SU371205A1 - METHOD OF OBTAINING NON-SYMMETRIC 1,4-DI-TRE OR 1,4-VTOR-TRET-AMINOVSC? CU! O.5HA-1 l i7Cl3Tt '! N Tfir' -''-- ^ - f.:^Stnhiitf"ls.Au ..., library * ^! - Google Patents

Description

one

This invention relates to a process for the preparation of new asymmetric sands based on 1,4-dibromides of conjugated dienes.

The compounds obtained have biological activity.

A known method for producing symmetric 1,4-di-g / 3t-aminoB with an unsaturated group consists of the interaction of 1,4-dibromides of conjugated dienes with secondary amines.

However, there are no data in the literature on the preparation of asymmetric diamines from 1,4 dibromides of conjugated dienes.

In accordance with the invention, a process for the preparation of amines of general formula is described.

RzN-CHj-C C-CHa -NRa or

RaN-CHa-C C-CHg-NHRi,

where RI and Ra are alkyl radicals consisting in the interaction of p-dialkylamino-propionitrile and 1,4-dibromide diene in the presence of organic solvents that do not dissolve the ammonium salt, for example, dry ether. Mono-quaternary ammonium salts are isolated, which are reacted with primary or secondary amyluiMH in an alcohol or water medium, with further treatment of the reaction products by alkalinization and isolation of the target products by extraction with ether.

Example 1. 1-Dimethylamino-4-diethylamminobutene-2.

To a solution of 21.4 g of 1,4-dibromobutene-2 in 150 nl of dry ether or other solvent in which the monoammonium salt does not dissolve when cooled with water, 9.8 g of p-dimethylaminopropionitrile are added dropwise. After 2 days, 31.2 g (100%) of dimethyl p-cyanoethyl-4-bromobutene-2-yl-ammonium bromide were obtained by filtration. 117 ° C.

Found%: N 8.80; Br 25.84.

SdNshNgVgg.

Calculated,%: N 8.97; Br 25.62.

15 g of diethylamine are added to a solution of 15.6 g (0.05 mol} of this Sun in 50 ml of methanol (or water). After four days the reaction mixture is alkalinized. 8.1 g (95.5%) of 1- dimethylamino-4 diethylaminobutene-2 with a bale of 114 ° C (56 mm Hg), df 0.8056, ° 1,4400. MRo 55.61, calculated 55.71.

Found,%: C, 70.16; H 12.91; N 16.29.

CioH22N9.

Calculated,%: C 70.5; H 12.9; N 16.4. Pikrat t. Pl. 159 ° C.

Example 2. 1-Diethylamino-4-dimet-lamino-2-methylbutene-2.

Similarly to the previous, 25.7 g (78.8%) of dimethyl b-p-dianethyl-4-bromo-3-methylbutene were obtained from 22.8 g of 1,4-dibromo-2-methylbuthen-2 and 9.8 g of p-dimethylaminopropionitrile -2-yl ammonium with m. Pl. 119-120 ° C.

Found,%: N 8.85; Br 24.72.

CioHisNzBrs.

Calculated,%: N 8.58; Br 24.54.

Out of 16.3 g of this salt and 15 g of diethylamine, 8.5 g (92.3%) of 1-diethylamino-4-dimethylamino-2-methyl butene-2 were obtained, with a boil. 88-90 ° C

(21 mm Hg. Art.); df 0.7895;

ni5

1.4390. Mro

60.62, calculated 60.43.

Found,%: C 72.06; H 13.15; N 14.98.

CiiH24N2.

Calculated,%: C, 71.70; H 13.06; N 15.20.

Pikrat t. Pl. 162 ° C.

Example 3. 1-Dimethylamino-4-phenylaminopentene-2.

Similarly to the previous one, 26 g (80%) of dimethyl p-cyanoethyl-4-bromopenten-2-yl-ammonium bromide with m. Pl. Were obtained from 22.8 g of 1,4-dibromoentene-2 and 9.8 g of p-dimethylaminopropionitrile. 147 ° C.

Found,%: N 8.80; Br 24.78.

C oHi8N2Br2.

Calculated,%: N 8.58; W 24.54. From 16.3 g of this salt and 18.6 g of aniline, 10.3 g (82%) of 1-dimethylamino-4-phenylaminopentene-2 was obtained with a bale. 189-19GS (20 mmH

st); df 0.9990; At 1.5573. MR about 65.66, calculated 65.70. Found,%: C 76.08; H 9.41; N 14.11.

Ci3H2oN2.

Calculated,%: C, 76.48; H 9.80; N 13.72. Pikrat t. Pl. 129 ° C.

Subject invention

A process for the preparation of asymmetric 1,4-ditert- or, 4-sec-tert-ayino, characterized in that the diene 1,4-dibromides are reacted with p-dialkylaminonopionitrile in an organic solvent such as ether, followed by sequential processing of the resulting product amine and alkali solution, and the selection of the target product in a known manner.