- THERMOLYSE DES ANHYDRIDES PERFLUOROALCANESULFONIQUES. MECANISME ET APPLICATION A LA SYNTHESE DES ESTERS RFSO3RF.
-
Perfluoroalkanesulfonic anhydrides FSO2)2O ; RF=CF3,C2F5,C4F9>, mixed with the parent acid, decompose thermally to give the corresponding perfluoroalkyl perfluoroalkanesulfonates (RFSO3RF) with liberation of SO2.If the perfluoroalkyl moieties in the anhydride and the acid are different, a mixture of symmetric and unsymmetric esters is obrained.An ionic bimolecular mechanism is deduced from the results, and a new easy synthesis of the symmetric perfluorinated sulfonic esters is proposed.
- Oudrhiri-Hassani, M.,Brunel, D.,Germain, A.,Commeyras, A.
-
-
Read Online
- Gas-phase structure and vibrational properties of trifluoromethyl trifluoromethanesulfonate, CF3SO2OCF3
-
Trifluoromethyl trifluoromethanesulfonate, CF3SO 2OCF3, has been synthesised and its gas-phase structure determined from electron-diffraction data. This structural study was supported by HF, MP2 and DFT (B3LYP and B1B95) calculations, which revealed a strong dependence of the theoretical structure on the polarisation of the basis set. Infrared spectra for the gas and solid and a Raman spectrum for the liquid were obtained, and the observed bands were assigned. The experimental vibrational data, along with theoretical (B3LYP) force constants, were used to define a scaled quantum mechanical force field, which enabled reproduction of the measured frequencies with a final root-mean-square deviation of 6 cm -1. Wiley-VCH Verlag GmbH & Co. KGaA, 2007.
- Tuttolomondo, Maria E.,Arganaraz, Pablo E.,Varetti, Eduardo L.,Hayes, Stuart A.,Wann, Derek A.,Robertson, Heather E.,Rankin, David W. H.,Altabef, Aida Ben
-
-
Read Online
- Palladium(II)-Catalyzed Enantioselective Aminotrifluoromethoxylation of Unactivated Alkenes using CsOCF3 as a Trifluoromethoxide Source
-
Asymmetric PdII-catalyzed intramolecular aminotrifluoromethoxylation of unactivated alkenes using readily accessible and stable CsOCF3 as a trifluoromethoxide source has been developed, which affords a wide variety of enantiomerically enriched β-substituted OCF3-containing piperidines in good yields. Introducing a sterically bulky group into pyridine-oxazoline (Pyox) ligands is crucial to increasing both reactivity and enantioselectivity for the reaction. Additionally, the reaction features good functional group compatibility and mild reaction conditions.
- Chen, Chaohuang,Pflüger, Philipp Miro,Chen, Pinhong,Liu, Guosheng
-
-
Read Online
- THERMAL STABILITY OF PERFLUOROALKANESULFONIC ACIDS AND THEIR ANHYDRIDES. NEW AND EASY APPROACH TO RFSO2ORF ESTERS.
-
Perfluoroalkanesulfonic anhydrides (RFSO2)2O when mixed with acids decompose into perfluoroalkanesulfonic esters RFSO2ORF, thereby providing a new facile synthesis of these esters from perfluoroalkanesulfonic acids and phosphorus pentoxide.
- Hassani, M. Oudrhiri,Germain, A.,Brunel, D.,Commeyras, A.
-
-
Read Online
- Tertiary-Amine-Initiated Synthesis of Acyl Fluorides from Carboxylic Acids and CF3SO2OCF3
-
A convenient method for deoxyfluorination of aromatic and aliphatic carboxylic acids with CF3SO2OCF3 in the presence of a suitable base at room temperature has been developed. The reaction allows a straightforward access to a variety of acyl fluorides and proves that CF3SO2OCF3 is an effective deoxyfluorination reagent for carboxylic acids. The method features simplicity, expeditiousness, high efficiency, ease of handling, good functional group tolerance, a wide range of substrates, excellent yields of products, compatibility of many amine initiators, use of environmentally friendly reagents, and effortless removal of byproducts. This reaction represents the first utilization of trifluoromethyl trifluoromethanesulfonate as a fluorination reagent.
