463-11-6Relevant articles and documents
Halogen-Exchange Fluorination of Primary Alkyl Halides Using 1B Metal Fluorides-Pyridine Derivatives
Yoneda, Norihiko,Fukuhara, Tsuyoshi,Yamagishi, Ken,Suzuki, Akira
, p. 1675 - 1678 (1987)
Deep purplish red semicrystalline precipitates were obtained by the treatment of Cu2O with HF.After calcination at 100 deg C or higher temperature, this compound was successfully used as a highly effective halogen-exchange fluorination reagent for primary alkyl halides in the presence of pyridine derivatives.AgF and a mixture of CuF2 with copper powder also exhibited high activity in the reaction.
LE FORMAMIDE, UN SUBSTITUT DE L'EAU XI : EFFET DU FORMAMIDE SUR LES REACTIONS D'ECHANGE CHLORE-FLUOR DANS LES CONDITIONS DE TRANSFERT DE PHASE LIQUIDE-SOLIDE
Escoula, B.,Rico, I.,Lattes, A.
, p. 1499 - 1500 (1986)
The fluoride-chloride exchange reaction RCl + KF = RF + KCl catalysed by ammonium salts takes place in presence of formamide in place of water, faster and qith better yields.
METHOD AND REAGENT FOR DEOXYFLUORINATION
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Paragraph 0148-0150; 0152; 0167, (2021/05/29)
A safe, simple, and selective method and reagent for deoxyfluorination is disclosed. With the method and reagent disclosed herein, organic compounds such as carboxylic acids, carboxylates, carboxylic acid anhydrides, aldehydes, and alcohols can be fluorinated by using the most common nucleophilic fluorinating reagents and electron deficient fluoroarenes as mediators under mild conditions, giving corresponding fluoroorganic compounds in excellent yield with a wide range of functional group compatibility and easy product purification. For example, directly utilizing KF for deoxyfluorination of carboxylic acids provides the most economical and the safest pathway to access acyl fluorides, key intermediates for syntheses of peptide, amide, ester, and dry fluoride salts.
Fluorination reagent and deoxygenation fluorination method
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Paragraph 0066-0116; 0127-0138; 0159-0160, (2020/12/30)
In order to overcome the problems of high cost and poor stability of the existing deoxidation fluorination reagent, the invention provides a fluorination reagent. The fluorination reagent comprises acation M and an anion, and the anion is selected from one or more of the following perfluoropolyether chain carboxylic acid anions: CF3 (OCF2) nCO2, and n is selected from 1-10. Meanwhile, the invention further discloses a deoxidation fluorination method. The fluorination reagent provided by the invention has the advantages that the materials are easy to obtain, the fluorination products can beobtained at higher yield for various alcohol substrates, and the universality for different alcohol substrates is better.
A Series of Deoxyfluorination Reagents Featuring OCF2Functional Groups
Cao, Wei,Chen, Qing-Yun,Guo, Yong,Su, Zhaoben,Wu, Chengying,Zhao, Shiyu
supporting information, (2020/11/03)
Research on perfluoroalkyl ether carboxylic acids (PFECAs) as alternatives for perfluoroalkyl substances continues with the goal of protecting the environment. However, very little is known about the utilization of decomposition products of PFECAs. We report herein a new series of deoxyfluorination reagents featuring OCF2 functional groups derived from certain PFECAs. Alkyl fluorides were generated from various alcohols in ≤97% yield by these novel reagents. The mechanistic experiment verified in situ generation of carbonic difluoride (COF2).
