Regioselective Bromination of 3, 4-Dimethoxytoluene with N-Bromosuccinimide

The selective brominations of 3, 4-dimethoxytoluene with N-bromosuccinimide were reported. The nuclear and side-chain brominated products were obtained under different reaction conditions. The mechanism was also discussed.

Product oriented oxidative bromination of methane over Rh/SiO_2 catalysts

Rh/SiO2 was prepared for the oxidative bromination of methane. The catalyst was prepared by calcination at different temperatures and for different times to obtain catalysts with different specific surface areas for the purposes of producing either CH3Br or CH3Br and CO. It was found that the catalyst having a low specific surface area （calcined at relatively high temperature） favors the selective oxidation of methane to prepare CH3Br, while the catalyst having a high specific surface area favors the deeper partial oxidation of methane, which is good for CH3Br and CO preparation, The 650 h on stream life-time test revealed that the catalytic performance of the 0.4Rh/SiO2-900-10 catalyst was excellent. Both methane conversion and CH3Br selectivity kept increasing trends during the life-time test. No matter how serious was the Rh leaching during the reaction, the 0.4Rh/SiO2-900-10 catalyst did not deactivate at all.

Investigation on Organic Solvent Free Toluene Oxidative Bromination Reaction Catalyzed by HTS Zeolite

The toluene oxidative bromination reaction catalyzed by hollow titanium silicalite(HTS)zeolite in aqueous medium was investigated by employing H2O2 and HBr under mild conditions without the need for organic solvent.A high toluene conversion(90.7%)and high selectivity of mono-bromotoluene(99.0%)was achieved under the optimal reaction conditions.The UV-Raman spectroscopy was applied for the mechanism study and the result reveals that HTS is efficient for catalyzing the oxidation reaction of HBr with H2O2 to produce abundant active bromine species,which can further facilitate the toluene electrophilic bromination reaction.A two-step toluene bromination reaction mechanism involving the HTS catalyzed active bromine species“generation-conversion-utilization”process is proposed based on the UV-Raman spectroscopy analysis.

Bromination of Pd Compounds during Thermal Decomposition of Tetrabromobisphenol A

We conducted thermal tests using the reagent tetrabromobisphenol A (TBBPA) and various Pd compounds to study the chemical forms of Pd obtained during the pyrolytic and oxidative decomposition of TBBPA. Thermal testing was conducted in an electric furnace at temperatures of 280°C - 800°C in an Ar or Ar-O2 (5%) atmosphere for a heating period of 40 min. Scanning electron microscopy-energy dispersive X-ray spectroscopy results revealed that Pd bromide was formed in the mixture of TBBPA and PdO after heating to 450°C in the Ar atmosphere. In addition, thermogravimetry-differential thermal analysis showed that as the heating temperature was increased from 350°C to 730°C, weight loss occurred at a nearly constant rate, indicating that Pd bromide decomposed in this temperature range.

Vanadium Haloperoxidases Model Compounds: Synthesis, Structural Characterization and Mimic Catalytic Bromination Activity of [VO(C_2O_4)(2,2′-bipy)(H_2O)]·C_2H_5OH and VO(C_2O_4)(phen)(H_2O)

Two oxo-vanadium（IV） complexes, [VO（C2O4）（2,2′-bipy）（H2O）]·C2H5OH（1） and VO（C2O4）（phen）（H2O） （2）, where 2,2′-bipy=2,2′-bipyridyl, phen=1,10-phenanthroline, were synthesized as potential functional models of vanadium haloperoxidases（VHPOs） in mixed solvent of ethanol and water at room temperature. The complexes were characterized by elemental analysis, infrared（IR）, UV-Vis and X-ray crystallography. Structural analyses showed that vanadium atom was coordinated by a terminal oxygen, one oxygen atom from coordinated water, two oxygen atoms from the carboxylate group of oxalic acid, and two nitrogen atoms（N1 and N2） from 2,2′-bipy/phen. Central vanadium atoms in complexes 1 and 2 were both in a distorted-octahedral environment, and some intermolecular hydrogen bonding linkages were also observed in each complex. Bromination reaction activity of the two complexes was evaluated with phenol red as organic substrate in the presence of H2O2, Br-and phosphate buffer, indicating that they can be considered as a potential functional model of VHPO. In addition, thermal analysis was also performed and discussed in detail.

