- Covalent Organic Frameworks toward Diverse Photocatalytic Aerobic Oxidations
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Photoactive two-dimensional covalent organic frameworks (2D-COFs) have become promising heterogenous photocatalysts in visible-light-driven organic transformations. Herein, a visible-light-driven selective aerobic oxidation of various small organic molecules by using 2D-COFs as the photocatalyst was developed. In this protocol, due to the remarkable photocatalytic capability of hydrazone-based 2D-COF-1 on molecular oxygen activation, a wide range of amides, quinolones, heterocyclic compounds, and sulfoxides were obtained with high efficiency and excellent functional group tolerance under very mild reaction conditions. Furthermore, benefiting from the inherent advantage of heterogenous photocatalysis, prominent sustainability and easy photocatalyst recyclability, a drug molecule (modafinil) and an oxidized mustard gas simulant (2-chloroethyl ethyl sulfoxide) were selectively and easily obtained in scale-up reactions. Mechanistic investigations were conducted using radical quenching experiments and in situ ESR spectroscopy, all corroborating the proposed role of 2D-COF-1 in photocatalytic cycle.
- Liu, Shuyang,Tian, Miao,Bu, Xiubin,Tian, Hua,Yang, Xiaobo
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supporting information
p. 7738 - 7744
(2021/05/07)
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- Method for preparing 8-fluoroquinoline and method for preparing 3-iodo-8-fluoroquinoline
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The invention provides a method for preparing 8-fluoroquinoline and a method for preparing 3-iodo-8-fluoroquinoline. Preparation of the 8-fluoroquinoline comprises the step of carrying out a ring-closure reaction between fluoroaniline and glycerin, and preparation of the 3-iodo-8-fluoroquinoline comprises the step of carrying out a substitution reaction among the prepared 8-fluoroquinoline, N-chlorosuccinimide and a metal iodide. The method has the characteristics that the raw materials are cheap and readily available, the cost is low, any special equipment is not needed, the various materialsare low in toxicity, safe, environmental-friendly, less in by-products and high in yield, and large-scale industrial production is easily realized.
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Paragraph 0061-0072
(2018/03/26)
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- Nucleophilic deoxyfluorination of phenols via aryl fluorosulfonate intermediates
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This report describes a method for the deoxyfluorination of phenols with sulfuryl fluoride (SO2F2) and tetramethylammonium fluoride (NMe4F) via aryl fluorosulfonate (ArOFs) intermediates. We first demonstrate that the reaction of ArOFs with NMe4F proceeds under mild conditions (often at room temperature) to afford a broad range of electronically diverse and functional group-rich aryl fluoride products. This transformation was then translated to a one-pot conversion of phenols to aryl fluorides using the combination of SO2F2 and NMe4F. Ab initio calculations suggest that carbon-fluorine bond formation proceeds via a concerted transition state rather than a discrete Meisenheimer intermediate.
- Schimler, Sydonie D.,Cismesia, Megan A.,Hanley, Patrick S.,Froese, Robert D.J.,Jansma, Matthew J.,Bland, Douglas C.,Sanford, Melanie S.
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supporting information
p. 1452 - 1455
(2017/02/10)
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- METHOD FOR AROMATIC FLUORINATION
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Disclosed is a fluorination method comprising providing an aryl fluorosuifonate and a fluorinating reagent to a reaction mixture; and reacting the aryl fluorosuifonate and the fluorinating reagent to provide a fluorinated aryl species. Also disclosed is a fluorination method comprising providing, a salt comprising a cation and an aryloxyiate, and SO2F2 to a reaction mixture; reacting the SO2F2 and the ammonium salt to provide a fluorinated aryl species. Further disclosed a fluorination method comprising providing a compound having the structure Ar-OH to a reaction mixture; where A is an aryl or heteroaryl; providing SO2F2 to the reaction mixture; providing a fluorinating reagent to the reaction mixture; reacting the SO2F2, the fluorinating reagent and the compound having the structure Ar-OH to provide a fluorinated aryl species having the structure Ar-F.
