355-63-5Relevant articles and documents
Battais et al.
, p. 481,483-484,488-489,492,494 (1978)
Radical additions to fluoroolefins. Thermal reaction of perfluoroallyl chloride with perfluoroalkyl iodides as a selective synthesis of terminal perfluoroolefins
Cirkva, Vladimir,Paleta, Oldrich,Ameduri, Bruno,Boutevin, Bernard
, p. 87 - 92 (1995)
Reaction of perfluoroallyl chloride with perfluoroalkyl iodides, RFI (RF = C4F9, C6F13, C8F17), in an autoclave at 180-250 deg C gave terminal perfluoroolefins, CF2=CF-CF2-RF (2-4) as the sole reaction products.Isomeric fluoroolefins containing an internal double bond and telomeric products were not observed in the reaction mixture.The yields were dependent on the reaction temperature and on the chain length of RFI: the highest preparative yield of olefin 2 (RF = C4F9) was obtained at 200 deg C (26percent), while in the syntheses of olefins 3 and 4 (RF = C6F13 and C8F17, respectively) highest yields were achieved at 250 deg C (41percent and 74percent, respectively).The presence of CuI or a peroxide initiator had a negative influence on the yield of products.Formulae have been assigned to the fragments in the mass spectra of products 2-4, and fragmentation sequences have been proposed. - Keywords: Perfluoroallyl chloride; Perfluoroalkyl iodides; Perfluoro-1-alkenes; Radical addition; Thermal initiation; Mass spectrometry
Gas-phase NMR studies of the thermolysis of perfluorooctanoic acid
Krusic, Paul J.,Marchione, Alexander A.,Roe, D. Christopher
, p. 1510 - 1516 (2005)
The thermolysis of perfluorooctanoic acid (CF3(CF 2)6COOH) has been studied kinetically by high-temperature gas-phase NMR in both sodium borosilicate glass and quartz ampoules. In both cases, 1-H-perfluoroheptane is the major product, but the decomposition is considerably slower in quartz. The decomposition in borosilicate ampoules at 307°C is greatly accelerated by the presence of crushed borosilicate glass and the reaction appears to be completely heterogeneous. Perfluoro-1-heptene is produced as a minor product and time-of-flight secondary ion mass spectrometry (ToF-SIMS) examination of the inner surface of the borosilicate glass ampoule after reaction reveals the presence of NaF. The thermolysis in quartz ampoules was studied by ex situ heating in the temperature range 355-385°C and produced moderate amounts of perfluoro-1-heptene and SiF4 in addition to 1-H-perfluoroheptane. Thermolysis in the presence of added crushed quartz accelerates the decomposition, as does increasing the concentration of perfluorooctanoic acid or carrying out the thermolysis in the presence of water. The thermolysis of perfluorooctanoic acid thus proceeds at widely different rates depending on concentration and on the physical and chemical environment. By contrast, the pyrolysis of ammonium perfluorooctanoate is more facile by orders of magnitude and proceeds by first-order kinetics at essentially the same rates in both quartz and borosilicate ampoules with an estimated half-life of 2 s at 307°C.
FREE-RADICAL INITIATED ADDITION OF CARBON TETRACHLORIDE TO FLUORO OLEFINS
Chen, Loomis S.
, p. 261 - 272 (2007/10/02)
The reaction between carbon tetrachloride and unsymmetrical fluoro olefins, e.g.RCF=CF2, where R=n-C5H11 and C6F5, has led to the addition product, RCFClCF2CCl3.Addition was apparently unidirectional under the conditions used since the isomeric adduct RCF(CCl3)CF2Cl could not be detected.The effects of experimental conditions such as free radical initiators, temperature, and time are discussed for the different reactions studied.A probable mechanism is suggested for these additions.
