SU1302665A1 - Method of producing 2-oxo-1,4,2-dioxaphospholanes - Google Patents

Abstract

This invention relates to the chemistry of heterocyclic organophosphorus compounds with a C-P bond, namely, to a new method of producing 1,4,2-dioxaphospholanes not previously described, a co-s pulling four coordination atom of phosphorus and alkyl radicals in the 3.5-position, total Formula R CH-0- (0) P (OR) -CHR-6, R and R - lower alkyl. The compounds obtained can be used as complexones and extractants of cations of various metals, as well as phosphorus-containing ligands in catalysts for stereo-directed synthesis of organic substances. The invention allows to obtain 2-oxo-1,4,2-dioxaphospholanes in high yields. The method consists in that a 0,0-dialkyl- (biscarbalkoxymethyl) phosphonite of the general formula (R o) PCH (COOR) 2, where R and R are lower alkyl, is reacted with a stoichiometric amount of aliphatic aldehyde (3 mol) at room temperature in an inert gas atmosphere. i (L co o to o o) SP

Description

The invention relates to the chemistry of organophosphorus compounds with a C-P bond, specifically to a new method for producing 1,4,2-dioxaphospholanes not previously described with the general formula

K-CH-0.

oh and

0 OR

where R and R are lower alkyl,

which can be used as complexones and extractants of cations of various metals, as well as phosphorus-containing ligands in catalysts for stereo-directed synthesis of organic substances

The aim of the invention is to develop a new available method for the preparation of 2-OXO - 1,4,2-dioxaphospholines.

The following examples illustrate the invention.

All reactions are carried out in an atmosphere of dry inert gas (argon).

EXAMPLE 1. To 0.05 mol of 0.0-diethyl- {biscarbethoxymethyl) phosphonite, 0.1 mol of acetic aldehyde was added to ensure that the temperature of the reaction mixture did not exceed 20 ° C. the mixture is stirred for 1 hour and 0.05 mol of aldehyde is added. After stirring the reaction mixture in vacuo, 5.85 g (65%) of 2-0-ztil-2 oxo-3,5-dimethyl-1,4,2-dioxaphospholane, b.p. (0.02 mm Hg),

p 1.4410 .. Spectrum, S J 22.42 m.

4 °

Found,%: C 39.85; H 7.07; P 17,14

SbN, s04r

Calculated,%: C 40.01; H 7.27; R 17.19.

Example2. In a similar procedure, from 0.05 mol of 0,0-diethyl- (bis-carbethoxymeth1) phosphonite and 0.15 mol of propionic aldehyde, the time of the first reaction stage is 2 hours, the time. The second stage of the reaction takes 2.5 hours. g (59%) 2-0-ethyl- -2-oxo-3, 5-diztil-1,4,2-dioxaphospholane, bp. 57 C (0.02 mmHg) 1.4467. NMR P spectrum: 24.84.

Found,%: C 46.05; H 8.08; R 15.48

SaN

G7

o

Q

five

50

0

five

0 5

Calculated,%: C 46,15; H 8.23; R 14.88.

Example According to the procedure outlined above, from 0.05 mol of 0,0-diethyl- (biscarbethoxymethyl) -phosphonnt and 0.015 mol of isobutyraldehyde, 5.05 g (43%) of 2-0-methyl-2-oxo- 3,5-diisopropyl-1,4,2-diox-phospholane, bp. 0.02 mm Hg P 1.4609. Spectrum H1-1R P: 23.02 ppm

Found%: C 51.02; H 8.94; R 12.73.

C ,, 04Р

Calculated,%: C 50.84; H 8.96; P 13.11

Example4. 0.05 mol of 0.0- | -diisopropsh1- (biscarbethoxymethyl) -phosphonite is added with O, mol of propionic aldehyde and the reaction mixture is stirred for 6 hours. Then another 0.05 mol of aldehyde is added to the reaction mixture and stirred at room temperature another 8 hours. After distillation in vacuo, 4.4 g (40%) of 2-0-isopropyl-2-oxo-3,5-diztil-1,4,2-dioxaphospholane, mp. 69 ° C (0.02 mmHg) n, 1.4654.

