“Dihydrolevoglucosenone”的意思、由来-开放百科全书

Dihydrolevoglucosenone can be prepared through the hydrogenation of unsaturated anhydrosugar levoglucosenone (LGO) – a chemical building block obtained by acid-catalysed pyrolysis^[6] at 300 °C of lignocellulosic biomass such as wood waste or sawdust. A significant amount of char is produced, as a by-product of LGO production, which can be used as a fuel.

When cellulose in tetrahydrofuran is heated to 210 °C with low concentrations of sulfuric acid in an autoclave, up to 51% levoglucosenone can be obtained through a solvent-assisted pyrolysis.^[7] Under optimized laboratory conditions, yields of up to 95% of levoglucosenone can be reached.^[8]

Cellulose-containing waste from biorefineries can also be converted into 6-8% LGO under microwave irradiation at 180 °C for 5 minutes, in addition to the usual decomposition products such as hydroxymethylfurfural HMF, formic acid, formaldehyde, CO₂ and water.^[9]

Hydrogenation of the α, β-unsaturated ketone levoglucosenone (LGO) with a metal catalyst such as palladium on alumina (Pd/Al₂O₃) at 40 °C, leads selectively to Dihydrolevoglucosenone.^[10]

At higher temperatures, dihydrolevoglucosenone can be converted to secondary alcohol levoglucosanol and further to tetrahydrofuran-2,5-dimethanol through hydrogenation.

Properties

Dihydrolevoglucosenone is a clear colorless, to light yellow, liquid with a comparatively high dynamic viscosity of 14.5 cP^[11] (for comparison DMF: 0.92 cP at 20 °C, NMP: 1.67 cP at 25 °C) and a mild, smoky ketone-like odor.^[12] It is miscible with water and many organic solvents.^[12] The compound is stable at temperatures up to 195 °C and weak acids and bases. H₂-LGO reacts with inorganic bases via an aldol condensation mechanism. Dihydrolevoglucosenone is readily biodegradable (99% within 14 days) and reacts to oxidants such as aqueous 30% hydrogen peroxide solution even at room temperature. Dihydrolevoglucosenone has a boiling point of 227 °C at 100.7 kPa (vs 202 °C for NMP).

Applications

Dihydroglucosenone as a precursor

Dihydrolevoglucosenone can be used as a bio-based building block to produce a number of higher value chemicals such as drugs, flavours and fragrances and specialty polymers.^[10]

The oxidation of dihydrolevoglucosenone with peracids such as peracetic acid in acetic acid produces optically pure 5-hydroxymethyldihydrofuranone [(S) - (+) - 4-hydroxymethyl-γ-butyrolactone],^[13] from which zalcitabine (2'-3'-dideoxycytidine, ddC), formerly a HIV drug, is available.^[14]

In a two-step hydrogenation process with a metal catalyst – first at 60 °C then at 180 °C – 1,6-hexanediol is mainly obtained via several intermediates.^[15] 1,6-hexanediol can be used as a starting material for the production of polyesters, polyurethanes and diamine 1,6-diaminohexane.

At elevated temperature and in the presence of a palladium catalyst, hydrogenolysis of dihydrolevoglucosenone via levoglucosanol selectively yields tetrahydrofuran-2,5-dimethanol (THF-dimethanol),^[10] which is a biodegradable solvent and a bio-based precursor to 1,6-hexanediol (and 1,6-diaminohexane).^[16]

Dihydroglucosenone as a polar solvent

The search for alternative "green" solvents made from biomass or low-cost renewable raw materials, which are accessible through high-efficiency processes, in high yields, and meet the performance of conventional solvents,^[17] has triggered intensive research activities in industry and academia worldwide.

Dihydrolevoglucosenone is considered a candidate as a "green" aprotic dipolar solvent.^[3] Several standard reactions of organic chemistry, e.g. Mannutkin reaction,^[3] Sonogashira coupling,^[18] Suzuki-Miyaura coupling,^[19] or the synthesis of organic ureas^[20] have been carried out in dihydroglucosenone.

Production

Circa Group produces dihydrolevoglucosenone from cellulose under the Cyrene brand and has built a 50-tonne demonstration plant with partners in Tasmania. The company estimates that dihydroglucosenone performs better than NMP in 45% and comparably to NMP in 20% of trials to date. Circa received authorization in 2018 from the European Chemicals Agency (ECHA) to produce or import up to 100 tonnes per year of dihydroglucosenone to the EU.^[21]

Literature

References

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