711-33-1

Usage

Chemical Properties

solid

InChI:InChI=1/C10H9F3O/c1-2-9(14)7-3-5-8(6-4-7)10(11,12)13/h3-6H,2H2,1H3

Upstream product

• 402-43-7 p-trifluoromethylphenyl bromide 
• 79-03-8 propionyl chloride 
• 592-02-9 diethylcadmium 
• 329-15-7 4-trifluoromethyl-phenyl acetyl chloride 
• 2786-01-8 (4-trifluoromethylphenyl)lithium 
• 42006-43-9 (E)-1-(prop-1-en-1-yl)-4-(trifluoromethyl)benzene 
• 79756-87-9 1-(prop-1-ynyl)-4-trifluoromethylbenzene 
• 74-96-4 ethyl bromide 
• 455-24-3 4-trifluoromethylbenzoic acid 
• 149946-79-2 1-(4'-(trifluoromethyl)phenyl)-allylalcohol 
• 709-63-7 1-(4-trifluoromethylphenyl)ethanone 
• 68-12-2 N,N-dimethyl-formamide 
• 74-88-4 methyl iodide 
• 67-56-1 methanol 

Downstream Products

• 126065-77-8 1-(1,1,2-Trichloro-propyl)-4-trifluoromethyl-benzene 
• 107075-67-2 2-methyl-1-(4-trifluoromethylphenyl)-3-pyrrolidino-1-propanone 
• 1977-67-9 3-Dimethylamino-2-methyl-1-(4-trifluoromethyl-phenyl)-propan-1-one 
• 95728-57-7 2-bromo-1-(4-trifluoromethylphenyl)propan-1-one 
• 67081-98-5 (R)-1-(4-(trifluoromethyl)phenyl)propan-1-ol 

Relevant academic research and scientific papers

α-Methylation of Ketones with Methanol Catalyzed by Ni/SiO2-Al2O3

α-Methylation of ketones with methanol catalyzed by a cheap and easy to handle Ni/SiO2-Al2O3 was explored. After optimization of the reaction between propiophenone and methanol, the desired product was obtained in 95 % isolated yield. A wide range of ketones was methylated under the optimized conditions (16 examples). This procedure was extended to a three-component cross-benzylation-methylation of acetophenone.

Ligand-Controlled Chemoselective C(acyl)-O Bond vs C(aryl)-C Bond Activation of Aromatic Esters in Nickel Catalyzed C(sp2)-C(sp3) Cross-Couplings

A ligand-controlled and site-selective nickel catalyzed Suzuki-Miyaura cross-coupling reaction with aromatic esters and alkyl organoboron reagents as coupling partners was developed. This methodology provides a facile route for C(sp2)-C(sp3) bond formation in a straightforward fashion by successful suppression of the undesired β-hydride elimination process. By simply switching the phosphorus ligand, the ester substrates are converted into the alkylated arenes and ketone products, respectively. The utility of this newly developed protocol was demonstrated by its wide substrate scope, broad functional group tolerance and application in the synthesis of key intermediates for the synthesis of bioactive compounds. DFT studies on the oxidative addition step helped rationalizing this intriguing reaction chemoselectivity: whereas nickel complexes with bidentate ligands favor the C(aryl)-C bond cleavage in the oxidative addition step leading to the alkylated product via a decarbonylative process, nickel complexes with monodentate phosphorus ligands favor activation of the C(acyl)-O bond, which later generates the ketone product.

A Coupling Approach for the Generation of α,α-Bis(enolate) Equivalents: Regioselective Synthesis of gem-Difunctionalized Ketones

Regioselective α,α-difunctionalization adjacent to a ketone is a significant synthetic challenge. Here, we present a solution to this problem through the transition-metal-free coupling of esters with geminal bis(boron) compounds. This forms an α,α-bis(enolate) equivalent which can be trapped with electrophiles including alkyl halides and fluorinating agents. This presents an efficient, convergent synthetic strategy for the synthesis of unsymmetrical blocked ketones.

METHOD OF PRODUCING 2'-TRIFLUOROMETHYL GROUP-SUBSTITUTED AROMATIC KETONE

A method produces a 2′-trifluoromethyl-substituted aromatic ketone and includes reacting a 2-halogen-substituted benzotrifluoride compound with magnesium metal to convert the compound to a Grignard reagent; and reacting the Grignard reagent with an acid anhydride; and then hydrolyzing the resultant to produce a 2′-trifluoromethyl-substituted aromatic ketone. The method of producing a 2′-trifluoromethyl-substituted aromatic ketone enables 2′-trifluoromethyl-substituted aromatic ketone to be produced without using expensive raw materials by generating a Grignard reagent as an intermediate and reacting this Grignard reagent with an acid anhydride in an efficient productivity. The 2′-trifluoromethyl-substituted aromatic ketone that is produced by the method of producing a 2′-trifluoromethyl-substituted aromatic ketone can be used as fine chemicals, raw materials for pharmaceuticals and agrochemicals, raw materials for resins and plastics, electronics and information related materials, optical materials, and the like.

