pestic. Sci. 7, 107-114 (1976); Collection 44, 1761-1771 (1979); Colection 43, 2415-2426 (1978).

New O- (2-chloroethyl) O-isobutyl O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) thiophosphate of formula II was now found.

C1-CH2CH2O1-c4h90 x

At the same time, a process for the preparation of the compound of formula II by reaction of O- (2-chloroethyl) O-iso-butylchlorothiophosphate of formula III with a salt of 1-methyl-5-methoxy-6 with the salt of 1-methyl-5-methoxy-6 was found. -oxo-1H-pyridazin-4-ol of formula IV,

wherein M is an alkali metal, especially sodium, potassium, tetraethylammonium, in the presence of a suitable organic diluent such as methyl ethyl ketone, acetone, acetic acid nitrile, butyl acetate, dioxane, toluene-like, at 40-110 ° C. It has also been found that the compound of formula II can be prepared by reacting O- (2-chloroethyl) O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) chlorothiophosphate of formula IN

C1CH2CH2O

with isobutyl alcohol using an alkali carbonate, a tertiary amine such as triethyl amine, pyridine and the like, or directly with an alkaline alkali in an organic diluent such as dioxane, nitrile acetic acid, methyl ethyl ketone, tolulene and the like, priteplote 0 to 60 ° C.

The compound of formula II may also be prepared by reaction of O-isobutyl O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) chlorothiophosphate of formula

VI

i-G 4 H 9 O

with 2-chloroethanol using an alkali carbonate, a tertiary amine such as triethyl amine, pyridine and the like, in an organic diluent such as dioxane, acetic acid nitrile, acetone, methyl ethyl ketone, butyl acetate, toluene, and the like; similar, at 0 to 60 ° C.

The following examples further illustrate, but are not limited to, the novel O- (2-chloroethyl) O-isobutyl-O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) thiophosphate and its method of preparation . Example 1 To 0.11 mol of 1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-ol potassium salt in 100 ml of methyl ethyl ketone was added 0.1 mol of isobutyl O- under stirring. (2-chloroethyl) chlorothiophosphate. The reaction mixture was stirred at 80 ° C for 4 hours, then cooled, and the precipitated potassium chloride was collected by filtration. Methyl ethyl ketone distilled from the filtrate under reduced pressure. The distillation residue was dissolved in 100 mL of toluene, this sapremyl 50 mL of 5% aqueous sodium carbonate solution and still with water. After drying, toluene was distilled off from the toluene solution under reduced pressure. The distillation residue was purified by SiO 2 chromatography using toluene or toluene with addition of acetone.

29.2 g of colorless liquid were obtained nD2 ° = 1.5248Analysis for C12H20ClN20gPS (mh = 370.62)

