5705-52-2

Upstream product

• 186581-53-3 diazomethane 
• 60-29-7 diethyl ether 
• 93-97-0 benzoic acid anhydride 
• 65-85-0 benzoic acid 
• 109-02-4 4-methyl-morpholine 
• 67-56-1 methanol 
• 2902-69-4 2,2,2-trichloroacetophenone 
• 98-91-9 thiobenzoic acid 
• 108-86-1 bromobenzene 
• 115-10-6 Dimethyl ether 
• 98-08-8 α,α,α-trifluorotoluene 
• 774-65-2 benzoic acid tert-butyl ester 
• 124-41-4 sodium methylate 
• 53907-33-8 acetic acid 1-bromo-2-oxo-2-phenyl-ethyl ester 

Downstream Products

• 7666-04-8 2-methylsulfanyl-1H-imidazole 
• 1565-71-5 3-phenylpentan-3-ol 
• 6324-60-3 Bis(2-methylphenyl)phenylmethanol 
• 52161-54-3 2,5-diphenyl-hex-2-ene 
• 31719-77-4 3-chloromethylbenzoic acid 
• 34040-63-6 methyl 3-(chloromethyl)benzoate 
• 6963-55-9 2-methyl-2-butyl benzoate 
• 83527-96-2 methyl 3’-nitro-[1,1’-biphenyl]-2-carboxylate 
• 89900-93-6 3'-nitro-[1,1'-biphenyl]-4-carboxylic acid methyl ester 
• 64407-08-5 methyl 2,2-dimethyl-3-oxo-3-phenylpropanoate 
• 95938-66-2 Bis-(3-methoxy-phenyl)-phenyl-methanol 
• 6333-10-4 Hydroxy-phenyl-bis-(2-methoxy-phenyl)-methan 
• 69239-35-6 Chlorbis(4-methylphenyl)phenylmethan 
• 859953-59-6 1-(2,4-dimethoxy-6-methyl-phenyl)-3-phenyl-propane-1,3-dione 

Relevant academic research and scientific papers

How Radical Are "radical" Photocatalysts? A Closed-Shell Meisenheimer Complex Is Identified as a Super-Reducing Photoreagent

Super-reducing excited states have the potential to activate strong bonds, leading to unprecedented photoreactivity. Excited states of radical anions, accessed via reduction of a precatalyst followed by light absorption, have been proposed to drive photoredox transformations under super-reducing conditions. Here, we investigate the radical anion of naphthalene monoimide as a photoreductant and find that the radical doublet excited state has a lifetime of 24 ps, which is too short to facilitate photoredox activity. To account for the apparent photoreactivity of the radical anion, we identify an emissive two-electron reduced Meisenheimer complex of naphthalene monoimide, [NMI(H)]-. The singlet excited state of [NMI(H)]- is a potent reductant (-3.08 V vs Fc/Fc+), is long-lived (20 ns), and its emission can be dynamically quenched by chloroarenes to drive a radical photochemistry, establishing that it is this emissive excited state that is competent for reported C-C and C-P coupling reactivity. These results provide a mechanistic basis for photoreactivity at highly reducing potentials via singlet excited state manifolds and lays out a clear path for the development of exceptionally reducing photoreagents derived from electron-rich closed-shell anions.

Activation of acyl phosphate monoesters by lanthanide ions: Enhanced reactivity of benzoyl methyl phosphate

