375-22-4Relevant articles and documents
Dibutyltin perfluoroalkanecarboxylates: Synthesis, NMR characterization and in vitro antitumour activity
Kemmer, Martine,Dalil, Hassan,Biesemans, Monique,Martins, José C.,Mahieu, Bernard,Horn, Ernst,De Vos, Dick,Tiekink, Edward R. T.,Willem, Rudolph,Gielen, Marcel
, p. 63 - 70 (2000)
Three dibutyltin perfluoroalkanecarboxylates have been synthesized, characterized by 1H-, 13C-, 19F- and 117Sn-NMR, M?ssbauer, IR and mass spectroscopy. The structure of tetra-n-butylbis(trifluoroacetato)distann
Aerobic biotransformation studies of two trifluoromethoxy-substituted aliphatic alcohols and a novel fluorinated C3-based building block
Fr?mel, Tobias,Knepper, Thomas P.
, p. 80 - 89 (2015)
Fluorinated substances play a significant role for many industrial and consumer products, but many of these chemicals are attributed with an adverse ecological profile and persistence in the environment. Herein, three potentially more environmentally benign substitutes were assessed for aerobic biotransformation, namely 3-(trifluoromethoxy)-propan-1-ol (TFMPrOH), 6-(trifluoromethoxy)-hexan-1-ol (TFMHxOH) and 1-(2,2,3,3,4,4,4-heptafluorobutoxy)-propan-2-ol (HFBPrOH). Analytical techniques involved different HPLC-ESI-MS/MS techniques as well as determination of fluoride in order to assess the extent of mineralization. The two trifluoromethoxy-substituted alcohols showed very different results concerning mineralization. Whereas TFMPrOH only yielded approximately 15% fluoride, TFMHxOH reached nearly quantitative release of fluoride after 37 days. The latter one yielded 6-trifluoromethoxy hexanoic acid (TFMHxA) as well as trifluoromethyl carbonate (TFMC) as transient transformation products, both of which were entirely degraded. TFMC was also detected during biotransformation of TFMPrOH, however, the major transformation product was 3-trifluoromethoxy-propanoic acid (TFMPrA), which did not show any further degradation within a 47 days period. The third compound under investigation, HFBPrOH, expectedly yielded perfluorobutanoic acid as a stable biotransformation product. Several acidic biotransformation intermediates as well as heptafluorobutan-1-ol were identified and a biotransformation pathway was postulated. TFMHxOH might therefore be incorporated into fluorinated substances, for instance by ester linkages assuming that biotransformation of such substances would yield the alcohol.
Electrocatalytic degradation of perfluorooctanoic acid by LaNixY1-xO3 (Y = Fe, Cu, Co, Sr) gas dispersion electrode
Chen, Yongyang,Guo, Dan,Dong, Xiaochun,Li, Yahui,Huang, Yixuan,Chen, Hao,Li, Shanping
, (2020/12/23)
Perfluorooctanoic acid (PFOA), as a refractory organic pollutant, seriously harms the environment and damages human health. Here, the electrocatalytic method was selected to degrade PFOA. In this work, perovskite catalysts doped with different elements, and corresponding gas diffusion electrodes (GDE) were prepared by the gel-sol method and citric acid complexation method. The crystal structure, microscopic morphology, and electrochemical properties of the LaNixY1-xO3 (Y = Fe, Cu, Co, Sr) perovskite catalyst electrode were analyzed by XRD, TEM, and CV. Moreover, the electrocatalytic performances of the as-prepared electrodes were assessed by the degradation of PFOA, and the Sr-doped GDE exhibited the highest degradation rate of PFOA. The optimum degradation conditions, such as the current density, pH, and initial concentration were also investigated. It was observed that when the current density was 20 mA/cm2, pH was 5, and initial concentration was 0.25 mmol/L, the Sr-doped GDE had the best degradation and defluorination efficiency of PFOA reached 90.0 % and 75.1 %, respectively. High performance liquid chromatography-mass spectrometry (HPLC-MS) was used to analyze the intermediate products of PFOA degradation and obtain the degradation pathway. With the combined action of [rad]OH and O2, PFOA was degraded by stepwise removal of CF2 groups, which were ultimately degraded into F? and CO2.
