Halogenation Reactions Research Articles

Catalytic Biotransformations and Inhibition Study of Peroxidase from Luffa aegyptiaca

Background:Present interest in catalytic bioconversions is concerned with 2 major environmental issues. (i) The replacement or substitution of oxidations which involves heavy metal salts and reagents by alternatives using H2O2 as the ecofriendly oxidant. (ii) The prominent issue is the increasing interest in the production of high chemoselectivity, regioselectivity and stereoselectivity of compounds in chemical reactions in order to achieve better byproducts. Keeping these points in view the work on peroxidases have been carried out which fullfills these two goals.Objective:To determine the enzyme activity in the available source to explore its catalytic efficiency in biotransformations of heavy metal compounds. Optimizing the effect of different oxidants for maximum activity of peroxidase and to study the nature of inhibition of peroxidase in presence of different metal ions.Methods:Enzyme extracted in large volume from Luffa aegyptiaca fruit. Peroxidase activity measured by spectrophotometric method. Peroxidase catalyzed rate of reaction was determined spectrophotometerically by making use of guaiacol as the substrate and in presence of H2O2, V2O5, VOSO4, VO(acac)2, (NH4)2(Ce(NO3)6), and (NH4)6Mo7.4H2O monitored at λmax = 470 nm. The haloperoxidase activity were assayed by monitoring the formation of halogen by UV/VIS spectra. The steady state velocity of the enzyme catalysed reaction was measured at different concentrations of metal ions like trivalent (Cr3+ and Al3+), divalent (Ca2+, Mg2+, Cd2+, Zn2+ and Ni2+) and monovalent (Na+ and K+) in the range of 0.0 mM to 100 mM at the fixed enzyme saturating concentration. Graph was plotted to determine the nature of enzyme activity inhibition.Results:Study of rate of reaction by steady state kinetics measurements confirmed peroxidase activity of order of 9.0 U in the fruit extract prepared. The oxidation potential required for the oxidation of guaiacol to tetraguaiacol is 0.575V and the reaction is irreversible. (NH4)2(Ce(NO3)6) and (NH4)6Mo7.4H2O oxidized guaiacol with the rate found to be 0.009 OD/sec in former substituent and the rate of formation of tetraguaiacol was much low in the later substituent found to be 0.003 OD/sec as compared to enzyme with rate 0.01 OD/sec. Enzyme peroxidase was able to oxidize Fe2+ and Mn2+ to Fe3+ and Mn3+ respectively in the reaction mixture. It is found that V2O5 is better oxidizing agent than H2O2 for catalytic oxidation of guaiacol as the substrate. Peroxidases in presence of H2O2 and KBr/KCl/KI act as a viable ecofriendly reagent for the halogenation reaction in organic synthesis. Nature of inhibition by Zn2+ and Ni2+ ions is competitive type. Enzyme activity is inhibited in presence of Cr3+ and Al3+ and the nature of inhibition is uncompetitive type.Conclusion:Luffa aegyptiaca is a better source of peroxidase having 9 U. UV-Visible spectrum analysis indicated that (NH4)2 (Ce(NO3)6 can substitute peroxidase enzyme under optimized conditions.( NH4)2(Ce(NO3)6 act as a cocatalyst by enhancing the activity twice. The enzyme with H2O2 and KBr/KCl/KI is a suitable environmentally suitable reagent for halogenation reaction in organic and inorganic synthesis. The rate of reaction is highest in presence of V2O5 as compared to other vanadium compounds. Thus V2O5 act as better oxidizing agent than H2O2. Chemical technology can be substituted by enzyme technology which should be developed to removal excess and toxic heavy metals. Salinity required for normal functioning of enzyme is 140mM NaCl and 90mM KCl. Enzyme activity enhanced in presence of Ca2+, Mg2+ and Cd2+ while inhibited in presence of Zn2+ and Ni2+. Nature of inhibition by Zn2+ and Ni2+ ions is competitive type. Enzyme activity is inhibited in presence of Cr3+ and Al3+ and the nature of inhibition is uncompetitive type. Extensive studies are needed to understand the mechanism of inhibition of manganese peroxidase activity by metal ions.

