Levoglucosenone

Last updated
Levoglucosenone
Levoglucosenone.svg
Names
Preferred IUPAC name
(1S,5R)-6,8-Dioxabicyclo[3.2.1]oct-2-en-4-one
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
PubChem CID
UNII
  • InChI=1S/C6H6O3/c7-5-2-1-4-3-8-6(5)9-4/h1-2,4,6H,3H2/t4-,6+/m0/s1
    Key: HITOXZPZGPXYHY-UJURSFKZSA-N
  • C1[C@@H]2C=CC(=O)[C@H](O1)O2
Properties
C6H6O3
Molar mass 126.111 g·mol−1
Appearanceyellow liquid
Density 1.304 g/cm3 (20 °C) [1]
Boiling point 231 °C; 448 °F; 504 K [1]
Vapor pressure 6.2 Pa (25 °C) [1]
1.5065 (20 °C) [1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Levoglucosenone is an organic compound with the formula [OCH2(CH)4CO2]. A pale yellow liquid, it is an unsaturated bicyclic ketone-diether formed from levoglucosan by loss of two molecules of water. As a product of the acid-catalysed pyrolysis of cellulose, D-glucose, and levoglucosan, this liquid hydrocarbon is of interest as a biofuel and biofeedstock. [2]

Contents

Production

The compound was first identified in 1970 as a product of the thermal decomposition of cellulose. [3]

Pyrolysis of Cellulose to form Levoglucosenone Cellulose-Pyrolyse zu LGO.svg
Pyrolysis of Cellulose to form Levoglucosenone

The primary way of obtaining levoglucosenone is via pyrolysis of carbohydrates, particularly cellulose. Levoglucosenone can be derived from biomass or from other cellulosic materials including domestic/commercial waste paper. The availability of multiple sources is a key advantage when compared to other platform chemicals which are solely derived from biomass.

The title compound is produced when cellulose is heated above 170 °C with sulfuric acid with various additives. [2] Alongside levoglucosenone as a major product, 2-furfuraldehyde is sometimes formed in 5-10%. The bio-oil can be vacuum distilled, resulting in purified levoglucosenone. [4] The use of polar, aprotic solvents such as THF, γ-valerolactone and sulfolane has been found to improve pyrolytic yields, as the solvents cause swelling of the cellulose and inhibit repolymerisation back to levoglucosan. These solvents also promote catalytic dehydration of levoglucosan to levoglucosenone. [5]

Microwave irradiation of microcrystalline cellulose can also be used to produce levoglucosenone. [6]

Catalytic hydrogenation of LGO Hydrierung von LGO zu Dihydrolevoglucosenon.svg
Catalytic hydrogenation of LGO

Cellulose-containing waste from biorefineries can also be converted into 6-8% LGO under microwave irradiation in addition to the usual decomposition products such as hydroxymethylfurfural HMF, formic acid, formaldehyde, CO2 and water. [7]

Reactions

As a highly functionalized, chiral compound, levoglucosenone is a precursor to a variety of compounds. [8] Levoglucosenone is a promising bio-renewable platform for the production of commodity chemicals, being especially interesting the new insight provided by Huber and co-workers into how to transform this molecule into α,ω-diols, monomers for the production of polyesters and polyurethanes. [9]

Palladium on carbon (and related Pd- and Pt-based catalysts) act on the title compound by hydrogenation (i.e. dihydrolevoglucosenone and levoglucosanol) and hydrogenolysis (i.e. tetrahydrofurandimethanol (THFDM) and 1,6-hexanediol). [10] [11]

Levoglucosenone is a Michael acceptor enabling its conversion to a variety of derivatives. [12]

See also

Related Research Articles

<span class="mw-page-title-main">Cellulose</span> Polymer of glucose and structural component of cell wall of plants and green algae

Cellulose is an organic compound with the formula (C
6H
10O
5)
n, a polysaccharide consisting of a linear chain of several hundred to many thousands of β(1→4) linked D-glucose units. Cellulose is an important structural component of the primary cell wall of green plants, many forms of algae and the oomycetes. Some species of bacteria secrete it to form biofilms. Cellulose is the most abundant organic polymer on Earth. The cellulose content of cotton fiber is 90%, that of wood is 40–50%, and that of dried hemp is approximately 57%.

