73671-92-8Relevant articles and documents
Hydrogenation reaction mother liquor recycling material preparation 3-carbonyl-4-aza-5-androstene -17 β carboxylic acid derivatives
-
Paragraph 0040-0041, (2017/03/23)
The invention provides a method for preparing 3-carbonyl-4-aza-5-androstene-17 beta carboxylic acid derivative 01 from mother solution reclaimed materials of a hydrogenation reaction. The method comprises the following steps: (1) dissolving the mother solution reclaimed materials, which are obtained by preparing 3-carbonyl-4-aza-5 alpha-androstane-17 beta carboxylic acid derivative 03 by performing hydrogenation reaction on 3-carbonyl-4-aza-5-androstene-17 beta carboxylic acid derivative 01, into glacial acetic acid, and adding a palladium-carbon catalyst, introducing oxygen, pressurizing and heating to perform dehydrogenation reaction; (2) cooling the reaction system, filtering to obtain a filter cake, washing the filter cake by using glacial acetic acid, and performing suction filtration until the filter cake is dried, thereby obtaining a waste palladium-carbon filter cake; and (3) performing vacuum concentration on a filtrate until the filtrate is almost dried, adding methanol into the system, performing freezing crystallization, performing swinging filtration to obtain a filter cake, washing the filter cake by using methanol, performing swinging filtration until the filter cake is dried, and drying to obtain the 3-carbonyl-4-aza-5-androstene-17 beta carboxylic acid derivative 01. By adopting the method provided by the invention, wastes are recycled to synthesize an important medical intermediate, the cost is reduced, and pollution is reduced. Original auxiliary materials are simple, easily available and recyclable, and the process is simple and is suitable for industrial implementation.
PROCESS FOR THE SYNTHESIS OF (5α,17β)-N-[(2,5-BIS(TRIFLUOROMETHYL)-PHENYL]-3-OXO-4-AZA-5-ANDROST-1-ENE-17-CARBOXAMIDE
-
Page/Page column 30; 53, (2013/03/26)
The synthesis consists of reaction steps as follows: oxidizing the α,β-unsaturated ketone system of ring "A" of pregn-4-ene-3,20-dion- of formula (II) with sodium metaperiodate in tert-butanol in the presence of potassium permanganate and alkali metal carbonate, reacting the obtained 3,5-seco acid with an ester of chloroformic acid in the presence of tertier organic base below 0°C, reacting the obtained new compound after isolation or without isolation with ammonia or ammonium acetate, cyclization of the resulting carboxamides with an acid, cathalytic hydrogenating the obtained ene lactame, and oxidizing the side chain at position 17 of the obtained pregnane compound with an alkali metal hypobromide in aqueous dioxane below 10°C. Thereafter on one hand the obtained (5α,17β)-3-oxo-4-aza-5-androstane-17-carboxylic acid is reacted with chloroformic acid ester, the obtained new compound is reacted with 2,5-bis(trifluoromethyl)-aniline in the presence of a Lewis acid, the obtained amide is reacted with trimethyl chlorosilane in inert atmosphere in the presence of Ν,Ν,Ν',Ν'-tetramethyl-ethylendiamine, then en excess iodine is added to the reaction mixture and the product of the iodination reaction is crystallized from acetonitrile, then the obtained 2-iodo-3-oxo-4-aza-17β-carboxamide is reacted with potassium tert-butylate to furnish final product. On the other hand, (5α,17β)-3-oxo-4-aza-5-androstane-17-carboxylic acid is transformed into methylester by known method, this latter is transformed into methyl (2α,5α,17β)-2-iodo-3-oxo-4-aza-5-androstane-17-carboxylate according to known method, the obtained compound is reacted with potassium-tert-butylate, the obtained (5α,17β)-3-oxo-4-aza-5-androst-1-ene-17-carboxylic acid is reacted with an ester of chloroformic acid, then the obtained new compound is coupled with 2,5-bis(trifluoromethyl)-aniline in the presence of a Lewis acid catalyst to gain final product.
NOVEL PROCESS FOR PREPARING 17 BETA-SUBSTITUTED 4-AZAANDROSTANE DERIVATIVES
-
, (2008/06/13)
The invention relates to a novel process for preparing 17 beta -substituted 4-azaandrostane derivatives of general formula (I) wherein R represents hydrogen or a C1-3alkyl group; R represents a carboxamido group mono- or disubstituted by C1-8alkyl group(s); or a free carboxyl group; or a carboxyl group esterified with a C1-5 alcohol; and the - &cir& _- &cir& _- &cir& _- &cir& _ bond line represents a single or double bond; as well as their salts. The process comprises reacting a 17-halogeno-4-azaandrostene derivative of general formula (II) wherein R and the - &cir& _- &cir& _- &cir& _- &cir& _ bond line are as defined above, and X is chlorine, bromine or iodine, with a primary or secondary alkylamine or a C1-5 alcohol, in dimethylformamide or dimethylsulfoxide medium in the presence of a palladium(II) salt and phosphines or a palladium(II) complex and a tertiary amine base in carbon monoxide atmosphere at a temperature between 35 DEG C and 80 DEG C, then, if desired, transforming an obtained compound of general formula (I) to another compound of general formula (I) by hydrogenation, hydrolysis or salt forming reaction.
