- Photolysis of hexafluoro-2-butyne/ozone mixtures in cryogenic matrices
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Matrix studies on the photolytic reaction between ozone and hexafluoro-2-butyne have been performed at 11 K in argon and nitrogen matrices. The matrices were photolyzed with 640 and 642 nm light from a laser source, and with 254 nm light from a Hg arc lamp. The final products of the reaction are perfluorobutanedione and bis(trifluoromethyl)ketene. An intermediate species was also observed. It has been identified as perfluoroacetylmethylmethylene, a ketocarbene. The ketocarbene was also trapped as trifluoromethyl trifluoroacetylketene, a ketoketene, when the matrix was doped with CO. Photolysis of the ketocarbene with 427 nm light results in the direct formation of the ketene. The ketocarbene and ketene form as a result of O atom addition to the butyne, whereas the butanedione appears to be predominantly produced by a reaction between the ketocarbene and O2. Product distribution was found to depend greatly on both matrix material and ozone concentration. This is the first direct evidence of a ketocarbene as an intermediate in the O atom addition to an alkyne.
- Singmaster,Jonnalagadda,Chan
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p. 9078 - 9088
(2007/10/03)
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- Heterocyclic Polyfluoro-compounds. Part 33. Competing 1,2- and 1,4-Photochemical Addition of Hexafluorobiacetyl to 1,2-Difluoroethylene
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Photochemical addition of hexafluorobiacetyl (λ > 300 nm) to either cis- or trans-1,2-difluoroethylene yields mainly cis-2,3-difluoro-5,6-bis(trifluoromethyl)-2,3-dihydro-p-dioxin (53 - 57percent), and the corresponding trans-dioxin (12percent) by 1,4-addition, together with r-2-trifluoromethyl-2-trifluoroacetyl-t-3,t-4-difluoro-oxetan (7 - 8percent) and the corresponding t-3,c-4- (7 - 8percent) and c-3,t-4-oxetans (6 - 7percent) by 1,2-addition.The cis-dioxin yields both cis- and trans-1,2-difluoroethylene upon pyrolysis, and with aluminium trichloride undergoes isomerisation to the trans-dioxin, and non-stereospecific exchange of one or both ring fluorines by chlorine atoms.
- Barlow, Michael G.,Coles, Barrie,Haszeldine, Robert N.
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p. 2523 - 2526
(2007/10/02)
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