教学课件学术资源columbia大学有机化学课件12.html.pptxVIP

20.6Sources of Esters;CH3COCH2CH2CH(CH3)2;Esters of Glycerol;Esters of Glycerol;Cyclic Esters (Lactones);Fischer esterification (Sections 15.8 and 19.14) from acyl chlorides (Sections 15.8 and 20.3) from carboxylic acid anhydrides (Sections 15.8and 20.5) Baeyer-Villiger oxidation of ketones (Section 17.16) ;20.7Physical Properties of Esters;Boiling Points;Solubility in Water;20.8Reactions of Esters:A Review and a Preview;with Grignard reagents (Section 14.10) reduction with LiAlH4 (Section 15.3) with ammonia and amines (Sections 20.13) hydrolysis (Sections 20.9 and 20.10) ;20.9Acid-Catalyzed Ester Hydrolysis;maximize conversion to ester by removing water maximize ester hydrolysis by having large excess of water equilibrium is closely balanced because carbonyl group ofester and of carboxylic acid are comparably stabilized;Example;Is the reverse of the mechanism for acid-catalyzed esterification. Like the mechanism of esterification, it involves two stages: 1) formation of tetrahedral intermediate (3 steps) 2) dissociation of tetrahedral intermediate  (3 steps);First stage: formation of tetrahedral intermediate;Second stage: cleavage of tetrahedralintermediate;Mechanism of formationoftetrahedral intermediate;Step 1;Step 1;Step 1;Step 2;Step 2;Step 3;Step 3;Cleavage of tetrahedralintermediate;Step 4;Step 4;Step 5;Step 5;Step 5;Step 6;Activation of carbonyl group by protonation of carbonyl oxygen Nucleophilic addition of water to carbonyl groupforms tetrahedral intermediate Elimination of alcohol from tetrahedral intermediate restores carbonyl group;18O Labeling Studies;18O Labeling Studies;20.10Ester Hydrolysis in Base:Saponification;is called saponification is irreversible, because of strong stabilization of carboxylateion if carboxylic acid is desired product, saponification is followedby a separate acidification step (simply a pH adjustment);Ester Hydrolysis in Aqueous Base;Example;Example;Soap-Making;Which bond is broken when esters a