有机化学课件 The SN2 Mechanism of Nucleophilic Substitution.ppt

8.3The SN2 Mechanism of Nucleophilic Substitution Kinetics Many nucleophilic substitutions follow asecond-order rate law.  CH3Br + HO – ? CH3OH + Br – rate = k[CH3Br][HO – ] inference: rate-determining step is bimolecular Bimolecular mechanism one stepconcerted Bimolecular mechanism one stepconcerted Bimolecular mechanism one stepconcerted 8.4Stereochemistry of SN2 Reactions Generalization Nucleophilic substitutions that exhibitsecond-order kinetic behavior are stereospecific and proceed withinversion of configuration. Inversion of Configuration Inversion of Configuration Stereospecific Reaction A stereospecific reaction is one in whichstereoisomeric starting materials givestereoisomeric products. The reaction of 2-bromooctane with NaOH (in ethanol-water) is stereospecific. (+)-2-Bromooctane ? (–)-2-Octanol (–)-2-Bromooctane ? (+)-2-Octanol Stereospecific Reaction Problem 8.4 The Fischer projection formula for (+)-2-bromooctaneis shown. Write the Fischer projection of the(–)-2-octanol formed from it by nucleophilic substitution with inversion of configuration. Problem 8.4 The Fischer projection formula for (+)-2-bromooctaneis shown. Write the Fischer projection of the(–)-2-octanol formed from it by nucleophilic substitution with inversion of configuration. 8.5How SN2 Reactions Occur 8.6Steric Effects in SN2 Reactions Crowding at the Reaction Site Table 8.2 Reactivity toward substitution by the SN2 mechanism Alkyl Class Relativebromide rate CH3Br Methyl 221,000 CH3CH2Br Primary 1,350 (CH3)2CHBr Secondary 1 (CH3)3CBr Tertiary too small to measure Decreasing SN2 Reactivity Decreasing SN2 Reactivity Crowding Adjacent to the Reaction Site Table 8.3 Effect of chain branching on rate of SN2 substitution Alkyl Structure Relativebromide rate Ethyl CH3CH2Br 1.0 Propyl CH3CH2CH2Br 0.8 Isobutyl (CH3)2CHCH2Br 0.036 Neopentyl (CH3)3CCH2Br 0.00002 25 25 24 25 29 29 30 31 31 31 HO – CH3Br + HOCH3 Br – + HO – CH3Br + HOCH3 Br – +