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Cas Database

105-58-8

105-58-8

Identification

  • Product Name:Diethyl carbonate

  • CAS Number: 105-58-8

  • EINECS:203-311-1

  • Molecular Weight:118.133

  • Molecular Formula: C5H10O3

  • HS Code:2920909090

  • Mol File:105-58-8.mol

Synonyms:Diatol;Diatol (carbonate);Ethyl carbonate;Ethyl carbonate((EtO)2CO);Eufin;H-DEC;NSC 8849;Carbonicacid, diethyl ester;

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Safety information and MSDS view more

  • Pictogram(s):ToxicT,IrritantXi

  • Hazard Codes:T,Xi

  • Signal Word:Warning

  • Hazard Statement:H226 Flammable liquid and vapour

  • First-aid measures: General adviceConsult a physician. Show this safety data sheet to the doctor in attendance.If inhaled Fresh air, rest. In case of skin contact Rinse and then wash skin with water and soap. In case of eye contact First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention. If swallowed Rinse mouth. Rest. High vapor concentrations can cause headache, irritation of eyes and respiratory tract, dizziness, nausea, weakness, loss of consciousness. (USCG, 1999) Basic Treatment: Establish a patent airway. Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Monitor for shock and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with normal saline during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 ml/kg up to 200 ml of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... . /Esters and related compounds/

  • Fire-fighting measures: Suitable extinguishing media ... FOAM, CARBON DIOXIDE, DRY CHEMICAL Excerpt from ERG Guide 128 [Flammable Liquids (Water-Immiscible)]: HIGHLY FLAMMABLE: Will be easily ignited by heat, sparks or flames. Vapors may form explosive mixtures with air. Vapors may travel to source of ignition and flash back. Most vapors are heavier than air. They will spread along ground and collect in low or confined areas (sewers, basements, tanks). Vapor explosion hazard indoors, outdoors or in sewers. Those substances designated with a (P) may polymerize explosively when heated or involved in a fire. Runoff to sewer may create fire or explosion hazard. Containers may explode when heated. Many liquids are lighter than water. Substance may be transported hot. For hybrid vehicles, ERG Guide 147 (lithium ion batteries) or ERG Guide 138 (sodium batteries) should also be consulted. If molten aluminum is involved, refer to ERG Guide 169. (ERG, 2016) Wear self-contained breathing apparatus for firefighting if necessary.

  • Accidental release measures: Use personal protective equipment. Avoid dust formation. Avoid breathing vapours, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust. For personal protection see section 8. Personal protection: filter respirator for organic gases and vapours adapted to the airborne concentration of the substance. Collect leaking and spilled liquid in sealable containers as far as possible. Absorb remaining liquid in sand or inert absorbent. Then store and dispose of according to local regulations. Pick up and arrange disposal. Sweep up and shovel. Keep in suitable, closed containers for disposal.

  • Handling and storage: Avoid contact with skin and eyes. Avoid formation of dust and aerosols. Avoid exposure - obtain special instructions before use.Provide appropriate exhaust ventilation at places where dust is formed. For precautions see section 2.2. Fireproof. Separated from strong oxidants. Cool. Well closed.

  • Exposure controls/personal protection:Occupational Exposure limit valuesBiological limit values Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday. Eye/face protection Safety glasses with side-shields conforming to EN166. Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU). Skin protection Wear impervious clothing. The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace. Handle with gloves. Gloves must be inspected prior to use. Use proper glove removal technique(without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands. The selected protective gloves have to satisfy the specifications of EU Directive 89/686/EEC and the standard EN 374 derived from it. Respiratory protection Wear dust mask when handling large quantities. Thermal hazards

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Relevant articles and documentsAll total 184 Articles be found

Fabrication of solid strong bases with a molecular-level dispersion of lithium sites and high basic catalytic activity

Sun, Lin-Bing,Shen, Jie,Lu, Feng,Liu, Xiao-Dan,Zhu, Li,Liu, Xiao-Qin

, p. 11299 - 11302 (2014)

New solid strong bases were fabricated at room temperature by grafting lithium-containing molecular precursors onto β-cyclodextrin. The solid bases show strong basicity with a molecular-level dispersion of lithium sites, which are highly active in transesterification reactions and impossible to realize through the traditional high-temperature method. the Partner Organisations 2014.

Magnesium oxide nanosheets as effective catalysts for the synthesis of diethyl carbonate from ethyl carbamate and ethanol

Li, Fengjiao,Li, Huiquan,Wang, Liguo,He, Peng,Cao, Yan

, p. 1021 - 1034 (2015)

A series of MgO catalysts were prepared by thermal decomposition and precipitation methods. Their catalytic performance was evaluated in the synthesis of diethyl carbonate (DEC) from ethyl carbamate (EC) and ethanol. Among them, MgO prepared using sodium carbonate as the precipitant and calcined at 450°C (MgO-SC-450) exhibited much higher catalytic activity. An excellent DEC yield of 58.0% with a high DEC selectivity of 92.1% could be achieved over the MgO-SC-450 catalyst under optimized reaction conditions: 210°C, ethanol/EC molar ratio of 10, and 3 h. Moreover, the catalytic activity could be essentially retained during recycling experiments. The structure and surface basicity of the MgO catalysts were characterized by X-ray diffraction (XRD), Mastersizer 2000, N2 adsorption, field-emission scanning electron microscopy (FE-SEM), and temperature-programmed desorption of CO2 (CO2-TPD). It was found that MgO-SC-450 possessed nanosheet morphology. Furthermore, a larger amount of appropriate medium basic β sites of MgO-SC-450 with the peak located between 225°C and 275°C was favourable for obtaining much superior catalytic activity. Quasi in situ FT-IR experiments were carried out to elucidate the adsorption behaviours of reactants. It was found that EC could be effectively activated and ethanol could be dissociated to a strong nucleophilic ethoxy group by MgO. In addition, theoretical calculation proved the co-adsorption of EC and ethanol on the MgO surface. Based on the results of quasi in situ FT-IR experiments and theoretical calculation, a plausible reaction mechanism has been proposed for the catalytic reaction.

Ambident ethyl N-nitrosocarbamate anion: Experimental and computational studies of alkylation and thermal stability

Benin, Vladimir,Kaszynski, Piotr,Radziszewski, J. George

, p. 14115 - 14126 (2002)

Alkylation of N-nitrosourethane tetrabutylammonium salt (2-Bu4N) with four electrophiles (Mel, Etl, i-Prl, and PhCH2Br) was studied by 1H NMR in CD2Cl2 and CD3CN solutions. The ratio of the three regioisomers N-alkyl-N-nitrosourethane 3, azoxy 4, and O-alkyldiazotate 5 was practically independent of solvent but dependent on the nature of the electrophile. The anion 2 and O-alkyl derivative 5 are thermally unstable and decompose to ethyl carbonates 9 and 10, respectively, with a first-order rate constant (2-Bu4N: k = 18.5 ± 0.1 × 10-5 S-1; 5b (R = Et): k = 1.77 ± 0.02 × 10-5 s-1; 5d (R = PhCH2): k = 4.78 ± 0.08 × 10-5 s-1 at 35 °C in CD2Cl2). Further kinetic measurements gave activation parameters for the decomposition of 2 (Ea = 24.2 ± 0.3 kcal/mol and In A = 30.9 ± 0.1). Gas-phase calculations at the MP2(fc)/6-31+G(d)//MP2(fc)/6-31G(d) level showed that the alkylation of 2 involves the lone electron pairs of the N-N-O atoms, and the calculated activation energies correspond well to the observed ratio of regioisomers 3-5. The theoretical analysis of the decomposition processes supports a concerted mechanism with a four-center transition state in the first step for all four compounds. The calculated activation energy order (2 5 3 4) is consistent with the observed order of stability. Decomposition of 2 and 5 is a unimolecular process, giving carbonates 9 and 10 in a single step. In contrast, rearrangement of 3 and 4 leads to alkyl diazonium ions. A detailed theoretical analysis indicates that the rate-determining step for thermal decomposition of 2 is the loss of molecular nitrogen, while in 5 it is the trans-cis isomerization process. The nonconcerted process involving homolytic cleavage of the O-N bond in 5 was found to be significantly less favorable.

