SYNTHESIS OF N-ACYLOXY-1-(DIMETHOXYPHOSPHORYLOXY)BENZIMIDATES FROM N-ACYLOXY-N-CHLOROBENZAMIDES

Authors

  • Vasiliy G. Shtamburg Ukrainian State University of Science and Technologies, Scientific and Educational Institute “Ukrainian State Chemical and Technological University" , Ukraine https://orcid.org/0000-0001-9491-9429
  • Evgeniy A. Klots Ukrainian State University of Science and Technologies, Scientific and Educational Institute “Ukrainian State Chemical and Technological University" , Ukraine
  • Victor V. Shtamburg Ukrainian State University of Science and Technologies, Scientific and Educational Institute “Ukrainian State Chemical and Technological University" , Ukraine https://orcid.org/0000-0001-7734-0896
  • Andrey A. Anishchenko Oles Honchar Dnipro National University, Ukraine https://orcid.org/0000-0001-5437-9499
  • Svitlana V. Shishkina SSI Institute for Single Crystals, National Academy of Sciences of Ukraine, Institute of Organic Chemistry of National Academy of Sciences of Ukraine, Ukraine https://orcid.org/0000-0002-9986-9261
  • Alexander V. Mazepa A.V. Bogatsky Physico-Chemical Institute of National Academy of Sciences of Ukraine, Ukraine https://orcid.org/0000-0002-9628-7514
  • Svetlana V. Kravchenko Dnipro State Agrarian and Economic University, Ukraine https://orcid.org/0000-0003-2479-3562

DOI:

https://doi.org/10.15421/jchemtech.v33i2.323425

Keywords:

N-acyloxy-N-chlorobenzamides, trimethyl phosphite, N-acyloxy-1-(dimethoxyphosphoryloxy)benzimidates, synthesis, structure, XRD study, intramolecular N–O-migration of dimethoxyphosphoryl group

Abstract

Aim. The objective of this research was to investigate the potential interaction between N-acyloxy-N-chlorobenzamides and trialkyl phosphites, along with the characterization of the resulting products' structures. Methods. Employing techniques such as 1H, 31P and 13C NMR spectroscopy, mass spectrometry, and single crystal X-ray diffraction, we have proved that the reaction of N-acyloxy-N-chlorobenzamides with trimethyl phosphite in diethyl ether produces N-acyloxy-1-(dimethoxyphosphoryloxy)benzimidates. Our research demonstrates that the reaction between N-acyloxy-N-chlorobenzamides and trialkyl phosphites offers a novel approach to synthesize Z-N-acyloxy-1-(dialkoxyphosphoryloxy)benzimidates. This discovery unveils a significant chemical transformation of N-acyloxy-N-chlorobenzamides. The structure of N-acyloxy-1-(dimethoxyphosphoryloxy)benzimidates has been confirmed by 1H, 31P and 13C NMR spectroscopy, mass spectrometry, and XRD study. The study of the N-(4-nitrobenzoyloxy)-1-(dimethoxyphosphoryloxy)benzimidate structure has revealed that the N-(4-nitrobenzoyloxy)-1-(dimethoxyphosphoryloxy)benzimidate is the Z-isomer, with the dimethoxyphosphoryloxy moiety and the N-4-nitrobenzoyloxy group being cis-oriented to the N=C double bond. The ether moiety and the N=C double bond are coplanar, while the dimethoxyphosphoryl substituent is orthogonal to the plane of the N=C double bond. The interaction of N-acyloxy-N-chlorobenzamides with trimethyl phosphite has led to a new synthesis of Z-N-acyloxy-1-(dialkoxyphosphoryloxy)benzimidates. The new chemical properties of N-acyloxy-N-chlorobenzamides have been established. The X-ray study of Z-N-4-nitrobenzoyoxy-1-benzimidate has demonstrated the peculiarities of its structure. Notably, an intriguing phenomenon of nitrogen-to-oxygen migration of the dimethoxyphosphoryl group has been observed.

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Published

2025-07-15

Issue

Vol. 33 No. 2 (2025): Journal of Chemistry and Technologies

Section

Organic Chemistry

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