9-C-substituted phenalenones as promising precursors for the synthesis of novel stable phenalenyl-type cations and radicals

Anamimoghadam, Ommid (2013) 9-C-substituted phenalenones as promising precursors for the synthesis of novel stable phenalenyl-type cations and radicals. PhD thesis, University of Glasgow.

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Abstract

Previous research in the Bucher group led to the generation of a novel phenalenyl derived radical, naphtho[2,1,8-mna]xanthenyl (NX). Through the photolysis of 9-phenyl-1H-phenalen-1-one (9-phenyl-PN), a transient 5aH-naphtho[2,1,8-mna]xanthene with a very weak C(sp3)-H bond was formed and could undergo hydrogen abstraction in the presence of an electron acceptor such as tetracyanoethylene (TCNE) or benzoquinone (BQ). As a result, NX was formed which exhibited a long persistence based on electronic stabilisation (Scheme A). This thesis deals with the practical preparation of potential precursors of NX type radicals involving new naphtho[2,1,8-mna]xanthenium (NX+) salts synthesised from 9-aryl-1H-phenalen-1-ones (9-aryl-PNs). 9-aryl-PNs will be prepared by a Michael-type Grignard addition which was introduced by C.F. Koelsch and J.A. Anthes. The key-step to the organic salts is the demethylation of the methoxy group at the o-position of the pendant 9-C aryl substituent of 9-aryl-PNs. Subsequently a reactive hemi-ketal will be formed which undergoes hydrolysis resulting in NX+.

Item Type: Thesis (PhD)
Qualification Level: Doctoral
Keywords: Pi-radicals, Aromaticity, Photochemistry, Electrochemistry
Subjects: Q Science > QD Chemistry
Colleges/Schools: College of Science and Engineering > School of Chemistry
Funder's Name: UNSPECIFIED
Supervisor's Name: Bucher, Dr. Götz
Date of Award: 2013
Depositing User: Mr Ommid Anamimoghadam
Unique ID: glathesis:2013-4433
Copyright: Copyright of this thesis is held by the author.
Date Deposited: 26 Jun 2013 15:52
Last Modified: 26 Jun 2013 15:54
URI: http://theses.gla.ac.uk/id/eprint/4433

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