1737-23-1

Upstream product

• 2923-18-4 sodium 2,2,2-trifluoroacetate 
• 620-23-5 m-tolyl aldehyde 
• 421-53-4 2,2,2-trifluoro-1,1-ethanediol 
• 407-38-5 2,2,2-trifluoroethyl trifluoroacetate 
• 625-95-6 3-Iodotoluene 
• 431-47-0 trifluoroacetic acid-methyl ester 
• 75-46-7 trifluoromethan 
• 1736-06-7 3'-methyl-2,2,2-trifluoroacetophenone 

Downstream Products

• 100664-06-0 Phosphoric acid bis-(2,2,2-trifluoro-ethyl) ester 2,2,2-trifluoro-1-m-tolyl-ethyl ester 
• 125657-21-8 m-methyl-α-trifluoromethylbenzyldichlorophosphate 
• 100664-11-7 Phosphoric acid bis-(2,2,3,3,4,4,5,5,5-nonafluoro-pentyl) ester 2,2,2-trifluoro-1-m-tolyl-ethyl ester 
• 125888-89-3 Phosphorochloridic acid 2,2,2-trifluoro-ethyl ester 2,2,2-trifluoro-1-m-tolyl-ethyl ester 
• 1422984-77-7 C₁₀H₁₀F₃NO₃ 
• 1736-06-7 3'-methyl-2,2,2-trifluoroacetophenone 
• 50562-00-0 1-methyl-3-(2,2,2-trifluoroethyl)benzene 

Relevant academic research and scientific papers

One-Pot Successive Turbo Grignard Reactions for the Facile Synthesis of α-Aryl-α-Trifluoromethyl Alcohols

A novel straightforward one-pot methodology for two successive turbo Grignard reagent (iPrMgCl·LiCl) reactions, was developed for a facile synthesis of α-aryl-α-trifluoromethyl alcohols, motifs of value in pharmaceutical chemistry. The method displayed broad functional group tolerance, including reducible groups. Dual roles of iPrMgCl·LiCl were exploited in the tandem reaction with commercially available iodoarenes or iodoheteroarenes and 2,2,2-trifluoroethyl trifluoroacetate. The process encompasses three successive reactions in a one-pot process: the iPrMgCl·LiCl-mediated iodine/magnesium-exchange reaction of iodoarenes or iodoheteroarenes; nucleophilic addition of various generated aryl or heteroarylmagnesium reagents to 2,2,2-trifluoroethyl trifluoroacetate; and the reduction of in-situ generated aryl trifluoromethyl ketones with iPrMgCl·LiCl, to produce the corresponding α-aryl or α-heteroaryl-α-trifluoromethyl alcohols bearing various substituents, including reducible functional groups in good to excellent yields.

Asymmetric Hydrogenation of Aryl Perfluoroalkyl Ketones Catalyzed by Rhodium(III) Monohydride Complexes Bearing Josiphos Ligands

The asymmetric hydrogenation of 2,2,2-trifluoroacetophenones and aryl perfluoroalkyl ketones was developed using a unique, well-defined chloride-bridged dinuclear rhodium(III) complex bearing Josiphos-type diphosphine ligands. These complexes were prepared from [RhCl(cod)]2, Josiphos ligands, and hydrochloric acid. As catalyst precursors, they allow for the efficient and enantioselective synthesis (up to 99 % ee) of chiral secondary alcohols with perfluoroalkyl groups. This system does not require an activating base for the hydrogenation of 2,2,2-trifluoroacetophenones. Additionally, the enantioselective C=O hydrogenations of 2-phenyl-3-(haloacetyl)-indoles, a class of privileged structures in medicinal chemistry, is reported for the first time.

