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Ring-Chain Tautomerism of the Condensation Products of 2-Mercaptobenzohydrazide with Aliphatic and Aromatic Aldehydes: Influence of Electronic and Steric Factors

DOI: 10.4236/oalib.1103584, PP. 1-10

Subject Areas: Organic Chemistry

Keywords: Hammett and Taft Equations, Ring-Chain Tautomerism 2-Mercaptobenzoylhydrazones, Benzo-1,3,4-Thiadiazepines

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Abstract

It has been shown by 1H and 13C NMR spectroscopy that 2-mercaptobenzoyl-hydrazones of aliphatic and aromatic aldehydes exist in solution as tautomeric mixtures of linear and cyclic benzo-1,3,4-thiadiazepine forms. The linear hydrazone form is represented by (E,E')-and (E,Z')-conformational isomers, differing in the disposition relative to the amide C–N bond. Growing bulk of the alkyl substituent at the C=N bond of the aliphatic aldehydes derivatives decreases the fraction of the cyclic tautomer; therewith the logarithms of the constants of the chain-ring tautomeric equilibrium correlate with the ES steric constants of the alkyl substituents. In the series of the aromatic aldehydes 2-mercaptobenzoylhydrazones the linear tautomer prevails, and the logarithms of the tautomeric equilibrium constants KT correlate with the σ-constants of the substituents in the aromatic nucleus.

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Ershov, A. Y. , Lagoda, I. V. , Vasileva, M. Y. , Yakimovich, S. I. , Chernitsa, B. V. , Kuleshova, L. Y. , Pavlova, L. V. and Yakimansky, A. V. (2017). Ring-Chain Tautomerism of the Condensation Products of 2-Mercaptobenzohydrazide with Aliphatic and Aromatic Aldehydes: Influence of Electronic and Steric Factors. Open Access Library Journal, 4, e3584. doi: http://dx.doi.org/10.4236/oalib.1103584.

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