Upper-rim-modified thioether thiacalix[4]arene used for liquid-liquid extraction of Au(Ⅲ)and Pd(Ⅱ)in hydrochloric acid medium

Gold(Au)and palladium(Pd)play an increasing role in the production and human life;Therefore,it is of great significance to study their recovery.A 5,11,17,23-tetra-ethylthio-25,26,27,28-tetra-hydroxyl thiacalix[4]arene(TCAET)was synthesized specifically for the capture of Au(Ⅲ)and Pd(Ⅱ)from HCl medium by liquid-liquid extraction.In a 0.1 mol·L^(-1)HCl medium,the transfer of Au(Ⅲ)and Pd(Ⅱ)from the aqueous phase to the organic phase was highly efficient,with a transfer ratio of 100%for Au(Ⅲ)and 98%for Pd(Ⅱ).Furthermore,the extraction equilibrium time for Au(Ⅲ)was just 5 min.Job's method data demonstrated that TCAET formed complexes with Au(Ⅲ)and Pd(Ⅱ)in a ratio of 2:3 and 1:1,respectively,during the extraction process.TCAET showed high selectivity toward Pd(Ⅱ)and Au(Ⅲ)over other competing metal ions.Moreover,both Au(Ⅲ)and Pd(Ⅱ)could be successfully stripped from the loaded organic phases with a 1.0 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl and 0.5 mol·L^(-1)thiourea in 0.5 mol·L^(-1)HCl,respectively.Results obtained from five consecutive extraction-stripping cycles showed good reusability of TCAET toward Au(Ⅲ)and Pd(Ⅱ)recovery.The conclusion can provide a certain reference for thiacalixarene in the recovery of precious metal species.

Green Synthesis of Aryl Thioethers through Cu-catalysed C-S Coupling of Thiols and Aryl Boronic Acids in Water

An efficient, practical, highly selective and environmentally benign method is reported for the synthesis of aryl thioethers via the coupling of thiols with aryl boronic acids in the presence of NaOH and a catalytic amount of CuSO4 at 130 ℃ using water as a green solvent. The products were obtained in moderate to excellent yields;more importantly, the use of toxic ligands and solvents was avoided. A broad range of aryl boronic acids and scalable processes make this methodology valuable and versatile for the synthesis of a broad range of aryl sulfides.

Synthesis of Some New Thioethers and 4-Thiazolidinones Bearing 3-(Pyridine-4'-yl)-1,2,4-Triazino[5,6-<i>b</i>]Indole Moiety as Antifungal Agents

Some new asymmetric thioethers 5 and 4-thiazolidinones 6 have been obtained from condensation of 5-formyl-3-(pyridin-4'-yl)-1,2,4-triazino[5,6-b] indole (3) with halogenated aromatic amines followed by addition of thiophenol and/or cycloaddition with thiolactic acids in nonpolar solvents. Structures of the products confirmed by elemental analysis and spectral measurements. The new systems obtained were evaluated as antifungal agents.

Preparation and Properties of Vegetable-Oil-Based Thioether Polyol and Ethyl Cellulose Supramolecular Composite Films

Ethyl cellulose(EC),an important biomass-based material,has excellent film-forming properties.Nevertheless,the high interchain hydrogen bond interaction leads to a high glass transition temperature of EC,which makes it too brittle to be used widely.The hydroxyl group on EC can form a supramolecular system in the form of a non-covalent bond with an effective plasticizer.In this study,an important vegetable-oil-based derivative named dimer fatty acid was used to prepare a novel special plasticizer for EC.Dimer-fatty-acid-based thioether polyol(DATP)was synthesized and used to modify ethyl cellulose films.The supramolecular composite films of DATP and ethyl cellulose were designed using the newly-formed van der Waals force.The thermal stability,morphology,hydrophilicity,and mechanical properties of the composite films were all tested.Pure EC is fragile,and the addition of DATP makes the ethyl cellulose films more flexible.The elongation at the break of EC supramolecular films increased and the tensile strength decreased with the increasing DATP content.The elongation at the break of EC/DATP(60/40)and EC/DATP(50/50)was up to 40.3%and 43.4%,respectively.Noticeably,the thermal initial degradation temperature of the film with 10%DATP is higher than that of pure EC,which may be attributed to the formation of a better supramolecular system in this composite film.The application of bio-based material(EC)is environmentally friendly,and the novel DATP can be used as a special and effective plasticizer to prepare flexible EC films,making it more widely used in energy,chemical industry,materials,agriculture,medicine,and other fields.

