SU639861A1 - Method of obtaining n-2,3-epoxypropyl derivatives of diphenylamine, n-phenylnaphthylamine-1 or n-phenylnaphthylamine-2 - Google Patents

Description

This invention relates to an improved process for the preparation of M-2,3-epoxypropyl derivatives of diphenylamine, M-phenylnaphthylamine-1 or N-phenylnaphtylamine-2, which are used to create chemically bonded dyes as monomers for the preparation of polymeric materials using electrography, and to obtain other derivatives of said secondary aromatic amines.

Known methods for the preparation of N-2,3-epoxypropyl derivatives of diphenylamine, M-phenylnaphthylamine-1 and N-phenylnaphtylamine-2.

There is also known a method for producing N-2,3epoxypropyl derivatives of diphenylamine, H-phenylnaphthylamine-1 or N-phenylnaphtylamine-2, based on the interaction of the corresponding secondary aromatic amine with epichlorohydrin in glacial acetic acid, followed by treatment of the selected intermediate with caustic soda.

M-phenyl-N-2,3-epoxypropyl naphthylamine-1 is obtained by heating N-phenylnaphtylamine-1 with epichlorohydrin in the presence of glacial acetic acid at 60-65 ° C for 120 h, then the reaction mass is extracted and the ether solution is treated with alkali (2 , 5-4-fold excess) at

heating (40-45 ° C) for 2-3 hours

The target product is obtained with a yield of 60%.

The disadvantages of this method are

the long duration of the process and the relatively low yield of the target product (in the case of the preparation of derivatives of diphenylamine and L-phenylnaphtylamine-2, the yield of the target products is 85 and

16%, respectively).

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

The goal is achieved by the fact that

The process is carried out in the presence of a 10-13 fold molar excess of potassium hydroxide with respect to the starting amine at room temperature. According to the proposed method of obtaining

M-2,3-epoxypropyl derivatives of diphenylamine, N-phenylnaphthylamine-1 or M-phenylnaphtylamine-2; the corresponding secondary aromatic amine is reacted with epichlorohydrin in the presence, as a rule, of a dehydrating agent, for example anhydrous potassium carbonate, and a large excess of caustic potash at room temperature temperature and vigorous stirring; raw material ratio secondary aromatic

amine: epichlorohydrin; caustic potash: the dehydrating agent is 1: 9-10: 10 - 13: 1-1.5. Target products are obtained with a yield of about 91-95%. The reaction time is 5-7 hours; the process is carried out in one stage.

Example 1. N-2-Z-epoxypropyl diphenylamine. 50.7 g (0.3 mol) of diphenylamine, 277.5 g (3.0 mol) of epichlorohydrin and 58.5 g (0.45 mol) of crushed anhydrous potassium carbonate are vigorously stirred for 20-30 minutes, and then added in portions 218.4 g (3.9 mol) of potassium hydroxide powder at such a rate that the temperature of the reaction mass does not exceed 25 ° C. The reaction is carried out at room temperature. The end of the reaction is determined by the method of those on Silufol UV-254 plates, eluting with a mixture of ether and petroleum ether at a ratio of 1: 1. The reaction time is 7 hours. The mixture is treated with chilled water and extracted with ether. After drying and removing the ether and the excess epichlorohydrin, the mass is distilled in vacuo. Collect fraction with t. Kip. 158-159 ° C / 1-2 mm Hg. Art.

Yield 61.8 g (91.5%).

Found,%: N 6.3; epoxy number 0,442 equiv. / 100 g

CisHisNO.

Calculated,%: N 6.2; epoxy number 0.444 equiv./100 g

Example 2. N-Phenyl-N-2,3-epoxypropyl naphthylamine-1. To a mixture of 21.9 g (0.1 mol) of H-phenylnaphthylamine-1, 83.3 g (0.9 mol) of epichlorohydrin and 13 g (0.1 mol) of crushed anhydrous potassium carbonate with vigorous stirring in portions add 61 , 6 g (1.1 mol) of powdered caustic potash at such a rate that

the temperature of the reaction mass did not exceed 25 ° C. The end of the reaction is determined in Example 1. The reaction time is 5 hours. The reaction mass is diluted with ether, the inorganic precipitate is filtered off and the filtrate is washed with water until neutral. After the ether and epichlorohydrin had been removed, the residue was distilled in vacuo. Collect fraction with t. Kip. 205- 210 ° C / 0.5-1 mm Hg. Art.

Yield 24.9 (90.7%).

Found,%: N 5.2; epoxy number 0.363 equiv. / 100 g

Ci9Hi7NO.

Calculated,%: N 5,1; epoxy number 0,366 EQV / 100 g

Example 3. N-Phenyl-H-2,3-epoxypropyl naphthylamine-2. To a mixture of 65.8 g (0.3 mol) N-phenylnaphthylamine-2 (a), 277.5 g (3.0 mol) of epichlorohydrin (b) and 58.5 g (0.45 mol) of ground anhydrous potassium carbonate (c) with vigorous stirring, 168 g (3.0 mol) of potassium powder (g) are added at such a rate that the temperature of the reaction mass does not exceed 25 ° C. The end of the reaction is determined in example 1, and the selection of the desired product in the example 2. Collect fraction with m. Kip. 215-218 ° C / 0.5-1 mm Hg. Art.

Found,%: N 5.2; epoxy number 0,364 EQV / 100 g

CigHirNO.

Calculated%

N 5.1; epoxy number 0,366 EQV / 100 g

The reaction conditions and yields of L-phenyl-N2, 3-epoxypropyl-naphtylamine-2 are listed in the table. (Used reagents should be well dried).