122590-75-4

Usage

Chemical Properties

Pale Yellow Solid

Uses

A protected photoaffinity reagent.

InChI:InChI=1/C8H3F4N3O2/c1-17-8(16)2-3(9)5(11)7(14-15-13)6(12)4(2)10/h1H3

Upstream product

• 727-55-9 dimethyl 2,3,5,6-tetrafluoroterephthalate 
• 36629-42-2 methyl pentafluorobenzoate 
• 602-94-8 Pentafluorobenzoic acid 
• 715-37-7 methyl 4-amino-2,3,5,6-tetrafluorobenzoate 

Downstream Products

• 715-37-7 methyl 4-amino-2,3,5,6-tetrafluorobenzoate 
• 125569-12-2 4-(N',N'-Diethyl-hydrazino)-2,3,5,6-tetrafluoro-benzoic acid methyl ester 
• 126695-77-0 4-cyclohexylamino-2,3,5,6-tetrafluoro-benzoic acid methyl ester 
• 122590-77-6 4-azido-2,3,5,6-tetrafluorobenzoic acid 
• 122590-82-3 methyl N-benzyl-4-amino-2,3,5,6-tetrafluorobenzoate 
• 122590-83-4 methyl N-(4-methylphenyl)-4-aminotetrafluorobenzoate 
• 122590-84-5 methyl N-(2-methylphenyl)-4-aminotetrafluorobenzoate 
• 125568-96-9 C₁₆H₆F₈N₂O₄ 
• 125568-99-2 2,2,3,3-tetramethyl-1-(2,3,5,6-tetrafluoro-4-carbomethoxyphenyl)aziridine 
• 126695-58-7 succinimidyl 4-azido-2,3,5,6-tetrafluorobenzoate 

Relevant academic research and scientific papers

A Potent Halogen-Bonding Donor Motif for Anion Recognition and Anion Template Mechanical Bond Synthesis

The covalent attachment of electron deficient perfluoroaryl substituents to a bis-iodotriazole pyridinium group produces a remarkably potent halogen bonding donor motif for anion recognition in aqueous media. Such a motif also establishes halogen bonding anion templation as a highly efficient method for constructing a mechanically interlocked molecule in unprecedented near quantitative yield. The resulting bis-perfluoroaryl substituted iodotriazole pyridinium axle containing halogen bonding [2]rotaxane host exhibits exceptionally strong halide binding affinities in competitive 50 % water containing aqueous media, by a factor of at least three orders of magnitude greater in comparison to a hydrogen bonding rotaxane host analogue. These observations further champion and advance halogen bonding as a powerful tool for recognizing anions in aqueous media.

Differentiating p Interactions by Constructing Concave/Convex Surfaces Using a Bucky Bowl Molecule, Corannulene in Liquid Chromatography

Convex-concave p conjugated surfaces in hemispherical bucky bowl such as corannulene (Crn) have shown increasing utility in constructing self-assembled new functional materials owing to its unique p electrons and strong dipole. Here, we investigate these specific molecular recognitions on Crn by developing new silica-monolithic capillary columns modified with Crn and evaluating their performance in the separation of different aromatic compounds by liquid chromatography (LC). We synthesized two Crn derivatives and conjugated them onto the surface of a silica monolith. The first Crn derivative was edge functionalized, which can undergo free inversion of a convex-concave surface. The second Crn derivative was synthesized by modifying the spoke of Crn, which suppresses the convex-concave inversion. Results of LC suggest that each surface showed different shape recognition based on p interaction. Furthermore, the concave surface of Crn showed strong CH-p interaction with a planar molecule, coronene, demonstrated by the shifts of the1H NMR signals of both Crn and coronene resulting from the multiple interactions between Crn and p electrons in coronene. These results clearly demonstrated the presence of CH-p interactions at multiple points, and the role of shape recognition.

A general method for the fabrication of graphene-nanoparticle hybrid material

We describe a simple and general approach to conjugate nanoparticles on pristine graphene. The method takes advantage of the high reactivity of perfluorophenyl nitrene towards the C=C bonds in graphene, where perfluorophenyl azide-functionalized nanoparticles are conjugated to pristine graphene through the [2+1] cycloaddition reaction by a fast photoactivation.

Photoactivatable Fluorogens by Intramolecular C-H Insertion of Perfluoroaryl Azide

Molecules, capable of fluorescence turn-on by light, are highly sought-after in spatio-temporal labeling, surface patterning, monitoring cellular and molecular events, and high-resolution fluorescence imaging. In this work, we report a fluorescence turn-on system based on photoinitiated intramolecular C-H insertion of azide into the neighboring aromatic ring. The azide-masked fluorogens were efficiently synthesized via a cascade nucleophilic aromatic substitution of perfluoroaryl azides with carbazoles. The scaffold also allows for derivatization with biological ligands, as exemplified with d-mannose in this study. This photoinitiated intramolecular transformation led to high yields, high photo-conversion efficiency, and well-separated wavelengths for photoactivation and fluorescence excitation. The mannose-derivatized structure enabled spatio-temporal activation and showed high contrast and signal amplification. Live cell imaging suggested that the mannose-tagged fluorogen was transported to the lysosomes.

Polyurethane (PU)-derived photoactive and copper-free clickable surface based on perfluorophenyl azide (PFPA) chemistry

The anchoring and capturing roles of perfluorophenyl azide (PFPA) were combined to produce a universal polyurethane (PU)-derived photoactive surface platform (PU-1-PFPA). The resultant platform was confirmed by contact angle, attenuated total reflectance Fourier transform infrared (ATR FT-IR) spectroscopy, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) analyses. Upon UV light activation, native heparin was coupled directly onto PU-1-PFPA to yield a substrate with antithrombogenic properties. The same level of antithrombogenic activity was achieved when the recovered heparin was photo-coupled onto PU-1-PFPA. In addition, at room temperature and in the absence of copper catalysts, PU-1-PFPA achieved oriented immobilization of functional moieties bearing an alkynyl functional group.

