Anthrone

Anthrone
Skeletal formula
Skeletal formula
Ball-and-stick model
Ball-and-stick model
Names
Preferred IUPAC name
Anthracen-9(10H)-one
Other names
  • Carbothrone
  • 9-Oxoanthracene
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.001.813 Edit this at Wikidata
UNII
  • InChI=1S/C14H10O/c15-14-12-7-3-1-5-10(12)9-11-6-2-4-8-13(11)14/h1-8H,9H2 checkY
    Key: RJGDLRCDCYRQOQ-UHFFFAOYSA-N checkY
  • InChI=1/C14H10O/c15-14-12-7-3-1-5-10(12)9-11-6-2-4-8-13(11)14/h1-8H,9H2
    Key: RJGDLRCDCYRQOQ-UHFFFAOYAA
  • O=C2c1c(cccc1)Cc3c2cccc3
Properties
C14H10O
Molar mass 194.233 g·mol−1
Appearance White to light yellow needles
Melting point 155 to 158 °C (311 to 316 °F; 428 to 431 K)
Insoluble
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkYX markN ?)

Anthrone is a tricyclic aromatic ketone. It is used for a common cellulose assay and in the colorimetric determination of carbohydrates.

In strongly acidic media, carbohydrates form furfural derivatives that react with anthrone to produce colored compounds. Anthrone-based reagents are also used as visualization stains in thin-layer chromatography for detecting sugars, particularly ketoses, and glycolipids such as cerebrosides.

Derivatives of anthrone are used in pharmacy as laxative. They stimulate the motion of the colon and reduce water reabsorption. Some anthrone derivatives can be extracted from a variety of plants, including Rhamnus frangula, Aloe ferox, Rheum officinale, and Cassia senna. Glycosides of anthrone are also found in high amounts in rhubarb leaves, and alongside concentrated amounts of oxalic acid are the reason for the leaves being inedible.

Synthesis and reactions

Anthrone can be prepared from anthraquinone by reduction with tin or copper.

An alternative synthesis involves cyclization of o-benzylbenzoic acid induced with hydrogen fluoride.

Anthrone syntheses

Anthrone condenses with glyoxal to give, following dehydrogenation, acedianthrone, a useful octacyclic pigment.

Tautomeric equilibrium for anthrone.

Anthrone is the more commonly encountered tautomer of anthrol, as has been established also by X-ray crystallography. The tautomeric equilibrium constant is estimated at 100 in aqueous solution. For the two other isomeric anthrols, the tautomeric equilibrium is reversed: they are phenolic.

Anthrone undergoes nitration using conventional conditions for aromatic nitration, implying that it is the hydroxy tautomer that is the reactant.

Applications

This is a list of some of the applications of anthrone: XE-991, DMP 543, maprotiline, 1-(9-Anthryloxy)-2-aminoethane (c.f. flunamine). In Lednicer's textbook it was said that melitracen was made from anthrone. However, since the time of publication it has now been discovered that there are other avenues to making the 10,10-dimethylanthrone [5447-86-9] precursor compound.

The Beckmann rearrangement or Schmidt reaction of anthrone would give 6-morphanthridinone [1211-06-9]. The relevance of this to drug chemistry is that it finds involvement in the synthesis of perlapine, epinastine, mianserin, prazepine & pitrazepin, for example.

