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Simultaneous Degradation, Dehalogenation, and Detoxification of Halogenated Antibiotics by Carbon Dioxide Radical Anions
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作者 Yanzhou Ding Xia Yu +8 位作者 Shuguang Lyu Huajun Zhen Wentao Zhao Cheng Peng Jiaxi Wang Yiwen Zhu Chengfei Zhu Lei Zhou Qian Sui 《Engineering》 SCIE EI CAS CSCD 2024年第6期78-86,共9页
Despite the extensive application of advanced oxidation processes(AOPs)in water treatment,the efficiency of AOPs in eliminating various emerging contaminants such as halogenated antibiotics is constrained by a number ... Despite the extensive application of advanced oxidation processes(AOPs)in water treatment,the efficiency of AOPs in eliminating various emerging contaminants such as halogenated antibiotics is constrained by a number of factors.Halogen moieties exhibit strong resistance to oxidative radicals,affecting the dehalogenation and detoxification efficiencies.To address these limitations of AOPs,advanced reduction processes(ARPs)have been proposed.Herein,a novel nucleophilic reductant—namely,the carbon dioxide radical anion(CO_(2)^(·-))—is introduced for the simultaneous degradation,dehalogenation,and detoxification of florfenicol(FF),a typical halogenated antibiotic.The results demonstrate that FF is completely eliminated by CO_(2)^(·-),with approximately 100%of Cland 46%of Freleased after 120 min of treatment.Simultaneous detoxification is observed,which exhibits a linear response to the release of free inorganic halogen ions(R^(2)=0.97,p<0.01).The formation of halogen-free products is the primary reason for the superior detoxification performance of this method,in comparison with conventional hydroxyl-radical-based AOPs.Products identification and density functional theory(DFT)calculations reveal the underlying dehalogenation mechanism,in which the chlorine moiety of FF is more susceptible than other moieties to nucleophilic attack by CO_(2)^(·-).Moreover,CO_(2)^(·-)-based ARPs exhibit superior dehalogenation efficiencies(>75%)in degrading a series of halogenated antibiotics,including chloramphenicol(CAP),thiamphenicol(THA),diclofenac(DLF),triclosan(TCS),and ciprofloxacin(CIP).The system shows high tolerance to the pH of the solution and the presence of natural water constituents,and demonstrates an excellent degradation performance in actual groundwater,indicating the strong application potential of CO_(2)^(·-)-based ARPs in real life.Overall,this study elucidates the feasibility of CO_(2)^(·-)for the simultaneous degradation,dehalogenation,and detoxification of halogenated antibiotics and provides a promising method for their regulation during water or wastewater treatment. 展开更多
关键词 Carbon dioxide radical anions Advanced reduction processes halogenated antibiotics DEhalogenation DETOXIFICATION
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非血红素铁酶中动态配位变化对C-H键选择性胺化反应的调控机制
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作者 张璇 刘佳 +2 位作者 廖浪星 王子宽 王斌举 《Chinese Journal of Catalysis》 SCIE CAS CSCD 2024年第7期131-144,共14页