Effect of Different Loadings on the Performance of Ni2P/Al2O3 Catalysts for Low-Temperature Thioethering and Selective Hydrogenation of Diolefins in Liquefied Petroleum Gas

In this study,different loadings of x%Ni_(2)P/γ-Al_(2)O_(3)(x=6%,9%,12%,15%,18%)catalysts with aluminum oxide(Al_(2)O_(3))as the carrier,nickel chloride(NiCl2)as the nickel(Ni)source,and ammonium hypophosphite(NH_(4)H_(2)PO_(2))as the phosphorus(P)source were prepared by the equal volume impregnation method to investigate the effects of different loadings on the performance of the selective hydrogenation of diolefins and thiol etherification in LPG.The physicochemical properties of the catalysts were characterized by XRD,BET,SEM,TEM,H_(2)-TPR,and XPS,and the catalytic activity of the catalysts was evaluated in a fixed-bed microreactor.The results showed that a change in the loading affected the catalyst crystalline phase structure and size,specific surface area,P coverage,active phase dispersion,and catalytic activity.At 6%,9%,and 12%loadings the catalysts had an Ni phase but there was no obvious Ni_(2)P phase in the nickel phosphide;at 15%loading a single Ni_(2)P phase was obtained,and at 18%loading both Ni_(2)P and Ni1_(2)P_(5) phases appeared.There was a P enrichment on the catalyst surface,and the higher the loading the more P species were enriched on the surface,but some of the P was lost during the catalyst reduction process due to the production of phosphine(PH3)gas.The 15%Ni_(2)P/γ-Al_(2)O_(3) catalyst had the largest Ni/Al ratio and the best dispersion.The Ni_(2)P active phase size was small at about 4.25 nm and Ni_(2)P was uniformly dispersed on the catalyst surface without agglomeration.The 15%Ni_(2)P/γ-Al_(2)O_(3) catalyst had the best catalytic activity at a pressure of 2.0 MPa,a liquid hourly space velocity(LHSV)of 3.0 h-1,and a hydrogen to hydrocarbon ratio of 12.The 1,3-butadiene conversion was 97.45%and the methanethiol removal was 100%at a temperature of 140℃.

基于银型苯基磺酸键合硅胶分离及高分辨质谱分析石油中不同形态含硫化合物

建立一种基于银型苯基磺酸键合硅胶(Ag+-SCX)分离石油中不同形态含硫化合物的方法,分离得到的含硫化合物组分进行甲基化反应和高分辨质谱(HRMS)分析,得到不同形态含硫化合物分子组成。通过模型化合物证明该分离方法的可行性,硫醚类、噻吩类含硫化合物被有效分离。该方法对石油馏分、原油和二次加工油均有良好的适用性,并将其应用于一套原油及其馏分中含硫化合物的分离及分析,详细表征了不同形态含硫化合物在原油和各馏分段的分子组成特点和分布规律。

硫醚氧化为亚砜和砜的研究进展

亚砜和砜是两类重要的化合物,在化学和生物领域有广泛的应用。虽然有很多方法合成亚砜和砜,但通过控制硫醚的化学选择性氧化是合成亚砜和砜的常用途径之一;常见氧化剂如空气/氧气、双氧水、单过硫酸氢钾复合盐(Oxone)、高碘酸钠等均可以实现硫醚的选择性氧化。本文依据氧化剂的种类对氧化反应进行分类,综述了近年来硫醚氧化制备亚砜和砜的研究进展。

混装分子筛脱除油田伴生气中硫醚的研究与应用

针对含有饱和水和微量羰基硫、硫醚等有机硫的油田伴生气,提出4A分子筛和13X改性分子筛混装的脱水脱硫方法。结合现场生产工况,利用工程模拟软件对主要有机硫组分在分子筛上的吸附和再生能量进行了核算,确定了再生气量、再生压力、再生温度等关键参数,实现了脱硫分子筛的吸附再生循环,在保证脱水效果的情况下,达到了脱硫的目的。

