1165-53-3

Basic information

• Product Name: 1,2,4-Triphenylbenzene
• Synonyms: 1,2,4-Triphenylbenzene;2'-Phenyl-1,1':4',1''-terbenzene;2'-Phenyl-1,1':4',1''-terphenyl;4'-Phenyl-1,1':2',1''-terbenzene;4'-Phenyl-1,1':2',1''-terphenyl;4'-Phenyl-m-terphenyl
• CAS NO: 1165-53-3
• Molecular Formula: C₂₄H₁₈
• Molecular Weight: 306.4
• Mol File: 1165-53-3.mol
• Article Data: 141

Chemical Properties

• Melting Point: 166-167 °C
• Boiling Point: 452.1±25.0 °C(Predicted)
• Appearance: /
• Density: 1.074±0.06 g/cm3(Predicted)
• CAS DataBase Reference: 1,2,4-Triphenylbenzene(CAS DataBase Reference)
• NIST Chemistry Reference: 1,2,4-Triphenylbenzene(1165-53-3)
• EPA Substance Registry System: 1,2,4-Triphenylbenzene(1165-53-3)

Safety Data

• Hazardous Substances Data: 1165-53-3(Hazardous Substances Data)

Usage

General Description

1,2,4-Triphenylbenzene is a chemical compound with the molecular formula C24H18. It is a symmetrical molecule with three phenyl groups attached to a central benzene ring, and it belongs to the class of aromatic hydrocarbons. 1,2,4-Triphenylbenzene is used as a building block in organic synthesis and has applications in the manufacturing of dyes, pigments, and pharmaceuticals. 1,2,4-Triphenylbenzene is also a valuable tool in the field of material science, as it has potential for use in organic light-emitting diodes (OLEDs) and other optoelectronic devices. Its unique structure and properties make it an important compound in the development of advanced materials and the study of organic chemistry.

Upstream product

• 54119-53-8 3,4-diphenylthiopnene 1,1-dioxide 
• 536-74-3 phenylacetylene 
• 5587-78-0 4-hydroxy-3,4-diphenylcyclopent-2-en-1-one 
• 100-47-0 benzonitrile 
• 75-05-8 acetonitrile 
• 71-43-2 benzene 
• 498-66-8 norborn-2-ene 
• 123-73-9 crotonaldehyde 
• 2689-88-5 diethyl 2,2-di(prop-2-yn-1-yl)malonate 
• 78-79-5 isoprene 
• 15226-74-1 dicobalt octacarbonyl 
• 201230-82-2 carbon monoxide 
• 100-42-5 styrene 
• 1942-46-7 5-decyne 

Downstream Products

• 612-71-5 1,3,5-triphenylbenzene 
• 3073-03-8 2-phenyltriphenylene 

Relevant articles and documents

First examples of homogeneous catalytic cyclotrimerization and polymerization of phenylacetylene and copolymerization of phenylacetylene and norbonene with dinuclear complexes containing unbridged metal-metal quadruple bond

First examples of application of dinuclear complexes containing unbrigded metal-metal quadruple bond as catalysts in cyclotrimerization, oligomerization and polymerization of substituted acetylene are reported. The d4-d4 dinuclear co

Solvent-free oligomerization of phenylacetylene catalyzed by (cyclopentadienyl)nickel complexes

The solvent-free reaction of phenylacetylene at 115°C in the presence of nickelocene, [(η-Cp)Ni]2(PhC≡CH), [(η-Cp)Ni(CO)]2, (η-Cp)Ni(NO), (η-Cp)Ni(GeBr3)(CO), (η-Cp)Ni[(P(OMe3)]Cl, (η-Cp)Ni(Ph3P)Cl, (η-Cp)Ni(Bu3nP)I, or (Ph3P)2Ni(CO)2 gives rise to a mixture of cyclotrimers, linear oligomers and poly(phenylacetylene), no reaction being observed in the case of internal acetylenes. Cyclotrimer formation is favoured by the presence of (a) added phosphine (2 equiv.), or (b) (cyclopentadienyl)nickel catalysts bearing a chloro substituent at Ni. A reduction in reaction temperature results in lower conversion but favours linear oligomer and polymer formation. The extent of reaction is greatly reduced in the case of (a) nickelocene in the presence of 2 equiv. PBu3n, (b) (η-Cp)Ni(GeBr3)(CO), or (c) (η-Cp)Ni(NO). The main effect of the presence of solvent, regardless of whether it is potentially coordinating (toluene) or not (n-octane), is to suppress almost completely reactions catalyzed by nickelocene. The Royal Society of Chemistry 2000.

