Synthesis of some analogues of n-substituted phthalimide and benzo-tetracyanoquinodimethane
McDermott, Gerard M. (2007) Synthesis of some analogues of n-substituted phthalimide and benzo-tetracyanoquinodimethane. PhD thesis, Dublin City University.
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This thesis will begin with a brief introduction of the photochemistry of the carbonyl group, followed by a detailed literature survey concerning the intra and intermolecular photochemical reactions of the phthalimide system.
It will also be shown that N-(2-hydroxypheny1)phthalimide and N-(2- aminopheny1)phthalimide do not behave in the same photochemical manner as the analogous N-(2-methylpheny1)phthalimide and N-(2-ethylphenyl)phthalimide, which both undergo &hydrogen abstraction forming a tetracyclic system, as well as a photoreduced product. However, N-(2-hydroxypheny1)phthalimide does undergo an interesting intra-molecular thermal process to yield 2-phenylbenzoxazole, while N-(2- aminopheny1)phthalimide also undergoes an intra-molecular thermal cyclisation to a tetra cyclic system, benzo[4,5]imidazo[2,1-alisoindol-11-one,w hich is believed is initiated by an inter-molecular reaction. It will also show that esters of N-(2- hydroxypheny1)phthalimide and amides of N-(2-aminopheny1)phthalimide are photochemically inert.
This thesis will describe the application of the Mitsunobu reaction for the synthesis and identification of N-alkyl derivatives of 3-dicyanomethylene-2,3-dihydroisoindol- 1-one. These derivatives are structural analogues of N-substituted phthalimides and also of benzo-tetracycnoquinodimethane. Electrochemical studies with some selected members of this series will show that, like the phthalimides and benzotetracyanoquinodimethane, these compounds are good electron acceptors. The photochemistry of this family of compounds has also been investigated.
It will also show that the Mitsunobu reaction with isopropyl alcohol give products from both N-alkylation and 0-alkylation. Molecular modelling calculations are in line with this observeration.
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