Phenanthrene

Phenanthrene
Ball-and-stick model of the phenanthrene molecule
Phenanthrene
Phenanthrene
Names
Preferred IUPAC name
Phenanthrene
Identifiers
CAS Number
3D model (JSmol)
Beilstein Reference
 1905428
ChEBI
ChemSpider
ECHA InfoCard 100.001.437
EC Number
  • 266-028-2
Gmelin Reference
 28699
KEGG
MeSH C031181
PubChem CID
UNII
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C14H10/c1-3-7-13-11(5-1)9-10-12-6-2-4-8-14(12)13/h1-10H ☒N
    Key: YNPNZTXNASCQKK-UHFFFAOYSA-N ☒N
  • InChI=1/C14H10/c1-3-7-13-11(5-1)9-10-12-6-2-4-8-14(12)13/h1-10H
    Key: YNPNZTXNASCQKK-UHFFFAOYAC
SMILES
  • C1=CC=C2C(=C1)C=CC3=CC=CC=C32
Properties
Chemical formula
 C14H10
Molar mass 178.234 g·mol−1
Appearance Colorless solid
Density 1.18 g/cm3[1]
Melting point 101 °C (214 °F; 374 K)[1]
Boiling point 332 °C (630 °F; 605 K)[1]
Solubility in water
 1.6 mg/L[1]
Magnetic susceptibility (χ)
 −127.9·10−6 cm3/mol
Hazards
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
1
1
0
Flash point 171 °C (340 °F; 444 K)[1]
Structure
Point group
 C2v[2]
Dipole moment
 0 D
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)
Infobox references

Phenanthrene is a polycyclic aromatic hydrocarbon (PAH) with formula C14H10, consisting of three fused benzene rings. It is a colorless, crystal-like solid, but can also appear yellow. Phenanthrene is used to make dyes, plastics, pesticides, explosives, and drugs. It has also been used to make bile acids, cholesterol and steroids.[3]

Phenanthrene occurs naturally and also is a man-made chemical. Commonly, humans are exposed to phenanthrene through inhalation of cigarette smoke, but there are many routes of exposure. Animal studies have shown that phenanthrene is a potential carcinogen.[3] However, according to IARC, it is not identified as a probable, possible or confirmed human carcinogen.[4]

Phenanthrene's three fused rings are angled as in the phenacenes, rather than straight as in the acenes. The compounds with a phenanthrene skeleton but with nitrogen atoms in place of CH sites are known as phenanthrolines.

History and etymology

Phenanthrene was discovered in coal tar in 1872 independently by Carl Graebe (article manuscript received on November 1st[5]) as well as by Wilhelm Rudolph Fittig and his doctoral student Eugen Ostermayer (manuscript received on November 19th[6] but Ostermayer defended his dissertation in August[7]). Fittig and Ostermayer were able to determine the structure of the compound by oxidizing it first to a corresponding quinone and then to diphenic acid, and soon Graebe confirmed it by a synthesis from stilbene.[8]

Prior to February 1873 Fittig sent a letter to Graebe where he proposed to name the hydrocarbon phenanthrene (German: Phenanthren) in order to account for its similarity to biphenyl and anthracene, which was swiftly adopted.[9]

Physical properties

Phenanthrene is nearly insoluble in water but is soluble in most low-polarity organic solvents such as toluene, carbon tetrachloride, ether, chloroform, acetic acid and benzene.

Phenanthrene is fluorescent under ultraviolet light, exhibiting a large Stoke shift.[10] It can be used in scintillators.

Chemistry

Reactions of phenanthrene typically occur at the 9 and 10 positions, including:

Productions

Phenanthrene is extracted from coal tar, of which it comprises 5% by weight.[16]

In principle it could be obtained by chemical synthesis. The Bardhan–Sengupta phenanthrene synthesis is a classic way to make phenanthrenes.[17]

Bardhan–Senguptam phenanthrene synthesis

This process involves electrophilic aromatic substitution using a tethered cyclohexanol group using diphosphorus pentoxide, which closes the central ring onto an existing aromatic ring. Dehydrogenation using selenium aromatizes the other rings into aromatic ones as well. The aromatization of six-membered rings produces H2Se.

Phenanthrene can also be obtained photochemically from certain diarylethenes (Mallory reaction):

Other synthesis routes include the Haworth reaction and the Wagner-Meerwein-type ring-expansion, as depicted below:

Commercially phenanthrene is not synthesized but extracted from the byproducts of coal coking, since it makes around 4–6% of coke oven coal tar.[18]

Natural occurrences of the phenanthrene derivatives

Structure of morphinan, which features a partially reduced phenanthroline core

Morphinan is the chemical structure found in several psychoactive drugs, consisting of opiate analgesics, cough suppressants, and dissociative hallucinogens, among others. Examples morphine, codeine, and dextromethorphan (DXM).[16]

Ravatite is a natural mineral consisting of phenanthrene.[19] It is found in small amounts among a few coal burning sites. Ravatite represents a small group of organic minerals.

