Fluorinated dihydroindeno[2,1-c][1,2,6]thiadiazines: The first synthesis, structural characterization and reactivity

[Display omitted] ► The first synthesis of fluorine-containing dihydroindeno[2,1-c][1,2,6]thiadiazines. ► Nontrivial chemical properties. ► Multinuclear NMR spectroscopy and single crystal X-ray diffraction. 3-(1-Amino-2,2,2-trifluoroethyliden)-1,1,4,5,6,7-hexafluoro-2-iminoindan (1) and 3-(1-amino-...

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Published in:Journal of fluorine chemistry 2012-03, Vol.135, p.254-260
Main Authors: Karpov, Victor M., Platonov, Vyacheslav E., Rybalova, Tatjana V., Gatilov, Yuri V., Shakirov, Makhmut M.
Format: Article
Language:English
Subjects:
DFT calculations
En-amino-imine
Fluorinated
Indeno[2,1-c][1,2,6]thiadiazine
NMR spectroscopy
Reactivity
Structure elucidation
Sulfur–nitrogen heterocycles
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Summary:[Display omitted] ► The first synthesis of fluorine-containing dihydroindeno[2,1-c][1,2,6]thiadiazines. ► Nontrivial chemical properties. ► Multinuclear NMR spectroscopy and single crystal X-ray diffraction. 3-(1-Amino-2,2,2-trifluoroethyliden)-1,1,4,5,6,7-hexafluoro-2-iminoindan (1) and 3-(1-amino-2,2,2-trifluoroethyliden)-1,1,4,5,6,7-hexafluoro-2-methyliminoindan (7) reacted with SOCl2 to give previously unknown 4a-chloro-5,6,7,8,9,9-hexafluoro-4-(trifluoromethyl)-4a,9-dihydroindeno[2,1-c][1,2,6]thiadiazine (2) and 5,6,7,8,9,9-hexafluoro-1-methyl-4-(trifluoromethyl)-1,9-dihydroindeno[2,1-c][1,2,6]thiadiazine 2-oxide (8), respectively. When treated with methanol, compound 2 formed 5,6,7,8,9,9-hexafluoro-4a-methoxy-4-(trifluoromethyl)-4a,9-dihydroindeno[2,1-c][1,2,6]thiadiazine (9), whereas the reaction with water gave 5,6,7,8,9,9-hexafluoro-4-(trifluoromethyl)-3,9-dihydroindeno[2,1-c][1,2,6]thiadiazine 2-oxide (5). The latter reacted with SOCl2, acetyl chloride and trifluoroacetic anhydride to give compound 2, 5,6,7,8,9,9-hexafluoro-4-(trifluoromethyl)-4a,9-dihydroindeno[2,1-c][1,2,6]thiadiazin-4a-yl acetate (13) and trifluoroacetate 15, respectively. Solution of compound 2 in trifluoromethanesulfonic acid generated 5,6,7,8,9,9-hexafluoro-4-trifluoromethyl-9H-indeno[2,1-c][1,2,6]thiadiazinylium (11), which was transformed, under the action of water, to sulfoxide 5. The structures of compounds 8, 9, 13 were confirmed by single crystal X-ray diffraction. The reaction pathways were analyzed on the basis of DFT calculations
ISSN:0022-1139
1873-3328
DOI:10.1016/j.jfluchem.2011.12.005