77504-84-8

Upstream product

• 271-89-6 1-benzofurane 
• 693-03-8 n-butyl magnesium bromide 
• 75-44-5 phosgene 
• 60-29-7 diethyl ether 
• 3991-61-5 1-methyl-2-phenoxybenzene 
• 611-20-1 salicylonitrile 
• 106-44-5 p-cresol 
• 615-37-2 ortho-methylphenyl iodide 
• 623-11-0 1-methyl-4-nitrosobenzene 
• 583-59-5 2-Methylcyclohexanol 
• 108-41-8 1-chloro-3-methylbenzene 
• 591-17-3 meta-bromotoluene 
• 625-95-6 3-Iodotoluene 
• 95-49-8 2-methylchlorobenzene 

Downstream Products

• 6161-86-0 2-methylphenoxyethanol 
• 408331-40-8 o-tolyl-trityl ether 
• 68097-75-6 2-methyl-4-piperidin-1-ylmethyl-phenol 
• 81439-01-2 acetoacetic acid o-tolyl ester 
• 5425-51-4 1-piperidino-3-o-tolyloxy-propan-2-ol 
• 96472-80-9 4-Furfuryl-2-methyl-phenol 
• 107057-92-1 2-Furfuryl-6-methyl-phenol 
• 111529-49-8 2,4-Difurfuryl-6-methyl-phenol 
• 103986-32-9 4-oxo-4-(4-hydroxy-3-methyl-phenyl)-trans-crotonic acid 
• 38443-98-0 succinic acid mono-o-tolyl ester 
• 6778-66-1 5,5-bis-(4-hydroxy-3-methyl-phenyl)-dihydro-furan-2-one 
• 854677-51-3 4-(2-hydroxy-3-methyl-phenyl)-4-oxo-butyric acid 
• 91541-03-6 4-(4-hydroxy-3-methyl-phenyl)-4-oxo-butyric acid 
• 28232-09-9 2,6-dimethyl-4-o-tolyloxy-pyridine 

Relevant academic research and scientific papers

Impact of oxygen vacancies in Ni supported mixed oxide catalysts on anisole hydrodeoxygenation

The hydrodeoxygenation (HDO) activity of anisole has been investigated over Ni catalysts on mixed metal oxide supports containing Nb–Zr and Ti–Zr in 1:1 and 1:4 ratios. XRD patterns indicate the incorporation of Ti (or Nb) into the ZrO2 framewo

Catalytic Activation of Unstrained C(Aryl)-C(Alkyl) Bonds in 2,2′-Methylenediphenols

Catalytic activation of unstrained and nonpolar C-C bonds remains a largely unmet challenge. Here, we describe our detailed efforts in developing a rhodium-catalyzed hydrogenolysis of unstrained C(aryl)-C(alkyl) bonds in 2,2′-methylenediphenols aided by removable directing groups. Good yields of the monophenol products are obtained with tolerating a wide range of functional groups. In addition, the reaction is scalable, and the catalyst loading can be reduced to as low as 0.5 mol %. Moreover, this method proves to be effective to cleave C(aryl)-C(alkyl) linkages in both models of phenolic resins and commercial novolacs resins. Finally, detailed experimental and computational mechanistic studies show that with C-H activation being a competitive but reversible off-cycle reaction, this transformation goes through a directed C(aryl)-C(alkyl) oxidative addition pathway.

Imidazolium-urea low transition temperature mixtures for the UHP-promoted oxidation of boron compounds

Different carboxy-functionalized imidazolium salts have been considered as components of low transition temperature mixtures (LTTMs) in combination with urea. Among them, a novel LTTM based on 1-(methoxycarbonyl)methyl-3-methylimidazolium chloride and urea has been prepared and characterized by differential scanning calorimetry throughout its entire composition range. This LTTM has been employed for the oxidation of boron reagents using urea-hydrogen peroxide adduct (UHP) as the oxidizer, thus avoiding the use of aqueous H2O2, which is dangerous to handle. This metal-free protocol affords the corresponding alcohols in good to quantitative yields in up to 5 mmol scale without the need of further purification. The broad composition range of the LTTM allows for the reaction to be carried out up to three consecutive times with a single imidazolium salt loading offering remarkable sustainability with an E-factor of 7.9, which can be reduced to 3.2 by the threefold reuse of the system.

