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.     

Transformation of white phosphorus in the coordination sphere of nickel complexes with σ-donating ligands

Oxidation of white phosphorus in the coordination sphere of the nickel(ii) complex with 1,1,1-tris(diphenylphosphinomethyl)ethane and 1,1",5,5"-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) was shown to be possible and accompanied by the transformation of P₄ into the -P₃ ligand. The change in the nickel state was monitored by cyclic voltammetry, ³¹P NMR spectroscopy, ESR, and IR spectroscopy.     

Dioxaborinanes with an exocyclic phosphino group

The reaction of diphenylphosphine with o-hydroxy aromatic aldehydes and a diphenylboric acid ester in the presence of tertiary amines gave ammonium 5,6-benzo-and 5,6-naphtho-4-diphenylphosphoryl-2,2-diphenyl-1, 3-dioxa-2-boratacyclohexanes. The borylation of (,2-dihydroxybenzyl)diphenylphosphine, generated in situ, with isobutyl phenylborate gave 5,6-benzo-4-diphenylphosphino-2-phenyl-1,3-dioxa-2-boracyclohexane, which, in contrast to 1,3,2,5-dioxa-boraphosphorinanes, has a high reactivity with respect to electrophilic and nucleophilic reagents and adds oxygen, sulfur, selenium, and pyridine to give the corresponding derivatives.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 196–200, January, 1992.     

Synthesis of novel paracyclophanes with linear P,N-containing spacers

Condensation of bis(hydroxymethyl)mesityl-and bis(hydroxymethyl)phenylphosphines with N,N′-disubstituted bis(4-aminophenyl)methanes and bis(4-amino-3-carboxyphenyl)methane occurred as covalent self-assembly spontaneously giving a mixture of trans-and cis-diastereomers of 1,5,19,23-tetra-R′-3,21-di-R-1,5,19,23-tetraaza-3,21-diphospha[5.1.5.1]paracyclophanes as the major products. The trans-isomer (R is mesityl; R′ is methyl) was isolated in the individual state and structurally characterized by X-ray diffraction analysis. Sulfurization of macrocyclic diphosphines (R = Ph; R′ is 3-pyridylmethyl or 4-pyridylmethyl) gave the corresponding diphosphine disulfides, the trans-stereoisomer being isolated in the individual state. Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1765–1774, September, 2007.     

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.