Alcohol Oxidations Using Reduced Polyoxovanadates

A full account of our recently communicated room temperature alcohol oxidation using reduced polyoxovanadates (r-POVs) is presented. Extensive optimizations revealed optimal conditions employing 0.02 equiv. of r-POV catalyst Cs5(V14As8O42Cl), 5 equiv. tert-butyl hydrogen peroxide (tBuOOH) as the terminal co-oxidant, in an acetone solvent for the quantitative oxidation of aryl-substituted secondary alcohols to their ketone products. The substrate scope tolerates most aryl substituted secondary alcohols in good to quantitative yields while alkyl secondary and primary activated alcohols were sluggish in comparison under similar conditions. Catalyst recyclability was successful on a 1.0?mmol scale of starting alcohol 1-phenylethanol. The oxidation was also successfully promoted by the VIV/VV mixed valent polyoxovanadate (POV) Cs11Na3Cl5(V15O36Cl). Finally, a third POV, Cs2.64(V5O9)(AsO4)2, was investigated for catalytic activity using our established reaction protocol, but proved ineffective as compared to the other two r-POV catalysts. This study expands the field of POM-mediated alcohol oxidations to include underexplored r-POV catalysts. While our catalysts do not supplant the best catalysts known for the transformation, their study may inform the development of other novel oxidative transformations mediated by r-POVs.

Stereoselective amination of racemic sec-alcohols through sequential application of laccases and transaminases

A one-pot/two-step bienzymatic asymmetric amination of secondary alcohols is disclosed. The approach is based on a sequential strategy involving the use of a laccase/TEMPO catalytic system for the oxidation of alcohols into ketone intermediates, and their following transformation into optically enriched amines by using transaminases. Individual optimizations of the oxidation and biotransamination reactions have been carried out, studying later their applicability in a concurrent process. Therefore, 17 racemic (hetero) aromatic sec-alcohols with different substitutions in the aromatic ring have been converted into enantioenriched amines with good to excellent selectivities (90-99% ee) and conversion values (67-99%). The scalability of the process was also demonstrated when two different amine donors were used in the transamination step, such as isopropylamine and cis-2-buten-1,4-diamine. Satisfyingly, both sacrificial amine donors can shift the equilibrium toward the amine formation, leading to the corresponding isolated enantioenriched amines with good to excellent results.

Room-temperature catalytic oxidation of alcohols with the polyoxovanadate salt Cs5(V14As8O42Cl)

While many known methods for oxidation mediated by polyoxometalates (POMs) employ environmentally friendly co-oxidants, they tend to employ large catalyst loadings (e.g. 40 mol%) and costly high reaction temperatures (~90-135 °C) that potentially contribute to the degradation of the catalyst and reduce their effectiveness. Herein, we present some initial results demonstrating a room temperature catalytic oxidation using the reduced salt-inclusion polyoxometalate, Cs5(V14As8O42Cl), that contains polyoxovanadate (POV) clusters as an efficient catalyst (e.g., 2 mol%) in the transformation of secondary alcohols to their corresponding ketones in very good to quantitative yields. Further, the catalyst can be suspended on celite and recycled.

Transition-Metal-Free Self-Hydrogen-Transferring Allylic Isomerization

Phenanthroline and tert-butoxide have been established as powerful radical initiators in reactions such as the SRN1-type coupling reactions due to the cooperation of large heteroarenes and a special feature of tert-butoxide. The first phenanthroline-tert-butoxide-catalyzed transition-metal-free allylic isomerization is described. The resulting ketones are key intermediates for indenes. The control experiments rule out the base-promoted allylic anion pathway. The radical pathway is supported by experimental evidence that includes kinetic study, kinetic isotope effect, isotope-labeling experiments, trapping experiments, and EPR experiments.

DMF as carbon source: Rh-catalyzed α-methylation of ketones

An unprecedented Rh-catalyzed direct methylation of ketones with N,N-dimethylformamide (DMF) is disclosed. The reaction shows a broad substrate scope, tolerating both aryl and alkyl ketones with various substituents. Mechanistic studies suggest that DMF delivers a methylene fragment followed by a hydride in the methylation process.

Rhodium-catalysed isomerisation of allylic alcohols in water at ambient temperature

An environmentally benign method for the transformation of allylic alcohols into carbonyl compounds is described. Using [Rh(COD(CH3CN) 2]BF4 (2) in combination with 1,3,5-triaza-7- phosphaadamantane (PTA, 1) as the catalytic system in water results in a very fast redox isomerisation of a variety of secondary allylic alcohols at ambient temperature. Also, some primary allylic alcohols can be isomerised into the corresponding aldehydes. The active complex, which in some cases can be used in catalyst loadings as low as 0.5 mol%, is formed in situ from commercially available reagents. Based on deuterium labelling studies, a tentative mechanism involving metal-enone intermediates is presented.