氮杂环丙烷结构广泛存在于天然生物碱中,具有杀菌、抗癌等作用.然而,目前关于生物体系在合成氮杂环丙烷结构过程中如何克服氮杂环丙烷高环张力带来的热力学不利因素,以及如何避免形成热力学更稳定的羟基化副产物的报道较少.TqaL_(NC)酶... 氮杂环丙烷结构广泛存在于天然生物碱中,具有杀菌、抗癌等作用.然而,目前关于生物体系在合成氮杂环丙烷结构过程中如何克服氮杂环丙烷高环张力带来的热力学不利因素,以及如何避免形成热力学更稳定的羟基化副产物的报道较少.TqaL_(NC)酶是目前非血红素酶家族中唯一一种能够依赖α-酮戊二酸活化C-H键,进而生成氮杂环丙烷结构的酶.深入探究TqaL_(NC)酶选择性生成氮杂环丙烷结构并避免羟基化副产物的机制,有助于深入理解非血红素铁酶家族在C-H键活化及官能化过程中的选择性调控机理.本文以TqaL_(NC)酶的晶体结构为基础,采用分子动力学(MD)模拟以及量子力学-分子力学(QM/MM)等多尺度模拟方法对TqaL_(NC)酶与L-缬氨酸(L-Val)、TqaL_(NC)酶与L-异亮氨酸(L-Ile)和F345A-TqaL_(NC)酶与L-异亮氨酸(L-Ile)三个反应过程进行了详细的机理研究.结果表明,TqaL_(NC)酶在反应过程中生成的直立式构象的Fe(Ⅳ)=O物种会通过构象异构化获得赤道面式构象,为底物(L-Val、L-Ile、L-homoalaine)上NH_(3)^(+)与Fe的配位提供结构基础.在水和关键酸性残基的介导下,底物NH_(3)^(+)两次脱去质子与Fe(Ⅳ)=O物种配位,生成HN-Fe(Ⅳ)=O结构.随后,Fe(Ⅳ)=O物种攫取底物H原子,生成HN-Fe(Ⅲ)-OH中间体.此时NH回弹反应比传统的OH回弹反应在动力学上更有优势,因此选择性地生成了氮杂环丙烷产物.在反应过程中,底物侧链与周围氨基酸的位阻效应是影响NH回弹反应能垒的重要因素.通过改变底物侧链大小(L-Val→L-Ile)以及附近氨基酸的突变(F345A)实验,证实了该结论.本文还通过理论计算预测了TqaL_(NC)酶与L-高丙氨酸的反应产物为羟基化产物,并通过新的实验证据进一步支持了理论预测的机理.此外,在HN-Fe(Ⅲ)-OH结构中,通过前线轨道理论分析发现,dπ*Fe-N,dπ*Fe-OH轨道的能量差是影响NH/OH回弹反应能垒的另一重要因素.当底物NH与Fe配位时,其配位作用能够使得dπ*Fe-N以及dπ*Fe-OH轨道有效分裂,这种分裂进而影响了反应路径的选择性,确保氮杂环丙烷产物的生成.综上,本文提出了依赖α-酮戊二酸酶催化合成氮杂环丙烷结构的新机理.研究发现,Fe中心的动态配位效应在实现C-H键选择性胺化反应并避免C-H键羟基化反应中起到了关键作用.该理论为非血红素Fe酶催化的非羟基化反应提供了新的见解,并为探索包括C-N/C-S/C-O等重要生物合成反应新机理的探究提供了新思路. 展开更多
关键词 联合量子力学-分子力学方法 c-h键活化 非血红素酶 胺化反应 羟基化反应
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Separation of halogens and recovery of heavy metals from secondary copper smelting dust
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作者 Zhi-lou LIU Zhi-kang CHEN +7 位作者 Fu-ze SUN Zhi-heng ZHANG Kang YAN Shui-ping ZHONG Hui LIU Rui-xiang WANG Jia-yuan LI Zhi-feng XU 《Transactions of Nonferrous Metals Society of China》 SCIE EI CAS CSCD 2024年第8期2686-2701,共16页
The separation of halogens and recovery of heavy metals from secondary copper smelting(SCS)dust using a sulfating roasting−water leaching process were investigated.The thermodynamic analysis results confirm the feasib... The separation of halogens and recovery of heavy metals from secondary copper smelting(SCS)dust using a sulfating roasting−water leaching process were investigated.The thermodynamic analysis results confirm the feasibility of the phase transformation to metal sulfates and to gaseous HF and HCl.Under the sulfating roasting conditions of the roasting temperature of 250℃ and the sulfuric acid excess coefficient of 1.8,over 74 wt.%of F and 98 wt.%of Cl were volatilized into flue gas.Approximately 98.6 wt.%of Zn and 96.5 wt.%of Cu in the roasting product were dissolved into the leaching solution after the water leaching process,while the leaching efficiencies of Pb and Sn were only 0.12%and 0.22%,respectively.The mechanism studies indicate the pivotal effect of roasting temperature on the sulphation reactions from various metal species to metal sulfates and the salting out reactions from various metal halides to gaseous hydrogen halides. 展开更多
关键词 secondary copper smelting dust sulfating roasting water leaching halogen volatilization heavy metal separation
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C-H bond activation of propane on Ga_(2)O_(2)^(2+) in Ga/H-ZSM-5 and its mechanistic implications
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作者 Zhaoqi Zhao Yunzhu Zhong +1 位作者 Xiaoxia Chang Bingjun Xu 《Chinese Journal of Catalysis》 SCIE CAS CSCD 2024年第9期32-43,共12页