- Song, Hai-Xia,Tian, Ze-Yu,Xiao, Ji-Chang,Zhang, Cheng-Pan
-
supporting information
p. 16261 - 16265
(2020/12/01)
-
- Silver-Mediated Trifluoromethoxylation of (Hetero)aryldiazonium Tetrafluoroborates
-
Here we report a silver-mediated trifluoromethoxylation of (hetero)aryldiazonium tetrafluoroborates by converting an aromatic amino group into an OCF3 group. This method, which can be considered to be a trifluoromethoxylation variation of the classic Sandmeyer-type reaction, uses readily available aryl and heteroaromatic amines as starting materials and AgOCF3 as trifluoromethoxylating reagents. The broad substrate scope and simple, mild reaction condition made this transformation a valuable method in constructing aryl-OCF3 bonds.
- Yang, Yu-Ming,Yao, Jian-Fei,Yan, Wei,Luo, Zhuangzhu,Tang, Zhen-Yu
-
supporting information
p. 8003 - 8007
(2019/10/11)
-
- Synthesis of heteroaromatic trifluoromethyl ethers with trifluoromethyl triflate as the source of the trifluoromethoxy group
-
A series of nitrogen-heterocycles have been transformed to the corresponding trifluoromethyl or higher perfluoroalkyl ethers by reaction of the corresponding N-oxides with trifluoromethyl or higher perfluoroalkyl triflate. Trifluoromethyl triflate, which has generally been used as a precursor to [OCF3]?, is used here as a bifunctional reagent to render the heteroarene more electrophilic and to deliver the trifluoromethoxy group. This reagent was easily prepared on a large scale (>100 grams) and is stable in either pure form or as a stock solution. Applications and limitations of this method are reported.
- Zhang, Qing-Wei,Hartwig, John F.
-
supporting information
p. 10124 - 10127
(2018/09/18)
-
- Silver-mediated direct trifluoromethoxylation of α-diazo esters: Via the -OCF3 anion
-
Silver-mediated direct trifluoromethoxylation of α-diazo esters and ketosteroid was disclosed. The reactions of alkyl α-diazo arylacetates with AgOCF3 or CF3SO2OCF3/AgF at -30 to 10 °C under a N2 atmosphere provided α-trifluoromethoxyl arylacetates in up to 90% yield, while alkyl α-diazo vinylacetates reacting with CF3SO2OCF3/AgF or AgOCF3 afforded γ-trifluoromethoxyl α,β-unsaturated esters in up to 94% yield. The α-diazo ketosteroid was also trifluoromethoxylated under the standard reaction conditions. This protocol allows for an effective and convenient access to a large number of synthetic building blocks, which are promising in the development of new functional OCF3-molecules.
- Zha, Gao-Feng,Han, Jia-Bin,Hu, Xiao-Qian,Qin, Hua-Li,Fang, Wan-Yin,Zhang, Cheng-Pan
-
supporting information
p. 7458 - 7461
(2016/06/14)
-
- PRODUCTION METHOD OF PERFLUOROALKYLPERFLUOROALKANE SULFONATE
-
PROBLEM TO BE SOLVED: To produce perfluoroalkylperfluoroalkane sulfonate efficiently with high selectivity. SOLUTION: A production method of perfluoroalkylperfluoroalkane sulfonate includes a step of introducing perfluoroalkanesulfonic acid preliminarily into a reaction vessel and adding perfluoroalkanesulfonic acid anhydride successively to the sulfonic acid to obtain a mixture comprising perfluoroalkylperfluoroalkane sulfonate and sulfur dioxide and a step of drawing the mixture from the reaction container, with the steps carried out continuously. COPYRIGHT: (C)2016,JPOandINPIT
- -
-
Paragraph 0051
(2016/12/26)
-
- METHOD FOR PRODUCING FLUOROALKANESULFONIC ANHYDRIDE
-
Disclosed is a method for producing a fluoroalkanesulfonic anhydride, which is characterized by that a reaction is conducted while kneading a fluoroalkanesulfonic acid and diphosphorus pentoxide at a temperature that is 40 °C or higher and is lower than 100 °C by using a kneader-type reactor having a maximum power of 1.0 kW or greater per an actual capacity of 100 L and equipped with at least two-shaft blades, that the fluoroalkanesulfonic anhydride to be generated is discharged, and that, while the residue in the reactor after the discharge is kneaded at a temperature that is 100 °C or higher and is lower than 140 °C, the unreacted fluoroalkylsulfonic acid is discharged, recovered and reused as the raw material. It is possible by this method to obtain a fluoroalkanesulfonic anhydride with a high yield.
