Lineare Oligophosphaalkane, XXV. Synthese von Ph₂PCH₂PH₂ und (ph₂PCH₂)₂PH durch Phosphinomethylierung von PH₃ unter Phasentransferkatalyse

Abstract

Linear Oligophosphaalkanes, XXV 1 . – Synthesis of Ph 2 PCH 2 PH 2 and (Ph 2 PCH 2 ) 2 PH by Phosphinomethylation of PH3 with Phase‐Transfer Catalysis Alkylation of Ph 2 PH with CH 2 Cl 2 under phase‐transfer conditions in the system dichloromethane/toluene/water affords Ph 2 P‐CH 2 Cl in high yields. Depending on the reaction conditions employed Ph 2 P‐CH 2 Cl reacts with PH 3 in the two phase system under phase‐transfer catalysis ( n Bu 4 NCl) to yield the tertiary‐primary methylenebis(phosphane) Ph 2 P‐CH 2 ‐Ph 2 ( 2 ) or the PH functional triphosphaalkane Ph 2 P‐CH 2 ‐PH‐CH 2 ‐PPh 2 ( 3 ), respectively. Metallation of 2 and 3 with RLi (R = n Bu, t Bu) and subsequent reaction with Me 3 siCl yields the silyl derivatives 2e and 3b , respectively. The analysis of the 1 H‐ 13 C‐ and 31 P‐NMR spectra is reported.