33350-73-1

Basic information

• Product Name: 2-Methyl-4'-nitrobiphenyl
• Synonyms: 2-Methyl-4'-nitrobiphenyl;2-Methyl-4'-nitro-1,1'-biphenyl
• CAS NO: 33350-73-1
• Molecular Formula: C₁₃H₁₁NO₂
• Molecular Weight: 213.23194
• Mol File: 33350-73-1.mol

Chemical Properties

• Boiling Point: 334.3°Cat760mmHg
• Flash Point: 151.6°C
• Appearance: /
• Density: 1.166g/cm³
• CAS DataBase Reference: 2-Methyl-4'-nitrobiphenyl(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Methyl-4'-nitrobiphenyl(33350-73-1)
• EPA Substance Registry System: 2-Methyl-4'-nitrobiphenyl(33350-73-1)

Safety Data

• Hazardous Substances Data: 33350-73-1(Hazardous Substances Data)

Usage

Synthesis

Under argon, ZnCl2 (0.5 M in THF, 3.15 mL, 1.6 mmol) was added by syringe to ?a Schlenk tube. o-Tolylmagnesium chloride (1.0 M in THF, 1.5 mL, 1.5 mmol) was then added dropwise, and the resulting mixture was stirred at room temperature for 20 min. NMP (2.2 mL) was added by syringe. After 5 min, Pd(P(t-Bu)3)2 (10.2 mg, 0.020 mmol) and 1-chloro-4-nitrobenzene (158 mg, 1.0 mmol) were added. The Schlenk tube was closed at the Teflflon stopcock, and the reaction mixture was stirred in a 100 °C oil bath for 2 h. It was then allowed to cool to room temperature, and aqueous hydrochloric acid (1.0 M, 6 mL) was added. The resulting mixture was extracted with ether (4 × 8 mL), and the organic extracts were combined, washed with water (5 × 10 mL), dried (MgSO4), and concentrated to afford a yellow solid. The crude product was purifified via flflash chromatography eluting with 3% ether in hexanes to furnish 200 mg (94%) of the biaryl as a pale-yellow solid. Reference: Dai, C.; Fu, G. C. J. Am. Chem. Soc. 2001, 123, 2719?2724.

Upstream product

• 100-01-6 4-nitro-aniline 
• 108-88-3 toluene 
• 16186-97-3 α-(4-nitrophenylazo)triphenylmethane 
• 33872-80-9 o-tolyl magnesium chloride 
• 100-00-5 4-chlorobenzonitrile 
• 201230-82-2 carbon monoxide 
• 16419-60-6 2-Methylphenylboronic acid 
• 456-27-9 4-nitrobenzenediazonium tetrafluoroborate 
• 84109-17-1 2-methylphenylzinc chloride 
• 636-98-6 p-nitrobenzene iodide 
• 4482-01-3 o-benzenedisulfonimide 

Downstream Products

• 18211-41-1 4'-nitro-[1,1'-biphenyl]-2-carboxylic acid 
• 70786-69-5 N-(2'-Methyl-biphenyl-4-yl)-hydroxylamine 
• 96371-51-6 2'-Methyl-4-<4-decyloxy-benzylidenamino>-biphenyl 

Relevant articles and documents

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.

N,S-chelating triazole-thioether ligand for highly efficient palladium-catalyzed Suzuki reaction

1,2,3-Triazole-thioether compounds could serve as efficient ligands for Pd-catalyzed Suzuki reactions of various aryl iodides, bromides and chlorides. The reactions feature wide substrate scope and mild reaction conditions. Besides, shorter reaction time, lower catalyst loadings and quantitative yields with a turnover-frequency (TOF) value of up to 11,880 h?1 are other advantageous of this attractive protocol. The crystal structure analyses and computational studies revealed that the higher catalytic activity of the corresponding chelated palladium complex ascribed to the lower energy gap and the lower redox potential.

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.

The Rational Design and Synthesis of Water-Soluble Thiourea Ligands for Recoverable Pd-Catalyzed Aerobic Aqueous Suzuki-Miyaura Reactions at Room Temperature

Eight precatalysts containing carboxylic-functionalized thiourea ligands are prepared and their activities and recyclability are evaluated in aerobic aqueous Suzuki-Miyaura reactions. A bulky monothiourea-Pd complex, functionalized with four carboxylic groups, shows the best activity and recyclability in the coupling of aryl bromides with arylboronic acids. The catalyst can be reused at least five times without any significant reduction in its catalytic activity. TEM analysis and the confirmed catalytic activity of the observed black precipitate reveal that Pd nanoparticles are formed during the reactions and are stabilized by the carboxylic-functionalized thiourea ligands.

Modular Functionalization of Arenes in a Triply Selective Sequence: Rapid C(sp2) and C(sp3) Coupling of C?Br, C?OTf, and C?Cl Bonds Enabled by a Single Palladium(I) Dimer

Full control over multiple competing coupling sites would enable straightforward access to densely functionalized compound libraries. Historically, the site selection in Pd0-catalyzed functionalizations of poly(pseudo)halogenated arenes has been unpredictable, being dependent on the employed catalyst, the reaction conditions, and the substrate itself. Building on our previous report of C?Br-selective functionalization in the presence of C?OTf and C?Cl bonds, we herein complete the sequence and demonstrate the first general arylations and alkylations of C?OTf bonds (in I dimer. This allowed the realization of the first general and triply selective sequential C?C coupling (in 2D and 3D space) of C?Br followed by C?OTf and then C?Cl bonds.

