Editing Phenanthrene

{{short description|Polycyclic aromatic hydrocarbon composed of three fused benzene rings}}
{{chembox
| Verifiedfields = changed
| Watchedfields = changed
| verifiedrevid = 444046459
| ImageFile=Phenanthrene-numbering.svg
| ImageSize=180px
| ImageFile1=Phenanthrene molecule ball.png
| ImageSize1=180px
| ImageAlt1 = Ball-and-stick model of the phenanthrene molecule
| ImageFile2 = Phenanthrene C14H10.JPG
| ImageName2 = Phenanthrene
| PIN = Phenanthrene <!-- Nomenclature of Organic Chemistry – IUPAC Recommendations and Preferred Names 2013 (Blue Book) -->
|Section1={{Chembox Identifiers
| CASNo_Ref = {{cascite|correct|CAS}}
| CASNo=85-01-8
| PubChem=995
| ChEBI_Ref = {{ebicite|changed|EBI}}
| ChEBI = 28851
| KEGG_Ref = {{keggcite|correct|kegg}}
| KEGG = C11422
| UNII_Ref = {{fdacite|correct|FDA}}
| UNII = 448J8E5BST
| SMILES = C1=CC=C2C(=C1)C=CC3=CC=CC=C32
| EINECS = 266-028-2
| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}}
| ChemSpiderID = 970
| InChI = 1/C14H10/c1-3-7-13-11(5-1)9-10-12-6-2-4-8-14(12)13/h1-10H
| InChIKey = YNPNZTXNASCQKK-UHFFFAOYAC
| StdInChI_Ref = {{stdinchicite|changed|chemspider}}
| StdInChI = 1S/C14H10/c1-3-7-13-11(5-1)9-10-12-6-2-4-8-14(12)13/h1-10H
| StdInChIKey_Ref = {{stdinchicite|changed|chemspider}}
| StdInChIKey = YNPNZTXNASCQKK-UHFFFAOYSA-N
| RTECS = 
| MeSHName = C031181
| Beilstein = 1905428
| Gmelin = 28699
  }}
|Section2={{Chembox Properties
| C=14 | H=10
| Appearance=Colorless solid
| Density=1.18 g/cm<sup>3</sup><ref name=GESTIS/>
| MeltingPtC=101
| MeltingPt_ref = <ref name=GESTIS>{{GESTIS|ZVG=22900|CAS=85-01-8}}</ref>
| BoilingPtC=332
| BoilingPt_ref = <ref name=GESTIS/>
| Solubility=1.6  mg/L<ref name=GESTIS/>
| MagSus = −127.9·10<sup>−6</sup> cm<sup>3</sup>/mol
  }}
|Section3={{Chembox Hazards
| NFPA-H = 1|NFPA-F = 1|NFPA-R=0|NFPA-S =
| MainHazards=
| FlashPtC = 171
| FlashPt_ref = <ref name=GESTIS/>
| AutoignitionPt =
  }}
|Section4={{Chembox Structure
| PointGroup = C<sub>2v</sub><ref>Peter Atkins, J. D. P., Atkins' Physical Chemistry. Oxford: 2010. P.&nbsp;443.</ref>
| Dipole = 0 [[Debye|D]]
  }}
}}

'''Phenanthrene''' is a [[polycyclic aromatic hydrocarbon]] (PAH) with formula C<sub>14</sub>H<sub>10</sub>, 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.<ref name="factsheet">{{cite web |title=Phenanthrene Fact Sheet |url=https://archive.epa.gov/epawaste/hazard/wastemin/web/pdf/phenanth.pdf |website=archive.epa.gov |publisher=U.S. Environmental Protection Agency |access-date=19 July 2019}}</ref>

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.<ref name="factsheet" /> However, according to IARC, it is not identified as a probable, possible or confirmed human carcinogen.<ref>{{cite web |title=Phenanthrene |website=Sigma-Alrdich |url=https://www.sigmaaldrich.com/catalog/product/aldrich/p11409}}</ref>

Phenanthrene's three fused rings are angled as in the [[phenacene]]s, rather than straight as in the [[acene]]s. The compounds with a phenanthrene skeleton but with nitrogen atoms in place of CH sites are known as [[phenanthroline]]s.

