SU535311A1 - Method for preparing phosphorylated -alkyl (-carbalkoxyethyl) vinylamines - Google Patents

Description

The invention relates to the field of chemistry of organophosphorus compounds with P-Cd linkage, specifically to a method for the preparation of phosphorylated N-alkyl-N (p-carbalkoxyethyl) vinylamines of the general formula I (P-tH CH-F-CHsCHzt OOR Ron1 OR where iR-alkyl or alkoxy; R, R, and -alkyl, which, due to their high reactivity, are promising intermediates of phosphorus synthesis, a method is known for producing phosphorylated thiosemicarbazones by reacting phosphorylated aldehydes with thiosemicarbazide in an organic solvent 1. The walls also produce a phosphoric ester amide based on the addition of a mobile hydrogen atom of the amino group of a phosphorus-containing compound to acrylic acid derivatives 2. However, the phosphorylated enamia have not been previously involved in such a reaction, and the method for preparing compounds of the formula I is not described in the literature and is an action. The preparation of new phosphorylated N-alkyl-N (p-carbalcoxyethyl) b 11 aluminum lamps, which are important intermediates of organophosphorus synthesis. The goal is achieved by the described method of obtaining phosphorylated N-alkyl-M (p -carbalkoxyethyl) viiyl amines, which consists in reacting the phosphorylated secondary enamia with an acrylic ester in an inert organic solvent at 80-90 ° C. Target products are recovered by known techniques, and distillation by vacuum distillation. Example 1. Preparation of N-butyl-M (| 3-carbmethoxyethyl) - - ethyl ethoxyphosphinylviyylamine. In a round-bottomed flask, a solution of 3.5 g (0.015 gmol) of ethyl ethyl β-butnaminovinylphosphinic acid, 1.4 g (0.017) is boiled under reflux. g-mol) methyl acrylate in 8 ml of acetonitrile for 16 hours. After the solvent is stripped off in vacuo, the residue is distilled twice in vacuo. 1.9 g (39% of theory) of the target iuro act were isolated. T. Kip. 142 ° C (1 10-s mm Hg. Art.). df 1.0656, p2o 1.4870. found MRD, 18, Calculated 81.72. H 9.00; 9.25; Found,%: C 54.90; 55.18; N 4.60; 4.72; P 9.90; 10.25. Ci4H28N04P. Calculated,%: C 55.08; H 9.18; N 4.75; R 10.16. The structure of the product is confirmed by IR and PMR spectra. In the IR spectrum there are absorption bands 1610 (7), 1736 cm (Y). 1183 (f J. in the PMR spectrum observes the SOR O resonant signal of 5 7.1 ppm (triplet), characteristic of the fragment F ett "ctt Example 2. Preparation of M-butyl-M (1p-carbomethoxyethyl) p-diisopropophosphonylphenylvinilamine. A solution of 7.5 g (0.027 gmol) of p-butylaminovinylphosphonic acid diisopropyl ester and 2.5 g (0.03 gmol) of methyl acrylate in 14 ml of acetonitrile is boiled for 16 hours. After distilling off the solvent in vacuo, the residue is distilled twice in vacuum, 3 g (36%) of the desired product were isolated. T. boils 142-144 (MO-3 mm Hg); d2o 1.0327; 1.4704. Found, 49; calculated MKv 93.16. Found,%: C 55.21, 54.92; H 9.18; 9.00; N 3.95; 4.23 ; R 9.00, 9.03. CrNsGYOZR. Calculated,%: C 55.0; H 9.16; N 4.01; P 8.88. The structure of the product was confirmed by IR and MNR spectra as in Example 1. Example 3. Preparation of M-propyl-M (p-carbmethoxyethyl) di-vgor-butoxyphosphonylvinylamine. A solution of 21 g (0.076 g-mol) of p-propylaminovinylphosphonic acid di-orgor-butyl ester, 6.5 g (0.076 g-mol) of methyl acrylate in 44 ml of acetonitrile is boiled for 16 hours. After distilling off the solvent in vacuo, the residue is distilled twice in vacuo. 10.5 g (38% of theory) of the desired product were isolated. T. Kip. 155-156 ° C (1-10-3 mm Hg. Art.); df 1.0312; p 1.4720. Found 57; calculated 98.76. Found,%: C 55.86, 56.11; H 9.24, 9.40; N 4.08, 4.15; R 8.37, 8.70. Cl7H34NOsP. Calculated,%: C 96.2; H 9.36; N 3.85; R 8.55. The structure of the substance is confirmed by IR and PMR spectra as in Examples 1 and 2. Example 4. Preparation of Mn-butyl-K (rcarbmethoxyethyl) -P-dipropoxyphosphonylvinylamine Analogously from 10 g (0.038 g-mol) dipropyl ester of p-propylamine vinylphosphonic acid, 3, 7 g (0.043 g-mol) of methyl acrylate and 36 ml of acetonitrile, 5.4 g (38% of theory) of the desired product were isolated. T. Kip. 161-162 (MO-5 mmHg. Art.); df 1.0485, p 1.4772. Found M | Rz) 94.08; calculated MNS 93 16 Found,%: C 54.87, 54.95; H 8.96, 9.12; N 4.10, 4.12; R 9.64, 9.77. CieHa NOgP. Calculated,%: C 55.0; H 9.16; N 4.01; R 8.88. The structure of the product is confirmed by IR and PMR spectra as in examples 1-3. Example 5. Preparation of N-B-op-by-l-N (Carbomethoxyethyl) -p - diproloxyphosphonylvinylamine. Similarly, 5 g (37% of theory) of the desired product was isolated from 11 g (0.042 g mol) of dipropyl ester of p-8go / 7-butylaminovinylphosphonic acid, 3.7 g (0.043 g mol) of methyl acrylate and 36 ml of acetonitrile. T. Kip. 146-147 (MO-5 mmHg. Art.); df 1.0535, p 1.4777. Found MiRo-93.72, calculated MRD 93.16. Found,%: C 54.90, 55.15; H 9.13, 9.30; N 3.91, 4.06; R 9.12, 9.30. CisHssNOsP. Calculated,%: C 55.0; H 9.16; N 4.01; R 8.88. Example 6. Preparation of H-butyl-H (p-carbmethoxyethyl) -, p-ethylisopropoxyphosphinylvinylamine Heated at 80 ° C 13.0 g (0.056 g-mol) of ethyl-p-butylaminovinylphosphinic acid isopropyl ether and 6 g (0.07 g -mol) methyl acrylate in 10 ml of dimethylformamide for 14 hours. After distilling off the solvent in vacuo, the residue is distilled twice in vacuo. 5.3 g (30%) of the desired product was isolated. T. Kip. 138-140 ° C (MO-mm Hg. Art.); j | ° 1.0295; p2 dO 1.4820. Found MRr) 87.36, calculated MKv 86.90. Found,%: C 56.28, 56.64; H 9.50, 9.63; N 4.40, 4.62; R 9.81, 10.07. Ci5H3oNO4P. Calculated,%: C 56,42; H 9.37; N 4.39; R 9.71. The structure of the product is confirmed by IR and PMR spectra as in the previous examples. Example 7. Preparation of M-butyl-; N (p-carbmethoxyethyl) -p-ethyl-sec-butoxyphosphinylvinylamine. 7.70 g (0.031 gmol) of ethyl p-butylaminovinylphosphinic acid secondary butyl ether, 3 g (0.035 gmmo) of methyl acrylate and 10 ml of dimethylformamide are heated at 90 ° C for 14 hours. After a similar treatment, 3 , 2 g (33%) of the target product. T. Kip. 152-153 ° С (1-10-4 mm p-j-. Cent.); 2 ° -1.0254; p2o 1.4820.

