75-46-7Relevant academic research and scientific papers
OXIDATIVE ADDITION OF SUBSTITUTED ARSINES AND STIBINES WITH BIS(TRIFLUOROMETHYL)NITROXYL
Ang, H. G.,Lien, W. S.
, p. 453 - 470 (1980)
Reactions of bis(trifluoromethyl)nitroxyl with a number of methyl- and trifluoromethyl- substituted arsines and stibines at room temperature lead to the formation of pentavalent arsenic and antimony derivatives, namely (CH3)3-n(CF3)nM2 (M = As, n = 0, 1, 2; M = Sb, n = 0, 1).The derivatives yield bis(trifluoromethyl)-hyroxylamine and the corresponding dichlorides on treatment with hydrogen chloride.A free radical mechanism is proposed for the oxidative addition reactions.
Rate constants for CF3 + H2 → CF3H + H and CF3H + H → CF3 + H2 reactions in the temperature range 1100-1600 K
Hranisavljevic,Michael
, p. 7668 - 7673 (1998)
The shock tube technique coupled with H-atom atomic resonance absorption spectrometry has been used to study the reactions (1) CF3 + H2 → CF3H + H and (2) CF3H + H → CF3 + H2 over the temperature ranges 1168-1673 K and 1111-1550 K, respectively. The results can be represented by the Arrhenius expressions k1 = 2.56 × 10-11 exp(-8549K/T) and k2 = 6.13 × 10-11 exp(-7364K/T), both in cm3 molecule-1 s-1. Equilibrium constants were calculated from the two Arrhenius expressions in the overlapping temperature range, and good agreement was obtained with the literature values. The rate constants for reaction 2 were converted into rate constants for reaction 1 using literature equilibrium constants. These data are indistinguishable from direct k1 measurements, and an Arrhenius fit for the joint set is k1 = 1.88 × 10-11 exp(-8185K/T) cm3 molecule-1 s-1. The CF3 + H2 → CF3H + H reaction was further modeled using conventional transition-state theory, which included ab initio electronic structure determinations of reactants, transition state, and products.
Mixed-valence thiophosphorus compounds. Fluoro- and (trifluoromethyl)(thiophosphorylthio)phosphines with chiral phosphorus centers
Cavell, Ronald G.,Doty, Leon F.
, p. 3086 - 3093 (1978)
Reactions of the acids (CF3)2PS2H and F2PS2H with the fluoro(trifluoromethyl)aminophosphine CF3(F)PN(CH3)2 and the reaction of the new acid F(CF3)P(S)SH with the fluoro- or (trifluoromethyl)aminophosphines X2PN(CH3)2 (X = F, CF3) provide new isomeric (thiophosphorylthio)phosphines XYP(S)SPX′Y′ (X, Y, X′, Y′ = F, CF3) with chiral phosphorus centers. The compounds were characterized chemically and by NMR spectroscopy. Geminal CF3-CF3 (9.0 Hz for CF3 on pentavalent P; 7.2 Hz for CF3 on trivalent P) and F-F (82.5 Hz for F on pentavalent P; 92.5 Hz for F on trivalent P) coupling constants are revealed in the NMR spectra of the molecules as a result of the presence of the chiral phosphorus centers. Directly bound geminal fluorine atoms on trivalent P show large chemical shift difference between the two fluorine atoms (4.4 ppm) accompanied by substantially different 1JPF coupling constants (1370 and 1291 Hz). Similar but smaller differences prevail between geminal CF3 substituents. Reaction of the new acid F(CF3)P(S)SH with CF3(F)PN(CH3)2 gave a mixture of (thiophosphorylthio)phosphine isomers each with two chiral phosphorus centers. Only partial assignment of the major features of this spectrum could be made.
REACTIONS OF BIS(TRIFLUOROMETHYL)NITROXYL WITH CF3PX2 (WHERE X=F, Cl, Br, I AND CN) AND P(CN)3
ANG, H. G.,SO, K. K.
, p. 221 - 242 (1982)
The reactions between bis(trifluoromethyl)nitroxyl and CF3PX2 (where X=F, Cl, Br and CN) in 2:1 molar ratio give addition products, 2P(CF3)X2.The bromo and cyano products are unstable.The former decomposes at room temperature to give bromine and perfluoro-2-azapropene, and the latter yields predominantly (CF3)2NOCF3.With CF3PI2, iodine displacement occurs to afford 2PCF3.On the other hand, P(CN)3 affords 3PO, (CF3)2NON(CF3)2 and paracyanogen.Mechanisms for these reactions are proposed.
