N,O-bis（trimethylsily）trifluoroacetamide （BSTFA） and N-methyl-N（trimethylsily） trifluoroacetamide （MSTFA） are common derivatization reagents used in the GC-MS analysis of estrogen steroids such as estrone （El...N,O-bis（trimethylsily）trifluoroacetamide （BSTFA） and N-methyl-N（trimethylsily） trifluoroacetamide （MSTFA） are common derivatization reagents used in the GC-MS analysis of estrogen steroids such as estrone （El） and 17α-ethinylestradiol （EE2）. In this study, three trimethylsilyl （TMS） steroid derivatives, mono- and di-trimethylsilyl EE2 and mono-trimethylsilyl El, were observed during the derivatization of EE2 with BSTFA or MSTFA and/or GC separation. Factors influencing the production of multiple TMS derivatives and their relative abundance were examined. It was found that both methanol and bisphenol A competed with estrogenic esteroids when reacting with silylation reagents, and thus affected the formation of TMS derivatives and their relative abundance in the derivatization products. Methanol was found to be more reactive than bisphenol A with the BSTFA reagent. None of the three solvents tested in this study could prevent the generation of multiple TMS derivatives during the derivatization of EE2 with BSTFA, followed by GC analysis. A similar result was observed using MSTFA as the derivative reagent followed by GC analysis. Thus, the suitability of BSTFA or MSTFA as the derivatization reagent for the determination of E1 and EE2 by GC-MS, under the conditions reported here, is questionable. This problem can be solved by adding trimethylsilylimidaz （TMSI） in the BSTFA reagent as recommended, and the performance of the method has been proved in this study.展开更多
Title compounds 2′,2′-dimethylcholesta-2,4-dien[3,2-b]-pyran-4′-one （3）, 2′,2′-dimethyl-3β-substituted cholesta-4,6-dien[7,6- b]-pyran-4′-one （6a,b） and （6c） were prepared by the cyclization of 2-acetylch...Title compounds 2′,2′-dimethylcholesta-2,4-dien[3,2-b]-pyran-4′-one （3）, 2′,2′-dimethyl-3β-substituted cholesta-4,6-dien[7,6- b]-pyran-4′-one （6a,b） and （6c） were prepared by the cyclization of 2-acetylcholesta-2,4-dien-3-ol （2）, 6-acetyl-3β-substituted- cholesta-4,6-dien-7-ol （Sa,b） and （5c） respectively, with pyrrolidine, dry benzene and dry acetone using Dean Stark separator through conventional heating. Furthermore, compounds were also found to be active against Mycobacterium tuberculosis.展开更多
Rocuronium bromide has been used as an aminosteroid non-depolarizing neuromuscular blocker and muscle relaxant.In this work,a new and efficient route for preparing a key intermediate 2β-（4-morpholinyl）-16β-（1-pyr...Rocuronium bromide has been used as an aminosteroid non-depolarizing neuromuscular blocker and muscle relaxant.In this work,a new and efficient route for preparing a key intermediate 2β-（4-morpholinyl）-16β-（1-pyrrolidinyl）-5α-androstan-3α,17β-diol（6） was developed through a ring-opening of epoxide followed by introducing and pyrrolidine.Compound 6 can easily provide rocuronium bromide and the overall yield of compound 6 in 5 steps increased to 57.8%,which was higher than currently reported methods.Extraordinarily,this method would avoid the generation of disubstituted impurities E and F which are difficult to remove.展开更多
基金Project supported by the National Basic Research Program (973) of China(No. 2007CB407301)Beijing Municipal Natural Science Foundation(No. 8061004).
文摘N,O-bis（trimethylsily）trifluoroacetamide （BSTFA） and N-methyl-N（trimethylsily） trifluoroacetamide （MSTFA） are common derivatization reagents used in the GC-MS analysis of estrogen steroids such as estrone （El） and 17α-ethinylestradiol （EE2）. In this study, three trimethylsilyl （TMS） steroid derivatives, mono- and di-trimethylsilyl EE2 and mono-trimethylsilyl El, were observed during the derivatization of EE2 with BSTFA or MSTFA and/or GC separation. Factors influencing the production of multiple TMS derivatives and their relative abundance were examined. It was found that both methanol and bisphenol A competed with estrogenic esteroids when reacting with silylation reagents, and thus affected the formation of TMS derivatives and their relative abundance in the derivatization products. Methanol was found to be more reactive than bisphenol A with the BSTFA reagent. None of the three solvents tested in this study could prevent the generation of multiple TMS derivatives during the derivatization of EE2 with BSTFA, followed by GC analysis. A similar result was observed using MSTFA as the derivative reagent followed by GC analysis. Thus, the suitability of BSTFA or MSTFA as the derivatization reagent for the determination of E1 and EE2 by GC-MS, under the conditions reported here, is questionable. This problem can be solved by adding trimethylsilylimidaz （TMSI） in the BSTFA reagent as recommended, and the performance of the method has been proved in this study.
文摘Title compounds 2′,2′-dimethylcholesta-2,4-dien[3,2-b]-pyran-4′-one （3）, 2′,2′-dimethyl-3β-substituted cholesta-4,6-dien[7,6- b]-pyran-4′-one （6a,b） and （6c） were prepared by the cyclization of 2-acetylcholesta-2,4-dien-3-ol （2）, 6-acetyl-3β-substituted- cholesta-4,6-dien-7-ol （Sa,b） and （5c） respectively, with pyrrolidine, dry benzene and dry acetone using Dean Stark separator through conventional heating. Furthermore, compounds were also found to be active against Mycobacterium tuberculosis.
基金the National Natural Science Foundation of China (No. 81373259 & No. 81573286)
文摘Rocuronium bromide has been used as an aminosteroid non-depolarizing neuromuscular blocker and muscle relaxant.In this work,a new and efficient route for preparing a key intermediate 2β-（4-morpholinyl）-16β-（1-pyrrolidinyl）-5α-androstan-3α,17β-diol（6） was developed through a ring-opening of epoxide followed by introducing and pyrrolidine.Compound 6 can easily provide rocuronium bromide and the overall yield of compound 6 in 5 steps increased to 57.8%,which was higher than currently reported methods.Extraordinarily,this method would avoid the generation of disubstituted impurities E and F which are difficult to remove.