Water-Soluble Anthraquinone Photocatalysts Enable Methanol-Driven Enzymatic Halogenation and Hydroxylation Reactions.

Peroxyzymes simply use H2O2 as a cosubstrate to oxidize a broad range of inert C–H bonds. The lability of many peroxyzymes against H2O2 can be addressed by a controlled supply of H2O2, ideally in situ. Here, we report a simple, robust, and water-soluble anthraquinone sulfonate (SAS) as a promising organophotocatalyst to drive both haloperoxidase-catalyzed halogenation and peroxygenase-catalyzed oxyfunctionalization reactions. Simple alcohols, methanol in particular, can be used both as a cosolvent and an electron donor for H2O2 generation. Very promising turnover numbers for the biocatalysts of up to 318 000 have been achieved.

Direct Intramolecular Aminoboration of Allenes.

Direct intramolecular aminoboration of sulfonamidoallenes was realized using BCl3 as a boron source. The reactions benefited from the interaction between BCl3 and sulfonamides and provided a variety of borylvinyl heterocycles in good isolated yields. When chiral substrates were involved in the reactions, high stereoselectivity was observed, as can be ascertained by single-crystal X-ray diffraction experiments. Derivatization of the thus-obtained borylvinyl compounds proceeded readily, and different functionalities could be obtained via oxidation, halogenation, and Suzuki coupling reactions.

Toward N,P-Doped π-Extended PAHs: A One-Pot Synthesis to Diannulated 1,4,2-Diazaphospholium Triflate Salts.

A novel method for the one-pot synthesis of diannulated 1,4,2-diazaphospholium triflate salts by a Me3SiOTf-mediated self-condensation of dichlorophosphaneyl aza-(poly)cyclic aromatic hydrocarbons (aza-(P)AHs; namely, pyridine, quinoline, phenanthridine, and benzo[d]thiazole) is reported. The diannulated 1,4,2-diazaphospholium triflate salts are characterized by multinuclear NMR spectroscopy, X-ray analysis, as well as their calculated NICS values, underlining their aromatic character. Quantum mechanical calculations shed light on the intermolecular reaction mechanism. Follow up chemistry, such as the halogenation reaction with XeF2 or SO2Cl2 with the dipyridinium derivative selectively yields the respective dihalo-σ4,λ5- and tetrahalo-σ5,λ6-diazaphospholium triflate salts. The dihalo-σ4,λ5-diazaphospholium triflate salt serves well as a surrogate for the introduction of the cationic 2-(1,2'-bipyridin)-1-iumyl ligand (1,2'-bipyl), the monocationic structural isomer of the prototypical 2,2'-bipyridine ligand (2,2'-bipy).

Tungstate-Catalyzed Biomimetic Oxidative Halogenation of (Hetero)Arene under Mild Condition.

SummaryAryl halide (Br, Cl, I) is among the most important compounds in pharmaceutical industry, material science, and agrochemistry, broadly utilized in diverse transformations. Tremendous approaches have been established to prepare this scaffold; however, many of them suffer from atom economy, harsh condition, inability to be scaled up, or cost-unfriendly reagents and catalysts. Inspired by vanadium haloperoxidases herein we presented a biomimetic approach for halogenation (Br, Cl, I) of (hetero)arene catalyzed by tungstate under mild pH in a cost-efficient and environment- and operation-friendly manner. Broad substrates, diverse functional group tolerance, and good chemo- and regioselectivities were observed, even in late-stage halogenation of complex molecules. Moreover, this approach can be scaled up to over 100 g without time-consuming and costly column purification. Several drugs and key precursors for drugs bearing aryl halides (Br, Cl, I) have been conveniently prepared based on our approach.

