Photorearrangement of allyl diphenyl phosphate via possible type-II reaction and phosphoranyl 1,3-biradicals
✍ Scribed by David R. Anderson; Claudia N. Eley
- Book ID
- 104229474
- Publisher
- Elsevier Science
- Year
- 1989
- Tongue
- French
- Weight
- 147 KB
- Volume
- 30
- Category
- Article
- ISSN
- 0040-4039
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✦ Synopsis
A Norrish type-11 reaction is proposed for the photorearrangement of ally1 diphenyl phosphate to o&o-allylphenyl phenyl phosphate. In contrast to the type-II mechanism in carbonyl compounds, the reaction is postulated to proceed through a fivemembered transition state to produce a phosphoranyl 1,3-biradical which subsequently rearranges to the observed product.
We report here the first proposed Norrish type-11 hydrogen atom abstraction in the photolysis of phosphate esters. Irradiation' of ally1 diphenyl phosphate (1) in deoxygenated methanol solution at 254 nm produces the rearranged product 5 as the major product.