4316-55-6Relevant academic research and scientific papers
Electron-Catalyzed Coupling of Magnesium Amides with Aryl Iodides
Kiriyama, Kazuya,Okura, Keisho,Tamakuni, Fumiko,Shirakawa, Eiji
supporting information, p. 4519 - 4522 (2018/03/13)
An electron was found to catalyze the coupling of magnesium diarylamides with aryl iodides giving triarylamines through a radical-anion intermediate. The transformation requires no transition metal catalysts or additives, and a wide array of products are formed in good-to-excellent yields.
METHOD FOR PRODUCING AROMATIC AMINE
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Paragraph 0047; 0050, (2018/06/13)
PROBLEM TO BE SOLVED: To provide a method for producing aromatic amine solving the problem that, in the case a halogen atom is selected as the well-known leaving group of a coupling reaction raw material compound, since harmful halogen waste is by-produced after reaction, waste liquid treatment is complicated and an environmental load is high and further solving the problem that, in the case a trifluoromethanesulfonyloxy group is selected as the leaving group, an environmental load upon the production of a raw material compound having a trifluoromethanesulfonyloxy group is high, and also, the production operation is complicated. SOLUTION: Provided is a method for producing an aromatic amine compound characterized in that an aromatic nitro compound and an amine compound are brought into cross coupling reaction in the presence of a metal catalyst. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPO&INPIT
Synthesis of Triarylamines via Sequential C-N Bond Formation
Modha, Sachin G.,Popescu, Mihai V.,Greaney, Michael F.
, p. 11933 - 11938 (2017/11/24)
A one-pot domino N-arylation protocol is described using diaryliodonium reagents under copper catalysis. The reaction uses both aryl groups of the diaryliodonium reagent to generate triarylamines starting from simple anilines, representing an atom-economical preparation of an important class of organic material building blocks.
N/O-doped carbon as a "solid ligand" for nano-Pd catalyzed biphenyl- and triphenylamine syntheses
Pang, Shaofeng,Zhang, Yujing,Huang, Yongji,Yuan, Hangkong,Shi, Feng
, p. 2170 - 2182 (2017/07/24)
A series of N/O-doped porous carbon supported nanopalladium catalysts have been successfully prepared, in which the N/O doped carbons were controllably produced via polypyrrole/furan synthesis followed by carbonization. These catalysts exhibit good performance in biphenylamine and triphenylamine syntheses with nitrobenzene and cyclohexanone as starting materials. Their catalytic activity can be tuned efficiently by the N/O functional groups on the carbon surface. TEM, XRD, XPS and laser Raman methods were applied to probe the structure of these catalysts. These results indicate that the Pd nanoparticles were supported on N/O-doped porous carbon via the "coordination" between Pd nanoparticles and N/O functional groups including O-CO, CN and tertiary nitrogen, and better catalytic performance was obtained if carbon with the highest N-species loading was used as the support. In addition, a mechanistic study proved that the reaction starts with the catalytic reduction of nitrobenzene with cyclohexanone as the hydrogen source. During this reaction, aniline was formed and the cyclohexanone was transformed into phenol. Then biphenylamine and triphenylamine were generated through the reaction of aniline and cyclohexanone. This work should facilitate the controllable preparation of carbon supported nanocatalysts with specific activity, and open up a promising pathway for the development of new methodologies for N-containing fine chemical synthesis.
Buchwald–Hartwig Amination of Nitroarenes
Inoue, Fumiyoshi,Kashihara, Myuto,Yadav, M. Ramu,Nakao, Yoshiaki
supporting information, p. 13307 - 13309 (2017/10/17)
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.
An efficient heterogeneous ligand free C-N coupling reaction catalyzed by palladium supported on magnetic nanoparticles
Rafiee, Ezzat,Ataei, Ali,Joshaghani, Mohammad
, p. 219 - 222 (2015/12/31)
The catalytic activity of palladium supported on magnetic nanoparticles in the amination coupling reaction of different nitrogen containing substrates with aryl halides was investigated. C-N bond formation was achieved in moderate to excellent yields and the catalyst could be separated by magnetic decantation.
