有机化学 （英文讲义）Chapter 16.pptVIP

* Chapter 16 Enolate and Other Carbon Nucleophiles 16.1 Introduction The acidity of hydrogen: enolate ion 烯醇离子 The order of acidity for the Hs of substituted methyl group: 16.2 Enols and enolate anions enolization: tautomerization 互变异构 16.3 Halogenation and alkylation of enolate anions a. Racemization of enolate anions Base-catalyzed enolization: enol tautomer Acid-catalyzed enolization: Racemization via enolization: b. Halogenation a comparison: c. Haloform (CHX3) reaction (卤仿反应） General reaction: The acidity of the a-Hs on the methyl group: The rate of halogenation: e.g. e.g. Iodoform test: (碘仿反应) d. Alkylation 16.4 Alkylation of more stabilized anions Active methylene compounds: stabilized anion 3 kinds of important reactions of active methylene compounds: alkylation(烷基化), acylation(酰基化), and Knoevenagel condensation (诺文葛尔) Some examples of synthetic uses of active methylene compounds: i. To form substituted acetones ketolytic decomp. (酮式分解) acidic decomp. (酸式分解) ethyl acetoacetate (乙酰乙酸乙酯) ii. To form substituted acetic acids diethyl malonate The reactions with CH2I2 or BrCH2(CH2)nCH2Br (n = 0,1,2,3): e.g. 16.5 Aldol condensation (羟醛缩合) a. Self-condensation of aldehydes or ketones Mechanism: General expression: Step 1 enolization: Step 2 nucleophilic addition: Step 3 acidification and Step 4 dehydration: aldol 羟醛 e.g. Step 4 羟酮 b. Cross-condensation of aldehydes e.g. e.g. The insertion of C=C double bond into the bond between the ?-C and the carbonyl C will not reduce the acidity of the H. c. Claisen-Schmidt reactions d. Intramolecular aldol condensation (糠醛) e. Condensation with nitroalkanes or nitriles f. Perkin condensation—to synthesize cinnamic acid Mechanism cinnamic acid 肉桂酸 E-cinnamic acid e.g. 16.6 Claisen condensation to form ?-keto esters a. Self-claisen condensation of esters Mechanism: b. Cross-Claisen condensation e.g. e.g. triethyl benzene- 1,3,5-tricarboxylate c. Intramolecular Claisen condensation—Dieckman