Production of renewable oleo-furan surfactants by cross-ketonization of biomass-derived furoic acid and fatty acids

Abstract

Synthesis of 2-dodecanoyl furan is a crucial step in the formulation of oleo-furan sulfonates as bio-surfactants from biomass-derived furans and vegetable-oil-derived molecules. Herein, cross-ketonization of 2-furoic acid and lauric acid...

Surfactants produced from carbohydrate derivatives: A review of the biobased building blocks used in their synthesis

“…Biomass‐derived 2‐furoic acid and lauric acid were used recently to synthesize 2‐dodecanoyl furan via cross‐ketonization to obtain biobased surfactant precursors. Cross‐ketonization enables easier separation and recyclability of solid catalysts and produces only water and carbon dioxide as byproducts, hence the novelty of the process (Nguyen et al, 2021). Furthermore, Renault et al (2021) used the direct transformation of uronates, found in natural alginate, or oligo‐alginates, into alkyl 5‐(dialkoxymethyl)‐2‐furoates, which after saponification result in anionic sodium 5‐(dialkoxymethyl)‐2‐furoates.…”

“…Fern andez et al (2005) applied a method to protect two pairs of hydroxyl with the isopropylidene ketal group to synthesize xylitol monoethers and other more complex compounds, following the series of reactions shown in Figure 36 propan-2-ol (XII) (Figure 36c). This mixture was reacted with methylated polypropylenedodecanol (1-O-methanesulfonyl-2-O-dodecyl-polypropyleneglycol, XIII).…”

5‐Hydroxymethylfurfural and Furfural Chemistry Toward Biobased Surfactants

“…A mixture of fatty carboxylic acids or diacids arising from an olefin metathesis/alkene oxidation sequence could also be used in the Friedel–Craft acylation step of furan (or methyl furan) leading to additional alkylfurans including symmetrical bis furanic systems [86] . An alternative clean and atom economical route to the acylfurans using the cross‐ketonization reaction of 2‐furoic acid and lauric acid under heterogeneous catalysis only giving H 2 O and CO 2 as side products was also recently proposed by Vlachos and co‐workers [98] . Other approaches towards long‐chain alkylfurans lubricants reported recently by Vlachos and co‐workers, [99–101] prepared by coupling alkylfurans with fatty aldehydes or ketones leading to di‐furanic products, or by conjugate addition of alkyl furans onto unsaturated aldehydes, might be also considered for extending the scope of possible amphiphilic targets.…”

Synthetic Routes for Designing Furanic and Non Furanic Biobased Surfactants from 5‐Hydroxymethylfurfural

“…In the last years, the need to prepare chemicals from renewable materials to face environmental concerns over fossil fuels consumption has motived the preparation of new oleofuran sulfonates from renewables with strong surfactant performance in minimal concentrations. [38,39] Thus, due to structural similarities with linear alkylbenzene sulfonates, furanmethane sulfonate esters and ethers can be an interesting alternative to the fossil-sourced LAS. Kraus and Lee [40] selectively prepared furanmethane sulfonate esters and ethers by reacting suitable aldehydes with an ether or ester alkyl tail, with a mild sulfonating agent such as sodium bisulfite, preserving the ester/ ether moiety and yielding 47-68 % ethers and 74-94 % esters (Scheme 5).…”