3582-05-6Relevant articles and documents
THERMOLYSE DES ANHYDRIDES PERFLUOROALCANESULFONIQUES. MECANISME ET APPLICATION A LA SYNTHESE DES ESTERS RFSO3RF.
Oudrhiri-Hassani, M.,Brunel, D.,Germain, A.,Commeyras, A.
, p. 219 - 232 (1984)
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.
Gas-phase structure and vibrational properties of trifluoromethyl trifluoromethanesulfonate, CF3SO2OCF3
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
, p. 1381 - 1389 (2007)
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.
Palladium(II)-Catalyzed Enantioselective Aminotrifluoromethoxylation of Unactivated Alkenes using CsOCF3 as a Trifluoromethoxide Source
Chen, Chaohuang,Pflüger, Philipp Miro,Chen, Pinhong,Liu, Guosheng
, p. 2392 - 2396 (2019)
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.
THERMAL STABILITY OF PERFLUOROALKANESULFONIC ACIDS AND THEIR ANHYDRIDES. NEW AND EASY APPROACH TO RFSO2ORF ESTERS.
Hassani, M. Oudrhiri,Germain, A.,Brunel, D.,Commeyras, A.
, p. 65 - 68 (1981)
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.
Tertiary-Amine-Initiated Synthesis of Acyl Fluorides from Carboxylic Acids and CF3SO2OCF3
Song, Hai-Xia,Tian, Ze-Yu,Xiao, Ji-Chang,Zhang, Cheng-Pan
supporting information, p. 16261 - 16265 (2020/12/01)
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.
Silver-Mediated Trifluoromethoxylation of (Hetero)aryldiazonium Tetrafluoroborates
Yang, Yu-Ming,Yao, Jian-Fei,Yan, Wei,Luo, Zhuangzhu,Tang, Zhen-Yu
supporting information, p. 8003 - 8007 (2019/10/11)
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.
Synthesis of heteroaromatic trifluoromethyl ethers with trifluoromethyl triflate as the source of the trifluoromethoxy group
Zhang, Qing-Wei,Hartwig, John F.
supporting information, p. 10124 - 10127 (2018/09/18)
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.
Silver-mediated direct trifluoromethoxylation of α-diazo esters: Via the -OCF3 anion
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)
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.
PRODUCTION METHOD OF PERFLUOROALKYLPERFLUOROALKANE SULFONATE
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Paragraph 0051, (2016/12/26)
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
METHOD FOR PRODUCING FLUOROALKANESULFONIC ANHYDRIDE
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Paragraph 0094-0096, (2014/11/12)
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.
