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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

The structural and spectroscopic characterisation of 2-aryl and 2-heteroaryl isatogens

Stoddart, Barry January 1990 (has links)
This work reviews the current knowledge of the synthesis , properties , structures and biological activities of isatogens. The unequivocal 2 C NMR assignment of 2-phenylisatogen 1S reported and used to assign the spectra for a range of 2-(4-substituted-phenyl)isatogens. Molecular dynamics of 2-phenylisatogen in chloroform are reported and indicate that there is little if any inter-ring mesomeric resonance in this compound. 1~C , ~N NMR and UV-Visible spectroscopic data are reported for a range of 2-(4-substituted-phenyl)isatogens. Analysis of this data indicates a small but significant degree of inter-ring mesomeric resonance is present in these compounds especially those with strongly electron donating or withdrawing substituents. An interesting correlation is found between ~sN substituent chemical shifts and molar absorbtivity of the visible transitions. The X-ray crystal structure of 2-(4-chlorophenyl)isatogen is reported and shows a small but significant shortening of the inter-ring bond length compared to 2-phenylisatogen , further supporting the hypothesis of inter-ring mesomeric resonance in these compounds. 1 H and ~C NMR data are reported for the 2-(pyrid-2-inium)isatogen cation and indifate the presence of intramolecular interaction between the ~---H and N~O groups in the molecule. The X-ray crystal structure of the perchlorate salt of the cation and the ~H solid state NMR spectrum both support this conclusion. The molecular structure indicates that the intramolecular interaction is comprised of coulombic and hydrogen bonding interactions leading to a near coplanar structure for the cation compared to the noncoplanar structure for the parent base, 2-(pyrid-2-yl)isatogen. A hypothesis is put forward to explain molecular packing and configuration differences in 2-heteroarylisatogens. The molecular packing and configuration is controlled by a balance of intermolecular dipole attraction and repulsion. Predictions of molecular packing and configuration are made for a number of 2-heteroarylisatogens. The X-ray crystal structure of 2-(pyrid-3-yl)isatogen is reported and found to be in complete agreement with the predictions of the hypothesis. Further studies are proposed involving the synthesis of ~N and ~~O labelled isatogens , the study of inclusion complexes with cyclodextrins and the study of isatogens with the potential for increased mesomeric interactions. ,

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