Solvent-Free Buchwald-Hartwig (Hetero)arylation of Anilines, Diarylamines, and Dialkylamines Mediated by Expanded-Ring N-Heterocyclic Carbene Palladium Complexes
Topchiy, Maxim A.,Dzhevakov, Pavel B.,Rubina, Margarita S.,Morozov, Oleg S.,Asachenko, Andrey F.,Nechaev, Mikhail S.
supporting information, p. 1908 - 1914 (2016/04/20)
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.
An Efficient Synthesis of N-(Hetero)arylcarbazoles: Palladium-Catalyzed Coupling Reaction between (Hetero)aryl Chlorides and N-Carbazolylmagnesium Chloride
Nakayama, Yuji,Yokoyama, Naota,Nara, Hideki,Kobayashi, Tohru,Fujiwhara, Mitsuhiko
supporting information, p. 2322 - 2330 (2015/07/27)
An efficient method for the synthesis of N-(hetero)arylcarbazoles, useful compounds for functional materials, is reported. Various (hetero)aryl chlorides reacted with N-carbazolylmagnesium chloride in the presence of a palladium catalyst (0.05 to 0.2 mol%) prepared from allylpalladium(II) chloride dimer {[PdCl(allyl)]2} and di-tert-butyl(2,2-diphenyl-1-methylcyclopropan-1-yl)phosphine (cBRIDP) under mild conditions (110°C) in a short period of time (15 min to 2 h) to give N-(hetero)arylcarbazoles in high yields. The reactions of bromochlorobenzenes proceeded in favour of the bromo group to afford N-(chlorophenyl)carbazoles in a highly selective manner. Functional materials for use in organic light-emitting diodes, such as mCP, 26mcPy, CBP and TCB, were also obtained in high yields within 15 min by the reaction of (hetero)aryl polyhalides. Optimization of the reaction conditions and a postulated catalytic cycle for the reaction are also discussed.
Method for producing hydroxytriarylamine (by machine translation)
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Paragraph 0034-0036, (2018/02/24)
PROBLEM TO BE SOLVED: To economically provide arylamines such as triarylamine. SOLUTION: An arylamine compound represented by formula (1) and an aryl compound having a leaving group represented by formula (2): X-Ar2-X1, are subjected to an arylamination reaction in the presence of a basic group, an alkaline metal salt and/or an alkaline earth metal salt, and an iron catalyst to thereby obtain arylamines such as triarylamines. In formula (1), Ar and Ar1are identical or different, and denote a substituted or non-substituted aryl group, and may be ring-condensed; and a denotes 1 or 2. In formula (2), X and X1are identical or different, and denote at least one leaving group selected from the group consisting of H or Br, I, CMs (mesylate), OTf (triflate) and OTs (tosylate), provided that X and X1are not simultaneously H, and have at least one leaving group; and Ar2denotes a substituted or non-substituted aryl group. COPYRIGHT: (C)2012,JPO&INPIT
Catalytic carbon-nitrogen bond-forming cross-coupling using N-trimethylsilylamines
Minami, Yasunori,Komiyama, Takeshi,Shimizu, Kenta,Hiyama, Tamejiro,Goto, Osamu,Ikehira, Hideyuki
, p. 1437 - 1446 (2015/11/16)
Carbon-nitrogen bond-forming cross-coupling reaction of haloarenes with N-trimethylsilyl (TMS)-substituted secondary and primary arylamines proceeded with the aid of a palladium catalyst and a fluoride activator. Various TMS-N(aryl)2, TMS-NH(aryl), and TMS-N(alkyl)2 reacted to give the corresponding coupled products in high yields. Multi-TMS-amine nucleophiles such as N,N-(TMS)2-aniline and N,N′-Ph2-N,N′-(TMS)2-p-phenylenediamine also participated in this C-N coupling to give multiply C-N coupled products in high yields. The novel C-N cross-coupling reaction was successfully applied to C-N bond-forming polymerization. Relative rates of the cross-coupling of p-bromotoluene with N-TMS-substituted primary and secondary amines showed that N-TMS-diphenylamine reacted faster than N-TMS-N-methylaniline or N-TMS-aniline, and N-TMS-morpholine was the least reactive, indicating that the low basicity of the nitrogen nucleophile is the key for the smooth coupling.