A Review of Methane Activation Reactions by Halogenation: Catalysis, Mechanism, Kinetics, Modeling, and Reactors

Methane is the central component of natural gas, which is globally one of the most abundant feedstocks. Due to its strong C–H bond, methane activation is difficult, and its conversion into value-added chemicals and fuels has therefore been the pot of gold in the industry and academia for many years. Industrially, halogenation of methane is one of the most promising methane conversion routes, which is why this paper presents a comprehensive review of the literature on methane activation by halogenation. Homogeneous gas phase reactions and their pertinent reaction mechanisms and kinetics are presented as well as microkinetic models for methane reaction with chlorine, bromine, and iodine. The catalysts for non-oxidative and oxidative catalytic halogenation were reviewed for their activity and selectivity as well as their catalytic action. The highly reactive products of methane halogenation reactions are often converted to other chemicals in the same process, and these multi-step processes were reviewed in a separate section. Recent advances in the available computational power have made the use of the ab initio calculations (such as density functional theory) routine, allowing for in silico calculations of energy profiles, which include all stable intermediates and the transition states linking them. The available literature on this subject is presented. Lastly, green processes and the production of fuels as well as some unconventional methods for methane activation using ultrasound, plasma, superacids, and light are also reviewed.

Pathway from N-Alkylglycine to Alkylisonitrile Catalyzed by Iron(II) and 2-Oxoglutarate-Dependent Oxygenases.

N-alkylisonitrile, a precursor to isonitrile-containing lipopeptides, is biosynthesized by decarboxylation-assisted -N≡C group (isonitrile) formation by using N-alkylglycine as the substrate. This reaction is catalyzed by iron(II) and 2-oxoglutarate (Fe/2OG) dependent enzymes. Distinct from typical oxygenation or halogenation reactions catalyzed by this class of enzymes, installation of the isonitrile group represents a novel reaction type for Fe/2OG enzymes that involves a four-electron oxidative process. Reported here is a plausible mechanism of three Fe/2OG enzymes, Sav607, ScoE and SfaA, which catalyze isonitrile formation. The X-ray structures of iron-loaded ScoE in complex with its substrate and the intermediate, along with biochemical and biophysical data reveal that -N≡C bond formation involves two cycles of Fe/2OG enzyme catalysis. The reaction starts with an FeIV -oxo-catalyzed hydroxylation. It is likely followed by decarboxylation-assisted desaturation to complete isonitrile installation.

Pathway from N‐Alkylglycine to Alkylisonitrile Catalyzed by Iron(II) and 2‐Oxoglutarate‐Dependent Oxygenases

AbstractN‐alkylisonitrile, a precursor to isonitrile‐containing lipopeptides, is biosynthesized by decarboxylation‐assisted ‐N≡C group (isonitrile) formation by using N‐alkylglycine as the substrate. This reaction is catalyzed by iron(II) and 2‐oxoglutarate (Fe/2OG) dependent enzymes. Distinct from typical oxygenation or halogenation reactions catalyzed by this class of enzymes, installation of the isonitrile group represents a novel reaction type for Fe/2OG enzymes that involves a four‐electron oxidative process. Reported here is a plausible mechanism of three Fe/2OG enzymes, Sav607, ScoE and SfaA, which catalyze isonitrile formation. The X‐ray structures of iron‐loaded ScoE in complex with its substrate and the intermediate, along with biochemical and biophysical data reveal that ‐N≡C bond formation involves two cycles of Fe/2OG enzyme catalysis. The reaction starts with an FeIV‐oxo‐catalyzed hydroxylation. It is likely followed by decarboxylation‐assisted desaturation to complete isonitrile installation.

