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Oximes in the Isoxazolone, Pyrazolone, and 1,2,3-Triazolone Series: Experimental and Computational Investigation of Energies and Structures of E/Z Isomers of α-Oxo-Oximes in the Gas Phase and in Solution

Rainer Koch A D , Hans-Joachim Wollweber B and Curt Wentrup B C D
+ Author Affiliations
- Author Affiliations

A Institut für Chemie and Center of Interface Science, Carl von Ossietzky Universität Oldenburg, PO Box 2503, 26111 Oldenburg, Germany.

B Fachbereich Chemie der Philipps-Universität Marburg, 35037 Marburg, Germany.

C School of Chemistry and Molecular Biosciences, The University of Queensland, Brisbane, Qld 4072, Australia.

D Corresponding authors. Email: rainer.koch@uni-oldenburg.de; wentrup@uq.edu.au

Australian Journal of Chemistry 68(9) 1329-1335 https://doi.org/10.1071/CH15095
Submitted: 26 February 2015  Accepted: 2 April 2015   Published: 29 April 2015

Abstract

The structures of a series of heterocyclic α-oxo-oximes, viz. 4-oximinoisoxazolone-5(4H)-ones 1 and 2,4-oximino-5(4H)-pyrazolones 35, and 4-oximino-1-phenyl-1,2,3-triazol-5(4H)-one 6, were investigated experimentally and computationally. Whereas the intramolecularly H-bonded ZZ isomers of these oximes are usually the most stable in the gas phase, this preference is overcome by intermolecular H-bonding to a solvent or another molecule. For 1,3-dimethyl-4-oximino-5(4H)-pyrazolone 3b a turnaround is seen when going from the solid (predominantly Z isomer) to DMSO solution (predominantly E isomer), which can be ascribed to an intermolecular H-bond between the oxime OH function and a DMSO molecule. Such isomerization is not seen in CDCl3, where intermolecular H-bonding is unimportant. The Z/E-isomerization in DMSO solution is accelerated by photolysis. Calculations of the energies of different conformers, and of 13C NMR data at the GIAO-ωb97xD/6-31G(d)//M06-2X/6-311++G(d,p) level permit a clear-cut correlation of conformer structures with observed 13C NMR spectra.


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