SU548611A1 - Method for preparing 3-chloro-3,4-dihydro-1,2,3-diazaphosphol - Google Patents

Description

one

The invention relates to a process for the preparation of novel chemical compounds, specifically to a process for the preparation of 1,2,3-dipazaphosphol of the general formula

R

K, R, R and R are methyl or R and R are methyl, and R is ethyl, or iR is methyl, and R and R are each a pentamethylium group.

The target compounds are biologically active substances that can be used in pharmacology and agriculture.

A known method for producing 3-chloro-2-acetyl-5-methyl-3,4-dihydro-1,2,3-diazaphospholium by reacting acetylhydrazone of acetone with phosphorus trichloride in pre-triethylphenium in methylene chloride 1.

It is also known that arylhydrazops of a number of methyl alkyl ketopes react with phosphorus trichloride to form 3-chloro-2-aryl-alkyl-1,2,3-diazaphosphol in an absolut ester medium even in the presence of a hydrogen chloride acceptor 2.

However, the interaction of phosphorus trichloride with acetyl lactone fiylhydrazoia has not been studied.

The goal of the acquisition is the obtained compounds, namely 3-chloro-3,4-dihydro1, 2,3-d azophosphols.

The proposed method consists in the interaction of feiylhydrazone 2-aceptl-3,4,4-trialkyl-2-butene-4-alpda with phosphorus trichloride in the presence of a tertiary amine at a molar ratio of reagents of 1: 1.5: 1.5, respectively, in an inert organic solvent at a temperature of about -10 ° C, followed by heating the reaction mixture to 30-60 C.

The yield of the target compounds is 52-

Triethylampn, iirpdin, N, N-dimethylaniline, etc. can be used as a tertiary amine. The use of trinethylamine is preferable since the corresponding chlorohydrate is filtered off more easily than in other cases, and the target product is isolated in a better way.

Methylene chloride is preferred as a solvent. The reaction can also be carried out in an environment of benzene, toluene, xylene, but the yield of the desired product significantly decreases.

The structure of the target compounds was confirmed by elemental analysis data and IR and PMR spectra data.

The IR spectra of the target compounds contain characteristic absorption frequencies in the 1755-1761 region (C O unsaturated Y-lactone), 1658-1666 cm (C N) and 1580-1603 cm-1 (phenyl).

In the PMR spectrum of 3-chloro-2-fecil-5 - (3,4,4-trimethyl-2-butene-4-olcdyl-2) -3,4-dihydro-1, 2,3-diazaphosphol, there are signals of protons of methyl groups, in positions 3 (2.07 ppm) and 4 (1.52 and 1.50 ppm) of butenolide, methylene soil of the diazaphosphol cycle (4.20 ppm) and the phenyl group (7 , 32m. D.).

The presence of the P-C1 bond is confirmed chemically by dehydrochloridation 3-chloro-2-phenyl-5- (3,4,4-trimethyl-2-butene-4-olidyl-2) -3,4-dihydro-1,2,3 -diazaphosphol in the presence of triethylamine to the corresponding unsaturated 1,2,3-diazaphosphol.

The purity and quality of the products was monitored by fine column chromatography of alumina of the second degree of activity.

Molecular weights are determined by cryoscopy using benzene as a solvent.

Example 1. 3-Chloro-2-phenyl-5- (3,4,4-trimethyl-2-butene-4-olidyl-2) -3,4-dihydro-1,2,3 detsa-phosphol.

A. To a solution of 3.2 g (0.023 mol) of phosphorus trichloride in 8 ml of methylene chloride cooled to O-5 ° C, a solution of 3.9 g (0.015 mol) of phenylhydrazone 2-acetyl-3 is added dropwise over 30 minutes , 4,4 trimethyl-2-butene - 4-olide and 2.3 g (0.023 mol) of triethylamine in 16 ml of methylene chloride. The reaction mixture is heated to 30-35 ° C for 4 hours and left at room temperature until next day. The precipitate is filtered off. After removal of the solvent and recrystallization of the residue from the filtrate, 4.2 g (88%) of the desired diazaphosphol are obtained; m.p. 252 ° С (from dioxane). Rf 0.95 (chloroform - ether, 2: 1).

Found,%: C 55.5; H 5.2; N 8.3; C1 11.1; P 9.6.

Mol weight 322.9.

CisHieNaClOjP.

Calculated,%: C 55.8; H 5.0; N 8.7; C1 11.0; P 9.6.

Mol weight 322.8.

B. Similarly to a solution of 2.8 g (0.02 mol) of phosphorus trichloride in 8 ml of methylene chloride, which is described above, a solution of 3.4 g (0.013 mol) of phenylhydrazone 2-acetyl-3 is added dropwise to 8 ml of methylene chloride. , 4,4 trimetlp-2-butene-4-olide and 1.6 g (0.02 mol) of pyridine in 16 ml of methylene chloride. The reaction mixture is heated to 30-35 ° C for 4 hours and left at room temperature until next day. The precipitate is filtered off. After removal of the solvent and recrystallization of the residue, the filtrate gives

1.7 g (73%) of the target substance with mp. 252 ° C (from dioxane), the shifted sample of which does not depress the melting point with the diazaphospholum obtained above. B. Similarly, from 2.8 g (0.02 mol) of phosphorus trichloride in 8 ml of methylene chloride, 3.4 g (0.013 mol) of 2-acetyl3 phenylhydrazone, 4.4 - trimethyl - 2 - butene-4 - olide and 2 , 4 g (0.02 mol) Ы, Н-dimethylaniline in 16 ml of methylene chloride get 4.9 g (75%) of the target diazaphosphol with m.p. 252 ° С (from dioxane).

