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Isotopically selective CO/sub 2/ transverse excitation laser induced chemical reactions of Cl/sub 2/CF/sub 2/ and Br/sub 2/CF/sub 2/ with olefins

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00476a029· OSTI ID:6820018
The CO/sub 2/ transverse excitation laser induced chemical reactions of Cl/sub 2/CF/sub 2/ and Br/sub 2/CF/sub 2/ with isobutylene, propylene, and ethylene have been investigated. In the (H/sub 3/C)/sub 2/C == CH/sub 2//Br/sub 2/CF/sub 2/ system, evidenced for the initial presence of laser-produced difluorocarbene was provided by the isolation of the CF/sub 2/--olefin addition compound 1,1-difluoro-2,2-dimethylcyclopropane in the product array. The yield of this product from the (H/sub 3/C)/sub 2/C == CH/sub 2//Cl/sub 2/CF/sub 2/ system was dependent upon the laser irradiation frequency. No analogous gem-difluorocyclopropanes were detected in the Br/sub 2/CF/sub 2//H/sub 3/CCH == CH/sub 2/ and Br/sub 2/CF/sub 2//C/sub 2/H/sub 4/ systems. Carbon isotopic segregation was noted in all experiments. The complex nature of these reaction systems is examined in some detail. The concept of utilizing a laser-produced, isotopically specific reactive intermediate such as :CF/sub 2/ for the direct synthesis of labelled compounds is presented. 1 figure, 3 tables, 24 references.
Research Organization:
National Bureau of Standards, Washington, DC
OSTI ID:
6820018
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 100:8; ISSN JACSA
Country of Publication:
United States
Language:
English