Anthracene 1

Anthracene
Gerd Collin, DECHEMA e.V., Frankfurt/Main, Federal Republic of Germany
Hartmut Höke, Weinheim, Federal Republic of Germany
Jörg Talbiersky, Dorsten, Federal Republic of Germany

1. Physical Properties . . . . . . . . . . . . . . 1 5. Uses . . . . . . . . . . . . . . . . . . . . . . . . 2

2. Chemical Properties . . . . . . . . . . . . . 1 6. Toxicology and Environmental Aspects 2
3. Production . . . . . . . . . . . . . . . . . . . 1
4. Analysis . . . . . . . . . . . . . . . . . . . . . 2 7. References . . . . . . . . . . . . . . . . . . . 3

Anthracene [120-12-7], C14 H10 , was disco-
vered in coal tar by J. Dumas and H. A. Laurent
in 1832.
1. Physical Properties
Anthracene, C14 H10 , M r 178.24, mp 218 ◦ C,
bp 340 ◦ C (at 101.3 kPa), d 4 25 = 1.252 color-
less plates with blue-violet fluorescence, sub-
limes readily and forms a continuous series of
mixed crystals with phenanthrene and carbazole
in binary and ternary systems. Anthracene is
slightly soluble in benzene, chloroform, and car-
bon disulfide; less soluble in diethyl ether and
ethyl alcohol; and almost insoluble in water.
Anthracene is readily hydrogenated to 9,10-di-
hydroanthracene. With homogeneous ruthenium
catalysts, anthracene is hydrogenated to 1,2,3,4-
tetrahydroanthracene [6]; further hydrogenation
yields 1,2,3,4,5,6,7,8-octahydroanthracene. Ox-
idation of anthracene in the liquid or gas phase
gives anthraquinone (→ Anthraquinone). An-
thracene is primarily halogenated and nitrated
in the 9- and 10-positions, and sulfonated in the
1- or 2-position, depending on the reaction con-
ditions. Anthracene undergoes Diels – Alder ad-
dition of maleic anhydride and other dienophiles
in the 9- and 10-positions.
With magnesium metal in THF anthracene
undergoes an addition reaction to form a mag-
nesium – anthracene adduct from which highly
reactive magnesium can be obtained that can be
converted to magnesium hydride and Grignard
reagents [7].

Specific heat capacity 1164 J/kg (at 24 ◦ C) 3. Production

Heat of fusion 162 kJ/kg
Heat of vaporization 294 kJ/kg
Heat of combustion 40110 kJ/kg (at 25 ◦ C) High-temperature coal tar contains, on aver-
age, 1.5 % of anthracene. Continuous tar distil-
lation concentrates the anthracene in the frac-
tion boiling between 300 and 360 ◦ C (anthra-
2. Chemical Properties cene oil I). This oil amounts to 15 – 20 % of
the raw tar and contains about 7 % anthracene;
Anthracene is converted to dianthracene by ir- it is cooled to 20 – 30 ◦ C and then centrifuged.
radiation with UV light in the absence of oxy- About 10–15 % of the crude anthracene oil I is
gen. In the presence of oxygen anthracene is obtained as a yellow-green crystalline material
converted to a peroxide by addition of oxygen with an anthracene content of 20 – 35 % (an-
to the 9,10-positions. Pyrocondensation gives thracene residues). These residues, which also
2,9-bianthryl and 9,10-dihydroanthracene [5]. contain 40 – 50 % phenanthrene and 12–20 %

