Dimethyl carbonate synthesis catalyzed by DABCO-derived basic ionic liquids via transesterification of ethylene carbonate with methanol

Easily prepared DABCO-derived (1,4-diazobicyclo[2.2.2]octane) basic ionic liquids were developed for an efficient synthesis of dimethyl carbonate (DMC) via the transesterification of ethylene carbonate (EC) with methanol. 1-Butyl-4-azo-1-azoniabicyclo[2.2.2]octane hydroxide ([C₄DABCO]OH) exhibited high catalytic activity and 81% DMC yield together with 90% EC conversion was obtained under mild reaction conditions. Notably, the catalyst could be recycled for four times without loss of catalytic activity. Moreover, a possible mechanism was also discussed.     

Synthesis of dimethyl carbonate (dmc) from co2, ethylene oxide and methanol using heterogeneous anion exchange resins as catalysts

Summary A two-step synthesis of dimethyl carbonate (DMC) from ethylene oxide (EO), carbon dioxide and methanol using heterogeneous anion exchange resins as catalysts is reported. The first step is the reaction of EO with CO₂ to form ethylene carbonate (EC), and the second one the transesterification of EC with methanol to yield DMC. Effect of various reaction parameters on the activity and selectivity of the catalysts used was investigated. After the first step, the crude mixture containing EC was directly reacted with methanol in the presence of a heterogeneous anion exchange resin catalyst to produce DMC in high yield and selectivity. Our process is highly economic.     

Synthesis of dimethyl carbonate from methanol and supercritical carbon dioxide

The synthesis of dimethyl carbonate (DMC) from methanol and supercritical carbon dioxide over various base catalysts has been studied. Compounds of group-I elements (Li, Na and K) were used as base catalysts. The promoter and the dehydrating agent were also used to enhance the yield of DMC. The effects of the catalysts, promoter and dehydrating agent on the yield of DMC were investigated. By-products such as dimethyl ether (DME) and C₁–C₂ hydrocarbons were formed with the DMC as a main product. The yield of DMC with different alkali metal catalysts ranked in the following order: K > Na > Li. The catalysts of the metal-CO₃ compounds were more effective than the metal-OH compounds in DMC synthesis. The maximum DMC yield reached up to about 12 mol% in the presence of K₂CO₃ (catalyst), CH₃I (promoter) and 2,2-dimethoxypropane (dehydrating agent) at 130–140°C and 200 bar. The reaction mechanism of DMC synthesis from methanol and supercritical carbon dioxide was proposed.     

Synthesis and characterization of bis[2-(1H-benzimidazol-2-yl)benzoato]nickel(II), and its use for preparation of dimethyl carbonate from methanol and CO2

A new complex, bis[2-(1H-benzimidazol-2-yl)benzoato]nickel(II) (NiL₂), has been synthesized and characterized. It was used as catalyst for synthesis of dimethyl carbonate (DMC) from methanol and CO₂ in the presence of dicyclohexyl carbodiimide (DCC) as promoter. The effects of temperature, reaction time, and amount of catalyst on the reaction, and the reusability of the catalyst, were investigated. A catalytic mechanism is proposed. The results revealed that NiL₂ + DCC had excellent catalytic activity, because this catalytic system promoted facile formation of DMC, with acceptable yield, in the presence of a small amount of NiL₂ and under moderate conditions (80 °C, 1.0 MPa). Moreover, the catalyst has been consecutively used five times without significant loss of activity.     

Protic ionic liquid-promoted synthesis of dimethyl carbonate from ethylene carbonate and methanol

In this work,the protic ionic liquid[DBUH][Im](1,8-diazabicyclo[5.4.0]-7-undeceniumimidazolide)was developed as an efficient catalyst for the transesterification of ethylene carbonate with methanol to produce dimethyl carbonate.At 70℃,up to 97%conversion of ethylene carbonate and 91%yield of dimethyl ca rbonate were obtained with 1 mol%[DBUH][Im](relative to ethylene carbonate)as catalyst in 2 h.Even at room temperature,the conversion of ethylene carbonate can reach 94%and the yield of dimethyl carbonate can approach 81%for 6 h.Catalytic mechanism investigation showed the high catalytic efficiency of this ionic liquid results from the synergistic activation effect,wherein the cation can activate ethylene carbonate and the anion can activate methanol through hydrogen bond formatio n.Although the reusability of the ionic liquid need to be further improved,high efficiency and comme rcial availability of[DBUH][Im]render it a promising catalyst for the preparation of dimethyl carbonate.     