Oxidation of fluoroalkyl alcohols using sodium hypochlorite pentahydrate [1]
Kirihara, Masayuki,Suzuki, Katsuya,Nakakura, Kana,Saito, Katsuya,Nakamura, Riho,Tujimoto, Kazuki,Sakamoto, Yugo,Kikkawa, You,Shimazu, Hideo,Kimura, Yoshikazu
, (2021/02/05)
Fluoroalkyl alcohols are effectivity oxidized to the corresponding fluoroalkyl carbonyl compounds by reaction with sodium hypochlorite pentahydrate in acetonitrile in the presence of acid and nitroxyl radical catalysts. Although the reaction proceeded slower under a nitroxyl radical catalyst- free condition, the desired carbonyl compounds were obtained in high yields. For the reaction with fluoroalkyl allylic alcohols, the corresponding α,β-epoxyketone hydrates were obtained in high yields.
Heptafluorobutyric acid and preparation method of derivative thereof
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Paragraph 0102; 0105-0107, (2017/07/18)
The invention provides a preparation method of heptafluorobutyric acid. The preparation method comprises the following steps: (A) carrying out an electrochemical fluoridation reaction on n-butyric acid, n-butyryl chloride or n-butyryl fluoride with anhydrous hydrogen fluoride, thus obtaining an electrolytic mixed gas, wherein the current density of the electrochemical fluoridation reaction is 0.025 to 0.033 A/cm, and the reaction temperature is 9 to 13 DEG C; a cooling reflux device is arranged in the electrochemical fluoridation reaction, and the temperature of a cooling medium of the cooling reflux device is -45 DEG C; (B) pumping the electrolytic mixed gas obtained in the step (A) into a reaction kettle filled with an acid-binding agent, thus obtaining heptafluorobutyryl fluoride, wherein the acid-binding agent is triethylamine; (C) mixing the heptafluorobutyryl fluoride obtained in the step (B) with water, and hydrolyzing, thus generating a heptafluorobutyric acid water solution; (D) mixing the heptafluorobutyric acid water solution with KOH, and naturally crystallizing until the concentration of the KOH is 40 to 45 percent, thus obtaining potassium heptafluorobutyrate; (E) acidizing the potassium heptafluorobutyrate by using sulfuric acid, thus obtaining the heptafluorobutyric acid.
Approaches to prepare perfluoroalkyl and pentafluorophenyl copper couples for cross-coupling reactions with organohalogen compounds
Kremlev, Mikhail M.,Mushta, Aleksej I.,Tyrra, Wieland,Yagupolskii, Yurii L.,Naumann, Dieter,Sch?fer, Mathias
, p. 19693 - 19699 (2015/11/27)
The reactions of iodoperfluoroalkanes CnF2n+1I (n = 2, 3, 4) and n-BuLi at low temperatures give NMR spectroscopic evidence for LiCnF2n+1 which were converted into LiCu(CnF2n+1)2 derivatives upon treatment with 0.5 mol copper(i) bromide, CuBr. An alternative route to obtain perfluoroorgano copper couples, Cu(Rf)2Ag (Rf = n-C3F7, n-C4F9, C6F5) was achieved from the reactions of the corresponding perfluoroorgano silver(i) reagents, AgRf, and elemental copper through redox transmetallations. The composition of the resulting reactive intermediates was investigated by means of 19F NMR spectroscopy and ESI mass spectrometry. Perfluoro-n-propyl and perfluoro-n-butyl copper-silver reagents prepared by the oxidative transmetallation route exhibited good properties in C-C bond formation reactions with acid chlorides even under moderate conditions. Substitution of bromine directly bound to aromatics for perfluoroalkyl groups was achieved at elevated temperatures, while success in halide substitution reactions using lithium copper couples remained poor.
