6590-44-9

Basic information

• Product Name: Benzenamine, N,2-dimethyl-N-phenyl-
• CAS NO: 6590-44-9
• Molecular Formula: C14H15N
• Molecular Weight: 197.28
• Mol File: 6590-44-9.mol

Chemical Properties

• CAS DataBase Reference: Benzenamine, N,2-dimethyl-N-phenyl-(CAS DataBase Reference)
• NIST Chemistry Reference: Benzenamine, N,2-dimethyl-N-phenyl-(6590-44-9)
• EPA Substance Registry System: Benzenamine, N,2-dimethyl-N-phenyl-(6590-44-9)

Safety Data

• Hazardous Substances Data: 6590-44-9(Hazardous Substances Data)

Upstream product

• 95-49-8 2-methylchlorobenzene 
• 100-61-8 N-methylaniline 
• 615-37-2 ortho-methylphenyl iodide 
• 95-46-5 2-methylphenyl bromide 
• 609-72-3 N,N-dimethyl-o-toluidine 
• 1222532-05-9 (2,4,6-trimethylphenyl)(2'-methylphenyl)iodonium tosylate 
• 121-69-7 N,N-dimethyl-aniline 
• 108-90-7 chlorobenzene 
• 611-21-2 N,2-dimethylaniline 
• 17763-67-6 Phenyl triflate 
• 80-48-8 methyl p-toluene sulfonate 
• 66107-34-4 2-methylphenyl triflate 

Downstream Products

• 4217-54-3 9,10-dihydro-10-methylacridine 
• 51570-52-6 o-methylaminodiphenylmethane 

Relevant articles and documents

Radical and ionic mechanisms in rearrangements of o-tolyl aryl ethers and amines initiated by the Grubbs-stoltz reagent, et3SiH/KOtbu

Rearrangements of o-tolyl aryl ethers, amines, and sulfides with the Grubbs-Stoltz reagent (Et3SiH + KOtBu) were recently announced, in which the ethers were converted to o-hydroxydiarylmethanes, while the (o-tol)(Ar)NH amines were transformed into dihydroacridines. Radical mechanisms were proposed, based on prior evidence for triethylsilyl radicals in this reagent system. A detailed computational investigation of the rearrangements of the aryl tolyl ethers now instead supports an anionic Truce-Smiles rearrangement, where the initial benzyl anion can be formed by either of two pathways: (i) direct deprotonation of the tolyl methyl group under basic conditions or (ii) electron transfer to an initially formed benzyl radical. By contrast, the rearrangements of o-tolyl aryl amines depend on the nature of the amine. Secondary amines undergo deprotonation of the N-H followed by a radical rearrangement, to form dihydroacridines, while tertiary amines form both dihydroacridines and diarylmethanes through radical and/or anionic pathways. Overall, this study highlights the competition between the reactive intermediates formed by the Et3SiH/KOtBu system.

1,2-Difunctionalization of Aryl Triflates: A Direct and Modular Access to Diversely Functionalized Anilines

ortho-Amino difunctionalization of aryl triflates has been achieved via a three-component reaction. The cascade reaction proceeds through a zincate base-mediated deprotonative formation of a reactive aryne intermediate, in situ nucleophilic addition, and coupling with electrophilic partners. This strategy leverages the advantageous reactivity of organozincate intermediates, enabling the installation of various functionalities such as amine, azide, oxygen, sulfur, halide, alkynyl, aryl, vinyl, and alkyl groups in a modular manner for the synthesis of diverse aniline skeletons.

A Highly Active Ylide-Functionalized Phosphine for Palladium-Catalyzed Aminations of Aryl Chlorides

Ylide-functionalized phosphine ligands (YPhos) were rationally designed to fit the requirements of Buchwald–Hartwig aminations at room temperature. This ligand class combines a strong electron-donating ability comparable to NHC ligands with high steric demand similar to biaryl phosphines. The active Pd species are stabilized by agostic C?H???Pd rather than by Pd–arene interactions. The practical advantage of YPhos ligands arises from their easy and scalable synthesis from widely available, inexpensive starting materials. Benchmark studies showed that YPhos-Pd complexes are superior to the best-known phosphine ligands in room-temperature aminations of aryl chlorides. The utility of the catalysts was demonstrated by the synthesis of various arylamines in high yields within short reaction times.

Solvent-free mechanochemical Buchwald-Hartwig amination of aryl chlorides without inert gas protection

A solvent-free Buchwald-Hartwig amination had been developed under high-speed ball-milling conditions, which afforded the desired products with moderate to high yields. The addition of sodium sulfate was found to be crucial for improving both the performance and the reproducibility. Comparative solvent-free stirring experiments implicated the importance of mechanical interaction for the transformation, and the inert gas was proved to be unnecessary for this amination.

