1159-53-1Relevant academic research and scientific papers
Urea as ammonia equivalent in aryl halides amination catalyzed by palladium complexes
Artamkina,Sergeev,Shtern,Beletskaya
, p. 1683 - 1689 (2006)
Urea reaction with nonactivated aryl bromides and chlorides under catalysis with palladium complexes led to the formation in 65-95% yield of triarylamines from para-and meta-substituted aryl halides and of diarylamines from ortho-isomers.
Dye-sensitized electron transfer from TiO2 to oxidized triphenylamines that follows first-order kinetics
DiMarco, Brian N.,Troian-Gautier, Ludovic,Sampaio, Renato N.,Meyer, Gerald J.
, p. 940 - 949 (2018)
Two sensitizers, [Ru(bpy)2(dcb)]2+ (RuC) and [Ru(bpy)2(dpb)]2+ (RuP), where bpy is 2,2′-bipyridine, dcb is 4,4′-dicarboxylic acid-2,2′-bipyridine and dpb is 4,4′-diphosphonic acid-2,2′-bipyridine, were anchored to mesoporous TiO2 thin films and utilized to sensitize the reaction of TiO2 electrons with oxidized triphenylamines, TiO2(e-) + TPA+ → TiO2 + TPA, to visible light in CH3CN electrolytes. A family of four symmetrically substituted triphenylamines (TPAs) with formal Eo(TPA+/0) reduction potentials that spanned a 0.5 eV range was investigated. Surprisingly, the reaction followed first-order kinetics for two TPAs that provided the largest thermodynamic driving force. Such first-order reactivity indicates a strong Coulombic interaction between TPA+ and TiO2 that enables the injected electron to tunnel back in one concerted step. The kinetics for the other TPA derivatives were non-exponential and were modelled with the Kohlrausch-William-Watts (KWW) function. A Perrin-like reaction sphere model is proposed to rationalize the kinetic data. The activation energies were the same for all of the TPAs, within experimental error. The average rate constants were found to increase with the thermodynamic driving force, consistent with electron transfer in the Marcus normal region.
Measurement and prediction of solubility of four arylamine molecules in benzene, hexane, and methanol
Manifar, Touraj,Rohani, Sohrab
, p. 1794 - 1800 (2005)
In this paper, the solubility of selected arylamine molecules in methanol, hexane, and benzene has been investigated. Solubility of mmmTTA in hexane and benzene is the highest while mTTA has the lowest solubility in benzene and hexane. The UNIFAC and the UNIQUAC binary adjustable parameters have been determined. On the basis of these parameters, the solubility of these molecules has been predicted and compared with the experimental data. The effect of meta or para substitutions in arylamine molecules on their solubility in organic solvents was experimentally determined and theoretically established. The adjustable parameters of the UNIFAC equation obtained in this study will help estimate the solubility of macromolecules with the same constitutional groups or estimate the solubility of mixture of arylamine molecules. Thermal properties such as specific heat, melting point, boiling point, and heat of vaporization of the selected arylamine molecules have been determined.
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)
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.
Sensitive and Repeatable Photoinduced Luminescent Radicals from A Simple Organic Crystal
Mu, Yingxiao,Liu, Yanyan,Tian, Haiyan,Ou, Depei,Gong, Li,Zhao, Juan,Zhang, Yi,Huo, Yanping,Yang, Zhiyong,Chi, Zhenguo
, p. 6367 - 6371 (2021)
Photoinduced organic radicals are important for chemical and physical processes of organic materials, which are extensively investigated and applied in organic synthesis, photoelectronic devices and biotechnology. However, there are rare reports of the luminescence for these photoinduced radicals, especially in the condensed state. Herein, an unexpected and interesting luminescent radical is described, which can be rapidly and reversibly generated from a simple organic crystal by gentle light irradiation in air. It was revealed that the twist and asymmetric conformation of isolated molecule in its crystal with only weak C?H???π intermolecular interactions, which led to the generation of such photoinduced luminescent radicals. In addition, dual-channel photosensitive device with rapid response and well repeatability can be obtained based on the thin film of this organic crystal, showing both photoswitching on luminescence and conducting.
C-H activation and nucleophilic substitution in a photochemically generated high valent iron complex
Lim, Jia Hui,Engelmann, Xenia,Corby, Sacha,Ganguly, Rakesh,Ray, Kallol,Soo, Han Sen
, p. 3992 - 4002 (2018)
The photochemical oxidation of a (TAML)FeIII complex 1 using visible light generated Ru(bpy)33+ produces valence tautomers (TAML)FeIV (1+) and (TAML+)FeIII (1-TAML+), depending on the exogenous anions. The presence of labile Cl- or Br- results in a ligand-based oxidation and stabilisation of a radical-cationic (TAML+)FeIII complex, which subsequently leads to unprecedented C-H activation followed by nucleophilic substitution on the TAML aryl ring. In contrast, exogenous cyanide culminates in metal-based oxidation, yielding the first example of a crystallographically characterised S = 1 [(TAML)FeIV(CN)2]2- species. This is a rare report of an anion-dependent valence tautomerisation in photochemically accessed high valent (TAML)Fe systems with potential applications in the oxidation of pollutants, hydrocarbons, and water. Furthermore, the nucleophilic aromatic halogenation reaction mediated by (TAML+)FeIII represents a novel domain for high-valent metal reactivity and highlights the possible intramolecular ligand or substrate modification pathways under highly oxidising conditions. Our findings therefore shine light on high-valent metal oxidants based on TAMLs and other potential non-innocent ligands and open new avenues for oxidation catalyst design.