Metal-Organic Framework-Confined Single-Site Base-Metal Catalyst for Chemoselective Hydrodeoxygenation of Carbonyls and Alcohols

Chemoselective deoxygenation of carbonyls and alcohols using hydrogen by heterogeneous base-metal catalysts is crucial for the sustainable production of fine chemicals and biofuels. We report an aluminum metal-organic framework (DUT-5) node support cobalt(II) hydride, which is a highly chemoselective and recyclable heterogeneous catalyst for deoxygenation of a range of aromatic and aliphatic ketones, aldehydes, and primary and secondary alcohols, including biomass-derived substrates under 1 bar H2. The single-site cobalt catalyst (DUT-5-CoH) was easily prepared by postsynthetic metalation of the secondary building units (SBUs) of DUT-5 with CoCl2 followed by the reaction of NaEt3BH. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) indicated the presence of CoII and AlIII centers in DUT-5-CoH and DUT-5-Co after catalysis. The coordination environment of the cobalt center of DUT-5-Co before and after catalysis was established by extended X-ray fine structure spectroscopy (EXAFS) and density functional theory. The kinetic and computational data suggest reversible carbonyl coordination to cobalt preceding the turnover-limiting step, which involves 1,2-insertion of the coordinated carbonyl into the cobalt-hydride bond. The unique coordination environment of the cobalt ion ligated by oxo-nodes within the porous framework and the rate independency on the pressure of H2 allow the deoxygenation reactions chemoselectively under ambient hydrogen pressure.

Selective upgrading of biomass-derived benzylic ketones by (formic acid)–Pd/HPC–NH2 system with high efficiency under ambient conditions

Upgrading biomass-derived phenolic compounds provides a valuable approach for the production of higher-value-added fuels and chemicals. However, most established catalytic systems display low hydrodeoxygenation (HDO) activities even under harsh reaction conditions. Here, we found that Pd supported on –NH2-modified hierarchically porous carbon (Pd/HPC–NH2) with formic acid (FA) as hydrogen source exhibits unprecedented performance for the selective HDO of benzylic ketones from crude lignin-derived oxygenates. Designed experiments and theoretical calculations reveal that the H+/H? species generated from FA decomposition accelerates nucleophilic attack on carbonyl carbon in benzylic ketones and the formate species formed via the esterification of intermediate alcohol with FA expedites the cleavage of C–O bonds, achieving a TOF of 152.5 h?1 at 30°C for vanillin upgrading, 15 times higher than that in traditional HDO processes (～10 h?1, 100°C–300°C). This work provides an intriguing green route to produce transportation fuels or valuable chemicals from only biomass under mild conditions.

Catalytic oxidation of a model volatile organic compound (toluene) with tetranuclear Cu(II) complexes

A tetranuclear Cu(II) cubane [Cu2(μ-1κONO’:2κOO’:3κO-HL)(μ-1κONO’:2κOO’-HL)]2?4dmf (1) derived form (2,3-dihydroxybenzylidene)-2-hydroxybenzohydrazide (H3L) was synthesized at room temperature and characterized by elemental analysis, IR spectroscopy, ESI-MS and single crystal X-ray diffraction. The known tetranuclear Cu(II) open-cubane [Cu(HL)]4?4EtOH (2) was synthesized from the same pro-ligand following a similar method or the reported one. The different tautomeric forms (keto and enol) of the organic ligands in 1 and 2 explain their different structural features. Both complexes were screened as catalysts for the peroxidative oxidation of toluene with tert-butyl hydroperoxide, achieving benzaldehyde and o-cresol as the main products. Complex 1 exhibits the highest activity (maximum product yield of 11%).

Insight into the chemoselective aromatic: Vs. side-chain hydroxylation of alkylaromatics with H2O2catalyzed by a non-heme imine-based iron complex

The oxidation of a series of alkylaromatic compounds with H2O2 catalyzed by an imine-based non-heme iron complex prepared in situ by reaction of 2-picolylaldehyde, 2-picolylamine, and Fe(OTf)2 in a 2?:?2?:?1 ratio leads to a marked chemoselectivity for aromatic ring hydroxylation over side-chain oxidation. This selectivity is herein investigated in detail. Side-chain/ring oxygenated product ratio was found to increase upon decreasing the bond dissociation energy (BDE) of the benzylic C-H bond in line with expectation. Evidence for competitive reactions leading either to aromatic hydroxylation via electrophilic aromatic substitution or side-chain oxidation via benzylic hydrogen atom abstraction, promoted by a metal-based oxidant, has been provided by kinetic isotope effect analysis. This journal is

Aromatic C?H Hydroxylation Reactions with Hydrogen Peroxide Catalyzed by Bulky Manganese Complexes

