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2,3-dimethoxyperhydro-1,4,2,3-dioxadiazine: Synthesis, conformation, and conversion to 1-(2-hydroxyethoxy)-2-methoxydiazene-1-oxide. Crystal structure of 1-[2-(para-nitrobenzoyloxy)-ethoxy]-2-methoxydiazene-1-oxide

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Abstract

The oxidation of 1,2-bis(methoxyaminooxy)ethane (3) with PbO2 afforded 2,3-dimethoxyperhydro-1,4,2,3-dioxadiazine (4) in the form of the 55:45 mixture of thetrans-4ee- andcis-4 isomers. The barrier of the ring conversion (ΔG238 =11.3 kcal/mole) of thecis-4 isomer was determined by the method of13C NMR. The regio- and stereospecific stereoelectronically controlled reaction of (4) withpara-nitrobenzoic acid gives the equimolar mixture of methylpara-nitrobenzoate and the 1,2-dialkoxydiazene oxide (5), the structure of which, and the (E)-configuration, were shown by the x-ray structural data of its acylation product — the diazene oxide (6).

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Additional information

N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, 117977 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2624–2632, November, 1992.

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Rudchenko, V.F., Ignatov, S.M., Chervin, I.I. et al. 2,3-dimethoxyperhydro-1,4,2,3-dioxadiazine: Synthesis, conformation, and conversion to 1-(2-hydroxyethoxy)-2-methoxydiazene-1-oxide. Crystal structure of 1-[2-(para-nitrobenzoyloxy)-ethoxy]-2-methoxydiazene-1-oxide. Russ Chem Bull 41, 2074–2081 (1992). https://doi.org/10.1007/BF00863376

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Keywords

  • dialkoxyaminyl biradicals
  • 2,3-dimethoxyperhydro-1,4,2,3-dioxadiazine
  • dialkoxydiazene oxides
  • conformation
  • inversion
  • x-ray structure analysis
  • stereoelectronic control