- Catalytic vapor-phase oxidation of 2,2,2-trifluoroethanol
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The synthesis of trifluoroacetaldehyde by vapor-phase oxidation of 2,2,2-trifluoroethanol using supported vanadium catalysts was studied. Significant differences were observed in the reaction outcomes resulting from different types of catalysts. The ZrO2- and Al2O3-supported catalyst demonstrated both high catalytic activity and selectivity. The addition of co-catalysts such as MoO3 or SnO2 improved catalytic performance (Selectivity: up to 91%; S.T.Y.: >200 g L-1 h-1). The experimental results on catalyst lifetime showed a marked decrease in the activity of the Al2O3-supported catalyst within tens of hours, while the ZrO2-supported catalyst showed little, if any, performance alterations for 2000 h.
- Mimura, Hideyuki,Watanabe, Akio,Kawada, Kosuke
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- A simple and practical synthesis of α-trifluoromethylated alcohols in water
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A simple and practical preparation of α-trifluoromethylated alcohols in water via indium-mediated allylation reaction and tin-mediated indium trichloride-promoted allylation reaction of trifluoroacetaldehyde hydrate and its ethyl hemiacetal is described in this paper.
- Loh, Teck-Peng,Li, Xu-Ran
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- Direct aldol reaction of trifluoroacetaldehyde ethyl hemiacetal with ketones by use of the combination of amines and acids
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Trifluoroacetaldehyde ethyl hemiacetal reacts with unmodified ketones in the presence of 30-50 each mol % of amines and acids at ambient temperature, affording the corresponding β-hydroxy-β-trifluoromethylated ketones in good yields with good to excellent diastereoselectivities.
- Funabiki, Kazumasa,Nagaya, Hideyuki,Ishihara, Mika,Matsui, Masaki
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- Ru-Catalyzed Deoxygenative Regioselective C8-H Arylation of Quinoline N-Oxides
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Regioselective C-H functionalization on quinolines is of high interest to lead to value-added products. Herein, we describe the development of Ru-catalyzed deoxygenative regioselective C8 arylation of quinoline N-oxides with arylboronic esters. Mechanistic studies revealed that it proceeds in a tandem process of arylation and then deoxygenation, wherein both steps were found to be catalytic with the ruthenium species.
- Kim, Jinwoo,Kim, Suhyeon,Kim, Dongwook,Chang, Sukbok
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supporting information
p. 13150 - 13158
(2019/08/22)
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- 1,2-Bis(trifluoromethyl)ethene-1,2-dicarbonitrile: (2+2) cycloadditions with vinyl ethers
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The title compound (short version: BTE) occurs in (E)- and (Z)-isomers (both with b.p. of ca. 100°) which equilibrate with nucleophilic catalysts. Both undergo (2+2) cycloadditions with methyl vinyl ether at 25°. Three stereogenic centers in the cyclobutanes led to four rac-diastereoisomers, which were obtained in pure and crystalline state. The structures were elucidated by 19F-NMR spectroscopy and confirmed by two X-ray analyses. The cycloadditions were not stereospecific: e.g., (E)-BTE furnished 73% trans-adducts (with respect to the CF3 groups) and 27% cis-adducts. The loss of stereochemical integrity occurs in the intermediate gauche-zwitterions which can cyclize or rotate, but not dissociate. Under extreme conditions (2M LiClO4 in Et2O, 70°, 3months), the thermodynamic equilibrium of the four cyclobutanes was achieved. Considerations of Coulombic attraction and conformational strain in the zwitterionic intermediates allow us to rationalize the observed proportions of diastereoisomeric cyclobutanes. Ethyl vinyl ether and butyl vinyl ether furnished cyclobutanes in similar diastereoisomer ratios. Copyright
- Urrutia-Desmaison, Gonzalo,Huisgen, Rolf,Noeth, Heinrich
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experimental part
p. 1 - 16
(2012/03/07)
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- Tetrahydropyridinyl and Dihydropyrrolyl Compounds and the Use Thereof
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The invention relates to tetrahydropyridinyl and dihydropyrrolyl compounds of Formula (I): and pharmaceutically acceptable salts, prodrugs, or solvates thereof, wherein X, Y, Z, R1, R2, m, and n are defined as set forth in the specification. The invention is also directed to the use of compounds of Formula (I) to treat a disorder responsive to the blockade of calcium channels, and particularly N-type calcium channels. Compounds of the present invention are especially useful for treating pain.
