Butenolide Derivatives of Biobased Furans: Sustainable Synthetic Dyes

Abstract

The dye and pigment manufacturing industry is one of the most polluting in the world. Each year, over one million tons of petrochemical colorants are produced globally, the synthesis of which generates a large amount of waste. Naturally occurring, plant‐based dyes, on the other hand, are resource intensive to produce (land, water, energy), and are generally less effective as colorants. Between these two extremes would be synthetic dyes that are fully sourced from biomass‐derived intermediates. The present work describes the synthesis of such compounds, containing strong chromophores that lead to bright colors in the yellow to red region of the visible spectrum. The study was originally motivated by an early report of an unidentified halomethylfurfural derivative which resulted from hydrolysis in the presence of barium carbonate, now characterized as a butenolide of 5‐(hydroxymethyl)furfural (HMF). The method has been generalized for the synthesis of dyes from other biobased platform molecules, and a mechanism is proposed.

A sustainable polymer and coating system based on renewable raw materials

“…1A). 34 First, we were encouraged to find that the experimental values for the FLY 450 absorption wavelength λ max = 450 nm (+2.76 eV) were in very strong agreement with the computed vertical excitation energies of +2.78 or +2.79 eV, simulated in DCM or MeOH, respectively (Fig. 1).…”

“…1A). 34 We envisioned that such biobased lactone-substituted furans might well generate singlet oxygen under aerobic irradiation, as similar organic dyes containing strong chromophores and high ε values often exhibit photosensitization properties. 35 To interrogate the potential of such dyes, we turned to computational chemistry to predict the properties of FLY 450.…”

Diversification of the Renewable Furanic Platform via 5‐(Chloromethyl)furfural‐Based Carbon Nucleophiles

“…The corresponding reaction with benzaldehyde gave the addition product in 99 % yield (see Supporting Information). 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 Finally, given our strong interest in the production of sustainable dyes, [17] the opportunity to create extended conjugation was clearly present in 12 and 13. That said, we tested acid-catalyzed dehydration on 12 and found it to be surprisingly sluggish.…”

“…Finally, given our strong interest in the production of sustainable dyes, [17] the opportunity to create extended conjugation was clearly present in 12 and 13 . That said, we tested acid‐catalyzed dehydration on 12 and found it to be surprisingly sluggish.…”

The sustainable materials roadmap

“…Researchers have been experimenting creatively on shortening the synthetic route and lowering the environmental impacts in the syntheses of organic conjugated molecules, by utilising abundant natural products with conjugated structures (e.g. indigo [129], theobromine [135], and biobased furans [136]) with impressive performances achieved. Moreover, incorporating natural products introduces biodegradation pathways for resulting molecules [129].…”