Synthesis and anti‐proliferative activity studies of 2‐(2‐(trifluoromethyl)‐6‐(substituted)imidazo[1,2‐b]pyridazin‐3‐yl)‐N‐(substituted)acetamide derivatives

AbstractA series of novel imidazo[1,2‐b]pyridazin‐3‐yl acetamide derivatives (9a‐9j) were synthesized from a 3,6‐dichloropyridazine. We have developed a simple strategy for the synthesis of functionally diverse imidazole, and pyridiazine derivatives were reported via a series of steps. The work involves bicyclic imidazo‐pyridazine ring formation, halogenation, cynation, hydrolysis, peptide coupling, and Buchwald reaction. The structure of the synthesized compounds was confirmed by IR, 1H NMR, 13C NMR,19F NMR, mass spectra, and elemental analysis, and purity is checked by HPLC. All synthesized compounds were screened for anticancer activity against A‐549 and Du‐145 cancer cell lines by MTT assay. The preliminary bioassay suggests that most of the compounds show anti‐proliferation with different degrees; doxorubicin was used as positive control. The synthesized compound shows IC50 values in the range of 1.74μM to 16.17μM in both cell lines. The compounds 9e, 9g, and 9h were active compared with doxorubicin in both the cell lines. The compounds having cyclopentyl ring are active compared with higher and lower carbon analogues.

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine.

This Review deals with the evolving field of polyhalogen chemistry, specifically polyhalogen anions (polyhalides). In addition to a historical outline, current progress in synthetic approaches towards the formation of polyfluorides, polychlorides, polybromides, and polyinterhalides is also illustrated. The structural diversity of polyhalides has substantially increased in the past decade, especially for polychlorides and polybromides, which are commonly characterized by single-crystal X-ray diffraction, Raman spectroscopy, and quantum-chemical calculations. Polyfluorides have been examined by sophisticated state-of-the-art quantum-chemical calculations and investigated spectroscopically in noble gas matrix-isolation experiments under cryogenic conditions at 4 K. The bonding in such polyhalide systems is also discussed. The last Section deals with applications of polyhalides in halogenation reactions and electrochemistry as well as their use as reactive ionic liquids, emphasizing the promising future of polyhalogen chemistry.

Oxidative addition of halogens to a Cycloneophylplatinum(II) complex and evidence for C–H bond activation at Platinum(IV)

The reactions of halogens or their equivalent with the cycloneophylplatinum (II) complex [Pt (CH2CMe2C6H4) (phen*)], phen* = 3,4,7,8-tetramethyl-1,10-phenanthroline, are reported. The reactions occur by kinetically controlled trans oxidative addition to form trans-[PtX2(CH2CMe2C6H4) (phen*)], X = Cl, Br, I, and, when X = Br or I, these equilibrate slowly with the products of cis oxidative addition cis-[PtX2(CH2CMe2C6H4) (phen*)], X = Br, I. The complex cis-[PtCl2(CH2CMe2C6H4) (phen*)] was prepared by reaction of [PtCl(CH2CMe2C6H5) (phen*)] with chlorine equivalent, in a reaction that involves a cyclometalation step at platinum (IV). The unusual complex [PtCl(CH2CMe2C6H4) (CH2CMe2C6H5) (phen*)], which contains both a neophyl and a cycloneophyl group, was isolated as a minor product from reaction of [Pt (CH2CMe2C6H4) (phen*)] with HCl. The mechanisms of several of these reactions are elucidated and seven structure determinations are reported.

Site-Selective C-H Functionalization via Synergistic Use of Electrochemistry and Transition Metal Catalysis.

