SU1278352A1 - Method of producing n-alkenylamidophosphites - Google Patents

Abstract

This invention relates to the chemistry of organophosphorus compounds,. and to a new method for the preparation of N-alkenylamidophosphites of the general formula K, K, P-HK2-CH CKK4, where R is a lower alkoxy or diethylamino group; R and R are lower alkyl; 4 hydrogen or lower alkyl, which may be used as monomers for the preparation of phosphorus-containing polymers. The aim of the invention is to simplify the process and increase the yield of the target products. The process is carried out by reacting dialkyl phosphoric acid iodohydride with azomethine of the general formula R R4CH-CH NR2, where R4 has the indicated values. The interaction is carried out in the environment of an organic solvent in the presence of triethylamine in an inert gas atmosphere at 9 at room temperature. The method is carried out in one stage, the target pro (O products are obtained with a yield of 73-84%,

Description

This invention relates to the chemistry of organophosphorus compounds, namely to a process for the preparation of N-alkenylamido-osphites of the general formula

(Ri) 2P-N-CH C- R3

% R (I)

where Rf is lower alkoxy or diethylamino; R-, and R, is lower alkyl;

R4 is hydrogen or lower alkyl, which may be used as monomers for the preparation of phosphorus-containing polymers having incombustibility, the ability to improve the quality of lubricating oils.

The purpose of the invention is a ynpoij; ein-ie process and an increase in the yield of total N-alkenyl amidophosphate (I).

Azomethine is reacted with dialkylphosphorous acid iodohydride in ether or methylene chloride at room temperature under argon in the presence of triethylamine.

EtrN (Ri) 2P —R3 — CH CH N,

C-CH-NR / t.

P (RO

I 2

Example 1, Obtaining N-tert-butyl-Y-propenylamidodiethylphosphite,

To a mixture of 11.4 g (0.1 mol) of N-tert-butyl propionalimine and 10, 1; g (O, 1 mol) of triethylamine in 200 ml of absolute ether, a solution of 24.8 g ( 0.1 mol) dystiliodiphosphate in 100 ml of absolute ether. The mixture is stirred for 10 hours. The amine iodohydrate precipitate is separated by centrifugation, the ether is distilled off, the residue is distilled in vacuo. Vykod 17.4 g (7-5%)., D 0.9433, p 1.4 197 / tp, 62 ° C / 1 mm Hg,

 5. 146 ppm IR: 1640

Found,%: C 56.2; H 11.03; R 12.3; N 5.87,

C ,, H, PN02,

Calculated, -%: C 56.65; H 10.8; R 13.3; N 6.01,

Example 2 Preparation of N-tert-butyl-N-npone N-Lamidodibutyl phosphite.

To a mixture of 11.4 g (0.1 mol) of N-trvt-butylpropionalimin and 10.1 g (O, 1 mol) of triethylamine in 200 ml of absolute ether, add g (0.1 mol) of dibutyl iodide to 100 ml of ether. The process is carried out under the conditions of Example 1. The yield is 28.2 g (84%), b.p. 60 ° C / 1, mm Hg,, 9350, n j, 1.4382,

NMR P: & 146 m, d, IR: 1635 cm,

Found,%: C 62.1; H 10.8; R 9.87; N 4.92,

C ,.

Calculated,%: C, 62.3; H 11.07; 5 P 10.73; N 4.85,

PRI me R 3. Obtaining N-tert-butyl-M-isobutaneLamidodibutylphosphite.

To a mixture of 12.7 g (0.1 mol) of N-tert-butyl-isobutyral1P-a and 10.1 g of 0 (0.1 mol) of triethylamine in 200 ml of ether, 30.4 g (0.1 mol) of dibu tiliodofosfita in 100 ml of ether. The process is carried out under the conditions of example 1, Yield-24.8 g (82%), t, kip, 112 s /

five

,20

th

0

five

0

/ 1 mmHg, St ,, d 0.9387, p 1.4525, 140 ppm, IR: 1–40 cm Found: C: 62.84; H 11.80; R 9.86 | N 4.52,

. H NPO, j,

 Calculated,%: C, 62.91; H 11.38; R 10.84; N 4.58,

EXAMPLE 4, Preparation of N-tert-butyl-N-isobutenylamido dibutylphosphite.

To a mixture of 12.7 g (0.1 mol) of N-tert-buti, lysobutyralimin and 10.1 g (0.1 mol) of triethylamine in 200 ml of methylene chloride was added 30.4 g (0.1 mol) of dibutyl iodiphosphite in 100ml, aorist methi, foam. The process is carried out under the conditions of Example 1. A yield of 22.07 g (73%), physicochemical constants, elemental analysis data, NMR and IR spectroscopy are given in Example 3,

PRI me R 5 Getting N.N-tett I

pa3Tjm-N-tert-butyl-N-propenyl tri-amidophosphite,

To a mixture of 11.4 g (0.1 mol) H-tert-0 b. Utilpropionalimin and 10.1 g

(0.1 mol) of triethylamine in 200 ml of absolute ether 30.2 g (0, 1 mol) of tetraethyl diamido iodophosphite in 100 MP ether are added. The process is carried out under the conditions of Example 1. The yield is 21.8 g (80%), b.p. 91 C / 1 mm Hg, Art.

1Lpp

five

five

, 9782, 1.4638.

. 94 MD, IR: -3 1635 cm

-one

Found%: C

9.9; N 14.87

C, H ,, PN.

