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| 1 | Dimethyl ether carbonylation over zeolites显示文摘Syngas to ethanol, consisting of dimethyl ether(DME) carbonylation to methyl acetate(MA) over zeolites and MA hydrogenation to ethanol on copper catalyst, has been developed in recent years.DME carbonylation over zeolites, a key step in this new process, has attracted increasing attention due to the high reaction efficiency and promising industrial application.In recent years, continuous efforts have been made on improving the activity and stability of the zeolites.From a mechanistic point of view, DME carbonylation to MA, involving the formation of C–C bond, is achieved via the Koch-type CO insertion into DME within the 8-member ring(8-MR) pores of zeolites, typically HMOR and HZSM-35.The unique geometric configuration of the 8-MR pore endowed the formation of the key intermediate(acetyl, CH3CO^*), possibly by a spatial confinement of the transition state during CO insertion into the surface O–CH3 group.This review article summarizes the main progress on zeolite-catalyzed DME carbonylation, including reaction kinetics and mechanism, theoretical calculations, and experimental strategies developed for populating acid sites and engineering pore structure of the zeolites in order to enhance the overall performance. | Ensheng Zhan Zhiping Xiong Wenjie Shen | 2019 | Journal of Energy Chemistry2019，28，9： | 8 |
| 2 | Isolated zinc in mordenite stabilizing carbonylation of dimethyl ether to methyl acetate显示文摘Herein, we prepared a series of H-Zn-mordenite (H-Zn-MOR) catalysts by adding zinc source into the initial sols during the synthesis of mordenite (MOR). The results indicated that isolated Zn ions were highly dispersed in the catalysts. The addition of zinc led to the increase of Si/Al in the framework of MOR,the change of the distribution of acid sites and the change of acid strength. We investigated the catalytic performance of the H-Zn-MOR catalysts and the HMOR catalysts for carbonylation of dimethyl ether to methyl acetate. The addition of zinc improved the catalytic performance and made the drop of the conversion over the Zn-0.003 and Zn-0.005 catalysts to be about the half of that over the HMOR catalyst.We attributed it to the change of the acid properties, which further change the rate of coke deposition. | Zhitao Zhang Na Zhao Kui Ma Qingpeng Cheng Jing Zhang Lirong Zheng Ye Tian Xingang Li | 2019 | Chinese Chemical Letters2019，30，2： | 3 |
| 3 | Highly active Pd containing EMT zeolite catalyst for indirect oxidative carbonylation of methanol to dimethyl carbonate显示文摘Palladium containing EMT zeolite catalyst(Pd/EMT) was prepared and used for the indirect oxidative carbonylation of methanol to dimethyl carbonate(DMC).The EMT zeolite was employed as a new catalyst support and compared with the conventional Pd containing FAU zeolite catalyst(Pd/FAU).The Pd/EMT in contrast to the Pd/FAU catalyst exhibited high intrinsic activity with the turnover frequency of 0.25 s^(-1) vs.0.11 s^(-1).The Pd/EMT catalyst showed high CO conversion of 82% and DMC selectivity of 79%,that maintained for at least 130 h,while the activity of the Pd/FAU catalyst rapidly deteriorated within 12 h.The enhanced interactions between Pd and EMT zeolite inhibited the sintering of palladium clusters and maintained the Pd2+ active sites in the Pd/EMT catalyst.The stabilization of the mono-dispersed Pd clusters within the EMT zeolite is paramount to the excellent performance of the catalyst for the indirect oxidative carbonylation of methanol to DMC. | Chunzheng Wang Weisong Xu Zhengxing Qin Hailing Guo Xinmei Liu Svetlana Mintova | 2021 | Journal of Energy Chemistry2021，30，1： | 3 |
| 4 | Ab initio study on the mechanism of rhodium-complex-catalyzed carbonylation of methanol to acetic acid显示文摘The whole catalytic cycle of the carbonylation of methanol to acetic acid catalyzed by Rh complex is theoretically studied. All structural geometries of reactant, intermediates, transition states and product are optimized at HF/LANL2DZ level under the ECP approximation. The potential energy profiles for elementary reactions of carbonylation are calculated respectively. The transition states are further confirmed by having one and only one imaginary vibrational frequency. The results indicate that the activation energy values of CH3I oxidative addition, carbonyl insertion and CH3COI reductive elimination fundamental steps are 216.03, 128.10 and 126.55 kJ/mol, respectively; and that the CH3I oxidative addition step is predicted to be the rate-determining one. | 雷鸣 冯文林 郝茂荣 冀永强 徐振锋 | 2001 | Science China Chemistry2001，44，5： | 3 |
