74-31-7Relevant articles and documents
Formation and photophysics of a stable concave-convex supramolecular complex of C60 and a substituted s-triazine derivative
Schuster, David I.,Rosenthal, Joel,MacMahon, Shaun,Jarowski, Peter D.,Alabi, Christopher A.,Guldi, Dirk M.
, p. 2538 - 2539 (2002)
Spectroscopic, electrochemical and computational data (show that C60 and a highly phenylated s-triazine derivative form a stable supramolecular complex at micromolar concentrations in solution at ambient temperatures, due to strong van der Waals attraction between their complementary surfaces.
Effect of Propanol-1 on the Reaction between Thiophenol and N,N'-Diphenyl-1,4-Benzoquinone Diimine in Chlorobenzene
Varlamov
, p. 644 - 651 (2019)
Abstract: It is found that the interaction between thiophenol and N,N '-diphenyl-1,4-benzoquinone diimine proceeds by two routes, one of which is a radical chain reaction and the other is a nonchain reaction between the reagents. The kinetic patterns of the reaction depend substantially on the concentration of propanol-1 in mixtures of it and chlorobenzene. It is shown that at 343 K, replacing chlorobenzene with propanol-1 results in an almost twentyfold increase in the total rate of the reaction. Increasing the concentration of propanol-1 raises the rate of both routes of the reaction, but that of the nonchain route grows more than that of the chain route. It is concluded that increasing the concentration of propanol-1 results in a simultaneous 20–30 times rise in the rate constants of both the stage of radical generation by the reaction between the reagents as well as the rate constant of the nonchain bimolecular reaction, and the chain length of the chain reaction is shortened. When chlorobenzene is replaced with propanol-1, the rate constant of the limiting stage of chain propagation (the reaction of quinone diimine with a phenylthiyl radical) is halved, due to the formation of H complexes between the π system of quinone diimine and the proton of propanol-1.
Design, preparation and characterization of aerogel NiO-CuO-CoO/SiO2 nanocomposite as a reusable catalyst for C-N cross-coupling reaction
Ghasemi, Amir Hossein,Naeimi, Hossein
supporting information, p. 5056 - 5063 (2020/04/09)
Aerogels are porous, non-crystalline solid materials with high specific surface space, plentiful three-dimensional (3D) porous construction, ultra-low density and significant porosity. The aerogel nanocomposite is produced using sol-gel and supercritical drying processes. CO2 supercritical drying (SCD) is the most powerful process, ensuring optimal product properties such as high porosity, low density, and high thermal conductivity. On this account, we used the CO2 supercritical drying method to produce NiO-CuO-CoO/SiO2 nanocomposite aerogels and applied it as a reusable catalyst for the C-N cross-coupling reaction (Buchwald-Hartwig amination). Powerful catalytic activity for the C-N cross-coupling reaction was obtained for the new nanocomposite aerogel, that is, NiO-CuO-CoO/SiO2. The catalyst was characterized by X-ray Powder Diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), elemental mapping and Brunauer-Emmett-Teller (BET). Also, organic compounds were identified by melting point, Fourier-transform infrared spectroscopy (FT-IR) and hydrogen-1 nuclear magnetic resonance (1H NMR) analyses.
Continuous Synthesis of Aryl Amines from Phenols Utilizing Integrated Packed-Bed Flow Systems
Ichitsuka, Tomohiro,Kobayashi, Shū,Koumura, Nagatoshi,Sato, Kazuhiko,Takahashi, Ikko
, p. 15891 - 15896 (2020/07/13)
Aryl amines are important pharmaceutical intermediates among other numerous applications. Herein, an environmentally benign route and novel approach to aryl amine synthesis using dehydrative amination of phenols with amines and styrene under continuous-flow conditions was developed. Inexpensive and readily available phenols were efficiently converted into the corresponding aryl amines, with small amounts of easily removable co-products (i.e., H2O and alkanes), in multistep continuous-flow reactors in the presence of heterogeneous Pd catalysts. The high product selectivity and functional-group tolerance of this method allowed aryl amines with diverse functional groups to be selectively obtained in high yields over a continuous operation time of one week.
Preparation method of diaryl p-phenylenediamine anti-aging agent
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Paragraph 0069-0076, (2020/02/10)
The invention provides a preparation method of a diaryl p-phenylenediamine anti-aging agent represented by a formula I, wherein the method comprises: carrying out a condensation dehydrogenation reaction on p-nitroaniline and a raw material B represented by a formula II in the presence of a solvent, a water-carrying agent and a catalyst, wherein R1 and R2 are respectively and independently H or C1-C6 alkyl, and R is H or C1-C6 alkyl.
Preparation method for aryl substituted p-phenylenediamine substance
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Paragraph 0042; 0043; 0044; 0045; 0046, (2017/06/02)
The invention provides a preparation method for an aryl substituted p-phenylenediamine substance. The aryl substituted p-phenylenediamine substance has the following structural formula defined in the specification, wherein R'' is phenyl or o-methyl phenyl, and R' and R'' are the same or different. The preparation method comprises the steps of carrying out a reaction of a raw material A and a raw materials B under the action of a hydrogen acceptor and a catalyst, to form the aryl substituted p-phenylenediamine substance, wherein the raw material A has the structural formula defined in the specification, the raw material B is cyclohexanone and/or o-methylcyclohexanone, and the hydrogen acceptor is a hydrogen acceptor which can accept hydrogen to be converted into the raw material B. The preparation method provided by invention has the advantages that the raw materials are cheap and easy to obtain, and reaction post-processing has no need of use of a lot of water. At the same time, the reaction conditions are mild, and equipment cannot be corroded. Therefore, the preparation method has the advantages of environmental protection and less pollution and can obtain better economic benefits.