Rh-POP pincer Xantphos complexes for C-S and C-H activation. Implications for carbothiolation catalysis

The neutral Rh(I)-Xantphos complex [Rh(κ3-P,O,P-Xantphos)Cl]n, 4, and cationic Rh(III) [Rh(κ3-P,O,P-Xantphos)(H)2][BArF4], 2a, and [Rh(κ3-P,O,P-Xantphos-3,5-C6H3(CF3)2)(H)2][BArF4], 2b, are described [ArF = 3,5-(CF3)2C6H3; Xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; Xantphos-3,5-C6H3(CF3)2 = 9,9-dimethylxanthene-4,5-bis(bis(3,5-bis(trifluoromethyl)phenyl)phosphine]. A solid-state structure of 2b isolated from C6H5Cl solution shows a κ1-chlorobenzene adduct, [Rh(κ3-P,O,P-Xantphos-3,5-C6H3(CF3)2)(H)2(κ1-ClC6H5)][BArF4], 3. Addition of H2 to 4 affords, crystallographically characterized, [Rh(κ3-P,O,P-Xantphos)(H)2Cl], 5. Addition of diphenyl acetylene to 2a results in the formation of the C-H activated metallacyclopentadiene [Rh(κ3-P,O,P-Xantphos)(ClCH2Cl)(σ,σ-(C6H4)C(H)=CPh)][BArF4], 7, a rare example of a crystallographically characterized Rh-dichloromethane complex, alongside the Rh(I) complex mer-[Rh(κ3-P,O,P-Xantphos)(η2-PhCCPh)][BArF4], 6. Halide abstraction from [Rh(κ3-P,O,P-Xantphos)Cl]n in the presence of diphenylacetylene affords 6 as the only product, which in the solid state shows that the alkyne binds perpendicular to the κ3-POP Xantphos ligand plane. This complex acts as a latent source of the [Rh(κ3-P,O,P-Xantphos)]+ fragment and facilitates ortho-directed C-S activation in a number of 2-arylsulfides to give mer-[Rh(κ3-P,O,P-Xantphos)(σ,κ1-Ar)(SMe)][BArF4] (Ar = C6H4COMe, 8; C6H4(CO)OMe, 9; C6H4NO2, 10; C6H4CNCH2CH2O, 11; C6H4C5H4N, 12). Similar C-S bond cleavage is observed with allyl sulfide, to give fac-[Rh(κ3-P,O,P-Xantphos)( η3-C3H5)(SPh)][BArF4], 13. These products of C-S activation have been crystallographically characterized. For 8 in situ monitoring of the reaction by NMR spectroscopy reveals the initial formation of fac-κ3-8, which then proceeds to isomerize to the mer-isomer. With the para-ketone aryl sulfide, 4-SMeC 6H4COMe, C-H activation ortho to the ketone occurs to give mer-[Rh(κ3-P,O,P-Xantphos)(σ,κ1-4-(COMe)C6H3SMe)(H)][BArF4], 14. The temporal evolution of carbothiolation catalysis using mer-κ3-8, and phenyl acetylene and 2-(methylthio)acetophenone substrates shows initial fast catalysis and then a considerably slower evolution of the product. We suggest that the initially formed fac-isomer of the C-S activation product is considerably more active than the mer-isomer (i.e., mer-8), the latter of which is formed rapidly by isomerization, and this accounts for the observed difference in rates. A likely mechanism is proposed based upon these data.

