SU763350A1 - Method of preparing 2-oxo-2-ethoxy-5-diethylphosphono-1,2-oxaphospholanes - Google Patents

Description

Invention; relates to the chemistry of organophosphorus compounds, specifically to the method of obtaining new 2-oxo-2-ETOXI-5-DIETHYLPHOSPHONO-1, 2-oxyaphospholanes of the general formula 1 y of P (o) (oc; rHv) g f B, Ovr-o where R, is hydrogen, methyl or phenyl Rj is hydrogen or methyl, which can be used as antiviral drugs and intermediates for the synthesis of physiologically active substances. 2-OXO-2-ETOXI-5-DIETHYLPHOSPHONO-1, 2-oxaphospholanes and methods for their preparation are not described in the literature. However, substances of a similar structure are known, for example, extinated 1-oxa-2-phosphacyclopentenes-4, obtained by the interaction of the partial esters of phosphorus (P1) acids with conjugated enones 1. In this way, cyclic compounds containing only one phosphorus atom in each kule. Based on this method, it is not possible to synthesize 2-oxo-2-ETOXI-5-DIETHYLPHOSPHONO-1, 2-oxaphospholanes with two phosphorus atoms. The aim of the invention is a method for preparing 2-OXO-2-ETOXI-5-diethylphosphono-1 , 2-oxaphospholanes of formula I. The goal is achieved by the described method for the preparation of 2-oxo-2-ETOXI-5-DIETHYLPHOSPHONO-1, 2-oxaphospholanes of the formula 1, concluded that the sodium salt of diethylphosphorous acid is reacted with an o, / b-unsaturated carbonyl compound, of the formula R CH — CHCORz, where R, and R2 have the indicated values, in the presence of dystilphosphorous acid at a temperature from (-) 5 to 40 ° C in the medium: a blackened organic solvent. The process is carried out in the following manner. To the sodium salt of diethylphosphorous acid, prepared from 0.1 g of sodium and 0.22 gmol of diethylphosphite in 100 ml of dry benzene or ether, is added with a 0.1 g / ml carbonate compound. After finishing rb

The mixture is neutralized with acid, washed with water. The 2-oxo-2-ethoxy-5-diethylphosphono-1, 2-oxaphospholanes are purified by fractionation in vacuo. Reactions proceed according to the scheme.

B, (jHe ((JtH50), FONa4 - ((JjH90) tPHO

H, N-YENG; O1 g () (°) °,

(oh, n),

one

- -B; CH- (iHi-c P (o)),

forerunner

Osip-OjdzHsOHj

(i

The formation of 1, 2-oxaphospholanes (1) occurs by the addition of two molecules of diethylphosphorous sodium both in and in C to O-fold bonds of the unsaturated carbonyl compound. The resulting 1-hydroxy-3-diethylphosphono-propane-phosphonic acid (J) derivatives, when heated or distilled under vacuum, do not regroup to phosphates, and the alcohol is cleaved, giving the compounds of formula 1.

The use of the sodium salt of dialkylphosphorous acid makes it possible to involve in the addition reaction both CbO and C – C multiple bonds of unsaturated carbonyl compounds. This extends the synthetic possibilities based on the partial esters of phosphorus (III) acids.

The desired compounds of formula 1 can serve as the basis for the synthesis of novel organophosphorus compounds. 2-OxO-2-ETOXI-5-DIETHYLPHOSPHONO-1, 2-oxaphospholane showed activation activity against the A2 influenza virus (Leningrad strain, 34/73).

The proposed method is extended to oi, p -limit aldehydes, and ketones. The optimal conditions for the synthesis of compounds (I) are: the use of an excess of diethylphosphorous sodium, the presence in the reaction mixture of diethylphosphorous acid, conducting ractions at a temperature of (-) 5 (+) (at elevated temperatures, the resinification of the reaction mixture occurs); the use of an inert organic solvent (ether, benzene) in which the starting diethylphosphorous sodium is capable of dissolving.

In general, the reactions of the sodium salts of dialkylphosphorous acids with:,, / L-unsaturated carbonyl compounds are complex. In addition to the target compounds, substances (4-5) are formed, which are addition products of dialkyl phosphites.

HE

R, H-dH2doB.j

E, YN "YH (; (k,) R (OYNN5),

(0 (J2He) j

C5;

by CgC or C O-fold bonds. In the case of acrolein, esters of 15 1-diethylphosphonopropanophosphoric acid (6) are also isolated

(J2H5dHOP (0) (0 {J2H5)

about p (oygN5) g

ABOUT

The structure of 2-oxo-2-ethoxy-5-diethylphosphono-1, 2-oxaphospholanes (1) is confirmed by elemental analysis, molecular refraction, and IR and NMR (31p) spectra. Purity control method. In the IR spectra of compounds (1), there are absorption bands (-5); 980, 1040-1050 (РОС) 1170-1180 (РОСгНз), 1260-1290 () 1505, 1610, 3070 (benzene core), there are no bands characterizing, OH groups. in the NMR (Enr) spectra, two signals are observed, the first of which (5pi-41 - 49 ppm) refers to the resonance of the p core entering the phospholane cycle, the second to the exocyclic phosphonogroup (Spj19 - 22 MD). The course of the reaction is confirmed by conducting it in stages.

Example. Preparation of 2-oxo-2-ETOXI-5-DIETHYLPHOSPHONO-1, 2-oxaphospholane.

To the sodium salt of diethylphosphorous acid, obtained from 2.87 g (0.125 g-atom) of sodium and 34.5 g (0.25 g-mol) of diethylphosphite in 100 ml of dry benzene, 7 g (0.125 g-mol) of acrolein and 30 ml of dry ether at (-) 5 - (+) 10 ° С. After completion of the reaction, the mixture is neutralized with an equimolar amount of acetic acid, washing with

water The organic extracts are dried over anhydrous and fractionated. The 1-hydroxypropane-3-enphosphonic acid distil ester, 1-diethylphosphonopropano-phosphoric acid 1-diethyl ester and 2-OXO-2-ETOXI-5-DIethylphosphono-1, 2-oxa-phosphonolane, was isolated in an amount of 3.6 g (10%). Bp 143C (0.06 mmHg), A 1.2232, p 1.4588 MRjj 63.30, vych. 63.89.

Found,%: C 37.87, H 7.20; P 2i; 25.

.

Claims (1)

Claim The method of obtaining 2-oxo-2-ethoxy-5-diethylphosphono-1,2-oxaphospholanes of the General formula R.-CH ^Y C I 0 = P - O OC ₂ H _ff R, is hydrogen, methyl or phenyl, R ₂ is hydrogen or methyl, which is the sodium salt of diethylphosphoris, where's that! that acid is reacted with coi, a p-unsaturated carbonyl compound of the general formula R <CH ^ CHCOR _Z , where K <and R ₂ have the indicated meanings, in the presence of diethylphosphorous acid at a temperature of (-) 5 to 40 ° C in an inert organic solvent.