Propane dehydrogenation(PDH)on Ga/H-ZSM-5 catalysts is a promising reaction for propylene production,while the detail mechanism remains debatable.Ga_(2)O_(2)^(2+) stabilized by framework Al pairs have been identified ... Propane dehydrogenation(PDH)on Ga/H-ZSM-5 catalysts is a promising reaction for propylene production,while the detail mechanism remains debatable.Ga_(2)O_(2)^(2+) stabilized by framework Al pairs have been identified as the most active species in Ga/H-ZSM-5 for PDH in our recent work.Here we demonstrate a strong correlation between the PDH activity and a fraction of Ga_(2)O_(2)^(2+) species corresponding to the infrared GaH band of higher wavenumber(GaHHW)in reduced Ga/H-ZSM-5,instead of the overall Ga_(2)O_(2)^(2+) species,by employing five H-ZSM-5 supports sourced differently with comparable Si/Al ratio.This disparity in Ga_(2)O_(2)^(2+) species stems from their differing capacity in completing the catalytic cycle.Spectroscopic results suggest that PDH proceeds via a two-step mechanism:(1)C-H bond activation of propane on H-Ga_(2)O_(2)^(2+) species(rate determining step);(2)β-hydride elimination of adsorbed propyl group,which only occurs on active Ga_(2)O_(2)^(2+) species corresponding to GaHHW. 展开更多
关键词 Propane dehydrogenation Ga_(2)O_(2)^(2+) Activation of c-h bond Ga species
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Progress in Analytical Methods of Halogenated Disinfection By-Products
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作者 Jing Wu 《Proceedings of Business and Economic Studies》 2024年第2期95-99,共5页
Ensuring the health and safety of drinking water is crucial for both nations and their citizens.Since the 20th century,the disinfection of drinking water,effectively controlling pathogens in water sources,has become o... Ensuring the health and safety of drinking water is crucial for both nations and their citizens.Since the 20th century,the disinfection of drinking water,effectively controlling pathogens in water sources,has become one of the significant advances in public health.However,the disinfectants used in the process,such as chlorine and chlorine dioxide,react with natural organic matter in the water to produce disinfection by-products(DBPs).Most of these DBPs contain chlorine,and if the source water contains bromine or iodine,brominated or iodinated DBPs,collectively referred to as Halogenated disinfection byproducts(X-DBPs),are formed.Numerous studies have found that X-DBPs pose potential risks to human health and the environment,leading to widespread concern.Mass spectrometry has become an important means of discovering new types of X-DBPs.This paper focuses on the study of methods for analyzing X-DBPs in drinking water using mass spectrometry. 展开更多
关键词 halogenated disinfection by-products Drinking water High-resolution mass spectrometry
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Light-driven activation of carbon-halogen bonds by readily available amines for photocatalytic hydrodehalogenation 被引量:1