One-pot synthesis of multisubstituted quaterphenyls and cyclopropanes

An efficient one-step synthetic route toward multifunctionalized quaterphenyls 3 or cyclopropanes 4 is developed from substituted chalcones 1 and sulfones 2 in good yields via a regioselective [3C+3C] or [1C+2C] annulation. The reaction features mild conditions, multisubstitution, and functional groups tolerance and is transition metal catalyst-free. The protocol provides a novel alternative to the conventional methodologies for the synthesis of quaterphenyls or cyclopropanes.

Regioselective Cyclotrimerization of Terminal Alkynes Using a Digermyne

The catalytic activation of small neutral molecules followed by the formation of C?C bonds is a highly important method to increase the complexity and/or value of simple starting materials. Reported is an isolable digermyne, a compound with a Ge≡Ge bond, which acts as a precatalyst for the cyclotrimerization of terminal arylacetylenes to afford the corresponding 1,2,4-triarylbenzenes with absolute regioselectivity. The results demonstrate that bespoke main-group-element compounds can catalytically activate and transform small neutral organic molecules and induce the formation of C?C bonds.

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Highly regioselective alkyne cyclotrimerization catalyzed by titanium complexes supported by proximally bridged p-tert-butylcalix[4]arene ligands [6]

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Ni-catalyzed cross-coupling reaction of aryl chlorides with arylboronic acids in IPA without using a reducing reagent

The coupling reaction of aryl chlorides with arylboronic acids was successfully performed in isopropanol (IPA) by using [NiCl(Ph2PCH2CH2OH)2(H2O)]Cl (5), a cationic Ni(II)-complex, as a precatalyst in the absence of a reducing agent. The coupling reaction proceeded smoothly under mild conditions to provide biaryls in satisfactory to excellent yields, and formation of the undesired dechlorination products of aryl chlorides was completely prevented.

Methylidynetricobalt nonacarbonyl catalyzed cyclotrimerization of alkynes

A cobalt carbonyl cluster, methylidynetricobalt nonacarbonyl, catalyzed inter- and intramolecular cyclotrimerization of alkynes producing substituted benzene derivatives in good to excellent yields.

Examining the Factors That Govern the Regioselectivity in Rhodium-Catalyzed Alkyne Cyclotrimerization

The electronic and steric factors that favor the formation of 1,2,4- and 1,3,5-regioisomers in the intermolecular [2 + 2 + 2] cyclotrimerization of terminal alkynes are not well understood. In this work, this problem was analyzed from a theoretical and ex

Influence of the number and substitution position of phenyl groups on the aggregation-enhanced emission of benzene-cored luminogens

The influence of the number and substitution position of phenyl groups on the aggregation-enhanced emission of benzene-cored luminogens is unambiguously revealed.

Ligands make the catalyst: Synthesis of novel functionalized phosphines

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Immobilized nickel catalysts for cyclotrimerizations of acetylenes: Enhancement of activities, stabilities, and lifetimes

Solid-state 31P NMR is used to optimize the stability and minimize leaching of nickel catalysts for alkyne cyclotrimerization immobilized by mono- and bidentate phosphine linkers on silica.

CpCo(CO)2-catalysed cyclotrimerisation of alkynes in supercritical carbon dioxide