c 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

10.1002/14356007.a02 343.pub2
2 Anthracene
carbazole, are crystallized or distilled. Distil-
lation yields a crude product containing 45 –
55 % anthracene (50s anthracene). A 50s an-
thracene with an improved quality can be pro-
duced by two-step continuous column distilla-
tion [8, 9]. The crude 50s anthracene then is
purified by recrystallization from selective sol-
vents and by distillation. Repeated recrystalliza-
tion from a three- to fourfold excess of pyridine
produces anthracene (95 % purity) from the 50s
anthracene in 80 % yield relative to the anthra-
cene content. Other selective solvents suitable
for recrystallization are acetone [10 – 14], ace-
tophenone [15], benzene – methanol [16], di-
alkyl sulfoxides [17], dialkylformamides [18],
N-methylpyrrolidone [19], dimethylacetamide
[20], and propylene carbonate [21].
High yield of anthracene (96 %) and low en-
ergy consumption can be achieved by solvent-
free, high-temperature melt crystallization of an-
thracene residues or anthracene oil I [22, 23].
Anthracene can be separated from the higher-
boiling carbazole by distillation with lower-
boiling hydrocarbon fractions as reflux medium
[24, 25] or by azeotropic distillation with ethyl-
ene glycol [26, 27]. Azeotropic distillation also
is used to separate the anthracene-accompanying
tetracene and to obtain very pure anthracene for
scintillation counting [28].
In principle, anthracene is also available from
the high-boiling oil of coal liquefaction [29].
Carbazole-free crude anthracene can be pre-
pared by distillation and crystallization of
residues obtained from the pyrolysis of hydro-
carbon fractions to olefins; however, the anthra-
cene content of these pyrolysis oils generally
is less than 1 % [30]. The anthracene yield can
be increased by selective hydrodealkylation of
the aromatic fraction containing methylphenan-
threnes and methylanthracenes [31].
Anthracene can be synthesized by hydro-
genation of phenanthrene, isomerization of the
resulting sym-octahydrophenanthrene to sym-
octahydroanthracene, and subsequent dehydro-
genation [32 – 35]. A mixture of sym-octahydro-
anthracene and sym-octahydrophenanthrene is
obtained by catalytic disproportionation of
tetralin [36 – 38]. In addition, anthracene is
formed from diphenylmethane in the presence
of HF/BF3 at 80 ◦ C [39, 40] and by thermal reac-
tion of o-methyldiphenylmethane at ca. 600 ◦ C
[41]. These syntheses have no commercial im-
portance to date because sufficient anthracene is
obtained from coal tar.
4. Analysis
Anthracene is determined quantitatively in the
presence of other coal tar constituents by oxi-
dation with chromic acid in glacial acetic acid
to produce anthraquinone; by Diels – Alder re-
action with maleic anhydride [42, 43]; by gas
chromatography [44]; by UV spectroscopy [45,
46]; or by luminescence spectroscopy [47].
5. Uses
On a commercial scale, about 10 000 t/a of an-
thracene is used, almost exclusively for the pro-
duction of anthraquinone (→ Anthraquinone).
The use of anthracene as a plasticizer for thermo-
setting resins and as a light stabilizer for poly-
mers has been proposed. The use of anthracene
derivatives as building blocks for engineering
plastics was also suggested. The polyether of
9,10-dihydoxyanthracene is an example [48].
Anthracene is a crystalline organic photocon-
ductor that can be used in electrophotography.
In its purest form, anthracene is frequently em-
ployed as a scintillant to detect high-energy ra-
diation, e.g., in nuclear physics.
6. Toxicology and Environmental
Aspects
Toxicology. As a polycyclic aromatic hydro-
carbon, anthracene is suspected to be carcino-
genic [49, 49, 50, 50, 51, 51 – 56]. This earlier
experience involving workers is based on crude
anthracene that was contaminated with various
other polycyclic aromatic hydrocarbons. Pure
anthracene, however, has no appreciable car-
cinogenic effect under experimental conditions
[54, 57 – 59]. This is underlined by consistently
negative findings in numerous in vitro and in
vivo genotoxicity tests [58, 59]. Only subcuta-
neous injections of an oily solution containing
20 mg of anthracene, given 33 times at the rate
of one per week, resulted in local development
of fibroma, to some extent with sarcoma-like ex-
crescences [54, 55]. An epicutaneous tumor ini-
tiation test conducted over 35 weeks on mice
 Anthracene 3
Table 1. Photoinduced anthracene toxicity
Test organism Effective concentration Exposure to UV light Ref.
Type (total test Value, mg/L Intensity, µW/cm2 Time
duration)
Selenastrum NOEC (36 h) 0.0015 – 0.003 A 410 – 765 22 h [94]
capricornutum (alga)
Daphnia magna NOEC (21 d) ca. 0.002 A 117 16 h/d [95, 96]
(crustacea)
Juvenile bluegill LC100 (24 – 72 h) 0.012 sunlight (Oct.) day-night cycle [93]
(freshwater fish)
Juvenile bluegill LC50 (96 h) 0.0012 B 170 96 h [92]
(freshwater fish)
Fathead minnow larvae LC50 (40 h) 0.0054 A 95 16 h [97]
(freshwater fish)
Fathead minnow NOEC (9 weeks) <0.0066 none [90]
(freshwater fish)

