Synthesis of Dimethyl Carbonate from Carbon Dioxide Catalyzed by Titanium Alkoxides with Polyether‐type Ligands

Kohno, Kazufumi; Choi, Jun‐Chul; Ohshima, Yoshihiro; Yasuda, Hiroyuki; Sakakura, Toshiyasu

doi:10.1002/cssc.200700113

Cited by 73 publications

(26 citation statements)

References 16 publications

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“…Other soluble alkoxides such as those of titanium(IV) [27,34] and Group 5 metals [17,35,36] exhibit activity for carbonate formation. In particular, the reaction mechanism with penta-alkoxo species of Group 5 elements [17,36] has been studied in depth, and the importance of the hemicarbonate (Fig.…”

Section: Niobium-based Catalystsmentioning

confidence: 99%

Reaction Mechanisms in the Direct Carboxylation of Alcohols for the Synthesis of Acyclic Carbonates

et al. 2014

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Dialkylcarbonates, (RO)2CO, can be prepared from alcohols and CO2. Such reaction is clean (water is the co-product) but thermodynamically disfavored. In principle, the reaction mechanism of formation of carbonates requires the acid-base activation of alcohols. Existing data support that the first step is the formation of the alkoxo group RO^- that reacts with CO2 to give the hemicarbonate moiety ROC(O)O^-. The latter converts into the relevant carbonate (RO)2CO following different pathways depending on the catalyst used. DFT calculations have been used in a few cases to support the reaction mechanism. Transition states relevant to various mechanistic scenarios have been identified. The results indicated that the relative energies of these transition states depend on the nature of the alkyl group and the molecularity of the reactive step. Organic catalysts, homogeneous-, heterogenized- and heterogeneous-metal systems are discussed in this paper and the known relevant mechanisms compared. Water represents a serious limitation to equilibrium shift to the right and can affect the catalysts. Techniques used to remove water are also discussed

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Section: Niobium-based Catalystsmentioning

confidence: 99%

Reaction Mechanisms in the Direct Carboxylation of Alcohols for the Synthesis of Acyclic Carbonates

et al. 2014

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“…The effects of the dehydrating alcohol are discussed in depth in the next section. They also achieved the DMC synthesis [88] under the same conditions with a Ti catalyst in the presence of polyether-type ligands, reaching a DMC yield of 41 %, which is higher than the 28 % obtained with the organotin catalyst [89].…”

Section: Homogenous Catalysismentioning

confidence: 82%

Review for the Direct Synthesis of Dimethyl Carbonate

et al. 2014

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This review summarizes the state-of-the-art for direct synthesis of dimethyl carbonate (DMC) from carbon dioxide and methanol. In addition, conventional and alternative processes are also discussed in order to understand the advantages and disadvantages of the direct synthesis of DMC. Furthermore, the major applications of DMC are described: solvent, fuels additive, and building block for organic synthesis. The major drawbacks of the direct synthesis of DMC are the low yield and reaction rate, mostly induced by the highly stable carbon dioxide molecules. The development of novel catalyst and strategies to enhance the DMC yield -such as dehydrating agents that remove the water from the reacting mixture -are pointed out as the key solution for this route. Therefore, the main catalysts (homogeneous and heterogeneous catalysts) used so far are presented, together with the respective operating conditions and catalyst performance. The use of different dehydrating agents to increase the DMC yield is also discussed.

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“…Several catalytic materials have been employed for the synthesis of DMC from CO 2 and methanol (Equation ) which include homogeneous and heterogeneous catalysts

2 MeOH + {CO}_{2} \to MeOC (normalO) OMe + {normalH}_{2} O

…”

Section: Synthesis Of Linear Carbonatesmentioning

confidence: 99%

Use of carbon dioxide as feedstock for chemicals and fuels: homogeneous and heterogeneous catalysis

Dibenedetto

Angelini

Stufano

2013

J of Chemical Tech & Biotech

199

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CO2 is considered to play a key role in an eventual climate change, due to its accumulation in the atmosphere. The control of its emission represents a challenging task that requires new ideas and new technologies. The use of perennial energy sources and renewable fuels instead of fossil fuels and the conversion of CO2 into useful products are receiving increased attention. The utilization of CO2 as a raw material for the synthesis of chemicals and fuels is an area in which scientists and industrialists are much involved: the implementation of such technology on a large scale would allow a change from a linear use of fossil carbon to its cyclic use, mimicking Nature. In this paper the use of CO2 as building block is discussed. CO2 can replace toxic species such as phosgene in low energy processes, or can be used as source of carbon for the synthesis of energy products. The reactions with dihydrogen, alcohols, epoxides, amines, olefins, dienes, and other unsaturated hydrocarbons are discussed, under various reaction conditions, using metal systems or enzymes as catalysts. The formation of products such as formic acid and its esters, formamides, methanol, dimethyl carbonate, alkylene carbonates, carbamic acid esters, lactones, carboxylic acids, and polycarbonates, is described. The factors that have limited so far the conversion of large volumes of CO2 are analyzed and options for large‐scale CO2 catalytic conversion into chemicals and fuels are discussed. Both homogeneous and heterogeneous catalysts are considered and the pros and cons of their use highlighted. © 2013 Society of Chemical Industry

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Synthesis of Dimethyl Carbonate from Carbon Dioxide Catalyzed by Titanium Alkoxides with Polyether‐type Ligands

Cited by 73 publications

References 16 publications

Reaction Mechanisms in the Direct Carboxylation of Alcohols for the Synthesis of Acyclic Carbonates

Reaction Mechanisms in the Direct Carboxylation of Alcohols for the Synthesis of Acyclic Carbonates

Review for the Direct Synthesis of Dimethyl Carbonate

Use of carbon dioxide as feedstock for chemicals and fuels: homogeneous and heterogeneous catalysis

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