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Page/Page column 37
(2011/06/24)
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- Magnesium metal-mediated reductive trifluoromethylation of aldehydes with phenyl trifluoromethyl sulfone
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An unprecedented reductive nucleophilic trifluoromethylation of aldehydes by using phenyl trifluoromethyl sulfone is reported. Mercury(II) chloride efficiently activates magnesium metal to induce the desulfonylative trifluoromethylation process. The new r
- Zhao, Yanchuan,Zhu, Jieming,Ni, Chuanfa,Hu, Jinbo
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scheme or table
p. 1899 - 1904
(2010/08/19)
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- Process of use in perfluoroalkyation and reactant for making use of this process
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The subject-matter of the present invention is a process of use in perfluoroalkylation and a reactant for making use of this process. This process is defined in that it comprises a stage in which a material of formula RfH and a base (or a species capable of generating a base) are brought into contact, in a polar and anhydrous medium, with a substrate carrying at least one electrophilic functional group. Application to organic synthesis.
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- Fluoroform: An efficient precursor for the trifluoromethylation of aldehydes
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Fluoroform is shown to be an efficient trifluoromethylating agent when deprotonated using standard reagents in DMF. The important role of DMF as a solvent but also as a reactant was demonstrated.
- Folléas, Beno?t,Marek, Ilan,Normant, Jean-F.,Saint-Jalmes, Laurent
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p. 275 - 283
(2007/10/03)
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- Effective nucleophilic trifluoromethylation with fluoroform and common base
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Common bases (alcoholate, dimsyl anion or amide) are able to deprotonate trifluoromethane to form a trifluoromethyl anion equivalent. In this reaction DMF plays a crucial role of stabilisation Trifluoromethyl aryl alcohols, ketones or sulfides can be obtained in good yields with the new reagent CF3H/Base/DMF.
- Russell, Jamie,Roques, Nicolas
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p. 13771 - 13782
(2007/10/03)
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- Coenzyme A hemithioacetals as easily prepared inhibitors of CoA ester-utilizing enzymes
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Hemithioacetals are formed by reactions of coenzyme A (CoA) with aldehydes in aqueous solution. Equilibria for hemithioacetal formation with four commercially available aldehydes and rate constants for hemithioacetal dissociation have been studied. The hemithioacetals are viewed as acyl-CoA analogs having a tetrahedral center in place of the planar trigonal thioester carbonyl carbon. These compounds may serve as mimics of the tetrahedral intermediate or transition state in the reactions of acyl-CoA dependent acyltransferase enzymes. The hemithioacetal generated by reaction of CoA with formaldehyde is a poor inhibitor of chloramphenicol acetyltransferase, with a K(i) more than 6-fold higher than the K(m) for the substrate acetyl-CoA. The hemithioacetals formed by reaction of CoA with acetaldehyde and trifluroacetaldehyde are substantially better inhibitors, with K(i) values approximately 2.4-fold and 10-fold lower than the K(m) values for acetyl-CoA, respectively. The hemithioacetal formed by reaction of CoA with succinic semialdehyde inhibits succinic thiokinase, with a K(i) 4-fold lower than the K(m) for the substrate succinyl-CoA. The CoA hemithioacetals provide a novel readily accessible new class of acyl-CoA analogs for use in mechanistic and structural studies of CoA ester-utilizing enzymes.
- Schwartz, Benjamin,Vogel, Kurt W.,Drueckhammer, Dale G.
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p. 9356 - 9361
(2007/10/03)
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- Synthese d'α-Hydroxysulfinates
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α-hydroxysulfinates 1 (table 1) are synthesized (path b, Fig. 1), by slowly adding aldehydes 3 to the mixture sodium dithionite 4 - sodium hydroxide.Owing to their limited stability the products 1 are readily separated from sodium sulfite 5 and isolated.They are easily distinguished (table 2) from their oxydation counterparts 2.
- Mulliez, Michel,Naudy, Carole
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p. 2469 - 2476
(2007/10/02)
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