In plants

Main article: Phenanthrenes

Phenanthrene derivatives occur in plants as phenanthrenoids. They have been reported from flowering plants, mainly in the family Orchidaceae, and a few in the families Dioscoreaceae, Combretaceae and Betulaceae, as well as in the lower plant class Marchantiophyta (liverworts).[20]

See also

References

  1. ^ a b c d e Record of CAS RN 85-01-8 in the GESTIS Substance Database of the Institute for Occupational Safety and Health
  2. ^ Peter Atkins, J. D. P., Atkins' Physical Chemistry. Oxford: 2010. P. 443.
  3. ^ a b "Phenanthrene Fact Sheet" (PDF). archive.epa.gov. U.S. Environmental Protection Agency. Retrieved 19 July 2019.
  4. ^ "Phenanthrene". Sigma-Alrdich.
  5. ^ Graebe, C. (1872). "Ueber einen neuen dem Anthracen isomeren Kohlenwasserstoff". Berichte der deutschen chemischen Gesellschaft. 5 (2): 861–863. doi:10.1002/cber.18720050279. ISSN 0365-9496.
  6. ^ Ostermayer, E.; Fittig, R. (1872). "Ueber einen neuen Kohlenwasserstoff aus dem Steinkohlentheer". Berichte der deutschen chemischen Gesellschaft. 5 (2): 933–937. doi:10.1002/cber.187200502100. ISSN 0365-9496.
  7. ^ Ostermayer, Eugen (1872). Ueber einen neuen Kohlenwasserstoff im Steinkohlentheeröl: Inaugural-Dissertation (in German). Druck v. Fues.
  8. ^ Graebe, C. (1873). "Ueber Synthese des Phenanthrens". Berichte der deutschen chemischen Gesellschaft. 6 (1): 125–127. doi:10.1002/cber.18730060147. ISSN 0365-9496.
  9. ^ Graebe, C. (1873). "Ueber das Verhalten der Chinone beim Erhitzen mit Natronkalk". Berichte der deutschen chemischen Gesellschaft. 6 (1): 63–66. doi:10.1002/cber.18730060124. ISSN 0365-9496.
  10. ^ "Spectrum [Phenanthrene] | AAT Bioquest". www.aatbio.com. Retrieved 2024-07-30.
  11. ^ Organic Syntheses, Coll. Vol. 4, p. 757 (1963); Vol. 34, p. 76 (1954).
  12. ^ Organic Syntheses, Coll. Vol. 4, p. 313 (1963); Vol. 34, p. 31 (1954).
  13. ^ Organic Syntheses, Coll. Vol. 3, p. 134 (1955); Vol. 28, p. 19 (1948).
  14. ^ Organic Syntheses, Coll. Vol. 2, p. 482 (1943); Vol. 16, p. 63 (1936).
  15. ^ Organic Syntheses, Coll. Vol. 5, p. 489 (1973); Vol. 41, p. 41 (1961).
  16. ^ a b Schmidt, Roland; Griesbaum, Karl; Behr, Arno; Biedenkapp, Dieter; Voges, Heinz-Werner; Garbe, Dorothea; Paetz, Christian; Collin, Gerd; Mayer, Dieter; Höke, Hartmut (2014). "Hydrocarbons". Ullmann's Encyclopedia of Industrial Chemistry. pp. 1–74. doi:10.1002/14356007.a13_227.pub3. ISBN 978-3-527-30673-2.
  17. ^ "Bardhan Sengupta Synthesis". Comprehensive Organic Name Reactions and Reagents. Vol. 49. 2010. pp. 215–219. doi:10.1002/9780470638859.conrr049. ISBN 978-0-470-63885-9.
  18. ^ Ma, Zhi-Hao; Wei, Xian-Yong; Liu, Guang-Hui; Liu, Fang-Jing; Zong, Zhi-Min (2021-05-15). "Value-added utilization of high-temperature coal tar: A review". Fuel. 292 119954. doi:10.1016/j.fuel.2020.119954. ISSN 0016-2361.
  19. ^ Ravatite Mineral Data
  20. ^ Kovács, Adriána; Vasas, Andrea; Hohmann, Judit (2008). "Natural phenanthrenes and their biological activity". Phytochemistry. 69 (5): 1084–1110. Bibcode:2008PChem..69.1084K. doi:10.1016/j.phytochem.2007.12.005. PMID 18243254.
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