Photochemical fragmentation of the 2‐phosphabicyclo[2.2.2]octa‐5,7‐diene ring system as a versatile method for generating 3‐coordinate methylene phosphine oxides and sulfides

Louis D. Quin, Jian‐Sheng ‐S Tang, Gyöngyi S. Quin, György Keglevich

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37 Citations (Scopus)

Abstract

1,6‐Dihydrophosphinine 1‐oxides with 4‐chloro‐3(or 5)‐methyl substituents give cycloadducts with dimethyl acetylenedicarboxylate having the 2‐phosphabicyclo[2.2.2]octa‐5,7‐diene ring system that can be fragmented easily on irradiation with ultraviolet light (254 nm). The phosphorus‐containing bridge is released as a derivative of the 3‐coordinate methylene phosphine oxide species, RP(O)CH2. This species is too reactive to observe but is readily trapped by an addition reaction with alcohols to give phosphinates (R = alkyl or aryl) or phosphonates (R = O‐alkyl). These experiments constitute the first demonstration of the existence of ROP(O)CH2. Phosphoryl oxygen in the cycloadducts has been replaced by sulfur, and these sulfides fragment smoothly on irradiation. The 3‐coordinate species PhP(S)CH2 has been generated by other workers, but the species ROP(S)CH2 was generated here for the first time. The power of the bicyclic fragmentation route for the generation of a variety of 3‐coordinate P‐methylene derivatives is made evident by this study.

Original languageEnglish
Pages (from-to)189-196
Number of pages8
JournalHeteroatom Chemistry
Volume4
Issue number2-3
DOIs
Publication statusPublished - 1993

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phosphine
Sulfides
Oxides
Irradiation
Derivatives
Organophosphonates
Addition reactions
Sulfur
Demonstrations
Alcohols
Oxygen
Experiments
ROP

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  • Chemistry(all)

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Photochemical fragmentation of the 2‐phosphabicyclo[2.2.2]octa‐5,7‐diene ring system as a versatile method for generating 3‐coordinate methylene phosphine oxides and sulfides. / Quin, Louis D.; Tang, Jian‐Sheng ‐S; Quin, Gyöngyi S.; Keglevich, György.

In: Heteroatom Chemistry, Vol. 4, No. 2-3, 1993, p. 189-196.

Research output: Contribution to journalArticle

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