Electrochemical synthesis of organic compounds has emerged as an attractive and environmentally benign alternative to conventional approaches for oxidation and reduction of organic compounds that utilizes electric current instead of chemical oxidants and reductants. As such, many useful transformations have been developed, including the Kolbe reaction, the Simons fluorination process, the Monsanto adiponitrile process, and the Shono oxidation, to name a few. Electrochemical C-H functionalization represents one of the most promising reaction types among many electrochemical transformations, since this process avoids prefunctionalization of substrates and provides novel retrosynthetic disconnections. However, site-selective anodic oxidation of C-H bonds is still a fundamental challenge due to the high oxidation potentials of C-H bonds compared to organic solvents and common functional groups. To overcome this issue, indirect electrolysis via the action of a mediator (a redox catalyst) is regularly employed, by which the selectivity can be controlled following reaction of said mediator with the substrate. Since the redox potentials of transition metal complexes can be easily tuned by modification of the ligand, the synergistic use of electrochemistry and transition metal catalysis to achieve site-selective C-H functionalization is an attractive strategy. In this Account, we summarize and contextualize our recent efforts toward transition metal-catalyzed electrochemical C-H functionalization proximal to a suitable directing group. We have developed C-H oxygenation, acylation, alkylation, and halogenation reactions in which a Pd(II) species is oxidized to a Pd(III) or Pd(IV) intermediate by anodic oxidation, followed by reductive elimination to form the corresponding C-O, C-C, and C-X bonds. Importantly, improved monofunctionalization selectivity is achieved in the Pd-catalyzed C(sp3)-H oxygenation compared to conventional approaches using PhI(OAc)2 as the chemical oxidant. Physical separators are sometimes used to prevent the electrochemical deposition of Pd black on the cathode resulting from reduction of high valent Pd species. We skirted this issue through the development a Cu-catalyzed electrochemical C(sp2)-H amination using n-Bu4NI as a redox cocatalyst in an undivided cell. In addition, we developed Ir-catalyzed electrochemical vinylic C-H functionalization of acrylic acids with alkynes in an undivided cell, affording various substituted α-pyrones in good to excellent yield. More importantly, chemical oxidants, including Ag2CO3, Cu(OAc)2, and PhI(OAc)2, resulted in much lower yields in the absence of electrical current under otherwise identical conditions. As elaborated below, progress in the area of electrochemical transition metal-catalyzed synthesis provides an effective platform for environmentally friendly and sustainable selective chemical transformations.

Direct C-H bond halogenation and pseudohalogenation of hydrocarbons mediated by high-valent 3d metal-oxo species.

Late-stage direct functionalization of the C-H bond is synthetically desirable. Metalloenzymes having metal-oxo active sites are well known to selectively catalyze hydroxylation and halogenation reactions with high efficiency. This review highlights the recent developments in the field of direct C-H halogenation and pseudohalogenation reactions catalyzed by the functional models of metalloenzymes.

Redox reactions of halogens for reversible electrochemical energy storage.

Along with the great success of traditional lithium-ion batteries, the increasing energy demand has been promoting the rapid development of novel battery systems for even large energy density and high power density, and good safety. Typically, novel types of rechargeable batteries based on redox reactions of halogens have attracted extensive attention because of the potential fundamental chemistry and promising applications. In this frontier, we give an overview of halogen chemistry in rechargeable batteries, and the key ideas for various halogen-based batteries are discussed with particular analysis on the underlying mechanisms. Finally, the existing issues and future perspectives are also addressed for the development of halogen-based battery systems.

Microwave Assisted Synthesis and Molecular Docking Studies of Some 4- (3H)-quinazolinone Derivatives as Inhibitors of Human Gamma- Aminobutyric Acid Receptor, the GABA (A)R-BETA3 Homopentamer.

