Alcoholysis of ester and epoxide catalyzed by solid bases

Hattori, Hideshi; Shima, Masaomi; Kabashima, Hajime

doi:10.1016/s0167-2991(00)80566-2

Cited by 87 publications

(39 citation statements)

References 5 publications

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“…Alcoholysis of Propylene Oxide with Alcohols Alcohols undergo transesterification with ethyl acetate, and alcoholysis with propylene oxide over solid base catalysts at room temperature 65) .…”

Section: Transesterification Of Ethyl Acetate Andmentioning

confidence: 99%

Solid Base Catalysts: Generation, Characterization, and Catalytic Behavior of Basic Sites

英¹

2004

J. Jpn. Petrol. Inst.

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Studies of solid base catalysis performed in our group are summarized. Strongly basic sites for most solid base catalysts are generated by removal of water and carbon dioxide by pretreatment at high temperatures from the surfaces. The nature of the surface basic sites varies with the severity of the pretreatment conditions. Rearrangement of surface and bulk atoms occurs, in addition to the removal of water and carbon dioxide, during the pretreatment. The optimum pretreatment temperature varies with the type of reaction. Characterization of basic sites by the indicator method, TPD of CO2, O exchange between adsorbed CO2 and MgO surface, NMR of 133 Cs and 19 F are described. The catalytic behaviors of solid base catalysts are described for the following reactions; (1) double bond migration, (2) hydrogenation, (3) amination, (4) aldol addition, (5) nitroaldol reaction, (6) Michael addition, (7) conjugate addition of alcohol, (8) cyanoethylation, (9) transesterification of ethyl acetate and alcoholysis of propylene oxide, and (10) the Tishchenko reaction. The strength of basic sites relevant to different reactions is discussed based on the activity order among alkaline earth oxides, and the optimum pretreatment temperatures of MgO for different reactions. Reactions with hydrocarbons need strongly basic sites, whereas reactions with compounds containing functional groups proceed even on weakly basic sites. Finally, important issues to be investigated for the development of solid base catalysis are pointed out.

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Section: Transesterification Of Ethyl Acetate Andmentioning

confidence: 99%

Solid Base Catalysts: Generation, Characterization, and Catalytic Behavior of Basic Sites

英¹

2004

J. Jpn. Petrol. Inst.

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“…As a consequence, the efficiency of such materials rely not only on the strengths of acid sites but also on the better accessibility of acid sites, enhancing their specific activity as catalyst, even with respect to synthetic resins, i.e. the Amberlyst family, as indeed has been observed experimentally for different reactions [25,26]. Moreover, it has been reported that this composite is both chemically (as expected due to the fluorocarbon nature of the backbone) and thermally stable up to 280 • C, at which temperature the sulphonic acid groups begin to decompose [25,27].…”

Section: Heterogeneous Acid Catalysismentioning

confidence: 86%

“…Kinetic studies of the transesterification mechanism in the presence of strong base sites suggested that the reacting molecules (which correspond to two esters in our case) have to adsorb on closely neighbouring free reactive sites. Therefore, a reasonable hypothesis, although based on evidences not yet fully established, is that the surface-mediated reaction step between two adsorbed species, more the adsorption of a single species from solution, as in the case of acid catalysis [27], may become the rate determining step [26,30]. This implies that effective catalysis critically could depend on geometric and spatial distribution of the surface catalytic sites other than on the basicity strength of the metal oxides.…”

Section: Heterogeneous Base Catalysismentioning

confidence: 99%

Co-production of butyrate methyl ester and triacetylglycerol from tributyrin and methyl acetate

Battistel

Calaprice

Gualdi

et al. 2011

Applied Catalysis A: General

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a b s t r a c tThe simultaneous synthesis of butyric acid methyl ester, the shortest component of the FAME (fatty acid methyl esters) family, and glycerol triacetate (TAG) from glycerol tributyrate (tributyrin) and methyl acetate was studied as a function of several reaction parameters, such as type of catalyst, temperature and products distribution. The reaction is an interesterification, a multistep consecutive ester interchange catalyzed by either acid or base catalyst. Under optimized conditions, a complete tributyrin conversion and an almost quantitative butyric acid methyl ester accumulation were achieved. The other reaction product, TAG, formed by the complete acetylation of the glycerol moiety, reached almost 70% yield, whereas the mono-and di-acetylated intermediates accumulated in the order of 5-8% and 24-27%, respectively. Similar final conversions and products yields were obtained with either acid or base homogeneous catalysts, suggesting that the final products mixture did not depend on the type of catalysis but might be limited by equilibrium conditions. In spite of similar final yields, base catalysis needed shorter reaction times (minutes instead of hours) and lower temperature (60 • C instead of 130 • C) with respect to the best acid catalyst. On the other hand, unlike heterogeneous basic catalysts, which showed low activity, a heterogeneous acid catalyst almost as active as the homogenous counterpart was found.

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“…Hattori et al previously reported that alcoholysis of PO was catalyzed by both solid acid and base catalysts [38]. It was also shown that synthetic smectites may have both acidic and basic sites [14,15].…”

Section: One-pot Synthesis Of Dmc From Propylene Oxide Co 2 and Methmentioning

confidence: 98%

“…So, one can assume that, when the content of alkali atoms in smectite was increased, its acid sites were deactivated by alkali hydroxide, which could result in the lower yields of 1-MP and 2-MP. However, this is excluded because Hattori et al also showed that base and acid catalysts gave different product distribution patterns for alcoholysis [38]. The base catalyst produces a larger amount of 1-alkoxy-2-propanol, while the solid acid catalyst gives a larger amount of 2-alkoxy-1-propanol.…”

Section: One-pot Synthesis Of Dmc From Propylene Oxide Co 2 and Methmentioning

confidence: 99%

Mesoporous smectites incorporated with alkali metal cations as solid base catalysts

Fujita

Bhanage

Aoki

et al. 2006

Applied Catalysis A: General

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A series of magnesium containing mesoporous smectites incorporated with alkali hydroxide (NaOH, KOH or LiOH) has been prepared and employed for such base-catalyzed model reactions as transesterification of ethyl acetate with methanol, Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate and one-pot synthesis of dimethyl carbonate (DMC) from propylene oxide, carbon dioxide and methanol. The effects of the quantity and kind of the incorporated alkali atoms on the catalytic properties of the smectites were investigated. Characterization of the smectites has shown that the incorporation of alkali atoms reduces their surface area and total pore volume but enhances the amount and strength of their basic sites. The product yield of the transesterification was increased with the content of alkali atoms incorporated. It has been suggested that the moderately basic sites are responsible for this reaction. The yield of the Knoevenagel reaction depends little on the alkali atom content. Increasing the content of alkali atoms causes the increase in the DMC yield of the one-pot synthesis and the decrease in the yield of methanolysis of propylene oxide, which is the side reaction of the one-pot synthesis. The incorporation of Li was less effective than Na and K for the one-pot reaction. The structures of basic sites over the alkali-incorporated smectites have been discussed.

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Alcoholysis of ester and epoxide catalyzed by solid bases

Cited by 87 publications

References 5 publications

Solid Base Catalysts: Generation, Characterization, and Catalytic Behavior of Basic Sites

Solid Base Catalysts: Generation, Characterization, and Catalytic Behavior of Basic Sites

Co-production of butyrate methyl ester and triacetylglycerol from tributyrin and methyl acetate

Mesoporous smectites incorporated with alkali metal cations as solid base catalysts

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