Stabilization of Photocatalytically Active Uranyl Species in a Uranyl - Organic Framework for Heterogeneous Alkane Fluorination Driven by Visible Light
Zhang, Xuan,Li, Peng,Krzyaniak, Matthew,Knapp, Julia,Wasielewski, Michael R.,Farha, Omar K.
supporting information, (2020/07/03)
When photoactivated, the uranyl ion is a powerful oxidant capable of abstracting hydrogen atoms from nonactivated C-H bonds. However, the highly reactive singly reduced [UVO2]+intermediate is unstable with respect to disproportionation to the uranyl dication and insoluble tetravalent uranium phases, which limits the usage of uranyl ions as robust photocatalysts. Herein, we demonstrate that photoactivated uranyl ions can be stabilized by immobilizing and separating them spatially in a uranyl-organic framework heterogeneous catalyst, NU-1301. The visible-light-photoactivated uranyl ions in NU-1301 exhibited longer-lived U(V) and radicals than those in homogeneous counterparts, as evidenced by X-ray photoelectron spectroscopy and time-dependent electron paramagnetic resonance, leading to higher turnovers and enhanced stability for the fluorination of nonactivated alkanes.
Photochemical activation of SF6 by N-heterocyclic carbenes to provide a deoxyfluorinating reagent
Tomar, Pooja,Braun, Thomas,Kemnitz, Erhard
supporting information, p. 9753 - 9756 (2018/09/10)
The activation of the greenhouse gas SF6 using electron-rich N-heterocyclic carbenes gave 2,2-difluoroimidazolines or 2,2-difluoroimidazolidines as well as 2-thio derivatives of the carbene precursors. The N-heterocyclic carbenes can also convert SF4 to give similar products. The difluoroimidazolidine derivatives were applied in deoxyfluorination reactions. Furthermore, the activation of SF6 and the fluorination can be coupled in a one-pot process to convert 1-octanol into 1-fluorooctane.
ORGANIC SYNTHESIS APPLICATIONS OF NON-AQUEOUS FLUORIDE SALT SOLUTIONS
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Paragraph 0178-0181, (2017/03/21)
Processes and reaction mixtures including non-aqueous solvent mixtures are presented. Non-aqueous solvent mixtures including fluoride salt and non-aqueous solvent combinations are provided that possess high fluoride ion concentrations useful for a range of applications, including organic synthesis. Further non-aqueous solvent mixtures are provided including a salt possessing a non-fluoride anion and a non-aqueous solvent that, when contacted with aqueous fluoride-containing reagents, extract fluoride ions to form non-aqueous fluoride-ion solutions possessing high fluoride-ion concentrations. The salts include an organic cation that does not possess a carbon in the β-position or does not possess a carbon in the β-position having a bound hydrogen. This salt structure facilitates its ability to be made anhydrous without decomposition. Example anhydrous fluoride salts include (2,2-dimethylpropyl)trimethylammonium fluoride and bis(2,2-dimethylpropyl)dimethylammonium fluoride. The combination of these fluoride salts with at least one fluorine-containing non-aqueous solvent (e.g., bis(2,2,2-trifluoroethyl)ether; (BTFE)) promotes solubility of the salt within the non-aqueous solvents.
Solvent free nucleophilic introduction of fluorine with [bmim][F]
Bouvet, Sébastien,Pégot, Bruce,Marrot, Jérome,Magnier, Emmanuel
, p. 826 - 829 (2014/02/14)
1-n-Butyl-3-methylimidazolium fluoride ([bmim][F]) proved very efficient fluorinated reagent for nucleophilic substitution over sulfonate esters and alkyl halides. Preparation of the ionic liquid as well as its use as the reagent has been performed to be the more eco-friendly as possible. No organic solvent is needed for the fluoride introduction, reaction times are reduced by using microwave as the heating source, and the ionic liquids carefully recycled. Furthermore, no special care has to be taken as the presence of water in [bmim][F] was not deleterious to the transformation yield.
Silver-catalyzed radical fluorination of alkylboronates in aqueous solution
Li, Zhaodong,Wang, Zhentao,Zhu, Lin,Tan, Xinqiang,Li, Chaozhong
, p. 16439 - 16443 (2015/01/09)
We report herein an efficient and general method for the deboronofluorination of alkylboronates. Thus, with the catalysis of AgNO3, the reactions of various alkylboronic acids or their pinacol esters with Selectfluor reagent in acidic aqueous solution afforded the corresponding alkyl fluorides under mild conditions. A broad substrate scope and wide functional group compatibility were observed. A radical mechanism is proposed for this site-specific fluorination.