Isoquinolinium bromochromate:An efficient and stable reagent for bromination of hydroxylated aromatic compounds and oxidation of alcohols

The new chromium （VI） oxidizing reagent isoquinolinium bromochromate （IQBC） was prepared and characterized. The IQBC has been found to be stable and an efficient solid reagent which can be easily prepared in good yield. It act as an efficient brominating reagent for hydroxylated aromatic compounds as well as good oxidizing reagent for the conversion of alcohols to carbonyl compounds in good to excellent yield. The synthesized isoquinolinium bromochromate is more ideal reagent, with number of specification including： higher yield, mild conditions and easy preparation. The results obtained with isoquinolinium bromochromate are satisfactory and suggest that the reagent has few advantages over the existing chromium （VI） reagents.

NaIO_4-Catalyzed Bromination of the Aromatic Ring of Lappaconitine

Treatment of lappaconitine 1 with NaIO_4 and Br_2-HOAc at room temperature for 7 h afforded smoothly the bromine-containing derivative 4 in 71% yield.

Trace Level Arsenic Quantification through Methyl Red Bromination

A simple protocol has been developed for the quantification of trace level arsenic through methyl red bromination. The proposed method is based on the oxidation of arsenic(III) to arsenic(V) by the bromine and the residual bromine’s reaction with methyl red to form colorless bromo methyl red. As the concentration of arsenic increases, the bleaching of the dye decreases due to bromine consumption. Measuring the intensity of the unreacted methyl red at 515 nm forms the basis of arsenic quantification. The molar absorptivity of this method has been found to be 2.25 × 103 L/mol/cm. The method obeys Beer’s law in the concentration range 0 - 0.25 μg/mL. The Sandell sensitivity and the limit of detection (LOD) were found to be 0.03 μg/mL/cm2 and 0.03 μg/mL respectively. The relative standard deviation has been found to be 0.35% at 1.0 μg/mL. The reaction conditions have been optimized and the interference due to various common cations and anions were studied. The proposed method has been successfully applied to the determination of trace level arsenic in various environmental samples like water, soil and vegetable samples.

Aromatic Bromination in Concentrated Nitric Acid

Action of bromine in concentrated nitric acid allows carrying out mono- and polybromination of moderately deactivated aromatic compounds. 4-Chloronitrobenzene and isophthalic acid turnes into 3-bromo-4-chloronitrobenzene and 5-bromoisophthalic acid at reaction with bromine in concentrated nitric acid at 20°C whereas in absence of bromine in the same conditions 4-chloro-1, 3-dinitrobenzene and 5-nitroisophthalic acid are formed accordingly. Presence of bromine in concentrated nitric acid changes nitrating capacity to brominating one. Terephthalic acid and phthalic anhydride at heating with bromine in concentrated nitric acid can be transformed to appropriating tetrabromo substituted compounds.

Competition of Aromatic Bromination and Nitration in Concentrated Sulfuric Acid

Composition of bromine and nitric acid in concentrated sulfuric acid is effective for bromination of strongly deactivated aromatic compounds and for nitration and bromination of moderately deactivated compounds in one stage. The question why brominating agent is more reactive than nitrating agent in relation to strongly deactivated aromatic compounds and is less reactive in relation to moderate deactivated ones is discussed.

Facile Bromination of Aromatic Ethers with Quaternary Ammonium Bromide and Iodosylbenzene

Aromatic ethers were conveniently brominated with quaternary ammonium bromide and iodosylbenzene in glacial acetic acid under mild conditions to give the corresponding monobromo-aromatic ethers in nearly quantitative yields.

Aza-BODIPY dye with unexpected bromination and high singlet oxygen quantum yield for photoacoustic imaging-guided synergetic photodynamic/photothermal therapy

Introducing heavy halogen atoms into organic small molecules is a practical strategy for efficient singlet oxygen(^(1)O_(2))generation.Generally,bromine or iodine atoms are introduced on the aza-borondipyrromethene(aza-BODIPY)core,rather than on the periphery aryl rings for efficient~1O_(2) generation.Herein,an aza-BODIPY dye NBDPBr with unexpected bromination on the periphery aryl rings was synthesized for photoacoustic(PA)imaging-guided synergistic photothermal therapy(PTT)and photodynamic therapy(PDT)in tumor cells.Owing to unexcepted bromination at the periphery aryl rings,NBDPBr demonstrated an outstanding singlet oxygen quantum yield(Φ_(Δ))of 66% which was superior to similar brominated photosensitizers previously reported.After encapsulation with amphiphilic polymer F-127,hydrophilic NBDPBr nanoparticles(NPs)were fabricated and exhibited an excellent photothermal conversion efficiency(η)of 43.0% under 660 nm photoirradiation.In vivo PA imaging results demonstrated that NBDPBr NPs could specifically accumulate at tumor sites and realized the maximum tumor retention at 7 h post-injection.All the in vitro and in vivo results indicated the significant potence of NBDPBr with unexpected bis-bromination for PA imaging-guided synergetic PDT/PTT.

