- One-Pot and Reducible-Functional-Group-Tolerant Synthesis of α-Aryl- and α-Heteroaryl-α-Trifluoromethyl Alcohols via Tandem Trifluoroacetylation and MPV Type Reduction
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We have developed a new one-pot synthesis of α-aryl- and α-heteroaryl-α-trifluoromethyl alcohols carrying not only arenes with electron-withdrawing groups but also electron-deficient nitrogen-containing heteroarenes, which are of increasing interest becau
- Funabiki, Kazumasa,Hayakawa, Ayaka,Kani, Ryunosuke,Inuzuka, Toshiyasu,Kubota, Yashuhiro
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p. 5978 - 5984
(2019/08/30)
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- Gas/Liquid-Phase Micro-Flow Trifluoromethylation using Fluoroform: Trifluoromethylation of Aldehydes, Ketones, Chalcones, and N-Sulfinylimines
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A micro-flow nucleophilic trifluoromethylation of carbonyl compounds using gaseous fluoroform was developed. This method also allows the first micro-flow transformation of N-sulfinylimines into trifluoromethyl amines with excellent diastereoselectivity. To demonstrate the synthetic utility of this micro-flow synthesis, the formal micro-flow synthesis of Efavirenz is described.
- Hirano, Kazuki,Gondo, Satoshi,Punna, Nagender,Tokunaga, Etsuko,Shibata, Norio
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p. 406 - 410
(2019/02/13)
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- METHOD FOR PRODUCING TRIFLUOROMETHYL GROUP-CONTAINING ALCOHOLS
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PROBLEM TO BE SOLVED: To provide a method for producing CF3 group-containing alcohols useful as production intermediates for medicines and agrochemicals. SOLUTION: The method for producing CF3 group-containing alcohols represented by formula (2) comprises
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Paragraph 0029-0031; 0033-0035
(2017/02/02)
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- Organocatalyzed Trifluoromethylation of Ketones and Sulfonyl Fluorides by Fluoroform under a Superbase System
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Fluoroform (HCF3, HFC-23) is a side product in the manufacture of polytetrafluoroethylene (Teflon). Despite its attractive properties, taming HCF3 for trifluoromethylation is quite problematic owing to its low acidity and the labilit
- Okusu, Satoshi,Hirano, Kazuki,Tokunaga, Etsuko,Shibata, Norio
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p. 581 - 585
(2015/10/20)
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- Nucleophilic trifluoromethylation of carbonyl compounds: Trifluoroacetaldehyde hydrate as a trifluoromethyl source
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A feasible nucleophilic trifluoromethylating protocol has been developed using trifluoroacetaldehyde hydrate as an atom-economical trifluoromethyl source. The reaction was found to be applicable to the nucleophilic trifluoromethylation of a broad spectrum of carbonyl compounds with satisfactory yields in general. DFT calculations have been performed to provide mechanistic insight into the present and related reactions employing 2,2,2-trifluoro-1- methoxyethanol and hexafluoroacetone hydrate.
- Surya Prakash,Zhang, Zhe,Wang, Fang,Munoz, Socrates,Olah, George A.
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p. 3300 - 3305
(2013/06/27)
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- Amidinate salt of hexafluoroacetone hydrate for the preparation of fluorinated compounds by the release of trifluoroacetate
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A powerful, new reagent, an amidinate salt of hexafluoroacetone hydrate, is an air-stable salt that can be used for the preparation of fluorinated organic molecules. Nucleophilic trifluoromethylation reactions are demonstrated following the base-promoted release of trifluoroacetate. This reagent is soluble in many polar organic solvents and produces fluoroform, following the release of trifluoroacetate. Reactions with this reagent and common electrophiles provide excellent yields of trifluoromethylated products.
- Riofski, Mark V.,Hart, Allison D.,Colby, David A.
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supporting information
p. 208 - 211
(2013/04/10)
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- COMPOSITIONS AND PROCESSES OF PREPARING AND USING THE SAME
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The present invention relates to compositions, for example, the DBU/Hexafluoroacetone hydrate salt, and processes of preparing and using the same for the modification of chemical compounds via the release of trifluoroacetate. The DBU/Hexafluoroacetone hydrate salt can perform trifluoromethylation reactions on chemical compounds, such as carbonyl group-containing compounds.