Unique Separation Behavior of a C60 Fullerene-Bonded Silica Monolith Prepared by an Effective Thermal Coupling Agent

Herein, we report a newly developed C60 fullerene-bonded silica monolith in a capillary with unique retention behavior due to the structure of C60 fullerene. N-Hydroxysuccinimide (NHS)-conjugated C60 fullerene was successfully synthesized by a thermal coupling agent, perfluorophenyl azide (PFPA), and assigned by spectroscopic analyses. Then, NHS-PFPA-C60 fullerene was attached onto the surface of a silica monolith in a capillary. The capillary provided specific separation ability for polycyclic aromatic hydrocarbons in liquid chromatography by an effective π-π interaction. Furthermore, corannulene, which has a hemispherical structure, was selectively retained in the capillary based on the specific structural recognition due to the spherical C60 fullerene. This is the first report revealing the spherical recognition ability by C60 fullerene in liquid chromatographic separation. Spherical recognition: A C60 fullerene-bonded silica monolithic medium was prepared by using a thermal coupling agent conjugated with C60 fullerene. The C60 fullerene-bonded monolith prepared in a capillary showed a very strong π-π interaction in liquid chromatography. Also, the hemispherical molecule corannulene was dramatically retained in the C60 fullerene-bonded monolith by the unique molecular recognition based on a buckyball (see figure).

Towards a biocompatible artificial lung: Covalent functionalization of poly(4-methylpent-1-ene) (TPX) with cRGD pentapeptide

Covalent multistep coating of poly(methylpentene), the membrane material in lung ventilators, by using a copper-free "click" approach with a modified cyclic RGD peptide, leads to a highly biocompatible poly(methylpentene) surface. The resulting modified membrane preserves the required excellent gas-flow properties while being densely seeded with lung endothelial cells.

Nickel Boride Catalyzed Reductions of Nitro Compounds and Azides: Nanocellulose-Supported Catalysts in Tandem Reactions

Nickel boride catalyst prepared in situ from NiCl2 and sodium borohydride allowed, in the presence of an aqueous solution of TEMPO-oxidized nanocellulose (0.01 wt%), the reduction of a wide range of nitroarenes and aliphatic nitro compounds. Here we describe how the modified nanocellulose has a stabilizing effect on the catalyst that enables low loading of the nickel salt pre-catalyst. Ni-B prepared in situ from a methanolic solution was also used to develop a greener and facile reduction of organic azides, offering a substantially lowered catalyst loading with respect to reported methods in the literature. Both aromatic and aliphatic azides were reduced, and the protocol is compatible with a one-pot Boc-protection of the obtained amine yielding the corresponding carbamates. Finally, bacterial crystalline nanocellulose was chosen as a support for the Ni-B catalyst to allow an easy recovery step of the catalyst and its recyclability for new reduction cycles.

Synthesis of nitrophenyl and fluorophenyl azides and diazides by SNAr under phase-transfer or microwave irradiation: Fast and mild methodologies to prepare photoaffinity labeling, crosslinking, and click chemistry reagents

Two fast and mild methodologies to prepare nitrophenyl and fluorophenyl azides are presented. These aryl azides are extensively used as crosslinking, photoaffinity labeling, and click chemistry reagents. Substituted aryl azides are prepared by performing a SNAr substitution on halogenated benzenes with a phase-transfer catalyst (PTC) such as tetraethylammonium tetrafluoroborate (TEATFB), the reaction proceeds in several hours under rather mild temperatures (25°C to 70°C). Furthermore, aryl azides are also prepared within minutes under microwave irradiation at slightly higher temperatures (50°C to 70°C). These procedures could be applied in the preparation of other aryl azides. In the case of substituted pentafluoro benzene (pF), the type of products obtained in each reaction depends on the amount of sodium azide and the strength and position of electron-withdrawing substituents (COH, COR, COOR, CN, NO2, or F). A discussion on the mechanisms and the products obtained in these SNAr reactions is presented.

Rh2(II)-Catalyzed intermolecular N-Aryl aziridination of olefins using nonactivated N atom precursors

The development of the first intermolecular Rh2(II)-catalyzed aziridination of olefins using anilines as nonactivated N atom precursors and an iodine(III) reagent as the stoichiometric oxidant is reported. This reaction requires the transfer of an N-aryl nitrene fragment from the iminoiodinane intermediate to a Rh2(II) carboxylate catalyst; in the absence of a catalyst only diaryldiazene formation was observed. This N-aryl aziridination is general and can be successfully realized by using as little as 1 equiv of the olefin. Di-, tri-, and tetrasubstituted cyclic or acylic olefins can be employed as substrates, and a range of aniline and heteroarylamine N atom precursors are tolerated. The Rh2(II)-catalyzed N atom transfer to the olefin is stereospecific as well as chemo- and diastereoselective to produce the N-aryl aziridine as the only amination product. Because the chemistry of nonactivated N-aryl aziridines is underexplored, the reactivity of N-aryl aziridines was explored toward a range of nucleophiles to stereoselectively access privileged 1,2-stereodiads unavailable from epoxides, and removal of the N-2,4-dinitrophenyl group was demonstrated to show that functionalized primary amines can be constructed.