The reactivity of mono-substituted HCCR (R=Ph, a; CH2OH, b; CH2CH2CH2CH3, c) and di-substituted RCCR (R=CH2CH3, d; CO2CH3, e; Ph, f) acetylenes was studied in supercritical carbon dioxide (scCO2) using the easily available complex CpCo(CO)2 as catalyst. The reaction of phenylacetylene produced a mixture of the isomeric cyclotrimers 1,3,5- (2a) and 1,2,4-triphenylbenzene (2a′), in a 1:5 ratio, and traces of cobaltcyclopentadienone complexes CpCo(η4-C4H2[Ph]2CO) (6a, mixture of isomers). The possible product formed by the incorporation of CO2 to alkynes, i.e. diphenylpyrone (7a) was not observed. The reaction of the cobaltacyclopentadiene complex CpCo(1.4-σ-C4[Ph]4)(PPh)3 (8f), in scCO2, was performed. No insertion of CO2 into the Co-C σ-bond to form tetraphenylpyrone (7f) by reductive elimination was observed, instead the cobaltcyclobutadiene complex CpCo(η4-C4[Ph]4) (9f) was formed. In the reactions with other alkynes, lower yields were obtained in general, except in the cyclotrimerisation of the highly activated alkyne, propargyl alcohol (b). Reaction of the non-activated alkynes, 1-hexyne (c) and 3-hexyne (d), produced complex mixtures of cobalt complexes in low yield in which the alkyne was coordinated to cobalt. Finally, the highly hindered diphenylacetylene (f) gave a mixture of the known complexes CpCo(η4-C4[Ph]4) (9f) and CpCo(η4-C4[Ph]4CO) (6f) in agreement with the results observed in conventional organic solvents.

Phenyl shifts in substituted arenes via Ipso arenium ions

The isomerization of substituted arenes through ipso arenium ions is an important and general molecular rearrangement that leads to interconversions of constitutional isomers. We show here that the superacid trifluoromethanesulfonic acid (TfOH), ca. 1 M in dichloroethane (DCE), provides reliable catalytic reaction conditions for these rearrangements, easily applied at ambient temperature, reflux (84 °C), or in a microwave reactor for higher temperatures. Interconversion of terphenyl isomers in TfOH/DCE at 84 °C gives an ortho/meta/para equilibrium ratio of 0:65:35, nearly identical to values reported earlier by Olah with catalysis by AlCl3. For the three triphenylbenzenes, TfOH-catalyzed equilibration strongly (>95%) favors the 1,3,5-triphenyl isomer. Equilibration of the three possible tetraphenylbenzenes gives a 61:39 mixture of the 1,2,3,5- and 1,2,4,5-substituted isomers. Under the reaction conditions explored, none of these structures undergoes significant Scholl cyclization. DFT calculations with inclusion of solvation support a mechanistic scheme in which all of the phenyl migrations occur among a series of ipso arenium ions. In every case studied, the preferred isomers at equilibrium are those that yield highly stable cations by the most exothermic, hence least reversible 1,2-H shift.

Dinuclear niobium(III) and tantalum(III) complexes with thioether and selenoether ligands [{MIIIX2(L)}2(μ-X) 2(μ-L)] (M = Nb, Ta; X = Cl, Br; L = R2S, R 2Se): Syntheses, structures, and the optimal conditions and the mechanism of the catalysis for regioselective cyclotrimerization of alkynes

A series of dinuclear niobium(III) and tantalum(III) halide complexes with chalcogen donors [{MIIIX2(L)}2(μ-X) 2(μ-L)] (M = Nb; X = Cl, Br; L = R2S, R2Se) (M = Ta; X = Cl, Br; L = R2S) have been prepared by the reaction of dimetal(V) decahalide (M2X10) with magnesium and L. The structures of five of those new complexes were determined by X-ray crystallography to have a M-M double bond. It is evidenced that the solvent and the temperature play important roles in achieving high yield and regioselectivity for cyclotrimerization of alkynes. The reaction of the niobium(III) chloride complexes (L = dimethyl sulfide (Me2S), tetrahydrothiophene (C4H8S, THT, thiolane)) with phenylacetylene at room temperature in toluene gave both head-to-tail cycloadded trimers of alkyne, 1,3,5-(Ph)3-2,4,6-(H)3-benzene and head-to-head cycloadded 1,2,4-(Ph)3-3,5,6-(H)3-benzene, in high yields. The smaller the thioether ligands, the higher the catalytic activity. The niobium(III) chloride complexes with selenoether (L = dimethyl selenide (Me2Se), tetrahydroselenophene (C4H 8Se, THSe, selenolane) have higher rates for the reaction with alkynes, but low activity for the cyclotrimerization. Tantalum(III) chloride complexes (L = Me2S, THT, tetrahydrothiopyran (C5H 10S, THTP, thiane)) have lower catalytic activities than the niobium(III) ones, because the Ta-S(μ-L) bond lengths are shorter than those of niobium analogs. The stability of the precursor complexes toward the first oxidative addition depends on the M-S(μ-L) bond strength, and controls the concentration of catalytic active species. The niobium(III) bromide complexes (L = Me2S, THT) and the tantalum(III) bromide one (L = Me2S) react with alkynes to give head-to-tail compounds regioselectively, but are less catalytically active than those of chloride complexes.

