Alvise Perosa - Academia.edu (original) (raw)
Papers by Alvise Perosa
Journal of CO2 Utilization
Journal of Chemical Education
Green chemistry is the name of a need, that of encompassing chemistry research and the environmen... more Green chemistry is the name of a need, that of encompassing chemistry research and the environmental, safety, health, and societal issues that have been creating unprecedent concerns at a global level. Green chemistry is a modern concept, as the label that represents the entry of chemical sciences in the realm of integrated sustainability studies. To do green chemistry research, we need approaches that take into account the use and availability of resources, as well as the direct or indirect impacts of the applications of new chemistry. Systems thinking is a powerful mindset for addressing the complexity of the interconnections between the traditional and the new aspects of chemistry research. Systems thinking can provide suitable and appropriate conceptual tools for the research, requiring that chemistry teaching provides the necessary familiarity with systemic concepts and practices. In this paper, an emergy (spelled with “m”) perspective is presented as suitable to address the green chemistry didactics toward a systemic conceptual framework, which is now more and more mandatory.
ACS Sustainable Chemistry & Engineering
A two-step methodology was implemented to prepare dialkyl carbonates from both primary and second... more A two-step methodology was implemented to prepare dialkyl carbonates from both primary and secondary alcohols, including glycerol acetals, tetrahydrofurfuryl alcohol, and cyclohexanol. Accordingly,...
ACS Sustainable Chemistry & Engineering
A new procedure for the transesterification of alkyl acetates and formates with model glycerol ac... more A new procedure for the transesterification of alkyl acetates and formates with model glycerol acetals (GAs: Solketal and glycerol formal) was explored in the absence of any catalysts at 180–275 °C. Highly selective transformations occurred in both batch and continuous-flow (CF) modes; particularly, the enol derivative isopropenyl acetate (iPAc) was the best performing reactant by which quantitative acetylation reactions were achieved with yields on GAs acetates >95%. An excess acylating agent was necessary (2–20 molar equivs), but the unconverted ester was fully recovered and could be reused. The reaction plausibly involved multiple mechanisms where either the electrophilic and the nucleophilic activation of reagents took place through both traces of acetic acid (formed in situ by the hydrolysis of esters) and the autoprotolysis of GAs. iPAc confirmed a superior performance than other esters also for the high-temperature conversion of glycerol; in this case, although acylation and acetalization processes...
Molecules, 2016
The caprylic, lauric, palmitic and stearic esters of solketal and glycerol formal were synthesize... more The caprylic, lauric, palmitic and stearic esters of solketal and glycerol formal were synthesized with high selectivity and in good yields by a solvent-free acid catalyzed procedure. No acetal hydrolysis was observed, notwithstanding the acidic reaction conditions.
RSC Adv., 2015
Luminescent anionic β-diketonate complexes of formula [P8,8,8,1][Ln(dbm)4], (Ln = Eu3+ and Sm3+, ... more Luminescent anionic β-diketonate complexes of formula [P8,8,8,1][Ln(dbm)4], (Ln = Eu3+ and Sm3+, [P8,8,8,1] = trioctylmethylphosphonium and dbm = 1,3-diphenylpropane-1,3-dione) were synthesized, characterized and their photoluminescence properties studied.
Catalysis Science & Technology
Reactive methanol removal either by adsorption or by azeotropic distillation promotes complete co... more Reactive methanol removal either by adsorption or by azeotropic distillation promotes complete conversion of different alcohols to the corresponding carbonates.
Current Organic Chemistry, 2016
ChemSusChem, 2017
The base-catalysed reactions of OH-bearing biobased derivatives (BBDs) including glycerol formal,... more The base-catalysed reactions of OH-bearing biobased derivatives (BBDs) including glycerol formal, solketal, glycerol carbonate, furfuryl alcohol and tetrahydrofurfuryl alcohol with non-toxic dialkyl carbonates (dimethyl and diethyl carbonate) were explored under continuous-flow (CF) conditions in the presence of three Na-exchanged Y- and X-faujasites (FAUs) and four Mg-Al hydrotalcites (HTs). Compared to previous etherification protocols mediated by dialkyl carbonates, the reported procedure offers substantial improvements not only in terms of (chemo)selectivity but also for the recyclability of the catalysts, workup, ease of product purification and, importantly, process intensification. Characterisation studies proved that both HT30 and KW2000 hydrotalcites acted as catalyst precursors: during the thermal activation pre-treatments, the typical lamellar structure of the hydrotalcite was broken down gradually into a MgO-like phase (periclase) or rather a magnesia-alumina solid solution, which was the genuine catalytic phase.
