Poly(Tertiary Phosphines and Arsines). XIII. Some Neopentyl Poly(Tertiary Phosphines).

摘要

Reaction of (Me3CCH2)2PH with (Me3CCH2)2PCH=CH2 in boiling toluene in the presence of potassium tert-butoxide gives the crystalline neopentyl di(tertiary phosphine) (Me3CCH2)2PCH2CH2P(CH2CMe3)2. A similar base-catalyzed reaction of C6H5PH2 with (Me3CCH2)2PCH=CH2 in boiling tetrahydrofuran gives the liquid tertiary-secondary diphosphine C6H5P(H)CH2CH2P(CH2CMe3)2. Base-catalyzed reaction of 2 equiv of (Me3CCH2)2PH with Me3CCH2P(S)(CH=CH2)2 in boiling tetrahydrofuran followed by desulfurization with sodium in boiling dioxane gives the viscous liquid neopentyl tri(tertiary phosphine) Me3CCH2P(CH2CH2P(CH2CMe3)2)2. Base-catalyzed reaction of phosphine with (Me3CCH2)2P(S)CH=CH2 gives the tetraphosphine trisulfide P(CH2CH2P(S)(CH2CMe3)2)3 which undergoes desulfurization with sodium metal in boiling dioxane to give the neopentyl tripod tetra(tertiary phosphine) P(CH2CH2P(CH2CMe3)2)3. The proton, phosphorus-31, and carbon-13 NMR spectra of these new neopentyl polyphosphines as well as the related neopentylphosphorus derivatives (ME3CCH2)3P, (Me3CCH2)2P(O)H, (Me3CCH2)n-P X(3-n) (n = 1 and 2; X = H, Cl, C6H5, and CH=CH2), (Me3CCH2)3PS, and (Me3CCH2)n P(S)R(3-n) (N = 1 and 2; R = C6H5 and CH = CH2) are described. (Author)