columbia大学有机化学课件 （三十四）.pptVIP

8.13Substitution and Eliminationas Competing Reactions Two Reaction Types Two Reaction Types Elimination versus Substitution The major reaction of a secondary alkyl halidewith an alkoxide ion is elimination by the E2mechanism. Example Figure 8.11 Figure 8.11 When is substitution favored? 1) decreased crowding at the carbon that bears the leaving group Uncrowded Alkyl Halides primary alkyl halide But a crowded alkoxide base can favor elimination even with a primary alkyl halide. primary alkyl halide + bulky base When is substitution favored? 1) decreased crowding at the carbon that bears the leaving group 2) decreased basicity of the nucleophile Weakly Basic Nucleophile Weakly Basic Nucleophile Tertiary Alkyl Halides Example Alkyl halides can react with Lewis bases in two different ways; nucleophilic substitution or elimination. C C H X + Y : – C C Y H X : – + C C + H Y X : – + b-elimination nucleophilic substitution How can we tell which reaction pathway is followedfor a particular alkyl halide? C C H X + Y : – C C Y H X : – + C C + H Y X : – + b-elimination nucleophilic substitution A systematic approach is to choose as a referencepoint the reaction followed by a typical alkyl halide(secondary) with a typical Lewis base (an alkoxideion). CH3CHCH3 Br NaOCH2CH3 ethanol, 55°C CH3CHCH3 OCH2CH3 CH3CH=CH2 + (87%) (13%) Br E2 CH3CH2 O ?? ?? ?? – Br SN2 CH3CH2 O ?? ?? ?? – Given that the major reaction of a secondaryalkyl halide with an alkoxide ion is elimination by the E2 mechanism, we can expect the proportion of substitution to increase with: Decreased crowding at carbon that bears the leaving group increases substitution relative to elimination.  CH3CH2CH2Br NaOCH2CH3 ethanol, 55°C CH3CH=CH2 + CH3CH2CH2OCH2CH3 (9%) (91%) CH3(CH2)15CH2CH2Br KOC(CH3)3 tert-butyl alcohol, 40°C + CH3(CH2)15CH2CH2OC(CH3)3 CH3(CH2)15CH=CH2 (87%) (13%) Given that the major reaction of a secondaryalkyl halide with an alkoxide ion is elimination by the E2 mecha