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作者 Di Meng Qian Zhu +5 位作者 Yan Wei Shengli Zhen Ran Duana Chuncheng Chen Wenjing Song Jincai Zhao 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 北大核心 2020年第10期1474-1479,共6页
A straightforward protocol using readily available aromatic amines,N,N,N',N'-tetramethyl-p-phenylenediamine or N,N,N',N'-tetramethylbenzidine,as photocatalysts was developed for theefficient hydrodehal... A straightforward protocol using readily available aromatic amines,N,N,N',N'-tetramethyl-p-phenylenediamine or N,N,N',N'-tetramethylbenzidine,as photocatalysts was developed for theefficient hydrodehalogenation of organic halides,such as 4'-bromoacetophenone,polyfluoroarenes,cholorobenzene,and 2,2',4,4'-tetrabromodiphenyl ether(a resistant and persistent organic pollu-tant).The strongly reducing singlet excited states of the amines enabled diffusion-controlled disso-ciative electron transfer to effectively cleave carbon-halogen bonds,followed by radical hydrogena-tion.Diisopropylethylamine served as the terminal electron/proton donor and regenerated theamine sensitizers. 展开更多
关键词 Carbon-halogen bond activation Photocatalysis halogenated organic pollutants Reductive dehalogenation Environmental remediation
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单原子合金对烷基C-H键活化调控的理论研究 被引量:1
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作者 乔聪聪 傅钢 《Chinese Journal of Chemical Physics》 SCIE EI CAS CSCD 2023年第4期427-433,I0035,共8页
单原子合金是指活性金属原子分散在Cu、Ag或Au载体上所构成的催化剂,近年来已成为单原子催化研究中的一颗“新星”.单原子合金上孤立活性位点与载体金属的电子结构不同,具有奇异的电子结构,故通常表现出独特的催化行为。目前尚缺乏一种... 单原子合金是指活性金属原子分散在Cu、Ag或Au载体上所构成的催化剂,近年来已成为单原子催化研究中的一颗“新星”.单原子合金上孤立活性位点与载体金属的电子结构不同,具有奇异的电子结构,故通常表现出独特的催化行为。目前尚缺乏一种可靠的单原子合金催化特性描述符.本文系统地考察了甲烷、丙烷和乙苯在15种Rh、Ir、Ni、Pd和Pt掺杂Cu(111)、Ag(111)和Au(111)单原子合金上初始C-H键活化.密度泛函计算表明,烷基C-H键的活化能垒与d带中心和H原子吸附相关较差,而与反应能之间相关性较好.理论分析表明,C原子在顶位的吸附与C-H活化过渡态之间存在着轨道相互作用的相似性,不仅涉及到对d,2轨道给予,也涉及day/dy≥轨道的元反馈.据此,C原子吸附能与甲烷、丙烷和乙苯C-H键活化能也具有很强的相关性(R2>0.9). 展开更多
关键词 单原子合金 c-h键活化 d带中心 热化学描述符 线性比例关系
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Investigation of Intermolecular C-H···Halogen Hydrogen Bonded Supramolecular Assemblies in Three Copper(Ⅰ) Complexes Formed by 3,3'-Dimethoxy-6,6'-dimethyl-2,2'-bipyridine Ligand
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作者 马军营 孙超伟 +1 位作者 邓冬生 吉保明 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2012年第4期513-520,共8页
Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3'-dimethoxy-6,6'-dimethyl-2,2'-bipyridine ligand(dmbp) with the corresponding Cu(Ⅰ) salts.Crystal data for 1:orthorhombic ... Three new crystalline compounds 1-3 were successfully obtained by the reactions of 3,3'-dimethoxy-6,6'-dimethyl-2,2'-bipyridine ligand(dmbp) with the corresponding Cu(Ⅰ) salts.Crystal data for 1:orthorhombic Pbca,a = 18.5858(12),b = 8.1821(5),c = 20.6066(13) ,V = 3133.7(3) 3,Z = 8,Dc = 1.843 g/cm3,F(000) = 1696,μ = 3.366 mm-1,the final R = 0.0223 and wR = 0.0542.Crystal data for 2:Orthorhombic Pbca,a = 18.7883(16),b = 8.3249(7),c = 19.0294(17) ,V = 2976.4(4) 3,Z = 8,Dc = 1.731 g/cm3,F(000) = 1552,μ = 4.154 mm-1,the final R = 0.0279 and wR = 0.0680.Crystal data for 3:monoclinic P21/c,a = 13.812(10),b = 9.910(7),c = 23.444(17) ,β = 104.3350(10)°,V = 3090(4) 3,Z = 4,Dc = 1.476 