20441-01-4

Upstream product

• 766-51-8 2-Chloroanisole 
• 122-39-4 diphenylamine 
• 108-86-1 bromobenzene 
• 90-04-0 2-methoxy-phenylamine 
• 91-23-6 2-Nitroanisole 
• 578-57-4 2-bromoanisole 
• 529-28-2 4-iodoanisol 
• 591-50-4 iodobenzene 

Downstream Products

• 550373-14-3 9-(2-methoxyphenyl)-9H-carbazole 

Relevant academic research and scientific papers

Metal-organic frameworks derived CuONPs@C nanocatalysts for synthesizing optoelectronic triarylamine molecules

Carbon encapsulated copper oxide nanoparticles (CuONPs@C) fabricated using copper metal organic frameworks (Cu-MOFs) used as reusable nanocatalysts in Ullmann C[sbnd]N coupling reactions for synthesizing optoelectronic triphenylamine (TPA) and carbazole (CBZ) derivatives. The formation of CuONPs in carbon matrix was confirmed by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS) and high-resolution transmission electron microscopy (HR-TEM). The catalytic activity of CuONPs@C was performed with diphenylamine/carbazole with substituted aryl halides in presence of mild K2CO3 base that produced triarylamines with 63–83% yields. Carbazole triarylamines exhibited strong solid state fluorescence (Φf = 14.54–36.32%) with λmax between 370 and 420 nm.

Buchwald–Hartwig Amination of Nitroarenes

The Buchwald–Hartwig amination of nitroarenes was achieved for the first time by using palladium catalysts bearing dialkyl(biaryl)phosphine ligands. These cross-coupling reactions of nitroarenes with diarylamines, arylamines, and alkylamines afforded the corresponding substituted arylamines. A catalytic cycle involving the oxidative addition of the Ar?NO2 bond to palladium(0) followed by nitrite/amine exchange is proposed based on a stoichiometric reaction.

Solvent-Free Buchwald-Hartwig (Hetero)arylation of Anilines, Diarylamines, and Dialkylamines Mediated by Expanded-Ring N-Heterocyclic Carbene Palladium Complexes

A highly efficient solvent-free protocol for the Buchwald-Hartwig (hetero)arylation of anilines, diarylamines, and dialkylamines mediated by the expanded-ring N-heterocyclic carbene palladium complex (THP-Dipp)Pd(cinn)Cl [THP-Dipp = 1,3-bis(2,6-diisopropylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene; cinn = cinnamyl, 3-phenylallyl] was developed. The catalytic protocol was efficient for the coupling of amines and (hetero)aryl chlorides and bromides bearing donor, acceptor, and bulky substituents.

Photochemical Synthesis of Complex Carbazoles: Evaluation of Electronic Effects in Both UV- and Visible-Light Methods in Continuous Flow

An evaluation of both a visible-light- and UV-light-mediated synthesis of carbazoles from various triarylamines with differing electronic properties under continuous-flow conditions has been conducted. In general, triarylamines bearing electron-rich groups tend to produce higher yields than triarylamines possessing electron-withdrawing groups. The incorporation of nitrogen-based heterocycles, as well as halogen-containing arenes in carbazole skeletons, was well tolerated, and often synthetically useful complementarity was observed between the UV-light and visible-light (photoredox) methods.

Solvent-free Buchwald-Hartwig reaction of aryl and heteroaryl halides with secondary amines

A highly efficient solvent-free protocol for the Buchwald-Hartwig amination of (hetero)aryl halides by secondary amines was developed. The reaction is mediated by a Pd(OAc)2/RuPhos catalytic system in air. Various (hetero)aryl halides were coupled with diaryl, alkyl-aryl, and dialkylamines in good to excellent yields (51 examples, 50-99% yield). Copyright

Copper-catalyzed synthesis of triarylamines from aryl halides and arylamines

A simple and efficient methodology for the synthesis of triphenylamines has been demonstrated using copper catalyst with a ligand and tripotassium phosphate as the base. The effect of parameters such as catalyst precursors, ligands, bases and solvents were studied and a series of triphenylamines were obtained with moderate to excellent yields in DMF. This reaction displays great functional groups compatibility in the presence of a broad range of functional groups.

