New routes to functionalised pyridines

Altuna-Urquijo, Marta (2005) New routes to functionalised pyridines. Doctoral thesis, Northumbria University.

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Abstract

A novel method of preparing substituted pyridines has been developed. This method uses readily available [3-ketoesters and amidrazone as starting materials. The pyridines obtained do not require purification and different substitution patterns, not available by known methods, can be obtained. The formation of 1,2,3-tricarbonyl compounds was achieved by oxidation of the alcohol precursors, following two different methods. a-Chloro-ct-acetoxy-f3-dicarbonyls were prepared in excellent yields and were shown to react as tricarbonyl equivalents in the formation of 1,2,4-triazines. Regioselective condensation reactions were observed between different amidrazones with tricarbonyl and tricarbonyl equivalents to produce a series of novel 1,2,4-triazines in good yields with no contamination by any regioisomer. When 1,2,4-triazines were obtained from a-chloro-a-acetoxy-P-dicarbonyls, 2.5 equivalents of amidrazone were required. However, decomposition of a-chloro-a-acetoxy-P-dicarbonyls prior to reaction with 1 equivalent of amidrazone yielded the 1,2,4-triazines in good yields. These 1,2,4-triazines underwent aza Diels-Alder cycloaddition reactions with 2,5- norbornadiene to give a series of novel 2,3,6-trisubstituted pyridines. The pyridines bearing electron withdrawing groups as substituents could also be obtained in a 'one- pot' reaction from their corresponding tricarbonyls or tricarbonyl derivatives. The 1,2,4- triazines bearing electron donating groups could be converted to their corresponding pyridines either by changing the reaction conditions or, when possible, by conversion of the electron donating group into a more electron withdrawing substituent by oxidation (e.g. sulphoxide substituent). Pyridines bearing a sulphoxide substituent undergo nucleophilic substitutions, giving great scope to introduce different functionality in the C-6 of the pyridines.

Item Type: Thesis (Doctoral)
Uncontrolled Keywords: Pyridine, Pyridine-Substitute products
Subjects: F100 Chemistry
Department: Faculties > Health and Life Sciences > School of Life Sciences > Applied Sciences
University Services > Research and Innovation Services > Graduate School > Doctor of Philosophy
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Depositing User: EPrint Services
Date Deposited: 26 Apr 2010 09:53
Last Modified: 16 May 2017 05:31
URI: http://nrl.northumbria.ac.uk/id/eprint/3327

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