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Paragraph 0047-0049
(2017/12/18)
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- PhenoFluorMix: Practical chemoselective deoxyfluorination of phenols
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A practical deoxyfluorination with novel deoxyfluorinating reagent PhenoFluorMix, a mixture of N,N'-1,3-bis(2,6-diisopropylphenyl)chloroimidazolium chloride and CsF, is presented. PhenoFluorMix overcomes the challenges associated with hydrolysis of PhenoFluor. PhenoFluorMix does not hydrolyze, is readily available on decagram scale, and is storable in air. In this paper, we demonstrate the practicality of the reagent and exhibit the deoxyfluorination of a variety of phenols and heterocycles.
- Fujimoto, Teppei,Ritter, Tobias
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supporting information
p. 544 - 547
(2015/03/05)
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- FLUORINATION OF ORGANIC COMPOUNDS
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Methods for fluorinating organic compounds are described herein.
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Page/Page column 24
(2012/11/06)
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- Deoxyfluorination of phenols
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An operationally simple ipso fluorination of phenols with a new deoxyfluorination reagent is presented.
- Tang, Pingping,Wang, Weike,Ritter, Tobias
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supporting information; experimental part
p. 11482 - 11484
(2011/10/02)
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- Elemental fluorine Part 15. Selective direct fluorination of quinoline derivatives
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Direct fluorination of various quinoline derivatives in acidic reaction media gives fluorinated quinoline products arising from electrophilic substitution processes.
- Chambers, Richard D.,Holling, Darren,Sandford, Graham,Batsanov, Andrei S.,Howard, Judith A.K.
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p. 661 - 671
(2007/10/03)
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- Selective direct fluorination of quinoline derivatives
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Direct fluorination of various quinoline derivatives in acidic reaction media gives fluorinated quinoline products arising from selective, efficient electrophilic substitution processes.
- Chambers, Richard D,Holling, Darren,Sandford, Graham,Puschmann, Horst,Howard, Judith A.K
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- Dual stimulatory and inhibitory effects of fluorine-substitution on mutagenicity: An extension of the enamine epoxide theory for activation of the quinoline nucleus
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Nineteen mono- and di-fluorinated derivatives of quinoline, 1,7- phenanthroline, 1,10-phenanthroline, benzo-[h]quinoline, and benzo[f]quinoline were subjected to analysis of their structure-mutagenicity relationships. For this purpose, six new fluorinated derivatives were synthesized. The results support that the enamine epoxide structure of the pyridine moiety, as well as the bay-region epoxide structure, is responsible for mutagenicity. Formation of K-region epoxides might involve a detoxification process rather than mutagenic activation.
- Saeki, Ken-Ichi,Kawai, Hiroshi,Kawazoe, Yutaka,Hakura, Atsushi
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p. 646 - 650
(2007/10/03)
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- Proton, Carbom-13 and FLuorine-19 NMR Studies of N-Alkyl-8-fluoroquinolinium Halides: Relative Signs of Through-space 1H-19F and 13C-19F Coupling Constants
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Because of experimental and theoretical interest in long-range 1H-19F and 13C-19F coupling constants between proximate atoms, a series of N-alkylfluoroquinolinium compounds was synthesized and the NMR parameters were accurately measured.By means of spin tickling and selective population inversion difference spectroscopy, the 5J(HF) and 4J(CF), which are associated with the proximate fluorine and mrthyl groups, were shown to be of the same (positive) sign as the directly bonded 13C-1H and vicinal 1H-1H coupling constants.In N-methyl-8-fluoroquinolinium iodide (1a) and chloride (1b) 5J(HF) = +8.8 and 4J(CF) = +16.3 Hz, and in N-ethyl-8-fluoroquinolinium iodide 5J(HF) = +3.0, 6J(HF) = +1.5, 4J(CF) = (+)15.8 and 5J(CF) = +/= 5.2 Hz. calculated molecular orbital results, which were based on the INDO-FPT method and a molecular geometry from the x-ray diffraction data for 1b, were in reasonable agreement with the 4J(CF) values, but the 5J(HF) values were of the wrong sign and magnitude.
- Barfield, M.,Walter, S. R.,Clark, K. A.,Gribble, G. W.,Haden, K. W.,et al.
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