-

McElvain,Weber

, p. 2192,2193 (1941)

-

Eisenhauer et al.

, p. 245,248 (1952)

Au (III)/N-containing ligand complex: A novel and efficient catalyst in carbonylation of alkyl nitrite

Li, Jinjin,Hu, Jianglin,Li, Guangxing

, p. 1401 - 1404 (2011)

High catalytic activity of a gold N-containing ligand complex in the homogenous carbonylation of alkyl nitrite to dialkyl carbonate with KI as the promoter is reported. [AuCl2(phen)]Cl/KI (phen = 1,10-phenanthroline) complex has been used as a catalyst in the carbonylation of ethyl nitrite. The use of iodide as a promoter resulted in a significant increase in activity (TOF: 35.8 mol?molAu- 1?h- 1) and selectivity (91.7%) for diethyl carbonate at 3.0 MPa, 80 °C and 5 h. Based on the results of ESI-MS, UV-Vis, and cyclic voltammetry (CV) experiments, a mechanism is proposed for the carbonylation of alkyl nitrite in a homogeneous system using a gold N-containing ligand complex as a catalyst.

Mesostructured graphitic carbon nitride as a new base catalyst for the efficient synthesis of dimethyl carbonate by transesterification

Xu, Jie,Long, Kai-Zhou,Chen, Ting,Xue, Bing,Li, Yong-Xin,Cao, Yong

, p. 3192 - 3199 (2013)

Mesostructured graphitic carbon nitride (CN-MCF) material has been prepared using carbon tetrachloride and ethylenediamine as precursors and mesocellular silica foam as a hard template, and characterized by XRD, N2 adsorption-desorption, TEM, FT-IR, and XPS techniques. The material was employed as a catalyst for the production of dimethyl carbonate (DMC) via transesterification of ethylene carbonate (EC) with methanol (MeOH). The influences of reaction conditions, including time, temperature, and the molar ratios of MeOH to EC, on the catalytic performance have been investigated in detail. Catalytic results revealed that CN-MCF could catalyze the transesterification reaction with high efficiency, affording a high DMC yield of 78% and stable catalytic activity for several running cycles. Furthermore, a possible reaction mechanism for the g-CN-catalyzing transesterification of EC with MeOH has been proposed. The Royal Society of Chemistry.

An effective combination catalyst of CeO2and zeolite for the direct synthesis of diethyl carbonate from CO2and ethanol with 2,2-diethoxypropane as a dehydrating agent

Chang, Tao,Choi, Jun-Chul,Fukaya, Norihisa,Hamura, Satoshi,Matsumoto, Seiji,Mishima, Takayoshi,Nakagawa, Yoshinao,Tamura, Masazumi,Tomishige, Keiichi

, p. 7321 - 7327 (2020)

The combination catalyst of CeO2 and H-FAU zeolite was effective for the direct synthesis of diethyl carbonate from CO2 and ethanol with 2,2-diethoxypropane as a dehydrating regent, where H-FAU catalyzed hydrolysis of 2,2-diethoxypropane. The combination catalyst provided high activity and a high diethyl carbonate yield of 72% based on 2,2-diethoxypropane at a low temperature of 393 K. This journal is

Construction of Polycyclic β-Ketoesters Using a Homoconjugate Addition/Decarboxylative Dieckmann Annulation Strategy

Chen, Zhiwei,Hong, Allen Y.,Linghu, Xin

, p. 6225 - 6234 (2018)

The construction of arene-fused cyclic β-ketoesters from 2-iodoaryl esters and 1,1-cyclopropane diesters is detailed. The synthetic method takes advantage of a CuI·SMe2-mediated homoconjugate addition followed by a decarboxylative Dieckmann cyclization to afford valuable polycyclic building blocks. Various iodoaryl esters and 1,1-cyclopropane diesters were evaluated, and the limitations of both reactions are discussed. Several mechanistic probes are detailed and synthetic applications are described.

Synthesis of ethyl octyl ether from diethyl carbonate and 1-octanol over solid catalysts. A screening study

Guilera,Bringué,Ramírez,Iborra,Tejero

, p. 21 - 29 (2012)

The synthesis of ethyl octyl ether (EOE) from a mixture of diethyl carbonate (DEC) and 1-octanol (1:2 molar ratio) over several solid catalysts was studied in batch mode at 150 °C and 25 bar. Catalyst screening revealed that EOE could be successfully obtained over some acid catalysts. In particular the highest yield was achieved over acid ion-exchange resins (33% after 8 h). A reaction scheme of the process is proposed. Selectivity to EOE was mainly affected by the production of diethyl ether (DEE) and di-n-octyl ether (DNOE). However, EOE was the main ether obtained (60 mol%), followed by DEE (20 mol%) and DNOE (20 mol%). By comparing the behavior of several acid resins, it was seen that the synthesis of EOE was highly related to the structural resin properties. It was found that the accessibility of DEC and 1-octanol to acid centers was improved over highly swollen and low polymer density resins. Thus, gel-type resins with low divinylbenzene content are the most suitable to produce EOE (e.g., Amberlyst 121, Dowex 50Wx2-100 and CT224).

Tsuyuki, T.,Simamura, O.

, p. 1079 - 1080 (1958)

Highly active and reusable ternary oxide catalyst for dialkyl carbonates synthesis

Unnikrishnan,Srinivas

, p. 42 - 49 (2015)

The application of ternary oxides, prepared through calcination of rare-earth modified Mg/Al-hydrotalcite (HT), as highly active, selective, and reusable solid catalysts for dialkyl carbonates synthesis by transesterification reaction is reported. Dimethyl carbonate, for example, was prepared by reacting ethylene carbonate with methanol in 100 mol% selectivity at a yield of 95 mol%. Among several rare-earth modified precursors, La (10 mol%)-HT showed the highest activity. This catalyst was active even at ambient conditions. Basicity of the catalyst played crucial role on its performance. The activity of these catalysts was superior to the hitherto known solid catalysts for this reaction.