- -
-
Paragraph 0094-0096
(2014/11/12)
-
- Efficient synthesis of 5′-fluoroalkoxythiazoles via α-bromo-α-fluoroalkoxyacetophenones Hantzsch type cyclization with thioureas or thioamides
-
Novel α-fluoroalkoxyacetophenones were synthesized by addition of the readily available 2,2-dimethoxy-2-phenylethanol to fluoroolefins. α-Bromination yielded α-bromo-α-fluoroalkoxyacetophenones, which on treatment with thioureas or thioamides gave thiazoles with fluoroalkoxy groups at the 5′-position by the Hantzsch-type cyclization. This provides a versatile methodology for the construction of heterocycles from aliphatic fluoroalkoxy containing building blocks.
- Sokolenko, Taras M.,Davydova, Yulia A.,Yagupolskii, Yurii L.
-
body text
p. 20 - 25
(2012/06/30)
-
- Interaction of acetonitrile with trifluoromethanesulfonic acid: Unexpected formation of a wide variety of structures
-
Interaction of acetonitrile with trifluoromethanesulfonic acid has been studied by multinuclear NMR and ESI-MS. It has been found that the interaction results in formation of a great variety of different cations and neutral compounds which is controlled by the ratio of CH3CN to TfOH. In the presence of an excess of the acid (molar ratio 1:8-14) diprotonated N-acetylacetamidine 1 is formed as the major product, which eventually transforms into protonated acetamidine 3 and acetic acid 4. At molar ratio of (1:1-2) diprotonated 2,4-dimethyl-6-methylidene-3H-1,3,5-triazine 12, tautomer of the diprotonated trimethyl-s-triazine 11, becomes the main product at an early stage of the reaction and diprotonated 1-(dimethyl-1,3,5-triazin-2-yl) prop-1-en-2-ol 15 at a later stage. In the case of a large excess of acetonitrile (4-20:1) trication 17 is formed as a result of the interaction between 11 and 12 along with some oligomers [(CH3CN) 3]n (n = 4-12). The Royal Society of Chemistry 2012.
- Salnikov, George E.,Genaev, Alexander M.,Vasiliev, Vladimir G.,Shubin, Vyacheslav G.
-
supporting information; experimental part
p. 2282 - 2288
(2012/04/10)
-
- Silver-mediated trifluoromethoxylation of aryl stannanes and arylboronic acids
-
A silver-mediated cross-coupling of trifluoromethoxide with aryl stannanes and arylboronic acids to give aryl trifluoromethyl ethers is reported. This is the first report of a transition-metal-mediated Caryl-OCF3 bond formation.
- Huang, Chenghong,Liang, Theresa,Harada, Shinji,Lee, Eunsung,Ritter, Tobias
-
supporting information; experimental part
p. 13308 - 13310
(2011/10/10)
-
- CF3 oxonium salts, O-(trifluoromethyl)dibenzofuranium salts: In situ synthesis, properties, and application as a real CF3+ species reagent
-
(Chemical Equation Presented) We report in situ synthesis of the first CF3 oxonium salts, thermally unstable O-(trifluoromethyl)- dibenzofuranium salts, which furthermore have different counteranions (BF 4-, PF6-, SbF6 -, and Sb2F11-) and ring substituents (tert-butyl, F, and OCH3), by photochemical decomposition of the corresponding 2-(trifluoromethoxy)biphenylyl-2′- diazonium salts at -90 to -100°C. The yields markedly increased in the order of BF4- 6- 6- 2F11-. The CF3 oxonium salts were fully assigned by means of 1H and 19F NMR spectroscopy at low temperature. The CF3 salts decomposed to form CF4 and dibenzofurans. The half-life times at -60°C of the 2-tert-butyl salts having different counteranions were 29 min for BF4- salt 2d, 36 min for PF6- salt 2c, 270 min for SbF6- salt 2a, and 415 min for Sb2F11- salt 2b. Those at -60°C of the Sb2F11- salts having different 2-substituents were 13 min for F salt 3b, 63 min for H (unsubstituted) salt 1b, and 415 min for tert-butyl salt 2b. Thus, the stability of the CF3 oxonium salts increased in the order of BF4- 6 - 6- 2F 11- and F 3+ species source to the direct O- and N-trifluoromethylations of alcohols, phenols, amines, anilines, and pyridines under very mild conditions. The thermal decomposition method with a mixture of diazonium salt 17a and aryl- or alkylsulfonic acids, pyridine, or pyridines having an electron-withdrawing group also afforded CF3O or CF 3N products. The trifluoromethylation mechanism is discussed and an SN2 mechanism containing the transient formation of free CF 3+ is proposed. Thus, the present study has demonstrated that the exceedingly reactive CF3+ species can be generated much easier than the CH3+ species, contrary to the common sense that CF3+ is extremely difficult to generate in solution.