Reactions of vanadium(V) and tantalum(V)-complexes with kinetically stabilized phosphaalkynes. A simple synthesis of 1,3,4-thia and 1,3,4-selenadiphospholes

A simple synthetic pathway to the unknown 1,3,4-thiadiphospholes 3 and 1,3,4-selenadiphospholes 4 has been developed involving reactions of the azaphosphavanada(V)-cyclobutenes 2, generated in situ from the imidovanadium(V) complex tBuN = VCl3 and the phosphaalkynes 1a-d, with an excess of elemental sulfur or grey selenium, respectively. The reactions of the phosphaalkynes 1a,b with TaOCl3 or VOCl3·DME furnish the 1,2-dichloro-phosphaalkenes 5a,b and 1,2,3,4-tetrachloro-3,4-di-tert-butyl-1,1-diphosphethane 7a. The metallacyclic species 2e-h with secondary or primary alkyl groups on the ring nitrogen atom are unstable and undergo quantitative conversion to the 1H-1,2,4-azadiphospholes 8, whereas in the presence of an excess of phenylacetylene the 1H-1,2-azaphospholes 9e-h, are formed selectively. A catalytic reaction course has been demonstrated for the cyclotrimerization of phenylacetylene and 2-butyne initiated by small amounts of TaSCl3. The syntheses of the vanadium(IV) complexes [tBuN = VCl2·2Py] and [tBuN = VCl2·TMEDA] are also described starting from tBuN = VCl3 and phosphaalkene 12.

Cyclotrimerization of Phenylacetylene Catalyzed by Halides of Niobium and Tantalum

Halides of niobium and tantalum (NbX5, TaX5; X=Cl, Br, F) catalyzed the cyclotrimerization of phenylacetylene in hydrocarbon and chlorinated hydrocarbon solvents at 0-90 deg C.When NbCl5 and TaCl5 were used as catalysts, two cyclic trimers, 1,2,4- and 1,3,5-triphenylbenzenes were exclusively formed, and their ratio varied from 17:83 to 94:6 depending on reaction conditions.The cyclotrimerization was more selective than those by other known catalysts.The cyclotrimerization by NbBr5 and TaBr5 occurred in a similar manner, but the reaction was less selective than that catalyzed by NbCl5 and TaCl5.Not only cyclotrimerization but also linear oligomerization proceeded by NbF5 and TaF5 as catalysts.The results obtained were discussed together with the linear polymerization of phenylacetylene catalyzed by MoCl5 and WCl6.

Synthesis and Reactivity of an Early-Transition-Metal Alkynyl Cubane Mn4C4 Cluster

While the coordination chemistry of monometallic complexes and the surface properties of extended metal particles are well understood, the control of metal nanocluster formation has remained challenging. The isolation of discrete metal clusters provides an especially rare snapshot at the nanoscale of cluster growth. The synthesis and full characterization of the first early-transition-metal alkynyl cubane and the first μ3-alkynyl Mn3 motif are reported.