Direct condensation reaction of carbon dioxide with alcohols using trisubstituted phosphine-carbon tetrabromide-base system as a condensing agent

Kadokawa, Jun-Ichi,Habu, Hideyuki

, p. 2205 - 2208 (1999)

This paper describes the preparation of carbonates by the direct condensation of CO2 with alcohols using a trisubstituted phosphine-carbon tetrabromide-base system as a condensing agent. The yield of dibenzyl carbonate from CO2 and benzyl alcohol was at most 90.7%. The reaction of CO2 with the other primary alcohols such as methanol, ethanol, butan-1-ol, hexan-1-ol, allyl alcohol, and ethylene glycol also gave corresponding carbonates in relatively high yields, whereas yields of carbonates from CO2 and secondary alcohols were low. Copyright 1999 by the Royal Society of Chemistry.

Porter et al.

, p. 577,580 (1976)

A FACILE PREPARATION OF DIALKYL CARBONATES FROM POTASSIUM CARBONATE AND ALKYL BROMIDES BY USING ORGANOSTANNYL COMPOUND AS A CATALYST

Fujinami, Tatsuo,Sato, Shinichi,Sakai, Shizuyoshi

, p. 749 - 752 (1981)

Dialkyl carbonates were easily prepared by the heterogeneous reaction of solid potassium carbonate with alkyl bromides in dimethylformamide or dimethylsulfoxide in the presence of organostannyl compound such as hexabutyldistannoxane or chlorotributylstannane.Mixed catalytic system consisting of a tributylstannyl compound and 18-Crown-6 was much effective even in less polar solvents.

Radical Cations of Organic Carbonates, Trimethyl Borate and Methyl Nitrate

Ganghi, Nader S.,Rao, D. N. Ramakrishna,Symons, Martyn C. R.

, p. 2367 - 2376 (1986)

Exposure of a range of dialkyl carbonates as dilute solutions in trichlorofluoromethane at 77 K gave rearranged cations in which hydrogen is transferred from carbon to the carbonyl oxygen.Similar species were obtained from the cyclic derivatives, ethylene and propylene carbonates.No evidence has been found for complex formation with solvent molecules such as occurs for methyl formate cations.For the dimethyl derivative the rearrangement appeared to occur even at ca. 4 K.For trimethyl borate a similar reaction occurred, giving either or H2COC(OMe)+MeOH.However, methyl nitrate gave NO2H+ radicals, thought to be derived from H2CONO2H+.These results are compared with those for ester and lactone cations and also with those for trimethyl phosphate and dimethyl sulphate cations.

Readily-fabricated supported MgO catalysts for efficient and green synthesis of diethyl carbonate from ethyl carbamate and ethanol

Li, Fengjiao,Wang, Liguo,Xu, Shuang,Liang, Shuting,Zhang, Ningning

, p. 15477 - 15485 (2021)

Developing cost-effective, high-efficiency and heterogeneous catalysts is of prime importance for the green synthesis of diethyl carbonate (DEC) from ethyl carbamate (EC) and ethanol. Herein, a series of MgO/γ-Al2O3 catalysts were readily fabricated by an impregnation method for DEC synthesis from EC and ethanol. The activities of the as-prepared MgO/γ-Al2O3 catalysts as well as the individual MgO or γ-Al2O3 were first tested in the batch reactor. Among the investigated samples, the MgO/γ-Al2O3 with a MgO loading of 10 wt% (denoted as 10% MgO/γ-Al2O3) exhibited the largest amount of stronger basic sites, and the highest activities with EC conversion of 41.8% and DEC yield of 30.4%, respectively. Furthermore, the DEC yield was greatly boosted to 52.1% with a high DEC selectivity of 93.8% over the 10% MgO/γ-Al2O3 catalyst under the optimized reaction conditions in the fixed bed reactor, outperforming most of the reported catalysts.

Synthesis of diethylcarbonate by ethanolysis of urea: A study on the recoverability and recyclability of new Zn-based heterogeneous catalysts

Dibenedetto, Angela,Angelini, Antonella,Aresta, Michele,Fasciano, Stefania,Cucciolito, Maria Elena,Ruffo, Francesco,Aresta, Brunella Maria,Curulla-Ferré, Daniel,De Giglio, Elvira

, p. 1 - 7 (2015)

New Zn-based catalysts are described that act as heterogenized or heterogeneous catalysts, with easy recovery and re-utilization with a limited or even zero Zn-leaching. For stabilizing in the heterogeneous form the catalytically active Zn centre, mixed oxides, ZIF-8 and Zn-tethered systems have been synthesized and found to sensibly reduce the leaching of Zn in solution with respect to ZnO, making possible their recovery and reuse. ZIF-8 can be used for long time of reaction, reaching high DEC yields (comparable or higher than those obtained with ZnO) without any significant loss of zinc.

-

Nefedov et al.

, (1972)

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Alkaline Earth (Ca, Mg) and Transition (La, Y) Metals Promotional Effects on Zn–Al Catalysts During Diethyl Carbonate Synthesis from Ethyl Carbamate and Ethanol

Shukla, Kartikeya,Srivastava, Vimal Chandra

, p. 1891 - 1902 (2017)

Diethyl carbonate, an important member in the family of organic carbonates, is a fuel additive like dimethyl carbonate (DMC). It holds an extra edge of having better gasoline/water distribution coefficient than DMC, and also DEC is widely used as an electrolyte in lithium ion batteries. Ethanolysis of ethyl carbamate (EC) is the most economical and greener route for DEC synthesis. Zn–Al–M (M=Ca, La, Mg and Y) have been synthesized using two methods and their activity have been explored DEC systhesis from EC and ethanol. The catalysts were characterized using thermogravimetric analysis, Brunauer, Emmett and Teller surface area, N2 adsorption–desorption textural analysis, X-ray diffraction (XRD), Fourier transform infrared spectroscopy, temperature-programmed desorption (TPD), atomic-force microscopy and Raman spectroscopy. Pure metal oxides were observed during the XRD analysis and Al2O3 was found to be in amorphous form. Third metal oxide prepared from impregnation method was found to be present on the surface as well as in impregnated form. CO2-TPD analysis showed close correlation between the basicity and the DEC yield. Zn–Al–Mg, prepared from precipitation method, being most basic, was found to be most effective although the performances of Zn–Al–Ca and Zn–Al–La were good. The effect of precipitants was also studied by synthesizing Zn–Al–Mg using NaOH and liquid NH3 as precipitants. DEC yield of 40.2% and turn over frequency of 1055?mgDEC?gcat?1?h?1 was obtained in 5?h at 190 °C using Zn–Al–Mg prepared from precipitation method. Effect of reaction conditions was also studied and equilibrium constant of the reaction was estimated using the Benson group contribution method. Graphical Abstract: [Figure not available: see fulltext.].

Synthesis of diethyl carbonate from ethyl carbamate and ethanol over ZnO-PbO catalyst

An, Hualiang,Zhao, Xinqiang,Guo, Lian,Jia, Chunyao,Yuan, Baoguo,Wang, Yanji

, p. 229 - 235 (2012)

The synthesis of diethyl carbonate (DEC) from ethyl carbamate and ethanol was investigated over a series of double metal oxides. Among the catalysts, ZnO-PbO showed the best catalytic activity and the highest DEC yield was 20.6%. Furthermore, ZnO-PbO had an excellent reusability. According to the results of XRD measurement, IR and element analysis, ZnO and PbO in ZnO-PbO catalyst were separately converted to Zn(NCO)2(NH3)2 and metal Pb during the reaction, indicating that the mixture of Zn(NCO) 2(NH3)2 and metal Pb may be the real active composition for DEC synthesis and ZnO-PbO is the precursor. In addition, a possible reaction mechanism for DEC synthesis was proposed.

