Dehalogenation Reactions Research Articles

Development of Palladium Surface‐Enriched Heteronuclear Au–Pd Nanoparticle Dehalogenation Catalysts in an Ionic Liquid

Heteronuclear Au-Pd nanoparticles were prepared and immobilized in the functionalized ionic liquid [C(2)OHmim][NTf(2)]. The structural and electronic properties of the nanoparticles were characterized by a range of techniques and the surface of the nanoparticles was found to be enriched in Pd. Moreover, the extent of Pd enrichment is easily controlled by varying the ratio of Au and Pd salts used in the synthesis. The heteronuclear nanoparticles were found to be effective catalysts in dehalogenation reactions with no activity observed for the pure Au nanoparticles and only limited activity for the pure Pd nanoparticles. The activity of the heteronuclear nanoparticles may be attributed to charge transfer from Pd to Au and consequently to more efficient reductive elimination.

Practical metal- and additive-free methods for radical-mediated reduction and cyclization reactions

Two facile, metal- and additive-free protocols for radical dehalogenation, deoxygenation and cyclization reactions are reported. Irradiation by household fluorescent light bulbs or the presence of an air atmosphere is shown to initiate the desired reactions, thus providing highly practical reaction setups for radical-mediated reductions and cyclizations.

Efficient indium-mediated dehalogenation of aromatics in ionic liquid media.

An efficient indium-mediated dehalogenation reaction of haloaromatics and haloheteroaromatics in ionic liquids has been studied. This method is simple and effective in the presence of [bmim]Br. Furthermore, this methodology is environmentally friendly compared with conventional ones.

A computational study on enzymatically driven oxidative coupling of chlorophenols: An indirect dehalogenation reaction

Density functional theory calculations have been used to describe the mechanism of the dimerization reaction catalyzed by peroxidases and predict whether it could be accompanied by chlorine isotopic fractionation when various chlorophenols are used as their substrates. Since free radicals formed during the catalytic cycle of peroxidases can undergo coupling reactions (either radical–radical or radical–molecule) that can lead to dimers and also polymers formation four different pathways have been considered: radical–anion, radical–cation, radical–radical (singlet state) and radical–radical (triplet state). The following substrates have been investigated: 2-chlorophenol, 4-chlorophenol, 2,4,6-trichlorophenol and 4-chloro-2,6-dimethylphenol. Based on the obtained energetic profiles radical–cation and radical–radical (singlet) coupling seem to be the most probable. Radical–anion coupling although energetically more expensive should not be disregarded taking into account the excess of the anionic form of the substrate being provided in the course of enzymatic reaction. Upon dimer formation halogen is released during radical–anion and radical–radical triplet coupling. However only the latter pathway exhibits chlorine isotopic fractionation. Radical–cation and radical–radical singlet couplings are two-step reactions where the second step comprises intramolecular chlorine transfer accompanied by large chlorine isotope effect.

ChemInform Abstract: Synthesis of Trifluoromethyl‐Substituted Cyclopropanes via Sequential Kharasch—Dehalogenation Reactions.

AbstractIt provides a new approach to trifluoromethylated cyclopropanes.

Highly Ordered Mesoporous TiO2–Fe2O3 Mixed Oxide Synthesized by Sol–Gel Pathway: An Efficient and Reusable Heterogeneous Catalyst for Dehalogenation Reaction

Highly ordered two-dimensional (2D) hexagonal TiO(2)-Fe(2)O(3) mixed-oxide material MFT-1, which is composed of very tiny nanoparticles, is synthesized using sodium dodecylsulfate (SDS) as a structure-directing agent. Interestingly, synthesis of an ordered mesophase was not possible using SDS as a template for mesoporous pure Fe(2)O(3) or TiO(2) phases. This mesoporous iron-titanium mixed-oxide material has been characterized by powder X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), N(2) sorption, ultraviolet-visible light diffuse reflectance spectroscopy (UV-vis DRS) studies. N(2) sorption analysis revealed high surface areas (126-385 m(2) g(-1)) and narrow pore size distributions (3.1-3.4 nm) for different samples. UV-vis DRS spectra and wide-angle powder XRD patterns indicate that the material is composed of α-Fe(2)O(3) and anatase TiO(2) phases. This TiO(2)-Fe(2)O(3) mixed-oxide material can act as a very efficient and reusable catalyst in the dehalogenation of aromatic chloride-, bromide-, and iodide-tolerating -F, -CN, -CH(3), -OCH(3) and -NO(2) functional groups in the aromatic ring using 2-propanol as the dispersion medium.

