Design of well balanced hydrophilic–lipophilic catalytic surfaces for the direct and selective monoesterification of various polyols

The transesterification process is a well known reaction of organic chemistry. However, the monoesterification of unprotected polyols such as glycerol or sucrose is much more complex and the design of selective catalysts is becoming a huge challenge in order to avoid many protection and deprotection steps, harmful for the cost and the environmental impact of the resulting process. In this study, we showed that the control of the hydrophilic–lipophilic balance of heterogeneous catalysts is a crucial key in order to tune both the catalyst activity and the monoester selectivity. Indeed, whereas homogeneous guanidine led to low selectivity toward monoesters, its anchorage on a hydrophilic solid support such as silica allowed us to prepare two basic hybrid organic–inorganic materials able to selectively afford monoesters in high yield and in an environmentally-friendly process, at low temperature and starting from an equimolecular mixture of unprotected polyols and various fatty methyl esters.

[1]  P. Anastas,et al.  Green Chemistry , 2018, Environmental Science.

[2]  Y. Pouilloux,et al.  Selective glycerol transesterification over mesoporous basic catalysts , 2004 .

[3]  Y. Queneau,et al.  The chemistry of unprotected sucrose: the selectivity issue , 2004 .

[4]  Dadan Kusdiana,et al.  Reactivity of triglycerides and fatty acids of rapeseed oil in supercritical alcohols. , 2004, Bioresource technology.

[5]  J. Barrault,et al.  “One pot” and selective synthesis of monoglycerides over homogeneous and heterogeneous guanidine catalysts , 2004 .

[6]  E. Sastre,et al.  Selective synthesis of fatty monoglycerides by using functionalised mesoporous catalysts , 2003 .

[7]  V. S. Lin,et al.  Organosulfonic acid-functionalized mesoporous silicas for the esterification of fatty acid , 2003 .

[8]  R. Maggi,et al.  TBD-catalysed solventless synthesis of symmetrically N,N′-substituted ureas from primary amines and diethyl carbonate , 2003 .

[9]  E. Lancelle-Beltran,et al.  Hybrid Materials Containing Metal(II) Schiff Base Complex Covalently Linked to the Silica Matrix by Two Si−C Bonds: Reaction with Dioxygen , 2003 .

[10]  R. Maggi,et al.  Cycloaddition of CO2 to epoxides over both homogeneous and silica-supported guanidine catalysts , 2003 .

[11]  E. Sastre,et al.  Synthesis of MCM-41 materials functionalised with dialkylsilane groups and their catalytic activity in the esterification of glycerol with fatty acids , 2003 .

[12]  U. Bornscheuer,et al.  Synthesis of 2‐monoglycerides by alcoholysis of palm oil and tuna oil using immobilized lipases , 2003 .

[13]  R. Maggi,et al.  MCM-41-TBD as a new, efficient, supported heterogeneous catalyst for the synthesis of thioureas , 2002 .

[14]  Y. Pouilloux,et al.  Catalysis and fine chemistry , 2002 .

[15]  E. Lancelle-Beltran,et al.  Ordered mesoporous hybrid materials containing cobalt(II) Schiff base complex , 2002 .

[16]  Uwe Schneidewind,et al.  10 Years after Rio—Concepts on the Contribution of Chemistry to a Sustainable Development , 2002 .

[17]  A. Sayari,et al.  Periodic Mesoporous Silica-Based Organic−Inorganic Nanocomposite Materials , 2001 .

[18]  Y. Pouilloux,et al.  Glycerol transesterification with methyl stearate over solid basic catalysts. I. Relationship between activity and basicity , 2001 .

[19]  G. Gelbard,et al.  Polynitrogen strong bases as immobilized catalysts , 2001 .

[20]  C. Torres,et al.  Emulsifiers from solid and liquid polyols : different strategies for obtaining optimum conversions and selectivities , 2001 .

[21]  E. Sastre,et al.  Selective synthesis of glycerol monolaurate with zeolitic molecular sieves , 2000 .

[22]  Nissim Garti,et al.  A DSC study of water behavior in water-in-oil microemulsions stabilized by sucrose esters and butanol , 2000 .

[23]  N. Garti,et al.  Non-ionic sucrose esters microemulsions for food applications. Part 1. Water solubilization , 2000 .

[24]  Y. Pouilloux,et al.  Reaction of glycerol with fatty acids in the presence of ion-exchange resins: Preparation of monoglycerides , 1999 .

[25]  R. Sheldon,et al.  Guanidines encapsulated in zeolite Y and anchored to MCM-41 : synthesis and catalytic activity , 1999 .

[26]  D. Vos,et al.  Mesoporous Sulfonic Acids as Selective Heterogeneous Catalysts for the Synthesis of Monoglycerides , 1999 .

[27]  Rogério Matheus Vargas,et al.  Preparation of monoglycerides by guanidine-catalyzed processes , 1998 .

[28]  G. Gelbard,et al.  Polynitrogen strong bases: 1-new syntheses of biguanides and their catalytic properties in transesterification reactions , 1998 .

[29]  A. Corma,et al.  Catalysts for the Production of Fine Chemicals: Production of Food Emulsifiers, Monoglycerides, by Glycerolysis of Fats with Solid Base Catalysts , 1998 .

[30]  D. Vos,et al.  1,5,7-Triazabicyclo[4.4.0]dec-5-ene Immobilized in MCM-41: A Strongly Basic Porous Catalyst† , 1997 .

[31]  D. Brunel,et al.  Monoglyceride Synthesis by Heterogeneous Catalysis Using MCM-41 Type Silicas Functionalized with Amino Groups. , 1997, The Journal of organic chemistry.

[32]  Ulf Schuchardt,et al.  Transesterification of soybean oil catalyzed by alkylguanidines heterogenized on different substituted polystyrenes , 1996 .

[33]  U. Schuchardt,et al.  Alkylguanidines as catalysts for the transesterification of rapeseed oil , 1995 .

[34]  R. Rowell,et al.  Emerging technologies for materials and chemicals from biomass. , 1992 .

[35]  N. Sonntag Glycerolysis of fats and methyl esters — Status, review and critique , 1982 .

[36]  M. Sahasrabudhe Chromatographic analysis of polyglycerols and their fatty acid esters , 1967 .

[37]  L. Hartman Advances In The Synthesis Of Glycerides Of Fatty Acids , 1958 .

[38]  D. Vos,et al.  Catalytic Activity of MCM-41–TBD in the Selective Preparation of Carbamates and Unsymmetrical Alkyl Carbonates from Diethyl Carbonate , 2002 .

[39]  T. Pinnavaia,et al.  Direct Synthesis of Hybrid Organic−Inorganic Nanoporous Silica by a Neutral Amine Assembly Route: Structure−Function Control by Stoichiometric Incorporation of Organosiloxane Molecules , 2000 .

[40]  D. Macquarrie,et al.  The preparation and use of novel immobilised guanidine catalysts in base-catalysed epoxidation and condensation reactions , 2000 .

[41]  E. Sastre,et al.  Esterification of lauric acid with glycerol using modified zeolite beta as catalyst , 2000 .

[42]  James H. Clark,et al.  Green chemistry: challenges and opportunities , 1999 .

[43]  D. B. Jackson,et al.  Organomodified hexagonal mesoporous silicates , 1999 .

[44]  U. Schuchardt,et al.  Transesterification of vegetable oils: a review , 1998 .

[45]  G. Renard,et al.  Guanidine linked to miceile-templated mesoporous silicates as base catalyst for transesterification. , 1998 .

[46]  J. Falbe Surfactants in consumer products : theory, technology, and application , 1987 .