120-12-7 Usage
Uses
1. Used in Dye Manufacturing:
Anthracene is used as a raw material for the manufacture of dyes due to its benzene-like structure and its presence in the heavyand green-oil fractions of crude oil.
2. Used in Plastics Production:
Anthracene is used as a component in the production of plastics, taking advantage of its chemical properties as a polycyclic aromatic hydrocarbon.
3. Used in Pesticide Production:
Anthracene is utilized in the production of pesticides, leveraging its characteristics as a PAH compound.
4. Used in Smoke Screens:
Anthracene has been used to create smoke screens, likely due to its ability to burn incompletely and produce smoke when combined with other materials.
5. Used in Scintillation Counter Crystals:
Anthracene is employed in the creation of scintillation counter crystals, which are used to detect or count the number of sparks or flashes that occur over a period of time.
6. Used in Research:
Most of the PAHs, including anthracene, are used for conducting research, as they are found naturally in the environment and can also be made synthetically. The majority of the information available is for the entire PAH group, with anthracene being a key component in these studies.
Production Methods
Anthracene is obtained from coal tar in the fraction distilling between 300° and 400 °C. This fraction contains 5–10% anthracene, from which, by fractional crystallization followed by crystallization from solvents, such as oleic acid, and washing with such solvents as pyridine, relatively pure anthracene is obtained. It may be detected by the formation of a blue-violet coloration on fusion with mellitic acid. Anthracene derivatives, especially anthraquinone, are important in dye chemistry.
Reactions
Anthracene reacts: (1) With oxidizing agents, e.g., sodium dichromate plus sulfuric acid, to form anthraquinone, C6H4(CO)2C6H. (2) With chlorine in water or in dilute acetic acid below 250 °C to form anthraquinol and anthraquinone, at higher temperatures 9,10-dichloroanthracene. The reaction varies with the temperature and with the solvent used. The reaction has been studied using, as solvent, benzene, chloroform, alcohol, carbon disulfide, ether, glacial acetic acid, and also without solvent by heating. Bromine reacts similarly to chlorine. (3) With concentrated sulfuric acid to form various anthracene sulfonic acids. (4) With nitric acid, to form nitroanthracenes and anthraquinone. (5) With picric acid (1)HO·C6H2(NO2)3(2,4,6) to form red crystalline anthracene picrate, melting point 138 °C.
Synthesis Reference(s)
Journal of the American Chemical Society, 82, p. 3653, 1960 DOI: 10.1021/ja01499a046Synthetic Communications, 7, p. 161, 1977 DOI: 10.1080/00397917708050729Tetrahedron Letters, 35, p. 1131, 1994 DOI: 10.1016/0040-4039(94)88004-2
Air & Water Reactions
Flammable. Insoluble in water.
Reactivity Profile
Anthracene will spontaneously burst into flame on contact with chromic acid, and other strong oxidants.
Hazard
A questionable carcinogen.
Health Hazard
Carcinogenicity of anthracene is not known.Its toxicity is very low. An intraperitonealLD50 in mice is recorded at 430 mg/kg(NIOSH 1986).
Health Hazard
Inhalation of dust irritates nose and throat. Contact with eyes causes irritation.
Fire Hazard
Anthracene is combustible.
Flammability and Explosibility
Nonflammable
Safety Profile
Moderately toxic by
intraperitoneal route. A skin irritant and
allergen. Questionable carcinogen with
experimental neoplas tigenic and tumorigenic
data. Mutation data reported. Combustible
when exposed to heat, flame, or oxidizing
materials. Moderately explosive when exposed to flame, Ca(OCl)z, chromic acid.
To fight fire, use water, foam, CO2, water
spray or mist, dry chemical. Explodes on
contact with fluorine.
Potential Exposure
It is used as an intermediate in dye
stuffs (alizarin), insecticides, and wood preservatives; making
synthetic fibers, anthraquinone, and other chemicals.
May be present in coke oven emissions, diesel fuel, and
coal tar pitch volitiles.
Carcinogenicity
Anthracene was negative in
mouse-skin-painting studies, and it is classified as a
noncarcinogen by the IARC based on inadequate
evidence. The methyl, anthryl, dimethyl, diprophyl,
dinaphthyl, and tetramethyl derivatives of anthracene were
noncarcinogenic except for 9,10-dimethyl anthracene, which
may have contained impurities when tested.
