- THE FACILE PREPARATION OF HF FREE POLYFLUORINATED ACYL FLUORIDES
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The reaction of polyfluorinated acids with the Ishikawa Reagent (FAR) in the presence of NaF gives 59 - 91 percent isolated yields of HF free polyfluorinated acyl fluorides.The reaction is rapid, safe, easily scaled up, and amenable to a one-pot procedure.
- Cox, Daryl G.,Sprague, Lee G.,Burton, Donald J.
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Read Online
- Homogeneous catalytic hydrogenation of perfluoro methyl esters
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The first example of perfluoroalkyl methyl ester RfC(O)OMe (Rf = C3F7, C5F11) reduction by homogeneous catalytic hydrogenation with the ruthenium catalyst Ru-MACHO is herein reported. The hydrogenation process leads to the corresponding perfluorinated alcohols thus replacing sodium borohydride that has so far represented the state of art in perfluoro ester reduction.
- Lazzari, Dario,Cassani, Maria Cristina,Bertola, Maurizio,Moreno, Francisco Casado,Torrente, Damiano
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Read Online
- Method for preparing perfluoroisobutyryl fluoride by reaction kettle liquid-phase method
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The invention belongs to the field of fluorine chemical industry, and particularly relates to a method for preparing perfluoroisobutyryl fluoride by a reaction kettle liquid-phase method; the perfluoroisobutyryl fluoride is prepared with hexafluoropropylene and carbonyl fluoride as raw materials and a 2-perfluoroalkylbenzothiazole compound as a catalyst. Compared with a traditional reaction kettleliquid-phase one-pot method for preparing perfluorobutyryl fluoride, the method has the advantages that the 2-perfluoroalkylbenzothiazole compound is used as the catalyst, can be dissolved in an acetonitrile solvent and is uniformly coated around the raw material hexafluoropropylene, and the electron donor and acceptor properties of the perfluorobutyryl fluoride can tightly combine carbonyl fluoride free radicals, hexafluoropropylene free radicals and isobutyryl fluoride free radicals generated under an alkaline condition, so as to be beneficial to shortening the reaction time.
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Paragraph 0014-0016
(2020/02/10)
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- Trifluoromethyl Benzoate: A Versatile Trifluoromethoxylation Reagent
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Trifluoromethyl benzoate (TFBz) is developed as a new shelf-stable trifluoromethoxylation reagent, which can be easily prepared from inexpensive starting materials using KF as the only fluorine source. The synthetic potency of TFBz is demonstrated by trifluoromethoxylation-halogenation of arynes, nucleophilic substitution of alkyl (pseudo)halides, cross-coupling with aryl stannanes, and asymmetric difunctionalization of alkenes. The unprecedented trifluoromethoxylation-halogenation of arynes proceeds smoothly at room temperature with the aid of a crown ether-complexed potassium cation, which significantly stabilizes the trifluoromethoxide anion derived from TFBz.
- Zhou, Min,Ni, Chuanfa,Zeng, Yuwen,Hu, Jinbo
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supporting information
p. 6801 - 6805
(2018/05/31)
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- Heptafluorobutyric acid and preparation method of derivative thereof
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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.
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Paragraph 0102; 0103
(2017/07/18)
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- Products formed at intermediate stages of electrochemical perfluorination of propionyl and n-butyryl chlorides. Further evidence in support of NiF 3 mediated free radical pathway
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The partially fluorinated HF soluble intermediates formed during the electrochemical perfluorination of propionyl chloride (PC) and n-butyryl chloride (n-BC) were analyzed after passing 0%, 25%, 50%, 75% and 100% of theoretical charge required for the fluorination of PC and n-BC. The acid fluorides formed were converted to their corresponding sodium salt by alkali treatment and were separated by methanol extraction. The methanol was subsequently removed from the extract by vacuum distillation and the residue containing partially fluorinated sodium carboxylates was analyzed using 19F and 1H NMR spectra. Initial perfluorination on activated electrode surface indicates the operation of 'zipper-mechanism'. Formation of partially fluorinated product mixture, initial selectivity towards primary and secondary carbon, carbon chain isomerization and formation of cleaved and coupled products support the general operation of free radical pathway in the overall electrochemical process.
- Rangarajan,Sathyamoorthi,Velayutham,Noel,Singh,Brahma, Raju
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experimental part
p. 107 - 113
(2011/03/23)
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- HYDROFLUOROETHER COMPOUNDS AND PROCESSES FOR THEIR PREPARATION AND USE
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A hydrofluoroether compound comprises two terminal, independently fluoroalkyl or perfluoroalkyl groups and an intervening oxytetrafluoroethylidene moiety (—OCF(CF3)—) bonded through its central carbon atom to an alkoxy- or fluoroalkoxy-substituted fluoromethylene moiety (—CF(OR)—), each of the terminal groups optionally comprising at least one catenated heteroatom.