with pure anthracene and phorbol ester as pro-
moter resulted in papilloma in a few cases (4
out of 28 animals) [60]. Anthracene is classi-
fied as “not classifiable as to its carcinogenicity
to humans” by IARC (Category 3) and by EPA
(Group D) [59].
Peroral application of 1.7 g/kg of pure an-
thracene has no lethal effect on mice [61]. An-
thracene is absorbed percutaneously: after topi-
cal application of a 14 C-labeled solution in hex-
ane or acetone (ca. 9 µg/cm3 ) to rat skin, some
50 % was absorbed in 6 d (ca. 29 % was reco-
vered from the urine, ca. 22 % from the feces,
and ca. 1 % from tissue, mainly the liver and
kidneys); after 1 d 20 % of the dose was already
present in the urine (ca. 17 %) and feces (ca.
3 %) [62]. Anthracene can sensitize the skin lo-
cally to light [63]. Gerarde proposes a TLV of
0.1 mg/m3 [56].
Environmental Fate and Toxicity. An-
thracene is inherently biodegradable in water
[64 – 67] and soil [68 – 72]. Most of the elimi-
nation half-lives found in experimental soil and
water systems are below 180 d. In water – sed-
iment mesocosm systems involving photolytic
and biological processes, short residence times
were observed with elimination rates of >98 to
>99.5 % for the parent substance from the water
phase within 17 and 40 d, respectively [73 – 75].
Several studies using [9-14 C]-radiolabeled an-
thracene gave evidence of partial mineralization
of the parent compound during the observation
period [64, 76, 77].
Photodegradation in air and water is rapid;
measured elimination half-lives were between 2
and 4 h in air [78, 79] and less than 1 to ca. 40 h
in water systems [64, 80 – 82].
The moderate to high water-partition coeffi-
cient (log Pow 3.9 – 4.5) [74, 83, 84] indicates
significant bioconcentration potential. This is
low to moderate in fish [64, 74, 85 – 90] and
daphnia [64, 87, 88, 91] with bioconcentration
factors (BCF) generally ranging between ca. 700
and 5000.
Photoinduced aquatic toxicity of anthracene
in aquatic organisms may be 2 – 3 orders of mag-
nitude higher than in the absence of UV light and
appears to depend on the accumulated body bur-
den, as fish previously exposed to anthracene in
the dark were void of any symptoms, but exhib-
ited severe signs of distress or showed increased
mortality when placed in clean water in the pres-
ence of UV light [92]. But also without prior or
concurrent UV irradiation, chronic toxic effects
of anthracene are reported to affect reproduction
of fish at low concentrations [90].
Acute lethal concentrations (LC50 ) and no-
observed-effect concentrations (NOEC) are be-
low 0.1 and 0.01 mg/L, respectively, and signif-
icantly lower than the water solubility of anthra-
cene (see Table 1).
7. References
General References
1. Beilstein, 5, 657; 5 (1), 321; 5 (2), 569; 5 (3),
2123.
2. H. J. V. Winkler: Der Steinkohlenteer und
seine Aufarbeitung, Verlag Glückauf, Essen
1951, p. 174–181.
3. H.-G. Franck, G. Collin: Steinkohlenteer,
Springer Verlag, Berlin - Heidelberg - New
York 1968, p. 56–58 136–137.
4 Anthracene
4. Rütgerswerke, Erzeugnisse aus
Steinkohlenteer, Frankfurt / Main 1958.
Specific References
5. S. E. Stein, L. L. Griffith, R. Billmers, R. H.
Chen, J. Org. Chem. 52 (1987) 1582–1592.
6. Rütgerswerke, DE 3303742, 1983 (B. Fell, G.
Maletz).
7. Studiengesellschaft Kohle mbH, U.S.
5069894, 1991 (B. Bogdanovic).
8. Rütgers AG, EU-PS 799813, 1997 (E.
Fuhrmann, J. Talbiersky, W. Erdmann, F.
