SU189773A1 - METHOD OF OBTAINING STEAROYLAMINOPHENOLS - Google Patents

Description

The present invention relates to a process for the preparation of novel acylaminophenol derivatives, which can be used as polypropylene stabilizers.

It is proposed to obtain stearoyl aminophenols having the following formula:

where RI and Ra have the above meaning, they are diazotized or nitrated. The resulting nitroso or nitro group is reduced to the amino group by any known method before the formation of an aminophenol having one of the following formulas:

-NHE

NHB

ten

where R is the residue of stearic acid, Ri is tertiary alkyl having from 4 to 8 carbon atoms, and Ro is a hydrogen atom or alkyl having from 1 to 8 carbon atoms.

The method is carried out as follows. Phenol having the formula

The aminophenol is then acylated with stearoyl chloride, usually in the presence of an acid binding agent, for example, pyridine. Example 1. a) Preparation of 4-greg-butyl-2 nitrophenol.

150 parts of 4-gret-butylphenol are dissolved in 300 parts of benzene, the solution is cooled to 15 ° C and a mixture of 128 parts of nitric acid (sp. 1.5) and 256 parts of water is added to it over 3 hours.

at a temperature of 15 ° C. Then the mixture is stirred for another 1 hour and poured into a mixture of ice water. The benzene is distilled off and the residue is distilled under the pressure of a water pump. 130 hours are obtained. 4-t / 71yy-butyl-2-nitrophenol b) Preparation of 2-amino-4-t / 7e-butylphenol. 60 parts of 4-greg-butyl-2-nitrophenol are dissolved in 2400 parts of a 10% solution of sodium hydroxide. The solution is heated to 80 ° C and 225 parts of sodium hydrosulfite are added at small temperatures of 80-82 ° C. . After cooling, crystals of the sodium salt of the product are formed. The mixture is acidified with diluted 1: 1 acetic acid to obtain a white crystalline product. This mixture is cooled to room temperature and filtered. The product is thoroughly washed with water and dried in an air oven. The yield of 2-amino-4-t / 7g-butylphenol is 52 hours, so pl. 152-164 ° C. After recrystallization from toluene, a product with m.p. 164 ° C. C) Preparation of 4-g; 7r-butyl-2-K-stearoylaminophenol. 16.5 parts of 2-amino-4-Guseg-butylphenol are dissolved at room temperature in 300 parts of chloroform, 7.9 parts of pyridine are added and the mixture is stirred at room temperature. Then 30.2 parts of stearoyl chloride are added dropwise to this mixture at room temperature and stirred for 1 hour at room temperature. Solid precipitate does not fall out. The chloroform solution is washed with water, dilute hydrochloric acid, and finally again with water until the acid is completely removed, and then dried over anhydrous sodium sulfate. Chloroform is evaporated under reduced pressure and the residue is recrystallized from aqueous isopropyl alcohol, treated with charcoal. Get 20 hours 4-Treg-butyl-2-M-stearoylaminophenol with T. pl. 86 ° C. Found in%: C 78.5; H 11.6; N 3,0. Calculated for dL in%: C 77.95; H 11.37; N 3.25. Example 2. a) Preparation of 2-nitroso-4-t / 9e, ctilphenol. 103 parts of 4-g / 7g-octylphenol are mixed with 500 parts of concentrated hydrochloric acid and 500 parts of water. The mixture is cooled to 0 ° C. Then slowly over 1 hour, 90 parts of sodium nitrite are added in small portions and stirred for 1 hour at a temperature ranging from 0 ° C to 5 ° C. The resulting product is filtered, washed with water until the acid is removed and dried. The dry product is recrystallized from toluene, mixed with petroleum ether (b.p. 40-60 ° C) to form a suspension, from which the product is isolated and dried. Get 62 hours 2-nitroso-4-7reg-octylphenol; m.p. 65 ° C. b) Preparation of 2-amino-4-gret-octylphenol. The solution is added in small portions to 50 parts of sodium hydrosulfite at a temperature of 80 ° C, as a result of which the solution becomes discolored. The solution is cooled and acidified with glacial acetic acid, and the precipitated product is filtered off, washed with water. After recrystallization from aqueous alcohol, 55.5 parts of 2-amino-4-7 / 7g-octylphenol are obtained; m.p. 63 ° C. C) Preparation of 4-t / 7r-octyl-4-M-stearoylaminophenol. 22.1 parts of 2-amine-4-g / 7g-octylphenol are dissolved in 300 parts of chloroform, 7.9 parts of pyridine are added and the mixture is stirred at room temperature. 30.2 parts of stearoyl chloride are added dropwise to the mixture at room temperature and stirred for 1 hour at room temperature. Solid precipitate does not fall out. The chloroform solution is washed with water, dilute hydrochloric acid, then again with water until acid, and dried over anhydrous sodium lofate. After evaporation of chloroform under reduced pressure, the residue is recrystallized from aqueous isopropyl alcohol, treated with charcoal. 30 parts of 4-7 / 7r-octyl-2-N-stearoylaminophenol are obtained; m.p. 35-36 ° C. Found in%: C 70; H 11.8; N 3,0. Calculated in%: C 78.8; H 11.7; N 2.8. Example 3. a) Preparation of 2,6-di-t / 9et-butyl-4-nitrosophenol. 75 parts of 95% ethyl alcohol are saturated with hydrogen chloride at a temperature of about-5 ° C and 400 parts of 95% ethanol are added to it, and then 82.4 parts of 2,6-di-t / er -butylphenol. To the stirred mixture, 30.4 parts of sodium nitrite dissolved in 40 parts of water are added dropwise at a temperature of 15-20 ° C. The mixture is stirred for 2 hours at room temperature, 200 parts of water are added and the precipitate formed is filtered off, washed with water until acid is removed and dried in vacuo (at 60 ° C. 140 parts of crude product are obtained with t. 210) -216 ° C. The product is mixed with 300 h of petroleum ether (b.p. 60-80 ° C), separated and washed with an additional 100 parts of petroleum ether, 85 parts of 2,6-di-7 / erbutyl-4 are obtained -nitrosophenol with mp 214-215 ° C. b) Preparation of 4-amino-2,6-di-treg-butyl-4nitrosophenol. 85 parts of 2,6-di-t / 7g-butyl-4-nitrosophenol are dissolved in 1000 parts of water containing 120 parts of sodium hydroxide. The solution is heated to 50 ° C and about 200 parts of sodium hydrosulfite are added in small portions at a temperature of 50-60 ° C until the solution becomes colorless. The solution is then acidified with hydrochloric acid and the precipitated 4-ammonia-2,6-di-t / 7et-butylphenol is filtered off, washed with water until acid is removed and dried in vacuo over calcium chloride.