Electrochemical synthesis of N1,N4-diphenyl-2-(phenylsulfonyl)benzene-1,4-diamine derivatives: Introducing an example of ECDispCMich mechanism
Kaihani, Sajad,Salehzadeh, Hamid,Nematollah, Davood
, p. 166 - 174 (2015/02/05)
The electrochemical oxidation of N,N'-diphenyl-l,4-phenylenediamine (DPD) has been studied using cyclic voltammetry and controlled potential coulometry methods. The results revealed that DPD shows two one-electron oxidation-reduction peaks. In the first step DPD via a single-electron process is converted to the related radical cation (DPD.+) and second step is conversion of DPD.+ to N-(4-(phenylimino) cyclohexa-2,5-dienylidene) benzenamine (CHD) via a one-electron/two-protons process. Our results also show that DPD.+ participates in disproportionation reaction and is converted to DPD and CHD. The rate of this reaction is pH dependent and increases with increasing pH. Furthermore, the electrochemical oxidation of DPD has been studied in the presence of arylsulfinic acids as nucleophiles. The results showed that electrochemically generated CHD participates in Michael addition reaction with arylsulfinic acids via a novel ECDispCMich mechanism and is converted to the N1,N4-diphenyl-2-(phenylsulfonyl)benzene-1,4-diamine derivatives. In this work, a facile and green electrochemical method for the synthesis of some new N1,N4-diphenyl-2-(phenylsulfonyl)benzene-1,4-diamine derivatives in good yields using controlled-potential electrolysis at a carbon electrode is also reported.
Modular Synthesis of Biaryl-Substituted Phosphine Ligands: Application in Microwave-Assisted Palladium-Catalyzed C-N Cross-Coupling Reactions
Singh, Chandani,Rathod, Jayant,Jha, Vishwajeet,Panossian, Armen,Kumar, Pradeep,Leroux, Frédéric R.
, p. 6515 - 6525 (2015/10/19)
Biaryl-substituted monophosphine-based ligands have been synthesized by transition-metal-free "ARYNE" cross-coupling reaction of aryllithiums with 1,2-dibromobenzene and subsequent regioselective functionalization through bromine-lithium interconversion. These ligands were employed in palladium-catalyzed C-N bond-forming reactions. The reaction was found to be general with wide substrate applicability. A wide variety of both primary and secondary amines were successfully coupled with an array of differently substituted halobenzenes under microwave irradiation to give the expected products in good to excellent yields. A number of biaryl-substituted phosphine ligands screened for the coupling reaction showed that steric bulk and the electronic properties of substituents on phosphorus play a crucial role in governing the catalytic activity of C-N cross-coupling reactions. Biaryl-substituted monophosphines have been synthesized by transition metal free ARYNE cross-coupling reactions and subsequent regioselective functionalization through bromine-lithium interconversion. These ligands were employed in palladium-catalyzed C-N bond-forming reactions.
Addressing challenges in palladium-catalyzed cross-couplings of aryl mesylates: Monoarylation of ketones and primary alkyl amines
Alsabeh, Pamela G.,Stradiotto, Mark
supporting information, p. 7242 - 7246 (2013/07/26)
Mor(DalPhos) for Me(sylates): Described are the first examples of ketone mono-α-arylation and primary aliphatic amine monoarylation employing aryl methanesulfonate coupling partners. A range of functionalized aryl mesylates were employed with dialkyl ketones, and also with primary and secondary amines as well as the otherwise challenging coupling partners acetone and methylamine. Ad=adamantyl. Copyright
BippyPhos: A single ligand with unprecedented scope in the Buchwald-Hartwig amination of (hetero)aryl chlorides
Crawford, Sarah M.,Lavery, Christopher B.,Stradiotto, Mark
supporting information, p. 16760 - 16771 (2014/01/06)
Over the past two decades, considerable attention has been given to the development of new ligands for the palladium-catalyzed arylation of amines and related NH-containing substrates (i.e., Buchwald-Hartwig amination). The generation of structurally diverse ligands, by research groups in both academia and industry, has facilitated the accommodation of sterically and electronically divergent substrates including ammonia, hydrazine, amines, amides, and NH heterocycles. Despite these achievements, problems with catalyst generality persist and access to multiple ligands is necessary to accommodate all of these NH-containing substrates. In our quest to address this significant limitation we identified the BippyPhos/[Pd(cinnamyl)Cl]2 catalyst system as being capable of catalyzing the amination of a variety of functionalized (hetero)aryl chlorides, as well as bromides and tosylates, at moderate to low catalyst loadings. The successful transformations described herein include primary and secondary amines, NH heterocycles, amides, ammonia and hydrazine, thus demonstrating the largest scope in the NH-containing coupling partner reported for a single Pd/ligand catalyst system. We also established BippyPhos/ [Pd(cinnamyl)Cl]2 as exhibiting the broadest demonstrated substrate scope for metal-catalyzed cross-coupling of (hetero)aryl chlorides with NH indoles. Furthermore, the remarkable ability of BippyPhos/[Pd(cinnamyl)Cl] 2 to catalyze both the selective monoarylation of ammonia and the N-arylation of indoles was exploited in the development of a new one-pot, two-step synthesis of N-aryl heterocycles from ammonia, ortho- alkynylhalo(hetero)arenes and (hetero) aryl halides through tandem N-arylation/hydroamination reactions. Although the scope in the NH-containing coupling partner is broad, BippyPhos/[Pd(cinnamyl)Cl]2 also displays a marked selectivity profile that was exploited in the chemoselective monoarylation of substrates featuring two chemically distinct NH-containing moieties.
