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    • 7. 发明授权
    • Process for the preparation of 20-keto-21 alpha-01-steroids
    • 制备20-keto-21α-01类固醇的方法
    • US5399685A
    • 1995-03-21
    • US75822
    • 1993-06-11
    • Jean BuendiaVeronique CrocqChristian MassonDenis PratMichel Vivat
    • Jean BuendiaVeronique CrocqChristian MassonDenis PratMichel Vivat
    • C07J9/00C07J21/00C07J33/00C07J41/00C07J75/00C12P33/00C12R1/865
    • C07J9/00C07J21/006C07J33/007C07J41/0094
    • A process for the preparation of a compound of the formula ##STR1## wherein R.sub.1 is alkyl of 1 to 3 carbon atoms, R.sub.2 is alkyl of 1 to 12 carbon atoms, R.sub.3 is alkyl of 1 to 4 carbon atoms comprising reacting a compound of the formula ##STR2## wherein R.sub.4 is a remainder of an easily cleavable ether, K is a protected ketone function in the form of ketal, thioketal or mixed ketal and R.sub.1 has the above definition with a magnesium organic compound reagent of the formulaHalMg--CH.sub.2 --R.sub.2 Awherein Hal is a halogen and R.sub.2 is defined as above to obtain a compound of the formula ##STR3## wherein R.sub.1, R.sub.2 and K are defined as above, reacting the latter with an acylation agent to obtain a compound of the formula ##STR4## wherein R.sub.5 is alkyl of 1 to 6 carbon atoms or aryl of 6 to 10 carbon atoms and R.sub.1, R.sub.2 and K are defined as above, reacting the latter with an appropriate alkylation agent to obtain a compound of the formula ##STR5## wherein R.sub.1, R.sub.2, R.sub.3 and K are defined as above, subjecting the latter to autoxidation to obtain a compound of the formula ##STR6## wherein R.sub.1, R.sub.2, R.sub.3 and K are defined as above, reacting the latter with an acid to obtain a reconjugated 3-keto compound of the formula ##STR7## wherein R.sub.1, R.sub.2 and R.sub.3 are defined as above and reacting the latter with a regio- and enantioselective reducing agent to obtain a compound of formula I and intermediates formed therein.
    • 一种制备式I化合物的方法,其中R 1是1至3个碳原子的烷基,R 2是1至12个碳原子的烷基,R 3是1至4个碳原子的烷基,包括使 其中R 4是易裂解醚的剩余部分,K是缩酮形式,缩醛缩醛或混合缩酮形式的被保护酮官能团,并且R 1具有上述定义与式HalMg- CH2-R2A其中Hal是卤素,R2如上定义,得到式III的化合物,其中R 1,R 2和K如上定义,使其与酰化剂反应,得到式 其中R 5是1至6个碳原子的烷基或6至10个碳原子的芳基,并且R 1,R 2和K如上定义,使其与适当的烷基化剂反应,得到下式的化合物:IMAGE > V其中R1,R2,R3和K如上所定义,对其进行处理 进行自氧化以获得式VI的化合物,其中R 1,R 2,R 3和K如上定义,使其与酸反应,得到下式的共轭3-酮化合物,其中R 1, R2和R3如上定义并使其与区域和对映选择性还原剂反应,得到式I化合物及其中形成的中间体。