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Page/Page column 36
(2012/10/08)
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- Substituent effects on the solvolysis of 1,1-diphenyl-2,2,2-trifluoroethyl tosylates. Part III. Effects of electron-donating substituents in the fixed aryl moiety
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The solvolysis rates of 1-ary1-1-(p-methoxyphenyl)-2,2,2-trifluoroethyl and 1-aryl-1-(p-phenoxyphenyl)-2,2,2-trifluoroethyl bromides and chlorides were conductimetrically measured at 25.0°C in 80% aqueous ethanol. The solvolysis rates of 1-(p-methylphenyl)-fixed series were also set up to analyze the substituent effect. The substituent effects on these Y-series of solvolyses were analyzed on the basis of the Yukawa-Tsuno equation. The p-methoxyphenyl-fixed series showed a linear correlation with p= -1.7 and r = 1.0 for the substituent range less reactive than p-Me including all meta substituents, and a discrete correlation with p = -3.9 and r = 1.26 for the strong π-donor class substituents more reactive than p-PhO. A similar bilinear correlation was obtained for the Y =p-PhO series. The partial correlations for the strong π-donor class substituents in both Y-series are nearly the same as the correlation p= -4.2 and r= 1.2 for symmetrically disubstituted (X = Y) series. These bilinear (or non-linear) correlations were explicable in terms of changes in the coplanarity of the two benzene rings depending upon the resonance capabilities of X and Y substituents. For strong π-donor class X substituents as strongly π-electron donating as the Y substituent, both aryl rings are equivalently twisted as in the symmetrical X = Y series, and for less electron-donating X substituents, the fixed p-methoxyphenyl (or p-phenoxyphenyl) ring remains in a coplanar conformation and X-phenyl is twisted more out of coplanarity. In the fixed Y=p-Me series, a significantly non-linear correlation was found, comprising three distinct correlations characteristic of three conformers, a conformer with the X-aryl coplanar and Y-aryl twisted, a symmetrical conformer with X being a weak or moderate π-electron donor and both aryls being equivalently twisted, and a conformer with Y-aryl coplanar and X-aryl twisted. The relative stabilities of these conformers, were estimated by the ab initio MO optimization of the mono-p-methoxycarbenium ion, confirming the conclusions above. Copyright
- Fujio, Mizue,Kim, Hyun-Joong,Morimoto, Hiroshi,Yoh, Soo-Dong,Tsuno, Yuho
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p. 843 - 857
(2007/10/03)
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- 19F nuclear magnetic resonance spectroscopy for the quantitative detection and classification of carbonyl groups in lignins
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A novel method that permits the quantitative detection and classification of various carbonyl groups in lignins has been developed. The proposed method was optimized with the quantitative trifluoromethylation of a series of carbonyl-containing lignin-like model compounds. This effort was followed by 19F NMR spectral analyses of the resulting fluorine derivatives allowing for a thorough understanding of their structure/19F chemical shift relationships. The various carbonyl groups present in lignins were also investigated by trifluoromethylating them in the presence of catalytic amounts of tetramethylammonium fluoride (TMAF), followed by hydrolysis with TMAF in tetrahydrofuran. By using a variety of selective reactions, it became possible to assign a number of prominent 19F NMR signals to a variety of carbonyl groups present in lignins. These studies demonstrated that the proposed method can be applied to the quantitative determination of carbonyl groups that are present in soluble native and technical lignins.
- Ahvazi, Behzad C.,Crestini, Claudia,Argyropoulos, Dimitris S.
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p. 190 - 201
(2007/10/03)
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- Substituent Effects on the Solvolysis of 1,1-Diphenyl-2,2,2-trifluoroethyl Tosylates: Comparison between Symmetrically Disubstituted and Monosubstituted Systems
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The solvolysis rates of 1-(substituted phenyl)-1-phenyl-2,2,2-trifluoroethyl and 1,1-bis(substituted phenyl)-2,2,2-trifluoroethyl tosylates or bromides were conductimetrically measured at 25.0 °C in 80% aqueous ethanol. The substituent effects on these so
- Fujio, Mizue,Morimoto, Hiroshi,Kim, Hyun-Joong,Tsuno, Yuho
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p. 1403 - 1411
(2007/10/03)
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- 19F Nuclear Magnetic Resonance Spectroscopy for the Elucidation of Carbonyl Groups in Lignins. 1. Model Compounds
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A new method for the detection of different classes of carbonyl groups in a series of carbonyl-containing lignin-like model compounds has been developed. The method is based on the selective fluoride-induced trifluoromethylation of carbonyl groups with (trifluoromethyl)trimethylsilane (TMS-CF3) in the presence of tetramethylammonium fluoride (TMAF), followed by hydrolysis with aqueous HF or TMAF in the case of quinones. In this study a series of ketones, aldehydes, quinones, and dimeric-lignin model compounds were quantitatively trifluoromethylated followed by 19F NMR spectral analyses of the resulting fluorine-containing derivatives, allowing for a thorough understanding of their structure/19F chemical shift relationships. These studies have shown that the 19F-NMR chemical shifts of the trifluoromethyl groups vary significantly and consistently for various classes of carbonyl groups which may be present in complex lignocellulosic materials. These studies are to form the basis for the development of a novel and sensitive method that can be used to obtain quantitative information on the various carbonyl groups present in such materials.
- Ahvazi, Behzad C.,Argyropoulos, Dimitris S.
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p. 2167 - 2175
(2007/10/03)
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- Quantitative trifluoromethylation of carbonyl-containing lignin model compounds
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The efficient trifluoromethylation of a series of carbonyl-containing lignin model compounds was made possible by using Ruppert's reagent in the presence of tetramethylammonium fluoride (TMAF), followed by hydrolysis with aqueous HF. These studies demonstrate that such a method can quantitatively convert carbonyl groups to the CF3-containing compounds, thus qualifying the procedure as a potential analytical tool for the determination of carbonyl groups in lignins.
- Ahvazi,Argyropoulos
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p. 195 - 198
(2007/10/03)
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