SU1456437A1 - Method of producing 1-(phosphorus(v)-substituted 1-acylalkyldiethyl phosphites - Google Patents

Abstract

The invention relates to phosphorus-containing substances, in particular the preparation of: 1-phosphorus (V) substituted 1-acyl alkane diethylphosphites with total (R, 0) aP (0) -CRiCC (0) R3J-0-P (.) J, where R and RJ-- lower alkyl of normal or isostructural; tert-butyl, semi-products for the synthesis of complexons and extragents. The goal is to create a new universal way. obtaining new substances of the specified class. The process is carried out by the reaction of 0,0-diethyl (acyl) phosphonite with the corresponding / -carbonylphosphonate at 50- in an inert gas atmosphere, and it is better to use o -carbonylphosphonate with a 5-10% excess of stoichiometry. Output, %; bp, & (mm Hg), gross f-la; a) 75; 128 (1); 1.4500; S.N.O. b) 71; 145 (1); 1.4565; C 134 (1); 1.4610; With f-ly. ,, c) 65; 0, P, 1C. with s ate

Description

one

This invention relates to the chemistry of organophosphorus compounds, namely, to a new method for producing novel 1-phosphorus (V) substituted 1-acylalkyldi-ethyl phosphites of the general formula

R.

-hv; o) 2p-s-o P (os2H5) g

about C (0) R,

(I)

 where R and R are normal or isostrate lower alkyl;

RJ - t-butyl,

these compounds include, along with the t-coordinated phosphorus-phosphorus (V) atom, the group containing and carbo. nip group and can be used as semi-finished products for

-production of complexones and extragents.

The aim of the invention is to develop a new universal method for the production of 1-phosphorus (V) substituted 1-acyl alkyl diethyl phosphites.

This goal is achieved by the proposed method of obtaining the desired products of formula (I), namely, that 0,0-diethyl (acyl) phosphonite is subjected to interaction with the corresponding o-carbonyl phosphonate, at 50-90 ° C in an inert gas atmosphere.

In the reaction, it is desirable to introduce o - carbonylphosphonate in 5-10% excess of stoichiometry.

four

sd

O5 4

oo

(RO) oP CR, F, CP (OC2H5) o- f 11 1 2 3 || gag

00 Oh

R.

.14564374

The assay of the target products (I) is confirmed by elemental analysis, IR and | NMR 1 H, 13 C, E1p,.

All reactions and the allocation of target i products (1) are carried out in a dry argon atmosphere.

Example 1. 1-Diisopropoxyphosphonoxido-1-pivaloylethylHdiethyl) phosph- .10; Fit1 (1a).

where R, s, R 3 the indicated values To 3.4 g (0.0158 mol, 5% of the proposed method allows an excess) of 0,0-diisopropyl-acetylphosphonate to emit compounds with a code up to 75%, and 3.2 g are added with stirring -, (0.0155 mol) 0, 0-diethylpivaloylphosphonos-like acylphosphonites and cf-carbonate, the mixture is stirred in

(B, 0)., P-C-0 t (OC2.H5) g.

about CiO) R,

nilphosphonates of various structures, due to which the widespread use of target products (1) in organic and element-organic synthesis becomes possible.

The absence of organic solute and precipitation during the process makes

the method of preparative 57.5 5J2 Hz; ) and agko reproducible; 12.43 ppm, d; J RS 2.6 GD; IIL

The proposed method is based on D-25 t33.75 ppm, d} ff Y 14.10 ppm, d; the action attaches the acylphosphonite J 5 9 Hz along the carbonyl carbon group (carbonylphosphonate with a broken phosphorus carbon bond and the formation of a fragment (0)) and is a new direction for the lazy condensation of two c-carbonyl containing phosphorus containing: reagents,

A minor excess of starting with (-carbonylphosphonate allows you to quickly complete -re & ktspyu and avoid the formation of by-products. Increase the excess o (carbonylphosphonate is not (0.015 mol)) 0 ,, 0-diethylpivaloylphosphine leads to an increase in the yield of the target fonite and 4.0 g (0.0165 mol, 10% product, and with a stoichiometric excess) 0.0-diisoprope 1 (isobutyryl), the ratio of reagents off-40 phosphonate during the process ko decreases. The process readily proceeds; at 90 ° C for 3 h, W obtained by heating, see baseline 4.7 g of phosphite (16), yield 71%, bp d - carbonylphosphorus containing reagents (1 mm Hg), p 1.4565. Fragments at 50-90 ° Sa. low. ment P (0) -C () - 0-P: V ()

45 1700cm-; 94.78 ppm, ro 148.3 Hz; fc () 212.47 ppm, d;

for 1 h until the characteristic yellow-green color of the starting pivaloyl phosphonite disappears and is distilled. 4.8 g of phosphite (la) are obtained, yield 75%, 20 bp. 128 C (1 mm Hg), n |, l, 4500, Fragment P (0)) - 0-P; V () 1700 J SGS 86.95 MD, d; J pc

Found,%: C 49.43; H 8.97; R 14.90,

With ttN 3

Calculated,%: C 49.27; H 8.76, R 14.95 ,.

