SU1293187A1 - Method of producing beta-nitroalkylphosphorylic compounds - Google Patents

Abstract

This invention relates to the chemistry of organophosphorus compounds with a C-P bond, namely, the production of / 3-nitroalkylphosphoryl compounds of the general formula RR P (0) CHR -CH2NO (I), where R is alkyl, alkoxy, phenyl, R-alkoxy or phenyl, R is hydrogen or alkyl, which can be used as intermediates for organophosphorus synthesis. Compounds of formula I are prepared by adding a solution of a hydrophosphoryl compound and 1-nitro-1-alkene in an aprotic solvent of trimethylchlorosilane, treating the mixture with triethylamine at an equimolar ratio of the reactants and a temperature of 0-20 ° C, followed by adding water to the resulting reaction mixture. The yield of products 82.7-100%. 1 tab. with (L

Description

The invention relates to the chemistry of organophosphorus compounds with a C — P bond, namely, an enhancement of a different method for the preparation of p-nitroalkyl-phosphoryl compounds of general chemistry.

P-CH-CH NO

 i About R (I)

The pot is kept for 0.5 h in the open air, then distilled in a vacuum. 18.8 g (89.0%) of 0,0-dimethyl-N-ethyl-p-nitroethylphosphinate with b.p. 5 (1.5 mm) n j 1-, 4490, df 1.2250, Found,%: C 34.10, H 6.70, N 6.72, P 14.60,. Calculated,%: C 34.12, H 6.64, N 6.64, R 14.69. IR (NaCl, cm): 1254 W (), 1032, 1060 (PO-C), 1380, 1562 (NOj). PMR (CCl4.5, ppm J, Hz): & (CCH) 1.07 /. J (W-0 6.6 /, (CF) 1, (PH) 17.8 /, & H) 2.65 / 2 J (RI;) 21.8, J (NCCY) 6.2 /, O (OCH) the number of intermediates of phosphorus boric acid is 15 3.74 / J (PH) 10.7 /. NMR P (ppm):

5p 30

Rimerz. To a solution of 1.38 g (0.01 mol) of diethylphosphite, 0.87 g (0.01 mol) of 1-nitro-1-propene and 1.09 g (0.01 mol) of trimethylchlorosilane in 10 ml of dieth1- while stirring ether, 1.0 g (0.0 mol) of triztilamine was added dropwise with stirring and 5 ml of water was added, and the filter cake was R - alkyl, alkoxy, phenyl;

R is alkoxy or phenyl;

R is hydrogen or alkyl, which can be used in any synthesis.

The purpose of the invention is to simplify the process and increase the yield of the target products.

Example 1. To a solution of 11, 0 g (0.1 mol) of dimethyl phosphite, 8.7 g (0.1 mol) of 1-nitro-1-propene and

10.8 g (0.1 mol) of trimethlchlorosilane in 70 ml of benzene with stirring and 0 ° C 10.1 g (0.1 mol) of triethylamine are added dropwise. After the total amount is added, it is stirred for another half hour, 15 ml of water are added to dissolve triethylamine hydrochloride. The upper benzene solution is separated, dried with sodium sulfate, and the benzene is distilled off. The residue is distilled under vacuum.

16.9g (85.8%) 0,0-dimethyl-оС-methyl-β-p-nitroethylphosphonate with a bp. 80-81 ° (0.05 mm), n ° 1.44476, 1.2640. Found,%: C 30.40,

H 5.98, N 7, p5, P 15.80. . Calculated,%: C 30.46, H 6.09, N 7.11, R 154. IR (NaCl, cm): 1256 (), 1030, 1062 (PO-C), 1382, 1565 (N0).

PMR (CC14, S, ppm J, Hz): 8 (L– –CH,) 1.29 / J (PH) 17.8 /, S (H) 2, (PH) 21.5, b (NSNHD) 7.1 / JnOCHj) 3.79 / J (PH) 10.6 /. NMR P (ppm) b 30. Lit. data T.kip. 80-814. (0.05 mm) rf ° 1,4473,

20

25

air is removed in vacuo, oj7.0

1.2635.

tatok 0.5 hours incubated in the open air. 2.04 g (90.5%) of 0,0-diethyl-iC-methyl-p-nitroethyl phosphonate with m, kip was isolated. 82-83 ° С (0.5 mm) 30 Pd ° 1.4412, df 1.1581. Found,%: C 37.38, .. H 7.19, N 6.50, P 13.70 C, H | tNOc.P. Calculated,%: C 37.33, H 7, lb N 6.22, P 13.78. . I

Example 4. To a solution of 14.2 g

35 (0.1 mol) O-chloroethylmethylphosphonite, 8.7 g (0.1 mol) of 1-nitro-1-propene and 10.8 g (0.1 mol) of trimethylchlorosilane in 100 ml of diethyl ether with stirring and 20 With pry 40 drop of 10.1 g (0.1 mol) of triethylamine. 15 ml of water are added, the ethereal solution is separated, washed with water, dried with sodium sulfate, the ether is removed in a vacuum of 0.1 mm until constant.

