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
• Article Data: 32

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

• 95-46-5 2-methylphenyl bromide 
• 5720-07-0 4-methoxyphenylboronic acid 
• 696-62-8 para-iodoanisole 
• 108-88-3 toluene 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 1432-38-8 (p-methoxyphenyl)dimethylsilane 
• 459-64-3 4-methoxybenzenediazonium tetrafluoroborate 
• 104-94-9 4-methoxy-aniline 
• 100-59-4 phenylmagnesium chloride 
• 1144-13-4 naphthalen-1-yl N,N-dimethylsulfamate 
• 932-31-0 ortho-tolylmagnesium bromide 
• 623-12-1 4-chloromethoxybenzene 
• 459-60-9 1-fluoro-4-methoxybenzene 
• 33397-21-6 tris(4-methoxyphenyl)bismuth 

Downstream Products

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

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.

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.

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.