g/cm3,F(000) = 1408,μ = 1.588 mm-1,the final R = 0.0479 and wR = 0.1081.The results of X-ray crystallographic analysis revealed that C14H16ICuN2O2(1) and C14H16BrCuN2O2(2) are isostructural compounds with the dimers connected by C-H···halogen hydrogen bonds to generate a three-dimensional(3D) supramolecular network in 1 and a two-dimensional(2D) sheet structure in 2,respectively,while the mononuclear complex C28H32Cl2Cu2N4O4(3) is ionic.In 3,the [Cu(dmbp)2]+ cations and [ClCuCl]-anions are connected by C-H···Cl hydrogen bonds to form a one-dimensional(1D) chain along the a axis.Therefore,in the three complexes,the C-H···halogen hydrogen bonds dominate their crystal structures.Additionally,The UV luminescent properties of complexes 1-3 were investigated. 展开更多
关键词 copper(Ⅰ) complex c-h···halogen hydrogen bond crystal structure 3 3'-dimethoxy-6 6'-dimethyl-2 2'-bipyridine
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Cyclization and halogenation of substituted o-allylphenols with diacetoxyiodobenzene in the presence of iodine or bromine
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作者 Qi Zhong Zhou Chun Lin He Zhen Chu Chen 《Chinese Chemical Letters》 SCIE CAS CSCD 2008年第6期661-664,共4页
Substituted 2-halomethyl-2,3-dihydrobenzofurans were synthesized in one pot and in mild yield from substituted o-allylphenols with diacetoxyiodobenzene in the presence of 12 or Br2 in dry CH2Cl2 under reflux.
关键词 2-Halomethyl-2 3-dihydrobcnzofuran Diacetoxyiodobenzene CYCLIZATION halogenation
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Quantitative structure-activity study on the reductive dehalogenation potency of the halogenated aromatics
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作者 Huang Qingguo Wang Liansheng Han Shuokui(Department of Environmental Science and Technology, Nanjing University , Nanjing 210008 , China) 《Journal of Environmental Sciences》 SCIE EI CAS CSCD 1995年第2期183-189,共7页
Quantitativestructure-activitystudyonthereductivedehalogenationpotencyofthehalogenatedaromaticsHuangQingguo;... Quantitativestructure-activitystudyonthereductivedehalogenationpotencyofthehalogenatedaromaticsHuangQingguo;WangLiansheng;Han... 展开更多
关键词 quantitative structure - activity relationship(QSAR) halogenated arornatics dehalogenation poten-cy discriminant function.
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Model for a UV Laser Based Local Polymer Surface Halogenation Process Using a Gaseous Precursor
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作者 Simon Kibben 《Modeling and Numerical Simulation of Material Science》 2014年第1期14-19,共6页
An analytical model describing the physical relations of a UV-based process for halogenation of polymeric surfaces is presented. The process allows, depending on the parameters, a local halogenation with sharp edges a... An analytical model describing the physical relations of a UV-based process for halogenation of polymeric surfaces is presented. The process allows, depending on the parameters, a local halogenation with sharp edges at the interfaces to areas where no halogenation is desired. This is achieved via a nonreactive halogen-containing gaseous precursor and a UV source providing photons which dissociate the precursor photolytically. Thus, only where the UV photons affect the precursor, halogens are generated and the polymer is being halogenated. 展开更多
