Synthesis of dimethyl carbonate from carbon dioxide: catalysis and mechanism

Sakakura, Toshiyasu; Choi, Jun‐Chul; Saito, Yuko; Sako, Takeshi

doi:10.1016/s0277-5387(99)00411-8

Cited by 141 publications

(79 citation statements)

References 20 publications

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“…Besides, orthoesters are expensive, which makes ketals much more attractive due to the low cost and the easy recycle. Sakakura et al have carried the reaction using a ketal [120,121], DMP, which is cheaper and also produces acetone that can be easily recycled into DMP by reacting with methanol. The conversion of DMC reached using DMP is much higher than from the direct methanol carbonylation: 88 % at 453 K and 200 MPa after 24 h. Nevertheless, methanol addition is necessary according to the mechanism suggested by Sakakura [120].…”

Section: Dehydrating Agentsmentioning

confidence: 99%

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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Section: Dehydrating Agentsmentioning

confidence: 99%

Review for the Direct Synthesis of Dimethyl Carbonate

et al. 2014

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“…The results are also shown in Table 5.1. Dialkyl carbonates with longer chains can be produced, although the yields were even lower than that of DMC (entries [10][11][12][13][14][15][16][17]. Diphenyl carbonate was not produced (entry 18).…”

Section: Direct Synthesis Of Various Organic Carbonates From Alcoholsmentioning

confidence: 99%

“…The mechanism of the homogeneous Me 2 Sn(OMe) 2 catalyst for direct DMC synthesis has been investigated in detail [15,16]. The methoxide complex readily reacts with CO 2 at room temperature to give another methoxide, Me 2 Sn (OMe)(OCOOMe) (Fig.…”

Section: Reaction Mechanismmentioning

confidence: 99%

“…A reaction process separating the reaction part from the dehydration part at room temperature was very effective for the improvement of the DMC yield in the organotin-based homogeneous system [44]. Use of the hydration reaction of organic molecules such as orthoesters and 2,2-dimethoxypropane has been also attempted for the organotin-based systems, successfully enhancing the carbonate yields [15,17,45]. The disadvantages of this approach include the high cost of the dehydrating agents and the side-reactions involving the dehydrating agents.…”

Section: Use Of Acetonitrile As a Dehydrating Agent For Dmc Synthesismentioning

confidence: 99%

“…Organotin-based complexes such as Me 2 Sn(OMe) 2 have been the most studied catalysts in the homogeneous systems for direct DMC synthesis [14][15][16]. High selectivities to DMC have been reported in these catalysts.…”

Section: Introductionmentioning

confidence: 99%

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