Anthraquinone

9,10-Anthraquinone
Names
Preferred IUPAC name
Anthracene-9,10-dione
Other names
  • Anthraquinone
  • 9,10-Anthracenedione
  • Anthradione
  • 9,10-Anthrachinon
  • Anthracene-9,10-quinone
  • 9,10-Dihydro-9,10-dioxoanthracene
  • Hoelite
  • Morkit
  • Corbit
Identifiers
3D model (JSmol)
390030
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.001.408 Edit this at Wikidata
EC Number
  • 201-549-0
102870
KEGG
RTECS number
  • CB4725000
UNII
UN number 3143
  • InChI=1S/C14H8O2/c15-13-9-5-1-2-6-10(9)14(16)12-8-4-3-7-11(12)13/h1-8H
    Key: RZVHIXYEVGDQDX-UHFFFAOYSA-N
  • O=C1c2ccccc2C(=O)c3ccccc13
Properties
C14H8O2
Molar mass 208.216 g·mol−1
Appearance Yellow solid
Density 1.438 g/cm3
Melting point 284.8 °C (544.6 °F; 558.0 K)
Boiling point 377 °C (711 °F; 650 K)
Insoluble
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 possible carcinogen
GHS labelling:
GHS08: Health hazard
Danger
H350
P201, P202, P281, P308+P313, P405, P501
Flash point 185 °C (365 °F; 458 K)
Related compounds
Related compounds
 quinone,
anthracene
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Anthraquinone, also called anthracenedione or dioxoanthracene, is an aromatic organic compound with formula C
14H
8O
2. Several isomers exist but these terms usually refer to 9,10-anthraquinone (IUPAC: 9,10-dioxoanthracene) wherein the keto groups are located on the central ring. It is used as a digester additive to wood pulp for papermaking. Many anthraquinone derivatives are generated by organisms or synthesised industrially for use as dyes, pharmaceuticals, and catalysts. Anthraquinone is a yellow, highly crystalline solid, poorly soluble in water but soluble in hot organic solvents. It is almost completely insoluble in ethanol near room temperature but 2.25 g will dissolve in 100 g of boiling ethanol. It is found in nature as the rare mineral hoelite.

Synthesis

There are several current industrial methods to produce 9,10-anthraquinone:

  1. The oxidation of anthracene. Chromium(VI) is the typical oxidant.
  2. The Friedel–Crafts reaction of benzene and phthalic anhydride in presence of AlCl3. o-Benzoylbenzoic acid is an intermediate. This reaction is useful for producing substituted anthraquinones.
  3. The Diels-Alder reaction of naphthoquinone and butadiene followed by oxidative dehydrogenation.
  4. The acid-catalyzed dimerization of styrene to give a 1,3-diphenylbutene, which then can be transformed to the anthraquinone. This process was pioneered by BASF.

It also arises via the Rickert–Alder reaction, a retro-Diels–Alder reaction.

Reactions

Hydrogenation gives dihydroanthraquinone (anthrahydroquinone). Reduction with copper gives anthrone. Sulfonation with oleum gives anthroquinone-1-sulfonic acid, which reacts with sodium chlorate to give 1-chloroanthraquinone.

Applications

Anthraquinone itself has few direct applications except as a precursor to some dyes. It has been used as a bird repellant on seeds, and as a gas generator in satellite balloons. It has also been mixed with lanolin and used as a wool spray to protect sheep flocks against kea attacks in New Zealand. Anthraquinone is utilized in the production of hydrogen peroxide via the Riedl–Pfleiderer process. Anthraquinone derivatives are considered more useful.

Anthraquinone has application in the synthesis of danitracen.

The Schmidt reaction on anthraquinone gives the lactam, 5H-Dibenz[b,e]azepine-6,11-dione [1143-50-6]. The relevance of this is that it has application in the synthesis of prazepine, enprazepine, epinastine, pitrazepin, perlapine, elantrine, BRN 0492972 [971-97-1] & BRN 0489793 [69352-71-2].

Other isomers

Several other isomers of anthraquinone exist, including the 1,2-, 1,4-, and 2,6-anthraquinones. They are of minor importance compared to 9,10-anthraquinone.

Safety

Anthraquinone has no recorded LD50, probably because it is so insoluble in water.

In terms of metabolism of substituted anthraquinones, the enzyme encoded by the gene UGT1A8 has glucuronidase activity with many substrates including anthraquinones.

See also

References

  1. 1 2 3 4 Haynes, William M., ed. (2016). CRC Handbook of Chemistry and Physics (97th ed.). CRC Press. p. 3.28. ISBN 9781498754293.
  2. ↑ International Union of Pure and Applied Chemistry (2014). Nomenclature of Organic Chemistry: IUPAC Recommendations and Preferred Names 2013. The Royal Society of Chemistry. p. 724. doi:10.1039/9781849733069. ISBN 978-0-85404-182-4.
  3. ↑ Vogel, A. "Anthraquinone". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a02_347. ISBN 978-3-527-30673-2.
  4. ↑ Macleod, L. C.; Allen, C. F. H. (1934). "Benzanthrone". Organic Syntheses. 14: 4. doi:10.15227/orgsyn.014.0004.
  5. ↑ Scott, W. J.; Allen, C. F. H. (1938). "Potassium Anthraquinone-α-Sulfonate". Organic Syntheses. 18: 72. doi:10.15227/orgsyn.018.0072.
  6. ↑ Scott, W. J.; Allen, C. F. H. (1938). "α-Chloroanthraquinone". Organic Syntheses. 18: 15. doi:10.15227/orgsyn.018.0015.
  7. ↑ "www.americanheritage.com". Archived from the original on 2009-06-09. Retrieved 2009-09-22.
  8. ↑ Dudding, Adam (29 July 2012). "How to solve a problem like a kea". Sunday Star Times. New Zealand. Retrieved 11 November 2014.
  9. ↑ Campos-Martin, Jose M.; Blanco-Brieva, Gema; Fierro, Jose L. G. (2006). "Hydrogen Peroxide Synthesis: An Outlook beyond the Anthraquinone Process". Angewandte Chemie International Edition. 45 (42): 6962–6984. doi:10.1002/anie.200503779. PMID 17039551.
  10. ↑ 谢云漫, et al. CN106543082A (2017 to HENAN CHEMICAL INDUSTRY RESEARCH INSTITUTE CO LTD).
  11. ↑ Winthrop, S. O., Davis, M. A., Herr, F., Stewart, J., Gaudry, Roger. (1 November 1962). "New Psychotropic Agents. 1 II. Derivatives of 5,6-Dihydrodibenz[b,e]azepine (5,6-Dihydromorphanthridine)". Journal of Medicinal and Pharmaceutical Chemistry. 5 (6): 1199–1206. doi:10.1021/jm01241a011.
  12. ↑ Ritter, J. K.; Chen, F.; Sheen, Y. Y.; Tran, H. M.; Kimura, S.; Yeatman, M. T.; Owens, I. S. (1992). "A Novel Complex Locus UGT1 Encodes Human Bilirubin, Phenol, and other UDP-Glucuronosyltransferase Isozymes with Identical Carboxyl Termini" (PDF). Journal of Biological Chemistry. 267 (5): 3257–3261. doi:10.1016/S0021-9258(19)50724-4. PMID 1339448.