Photochemistry of a model lignin compound. Spin trapping of primary products and properties of an oligomer
1994; NRC Research Press; Volume: 72; Issue: 1 Linguagem: Inglês
10.1139/v94-007
ISSN1480-3291
AutoresL. R. C. Barclay, G.R. Cromwell, James W. Hilborn,
Tópico(s)Photochemistry and Electron Transfer Studies
Resumoα-Guaiacoxylacetoveratrone, 1, was selected as a model of a lignin structure component for photolysis and free radical spin trapping studies. The 3,4-dimethoxyphenacyl radical, Ar-COĊH 2 , 2, thermally generated from α-bromoacetoveratrone with trimethyltin, was spin trapped by phenyl-tert-butylnitrone (PBN), and the spin-trapped radical identified by ESR and mass spectroscopy. Spin trapping by PBN of radical photoproducts from 1 gave a mixture of trapped radicals, according to ESR. These were separated as their hydroxylamines and identified by liquid chromatography/mass spectroscopy (LC/MS) under chemical ionization (CI) conditions. This LC/MS (CI) method identified the same phenacyl fragment, 2 (reduced), as well as a fragment tentatively attributed to a spin-trapped guaiacoxyl radical, chemically reduced to the hydroxylamine. Extended direct photolysis of 1 yields colored paramagnetic oligomers. The synthesis of 1-(3,4-dimethoxyphenyl)-2-(4-hydroxy-3-methoxyphenylethanone(10), a rearranged, recombination photoproduct of 1, is described. A pathway for formation of oligomers as unstable dimers of 10 is presented.
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