10-3 醇(1).pptVIP免费

六、频呐醇重排（嚬哪，片呐醇，频哪醇）频呐醇就是邻二叔醇。频呐醇在酸的作用下发生重排生成酮的反应称为嚬哪醇重排。CH3CCCH3CH3OHOHCH3CH3CCCH3CH3CH3OH2SO4orHCl历程：+H+CH3CCCH3CH3OHOH2CH3CH3CCCH3CH3OHCH3-H2OCH3CCCH3OHCH3CH3CH3CCCH3OHCH3CH3-H+CH3CCCH3CH3CH3O30碳正离子质子化的酮CH3CCCH3CH3OHCH3CH3CCCH3OHCH3CH3重排反应的动力是：由三级C+生成更加稳定的质子化的酮H2SO4OHOHO-H+OHOHHO+H+-H2O+H2O30碳正离子质子化的酮重排反应注意事项：C6H5CCCH3C6H5OHC6H5OHC6H5CCCH3C6H5OH2C6H5OHC6H5CCCH3C6H5C6H5OH-H2O+H+C6H5CCCH3C6H5OHC6H5C6H5CCCH3C6H5C6H5O-H+稳定的碳正离子优先生成，电子云密度大的基团优先转移。C6H5CCCH3C6H5C6H5OHC6H5CCCH3C6H5C6H5OH>稳定性：⑴、如迁移基团是烷基则：3o>2o>1o基团迁移的优先次序：CH3OCH3C6H5ClVÏà¶Ô500161210.7⑵、如迁移基团是芳基KMnO4/OH-H+OHOHO第四节醇的制备一、卤代烃的水解H2C=CHCH2ClH2C=CHCH2OHNaOH-H2ONaOH-H2OCH2ClCHOH在实验室里卤代烃通常由醇来制备，只有当相应的卤代烃比醇更容易得到时才用这种方法来制备醇。NaOH-H2OClOH二、由烯烃来制备1、烯烃的水合CH3CH=CH2+H2OH3PO4300ºC10MPaH2SO4CH3-CH-CH3OSO3HCH3-CH-CH3OHH2O直接水合间接水合两种方法是殊途同归，都遵循马氏规则。但有时会伴随重排反应的发生。CH3CHCH=CH2OHCH31.H2SO42.H2OCH3CCH2CH3CH3CH3CHCHCH3CH3OH+正常产物（次）重排产物（主）2、羟汞化–脱汞反应(CH3COO)2HgHgOCCH3OH2OCH3CCH=CH2CH3CH3CH3CCH-CH3CH3CH3NaBH4CH3CCH-CH3CH3CH3OH2、硼氢化–氧化反应（1）遵从马氏规则，（2）无重排，（3）反应条件温和用于制备仲醇、叔醇。反应特点：反应特点：（1）加成取向：反马氏规则，（2）加成的立体化学：通过四元环状过渡态所进行的顺式加成。CH3(CH2)7CH2-CH2OH98%CH3(CH2)7CH=CH21.B2H62.H2O2,OH-1.B2H62.H2O2,OH-CH3OCH=CH2CH3OCHCH2OH90%H2O2CH3CH=CH2++--+HBHCH3CHCH2HBH2OH-CH2CHCH2HOHNaBH4CH3H2O2OH-H3CHHHO+CH3HHOHNaBH4H2O2OH-CH3C2H5HCH3HCH3HHOCH3C2H5例1、例2、三、通过格氏试剂制备醇-+CROMgXC=OR__MgX++-CROHH3O+通式：常见反应类型：=OR__MgX+H3O+HCH=OR_CH2OHOH3O+RCCCH3CH=OH3O+H3O+RCHCH3OHCH3CCH3CH3CCH3OHR¶à1CµÄ²®´¼¶à2CµÄ²®´¼ÖÙ´¼Êå´¼ÎÞË®ÒÒÃÑÎÞË®ÒÒ...