Novel Type Elimination Reactions of Sulfoxides Bearing Several Heteroaromatics: Trapping of Sulfines with 2,3-Dimethyl-1,3-butadiene.
Previously we reported the novel thioaldehydes generation via thermolyses of phenacyl sulfoxides bearing some heteroaromatics. Thermolysis of sulfoxides (1a,b and 2a-4a) bearing other heterocycles such as thiadiazole, triazole, and tetrazole in the presence of 2,3-dimethyl-1,3-butadiene in dioxane at 100 degrees C led to the unexpected products 6-substituted-5,6-dihydro-3,4-dimethyl-2H-thiapyran 1-oxide (5a,b). These products were considered to be formed by the Diels-Alder reaction of the diene with the sulfines formed initially by the thermal decomposition of the sulfoxides. The rate acceleration and the improvement of the yield by addition of 1.5 equiv of triethylamine, especially in the case of ethoxycabonylmethyl sulfoxide 1c, was observed. The cis-trans selectivity for sulfine cycloadducts was also studied by NMR spectrometry. The reactions of alpha-substituted phenacyl sulfoxides 1d-f bearing a phenyl-substituted tetrazolyl group in the presence of the same diene were also studied.
Morita
Hiroyuki
H
Department of System Engineering of Materials and Life Science, Faculty of Engineering, Toyama University, 3190 Gofuku, Toyama 930-8555, Japan.
Takeda
Masahiro
M
Yoshimura
Toshiaki
T
Fujii
Takayoshi
T
Ono
Shin
S
Shimasaki
Choichiro
C