D. To a solution of 3.2 g (0.023 mol) of phosphorus trichloride in 8 ml cooled to 6–8 ° C

benzene was added an ionic acid solution of 3.9 g (0.015 mol) of 2-acetyl-3,4,4-trimethyl-2-butene-4-olyl phenylhydrazone and 2.3 g (0.023 mol) of triethylamine in 16 ml of benzene. The reaction mixture is heated at 50-60 ° C for 5-

6 hours and leave to stand at room temperature for 2-3 days. The precipitate is filtered off. From the filtrate, after removal of the solvent and recrystallization of the residue, 2.3 g (52%) of the desired diazaphosphol with m.p. 251 -

252 ° С (from dioxane).

D. Similarly, in a solution of toluene or xylene at an initial temperature of -5 ° C, followed by heating at 50-60 ° C for 4 hours, the target diazaphosphol is obtained with

yield 53%; m.p. 251-252 ° С (from dioxane).

Example 2. 3-Chloro-2-phenyl-5- (3,4-dimethyl-4-ethyl-2-butene-4-olidyl-2) -3,4-dihydro-1, 2,3-diazaphosphol.

To a solution of 3.2 g cooled to О-5 ° С

(0.023 mol) of phosphorus trichloride in 8 ml of methylene chloride is added dropwise a solution of 4.1 g (0.015 mol) of 2-acetyl-3,4-dimethyl-4-ethyl-2-buten-4-olyl phenylhydrazone and 2, 3 g (0.023 mol) of triethylamine in 16 ml of methylene chloride. After heating for 4 hours at a temperature of 30-35 ° C and a corresponding treatment according to Example 1, 4.4 g (88%) of the desired diazaphosphol are obtained; m.p. 253-254 ° С (from dioxane). 0.92 (chloroform - ether, 2: 1).

Found,%: C 57.1; H 5.3; -N 8.1, C1 10.9; R 9.5.

Mol weight 336.7. CieHisNzClOaP.

Calculated,%: C 57.1; H 5.4; N 8.3; C1 10.6; P9,2. Mol weight 336.8.

Example 3. 3-Chloro-2-phenyl-5- (3-methyl4, 4-pentamethylene-2-butene-4-olidyl-2) -3.4 dihydro-1, 2,3-diazaphosphol.

Claims (2)

Similarly, the interaction of 6.0 g (0.025 mol) of phenylhydrazone 2 - acetyl - 3methyl - 4,4-pentamethylene - 2-butene-4-olide and 3.8 g (0.038 mol) of triethylamine in 30 ml of methylene chloride with 5.23 g (0.038 mol) of phosphorus trichloride in 10 ml of methylene chloride, 6.4 g (71%) of the desired diazaphosphol with m.p. 260 ° C (from dioxane). RJ 0.90 (chloroform - ether, 2: 1). 5 Found 59.4; H 5.9; N 8.0; C1 9.5; Р8,8. Mol weight 362.8. CisHaoNzClOsP. Calculated,%: C 59.6; H 5.5; N 7.7; C1 9.8; R8,6. Mol weight 362.8. Example 4. 2-Feiyl-5 - (3,4,4-trimethyl-2 butene - 4-olidyl-2) -1,2,3-diazaphosphol. To a solution of 1 g (0.032 mol) of 3-chloro-2-phenyl-5- (3,4,4-trimethyl-2-butene-4-olidyl-2) cooled to 0 ° C - 3,4-dihydro-1,2 , 3 - diazaphosphol in 20 ml of absolute ether, a solution of 0.32 g (0.032 mol) of triethylamine in 10 ml of ether is added dropwise. The precipitate is filtered off. After removal of the solvent and recrystallization of the residue from the filtrate, 0.5 g (56%) of diazaphosphol with m.p. 189-190 ° C (from a mixture of chloroform - hexane). Rf 0.87 (chloroform - ether, 7: 2). Found,%: C 63.1; H 5.5; N 9.4; R 10.5. Mol weight 286.2. CisHisNaOaP. Calculated,%: C, 62.9; H 5.2; N 9.8; R 10.8. Mol weight. 286.3. Claim 1. Investigation method of 3-chloro-3,4-dihydro-1, 2,3-dnazaphosphol of the general formula Hp Vj i X 1 11 I -. where R, R and R are metl pl or R n R is methyl, and R is ethyl, or R is methyl, and R and R are together a pentamethlenlen group, characterized in that fennhydrazone 2-acetyl-3,4,4 - trialkyl-2-butene-4-olide is reacted with phosphorus trichloride in the presence of a tertiary amine at a molar ratio of reagents of 1: 1.5: 1.5, respectively, in an inert organic solvent irn medium of temperature O-10 ° C, followed by heating the reaction mixtures up to 30-60 ° C. Sources of information received during the examination of the invention: 1. Shvetsov-Shilovskiy N. I., Ignatova N. P., Melnikov N. I., Reactions of substituted hydrazones with phosphorus trichloride, JOH, 40, 1501 (1970). 2. Ignatova N. I., Melnikov N. N., Shvetsov-Shilovsky N. I., On some products of the reaction of phenylhydrazones with phosphorus trichloride, HGS, 1967, 753.