1594-86-1

Basic information

• Product Name: BIPHENYL-UL-14C
• Synonyms: BIPHENYL-UL-14C
• CAS NO: 1594-86-1
• Molecular Formula: C12H10
• Molecular Weight: 178.42
• Mol File: 1594-86-1.mol
• Article Data: 1190

Chemical Properties

• Appearance: /toluene solution
• Storage Temp.: 2-8°C
• CAS DataBase Reference: BIPHENYL-UL-14C(CAS DataBase Reference)
• NIST Chemistry Reference: BIPHENYL-UL-14C(1594-86-1)
• EPA Substance Registry System: BIPHENYL-UL-14C(1594-86-1)

Safety Data

• Hazard Codes: F,Xn
• Statements: 11-38-48/20-63-65-67
• Safety Statements: 36/37-62
• RIDADR: UN 2910 7
• Hazardous Substances Data: 1594-86-1(Hazardous Substances Data)

Upstream product

• 110-86-1 pyridine 
• 65-85-0 benzoic acid 
• 94-36-0 dibenzoyl peroxide 
• 108-31-6 maleic anhydride 
• 60-29-7 diethyl ether 
• 28557-00-8 phenylzinc chloride 
• 693-03-8 n-butyl magnesium bromide 
• 75-44-5 phosgene 
• 92-66-0 4-bromo-1,1'-biphenyl 
• 56-23-5 tetrachloromethane 
• 119-61-9 benzophenone 
• 3003-04-1 thallium(III) triphenyl 
• 15719-64-9 methylammonium carbonate 
• 113490-26-9 bis(4-phenylbenzoyl) peroxide 

Downstream Products

• 14584-23-7 4,4'-dipropylbiphenyl 
• 10289-45-9 4-propyl-1,1'-biphenyl 
• 3478-90-8 4,4'-diphenylbenzophenone 
• 81937-29-3 4,4'-Dicyclohexyl-biphenyl 
• 860563-96-8 4-dimethylamino-4'-phenyl-benzophenone 
• 82941-04-6 biphenyl-4-yl-[2]furyl ketone 
• 34715-95-2 (1,1'-biphenyl)-4-yl-2-thienylmethanone 
• 92688-34-1 3,3-di([1,1'-biphenyl]-4-yl)isobenzofuran-1(3H)-one 
• 26892-90-0 ethyl 4-hydroxy-3-quinolinecarboxylate 
• 70271-77-1 6-chloro-4-hydroxyquinoline-3-carboxylic acid ethyl ester 
• 73987-37-8 8-chloro-4-hydroxy-quinoline-3-carboxylic acid ethyl ester 
• 103514-53-0 6-nitro-4-hydroxy-quinoline-3-carboxylic acid ethylester 
• 2845-82-1 5-(pyridin-4-yl)-3H-1,3,4-oxadiazol-2-one 
• 102170-77-4 2-(biphenyl-4-carbonyl)-3,4,5,6-tetrabromo-benzoic acid 

Relevant articles and documents

Catalysis of the Suzuki reaction by acyclic diaminocarbene palladium complexes generated in situ

Acyclic diaminocarbene palladium complexes generated in situ by nucleophilic attack of morpholine, 4-nitrophenylhydrazine, or benzhydrazide on bis(isocyanide) palladium(II) complexes catalyzed the Suzuki reaction of 4-iodo- or 4-bromoanisole with phenylboronic acid. Morpholine turned out to be the best catalyst modifier. The cross coupling reaction under fairly mild conditions (reflux in ethanol in the presence of potassium carbonate) in 2 h afforded 4-methoxybiphenyl whose yield was insignificantly lower than in the presence of preliminarily prepared catalyst. Neither preliminary degassing nor protection from atmospheric moisture and oxygen was necessary.

