The cyanide catalyzed dimerization of 2,3 naphthalenedicarboxaldehyde: a unique oxidative condensation product and derivatives
dc.contributor.author | McGill, Colin | |
dc.date.accessioned | 2015-09-02T20:37:57Z | |
dc.date.available | 2015-09-02T20:37:57Z | |
dc.date.issued | 2005-05 | |
dc.identifier.uri | http://hdl.handle.net/11122/5918 | |
dc.description | Thesis (M.S.) University of Alaska Fairbanks, 2005 | en_US |
dc.description.abstract | 2,3 Naphthalenedicarboxaldehyde (NDA), in the presence of cyanide, is commonly used for the derivitization of amino acids and peptides to fluorescent 2-substituted 1-cyanobenzo[f]isoindoles, providing high sensitivity in capillary electrophoresis (CE) and high performance liquid chromatography (HPLC) separations. CE studies of the neurotransmitters glutamate and aspartate have shown the formation of a number of competitive side products. Although mentioned in the literature, these side products have not been characterized. The product, 15-hydroxybenzo[g]benzo [6, 7]isochromeno[4,3-c]isochromen- 7(15H)-one (2), is reported here, as a dimerization of NDA in the presence of cyanide and atmospheric oxygen. The structure is confirmed by IR, LRFAB-MS, IRMS, and NMR spectra. Possible mechanisms for the formation of 2, its air oxidation, and an alternative benzoin condensation product are discussed. 15-hydroxybenzo[g]benzo [6,7]isochromeno[4,3-c]isochromen-7(15H)-one (2) is easily converted to full acetals via reflux in an alcohol solvent in the presence of an acid catalyst. Oxidation by NaOCI (aq) yields 3-(3-chloro-1,4-dioxo-3,4-dihydro-1H-benzo[g]isochromen-3-yl)-2-napthaldahyde (4) by capturing hypochlorite at the position æ the enolate. Oxidation by pyridinium chlorochromate (PCC) yields naptho[2,3-c]furan-1,3-dione (5) by multiple oxidations and the formation of the anhydride. | en_US |
dc.language.iso | en_US | en_US |
dc.subject | Naphthalene | en_US |
dc.subject | Sodium hypochlorite | en_US |
dc.subject | Benzoin | en_US |
dc.subject | Anhydrides | en_US |
dc.title | The cyanide catalyzed dimerization of 2,3 naphthalenedicarboxaldehyde: a unique oxidative condensation product and derivatives | en_US |
dc.type | Thesis | en_US |
dc.type.degree | ms | en_US |
refterms.dateFOA | 2020-03-13T01:27:25Z |
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Chemistry and Biochemistry
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