Beilstein Journal of Organic Chemistry, 2016
The use of ionic liquids (ILs) as organocatalysts is reviewed for transesterification reactions, ... more The use of ionic liquids (ILs) as organocatalysts is reviewed for transesterification reactions, specifically for the conversion of nontoxic compounds such as dialkyl carbonates to both linear mono-transesterification products or alkylene carbonates. An introductory survey compares pros and cons of classic catalysts based on both acidic and basic systems, to ionic liquids. Then, innovative green syntheses of task-specific ILs and their representative applications are introduced to detail the efficiency and highly selective outcome of ILs-catalyzed transesterification reactions. A mechanistic hypothesis is discussed by the concept of cooperative catalysis based on the dual (electrophilic/nucleophilic) activation of reactants.
Advanced Synthesis Catalysis, Aug 6, 2007
A liquid triphasic system made of isooctane, water, and trioctylmethylammonium chloride allows on... more A liquid triphasic system made of isooctane, water, and trioctylmethylammonium chloride allows one to carry out the hydroformylation of model olefins using neat RhCl 3 as catalyst precursor. By using the triphasic system, the catalyst is kept separate from the reagents and products. This allows one to simply remove the product and to recycle the catalyst numerous times. No leaching of rhodium into the organic phase is observed.
ACS Sustainable Chemistry & Engineering, 2014
ABSTRACT Four renewable lactones, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε-caprol... more ABSTRACT Four renewable lactones, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε-caprolactone (GBL, GVL, DVL, ECL, respectively) were shown to react with dimethyl-, diethyl-, and dibenzyl-carbonate (DMC, DEC, DBnC, respectively) in the presence of K2CO3 as basic catalyst, to yield selectively either the α-alkyl derivatives 1c–6c in the case of the five-membered ring GBL and GVL or the highly oxygenated acyclic monomeric derivatives 7a, 8a, and 9a in the case of the six- and seven-membered rings DVL and ECL. Selectivity and reaction conditions are investigated and a reaction mechanism is proposed. The organic carbonates act both as reagent and as reaction solvents, and the catalyst can be recovered by filtration and recycled.
Journal of CO2 Utilization
Journal of Chemical Education
Green chemistry is the name of a need, that of encompassing chemistry research and the environmen... more Green chemistry is the name of a need, that of encompassing chemistry research and the environmental, safety, health, and societal issues that have been creating unprecedent concerns at a global level. Green chemistry is a modern concept, as the label that represents the entry of chemical sciences in the realm of integrated sustainability studies. To do green chemistry research, we need approaches that take into account the use and availability of resources, as well as the direct or indirect impacts of the applications of new chemistry. Systems thinking is a powerful mindset for addressing the complexity of the interconnections between the traditional and the new aspects of chemistry research. Systems thinking can provide suitable and appropriate conceptual tools for the research, requiring that chemistry teaching provides the necessary familiarity with systemic concepts and practices. In this paper, an emergy (spelled with “m”) perspective is presented as suitable to address the green chemistry didactics toward a systemic conceptual framework, which is now more and more mandatory.
ACS Sustainable Chemistry & Engineering
A two-step methodology was implemented to prepare dialkyl carbonates from both primary and second... more A two-step methodology was implemented to prepare dialkyl carbonates from both primary and secondary alcohols, including glycerol acetals, tetrahydrofurfuryl alcohol, and cyclohexanol. Accordingly,...
ACS Sustainable Chemistry & Engineering
A new procedure for the transesterification of alkyl acetates and formates with model glycerol ac... more A new procedure for the transesterification of alkyl acetates and formates with model glycerol acetals (GAs: Solketal and glycerol formal) was explored in the absence of any catalysts at 180–275 °C. Highly selective transformations occurred in both batch and continuous-flow (CF) modes; particularly, the enol derivative isopropenyl acetate (iPAc) was the best performing reactant by which quantitative acetylation reactions were achieved with yields on GAs acetates >95%. An excess acylating agent was necessary (2–20 molar equivs), but the unconverted ester was fully recovered and could be reused. The reaction plausibly involved multiple mechanisms where either the electrophilic and the nucleophilic activation of reagents took place through both traces of acetic acid (formed in situ by the hydrolysis of esters) and the autoprotolysis of GAs. iPAc confirmed a superior performance than other esters also for the high-temperature conversion of glycerol; in this case, although acylation and acetalization processes...
