有机化学第九章2.ppt

Summary and Key Words Aldehydes and ketones are similar in their reactivity and are distinguished by the fact that the substituents on the acyl carbon cant act as leaving groups. Carboxylic acids and their derivatives-acid chlorides, acid anhydrides, esters, and amides-are distinguished by the fact that the substituents on the acyl carbon can act as leaving groups. A carbon-oxygen double bond is structurally similar to a carbon-carbon double bond. The carbonyl carbon atom is sp2-hybridized and forms both an sp2 σ bond and a p π bond to oxygen. Carbonyl groups are strongly polarized because of the electronegativity of oxygen. Aldehydes are usually prepared by oxidation of primary alcohols. Ketones are similarly prepared by oxidation of secondary alcohols. Aldehydes and ketones behave similarly in much of their chemistry. Both undergo nucleophilic addition reactions, and a variety of products can be prepared. For example, aldehydes and ketones undergo a reversible addition reaction with water to yield 1,1-dialcohols, or gem diols. Similarly they react with alcohols to yield acetals, R2C(OR)2, which are valuable as carbonyl protecting groups. Primary amines add to aldehydes and ketones to give imines, R2C=NR. In addition, aldehydes and ketones are reduced by NaBH4 to yield primary and secondary alcohols, respectively and they react with Grignard reagents to give alcohols. * 9.7 Nucleophilic Addition of Alcohols: Acetal Formation Aldehydes and ketones react with alcohols in the presence of an acid catalyst to yield acetals： Ketone/aldehyde An acetal Acetal formation involves the acid-catalyzed nucleophilic addition of an alcohol to the carbonyl group in a manner similar to that of the acid-catalyzed hydration。 The initial nucleophilic addition step yields a hydroxy ether called a hemiacetal, which reacts further with a second equivalent of alcohol to yield the acetal plus water. A ketone A hemiacetal An acetal As with hydra