Catalysis over zinc-incorporated berlinite (ZnAlPO4) of the methoxycarbonylation of 1,6-hexanediamine with dimethyl carbonate to form dimethylhexane-1,6-dicarbamate

Background  

The alkoxycarbonylation of diamines with dialkyl carbonates presents promising route for the synthesis of dicarbamates, one that is potentially 'greener' owing to the lack of a reliance on phosgene. While a few homogeneous catalysts have been reported, no heterogeneous catalyst could be found in the literature for use in the synthesis of dicarbamates from diamines and dialkyl carbonates. Because heterogeneous catalysts are more manageable than homogeneous catalysts as regards separation and recycling, in our study, we hydrothermally synthesized and used pure berlinite (AlPO₄) and zinc-incorporated berlinite (ZnAlPO₄) as heterogeneous catalysts in the production of dimethylhexane-1,6-dicarbamate from 1,6-hexanediamine (HDA) and dimethyl carbonate (DMC). The catalysts were characterized by means of XRD, FT-IR and XPS. Various influencing factors, such as the HDA/DMC molar ratio, reaction temperature, reaction time, and ZnAlPO₄/HDA ratio, were investigated systematically.     

Transesterification of dimethyl carbonate with phenol over a bimetallic molybdenum and copper catalyst

Mo-Cu bimetallic oxides were found to be efficient heterogeneous catalysts for the transesterification of dimethyl carbonate (DMC) with phenol. When the reaction was carried out between 150 and 180°C, with a molar of Mo/Cu of 1:1, molar ratio of phenol/DMC of 1:1, 4.8 wt.% of the catalyst, 9 h, the conversion of phenol was 49.9%, and the total yield of MPC and DPC was 45.4%. Catalyst reuse showed a gradual decline in the catalytic activity. The decrease in catalytic activity might be due to leaching out of Mo and Cu, and/or carbon deposition.     

Synthesis of glycerol carbonate from glycerol and dimethyl carbonate catalyzed by K2CO3/MgO

A series of M/MgO (M?=?CaO, KNO₃, KOH, K₂CO₃) catalysts were prepared by a dry impregnation method and used for synthesis of glycerol carbonate from glycerol and dimethyl carbonate. It was found that K₂CO₃/MgO was the most efficient catalyst, with a glycerol carbonate yield of approximately 99% under the conditions: DMC/glycerol molar ratio 2.5:1, catalyst/raw material weight ratio 1%, reaction time 2?h, and reaction temperature 80?°C. FTIR, BET, TEM, and XRD were used for characterization of the catalyst and showed that the active sites seemed to be K₂O formed on the K₂CO₃/MgO catalyst. Finally, a recycling experiment showed that the catalyst was relatively stable and could be reused up to four times, at least, by regeneration.     

Synthesis of 2-amino-4,6-dimethoxypyrimidine with dimethyl carbonate as methylating agent

2-amino-4,6-dimethoxypyrimidine (ADM) was prepared from 2-amino-4,6-dihydroxypyrimidine (ADH) in the presence of potassium carbonate and phase transfer catalyst (PTC), with dimethyl carbonate (DMC) instead of conventional toxic reagents (such as haloalkane and dimethyl sulfate, etc.). The best conversion (87.7 %) of ADH and selectivity (40.5 %) toward ADM were achieved under optimized conditions: tetrabutyl ammonium bromide (TBAB) as PTC, n(ADH):n(DMC):n(TBAB):n(K₂CO₃) = 1:5:0.1:3, reaction time = 10 h and reaction temperature = 150 °C.     

NaF含量对以水滑石结构为前驱体的固体碱催化剂F-Ca-Mg-Al及碳酸二甲酯合成的影响（英文）

以碳酸丙烯(PC)和甲醇为原料,经酯交换反应合成的多功能、环保的碳酸二甲酯(DMC)是一种绿色、节能的合成方法。CaO固体碱催化剂对该反应具有良好的催化性能,但其再生性不理想。以F-Ca-Mg-Al水滑石(LDHs)为原料,制备了一系列不同Na F用量的固体碱催化剂,并对其进行了表征和酯交换反应测试。与不加氟的FCMA-0催化剂相比,经氟改性后的催化剂的比表面积、碱量、催化活性等性能均有明显提高。催化活性由高到低依次为:FCMA-0.8> FCMA-0.4>FCMA-1.2> FCMA-1.6> FCMA-0,这与总碱位量和强碱位量一致。FCMA-0.8催化剂活性最好,与纯CaO催化剂的相当,PC转化率为66.8%,DMC选择性为97.4%,DMC收率为65.1%。在10次循环使用后,FCMA-0.8催化剂的DMC收率仅下降3.9%(CaO催化剂下降33.2%)。FCMA-0.8在PC与甲醇酯交换制DMC方面具有良好的工业应用前景。     

