O-N-Cl GEMINAL SYSTEMS. STRUCTURE OF N-CHLORO-N-METHOXY-4-TOLUENESULFONAMIDE AND N-METHOXY-4-TOLUENESULFONAMIDE

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 Institute of Organic Chemistry of National Academy of Sciences of Ukraine, State Scientific Institution "Institute of Single Crystals" of the NAS 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.v34i2.346200

Keywords:

N-chloro-N-methoxy-4-toluenesulfonamide, a single crystal X-ray diffraction study, anomeric amides.

Abstract

Aim.  Structural analysis of chemical compounds plays a crucial role in understan

Aim.Structural analysis of chemical compounds plays a crucial role in understanding their properties and chemical behavior. In this study, the aim is to investigate the structure of N-chloro-N-methoxy-4-toluenesulfonamide and to compare it with N-methoxy-4-toluenesulfonamide structure. Methods. 1H, and 13C NMR spectroscopy, mass spectrometry, a single crystal X-ray diffraction study. Results. It was found that in the molecule of N-chloro-N-methoxy-4-toluenesulfonamide the amide nitrogen atom has a strongly pyramidal configuration. The sum of the bond angles centered on thisnitrogen atom is 324.1°. In N-methoxy-4-toluenesulfonamide the degree of pyramidality  of the nitrogen atom is significantly lower, the sum of the bond angles centered on thisnitrogen atom is 331.0°.   Structural analysis shows two notable features in N-chloro-N-methoxy-4-toluenesulfonamide. First, the N–Cl bond is elongated to 1.767(3) Å, exceeding the corresponding bond lengths in N-chloro-N-methoxyurea and N-chloro-N-methoxy-4-nitrobenzamide. Second, the N(1)–O(3) Me bond is shortened to 1.405(3) Å, relative to the values observed in N-methoxy-4-toluenesulfonamide and in dimethyl N-methoxy-N-(4-toluenesulfonyl)phosphoramidate. The most plausible explanation is that this bonds deformation may be caused by the action of the nO(Me)→ϭ•N-Clanomeric effect. Conclusions. N-Chloro-N-methoxy-4-toluenesulfonamide, together with related N-alkoxy-N-chloro-R-sulfonamides, represents a distinct class of anomeric amides characterized by weakening of the N–Cl bond through an nO(Alk)→ϭ•N-Clanomeric interaction. Thus, this work is important because it establishes a new concept in the chemistry of N-alkoxy-N-chloro-R-sulfonamides.

behavior. In this study, the aim is to investigate the structure of N-chloro-N-methoxy-4-toluenesulfonamide and to compare it with N-methoxy-4-toluenesulfonamide structure.  Methods. 1H, and 13C NMR spectroscopy, mass spectrometry, a single crystal X-ray diffraction study. Results.  It was found that in the molecule of N-chloro-N-methoxy-4-toluenesulfonamide the amide nitrogen atom has a strongly pyramidal configuration. The sum of the bond angles centered on this nitrogen atom is 324.1°. In N-methoxy-4-toluenesulfonamide the degree of pyramidality  of the nitrogen atom is significantly lower, the sum of the bond angles centered on this nitrogen atom is 331.0°.   Structural analysis shows two notable features in N-chloro-N-methoxy-4-toluenesulfonamide. First, the N–Cl bond is elongated to 1.767(3) Å, exceeding the corresponding bond lengths in N-chloro-N-methoxyurea and N-chloro-N-methoxy-4-nitrobenzamide. Second, the N(1)–O(3)Me bond is shortened to 1.405(3) Å, relative to the values observed in N-methoxy-4-toluenesulfonamide and in dimethyl N-methoxy-N-(4-toluenesulfonyl)phosphoramidate. The most plausible explanation is that this bonds deformation may be caused by the action of the nO(Me)→ϭ•N-Cl anomeric effect.  Conclusions. N-Chloro-N-methoxy-4-toluenesulfonamide, together with related N-alkoxy-N-chloro-R-sulfonamides, represents a distinct class of anomeric amides characterized by weakening of the N–Cl bond through an nO(Alk)→ϭ•N-Cl anomeric interaction. Thus, this work is important because it establishes a new concept in the chemistry of N-alkoxy-N-chloro-R-sulfonamides.

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Published

2026-06-19

Issue

Vol. 34 No. 2 (2026): Journal of Chemistry and Technologies

Section

Organic Chemistry

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