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Photo-Arbuzov Rearrangements of Dimethyl Benzyl and Dimethyl p-Acetylbenzyl Phosphite
- Source :
- Journal of the American Chemical Society. 121:2085-2096
- Publication Year :
- 1999
- Publisher :
- American Chemical Society (ACS), 1999.
-
Abstract
- The direct ultraviolet irradiation of dimethyl benzyl phosphite (1) and dimethyl p-acetylbenzyl phosphite (8) was investigated in acetonitrile, cyclohexane, and benzene. Phosphite 1 gives predominantly the photo-Arbuzov product, dimethyl benzylphosphonate (2), in 67−81% accountability yields, based of phosphite consumed, along with minor amounts of bibenzyl (20) and dimethyl phosphite (10). The quantum yield for formation of 2 in cyclohexane, φP, is 0.43. By contrast, irradiation of phosphite 8 yields only 7−13% of photo-Arbuzov phosphonate (9) but relatively large amounts of radical diffusion products: dimethyl phosphite (10) the p-acetylbenzyl radical dimer (11); and p-acetyltoluene (12). Evidently 8, closely related to acetophenone, reacts predominantly via the triplet excited estate to generate long-lived, triplet, free-radical pairs (6 and 7a). In benzene, further products (15, 16, 17a and 17b) are identified that result from addition of the phosphinoyl radical (6) to benzene to give cyclohexadienyl...
Details
- ISSN :
- 15205126 and 00027863
- Volume :
- 121
- Database :
- OpenAIRE
- Journal :
- Journal of the American Chemical Society
- Accession number :
- edsair.doi...........e11061928023a96ec3dd78612ccbf77b