Direct Synthesis of TiO2-Supported MoS2 Nanoparticles by Reductive Coprecipitation

Molybdenum disulfide nanoparticles supported on titania were synthesized from aqueous solutions containing Ti and Mo precursor salts by an in situ redox reaction. The synthesis involves a redox process between Ti3+ and MoS42-, which proceeds readily under mild conditions in aqueous solution. Catalysts were made in a single step, yielding amorphous catalysts with high Mo content, or in two steps to obtain MoS2 supported on well-defined TiO2 with lower Mo content. Catalysts obtained by single-step reductive coprecipitation were highly active in the hydrodesulfurization of dibenzothiophene, exceeding the activity of an alumina-supported Co-Mo reference. In contrast to alumina-supported catalysts, the addition of Co as promoter did not enhance the catalytic activity of MoS2/TiO2 to the same extent (+30 %) as for alumina-supported Co-Mo catalysts. Instead, a change in selectivity towards hydrogenolysis products at the expense of hydrogenation products was observed. It is suggested that Ti may act as a promoter for MoS2 in hydrogenation reactions.

Sacrificial carbonaceous coating over alumina supported Ni-MoS2 catalyst for hydrodesulfurization

Recent results have evidenced that carbon plays an important role in stabilizing the structure of the active phase in catalysts. In this work, carbon-coated alumina was prepared by applying polydopamine (PDA) as a sacrificial carbon source to modify the surface properties of γ-alumina, which then was used as a support to prepare supported NiMo catalysts for hydrodesulfurization (HDS) of dibenzothiophene (DBT). NiMo/Al2O3 catalysts exhibited limited hydrodesulfurization performances due to their strong metal-support interaction. Herein, we report an unexpected phenomenon that sacrificial carbon layers can be constructed on the surface of the Al2O3 support from the carbonization of polydopamine (PDA) and mediated the interaction between the active site and support. Through the removal of carbon layers and sulfidation, the resulting NiMo catalysts exhibit excellent performance for HDS reaction of dibenzothiophene (DBT), which is associated with adequate loading of residual carbon species, leading to an enhanced amount of active species under sulfidation conditions. Moreover, the facile synthetic strategy can be extended to the stabilization of the active phase on a broad range of supports, providing a general approach for improving the metal-support interaction supported nanocatalysts.

Nickel-Catalyzed Intramolecular 1,2-Aryl Migration of Mesoionic Carbenes (iMICs)

Intramolecular 1,2-Dipp migration of seven mesoionic carbenes (iMICAr) 2 a–g (iMICAr=ArC{N(Dipp)}2CHC; Ar=aryl; Dipp=2,6-iPr2C6H3) under nickel catalysis to give 1,3-imidazoles (IMDAr) 3 a–g (IMDAr=ArC{N(Dipp)CHC(Dipp)N}) has been reported. The formation of 3 indicates the cleavage of an N?CDipp bond and the subsequent formation of a C?CDipp bond in 2, which is unprecedented in NHC chemistry. The use of 3 in accessing super-iMICs (5) (S-iMIC=ArC{N(Dipp)N(Me)C(Dipp)}C) has been shown with selenium (6), gold (7), and palladium (8) compounds. The quantification of the stereoelectronic properties reveals the superior σ-donor strength of 5 compared to that of classical NHCs. Remarkably, the percentage buried volume of 5 (%Vbur=45) is the largest known amongst thus far reported iMICs. Catalytic studies show a remarkable activity of 5, which is consistent with their auspicious stereoelectronic features.

LiCl-Accelerated Nickel Catalyzed Cross-Coupling of Aryl Tosylates with the Aryl Grignard Reagents

A mild coupling reaction catalyzed by Ni(acac)2-L4 has been studied. The catalyst acts efficiently in the reaction of biaryl coupling between various electrophiles and common or functionalized aryl Grignard reagents with high functional group tolerance. The study demonstrates that LiCl acts as an essential component in efficient cross-coupling by accelerating reduction of Ni(II) to Ni(0). The new catalytic system for selective couplings of aryl tosylates with aryl chlorides has been developed.

