Miyake Y, Kubo Y, Iwabuchi S, Kojima M
Steroids. 1982 Sep;40(3):245-59. doi: 10.1016/0039-128x(82)90037-x.
Syntheses of 15 alpha- and 15 beta-carboxymethyltestosterone (15 alpha- and 15 beta-CMT) were investigated in order to prepare testosterone-bovine serum albumin conjugates for radioimmunoassays of testosterone. A mixture of 15 alpha- and 15 beta-bis(ethoxycarbonyl)methyl-3 beta-hydroxy-5-androsten-17-one (IIa and IIb) obtained by a reaction of 3 beta-hydroxy-5,15-androstadien-17-one (I) and sodium diethyl malonate was oxidized to afford a mixture of 15 alpha- and 15 beta-bis(ethoxycarbonyl)methyl-4-androstene-3, 17-dione (Va and Vb). After the separation by silica gel chromatography, each epimer obtained was hydrolyzed by acid, followed by decarboxylation, and selective reduction of the 17-ketone to give 15 alpha- and 15 beta-CMT. The antisera, generated in rabbits by immunization with the bovine serum albumin (BSA) conjugates of 15 alpha- and 15 beta-CMT, respectively, exhibited high specificity for testosterone.
为了制备用于睾酮放射免疫分析的睾酮-牛血清白蛋白缀合物，对15α-和15β-羧甲基睾酮（15α-和15β-CMT）的合成进行了研究。通过3β-羟基-5,15-雄甾二烯-17-酮（I）与丙二酸二乙酯钠反应得到的15α-和15β-双（乙氧基羰基）甲基-3β-羟基-5-雄甾烯-17-酮（IIa和IIb）混合物被氧化，得到15α-和15β-双（乙氧基羰基）甲基-4-雄甾烯-3,17-二酮（Va和Vb）混合物。通过硅胶柱色谱分离后，将得到的每个差向异构体进行酸水解，然后脱羧，并选择性还原17-酮，得到15α-和15β-CMT。分别用15α-和15β-CMT的牛血清白蛋白（BSA）缀合物免疫兔子产生的抗血清，对睾酮表现出高特异性。