Gold catalysed Suzuki-Miyaura coupling of arenediazonium o-benzenedisulfonimides

Arenediazonium o-benzenedisulfonimides have been used as efficient electrophilic partners in Au(I) catalysed Suzuki coupling reactions. The synthetic protocol is general, easy and produced either biaryls or heteroaryl arenes in good yields (51 positive examples, average yield 80%). o-Benzenedisulfonimide was recovered at the end of the reactions and was reused to prepare the starting salts for further reactions. Mechanistic insights suggest that the o-benzenedisulfonimide anion act as an electron transfer agent and promotes a catalytic cycle which does not require the presence of photocatalysts or external oxidants.

Palladium–cadmium sulfide nanopowder at oil–water interface as an effective catalyst for Suzuki–Miyaura reactions

A simple and effective strategy is described for the synthesis of Pd–CdS nanopowder by the reduction of an organopalladium(II) complex, [PdCl2(cod)] (cod = cis,cis-1,5-cyclooctadiene), in the presence of CdS quantum dots (QDs) at a toluene–water interface. We investigated the impact of addition of CdS QDs on catalytic activity of Pd nanoparticles (NPs). The Pd–CdS nanopowder functions as an efficient catalyst for Suzuki–Miyaura reactions for the formation of carbon–carbon bonds. There is a high electron density on Pd NPs and due to their high electron affinity they behave as an electron scavenger from CdS increasing the rate of oxidative addition, which is the rate-determining step of the catalytic cycle, and, just as we expect, the C─C coupling reaction with the Pd–CdS nanopowder is faster and occurs in less time than that with Pd nanocatalysts. Compared to classical reactions, this method consistently has the advantages of short reaction times, high yields in a green solvent, reusability of the catalyst without considerable loss of catalytic activity and low cost, and is a facile method for the preparation of the catalyst.

Efficient symmetrical bidentate dioxime ligand-accelerated homogeneous palladium-catalyzed Suzuki-Miyaura coupling reactions of aryl chlorides

A series of N,O-bidentate ligands were synthesized using the Vilsmeier-Haack reaction and oximation. 2,5-Dihydroxyterephthalaldehyde dioxime (L8) as an efficient N,O-symmetrical bidentate ligand was prepared from hydroquinone. It was studied as a high activity ligand for palladium-catalyzed Suzuki-Miyaura cross-coupling reactions of aryl chlorides with arylboronic acids under mild conditions. The coupling reactions were performed in the presence of PdCl2 as the catalyst, L8 as the ligand, Na2CO3 as the base, PEG-400 as the PTC and in ethanol/water (1?:?1) as an environmentally benign solvent at 85 °C. Plentiful biaryls were obtained by the optimized reaction with good yields at a low palladium loading of 0.20 mol%.

Palladium nanoparticles in catalytic carbon nanoreactors: The effect of confinement on Suzuki-Miyaura reactions

We explore the construction and performance of a range of catalytic nanoreactors based on palladium nanoparticles encapsulated in hollow graphitised nanofibres. The optimum catalytic material, with small palladium nanoparticles located almost exclusively at the graphitic step-edges within nanoreactors, exhibits attractive catalytic properties in Suzuki-Miyaura cross-coupling reactions. Confinement of nanoparticles at the step-edges facilitates retention of catalytic centres and recycling of catalytic nanoreactors without any significant loss of activity or selectivity over multiple catalytic cycles. Furthermore, careful comparison of the catalytic properties of palladium nanoparticles either on or in nanoreactors reveals that nanoscale confinement of catalysts fundamentally affects the pathways of the Suzuki-Miyaura reaction, with the yield and selectivity for the cross-coupled product critically dependent on the steric properties of the aryl iodide reactant, whereas no effects of confinement are observed for aryl boronic acid reactants possessing substituents in different positions. These results indicate that the oxidative addition step of the Suzuki-Miyaura reaction occurs at the step-edge of nanofibres, where the mechanisms and kinetics of chemical reactions are known to be sensitive to nanoscale confinement, and thus the extent of confinement in carbon nanoreactors can be discretely controlled by careful selection of the aryl iodide reactant.

Water-soluble palladium click chelating complex: An efficient and reusable precatalyst for Suzuki-Miyaura and Hiyama reactions in water

A water-soluble ionic palladium(II) nitrogen-containing chelating complex, [palladium(II) 1-(4-N,N′,N′′-trimethylbutylammonium)-4-(2- pyridyl)-1H-1,2,3-triazole dichloride] chloride (3), was prepared through the click reaction of 1-chloro-4-bromobutane, sodium azide, and 2-ethynylpyridine, followed by the quarternization of Me3N and subsequent reaction with [Pd(cod)Cl2] (cod=1,5-cyclooctadiene). The catalytic performances of complex 3 were preliminarily evaluated through Suzuki-Miyaura and Hiyama cross-coupling reactions of aryl bromides; excellent catalytic activity in water was observed. TEM analysis revealed that small palladium nanoparticles (NPs) with a narrow size distribution were formed after the catalytic reaction. The NPs were stabilized by the synergetic effect of coordination and electrostatic interactions from the ionic, bidentate, nitrogen-containing ligand; no palladium black was detected after the aqueous solution of palladium NPs was stored in air for months. The use of 3 as a precursor in the formation of palladium NPs was further explored by using NaBH4 and hydrogen as reductive reagents. The resulting NPs displayed different sizes, surface properties, and catalytic performances in the Suzuki-Miyaura cross-coupling reaction in water. Copyright