Reduction of alkyl‐substituted benzoic acids with lithium in liquid ammonia: Synthesis of 1‐alkyl‐2,5‐cyclohexadiene‐1‐carboxylic acids

Abstract

Abstract The reduction of alkyl‐substituted benzoic acids with lithium in liquid ammonia has been investigated. Without added proton donor the aromatic acid yields a dianion which can either be protonated with ammonium chloride or alkylated to give the corresponding 1,4‐dihydrobenzoic acid and 1‐alkyl 2,5‐cyclohexadiene‐1‐carboxylic acid, respectively. In the presence of ethanol, 3‐ and 4‐alkylbenzoic acids yield either 1,4‐dihydro or 4,5‐dihydro products depending on the working up procedure Benzoic acid behaves similarly. Water is shown to be a useful proton donor in the reduction of 3‐ and 4‐alkylbenzoic acids to 1,4‐dihydro products. 2‐Alkylbenzoic acids yield 1,4‐dihydro products, irrespective of the experimental procedure. Experiments with 4‐deuterobenzoic acid show the first proton addition to be irreversible in ammonia as well as in ammonia‐ethanol. Some thirty new alkyl‐ and dialkyl‐cyclohexadienecarboxylic acids are described.