5216-17-1

Usage

Chemical Properties

white crystalline mass

InChI:InChI=1/C9H8ClFO/c10-9(12)6-5-7-3-1-2-4-8(7)11/h1-4H,5-6H2

Upstream product

• 773-82-0 Pentafluorobenzonitrile 
• 99-75-2 4-methyl-benzoic acid methyl ester 
• 1897-46-7 2,3,5,6-tetrachlorobenzonitrile 
• 33104-02-8 1-(allyloxy)-2,3,4,5,6-pentafluorobenzene 
• 617-86-7 triethylsilane 
• 653-37-2 perfluorobenzaldehyde 
• 20925-85-3 pentachlorobenzonitrile 
• 344-04-7 bromopentafluorobenzene 
• 344-07-0 1-chloro-2,3,4,5,6-pentafluorobenzene 
• 827-15-6 1,2,3,4,5-pentafluoro-6-iodobenzene 
• 31469-84-8 4-chloro-2,3,5,6-tetrafluorobenzonitrilev 
• 68-12-2 N,N-dimethyl-formamide 
• 31469-85-9 4-iodo-2,3,5,6-tetrafluoro-benzonitrile 
• 67-56-1 methanol 

Downstream Products

• 306739-71-9 2,3,5,6-tetrafluorobenzaldehyde dimethylacetal 
• 19842-76-3 2,3,5,6-tetrafluorobenzaldehyde 
• 209995-38-0 (2,4,5-trifluorophenyl)acetic acid 

Relevant academic research and scientific papers

Diazaphospholene-Catalyzed Hydrodefluorination of Polyfluoroarenes with Phenylsilane via Concerted Nucleophilic Aromatic Substitution

The metal-free catalytic C-F bond activation of polyfluoroarenes was achieved with diazaphospholene as the catalyst and phenylsilane as the terminal reductant. Density functional theory calculations suggested a concerted nucleophilic aromatic substitution mechanism.

Catalyst-Free Hydrodefluorination of Perfluoroarenes with NaBH4

Presented is an economical means of removing fluorine from various highly fluorinated arenes using NaBH4. The procedure was adapted for different classes of perfluoroarenes. A novel isomer of an emerging class of organic dyes based on the carbazole phthalonitrile motif was succinctly synthesized in two steps from tetrafluorophthalonitrile, demonstrating the utility of the hydrodefluorination procedure. Initial exploration of the dye shows it to be photoactive and capable of facilitating contrathermodynamic styrenoid E/Z isomerization.

Catalytic Hydrodefluorination via Oxidative Addition, Ligand Metathesis, and Reductive Elimination at Bi(I)/Bi(III) Centers

Herein, we report a hydrodefluorination reaction of polyfluoroarenes catalyzed by bismuthinidenes, Phebox-Bi(I) and OMe-Phebox-Bi(I). Mechanistic studies on the elementary steps support a Bi(I)/Bi(III) redox cycle that comprises C(sp2)-F oxidative addition, F/H ligand metathesis, and C(sp2)-H reductive elimination. Isolation and characterization of a cationic Phebox-Bi(III)(4-tetrafluoropyridyl) triflate manifests the feasible oxidative addition of Phebox-Bi(I) into the C(sp2)-F bond. Spectroscopic evidence was provided for the formation of a transient Phebox-Bi(III)(4-tetrafluoropyridyl) hydride during catalysis, which decomposes at low temperature to afford the corresponding C(sp2)-H bond while regenerating the propagating Phebox-Bi(I). This protocol represents a distinct catalytic example where a main-group center performs three elementary organometallic steps in a low-valent redox manifold.

Defluorodearomatization: A Photocatalytic Birch-Like Reduction That Enables C-C Bond Formation and Provides Access to Unnatural Cannabinoids

Within the framework of discovery chemistry, polyfluorination remains a synthetic challenge despite its ability to provide useful characteristics, such as a reduction in the number of hydrogen bond donors and metabolic stability. Coupling a reversal of this methodology with photocatalysis has been demonstrated to allow the rapid synthesis of previously difficult or impossible targets by starting with fluorines everywhere and selectively removing or functionalizing them. Herein, we demonstrate a novel method to synthesize 1,4-cyclohexadienes through a dearomative photocatalytic C-C coupling reaction. This allows for access to materials that are orthogonal to the selectivity of the Birch reaction and are more functional-group-tolerant. The reaction also allows the efficient synthesis of polyfluorinated cannabinoids. While the yields are modest, the access to the new chemical space provided by the reaction is unprecedented by any means. The trifluorinated analog of THC, 1-deoxy-1,2,4-trifluoro-THC, is synthesized, demonstrating the importance of discovery chemistry and the ability to explore otherwise unknown structure-activity relationships.