Selective oxidative ligand coupling of organoborates bearing an alkynyl group

Selective oxidative ligand coupling of alkynyl(triaryl)borates was achieved by treatment with ethoxyvanadyl dichloride [VO(OEt)Cl2] to form the sp-sp2 carbon-carbon bond. A one-pot procedure through the in situ preparation of the bor

Oxidative C-H activation/C-C bond forming reactions: Synthetic scope and mechanistic insights

This paper describes a new palladium-catalyzed method for C-H activation/carbon-carbon bond formation with hypervalent iodine arylating agents. This transformation has been applied to a variety of arene and benzylic substrates containing different directing groups (pyridines, quinolines, oxazolidinones, and amides) and proceeds with high levels of regiocontrol. Mechanistic experiments provide preliminary evidence in support of an unusual mechanism for this transformation involving a Pd(II)/Pd(IV) catalytic cycle. Copyright

Photochemistry of adsorbed phenyl iodide: Desorption and photofragmentation dynamics

The photodissociation and photodesorption dynamics of iodobenzene adsorbed at 150 K on LiF substrates has been investigated at 222 nm using the time-of-flight/resonance-enhanced multiphoton ionization/mass spectrometry technique.The Maxwell-Boltzmann (MB)

Synthesis and hydrodesulfurization properties of NiW catalyst supported on high-aluminum-content, highly ordered, and hydrothermally stable Al-SBA-15

Highly ordered mesoporous Al-SBA-15 with high aluminum content and high hydrothermal stability has been synthesized by a new pH-adjusting and high-temperature hydrothermal treatment approach. Thus-prepared samples were characterized by X-ray fluorescence spectroscopy, X-ray powder diffraction, 27Al nuclear magnetic resonance spectroscopy, N2 adsorption-desorption, temperature-programmed desorption of ammonia, Fourier transformed infrared spectroscopy with pyridine adsorption, temperature- programmed reduction with hydrogen, and high-resolution transmission electron microscopy. The results showed that Al-SBA-15 had high aluminum loading (with its molar Si/Al ratio of 5.1, similar to that of the initial gel mixture) and homogenously distributed Al species in the walls. Moreover, the product showed extremely high hydrothermal stability (with only a 15.2% decrease in surface area after steaming at 800 °C for 5 h) and moderate acidity. An Al-SBA-15-supported NiW hydrodesulfurization catalyst was prepared and evaluated using dibenzothiophene hydrodesulfurization. Compared with γ-Al 2O3- and SBA-15-supported catalysts, the Al-SBA-15-supported NiW catalyst showed outstanding hydrodesulfurization activity.

C-C Bond Forming Reductive Elimination from Diarylplatinum Complexes Driven by Visible-Light-Mediated Photoredox Reactions

A series of dinuclear Pt(II) bis-aryl complexes with visible-light-absorbing Ir(III)-cyclometalate units were synthesized, and their molecular structure and photophysical and electrochemical properties were investigated. The dinuclear complexes underwent reductive elimination upon visible-light irradiation at ambient temperature to afford the corresponding biaryls. The photoredox process at the Ir center induces the oxidation of the Pt(II)-Ar2 center to [Pt-Ar2](III) to accelerate reductive elimination.

Use of external radical sources in flash vacuum pyrolysis to facilitate cyclodehydrogenation reactions in polycyclic aromatic hydrocarbons

A new process to facilitate the cyclodehydrogenation of polycyclic aromatic hydrocarbons (PAHs) in flash vacuum pyrolysis (FVP) using an external radical source is described. Using hexanes as an external radical source the conversion of various PAHs to their cyclodehydrogenated products is vastly increased. Various other volatile organic compounds were also examined to determine their ability to act as external radical sources in FVP.

Synthesis of an Ni2P catalyst supported on Na-MCM-41 with highly activity for dibenzothiophene HDS under mild conditions

A novel and simple method to synthesize supported Ni2P/Na(x)-MCM-41 catalysts (where x is the mass fraction of Na-to-MCM-41 in terms of percentage) at a lower reduction temperature by incorporation of Na was described. The catalysts were characterized by H2 temperature-programmed reduction (H2-TPR), X-ray diffraction (XRD), N2 adsorption–desorption, CO uptake, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The effect of Na on the structure of catalysts and catalytic properties for the dibenzothiophene (DBT) hydrodesulfurization (HDS) was investigated, which confirmed that a suitable amount of Na can promote highly dispersed Ni2P particles. The Na preferentially interacts with phosphate to generate the sodium phosphate and therefore suppresses the formation of stronger P–O–P bonds, which enables the phosphide catalyst to be easily formed at a lower reduction temperature. Compared with conventional phosphate (973–1273?K), the reduction temperature of Ni2P/Na(x)-MCM-41 catalyst was relatively low (773?K). The Ni2P/Na(x)-MCM-41 catalyst with x = 1.0 showed the maximum DBT conversion of 91.6%, which is higher than that of Ni2P/M41 without Na (80.3%).

