columbia大学有机化学课件 （二十六）.pptVIP

6.14Addition of Halogensto Alkenes General features electrophilic addition to double bond forms a vicinal dihalide Example Scope F2 addition proceeds with explosive violence I2 addition is endothermic: vicinal diiodidesdissociate to an alkene and I2  6.15Stereochemistry of Halogen Addition anti addition Example Example 6.16Mechanism of Halogen Addition to Alkenes: Halonium Ions Mechanism is electrophilic addition Br2 is not polar, but it is polarizable two steps (1) formation of bromonium ion (2) nucleophilic attack on bromonium  ion by bromide Relative Rates of Bromination ethylene H2C=CH2 1 propene CH3CH=CH2 61 2-methylpropene (CH3)2C=CH2 5400 2,3-dimethyl-2-butene (CH3)2C=C(CH3)2 920,000 More highly substituted double bonds react faster.Alkyl groups on the double bond make itmore “electron rich.” Mechanism? No obvious explanation for anti addition provided by this mechanism. Mechanism Cyclic bromonium ion Formation of Bromonium Ion Formation of Bromonium Ion Formation of Bromonium Ion Stereochemistry Example Cyclopentene +Br2 Bromonium ion Bromide ion attacks the bromonium ion from side opposite carbon-bromine bond trans-Stereochemistry in vicinal dibromide 6.17Conversion of Alkenes to Vicinal Halohydrins Examples Mechanism bromonium ion is intermediate water is nucleophile that attacks bromonium ion Examples Cyclopentene + Cl2 Chloronium ion Water attacks chloronium ion from side opposite carbon-chlorine bond trans-Stereochemistry in oxonium ion trans-2-Chlorocyclopentanol Regioselectivity Markovnikovs rule applied to halohydrin formation: the halogen adds to the carbon having the greater number of hydrogens. Explanation transition state has for attack of water on bromonium ion has carbocation character; more stable transition state (left) has positive charge on more highly substituted carbon (77%) H3C C CH2 H3C CH3 OH C CH2Br CH3 Br2 H2O CH2 H3C C H3C H3C CH2 H3C Br : : d+ d+ H O H d+ .. Br : : H O H d+ .. C d+ d+ 1 2 4 3 5 6 6 7 8 6