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

Yang, Zhen-Zhen,He, Liang-Nian,Dou, Xiao-Yong,Chanfreau, Sébastien

, p. 2931 - 2934 (2010)

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.

Production of diethyl carbonate from ethylene carbonate and ethanol over supported fluoro-perovskite catalysts

Iida, Hajime,Kawaguchi, Ryuhei,Okumura, Kazu

, p. 7 - 11 (2018)

The KCaF3/C (K-Ca(A)) catalyst was shown to be effective as heterogeneous basic catalysts for the transesterification of ethylene carbonate (EC) and ethanol among fluoro-perovskite (XYF3)/C (X = K, Cs, Y = Mg, Ca) catalysts. Although the KMgF3/C (K-Mg (A)) catalyst exhibited the highest catalytic activity among the XYF3/C catalysts studied, the potassium leaching was observed on K-Mg (A). CO2 temperature programmed desorption (TPD) revealed that the superior catalytic activity of the XYF3/C was due to its strong basic sites. CO2-TPD and XPS measurements indicated that strong basic sites are generated by an increase in the electron density of fluorine.

Single-Pulse shock tube studies of the decomposition of ethoxy compounds

Herzler, Juergen,Manion, Jeffrey A.,Tsang, Wing

, p. 5494 - 5499 (1997)

Tetraethyl orthocarbonate (TEOC), diethyl carbonate (DEC), and diethoxymethane (DEM) have been decomposed in single-pulse shock tube experiments. TEOC decomposes to give DEC, ethylene, and ethanol as organic products, while DEC results in only the latter two. In both cases the ethylene to ethanol ratio is equal to 1, and the mechanisms appear to involve molecular eliminations. The rate expressions for the initial processes are the following: k(TEOC → products) = 1013.91±0.14 exp((-27 529 ± 348)K/T) s-1, T = 1005-1180 K; k(DEC → C2H5OCO2H + C2H4) = 1013.03±0.11 exp((-23 290 ± 26 7 K/T) s-1, T = 955-1095 K. The listed uncertainties are one standard deviation. DEM decomposes more slowly than the other two compounds. For each DEM reacted, 1.2 ethylene and 0.5 ethanol are produced. Methane and ethane are also observed as products. The mechanism is postulated to involve both molecular and bond-breaking channels. It is concluded that ethanol arises only through the molecular channel, and on this basis the following rate expressions have been derived: k(DEM → products) = 1015.93±0.15 exp((-36 179 ± 403 K/T) s-1, T = 1150-1260 K; k(DEM → ethanol + products) = 1015.07±0.45 exp((-34 517 ± 1090 K/T) s-1, k(DEM → ethyl + OCH2OC2H5) = 1016.32±0.45 exp((-38 214 ± 1160 K/T) s-1. The results are compared with those dealing with the stability of analogous ethers, esters, and silicon compounds. For carbon compounds the addition of ethoxy groups to the compound destabilizes the molecule. It is further concluded that rate data on the molecular decompositions of ethoxy carbon compounds cannot be easily extrapolated to silicon-containing species.

Catalytic decomposition of dialkyl pyrocarbonates to dialkyl carbonates and carbon dioxide in dichloromethane by a discrete cobalt(II) alkoxide species generated in situ

Greener, Bryan,Walton, Paul H.

, p. 3733 - 3740 (1997)

Dimethyl pyrocarbonate (dmpc) [dimethyl μ-oxo-bis(dioxocarbonate)] and diethyl pyrocarbonate (depc) were catalytically decomposed to dimethyl and diethyl carbonate respectively and carbon dioxide in the presence of [CoL(OR)]+ [L = cis,cis-1,3,5-tris(E,E-cinnamylideneamino)cyclohexane, R = methyl or ethyl] which we propose to be generated in situ during reaction in dichloromethane. The activity of the catalyst is undiminished after 60 000 turnovers. In both cases the catalytic rate enhancement for the decomposition is in excess of 107 dm3 mol-1 of catalyst. The catalytic process follows Michaelis-Menten type kinetics and kobs is 2.2(2) s-1 for dmpc decomposition and 1.3(2) s-1 for depc decomposition. Activation energies for the catalytic decomposition are Edmpc = 113(5) and Edepc = 120(11) kJ mol-1. A mechanism involving cobalt-bound alkoxide attack on dialkyl pyrocarbonate is proposed. The crystal structure of [CoL(Cl)] BPh4 has been determined by single-crystal X-ray diffraction.

Catalytic CO2esterification with ethanol for the production of diethyl carbonate using optimized CeO2as catalyst

Buchmann, Marco,Lucas, Martin,Rose, Marcus

, p. 1940 - 1948 (2021)

The direct conversion of (bio)ethanol and CO2is a promising route to diethyl carbonate (DEC) since both reactants are cheap and originate from renewable resources in bioethanol production. In this work we present a detailed characterization and correlation between catalyst synthesis parameters and catalytic activity of pure ceria for DEC formation. An interaction between surface acidity and basicity as well as sufficiently high specific surface area is required for optimal catalytic activity which is obtained by using urea as the precipitation agent. Catalytic activity towards DEC formation is increased when adding both cerium nitrate solution and aqueous ammonia solution in a controlled manner at a pH of 10 at 50 °C for precipitation. When combining temperature-programmed desorption (TPD) experiments and catalytic testing, mainly weak basic sites appear to be relevant for the DEC formation.

Fast and facile preparation of metal-doped g-C3N4 composites for catalytic synthesis of dimethyl carbonate

Xu, Jie,Long, Kai-Zhou,Wang, Yue,Xue, Bing,Li, Yong-Xin

, p. 1 - 8 (2015)

Zn-doped g-C3N4 materials (Zn-g-C3N4) were prepared by a simple mixing and calcination, using dicyandiamide as a precursor and zinc halide as a dopant. The characterization results of CO2 temperature-programmed desorption and elemental analysis revealed that the introduction of Zn species enhanced the overall basic quantity of g-C3N4. In the transesterification of ethylene carbonate with CH3OH to dimethyl carbonate (DMC), the Zn-g-C3N4 catalysts showed superior catalytic activity to the pure g-C3N4, and the highest DMC yield reached 83.3%, along with stable catalytic reusability and reproducibility. Furthermore, other transition-metal halides (including FeCl3, CuCl2, NiCl2, etc.) could be utilized as dopants for g-C3N4, and the obtained doped g-C3N4 materials also showed high EC conversions above 70%. The upgradation of basic quantity of g-C3N4 was attributed to the reaction between metal halide and the active amine species of g-C3N4. Despite their low surface areas, under the same catalytic conditions, Zn-g-C3N4 catalysts demonstrated remarkably higher catalytic activity than other mesoporous carbon nitride materials.