无金属催化β-取代硫醚的合成研究

研究以多种简单易得的烯烃与苯硫酚为原料,以高产率合成2类不同类型的β-氯代硫醚及β-羟基取代硫醚.反应通过选择不同的反应溶剂,实现不同产物的选择性合成.当以无水乙腈为溶剂时,可以中等至高的收率生成得到β-氯代硫醚;而在溶剂二甲基亚砜中,则可选择性地生成β-羟基取代硫醚.该反应有较好的底物适应性,官能团容忍度,并具有操作简便、反应条件温和等优点.

Co(Ⅱ)2,2',4,4'-四羟基二苯甲酮-乙二胺席夫碱配合物的合成及其催化硫醚不对称氧化的探究

手性席夫碱(Schiff base)配合物催化的硫醚不对称氧化反应是现有最有效的方法之一。利用2,2’,4,4’-四羟基二苯甲酮-乙二胺反应合成席夫碱配体,水热法合成配合物(CoL_(1))。考察了在牛血清白蛋白存在下CoL_(1)催化硫醚不对称氧化反应的催化活性,并考察了缓冲溶液pH、氧化剂浓度、底物浓度、氧化剂种类、反应温度等反应条件对催化活性的影响。通过单因素实验探究实验,得到了CoL_(1)催化苯基甲基硫醚不对称氧化反应的最优反应条件,获得了79.72%的转化率和99.13%的化学选择性,但对映体选择性较低(7.91%)。

Synthesis and Adsorption Studies on Magnetic Microbeads of Polythioether-arylamine Resins

By the suspended condensation reaction of poly(choloromethylthiirane)with o-tolidine and o- dianisidine respectively, two newmicrobeads chelating resins were synthesized by usingγ-Fe_2O_3 asmagnetic core. Their adsorption properties for Hg(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Pb(Ⅱ), Au(Ⅲ), Pd(Ⅱ), Pt (Ⅳ)and Ag(Ⅰ)were investigated. Themicrobeads posses excellent adsorbability for Hg(Ⅱ) and noble metalions, and predominantly adsorbed Pd(Ⅱ)or Hg(Ⅱ)in the coexistence ofCu(Ⅱ), Zn(Ⅱ)and Mg(Ⅱ).

A thioether-functionalized pyrene-based covalent organic framework anchoring ultrafine Au nanoparticles for efficient photocatalytic hydrogen generation

Covalent organic frameworks(COFs)have lately emerged as a blooming class of potential materials for photocatalytic water splitting because of their high crystallinity,huge surface areas,and structural versatility.However,the photocatalytic performance for most pure COFs face some limitations factors,such as the significant recombination of photogenerated carriers and slow charge transfer.Herein,a novel thioether-functionalized pyrene-based COF(S_(4)-COF)was effectively produced and chosen as a support for the immobilization of ultrafine gold nanoparticles(Au NPs).S_(4)-COF photocatalyst with Au as cocatalyst demonstrates remarkable photocatalytic activity with a H_(2) generation rate of 1377μmol g^(−1) h^(−1) under visible light(>420 nm),which is ca.4.5-fold increase comparing to that of pure S_(4)-COF(302μmol g^(−1) h^(−1)).Au NPs anchored on S_(4)-COF possess an ultrafine size distribution ranging from 1.75 to 6.25 nm with an average size centered at 3.8 nm,which benefits from the coordination interaction between thioether groups and Au.Meanwhile,the produced Au@S_(4)-COF can generate a stable photocatalytic H_(2) generation during the four recycles and preserve its crystallinity structure after the stability testing.The Au NPs anchored on the S_(4)-COF photocatalyst can greatly accelerate the separation of photogenerated carriers and increase charge transfer because of the combined function of Au NPs and thioether groups.Such a method can not only prevent the aggregation of Au NPs onto thioether-containing COFs to achieve long-term photostability but also allow uniform dispersion for an ordered structure of photocatalysts.This work provides a rational strategy for designing and preparing COF-based photocatalysts for solar-driven H_(2) production.

