Photo-Fries rearrangement 1-naphthyl acetate

Andrew, D. Des Islet, B. T. Margaritis, A. Weedon, A. C. Photo-Fries Rearrangement of Naphthyl Acetate in Supercritical Carbon Dioxide Chemical Evidence for Solvent-Solute Clustering. J. Am. Chem. Soc. 1995, 117, 6132-6133. 

Cui and Weiss reported the photo-Fries rearrangements of 2-naphthyl myristate and 2-naphthyl acetate (Fig. 35) in unstretched and stretched low-density polyethylene films [116]. It was argued that the radical pair generated by irradiation is held in a cavity shaped like the starting ester and whose walls relax more slowly than the radicals recombine. The preferred solution product is too different in shape from the starting ester to be formed. 

Figure 35 Photo-Fries rearrangement of 2-naphthyl acetates in solution and within low-density polyethylene films.

Figure 36 Photo-Fries rearrangement of 1-naphthyl acetates within Y-zeolite and low-density polyethylene films.

In order to address this issue, a process which involves a much shorter-lived radical pair needed to be examined. Toward this end, Weedon, et al. examined the photo-Fries rearrangement of naphthyl acetate (Scheme 4.4-6) in SCCO2 at 35 and 46 C [56]. Photolysis of 1 leads to caged pair [2/3] reaction in-cage yields the photo-Fries products, 2- or 4-acetylnaphthol (4 and 5). However, cage escape, followed by hydrogen abstraction (isopropanol was present as a hydrogen atom donor) leads to a-naphthol (6). 

Serum albumins have been employed as hosts for the photo-Fries rearrangement of 4-methoxy-l-naphthyl esters, at site I (acetate) and site II (monoglutarate) of the proteins. A species- and site-dependent quantum yield of product formation is observed the best results are obtained within site I of bovine serum albumin. ... 

D Andrew, BT Des Islet, A Margaritis, AC Weedon. Photo-Fries rearrangement of naphthyl acetate in supercritical carbon dioxide chemical evidence for solvent-solute clustering. J Am Chem Soc 117 6132-6133, 1995. 

Nakagaki, R, Hiramatsu, M., Watanabe, T, Tanimoto, Y., and Nagakura, S., Magnetic isotope and external magnetic field effects upon the photo-Fries rearrangement of 1-naphthyl acetate, /. Phys. Chem., 89, 3222, 1985. 

Gu, W. Q., Bi, S. G., and Weiss, R. G., Photo-Fries rearrangements of 1-naphthyl esters in the glassy and melted states of poly(vinyl acetate). Comparisons with reactions in less polar polymers and low-viscosity solvents, Photochem. PhotobioL Sci., 1, 52, 2002. 

Photodecarboxylation in the presence of photocatalysts such as TiOj has also been studied. For example, the photodegradation of (4-chloro-2-methylphenoxy)acetic acid, a herbicide, in an aqueous solution of TiOj involves elimination of carbon dioxide from the initially formed radical species on the catalyst surface. The templating of carboxyHc acids with polyethylene films has been found to enhance the photodecarboxylation at the expense of the photo-Fries rearrangement in simple aryl esters such as phenyl and 1-naphthyl esters." ... 

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