Sahlberg B L
J Steroid Biochem. 1987 Apr;26(4):481-5. doi: 10.1016/0022-4731(87)90060-4.
The excretion of ethynyl steroids in milk from a lactating woman taking a daily dose of an oral contraceptive (Conlumin) containing 1 mg of norethindrone and 50 micrograms of mestranol has been studied. Milk was diluted with aq. triethylamine sulphate and steroids were extracted on a Sep-Pak C18 cartridge at 60-64 degrees C. Groups of unconjugated steroids, glucuronides, mono- and disulphates were separated on triethylaminohydroxypropyl Sephadex LH-20. Following hydrolysis and further purification, steroids possessing an ethynyl-substituent were isolated by chromatography on sulphohydroxypropyl Sephadex LH-20 in silver form. Gas chromatographic-mass spectrometric analysis of the O-methyloxime-trimethylsilyl ether derivatives of these steroids, showed the presence of norethindrone and mestranol in the free fraction and of tetrahydro metabolites of norethindrone with 3 alpha,5 alpha, 3 alpha,5 beta and 3 beta,5 alpha configurations in the mono- and disulphate fractions. The disulphate of the 3 alpha,5 alpha isomer was the most abundant ethynyl steroid in milk after 13 days of administration. The site of conjugation of the monosulphates was established by acetylation prior to solvolysis and analysis by gas chromatography-mass spectrometry. This showed that the 3 alpha,5 alpha isomer was conjugated mainly in the 17 beta-position while the 3 alpha,5 beta isomer was conjugated at C-3.
对一名每日服用含1毫克炔诺酮和50微克炔雌醇甲醚的口服避孕药（康禄明）的哺乳期妇女乳汁中乙炔基甾体的排泄情况进行了研究。乳汁用硫酸三乙胺水溶液稀释，甾体在60 - 64℃下于Sep - Pak C18柱上萃取。未结合甾体、葡萄糖醛酸苷、单硫酸盐和双硫酸盐在三乙氨基羟丙基葡聚糖凝胶LH - 20上分离。经过水解和进一步纯化后，通过在银型磺基羟丙基葡聚糖凝胶LH - 20上进行色谱分离，分离出具有乙炔基取代基的甾体。对这些甾体的O - 甲基肟 - 三甲基硅醚衍生物进行气相色谱 - 质谱分析，结果显示游离部分存在炔诺酮和炔雌醇甲醚，单硫酸盐和双硫酸盐部分存在具有3α,5α、3α,5β和3β,5α构型的炔诺酮四氢代谢物。给药13天后，3α,5α异构体的双硫酸盐是乳汁中含量最高的乙炔基甾体。通过在溶剂解之前进行乙酰化并通过气相色谱 - 质谱分析，确定了单硫酸盐的结合位点。结果表明，3α,5α异构体主要在17β位结合，而3α,5β异构体在C - 3位结合。