| 5 | Mechanism of CO_(2)reduction in carbonylation reaction promoted by ionic liquid additives:A computational and experimental study显示文摘The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation,which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl~B3MimCl>BmmimCl~LiCl.Taking the hydroesterification with MeOH as a representative example,BmimCl bearing C-H functionality at the C^(2)site of the cation assists the reduction of CO_(2)to CO as a hydrogen donor medium,with the anion and cation acting in a synergistic fashion.Subsequent insertion of CO_(2)into the formed Ru-H bond with the assistance of chloride anion produces the Ru-COOH species,which ultimately accelerates the activation of CO_(2). | Kai-Lun Bi Bao-Hua Xu Wei-Lu Ding Li-Jun Han Lin Ji | 2023 | Green Energy & Environment2023，8，1： | 2 |
| 6 | Palladium-Catalyzed Tandem Carbonylative Aza-Wacker-Type Cyclization of Nucleophile Tethered Alkene to Access Fused N-Heterocycles显示文摘Although tandem reactions offer rapid access to structurally complex molecules in one-pot reaction,the selectivity issue needs to be addressed particularly when incompatible step reactions are involved.Herein,we report the selective synthesis of fused N-heterocycles from nucleophile-tethered alkenylamide and carbon monoxide via palladium(Pd)-catalyzed tandem carbonylative aza-Wacker-type cyclization.The electron-deficient nature of amide N—H and the intramolecular coordination of Pd with alkene accelerate the aminopalladation and effectively prevent the side oxidative carbonylation of diamine moiety to form urea.It is also found that the reported acyl Pd chloride intermediate may not be involved in this tandem cyclization.This work not only provides an efficient synthetic route to fused 1,4-diazepanones and 1,4-diazepanes but also inspires further development of tandem reactions for the diverse synthesis of heterocycles. | Lijun Shi Mingshan Wen Fuwei Li | 2021 | Chinese Journal of Chemistry2021，39，2： | 2 |
| 7 | Oxycarbonylation of methanol over modified CuY: Enhanced activity by improving accessibility of active sites显示文摘CuY zeolite is a promising catalyst in the field of manufacturing dimethyl carbonate(DMC) through oxidative carbonylation of methanol. Cu^+ exchanged with Br?nsted acid sites are supposed to be active for this reaction. However, the location of Cu^+ in small cages can not interact with reactants because of steric hindrance, which lead to a waste of Cu species. In this work, NH_4F solution was used to modify the pore structure of zeolite Y by etching the framework T atoms. Physical and chemical adsorption of probe molecules with different size are used to determine the changes of porosity as well as the accessibility of Cu^+ sites. At an optimized etching time, the small cages were opened with maintained zeolitic framework. As a result, more Cu^+ species located in small cages become accessible to reactants, which contributes to the enhanced activity in this reaction. | Hexin Zhou Shengping Wang Baowei Wang Xinbin Ma Shouying Huang | 2019 | Chinese Chemical Letters2019，30，3： | 2 |
| 8 | Kinetics Modeling of Calcium Formate Synthesis by Calcium Hydroxide Carbonylation显示文摘The synthesis of calcium formate by Ca(OH)_2 carbonylation was studied in a semi-batch stirred tank.The reaction mechanism was analyzed theoretically and the rate of each step was compared.The influence ofreaction conditions on the formation of calcium formate was investigated.The results indicate that the rate-controlling step is the reaction between dissolved CO and dissolved Ca(OH)_2,and the gaseous diffusion resistance can be eliminated when the stirring speed reached 1000 r/min.Furthermore,the reaction kinetics was studied at a stirring speed of 1000 r/min,temperature of 423–453 K,pressure of 2.0–3.5 MPa and different initial concentrations of Ca(OH)_2.An effective method was proposed to measure the reaction rate of CO.A mathematical model was developed using the dual-film theory,and the parameters were obtained using regression of experimental data.The reaction rates calculated using the kinetics model were compared with experimental data.The results show that the deviations are within ±10%,proving that the established model is valid and can provide a basis for industrial amplification. | Zhenhua Li Chunfang Xie Weihan Wang Jing Lv Xinbin Ma | 2018 | Transactions of Tianjin University2018，24，2： | 1 |