Off: 8.36% P 8.64% S 7.57% NZist .: 8.42% P 8.78% S 7.88% N

Claims

3 The structure of the compound was confirmed by spectral methods: IR in chloroform 1 H NMR in CDCl 3: k: v (C: = 0) 1662 cm -1 V (c = N) 1622 cm -1 V (p = s> θθ 3 cm) 1675 cm < -1 > CH- 7.91 [mu] (ppm) -ch2-o-4.59 [mu] (ppm) CH3-O- 4.34 (ppm) -CHa-Cl 4.15 < n 3.88 δ (ppm) CH 2,3 2.31 δ (ppm) CH 3 -CH 1.17 δ (ppm) v (c = 0) cm -1 cm 11V (cn> 1622 cm -1 UV spectrum in methanol: Amax 214.3 nm (loge: 4.37) and 280.0 nm (loge: 3.70) Molecular ion was confirmed in the mass spectrum: 370+ 13 C NMR in CDCl 3: C = O 158.8 δ (ppm) P — O — c = c <144.8 δ (ppm) ch 3 —O — c = c <138.6 δ (ppm) H — C = N— —CH 2 —O — P—> CH— CH2 —O — P — ch3 - o - ci - ch2 - ch3n -> CH - ch3 - 133,7 δ (ppm) 75.7 δ (ppm) 68.5 δ (ppm) 59.9 δ (ppm) 42.7 ((ppm) 39.8 δ (ppm) 28.5 ((ppm) 18.5 δ (ppm) Example 2 To 0.22 mol of 1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-ol tetraethylammonium salt in 300 ml of dioxane was 0.2 mol of O- (2-chloroethyl) O-isobutylchlorothiophosphate was added. The mixture was stirred for 4 hours at 60 ° C, and the precipitated tetraethylammonium chloride was separated by filtration. From the filtrate, the pressure was distilled off with dioxane. The distillation residue was dissolved in 100 ml of toluene, washed with 50 ml of 5% aqueous sodium carbonate solution and then with water. After drying, the toluene was distilled off under reduced pressure from the toluene solution. The distillation residue was purified by column chromatography on SiO 2 using toluene or toluene with a small addition of acetone. Obtained was: 60.3 g (81.3% yield) of the compound of Example 1. Example 3: 0.04 mole of O- (2-chloroethyl) -O- (1-methyl-5-methoxy-6-oxo- 1H-pyridazin-4-yl) chlorothiophosphate in 80 mL of toluene was added with 0.044 mol of potassium isobutyrate in 40 mL of toluene at 10-15 ° C with stirring. Stirring was continued at 20 ° C for 6 h. The precipitated potassium chloride was dissolved in water, the toluene layer was washed once more with 100 ml of water, the toluene was distilled off under reduced pressure and the residue was then purified by column chromatography. This gave 11.6 g of a colorless liquid, nD2O = 1.5250, identical to the compound of Example 1. Example 4 K 0.04 mole of O-isobutyl-O- (1-methyl-5-methoxy-6- of oxo-1H-pyridazin-4-yl) chlorothiophosphate dissolved in 80 ml of toluene and 0.004 mol of ethylbenzylammonium chloride as catalyst were added, under stirring, 0.1 mol of ethylene chlorohydrin and 0.05 mol of triethylamine in 40 ml of toluene at 20 ° C . Stirring was continued at the same temperature for 5 h. The reaction mixture was washed with water, 5% acid salt and, after drying, toluene was distilled off under reduced pressure. The residue was purified by column chromatography. 10.9 g of colorless liquid nD20 - 1.5251 were obtained, identical to the compound of Example 1.

1. New O- (2-chloroethyl) O-isobutyl-O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) thiophosphate of Formula II. C1-CH2CH2;

2. A process for the preparation of a compound according to claim 1, characterized in that O- (2-chloroethyl) O-isobutylchlorothiophosphate of formula III is reacted with C1-CHOCH2O2 with C1-C4hCl with a salt of 1-methyl 5-methoxy-6-oxo-1H-pyridazin-4-ol of formula IV,

In which M is an alkali metal, most hydrogen, potassium, further tetraethylammonium, in a suitable organic diluent such as methyl ethyl ketone, acetone, acetic acid nitrile, butyl acetate, dioxane, toluene, at 40-110 ° C.

3. A process for the preparation of the compound of claim 1, which comprises reacting O- (2-chloroethyl) O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) chlorothiophosphate of formula V C1CH2CH2O

with isobutyl alcohol using a carbonate-alkali, tertiary amine such as triethylamine, pyridine, or directly with butyric acid in an organic diluent such as dioxane, acetic acid nitrile, methyl ethyl ketone, toluene, at 0 to 60 ° C.

4. A process for preparing the compounds according to claim 1, wherein 0-isobutyl O- (1-methyl-5-methoxy-6-oxo-1H-pyridazin-4-yl) chlorothiophosphate is reacted. of formula VI-c4h90

With 2-chloroethanol using an alkali carbonate, a tertiary amine such as triethyl amine, pyridine, in an organic solvent such as dioxane, acetic nitrile, acetone, methyl ethyl ketone, butyl acetate, toluene, at 0 to 60 ° C. Printed by TSNP, n. Martin Price Kčs 2.40