Regiochemistry of the reaction between dibenzothiophene radical cation and nucleophiles or nitrogen dioxide

Craig P. Butts, Lennart Eberson*, Michael P. Hartshorn, Finn Radner, Ward T. Robinson, Bryan R. Wood

*Corresponding author for this work

    Research output: Contribution to journalArticle (Academic Journal)peer-review

    10 Citations (Scopus)

    Abstract

    The regiochemistry of nucleophile or radical attack upon dibenzothiophene radical cation (2•+) has been studied, using the photolysis of 2-tetranitromethane, the NO2 or nitrous acid catalyzed (NAC) nitration of 2 and the silver(II) mediated acetoxylation of 2 as test reactions in all likelihood mediated by 2•+. The results are discussed in relation to theoretical predictions based on the VBCM model. The photolysis of the charge-transfer complex of 2 and tetranitromethane in dichloromethane gives mainly dibenzothiophene sulfoxide (3) and minor amounts of 2-nitrodibenzothiophene (4), r-1-hydroxy-c-4-trinitromethyl-1,4-dihydro-dibenzothiophene (5), t-2-nitro-r-1 -trinitromethyl-1,2-dihydrodibenzothiophene (6) and c-1-nitro-r-4-trinitromethyl-1,4-dihydro-dibenzothiophene 7. In aceto-nitrile the major product is the sulfoxide 3 together with 2-nitrodibenzothiophene (4) and 4-nitrodibenzothiophene (9). The photolysis in 1,1,1,3,3,3-hexafluoro-propan-2-ol yields only the sulfoxide 3 and minor amounts of the 2-nitroarene 4. Nitration of 2 by NO2 in dichloromethane gives largely 3 and the 2-nitro isomer 4, as does NAC nitration in acetic acid. The oxidation of 2 by an AgII complex of 2,2′-bipyridine gave mainly 1- and 4-acetoxydibenzothiophene and a minor proportion of the 3-acetoxy isomer, no sulfoxide 3 being formed. The X-ray crystal structure is reported for compound 5.

    Original languageEnglish
    Pages (from-to)839-848
    Number of pages10
    JournalActa Chemica Scandinavica
    Volume51
    Issue number8
    DOIs
    Publication statusPublished - Aug 1997

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