SU417434A1 - METHOD FOR OBTAINING DIALKYL EFFRUCTIVE FUNCTIONAL DEPENDENCES OF PHOSPHONIC ACIDS - Google Patents

Description

one

The invention relates to the field of production of phosphonous acid derivatives, namely, to a process for the preparation of new dialkyl esters of functionalized phosphonous acids of the general formula

(RO), PCH, CH, X,

where R is a kil,

X-functional double bond activating group, for example

COOAIk, CN, P (OAIk) 2.

II Oh

These compounds can be used as antioxidants.

The known reaction of attaching organophosphorus substances containing PHI bond to unsaturated compounds is m.

The proposed method for the preparation of dialkyl esters of functionally substituted phosphonous acids consists in the fact that dialkoxyphosphines of the general formula

(RO) PH

where R is alkyl, is reacted with compounds containing an activated double bond of the general formula

sn, snh,

where X is a functional group that activates a double bond, for example

COOAIk, CN, P (OAIk) 2. II Oh

The process is preferably carried out in a stream of inert gas, such as argon.

Target products are recovered by known techniques.

Example 1. All operations are carried out in an argon flow. 7.5 g (0.042 mol) of dibutoxyphosphine and 4.35 g (0.042 mol) of ethyl acrylate are poured off, the mixture is kept for 9-10 hours at 20 ° C.

After distillation, 4.6 g (40% of theoretical) of 3-carbethoxyethylphosphonic acid dibutyl ester (I) are isolated; m.p. 92-93 ° C / 0.5 mm; 115 ° 1.4465.

Found,%: C 59.19; H 9.85; R 10.81.

CigHaiO.P.

Calculated,%: C 56.09; H 9.77; R 11.

Example 2. All operations are carried out in an argon flow. To a solution of 4.4 g (0.024 mol) of dibutoxyphosphine in 10 ml of absolute ether, 2.5 g (0.048 mol) of acrylonitrile was added. The mixture is boiled for 6 hours, the polymeric precipitate is filtered off and distilled.

Get 3 g (52% of theoretical) dibutyl ether p-nitrile ethylphosphonate

acids (II); m.p. 110-113 ° C / 2 mm; p 1.4520.

Found,%: C 56.90; H 9.48; P 13.63.

Calculated,%; C 57.12; H 9.5; R 13.39.

Similarly, d-butyl ester of P-phosphonethyl phosphonic acid (III) is obtained; m.p. 130-131 ° C / 1 mm; ng 1.4520.

Found,%: C 48.87; H 9.24; P 18.05.

Ci4H3205P2.

Calculated,%: C 49.11; H 9.42; P 18.09.

The structure of the compounds obtained is proved by the data of IR and PMR spectroscopy.

In the IR spectra of compounds I and III there are intense absorption bands in the 1720 and 1250 regions, respectively, in the IR spectrum of compound II there is a characteristic absorption in the 2240 region

In the PMR spectrum of substance I, there are groups of signals corresponding to the following fragments of the molecule: a triplet from an OCH fragment of an ethoxy group (3.90-4.06 ppm); the quartet from the CH3 fragment of the ethoxy group (0.91-1.05 MD); two multiplets from CH3 and -CH-CH2-fragments of the butoxy group (0.6-0.82 ppm) and (1.40-1.60 ppm), respectively, and a multiplet from the SNG of the butoxy group. The protons of the P-CHa-CHa-0 0 part of the molecule (AAMMH system) give two complex multiplets in the region of 1.7-2.3 ppm (PCH2) and 2.30-2.60 ppm (SNgCOO) . This part of the spectrum cannot be interpreted in the first order, which is due to the non-equivalence of protons of methylene groups (AAMM system).

The PMR spectrum of substance II is similar to the spectrum

substance I and also corresponds to the proposed structure. In the NMR-spectrum of substance III

there is a complex proton multiplet

P-CH2-CH2R (O) fragment in the region of 1.6

2.1 MD, multiplet from protons of OCH2-groups

in the region of 3.4–4.2 ppm and the multiplet from protons of methyl and lopilny fragments

ethoxy - and butoxy groups (0.5-1.6 MD).

The magnitudes of the integral intensities correspond to the proposed structures.

Subject invention

Claims (2)

1. Method for preparing dialkyl ethers of functional substituted phosphonous acids of general formula (RO), PCH, CH, X, where R is al kil, X-functional double bond activating group, characterized in that dialkoxyphosphines interact with compounds containing activated double bond, followed by isolation of the target product by known methods. 2. A method according to claim 1, characterized in that the process is conducted in a flow of an inert gas, for example argon.