TY - JOUR
T1 - Addition of thianthrene cation radical to non-conjugated dienes - Part II
T2 - Addition to two double bonds
AU - Zhao, Bing Jun
AU - Shine, Henry J.
AU - Marx, John N.
AU - Kelly, Anna T.
AU - Hofmann, Cristina
AU - Ould-Ely, Teyeb
AU - Whitmire, Kenton H.
PY - 2006/4
Y1 - 2006/4
N2 - Reaction of thianthrene cation radical tetrafluoroborate with 1,5-hexadiene, 1,7-octadiene, 1,8-nonadiene and 1,9-decadiene in the molar ratio 4:1 caused addition to occur to one and both of each diene's double bonds. A mixture of four adducts was thus obtained, namely a bisadduct (12a-d), a monoadduct (13a-d), a di(bis)adduct (14a-d) and a di(mono)adduct (15a-d). The di(mono)adducts (15b-d) were isolated and characterized with 1H and 13C NMR spectroscopy. Under the same condition of excess of cation radical, addition occurred to only one double bond of 1,4-cyclohexadiene and 1,5-cyclooctadiene. Addition to both double bonds was not observed. The bisadduct (16) of 1,4-cyclohexadiene was characterized with 1H and 13C NMR spectroscopy and X-ray crystallography. On activated alumina, 15b-d underwent fast opening of dicationic rings to form mixtures of (E, E)- (17b-d) and (E, Z)-di(5-thianthreniumyl)diene (18b-d) in which the (E, E)-isomer was dominant and was characterized with 1H and 13C NMR spectroscopy.
AB - Reaction of thianthrene cation radical tetrafluoroborate with 1,5-hexadiene, 1,7-octadiene, 1,8-nonadiene and 1,9-decadiene in the molar ratio 4:1 caused addition to occur to one and both of each diene's double bonds. A mixture of four adducts was thus obtained, namely a bisadduct (12a-d), a monoadduct (13a-d), a di(bis)adduct (14a-d) and a di(mono)adduct (15a-d). The di(mono)adducts (15b-d) were isolated and characterized with 1H and 13C NMR spectroscopy. Under the same condition of excess of cation radical, addition occurred to only one double bond of 1,4-cyclohexadiene and 1,5-cyclooctadiene. Addition to both double bonds was not observed. The bisadduct (16) of 1,4-cyclohexadiene was characterized with 1H and 13C NMR spectroscopy and X-ray crystallography. On activated alumina, 15b-d underwent fast opening of dicationic rings to form mixtures of (E, E)- (17b-d) and (E, Z)-di(5-thianthreniumyl)diene (18b-d) in which the (E, E)-isomer was dominant and was characterized with 1H and 13C NMR spectroscopy.
KW - Adducts of dienes
KW - NMR
KW - Thianthrene cation radical
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U2 - 10.1080/17415990600578467
DO - 10.1080/17415990600578467
M3 - Article
AN - SCOPUS:33645008813
VL - 27
SP - 139
EP - 147
JO - Journal of Sulfur Chemistry
JF - Journal of Sulfur Chemistry
SN - 1741-5993
IS - 2
ER -