SU399509A1 - METHOD OF OBTAINING N, N-TETRA-ALKYL DIAMIDIDE S-ALKYD DIOPHOSPHORIC ACIDS - Google Patents

Description

one

The invention relates to the field of the preparation of phosphorus acid ester amides, in particular, to a process for the preparation of the new I N-tetraalkyldiamides S-alkyl dithiophosphoric acids of the general formula

(R, N), PSR

These compounds can be used as physiologically active substances.

i (R7N)) H + 2P-jS5-5Et - 5i-R t5) 2Pt

(, + EtjlQ-Hal

The method of obtaining N, N-tetraalkyl diamonds of S-alkyl dithiophosphoric acids is based on a reaction that has no analogy in the literature. The essence of the method is that 1, K-tetraalkyl diamide of phosphorous acid is reacted with phosphorus pentasulfide B in the presence of a tertiary amine, for example triethylamine, In an inert organic solvent, for example tetrahydrofuran, followed by treatment of the reaction mixture with alkyl halide.

The reaction proceeds according to the scheme:

Rhal

Ijh-et bc

The interaction of acidic amide of phosphorous acid with phosphorus pentasulfide occurs with self-grinding of the reaction mixture. Alkylation of the resulting salts with alkyl halides is also easy.

Target products are isolated by means of production, yield up to 73%. Products were chromatographed on alumina grade III

Vrokman activity in the A-acetone system:: benzene (1: 2).

Example 1. Tetraethyldiamide methyldithiophosphoric acid.

57 g (0.029 mol) of tetraethyldiamide phosphoric acid are added dropwise to 2.6 g (O, C 12 mol of phosphorus nentasulfide in 15 ml of tetrahydrofurap and 3 g (0.029 mol) of triethylamine. After the mixture is stirred for 1.5 hours and added 4.3 g (0.029 mol) of methyl iodide are dripped in. The precipitate precipitates. The mixture is stirred for 15 minutes and spilled,

the filtrate is diluted. Yield 4 g (68%).

T. Kip.

/20

125-127-С / 1 mmHg v .; one

1.177o;

but

Rf 0.9

 Paidepo 73.67; calculated 73,32;

in system A.

-1aid%: N 10.91.

Calculated%; N 11.01.

P p i; meper 2. Tetramethyldiamide methyldithiophosphory acid.

The product is prepared from 5.5 g (0.041 mol of tetramethyldiamid phosphorous acid, 3.6 g (0.016 mol of phosphorus pentasulfide, 4.1 g (0.041 mol) of triethylamine, 5.8 g (0.041 mol) of methyl iodide in 30 ml of tetrahydrofurap analogue to example 1. Yield 4 g (50%).

 1.5495; df

T. Kip. 90-93 ° C / 1 mm Hg. v .;

1.1252; .MRo: peydepo

56.10; calculated 55.84; A / 0.9 in system A.

Found,%: C 30,62; H 7.80; P 15.13; S 31.48; N 14.74.

Calculated,%: C 30.28; P 7.62; R 15.62; S 32.34; N 14.12.

Example 3. Ethyldithiophosphoryic acid tetramethyldiamide.

The product is obtained from 7.3 g (0.053 mol) of tetramethyl lassamide phosphorous acid, 5 g (0.022 mol) of phosphorus peptasulfide, 5.6 g (0.053 mol) of triethylamine, about g (0.053 mol) of ethyl bromide in 35 ml of tetrahydrofuran as in Example 1, After ethyl bromide was added, the reaction mixture was heated at 40-45 ° C for 1 hour. Yield 5 g (44%). T. Kip. 105-107 ° C / 1 mm Hg. v .; 1.5457: 1.0894;

MRo is 11.61; calculated 60.46; Rf 0.9 p ciiCTCMe A.

Found %: C, 33.85; H 8.41; R 14.09 Bn: iso with o,%: C 33.94; H 8.07; R 14.58 P i m i r 4. Tc-traetilllpamid pronyldithiof (; s: (loric acid.

Pro, .ukt is obtained from 5.7 g (0.03 mole tetpriiiT .U, jiaMn;: a phosphorous acid, 2.7 g (0.01;,;.; &Amp;) phosphorus petiasulfide, 3 g (0, 03 mo of triethylamine, 5 g (0.03 mol) of nropyl iodide in 15 ml of tetrahydrofuraa is analogous to Example 1. After adding iodide of propyl, the reaction mixture is stirred at 60-66 ° C for 30 minutes Yield 6.1 g (73%). T. bale 80-85Т / 3-10 mm Hg - 1.5197; rff L02I6; MRn- found 84.00; calculated 83.55; Rf 0.9 in the benzene system. 84; H 9.73; P 10.38.

C, 46.77; H 9.63; R 10.96.

Calculated

Subject invention

The method of obtaining N, M-tetraalkyldiamide Z-alkyldithiophosphoric acids of General formula

(R, N), PSR

where R p R is alkyl,

characterized in that phosphoric acid K-tetraalkyldiamide is reacted with phosphorus nentasulfide in the presence of a tertiary amine in an inert orycanic solvent, followed by eG1 by treating the reaction mixture with alkyl halide and isolating the target product with known namisamn.