Example 2. 1-Diisopropoxy-phosphine sido-1-pivalo or isobutyl (diethyl) phosphite (16).

temperatures, the reaction rate slows down dramatically, and the yield decreases significantly; at higher temperatures, a decrease in the yield is observed due to a significant resinification of the reaction mixture and the formation of by-products. The presence of an inert gas atmosphere prevents the oxidation of three-coordinated phosphorus.

J pc 2.4 Hz; fp III 133.46 ppm, s; “PP Y 14.29 MD, p.

Found,%: C 51.69; H 9.15; 50 P 3.92.

C 19 N

Calculated,%: C, 51.57; H 9.11; R 14.00.

Example 3. 1-Diethoxyphosphine-Received Compounds (1) -stable-gg Noxidho-1-pivaloipizobuch1 (diethyl) feed liquids, distilled at. Spit (1c).

Analogously to example 1 of 3.7 g

(0,0179 mol) 0,0-diethylpivaloylphosphonite and 4.0 g (0.0192 mol, 8%

reduced pressure, can be stored in an inert gas atmosphere for a long time. Composition and structure 57, 5 5J2 Hz; ) 12.43 ppm, d; J RS 2.6 GD; IIL

for 1 h until the characteristic yellow-green color of the starting pivaloyl phosphonite disappears and is distilled. 4.8 g of phosphite (la) are obtained, yield 75%, b.p. 128 C (1 mm Hg), n |, l, 4500, Fragment P (0)) - 0-P; V () 1700 J SGS 86.95 MD, d; J pc

t33.75 ppm, d} ff Y 14.10 ppm, d; J 5 9 Hz

 Analogously to Example 1 of 3.1 g (0.015 mol) 0,, 0-diethylpivaloylphosphonite and 4.0 g (0.0165 mol, 10% excess) of 0.0-diisopropsh 1 (isobutyryl) Phosphonate during the process with 90 ° C for 3 hours, 4.7 g of phosphite (16) are obtained, yield 71%, b.p. (1 mm Hg), p 1.4565. Fragment P (0) -C () - 0-P: V ()

Found,%: C 49.43; H 8.97; R 14.90,

With ttN 3

Calculated,%: C 49.27; H 8.76, R 14.95,

Example 2. 1-Diisopropoxy-phosphine sido-1-pivalo or isobutyl (diethyl) phosphite (16).

1700cm; 94.78 ppm, ro 148.3 Hz; fc () 212.47 ppm, d;

J pc 2.4 Hz; fp III 133.46 ppm, s; “PP Y 14.29 MD, p.

Found,%: C 51.69; H 9.15; P 3.92.

C 19 N

Calculated,%: C, 51.57; H 9.11; R 14.00.

excess) 0,0-diethylisobutyrphosphonate with after 3.5 h of heating, 4.8 g of phosphite (1c) is obtained, yield 65%, bp. (1 mm Hg), p I, 1.4610. Fragment; P (0) -C () - 0V () 1700 L 94.72 ppm, d; JpcU6.1 Hz; L) 212.37 m. d; Jpc2.1 Hz; cGy III 134.57 ppm, s

cfp, 23 MD, p.

Found,%: C 49.33; H 8.56; R 14.64.

Calculated,%: C 49.27; H 8.76;

R 14.95. . Example 4. 1-Diisopropoxy-phosphoxyoxido 1-brew aloilis on SDITSH1) PHOSPHIT (16) salvos:

Analogously to Example 2, of 3.9 g (0.0189 mol) of 0,0-diethylpivaloyl phosphonite and 4.5 g (0.0189 mol, no excess) of O, 0-diisopropylisobutyryl phosphonate in 3 hours at 4.5 g phosphite (16), yield 53%, physico-chemical costants are given in example 2.

Thus, the proposed method of obtaining the desired products (I) allows to obtain these compounds with high yields under relatively mild conditions.

The method is simple, does not require complex instrumentation and, if necessary, can be easily extended to the target products (I) of various structures - important intermediates of organophosphorus synthesis. The method is an example of a new condensation of two o-carbonylphosphorus-containing reagents to create a fragment of P (0) -C ()

in organophosphorus compounds.

Claims (2)

1. A method of producing 1-phosphorus (V) of measured D-acylacipylethyl phosphites of the general formula  . (I O), - c-O-RSOsOnch)   I about with (osh where R and R j are lower normal or iso-alkyl; tert-butyl, consisting in that 0,0-diethyl (acyl) phosphonite is reacted with the corresponding o-carbonyl phosphonate when heated to 50-90 ° C in an inert gas atmosphere. 2. The method of claim 1, wherein the o / -carbonylphosphonate is used in a 5-10% excess of stoichiometry.