Quinazolines and quinazolinones constitute a major class of biologically active molecules, both from natural and synthetic sources. The quinazolinone moiety is an important pharmacophore showing many types of pharmacological activities as shown in recent exhaustive review on the chemistry of 2-heteroaryl & heteroalkyl-4-quinazolinones4-quinazolinones that are the formal condensation products of anthranilic acid and amides. They can also be prepared in this fashion through the Niementowski quinazolinone synthesis, named after it's discoverer Stefan Niementowski. Quinazoline and condensed quinazoline exhibit potent central nervous system (CNS) activities like anti-anxiety, analgesic, anti-inflammatory and anticonvulsant. Quinazolin-4- ones with 2, 3-disubstitution is reported to possess significant analgesic, anti-inflammatory and anticonvulsant activities. To expand these views and application profiles, efforts have been made for the synthesis of a new class of quinazolinone by incorporating different amines into synthesized benzoxazinone ring by replacing O atom in the ring. Up till now, a great number of various procedures have been proposed for the synthesis of quinazolin-4-ones in the past few years. Using microwave radiation, this reaction could be easily and rapidly performed in very good yields, providing a large number of various 3-substituted-2- propyl-quinazolin-4-one derivatives which can be employed as useful bioactive compounds. We report a facile and efficient method for the synthesis of 3-substituted-2- propyl-quinazolin-4-one by the condensation reaction of anthranilic acid or halogen substituted anthranilic acid or methyl anthranilate, butanoic anhydride with various amines. We also report a drug/ligand or receptor/protein interactions by identifying the suitable active sites in the human gamma-aminobutyric acid receptor, the gaba (a)r-beta3 homopentamer human gammaaminobutyric acid receptor, and the gaba (a)r-beta3 homopentamer protein. It was observed in the reaction, 3-alkyl/aryl-2-alkyl-quinazolin-4-one gave good yield as well as good quality of the product by using MW. All the synthesized compounds were subjected to grid-based molecular docking studies. The results show that compound 4t has good affinity to the active site residue of the human gamma-aminobutyric acid receptor, and the gaba (a)r-beta3 homopentamer. The Microwave irradiation for the synthesis of the title compounds offers a reduction in reaction time, operation simplicity, cleaner reaction, easy work-up and improved yields. The procedure clearly highlights the advantages of green chemistry. The data reported in this article may be helpful for the medicinal chemists who are working in this area. The protein-ligand interaction plays a significant role in structural based drug designing. In the present work, we have docked the ligand, 2, 3-disubstituted quinazolinone with the proteins that are used as the target for GABA-A receptor.

Synthesis of 2-Chloro-4-(3-Nitrophenoxy) -6-(Thiophen-2-Yl) Pyrimidine

2-chloro-4-(3-nitrophenoxy)-6-(thiophen-2-yl) pyrimidine (8) is an important intermediate for small molecule anticancer drugs. A rapid and high yield synthetic method for 2-chloro-4-(3-nitrophenoxy)-6-(thiophen-2-yl) pyrimidine (8) was established in this work. The target compound was synthesized from the commercially available pyrimidine-2, 4, 6(1H, 3H, 5H)-trione (5) through three steps including halogenation reaction, coupling reaction and nucleophilic reaction. The structure of the target product was confirmed by 1H NM. In addition, the synthetic method was optimized. The total yield of the three steps was high up to 85%.

C-H Halogenation of Pyridyl Sulfides Avoiding the Sulfur Oxidation: A Direct Catalytic Access to Sulfanyl Polyhalides and Polyaromatics.

Palladium-catalyzed oxidative C–H halogenation and acetoxylation reactions of S-unprotected sulfides, selectively directed by pyridinyl groups, allows the formation of C–X bonds (X = I, Br, Cl, OAc) by using simple halosuccinimide or phenyliodine diacetate (PIDA) oxidants. The undesired formation of sulfoxides and/or sulfones, which are usually observed under oxidative conditions, is fully obviated. Under the solvent-dependent conditions that we proposed, sulfide C–H functionalization is achieved in less than 1 h without any direct electrophilic halogenation at the pyridine moiety. N-Directed ortho-C–H activation of aryl also facilitates dibromination reactions which are hardly accessible with sulfone and sulfoxide counterparts because of their higher structural rigidity. This general method gives a straightforward access to polyhalide sulfides, without an organosulfur reduction step or protection–deprotection sequence. Polyhalide sulfides are valuable synthons that give a practical entry to new constrained polyaromatic and biphenyl sulfides, including synthetically challenging unsymmetrical examples.

Vanadium(V) and Molybdenum(VI) Complexes Containing ONO Tridentate Schiff Bases and Their Application as Catalysts for Oxidative Bromination of Phenols

