Cyclisation of bis(dichlorophosphino)-, bis(dichlorophosphinoyl)-, and bis(dichlorophosphinothioyl)-amines by primary amines
- 1 January 1974
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 18,p. 2010-2014
- https://doi.org/10.1039/dt9740002010
Abstract
The compounds [Cl2P(X)]2NR (IIIa, X = lone pair, R = Me, Et, or But; IIIb, X = O, R = Me or Et; IIIc, X = S, R = Me) react with 3 mol equiv. of t-butylamine to give cyclodiphosphazanes Cl(X)[graphic omitted]But, (V). Preparation of the long-sought cyclophosph(III)azanes (ClPNR)n(R = Me or Et) from (IIIa) has also been attempted by the same route, and new n.m.r. and mass-spectroscopic evidence has been obtained for formation of these derivatives (n= 3 and 4, R = Me; n= 2 and 3, R = Et), but no pure products have been isolated. Only when X = O and R = Me or Et could evidence for the formation of derivatives Cl2P(X)·NR·P(X)Cl·N(H)But, (II), be obtained, and possible reasons for the rapid cyclisation step involved are discussed. The known derivative Cl2P(O)·NMe·P(O)Cl·N(H)Me, (IIb), was readily cyclised by t-butylamine to give [ClP(O)·NMe]2, (Ib). Phosphoryl chloride reacts with 3 mol equiv. of primary amines to give mixtures of the derivatives Cl2P(O)·N(H)R (R = Me, Et, Pri, or But) and ClP(O)[N(H)R]2(R = Me, Et, or Pri), rather than cyclodiphosphazanes as obtained in analogous reactions with phosphorus trichloride.Keywords
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