Hydrolysis of Acid Derivatives Acid chlorides and anhydrides Y = Cl or OCOR - room temperature USUALLY UNWANTED SIDE REACTIONS

Hydrolysis of Esters and Amides Require acid or base catalyst and heat ESTERS - REVIEW SAPONIFICATION AMIDES - 6M HCl or 40% NaOH and prolonged heating DEPROTECTION OF ACETANILDES

Cyclic compounds RNH2 + Phthalic acid

Reactions of Cyclic Anhydrides with ROH Half Acid

Lactones with ROH & Amines HO-(CH2)4COOR HO-(CH2)4CONHR

Reduction Reactions RCO2R RCH2OH LAH Recall Reduction of amides to give amines Acid chlorides to aldehydes

Look over carefully: Summary of the Chemistry of Acid Chlorides 1) Synthesis - acid + SOCl2 2) Reactions a. Conversion to all other acid derivatives: NO catalyst b. Rx with organmetallics (p. 977) RMgX or RLi ----> alcohols LAH ---> primary alcohols R2CuLi -------> ketones Li(t-BuO)3H -------> aldehyde Friedel-Acylation (AlCl3)

Acid Anhydrides 1. Preparation - from acid chlorides and carboxylic acids 2. Reactions 1. Conversion to less reactive acid derivatives No Catalyst 2. Friedel-Craft Acylations - catalyst required + NOTE above: One part of anhydride adds to ring: the other is sacrificed

Mechanism of FC THINK OF THE MECHANISM AS A TYPICAL ACID CATALYZED ADDITION-ELIMINATION MECHANISM OF NUCLEOPHILIC ACYL SUBSTITUTION Y Y Y ELIMINATION ADDITION Think of AlCl3 as big proton!!!!! IT IS E+ WHAT IS Y? WHERE DOES E+ (AlCl3) ADD? The C=O oxygen WHICH IS NUKE? ELECTRON PAIR ON AROMATIC RING

ACTUAL MECHANISM AlCl3 - -

Please don’t do problem 31a, but please do problem 32c

Chapter 22 Alpha Substitutions and Condensations of Enols and Enolate Ions Actually this the chemistry of a-hydrogen atoms enolate ion Aldehydes, ketones and esters IMPORTANT: enolate is a nuke; attacks via of its alpha carbon

Reactions of Enolates with Electrophiles

ALDOL REACTION - Borodin

C

EXAMPLES Dangle the group attached to alpha carbon nuke portion electrophilic portion

MECHANISM OF ALDOL REACTION + H