Heterologous expression, purification and cofactor reconstitution of the reductive dehalogenase PceA from Dehalobacter restrictus

Organohalide respiration is used by a limited set of anaerobic bacteria to derive energy from the reduction of halogenated organic compounds. The enzymes that catalyze the reductive dehalogenation reaction, the reductive dehalogenases, represent a novel and distinct class of cobalamin and Fe-S cluster dependent enzymes. Until now, biochemical studies on reductive dehalogenases have been hampered by the lack of a reliable protein source.Here we present an efficient and robust heterologous production system for the reductive dehalogenase PceA from Dehalobacter restrictus. Large quantities of Strep-tagged PceA fused to a cold-shock induced trigger factor could be obtained from Escherichia coli. The recombinant enzyme was conveniently purified in milligram quantities under anaerobic conditions by StrepTactin affinity chromatography, and the trigger factor could be removed through limited proteolysis. Characterization of the purified PceA by UV–Vis and electron paramagnetic resonance (EPR) spectroscopy reveal that the recombinant protein binds methylcobalamin in the base-on form after proteolytic cleavage of the trigger factor, and that 4Fe-4S clusters can be chemically reconstituted under anoxic conditions. This study demonstrates a novel PceA production platform that allows further study of this new enzyme class.

Electrocatalytic dechlorination of volatile organic compounds at a copper cathode. Part I: Polychloromethanes

The electrochemical reductive dehalogenation of CCl4, CHCl3, CH2Cl2 and CH3Cl was investigated at Cu in dimethylformamide (DMF). The principal aim of the study was to check whether Cu has good electrocatalytic properties and is stable to fouling in preparative-scale electrolyses. All polychloromethanes (PCMs) have been investigated by cyclic voltammetry in DMF+0.1M Pr4NBF4 in order to evaluate the reduction mechanism and the catalytic activity of Cu. The electrochemical reduction of CCl4 and CHCl3 has also been studied by controlled-potential electrolysis in DMF+0.1M Pr4NBF4 both in the absence and presence of H2O or CH3CO2H, using chromatographic techniques to determine the intermediates and final products of the process. Cu exhibits a good electrocatalytic activity, in some cases the positive shifts of the reduction potentials with respect to GC being comparable with those at Ag, which is considered to be one of the best candidates for environmental applications in dehalogenation reactions. The results point out that the reduction mechanism at Cu is similar to what was already observed for Ag on which reduction of PCMs takes place through two competing reaction pathways: hydrodehalogenation and hydrogenolysis of carbenes. The proton availability of the medium affects drastically both the catalytic effect of Cu and the distribution of reduction products. The presence of an added proton donor promotes the hydrodehalogenation pathway, enhancing the concentration of intermediate PCMs and the final yield of methane, which is the main product of the exhaustive electrolysis.

Catalytic Transformation of Persistent Contaminants Using a New Composite Material Based on Nanosized Zero-Valent Iron

A new composite material based on deposition of nanosized zerovalent iron (nZVI) particles and cyanocobalamine (vitamin B12) on a diatomite matrix is presented, for catalytic transformation of organic contaminants in water. Cyanocobalamine is known to be an effective electron mediator, having strong synergistic effects with nZVI for reductive dehalogenation reactions. This composite material also improves the reducing capacity of nZVI by preventing agglomeration of iron nanoparticles, thus increasing their active surface area. The porous structure of the diatomite matrix allows high hydraulic conductivity, which favors channeling of contaminated water to the reactive surface of the composite material resulting in faster rates of remediation. The composite material rapidly degrades or transforms completely a large spectrum of water contaminants, including halogenated solvents like TCE, PCE, and cis-DCE, pesticides like alachlor, atrazine and bromacyl, and common ions like nitrate, within minutes to hours. A field experiment where contaminated groundwater containing a mixture of industrial and agricultural persistent pollutants was conducted together with a set of laboratory experiments using individual contaminant solutions to analyze chemical transformations under controlled conditions.

Synthesis of Trifluoromethyl-Substituted Cyclopropanes via Sequential Kharasch–Dehalogenation Reactions

A two-step process for the synthesis of trifluoromethyl-substituted cyclopropanes is described. Halothane, an anesthetic agent, is added to olefins in a ruthenium-catalyzed Kharasch reaction. The resulting 1,3-dihalides are converted into cyclopropanes by dehalogenation with magnesium. This procedure represents an alternative to metal-catalyzed cyclopropanations involving trifluoromethyl diazomethane.