关键词 LOCAL SURFACE halogenation POLYMER MODIFICATION UV-Laser-Based SURFACE MODIFICATION
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Tuning of interactions between cathode and lithium polysulfide in Li-S battery by rational halogenation
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作者 Samson O.Olanrele Zan Lian +2 位作者 Chaowei Si Shuo Chen Bo Li 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2020年第10期147-152,共6页
Li-S batteries have aroused intense interests as one of the most promising high-energy-density storage technology.However,the complex undesired shuttle effect induced by dissolution and diffusion of lithium polysulfid... Li-S batteries have aroused intense interests as one of the most promising high-energy-density storage technology.However,the complex undesired shuttle effect induced by dissolution and diffusion of lithium polysulfide intermediates remains the major setback of this technology.Chemical modification of carbon cathode through heteroatom-doping is widely accepted as an effective method to inhibit the shuttle effect in Li-S battery cathode.Herein,using first principle calculations,we systematically examined the interaction between halogenated graphene and lithium polysulfide species.It is found that the halogen dopants(F,Cl,Br,I)significantly modify the local electronic structure of adsorption site and further induce a polarization to trap the polysulfides.Interestingly,a concave curve is observed from F to I for lithium polysulfide adsorption rather than a linear relation.The exceptions demonstrated from iodine dopant is carefully analyzed and attributed to its unique charge state.Moreover,boron as second dopant further strengthens the interaction between halogenated graphene and polysulfide molecule.Based on halogenation strategy,lithium polysulfide/cathode interactions are tuned in a wide range,which can also be of great importance to accelerate redox reaction in Li-S battery.Overall,an effective method by halogenation is verified to regulate the adsorption of lithium polysulfide and also enhance the reaction kinetics of the Li-S battery system. 展开更多
关键词 Li-S battery halogenation Shuttle effect CO-DOPING
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Environmentally Benign Electrophilic Halogenation of Naphthalenes by H<sub>2</sub>O<sub>2</sub>—Alkali Metal Halides in An Aqueous Cationic Micellar Media
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作者 Kancharla Rajendar Reddy Sariah Sana +2 位作者 Kusampally Uppalaiah Kamatala Chinna Rajanna Puppala Veerasomaiah 《International Journal of Organic Chemistry》 2012年第3期254-261,共8页
