title: Reaction of CF3 radicals with CO and O2. Isolation of bis(trifluoromethyl)peroxydicarbonate, CF3OC(O)OOC(O)OCF3, and identification of bis(trifluoromethyl)trioxydicarbonate, CF3OC(O)OOOC(O)OCF3.
abstract: The synthesis of CF3OC(O)OOCF3, CF3OC(O)OOC(O)OCF3, and CF3OC(O)OOOC(O)OCF3 is accomplished by the photolysis of a mixture of (CF3CO)2O, CO, and O2. Pure CF3OC(O)OOCF3 and CF3OC(O)OOC(O)OCF3 are isolated after thermal decomposition of CF3OC(O)OOOC(O)OCF3 and repeated trap-to-trap condensation. Additional spectroscopic data of known CF3OC(O)OOCF3 are obtained by recording NMR, IR, Raman, and UV spectra: At room temperature CF3OC(O)OOC(O)OCF3 is stable for days in the liquid or gaseous state. The melting point is -38 degrees C, and the boiling point is extrapolated to 73 degrees C from the vapor pressure curve log p = 8.657-1958/T (p/mbar, T/K). The new compound is characterized by molecular mass determination and by NMR, vibrational, and UV spectroscopy. The new trioxide CF3OC(O)OOOC(O)OCF3 cannot be separated from CF3-OC(O)OOC(O)OCF3 by distillation due to their similar boiling points. CF3OC(O)OOOC(O)OCF3 decomposes at room temperature within hours into a mixture of CF3OC(O)OOC(O)OCF3, CF3OC(O)OOCF3, CO2, and O2. Its characterization is discussed along with a possible mechanism for formation and decomposition reactions.
authors.affiliation: Universität GH Duisburg, Lotharstrasse 1, D-47048 Duisburg, Germany.
authors.forename: G A
authors.initials: GA
authors.lastname: Argüello
authors.forename: H
authors.initials: H
authors.lastname: Willner
authors.forename: F E
authors.initials: FE
authors.lastname: Malanca