Acyl phosphate monoesters are intermediates in many biochemical acylation reactions, such as those involving aminoacyl adenylates. Benzoyl methyl phosphate, a typical acyl phosphate monoester, is slowly hydrolyzed in neutral solutions but reacts rapidly with amines. Since biochemical processes of acyl phosphate monoesters involve accelerated reactions with oxygen-centered nucleophiles, we sought catalysts for hydrolysis and methanolysis of benzoyl methyl phosphate to mimic the biochemical outcome. Lanthanide ions are particularly effective catalysts, accelerating reactions much more than comparable levels of magnesium ion. Detailed kinetic analysis of the hydrolysis reactions reveals formation of a 1:1 complex, followed by rapid reaction with a nucleophile. The hydroxide-dependent hydrolysis rate in the europium complex is about 105 times that of free substrate with hydroxide. A mechanism that accounts for the data and observed behavior involves bidentate coordination of the metal ion by the acyl phosphate through phosphate and carbonyl oxygens, lowering the energy of the tetrahedral addition intermediate and the associated transition states. The dependence of the metal ion catalyzed process on the concentration of hydroxide ion is consistent with coordinated hydroxide acting as a nucleophile. The reaction of benzoyl methyl phosphate with methanol to form methyl benzoate and methyl phosphate is 30 000 times more rapid in the presence of 0.0001 M lanthanum triflate (in the absence of the metal ion kobs = 2.1 × 10-7 s-1, at 25°C). Thus, the combination of acyl phosphate esters and lanthanide salts appears to be a promising method for biomimetic acylation of hydroxyl groups.

Transesterification and esterification with subcritical methanol. Synthesis of biodiesel

Benzoic acid esterification and ethyl benzoate transesterification with subcritical methanol were carried out at 220 °C without any catalyst. A procedure for biodiesel production from vegetable oil under indicated conditions was proposed.

Synthesis of Naphthoquinolizinones through Rh(III)-Catalyzed Double C(sp2)-H Bond Carbenoid Insertion and Annulation of 2-Aryl-3-cyanopyridines with α-Diazo Carbonyl Compounds

An unprecedented Rh(III)-catalyzed double C(sp2)-H bond carbenoid insertion and annulation of 2-aryl-3-cyanopyridines with α-diazo carbonyl compounds is presented. Through this cascade reaction, a series of naphthoquinolizinone derivatives with a large π-system were efficiently prepared. The reactions could selectively afford naphthoquinolizinones with either an amine or an amide unit attached on the 11-position depending on the nature of the solvent and the additive used. Compared with literature methods, this is a more efficient, convenient, and atom-economic way to provide polycyclic heteroaromatic compounds through direct π-extension of simple aromatics via inert C-H bond activation and functionalization.

Anion effects on construction of ZnII compounds with a chelating ligand bis(2-pyridylmethyl)amine and their catalytic activities

Three ZnII complexes containing bispicam ligands (bispicam = bis(2-pyridylmethyl)amine), [Zn(bispicam)2](NO3) 2·2CH3OH 4A, [Zn(bispicam)(NO3) 2] 4B, and [Zn(bispicam)2](OTf)2 6, were obtained, and their structures were determined by X-ray crystallography. Complexes of the general formulation [Zn(bispicam)2]X2 (X = Cl- (1), Br- (2), I- (3), NO3 - (4A), ClO4- (5), and OTf- (6)) show fac geometric isomers (a) or enantiomers (c) and (d) according to anions. Moreover, complexes 4-6 could carry out the catalytic transesterification of a range of esters with methanol under the mild conditions. Importantly, the catalyst 4B with an unsaturated structure has shown better efficiency than the catalysts, 4A, 5, and 6, having saturated structures. To explain this reactivity difference, two different reaction mechanisms have been proposed (metal-based vs. amide N-H-based).

Biomimetic Syntheses of Analogs of Hongoquercin A and B by Late-Stage Derivatization

The hongoquercins are tetracyclic meroterpenoid natural products with the trans-transoid decalin-dihydrobenzopyran ring system, which display a range of different bioactivities. In this study, the syntheses of a range of hongoquercins using gold-catalyzed enyne cyclization reactions and further derivatization are described. The parent enyne resorcylate precursors were synthesized biomimetically from the corresponding dioxinone keto ester via regioselective acylation, Tsuji-Trost allylic decarboxylative rearrangement, and aromatization. The dioxinone keto ester 12 was prepared in 6 steps from geraniol using allylic functionalization and alkyne synthesis.

