ISSN:
0009-2940
Keywords:
Selenocarbonyl compounds, perfluorinated
;
1,3-Diselenetanes, perhalogenated
;
2-Selenabicyclo[2.2.1]hept-5-enes
;
1,3-Diselenetan-2-ylium hexafluoroarsenates
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Preparation of (Perfluoroalkyl)halogeno-1,3-diselenetanes from the Corresponding Selenocarbonyl Fluorides and Reactions with Boron Trichloride or Arsenic Pentafluoride1)Reactions of Hg(SeRt)2 (Rt = C2F5, C3F7, CF3) with (C2H5)2 All or All3 in octamethylcyclotetrasiloxane produce the unstable perfluoroalkaneselenocarbonyl fluorides 1 [R1 = CF3 (1 a), C2F5 (1 b), CF3Se (1 c)]. These compounds are very reactive and polymerize to rubberlike products. On heating the polymers decompose almost quantitatively to the monomers or dimers. In CFCl3 solution 1 dimerizes at 20°C in sunlight to the corresponding cis/trans-1,3-diselenetanes 2. The structure of 2 b is determined by single crystal X-ray diffraction. Different selenocarbonyl derivatives add to unsymmetrically substituted 1,3-diselenetanes 3. 1 a and 1 b react with cyclopentadiene to form the [4 + 2] cycloaddition products 4a and 4c. Halogen exchange reactions take place between 2a - d and BCl3. The cis-isomers react much faster than the trans-isomers to give a mixture of cis-, trans-forms of 5. When 2c,d is treated with BCl3 it is possible to isolate and characterize the pure trans-isomer 2d, which is separated by preparative gas chromatography from 5c,d. Fluorine abstraction with formation of 1,3-diselenetan-2-ylium ions (6a - f) are accomplished by reactions of 2 or 3 with AsF5 in SO2.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19911240109
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