Synthesis and properties of 2,4-dialkoxy-1,3-di-t-butylcyclodiphosph(III)-azanes

Abstract

A series of alkoxycyclodiphosph(III)azanes, XP(NBu^t)₂PY [X = Y = OMe (two isomers); X = Y = OEt (two isomers); X = Y = OCH₂CF₃(one isomer); X = Y = OBu^t(one isomer); X = Cl, Y = OMe (one isomer)] has been prepared from the reactions of CIP(NBu^t)₂PCl with alcohols in the presence of triethylamine. The product of reaction with Bu^tOH is easily converted into (Bu^tO)P(NBu^t)₂P(O)H. Analogous reactions with ethane-1,2- and propane-1,3-diols give the cage compounds [graphic omitted] (n= 2 or 3) and polymeric materials. Geometrical isomers of (MeO)P(NBu^t)₂P(OMe) showed a different degree of reactivity towards methyl iodide, elemental sulphur, or selenium. Isomeric forms of the sulphides and selenides, (MeO)P(NBu^t)₂P(X)(OMe)(X = S or Se), (MeO)(X)P(NBu^t)₂P(X)(OMe)(X = S or Se), and of methyl iodide adducts have been obtained. Aspects of the ¹H, ¹³C, and ³¹P n.m.r. and i.r. spectra of cyclodiphosph(III)azanes are discussed.