Abstract
The stereochemical peculiarities of N-substituted perhydro-1,3,2-dioxazines were analyzed thoroughly on the basis of NMR spectroscopic data, the results of x-ray diffraction analysis, and quantitative MO theory. It is shown that in solutions and in the crystalline state these compounds exist in a “chair” conformation with an equatorial orientation of the substituents in the 2 and 4 positions; the high degree of crimped character of the heteroring (the angle of inflection along the 0...0 line is 70.3°) is due to repulsion of the unshared electron pairs of the N and 0 atoms and n-σ interactions. An increase in the n-σ interaction in dialkoxy amines and acetals on passing from Cs to C2 symmetry of the molecules was demonstrated.
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See [1] for communication 38. Communication 39 is also communication 25 of the series “Geminal systems.” See [2] for communication 24.
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1341–1347, October, 1985.
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Zolotoi, A.B., D'yachenko, O.A., Chervin, I.I. et al. Asymmetric unbridged nitrogen. 39. Configuration and conformations of N-substituted perhydro-1, 3,2-dioxazines. Chem Heterocycl Compd 21, 1098–1104 (1985). https://doi.org/10.1007/BF00515246
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DOI: https://doi.org/10.1007/BF00515246