Source
Concentrations in 8 diesel fuels ranged from 0.026 to 40 mg/L with a mean value of
6.275 mg/L (Westerholm and Li, 1994). Lee et al. (1992) reported concentration ranges of 100–
300 mg/L and 0.04–2 μg/L in diesel fuel and corresponding aqueous phase (distilled water),
respectively. Schauer et al. (1999) reported anthracene in diesel fuel at a concentration of 5 μg/g
and in a diesel-powered medium-duty truck exhaust at an emission rate of 12.5 μg/km. Anthracene
was detected in a distilled water-soluble fraction of used motor oil at concentrations ranging from
1.1 to 1.3 μg/L (Chen et al., 1994).
California Phase II reformulated gasoline contained anthracene at a concentration of 4.35 μg/kg.
Gas-phase tailpipe emission rates from gasoline-powered automobiles with and without catalytic
converters were 3.69 and 148 μg/km, respectively (Schauer et al., 2002).
Thomas and Delfino (1991) equilibrated contaminant-free groundwater collected from
Gainesville, FL with individual fractions of three individual petroleum products at 24–25 °C for
24 h. The aqueous phase was analyzed for organic compounds via U.S. EPA approved test method
625. Average anthracene concentrations reported in water-soluble fractions of kerosene and diesel
fuel were 12 and 25 μg/L, respectively. Anthracene was ND in the water-soluble fraction of
unleaded gasoline.
The concentration of anthracene in coal tar and the maximum concentration reported in
groundwater at a mid-Atlantic coal tar site were 5,000 and 0.02 mg/L, respectively (Mackay and
Gschwend, 2001). Based on laboratory analysis of 7 coal tar samples, anthracene concentrations
ranged from 400 to 8,600 ppm (EPRI, 1990). A high-temperature coal tar contained anthracene at
an average concentration of 0.75 wt % (McNeil, 1983). Lehmann et al. (1984) reported an
anthracene concentration of 34.8 mg/g in a commercial anthracene oil.
Nine commercially available creosote samples contained anthracene at concentrations ranging
from 5,500 to 14,000 mg/kg (Kohler et al., 2000).
Anthracene was detected in asphalt fumes at an average concentration of 45.89 ng/m3 (Wang et
al., 2001).
Schauer et al. (2001) measured organic compound emission rates for volatile organic
compounds, gas-phase semi-volatile organic compounds, and particle-phase organic compounds
from the residential (fireplace) combustion of pine, oak, and eucalyptus. The respective gas-phase
and particle-phase emission rates of anthracene were 3.44 and 0.228 mg/kg of pine burned, 2.13
and 0.0230 mg/kg of oak burned, and 1.76 and 0.0061 mg/kg of eucalyptus burned.
Under atmospheric conditions, a low rank coal (0.5–1 mm particle size) from Spain was burned
in a fluidized bed reactor at seven different temperatures (50 °C increments) beginning at 650 °C.
The combustion experiment was also conducted at different amounts of excess oxygen (5 to 40%)
and different flow rates (700 to 1,100 L/h). At 20% excess oxygen and a flow rate of 860 L/h, the
amount of anthracene emitted ranged from 558.7 ng/kg at 900 °C to 2,449.7 ng/kg at 800 °C. The
greatest amount of PAHs emitted were observed at 750 °C (Mastral et al., 1999).
Environmental fate
Biological. Catechol is the central metabolite in the bacterial degradation of anthracene.
Intermediate by-products included 3-hydroxy-2-naphthoic acid and salicylic acid (Chapman,
1972). Anthracene was statically incubated in the dark at 25 °C with yeast extract and settled
domestic wastewater inoculum. Significant biodegradation with gradual adaptation was observed.
At concentrations of 5 and 10 mg/L, biodegradation yields at the end of 4 wk of incubation were
92 and 51%, respectively (Tabak et al., 1981). A mixed bacterial community isolated from
seawater foam degraded anthraquinone, a photodegradation product of anthracene, to traces of
benzoic and phthalic acids (Rontani et al., 1975). In activated sludge, only 0.3% mineralized to
carbon dioxide after 5 d (Freitag et al., 1985).
