columbia大学有机化学课件 （二十一）.pptVIP

6.8Free-radical Addition of HBr to Alkenes The peroxide effect Markovnikovs Rule Addition of HBr to 1-Butene Addition of HBr to 1-Butene Photochemical Addition of HBr Addition of HBr with a regiochemistry oppositeto Markovnikovs rule can also occur wheninitiated with light with or without added peroxides. Mechanism Addition of HBr opposite to Markovnikovs rule proceeds by a free-radical chain mechanism. Initiation steps: Mechanism Addition of HBr opposite to Markovnikovs rule proceeds by a free-radical chain mechanism. Initiation steps: Mechanism Mechanism 6.9Addition of Sulfuric Acid to Alkenes Addition of H2SO4 follows Markovnikovs rule: yields an alkyl hydrogen sulfate Mechanism Alkyl hydrogen sulfates undergo hydrolysis in hot water Application: Conversion of alkenes to alcohols But... not all alkenes yield alkyl hydrogen sulfateson reaction with sulfuric acid these do: H2C=CH2, RCH=CH2, and RCH=CHR these dont: R2C=CH2, R2C=CH2, and R2C=CR2 acetic acid Br CH3CH2CHCH3 CH2 CH3CH2CH HBr (80%) only product inabsence of peroxides CH3CH2CH2CH2Br only product when peroxides added to reaction mixture Br CH3CH2CHCH3 CH2 CH3CH2CH HBr CH3CH2CH2CH2Br only product when peroxides added to reaction mixture CH2 CH3CH2CH HBr addition opposite to Markovnikovs rule occurs with HBr (not HCl or HI) + HBr hn (60%) CH2 CH2Br H .. .. O R R O .. .. O . R .. .. .. .. O R . + .. .. O R R O .. .. + Br O . R .. .. .. .. O R . + O . R .. .. H .. .. : + O R .. .. H . Br .. .. : Propagation steps: + CH3CH2CH CH2 . Br .. .. : . CH3CH2CH CH2 Br : .. .. Propagation steps: + + CH3CH2CH CH2 . Br .. .. : . CH3CH2CH CH2 Br : .. .. . CH3CH2CH CH2 Br : .. .. H Br .. .. : .. CH3CH2CH2CH2 Br : .. . Br .. .. : CH3CHCH3 OSO2OH CH3CH CH2 HOSO2OH Isopropylhydrogen sulfate + slow + fast CH3CH CH2 H .. SO2OH .. + CH3CH CH3 .. SO2OH .. : – O O CH3CHCH3 OSO2OH : .. H—OH HO—SO2OH + CH3CHCH3 O SO2OH heat CH3CHCH3 O H + 1. H2SO4 2. H2O, heat (75%) OH 17 9 18 18 19 20 20 21 21 22 23 17 9 18 18