43141-66-8Relevant academic research and scientific papers
Preparation method of florfenicol intermediate fluoromethanesulfonyl oxazole
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Paragraph 0016; 0022-0028, (2021/07/31)
The invention provides a preparation method of florfenicol intermediate fluoromethanesulfone oxazole; 1-chloro-4-(difluoromethyl)benzene is adopted as a fluorinating reagent, and the preparation method comprises the steps: adding 1-chloro-4-(difluoromethyl)benzene, a cyclization compound oxazoline and dichloromethane, heating to 80-100 DEG C, and reacting for 1.5-3 hours. According to the process, 1-chloro-4-(difluoromethyl)benzene is adopted as the fluorination reagent, the complex process of fluorination of an lshikawa reagent prepared through mixed reaction of hexafluoropropylene and diethylamine in a traditional process is omitted, compared with the prior art, preparation of the 1-chloro-4-(difluoromethyl)benzene fluorination reagent has the advantages of being high in reaction speed, high in conversion rate, few in by-products and the like; in addition, in the process of fluorinating the florfenicol intermediate cyclization compound by using 1-chloro-4-(difluoromethyl)benzene, the main by-product is p-chlorobenzaldehyde, and the p-chlorobenzaldehyde can be used as a by-product after separation and purification, so that the atom utilization rate is increased.
PROCESSES FOR FLUORINATION
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Paragraph 0179; 0184-0187; 0191, (2021/04/10)
The present technology relates to fluorination reactions. Specifically, processes useful for making the fungicide compound, DFT are disclosed. More broadly, also disclosed herein are processes useful for deoxyfluorination at the α-aromatic position of a given compound.
Base-Catalyzed H/D Exchange Reaction of Difluoromethylarenes
Huang, Linwei,Liu, Wei,Zhao, Liang-Liang,Zhang, Zengyu,Yan, Xiaoyu
, p. 3981 - 3988 (2021/03/09)
The budding deuteriodifluoromethyl group (CF2D) is a potentially significant functional group in medicinal chemistry. Herein, we investigated t-BuOK-catalyzed H/D exchange reaction of difluoromethylarenes in DMSO-d6 solution. The method provides excellent
PROCESSES FOR FLUORINATION
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Paragraph 0188, (2020/03/05)
The present technology relates to fluorination reactions. Specifically, processes useful for making the fungicide compound, DFT are disclosed. More broadly, also disclosed herein are processes useful for deoxyfluorination at the α-aromatic position of a given compound.
Precatalyst Effects on Pd-Catalyzed Cross-Coupling Difluoromethylation of Aryl Boronic Acids
Hori, Kaishi,Motohashi, Hirotaka,Saito, Daichi,Mikami, Koichi
, p. 417 - 421 (2019/01/11)
The Pd-catalyzed difluoromethylation of aryl boronic acids with difluoroiodomethane is shown to provide the difluoromethyl compounds in high to moderate yields by Pd(PPh3)2/DPEphos catalyst in H2O/toluene. Mechanistic studies show that the oxidative addition by Pd(PPh3)4 rather than Pd2(dba)3 precatalyst to difluoroiodomethane provides a square-planar trans-(PPh3)2Pd(II)(CF2H)I complex defined by X-ray crystallographic analysis. The trans-(PPh3)2Pd(CF2H)I complex is transformed to cis-(PPh3)2Pd(CF2H)Ph detected by low temperature NMR analysis, via transmetalation with phenylboronic acids. The reductive elimination occurs via ligand exchange to DPEphosPd(CF2H)Ph to give Ph-CF2H (t1/2 = 144.7 min at 20 °C) with formation of the Pd(0)(PPh3)2/DPEphos catalyst.