Synthesis of core-shell structured polymers with inserted thioether from a multi-functional scaffold

The synthesis of a thioether inserted, core-shell structured polymer from the scaffold of hyperbranched polyglycerol (PG) was described. PG was first allyl functionalized, and in the presence of AlBN, the allyl groups further underwent radical addition to thiol compounds, thus thiol functional polyethylene oxide monomether (MPEO) were grafted onto PG. Similarly, 2-mercaptoethylammonium chloride was introduced onto PG via thiol addition, and the residual amino groups were further quaternized with decyl bromide, leading to an amphiphilic core-shell structure polymer. (c) 2007 De Cheng Wan. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

A Novel Method of Preparing Unsymmetrical Thioether from Disulfides

The disulfides reacted with zinc in DMF, followed by alkyl halides, giving unsymmetrical thioether in excellent yields. This reaction takes place under mild and neutral conditions.

Indium-mediated Facile Synthesis of (6-Chloropyridine-3-yl) methyl Heterocyclic Thioether Derivatives in Aqueous Media

A series of substituted (6-chloropyridine-3-yl)methyl heterocyclic thioether derivatives were prepared by indium mediating in water. The preliminary biological tests showed that compound 3d exhibited good antiviral activity.

MODIFICATION OF PALLADIUM METALLIC CATALYST WITH POLYMER-ANCHORED THIOETHER LIGANDS

A well-dispersed metallic palladium catalyst modified by polymer-anchored thioether ligands was used for the hydrogenation of cyclopentadiene to cyclopentene with high activity and selectivity in ambient condition. The evidences to show the modification of catalytic properties by polymer anchored ligands were given.

CROSS-LINKING OF AROMATIC POLY(THIOETHER)S

A novel cross-linking process using two high molecular weight aromatic poly（thioether）s, which were synthesized by the reactions of 4,4＇-thiobisbenzenethiol with 4,4＇-difluorobenzophenone and 4,4＇-difluorodiphenylsulfone, respectively, and commercially available lower molecular weight poly（p-phenylene sulfide） was investigated. These reactions were carried out in bulk by the addition of silver tetrafluroborate and α,α＇-dibromo-p-xylene at 190℃ over a period of 45 min. Furthermore, the same procedure could be modified to cross-link compression-molded films of these three polymers. The thermal and solubility behaviors of these polymers before and after cross-linking reactions, are presented.

INTERACTION OF PLASMA—LIQUID IN AN OXYGEN GLOW DISCHARGE Ⅲ.OXIDATION DESULFURIZATION OF ETHYL—THIOETHER

A few factors affecting plasma oxidation desulfurization of ethyl- thioether were investigated.Under the typical conditions,the conversion and degree of desulfurization of ethyl-thioether can be achieved up to 88% and 79% respectively.

深海放线菌Streptomyces koyangensis SCSIO 5802中次级代谢产物neoabyssomicin H的分离鉴定

深渊霉素类化合物具有抗结核分枝杆菌、抗MRSA(methicillin-resistant Staphylococcus aureus)、选择性激活潜伏HIV病毒等生物活性,具有显著的开发利用潜力。本文在前期研究基础上,进一步对深海链霉菌Streptomyces koyangensis SCSIO 5802新型深渊霉素类化合物的生产潜力进行发掘,综合利用多种色谱分离手段,获得一个结构新颖的深渊霉素硫醚二聚体化合物,命名为neoabyssomicin H。该化合物的结构通过UV、IR、HR-ESI-MS,1D和2D NMR及X-Ray单晶铜靶衍射等进行了鉴定。活性测试结果表明,neoabyssomicin H对金黄色葡萄球菌和系列临床MRSA的MIC(minimum inhibitory concentration)值大于128μg·m L^(-1)。该研究进一步丰富了深渊霉素类化合物,为硫醚二聚体类深渊霉素活性化合物的研究提供了新的分子实体。

Synthesis of Novel Cyclic Aryl Ether Thioether Ketone (Sulfone) Oligomers

Two kinds of macrocyclic oligomers containing aromatic sulfide linkages have been synthesized by the solution polycondensation in high yield. The cyclic compounds were characterized by H-1 and C-13 NMR, by and MALDI - TOF MS.