G. N. Nikonov

Synthesis of New Phosphines and P-Heterocycles from Phosphonates Containing Allyl Group

Addition of phenylphosphine to allylphosphonate followed by reduction of the resulting diphosphonate gives a new branched phosphine, bis(3-phosphinopropyl)phenylphosphine. Its reaction with paraform and p-toluidine yields oligomeric 3-[3-(propylenophenylphosphino)propyl]-1,5-di-p-tolyl-1,5,3,7-diazadiphosphacyclooctane. Diethyl (5-allyl-2-ethoxybenzyl)phosphonate was obtained. Its reduction gives unsaturated (5-allyl-2-ethoxybenzyl)phosphine. This product adds two moles of formaldehyde to give bis(hydroxymethyl)(5-allyl-2-ethoxybenzyl)phosphine. The reaction of this compound with p-toluidine yielded, depending on the conditions, the corresponding bis(aminomethyl)phosphine, 1,3,5-diazaphosphorinane, and 1,5,3,7-diazadiphosphacyclooctane, and also their derivatives containing allyl substituents.

Reactions of p-Hydroxyphenylphosphine and Functionally Substituted Bis(hydroxymethyl)phosphines with Heterocumulenes

Reactions of p-hydroxyphenylphosphine, bis(hydroxymethyl)(p-hydroxyphenyl)phosphine, and bis(hydroxymethyl)(5-allyl-2-ethoxybenzyl)phosphine with nitrogen-containing heterocumulenes were studied. The competitive reactivity of the phenol, phosphine, and hydroxymethyl groups in these reactions was examined.

Synthesis of Aminomethylphosphines with Triazaadamantane Fragments

The reaction of (hydroxymethyl)diphenylphosphine with 7-amino-1,3,5-triazaadamantane, followed by ready oxidation of the initially formed aminomethylphosphine gave diphenyl[(1,3,5-triazaadamantan-7-yl)aminomethyl]phosphine oxide. The reactions of bis(hydroxymethyl)phenylphosphine with 2 mol of 7-amino-1,3,5-triazaadamantane in the absence and in the presence of Paraform provided bis[(1,3,5-triazaadamantan-7-yl)aminomethyl]phenylphosphine and 1,3-bis(1,3,5-triazaadamantan-7-yl)-5-phenyl-1,3,5-diazaphosphorinane, respectively.