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Unexpected Z/E isomerism of N-methyl-O-phosphothioyl benzohydroxamic acids, their oxyphilic reactivity and inertness to amines
Abstract
Thiophosphinoylation of N-methyl p-substituted benzohydroxamic acids using disulfanes (method A) or diphenylphosphinothioyl chloride (method B) provides only one conformer of the respective O-phosphothioyl derivative (Xray and NMR analysis). Undergoing the P-transamidoxylation reaction is an evidence of the reversibility of thiophosphinoylation. Only those products containing strong EWG substituents in the aroyl residue or bulky substituents at the phosphorus atom possess E conformation. DFT calculations confirmed the energetic domination of each isomer. The Z-isomers are distorted amides having both high degree of nitrogen pyramidalization (38–55°) and amide twist (12–30°). In solution they exist in a defined conformation that is evidenced by the presence of a sharp signal of N-methyl protons at low temperature. They do not isomerize in solutions. Some of them slowly undergo the N-O bond scission above 100 °C. Both isomers are not as sensitive to neutral hydrolysis as twisted amides can be and are inert toward amines. The rate of alkaline hydrolysis can be correlated with pKa of hydroxamic acid. Because of their outstanding oxyphilicity, these compounds can be defined as nerve agent surrogates and safer alternatives of phosphorus fluorides for serine-active enzyme inhibition studies
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- Accepted or Published Version
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- Copyright (2021 Springer Science Business Media, LLC part of Springer Nature)
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- Category:
- Articles
- Type:
- artykuły w czasopismach
- Published in:
-
STRUCTURAL CHEMISTRY
no. 32,
pages 1077 - 1091,
ISSN: 1040-0400 - Language:
- English
- Publication year:
- 2021
- Bibliographic description:
- Majewski A., Chojnacki J., Przychodzeń W.: Unexpected Z/E isomerism of N-methyl-O-phosphothioyl benzohydroxamic acids, their oxyphilic reactivity and inertness to amines// STRUCTURAL CHEMISTRY -Vol. 32, (2021), s.1077-1091
- DOI:
- Digital Object Identifier (open in new tab) 10.1007/s11224-020-01719-1
- Sources of funding:
-
- Grant Ministerstwa Nauki i Informatyzacji No. 1T09A07830.
- Verified by:
- Gdańsk University of Technology
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