Na2S-Mediated One-Pot Selective Deoxygenation of α-Hydroxyl Carbonyl Compounds including Natural Products

A practical method for the deoxygenation of α-hydroxyl carbonyl compounds under mild reaction conditions is reported here. The use of cheap and easy-to-handle Na₂S·9H₂O as the reductant in the presence of PPh₃ and N-chlorosuccinimide (NCS) enables the selective dehydroxylation of α-hydroxyl carbonyl compounds, including ketones, esters, amides, imides and nitrile groups. The synthetic utility is demonstrated by the late-stage deoxygenation of bioactive molecule and complex natural products.     

不同碱基物质对燃煤烟气脱氯的影响

实验探究NaOH、Na₂CO₃、NaHCO₃这三种常见的碱基物质在模拟燃煤烟气中的实际表现,发现三种碱基物质均具有一定的脱氯性能,NaOH、Na₂CO₃、NaHCO₃的脱氯性能依次下降,以脱氯效率70%为目标,使用三种碱基物质Na/Cl比分别需要达到5.8、7.1、8.7。高浓度SO₂的存在对烟气脱氯有竞争作用,随着SO₂浓度的提高,脱氯效率线性下降,不同碱基物质下,SO₂浓度对脱氯效率的影响规律基本一致,SO₂浓度每增加100 mg/m³,脱氯效率下降约1.4%。由于三种碱基物质达到相同脱氯效率时的Na/Cl比不同,综合考虑成本和溶解性,NaOH最具工业应用价值。     

Fe1/2Al1/2PO4催化1,2-二氯丙烷脱氯氧化制备环氧丙烷

Fe1/2Al1/2PO4催化1;2-二氯丙烷脱氯氧化制备环氧丙烷     

Electrochemical reductive dehalogenation of chlorobenzenes

Electrochemical dechlorination of 1,2,3,5-tetrachlorobenzene in methanol and chlorobenzene in dimethylsulfoxide with tetraalkylammonium salts as supporting electrolytes was carried out. The extent of dechlorination depends significantly on the electrode composition.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1129–1133, June, 1995.     

官能化蒙脱土负载双金属催化芳香氯化物水相脱氯

用PVP(聚乙烯吡咯烷酮)络合双金属Pd^2 ,Sn^4 后，再负载于用PEG400(平均分子量为400的聚乙二醇)官能化的蒙脱土上，制成双金属催化剂PVP—PdCl2-SnCl4/Montk10-PEG400,用于催化难溶于水的芳香卤化物水相脱卤，芳香族氮化物转化率达100％，该催化剂可重复使用。对催化剂进行了IR及TEM表征。     

Fe-Ni/TiO2纳米管阵列电极的制备、表征及光电催化还原五氯酚活性

采用阳极氧化法和浸渍电沉积联用法制备了不同负载量的Fe-Ni/TiO2纳米管阵列电极. 通过扫描电子显微镜(SEM)、 X射线光电子能谱(XPS)和电化学测量等手段对样品的微观形貌、 晶体结构和光电响应等特性进行分析. 考察了在0.6 V偏压下, 所制备的电极对五氯酚的光电催化还原性能. 结果表明, 适量的Fe和Ni纳米颗粒的负载, 降低了TiO2纳米管阵列光生电子-空穴对的复合几率; 浸渍电沉积5次的Fe-Ni/TiO2纳米管阵列电极光电催化还原降解五氯酚的效率为91.35%, 明显高于TiO2纳米管阵列电极.     

Synthesis of Nanoscale Bimetallic Particles in Polyelectrolyte Membrane Matrix for Reductive Transformation of Halogenated Organic Compounds

Nanosized Fe/Ni and Fe/Pd particles were synthesized in the polyacrylic acid (PAA)/polyether sulfone (PES) composite membrane matrix for reductive transformation of halogenated organic compounds (HOCs). The advantages of using membrane to immobilize nanoparticles are the reduction of particles loss, prevention of particles agglomeration, and potential application of convective flow. Cross-linked PAA/PES composite membranes containing metal ions as particles precursor were prepared by heat treatment with ethylene glycol (EG) as a cross-linking agent. Nanoscale metal particles were formed and immobilized inside the membrane matrix after reduction with sodium borohydride. Membrane morphology and structure were observed by scanning electron microscopy (SEM). Particle size and distribution were characterized by SEM and transmission electron microscopy (TEM). Energy dispersive X-ray spectroscopy (EDS) was used to obtain the qualitative and quantitative element information of particles. A specimen-drift-free EDS line profile and EDS mapping system was performed in a scanning transmission electron microscopy (STEM) to determine the two-dimensional element distribution of iron and nickel in the nano domain. In the dechlorination study with trichloroethylene (TCE) as a representative HOCs, rapid and complete destruction of TCE was achieved by using nanosized bimetallic Fe/Ni or Fe/Pd in PAA/PES composite membranes. Typically more than 95% of 10 mg/l TCE was reduced within 1 h. Ethane was found in the headspace as the main product.     

