372-46-3Relevant articles and documents
A MELAMINE/HF-CARBON TETRACHLORIDE LIQUID-LIQUID TWO-PHASE MIXTURE. A HIGHLY VERSATILE HYDROFLUORINATING AGENT FOR ALKENES TO FACILITATE CONTINUOUS OPERATIONS
Yoneda, Norihiko,Nagata, Seiji,Fukuhara, Tsuyoshi,Suzuki, Akira
, p. 1241 - 1242 (1984)
A melamine/hydrogen fluoride-pentane or carbon tetrachloride liquid-liquid two phase mixture has been found to be a highly convenient hydrofluorinating agent for alkenes and a suitable system for the repeated use.
Stable dialkyl ether/poly(hydrogen fluoride) complexes: Dimethyl ether/poly(hydrogen fluoride), a new, convenient, and effective fluorinating agent
Bucsi, Imre,Toeroek, Bela,Marco, Alfonso Iza,Rasul, Golam,Prakash, G. K. Surya,Olah, George A.
, p. 7728 - 7736 (2002)
The preparation, 1H, 13C, and 19F NMR structural characterization as well as with DFT-based theoretical calculations of stable dialkyl ether/poly(hydrogen fluoride) complexes are reported. Dimethyl ether/poly(hydrogen fluoride) (DMEPHF), are stable complexes of particular interest and use. The DFT calculations, that are in agreement with NMR data, suggest a cyclic poly(hydrogen fluoride) bridged structure for DMEPHF. The complex, DME-5 HF was found to be a convenient and effective new fluorinating agent with the ease. of workup and applied to several fluorination reactions, such as the hydrofluorination and bromofluorination of alkenes, and fluorination of alcohols giving good to excellent yield with high selectivity. Homologous dialkyl ether/poly(hydrogen fluoride) (R2O/[HF]n R = Et, nPr) systems are also stable and suitable for fluorination reactions.
Process For Synthesizing Fluorinated Cyclic Aliphatic Compounds
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Paragraph 0121-0127, (2021/08/27)
The present invention relates to a novel method for producing fluorinated cycloaliphatic compounds from the analogous aromatic compounds by hydrogenation with an Rh-carbene catalyst system.
Selective hydrogenation of fluorinated arenes using rhodium nanoparticles on molecularly modified silica
Bordet, Alexis,Emondts, Meike,Kacem, Souha,Leitner, Walter
, p. 8120 - 8126 (2020/12/28)
The production of fluorinated cyclohexane derivatives is accomplished through the selective hydrogenation of readily available fluorinated arenes using Rh nanoparticles on molecularly modified silica supports (Rh?Si-R) as highly effective and recyclable catalysts. The catalyst preparation comprises grafting non-polar molecular entities on the SiO2 surface generating a hydrophobic environment for controlled deposition of well-defined rhodium particles from a simple organometallic precursor. A broad range of fluorinated cyclohexane derivatives was shown to be accessible with excellent efficacy (0.05-0.5 mol% Rh, 10-55 bar H2, 80-100 °C, 1-2 h), including industrially relevant building blocks. Addition of CaO as scavenger for trace amounts of HF greatly improves the recyclability of the catalytic system and prevents the risks associated to the presence of HF, without compromising the activity and selectivity of the reaction.
Hydrogenation of fluoroarenes: Direct access to all-cis-(multi)fluorinated cycloalkanes
Wiesenfeldt, Mario P.,Nairoukh, Zackaria,Li, Wei,Glorius, Frank
, (2017/09/23)
All-cis-multifluorinated cycloalkanes exhibit intriguing electronic properties. In particular, they display extremely high dipole moments perpendicular to the aliphatic ring, making them highly desired motifs in material science. Very few such motifs have been prepared, as their syntheses require multistep sequences from diastereoselectively prefunctionalized precursors. Herein we report a synthetic strategy to access these valuable materials via the rhodium-cyclic (alkyl)(amino)carbene (CAAC)-catalyzed hydrogenation of readily available fluorinated arenes in hexane. This route enables the scalable single-step preparation of an abundance of multisubstituted and multifluorinated cycloalkanes, including all-cis-1, 2, 3, 4, 5, 6-hexafluorocyclohexane as well as cis-configured fluorinated aliphatic heterocycles.
The Uranyl Cation as a Visible-Light Photocatalyst for C(sp3)?H Fluorination
West, Julian G.,Bedell, T. Aaron,Sorensen, Erik J.
supporting information, p. 8923 - 8927 (2016/07/26)
The fluorination of unactivated C(sp3)?H bonds remains a desirable and challenging transformation for pharmaceutical, agricultural, and materials scientists. Previous methods for this transformation have used bench-stable fluorine atom sources; however, many still rely on the use of UV-active photocatalysts for the requisite high-energy hydrogen atom abstraction event. Uranyl nitrate hexahydrate is described as a convenient, hydrogen atom abstraction catalyst that can mediate fluorinations of certain alkanes upon activation with visible light.
METAL OXIDE CATALYZED RADIOFLUORINATION
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Paragraph 0111; 0113, (2016/02/28)
Inter alia, the first titania-catalyzed [18F]-radiofluorination in highly aqueous medium is provided. In embodiments, the method utilizes titanium dioxide, 1 : 1 acetonitrile- thexyl alcohol solvent mixture and tetrabutylammonium bicarbonate as a base. Radiolabeling may be directly performed with aqueous [18F]fluoride without the need for drying/azeotroping step, which reduces radiosynthesis time while keeping high fluoride conversion. The general applicability of the synthetic strategy to the synthesis of the wide range of PET probes from tosylated precursors is demonstrated.
A photocatalyzed aliphatic fluorination
Bloom, Steven,Knippel, James Levi,Lectka, Thomas
, p. 1175 - 1178 (2014/03/21)
We disclose a new approach to the catalysis of alkane fluorination employing ultraviolet light and a photosensitizer, 1,2,4,5-tetracyanobenzene (TCB). The process is efficient, mild, and operationally straightforward. We demonstrate reaction utility on a variety of substrates, from simple hydrocarbons to complex natural products. In a showcase example, we establish that the well-known photochemical rearrangement of α-santonin can be supplanted by a highly selective catalyzed fluorination. The Royal Society of Chemistry 2014.
Visible light-promoted metal-free sp3-C-H fluorination
Xia, Ji-Bao,Zhu, Chen,Chen, Chuo
supporting information, p. 11701 - 11704 (2015/05/20)
Photoexcited acetophenone can catalyze the fluorination of unactivated C(sp3)-H groups. While acetophenone, a colorless oil, only has a trace amount of absorption in the visible light region, its photoexcitation can be achieved by irradiation with light generated by a household compact fluorescent lamp (CFL). This operational simple method provides improved substrate scope for the direct incorporation of a fluorine atom into simple organic molecules. CFL-irradiation can also be used to promote certain classic UV-promoted photoreactions of colorless monoarylketones and enones/enals.
C-HALOGEN BOND FORMATION
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Paragraph 0139-0140; 0142-0144; 0151; 0163-0164, (2013/03/26)
Methods of halogenating a carbon containing compound having an sp3 C-H bond are provided. Methods of fluorinating a carbon containing compound comprising halogenation with Cl or Br followed by nucleophilic substitution with F are provided. Methods of direct oxidative C-H fluorination of a carbon containing compound having an sp3 C-H bond are provided. The halogenated products of the methods are provided.
