columbia大学有机化学课件 （三十九）.pptVIP

8.8Unimolecular Nucleophilic SubstitutionSN1 A question... Yes. But by a mechanism different from SN2. The most common examples are seen in solvolysis reactions. Example of a solvolysis. Hydrolysis of tert-butyl bromide. Example of a solvolysis. Hydrolysis of tert-butyl bromide. Example of a solvolysis. Hydrolysis of tert-butyl bromide. Example of a solvolysis. Hydrolysis of tert-butyl bromide. Example of a solvolysis. Hydrolysis of tert-butyl bromide. Kinetics and Mechanism Proposed mechanism is called SN1, which stands forsubstitution nucleophilic unimolecular Mechanism Mechanism Characteristics of the SN1 mechanism first order kinetics: rate = k[RX] unimolecular rate-determining step carbocation intermediate rate follows carbocation stability rearrangements sometimes observed reaction is not stereospecific much racemization in reactions of optically active alkyl halides 8.9Carbocation Stability and SN1 Reaction Rates Electronic Effects Govern SN1 Rates Table 8.5 Reactivity toward substitution by the SN1 mechanism Alkyl bromide Class Relative rate CH3Br Methyl 1 CH3CH2Br Primary 2 (CH3)2CHBr Secondary 43 (CH3)3CBr Tertiary 100,000,000 Decreasing SN1 Reactivity 8.10Stereochemistry of SN1 Reactions Generalization Nucleophilic substitutions that exhibitfirst-order kinetic behavior are not stereospecific. Stereochemistry of an SN1 Reaction Figure 8.8 Figure 8.8 8.11Carbocation Rearrangementsin SN1 Reactions Because... carbocations are intermediatesin SN1 reactions, rearrangementsare possible. Example Example 8.12Solvent Effects In general... SN1 Reaction Rates Increase in Polar Solvents Table 8.6SN1 Reactivity versus Solvent Polarity In general... SN2 Reaction Rates Increase inPolar Aprotic Solvents Table 8.7SN2 Reactivity versus Type of Solvent Solvent Type Relative  rate CH3OH polar protic 1 H2O polar protic 7 DMSO polar aprotic 1300 DMF polar aprotic 2800 Acetonitrile polar aprotic 5000 Mechanism SummarySN1 and SN2 When... p