A mechanical to urge the enters the carbon - [...] forming method (by machine translation)

The invention discloses a mechanical to urge the enters the carbon - [...] forming method, said method comprising: in order to type 2 shown in formulae of organic amine 3 shown the chlorinated aromatic hydrocarbon as the raw material, the catalyst, ligand, in the presence of alkali and additive, the reaction is carried out by the mechanical grinding method, after the reaction mixture after the separation and purification, obtains the type 1 compound shown; in the present invention relates to mechanical grinding promotion to the chlorinated aromatic hydrocarbon as the substrate of the Buchwald - Hartwig reaction mainly adopts the organic phosphonate ligands, in the palladium catalyst under the action of the organic amine compound with the chlorinated aromatic hydrocarbon of the between the coupling, so as to obtain high yield of the target product, the majority of the reaction can be 90% or more yield. The mild reaction conditions, can be in the 1 - 2 H to complete the reaction. (by machine translation)

NIXANTPHOS: A highly active ligand for palladium catalyzed Buchwald-Hartwig amination of unactivated aryl chlorides

Xantphos is one of the two most common ligands used in palladium catalyzed Buchwald-Hartwig amination reactions, because of its broad scope and high probability of success. It does not, however, work well with unactivated aryl chlorides. Herein NIXANTPHOS is compared to Xantphos and an array of mono- and bidentate phosphines. NIXANTPHOS outperforms Xantphos and all other bidentate ligands examined. Under the optimal reaction conditions, unactivated aryl chlorides afford the expected products in good to excellent yield with as low as 0.05 mol% (500 ppm) palladium loading.

Direct arylation of tertiary amines via aryne intermediates using diaryliodonium salts

With a strategy by using diaryliodonium salts as the precursors of benzynes, direct N-arylation of tertiary amines with diaryliodonium salts was reported. Thus, the desired aromatic tertiary amines with a wide range of substituents were synthesized in moderate to excellent yields of 55–91%.

Flexible Steric Bulky Bis(Imino)acenaphthene (BIAN)-Supported N-Heterocyclic Carbene Palladium Precatalysts: Catalytic Application in Buchwald-Hartwig Amination in Air

To achieve efficient palladium-catalyzed cross-coupling reaction under mild reaction conditions with the flexible steric bulk strategy, a series of Pd-PEPPSI (PEPPSI: pyridine-enhanced precatalyst preparation, stabilization, and initiation) complexes C1-C6 were synthesized and characterized, in which unsymmetric flexible steric bulk was introduced on the N-aryl of ancenaphthyl skeleton. These well-defined palladium complexes were found to be excellent precatalysts for Buchwald-Hartwig amination of aryl chlorides with amines in air. The electronic effect of the Pd-PEPPSI complexes and the effect of ancillary pyridine ligands were evaluated, among which complex C3 exhibited the most efficiency. It was demonstrated that the cross-coupling products were obtained in excellent yields in the presence of 0.5-0.1 mol % palladium loading. A wide range of aryl- and heteroaryl chlorides as well as various amines were compatible. The oxidative addition of aryl chlorides is revealed to be the rate-determining step in the catalytic cycle. The catalytic activity can be enhanced by introducing electron-donating groups to the Pd-PEPPSI complexes. This type of Pd-PEPPSI precatalyst showed the most efficiency reported to date for the challenging C-N cross-coupling reactions requiring no anhydrous and inert atmosphere protections, suggesting flexible steric bulk as a promising catalyst design strategy.

Application of a 2-aryl indenylphosphine ligand in the Buchwald-Hartwig cross-coupling reactions of aryl and heteroaryl chlorides under the solvent-free and aqueous conditions

An efficient solvent-free protocol for the Buchwald-Hartwig cross-coupling reaction of aryl and heteroaryl chlorides with primary and secondary amines using the Pd(dba)2/ligand 1 catalytic system has been developed. Notably, the catalytic system also efficiently catalyzed the reaction under aqueous conditions.

An Expedient Synthesis of Carbazoles through Potassium tert-Butoxide-Promoted Intramolecular Direct C–H Bond Arylation

Transition-metal-free access to carbazoles was achieved through base-mediated intramolecular C–C bond formation. Reactions of N-substituted o-halodiarylamines with potassium tert-butoxide in the presence of ethylene glycol or 1,10-phenanthroline provided carbazoles in moderate to excellent yields. This transformation may proceed through a radical pathway according to a control experiment with a radical scavenger.