366-29-0Relevant academic research and scientific papers
CuBr/H2O2-mediated oxidative coupling of N,N-dialkylarylamines in water: A practical synthesis of benzidine derivatives
Jiang, Yanfeng,Xi, Chanjuan,Yang, Xianghua
, p. 1381 - 1384 (2005)
CuBr/H2O2 was deployed into mediating the oxidative coupling reaction of N,N-dialkylarylamines in water, which gave benzidine derivatives in an economically and environmentally satisfying manner. Georg Thieme Verlag Stuttgart.
Detection of the Short-Lived Radical Cation Intermediate in the Electrooxidation of N,N-Dimethylaniline by Mass Spectrometry
Brown, Timothy A.,Chen, Hao,Zare, Richard N.
, p. 11183 - 11185 (2015)
The N,N-dimethylaniline (DMA) radical cation DMA.+, a long-sought transient intermediate, was detected by mass spectrometry (MS) during the electrochemical oxidation of DMA. This was accomplished by coupling desorption electrospray ionization (DESI) MS with a waterwheel working electrode setup to sample the surface of the working electrode during electrochemical analysis. This study clearly shows that DESI-based electrochemical MS is capable of capturing electrochemically generated intermediates with half-lives on the order of microseconds, which is 4–5 orders of magnitude faster than previously reported electrochemical mass spectrometry techniques.
Remarkably efficient oxidative coupling of N,N-dialkylarylamines in water mediated by cerium(IV) ammonium nitrate
Xi, Chanjuan,Jiang, Yanfeng,Yang, Xianghua
, p. 3909 - 3911 (2005)
A highly effective, economical, and environmentally friendly method using of CAN as oxidant and water as solvent for oxidative coupling of N,N-dialkylarylamines was reported.
Oxidative coupling reaction of N,N-dialkylanilines with cerium(IV) ammonium nitrate in the solid state
Yang, Xianghua,Xi, Chanjuan,Jiang, Yanfeng
, p. 2413 - 2419 (2006)
Oxidative coupling reactions of N,N-dialkylanilines with cerium(IV) ammonium nitrate can be achieved by grinding at room temperature in the absence of solvents. Copyright Taylor & Francis Group, LLC.
Electrochemical Thermospray Mass Spectrometry
Hambitzer, Guenther,Heitbaum, Joachim
, p. 1067 - 1070 (1986)
Thermospray ionization combined with a quadrupole mass spectrometer was used on line to detect electrochemically generated products directly from solution.To do so, an electrochemical cell was constructed and connected with the mass spectrometer in such a way that the electrolyte was forced by pressure from the working electrode into the heated capillary tube of the thermospray system.The fast response achieved allowed analysis to be performed in parallel with a cyclic voltammetry curve.The utility of the method is demonstrated by means of the electrooxidation of N, N -dimethylaniline in an aqueous medium.The potential-dependent formation of dimers and trimers is shown.
Detection of the short-lived cation radical intermediate in the electrochemical oxidation of N, N -dimethylaniline by scanning electrochemical microscopy
Cao, Fahe,Kim, Jiyeon,Bard, Allen J.
, p. 18163 - 18169 (2014)
The short-lived intermediate N,N-dimethylaniline (DMA) cation radical, DMA?+, was detected during the oxidation of DMA in MeCN with 0.1 M tetra-n-butylammonium hexafluorophosphate. The detection was accomplished at steady state by scanning electrochemical microscopy (SECM) with ultramicroelectrodes using the tip generation/substrate collection mode. Cyclic voltammetry (CV) with a 2 mm Pt electrode indicates that DMA oxidation in acetonitrile is followed by a dimerization and two electrochemical reactions, which is consistent with previous results. The DMA?+ intermediate is detected by SECM, where the DMA?+ generated at the ca. 500 nm radius Pt tip is collected on a 5 μm radius Pt substrate when the gap between the tip and the substrate is a few hundred nanometers. Almost all of the DMA?+ is reduced at the substrate when the gap is 200 nm or less, yielding a dimerization rate constant of 2.5 × 108 M-1·s-1 based on a simulation. This is roughly 3 orders of magnitude larger than the value estimated by fast-scan CV. We attribute this discrepancy to the effects of double-layer capacitance charging and adsorbed species in the high scan rate CV.