One pot oxidative esterification of benzaldehyde over a supported Cs-salt of mono nickel substituted phosphotungstate

As a cleaner alternative to traditional two steps procedures, the one pot oxidative esterification of benzaldehyde to methyl ester was carried out over a supported Cs salt of mono nickel substituted phosphotungstate (CsPW11Ni). CsPW11Ni was supported on ZrO2 and characterized using various physico-chemical techniques. The influence of reaction parameters, such as molar ratio of substrate to H2O2, amount of catalyst, reaction time, and reaction temperature, on the oxidative esterification reaction was investigated. Moreover, the catalyst could be recovered and reused up to three cycles without significant loss in selectivity. The present heterogeneous catalytic system was found to be efficient not only in terms of activity (63%) but also in selectivity (79%) of the desired product.

Titanium Dioxide/Graphene Oxide Nanocomposites as Heterogeneous Catalysts for the Esterification of Benzoic Acid with Dimethyl Carbonate

Graphene oxide (GO) was prepared by modified Hummers' method starting from commercially available graphite. Different amounts of titanium dioxide nanoparticles (TiO2) were loaded on the sheets of GO to obtain titanium dioxide/graphene oxide (TiO2/GO) nanocomposites. The as-synthesized 5wt% TiO2/GO nanocomposite was characterized by UV/Vis spectroscopy, photoluminescence spectroscopy, FTIR, powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and atomic force microscopy techniques. The catalytic activity of the 5wt% TiO2/GO nanocomposite was evaluated in the esterification of benzoic acid using dimethyl carbonate (DMC) as a green methylating agent. Furthermore, the activity of this nanocomposite for the conversion of benzoic acid was higher than that of the parent GO, TiO2, TiO2/activated carbon, and TiO2/graphite.

Anion effects on construction of cadmium(II) compounds with a chelating ligand bis(2-pyridylmethyl)amine: Their photoluminescence and catalytic activities

Four new structures of CdII complexes containing bis(2-pyridylmethyl)amine (bispicam) ligands have been determined. Chloride anions bridge two CdII ions to form a dinuclear complex [(Cd(bispicam)Cl)2(μ2-Cl2)] (1), and bromide and iodide ions produce two halide-coordinated [Cd(bispicam)X2] complexes (X = Cl for 2 and Br for 3). Nitrate anions produce both nitrate-coordinated [Cd(bispicam)2(NO3)]+ and simple [mer-Cd(bispicam)2]2+ with three nitrate counter-anions (4). These results indicate that anion effects play very important roles for construction of crystal structures and geometrical isomerism. Moreover, the homogeneous catalyst [Cd(bispicam)2] (ClO4)2 (5) catalyzed efficiently the transesterification of a variety of esters with methanol, while rest of the complexes have displayed very slow conversions. Furthermore, 1-5 showed the intense emissions at room temperature, which could be used as a good candidate for a potential hybrid inorganic-organic photoactive material.

The role of Pd colloids as catalysts in the phosphane-free methoxycarbonylation of iodobenzene

The catalytic activity of PdCl2(cod) (1) in the methoxycarbonylation of iodobenzene (at 40-70°C, 1-5 atm of CO, in methanol solution) increased remarkably when tetra-n-butylammonium salts [ nBu4N]X (X = Br, Cl, I, BF4, PF6) were added to the system. XRD analyses confirmed that under methoxycarbonylation reaction conditions palladium was reduced to a Pd colloid of nanometer size, 2.0-5.6 nm, which was responsible for the catalytic activity. In the absence of ammonium salts fast deactivation of the colloid was observed, even when PVP (polyvinylpyrrolidone) was added as a stabilizer. Catalytic tests performed with isolated Pd colloid demonstrated its high catalytic activity in methoxycarbonylation when used together with [nBu4N]X salts. A mechanism of palladium reduction to Pd nanoparticles is proposed.