The species [Ph2PO]M in THF were found to exist as Ph2P–O–M by 31P-NMR, and [Ph2PS]MgCl as Ph2P–S–MgCl by Raman spectrum. The species [Ph2PS]M undergo easy disproportionation by heating.
Lithium diphenylphosphinylide or diphenylphosphinothioylide ([Ph2PX]Li; X=O, S), prepared from diphenylphosphine oxide or sulfide and n-butyllithium, reacted with methyl iodide, acetaldehyde and benzaldehyde to give the corresponding phosphine oxides or sulfides in good yields, indicating the formation of C–P bond. Formation of [Ph2PS]MgCl from diphenylphosphinothioyl chloride (1) and magnesium was confirmed by the similar reactions. When 1 was allowed to react with magnesium or sodium for a long time, diphenylphosphides ([Ph2P]M) were produced by desulfurization, together with [Ph2PS]M (M=MgCl, Na). Reaction of 1 with [Ph2PS]M gave tetraphenyldiphosphine disulfide through formation of P-P bond, while diphenylphosphinyl chloride and [Ph2PO]M reacted through formation of P–O bond. The difference has been explained by soft-hard-acid-base concept.
Reactions of [Ph2PO]M with benzaldehyde gave benzyl benzoate and benzyldiphenylphosphine oxide (3) in the case of M=Na, 3, α-hydroxybenzyldiphenylphosphine oxide, benzyl alcohol, benzoin and benzil in the case of M=MgCl, and 3 in the case of M=ZnCl. Reactions of [Ph2PX]M with p-benzoquinone gave 2,5-dihydroxyphenyldiphenylphosphine oxide or sulfide and p-hydroxyphenyl diphenylphosphinate in the cases X=O, S and M=Li, MgCl, Al, and 1,4-phenylene bis(diphenylphosphinate) or bis(diphenylphosphinothioate) in the cases X=O, S and M=FeCl. The reaction mechanisms have been discussed.
Reaction of acetone with [Ph2PO]Li gave 1-hydroxy-1-methylethyl- (2a), 1,1-dimethyl-3-oxobutyldiphenylphosphine oxides (3a) and 2,6-bis(diphenylphosphinyl)-2,6-dimethylheptan-4-one (4a). The corresponding sulfide 2b was obtained in the case of Ph2P(S)H, and 3b and 4b in the case of [Ph2PS]Li (5b). Bromoacetone reacted with 5b through substitution reaction.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.