Explorations into the sustainable synthesis of cyclic and polymeric carbonates and thiocarbonates from eugenol-derived monomers and their reactions with CO₂, COS, or CS₂

Abstract

Polymers obtained utilizing renewable monomers (bio-based polymers) have attracted much attention recently due to their intrinsic ability to address environmental issues and depletion of fossil fuels, which are the main...

Sustainable Synthesis of CO2-Derived Polycarbonates from the Natural Product, Eugenol: Terpolymerization with Propylene Oxide

“…The eugenol epoxide was synthesized in multigram quantities by following our recently reported procedure . The eugenol was protected by using pivaloyl chloride/triethylamine, and epoxidation was achieved using meta -chloroperoxybenzoic acid ( m -CPBA).…”

“…The eugenol epoxide was synthesized in multigram quantities by following our recently reported procedure. 25 The eugenol was protected by using pivaloyl chloride/triethylamine, and epoxidation was achieved using meta-chloroperoxybenzoic acid (m-CPBA). The protection was necessary to ensure that the −OH group of unprotected eugenol epoxide would not act as a chain transfer agent and deactivate the catalyst at higher concentrations.…”

Chemoselective cycloadditions to epoxide derivatives of erucic acid with CO2and CS2: controlled access to value-added bio-derived compounds

“…In comparison to the cycloaddition reaction with CO 2 , little attention has been paid to this analogous reaction. 16,17 CS 2 is a toxic gas, mainly produced during the manufacture of viscose fibres. 18 The CS 2 produced in this process predominantly arises from evaporative emissions as CS 2 is used as solvent.…”

Synthesis and applications of the sulfur containing analogues of cyclic carbonates

“…Most recently in 2022, using the same ligand, Darensbourg presented a Cr-based salen catalyst system that was able to realise the 1,3-oxathiolane-2-thione derived from a bio-based eugenol substrate, using 0.4 mol% of the Cr(salen) complex along with an equimolar loading of bis (triphenylphosphine)iminium chloride (PPNCl) co-catalyst, at only 40 °C. 73 Shi/Cao and co-workers have described a catalyst system based on an N-heterocyclic carbene (NHC) which was prepared in situ through the reaction of 4,5-dihydro-1,3-bis(2,6-diisopropylphenyl)-1H-imidazolinium chloride with K 2 CO 3 . 74 With a 5.0 mol% loading of the NHC it was possible to obtain moderate to high selectivities from several monosubstituted epoxides towards the dithiocarbonate over the trithiocarbonate product, at 80 °C.…”

“…Most recently in 2022, using the same ligand, Darensbourg presented a Cr-based salen catalyst system that was able to realise the 1,3-oxathiolane-2-thione derived from a bio-based eugenol substrate, using 0.4 mol% of the Cr(salen) complex along with an equimolar loading of bis(triphenylphosphine)iminium chloride (PPNCl) co-catalyst, at only 40 °C. 73…”