Calculated

3

61.5}

H 12.01;

12

%: C 62.72; H 11.85; P 10.80; N 14.63.

Thus, the proposed method allows to simplify the process by carrying out the synthesis in one stage and eliminating hard-to-reach reagents and increase the yield of the target products in comparison with the known method from 58-69 to 75-84%.

Claims (1)

The invention relates to the chemistry of organophosphorus compounds, namely to a method for producing N-alkenylamido phosphites of the general formula (Ri) 2P-N-CH C-R3% R (I) where Rf is lower alkoxy or diethylamino; R-, and R, is lower alkyl; R4 is hydrogen or lower alkyl, which may be used as monomers for the preparation of phosphorus-containing polymers having incombustibility, the ability to improve the quality of lubricating oils. The purpose of the invention is a ynpoij; ein-ie process and an increase in the yield of total (I) N-alkenylamide phosphites. Azomethine is reacted with dialkylphosphorous acid iodohydrin in ether or methylene chloride at room temperature under argon in the presence of tr ethylamine EtrN (Ri) 2P -R3-CH CH N R; -R-C-CH-NR / t. Example 1, Preparation of N-tert-butyl-L-propenylamidodiethylphosphite, To a mixture of 11.4 g (0.1 mol) of N-tert butylpropionalimin and 10, 1; g (O, 1 mol) of triethylamine in 200 ml of ablutyl ether in 24.8 g (0.1 mol) of dimethyl iodophosphate in 100 ml of absolute ether are added at room temperature for T hours. The mixture was stirred for 10 hours. The amine iodohydrate precipitate was separated by centrifugation, the ether was distilled off, and the residue was distilled in vacuo. Vykod 17.4 g (7-5%)., D 0.9433, p 1.4 197 / tpd, 62 ° C / 1 mm Hg, 5. 146 ppm, IR: 1640 cm Found,%: C 56.2; H 11.03; R 12.3; N 5.87, C ,, H, PN02, Calculated, -%: C 56.65; H 10.8; R 13.3; N 6.01, Example 2, Preparation of N-tert-butyl-N-nponeNI lamidodibutylphosphite to a mixture of 11.4 g (0.1 mol) of N-trvutylpropionalimin and 10.1 g (O, 1 mol) of triethylamine in 200 ml of absolute ether added g (0.1 mol) of dibutyl iodine in 100 ml fira. The process is carried out under the conditions of Romer 1. Yield: 28.2 g (84%), b.p. 60 ° C / 1 mm Hg, 9350, j, 1.4382 °, NMR: & 146 m, d., IR: 1635 cm, Found,%: C 62.1; H 10.8; R 9.87; N 4.92, C ,. Calculated,%: C, 62.3; H 11.07; P 10.73; N 4,85, PRI me R 3. Getting N-tertbutyl-M-isobutaneLamidodibutylphosphate. Ksmesi 12.7 g (0.1 mol) of N-tert-butylisobuteral 1P-a and 10.1 g (0.1 mol) of triethylamine in 200 ml of ether are added to 30.4 g (0.1 mol) of dibutyl iodophosphite in 100 ml of ether. The process was carried out under the conditions of Example 1, Yield-24.8 g (82%), t, kip, 112s / 1 mm Hg, st, d 0.9387, p 1.4525, 140 ppm ,, IR: 1–40 cm Found;%: C 62.84; H 11.80; R 9.86 | N 4.52,. H NPO, j, Calculated,%: C 62.91; H 11.38; R 10.84; N 4.58, PRI me R 4, Getting N-tertbutyl-N-isobutyramide dibutylphosphite. To a mixture of 12.7 g (0.1 mol) of N-tertbuty, lysobutyralimine and 10.1 g (0.1 mol) of triethylamine in 200 ml of methylene chloride was added 30.4 g (0.1 mol) of dibutyl iodophosphite in 100 ml x, aorist methi, foam. The process is carried out under the conditions of Example 1. A yield of 22.07 g (73%), physicochemical constants, elemental analysis data, NMR and IR spectroscopy are given in Example 3, Example 5, Preparation of NN-tett I pa3Tjm-N-tert-butyl-N-propenyl triamide phosphite, To a mixture of 11.4 g (0.1 mol) H-tertbutyl propionalimine and 10.1 g (0.1 mol) of triethylamine in 200 ml of absolute ether are added 30 , 2 g (O, 1 mol) of tetraethyl diamido iodophosphite in 100 MP ether. The process is carried out under the conditions of Example 1. The yield is 21.8 g (80%), b.p. 91C / 1 mmHg, Art. 1Lpp, 9782, 1.4638. . 94 MD, IR: -3 1635 cm H 12.01; Found,%: C 9.9; N 14.87 C, H ,, PN. %: C 62.72; H 11.85; Calculated R 10.80; N 14.63. Thus, the proposed method allows to simplify the process by carrying out the synthesis in one stage and eliminating hard-to-reach reagents and increase the yield of target products compared to the known method from 58-69 to 75-84%. The invention of the method for producing N-alkenylamidophosphites of the general formula (H02P-1-cc-C2-2-lower alkoxy or diethyl-amino group; R, and R- "lower alkyl; hydrogen or lower alkyl, using phosphorous acid halide in an organic medium a solvent in the presence of triethylamine in an inert gas atmosphere, characterized in that, in order to simplify the process and increase the yield of the target products, dialkylphosphorous acid iodoanhydride is used as phosphorous acid halide, which is subjected to with azomethine of the general formula i s-CH-CH? S-R where K 1 have the indicated values at room temperature