1549-45-7Relevant academic research and scientific papers
Mechanism of Addition of Neat Trifluoroacetic Acid to Protoadamantene
Nordlander, J. Eric,Haky, Jerome E.,Landino, John P.
, p. 7487 - 7493 (1980)
Protoadamantene (1) reacts smoothly with neat trifluoroacetic acid at 25 deg C to give 2-adamantyl trifluoroacetate (2-OTFA) and a trace of metastable exo-4-protoadamantyl trifluoroacetate (4-OTFA), which isomerizes to 2-OTFA.The rearrangement attending a
Selective Markovnikov's Addition of Trifluoroacetic Acid to Alkenes using Vanadium(v) Oxide
Choudary, B. M.,Reddy, P. N.
, p. 405 - 407 (1993)
A simple and efficient method for trifluoroacetoxylation of alkenes using catalytic amounts of V2O5 in trifluoroacetic acid to give the Markovnikov's product selectively in excellent yields for the first time is described.
Observations on the transition-metal catalysed oxidation of alkanes in trifluoroacetic acid: Urea-hydrogen peroxide/TFA as a convenient method for the oxidation of unactivated C-H bonds
Moody, Christopher J.,O'Connell, Jenny L.
, p. 1311 - 1312 (2000)
Oxidation of cyclohexane in TFA using 30% aqueous H2O2 or urea-H2O2 (UHP) gives cyclohexyl trifluoroacetate in good yield, although the reaction is not accelerated by rhodium or ruthenium catalysts casting doubt
Synthesis and Structure of New Pt(IV) Perfluorocarboxylate Complexes and Their Reactivity with Respect to Alkanes and Cycloalkanes
Stolyarov,Cherkashina,Churakov,Naumkin,Kornev,Chernyak,Martynenko
, p. 49 - 55 (2019)
New Pt(IV) perfluorocarboxylate complexes of the composition [Pt(RFCOO)4]n and M2[Pt(RFCOO)6] (RF = CF3, C2F5; M = Li, Na, K, Rb, Cs, NMe4/
Electrocatalytic Oxyesterification of Hydrocarbons by Tetravalent Lead
Haviv, Eynat,Herman, Adi,Khenkin, Alexander M.,Neumann, Ronny
, p. 10494 - 10501 (2021)
The selective catalytic oxidative monofunctionalization of gaseous alkanes found in natural gas and commodity chemicals such as benzene and cyclohexane is an important objective in the field of carbon-hydrogen bond activation. Past research has demonstrated the possibility of stoichiometric oxyesterification of such substrates using lead(IV) trifluoroacetate (PbIV(TFA)4) as oxidant, which is driven by the high 2-electron redox potential of lead(IV). However, this redox potential then precludes reoxidation of lead(II) by a convenient oxidant such as O2, nullifying an effective catalytic cycle. In order to utilize renewable energy resources as alternatives to high-temperature thermocatalysis, we demonstrate the room-temperature electrocatalytic oxyesterification of alkanes and benzene with PbIV(TFA)4 as catalysts. At 1.67 V versus SHE, alkanes and benzene yielded the corresponding trifluoroacetate esters at room temperature; typically, good yields and high faradaic efficiencies were observed. High intrinsic turnover frequencies were obtained, for example, of >1000 min-1 for the oxyesterification of ethane at 30 bar. An analysis of the possible mechanistic pathways based on previously investigated stochiometric reactions, cyclic voltammetry measurements, kinetic isotope effects, and model compounds led to the conclusion that catalysis involves lead-mediated proton-coupled electron transfer of alkanes at and to the anode, followed by reductive elimination through an SN2 reaction to yield the alkyl-TFA products. Similarly, lead-mediated electron transfer from benzene at and to the anode leads to phenyl-TFA. Cyclic voltammetry also shows the viability of in situ reoxidation of Pb(II) species. The synthesis results obtained as well as the mechanistic insight are important advances towards the realization of selective alkane and arene oxidation reactions.
Enthalpies of Hydration of Alkenes. 3. Cycloalkenes
Wiberg, Kenneth B.,Wasserman, David J.,Martin, Eric J.,Murcko, Mark A.