<span class="mw-page-title-main">Tetrahydrofuran</span> Cyclic chemical compound, (CH₂)₄O

Tetrahydrofuran (THF), or oxolane, is an organic compound with the formula (CH2)4O. The compound is classified as heterocyclic compound, specifically a cyclic ether. It is a colorless, water-miscible organic liquid with low viscosity. It is mainly used as a precursor to polymers. Being polar and having a wide liquid range, THF is a versatile solvent.

Nitromethane, sometimes shortened to simply "nitro", is an organic compound with the chemical formula CH
3NO
2. It is the simplest organic nitro compound. It is a polar liquid commonly used as a solvent in a variety of industrial applications such as in extractions, as a reaction medium, and as a cleaning solvent. As an intermediate in organic synthesis, it is used widely in the manufacture of pesticides, explosives, fibers, and coatings. Nitromethane is used as a fuel additive in various motorsports and hobbies, e.g. Top Fuel drag racing and miniature internal combustion engines in radio control, control line and free flight model aircraft.

<span class="mw-page-title-main">Pyrolysis</span> Thermal decomposition of materials at elevated temperatures in an inert atmosphere

The pyrolysis process is the thermal decomposition of materials at elevated temperatures, often in an inert atmosphere.

Furfural is an organic compound with the formula C4H3OCHO. It is a colorless liquid, although commercial samples are often brown. It has an aldehyde group attached to the 2-position of furan. It is a product of the dehydration of sugars, as occurs in a variety of agricultural byproducts, including corncobs, oat, wheat bran, and sawdust. The name furfural comes from the Latin word furfur, meaning bran, referring to its usual source. Furfural is only derived from dryed biomass, In addition to ethanol, acetic acid, and sugar, furfural is one of the oldest organic chemicals available readily purified from natural precursors.

Humins are carbon-based macromolecular substances, that can be found in soil chemistry or as a by-product from saccharide-based biorefinery processes.

<span class="mw-page-title-main">Biorefinery</span> Refinery that converts biomass to energy and other beneficial byproducts

A biorefinery is a refinery that converts biomass to energy and other beneficial byproducts. The International Energy Agency Bioenergy Task 42 defined biorefining as "the sustainable processing of biomass into a spectrum of bio-based products and bioenergy ". As refineries, biorefineries can provide multiple chemicals by fractioning an initial raw material (biomass) into multiple intermediates that can be further converted into value-added products. Each refining phase is also referred to as a "cascading phase". The use of biomass as feedstock can provide a benefit by reducing the impacts on the environment, as lower pollutants emissions and reduction in the emissions of hazard products. In addition, biorefineries are intended to achieve the following goals:

  1. Supply the current fuels and chemical building blocks
  2. Supply new building blocks for the production of novel materials with disruptive characteristics
  3. Creation of new jobs, including rural areas
  4. Valorization of waste
  5. Achieve the ultimate goal of reducing GHG emissions
<span class="mw-page-title-main">Meldrum's acid</span> Chemical compound

Meldrum's acid or 2,2-dimethyl-1,3-dioxane-4,6-dione is an organic compound with formula C6H8O4. Its molecule has a heterocyclic core with four carbon and two oxygen atoms; the formula can also be written as [−O−(C 2)−O−(C=O)−(CH2)−(C=O)−].

<span class="mw-page-title-main">Levulinic acid</span> Chemical compound

Levulinic acid, or 4-oxopentanoic acid, is an organic compound with the formula CH3C(O)CH2CH2CO2H. It is classified as a keto acid. This white crystalline solid is soluble in water and polar organic solvents. It is derived from degradation of cellulose and is a potential precursor to biofuels, such as ethyl levulinate.

Guaiacol is an organic compound with the formula C6H4(OH)(OCH3). It is a phenolic compound containing a methoxy functional group. Guaiacol appears as a viscous colorless oil, although aged or impure samples are often yellowish. It occurs widely in nature and is a common product of the pyrolysis of wood.

Hydrodeoxygenation (HDO) is a hydrogenolysis process for removing oxygen from oxygen-containing compounds. Typical HDO catalysts commonly are sulfided nickel-molybdenum or cobalt-molybdenum on gamma alumina. An idealized reaction is:

Pyrolysis oil, sometimes also known as bio-crude or bio-oil, is a synthetic fuel with limited industrial application and under investigation as substitute for petroleum. It is obtained by heating dried biomass without oxygen in a reactor at a temperature of about 500 °C (900 °F) with subsequent cooling, separation from the aqueous phase and other processes. Pyrolysis oil is a kind of tar and normally contains levels of oxygen too high to be considered a pure hydrocarbon. This high oxygen content results in non-volatility, corrosiveness, partial miscibility with fossil fuels, thermal instability, and a tendency to polymerize when exposed to air. As such, it is distinctly different from petroleum products. Removing oxygen from bio-oil or nitrogen from algal bio-oil is known as upgrading.