== History and etymology ==
Phenanthrene was discovered in [[coal tar]] in 1872 independently by [[Carl Graebe]] (article manuscript received on November 1st<ref>{{Cite journal |last=Graebe |first=C. |date=1872 |title=Ueber einen neuen dem Anthracen isomeren Kohlenwasserstoff |url=https://books.google.com/books?id=cwaLZrjMd0oC&pg=PA861 |journal=Berichte der deutschen chemischen Gesellschaft |language=en |volume=5 |issue=2 |pages=861–863 |doi=10.1002/cber.18720050279 |issn=0365-9496|url-access=subscription }}</ref>) as well as by [[Wilhelm Rudolph Fittig]] and his doctoral student {{Ill|Eugen Ostermayer|de}} (manuscript received on November 19th<ref>{{Cite journal |last=Ostermayer |first=E. |last2=Fittig |first2=R. |date=1872 |title=Ueber einen neuen Kohlenwasserstoff aus dem Steinkohlentheer |url=https://books.google.com/books?id=cwaLZrjMd0oC&pg=PA933 |journal=Berichte der deutschen chemischen Gesellschaft |language=en |volume=5 |issue=2 |pages=933–937 |doi=10.1002/cber.187200502100 |issn=0365-9496}}</ref> but Ostermayer's dissertation defended in August<ref>{{Cite book |last=Ostermayer |first=Eugen |url=https://books.google.com/books?id=K5NTAAAAcAAJ |title=Ueber einen neuen Kohlenwasserstoff im Steinkohlentheeröl: Inaugural-Dissertation |date=1872 |publisher=Druck v. Fues |language=de}}</ref>). Fittig and Ostermayer were able to determine the structure of the compound by oxidizing it first to a [[Phenanthrenequinone|corresponding quinone]] and then to [[diphenic acid]], and soon Graebe confirmed it by a synthesis from [[(Z)-Stilbene|stilbene]].<ref>{{Cite journal |last=Graebe |first=C. |date=1873 |title=Ueber Synthese des Phenanthrens |url=https://books.google.com/books?id=vCxJAAAAYAAJ&pg=PA125 |journal=Berichte der deutschen chemischen Gesellschaft |language=en |volume=6 |issue=1 |pages=125–127 |doi=10.1002/cber.18730060147 |issn=0365-9496}}</ref>

Prior to February 1873 Fittig sent a letter to Graebe where he proposed to name the hydrocarbon phenanthrene ({{Langx|de|Phenanthren}}) in order to account for its similarity to [[biphenyl]] and [[anthracene]], which was swiftly adopted.<ref>{{Cite journal |last=Graebe |first=C. |date=1873 |title=Ueber das Verhalten der Chinone beim Erhitzen mit Natronkalk |url=https://books.google.com/books?id=vCxJAAAAYAAJ&pg=PA63 |journal=Berichte der deutschen chemischen Gesellschaft |volume=6 |issue=1 |pages=63–66 |doi=10.1002/cber.18730060124 |issn=0365-9496|url-access=subscription }}</ref>

==Physical properties==

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

Phenanthrene is fluorescent under ultraviolet light, exhibiting a large [[Stokes shift|Stoke shift]].<ref>{{Cite web |title=Spectrum [Phenanthrene] {{!}} AAT Bioquest |url=https://www.aatbio.com/fluorescence-excitation-emission-spectrum-graph-viewer/phenanthrene |access-date=2024-07-30 |website=www.aatbio.com}}</ref> It can be used in [[Scintillator|scintillators]].

==Chemistry==

Reactions of phenanthrene typically occur at the 9 and 10 positions, including:
* [[Organic oxidation|Oxidation]] with [[chromic acid]] gives gives [[phenanthrenequinone]].<ref>[[Organic Syntheses]], Coll. Vol.&nbsp;4, [http://www.orgsynth.org/orgsyn/pdfs/CV4P0757.pdf  p.&nbsp;757] (1963); Vol.&nbsp;34, p.&nbsp;76 (1954).</ref>
* [[Organic reduction]] to 9,10-dihydrophenanthrene with [[hydrogen]] gas and [[raney nickel]]<ref>[[Organic Syntheses]], Coll. Vol.&nbsp;4, [http://www.orgsynth.org/orgsyn/pdfs/CV4P0313.pdf p.&nbsp;313] (1963); Vol.&nbsp;34, p.&nbsp;31 (1954).</ref>
* [[Electrophilic halogenation]] to 9-bromophenanthrene with [[bromine]]<ref>[[Organic Syntheses]], Coll. Vol.&nbsp;3, [http://www.orgsynth.org/orgsyn/pdfs/CV3P0134.pdf p.&nbsp;134] (1955); Vol.&nbsp;28, p.&nbsp;19 (1948).</ref>
* [[Aromatic sulfonation]] to 2 and 3-phenanthrenesulfonic acids with [[sulfuric acid]]<ref>[[Organic Syntheses]], Coll. Vol.&nbsp;2, [http://www.orgsynth.org/orgsyn/pdfs/CV2P0482.pdf p.&nbsp;482] (1943); Vol.&nbsp;16, p.&nbsp;63 (1936).</ref>
* [[Ozonolysis]] to diphenylaldehyde<ref>[[Organic Syntheses]], Coll. Vol.&nbsp;5, [http://www.orgsynth.org/orgsyn/pdfs/CV5P0489.pdf p.&nbsp;489] (1973); Vol.&nbsp;41, p.&nbsp;41 (1961).</ref>

