The reaction of octafluoro-2,3-epoxybutane
1 with 2-aminothiophenol gave three kinds of novel fluorocontaining
N,
S-heterocyclic compounds depending on the solvent nature: 2,3-bis(trifluoromethyl)-3,4-dihydro-2
H-1,4-benzothiazin-2-ol
2, 2-trifluoromethyl-2-[1-(2-aminophenylthio)-2,2,2-trifluoroethyl]-1,3-benzothiazolidine
6 and 5a,11a-bis(trifluoromethyl)-5a,6,11a,12-tetrahydro-5,11-dithia-6,12-diazanaphthacene
5. Use of the toluene, dioxane, tetrahydrofuran, acetonitrile and dimethoxyethane gave the unexpected dihydrobenzothiazine
2 (
RS,
SR >
RR,
SS) in good to moderate yields. In dimethylsulfoxide and
N,
N-dimethylacetamide, unusual cyclization occurred resulting in benzothiazolidine
6 (
RS,
SR/
RR,
SS ∼ 1:1) in moderate yields. Formation of minor 1,1,1,3,4,4,4-heptafluoro-3-(2-aminophenylthio)-2,2-dihydroxybutane
4 which was converted into bis(benzothiazine)
5 was observed in all solvents tested with the exception of toluene and dioxane. The molecular structure of the
RS,
SR-diastereomer of dihydrobenzothiazine
2, bis(benzothiazine)
5 and the
RS,
SR-diastereomer of benzothiazolidine
6 has been established by X-ray crystallography.
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