Dihydrolevoglucosenone

Chemical compound From Wikipedia, the free encyclopedia

Dihydrolevoglucosenone (Cyrene) is a bicyclic, chiral, seven-membered heterocyclic cycloalkanone which is a waste derived and fully biodegradable aprotic dipolar solvent.[4][5][6] It is an environmentally friendly alternative to dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP).[7]

Quick facts Names, Identifiers ...
Dihydrolevoglucosenone
Names
IUPAC name
(1R,5S)-7,8-Dioxabicyclo[3.2.1]octan-2-one
Other names
Cyrene
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.234.612 Edit this at Wikidata
EC Number
  • 807-130-4
  • InChI=1S/C6H8O3/c7-5-2-1-4-3-8-6(5)9-4/h4,6H,1-3H2/t4-,6+/m0/s1
    Key: WHIRALQRTSITMI-UJURSFKZSA-N
  • [C@H]12CCC([C@H](OC1)O2)=O
Properties
C6H8O3
Molar mass 128.127 g·mol−1
Appearance clear to yellowish liquid
Density 1.2473 g/cm3 (25 °C) [1]
Boiling point 226 Â°C (439 Â°F; 499 K)[2]
miscible
Vapor pressure 12.98 Pa (25 °C) [1]

14.4 Pa (25 °C) [2]

1.4732 (20 °C) [2]
Hazards[3]
GHS labelling:
GHS07: Exclamation mark
Warning
H319
P305+P351+P338, P313
Flash point 108 Â°C (226 Â°F; 381 K)
296 Â°C (565 Â°F; 569 K)
Except where otherwise noted, data are given for materials in their standard state (at 25 Â°C [77 Â°F], 100 kPa).
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Preparation

Dihydrolevoglucosenone can be prepared through the hydrogenation of unsaturated ketone levoglucosenone (LGO) with heterogenous palladium catalysts under mild conditions.[8][9] LGO is a chemical building block obtained by acid-catalyzed pyrolysis[10] of lignocellulosic biomass such as sawdust.

Acidic pyrolysis of cellulose to yield levoglucosenone (LGO)

Properties

Dihydrolevoglucosenone is a clear colorless, to light-yellow liquid with a mild, smoky ketone-like odor.[11] It is miscible with water and many organic solvents.[11] Dihydrolevoglucosenone has a boiling point of 226 Â°C at 101.325 kPa (vs 202 Â°C for NMP), and a vapor pressure of 12.98 Pa near room temperature (25  Â°C).[1] It has a comparatively high dynamic viscosity of 14.5 cP (for comparison DMF: 0.92 cP at 20 Â°C, NMP: 1.67 cP at 25 Â°C).[12]

The compound is stable at temperatures up to 195 Â°C and weak acids and bases.[citation needed] Dihydrolevoglucosenone can react with inorganic bases via an aldol condensation mechanism.[citation needed] Dihydrolevoglucosenone is readily biodegradable (99% within 14 days) and reacts to oxidants such as aqueous 30% hydrogen peroxide solution even at room temperature.[citation needed]

Applications

Dihydroglucosenone as a precursor

Dihydrolevoglucosenone can be used as a renewable building block to produce valuable chemicals such as drugs, flavours and fragrances and specialty polymers.[8]

As dihydrolevoglucosenone is produced as a single enantiomer, it can be used for chiral pool synthesis. For instance, oxidation with peroxy acids such as peroxyacetic acid produces optically pure 5-hydroxymethyldihydrofuranone,[13] from which zalcitabine, formerly a HIV drug, is available.[14]

Formation of 5-hydroxymethyldihydrofuranone [(S) - (+) - 4-hydroxymethyl-γ-butyrolactone

]

In a two-step hydrogenation process with a metal catalyst – first at 60 Â°C then at 180 Â°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),[8] which is a biodegradable solvent and a bio-based precursor to 1,6-hexanediol (and 1,6-diaminohexane).[16]

Hydrogenation of LGO zu tetrahydrofuran-2,5-dimethanol

Dihydroglucosenone as a safer 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 "green" replacement for DMF.[5] Several standard reactions of organic chemistry, e.g. Menshutkin reaction,[5] Sonogashira coupling,[18] Suzuki-Miyaura coupling[19] and the production of ureas[20] have been carried out in dihydrolevoglucosenone.

Formation of ureas using dihydrolevoglucosenone as a solvent

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

  • DS van Es: Study into alternative (biobased) polar aprotic solvents. Wageningen University, Wageningen 2017 (wur.nl [PDF]).
  • JH Clark, A. Hunt, C. Topi, G. Paggiola, J. Sherwood: Sustainable Solvents: Perspectives from Research, Business and Institutional Policy . Royal Society of Chemistry, London 2017, ISBN 978-1-78262-335-9 .
  • Dickson Kong and Anton V. Dolzhenko. "Cyrene: A Bio-Based Sustainable Solvent for Organic Synthesis." Sustainable Chemistry and Pharmacy 25 (April 1, 2022): 100591. https://doi.org/10.1016/j.scp.2021.100591

References

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