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Page/Page column 14-15
(2008/12/06)
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- FLUORINE-CONTAINING ETHER COMPOUND
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A novel fluorinated ether compound useful as an inert medium is provided. The compound is represented by the following formula (1) such as the compound represented by the following formula (1a) or the compound represented by the following formula (1b): ????????RF1OCFRF2CFRF2ORF1?????(1) ????????F (CF2)4OCF(CF3)CF(CF3)O(CF2)4F?????(1a) ????????F(CF2)6OCF(CF3)CF(CF3)O(CF2)6F?????(1b) wherein the symbols have the following meanings: RF1 is a C4-7 linear perfluoroalkyl group; andRF2 is a fluorine atom or a trifluoromethyl group.
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Page/Page column 10
(2008/06/13)
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- Carbon-chain isomerization during the electrochemical fluorination in anhydrous hydrogen fluoride - A mechanistic study
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The compounds i-C4H9SO2F, i-C3H7SO2F and cyclo-C3 H7C(O)F have been subjected to electrochemical fluorination in anhydrous hydrogen fluoride. The resulting products were fully analyzed by NMR spectroscopy. From the reaction balances, literature data and quantum chemical calculations, a new mechanism for carbon-chain isomerization during the electrochemical fluorination (ECF) is proposed. The key step in the formation of isomeric products is believed to be a ring closure reaction involving carbo-cationic or biradical intermediates.
- Ignat'ev, Nikolai V.,Welz-Biermann, Urs,Heider, Udo,Kucheryna, Andriy,von Ahsen, Stefan,Habel, Wolfgang,Sartori, Peter,Willner, Helge
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- Electrochemical fluorination of several methyl and/or ethyl esters of morpholino-substituted carboxylic acids
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Seven methyl and/or ethyl esters of carboxylic acids (-CH2CH2C(O)OEt, -CH2CH2CH2C(O)OMe, -CH2CH2CH2C(O)OEt, -CH(C2H5)C(O)OMe, -CH(n-C3H7)C(O)OMe, -CH2CH2CH2CH2C(O)OEt and -CH2CH2CH2CH2CH2C(O) OEt) having a morpholino group were subjected to electrochemical fluorination (ECF). On ECF, the corresponding perfluoroacid fluorides bearing a perfluoromorpholino group were obtained in fair to good yields. Yields of the targeted perfluoromorpholino-containing perfluoroacid fluorides were influenced by the α-bond cleavage of the carboxylic acid and also by the kind of alkyl group of the carboxylic acid (the latter offering the possibility of cyclization side reactions). Perfluorooxolanes were formed as a major cyclization by-product from the ECF of morpholino-substituted carboxylic acids when the chain length of the alkyl group of the carboxylic acids had a carbon number of three or more and the structure of the alkyl group was branched in such a way as to allow cyclization. Perfluorodioxolanes were obtained in only small yields as the specific cyclization products when the ethyl esters of carboxylic acids were subjected to ECF. Spectroscopic data, as well as physicochemical properties, are described for the new perfluoroheterocyclic compounds with a perfluoromorpholino group that were produced.
- Abe,Baba,Okuhara,Fukaya
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p. 115 - 128
(2007/10/03)
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- Electrochemical fluorination of 1-ethylpiperazine and 4-methyl- and/or 4-ethylpiperazinyl substituted carboxylic acid methyl esters
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Electrochemical fluorination (ECF) of 1-ethylpiperazine and eight methyl esters of 4-methyl- and/or 4-ethylpiperazinyl substituted carboxylic acids were studied. Corresponding perfluoro(4-fluoro-1-ethylpiperazine) was obtained from 1-ethylpiperazine in a small yield along with perfluoro(1-methyl-3-ethylimidazolidine), perfluoro[2-(N′,N′-difluoroaminoethyl)-N,N-diethylamine)] and perfluorotriethylamine. The corresponding mono-basic perfluoroacid fluorides with a perfluoro(4-alkylpiperazinyl) group were obtained in fair to good yields from the fluorination of methyl esters of 4-alkylpiperazinyl-substituted carboxylic acids. Yields of the targeted perfluoro(4-alkylpiperazinyl) group containing perfluorocarboxylic acid fluorides varied depending on both the type of N-alkyl (alkyl=CH3- or C2H5-) group at the 4-position and the (ω-methoxycarbonylalkyl) group at the 1-position of the piperazine ring of the substrate. Higher yields of perfluoroacid fluorides were obtained by the ECF of 4-ethyl substituted piperazine derivatives than of the 4-methyl substituted piperazine derivatives when 4-alkylpiperazines with the same carboxylic acid ester group were fluorinated electrochemically. Spectroscopic data as well as physical properties are described for new perfluoro(1,4-dialkylpiperazines) and N-containing perfluorocarboxylic acids with a perfluoropiperazinyl group.
