Synthesis, structure determination and mechanism in thiophene derivatives

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Weddell, D.A., 2001. Synthesis, structure determination and mechanism in thiophene derivatives. PhD, Nottingham Trent University.

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Abstract

A series of O2N2 and O3N2 macrocycles incorporating thiophene have been prepared. Various carbon chain lengths exist between the donor atoms (nitrogen or oxygen) giving a range of macrocycles with ring sizes varying from 14 to 20 atoms. Semi-large scale synthesis (circa 50 g) was carried out on the production of (3-oxythienyl) alkanes from the starting material methyl 3-hydroxythiophene-2-cai'boxylate. A series of N,N'~ bis-(R,R'-benzyl)-alkane-diamine compounds was also synthesised on a semi-large scale. The aminomethylation of thiophene (the Mannich reaction) was used to facilitate the production of thiophene-based macrocycles from the mentioned starting material without resorting to elaborate purification techniques. Thiophene-based macrocycles (where R = NH2) were appended to a polymeric support (a Merrifield based resin).

Competition ring formation has been found during some Mannich reactions, in some cases preventing effective synthesis of the intended macrocycles. Along with observations, some limitations to ring formation using the Mannich reaction are discussed.

The X-ray crystallographic data for a 15-membered thiophene-based macrocycle is presented together with discussion of its geometry. Intramolecular non-bonded contacts between nitrogen and phenyl-H explain the unexpected geometry of this compound. The calculation of the bonding cavity size of this 15-membered macrocycle along with metal-ion binding studies are discussed.

Item Type:

Thesis

Creators:

Weddell, D.A.

Date:

2001

ISBN:

9781369325775

Identifiers: