Solvent-Dependent Photochemistry of 2,2,2-Tribromoethyl-(2′-phenylacetate)

Abstract

Photolysis (254 nm) of the title compound 1 produces a variety of stable products, which vary significantly with the nature of the solvent. Solvents that serve as efficient H atom donors (methanol, ethanol, isopropyl alcohol) favor products arising from a net reduction of one or more of the C-Br bonds. These include 2,2-dibromoethyl-(2'-phenylacetate) 2 and 2-bromoethyl-(2'-phenylacetate) 3. In the presence of nucleophiles, products such as 2-(2'-phenylacetoxy)acetic acid 5a and/or its ester derivatives are produced. Phenylacetic acid 6 is formed in some cases but under the conditions studied appears to be a minor product. The results are interpreted in terms of a general mechanism that features formation of an iso-tribromo intermediate 9 and/or a geminate radical-atom pair.