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; Hans-Joachim Wollweber; Curt Wentrup

doi:10.1071/CH15095

RESEARCH FRONT

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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 3–5, 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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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

Abstract

References

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