AQUEOUS HIGH-TEMPERATURE CHEMISTRY OF CARBOCYCLES AND HETEROCYCLES .2. MONOSUBSTITUTED BENZENES - BENZYL ALCOHOL, BENZALDEHYDE, AND BENZOIC-ACID

Benzyl alcohol is not very reactive under aquathermolysis conditions, except in the presence of acids. Almost all the products are formed by ionic pathways. It undergoes reversible dehydration to dibenzyl ether, disproportionation to benzaldehyde and toluene, and self-benzylation to 2- and 4-benzylbenzyl alcohols. These benzylbenzyl alcohols can react further, but major amounts of polyalkylated products are formed by the mono- and dibenzylation of toluene to give a range of dibenzyltoluenes and (benzylbenzyl)toluenes. Small amounts of diphenylmethane and bibenzyl and their benzylated products are also formed. The behavior of benzyl alcohol in the presence of phenol, pyridine, benzaldehyde, and benzene is also studied and rationalized. Benzaldehyde is much less reactive, except in the presence of formaldehyde, and especially in the presence of formic acid, when considerable formation of benzyl alcohol occurs and siphoning into this reaction matrix is observed. Benzoic acid is still less reactive. © 1990, American Chemical Society. All rights reserved.