Doping of biogenic Pd catalysts with Au enables dechlorination of diclofenac at environmental conditions

By using the metal reducing capacities of bacteria, Pd nanoparticles can be produced in a sustainable way (‘bio-Pd’). These bio-Pd nanoparticles can be used as a catalyst in, for example, dehalogenation reactions. However, some halogenated compounds are not efficiently degraded using a bio-Pd catalyst. This study shows that the activity of bio-Pd can be improved by doping with Au(0) (‘bio-Pd/Au’). In contrast with bio-Pd, bio-Pd/Au could perform the removal of the model pharmaceutical compound diclofenac from an aqueous medium in batch experiments at neutral pH and with H2 as the hydrogen donor (first order decay constant of 0.078 ± 0.009 h−1). Dehalogenation was for both catalysts the only observed reaction. For bio-Pd/Au, a disproportional increase of catalytic activity was observed with increasing Pd-content of the catalyst. In contrast, when varying the Au-content of the catalyst, a Pd/Au mass ratio of 50/1 showed the highest catalytic activity (first order decay value of 0.52 ± 0.02 h−1). The removal of 6.40 μg L−1 diclofenac from a wastewater treatment plant effluent using bio-Pd was not possible even after prolonged reaction time. However, by using the most active bio-Pd/Au catalyst, 43.8 ± 0.5% of the initially present diclofenac could be removed after 24 h. This study shows that doping of bio-Pd nanoparticles with Au(0) can be a promising approach for the reductive treatment of wastewaters containing halogenated contaminants.

Parallel synthesis of 1,2,4-triazole derivatives using microwave and continuous-flow techniques

An efficient and convenient solution-phase synthesis of a 1H-1,2,4-triazole library with potential agrochemical activity is reported employing microwave-assisted organic synthesis (MAOS) and continuous-flow microfluidic synthetic methods starting from commercially available 3,5-dibromo-1H-1,2,4-triazole (1). MAOS was used for the synthesis of 5-amino-3-bromo-1,2,4-triazole analogs 3 and for their 3-aryl derivatives 4 via Suzuki-Miyaura coupling with polymer-supported catalyst. A microfluidic hydrogenation reactor integrated into an automated parallel synthesis platform was built and utilized for the reductive dehalogenation reactions providing 5-aminotriazoles (5).

ChemInform Abstract: Methods for the Preparation of Allenes Employing Indium‐ and Zinc‐Mediated Dehalogenation Reactions in Aqueous Solutions.

Simple and mild methods for the synthesis of allenes, employing indium- and zinc-mediated dehalogenation reactions of vicinal dihalides in an aqueous solvent, are described. By using these procedures, various allenylmethyl aryl ethers and monosubstituted allenes have been prepared in good to excellent yields.

Generation of an Organotellurium(II) Cation

AbstractWe expected that the chemical trapping products of low‐coordinated tellurenyl cation species can also be kinetically stabilized by the Tbt or Bbt group. Recently, we have reported the halogenation reactions of Bbt‐substituted ditelluride, BbtTeTeBbt, leading to the formation of the TeII–TeIV mixed‐valent tellurenyl fluoride, BbtTeTe(F)2Bbt, and tellurenyl halides, BbtTeX (X = Cl, Br, I). During the dehalogenation reactions of these tellurium halides, it is rational to postulate the formation of a tellurenyl cation species as an intermediate. In this paper, we report the successful trapping of tellurenyl cation species with butadienes or triphenylphosphane, and the regeneration of the tellurenyl cation species by thermal retro [1+4] cycloaddition of the diene adducts.

Ni@Fe2O3 heterodimers: controlled synthesis and magnetically recyclable catalytic application for dehalogenation reactions

Ni@Fe(2)O(3) heterodimer nanoparticles (NPs) were synthesized by thermal decomposition of organometallic reactants. After functionalization, these Ni@Fe(2)O(3) heterodimers became water soluble. The pristine heterodimeric NPs were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Mössbauer spectroscopy and magnetic susceptibility measurements. A special advantage of the heterodimers lies in the fact that nanodomains of different composition can be used as catalysts for the removal of environmentally hazardous halogenated pollutants.

Effect of Solvent Polarity Properties on the Selectivity and Activity for 3,4-Dichloronitrobenzene Hydrogenation over Pd/C Catalyst

Several representative solvents classified in three categories: 1) aprotic apolar solvents: 2) protic solvents; 3) aprotic polar solvents were chosen to investigate the effect on the catalytic activity and selectivity for the selective hydrogenation of 3,4-dichloronitrobenzene (3,4-DCNB) over Pd/C catalyst. The solvent polarity increases the hydrogenation rate apparently, but also increases the selectivity to 3-chloroaniline and 4-chloroaniline from dehalogenation reaction. The solvents with the high polarity and hydrogen-bond donation capability can generate the strong interaction and the H-bond with nitro group of 3,4-DCNB, and then promote the activation and polarization of nitro group. However, on basis of the result of water as solvent, the higher hydrogenation rate in polarity solvents, to a larger extent, may be attributed to the increase of the amount of reactive chemisorbed hydrogen resulting from the dissociative chemisorption of aprotic polar solvents over the activated metal surface. At the same time, this is why the selectivity to 3-chloroaniline and 4-chloroaniline from dehalogenation reaction increase obviously with the increase of solvent polarity, because the amount of reactive chemisorbed hydrogen on the catalytic activated sites exceeds the needs of nitro group reduction and then surplus hydrogen reacts with the C-X bond.