NMR P spectrum 8: 21.05 ppm

Found,%: C 48.50; H 8.42; Р 213.62

SdN „0ts P

Calculated,%; C 48.64; H 8.62; R 13, -94,

Examples of the influence of the ratios of reagents in the first stage of the process, when using the ratios of aliphatic aldehyde and starting methylphosphonite 1: 1 in the second stage (the reaction was monitored using the method)

Example5. CO, 05 mol of 0,0- -distil- (biscarbethoxy) -methylphosphonite, 0.05 mol of acetic aldehyde (is) is added and the reaction mixture is stirred for 1 hour. According to the spectrum, the reaction mixture contains 56% of the original methylphosphonite and 44% ylide. A further 0.05 mol of acetic aldehyde is added, the reaction mixture contains 72% ylide, 12% starting methylphosphonite and I6% 2-0-ZTIL-2-OXO-3,5-dimethyl-1,4, 2-dioxaphospholane. After distillation, 10% of the initial methylphosphonite, 14% of 1,4,2-dioxaphospholane was isolated. During the distillation, the ilide decomposes into a mixture of non-identified phosphorus-containing products.

For example, K0.05 mol of 0.0-di ethyl- (biscarbethoxy) methylphosphonite, 0.075 mol of acetic aldehyde (1: 1.5) is added and the reaction mixture is stirred for 1 h, it contains 37% of the starting methylphosphonite and 63% ylide; 0.05 mol of acetaldehyde is added to the reaction mixture. After distillation, the reaction mixture gives 2% 1,4,2-dioxaphospholane.

-Example 7. To 0.05 mol of 0,0-di ethyl- (biscarbethoxy) methylphosphonite, 0.125 mol of acetic aldehyde (1: 2.5) is added. After stirring for 1 h, the reaction mixture contains 42% oi-alkoxyalkylphosphine - ta linear structure and 58% ylide. An additional 0.05 mol of acetic aldehyde was added to the reaction mixture and stirred.

Examples of the effect of the ratio of aliphatic aldehyde used in the second stage of the process and the starting methylphosphonite with the ratio of methylphosphonite and aliphatic aldehyde in the first stage are 1: 2.

Example CO, 05 mol of 0,0-β-diethyl- (biscarbmethoxy) -methylphosphonite was added 0.05 mol of acetic aldehyde and the reaction mixture was stirred for 1 hour. Then 0.025 mol of acetic aldehyde (1: 0.5) was added to the reaction mixture. and stirred for an additional hour. After over-distillation of the reaction mixture, 1, 4,2-dioxaphospholane is obtained with a yield of 21%.

Sample 0.05 moles of propionic aldehyde are added to 0.05 moles of 0,0-di eth1 (biscarbethoxy) -methylphosphonite and the reaction mixture is stirred for 2 hours. Then, 0 mol, is added to the reaction mixture.

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Compiled by L. Karunina

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.VNIIPI USSR State Committee

for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5

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. „

26654

aliphatic aldehyde (1: 2), stir the resulting mixture for an additional 2.5 hours. After distillation of the reaction mixture, 6.2 g (61%) of 2-0-ETHIL-2-OXO-3,5-diethyl-1 are obtained, 4,2-dioxaphospholane. Thus, an increase in the amount of aldehyde in the second stage has virtually no effect on the yield of the final product and, therefore, is impractical.

Claims (1)

Invention Formula The method of obtaining 2-oxo-1,4,2-dioxaphospholanes of the general formula R-CH-0 p, 0  OR I R where R and R are lower alkyl, consisting in that 0,0-dialksh1- .- (biscarbapkoxy) -metx1phosphonite of the general formula five 0 0 II (R O), PCH (cooR) R g lower alkyl. where r and interact with two equivalents of aliphatic aldehyde at room temperature under an inert gas atmosphere, followed by treatment of the resulting ylide of the general formula CH-0. P “C (COOR) 2 g / R where oh I r R, R and R OB have the indicated meanings one equivalent of aliphatic aldehyde under the conditions specified.