<span class="mw-page-title-main">Lignocellulosic biomass</span> Plant dry matter

Lignocellulose refers to plant dry matter (biomass), so called lignocellulosic biomass. It is the most abundantly available raw material on the Earth for the production of biofuels. It is composed of two kinds of carbohydrate polymers, cellulose and hemicellulose, and an aromatic-rich polymer called lignin. Any biomass rich in cellulose, hemicelluloses, and lignin are commonly referred to as lignocellulosic biomass. Each component has a distinct chemical behavior. Being a composite of three very different components makes the processing of lignocellulose challenging. The evolved resistance to degradation or even separation is referred to as recalcitrance. Overcoming this recalcitrance to produce useful, high value products requires a combination of heat, chemicals, enzymes, and microorganisms. These carbohydrate-containing polymers contain different sugar monomers and they are covalently bound to lignin.

Bis(trimethylsilyl)amine (also known as hexamethyldisilazane and HMDS) is an organosilicon compound with the molecular formula [(CH3)3Si]2NH. The molecule is a derivative of ammonia with trimethylsilyl groups in place of two hydrogen atoms. An electron diffraction study shows that silicon-nitrogen bond length (173.5 pm) and Si-N-Si bond angle (125.5°) to be similar to disilazane (in which methyl groups are replaced by hydrogen atoms) suggesting that steric factors are not a factor in regulating angles in this case. This colorless liquid is a reagent and a precursor to bases that are popular in organic synthesis and organometallic chemistry. Additionally, HMDS is also increasingly used as molecular precursor in chemical vapor deposition techniques to deposit silicon carbonitride thin films or coatings.

γ-Valerolactone Chemical compound

γ-Valerolactone (GVL) or gamma-valerolactone is an organic compound with the formula C5H8O2. This colourless liquid is one of the more common lactones. GVL is chiral but is usually used as the racemate. It is readily obtained from cellulosic biomass and is a potential fuel and green solvent.

Reactive flash volatilization (RFV) is a chemical process that rapidly converts nonvolatile solids and liquids to volatile compounds by thermal decomposition for integration with catalytic chemistries.

<span class="mw-page-title-main">Levoglucosan</span> Chemical compound

Levoglucosan (C6H10O5) is an organic compound with a six-carbon ring structure formed from the pyrolysis of carbohydrates, such as starch and cellulose. As a result, levoglucosan is often used as a chemical tracer for biomass burning in atmospheric chemistry studies, particularly with respect to airborne particulate matter. Along with other tracers such as potassium, oxalate, and gaseous acetonitrile, levoglucosan has been shown to be highly correlated with regional fires. This is because the gas emitted by the pyrolysis of wood (biomass) contains significant amounts of levoglucosan.

Hydrothermal liquefaction (HTL) is a thermal depolymerization process used to convert wet biomass, and other macromolecules, into crude-like oil under moderate temperature and high pressure. The crude-like oil has high energy density with a lower heating value of 33.8-36.9 MJ/kg and 5-20 wt% oxygen and renewable chemicals. The process has also been called hydrous pyrolysis.

The OxFA process is a process to produce formic acid from biomass by catalytic oxidation using molecular oxygen or air. Polyoxometalates of the Keggin-type are used as catalysts.

