43141-66-8Relevant academic research and scientific papers
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
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.
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.
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
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.