High selectively oxidative bromination of toluene derivatives by the H_2O_2-HBr system

An aqueous solution of hydrogen peroxide and hydrogen bromide illuminated by a 60 W incandescent light bulb serves as a source of bromine radicals.Various substituted toluenes（NO2,Cl,Br,H,CH3） were high selectively brominated at the benzyl position for monobromination in CH2C12 at ice water with catalyst free.This simple but effective bromination of toluene derivatives with an aqueous H2O2-HBr system is characterized with the use of inexpensive reagents and a lower impact on the environment, which make it a good alternative to the existing bromination methods.

Polyvinylpolypyrrolidone-bromine complex:Mild and efficient polymeric reagent for bromination of activated aromatic compounds

Mild and efficient method for bromination of electron-rich aromatic compounds is described using polyvinylpolypyrrolidone- bromine complex （PVPP-Br2）. The reaction proceeded smoothly with phenols and N.N-alkylated amines to afford the correspond- ing monobrominated product in good yields at ambient temperature.

Iron-catalyzed bromination of aryl azides by N-bromosuccinimide:Efficient method for the synthesis of brominated aryl azides

An efficient and mild protocol for bromination of aryl azides with N-bromosuccinimide（NBS） under FeCl_3 catalysis in 1,2- dichloroethane was developed.It is proved to be an efficient method for obtaining brominated aryl azides.

Enhanced debromination of 4-bromophenol by the UV/sulfite process：Efficiency and mechanism

Halogenated aromatic compounds have attracted increasing concerns due to their toxicity and persistency in the environment, and dehalogenation is one of the promising treatment and detoxification methods. Herein, we systematically studied the debromination efficiency and mechanism of para-bromophenol（4-BP） by a recently developed UV/sulfite process. 4-BP underwent rapid degradation with the kinetics accelerated with the increasing sulfite concentration, pH（6.1–10） and temperature, whereas inhibited by dissolved oxygen and organic solvents. The apparent activation energy was estimated to be 27.8 kJ/mol. The degradation mechanism and pathways of 4-BP were explored by employing N2O and nitrate as the electron scavengers and liquid chromatography/mass spectrometry to identify the intermediates. 4-BP degradation proceeded via at least two pathways including direct photolysis and hydrated electron-induced debromination. The contributions of both pathways were distinguished by quantifying the quantum yields of 4-BP via direct photolysis and hydrated electron production in the system. 4-BP could be readily completely debrominated with all the substituted Br released as Br-, and the degradation pathways were also proposed. This study would shed new light on the efficient dehalogenation of brominated aromatics by using the UV/sulfite process.

Green,mild and efficient bromination of aromatic compounds by HBr promoted by trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane in water as a solvent

A combination of HBr and trans-3,5-dihydroperoxy-3,5-dimethyl-1,2-dioxolane as anew and powerful oxidant was found effective for facile brotnination of different aromatic compounds at room temperature in water as a green solvent.Mild reaction conditions,high selectivity and yield,high reaction rate and non-toxicity are some of the major advantages of this synthetic protocol.

Ammonium persulphate promoted synthesis of polyethylene glycol entrapped potassium tribromide and its application in acylation and bromination of some selective organic compounds

In this study, a new method of synthesis of polyethylene glycol supported potassium tribromide （PEG KBr3） and its application in acylation and bromination reactions are reported. Ammonium persulphate oxidizes I（Br to the corresponding tribromide which is entrapped by polyethylene glycol leading to stable PEG KBr3. The reagent is proved to be highly efficient for the acylation of variety of alcohols and bromination of activated aromatic substrates. The method is a mild, one pot reaction and involves no use of toxic reagents.

Decarboxylative bromination of α,β-unsaturated carboxylic acids via an anodic oxidation

A novel bromination of α,β-unsaturated carboxylic acids was developed via a decarboxylation by virtue of a direct anodic electro-oxidation.In this method,ammonium bromide was employed as a bromine source and the reaction features transition-metal-free,short time,and no additional supporting electrolyte.

Catalyst-free Photochemical Bromination of Unprotected Aromatic Amino Acid Derivatives by Using a Rotating Ultraviolet Photoreactor

Aromatic amino acid halides are valuable amino acid derivatives and fundamental building blocks that are used to various coupling reaction^1-3!,such as Heck,Suzuki and Ullmann reaction[4-7],and also important precursors of active natural products,pharmaceuticals and chiral auxiliaries[8-9].