92495-54-0

Basic information

• Product Name: 4'-METHOXY-2-METHYL-BIPHENYL
• Synonyms: 4'-METHOXY-2-METHYL-BIPHENYL;4-METHOXY-2'-METHYL-1,1'-BIPHENYL;AKOS BAR-1281;Anisole, p-(o-tolyl)- (7CI);4-o-Tolylanisole
• CAS NO: 92495-54-0
• Molecular Formula: C₁₄H₁₄O
• Molecular Weight: 198.26
• Mol File: 92495-54-0.mol

Chemical Properties

• Melting Point: 97.8-98.6℃
• Boiling Point: 140-141.5℃ (13 Torr)
• Appearance: /
• CAS DataBase Reference: 4'-METHOXY-2-METHYL-BIPHENYL(CAS DataBase Reference)
• NIST Chemistry Reference: 4'-METHOXY-2-METHYL-BIPHENYL(92495-54-0)
• EPA Substance Registry System: 4'-METHOXY-2-METHYL-BIPHENYL(92495-54-0)

Safety Data

• Hazardous Substances Data: 92495-54-0(Hazardous Substances Data)

Usage

Synthesis

Open to the atmosphere, 4-bromoanisole (1.87 g, 10 mmol), o-tolylboronic acid (1.50 g, 11 mmol), KF (spray dried, dried in an oven overnight prior to use, 1.92 g, 33 mmol), and THF (10 mL) were added to a 100-ml round-bottomed Schlenk flflask equipped with a stir bar. The reaction system was flflushed with argon for about 5 min. P(t-Bu)3 (1.9 × 10–4 M stock solution in THF; 2.31 mL, 5.0 × 10–5 mmol) and Pd2(dba)3 (2.16 × 10–5 M stock solution in THF; 2.31 mL, 5.0 × 10–5 mmol) in THF were added sequentially. After 48 h at room temperature, the reaction mixture was diluted with ether or EtOAc, fifiltered through a pad of silica gel with copious washings, and then concentrated. The crude product was then purifified via column chromatography eluting with 5% ether in hexane to yield 1.94 g (98%) of 4-methoxy-2′-methylbiphenyl as a colorless liquid.

Upstream product

• 14774-77-7 p-methoxyphenyllithium 
• 6699-93-0 (2-methylphenyl)lithium 
• 201230-82-2 carbon monoxide 
• 16419-60-6 2-Methylphenylboronic acid 
• 459-64-3 4-methoxybenzenediazonium tetrafluoroborate 
• 95-46-5 2-methylphenyl bromide 
• 33397-21-6 tris(4-methoxyphenyl)bismuth 
• 5720-07-0 4-methoxyphenylboronic acid 
• 696-62-8 para-iodoanisole 
• 108-88-3 toluene 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 932-31-0 ortho-tolylmagnesium bromide 
• 459-60-9 1-fluoro-4-methoxybenzene 
• 623-12-1 4-chloromethoxybenzene 

Downstream Products

• 103594-14-5 1-Methyl-2-(1,4,4-trimethoxy-cyclohexa-2,5-dienyl)-benzene 
• 68623-29-0 4'-Methoxy-2-((Z)-styryl)-biphenyl 
• 68623-30-3 4'-Methoxy-2-((E)-styryl)-biphenyl 
• 68623-36-9 2-methoxy-10-phenyl-9,10-dihydrophenanthrene 
• 18110-71-9 4'-methoxybiphenyl-2-carboxylic acid 

Relevant articles and documents

Synthesis of Biaryls via Decarbonylative Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling of Aryl Anhydrides

Transition metal-catalyzed cross-couplings have been widely employed in the synthesis of many important molecules in synthetic chemistry for the construction of diverse C-C bonds. Conventional cross-coupling reactions require active electrophilic coupling partners, such as organohalides or sulfonates, which are not environmentally friendly enough. Herein, we disclose the first nickel-catalyzed Suzuki-Miyaura cross-coupling of aryl anhydrides and arylboronic acids for the synthesis of biaryls in a decarbonylation manner. The reaction tolerates a wide range of electron-withdrawing, electron-neutral, and electron-donating substituents in this process.

Copper catalysed Gomberg-Bachmann-Hey reactions of arenediazonium tetrafluoroborates and heteroarenediazonium o-benzenedisulfonimides. Synthetic and mechanistic aspects

Gomberg-Bachmann-Hey reactions were carried out in the presence of copper as a catalyst and gave rise to biaryls or heterobiaryls in good yields and in mild reaction conditions. A computational study of some key points of the reaction was performed. The results are coherent with the experimental data and confirm some aspects of the mechanism. The reaction free energies for the reduction in benzene by CuI of a set of 40 (hetero)arenediazonium tetrafluoroborates were calculated. Both the experiments and the calculations showed that in the coupling with substituted solvents (toluene, bromobenzene, nitrobenzene and anisole) the binding to the ortho position was always favoured.

Urea-based organocatalyst catalyzed direct C–H bond arylations of unactivated arenes

A simple 1,3-diethylurea was demonstrated to catalyze transition-metal-free arylations of unactivated aromatic C–H bonds with aryl iodides in the presence of t-BuOK. A broad range of aryl iodides with different arenes could couple in moderate to excellent yields. The mechanistic experiment results indicated that the radical is involved in this transformation.