Alsmeier).
9. J. Talbiersky, Erdöl Erdgas Kohle 9 (1998)
436–439.
10. Ukrainian Scientific-Research Institute of Coal
Chemistry, SU 386889, 1971 (V. E. Privalov,
K. A. Belov, E. I. Vail, Y. T. Rezunenko).
11. B. Karabon, A. Zin, K. Mnich, Koks Smola
Gaz 19 (1974) 33–37.
12. M. S. Litvinenko, L. D. Gluzman, A. A. Rok,
S. N. Kipat, V. P. Bogunets, N. I. Zhuravskaya,
R. M. Zil’berman, L. I. Didenko, Koks Khim.
1976, no. 3 33–36
Coke Chem. 1976, no. 3 38–42.
13. L. S. Kuznetsova, V. I. Borodin, A. A.
Stepanenko, A. A. Tolochko, V. N. Nazarov,
Koks Khim. 1978, no. 1 38–40
Coke Chem. 1978, no. 1 50–52.
14. B. Karabon, A. Zin, Koks Smola Gaz 26
(1980) 95–98.
15. Rütgerswerke, DE 2020973, 1970 (H. Buffleb,
J. Falenski, H.-G. Franck, J. Turowski, F.
Melichar, G. Collin, M. Zander).
16. I. Jurkiewicz, K. Wiszniowski, Koks Smola
Gaz 5 (1960) 117–121.
17. B. Marciniak, Mol. Cryst. Liq. Cryst. 162 B
(1988) 301–313.
18. Union Rhein. Braunkohlen Kraftstoff, DE
1046002, 1957 (F. Hübenett, G. Altena).
19. J. Polaczek, Z. Lisicki, T. Tecza, Przem. Chem.
60 (1981) 169–171.
20. Charkovskij politechnitsheskij institut imeni V.
T. Lenina, Ukrainskij nautshnoissledovatelskij
Uglechimit sheskij institut, DE-OS 2626361,
1976 (V. J. Privalov, J. I. Vail, L. S. Kusnezova,
K. A. Belov, I. M. Nosalevich, I. V. Romanov).
21. G. Kesicka, S. Trybuta, Przem. Chem. 65
(1986) 145–148.
22. Rütgers AG, DE 10103208, 2002 (R. Bischof,
K. Dialer, A. Nikzad, T. Büttner, E. Fuhrmann,
U. Knips, D. Scholl, B. Vierhaus, F. Alsmeier,
W. Bergins, S. Giertler, K. Stolzenberg, J.
Talbiersky).
23. D. Scholl, H. Appler, V. Marx, E. Fuhrmann, J.
Talbiersky, Erdöl Erdgas Kohle 10 (2004)
336–339.
24. A. Zboril, J. Ruzek, CS 150737, 1971.
25. J. Komurka, I. Koropecky, V. Vlcek, J. Jelinek,
J. Mixa, J. Ruzek, CS 164058, 1973.
26. Soc. Chim. Gerland, FR 976 773, 1948 (A. J.
M. Saunier).
27. Chem. Systems, DE-OS 2123342, 1971 (G. M.
Sugarman).
28. R. Sizmann, Angew. Chem. 71 (1959)
243–245.
29. E. Wolowski, H. Hosang, Chemie-Technik 8
(1980) 395–399
30. Rütgerswerke, DE 2000351, 1970 (H. Buffleb,
H.-G. Franck, J. Turowski, G. Collin, M.
Zander).
31. Rütgerswerke, DE 1906807, 1969 (H. Buffleb,
H.-G. Franck, R. Oberkobusch, J. Turowski,
G. Collin, M. Zander).
32. Koppers Co., US 3389188, 1966 (W. A.
Michalowicz).
33. G. Kölling, Erdöl Kohle Erdgas Petrochem. 20
(1967) 726–729.
34. K. Handrick, W. Hodek, F. Mensch,
DGMK-Compendium 78/79, 2 (1978)
1089–1106.
35. Bergwerksverband, DE 2952062, 1979 (K.
Handrick, G. Kölling, F. Mensch).
36. Tetralin, DE 333158, 1919.
37. Sun Oil, US 3320332, 1964 (A. Schneider).
38. Sun Oil, DE-OS 1493030, 1965 (R. D.
Bushick, G. Mills).
39. F. Meyer, D. Hausigk, G. Kölling, Liebigs
Ann. Chem. 736 (1970) 140–141.
40. Bergwerksverband, DE 1951127, 1969 (F.
Meyer, G. Kölling, D. Hausigk).
41. Bayer, DE-OS 2218004, 1972 (H. Wolz, R.
Wenzel, M. Martin, G. Scharfe).
42. H. P. Kaufmann, J. Baltes, Fette Seifen 43
(1936) 93–95.
43. E. Funakubo, Y. Matsumoto, M. Fujiura, I.
Kawanshi, S. Hiroike, Brennst. Chem. 40
(1959) 377–383.
44. M. Zander, H. D. Sauerland, Erdöl Kohle
Erdgas Petrochem. 25 (1972) 526–530.
45. H. Schmidt, Erdöl Kohle Erdgas Petrochem.
19 (1966) 275–278.
46. F. P. Hazlett, R. B. Hannan, J. H. Wells, Anal.
Chem. 22 (1950) 1132–1136.
47. M. Zander, Angew. Chem. Int. Ed. Engl. 4
(1965) 930–938.
48. V. Sinigersky, K. Müllen, M. Klapper, I.
Schopov, Macromol. Chem. Phys. 201 (2000)
1134–1140.