Non-Arrhenius Behaviour in the Reaction of CF3 Radicals with CH3CN and CD3CN
Pasteris, L.,Staricco, E. H.
, p. 1303 - 1310 (1985)
Evidence is presented that rate measurements over a wide temperature range, 298-648 K, for the reaction of CF3 radicals with methyl cyanide show non-Arrhenius behaviour when the photolysis of trifluoromethyl iodide is used as a source radicals.The results presented here support the fact that the curved Arrhenius plot may be explained in terms of two reaction channels giving the same product, CF3H.One is the abstraction by the CF3 radicals and the other involves the iodine atom produced in the photolysis of CF3I.In order to obtain further information on the reaction mechanism the kinetic isotope effect has also been studied.
The gas-phase reaction of the CF3 radical with thiophene
Herrera, Olga S.,Nieto, Jorge D.,Lane, Silvia I.,Oexler, Elena V.
, p. 1477 - 1481 (2003)
The reaction of CF3 radicals, generated by photolysis of CF 3I or hexafluoroacetone with thiophene, was studied in the gas phase at 25°C. At conversion of thiophene less than 20%, monosubstituted CF 3-thiophenes were found as the main reaction products, in addition to CF3H, C2F6, and monosubstituted dihydro-CF3-thiophene, the latter in very low proportion. An isomeric mixture of 2- and 3-CF3-thiophene was obtained in a ratio of about 16, independent of the radical source used (CF3I or hexafluoroacetone) to produce the CF3 radicals. A plausible mechanism that accounts for the observed products is proposed, and the reactivity of thiophene toward the CF3 radical at 25°C was determined as kadd/kc1/2 = 106 ± 4 cm3/2 mol-1/2 s-1/2.
Conversion of CFC-13 to trifluoroacetic acid by electrochemical reaction with carbon dioxide
Sonoyama, Noriyuki,Sakata, Tadayoshi
, p. 444 - 445 (2002)
The electrochemical conversion of CFC-13 (CClF3) and carbon dioxide into trifluoroacetic acid (TFAA) was attempted at a Ag wire electrode under high pressure. TFAA was efficiently produced and the current efficiency was slightly dependent on the potential during electrolysis and pressure of co-existing carbon dioxide.
Trifluoromethylation et F-alkylation de l'acide sorbique
Requirand, N.,Andrieu, A.,Blancou, H.,Commeyras, A.
, p. 57 - 60 (1994)
5-Trifluoromethylhex-3-enoic and 5-F-alkylhex-3-enoic acids, respectively, are prepared in good yield by the reductive trifluoromethylation and F-alkylation of sorbic acid.
Evaluation of the kinetic parameters for the reaction of trifluoromethyl radicals with CH3Cl in the gas phase in temperature range from 416 to 63 K
Taccone,Olleta,Salinovich
, p. 353 - 362 (1993)
The hydrogen and chlorine atom abstraction reactions from CH3Cl by CF3 radicals produced by the photolysis of hexafluoroacetone (HFA) and CF3I were studied relative to the recombination of CF3 radicals:
Direct C(sp3)?H Trifluoromethylation of Unactivated Alkanes Enabled by Multifunctional Trifluoromethyl Copper Complexes
Choi, Geunho,Lee, Geun Seok,Park, Beomsoon,Kim, Dongwook,Hong, Soon Hyeok
supporting information, p. 5467 - 5474 (2021/01/20)
A mild and operationally simple C(sp3)?H trifluoromethylation method was developed for unactivated alkanes by utilizing a bench-stable CuIII complex, bpyCu(CF3)3, as the initiator of the visible-light photoinduced reaction, the source of a trifluoromethyl radical as a hydrogen atom transfer reagent, and the source of a trifluoromethyl anion for functionalization. The reaction was initiated by the generation of reactive electrophilic carbon-centered CF3 radical through photoinduced homolytic cleavage of bpyCu(CF3)3, followed by hydrogen abstraction from an unactivated C(sp3)?H bond. Comprehensive mechanistic investigations based on a combination of experimental and computational methods suggested that C?CF3 bond formation was enabled by radical–polar crossover and ionic coupling between the resulting carbocation intermediate and the anionic CF3 source. The methylene-selective reaction can be applied to the direct, late-stage trifluoromethylation of natural products and bioactive molecules.