| 9 | Radical Carbonylation under Low CO Pressure:Synthesis of Esters from Activated Alkylamines at Transition Metal-Free Conditions显示文摘Main observation and conclusion High CO pressure(>40 bar)is usually needed in radical carbonylation reactions in the absence of metal catalyst.In this communication,we developed a transition-metal-free radical carbonylation of activated alkylamines with phenols and alcohols under low CO pressure(1-6 bar).Various esters were obtained in moderate to excellent yields under simple reaction conditions with good functional group compatibility. | Fengqian Zhao Han-Jun Ai Xiao-Feng Wu | 2021 | Chinese Journal of Chemistry2021，39，4： | 1 |
| 10 | Aberrant post-translational protein modifications in the pathogenesis of alcohol-induced liver injury显示文摘It is likely that the majority of proteins will undergo post-translational modification, be it enzymatic or non-enzymatic. These modified protein(s) regulate activity, localization and interaction with other cellular molecules thereby maintaining cellular hemostasis. Alcohol exposure significantly alters several of these post-translational modifications leading to impairments of many essential physiological processes. Here, we present new insights into novel modifications following ethanol exposure and their role in the initiation and progression of liver injury. This critical review condenses the proceedings of a symposium at the European Society for the Biomedical Research on Alcoholism Meeting held September 12-15, 2015, in Valencia, Spain. | Natalia A Osna Wayne G Carter Murali Ganesan Irina A Kirpich Craig J Mc Clain Dennis R Petersen Colin T Shearn Maria L Tomasi Kusum K Kharbanda | 2016 | World Journal of Gastroenterology2016，22，27： | 1 |
| 11 | 溴化1,10-菲啰啉铜配合物催化甲醇氧化羰基化合成碳酸二甲酯(英文)显示文摘In order to develop the catalysts with low corrosiveness for the oxidative carbonylation of methanol to dimethyl carbonate(DMC), Cu Br2 was selected as the metal source to prepare Cu coordination compounds, Cu(phen)Br2,[Cu(phen)2Br]Br and [Cu(phen)3]Br2(phen = 1,10-phenanthroline). These complexes were characterized by thermogravimetric analysis and temperature-programmed reduction. Their catalytic performances were investigated. It was found that the metal coordination environments and thermal stability of the complexes played an important role in their catalytic activities. Cu(phen)Br2exhibited the highest activity due to the lowest steric hindrance, the most positions occupied by the bromide ions and the highest thermal stability. The turnover number was up to 47.6 DMC mol·(Cu mol)-1with selectivity of 92.8% under conditions of 120 °C, ratio of partial pressure of CO to O2 of 19:1(below the explosion limit of CO) and catalyst concentration of 0.011 mol·L-1.Furthermore, a plausible reaction mechanism was suggested on the basis of the experimental data. | 杜治平 熊利花 林志坤 李徐立 丁一刚 吴元欣 | 2014 | Chinese Journal of Chemical Engineering2014，22，10： | 1 |
| 12 | A Novel Synthesis of Dimethyl Malonate by Carbonylation of Methyl Chloroacetate Catalyzed by Cobalt Complex显示文摘A novel method of preparing dimethyl malonate by carbonylation of methyl chloroacetate catalyzed by Na[Co(CO)4] was proposed. Na[Co(CO)4] was synthesized in situ in the presence of Na2S2O3and iron powder. The effects of some reaction parameters such as temperature, CO pressure and the concentrations of catalyst on the yields of dimethyl malonate were discussed. The kinetic data were studied and a possible reaction mechanism was proposed. | Wei Hong SONG, Xuan Zhen JIANG* Department of Chemistry, Zhejiang University, Hangzhou 310027 | 2001 | Chinese Chemical Letters2001，12，3： | 0 |