- Umemoto, Teruo,Adachi, Kenji,Ishihara, Sumi
-
p. 6905 - 6917
(2008/02/11)
-
- THE THERMAL CLEAVAGE OF BORON TRIS-TRIFLUOROMETHANESULFONATE (TRIFLATE) AND BORON TRIS-PENTAFLUOROETHANESULFONATE (PENTFLATE) TO TRIFLIC (PENTFLIC) ANHYDRIDE AND TRIFLUOROMETHYL TRIFLATE (PENTAFLUOROETHYL PENTFLATE)
-
Cleavage of boron tris-trifluoromethanesulfonate(triflate) and boron tris-pentafluoroethanesulfonate(pentflate) was studied at 200 degC.Complete cleavage giving boron trifluoride, sulfur dioxide, carbonyl fluoride (trifluoroacetyl fluoride), triflic (pentflic) anhydride, triflic (pentflic) triflate (pentflate) and boric acid was observed.A mechanism for the cleavage based on formation of the identified compounds is suggested.
- Olah, G. A.,Weber, T.,Farooq, O.
-
p. 235 - 242
(2007/10/02)
-
- BORON, ALUMINUM, AND GALLIUM TRIS(TRIFLUOROMETHANESULFONATE) (TRIFLATE): EFFECTIVE NEW FRIEDEL-CRAFTS CATALYSTS.
-
Boron, aluminum, and gallium tris(trifluoromethanesulfonate) (triflate) were prepared from the corresponding chlorides (bromides) and triflic acid. The group IIIA triflates were isolated in pure form and fully characterized (elemental analysis, molecular weight, and NMR and IR spectroscopy). Boron tris(triflate) is a monomeric, relatively volatile compound left bracket mp 43-45 degree C, bp 68-73 degree C (0. 5 Torr) right bracket , whereas aluminum and gallium triflate are associated, high-melting associated solids. Boron, aluminum, and gallium tris(triflate) are efficient new Friedel-Crafts catalysts as shown in alkylation, isomerization, and acylation reactions. Alkylation of benzene and toluene with methyl, ethyl, isopropyl, and tert-butyl halides (fluoride, chloride, and bromide) were carried out with boron, aluminum, and gallium tris(triflate) as catalyst in CH//2Cl//2 and CH//3NO//2 solvent at room temperature.
- Olah,Farooq,Morteza,Farnia,Olah
-
p. 2560 - 2565
(2007/10/02)
-
- Trifluoromethyl Triflate: Synthesis and Reactions
-
A new and convenient synthesis of trifluoromethyl trifluoromethanesulfonate (trifluoromethyl triflate, TFMT) has been devised.The addition of triflic anhydride to a catalytic amount of antimony pentafluoride at 25 deg C produces TFMT in 94percent yield, utilizing a new and stronger Lewis acid catalyst produced in the reaction, F4SbOSO2CF3.This reaction makes pure TFMT conveniently and economically available in large quantities.A mechanism is presented that accounts for the substitution of a triflate ligand on antimony, as well as for the formation of TFMT.Trifluoromethyltriflate does not trifluoromethylate nucleophiles (pyridine, triethylamine, iodide, phenyllithium, phenylmagnesium bromide, lithium thiophenolate, or sodium naphthalenide) but gives products that result from an initial attack of the nucleophile at sulfur.Fluoride ion, which is formed by fragmentation of the trifluoromethoxide ion displaced from sulfur, is a chain carrier in the rapid decomposition of TFMT to give trifluoromethanesulfonyl fluoride and fluorophosgene.This limits the synthetic utility of trifluoromethyl triflate.
- Taylor, S. L.,Martin, J. C.
-
p. 4147 - 4156
(2007/10/02)
-
- REACTIVITE DES ESTERS SULFONIQUES ET PYROSULFONIQUES PERFLUORES RFSO3RF ET RFSO3SO3RF. HETEROLYSE DE LA LIAION S-O
-
Perfluoroalkyl perfluoroalkanesulfonates RFSO3R'F (RF, R'F = CF3, C2F5) and perfluoroalkyl perfluoroalkanepyrosulfonates RFSO3SO3RF, mixed with perfluoroalkanesulfonic acids (CF3SO3H or C2F5SO3H) decompose thermally.Depending on the starting materials, different products result from nucleophilic attack of a perfluoroalkanesulfonate anion of the acid on the sulfur atom of the sulfonate group of the ester, with heterolysis of the S-O bond.Therefore, under these conditions, the perfluorinated esters are not perfloroalkylating agents, but rather perfluorosulfonylating agents.
