Synthesis of 3-alkoxypropan-1,2-diols from glycidol: experimental and theoretical studies for the optimization of the synthesis of glycerol derived solvents

Abstract

Optimized green synthesis of glyceryl monoethers from alcohols and glycidol through experimental and computational studies.

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.…”

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

“…MAGEsh ave been also synthesized by glycerol etherification with n-butanol( 150 8C, 6.5 mol %B i(OTf) 3 as catalyst, 24 h) and 1-dodecanol (130 8C, 1equivcetyltrimethylammonium bromide (CTAB) and 10 wt %o fH + as catalysts,2 4h)i nt he presence of homogeneous catalysts with good yields (70 %a nd 60 %r espectively). [11] Only af ew studies have reported the preparation of MAGEs startingf rom glycidol [8,[14][15][16] and, in this context,M AGEs have been obtained with high selectivity by using homogeneous catalysts and very preliminary results have been reported in the presence of heterogeneous basic catalysts (71 %w /w toward glycidol with Amberlyst IRA-400). [8,35] Generally,t his approachp ermitsM AGEst ob eo btained with high selectivity,f avoring the developmento fs olvents,i nm ostc ases with av ery low eco-toxicity [36] and with tunable properties.…”

“…[33,34] Industrial building blocks, alternative to glycerol, have been successfully used to prepareM AGEs, such as glycidol, epichlorohydrin, allyl alcohol, and 3-chloro-1,2-propanediol. [16] In our previousstudies, [14,15] we reported the selectivepreparation of MAGEs under mild reactionc onditions (80 8C, 0.01 mol %c atalyst, alcohol/glycidol 9:1m olarr atio, 1h), by Scheme1.Investigated routes for the synthesis of glycidol. [11] Only af ew studies have reported the preparation of MAGEs startingf rom glycidol [8,[14][15][16] and, in this context,M AGEs have been obtained with high selectivity by using homogeneous catalysts and very preliminary results have been reported in the presence of heterogeneous basic catalysts (71 %w /w toward glycidol with Amberlyst IRA-400).…”

“…[8] MAGEsa re high-value compounds with severali ndustrial applications in the field of cosmetics,p harmaceuticals, solvents, andd etergents. [8,[14][15][16] Furthermore,g lycidol is a very reactive molecule employeda lso for the production of severalinteresting compounds (diols, organic carbonates, pharmaceuticals, polymers, etc.) [12,13] Glycidol was also recently recognizeda sa ni nteresting and valuable starting chemicalt op roduce MAGEs.…”