350-52-7

Upstream product

• 108-37-2 1-bromo-3-chlorobenzene 
• 373-52-4 bromofluoromethane 
• 766-80-3 1-bromomethyl-3-chlorobenzene 
• 108-41-8 1-chloro-3-methylbenzene 

Downstream Products

• 113399-26-1 α-fluoro-α,m-dichlorotoluene 
• 113399-27-2 α-bromo-α-fluoro-m-chlorotoluene 

Relevant academic research and scientific papers

Thiourea-Catalyzed C?F Bond Activation: Amination of Benzylic Fluorides

We describe the first thiourea-catalyzed C?F bond activation. The use of a thiourea catalyst and Ti(OiPr)4 as a fluoride scavenger allows the amination of benzylic fluorides to proceed in moderate to excellent yields. Preliminary results with S- and O-based nucleophiles are also presented. DFT calculations reveal the importance of hydrogen bonds between the catalyst and the fluorine atom of the substrate to lower the activation energy during the transition state.

Nickel-catalyzed monofluoromethylation of (hetero)aryl bromides via reductive cross-coupling

A mild and efficient nickel-catalyzed direct monofluoromethylation of (hetero)aryl bromides by reductive cross-coupling has been developed. This method exhibits good efficiency, wide functional-group compatibility, and suitability for aryl and heteroaryl bromides with abundant industrial raw material BrCH2F. This strategy provides an efficient way to synthesize monofluoromethylated molecules for drug discovery.

Friedel-crafts reaction of benzyl fluorides: Selective activation of C-f bonds as enabled by hydrogen bonding

A Friedel-Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1-diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C-F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C-F bonds in the presence of other benzylic leaving groups.

Novel Synthesis of 2,2,2-Trifluoroethyl Compounds from Homoallylic Alcohols: A Copper(I) Iodide-initiated Trifluoromethyl-Dehydroxylation Process

Benzyl, prop-2-enyl and allyl chlorodifluoroacetates 3a, bromodifluoroacetates 3b or fluorosulfonyldifluoroacetates 3c, when decomposed in the presence of 1 equivalent of copper(I) iodide at an appropriate temperature in dimethylformamide, gave the corresponding trifluoromethyl derivatives in good to excellent yields.The products can also be obtained directly by ester exchange of XCF2CO2Et (X = FSO2, Cl, Br) 6 and the corresponding alcohols in the presence of KF and CuI.A trifluoromethylation-dehydroxylation mechanism, initiated by CuI, is proposed.

Acceleration of the Fluorination of Benzyl Halide by the Combination of Lead Fluoride and Sodium Salt

A new composite reagent, a combination of lead fluoride (PbF2) and a small amount of sodium salt (NaX, X=F, Br etc.) was found to be useful for facilitating heterogeneous fluorination of substituted benzyl halides in acetonitrile.

Substituent modulation of mild fluorination of aromatic molecules with caesium fluoroxysulphate

Functionalization of mono- and di-substituted benzene derivative with CsSO4F has been modulated by substituents on the benzene ring. α-Hydroxyalkylbenzenes, with a deactivated ring, were oxidized to phenones, while fluorodealkylation was achieved in high yield when electron-donating groups were present in a para position. Electron-withdrawing substituents favoured chain fluorofunctionalization in alkylbenzenes, while ring fluorination was found exclusively in acylamino-derivatized alkylbenzenes; fluoro-addition products were formed in the case of p-alkoxy-substituted alkylbenzene derivatives.

MECHANISMS OF FREE-RADICAL REACTIONS. XX. REACTIVITY IN THE FREE-RADICAL HALOGENATION REACTIONS OF ARYLFLUOROALKANES

The free-radical chlorination and bromination of meta- and para-substituted benzyl fluorides and 1,1-difluoro-2-phenylethane and also the chlorination of 1-fluoro-2-arylethanes by phenylchloroiodonium chloride and the bromination of meta- and para-substituted benzyl bromides were studied by the method of competing reactions.In all cases a good correlation is observed between log krel and the Brown ?+ constants.In cases where change in the reactivity in the transition from one reaction series to another is due mainly to the polar effect of the substituent whilethe selectivity is measured in relation to the polar effect direct relationships are observed between the reactivity and the selectivity.