22. Carboxylic Acid Derivatives: NAS

Propose a mechanism for the reaction of aniline with acetic anhydride to give acetanilide.

Propose a mechanism for the reaction of benzoic acid with acetyl chloride to give acetic benzoic anhydride.

Propose a mechanism for the reaction of benzyl alcohol with acetyl chloride to give benzyl acetate.

Show how you would accomplish the following synthetic conversions efficiently and in good yield. You may use any necessary additional reagents and solvents.

(g)

Show how you would use an acid chloride as an intermediate to synthesize.

(a) N-phenylbenzamide (PhCONHPh) from benzoic acid and aniline.

Show how you would convert the following starting materials to the indicated nitriles:

(a) phenylacetic acid → phenylacetonitrile

Show how to synthesize the following compounds, using appropriate carboxylic acids and amines.

(a)

Show how to synthesize the following compounds, using appropriate carboxylic acids and amines.

(b)

Show how to synthesize the following compounds, using appropriate carboxylic acids and amines.

(c)

Propose a second mechanism for the reaction of benzoic acid with acetyl chloride to give acetic benzoic anhydride. This time, let the other oxygen of benzoic acid serve as the nucleophile to attack the carbonyl group of acetyl chloride. Because proton transfers are fast between these oxygen atoms, it is difficult to differentiate between these two mechanisms experimentally.

Propose a mechanism for the reaction of aniline with ethyl acetate to give acetanilide. What is the leaving group in your proposed mechanism? Would this be a suitable leaving group for an S_N2 reaction?

Show how you would synthesize the following esters from appropriate acyl chlorides and alcohols.

(e) tert-butyl acetate

(f) diallyl succinate

Show how you would use appropriate acyl chlorides and amines to synthesize the following amides.

(a) N,N-dimethylacetamide

(b) acetanilide (PhNHCOCH₃)

Show how you would use acetic anhydride and an appropriate alcohol or amine to synthesize (i) benzyl acetate and (ii) N,N-diethylacetamide.

Show how you would accomplish the following syntheses. Some of these conversions may require more than one step.

(e) cyclohexylamine → N-cyclohexylacetamide

(f) bromocyclohexane → dicyclohexylmethanol