The effect of Al2O3 and ionic liquids in palladium catalyzed arylation of cyclohexene. Interaction of Hg(0) with immobilized palladium

Three-component systems containing Pd(OAc)2, Al2O3, and an IL (IL = ionic liquid) were applied in the Heck arylation of cyclohexene. The highest productivity and selectivity to 4-phenylcyclohexene was noted in reaction catalyzed by Pd/Al2O3 in the presence of a small amount of an IL, dimethyldidodecylammonium lactate (C). The addition of Al2O3 alone to the reaction catalyzed by soluble precursors, PdCl2(PhCN)2 or Pd(OAc)2 and IL, remarkably increased conversion to 4-phenylcyclohexene. Hg(0) inhibited the reaction catalyzed by Pd/Al2O3 by formation of Pd-Hg amalgam immobilized on Al2O3. SEM/EDX studies of Pd/Al2O3 performed after treatment with Hg(0) showed that the IL modified the surface properties of Pd/Al2O3.

Recoverable palladium catalysts for Suzuki-Miyaura cross-coupling reactions based on organic-inorganic hybrid silica materials containing imidazolium and dihydroimidazolium salts

The systems formed by palladium acetate [Pd(OAc)2] and hybrid silica materials prepared by sol-gel from monosilylated imidazolium and disilylated dihydroimidazolium salts show catalytic activity in Suzuki-Miyaura cross-couplings with challenging aryl bromides and chlorides. They are very efficient as recoverable catalysts with aryl bromides. Recycling is also possible with aryl chlorides, although with lower conversions. In situ formation of palladium nanoparticles has been observed in recycling experiments.

Palladium nanoparticles on carbon nanotubes as catalysts of cross-coupling reactions

The macroscopic properties of composite nanotube-nanoparticle superstructures are determined by a complex interplay of structural parameters at the nanoscale. The catalytic performance of different carbon nanotube-palladium nanoparticle catalysts, where nanoparticles were formed either directly onto nanotubes or preformed prior to deposition on nanotubes using different types of surfactants, were tested in cross-coupling reactions. The decoration of multi-walled carbon nanotubes with preformed thiolate-stabilised palladium nanoparticles yielded the optimum catalyst, exhibiting high activity and stability towards carbon-carbon bond formation and excellent recyclability, retaining high activity from cycle to cycle. The type of carbon nanotube support has pronounced effects on the density of deposited nanoparticles, with more polarisable MWNT able to uptake the highest number of nanoparticles per unit surface area as compared to other carbon nanostructures (MWNT > DWNT > SWNT ～ GNF). Microscopic investigation of the nanoscale morphology found that nanoparticles increase in size during catalysis. The extent of growth is dependent on the type of nanocarbon support, with wider MWNT possessing lower curvature and thus retarding the growth and coalescence of nanoparticles to a greater extent than other carbon nanostructures (SWNT ? DWNT > MWNT ～ GNF). The type of halogen X in the C-X bond activated by palladium appears to influence the evolution of nanoparticles during catalysis, with X = Br having the greatest effect as compared to X = Cl or I. Overall, preformed thiolate-stabilised palladium nanoparticles deposited on MWNT from solution was found to possess the most functional catalytic properties, with optimum activity, stability and recyclability in a range of cross-coupling reactions.

Iodine-promoted efficient homocoupling of arylboronic acids in PEG-400 under Aerobic conditions

Iodine is able to catalyze the homocoupling of arylboronic acids in moderate to good yields in PEG-400 under aerobic conditions. This transition-metal-free catalytic system is readily available at low cost, which is practical and useful. It is noteworthy that a high activity of our catalytic system could be maintained under mild conditions (100 °C) by addition of water.

