Dihydrolevoglucosenone (Cyrene) as a bio-based alternative for dipolar aprotic solvents

Abstract

Dihydrolevoglucosenone (Cyrene) is a bio-based molecule, derived in two simple steps from cellulose, which demonstrates significant promise as a dipolar aprotic solvent. The dipolarity of dihydrolevoglucosenone is similar to NMP, DMF and sulpholane. Dihydrolevoglucosenone demonstrates similar performance to NMP in a fluorination reaction and the Menschutkin reaction.

Tools and techniques for solvent selection: green solvent selection guides

“…Although the vast majority of solvents are produced from fossil resources, any progress in green solvent selection is short sighted unless renewable solvents are considered on an equal footing. The unconventional functionality of neoteric solvents can offer the same properties as conventional solvents but avoid the drawbacks of familiar chemical moieties such as the reprotoxic amides [69,70]. Please note the general definition of a neoteric solvent also extends to ionic liquids [71], aqueous solvent systems [72], supercritical fluids [73], and tunable solvent systems [74], without relating to the origin of the solvent.…”

“…Despite being considered as 'problematic' , p-cymene has no red shaded scores, and as a renewable hydrocarbon is well placed to substitute toluene and other aromatic solvents [79][80][81][82][83][84]. Cyclic carbonates [70,85], and Cyrene [69], suffer in the environmental assessment because of their high boiling points, but offer clear health advantages over classical dipolar aprotic solvents (Fig. 13).…”

Synthesis of ureas in the bio-alternative solvent Cyrene

“…The viability of Cyrene as a DMF replacement was recently demonstrated by Watson et al in palladium mediated cross-coupling reactions. 27 In addition, Cyrene 28,29 was shown to be an effective solvent in S N 2 and S N Ar reactions 24 as well as for the synthesis of MOFs. 30 Interestingly, the use of Cyrene as a solvent for the addition of a nucleophile to a carbonyl has not been investigated despite the fact that these processes are known to be promoted by polar aprotic solvents.…”

“…22,23 A possible alternative to DMF and other polar aprotic solvents is Cyrene (7, dihydrolevoglucosenone, Figure 2). 24 Cyrene is synthesised in a two-step process from waste cellulose. 25,26 Importantly, it has similar physical properties to other dipolar aprotic solvents, including DMF.…”

A methodical selection process for the development of ketones and esters as bio-based replacements for traditional hydrocarbon solvents

“…The best candidates were characterised in terms of their solubility properties using the KamletAbboud-Taft (KAT) parameters [28][29][30] and a model Menschutkin reaction. [31][32][33] Solubility tests using natural rubber as an industrially-relevant probe solute were also carried out. Physical, flammability and toxicity (Ames test) properties were also determined.…”