Electrochemical synthesis of symmetrical benzidines through dehydrogenative cross-coupling reaction
Liu, Xiaoying,Cai, Tian-Cheng,Guo, Dingyi,Wang, Bin-Bin,Ying, Shengneng,Wang, Huixian,Tang, Shiyun,Shen, Qinpeng,Gui, Qing-Wen
supporting information, (2021/04/09)
Synthesis of diversely functionalized symmetrical benzidines through electrochemical dehydrogenative cross-coupling reaction of two N,N-disubstituted anilines, is described. The reactions conducted under mild conditions with no oxidizing reagents and transition metal catalysts.
Cobalt-catalyzed cross-coupling reactions of aryl- And alkylaluminum derivatives with (hetero)aryl and alkyl bromides
Dilauro, Giuseppe,Messa, Francesco,Bona, Fabio,Perrone, Serena,Salomone, Antonio
supporting information, p. 10564 - 10567 (2021/10/19)
A simple cobalt complex, such as Co(phen)Cl2, turned out to be a highly efficient and cheap precatalyst for a host of cross-coupling reactions involving aromatic and aliphatic organoaluminum reagents with aryl, heteroaryl and alkyl bromides. New C(sp2)-C(sp2) and C(sp2)-C(sp3) bonds were formed in good to excellent yields and with high chemoselectivity, under mild reaction conditions.
Catalytic and Aerobic Oxidative Biaryl Coupling of Anilines Using a Recyclable Heterogeneous Catalyst for Synthesis of Benzidines and Bicarbazoles
Matsumoto, Kenji,Toubaru, Yasunori,Tachikawa, Shohei,Miki, Ayaka,Sakai, Kentaro,Koroki, Syota,Hirokane, Tsukasa,Shindo, Mitsuru,Yoshida, Masahiro
, p. 15154 - 15166 (2020/12/23)
In this study, a heterogeneous rhodium-catalyzed oxidative homocoupling reaction of anilines utilizing molecular oxygen as the sole oxidant is reported. Employing a commercially available and recyclable Rh/C catalyst enabled the oxidative dimerization of various anilines, including N,N-disubstituted and N-monosubstituted anilines, as well as diarylamines, triarylamines, and carbazoles. Additionally, the catalytic protocol was extended to the ortho-ortho coupling of anilines, affording 2,2′-diaminobiphenyls with high regioselectivity. Notably, the developed approach provides rapid access to diversely functionalized benzidines and diaminobiphenyls in an operationally simple, practical, and environmentally friendly manner.
Single-Site Cobalt-Catalyst Ligated with Pyridylimine-Functionalized Metal-Organic Frameworks for Arene and Benzylic Borylation
Akhtar, Naved,Antil, Neha,Balendra,Begum, Wahida,Kumar, Ajay,Manna, Kuntal,Newar, Rajashree,Shukla, Sakshi
supporting information, p. 10473 - 10481 (2020/08/05)
We report a highly active single-site heterogeneous cobalt-catalyst based on a porous and robust pyridylimine-functionalized metal-organic frameworks (pyrim-MOF) for chemoselective borylation of arene and benzylic C-H bonds. The pyrim-MOF having UiO-68 topology, constructed from zirconium-cluster secondary building units and pyridylimine-functionalized dicarboxylate bridging linkers, was metalated with CoCl2 followed by treatment of NaEt3BH to give the cobalt-functionalized MOF-catalyst (pyrim-MOF-Co). Pyrim-MOF-Co has a broad substrate scope, allowing the C-H borylation of halogen-, alkoxy-, alkyl-substituted arenes as well as heterocyclic ring systems using B2pin2 or HBpin (pin = pinacolate) as the borylating agent to afford the corresponding arene- or alkyl-boronate esters in good yields. Pyrim-MOF-Co gave a turnover number (TON) of up to 2500 and could be recycled and reused at least 9 times. Pyrim-MOF-Co was also significantly more robust and active than its homogeneous control, highlighting the beneficial effect of active-site isolation within the MOF framework that prevents intermolecular decomposition. The experimental and computational studies suggested (pyrim?-)CoI(THF) as the active catalytic species within the MOF, which undergoes a mechanistic pathway of oxidative addition, turnover limiting σ-bond metathesis, followed by reductive elimination to afford the boronate ester.