45 full weight. 23.0 g of () O-p-chloroethylmethyl-o-methyl-β-nitroethyl phosphinate are obtained in a B-section of a viscous, non-distilled liquid with Pr 1.4850. Found,%: C 31.00, H 5.75, N 5.90,

50 P 13.78. (; gK ,,. Calculated,%: C 31.37, H 5.66, N 6.10, P 13.51. NMR data P: B. p 58 ppm

Example2. To a solution of 11.0 g (0.1 mol) of dimethylphosphite, 10.1 g (0.1 mol) of 1-nitro-1-butene and 10.8 g (0.1 mol) of trimethylchlorosilane in 60 ml of dioxane with stirring and 20 ° C, 10.1 g (0.1 mol) of triethylamine was added dropwise and 15 ml of water was added. After completion of the reaction, the precipitate is filtered off, the dioxane is distilled off, or the mixture is evaporated. To a solution of 1.38 (0.01 mol) diethylphosphite, 0.87 g (0.01 mol) of 1-nitro-1-propene, and 1.09 g (0.01 mol) of trimethylchlorosilane in 10 ml of dieth 1.0 g (0.0 mol) of triztilamine is added dropwise with stirring and 5 ml of water are added, the filter cake is filtered.

The ether is removed in vacuo, the residue is kept in the open air for 0.5 hours. 2.04 g (90.5%) of 0,0-diethyl-iC-methyl-p-nitroethyl phosphonate with m, kip was isolated. 82-83 ° C (0.5 mm) 0 Pd ° 1.4412, df 1.1581. Found,%: C 37.38, .. H 7.19, N 6.50, P 13.70 C, H | tNOc.P. Calculated,%: C 37.33, H 7, lb N 6.22, P 13.78. . I

Example 4. To a solution of 14.2 g

5 (0.1 mol) O-α-chloroethylmethylphosphonite, 8.7 g (0.1 mol) of 1-nitro-1-propene and 10.8 g (0.1 mol) of trimethylchlorosilane in 100 ml of diethyl ether with stirring and 20 ° C drip 10.1 g (0.1 mol) of triethylamine. 15 ml of water are added, the ethereal solution is separated, washed with water, dried with sodium sulfate, the ether is removed in a vacuum of 0.1 mm until constant.

5 full weight. 23.0 g of () O-p-chloroethylmethyl-o-methyl-β-nitroethyl phosphinate are obtained in a B-section of a viscous, non-distilled liquid with Pr 1.4850. Found,%: C 31.00, H 5.75, N 5.90,

0 P 13.78. (; gK ,,. Calculated,%: C 31.37, H 5.66, N 6.10, P 13.51. NMR data P: B. p 58 ppm

Example5. To a solution of 1.25 g. (0.01 mol) of 0-methylphenylphosphonite,

5 g (0.01 mol) of 1-nitro-1-butene and 1.09 g (0.01 mol) of trimethylchlorosilane in 10 ml of diethyl ether were added dropwise with 1.0 g (0.01 mol) of triethylamine. Add

5 ml of water, after dissolving the precipitate, an additional 20 ml of ether is added, the ether solution is separated, it is washed with water, dried with sodium sulfate, the ether is removed in a vacuum of 0.1 mm to constant weight. 2.2 g (98.5%) of 0-methylphenyl-c-ethyl-p-nitroethylphosphinate are obtained in the form of a viscous, non-distilled liquid, 5265. Found: C, 51.39; H, 6.15; N5.20; P, 12.20. C ,, H, 5N04P .. Calculated,%: C 51.36, .H 6.23, N 5.45, P 12.06. R: 8p 43 ppm

Example To a solution of 2.0 g (0.01 mol) of diphenylphosphinite, 0.87 g (0.01 mol) of 1-nitro-1-propene and 1.09 g (0.01 mol) of 8 trimethylchlorosilane in 15 ml of diethyl ether with stirring and 20 ° C. was added dropwise with 1.0 g (0.01 mol) of triethylamine. 5 ml of water are added, after dissolving the precipitate, an additional 20 ml of ether is added, the ether solution is separated, washed with water, dried with sodium sulfate, the ether is removed in a vacuum of 0.1 mm. 2.7 g (93.4%) of diphenyl-o1-methyl | -nitroethylphosphine with so pl. 128-129 ° C (recrystallization from a mixture of benzene and hexane). Found: C, 66.08; H, 5.68; N, 4.97; P, 10.67. CijHt NOjP. Calculated,%: C, 62.29; H, 5.54; E, 4.84; P, 10.76.

Compiled by L. Karunina Editor I. Segl nick Tehred V. Kadar Proofreader A. Ilyin

Order 344/26. Circulation 348. Subscription VNISHS USSR State Committee

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

Production and printing company, Uzhgorod, st. Project, 4

Other nitroalkylphosphoryl compounds shown in the table are prepared similarly.

Claims (1)

Invention Formula The method of obtaining / 3-n 1troalklphosphoryl compounds of General formula R Lr-ns-sh 1 / n I Oh i R where R is alkyl, alkoxy, phenyl; R is alkoxy or phenyl; To - hydrogen or alkyl, the interaction of hydrophosphoryl derivative with 1-nitro-1-alkene, characterized in that, in order to simplify the process and increase the yield of the target products, the process is carried out by adding trimethylchlorosilane to the solution of the hydrophosphoryl compound and 1-nitro-1-alkene in an aprotic solvent, processing this mixture with triethylamine at equimolar ratios of all reagents and temperature 0-20 C, followed by adding water to the resulting reaction mixture.