Liquid chromatography–high-resolution mass spectrometry for identifying aqueous chlordecone hydrate dechlorinated transformation products formed by reaction with zero-valent iron

Chlordecone (CLD) is a persistent toxic chlorinated pesticide which contaminates different ecosystems in French West Indies. A soil remediation process including zero-valent iron (ZVI) has produced promising results but failed to completely degrade CLD, and the analytical procedures used yielded little information on the transformation products. To fill these gaps, dechlorination of aqueous CLD by micrometric particles of ZVI has been investigated. Aliquots of water with 25% (v/v) of acetone spiked with 100 ppm CLD were taken at different times during a 30-day ZVI treatment and directly analysed by ultra-high-performance liquid chromatography in negative electrospray ionisation mode. CLD has been totally transformed after 14 days into 14 dechlorinated degradation products, including 9 isomeric compounds. The maximum chloride concentrations appearing in the medium represent 44% of that which would result from total dechlorination of CLD. The CLD transformation products identified by accurate mass measurements on an ultra-high-resolution Q-TOF mass spectrometer (Q-TOF-MS) were C₁₀H₃Cl₉O₂, C₁₀H₄Cl₈O₂, C₁₀H₅Cl₇O₂, C₁₀H₆Cl₆O₂ and C₁₀H₇Cl₅O₂. The results show the interest of LC-Q-TOF-MS for identifying transformation products of organic contaminants, and the effectiveness of micrometric ZVI particles to totally transform CLD into less chlorinated products.     

Porphyrin-Catalyzed Oxidation of Trichlorophenol

Porphyrin-metal complexes are potentially useful to catalyze redox reactions, which convert toxic and biologically recalcitrant compounds to compounds that are less toxic and more amenable to biotreatment. Porphyrins, in the absence of proteins as in ligninases, peroxidases, and oxidases, are potentially more robust than enzymes and microbial cultures in the treatment of inhibitory substances. 2,4,6-Trichlorophenol was used as a model compound for chlorinated phenols and as a substrate for various porphyrin-metal complexes acting as oxidation catalysts. t-Butyl hydroperoxide was the oxidizing agent. TCP was shown to be at least partially dechlorinated and the aromatic ring broken in reaction products. All porphyrins exhibited saturation kinetics with regard to the initial TCP concentration in reaction mixtures. Electron-withdrawing substituents on the porphyrins were observed to increase stability of the catalysts to inactivating ring-centered oxidation.     

Supramolecular system composed of B12 model complex and organic photosensitizer: impact of the corrin framework of B12 on the visible-light-driven dechlorination without the use of noble metals

The visible-light-driven dechlorination system without the use of a noble metal has been developed. We screened the combination of cobalt catalysts having square-planar monoanionic ligands (hydrophobic B₁₂ model complex 1/imine-oxime type complex 2) and typical red dyes (Rose Bengal 3/Rhodamine B 4/Nile Red 5) for the construction of a dehalogenation system via a noble-metal-free and visible-light-driven process. The combination of the hydrophobic B₁₂ model complex 1 and Rose Bengal 3 exhibited the highest catalytic activity to 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (DDT) to form the monodechlorinated compound, 1,1-bis(4-chlorophenyl)-2,2-dichloroethane, as the major product. The prolonged photocatalysis of DDT by the B₁₂–Rose Bengal system afforded the tri-dechlorinated compound, trans-4,4′-dichlorostilbene, as the major product. Furthermore, we investigated the mechanism of the dehalogenation cycle using various methods such as UV–vis spectroscopy and laser flash photolysis. Finally, we clarified the advantage of using the hydrophobic B₁₂ model complex 1 as an electron acceptor as well as a cobalt catalyst in the organic dye-involved photocatalysis.