Oxidative carbonylation of phenol to diphenyl carbonate catalyzed by palladium complexes bridged with N,N‐ligands over functionalized silica

Heterogeneous palladium catalysts anchored on functionalized silica were prepared by sol–gel methods and their catalytic properties for the oxidative carbonylation of phenol to diphenyl carbonate (DPC) were investigated. The catalysts were characterized by means of IR, XPS, EA and BET. The Pd loading in the heterogeneous catalysts and leaching in solution were detected by atomic absorption. The effects of different reaction parameters such as temperature, solvent and inorganic cocatalyst on the yield of DPC and Pd leaching were also studied. It was found that Cu₂O and tetrahydrofuran (THF) were the best partners with these heterogeneous catalysts. In the presence of 3 Å molecular sieves as dehydrating agent, the heterogeneous palladium catalyst prepared from 2‐acylpyridine revealed excellent catalytic performance and stability at 110 °C for 5 h, giving 13.7% yield of DPC based on phenol and 4.0% Pd loss in solution. The heterogeneous catalyst was more active and stable compared with traditional supported Pd? C catalyst under the same reaction conditions. Copyright © 2005 John Wiley & Sons, Ltd.     

Mg-Al-O-t-Bu hydrotalcite as an efficient catalyst for the transesterification of dimethyl carbonate with ethanol

Mg-Al-O-t-Bu hydrotalcite was synthesized and characterized by XRD, FT-IR and TGA-DTA. It was proved to be an active heterogeneous catalyst for the transesterification of dimethyl carbonate (DMC) with ethanol. When the reaction was carried out over Mg-Al-O-t-Bu hydrotalcite at 80°C, 7 h, molar ratio of ethanol to DMC 5:1, 1.0 wt.% of catalyst, the conversion of DMC was 86.4%, the selectivity to diethyl carbonate (DEC) was 61.2%. This heterogeneous catalyst could be used 5 times without loss of its activity.     

Dual nucleophilic catalysis with DABCO for the N-methylation of indoles

DABCO is an extremely active catalyst for the methylation of indoles in conjunction with dimethyl carbonate (DMC). This green chemistry is highly effective and produces N-methylindoles in nearly quantitative yields. The reaction sequence consists of competing alkylation and acylation pathways and involves 1,4-diazabicyclo[2.2.2]octane (DABCO) dually as a nucleophilic catalyst, ultimately resulting in a single product: the N-methylated indole.     

Fixation of CO_2 by electrocatalytic reduction to synthesis of dimethyl carbonate in ionic liquid using effective silver-coated nanoporous copper composites

<正>With high surface area,open porosity and high efficiency,a catalyst was prepared and firstly employed in electrocatalytic reduction of CO_2 and electrosynthesis of dimethyl carbonate(DMC).The electrochemical property for electrocatalytic reduction of CO_2 in ionic liquid was studied by cyclic voltammogram(CV).The effects of various reaction variables like temperature,working potential and cathode materials on the electrocatalytic performance were also investigated.80%yield of DMC was obtained under the optimal reaction conditions.     

酯交换法合成碳酸甲乙酯研究进展

碳酸甲乙酯(EMC)具有诸多优异的物理和化学性能,作为锂电池电解液溶剂已经被行业广泛认可,酯交换法是中国目前工业生产EMC的主要方法。本研究系统综述了碳酸酯交换反应热力学、动力学、均相及非均相催化剂、反应机理及反应工艺等方面的研究,重点评述了近五年酯交换法制备EMC的最新进展。均相催化剂中以pK_b值(碱度系数)为标准讨论了可溶碱类催化剂碱强度和催化效率之间的关系,探究了咪唑类离子液体阴、阳离子结构对反应效果的影响规律。针对工业上普遍采用的甲醇钠催化剂,描述了其失活现象并阐述了失活机理。详细比较和讨论了非均相催化剂的制备方法、表面酸碱性与催化效率之间的关系,综合评价了不同类别的催化剂催化酯交换反应的优缺点。着眼绿色、高纯、低成本EMC合成技术,高效固体碱催化剂和涉及气、液、固三相的催化精馏技术是今后开发的重点和发展方向。     