Molecules, 2016
The caprylic, lauric, palmitic and stearic esters of solketal and glycerol formal were synthesize... more The caprylic, lauric, palmitic and stearic esters of solketal and glycerol formal were synthesized with high selectivity and in good yields by a solvent-free acid catalyzed procedure. No acetal hydrolysis was observed, notwithstanding the acidic reaction conditions.
RSC Adv., 2015
Luminescent anionic β-diketonate complexes of formula [P8,8,8,1][Ln(dbm)4], (Ln = Eu3+ and Sm3+, ... more Luminescent anionic β-diketonate complexes of formula [P8,8,8,1][Ln(dbm)4], (Ln = Eu3+ and Sm3+, [P8,8,8,1] = trioctylmethylphosphonium and dbm = 1,3-diphenylpropane-1,3-dione) were synthesized, characterized and their photoluminescence properties studied.
Catalysis Science & Technology
Reactive methanol removal either by adsorption or by azeotropic distillation promotes complete co... more Reactive methanol removal either by adsorption or by azeotropic distillation promotes complete conversion of different alcohols to the corresponding carbonates.
Current Organic Chemistry, 2016
ChemSusChem, 2017
The base-catalysed reactions of OH-bearing biobased derivatives (BBDs) including glycerol formal,... more The base-catalysed reactions of OH-bearing biobased derivatives (BBDs) including glycerol formal, solketal, glycerol carbonate, furfuryl alcohol and tetrahydrofurfuryl alcohol with non-toxic dialkyl carbonates (dimethyl and diethyl carbonate) were explored under continuous-flow (CF) conditions in the presence of three Na-exchanged Y- and X-faujasites (FAUs) and four Mg-Al hydrotalcites (HTs). Compared to previous etherification protocols mediated by dialkyl carbonates, the reported procedure offers substantial improvements not only in terms of (chemo)selectivity but also for the recyclability of the catalysts, workup, ease of product purification and, importantly, process intensification. Characterisation studies proved that both HT30 and KW2000 hydrotalcites acted as catalyst precursors: during the thermal activation pre-treatments, the typical lamellar structure of the hydrotalcite was broken down gradually into a MgO-like phase (periclase) or rather a magnesia-alumina solid solution, which was the genuine catalytic phase.
Beilstein Journal of Organic Chemistry, 2016
The use of ionic liquids (ILs) as organocatalysts is reviewed for transesterification reactions, ... more The use of ionic liquids (ILs) as organocatalysts is reviewed for transesterification reactions, specifically for the conversion of nontoxic compounds such as dialkyl carbonates to both linear mono-transesterification products or alkylene carbonates. An introductory survey compares pros and cons of classic catalysts based on both acidic and basic systems, to ionic liquids. Then, innovative green syntheses of task-specific ILs and their representative applications are introduced to detail the efficiency and highly selective outcome of ILs-catalyzed transesterification reactions. A mechanistic hypothesis is discussed by the concept of cooperative catalysis based on the dual (electrophilic/nucleophilic) activation of reactants.
Advanced Synthesis Catalysis, Aug 6, 2007
A liquid triphasic system made of isooctane, water, and trioctylmethylammonium chloride allows on... more A liquid triphasic system made of isooctane, water, and trioctylmethylammonium chloride allows one to carry out the hydroformylation of model olefins using neat RhCl 3 as catalyst precursor. By using the triphasic system, the catalyst is kept separate from the reagents and products. This allows one to simply remove the product and to recycle the catalyst numerous times. No leaching of rhodium into the organic phase is observed.
ACS Sustainable Chemistry & Engineering, 2014
ABSTRACT Four renewable lactones, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε-caprol... more ABSTRACT Four renewable lactones, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε-caprolactone (GBL, GVL, DVL, ECL, respectively) were shown to react with dimethyl-, diethyl-, and dibenzyl-carbonate (DMC, DEC, DBnC, respectively) in the presence of K2CO3 as basic catalyst, to yield selectively either the α-alkyl derivatives 1c–6c in the case of the five-membered ring GBL and GVL or the highly oxygenated acyclic monomeric derivatives 7a, 8a, and 9a in the case of the six- and seven-membered rings DVL and ECL. Selectivity and reaction conditions are investigated and a reaction mechanism is proposed. The organic carbonates act both as reagent and as reaction solvents, and the catalyst can be recovered by filtration and recycled.