Chem 342 • Organic Chemistry II Lecture Summary 26 - 17 Apr 2009

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Chem 342 • Organic Chemistry II Lecture Summary 26 - 17 Apr 2009 Chapter 21 - Carboxylic Acid Derivatives and Nucleophilic Acyl Substitution Acid Chlorides Recall from last lecture that we can make acid chlorides from acids with thionyl chloride. Preparation of Acid Chlorides O O + SOCl2 + SO2 + HCl R OH R Cl The most reactive and versatile derivative, acid chlorides can be used to make many acid derivatives. Reactions of Acid Chlorides O O + H2O + HCl Hydrolysis R Cl R OH O pyridine O + R'OH + Pyridine-HCl Alcoholysis R Cl R OR' O O + 2 NH3 + NH4Cl Aminolysis R Cl R NH2 Use 2 equiv. of amine or 1 equiv. amine and 1 equiv. of pyridine as base. Acid Anhydrides Anhydrides can be made from readily available inexpensive acids by heating to drive off the water. This is pretty much limited to simple acids like acetic acid and diacids. If an unsymmetric anhydride is desired, a more controlled reaction is required to avoid statistical mixtures of products. Acid halides can be reacted with carboxylate salts to form unsymmetric anhydrides with complete control. Acid Anhydrides O O Heat O O + + HOH R OH HO R R O R limited to symmetric O O anhydrides Heat OH + HOH OH O O O O O O O can make unsymmetric + + NaCl anhydrides R Cl NaO R' R O R' Chem 342 page 1 Spring 2009 Anhydrides will react very similar to acid chlorides. They are less reactive than acid chlorides which makes handling them easier. Usually we use anhydrides when we need to introduce simple, readily available acyl groups like acetyl. O O heat OH Hydrolysis O + H2O OH O O O O CO H CO H 2 O 2 O Alcoholysis OH O acetosalicylic acid (asprin) salicylic acid O O H NH N 2 O Aminolysis O HO HO acetaminophen Preparation of Esters As we have seen, esters can be prepared by alcoholysis of acid chlorides and anhydrides. But some of the more common simple esters can be made directly from the carboxylic acid. The preparation of esters from acids is limited, however. A deprotonated acid (carboxylate) will react with methyl or primary alkyl halides via a SN2 reaction. CH I O NaOH O 3 O R OH R O Na R OCH3 Chem 342 page 2 Spring 2009 Daily Quiz Chem 342 page 3 Spring 2009.

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