Reactions of Alkyl Diphenylphosphinates and Related Thio Esters with Some Nucleophiles. SN2 (S) Reaction and Wittig Type Rearrangement
- 1 January 1978
- journal article
- Published by Oxford University Press (OUP) in Bulletin of the Chemical Society of Japan
- Vol. 51 (1) , 260-264
- https://doi.org/10.1246/bcsj.51.260
Abstract
Reactions of alkyl diphenylphosphinates Ph2P(=X)YCHR1R2 (X, Y=O,S) with organolithiums and Grignard reagents afforded different types of products depending on the combination of X and Y. When Y=O, the reagents (R3M) mainly attacked the phosphorus atom to give Ph2P(=X)R3 and R1R2XCHO− irrespective of X, while, when X=Y=S, the reaction occurred exclusively at the ester sulfur atom, SN2(S), to give R3SCHR1R2 and [Ph2PS]−. When the X=O and Y=S, a Wittig type rearrangement of a carbanion [Ph2P(=O)SCR1R2]− was observed along with attacks on the phosphorus (major) and the sulfur (minor) atoms. Reactions with some other nucleophiles (hydride, amide and alkoxide ions) are also described.This publication has 14 references indexed in Scilit:
- Metal Phosphinylides and Phosphinothioylides. VII. The Structure of [Ph2PX]M (X=O, S) in Solution and Their DisproportionationBulletin of the Chemical Society of Japan, 1977
- Chemistry of Nitrosoimines. XIII. Reactions of 3-Substituted 2-Nitrosoimino-2,3-dihydrobenzothiazoles with OrganolithiumsBulletin of the Chemical Society of Japan, 1975
- Thiophile Addition von Phenyllithium an ThioketeneEuropean Journal of Inorganic Chemistry, 1974
- Thiophilic additions of organometallics to thiobenzophenones and of phenyllithium to phenyl dithiobenzoate and phenyl trithiocarbonateJournal of the American Chemical Society, 1972
- Synthesis and absolute configuration of optically active phosphine oxides and phosphinatesJournal of the American Chemical Society, 1968
- Nucleophilic displacement reactions on organophosphorus esters by Grignard reagents. III. The reaction of alkyl diphenylphosphinates with alkyl GrignardsThe Journal of Organic Chemistry, 1967
- Nucleophilic displacement reaction on organophosphorus esters by Grignard reagents. II. Evidence for competitive displacement on carbon and phosphorus in the reaction of Grignard reagents with simple phosphatesThe Journal of Organic Chemistry, 1967
- The Formation of Linear Polymers from Diene Monomers by a Cyclic Polymerization Mechanism. V. Phosphorus-containing Dienes1Journal of the American Chemical Society, 1960
- Aromatic Phosphinic Acids and Derivatives. II. Direct Esterification of Diphenylphosphinodithioic Acid1Journal of the American Chemical Society, 1956
- Aromatic Phosphinic Acids and Derivatives. I. Diphenylphosphinodithoic Acid and Its DerivativesJournal of the American Chemical Society, 1955