| 13 | Preparation of 9,13-dicis double bonds locked retinoids显示文摘Synthesis of two retionids in which the 9, 13-dicis double bonds were locked in cycloalkene or thiophene was described. The key steps were the Wittig olefination of phosphonium salt 3 and 23 with aldehyde 14, followed by carbonylation of vinyl bromide 17 and 24 with carbon monoxide in the presence ofPd(PPh3)4. | 卿凤翎 岳祥军 | 2000 | Chinese Journal of Chemistry2000，18，1： | 0 |
| 14 | Cu/Pd-catalyzed borocarbonylative trifunctionalization of alkynes and allenes:synthesis ofβ-geminal-diboryl ketones显示文摘Functionalized bisboryl compounds have recently emerged as a new class of synthetically useful building blocks in organic synthesis.Herein,we report an efficient strategy to synthesizeβ-geminal-diboryl ketones enabled by a Cu/Pd-catalyzed borocarbonylative trifunctionalization of readily available alkynes and allenes.This reaction promises to be a useful method for the synthesis of functionalizedβ-geminal-diboryl ketones with broad functional group tolerance.Mechanistic studies suggest that the reaction proceeds through borocarbonylation/hydroboration cascade of both alkynes and allenes. | Yang Yuan Fu-Peng Wu Anke Spannenberg Xiao-Feng Wu | 2021 | Science China Chemistry2021，64，12： | 0 |
| 15 | Generation and transformation ofα-oxy carbene intermediates enabled by copper-catalyzed carbonylation显示文摘Since the Fischer-Tropsch reaction was discovered by Otto Roelen in 1938,transition metal-catalyzed carbo-nylation reactions come in as one of the most important methods for preparing carbonyl-containing and carbon chain-increased compounds.As a result,the field of carbonylation research has received considerable attention over the past decades and continues to increase.With the continuous development of carbonylation and the in-depth study of the mechanism,more mechanistic details and variations have been revealed,which provide more possibilities for organic synthesis.Recently,copper catalysis has been introduced to the carbonylative functio-nalization of alkenes,thus enabling the rapid assembly of functionalized carbonyl compounds from simple starting materials.In this Account,we summarize the new findings in the Cu-catalyzed borocarbonylation of alkenes based on the generation and transformation ofα-oxy carbene intermediates.We believe that the results presented in this Account will further inspire the design of new carbonylation reactions. | Yang Yuan Xiao-Feng Wu | 2024 | Green Carbon2024，2，1： | 0 |
| 16 | Kinetic Study of Homogeneous Rhodium-Catalyzed Ethanol Carbonylation Using Bis(diphenylphosphino)methane Ligands显示文摘Homogeneous rhodium-catalyzed carbonylation of ethanol is a potential route for the preparation of propionic acid,although its commercialization has been hindered by a low reaction rate.In this work,various bis(diphenylphosphine)ligands were evaluated in the rhodium-catalyzed reaction system in an effort to improve the reaction rate.By comparing the space-time yield and selectivity of the catalytic system in a Hastelloy autoclave reactor,the effects of the choice of ligand,ligand:rhodium ratio,carbon monoxide pressure,temperature,rhodium concentration,ethyl iodide content,and lithium iodide content were investigated.In the presence of the ligand bis(diphenylphosphino)methane disulfide(dppmS_(2)),the activity of the catalyst was improved significantly.The results revealed that the optimal conditions included a dppmS_(2):Rh molar ratio of 0.5:1,a rhodium concentration of 1000μg/g,an ethyl iodide content of 10%,and a lithium iodide content of 10%.The most suitable reaction temperature and carbon monoxide pressure were 463 K and 3.0 MPa,respectively,which resulted in a maximum space-time yield of 4.30 mol/(h·L).A kinetic model was established in the temperature range of 442-463 K,and the model data were regressed and validated,revealing an activation energy of 28.01 kJ/mol.Residual analysis and statistical tests demonstrated the reliability of the kinetic experiments. | Long Haoyu Xu Lin Song Jianhua Wang Xiaoping Wang Weichong Liu Dianhua | 2022 | China Petroleum Processing & Petrochemical Technology2022，24，2： | 0 |
