Nucleophilic substitution vs elimination reactions亲核取代反应、消除反应.pptVIP

An energy diagram for the SN1 reaction: In multistep reactions, the rate of the slowest step will be the rate of the entire reaction This is called the rate determining step In the case to the right, k1k2 or k3 and the first step is rate determining. Step 1: An acid/base reaction. Protonation of the alcoholic oxygen to make a better leaving group. This step is very fast and reversible.? The lone pairs on the oxygen make it a Lewis base.? ? Step 2: Cleavage of the C-O bond allows the loss of the good leaving group, a neutral water molecule, to give a carbocation intermediate. This is the rate determining step (bond breaking is endothermic)? ? Step 3: Attack of the nucleophilic bromide ion on the electrophilic carbocation creates the alkyl bromide.? SN1 MECHANISM FOR REACTION OF ALCOHOLS WITH HBr To understand the stereochemistry of the SN1 reaction, we must examine the geometry of the carbocation intermediate. The more highly substituted a carbocation is, the more stable it is. The more stable a carbocation is, the easier it is to form. 30 20 10 methyl Loss of the leaving group in Step [1] generates a planar carbocation that is achiral. In Step [2], attack of the nucleophile can occur on either side to afford two products which are a pair of enantiomers. Because there is no preference for nucleophilic attack from either direction, an equal amount of the two enantiomers is formed called a racemic mixture. We say that racemization has occurred. (transformation of of optically active compound to a racemic mixture components of the reaction influence the reaction pathway: R- Reactivity order :?? (CH3)3C-? ? (CH3)2CH-?? ? CH3CH2-? ? CH3- In an SN1 reaction, the rate determining step is the loss of the leaving group to form the intermediate carbocation. The more stable the carbocation is, the easier it is to form, and the faster the SN1 reaction will be.? Since a carbocation intermediate is formed, there is the possibility of rearrangements (