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    • 1. 发明授权
    • 9,10-Seco-steroids
    • 9,10-类固醇
    • US4064173A
    • 1977-12-20
    • US651763
    • 1976-01-23
    • Jean-Marie CassalAndor FurstWerner Meier
    • Jean-Marie CassalAndor FurstWerner Meier
    • C07C401/00C07C49/27
    • C07C205/45C07C2102/24
    • A process for the preparation of 9,10-seco-steroids of the formula ##STR1## WHEREIN R.sup.1 and R.sup.2 independently are hydrogen, amino, OR.sup.5, OCOR.sup.6 or NHCOR.sup.5 wherein R.sup.5 is hydrogen or lower alkyl and R.sup.6 is lower alkyl or phenyl; R.sup.3 is lower alkyl; R.sup.4 is oxo, ##STR2## wherein R.sup.13 is lower alkyl, lower alkoxy -- lower alkylene, tetrahydropyranyl or tetrahydrofuryl, R.sup.14 is lower alkyl or aryl and R.sup.15 and R.sup.16 are lower alkyl or taken together form lower alkylene or arylene, and n is 1 or 2 is disclosed. The 9,10-seco-steroids of this invention are useful intermediates for the preparation of steroids.
    • 其中R 1和R 2独立地为氢,氨基,OR 5,OCOR 6或NHCOR 5,其中R 5为氢或低级烷基且R 6为低级烷基或苯基; R3是低级烷基; R4是氧代,其中R13是低级烷基,低级烷氧基 - 低级亚烷基,四氢吡喃基或四氢呋喃基,R14是低级烷基或芳基,R15和R16是低级烷基或一起形成低级亚烷基或亚芳基,n是1或 2。 本发明的9,10-秒类固醇是制备类固醇的有用中间体。
    • 5. 发明授权
    • Stereospecific total steroidal synthesis via substituted C/D-trans indanones
    • 通过取代的C / D反式茚满酮进行立体特异性总体甾体合成
    • US3927031A
    • 1975-12-16
    • US48271474
    • 1974-06-24
    • HOFFMANN LA ROCHE
    • HAJOS ZOLTAN GEORGE
    • C07C62/26C07C62/38C07C49/27C07D317/26
    • C07C49/523C07C62/26C07C62/38C07C205/43C07C2603/16
    • Total synthesis of known progestationally active steroidal materials. The steroids can be synthesized depending on the particular starting reactants selected by employing as intermediates bicyclic compounds of the formula
      and lower alkyl; R7 is lower alkyl; R15 is selected from the group consisting of oxo, lower alkylenedioxy or (hydrogen and lower alkoxy); B is selected from the group consisting of lower alkoxy-carbonyl-methylene, lower-aryloxy-carbonyl-methylene, cyanomethylene, lower alkyl sulfinyl-methylene, lower alkyl sulfonyl-methylene, and R25 and R26 are independently selected from the group consisting of hydrogen, hydroxyl and lower alkyl.

      wherein R6 is selected from the group

      WHEREIN M IS AN INTEGER HAVING A VALUE OF 1 OR 2; R4 is hydrogen or lower alkyl;; Z is lower alkylenedioxymethylene, CH(OR2) and carbonyl; R8 when taken alone is hydrogen; R9 when taken alone is lower alkoxycarbonyl, aryloxy-carbonyl, lower cycloalkyloxycarbonyl, carbonyl-halide, hydrogen, carboxy, formyl and methylene-X, where X is a leaving group and when taken together are methylene; with the proviso that when Z is carbonyl R8 when taken alone is hydrogen; R9 when taken alone is carbonyl halide, hydrogen, carboxy, formyl and methylene-X where X is a leaving group and when taken together are methylene and R2 is hydrogen, lower alkyl, lower alkoxy-lower alkyl, phenyllower alkyl, tetrahydropyranyl, lower alkanoyl, benzoyl, nitrobenzoyl, carboxy-lower alkanoyl, carboxybenzoyl, trifluoroacetyl and camphorsulfonyl AND REACTING THEM IN THE CASE WHERE R8 and R9 taken together are methylene or R8 is hydrogen and R9 is methylene-X with Beta keto esters and other analogs of the formula


      D R A W I N G
    • 已知的促孕活性甾体材料的全合成。 可以根据通过使用作为中间体选择的特定起始反应物来合成类固醇,其具有下式的双环化合物,其中M是具有1或2的值的整数; R4是氢或低级烷基; Z是低级亚烷基二氧基亚甲基,CH(OR 2)和羰基; 单独使用时为R8; 当单独使用时,R 9为低级烷氧基羰基,芳氧基羰基,低级环烷氧基羰基,羰基卤化物,氢,羧基,甲酰基和亚甲基-X,其中X为离去基团,并且一起为亚甲基时; 条件是当Z为羰基时,当单独使用时为氢; 当单独使用时,R 9是卤素,氢,羧基,甲酰基和亚甲基-X,其中X是离去基团,当它们一起是亚甲基且R 2是氢时,低级烷基,低级烷氧基 - 低级烷基,苯基 - 低级烷基,四氢吡喃基, 低级烷酰基,苯甲酰基,硝基苯甲酰基,羧基 - 低级烷酰基,羧基苯甲酰基,三氟乙酰基和樟脑磺酰,并在其中反应。其中R8和R9一起为亚甲基或R8为氢,R9为亚甲基-X,带有β-酮酯和其他类似物 式O-PARALLEL R6-CBV其中R6选自基团R26R25 || R7-C-CH-CH2-PAR-PARALLELR15和低级烷基; R7是低级烷基; R 15选自氧代,低级亚烷基二氧基或(氢和低级烷氧基); B选自低级烷氧基 - 羰基 - 亚甲基,低级 - 芳氧基 - 羰基 - 亚甲基,氰基亚甲基,低级烷基亚磺酰基 - 亚甲基,低级烷基磺酰基 - 亚甲基,R 25和R 26独立地选自氢 ,羟基和低级烷基。