Synthesis of Ditetrahydrofurfuryl Carbonate as a Fuel Additive Catalyzed by Aminopolycarboxylate Ionic Liquids

Huang, Wei,Tao, Duan-Jian,Chen, Feng-Feng,Hui, Wei,Zhu, Jia,Zhou, Yan

, p. 1347 - 1354 (2017)

Abstract: A new series of aminopolycarboxylate ionic liquids were designed, synthesized, and applied for efficient and selective synthesis of ditetrahydrofurfuryl carbonate (DTC). Tetraethylammonium nitrilotriacetate ([N2222]3[NTA]) was demonstrated to show the best catalytic performance, in which DTC could be obtained at a yield of 80% under optimum conditions. Graphical Abstract: [Figure not available: see fulltext.].

Gold nanoparticles promote the catalytic activity of ceria for the transalkylation of propylene carbonate to dimethyl carbonate

Juarez, Raquel,Corma, Avelino,Garcia, Hermenegildo

, p. 949 - 952 (2009)

A series of metal oxide nanoparticles with acid or basic properties exhibit low to moderate activity towards the transalkylation of propylene carbonate with methanol; deposition of gold nanoparticles on nanoparticulated ceria significantly increases the activity of this metal oxide towards transalkylation.

NaZSM-5-catalyzed dimethyl carbonate synthesis via the transesterification of ethylene carbonate with methanol

Yang, Zhen-Zhen,Dou, Xiao-Yong,Wu, Fang,He, Liang-Nian

, p. 544 - 548 (2011)

NaZSM-5 zeolite was found to be an efficient heterogeneous catalyst for the synthesis of dimethyl carbonate (DMC), which can serve as a building block, an additive to fuel oil, and an electrolyte in batteries, via the transesterification of ethylene carbonate (EC) with methanol. Notably, 77% DMC yield and 97% selectivity were achieved under mild reaction conditions. Furthermore, the effects of various reaction parameters such as catalyst loading, reaction time, and methanol/EC molar ratio on the catalytic performance were investigated in detail. This protocol was found to be applicable to a variety of alcohols, producing the corresponding dialkyl carbonates with moderate yields and selectivities. Moreover, the catalyst can be recovered by simple filtration with retention of catalytic activity; a stable crystal configuration and a slight alteration of its superficial structure were observed by X-ray diffraction and BET measurements.

Effect of hydrophobic modification on the catalytic performance of PdCl2/Cu-HMS with different silylation temperatures

Zhang, Pingbo,Zhou, Yan,Fan, Mingming,Jiang, Pingping,Huang, Xianglan,Lou, Jiang

, p. 320 - 324 (2014)

A new class of organic-inorganic hybrid materials were prepared by combining Cu-HMS with a silylation agent, trimethylchlorosilane (TMCS) via a simple silylation process at different silylation temperatures. They were characterized by a series of techniques including FT-IR, powder XRD, Nitrogen adsorption-desorption, TG analysis and water adsorption capacity test. It was demonstrated that silylation of PdCl2/Cu-HMS catalysts with TMCS enhanced their hydrophobicity, improved their activity and stability and importantly kept the excellent selectivity to diethyl carbonate (DEC) by oxidative carbonylation of ethanol in the gas-phase reaction. Moreover, the silylated samples obtained at 60 °C showed a better conversion of EtOH of 6.1 % and STY of DEC of 140.8 mg g-1 h-1. Springer Science+Business Media New York 2013.

Efficient synthesis of dimethyl carbonate via transesterification of ethylene carbonate over a new mesoporous ceria catalyst

Xu, Jie,Long, Kai-Zhou,Wu, Fei,Xue, Bing,Li, Yong-Xin,Cao, Yong

, p. 1 - 7 (2014)

Mesoporous ceria materials (CeO2-meso) have been prepared through a soft-templating method using cetyltrimethylammonium bromide as a template and cerium nitrate as a precursor. The synthesized CeO2-meso materials possess narrow pore size distributions of 5.1-5.4 nm and tunable surface areas (109-182 m2 g-1). As heterogeneous catalysts in the transesterification of ethylene carbonate (EC) with methanol to dimethyl carbonate (DMC), CeO2-meso materials demonstrate superior catalytic performance to the commercial ceria. N2 adsorption-desorption and CO2-TPD characterization results indicate that the catalytic activity obtained over various CeO2-meso samples depends on their surface areas and basicity. The highest activity is achieved over CeO 2-meso-400, affording a DMC yield as much as 73.3%, together with excellent recycling ability. Besides the transesterification of EC with methanol, CeO2-meso is found to be able to catalyze the reactions of other cyclic carbonates and alcohols. In view of the high catalytic performance along with the convenience in catalyst preparation, CeO2-meso-400 compares favorably with the ionic liquids as well as other ceria-based catalytic systems.

Synthesis of nitrogen-containing ordered mesoporous carbon materials with tunable nitrogen distributions and their application for metal-free catalytic synthesis of dimethyl carbonates

Gan, Yu-Lin,Wen, Lin-Zhi,Xu, Jie,Xue, Bing

, (2020)

Dicyandiamide (DCDA) was utilized as a facile nitrogen source for the fabrication of nitrogen-containing ordered mesoporous carbon (NOMC) samples via a one-pot soft-templating approach under aqueous phase. X-ray diffraction, N2 adsorption–desorption, Transmission electron microscopy, Scanning electron microscopy, Raman and X-ray photoelectron spectroscopy have been applied to analyze the physicochemical properties of the synthesized NOMC materials. The characterization results showed that the textural parameters (545–589 m2 g?1), graphitic crystallinity and distribution of various nitrogen species of the synthesized NOMC materials were largely dependent on the adding mass of DCDA. Besides DCDA, NOMC materials have been also successfully fabricated by employing urea and melamine as nitrogen sources. As metal-free heterogeneous catalysts, the NOMC materials showed good catalytic activity and selectivity in the transesterification of ethylene carbonate to dimethyl carbonate, affording a maximum yield of dimethyl carbonate up to 76 % at 3 h under 120 °C.

(n-Bu2Sn)2O(CO3): An active, robust and recyclable organotin(IV) for the direct synthesis of linear organic carbonates from carbon dioxide and alcohols

Sanapureddy, Sreevardhan Reddy,Plasseraud, Laurent

, p. 2335 - 2342 (2017)

Organotin(IV) compounds are known to promote the direct synthesis of organic carbonates from carbon dioxide and alcohols. In the past, structural studies have highlighted that the carbonato moiety is a recurring ligand of tin species collected during CO2 pressurized reactions. In a mimetic approach and in order to achieve an available and recyclable precursor, the title compound (n-Bu2Sn)2O(CO3) (1) was prepared in a single step by reacting commercial di-n-butyltin dichloride with an aqueous solution of sodium carbonate. Compound 1 was characterized using infrared spectroscopy and thermogravimetric and elemental analyses. Multinuclear NMR investigations in solution were also conducted. Compound 1 was then evaluated for the direct carbonation of alcohols (methanol, ethanol, n-butanol and isopropanol) under CO2 pressure. Recycling experiments were performed showing the efficient reuse of 1 without loss of activity. Furthermore, the infrared fingerprint of 1 was preserved even after several runs demonstrating a good stability. The effects of pressure and of reaction time on dimethyl carbonate formation were also studied.

Effects of support composition and pretreatment on the activity and selectivity of carbon-supported PdCunClx catalysts for the synthesis of diethyl carbonate

Briggs, Daniel N.,Bong, Gerry,Leong, Eric,Oei, Kevin,Lestari, Gabriella,Bell, Alexis T.