Heterogeneous aromatic amination of aryl halides with arylamines in water with PS-PEG resin-supported palladium complexes

Catalytic aromatic amination is achieved in water under heterogeneous conditions by the use of immobilized palladium complexes coordinated with the amphiphilic polystyrene-poly-(ethylene glycol) resin-supported di(tert-butyl)phosphine ligand. Aromatic amination of aryl halides with diphenylamine and N,N-double arylation of anilines with bromobenzene were found to proceed in water with broad substrate tolerance to give the triarylamines in high yield with high recyclability of the polymeric catalyst beads. Very little palladium leached from the polymeric catalyst under the waterbased reaction conditions to provide a green and clean (metal-uncontaminated) protocol for the preparation of triarylamines, including the optoelectronically active N,N,N',N'-tetraaryl-1,1'-biphenyl-4,4'-diamines (TPDs).

Evaluation of aromatic amination catalyzed by palladium on carbon: A practical synthesis of triarylamines

A heterogeneous palladium on carbon (Pd/C)-catalyzed coupling between amines and aromatic halides including aromatic chlorides has been achieved using sodium tert-butoxide (NaO-t-Bu) and 1,1′-bis(diphenylphosphino)ferrocene (dppf) as a ligand in cyclopentyl methyl ether (CPME). The use of potassium tert-butoxide (KO-t-Bu) in place of NaO-t-Bu brought about the benzyne-mediated aromatic amination even without Pd/C and dppf, giving a mixture of regioisomers when 4-substituted bromobenzenes were employed as the substrate. The combination of Pd/C, dppf, NaO-t-Bu could be utilized for the syntheses of a broad range of triarylamines by replacing CPME with mesitylene which can provide a higher reaction temperature. The Pd/C could be quantitatively recovered and reused until at least the fourth cycle without any loss in catalytic activity. The quite low leaching of palladium (1.1%) was demonstrated by an inductively coupled plasma-atomic emission spectrometric analysis.

Catalyst for aromatic C—O, C—N, and C—C bond formation

The present invention is directed to a transition metal catalyst, comprising a Group 8 metal and a ligand having the structure wherein R, R′ and R″ are organic groups having 1-15 carbon atoms, n=1-5, and m=0-4. The present invention is also directed to a method of forming a compound having an aromatic or vinylic carbon-oxygen, carbon-nitrogen, or carbon-carbon bond using the above catalyst. The catalyst and the method of using the catalyst are advantageous in preparation of compounds under mild conditions of approximately room temperature and pressure.

Air stable, sterically hindered ferrocenyl dialkylphosphines for palladium-catalyzed C-C, C-N, and C-O bond-forming cross-couplings

Pentaphenylferrocenyl di-tert-butylphosphine has been prepared in high yield from a two-step synthetic procedure, and the scope of various cross-coupling processes catalyzed by complexes bearing this ligand has been investigated. This ligand creates a remarkably general palladium catalyst for aryl halide amination and for Suzuki coupling. Turnovers of roughly 1000 were observed for aminations with unactivated aryl bromides or chlorides. In addition, complexes of this ligand catalyzed the formation of selected aryl ethers under mild conditions. The reactions encompassed electron-rich and electron-poor aryl bromides and chlorides. In the presence of catalysts containing this ligand, these aryl halides coupled with acyclic or cyclic secondary alkyl- and arylamines, with primary alkyl- and arylamines, and with aryl- and primary alkylboronic acids. These last couplings provide the first general procedure for reaction of terminal alkylboronic acids with aryl halides without toxic or expensive bases. The ligand not only generates highly active palladium catalysts, but it is air stable in solution and in the solid state. Palladium(0) complexes of this ligand are also air stable as a solid and react only slowly with oxygen in solution.