Difluoromethyl-substituted compound (by machine translation)
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Paragraph 0068; 0069; 0072, (2019/10/17)
[Problem] to provide a, simple and inexpensive manufacturing method is difluoromethyl substituted compounds using a reagent. [Solution] a method for producing a compound using a catalyst [...] difluoromethyl-substituted,(I) the catalyst, a nickel compound and nitrogen in the bidentate ligand, raw Ar a-Z " in the formula, the Ar, substituted or unsubstituted aryl group or a substituted or unsubstituted 5 - 10 membered heteroaryl group C6 a-14, Z is, (OR) B2 Or a group represented by a is represented MgX. " Compound represented, difluoromethyl-substituted compounds, Ar e CF2 A method for producing a compound represented by H, or(II) catalyst, a palladium compound and a diphosphine ligand, raw material is Q-a B (OR1 )2 " In the formula, Q is, substituted or unsubstituted aryl C6 a-10, 5 - 10 membered heteroaryl or substituted or unsubstituted, or Ar1 A group represented by - CH=CH - shown. R1 Is, a hydrogen atom or an alkyl group C1 a-6. " Compounds, a compound represented by Q-a Zn-to-Q or, difluoromethyl-substituted compounds, Q-to-CF2 A method for producing a compound represented by H. [Drawing] no (by machine translation)
Room Temperature Deoxyfluorination of Benzaldehydes and α-Ketoesters with Sulfuryl Fluoride and Tetramethylammonium Fluoride
Melvin, Patrick R.,Ferguson, Devin M.,Schimler, Sydonie D.,Bland, Douglas C.,Sanford, Melanie S.
supporting information, p. 1350 - 1353 (2019/03/08)
A method for the room temperature deoxyfluorination of benzaldehydes and α-ketoesters using sulfuryl fluoride and Me4NF is described. A large scope of aryl and heteroaryl substrates is demonstrated, and this method compares favorably to other common deoxyfluorination methods for many substrates.
Metallaphotoredox Difluoromethylation of Aryl Bromides
Bacauanu, Vlad,Cardinal, Sébastien,Yamauchi, Motoshi,Kondo, Masaru,Fernández, David F.,Remy, Richard,MacMillan, David W. C.
supporting information, p. 12543 - 12548 (2018/09/18)
Herein, we report a convenient and broadly applicable strategy for the difluoromethylation of aryl bromides by metallaphotoredox catalysis. Bromodifluoromethane, a simple and commercially available alkyl halide, is harnessed as an effective source of difluoromethyl radical by silyl-radical-mediated halogen abstraction. The merger of this fluoroalkyl electrophile activation pathway with a dual nickel/photoredox catalytic platform enables the difluoromethylation of a diverse array of aryl and heteroaryl bromides under mild conditions. The utility of this procedure is showcased in the late-stage functionalization of several drug analogues.
Nickel-Catalyzed Aromatic Cross-Coupling Difluoromethylation of Grignard Reagents with Difluoroiodomethane
Motohashi, Hirotaka,Mikami, Koichi
supporting information, p. 5340 - 5343 (2018/09/12)
The nickel-catalyzed cross-coupling difluoromethylation of the Grignard reagents with difluoroiodomethane is shown to provide the corresponding aromatic difluoromethyl products in excellent to moderate yields. The difluoromethylation proceeds smoothly within 1 h at room temperature with 1.5 equiv of the Grignard reagents in the presence of Ni(cod)2/TMEDA (2.5-0.5 mol %). Mechanistic studies clarify that the oxidative addition of the Ni(0) catalyst to difluoroiodomethane provides the TMEDA-Ni(II)(CF2H)I complex. This intermediate is transformed to TMEDA-Ni(II)(CF2H)Ph via transmetalation with PhMgBr. The reductive elimination takes place to give the aromatic cross-coupling difluoromethylation product along with regeneration of the TMEDA-Ni(0) catalyst. Electron paramagnetic resonance (EPR) and radical clock analyses of the nickel-catalyzed reaction provide no EPR active Ni(I) and Ni(III) species at around g = 2 and only a trace amount of the cyclization product.
Method for preparing alpha-aryl/heteroaryl/alkenyl-alpha,alpha-difluoromethyl compounds
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Paragraph 0141; 0142; 0143; 0150; 0151; 0152; 0183; 0184, (2018/09/08)
The invention discloses a method for preparing alpha-aryl/heteroaryl/alkenyl-alpha,alpha-difluoromethyl compounds. The preparation method for the alpha-aryl/heteroaryl/alkenyl-alpha,alpha-difluoromethyl compounds as shown in a formula C which is described
