13.2.3.3.2QuaternaryAmmoniumAgOH(CH3)4NI(CH3)4tNOH + AgI(CH3)3N +CH3I季铵盐季铵碱OH + CH3(SN2)N(CH3)3CH3OH+(CH3)3NOH+H-CH,二CH2+N(CH3)31(E2)H,O+CH2CH,+N(CH3)3
13.2.3.3.2 Quaternary Ammonium OH - CH3 +N(CH3 )3 CH3OH (CH3 )3N (SN2) OH - H CH2 CH (E2) 2 +N(CH3 )3I - H2O CH2 CH2 N(CH3 )3 (CH3)3N CH3I (CH3)4NI AgOH (CH3)4 +NOH AgI 季铵盐 季铵碱
Hofmann彻底甲基化AgOH3CHl_RCH2CH,*N(CH3)3lRCH,CH2*N(CH3)3OHRCHCHNH2RCHCH2 + N(CH3)3 +H20egAgOH2CH31+ H0OHLHCH3CH3CH3CH3CH3CH3
Hofmann彻底甲基化 eg RCH2CH2NH2 3CH3I RCH2CH2 +N(CH3 )3I - RCH2CH2 +N(CH3 )3OH - RCH CH2 N(CH3 )3 H2O AgOH N H 2CH3I +N CH3 CH3 I AgOH +N CH3 CH3 OH N CH3 CH3 H2O
Hofmann rules:>R2CH-CH3 > RCH2egKOCHCH3CH,CH-CH2 +CH3CHCHCHCH3CH,CH2CHCHCH3CHOH2%98%X+N(CH3)3
Hofmann rules： CH3 > RCH2 > R2CH eg. CH3CH2CH2CHCH3 N(CH3 )3 KOC2H5 C2H5OH CH3CH2CH CH2 CH3CH2CH CHCH3 + 98% 2%
影响反应的因素：(1)β一H的酸性(2)β一H的空间位阻CH3+ CH3OH-C—CH2CH2-N(CH3)2→(CH3)3CCH,CH2N(CH3)2CH3-CH3CH3OHCH3150℃CH2CH2NCH,CH,OHCHCH2+CH2CH2CH393%0.4%
影响反应的因素: (CH3)3CCH2CH2N(CH3)2 CH3OH OH - C CH3 CH3 CH3 CH2CH2 N(CH3)2 CH3 + (1)β—H的酸性 (2)β—H的空间位阻 93% 0.4% CH2CH2 N CH3 CH3 CH2CH3OH 150 oC CH CH2 CH2 CH2
QuaternaryAmmoniumPhaseTransferCatalyst(Bu)4NBrRBr + NaOAcROAc+NaBrH.O100%TEBAArOSO2NR2ArOH+R2NSO2CI苯/H097%TEBA=PhCH,+N(C,Hs)3CI芳胺的烷基化OHNHCH3+I +H2ONH2+CH3I
Quaternary Ammonium Phase Transfer Catalyst 芳胺的烷基化 NH2 CH3I OH- NHCH3 I H2O 100% RBr NaOAc ROAc NaBr (Bu)4NBr H2O ArOH R2NSO2Cl TEBA 苯/H2O ArOSO2NR2 97% TEBA=PhCH2 +N(C2H5 )3Cl