卤代反应 亲核取代与消去反应大学英文课件.pptVIP

Based on McMurry, Organic Chemistry, 6th edition, (c) 2003 11. Reactions of Alkyl Halides: Nucleophilic Substitutions and Eliminations Based on McMurry’s Organic Chemistry, 6th edition Alkyl Halides React with Nucleophiles and Bases Alkyl halides are polarized at the carbon-halide bond, making the carbon electrophilic Nucleophiles will replace the halide in C-X bonds of many alkyl halides(reaction as Lewis acid) Nucleophiles that are Br?nsted bases produce elimination 11.1 The Discovery of the Walden Inversion In 1896, Walden showed that (-)-malic acid could be converted to (+)-malic acid by a series of chemical steps with achiral reagents This established that optical rotation was directly related to chirality and that it changes with chemical alteration Reaction of (-)-malic acid with PCl5 gives (+)-chlorosuccinic acid Further reaction with wet silver oxide gives (+)-malic acid The reaction series starting with (+) malic acid gives (-) acid Reactions of the Walden Inversion Significance of the Walden Inversion The reactions alter the array at the chirality center The reactions involve substitution at that center Therefore, nucleophilic substitution can invert the configuration at a chirality center The presence of carboxyl groups in malic acid led to some dispute as to the nature of the reactions in Walden’s cycle 11.2 Stereochemistry of Nucleophilic Substitution Isolate step so we know what occurred (Kenyon and Phillips, 1929) using 1-phenyl-2-propanol Only the second and fifth steps are reactions at carbon So inversion certainly occurs in the substitution step Hughes’ Proof of Inversion React S-2-iodo-octane with radioactive iodide Observe, initially that racemization of mixture is twice as fast as incorporation of label so it must be with inversion Racemization in one reaction step would occur at same rate as incorporation The Nature of Substitution Substitution, by definition, requires that a leaving group, which is also a Lewis base, departs from the reacti