Enhanced catalytic activity of monodispersed porous Al2O3 colloidal spheres with NiMo for simultaneous hydrodesulfurization and hydrogenation

Novel composites made from monodispersed porous Al-glycolate spheres (NiMo/Al-SP) were synthesized through alcoholysis or hydrolysis treatments. The obtained samples were characterized by a complementary combination of X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), N2 physisorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), hydrogen temperature-programmed reduction (H2-TPR), and pyridine Fourier transform infrared spectroscopy (Py FT-IR). In addition, the catalytic performances of the resultant catalysts were evaluated in the simultaneous HDS of dibenzothiophene (DBT) and HYD of naphthalene (DBT and naphthalene represent the sulfur-containing compounds and polycyoalkanes, respectively). The experimental results showed that, 71.22% DBT and 88.28% naphthalene were converted by NiMo/Al-SP(H) under the conditions of 270 °C temperature, 5 MPa H2 (initial pressure at room temperature) and 10 h reaction time. The design and preparation of NiMo/Al-SP provide an effective and novel pathway for the development of high-performance catalysts and production processes.

The Influence of the Nature of the Support on the Copper-Palladium Catalysed Suzuki-Miyaura-Coupling

Copper-palladium bimetallic catalysts supported on mixed oxides (MgO)0.75(Al2O3)0.25 (MgAlO) were prepared with two step impregnation (TSI) and co-impregnation (CI). These materials were studied to determine the effect of the support on the activity and stability in the Suzuki-Miyaura reaction and on the properties of a catalyst. The catalyst prepared by CI was active and selective during 6 catalytic cycles in Suzuki coupling, whereas the activity of the catalyst prepared with TSI dropped at the sixth use. The kinetics of the reaction was examined along with its scope. The relationship between the basic properties of the support and the catalytic performances were examined too. The importance of the nature of the support was also studied by catalyst characterization methods. (Chemical Equation Presented).

Further Studies on the Photoisomerization and Hydrolysis of Chlorobiphenyls in Water. Common Ion Effect in the Photohydrolysis of 4-Chlorobiphenyl

The photochemistry of 14C-labeled 2-chlorobiphenyl (2-ClBP) and 3-chlorobiphenyl (3-ClBP) in water was studied by isotopic dilution. 2-ClBP yielded 2-hydroxybiphenyl (2-HOBP) exclusively. 3-ClBP, on the other hand, yielded 3-HOBP, 2-HOBP, and 4-HOBP and a small amount of biphenyl (2percent).Thus, 2-ClBP reacts exclusively by a heterolytic process, whereas 3-ClBP reacts not only by a heterolytic pathway but also by competing isomerization (to 2-ClBP and 4-ClBP) and homolytic pathways.The photochemistry of 4-ClBP in 80:20 (v:v) H2O-CH3CN with added HCl or NaCl was also studied.These reactions were suppressed in the presence of HCl or NaCl.Further experiments demonstrated that the suppression was not due to any great extent to the ionic strength of the solution, spin orbit effects of heavy atoms, and proton quenching.These results are compatible with a mechanism originally proposed by Kropp in which the excited state of 4-ClBP, likely the triplet excited state, undergoes homolysis of the aryl carbon-chlorine bond to form a radical pair.Once formed the radical pair undergoes an electron transfer from the aryl radical to the chlorine atom to form a highly reactive aryl cation and chloride.Reaction of the aryl cation with added chloride then regenerates 4-ClBP.The overall reaction is equivalent to a common ion effect.The role of other mechanisms in the observed chemistry is also discussed.

Ozonolysis of Diphenylvinylene Carbonate. Synthesis and Thermolysis of Dibenzoyl Monoperoxycarbonate

Dibenzoyl monoperoxycarbonate (2) was prepared by the reaction of diphenylvinylene carbonate (1) with ozone.The thermolysis of 2 in benzene gives products typical of the formation of benzoyloxy radicals.The reaction rate was investigated at different temperatures, and the activation parameters were determined (ΔH% = 27.8 +/- 1.2 kcal/mol, ΔS% = 6.1 +/- 3.5 eu).The thermolysis of 2 in the presence of the stable free radical gavinoxyl was investigated also.These experiments revealed that the fraction of radical escape from the solvent cage is 60 +/- 5 percent.