c) Preparation of 2,6-di-g / et-butyl-4-H-stearoylaminophenol.

22.1 parts of 4-amino-2,6-di-7-but-11-phenol are dissolved at room temperature in 300 parts of chloroform and 7.9 parts of pyridine are added. 30.2 parts of stearoyl chloride are added to the stirred liquid at room temperature. The mixture is stirred at the same temperature esh, e for 1 hour. Solid precipitate does not fall out. The chloroform solution is washed successively with dilute hydrochloric acid and water, and then dried over anhydrous sodium sulfate. After removing the chloroform by distillation, the solid residue is dissolved in ethyl alcohol and a solution of 1 part of sodium hydrosulfite in 10 parts is added. The mixture is filtered while hot and some water is poured into it, resulting in a precipitate of the final product.

Get 30 hours 2,6-di-t / 7eg-butyl-4-stearoylaminophenol with so pl. 85-87 ° C.

Found in%: C 78.2; P 11.2; N 2.7.

Calculated for C32H57NO2, in%; C, 78.8; H 11.7; N 2.8.

Example 4. a) Obtaining 6-tert-butyl-Zmethyl-4-nitrosophenol.

This compound is obtained from b-greg-butyl-Zmethylphenol as described in Example 3, and, the melting point of the product is 184 ° C (decomposed).

b) Preparation of 4-amino-6-treg-butyl-3-methylphenol.

This compound is obtained by reducing the previous nitroso compound to the amino compound with sodium hydrosulfite. T. pl. product 186-187 ° C.

c) Preparation of 6-g / 7g-butyl-8-methyl-4-N-stearoylaminophenol.

17.9 parts of 4-amn-6-7 /: gt-butyl-3-methylphenol are dissolved at room temperature in 300 parts of chloroform and 7.9 parts of pyridine are added. To the stirred solution is added dropwise at room temperature with 30.2 parts of stearoyl chloride and stirring is continued for 1 hour at the same temperature. The solid precipitate is filtered off, washed with cold chloroform, dried and recrystallized from a mixture of ethyl alcohol and water.

37.5 parts of 6-t / 7g-butyl-3-methyl-4-x-esteroylaminopheiol are obtained with m.p. 126 ° C.

Found in%: C 75.2; H 11.3; N 3,0.

Calculated for CagHsiNOs in%: C 78.2; H 11.4; N 3.2.

Subject invention

A method of producing stearoylaminophenols, characterized in that alkylaminophenols of the general formula

25

or

thirty

where RI is tertiary alkyl having 4 to 8 carbon atoms, and Ra-H or alkyl having 1 to 8 carbon atoms is treated with ch.oroyl stearoyl in the presence of acid-binding substances, for example pyridine