- Oudrhiri-Hassani, M.,Brunel, D.,Germain, A
-
p. 163 - 178
(2007/10/02)
-
- Further reactions of chlorine(I) and bromine(I) trifluoromethanesulfonate and bromine(I)fluorosulfate
-
Substitutive electrophilic dehalogenation reactions of CF3SO2OX (X=Cl,Br) are reported with some covalent inorganic chlorides. These reactions result in the formation of XX′(X,X′Cl,Br) and several new trifluoromethanesulfonate derivatives in excellent yields. Chlorine(I) trifluoromethanesulfonate also oxidatively adds to unsaturated inorganic substrates such as CO, SO2 and SF4 forming new compounds. The reactivity of CF3SO2OCl is rather similar to that of FSO2OBr and some comparisons between the two are given.
- Johri, Kamalesh K.,Katsuhara, Yutaka,DesMarteau, Darryl D.
-
p. 227 - 242
(2007/10/02)
-
- Synthesis and properties of chlorine(I) and bromine(I) trifluoromethanesulfonates and Raman spectra of CF3SO2X (X = F, OH, OCl)
-
The synthesis and characterization of the new hypohalites CF3SO3Cl and CF3SO3Br are described. Both compounds are thermally unstable at 22°C, decomposing to CF3Cl and SO3 for the hypochlorite and CF3SO3CF3, CF3SO2OSO2OCF3, SO3 and Br2 for the hypobromite. The hypochlorite is prepared by reaction of CF3SO3H with ClF and the hypobromite by reaction of CF3SO3Cl with bromine. The low-temperature Raman spectrum of CF3SO3Cl suggests C1 symmetry and assignments of 20 of the expected 21 fundamentals are given. These assignments were aided by an analysis of the Raman spectra of CF3SO2F and CF3SO2OH, which are reported for the first time.
- Katsuhara, Yutaka,Hammaker, Robert M.,DesMarteau, Darryl D.
-
p. 607 - 615
(2008/10/08)
-
- Synthesis of Perfluoroalkyl Trifluoromethanesulfonates from Perfluoroalkyl Halides. Substitutive Electrophilic Dehalogenation with Chlorine(I) and Bromine(I) Trifluoromethanesulfonates
-
The reactions of chlorine(I) and bromine(I) trifluoromethanesulfonates with a variety of perfluoroalkyl halides are reported.The reactions form Br2, Cl2, or BrCl and the corresponding trifluoromethanesulfonate derivatives of the alkyls in good yields.Twelve new esters are reported and characterized.An SEi-type mechanism for the reactions is proposed with complete retention of configuration by the alkyl on substitution.
- Katsuhara, Yutaka,DesMarteau, Darryl D.
-
p. 2681 - 2686
(2007/10/02)
-
- Synthesis of Haloalkyl Esters of Trifluoromethanesulfonic Acid by the Regio- and Stereospecific Addition of Chlorine(I) and Bromine(I) Trifluoromethanesulfonate to Alkenes
-
The synthesis of a variety of haloalkyl esters of trifluoromethanesulfonic acid was achieved by the addition of CF3SO2OCl and CF3SO2OBr to alkenes.Addition to simple alkenes such as CH2CH2, CF2CH2, CF2CF2, CF2CFCl, CF2CCl2, CHClCHCl, and CHFCHF occur readily at low temperature to give the esters in high yield.With unsymmetrical alkenes, only one structural isomer is observed in every case.With the hypochlorite, cis- and trans-CHFCHF form a single different diastereomer.With the hypobromite, the same result is observed, and trans-CHClCHCl also gives only one diastereomer.A regio- and stereospecific cis-addition mechanism is proposed.
- Katsuhara, Yutaka,DesMarteau, Darryl D.
-
p. 2441 - 2446
(2007/10/02)
-
- Preparation and properties of bis(trifluoromethylsulfuryl) peroxide and trifluoromethyl trifluoromethanesulfonate
-
Electrolysis of trifluoromethanesulfonic acid at -23° yields the unstable compound bis(trifluoromethylsulfuryl) peroxide, which decomposes explosively to perfluoroethane, sulfur trioxide, and the ester, trifluoromethyl trifluoromethanesulfonate.
- Noftle, Ronald E.,Cady, George H.
-
p. 1010 - 1012
(2008/10/08)
-