49. K. B. Lehmann, F. Flury: Toxicology and
Hygiene of Industrial Solvents, Williams and
Wilkins Co., Baltimore 1943.
50. W. C. Hueper: Occupational Tumors and
Allied Diseases, C. C. Thomas, Springfield
1942.
51. National Institut for Occupational Safety and
Health (NIOSH): Registry of Toxic Effects of
Chemical Substances, U.S. Government
Printing Office, Washington, D.C., July 1982,
p. 1277.
52. N. I. Sax: Cancer-Causing Chemicals, Van
Nostrand Reinhold Comp., New York 1981, p.
288.
53. N. I. Sax: Dangerous Properties of Industrial
Materials, 5th ed., Van Nostrand Reinhold
Comp., New York 1981, p. 288.
54. D. Schmähl, Z. Krebsforsch. 60 (1955)
697–710.
55. H. Druckrey. D. Schmähl,
Naturwissenschaften 42 (1955) 159–160.
56. H. W. Gerarde: Toxicology and Biochemistry
of Aromatic Hydrocarbons, Elsevier,
Amsterdam 1960, pp. 240–248.
57. E. L. Kennaway, J. Ind. Hyg. 5 (1924) 462.
58. WHO: Selected Non-heterocyclic Polycyclic
Aromatic Hydrocarbons, Environmental
Health Criteria (EHC) 202, International
Programme on Chemical Safety (IPCS),
Geneva, 1998.
59. U.S. EPA: Anthracene, IRIS (Integrated Risk
Information System), last update 01 April
1997 [http://www.epa.gov/iris/subst/0434.htm]
60. J. D. Scribner. J. Natl. Canc. Inst. 50 (1973)
1717–1719.
61. P. A. Nagornyi. Gig. Tr. Prof. Zabol. 13 (1969)
59–61.
62. J. J. Yang, T. A. Roy, C. R. Mackerer. Toxicol.
Ind. Health 2 (1986) 79–84.
63. I. E. Kochevar, R. B. Armstrong, J. Einbinder
et al., Photochem. Photobiol. 36 (1982) 65–69
64. G. R. Southworth, ASTM Spec. Tech. Publ.
667 (1979) 359–380.
65. A. Männisto, E. S. Melin, J. A. Puhakka, J. F.
Ferguson, Polycyclic Arom. Compd. 11 (1996)
27–34.
66. H. H. Tabak, S. A. Quave, C. I. Mashni, E. F.
Barth, J. Water Pollut. Control Fed. 53 (1981)
1503–1518.
67. T. Nishihara, S. Hasebe, J. Nishikawa, M.
Kondo, J. Appl. Microbiol. 82 (1997) 441–447.
68. K. S. Park, R. C. Sims, R. R. Dupont, W. J.
Doucette, J. E. Matthews, Environ. Toxicol.
Chem. 9 (1990) 187–195.
Anthracene 5
69. M. P. Coover, R. C. Sims, Hazard. Waste
Hazard. Mater. 4 (1987) 69–82.
70. S. R. Wild, K. C. Jones, Environ. Toxicol.
Chem. 12 (1993) 5–12.
71. K. A. Reilley, M. K. Banks, A. P. Schwab, J.
Environ. Qual. 25 (1996) 212–219.
72. J. D. Goodin, M. D. Webber, J. Environ. Qual.
