SU1058971A1 - Process for preparing methylchlorovinyl esters of n-substituted amidophosphoric acids - Google Patents

Abstract

METHOD FOR OBTAINING MEDIUM AND SINGLE METHYL DIHLORVINYLOBMKH ETHERS OF N-3 ABBLIXES WITH AMIDOPHOSPHORIC ACIDS OF GENERAL FORMULA O C “N 1) YAGZO-R-1 C. I OR o-Sn Scij where R is methyl or ethyl, which means that dimethyl cellulose is xyroxycellulose Scij at 10–20 s in an inert gas atmosphere at an equimolar ratio S of reagents. 1 (L SP ac with

Description

This invention relates to the chemistry of organophosphorus compounds, and specifically to a process for the preparation of new mixed methyldichlorvinyl ethers of N-e-substituted amidophosphoric acids of the general formula

About II

bsch SNCHO-RK (

 I

R

0- (JH

"

CCl.

where R is methyl or ethyl, which can be used as intermediates in the synthesis of biologically active drugs.

A method for producing dialkyl esters of N- (1-dialkylphosphonylalkyl) amidophosphoric acid by reacting sodium di-dialkylphosphites with oximes in ether or benzene at room temperature is known. The yield of the target products is 14-30% l,.

A known method for preparing /, p, rtrichloroethylideneamido-0, 0-dialkyl phosphates by reacting dialkylamidophosphates with chloral when heated, followed by reacting to form dialkyl ethers-oxy-p, p, -trichloroethylamidophos 6 5) 2 P-1 + CClj Cry / Cryl

CC1, - (- 05 I

L

And CH :, -CH.ci0-dJi II, as a result of the nucleophilic attack of the phosphorus atom of methyleneamidophosphite on the carbonyl group, a bipolar ion is formed, further stabilizing which in the enolphosphonium compound occurs as a result of the phosphonate-phosphate rearrangement with the elimination of the halogenion. Dealkylation of the enolphosphonic compound leads to the final product {I). In the described method, dimethylalkoxyphenylmethylene amidophosphites are reacted with chloral for the first time, as a result of which the mixed methyldichlorvinyl ethers M of substituted agdadophosphoric

foric acid with thionyl chloride and the treatment of the resulting dialkyl esters of, (,, (5-tetrachloroethylamine phosphoric acid with triethylamine 2}.

The disadvantages of this method are the harsh reaction conditions, since it requires heating, a multistage process, the hygroscopicity of the target products, the impossibility of obtaining mixed esters of amidophosphoric acid.

The mixed methyldichlorovinyl esters of N-substituted amidophosphoric acids of formula (1) were not obtained by these methods and are new.

The purpose of the invention is to develop a simple and affordable process for the preparation of mixed methyldichlorvinyl ethers of N-substituted amidophosphoric acids of the formula (11,

This goal is achieved in that according to the method for preparing the mixed methyldichlorovinyl ethers of K-substituted amidophosphoric acids of formula (1), which implies that dimethylalkoxyphenylmethyl. Amidophosphite reacts with chloral at 0O-ZO C in an inert atmosphere with equimol

The reaction proceeds according to the scheme:

“NZO. Seid; r-1g

 icH 11 (11CC12 acids, containing in one of the ether radicals O, p-unsaturated grouping, in high yield. These are stable compounds that are distilled under vacuum without decomposition. Formation of mixed methyldichlorovinyl ethers of N-substituted amidophosphoric acids of formula (I) not It is obvious, since it is known that derivatives of trivalent phosphorus, having unsaturated groups, such as isocyanatophosphites, react with chloral to form cycloaddition products. fate of phosphorus atom;..

Thus, the formation in the reaction of dimethylalkoxyphenylmethylene amidophosphites with chloralum the mixed methyldichlorvinyl ethers of N-substituted amidophosphoric acids of formula (I) is a new process for the preparation of compounds of this type.

In order to prepare the mixed methyl vinyl ethers of N-substituted amidophosphoric acids in this way. Formulas (I) an equivalent amount of chloral is added to dimethylalkoxyphenylmethylene amidophosphite under argon at 10-20 ° C. From the reaction mixture, the desired product of formula (I

The structure of the compounds of formula (1) is confirmed by the data of elemental analysis, IR, NMR and H-spectroscopy.

The IR spectra contain bands (9), cm: 1050 (Р-О-С); 1280 (); 1595 (); 1610 (); 2640 3070 (). In the NMR P spectrum there are 3 ppm signals. (,) In the PMR spectrum of methyl-p, | - d-chlorovinyl ether of N-methoxyphenylmethylene amidophosphoric acid, there are a triplet of methyl protons of the ethoxy group (S 1.38 MD), a doublet of methyl protons of the methoxy group (S 3.62 ppm DRI 12 Hz), a quartet of methylene protons (b 4.30 ppm), methylene proton doublet (S 6.85 ppm of JPH 6 Hz), the protons of the benzene core resonate 5 7.50 ppm

Example. Preparation of methyl /, (- N-methoxyphenylmethylene amidophosphoric dichlorovinyl ester

To 3.27 g (0.02 g-mol) of dimethylmethoxyphenylmethylene amidophosphite, 3.29 g (0.02 g-mol) of chloral are added dropwise: under an atmosphere of argon at 10-200 ° C. After removal of methyl chloride, the product is dispersed in vacuo. 120123 With aO-mm Hg), 1.5440. 75% yield.

Found,%: C 40.93; And 4.02; P 9.16. WITH" .

Calculated,%: C 40.74; H 3.70; R 9.57.

EXAMPLE 2. Preparation of Methyl, N-ethoxyPhenylmethylenamidophosphoric Acid p-dichlorovinyl Ester.

To 6.66 g (0.027 g-mol) of dimethylethoxyphenylmethylene amidophosphite, 4/06 g (0.027 g-mol) of chloral was added dropwise in an atmosphere of argon at 10-20 ° C. After removal of methyl chloride, the product was dispersed in vacuo. . 122-12bs (10 mm Hg), p 1.5327. The yield is 78%.

Found,%: C 42.57; H 4.14; R 9.16. C, 5.

Calculated,%: C 42, 4,14; R 9.16.

The optimal conditions for the implementation of the method are the use of equimolar amounts of the initial reagents, since the use of an excess of one or another reagent makes it difficult to purify the target products; carrying out the reaction in a stream of dry inert gas to prevent oxidation and hydrolysis of the final products; the implementation of the method at 1020 0, since a decrease in temperature slows down the reaction, and an increase leads to resinification and lowers the yield of the final products.

When using the described method for the preparation of mixed methyldichlorovinyl ethers of N-substituted5 N1 amidophosphoric acids of formula (I), it is possible to synthesize them on the basis of dimethylalkoxyphenylmethylene amidophosphites, used for the first time in reactions with chloral; Q is the simplicity of the method of the method (the method is carried out in one stage under mild conditions), reliable reproduction of the results, availability of initial reagents, good yield of products (75-78%).

Claims (1)

METHOD FOR PRODUCING MIXED N-3AMETHYL METHYLCHLORVINYL ETHERS, SUBSTITUTED AMIDOPHOSPHORIC ACIDS OF THE GENERAL FORMULA “ СНхО-Р-Х = <к ¹ а 0® о-η CC1 ₂ where R is methyl or ethyl, which consists in the fact that dimethylalkoxyphenylmethyleneamidophosphite is reacted with chloral at 10-20 ° С in an inert gas atmosphere at an equimolar ratio of reactants. Q SHT ” ⁰ ns With