AbstractCondensation of 2,4‐dihydroxyacetophenone with isonicotinoyl hydrazide and nicotinoyl hydrazide in an equimolar ratio in methanol results in the formation of two stable ONO donor ligands, H2dhap‐inh (I) and H2dhap‐nah (II), respectively. These ligands react with [VIVO(acac)2] (Hacac=acetylacetone) in 1:1 molar ratio to give the corresponding neutral dioxidovanadium(V) complexes, [VVO2(Hdhap‐inh)] (1) and [VVO2(Hdhap‐nah)] (2), after overnight aerial oxidation in the presence of K2CO3. In the absence of K2CO3, they result in (μ‐O){bisoxidovanadium(V)} complexes, [{VVO(dhap‐inh)}2(μ‐O)] (3) and [{VVO(dhap‐nah)}2(μ‐O)] (4). Treatment of neutral dioxidovanadium(V) complexes,1and2, with H2O2yields oxidoperoxidovanadium(V) complexes K[VVO(O2)(dhap‐inh)(H2O)] (5) and K[VVO(O2)(dhap‐nah)(H2O)] (6). The ligands also react with [MoVIO2(acac)2] in 1:1 molar ratio to form [MoVIO2(dhap‐inh)]n(7) and [MoVIO2(dhap‐nah)]n(8). The reaction of oxidoperoxidomolybdenum(VI) species, generated in situ by the reaction of MoO3with H2O2with ligandsIandII, gives the oxidoperoxidomolybdenum(VI) complexes, [MoVIO(O2)(dhap‐inh)(MeOH)] (9) and [MoVIO(O2)(dhap‐nah)(MeOH)] (10), respectively. All synthesized complexes are characterized by elemental analysis, thermogravimetric, electrochemical, spectroscopic (IR, UV–Vis,1H,13C and51V NMR) and single crystal X‐ray diffraction (for1,2and8). Complexes are explored as catalysts for the oxidative bromination of phenol, a model oxidative halogenation reaction, in the presence of HClO4and KBr, using 30% H2O2as oxidant. Under optimized reaction conditions, the product selectivity follows the order: 4‐bromophenol>2‐bromophenol, both for molybdenum and vanadium complexes. Products characterized by GC analysis showed very good conversion of phenol.

Natural Formation of Chloro- and Bromoacetone in Salt Lakes of Western Australia

Western Australia is a semi-/arid region known for saline lakes with a wide range of geochemical parameters (pH 2.5–7.1, Cl− 10–200 g L−1). This study reports on the haloacetones chloro- and bromoacetone in air over 6 salt lake shorelines. Significant emissions of chloroacetone (up to 0.2 µmol m−2 h−1) and bromoacetone (up to 1. 5 µmol m−2 h−1) were detected, and a photochemical box model was employed to evaluate the contribution of their atmospheric formation from the olefinic hydrocarbons propene and methacrolein in the gas phase. The measured concentrations could not explain the photochemical halogenation reaction, indicating a strong hitherto unknown source of haloacetones. Aqueous-phase reactions of haloacetones, investigated in the laboratory using humic acid in concentrated salt solutions, were identified as alternative formation pathway by liquid-phase reactions, acid catalyzed enolization of ketones, and subsequent halogenation. In order to verify this mechanism, we made measurements of the Henry’s law constants, rate constants for hydrolysis and nucleophilic exchange with chloride, UV-spectra and quantum yields for the photolysis of bromoacetone and 1,1-dibromoacetone in the aqueous phase. We suggest that heterogeneous processes induced by humic substances in the quasi-liquid layer of the salt crust, particle surfaces and the lake water are the predominating pathways for the formation of the observed haloacetones.

H2 O2 Production at Low Overpotentials for Electroenzymatic Halogenation Reactions.

Various enzymes utilize hydrogen peroxide as an oxidant. Such “peroxizymes” are potentially very attractive catalysts for a broad range of oxidation reactions. Most peroxizymes, however, are inactivated by an excess of H2O2. The electrochemical reduction of oxygen can be used as an in situ generation method for hydrogen peroxide to drive the peroxizymes at high operational stabilities. Using conventional electrode materials, however, also necessitates significant overpotentials, thereby reducing the energy efficiency of these systems. This study concerns a method to coat a gas‐diffusion electrode with oxidized carbon nanotubes (oCNTs), thereby greatly reducing the overpotential needed to perform an electroenzymatic halogenation reaction. In comparison to the unmodified electrode, with the oCNTs‐modified electrode the overpotential can be reduced by approximately 100 mV at comparable product formation rates.