Integrating Organic Lewis Acid and Redox Catalysis: The Phenalenyl Cation in Dual Role

In recent years, merging different types of catalysis in a single pot has drawn considerable attention and these catalytic processes have mainly relied upon metals. However, development of a completely metal free approach integrating organic redox and organic Lewis acidic property into a single system has been missing in the current literature. This study establishes that a redox active phenalenyl cation can activate one of the substrates by single electron transfer process while the same can activate the other substrate by a donor-acceptor type interaction using its Lewis acidity. This approach has successfully achieved light and metal-free catalytic C-H functionalization of unactivated arenes at ambient temperature (39 entries, including core moiety of a top-selling molecule boscalid), an economically attractive alternative to the rare metal-based multicatalysts process. A tandem approach involving trapping of reaction intermediates, spectroscopy along with density functional theory calculations unravels the dual role of phenalenyl cation.

A Foldamer-Based Organocatalyst for Direct Arylations of Unactivated Arenes

It was demonstrated that a simple yet well-folded pyridone dimer, possessing two convergently aligned electron-rich O atoms for potassium binding, can serve as a highly efficient organocatalyst for catalyzing transition-metal-free arylations of unactivated aromatic C-H bonds with aryl halides in the presence of t-BuOK. A wide range of aryl iodides could be cross-coupled with unactivated arenes in moderate to excellent yields. The experiments using radical-scavenging reagents confirm the participation of radicals in this catalytic transformation.

Rhodium Complexes of 2,6-Bis(dialkylphosphinomethyl)pyridines: Improved C-H Activation, Expanded Reaction Scope, and Catalytic Direct Arylation

The reactivity of (PNP)Rh(Ph) (PNP = 2,6-bis(dialkylphosphinomethyl)pyridine) toward a variety of electrophiles (Ar-I, ArCH2Cl, O2, I2, B2pin2, and ArSO3H) was explored, and several new modes of oxidative reactivity were observed. Substituting tBu2P for iPr2P provided 100-fold rate enhancement toward C-H bond activation and addressed the previously reported challenge of N2 inhibition. Studying the stoichiometric reactivity of (PNP)Rh complexes toward C-H cleavage and oxidative functionalization led to (PNP)Rh-catalyzed cross-coupling of aryl iodides with sp2 and sp3 C-H bonds.

Amide-ligand-controlled highly para-selective arylation of monosubstituted simple arenes with arylboronic acids

Pd-catalyzed highly para-selective arylations of monosubstituted simple arenes with arylboronic acids to widely existed biaryls have been developed. Inspired by requisite amide-directing groups in reported selective oxidative couplings, amide ligands, especially DMF, are designed and found to be critical for the selectivity control in current arylations.

Mechanistic study of an improved Ni precatalyst for Suzuki-Miyaura reactions of aryl sulfamates: Understanding the role of Ni(I) species

Nickel precatalysts are potentially a more sustainable alternative to traditional palladium precatalysts for the Suzuki-Miyaura coupling reaction. Currently, there is significant interest in Suzuki-Miyaura coupling reactions involving readily accessible phenolic derivatives such as aryl sulfamates, as the sulfamate moiety can act as a directing group for the prefunctionalization of the aromatic backbone of the electrophile prior to cross-coupling. By evaluating complexes in the Ni(0), (I), and (II) oxidation states we report a precatalyst, (dppf)Ni(σ-tolyl)(Cl) (dppf = 1,1'-bis(diphenylphosphino)-ferrocene), for Suzuki-Miyaura coupling reactions involving aryl sulfamates and boronic acids, which operates at a significantly lower catalyst loading and at milder reaction conditions than other reported systems. In some cases it can even function at room temperature. Mechanistic studies on precatalyst activation and the speciation of nickel during catalysis reveal that Ni(I) species are formed in the catalytic reaction via two different pathways: (i) the precatalyst (dppf)Ni(σ-tolyl)(Cl) undergoes comproportionation with the active Ni(0) species; and (ii) the catalytic intermediate (dppf)Ni(Ar) (sulfamate) (Ar = aryl) undergoes comproportionation with the active Ni(0) species. In both cases the formation of Ni(I) is detrimental to catalysis, which is proposed to proceed via a Ni(0)/Ni(II) cycle. DFT calculations are used to support experimental observations and provide insight about the elementary steps involved in reactions directly on the catalytic cycle, as well as off-cycle processes. Our mechanistic investigation provides guidelines for designing even more active nickel catalysts.

Ligand-controlled chemoselectivity in potassium tert-amylate-promoted direct C-H arylation of unactivated benzene with aryl halides

Direct C-H arylation of unactivated benzene with aryl halides under various simple ligands (EDA, DMEDA, ethylene glycol, etc.) in the presence of potassium tert-amylate (t-AmOK) base at mild temperature (80 °C) have been developed. This transition-metal-free radical cross-coupling offers an efficient way to synthesize various biaryls in good yields through base-promoted homolytic aromatic substitution. And mechanistic investigations have provided insight into the chemoselectivity of couplings between haloiodobenzenes and benzene and showed that phenanthroline and its derivatives not only initiate these radical reactions like most of other ligands (EDA, DMEDA, ethylene glycol, etc.), but also participate in the electron transfer process of biaryl radical anion intermediates.

Mechanistic significance of the Si-O-Pd bond in the palladium-catalyzed cross-coupling reactions of arylsilanolates

Through the combination of reaction kinetics (both stoichiometric and catalytic), solution- and solid-state characterization of arylpalladium(II) arylsilanolates, and computational analysis, the intermediacy of covalent adducts containing Si-O-Pd linkages