METHOD FOR PRODUCING TRIFLUOROMETHYL GROUP-CONTAINING ALCOHOLS

PROBLEM TO BE SOLVED: To provide a method for producing trifluoromethyl group-containing alcohols useful as synthetic intermediates for medicines and agrochemicals. SOLUTION: This invention relates to a method for producing trifluoromethyl group-containing alcohols expressed by a formula (2), comprising: making carbonyl compounds expressed by a formula (1) react with trifluoromethane in an organic solvent in the presence of polyvalent ethers and potassium tert-butoxide, or kalium hexamethyldisilazide. (R1 and R2 are each independently a phenyl group etc.; R2 may combine with R1, to form a ring, and both R1 and R2 are not hydrogen atoms). SELECTED DRAWING: None COPYRIGHT: (C)2018,JPOandINPIT

DIRECT TRIFLUOROMETHYLATIONS USING TRIFLUOROMETHANE

A direct trifluoromethylation method preferably using a trifluoromethane as a fluoro-methylating species. In particular, the present method is used for preparing a trifluoromethylated substrate by reacting a fluoromethylatable substrate with a trifiuoromethylating agent in the presence of an alkoxide or metal salt of silazane under conditions sufficient to trifluoromethylate the substrate; wherein the fluoromethylatable substrate includes chlorosilanes, carbonyl compounds such as esters, aryl halides, aldehydes, ketones, chalcones, alkyl formates, alkyl halides, aryl halides, alkyl borates, carbon dioxide or sulfur.

Nucleophilic trifluoromethylation of carbonyl compounds: Trifluoroacetaldehyde hydrate as a trifluoromethyl source

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.

Taming of fluoroform: Direct nucleophilic trifluoromethylation of Si, B, S, and C centers

Fluoroform (CF3H), a large-volume by-product of the manufacture of Teflon, refrigerants, polyvinylidene fluoride (PVDF), fire-extinguishing agents, and foams, is a potent and stable greenhouse gas that has found little practical use despite the growing importance of trifluoromethyl (CF3) functionality in more structurally elaborate pharmaceuticals, agrochemicals, and materials. Direct nucleophilic trifluoromethylation using CF3H has been a challenge. Here, we report on a direct trifluoromethylation protocol using close to stoichiometric amounts of CF3H in common organic solvents such as tetrahydrofuran (THF), diethyl ether, and toluene. The methodology is widely applicable to a variety of silicon, boron, and sulfur-based electrophiles, as well as carbon-based electrophiles.

Sodium trifluoroacetate: An efficient precursor for the trifluoromethylation of aldehydes

In a convenient and efficient procedure, the nucleophilic trifluoromethylation of aldehydes with sodium trifluoroacetate was achieved, using copper(I) halides as the catalyst.

Remarkably Facile Solvolyses of Triflates via Carbocationic Processes in Dimethyl Sulfoxide

A number of triflates have been shown to undergo clean pseudo-first-order solvolysis reactions in DMSO-d6 to give products derived from carbocationic intermediates. Thus, t-BuCH(OTf)CO-t-Bu (5) and t-BuCH 2OTf (9) react readily in DMSO-d6 at 25 °C to give a rearranged oxosulfonium salts, and subsequent alkene products where methyl migration to the incipient cationic center occurs. t-BuCH(OTf)CO 2CH3 (14) gives analogous rearranged products, and 1-methylcyclopropyl triflate (21) gives a ring-opened allylic oxosulfonium salt. These triflates react primarily via kΔ pathways. 6-Methylbicyclo[3.1.0]hex-6-yl triflate (23), bicyclo[2.2.1hept-1-yl triflate (24), 1,6-methano[10]-annulen-11-yl triflate (25), (CH3) 2C(OTf)CO2CH3 (26), and (CH3) 2CCN(OTf) (29) all react in DMSO-d6 to give carbocation-derived products. PhCH(OTf)CF3 (33) and substituted analogues also react readily in DMSO-d6, and the Hammett ρ + value is -3.7. This suggests a "borderline" mechanism where the transition state has substantial charge development. The primary feature of these solvolyses is the high reactivity of all of these triflates in DMSO-d6. Thus, these triflates are all more reactive in DMSO-d 6 than in HOAc, and for most, rates are faster than in CF 3CH2OH. Triflates 5, 21, 29, and 33 are 10 8-109 times more reactive in DMSO-d6 than the corresponding mesylates. It is suggested that the decreased need for electrophilic solvation of trifiate anion, and the high cation solvating ability of DMSO, are the reasons for the high triflate reactivity in DMSO-d 6.

Coupling of fluoroform with aldehydes using an electrogenerated base

Trifluoromethylated alcohols are easily obtained in a one pot electroreaction in which cathodic reduction of iodobenzene generates a strong base which deprotonates fluoroform, inducing its coupling with aldehydes.