, p. 215 - 228 (2010)

The oxidative carbonylation of ethanol to diethyl carbonate (DEC) has been investigated on catalysts prepared by dispersing CuCl2 and PdCl 2 on activated carbon and carbon nanofibers. The objectives of this work were to establish the effects of support structure and pretreatment on the dispersion of the catalytically active components and, in turn, on the activity and selectivity of the catalyst for DEC synthesis. At the same surface loading of CuCl2 and PdCl2, partially oxidized carbon nanofibers resulted in a higher dispersion of the active components and a higher DEC activity than could be achieved on activated carbon. Catalyst characterization revealed that nearly atomic dispersion of CuCl2 and PdCl2 could be achieved on the edges of the graphene sheets comprising the carbon nanofibers. Over oxidation of the edges or their removal by heat treatment of the nanofibers resulted in a loss of catalyst activity. The loss of catalyst activity with time on stream could be overcome by the addition of ppm levels of CCl4 to the feed. While catalysts prepared with CuCl2 alone were active, a fivefold increase in activity was realized by using a PdCl2/CuCl2 ratio of 1/20. It is proposed that the Pd 2+ cations interact with [CuCl2]- anions to form Pd[CuCl2]2 complexes that are stabilized through dative bonds formed with oxygen groups present at the edges of the graphene sheets of the support. A mechanism for DEC synthesis is discussed, and a role for the Pd2+ cations as part of this mechanism is proposed.

-

Kondo,K. et al.

, p. 108 - 111 (1975)

-

Characterization of KF/γ-Al2O3 catalyst for the synthesis of diethyl carbonate by transesterification of ethylene carbonate

Qiu, Peng,Yang, Bolun,Yi, Chunhai,Qi, Suitao

, p. 232 - 238 (2010)

KF/γ-Al2O3 catalysts were prepared by impregnation method and investigated for the transesterification of ethylene carbonate (EC) with ethanol to synthesize diethyl carbonate (DEC). The KF/γ-Al2O3 catalysts were characterized by nitrogen physisorption, XRD and FT-IR techniques, and three new species: K 3AlF6, KOH and K2CO3 were found on the catalysts. Experimental results indicate that KOH and K2CO 3 are the major active species and K3AlF6 is inactive for DEC synthesis. Increasing the KF loading favors the formation of K2CO3 and consequently menhances the activity of the KF/γ-Al2O3 catalysts. However, when KF loading exceeded 50 mmol/g, the activity of the KF/γ-Al2O3 catalysts decreased. This may be due to the presence of intact KF on the catalyst, which may dilute the content of active species in the catalyst and cover the active species. The KF/γ-Al2O3 (50 mmol/g) catalyst exhibits the best catalytic performance. With this catalyst, a 72 mol% yield of DEC (based on EC) was obtained at 298 K. Springer Science+Business Media, LLC 2010.

Tetrachloromethane Hydrodechlorination over Palladium-Containing Nanodiamonds

Belkina, E. G.,Gruzdev, M. S.,Kalmykov, P. A.,Klyuev, M. V.,Lysenok, A. A.,Magdalinova, N. A.

, p. 1148 - 1153 (2020)

Abstract: Using nanodiamonds of the UDD-STP brand 1 wt % palladium-containing nanodiamonds are obtained and tested as catalysts of tetrachloromethane hydrodechlorination under mild conditions (solvents, ethanol and methanol; Т = 298–318 K; PH2 = 0.1 MPa). The catalytic properties of the obtained material and a palladium-containing analog based on activated carbon are compared. It is shown that the hydrodechlorination reaction occurs in a stepwise manner via two pathways: to form products with a smaller content of chlorine, for example, chloroform, and to yield oxygen-containing products, for example, diethyl carbonate. The qualitative and quantitative compositions of reaction products are determined by gas chromatography/mass spectrometry.

-

Douglass,Marascia

, p. 1899 (1955)

-

A catalyst-free novel synthesis of diethyl carbonate from ethyl carbamate in supercritical ethanol

Zhao, Li-Cai,Hou, Zhi-Qiang,Liu, Chun-Ze,Wang, Yuan-Yuan,Dai, Li-Yi

, p. 1395 - 1398 (2014)

Diethyl carbonate has been synthesized via the alcoholysis of ethyl carbamate in supercritical ethanol under catalyst-free conditions. The influences of various parameters such as reaction temperature, reaction time, reaction pressure, ethanol/ethyl molar ratios and reaction loading volume on the yield of DEC were studied systematically. The experimental results indicated that the alcoholysis of ethyl carbamate was greatly improved in supercritical ethanol. The optimal reaction conditions were as follows: a reaction temperature of 573 K, a reaction time of 30 min, a reaction pressure of 13.2 MPa, an ethanol/ethyl carbamate molar ratio of 10 and a reactor loading volume of 285 μL respectively. The optimal yield of DEC was 22.9%.

Catalytic alcoholysis of urea to diethyl carbonate over calcined Mg-Zn-Al hydrotalcite

Wang, Peixue,Liu, Shimin,Zhou, Feng,Yang, Benqun,Alshammari, Ahmad S.,Deng, Youquan

, p. 19534 - 19540 (2015)

The synthesis of diethyl carbonate (DEC) from urea and ethanol was carried out over Mg-Zn-Al composite oxide catalysts derived from hydrotalcites (HTs). The catalytic results showed that the ternary hydrotalcites calcined at 450 °C with Mg:Zn:Al = 1:1.7:1 exhibited superior catalytic activity, and the highest DEC yield was 67.8%. Similar to ethanol, other alcohols such as methanol and butanol can also be transformed to corresponding dialkyl carbonates. Catalysts were characterized by XRD, BET, SEM and TPD with the aim of establishing a relationship between performance and structure. The results indicated that MgZn1.7Al-450 with nanoplate morphology and more accessible active medium basic sites were favourable for obtaining much superior catalytic activity. Recycling experiments demonstrated that the catalyst could be successfully reused. This journal is

Development of complex approach to the synthesis of trimethylene carbonate as a monomer for biodegradable polymers

Kuznetsov,Pervova,Pestov

, p. 654 - 658 (2014)

With the aim of production of polymers for medicine a new preparation method was developed for trimethylene carbonate based on transesterification with trimethylene glycol of dialkyl carbonates obtained without the use of phosgene. As initial reagents alkylene carbonates or polycarbonates and titanium alkoxides can be utilized. The advantages of this approach consist in obtaining some additional useful substances and the possibility of reprocessing polycarbonate wastes.

Dittmar,Cranston

, (1869)

Synthesis of diethylcarbonate by ethanolysis of urea catalysed by heterogeneous mixed oxides

Angelini,Dibenedetto,Curulla-Ferré,Aresta

, p. 88401 - 88408 (2015)

New Zn- and Ca-based mixed oxides have been tested in the ethanolysis of urea. Cerium and magnesium have revealed to be able to stabilize and enhance the activity of Zn and Ca. All the used compounds act as heterogeneous catalysts in a batch reactor and can be easily recovered and re-used in several catalytic runs. However, although ZnO dissolves as Zn(NCO)2(NH3)2 in the reaction medium under the operative conditions and then partly precipitates at room temperature ensuring a modest immediate recoverability and recyclability, 2CaO/CeO2 is insoluble also at the reaction temperature that makes it well suited even for the use in a flow reactor. MgO-ZnO and SiO2-ZnO have also been tested. The former has an interesting performance, but still not equal to that of 2CaO-CeO2. Interestingly, the latter catalyst is able to convert urea and ethanol into DEC with 91% conversion of urea and 98% selectivity in the long term.