| 17 | The Activation and Carbonylation of the C-Cl Bond Catalyzed by Transition-Metal Complexes显示文摘Diethyl malonate was synthesized by transition-metal catalyzed alkoxycarbonylation of ethyl chloroacetate. The results show that the conversion of ethyl chloroacetate is greater than 92%, and the selectivity to diethyl malonate is 67.5%. | Wei Zhong ZHENG Wen WAN Fu Jiang DING Liang Fu ZHANG(Chengdu Institute of Organic Chemistry, Academia Sinica, P. O. Box 415, Chengdu 610041 Laboratory of Organomctallic Chemistry, Shanghai Institute of Organic Chemstry, Academia Sinica, Shanghai 20003 | 1998 | Chinese Chemical Letters1998，9，4： | 0 |
| 18 | Kinetic Study of Carbonylation of Methyl Acetate to Acetic Anhydride Catalyzed by Rhodium Complex with a Ligand of Copolymer of Vinyl-acetic Ester and Acrylonitrile显示文摘The copolymer of vinyl acetic ester and acrylonitrile is used to react with [Rh(CO)2Cl]2to form a complex which can be used in the carbonylation of methyl acetate to acetic anhydride. Many factors affecting the reaction rate, catalytic activity and selectivity have been investigated. The reaction rate depends on rhodium complex and methyl iodide, and is differant from that of homogenous small molecular rhodium complex catalyst. It is revealed thatthe reaction rate is zero order in CO, first order in Rh and LiOAc, but the order in CH3I is complicated. The causes of these phenomena are discussed based on the mechanism of carbonylation of methyl acetate. | 王晓筠 | 1997 | High Technology Letters1997，3，2： | 0 |
| 19 | VAPOR PHASE CARBONYLATION OF ETHANOL WITH Ni-Zn/C CATALYST显示文摘Vapor phase carbonylation of ethanol with Ni/C and Ni-Zn/C catalyst was investigatedunder atmospheric pressure.Ni-Zn/C was found to have a significantly higher activity andselectivity than Ni/C.Effects of Zn and Ni loading on ethanol conversion and productdistributions were also investigated,and the sequence of metal loading was compared.The cata-lyst was characterized by XRD(X-ray diffraction)and SEM-EDS.The spectra of XRDdemonstrated that the catalyst structure was changed from crystalline to non-crystalline in theprocess of carbonylation.Stable iodide compound was formed due to the interaction betweenC2H5I and active metals.The authors believe that the active phase of carbonylation might havebeen non-crystalline. | 彭峰 黄仲涛 | 1997 | Chinese Journal of Chemical Engineering1997，5，3： | 0 |
| 20 | Cationic Palladium Catalyzed Nonalternating Copolymerization of Ethylene with Carbon Monoxide: Microstructure Analysis and Computational Study显示文摘The introduction of carbonyl group with a high density in polyethylene backbone corresponds to polyketone materials,which features excellent mechanical strength,crystallinity,photodegradability,hydrophilicity,surface and barrier properties.Due to the extremely high binding affinity of carbon monoxide(CO)and kinetic preference for its subsequent insertion,the formation of nonalternating structure with extra ethylene insertion is exceptionally challenging,however,this nonalternating strategy is of significant importance for polymer modification in term of processing and solubility.Here,we have communicated our study on cationic palladium coordinated diphosphazane monoxide(PNPO)for the nonalternating copolymerization of ethylene with CO,the systematical investigation on the amine and phosphine oxide moieties in PNPO platform in term of electronic and steric modulation has been performed.It is discovered that the installation of aliphatic structure on amine moiety favors the improvement of catalyst activity and longevity,while the amino groups on phosphine oxide moiety promotes the nonalternating copolymerization.In particular,we have computationally investigated herein the aspects of the nonalternating degree by comparing with PNPO platform and 1,3-bis(diphenylphosphanyl)propane ligands based palladium catalysts.These mechanistic studies can help to understand the catalyst structure and polyketone property relationships and shed light on future design of high-performance copolymerization catalysts. | Shi-Huan Li Ru-Chao Pan Bai-Hao Ren Jian-Wei Yang Xiaohui Kang Ye Liu | 2023 | Chinese Journal of Chemistry2023，41，4： | 0 |
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