An efficient and greener protocol for the synthesis of 1-halo-naphthols by the action of hydrogen peroxide and alkali metal halides in aqueous micellar media is been described in the present work. This is an environme... An efficient and greener protocol for the synthesis of 1-halo-naphthols by the action of hydrogen peroxide and alkali metal halides in aqueous micellar media is been described in the present work. This is an environmentally clean and safe procedure, which involved insitu generation of the active halogen in presence of alkali halides. Cationic surfactants such as cetyltrimethylammoniumbromide (CTAB) and cetyltrimethylammoniumchloride (CTAC) were found to facilitate efficiency of halogenation in aqueous media. 展开更多
关键词 Green Chemistry halogenation Synthesis 1-halo-naphthols Alkali Metal Halides 2-Naphthols AQUEOUS Micellar Media CTAB (Cetyl Trimethyl AMMONIUM Bromide) CTAC (Cetyl Trimethyl AMMONIUM Chloride)
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基于过硫酸钠氧化的烯丙位C-H键官能团化的研究
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作者 杨彩云 张舒婷 +6 位作者 白露露 徐晴 潘庚辰 魏玮 潘馨慧 刘青广 王金辉 《广州化工》 CAS 2023年第5期67-70,80,共5页
设计一种Na_(2)S_(2)O_(8)与金属Cu^(2+)和Co^(2+)催化氧化的交叉脱氢偶联反应,从而实现烯丙位C-H键官能团化的新方法。研究发现,以0.2当量CuSO 4和0.1当量CoCl 2为催化剂,2.0当量Na_(2)S_(2)O_(8)为氧化剂,乙腈为溶剂,80℃下进行环己... 设计一种Na_(2)S_(2)O_(8)与金属Cu^(2+)和Co^(2+)催化氧化的交叉脱氢偶联反应,从而实现烯丙位C-H键官能团化的新方法。研究发现,以0.2当量CuSO 4和0.1当量CoCl 2为催化剂,2.0当量Na_(2)S_(2)O_(8)为氧化剂,乙腈为溶剂,80℃下进行环己烯与乙酰丙酮的交叉脱氢偶联反应,可以实现环己烯烯丙位C-H键的直接官能团化,此方法也适用于与环己烯和乙酰丙酮相似结构的化合物,产率41%~56%。该方法成本低、毒性小、操作简单且易于实现烯丙位C-H键的直接官能团化,具有底物及亲核试剂应用的广泛性。 展开更多
关键词 过硫酸钠 烯丙位c-h键活化 交叉脱氢偶联反应
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Regioselective Halogenation and Dimerization of 2-Naphthol and 6-Br-2-naphthol by the Use of Inorganic-Supported Copper (II) Halides
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《厦门大学学报(自然科学版)》 CAS CSCD 北大核心 1999年第S1期286-286,共1页
关键词 II HALIDES Regioselective halogenation and Dimerization of 2-Naphthol and 6-Br-2-naphthol by the Use of Inorganic-Supported Copper BR
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K_(2)CO_(3)辅助钯催化C-H活化反应的理论研究
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作者 白文己 石宇冰 +2 位作者 李江平 于嘉玮 母伟花 《广州化工》 CAS 2023年第2期6-12,24,共8页
K_(2)CO_(3)是一种常见的碱金属碳酸盐,在有机合成中常被用作碱性添加剂,以加快过渡金属尤其是钯催化C-H活化反应的速率或提高反应产率。因此,研究K_(2)CO_(3)辅助的钯催化C-H活化反应成为近年来有机合成和理论计算领域的热点之一。本... K_(2)CO_(3)是一种常见的碱金属碳酸盐,在有机合成中常被用作碱性添加剂,以加快过渡金属尤其是钯催化C-H活化反应的速率或提高反应产率。因此,研究K_(2)CO_(3)辅助的钯催化C-H活化反应成为近年来有机合成和理论计算领域的热点之一。本文对近十年来K_(2)CO_(3)辅助钯催化C-H活化反应的最新理论研究进展进行分类总结,重点对钯催化C-H活化反应的微观机理、K_(2)CO_(3)的作用机制等进行了深入探讨,并对该领域的发展前景进行展望。 展开更多
关键词 K_(2)CO_(3) c-h活化 钯催化 反应机理 反应选择性
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Textural and compositional variation of mica from the Dexing porphyry Cu deposit:constraints on the behavior of halogens in porphyry systems
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作者 Yan Liu Jian-Feng Gao +1 位作者 Liang Qi Kang Min 《Acta Geochimica》 EI CAS CSCD 2023年第2期221-240,共20页
The Dexing porphyry deposit is the largest porphyry Cu–Mo–Au deposit in South China.Biotite composition can record the physicochemical conditions and evolution history of magmatic-hydrothermal system.Biotite from th... The Dexing porphyry deposit is the largest porphyry Cu–Mo–Au deposit in South China.Biotite composition can record the physicochemical conditions and evolution history of magmatic-hydrothermal system.Biotite from the Dexing porphyry deposit could be divided to three types:primary magmatic biotite(Bi-M),hydrothermal