==Productions==
Phenanthrene is extracted from coal tar, where it comprises 5% by weight.<ref name=Ullmann/>

In principle it could be obtained by chemical synthesis. The '''Bardhan–Sengupta phenanthrene synthesis''' is a classic way to make phenanthrenes.<ref>{{cite book |year= 2010 |chapter= Bardhan Sengupta Synthesis |title= Comprehensive Organic Name Reactions and Reagents |volume= 49 |pages= 215–219 |doi= 10.1002/9780470638859.conrr049 |isbn= 9780470638859 }}</ref>
:[[File:Bardhan-SenguptaPhenanthreneSynthesis.png|480px|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 [[hydrogen selenide|H<sub>2</sub>Se]].

Phenanthrene can also be obtained photochemically from certain [[diarylethene]]s ([[Mallory reaction]]):[[File:Scheme 7 Rev.png|thumb]]

Other synthesis routes include the [[Haworth reaction]] and the [[Wagner-Meerwein rearrangement|Wagner-Meerwein]]-type [[Ring expansion and contraction|ring-expansion]], as depicted below: [[File:StilAlt.png|thumb]]Commercially phenanthrene is not synthesized but extracted from the byproducts of coal coking, since it makes around 4–6% of [[coke oven]] coal tar.<ref>{{Cite journal |last=Ma |first=Zhi-Hao |last2=Wei |first2=Xian-Yong |last3=Liu |first3=Guang-Hui |last4=Liu |first4=Fang-Jing |last5=Zong |first5=Zhi-Min |date=2021-05-15 |title=Value-added utilization of high-temperature coal tar: A review |url=https://www.sciencedirect.com/science/article/abs/pii/S0016236120329501 |journal=Fuel |volume=292 |pages=119954 |doi=10.1016/j.fuel.2020.119954 |issn=0016-2361|url-access=subscription }}</ref>

== Natural occurrences of the phenanthrene derivatives==
[[Image:Morphinan.svg|Structure of morphinan, which features a partially reduced phenanthroline core|thumb|left|120px]]
[[Morphinan]] is the [[chemical structure]] found in several [[psychoactive drug]]s, consisting of [[opiate]] [[analgesic]]s, [[cough suppressant]]s, and [[dissociative drug|dissociative]] [[hallucinogen]]s, among others. Examples [[morphine]], [[codeine]], and [[dextromethorphan]] (DXM).<ref name=Ullmann>{{cite book |doi=10.1002/14356007.a13_227.pub3 |chapter=Hydrocarbons |title=Ullmann's Encyclopedia of Industrial Chemistry |date=2014 |last1=Schmidt |first1=Roland |last2=Griesbaum |first2=Karl |last3=Behr |first3=Arno |last4=Biedenkapp |first4=Dieter |last5=Voges |first5=Heinz-Werner |last6=Garbe |first6=Dorothea |last7=Paetz |first7=Christian |last8=Collin |first8=Gerd |last9=Mayer |first9=Dieter |last10=Höke |first10=Hartmut |pages=1–74 |isbn=978-3-527-30673-2 }}</ref>

[[Ravatite]] is a natural mineral consisting of phenanthrene.<ref>[http://webmineral.com/data/Ravatite.shtml Ravatite Mineral Data]</ref> 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 [[Phenanthrenoid|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).<ref name="Kovacs">{{cite journal |last1=Kovács |first1=Adriána |last2=Vasas |first2=Andrea |last3=Hohmann |first3=Judit |year=2008 |title=Natural phenanthrenes and their biological activity |journal=Phytochemistry |volume=69 |issue=5 |pages=1084–1110 |bibcode=2008PChem..69.1084K |doi=10.1016/j.phytochem.2007.12.005 |pmid=18243254}}</ref>

==See also==
* [[Chrysene]]
* [[Anthracene]]
* [[1,10-Phenanthroline|Phenanthroline]]

== References ==
{{reflist}}

== External links ==
* [http://www.scorecard.org/chemical-profiles/summary.tcl?edf_substance_id=85%2d01%2d8 Phenanthrene] at scorecard.org

{{Hydrocarbons}}
{{PAHs}}
{{Organic reactions}}
{{Chemical classes of psychoactive drugs}}
{{Authority control}}

[[Category:Phenanthrenes| ]]
[[Category:Polycyclic aromatic hydrocarbons]]