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DOI: 10.1039/A900623K (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 1, 1999, 1347-1352

Intramolecular nucleophilic displacement of halogen by phosphinate and thiophosphinate anions: relative rates of formation of five- and six-membered rings[hair space]1

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Amirah Chaudhry, Martin J. P. Harger, Philippa Shuff and Alison Thompson

Abstract

Intramolecular nucleophilic substitution transforms the phosphinate anions XCH2CH2(CH2)nCH2(Ph)P(O)O– (n = 0, 1; X = Br, Cl) (Et3NH+ salts; CH2Cl2 solution) into cyclic phosphinate esters 14 (n = 0, 1); unusually the five-membered ring product (n = 0) is formed only 4.3 (X = Br) or 5.7 (X = Cl) times faster than the six (n = 1). The analogous cyclisation of the thiophosphinate anions ClCH2CH2(CH2)nCH2(Ph)P(S)O– (n = 0, 1) gives the products 16 (n = 0, 1) with the sulfur atom in the ring; the five-membered ring is now formed 30 times faster than the six, still a rather modest rate advantage.

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