The oxidation of aromatic substrates to phenols with H2O2 as a benign oxidant remains an ongoing challenge in synthetic chemistry. Herein, we successfully achieved to catalyze aromatic C?H bond oxidations using a series of biologically inspired manganese catalysts in fluorinated alcohol solvents. While introduction of bulky substituents into the ligand structure of the catalyst favors aromatic C?H oxidations in alkylbenzenes, oxidation occurs at the benzylic position with ligands bearing electron-rich substituents. Therefore, the nature of the ligand is key in controlling the chemoselectivity of these Mn-catalyzed C?H oxidations. We show that introduction of bulky groups into the ligand prevents catalyst inhibition through phenolate-binding, consequently providing higher catalytic turnover numbers for phenol formation. Furthermore, employing halogenated carboxylic acids in the presence of bulky catalysts provides enhanced catalytic activities, which can be attributed to their low pKa values that reduces catalyst inhibition by phenolate protonation as well as to their electron-withdrawing character that makes the manganese oxo species a more electrophilic oxidant. Moreover, to the best of our knowledge, the new system can accomplish the oxidation of alkylbenzenes with the highest yields so far reported for homogeneous arene hydroxylation catalysts. Overall our data provide a proof-of-concept of how Mn(II)/H2O2/RCO2H oxidation systems are easily tunable by means of the solvent, carboxylic acid additive, and steric demand of the ligand. The chemo- and site-selectivity patterns of the current system, a negligible KIE, the observation of an NIH-shift, and the effectiveness of using tBuOOH as oxidant overall suggest that hydroxylation of aromatic C?H bonds proceeds through a metal-based mechanism, with no significant involvement of hydroxyl radicals, and via an arene oxide intermediate. (Figure presented.).

Visible light-induced photodeoxygenation of polycyclic selenophene Se-oxides

Photodeoxygenation of dibenzothiophene S-oxide (DBTO) is believed to produce ground-state atomic oxygen [O(3P)] in solution. Compared with other reactive oxygen species (ROS), O(3P) is a unique oxidant as it is potent and selective. Derivatives of DBTO have been used as O(3P)-precursors to oxidize variety of molecules, including plasmid DNA, proteins, lipids, thiols, and other small organic molecules. Unfortunately, the photodeoxygenation of DBTO requires ultraviolet irradiation, which is not an ideal wavelength range for biological systems, and has a low quantum yield of approximately 0.003. In this work, benzo[b]naphtho[1,2-d]selenophene Se-oxide, benzo[b]naphtho[2,1-d]selenophene Se-oxide, dinaphtho[2,3-b:2’,3’-d]selenophene Se-oxide, and perylo[1,12-b,c,d]selenophene Se-oxide were synthesized, and their ability to utilize visible light for generating O(3P) was interrogated. Benzo[b]naphtho[1,2-d]selenophene Se-oxide produces O(3P) upon irradiation centered at 420 nm. Additionally, benzo[b]naphtho[1,2-d]selenophene Se-oxide, benzo[b]naphtho[2,1-d]selenophene Se-oxide, and dinaphtho[2,3-b:2’,3’-d]selenophene Se-oxide produce O(3P) when irradiated with UVA light and have quantum yields of photodeoxygenation ranging from 0.009 to 0.33. This work increases the utility of photodeoxygenation by extending the range of wavelengths that can be used to generate O(3P) in solution.

Crystal Facet Engineering of Copper-Based Metal-Organic Frameworks with Inorganic Modulators

Manipulating the exposed facets of metal-organic frameworks (MOFs) is of importance toward understanding their facet-dependent property in a variety of applications. Herein, we apply a novel inorganic competitive coordination strategy to control the growth orientation of copper-based MOFs (HKUST-1, MOF-14, and Cu-MOF-74) without sacrificing the pore accessibility and crystallinity. Through monitoring the reactant composition, we find that the competitive coordination induced by the added aluminium nitrate mainly affects the crystal growth stage rather than the nucleation stage. The kinetic study further reveals that Al3+ competes with Cu2+ to coordinate with ligands, restraining the growth rate of certain facets and resulting in the orientated growth of copper-based MOFs. Compared to the reduced pore accessibility of HKUST-1 crystals modulated by the organic modulation method, Al3+-modulated HKUST-1 displays a much larger surface area (>2200 m2/g) and more accessible Cu active sites. Hydroxylation of toluene was utilized as a model reaction to investigate the facet-catalytic activity for as-synthesized HKUST-1. The selectivity of the preferred product cresol increases with the morphology transformation of HKUST-1 from octahedron to cube.