First Attempt of Glycidol‐to‐Monoalkyl Glyceryl Ethers Conversion by Acid Heterogeneous Catalysis: Synthesis and Simplified Sustainability Assessment

Abstract

The selective preparation of monoalkylglyceryl ethers (MAGEs) is a task for researchers owing to their broad range of applications. In this work, green feedstocks such as glycidol and alcohols were used to prepare MAGEs under mild reaction conditions (80 °C, 3 h, 0.5 mol % catalyst) in the presence of acid heterogeneous catalysts. Nafion shows the best performances in terms of conversion and selectivity to MAGES and also high stability. A comparison of the environmental performances with the most consolidated pathway from glycerol has shown that the usage of glycidol (recovered as a value-added product from Epicerol process) and Nafion leads to a lower impact on ecosystems. In addition, results achieved from a simplified socio-economic analysis show that the innovative route here proposed has potential (at the laboratory scale) of enhancing potential gains and of reducing the social implications resulting from externalities associated with environmental impacts (e.g., CO equivalents).

Regioselective Ring‐Opening of Glycidol to Monoalkyl Glyceryl Ethers Promoted by an [OSSO]‐FeIII Triflate Complex

“…[8][9][10][11] Among oxiranes,g lycidol (GLY) has attracted much attention, not only because it can act as cornerstone for the synthesis of more complexm olecules, but also because the presence of ah ydroxy group profoundly influences its reactivity. [24,25] Nevertheless, such as ynthesis was recently accomplished both under basic conditions [26] and in the presence of acidic heterogeneous (i.e.,A mberlyst IRA-400a nd Nafion NR50) [27,28] and homogenous( metal triflates) [29,30] catalytic systems. [12,13] Among the possible products that can be obtained by nucleophilic ring-opening of GLY, monoalkyl glyceryl ethers (MAGEs) are ar elevant class of molecules, not only because they represent one of the most successful examples of glycerol valorizationb ut also because they find application in many significant industrial areas.…”

“…[12,13] Among the possible products that can be obtained by nucleophilic ring-opening of GLY, monoalkyl glyceryl ethers (MAGEs) are ar elevant class of molecules, not only because they represent one of the most successful examples of glycerol valorizationb ut also because they find application in many significant industrial areas. [24,25] Nevertheless, such as ynthesis was recently accomplished both under basic conditions [26] and in the presence of acidic heterogeneous (i.e.,A mberlyst IRA-400a nd Nafion NR50) [27,28] and homogenous( metal triflates) [29,30] catalytic systems. [24,25] Nevertheless, such as ynthesis was recently accomplished both under basic conditions [26] and in the presence of acidic heterogeneous (i.e.,A mberlyst IRA-400a nd Nafion NR50) [27,28] and homogenous( metal triflates) [29,30] catalytic systems.…”

Bio-Glycidol Conversion to Solketal over Acid Heterogeneous Catalysts: Synthesis and Theoretical Approach

“…Several heterogeneous catalysts (both Lewis and Brønsted acids) have been used to promote glycidol acetalization to solketal. Nafion NR50, Montomorillonite K10 and Amberlyst-15 are commercially available whereas sulfonated charcoal, sufonated mesoporous silica and supported metal triflates have been prepared and successfully employed in acid-demanding processes [18]. As shown in Table 1, glycidol is successfully converted into the desired product using both Lewis and Brønsted heterogeneous acid catalysts.…”

“…The best results in terms of conversion and selectivity to solketal are obtained in the presence of supported metal triflates (see entries [3][4][5] and Nafion NR50 (see entry 1). No reaction took place using Montmorillonite K10, sulfonated activated charcoal (AC-SO 3 H) and sulfonated mesoporous silica (MS-SO 3 H) (see Table S1) due to their known lower total acidity (0.21 mmol/g for Montmorillonite K10, 0.15 mmol/g for MPS-SO 3 H and 0.18 mmol/g for AC-SO 3 H) [18]. Amberlyst-15 (sulfonated styrene-divinyl benzene resin with a total acidity of 4.7 mmol/g) promotes the quantitative conversion of glycidol but a dramatic reduction of the selectivity is observed due to a competitive glycidol oligomerization, as reported in our previous works for glycidol etherification with alcohols [18,22].…”

“…The use of glycidol as starting material for solketal preparation becomes more interesting in the light of the recently investigated bio-based routes for its preparation. More in detail, we recently described the preparation of glycidol through the conversion of 2-chloro-1,3-propanediol (β-MCH), a by-product in the bio-based epichlorohydrin production plant [4,17,18]. This approach allows to valorize the entire production chain to bio-epichlorohydrin minimizing the production of waste in agreement with the twelve principles of Green Chemistry.…”