Catalysis by lead oxide for diethyl carbonate synthesis from ethyl carbamate and ethanol

Guo, Lian,Zhao, Xinqiang,An, Hualiang,Wang, Yanji

, p. 595 - 600 (2012)

The catalysis by lead oxide in the reaction of ethyl carbamate (EC) with ethanol to form diethyl carbonate (DEC) was studied. The lead oxide catalyst exhibited an excellent stability, which could be reused five times without a significant loss in catalytic activity. X-Ray powder diffraction analysis showed that the recovered catalyst was a mixture of cubic metal Pb and orthorhombic PbO2, with the latter shown to be the real active component for the synthesis of DEC. Verification experiments showed that the reaction between DEC and PbO was the main reason for the reduction of PbO to metal Pb.

Sensitized Photooxygenation of 6-Heteroatom-Substituted Fulvenes: Primary Products and Their Chemical Transformations

Zhang, Xiaojun,Lin, Feng,Foote, Christopher S.

, p. 1333 - 1338 (1995)

Sensitized photooxygenation of 6,6-diethoxyfulvene (1) and 6,6-(ethylenedithio)fulvene (9) at -78 deg C afforded diethoxyfulvene endoperoxide 2 and (ethylenedithio)fulvene endoperoxide 10, respectively, as primary products.Further irradiation resulted in formation of the novel bisperoxides 3 and 11 from cycloaddition of 1O2 to the exocyclic double bond of the corresponding endoperoxides.The initial endoperoxides were characterized by NMR at low temperature and underwent a variety of chemical transformations to give highly oxygenated cyclopentane derivatives.In contrast, photooxygenation of 6,6-dipiperidinofulvene (16) and 6-(dimethylamino)fulvene (17) did not lead to chemical reaction; these compounds physically quench 1O2 with rate constants on the order of 1E8 M-1 s-1.

The influence of various synthesis methods on the catalytic activity of cerium oxide in one-pot synthesis of diethyl carbonate starting from CO 2, ethanol and butylene oxide

Leino, Ewelina,M?ki-Arvela, P?ivi,Eta, Valerie,Kumar, Narendra,Demoisson, Frédéric,Samikannu, Ajaikumar,Leino, Anne-Riikka,Shchukarev, Andrey,Murzin, Dmitry Yu.,Mikkola, Jyri-Pekka

, p. 47 - 54 (2013)

Different synthesis methods such as homogeneous precipitation at room temperature and supercritical water (T > 647 K and P > 22.1 MPa) were employed for cerium oxide preparation. Additionally, deposition of ceria on silica mesoporous material, SBA-15, was carried out. The obtained materials were characterized by means of X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, nitrogen physisorption, X-ray photoelectron spectroscopy and CO2 temperature programmed desorption. Considerable variations in physico-chemical properties of the resulting materials were observed. The catalytic activities of pristine cerium oxide and ceria loaded on SBA-15 support were compared. The test reaction was synthesis of diethyl carbonate starting from carbon dioxide and ethanol using butylene oxide as the dehydrating agent.

Highly efficient and selective synthesis of dibutyl carbonate via the synergistic dual activation catalysis of tetraethylammonium prolinate ionic liquids

Ouyang, Fan,Wang, Zhen-Zhen,Zhou, Yan,Cheng, Zheng,Lu, Zhang-Hui,Yang, Zhen,Tao, Duan-Jian

, p. 177 - 183 (2015)

A facile, highly efficient and phosgene-free synthesis process of dimethyl carbonate (DMC) with nbutanol (BuOH) to dibutyl carbonate (DBC) by transesterification reaction has been studied in detail using tetraethylammonium-based amino acid ionic liquids ([N2222][AA]) as homogeneous catalysts. The results indicated that tetraethylammonium prolinate ([N2222][Pro]) exhibited the best catalytic activity in compared to other four [N2222][AA], and DBC could be obtained at a yield of 72% under optimum conditions. Furthermore, quantum-mechanical calculations manifested that such high DBC yield originated from the synergistic dual activation catalysis of [N2222][Pro]. [N2222][Pro] could activate BuOH and DMC well at the same time, which enhances the electrophilicity of BuOH and the nucleophilicity of DMC respectively, leading to the excellence catalytic performance.

Organic carbonate synthesis from CO2 and alcohol over CeO 2 with 2-cyanopyridine: Scope and mechanistic studies

Honda, Masayoshi,Tamura, Masazumi,Nakagawa, Yoshinao,Nakao, Kenji,Suzuki, Kimihito,Tomishige, Keiichi

, p. 95 - 107 (2014)

The combination system of CeO2-catalyzed carboxylation and 2-cyanopyridine hydration (CeO2 + 2-cyanopyridine system) is effective for the direct synthesis of organic carbonates from CO2 and alcohols. This catalyst system can be applied to various alcohols to afford the corresponding carbonates in high alcohol-based yields. The hydration of 2-cyanopyridine over CeO2 rapidly proceeds under the low concentration of water, which can remove the water from the reaction media. Since the reaction is limited by the chemical equilibrium, the removal of water remarkably shifts the chemical equilibrium to the carbonate side, leading to high carbonate yields. In addition, 2-picolinamide that is produced by hydration of 2-cyanopyridine forms an intramolecular hydrogen bonding between H atom of the amide group and N atom of the pyridine ring, which weakens the adsorption of 2-picolinamide on CeO2 by reduction of the acidity. The reaction mechanism of DMC formation in CeO2 + 2-cyanopyridine system is also proposed.

-

Bergman

, p. 476 (1958)

-

Visible-Light-Initiated Hydrooxygenation of Unactivated Alkenes─A Strategy for Anti-Markovnikov Hydrofunctionalization

Quach, Linda,Dutta, Subhabrata,Pflüger, Philipp M.,Sandfort, Frederik,Bellotti, Peter,Glorius, Frank

, p. 2499 - 2504 (2022/02/17)

Hydrofunctionalization of unactivated alkenes is an indispensable mean in synthetic chemistry. Given that addition of electrophilic species into alkenes intrinsically follows the Markovnikov rule, a regioselectivity switch presents a major challenge. Herein, we present a visible-light-promoted strategy for the selective anti-Markovnikov hydrooxygenation of unactivated alkenes. Therefore, an innovative reagent was carefully designed to release a highly reactive and strongly underdeveloped alkoxycarbonyloxyl radical upon reduction, which selectively adds into alkenes. Hydrogen atom abstraction from 2-phenylmalononitrile is the key to form the product. We believe that this methodology enlarges the toolbox for regioselective hydrofunctionalization and could serve as a complementary strategy to the established hydroboration/oxidation protocol.

