21650-53-3Relevant academic research and scientific papers
Au@zirconium-phosphonate nanoparticles as an effective catalytic system for the chemoselective and switchable reduction of nitroarenes
Ferlin, Francesco,Cappelletti, Matteo,Vivani, Riccardo,Pica, Monica,Piermatti, Oriana,Vaccaro, Luigi
, p. 614 - 626 (2019)
In the present paper, a novel inorganic-organic layered material, a zirconium phosphate aminoethyl phosphonate, ZP(AEP), bearing aminoethyl groups on the layer surface, was used to immobilize AuNPs by a two-step procedure. The gold-based catalyst, Au1@ZP(AEP), containing 1 wt% Au, was characterized in terms of physico-chemical properties and TEM analysis revealed that the AuNPs have a spherical shape and an average size of 7.8 (±2.4) nm. Au1@ZP(AEP) proved its high efficiency for the chemoselective reduction of nitroarenes under mild conditions. Both batch and flow condition protocols have been defined. The catalytic system has been proven to be able to easily switch chemoselectivity allowing the control of the reduction of a series of nitroaromatics towards their corresponding azoxyarenes (2a-k) or anilines (2a-l) in 96% EtOH or abs EtOH, respectively, by using NaBH4 as a reducing agent, in good to excellent yields. Recovery and reuse of the catalytic system has been investigated proving the benefits of the flow approach.
A combined optical and EPR spectroscopy study: Azobenzene-based biradicals as reversible molecular photoswitches
Jaumann, Eva A.,Steinwand, Sabrina,Klenik, Szabina,Plackmeyer, J?rn,Bats, Jan W.,Wachtveitl, Josef,Prisner, Thomas F.
, p. 17263 - 17269 (2017)
Azobenzene compounds are known as versatile examples for photoswitchable systems because of their isomeric cis- and trans-configurations. The switching between these isomers can be reversibly controlled by light excitation. In this study we characterize t
Active ester functionalized azobenzenes as versatile building blocks
Schultzke, Sven,Staubitz, Anne,Walther, Melanie
supporting information, (2021/07/12)
Azobenzenes are important molecular switches that can still be difficult to functionalize selectively. A high yielding Pd-catalyzed cross-coupling method under mild conditions for the introduction of NHS esters to azobenzenes and diazocines has been established. Yields were consistently high with very few exceptions. The NHS functionalized azobenzenes react with primary amines quantitatively. These amines are ubiquitous in biological systems and in material science.
Photocatalytic oxidative coupling of arylamines for the synthesis of azoaromatics and the role of O2 in the mechanism
Sitter, James D.,Vannucci, Aaron K.
supporting information, p. 2938 - 2943 (2021/03/01)
The photocatalytic oxidative coupling of aryl amines to selectively synthesize azoaromatic compounds has been realized. Multiple different photocatalysts can be used to perform the general reaction; however, Ir(dF-CF3-ppy)2(dtbpy)+, where dF-CF3-ppy is 2-(2,4-difluorophenyl)-5-(trifluoromethyl)-pyridine and dtpby is 4,4′-tert-butyl-2,2′-bipyridine, showed the greatest range of reactivity with various amine substrates. Both electron-rich and -deficient amines can be coupled with yields up to 95% under an ambient air atmosphere. Oxygen was deemed to be essential for the reaction and is utilized in the regeneration of the photocatalyst. Fluorescence quenching and radical trap experiments indicate an amine radical coupling mechanism that proceeds through a hydrazoaromatic intermediate before further oxidation occurs to form the desired azoaromatic products.
Electrosynthesis of Azobenzenes Directly from Nitrobenzenes
Ma, Yanfeng,Wu, Shanghui,Jiang, Shuxin,Xiao, Fuhong,Deng, Guo-Jun
, p. 3334 - 3338 (2021/10/29)
The electrochemical reduction strategy of nitrobenzenes is developed. The chemistry occurs under ambient conditions. The protocol uses inert electrodes and the solvent, DMSO, plays a dual role as a reducing agent. Its synthetic value has been demonstrated by the highly efficient synthesis of symmetric, unsymmetric and cyclic azo compounds.
Trichloroisocyanuric Acid Mediated Oxidative Dehydrogenation of Hydrazines: A Practical Chemical Oxidation to Access Azo Compounds
Cao, Guiyan,Hu, Yulai,Huang, Danfeng,Huo, Congde,Liu, Xuan,Su, Yingpeng,Wang, Ke-Hu,Yu, Jie,Zhang, Rong,Zhao, Yanan
supporting information, p. 1103 - 1112 (2020/04/01)
A highly efficient, metal-free, chemical oxidation of hydrazines has been implemented using environmentally friendly TCCA as oxidant. This benign protocol provides straightforward access to a wide range of azo compounds in THF in excellent yield. Altogether, 35 azo compounds were obtained in this way and scale-up preparations were performed. Additionally, a plausible mechanism was also proposed. Step-economical process, mild reaction conditions, operational simplicity, high reaction efficiency, and easy scale-up highlight the practicality of this methodology.
