58273-38-4

Upstream product

• 104-94-9 4-methoxy-aniline 
• 108-46-3 recorcinol 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 591-27-5 m-Hydroxyaniline 
• 5720-07-0 4-methoxyphenylboronic acid 
• 36646-77-2 3-(4-methoxyphenylamino)cyclohex-2-en-1-one 

Downstream Products

• 109601-04-9 2-{[3-(2-hydroxy-ethoxy)-phenyl]-(4-methoxy-phenyl)-amino}-ethanol 
• 3661-49-2 3-methoxy-N-(4-methoxyphenyl)benzenamine 
• 109688-74-6 2-methoxy-N⁴-(4-methoxy-phenyl)-p-phenylenediamine 

Relevant academic research and scientific papers

Copper(ii)-catalyzed Chan-Lam cross-coupling: chemoselective N-arylation of aminophenols

Copper(ii)-catalyzed boronic acid promoted chemoselective N-arylation of unprotected aminophenols has been developed. Selective N-arylation of 3-aminophenol is achieved with a Cu(OAc)2/AgOAc combination in MeOH at rt, whereas the chemoselective N-arylated products of 4-aminophenol can be obtained with a Cu(OAc)2/Cs2CO3 system and benzoic acid as an additive. These ligand-free conditions and “open-flask” chemistry are robust and compatible with a wide range of functional groups. The mechanistic investigation for this selective N-arylation has been studied by considering Density Functional Theory (DFT) calculations.

Palladium-catalyzed synthesis of natural and unnatural 2-, 5-, and 7-oxygenated carbazole alkaloids from N-arylcyclohexane enaminones

A palladium-catalyzed synthesis of the carbazole framework is described, including the preparation of 2-, 5-, and 7-oxygenated natural and unnatural carbazole alkaloids. A series of N-arylcyclohexane enaminones, generated by condensation of cyclohexane-1,3-dione with diverse anilines, were aromatized by a Pd(0)-catalyzed thermal treatment to afford the corresponding diarylamines. The latter were submitted to a Pd(II)-catalyzed cyclization and methylation processes to provide the desired carbazoles, including clausine V. Following an inverse strategy, a new and short total synthesis of glycoborine is also reported.

Orthogonal Cu- and Pd-based catalyst systems for the O- and N-arylation of aminophenols

O- or N-arylated aminophenol products constitute a common structural motif in various potentially useful therapeutic agents and/or drug candidates. We have developed a complementary set of Cu- and Pd-based catalyst systems for the selective O- and N-arylation of unprotected aminophenols using aryl halides. Selective O-arylation of 3- and 4-aminophenols is achieved with copper-catalyzed methods employing picolinic acid or CyDMEDA, trans-N,N′-dimethyl-1,2- cyclohexanediamine, respectively, as the ligand. The selective formation of N-arylated products of 3- and 4-aminophenols can be obtained with BrettPhos precatalyst, a biarylmonophosphine-based palladium catalyst. 2-Aminophenol can be selectively N-arylated with CuI, although no system for the selective O-arylation could be found. Coupling partners with diverse electronic properties and a variety of functional groups can be selectively transformed under these conditions.

Process for the preparation of hydroxy-diphenylamines

A process for the preparation of hydroxy-diphenylamines by condensation of dihydroxybenzene with an excess amount of primary aromatic amine in the presence of a catalytic amount of an acid at elevated temperature is described wherein the excess aromatic amine and, if appropriate, the reaction product is distilled off from the reaction mixture in the presence of a base.

Manufacture of arylamines

Arylamines are manufactured by reacting alcohols with amines in the presence of phosphorus-III compounds. The arylamines I manufactured by the process of the invention are intermediates for the manufacture of crop protection agents, optical brighteners, especially amino-coumarin derivatives, and dyes, especially of the xanthene, pyronine, rhodamine, oxazine, azo, triphenylmethane and diphenylmethane series.