Insight into the Activation of In Situ Generated Chiral RhI Catalysts and Their Application in Cyclotrimerizations

We report a detailed study concerning the efficient generation of highly active chiral rhodium complexes of the general structure [Rh(diphosphine)(solvent)2]+ as well as their exemplary successful utilization as catalysts for cyclotrimerizations. Such solvent complexes could likewise be prepared from novel ammonia complexes of the type [Rh(diphosphine)(NH3)2]+. A valuable, feasible approach to generate novel chiral RhI complexes was found by in situ generation from Wilkinson's catalyst [RhCl(PPh3)3] with chiral P,N ligands. The generated catalysts led to moderate to good enantioselectivities and excellent yields in the cyclotrimerizations of triynes, showcasing their usefulness in the synthesis of axially chiral benzene derivatives.

Transition-metal variation as a probe into the catalytic activity of metallaboranes

The reactivity of two isoelectronic and isostructural metallaboranes, nido-[(Cp*Rh)2B6H10], 1 and nido-[(Cp*Ru)2B6H12], 2 with alkynes demonstrates that a change in metal from group 9 to group 8 creates difference in the reactivity pattern. Compound 1 catalyzes the cyclotrimerization of a variety of internal and terminal alkynes to yield 1,3,5- and 1,2,4-substituted benzene. In contrast, compound 2 shows no reactivity toward alkynes. A set of alkynes have been verified with nido-1 that yielded several benzene derivatives in satisfactory yields.

The cyclooligomerization of arylethynes in ionic liquids catalysed by ruthenium porphyrins: A case of real catalyst recycling

An efficient cyclooligomerization of arylethynes, catalysed by ruthenium(II) porphyrins in environmentally friendly ionic liquids, with an effective recycling of the catalyst and easy isolation of the products is described. The Royal Society of Chemistry 2005.

Monometallic Ni0 and Heterobimetallic Ni0/AuI Complexes of Tripodal Phosphine Ligands: Characterization in Solution and in the Solid State and Catalysis

The tridentate chelate nickel complexes [(CO)Ni{(PPh2CH2)3CMe}] (2), [(CO)Ni{(PPh2CH2CH2)3SiMe}] (6), and [Ph3PNi{(PPh2CH2CH2)3SiMe}] (7), as well as the bidentate complex [(CO)2Ni{(PPh2CH2)2CMeCH2PPh2}] (3) and the heterobimetallic complex [(CO)2Ni{(PPh2CH2)2CMeCH2Ph2PAuCl}] (4), have been synthesized and fully characterized in solution. All 1H and 13C NMR signal assignments are based on 2D-NMR methods. Single crystal X-ray structures have been obtained for all complexes. Their 31P CP/MAS (cross polarization with magic angle spinning) NMR spectra have been recorded and the isotropic lines identified. The signals were assigned with the help of their chemical shift anisotropy (CSA) data. All complexes have been tested regarding their catalytic activity for the cyclotrimerization of phenylacetylene. Whereas complexes 2-4 display low catalytic activity, complex 7 leads to quantitative conversion of the substrate within four hours and is highly selective throughout the catalytic reaction.

Suzuki cross-coupling of hexachlorobenzene promoted by the Buchwald ligands

The study of cross-coupling between hexachlorobenzene and phenylboronic acid comprised five Buchwald ligands, from which 2-dicyclohexylphosphino-2′-(dimethylamino)biphenyl (DavePHOS) provided the best conversion. When excess of phenylboronic acid was used, a mixture of isomeric tri-, tetra- and pentaphenyl-substituted derivatives in the ～10:70:20 ratio was obtained, along with minor amounts of hydrodechlorination products.

H-BPin/KOtBu Promoted Activation of Cobalt Salt to a Heterotopic Catalyst for Highly Selective Cyclotrimerization of Alkynes

A mixture of HBPin with KOtBu was found to activate cobalt salt to form a heterotopic cobalt species that is highly active for catalytic intermolecular trimerization of alkynes. This protocol affords 1,2,4-regioisomers in good yields with high regioselectivities under mild conditions. These salient features, together with the operational simplicity and high efficiency, as well as obviating the use of any costly and/or air sensitive ligands, renders the protocol promising for practical applications.