公开(公告)号：US4292454A

公开(公告)日：1981-09-29

申请号：US131534

申请日：1980-03-18

申请人： Carlos G. Cardenas ,  Zia Ud Din

发明人： Carlos G. Cardenas ,  Zia Ud Din

IPC分类号： C07C11/00 ,  C07C11/21 ,  C07C17/10 ,  C07C29/09 ,  C07C45/60 ,  C07C45/62 ,  C07C45/63 ,  C07C45/68 ,  C07D317/12 ,  C07D317/16 ,  C07F3/02

CPC分类号： C07F3/02 ,  C07C11/00 ,  C07C11/21 ,  C07C17/10 ,  C07C29/095 ,  C07C45/60 ,  C07C45/62 ,  C07C45/63 ,  C07C45/68 ,  C07D317/12 ,  C07D317/16 ,  Y10S585/90

摘要： Disclosed is a process for the coupling of a Grignard reagent RMgX with an allylic halide in the presence of a dipolar aprotic solvent wherein the improvement, for obtaining improved yield and selectivity, comprises adding a catalyst to said Grignard or allylic halide and then carrying out the coupling reaction by the addition of the Grignard reagent to the allylic halide, said reaction being characterized by the displacement at the gamma position (relative to the halide) of the allylic halide with R of the Grignard reagent, migration of the allylic double bond in the direction of the halogen atom and loss of halogen. The present invention also resides in the discovery of certain novel procedures for the synthesis of Vitamin E. Specific embodiments of this aspect of the invention reside in the syntheses of 6,7-dehydrophytol, 10,11-dihydrofarnesene, phytone, hexahydropseudoionone, and related compounds as precursors for Vitamin E.

摘要翻译： 公开了在偶极非质子溶剂存在下将格氏试剂RMgX与烯丙基卤偶合的方法，其中为了获得改善的产率和选择性而改进，包括向所述格利雅或烯丙基卤加入催化剂，然后进行 通过将格利雅试剂加入到烯丙基卤化物中进行偶联反应，所述反应的特征在于在格列尼试剂的R处将烯丙基卤化物的γ位置（相对于卤化物）置换，其中烯丙基双键的迁移 卤素原子的方向和卤素的损失。 本发明还在于合成维生素E的某些新颖方法的发现。本发明的这个方面的具体实施方案在6,7-脱水糠醇，10,11-二氢法呢烯，植物酮，六氢假戊酸和相关的合成中 化合物作为维生素E的前体。

公开(公告)号：US4292459A

公开(公告)日：1981-09-29

申请号：US786973

申请日：1977-04-13

申请人： Carlos G. Cardenas ,  Zia Ud Din

发明人： Carlos G. Cardenas ,  Zia Ud Din

IPC分类号： C07C1/32 ,  C07C11/21 ,  C07C17/08 ,  C07C17/10 ,  C07C29/09 ,  C07D311/72 ,  C07F3/02 ,  C07C1/26

CPC分类号： C07C17/10 ,  C07C1/326 ,  C07C11/21 ,  C07C17/08 ,  C07C29/095 ,  C07D311/72 ,  C07F3/02

摘要： Disclosed is a process for the coupling of a Grignard reagent RMgX with an allylic halide in the presence of a dipolar aprotic solvent wherein the improvement, for obtaining improved yield and selectivity, comprises adding a catalyst to said Grignard or allylic halide and then carrying out the coupling reaction by the addition of the Grignard reagent to the allylic halide, said reaction being characterized by the displacement at the gamma position (relative to the halide) of the allylic halide with R of the Grignard reagent, migration of the allylic double bond in the direction of the halogen atom and loss of halogen. The present invention also resides in the discovery of certain novel procedures for the synthesis of Vitamin E. Specific embodiments of this aspect of the invention reside in the syntheses of 6,7-dehydrophytol, 10,11-dihydrofarnesene, phytone, hexahydropseudoionone, and related compounds as precursors for Vitamin E.