Oleochemicals such as functionalized fatty acid esters and vegetable oils are classes of renewably sourced compounds that are increasingly attracting attention in sustainable chemistry as replacement for fossil-fuel based chemicals. The possibility of coupling CO2 with epoxidized fatty acids esters (EFAEs) and epoxidized vegetable oils (EVOs) to afford compounds that are attractive as additives or chemical intermediates in the synthesis of non-isocyanate polyhydroxyurethanes (NIPU) can conjugate highly sought-after CO2 valorization with the exploitation of bio-based substrates. In this context, there have been very few attempts to employ organocatalytic hydrogen bond donors (HBDs) in the cycloaddition reaction of CO2 to EFAEs and EVOs and no studies focusing on bio-based and readily available HBDs. In this work we show that ascorbic acid is an efficient HBD for the cycloaddition of CO2 to EFAEs and EVOs under mild reaction conditions of temperature (80–100 °C) and pressure (5–10 bar) that could be applied to several kinds of substrates (monounsaturated EFAEs, polyunsaturated EFAEs and EVOs). In all cases, the formed by-products (ketones, allylic alcohols, cyclic ethers etc.) were identified and the reaction conditions were tuned in order to obtain the target carbonates, generally, in high yields and selectivity.
Synthesis of Bio-Based Cyclic Carbonates Using a Bio-Based Hydrogen Bond Donor: Application of Ascorbic Acid to the Cycloaddition of CO2 to Oleochemicals
D'Elia V.
Ultimo
2020-01-01
Abstract
Oleochemicals such as functionalized fatty acid esters and vegetable oils are classes of renewably sourced compounds that are increasingly attracting attention in sustainable chemistry as replacement for fossil-fuel based chemicals. The possibility of coupling CO2 with epoxidized fatty acids esters (EFAEs) and epoxidized vegetable oils (EVOs) to afford compounds that are attractive as additives or chemical intermediates in the synthesis of non-isocyanate polyhydroxyurethanes (NIPU) can conjugate highly sought-after CO2 valorization with the exploitation of bio-based substrates. In this context, there have been very few attempts to employ organocatalytic hydrogen bond donors (HBDs) in the cycloaddition reaction of CO2 to EFAEs and EVOs and no studies focusing on bio-based and readily available HBDs. In this work we show that ascorbic acid is an efficient HBD for the cycloaddition of CO2 to EFAEs and EVOs under mild reaction conditions of temperature (80–100 °C) and pressure (5–10 bar) that could be applied to several kinds of substrates (monounsaturated EFAEs, polyunsaturated EFAEs and EVOs). In all cases, the formed by-products (ketones, allylic alcohols, cyclic ethers etc.) were identified and the reaction conditions were tuned in order to obtain the target carbonates, generally, in high yields and selectivity.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
