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A study on the ability of 2,5-dihydro- and 2,3,4,5-tetrahydro-1h-phosphole oxides, as well as 7-phosphanorbornene 7-oxide derivatives to undergo uv light-mediated fragmentation-related phosphinylation of methanol

✍ Scribed by Gyöurgy Keglevich; János Kovács; Helga Szelke; Tamás Köurtvéalyesi


Publisher
Journal of Heterocyclic Chemistry
Year
2006
Tongue
English
Weight
640 KB
Volume
43
Category
Article
ISSN
0022-152X

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✦ Synopsis


Abstract

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Reactivity of the title P‐heterocycles (1‐14) in the photoinduced fragmentation‐related phosphinylation of methanol was found to be influenced by the extent of ring strain and the UV absorption at 254 nm. The 7‐phosphanorbornene oxides (7‐14) are universal precursors due to their ring strain, no matter if they are UV‐active or not at 254 nm. The easily available 2,5‐dihydro‐1__H__‐phosphole oxides can be applied only in case of 1‐phenyl substitution that enhances the absorption at 254 nm. The ring strain of representative P‐heterocycles (5‐8) was evaluated by HF/6‐31G* and B3LYP/6‐31+G* calculations. UV spectra of compounds 5‐8 were interpreted by ZINDO/S and MNDO‐d calculations. The new precursors (11‐14) made possible the extension of the phosphinylations.