- Abe, Takashi,Baba, Hajime,Soloshonok, Irina
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- Electrochemical fluorination of (N,N-dialkylamino)alcohols
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Series of amino alcohols including 2-(N,N-dialkylamino)ethanols, 3-(N,N-dimethylamino)propanol and 4-(N,N-dimethylamino)butanol were subjected to electrochemical fluorination. In the case of 2-(N,N-dialkylamino)ethanols, the F-(2-N,N-dialkylamino)acetyl fluorides were obtained in fair to good yields. Yields of each target compound were strongly dependent on the kind of the dialkylamino group. Cyclic amines having an N-(2-hydroxylethyl) group afforded the corresponding F-[N-(c-alkylamino)-substituted acetyl fluorides]. Their yields were generally better than those of acyclic analogs. Several 2-(N,N-dialkylamino)ethanols and 3-(N,N-dimethylamino)propanol were converted into the corresponding trimethylsilylethers, aminoalkyl methyl carbonates and bis-aminoalkyl carbonate, respectively, and they were subjected to fluorination for a comparison of the yield with that obtained from that of the parent aminoalcohol.
- Abe, Takashi,Fukaya, Haruhiko,Hayashi, Eiji,Ono, Taizo,Nishida, Masakazu,Soloshonok, Irina,Okuhara, Kunio
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p. 229 - 237
(2007/10/03)
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- Synthesis and studies of nucleophilic reactions of vicinal bis(fluorosulfonyloxy)perfluoroisononanes
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The addition of peroxydisulfuryl difluoride (FSO3)2 to isomeric perfluoroisononenes (perfluoropropylene trimers) was studied. Isomers containing the trisubstituted C=C bond form adducts which were converted to the corresponding ketofluorosulfates under the action of weak nucleophiles (DMF and AcONa/AcOH) and underwent haloform-type decomposition under the action of CsF to form perfluoroalkenyl fluorosulfates and products of their subsequent conversions.
- Avetisyan,Cherstkov,Tumanskii,Sterlin
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p. 2429 - 2433
(2007/10/03)
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- Some Novel Reactions of Perfluoro-2,3-dialkyloxaziridines
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Perfluoro-2,3-dialkyloxaziridines rearrange at 120-160 deg C into RfN=CF-OR'f quantitatively.Reaction with SbF5 at elevated temperature leads to the formation of the isomeric alkoxy imines RfON=CFR'f.Reaction with CsF in the absence of a solvent results in formation of a mixture of the corresponding acyl fluoride R'fC(O)F and N-fluoro imine R'fCF=NF.In contrast, reaction between perfluoro-2-butyl-3-propyloxaziridine and CsF in MeCN produces C4F9ON=CFC3F7.Interaction of this oxaziridine with polyfluoro ketones and COF2 in the presence of CsF in polar solvents leads to the formation of alkoxy imines R''fON=CFC3F7.
- Petrov, Viacheslav A.,DesMarteau, Darryl D.
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p. 505 - 510
(2007/10/02)
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- PERFLUOROACYLFLUOROSULFONYLFLUOROACETIC ESTERS
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In the presence of triethylamine the esters of fluorosulfonylfluoroacetic acid are acylated by the chlorides and anhydrides of perfluorinated carboxylic acids to form previously unknown esters of perfluoroacylfluorosulfonylfluoroacetic acids.A characteristic feature of the latter is the presence of carbonyl, alkoxycarbonyl, and fluorosulfonyl groups at one carbon atom.
- Eleev, A. F.,Ermolov, A. F.,Kutepov, A. P.,Sokol'skii, G. A.,Chekholin, V. K.
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p. 1467 - 1471
(2007/10/02)
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- Synthesis of Halogenated Esters of Fluorinated Carboxylic Acids by the Regio- and Stereospecific Addition of Acyl Hypochlorites to Olefins
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Addition reactions of the fluorinated acyl hypochlorites CF3CO2Cl, C2F5CO2Cl, n-C3F7CO2Cl, ClCF2CO2Cl, and HCF2CO2Cl with CF2=CF2 and CF2=CH2 form the respective esters in varying yields.The reactions are regiospecific with CF2=CH2.Additional reactions of CF3CO2Cl with CF2=CFCl, CF2=CCl2, CH2=CH2, and cis- and trans-CFH=CFH further illustrate the potential of the acyl hypochlorites for the synthesis of a variety of esters.In addition, the latter reactions provide further examples of the regiospecificity of these additions and two examples of their stereospecificity.A concerted cis addition is proposed.The new esters exhibit excellent thermal stability, but are unstable in the presence of KF.
- Tari, Isao,DesMarteau, Darryl D.
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p. 1214 - 1217
(2007/10/02)
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