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Durham e-Theses
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Some studies of the reactions of carbon nucleophiles with aromatic nitro compounds

Duffield, Gaynor Louise (1996) Some studies of the reactions of carbon nucleophiles with aromatic nitro compounds. Doctoral thesis, Durham University.



Some reactions of aromatic nitro-compounds with carbon nucleophiles have been investigated. The techniques used include NMR spectroscopy, UV-visible spectroscopy and stopped-flow spectrophotometry. The initial rapid reactions of carbanions derived from ring-substituted phenylacetonitriles with 1,3,5-trinitrobenzene yield σ-adducts. Carbanions were generated from the phenylacetonitriles by reaction with sodium methoxide in methanol. Values of the equilibrium constants for the deprotonation reaction were determined spectrophotometrically. Rate constants for the σ-adduct forming reactions were measured in methanol using the stopped-flow method. With increasing carbanion reactivity rate constants for the C-C bond forming reaction increase to a limit of circa 10(^9) dm(^3) mol(^-1) s(^-1) close to the diffusion limit. Data were also obtained for reaction of the carbanions with 4-nitrobenzofuroxan and with 4-nitrobenzofurazan.An interesting slower reaction was observed in the reaction of carbanions with 1,3,5- TNB, 4-nitrobenzofuroxan and 4-nitrobenzofurazan. This yields coloured products and the nature of the process has been investigated. Attempts have been made to isolate the σ-adducts formed from carbanions. The adduct formed from 1,3,5-trinitrobenzene and phenylacetonitrile in the presence of triethylamine has been produced in crystalline form. NMR measurements in situ have indicated the formation of adducts from 4-nitrobenzofuroxan and from 4-nitrobenzofiirazan with deuterated nitromethane in the presence of triethylamine.

Item Type:Thesis (Doctoral)
Award:Doctor of Philosophy
Thesis Date:1996
Copyright:Copyright of this thesis is held by the author
Deposited On:09 Oct 2012 11:50

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