Synthesis, structure determination and mechanism in thiophene derivatives

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

Preview

Text 10290328.pdf - Published version Download (20MB) | Preview

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:	Number Type PQ10290328 Other
Divisions:	Schools > School of Science and Technology
Record created by:	Laura Ward
Date Added:	08 Jul 2021 09:24
Last Modified:	22 May 2024 14:40
URI:	https://irep.ntu.ac.uk/id/eprint/43375

Actions (login required)

Edit View

Statistics

Views

Downloads