Found M., 9; calculated MRc 92.58.

Found,%: C 57.60, 57.83; H 9.72, 9.84; N 4.35, 4.65; R 8.93, 9.09.

С1бНз2ЫО4Р.

Calculated,%: C 57.66; H 9.60; N 4.20; P 9.30.

The structure of the product is confirmed by IR and PMR spectra.

Example 8. Preparation of N-butyl-1M (p-carbbutyloxyethyl) -p-ethylisopropoxyphosphinylvinylmine.

Similarly, 7.7 g (30%) of the desired product was isolated from 15.7 g (0.067 g mol) of ethyl p-butylaminovinylphosphinic acid isopropyl ester, 10 g (0.078 g mol) of butyl acrylate, 10 ml of dimethylformamide. T. Kip. 152-153 (1-10-4 mm Hg. Art.), Df 1,0090, 1,4800.

Found 53; calculated MRD

:: 100.75.

Found,%: C 59.65; 59.70; H 10.11; 10.19;

N 3.51, 3.77; P 9.03; 9.05.

CisHseNOiP.

Calculated,%: C 59.83; H 9.99; N 3.87; R

8.58.

The structure of the product is confirmed by IR and

PMR spectra.

Claims (2)

1.Avt. St. 362022, M.C. From 07F 9/02, 1973. 2.D. Purdela, R. Valchana. “Chemistry of organic phosphorus compounds. Ed. “Chemistry, M., 1972, p. 540.