, p. 6019 - 6022 (1985)
The enthalpies of reaction of cyclopentene, cyclohexene, 1-methylcyclopentene,methylcyclohexane, methylenecyclopentane, 1-methylcyclohexene, bicyclohept-2-ene, and bicyclohex-2-ene with trifluoroacetic acid were measured.This gives the diff
Aerobic Partial Oxidation of Alkanes Using Photodriven Iron Catalysis
Coutard, Nathan,Goldberg, Jonathan M.,Valle, Henry U.,Cao, Yuan,Jia, Xiaofan,Jeffrey, Philip D.,Gunnoe, T. Brent,Groves, John T.
supporting information, p. 759 - 766 (2022/01/11)
Photodriven oxidations of alkanes in trifluoroacetic acid using commercial and synthesized Fe(III) sources as catalyst precursors and dioxygen (O2) as the terminal oxidant are reported. The reactions produce alkyl esters and occur at ambient temperature in the presence of air, and catalytic turnover is observed for the oxidation of methane in a pure O2 atmosphere. Under optimized conditions, approximately 17% conversion of methane to methyl trifluoroacetate at more than 50% selectivity is observed. It is demonstrated that methyl trifluoroacetate is stable under catalytic conditions, and thus overoxidized products are not formed through secondary oxidation of methyl trifluoroacetate.
METHOD FOR PRODUCING DICARBOXYLIC ACID
-
Paragraph 0118, (2021/05/21)
A method for producing dicarboxylic acid. The method includes: subjecting a raw material system including a cyclic olefin and a lower monocarboxylic acid to an addition reaction in the presence of an addition reaction catalyst to generate an intermediate product system including cyclic carboxylic acid ester; and subjecting the intermediate product system including cyclic carboxylic acid ester to a ring-opening and oxidation reaction in the presence of an oxidant and an oxidation catalyst to generate a corresponding dicarboxylic acid product. The addition reaction in the dicarboxylic acid synthesis route achieves a high single-pass conversion rate, and the selectivity of the corresponding cyclic carboxylic acid ester is high. The addition-oxidation synthesis route achieves faster reaction rates for both the addition reaction and oxidation reaction, and high yield of corresponding dicarboxylic acid product. The addition-oxidation based synthesis route is suitable for continuous, stable and large-scale production of corresponding dicarboxylic acid product.
Selective Photo-Oxygenation of Light Alkanes Using Iodine Oxides and Chloride
Liebov, Nichole S.,Goldberg, Jonathan M.,Boaz, Nicholas C.,Coutard, Nathan,Kalman, Steven E.,Zhuang, Thompson,Groves, John T.,Gunnoe, T. Brent
, p. 5045 - 5054 (2019/10/28)
Partial oxidation of light alkanes to generate alkyl esters has been achieved under photochemical conditions using mixtures of iodine oxides and chloride salts in trifluoroacetic acid (HTFA). The reactions are catalytic in chloride and are successful using compact fluorescent light, but higher yields are obtained using a mercury lamp. In this photo-initiated oxyesterification process, the robust alkyl ester products are resistant to over-oxidation, and under optimized conditions yields for alkyl ester production of ～50 % based on methane, ～60 % based on ethane (with a total functionalized yield of EtX (X=TFA or Cl) of 80 %) and ～30 % based on propane have been demonstrated. The reaction also proceeds in aqueous HTFA and dichloroacetic acid with lower yields. Mechanistic studies indicate that the process likely operates by a chlorine hydrogen atom abstraction pathway wherein alkyl radicals are generated, trapped by iodine, and converted to alkyl trifluoroacetates in situ.
Trifluoroacetic acid promoted hydration of styrene catalyzed by sulfonic resins: Comparison of the reactivity of styrene, n-hexene and cyclohexene
Bianchini, Edoardo,Pietrobon, Luca,Ronchin, Lucio,Tortato, Claudio,Vavasori, Andrea
, p. 130 - 138 (2018/11/26)
Alcohol production by olefin hydration is an important reaction in the modern intermediate chemistry. The use of trifluoroacetic acid (TFA) could be a way to increase alcohol productivity by addition of the TFA to the double bond forming the corresponding ester. The product obtained by addition is then hydrolyzed to alcohol by sulfonic resins. The study of the overall multiphase equilibrium aqueous TFA solution/olefin ester cyclohexene is carried out together with the initial rate of reaction for cyclohexene hydration. Reaction profiles and a likely reaction path is also given. The influence of the operative variable on both equilibria and initial reaction rate are studied in the range of temperature typical of the sulfonic resin as catalysts (383–413 K). The use of aqueous TFA allows fast reaction and high conversion as well as an easily separable aqueous system compared with other organic acid.