Kinetic study of methoxycarbonylation of 1,6‐hexanediamine with dimethyl carbonate using Mn(OAc)2 catalyst

Clean synthesis of dimethylhexane‐1,6‐dicarbamate (HDC) from methoxycarbonylation of 1,6‐hexanediamine (HDA) with dimethyl carbonate (DMC) was studied. Among several heterogeneous and homogeneous catalysts, Mn(OAc)₂ was screened as the most effective catalyst over which the kinetic balance could be reached within 2–3 h. Then the kinetic model of the methoxycarbonylation of HDA with DMC using Mn(OAc)₂ catalyst, under the real reaction conditions was established. Results indicated that the reaction orders were confirmed to be 4.5 for the first step reaction and 4.3 for the second step reaction by the numerical differential method. In addition, the activation energies for the first and second step reaction were 47.0514 and 60.4504 kJ·mol⁻¹ and the frequency factors were 1.4645 × 10² and 3.6519 × 10⁴ min⁻¹, respectively. Moreover, the kinetic model correlated well with experimental data. This study not only provides a highly efficient catalyst for the methoxycarbonylation of HDA with DMC but also gives the guidance for the design of the reactor by studying its kinetic under real reaction conditions.     

Zn-La复合氧化物催化剂用于甲醇与碳酸乙烯酯酯交换反应的研究

ZnO、La₂O₃和Zn-La复合氧化物催化剂用于甲醇与碳酸乙烯酯反应制备碳酸二甲酯和乙二醇。催化剂采用共沉淀法进行制备,并用BET、XRD、TG-DSC、CO₂-TPD和Hammett滴定等对催化剂进行表征。考察了Zn-La物质的量比、焙烧温度,反应条件（反应温度、反应时间、催化剂用量等）对催化剂活性的影响。结果表明,ZnLa复合氧化物物质的量比为2：1,焙烧温度为500℃时,催化剂表现了较好的催化效果。催化剂的活性与催化剂表面的碱性强度和碱量有关,碱量越多催化剂的活性越好。     

甲醇和碳酸丙烯酯合成碳酸二甲酯的研究

采用浸渍法以ZrO2为载体，以碱金属氢氧化物和碳酸盐为前驱体制备了不同的固体碱催化剂，在温和反应条件下考察了催化剂的酯交换扳应性能，并通过BET、XRD和CO2－TPD等方法对催化剂进行了表征，结果表明：Na2CO3负载到不同载体上，其催化性能明显不同，Na2CO3/ZrO2催化剂获得了较高的酯交换活性。载体的比表面和孔结构与催化剂的反应活性无一定的依存关系。而催化剂表面的酸碱性是影响酯交换活性的重要因素。     

Heterogeneous synthesis of glycerol carbonate from glycerol and dimethyl carbonate catalyzed by LiCl/CaO

In this article, a CaO-based catalyst was prepared by impregnating chloride salts on CaO to develop a highly efficient heterogeneous catalyst for the synthesis of glycerol carbonate (GC) from glycerol and dimethyl carbonate. LiCl/CaO exhibited a high catalytic activity under moderate reaction conditions. The effects of the LiCl loadings, the amount of catalyst and the calcination temperature on the catalytic activity were investigated. The highest yield of 94.19% glycerol carbonate was obtained at 65 °C on CaO loaded with 10% LiCl after 1 h, and the catalyst had high stability in reusing work. Scanning electron microscopy (SEM), X-ray diffraction (XRD), BET, CO₂-TPD, XPS and thermalgravity (TG) were used to characterize the prepared catalyst. It was found that the high catalytic activity of CaO after modification with LiCl is associated with the structural aspects and the amount of basicity of the catalyst. The Li₂O₂ species, which is a strong basic site that is formed by the substitution of the Ca²⁺ in CaO lattice by Li⁺, has great activity for transesterification.     

Effective and recoverable homogeneous catalysts for the transesterification of dimethyl carbonate with ethanol: Lanthanide triflates

The catalytic activities of metal triflates were tested for the transesterification of dimethyl carbonate (DMC) with ethanol. It was found that yttrium triflate was the most efficient homogeneous catalyst. When the transesterification reaction was catalyzed by yttrium triflate at 76–80°C, 7 h, ethanol to DMC in 6: 1 molar ratio, 0.35 mol % of catalyst based on DMC, the conversion of DMC was 89.2%, the selectivities of diethyl carbonate (DEC) and ethyl methyl carbonate (EMC) were 85.1 and 13.6%, respectively. Yttrium triflate was reused 5 times for the transesterification without loss of its catalytic activity.