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Abstract

The present investigation was concerned with the synthesis and spectral studies
of quinoline and quinolone derivatives.

The Combes synthesis of quinolines has been extended to the synthesis of
several 2,4-dialkyl- substituted quinolines. The experimental procedures of the
von Miller-Kinkelin and Beyer syntheses have been improved and the revised techniques applied to the synthesis of some new 3-alkyl- and 3,4-disubstituted- quinoline derivatives, The orientation effects in the Beyer synthesis with asymmetric ketones have been established.

A detailed study has been undertaken of the orientation effects in quinoline
syntheses commencing from asymmetrically substituted aniline derivatives, reactions
leading to quinolines substituted in the heterocyclic ring have especially been
studied. Through the use of exhaustive analytical procedures, reliable properties
and product ratios have been established. The nitration of 7-alkylquinolines has
been re-investigated and clarified.

A study of long range 35 - 1g coupling constants at the methyl carbon in
methylquinoline and methylquinolone derivatives has been undertaken. The coupling
constants have been correlated with the appropriate 1H - 1H vicinal interactions
and their diagnostic uses discussed. Certain long range 13c-1H couplings at the ring carbons have also been investigated.

The chemical shift of the NH proton in a series of methyl substituted 2- and 4- quinolone derivatives has been determined and the results interpreted on the basisof
steric inhibition to hydrogen bonding, which was confirmed by infra-red spectroscopy. The diagnostic value of the NH proton chemical shifts in the identification of quinolone
alkaloids, for example, has been propounded.

The 135 chemical shifts for a series of methyl substituted 2- and 4- quinolone
derivatives have been determined. The use of 135 n.m.r. spectroscopy to distinguish
and differentiate hetween the two quinolone series has been discussed. A subsequent
study of some 1-methyl-2-quinolone derivatives has shown that similar characteristic
peri-substituent effects to those previously noted in the naphthalene series also
occur in the quinolones. These effects must be considered in the course of spectral
assignments.

In the course of the present work, 54 new compounds have been synthesised and
characterised.

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

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