SU375299A1 - METHOD OF OBTAINING O. O-DIALKIL-Y-ACETIMIDO-p-CYAN- - Google Patents

Description

one

The invention relates to a process for the preparation of new O, O-dialkyl-M-acetimido-p-cyanoalkylphosphonates of the general formula

(RO) 2P-CHR-CHR-CH

II

N-C-СНз il О

where R and RI are hydrogen or alkyl.

These compounds can be used as intermediates in the synthesis of biologically active substances.

The proposed method for the preparation of compounds of the above formula is based on the known reaction of hydrogen addition of an amide soil to nitriles of a, p-non-hazardous carboxylic acids, and is that O, O-dialkyl-S - acetamide phosphites are reacted with nitriles of a, p-unsaturated carboxylic acids.

It is desirable to conduct the process either in the medium of an organic solvent, for example benzene, when heated to 120-130 ° C or in the presence of an alkali metal alcohol as a catalyst, for example sodium ethylate, at room temperature.

Target products with a yield of 50-60% are recovered by known methods.

The structure of the adducts is confirmed by IR spectra. IR spectra

there is an intense absorption characteristic of the phosphimide bond with a maximum at 1370, an absorption of the carboxyl group conjugated with P-N at 1620, an absorption of pH-C-alkyl nr 1020-1070 and nitrile priming in the region of 2250 cm.

Example 1. An equimolar amount (0.04 mol) of acrylic acid nitrile is added to 8.3 g (0.4 mol) of diethylphosphoric acid N-acetimide in 10 ml of benzene. The reaction mixture is heated for 7 hours at a temperature of 120-130 ° C in a stream of argon and left overnight.

The solvent is removed under reduced pressure and the residue is distilled. As a result of the reaction, 5.2 g (50%) of 0.0 dipethyl-N-acetimido- (3-cyanoethylphosphonate with tn. 100-101 ° C / 0.04 mm Hg; 1.4590, 1.1069) are obtained.

Paydeio,%: P 13.33; N 12.18; MRo 63.35. CsHi-NaOsP

Calculated,%: R 13.36; N 12.06; MRn 63.08.

EXAMPLE 2: To 8.3 g (0.04 mol) of diethylphosphorous acid N-acetimide in a stream of argon, an equimolar amount (0.04 mol) of acrylic acid nitrile and a few drops of ethylate ethylate and sodium are added. Warming up to 80 ° C is observed. The next day, the reaction mixture is distilled. As a result of the reaction, 0,0-diethyl-1H-acet-imido-p-cyaethylethylphosphonate with m.p. 100-

101 ° C / 0.004 mm Hg v .; at 1.4588; 1D069.

CgHiTN.OaP

Found,%; P 12.90; N 12.18. Calculated,%: R 13.36; N 12.06.

Subject invention

1. Method for preparing 0, O-dialkyl-L-acetimido-p-cyanoalkylphosphonates of the general formula (RO) 2P - CHR - CHR - CN

sn.

ns II o

where H and RI are hydrogen or alkyl, characterized in that the O, O-dialkyl-M-acetamidophosphite is reacted with a N-nitrile of the carboxylic acid, followed by isolation of the target product by known methods.

2. Method according to n. 1, characterized in that the process is carried out in an organic solvent medium, such as benzene, and heated.

3. Method but n. 1, characterized in that the process is carried out in the presence of an alkali metal alcohol, for example sodium ethnlate, as a catalyst.