The effect of oxygen in the photocatalytic oxidation pathways of perfluorooctanoic acid
Sansotera, Maurizio,Persico, Federico,Rizzi, Valentina,Panzeri, Walter,Pirola, Carlo,Bianchi, Claudia L.,Mele, Andrea,Navarrini, Walter
, p. 159 - 168 (2015/11/10)
The influence of oxygen in the photocatalytic oxidation of perfluorooctanoic acid (PFOA) promoted by a commercial nano-sized titanium dioxide was studied by testing the reaction in different conditions: static air, oxygen flux, nitrogen flux and pre-saturated nitrogen flux. The reaction was monitored by Total Organic Carbon (TOC) analysis and Ionic Chromatography (IC). Shorter chain perfluorocarboxylic acids (PFCAs; Cn, n = 1-7) intermediate degradation products were quantitatively determined by High-Performance Liquid Chromatography combined with Mass Spectrometry (HPLC-MS) analysis. The presence of shorter chain PFCAs in solution was also monitored by 19F NMR. The experimental findings are in agreement with two major oxidative pathways: Cn → Cn-1 photo-redox and β-scissions routes mediated by COF2 elimination. Depending on the experimental conditions, the mutually operating mechanisms could be unbalanced up to the complete predominance of one pathway over the other. In particular, the existence of the β-scissions route with COF2 elimination was corroborated by the isolation and characterization of carbonyl difluoride, a predicted fluorinated decomposition by-product.
Free-radical selective functionalization of 1,4-naphthoquinones by perfluorodiacyl peroxides
Sansotera, Maurizio,Gambarotti, Cristian,Famulari, Antonino,Baggioli, Alberto,Soave, Raffaella,Venturini, Francesco,Meille, Stefano V.,Wlassics, Ivan,Navarrini, Walter
, p. 5298 - 5309 (2014/07/08)
Perfluoroalkyl radicals, generated by thermal decomposition of perfluorodiacyl peroxides, react selectively with quinone rings of 1,4-naphthoquinones. In the presence of a non-conjugated alkene such as 1-hexene, perfluoroalkyl radicals add to the double bonds of the olefin forming a radical adduct, which selectively adds to the naphthoquinone ring. Several perfluorodiacyl peroxides have been synthesized and used for the direct and alkene-mediated functionalization of naphthoquinones. Geometrical parameters and electron density topology of all perfluorodiacyl peroxides have been calculated by the density functional formalism and quantum theory of atoms in molecules to attempt a rationalization of the experimental reactivity.
Nucleofugality of aliphatic carboxylates in mixtures of aprotic solvents and water
Mati, Mirela,Denegri, Bernard,Kronja, Olga
, p. 375 - 384 (2015/10/12)
The leaving group ability (nucleofugality) of fluoroacetate, chloroacetate, bromoacetate, dichloroacetate, trifluoroacetate, trichloroacetate, heptafluorobutyrate, formate, isobutyrate, and pivalate have been derived from the solvolysis rate constants of the corresponding X,Y-substituted benzhydryl carboxylates in 60 % and 80 % aqueous acetonitrile and 60 % aqueous acetone, applying the LFER equation: log k = sf(Ef + Nf). The experimental barriers (ΔG?,exp) for solvolyses of 11 reference dianisylmethyl carboxylates in these solvents correlate very well (r = 0.994 in all solvents) with ΔG?,model of the model σ-assisted heterolytic displacement reaction of cis-2,3-dihydroxycyclopropyl trans-carboxylates calculated earlier. Linear correlation observed between the log k for the reference dianisylmethyl carboxylates and the sf values enables estimation of the reaction constant (sfestim). Using the ΔG?,exp vs. ΔG?,model correlation, and taking the estimated sfestim, the nucleofugality parameters for other 34 aliphatic carboxylates have been determined in 60 % and 80 % aqueous acetonitrile and 60 % aqueous acetone. The most important variable that determines the reactivity of aliphatic carboxylates in aprotic solvent/water mixtures is the inductive effect of the group(s) attached onto the carboxylate moiety.
A general, regiospecific synthetic route to perfluoroalkylated arenes via arenediazonium salts with RFCu(CH3CN) complexes
Jiang, Dong-Fang,Liu, Chao,Guo, Yong,Xiao, Ji-Chang,Chen, Qing-Yun
supporting information, p. 6303 - 6309 (2015/03/30)
A mild method of converting arylamines into perfluoroalkylated arenes is described. Relatively stable RFCu(CH3CN) complexes are used as perfluoroalkylating agents, which react smoothly with arenediazonium salts to produce various perfluoroalkylarenes in good yields. Based on the results of clock trapping experiments with diallyl ether, a radical process might be involved in the reaction.