altered magmatic biotite(Bi-A)and hydrothermal biotite(Bi-H).The temperature of Bi-M and Bi-H range from 719 to 767℃ and 690 to 727℃,respectively.Both magmatic and hydrothermal biotite have high Fe^(3+)/Fe^(2+)ratios(from 0.18 to 0.24)and XMgvalues(from 0.57 to 0.66),indicating a high oxygen fugacity.BiM has F lower than Bi-A and Bi-H(up to 0.26 wt%),but has Cl(Cl=0.18–0.30 wt%)similar to Bi-A and Bi-H(Cl=0.21–0.35 wt%),suggesting that high Cl/F ratios of early hydrothermal fluid may result from the exsolution from high Cl magma.From potassic alteration zone to phyllic and propylitic alteration zones,Cl decreases with increasing Cu,whereas F increases roughly.Therefore,Cl mostly originate from magma,but enrichment of F possibly results from reaction of fluids and Neoproterozoic strata.Negative correlation between Cl and Cu indicates that Cl might act as an important catalyst during Cu mineralization process.Biotite from Dexing has similar halogen compositions to other porphyry Cu-/Mo deposits in the world.Chlorine contents of hydrothermal fluid may be critical for Cu transportation and enrichment,while consumption of Cl would promote Cu deposition. 展开更多
关键词 halogen Dexing porphyry deposit BIOTITE GEOCHEMISTRY Porphyry Cu deposit
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双功能CuX_(2)参与的芳基-7-氮杂吲哚邻位C-H键的卤化反应
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作者 周鲜颖 张媛媛 刘珊珊 《广州化学》 CAS 2023年第4期57-60,共4页
开发了一种双功能铜参与催化芳基-7-氮杂吲哚的芳基卤化反应,该方法以N-苯基-7-氮杂吲哚类化合物为底物,CuX_(2)既为卤素源,又可以作为C-H键活化试剂,在无外加催化剂下,通过7-氮杂吲哚的导向作用选择性地发生芳环的亲电卤代反应。经过... 开发了一种双功能铜参与催化芳基-7-氮杂吲哚的芳基卤化反应,该方法以N-苯基-7-氮杂吲哚类化合物为底物,CuX_(2)既为卤素源,又可以作为C-H键活化试剂,在无外加催化剂下,通过7-氮杂吲哚的导向作用选择性地发生芳环的亲电卤代反应。经过一系列条件筛选之后得到最佳反应条件为:CuCl_(2)(0.65eq)为催化剂,DMAP(0.25 eq)为配体,苯甲酸(1.2 eq)为添加剂,氯苯为溶剂,于120℃下反应24小时,产率最高达到95%。除7-氮杂吲哚导向基团外,还成功兼容了吡啶、喹啉等导向基团,该反应可应用于较多的底物范围。 展开更多
关键词 双功能 铜催化 7-氮杂吲哚 卤化 c-h键活化 自催化剂
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铜催化C-H活化/C-S偶联反应合成环烷基芳基硫醚
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作者 吴嘉豪 吴杨昊 +4 位作者 宋绍睿 杨毓恒 徐英倩 黄凌 陈定奔 《合成化学》 CAS 2023年第3期193-198,共6页
为设计一种利用廉价催化剂以达成C-H活化构建C-S的方法,本文研究了铜催化C-H活化/C-S偶联反应合成系列环烷基芳基硫醚化合物。以芳基磺酰肼与环烷烃为原料,溴化亚铜为催化剂,二叔丁基过氧化物(DTBP)为氧化剂,120℃反应24 h,经氧化脱氮C-... 为设计一种利用廉价催化剂以达成C-H活化构建C-S的方法,本文研究了铜催化C-H活化/C-S偶联反应合成系列环烷基芳基硫醚化合物。以芳基磺酰肼与环烷烃为原料,溴化亚铜为催化剂,二叔丁基过氧化物(DTBP)为氧化剂,120℃反应24 h,经氧化脱氮C-H活化/C-S偶联串联反应过程,合成了系列环烷基芳基硫醚化合物。该反应适合环戊烷、环己烷、环庚烷、环辛烷和环十二烷等环烷烃和不同取代基团(甲氧基、硝基、氯和甲基)的芳基酰肼,合成得到了18个芳基硫醚类化合物,产率为41%~72%。其结构经^(1)H NMR、^(13)C NMR和HR-MS进行了表征。 展开更多
关键词 铜催化 c-h活化 C-S偶联 环烷基芳基硫醚 环烷烃
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自由基协助的C-H键官能团化反应研究进展
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作者 杨金山 冯尧清 +3 位作者 姚星辉 袁森 符艺 毛艺洁 《西华大学学报(自然科学版)》 CAS 2023年第4期96-112,共17页
过去几十年中,过渡金属催化的碳氢键官能团化反应研究取得了重要进展。最近,自由基协助的碳氢键官能团化反应正逐渐引起化学工作者的兴趣。依据自由基产生方式,本文分为光、热致自由基协助碳氢键官能团化反应和电致自由基协助碳氢键官... 过去几十年中,过渡金属催化的碳氢键官能团化反应研究取得了重要进展。最近,自由基协助的碳氢键官能团化反应正逐渐引起化学工作者的兴趣。依据自由基产生方式,本文分为光、热致自由基协助碳氢键官能团化反应和电致自由基协助碳氢键官能团化反应两个部分,随后在各部分按照成键类型进行论述。综合比较上述两类自由基协助的碳氢键官能团化研究成果,相较于光、热致自由基协助的碳氢键官能团化反应,电致自由基反应有效避免了前者的缺陷,因此发展电化学碳氢键活化反应是自由基协助的碳氢键官能团化反应的重要研究方向。 展开更多
关键词 自由基 c-h键活化 官能团化反应 光致自由基 热致自由基 电致自由基 有机合成
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