Ammonolysis, acyl chlorides esters

Ammonolysis. Reactions involving ammonia. Ammonolysis of esters, acyl chlorides, and anhydrides give amides aniline is produced by ammonolysis of chlorobenzene. The reaction is analogous to hydrolysis, with ammonia substituted for water. 

The acylation of simple /3-keto esters with acyl chlorides to form di-acylacetic esters proceeds readily however, the subsequent cleavage for removing the smaller acyl group is complicated in that the original keto ester may be regenerated. The optimum conditions for the conversion of benzoylacetoacetic ester to benzoylacetic ester with ammonium chloride and ammonium hydroxide have been studied. The over-all synthesis of this ester has been described (57%). An improved procedure for the ammonolysis of ethyl a-acetyl-/3-oxocaproate using gaseous ammonia has been described. By a similar process, a series of alicyclic /3-keto esters has been prepared in over-all yields of 20-40%. ... 

Several improvements in acylation techniques were announced. Butyllithium wwas determined to be superior to sodium amide in preparation of amide ions for ammonolysis reactions with esters. Phosgene is more reactive than ethyl chloroformate toward eneamines. The intermediate acyl chlorides may then be converted to a variety of products. a-Acetylenic aldehydes are easily prepared by the action of acetylenic Grignard reagents upon ethyl formate. ... 

Esters undergo nucleophilic addition—elimination at their acyl carbon atoms when they are treated with ammonia (called ammonolysis) or with primary and secondary amines. These reactions take place much more slowly than those of acyl chlorides and anhydrides, but they can still be synthetically useful ... 

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