C60 as a Photocatalyst of Electron-Transfer Processes: Reactions of Triplet C60 with Chloranil, Perylene, and Tritolylamine Studied by Flash Photolysis and FT-EPR
Steren, Carlos A.,Willigen, Hans van,Biczok, Laszlo,Gupta, Neeraj,Linschitz, Henry
, p. 8920 - 8926 (1996)
Photoprocesses in benzonitrile solutions of C60 and chloranil (CA) have been studied by complementary techniques of nanosecond laser photolysis and Fourier transform EPR.Direct oxidation of 3C60 by CA is slow (k = (2.0 +/- 0.3)E7 M-1 s-1), consistent with the high oxidation potential of 3C60.However, the formation rate and yield of CA(1-) are much increased by addition of perylene (Pe) or tritolylamine (TTA) via the fast reactions 3C60 + Pe -> C60 + 3Pe, followed by 3Pe + CA -> Pe(1+) + Ca(1-), or 3C60 +TTA -> C60(1-) + TTA(1+), followed by C60(1-) + CA -> C60 + CA(1-).These reactions utilize the broad absorption and initial high triplet yield of C60, as well as the low oxidation potential of 3Pe or high reduction potential of 3C60, to catalyze efficient formation of CA(1-) and enhance separation of radicals.Triplet C60 also reacts with Pe by electron transfer, forming Pe(1+) and C60(1-) with rate one-third that of energy transfer.However, the Ca(1-) formed in the Pe-catalyzed reaction is strongly spin-polarized, indicating that it is formed primarily via the 3Pe pathway.The extinction coefficient of C60(1-) at 1080 nm is measured (ε = 18300 +/- 1100 M-1 cm-1) using the TTA reaction.
Diazabutadiene: a simple and efficient ligand for copper-catalyzed N-arylation of aromatic amines
Liu, Yu-Hua,Chen, Chen,Yang, Lian-Ming
, p. 9275 - 9278 (2006)
Diazabutadienes (DABs) were chosen as ancillary ligands in the Cu-catalyzed C-N coupling reaction for the synthesis of triarylamines. A combination of CuI/DAB (1) [1: N,N′-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene] was found to be an efficient catalyst system for N-arylation of diarylamines and anilines with aryl iodides, affording the desired products in good to excellent yields.
Mixed er-NHC/phosphine Pd(ii) complexes and their catalytic activity in the Buchwald-Hartwig reaction under solvent-free conditions
Ageshina, Alexandra A.,Sterligov, Grigorii K.,Rzhevskiy, Sergey A.,Topchiy, Maxim A.,Chesnokov, Gleb A.,Gribanov, Pavel S.,Nechaev, Mikhail S.,Asachenko, Andrey F.,Bermeshev, Maxim V.,Melnikova, Elizaveta K.
supporting information, p. 3447 - 3452 (2019/04/30)
A series of novel (NHC)PdCl2-PR3 complexes were synthesized and fully characterized by 1H, 13C, 31P NMR and FT-IR spectroscopy. These complexes showed high catalytic activity toward solvent-free Buchwald-Hartwig amination. Both primary and secondary amines were efficiently utilized under the same reaction conditions. The solvent-free synthesis of valuable N-aryl carbazoles and similar N-heterocyclic systems was described.
PdCl2(Ph3P)2/Salicylaldimine Catalyzed Diarylation of Anilines with Unactivated Aryl Chlorides
Tao, Xiaochun,Li, Lei,Zhou, Yu,Qian, Xuanying,Zhao, Min,Cai, Liangzhen,Xie, Xiaomin
supporting information, p. 1749 - 1754 (2017/10/06)
Triphenylphosphine and salicylaldimine could be used as a mixed ligand system to obtain a high catalytic activity for palladium catalyzed diarylation of primary anilines with unactivated aryl chlorides by the synergistic effect of ligands. The activity and selectivity of the catalytic system could be improved by modifying the structure of salicylaldimine. In refluxing o-xylene, PdCl2(Ph3P)2 with 2,5-ditrifluoromethyl N-phenylsalicylaldimine as a coligand shows high efficiency for the diarylation of various anilines. The catalytic system shows good toleration for the steric hindrance of the substrates. The facile catalytic system works as well on the multiple arylation of 1,1′-biphenyl- 4,4′-diamine with aryl chlorides to afford N,N,N′,N′-tetraaryl-1,1′-biphenyl-4,4′-diamines which are important intermediates of organic light emitting diode (OLED) hole transport materials.
