A study of the stereochemistry and electronic transitions of cyclic and acyclic thioamides by crystallography, spectroscopy and computational methods

Research output: ThesisDoctoral Thesis (compilation)

Abstract

Analysis of conformations and electron transitions of 3-(alkyl or aralkyl)-5-(methyl or phenyl)rhodanines with analogues and N,N'-bis[(S)-1-phenylethyl]-thiourea have been performed by X-ray crystallography, 1H NMR, molecular mechanics, ultraviolet spectroscopy and for the chiral rhodanines, enantiomer chromatography and circular dichroism spectroscopy. The magnitude of rotational barriers has been determined. Attractive steric effect is determined in the syn form of 3-neopentyl-5-phenylrhodanine. Absolute configurations are determined for the anti and syn forms of 3-(S)-(1-phenylethyl)-5-methylrhodanine. A special study is made with the N-[(S)-(1-phenylethyl)]-dithiocarbamate anion and the equilibrium of its ammonium salt.

Details

Authors
  • Knut Rang
Organisations
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Organic Chemistry

Keywords

  • UV and CD spectroscopy, rotational barriers, DNMR, X-ray, N'-bis[(S)-1-phenylethyl]-thiourea, N, attractive steric effect, chiral, phenyl or H-)rhodanines, 3-(alkyl or aralkyl)-5-(methyl, Conformations, electronic transitions, molecular mechanics, enantiom, Organic chemistry, Organisk kemi
Original languageEnglish
QualificationDoctor
Awarding Institution
Supervisors/Assistant supervisor
  • [unknown], [unknown], Supervisor, External person
Award date1998 May 29
Publisher
  • Organic Chemistry, Lund University
StatePublished - 1998

Bibliographic note

Defence details Date: 1998-05-29 Time: 13:15 Place: Room F External reviewer(s) Name: Mannschreck, Albrecht Title: Professor Affiliation: Universität Regensburg, Institut für Organische Chemie, D-93040 Regensburg, Deutschland --- Article: K. Rang, J. Sandström, L.Thell and Q. Yang, Crystal and Molecular structure of 3-isopropyl-5-phenylrhodanine, Acta Chemica Scandinavica B 39 (1985) 123. Article: I. Pettersson, K. Rang and J. Sandström., Conformational studies of 3-alkylrhodanines and an analogous mesoionic compound., Acta chemica Scandinavica B 40 (1986) 751. Article: K. Rang, F.-L. Liao, J. Sandström and S.-L. Wang., Conformations and conformational changes of 3-isobutyl- and 3-neopentylrhodanines. A case of steric attraction studied by X-ray crystallography, NOE effects and force-field calculations, J. Chem. Soc. Perkin Trans. 2 (1995) 1521. Article: K. Rang, R. Isaksson and J. Sandström, Chromatographic enantiomerseparation and circular dichroism spectra of chiral rhodanines, J. Chem. Soc. Perkin Trans. 2 (1996) 1493. Article: K. Rang, F.-L. Liao, J. Sandström and S.- L. Wang, Diastereomers of 3-(S)-(1-phenylethyl)-5-methyl and -5-phenylrhodanine: crystal structures, conformations and circular dichroism spectra, Chirality 9 (1997) 568. Article: K. Rang, J. Sandström and C. Svensson, The conformational equilibrium of N,N'-bis[(S)-1-phenylethyl]-thiourea and its solvent dependence, studied by NMR and CD spectra and by X-ray crystallography, Accepted for publication by Canadian Journal of Chemistry. Article: K. Rang and J. Sandström, The N-(1-phenylethyl)-dithiocarbamate anion, electronic transitions, ultraviolet and CD spectra and reversible formation of its ammonium salts, Manuscript. The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Organic chemistry (S/LTH) (011001240)