Development of a Magnetically Recyclable Molybdenum Disulfide Catalyst for Direct Hydrodesulfurization

Superparamagnetic MoS2/SiO2/Fe3O4 catalysts that consist of magnetite as the core, silica as the covering layer, and molybdenum sulfide as the top layer were prepared in easy steps. Two different surfactants (anionic and cationic) were used to assist with the synthesis of two of the samples, and one sample was prepared without surfactant. The surfactant was found to have a significant effect on the properties and activity of the final catalysts. Hydrodesulfurization (HDS) tests of the catalysts show higher activity for the cationic-surfactant-assisted catalyst. Between the direct desulfurization (DDS) and hydrogenation pathways for the prepared catalysts, the DDS pathway was found to be dominant for the HDS of dibenzothiophene. As a result of the magnetic properties of this catalyst, it can be separated easily from the reaction media by a magnetic field applied externally and reused, which makes it an ideal choice for slurry reactors that process heavy and extra-heavy crude oil.

A new method for the selective synthesis of biphenyl by dehydrogenative coupling of benzene

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NiMo catalysts supported on graphene-modified mesoporous TiO2 toward highly efficient hydrodesulfurization of dibenzothiophene

The graphene-covered mesoporous TiO2 (SBET > 90 m2 g-1) were successfully prepared by using graphene oxide (GO) as graphene source via one-step hydrothermal reduction, and then were prepared supported NiMo catalysts for hydrodesulfurization (HDS) of dibenzothiophene (DBT). The active species were incorporated by incipient impregnation. Compared with the unmodified NiMo/TiO2 catalyst, all modified catalysts exhibited higher HDS activity under mild conditions of 280 °C, 2.0 MPa, liquid hourly space velocity of 4 h-1 and hydrogen/feed ratio of 400 (V/V). Among of them, the catalyst with the appropriate mass ratio of rGO/TiO2(0.5) showed the highest DBT conversion of 99.9%. The prepared catalysts were characterized by various techniques (N2 adsorption-desorption, XRD, Raman, Pyridine FT-IR, NH3-TPD, H2-TPR, CO uptake, SEM and TEM). The enhanced HDS activity can be ascribed to (i) The incorporation of rGO (reduced graphene oxide) induces proper enhanced Lewis acidity of the modified catalysts, which promotes the adsorption of DBT molecules and facilitates the hydrogenation route. (ii) The introduction of rGO changes the HDS product (H2S) desorption behaviors, accelerating H2S desorption rate from catalyst surface and promoting the efficiency of catalyst immediately.

Stannane-Mediated Radical Addition to Arenes. Generation of Cyclohexadienyl Radicals and Increased Propagation Efficiency in the Presence of Catalytic Benzeneselenol

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Palladium-catalyzed aryl group transfer from triarylphosphines to arylboronic acids

A study of Pd-catalyzed arylation of arylboronic acids with triarylphosphines is presented. Various parameters of this transformation, such as the oxygen presence, choice of solvent, temperature, palladium source, bases and oxidants, were tested and the optimal conditions of the aryl transfer were determined. The effect of electron-withdrawing and electron-donating substituents on the aryl groups of both reactants was also investigated. The unusual transfer of the acetate group from Pd(OAc)2 to p-nitrophenylboronic acid in the presence of PAr3 is reported. A plausible mechanism of the Pd-catalyzed aryl group transfer from PAr3 to the arylboronic acid is proposed.

Silk?Fibroin-Supported Palladium Catalyst for Suzuki-Miyaura and Ullmann Coupling Reactions of Aryl Chlorides

Recently, we have reported the preparation of a silk fibroin-supported Palladium catalyst (Pd/SF) and its use in the Suzuki-Miyaura cross-coupling of aryl iodides. Since its synthetic applicability and structural features are still far from being fully ex

Effect of pre-activation treatment temperature on hydrodesulfurization catalytic activity of CoMoS/KIT-6

Mesoporous silica-supported cobalt–molybdenum hydrodesulfurization catalysts have been prepared by wetness impregnation, drying and a thermal pre-treatment of impregnated support before activation. Characterization of materials was made by nitrogen adsorption, thermogravimetric analysis, Raman spectroscopy, TEM and XPS. Catalytic activity was determined by hydrodesulfurization of dibenzothiophene (DBT). The results indicate that the thermal pre-treatment carried out at the lower temperature allows the formation of smaller and less stacked active phase structures, with a higher amount of CoMoS phase.