Enzymes involved in the anaerobic degradation of meta‐substituted halobenzoates

Organohalides are environmentally relevant compounds that can be degraded by aerobic and anaerobic microorganisms. The denitrifying Thauera chlorobenzoica is capable of degrading halobenzoates as sole carbon and energy source under anaerobic conditions. LC-MS/MS-based coenzyme A (CoA) thioester analysis revealed that 3-chloro- or 3-bromobenzoate were preferentially metabolized via non-halogenated CoA-ester intermediates of the benzoyl-CoA degradation pathway. In contrast, 3-fluorobenzoate, which does not support growth, was converted to dearomatized fluorinated CoA ester dead-end products. Extracts from cells grown on 3-chloro-/3-bromobenzoate catalysed the Ti(III)-citrate- and ATP-dependent reductive dehalogenation of 3-chloro/3-bromobenzoyl-CoA to benzoyl-CoA, whereas 3-fluorobenzoyl-CoA was converted to a fluorinated cyclic dienoyl-CoA compound. The reductive dehalogenation reactions were identified as previously unknown activities of ATP-dependent class I benzoyl-CoA reductases (BCR) present in all facultatively anaerobic, aromatic compound degrading bacteria. A two-step dearomatization/H-halide elimination mechanism is proposed. A halobenzoate-specific carboxylic acid CoA ligase was characterized in T. chlorobenzoica; however, no such enzyme is present in Thauera aromatica, which cannot grow on halobenzoates. In conclusion, it appears that the presence of a halobenzoate-specific carboxylic acid CoA ligase rather than a specific reductive dehalogenase governs whether an aromatic compound degrading anaerobe is capable of metabolizing halobenzoates.

Methods for the Preparation of Allenes Employing Indium- and Zinc-Mediated Dehalogenation Reactions in Aqueous Solutions

Simple and mild methods for the synthesis of allenes, employing indium- and zinc-mediated dehalogenation reactions of vicinal dihalides in an aqueous solvent, are described. By using these procedures, various allenylmethyl aryl ethers and monosubstituted allenes have been prepared in good to excellent yields.

Continuous flow hydrogenation using polysilane-supported palladium/alumina hybrid catalysts

Continuous flow systems for hydrogenation using polysilane-supported palladium/alumina (Pd/(PSi–Al2O3)) hybrid catalysts were developed. Our original Pd/(PSi–Al2O3) catalysts were used successfully in these systems and the hydrogenation of unsaturated C–C bonds and a nitro group, deprotection of a carbobenzyloxy (Cbz) group, and a dehalogenation reaction proceeded smoothly. The catalyst retained high activity for at least 8 h under neat conditions.

Palladium nanoparticles produced by fermentatively cultivated bacteria as catalyst for diatrizoate removal with biogenic hydrogen

A new biological inspired method to produce nanopalladium is the precipitation of Pd on a bacterium, i.e., bio-Pd. This bio-Pd can be applied as catalyst in dehalogenation reactions. However, large amounts of hydrogen are required as electron donor in these reactions resulting in considerable costs. This study demonstrates how bacteria, cultivated under fermentative conditions, can be used to reductively precipitate bio-Pd catalysts and generate the electron donor hydrogen. In this way, one could avoid the costs coupled to hydrogen supply. The catalytic activities of Pd(0) nanoparticles produced by different strains of bacteria (bio-Pd) cultivated under fermentative conditions were compared in terms of their ability to dehalogenate the recalcitrant aqueous pollutants diatrizoate and trichloroethylene. While all of the fermentative bio-Pd preparations followed first order kinetics in the dehalogenation of diatrizoate, the catalytic activity differed systematically according to hydrogen production and starting Pd(II) concentration in solution. Batch reactors with nanoparticles formed by Citrobacter braakii showed the highest diatrizoate dehalogenation activity with first order constants of 0.45 ± 0.02 h⁻¹ and 5.58 ± 0.6 h⁻¹ in batches with initial concentrations of 10 and 50 mg L⁻¹ Pd, respectively. Nanoparticles on C. braakii, used in a membrane bioreactor treating influent containing 20 mg L⁻¹ diatrizoate, were capable of dehalogenating 22 mg diatrizoate mg⁻¹ Pd over a period of 19 days before bio-Pd catalytic activity was exhausted. This study demonstrates the possibility to use the combination of Pd(II), a carbon source and bacteria under fermentative conditions for the abatement of environmental halogenated contaminants.