References

  1. ↑ Trevelyan, W. E.; Forrest, RS; Harrison, JS (1952). "Determination of Yeast Carbohydrates with the Anthrone Reagent". Nature. 170 (4328): 626–627. Bibcode:1952Natur.170..626T. doi:10.1038/170626a0. PMID 13002392. S2CID 4184596.
  2. ↑ Jork, Hellmut; Werner Funk; Walter Fischer; Hans Wimmer (1990). Thin-Layer Chromatography: Reagents and Detection Methods. Vol. 1a. VCH. pp. 202–204. ISBN 3-527-27834-6.
  3. ↑ van Gent, C. M.; O. J. Roseleur; P. van der Bijl (1973). "The detection of cerebrosides on thin layer chromatograms with an anthrone spray reagent". Journal of Chromatography. 85 (1): 174–176. doi:10.1016/S0021-9673(01)91884-9.
  4. ↑ Niaz, Kamal; Khan, Fazlullah (2020-01-01), "Chapter 3 - Analysis of polyphenolics", in Sanches Silva, Ana; Nabavi, Seyed Fazel; Saeedi, Mina; Nabavi, Seyed Mohammad (eds.), Recent Advances in Natural Products Analysis, Elsevier, pp. 39–197, doi:10.1016/b978-0-12-816455-6.00003-2, ISBN 978-0-12-816455-6, retrieved 2024-06-01
  5. ↑ Macleod, L. C.; Allen, C. F. H. (1934). "Benzanthrone". Organic Syntheses. 14: 4. doi:10.15227/orgsyn.014.0004.
  6. ↑ Fieser, Louis F.; Hershberg, E. B. (May 1939). "Inter- and Intramolecular Acylations with Hydrogen Fluoride". Journal of the American Chemical Society. 61 (5): 1272–1281. Bibcode:1939JAChS..61.1272F. doi:10.1021/ja01874a079.
  7. ↑ Bien, H.-S.; Stawitz, J.; Wunderlich, K. (2005). "Anthraquinone Dyes and Intermediates". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a02_355. ISBN 978-3-527-30673-2.
  8. ↑ Lian, Jian-Jou; Lin, Chung-Chang; Chang, Hsu-Kai; Chen, Po-Chiang; Liu, Rai-Shung (2006). "Thermal and Metal-Catalyzed Cyclization of 1-Substituted 3,5-Dien-1-ynes via a [1,7]-Hydrogen Shift: Development of a Tandem Aldol Condensation−Dehydration and Aromatization Catalysis between 3-En-1-yn-5-al Units and Cyclic Ketones". Journal of the American Chemical Society. 128 (30): 9661–9667. Bibcode:2006JAChS.128.9661L. doi:10.1021/ja061203b. PMID 16866518.
  9. ↑ Ośmiałowski, Borys; Raczyńska, Ewa D.; Krygowski, Tadeusz M. (2006). "Tautomeric Equilibria and Pi Electron Delocalization for Some Monohydroxyarenes Quantum Chemical Studies". The Journal of Organic Chemistry. 71 (10): 3727–3736. doi:10.1021/jo052615q. PMID 16674042.
  10. ↑ Kurt H. Meyer (1928). "Nitroanthrone". Organic Syntheses. 8: 78. doi:10.15227/orgsyn.008.0078.
  11. ↑ Wilkerson, W., Earl, R., Calabrese, J., Drammond, S., Teleha, C., Voss, M., Zaczek, R. (January 1996). "Acetylcholine release enhancers related to linopirdine: A structure—activity relationship study. II". European Journal of Medicinal Chemistry. 31 (4): 319–330. doi:10.1016/0223-5234(96)80369-2.
  12. ↑ Earl, R. A., Zaczek, R., Teleha, C. A., Fisher, B. N., Maciag, C. M., Marynowski, M. E., Logue, A. R., Tam, S. W., Tinker, W. J., Huang, S.-M., Chorvat, R. J. (1 November 1998). "2-Fluoro-4-pyridinylmethyl Analogues of Linopirdine as Orally Active Acetylcholine Release-Enhancing Agents with Good Efficacy and Duration of Action". Journal of Medicinal Chemistry. 41 (23): 4615–4622. doi:10.1021/jm9803424.
  13. ↑ Wilhelm, M., Schmidt, P. (January 1969). "Synthese und Eigenschaften von 1‐Aminoalkyl‐dibenzo[ b , e ]bicyclo[2.2.2]octadienen". Helvetica Chimica Acta. 52 (6): 1385–1395. doi:10.1002/hlca.19690520602.
  14. ↑ Lednicer, D. (13 October 2008). Strategies for Organic Drug Synthesis and Design (1st ed.). Wiley. doi:10.1002/9780470399613. ISBN 9780470190395.
  15. ↑ Weinreb, S. M., Schaumann, E., eds. (2004). Category 2, Hetarenes and Related Ring Systems: Six-Membered Hetarenes with Two Unlike or More than Two Heteroatoms and Fully Unsaturated Larger-Ring Heterocycles. Georg Thieme Verlag. doi:10.1055/b-003-121805. ISBN 9783131186713.