CS220713B1 - Dialkylesters acids of the p-toluensulfonyloxymethanforfon and method of preparation of the same - Google Patents

Abstract

The present invention provides novel dialkyl esters p-toluenesulfonyloxymethanephosphonic acid of formula (1) O p-CH 2 C 6 H 2 SO 2 OCH 2 -P 1 -OR STEED (AND), wherein R is alkyl of 1 and 2 carbon atoms, suitable for the preparation of a wide range of organophosphorus compounds, for example alkoxy derivatives, amino-, alkyl- and dialkylaminomethanephosphonic, which are used, for example, as herbicides, insecticides. The invention further provides a method of preparation of these substances from dialkyl esters hydroxymetha phosphonic reaction of this compound with p-toluenesulfonyl chloride in the presence of tertiary base.

Description

(54) p-Toluenesulfonyloxymethanephosphonic acid dialkyl esters and process for their preparation

2

SUMMARY OF THE INVENTION The present invention provides novel p-toluenesulfonyloxymethanephosphonic acid dialkyl esters of formula (1): p-CH 2 C ⁶ H ⁶ SO 2 OCH 2 -P ¹ —OR

OR (I) wherein R is alkyl having 1 and 2 carbon atoms, suitable for the preparation of a variety of organophosphorus compounds, for example alkoxy-, amino-, alkyl and dialkylaminomethanephosphonic acid derivatives, which are used, for example, as herbicides, insecticides.

The present invention further provides a process for the preparation of these compounds from hydroxymethylphosphonic acid dialkyl esters by reacting the latter with p-toluenesulfonyl chloride in the presence of a tertiary base.

The present invention provides p-toluenesulfonyloxymethanephosphonic acid dialkyl esters and processes for their preparation. Said chemical compounds have the general formula I

O

P-CH 3 C 6 H 4 SO 2 OCH 2 —P-OR

OR (I) wherein R is alkyl of 1 to 2 carbon atoms.

These are new compounds suitable for the preparation of a wide variety of organophosphorus substances, for example alkoxy-, amino-, alkyl- and dialkylaminomethanesulfonic acid derivatives, which are used, for example, as herbicides, insecticides and the like.

The present invention further relates to a process for the preparation of these compounds, which process is characterized in that dialkyl esters of hydroxymethanephosphonic acid

O

II

HOCH2P — OR

OR (Π), where R is alkyl of 1 and 2 carbon atoms, is reacted with p-toluenesulfonyl chloride in benzene or ether in the presence of an equimolar amount of tertiary base, calculated on the chloride used, preferably triethylamine or pyridine, at temperatures from -10 to + 10 ° C, and then the product is isolated by crystallization or chromatography.

Thus, the starting materials for their preparation are dialkyl esters of hydroxymethanephosphonic acid.

These are prepared either by reacting phosphorous diesters with paraformaldehyde in the presence of basic catalysts such as triethylamine, sodium methoxide and the like (U.S. Pat. Nos. 2,593,213, 2,579,810) or by reacting dlalkyl phosphite sodium with acetooxymethyl bromide, followed by formation of the acid diester. acetoxymethanephosphonic alcoholysis converts the desired dialkyl ester. (Czech Author's Certificate No. 22: 0 714.)

The reaction of the hydroxymethyl methanesulfonic acid dialkyl esters with p-toluenesulfonyl chloride proceeds with little yield in pyridine, but can be conveniently performed with p-toluenesulfonyl chloride in an inert solvent (benzene, ether) in the presence of an equimolar amount to the tertiary base chloride used (e.g.

triethylamine, pyridine). The compounds of formula (I) obtained, after filtration of the salts and evaporation of the solvent, are obtained either directly by crystallization or by chromatography of the reaction mixture. Their distillation is not suitable even under reduced pressure, but the pure compounds of formula I are stable at room temperature for an unlimited period.

In the following, the invention is illustrated by way of examples, without being limited thereto.

Example 1 Methyl p-toluenesulfonyloxymethane phosphonate

To a solution of 0.22 moles of methyl hydroxyethane phosphonate in 300 ml of ether was added, 3 µl, 5 ml of triethylamine and, with stirring and cooling, a solution of 42.9 g of p-toluenesulfonyl chloride in 300 ml of ether was added dropwise over 60 min. . The mixture was stirred at 0 ° C for 3 hours and at room temperature for 15 hours, filtered off with suction and the filtrate evaporated in vacuo. The residue was crystallized by stirring with 200 ml of petroleum ether, filtered off with suction, washed with petroleum ether and dried in vacuo. 50-60% of a white crystalline product is obtained, mp 55-36 ^and C. Mass spectrum: 294 (M ^& lt ^{; +} & gt ^; ), 263 (M-OCH3), 230 (M-SOa).

Example 2 Ethyl p-toluenesulfonyloxymethanephosphonate

The reaction is carried out with 0.22 moles of ethyl hydroxymethanephosphonate as described in Example 1. After the ether solution is filtered off with suction, the filtrate is evaporated in vacuo and the residue in 50 ml of benzene is again filtered and evaporated. The residue is chromatographed in 50 ml of chloroform on a column of 200 g of silica gel (30 to 60 μm) and the eluate is monitored by chromatography on Silufol plates in chloroform. The product _(Rf = 0.15) was detected in UV light or iodine vapors. Product containing fractions were combined, evaporated and dried in vacuo. 70-80% of a yellowish oily product is obtained.

IR (cm ^-1 ): in the ring 1598, 1494, 1449; v (SOa): 1.374, 1190, 1177; v (P-O) 1260; in (P-O-alkyl) 1042.

¹ H-NMR-spectrum (CDCl 3):

P-CH ₂ 4.23, P-O-alkyl 3.87, 3.69, CH 2 -phenyl 2.46, arom. 7.80, 7.35.

Claims (2)

Subject 1. p-Toluenesulfonyloxymethanephosphonic acid dialkyl esters of the general formula I II P-CH 3 C 6 H 4 SO 2 OCH 2 -P-OR AND OR (I) wherein R is alkyl of 1 and 2 carbon atoms. 2. A process for the preparation of the p-toluenesulfonyloxymethanephosphonic acid dialkyl ester of formula (I) according to claim 1, characterized in that the hydroxymethylphosphonic acid dialkyl esters of formula (II) are II HOGH2P — OR OR (Π), where R is alkyl of 1 and 2 carbon atoms, is reacted with p-toluenesulfonyl chloride in benzene or ether in the presence of an equimolar amount of tertiary base, calculated on the chloride used, preferably triethylamine or pyridine, at temperatures of -10 to 10 + 10 ° C and then isolated by crystallization or chromatography.