Conversion of anilines into azobenzenes in acetic acid with perborate and Mo(VI): correlation of reactivities
Karunakaran,Venkataramanan
, p. 375 - 385 (2019/02/14)
Azobenzenes are extensively used to dye textiles and leather and by tuning the substituent in the ring, vivid colours are obtained. Here, we report preparation of a large number of azobenzenes in good yield from commercially available anilines using sodium perborate (SPB) and catalytic amount of Na2MoO4 under mild conditions. Glacial acetic acid is the solvent of choice and the aniline to azobenzene conversion is zero, first and first orders with respect to SPB, Na2MoO4 and aniline, respectively. Based on the kinetic orders, UV–visible spectra and cyclic voltammograms, the conversion mechanism has been suggested. The reaction rates of about 50 anilines at 20–50?°C and their energy and entropy of activation conform to the isokinetic or Exner relationship and compensation effect, respectively. However, the reaction rates, deduced by the so far adopted method, fail to comply with the Hammett correlation. The specific reaction rates of molecular anilines, obtained through a modified calculation, conform to the Hammett relationship. Thus, this work presents a convenient inexpensive non-hazardous method of preparation of a larger number of azobenzenes, and shows the requirement of modification in obtaining the true reaction rates of anilines in acetic acid and the validity of Hammett relationship in the conversion process, indicating operation of a common mechanism.
In Situ Coupling of Single Molecules Driven by Gold-Catalyzed Electrooxidation
Zang, Yaping,Stone, Ilana,Inkpen, Michael S.,Ng, Fay,Lambert, Tristan H.,Nuckolls, Colin,Steigerwald, Michael L.,Roy, Xavier,Venkataraman, Latha
supporting information, p. 16008 - 16012 (2019/07/16)
A single-molecule method has been developed based on the scanning tunneling microscope (STM) to selectively couple a series of aniline derivatives and create azobenzenes. The Au-catalyzed oxidative coupling is driven by the local electrochemical potential at the nanostructured Au STM tip. The products are detected in situ by measuring the conductance and molecular junction elongation and compared with analogous measurements of the expected azobenzene derivatives prepared ex situ. This single-molecule approach is robust, and it can quickly and reproducibly create reactions for a variety of anilines. We further demonstrate the selective synthesis of geometric isomers and the assembly of complex molecular architectures by sequential coupling of complementary anilines, demonstrating unprecedented control over bond formation at the nanoscale.
Oxidative dimerization of anilines with heterogeneous sulfonic acid catalysts
Paris, Emanuele,Bigi, Franca,Cauzzi, Daniele,Maggi, Raimondo,Maestri, Giovanni
supporting information, p. 382 - 386 (2018/02/07)
We report herein that suitably supported perfluorosulfonic acids can catalyze the oxidative dimerization of anilines using hydrogen peroxide as a clean oxidant. The reaction does not require the use of organic solvents and affords desired azobenzenes and water as products, minimizing the formation of wastes. The metal-free solid catalyst shows remarkable activity and selectivity for the reaction, which occurs under very mild conditions and with broad functional group tolerance.
Automatic regulation and control type photoelectric conversion molecule and preparation method thereof
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Paragraph 0097; 0101; 0102, (2018/07/30)
The invention provides an automatic regulation and control type photoelectric conversion molecule. The automatic regulation and control type photoelectric conversion molecule comprises an optical switch molecule, an electron donor which is connected to one end of the optical switch molecule through a covalent bond and an electron acceptor which is connected to the other end of the optical switch molecule through an acetylene group, wherein the optical switch molecule is a group comprising a photochromic compound; the electron donor is a group capable of providing electrons; the electron acceptor is a group which has an electron accepting capability and has electronegativity stronger than that of the electron donor and the optical switch molecule. The automatic regulation and control type photoelectric conversion molecule can be used for efficiently collecting solar energy and converting the solar energy into excitation-state electron energy. The automatic regulation and control type photoelectric conversion molecule is of an open structure at an initial state; electrons are transferred to the acceptor from the donor and an optical switch under light illumination; the optical switchis triggered to be automatically closed and charge flowing in the molecule is stopped; excited electrons cannot reflow and compound, so that efficient separation of charges in an organic molecule system is realized; the closed optical switch absorbs light and is converted back to an opening state after the excited electrons are consumed, so that automatic circulation is realized.
