340-03-4

Upstream product

• 115262-00-5 [chloro(difluoro)methyl]trimethylsilane 
• 100-52-7 benzaldehyde 
• 383-62-0 ethyl 2-chloro-2,2-difluoroacetate 
• 591-51-5 phenyllithium 
• 108-86-1 bromobenzene 
• 384-67-8 2-chloro-2,2-difluoroacetophenone 

Downstream Products

• 74492-23-2 1-Chlor-1,1-difluor-2-methoxy-2-phenylethan 
• 78693-69-3 Toluene-4-sulfonic acid 2-chloro-2,2-difluoro-1-phenyl-ethyl ester 
• 74492-27-6 (1-Bromo-2-chloro-2,2-difluoro-1-methoxy-ethyl)-benzene 
• 648-78-2 (1-Bromo-2-chloro-1,2,2-trifluoro-ethyl)-benzene 
• 78693-67-1 2,2-difluoro-2-chloro-1-phenylethane 
• 124095-23-4 (S)-2-chloro-2,2-difluoro-1-phenylethan-1-ol 
• 119454-39-6 (R)-2-chloro-2,2-difluoro-1-phenylethanol 
• 56135-05-8 Methyl-2,2-difluor-1-phenylvinylether 
• 447-14-3 1,2,2-trifluorostyrene 
• 394-98-9 α-chloro-β,β-difluorostyrene 
• 384-65-6 1-chloro-2,2,2-trifluoroethylbenzene 
• 124095-25-6 Acetic acid 2-chloro-2,2-difluoro-1-phenyl-ethyl ester 
• 74492-24-3 1-Chlor-1,1-difluor-2-iod-2-phenylethan 
• 74492-18-5 2-chloro-1-phenyl-1,2,2-trifluoroethane 

Relevant academic research and scientific papers

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.

Unusual reactions of Grignard reagents toward fluoroalkylated esters

Fluorine-containing esters were demonstrated to be convenient substrates for construction of the corresponding ketones by low temperature reaction with Grignard reagents followed by warming up to 0 °C, while heating the mixture up to 80 °C readily promoted the reduction of the ketones obtained by the generated magnesium alkoxides whose mechanism was speculated as Meerwein-Ponndorf-Verley type reduction by computational technique.

A highly efficient room temperature non-organometallic route for the synthesis of α,β,β-trifluorostyrenes by dehydrohalogenation

Various 1-aryl-1,2,2,2-tetrafluoroethanes (ArCHFCF3, Ar=phenyl, substituted phenyl, naphthyl, heteroaryl) were synthesized by the fluorination of the corresponding alcohols with DAST. Dehydrofluorination of ArCHFCF3 using lithium hexamethyldisilazide (LHMDS) base in THF at room temperature produced 1,2,2-trifluorostyrenes (ArCF=CF2) in 61-91% isolated yields. This procedure provides an excellent non-organometallic alternative to the generally used metallation-Pd(0) coupling methods.

Preparation of and fluoroalkylation with (chlorodifluoromethyl)trimethylsilane, difluorobis(trimethylsilyl)methane, and 1,1,2,2-tetrafluoro-1,2-bis(trimethylsilyl)ethane

CF2BrCl reacts with aluminum/N-methylpyrrolidinone in the presence of chlorotrimethylsilane to give Me3SiCF2Cl in high yield. Similarly, CF2Br2 gives Me3SiCF2Br with bromotrimethylsilane. Chlorodifluoromethylation of aldehydes using Me3SiCF2Cl and a catalytic amount of TBAF in polar solvents occurs at room temperature, providing difluoromethylated alcohols in two steps. Electroreduction of Me3SiCF2Cl in the presence of chlorotrimethylsilane gives Me3SiCF2SiMe3 (anion-derived product) and Me3SiCF2CF2SiMe3 (radical-derived product). Using THF/HMPA strongly favors the former, whereas THF/TDA-1 (tris(3,6-dioxaheptyl)amine) the latter. Me3SiCF2SiMe3 difluoromethylates aldehydes acting as a difluoromethylene dianion ('CF22-'/equivalent), whereas Me3SiCF2CF2SiMe3 acts at room temperature as an in situ source for the perfluorovinyl anion (due to β-elimination of fluorotrimethylsilane). However, at low temperature the elimination pathway is suppressed and tetrafluoroethylene dianion ('-CF2CF2-'/equivalent) behavior is observed. The structure of Me3SiCF2CF2SiMe3 was analyzed by X-ray diffraction. All of the studied fluoroalkylating reagents are moisture- and air-stable and can be readily obtained from a single convenient precursor (CF2BrCl).

Lewis Acid Catalyzed Aldol-Type Reaction of 1,1-Difluorovinyl Methyl Ether Derivatives

In the presence of Lewis acid, such as SbCl5, SbCl6*NAr3 or Cu(OTf)2, difluorovinyl methyl ether (1,1-difluoro-2-methoxy-1-alkene) 1 reacted with carbonyl compounds to give O-methylated aldol-type products 3 in good yields, while Lewis acid, such as TMSOT

A microbially-based approach for the synthesis of chiral secondary alcohols bearing the difluoromethyl or chlorodifluoromethyl group

A synthetic approach to both enantiomers of the secondary alcohols , involving the stereoselective hydrolysis of ester derivatives, is described.The absolute configurations of these difluoromethylated or chlorodifluoromethylated molecules were determined.

Proton-Transfer Reactions. 2. Effects of Internal Return on Reactivity Difference between Alkoxide-Promoted Eliminations in tert-Butyl alcohol and Ethyl Alcohol

Kinetics of alkoxide-promoted dehydrofluorination reactions are reported for the series C6H5CH2CH2F (I), C6H5CH2CHF2 (II), C6H5CH2CF3 (III), and C6H5CH2CF2CF3 (V).Rates and activation parameters 3 (M-1 s-1)(50 deg C), ΔH* (kcal mol-1), and ΔS*, (eu)> are respectively: (a) using potassium tert-butoxide in tert-butyl alcohol, I (1.88 * 10-4, 19.1, -16.8), II (1.18 * 10-3, 20.3, -9.3), III (2.15 * 10-3, 22.1, -2.4), V (3.93 * 10-2, 16.9, -12.7); and (b) using sodium ethoxide in ethanol, I (1.32 * 10-6, 25.6, -6.5), II (5.28 * 10-7, 29.7, 3.0), III (3.45 * 10-7, 32.6, 12.5), V (5.41 * 10-5, 27.7, 7.6).The variation in tert-butoxide:ethoxide ratios of 140 (I), 2200 (II), 6200 (III), and 730 (V) are discussed in terms of a two-step mechanism with varying amounts of internal return for II, III, and V.Differences in reactivity for groups attached to the benzylic carbon (-CF3, -CF2Cl, -CHF2, -CF2CF3) and variation of ΔS* values for these reactions are also discussed in terms of a two-step mechanism.