Comparisons of Photo-Fries Rearrangements of 4-Dodecylphenyl Phenylacetate and Two Structurally Related Esters in Hexane and Polyethylene Cages. How Important Are Anchoring Chains?


  • This paper is part of a special issue dedicated to Professor J. C. (Tito) Scaiano on the occasion of his 60th birthday.


Photo-Fries rearrangements of 4-dodecylphenyl phenylacetate have been investigated in polyethylene films with 0–71% crystallinity and in hexane over a range of temperatures. The results are compared to those reported previously from phenyl phenylacetate and 1-naphthyl tetradecanoate to assess the influence of a long alkyl chain on the in-cage motions of the intermediate singlet radical pairs. It is demonstrated that the reactivity and selectivity of intimate singlet radical pairs can be tuned by judicious placement of long-chain substituents and selection of a specific polyethylene type as the reaction matrix.