<span class="mw-page-title-main">Dihydrolevoglucosenone</span> Chemical compound

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

References

  1. 1 2 3 4 Baird, Zachariah Steven; Uusi-Kyyny, Petri; Pokki, Juha-Pekka; Pedegert, Emilie; Alopaeus, Ville (6 Nov 2019). "Vapor Pressures, Densities, and PC-SAFT Parameters for 11 Bio-compounds". International Journal of Thermophysics. 40 (11): 102. Bibcode:2019IJT....40..102B. doi: 10.1007/s10765-019-2570-9 .
  2. 1 2 Klepp, J.; Dillon, W.; Lin, Y.; Feng, P.; Greatrex, B. W. (2020). "Preparation of (-)-Levoglucosenone from Cellulose Using Sulfuric Acid in Polyethylene Glycol". Organic Syntheses. 97: 38–53. doi: 10.15227/orgsyn.097.0038 . S2CID   216214489.
  3. ↑ Tsuchiya, Yoshio; Sumi, Kikuo (1970). "Thermal decomposition products of cellulose". Journal of Applied Polymer Science. 14 (8): 2003–2013. doi:10.1002/app.1970.070140808. ISSN   0021-8995. S2CID   98167855.
  4. ↑ Comba, María B.; Tsai, Yi-hsuan; Sarotti, Ariel M.; Mangione, María I.; Suárez, Alejandra G.; Spanevello, Rolando A. (2017-12-19). "Levoglucosenone and Its New Applications: Valorization of Cellulose Residues". European Journal of Organic Chemistry. 2018 (5): 590–604. doi:10.1002/ejoc.201701227. ISSN   1434-193X.
  5. ↑ Kudo, Shinji; Goto, Nozomi; Sperry, Jonathan; Norinaga, Koyo; Hayashi, Jun-ichiro (2016-12-21). "Production of Levoglucosenone and Dihydrolevoglucosenone by Catalytic Reforming of Volatiles from Cellulose Pyrolysis Using Supported Ionic Liquid Phase". ACS Sustainable Chemistry & Engineering. 5 (1): 1132–1140. doi:10.1021/acssuschemeng.6b02463. ISSN   2168-0485.
  6. ↑ Sarotti, Ariel M.; Spanevello, Rolando A.; Suárez, Alejandra G. (2007). "An efficient microwave-assisted green transformation of cellulose into levoglucosenone. Advantages of the use of an experimental design approach". Green Chemistry. 9 (10): 1137. doi:10.1039/b703690f. ISSN   1463-9262.
  7. ↑ Clark, J. H.; McQueen-Mason, S. J.; Raverty, W. D.; Farmer, T. J.; Simister, R.; Gomez, L. D.; Macquarrie, D. J.; Budarin, V. L.; Fan, J. (2016-08-02). "A new perspective in bio-refining: levoglucosenone and cleaner lignin from waste biorefinery hydrolysis lignin by selective conversion of residual saccharides". Energy & Environmental Science. 9 (8): 2571–2574. doi: 10.1039/C6EE01352J . ISSN   1754-5706.
  8. ↑ Sarotti, Ariel M.; Zanardi, María M.; Spanevello, Rolando A.; Suárez, Alejandra G. (2012-11-01). "Recent applications of levoglucosenone as chiral synthon". Current Organic Synthesis. 9 (4): 439–459. doi:10.2174/157017912802651401.
  9. ↑ Huber, George W.; Dumesic, James A.; Hermans, Ive; Maravelias, Christos T.; Banholzer, Williams F.; Walker, Theodore; Burt, Samuel P.; Brentzel, Zachary J.; Alonso, David M. (2017-09-20). "New catalytic strategies for α,ω-diols production from lignocellulosic biomass". Faraday Discussions. 202: 247–267. Bibcode:2017FaDi..202..247H. doi:10.1039/C7FD00036G. ISSN   1364-5498. PMID   28678237.
  10. ↑ Krishna, Siddarth H.; McClelland, Daniel J.; Rashke, Quinn A.; Dumesic, James A.; Huber, George W. (2016-12-12). "Hydrogenation of levoglucosenone to renewable chemicals". Green Chemistry. 19 (5): 1278–1285. doi:10.1039/C6GC03028A. OSTI   1477850.
  11. ↑ Mazarío, Jaime; Parreño Romero, Míriam; Concepción, Patricia; Chávez-Sifontes, Marvin; Spanevello, Rolando A.; Comba, María B.; Suárez, Alejandra G.; Domine, Marcelo E. (2019-07-26). "Tuning zirconia-supported metal catalysts for selective one-step hydrogenation of levoglucosenone". Green Chemistry. 21 (17): 4769–4785. doi:10.1039/C9GC01857C. hdl: 11336/108039 . ISSN   1463-9270. S2CID   199647263.
  12. ↑ Lefebvre, Corentin; Van Gysel, Terence; Michelin, Clément; Rousset, Elodie; Djiré, Djibril; Allais, Florent; Hoffmann, Norbert (2022). "Photocatalytic Radical Addition to Levoglucosenone" (PDF). European Journal of Organic Chemistry. 2022. doi:10.1002/ejoc.202101298. S2CID   245305312.
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