New oligophosphines and (hydroxymethyl)phosphonium chlorides.
The new oligophosphines [H2P(CH2)2]2PH, [H2P(CH2)2P(H)CH2]2, and{[(H2P(CH2)2]2PCH2}2 have been made by hydrophosphination of diethyl vinylphosphonate (2) with H2P(CH2)2PH2 (1), using different ratios of 2/1, followed by LiAlH4 reduction of the phosphonate intermediates; the three phosphonate precursors were obtained as oils of varying purity (approximately 90-95%) in low (approximately 20%) to almost quantitative yield. The tri-, tetra-, and hexaphosphines were then treated with formaldehyde in the presence of hydrochloric acid to generate the corresponding water-soluble (hydroxymethyl)phosphonium chlorides {(HOCH2)3P[(CH2)2P(CH2OH)2]n(CH2)2P(CH2OH)3}Cl m (n = 1, m = 3; n = 2, m = 4) and {[(HOCH2)3P(CH2)2]2P(CH2OH)CH2}2Cl6 that were characterized by NMR spectroscopy and elemental analysis. The known (hydroxymethyl)bisphosphonium chloride [(HOCH2)3P(CH2)2]2Cl2 was similarly prepared from H2P(CH2)2PH2, and the determined crystal structure revealed strong hydrogen bonding between the chloride anions and the hydrogen atoms of the hydroxymethyl groups.
Department of Chemistry, University of British Columbia, Vancouver, British Columbia, Canada V6T 1Z1.
Dmitry
D
Moiseev
Brian R
BR
James
Brian O
BO
Patrick
Thomas Q
TQ
Hu