Phosphorylinitrile oxides. 7. Quantum chemical study of the dimerization of nitrile oxides

Abstract

A semiempirical MNDO calculation was carried out for the singlet potential energy surface for the dimerization of acetonitrile oxide leading to dimethylfuroxane. The dimerization of nitrile oxides proceeds by a two-step mechanism. The rate-limiting step is formation of a dinitrosoethylene intermediate. A semiempirical AMI calculation was carried out to study the effect of phosphoryl substituents on formation of the transition state of the rate-limiting step in the dimerization of dimethoxyphosphorylnitrile oxide. Independently of the initial orientation of the two phosphorylnitrile oxide molecules, a gauche-oriented dimeric species is formed in the first step in the dimerization. There is hardly any specific effect ofthe phosphoryl substituents in the first step of phosphorylnitrile oxide dimerization.

How to Cite
Kurdyukov, A. I.; Pavlov, V. A.; Gorin, B. I. Chem. Heterocycl. Compd. 1994, 30, 1101. [Khim. Geterotsikl. Soedin. 1994, 1269.]

For this article in the English edition, see DOI https://doi.org/10.1007/BF01171174