24 (1995) 271–278.
73. R. F. Lee, W. S. Gardner, J. W. Anderson et al.,
Environ. Sci. Technol. 12 (1978) 832–838.
74. P. Lu, R. L. Metcalf, E. M. Carlson, Environ.
Health Persp. 24 (1978) 201–208.
75. K. T. J. Bestari, R. D. Robinson, K. R.
Solomon et al., Environ. Toxicol. Chem. 17
(1998) 2359–2368.
76. W. S. Gardner, R. F. Lee; K. R. Tenore, L. W.
Smith, Water Air Soil Pollut. 11 (1979)
339–347.
77. S. E. Herbes, L. R. Schwall, Appl. Environ.
Microbiol. 35 (1978) 306–316.
78. H. W. Biermann, H. MacLeod, R. Atkinson et
al., Environ. Sci. Technol. 19 (1985) 244–248.
79. R. Atkinson, D. L. Baulch, R. A. Cox et al., J.
Phys. Chem. Ref. Data Suppl. III 18 (1985)
881–1097.
80. R. G. Zepp, P. F. Schlotzhauer in P. W. Jones,
P, Leber (eds.): Polynuclear Aromatic
Hydrocarbons, 141–158, Ann Arbor Sci.
Publ., Ann Arbor, MI, 1979.
81. P. F. Landrum, S. M. Bartell, J. P. Giesy et al.,
Ecotox. Environ. Safety 8 (1984) 183–201.
82. J. W. Bowling, G. Leversee, P. F. Landrum, J.
P. Giesy, Aquat. Toxicol. 3 (1983) 79–90.
83. M. M. Miller, P. Wasik, G.-L. Huang et al.,
Environ. Sci. Technol. 19 (1985) 522–529.
84. S. W. Karickhoff, D. S. Brown, T. A. Scott,
Water Res. 13 (1979) 241–248.
85. A. Spacie, P. F. Landrum, G. J. Leversee,
Ecotoxicol. Environ. Safety 7 (1983) 330–334.
86. NITE: Anthracene. Japan Chemicals
Inventories, National Institute of
Technology/Japan, 2005
[http://www.safe.nite.go.jp/].
87. J. L. Newsted, J. P. Giesy, Environ. Toxicol.
Chem. 6 (1987) 445–461.
88. J. T. Oris, A. T. Hall, J. D. Tylka, Environ.
Toxicol. Chem. 9 (1990) 575–584.
89. P. de Voogt, B. van Hattum, P. Leonards et al.,
Aquatic Tox. 20 (1991) 169–194.
90. A. T. Hall, J. T. Oris, Aquat. Toxicol. 19 (1991)
249–264
91. S. E. Herbes, G. F. Risi, Bull. Environ.
Contam. Tox. 19 (1978) 147–155.
92. J. T. Oris and J. P. Giesy, Aquat. Toxicol. 6
(1985) 133–146.
6 Anthracene

93. J. W. Bowling, G. Leversee, P. F. Landrum, J. 96. J. A. Foran, L. L. Holst, J. P. Giesy, Environ.

P. Giesy, Aquat. Toxicol. 3 (1983) 79–90.
94. W. R. Gala, J. P. Giesy, Aquat. Environ.
Contam. Toxicol. 23 (1992) 316–323.
95. L. L. Holst, Giesy, Toxicol. Chem. 8 (1989)
933–942.
Toxicol. Chem. 10 (1991) 425–427.
97. J. T. Oris, J. P. Giesy, Chemosphere 16 (1987)
1395–1404.