Rearrangement and degradation of alpha-heterofunctional substituted phosphonium salts

cf. CA 55, 23400c; Hellmann and Bader, CA 56, 11615h. Treatment of phosphonium salts of the type (Ph3PCH2X)OH(I, X = SMe; II, X = Cl; III, X = Br) with N aq. NaOH gave Ph3PO and MeX. With II and III a Ph group migrated to give Ph2(PhCH2)PO (17% from II, 33% from III). BuLi or PhLi also initiated this rearrangement in nonaq. solvents. The reaction is formulated II + RLi -> Ph3P:CHCl (IV); IV + RLi -> Ph3PRCHCl (V); V -> Ph2PR:CHPh (R = Bu, Ph, or OH). [on SciFinder (R)]

Published in:
Angewandte Chemie, International Edition, 1, 266
CAN 57:62878 33 Organometallic and Organometalloidal Compounds Univ. Heidelberg,Germany. Journal language unavailable. 603-35-0 (Phosphine, triphenyl-) (nitrogen derivs.); 2959-74-2 (Phosphine oxide, benzyldiphenyl-); 16721-45-2 (Phosphorane, benzylidenetriphenyl-); 98424-42-1 (Phosphorane, benzylidenebutyldiphenyl-); 98863-29-7 (Phosphonium, benzylidenediphenyl-, hydroxide) (prepn. of); 98863-34-4 (Phosphonium, (bromomethyl)triphenyl-, hydroxide); 99100-84-2 (Phosphonium, (chloromethyl)triphenyl-, hydroxide); 100301-40-4 (Phosphonium, [(methylthio)methyl]triphenyl-, hydroxide) (reaction with NaOH); 109-72-8 (Lithium, butyl-); 591-51-5 (Lithium, phenyl-) (reaction with phosphonium compds.); 1310-73-2 (Sodium hydroxide) (reaction with phosphonium compounds); 107420-42-8 (Phosphonium, [2,3-quinoxalinediylbis(p-phenylenemethylene)]bis[triphenyl-, bromide) (rearrangement of)

 Record created 2006-03-03, last modified 2018-01-27

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