Mechanistic Insights into C(sp2)?C(sp)N Reductive Elimination from Gold(III) Cyanide Complexes

A new family of phosphine-ligated dicyanoarylgold(III) complexes has been prepared and their reactivity towards reductive elimination has been studied in detail. Both, a highly positive entropy of activation and a primary 12/13C KIE suggest a late concerted transition state while Hammett analysis and DFT calculations indicate that the process is asynchronous. As a result, a distinct mechanism involving an asynchronous concerted reductive elimination for the overall C(sp2)?C(sp)N bond forming reaction is characterized herein, for the first time, complementing previous studies reported for C(sp3)?C(sp3), C(sp2)?C(sp2), and C(sp3)?C(sp2) bond formation processes taking place on gold(III) species.

Method for preparing polyfluorobenzonitrile through catalytic fluorination of polychlorobenzonitrile

The invention discloses a method for preparing polyfluorobenzonitrile through catalytic fluorination of polychlorobenzonitrile, and belongs to the field of preparation of fine chemical industry intermediates. The preparation method comprises the following steps: carrying out a heating activation reaction on a fluoride salt, an organic solvent and electron-withdrawing substituted phenylborate; andadding polychlorobenzonitrile, heating to 80-120 DEG C, rectifying while reacting, then supplementing polychlorobenzonitrile and potassium fluoride, and rectifying while reacting to obtain polyfluorobenzonitrile. According to the invention, the reaction system is high in catalytic activity, the technical problems of low conversion rate/medium selectivity and the like of the single nitrile compounds with low activity during fluoridation reactions are solved, the mode simultaneously performing reacting and product distilling in the reaction process promotes the continuous forward proceeding of the reaction so as to improve the reaction yield, and the method is suitable for industrial production.

Dihydridoboranes: Selective Reagents for Hydroboration and Hydrodefluorination

The preparation of a new series of dihydridoboranes supported by N,N-chelating ligands, [R2NCH2CH2NAr]- (R = alkyl, Ar = aryl), is reported. These new boranes react selectively with carbonyls, imines, and a series of electron-deficient fluoroarenes. The reactivity is complementary to recognized reagents such as pinacolborane, catecholborane, NHC-BH3, and borane (BH3) itself. Selectivities are rationalized by invoking both open- A nd closed-chain forms of the reagents as part of equilibrium mixtures.

Prenyl Praxis: A Method for Direct Photocatalytic Defluoroprenylation

The prenyl fragment is the quintessential constituent of terpenoid natural products, a diverse family which contains numerous members with diverse biological properties. In contrast, fluorinated and multifluorinated arenes make up an important class of anthropogenic molecules which are highly relevant to material, agricultural, and pharmaceutical industries. While allylation chemistry is well developed, effective prenylation strategies have been less forthcoming. Herein, we describe the photocatalytic defluoroprenylation, a powerful method that provides access to "hybrid molecules" that possess both the functionality of a prenyl group and fluorinated arenes. This approach involves direct prenyl group transfer under very mild conditions, displays excellent functional group tolerance, and includes relatively short reaction times (4 h), which is the fastest photocatalytic C-F functionalization developed to date. Additionally, the strategy can be extended to include allyl and geranyl (10 carbon fragment) transfers. Another prominent finding is a reagent-dependent switch in regioselectivity of the major product from para to ortho C-F functionalization.

Transition-Metal-Free Catalytic Hydrodefluorination of Polyfluoroarenes by Concerted Nucleophilic Aromatic Substitution with a Hydrosilicate

A transition-metal-free catalytic hydrodefluorination (HDF) reaction of polyfluoroarenes is described. The reaction involves direct hydride transfer from a hydrosilicate as the key intermediate, which is generated from a hydrosilane and a fluoride salt. The eliminated fluoride regenerates the hydrosilicate to complete the catalytic cycle. Dispersion-corrected DFT calculations indicated that the HDF reaction proceeds through a concerted nucleophilic aromatic substitution (CSNAr) process.

Hydrodefluorination of Fluoroarenes Using Hydrogen Transfer Catalysts with a Bifunctional Iridium/NH Moiety

The hydrodefluorination of fluoroarenes with transfer hydrogenation catalysts using 2-propanol or potassium formate is described. With the aid of metal/NH cooperation, the C-N chelating Ir complexes derived from benzylic amines can efficiently promote the reduction involving the C-F bond cleavage under ambient conditions even in the absence of hydrosilanes or H2 gas, leading to the partially fluorinated products in good yields and with high selectivity.