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Abstract

In order to investigate the bonding of the imino hydrogen, a number of imidates were prepared and the infra-red spectra of the vapour, liquid and solution phases recorded, the N.M.R. spectra were studied and dipole moments measured. Results were interpreted in terms of the imino hydrogen being intermolecularly bonded in the aliphatic imidates, sterically hindered in the benzimidates and intramolecularly bonded in the trichloroacetimidates. The shoulder on the νNH mode in the infra-red spectra of benzimidates and phenylacetimidates is believed to be a νC=N overtone and not due to the presence of intermolecularly bonded species. Complete assignments of the infra-red spectra were also attempted.

Multiple regression analyses have been performed to relate the infra-red solvent effect shifts with the physical parameters of the solvents used for the νC=O vibration of a wide variety of carbonyl solutes. Relationships have been empirically deduced which have been shown to be statistically more favourable than the Buckingham or KBM relationships for carbonyl solutes. The order of the solvent molecules, as described by the standard entropy S^O, or E_T value of the solvent, and the distance of approach of the solvent molecule appear more important than solvent-solute interaction effects.

From a study of the infra-red spectra of phthalic anhydride in solution at various temperatures the bands associated with the νC=O modes have been identified.

Publication Type:	Thesis (Doctoral)
Subjects:	Q Science > Q Science (General) Q Science > QD Chemistry
Departments:	School of Science & Technology > School of Science & Technology Doctoral Theses Doctoral Theses

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