Synthesis of dimethyl carbonate from methanol and CO2under low pressure

Liu, Chun,Liu, Kai

, p. 35711 - 35717 (2021/12/04)

A mild and highly efficient approach has been developed for the direct synthesis of dimethyl carbonate (DMC) from methanol and CO2 under low initial pressure. The key to a successful transformation is the use of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), CH2Br2 and ionic liquid. Under the optimized reaction conditions, the yield of DMC was obtained up to 81% under 0.25 MPa. The direct synthesis of DMC can be carried out at balloon pressure using CH2Br2 and DBU. In this case, after the reaction, DBU was proved to be recyclable after having been treated with KOH in ethanol. In addition, a plausible mechanism for this synthetic reaction was proposed according to the experimental results.

METHOD FOR PRODUCING CARBONATE ESTERS, AND CATALYTIC STRUCTURE FOR PRODUCING CARBONATE ESTERS

-

Paragraph 0148-0149; 0179-0180, (2021/09/17)

Provided are a method for producing carbonate esters, and a catalytic structure for producing carbonate esters, whereby solid catalyst powder formation and detachment are suppressed and superior carbonate ester reaction efficiency is yielded when a catalytic structure constituted by a sufficient quantity of a cerium-oxide-containing solid catalyst supported on a substrate is used. The method for producing carbonate esters includes reacting a monohydric alcohol and carbon dioxide in the presence of a catalytic structure and a hydrating agent. The catalytic structure includes a substrate and a catalytic layer that is formed on at least a portion of the surface of the substrate and contains a solid catalyst and an inorganic binder. The solid catalyst contains cerium oxide. The supported quantity of the solid catalyst is 15 g/m2 to 200 g/m2, inclusive. The inorganic binder contains silica and/or alumina.

Process route upstream and downstream products

Process route

ethanol
64-17-5

ethanol

propane-1,1,1-tricarboxylic acid triethyl ester
16515-91-6

propane-1,1,1-tricarboxylic acid triethyl ester

sodium ethanolate
141-52-6

sodium ethanolate

ethyl diethyl malonate
133-13-1

ethyl diethyl malonate

Diethyl carbonate
105-58-8,76619-83-5

Diethyl carbonate

Conditions
Conditions Yield
carbonic acid ethyl ester-(2-diethylamino-ethyl ester)
20570-43-8

carbonic acid ethyl ester-(2-diethylamino-ethyl ester)

2-(Diethylamino)ethanol
100-37-8

2-(Diethylamino)ethanol

Diethyl carbonate
105-58-8,76619-83-5

Diethyl carbonate

Conditions
Conditions Yield
Methyltriethoxysilan
2031-67-6

Methyltriethoxysilan

carbon dioxide
124-38-9,18923-20-1

carbon dioxide

1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane
18001-60-0

1,1,3,3-tetraethoxy-1,3-dimethyldisiloxane

Diethyl carbonate
105-58-8,76619-83-5

Diethyl carbonate

Conditions
Conditions Yield
With zirconium(IV) ethoxide; at 180 ℃; under 37503.8 Torr; Autoclave;
41 %Chromat.
tert.-butylhydroperoxide
75-91-2

tert.-butylhydroperoxide

[diethoxy(<sup>2</sup>H)methoxy]ethane
26387-53-1

[diethoxy(2H)methoxy]ethane

ethyl deuterioformate
35976-76-2

ethyl deuterioformate

<i>tert</i>-butyl alcohol
75-65-0

tert-butyl alcohol

Diethyl carbonate
105-58-8,76619-83-5

Diethyl carbonate

Conditions
Conditions Yield
In chlorobenzene; at 130 ℃; Rate constant; kinetic isotope effect;
Triethoxysilane
998-30-1

Triethoxysilane

carbon dioxide
124-38-9,18923-20-1

carbon dioxide

1,1,3,3-tetraethoxy-disiloxane
15417-65-9

1,1,3,3-tetraethoxy-disiloxane

Diethyl carbonate
105-58-8,76619-83-5

Diethyl carbonate

Conditions
Conditions Yield
With zirconium(IV) ethoxide; at 180 ℃; under 37503.8 Torr; Autoclave;
7 %Chromat.
tetrachloromethane
56-23-5

tetrachloromethane

1,1-dimethoxyethane
534-15-6

1,1-dimethoxyethane

formaldehyde ethyl methyl acetal
22251-34-9

formaldehyde ethyl methyl acetal

acetic acid methyl ester
79-20-9

acetic acid methyl ester

acetaldehyde
75-07-0,9002-91-9

acetaldehyde

Diethyl carbonate
105-58-8,76619-83-5

Diethyl carbonate

Conditions
Conditions Yield
With sodium tetrahydroborate; water; In ethanol; at 34.84 ℃; for 1h; under 750.075 Torr; Kinetics; Catalytic behavior;
1,2-propylene cyclic carbonate
108-32-7

1,2-propylene cyclic carbonate

ethanol
64-17-5

ethanol

propylene glycol
57-55-6,63625-56-9

propylene glycol

Diethyl carbonate
105-58-8,76619-83-5

Diethyl carbonate

Conditions
Conditions Yield
at 168.323 ℃; for 162h;
magnesium 2-methylpropan-2-olate; at 168 ℃; under 13426.3 Torr; Product distribution / selectivity;
potassium ethyl xanthogenate
140-89-6

potassium ethyl xanthogenate

chloro(chlorosulfanyl)methanone
2757-23-5

chloro(chlorosulfanyl)methanone

bis-ethoxythiocarbonyldisulfane
502-55-6

bis-ethoxythiocarbonyldisulfane

<ethoxy(thiocarbonyl)>(chlorocarbonyl)disulfane
100244-68-6

(chlorocarbonyl)disulfane

Diethyl carbonate
105-58-8,76619-83-5

Diethyl carbonate

Conditions
Conditions Yield
In chloroform; at 25 ℃; for 0.5h; Yield given;
28%
In chloroform; at 25 ℃; for 0.5h; Yields of byproduct given;
28%
tetrachloromethane
56-23-5

tetrachloromethane

ethanol
64-17-5

ethanol

diethyl acetal
105-57-7,30846-29-8

diethyl acetal

chloroform
67-66-3,8013-54-5

chloroform

hexachloroethane
67-72-1

hexachloroethane

Diethyl carbonate
105-58-8,76619-83-5

Diethyl carbonate

Conditions
Conditions Yield
With hydrogen; PdAC; at 49.85 ℃; for 12h; Further Variations:; Catalysts; Product distribution;
tetrachloromethane
56-23-5

tetrachloromethane

ethanol
64-17-5

ethanol

diethyl acetal
105-57-7,30846-29-8

diethyl acetal

phosgene
75-44-5

phosgene

chloroform
67-66-3,8013-54-5

chloroform

hexachloroethane
67-72-1

hexachloroethane

carbonochloridic acid 1-chloro-ethyl ester
50893-53-3

carbonochloridic acid 1-chloro-ethyl ester

chloroformic acid ethyl ester
541-41-3

chloroformic acid ethyl ester

acetaldehyde
75-07-0,9002-91-9

acetaldehyde

ethyl acetate
141-78-6

ethyl acetate

Diethyl carbonate
105-58-8,76619-83-5

Diethyl carbonate

Conditions
Conditions Yield
With Amberlite IRA-900 (Cl- form); at 22 ℃; for 24h; UV-irradiation;
51.7 μmol
47.2 μmol
24.8 μmol
19.9 μmol
15 μmol
3.7 μmol
2.5 μmol
0.3 μmol
0.2 μmol

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