Soil. In a 14-d experiment, [14C]anthracene applied to soil-water suspensions under aerobic and
anaerobic conditions gave 14CO2 yields of 1.3 and 1.8%, respectively (Scheunert et al., 1987). The
reported half-lives for anthracene in a Kidman sandy loam and McLaurin sandy loam are 134 and
50 d, respectively (Park et al., 1990).
Surface Water. The removal half-lives for anthracene in a water column at 25 °C in midsummer
sunlight were 10.5 h for deep, slow, slightly turbid water; 21.6 h for deep, slow, muddy water; 8.5
h deep, slow, clear water; 3.5 h for shallow, fast, clear water, and 1.4 h for very shallow, fast, clear
water (Southworth, 1977).
Photolytic. Oxidation of anthracene adsorbed on silica gel or alumina by oxygen in the presence
of UV-light yielded anthraquinone. This compound additionally oxidized to 1,4-dihydroxy-
9,10-anthraquinone. Anthraquinone also formed by the oxidation of anthracene in diluted nitric
acid or nitrogen oxides (quoted, Nikolaou et al., 1984) and in the dark when adsorbed on fly ash
(Korfmacher et al., 1980). Irradiation of anthracene (2.6 mM) in cyclohexanone solutions gave
9,10-anthraquinone as the principal product (Korfmacher et al., 1980). Photocatalysis of
anthracene and sulfur dioxide at -25 °C in various solvents yielded anthracene-9-sulfonic acid
(Nielsen et al., 1983). Schwarz and Wasik (1976) reported a fluorescence quantum yield of 0.25
for anthracene in water.
Chemical/Physical. In urban air from St. Louis, MO, anthracene reacted with NOx forming 9-
nitroanthracene (Ramdahl et al., 1982).
Shipping
UN2811 Toxic solids, organic, n.o.s., Hazard
Class: 6.1; Labels: 6.1-Poisonous materials, Technical
Name Required.
Purification Methods
Likely impurities are anthraquinone, anthrone, carbazole, fluorene, 9,10-dihydroanthracene, tetracene and bianthryl. Carbazole is removed by continuous-adsorption chromatography [see Sangster & Irvine J Phys Chem 24 670 1956] using a neutral alumina column and eluting with n-hexane. [Sherwood in Purification of Inorganic and Organic Materials, Zief (ed), Marcel Dekker, New York, 1969.] The solvent is evaporated, and anthracene is sublimed under vacuum, then purified by zone refining, under N2 in darkness or non-actinic light. It has also been purified by co-distillation with ethylene glycol (boils at 197.5o), from which it can be recovered by addition of water, followed by crystallisation from 95% EtOH, *benzene, toluene, a mixture of *benzene/xylene (4:1), or Et2O. It has also been chromatographed on alumina with pet ether in a dark room (to avoid photo-oxidation of adsorbed anthracene to anthraquinone). Other purification methods include sublimation in a N2 atmosphere (in some cases after refluxing with sodium), and recrystallisation from toluene [Gorman et al. J Am Chem Soc 107 4404 1985]. Anthracene has been crystallised from EtOH, chromatographed through alumina in hot *benzene (fume hood) and then sublimed in a vacuum in a pyrex tube that has been cleaned and baked at 100o. (For further details see Craig & Rajikan J Chem Soc, Faraday Trans 1 74 292 1978, and Williams & Zboinski J Chem Soc, Faraday Trans 1 74 611 1978.) It has been chromatographed on alumina, recrystallised from n-hexane and sublimed under reduced pressure. [Saltiel J Am Chem Soc 108 2674 1986, Masnori et al. J Am Chem Soc 108 1126 1986.] Alternatively, recrystallise it from cyclohexane, chromatograph it on alumina with n-hexane as eluent, and recrystallise two more times [Saltiel et al. J Am Chem Soc 109 1209 1987]. Anthracene is fluorescent and forms a picrate complex, m 139o, on mixing the components in CHCl3 or *C6H6, but decomposes on attempted crystallization. [Beilstein 5 IV 228.]
Incompatibilities
Finely dispersed powder may form
explosive mixture in air. Contact with strong oxidizers
(chlorates, nitrates, peroxides, permanganates, perchlorates,
chlorine, bromine, fluorine, etc.); contact may cause fires
or explosions. Keep away from alkaline materials, strong
bases, strong acids, oxoacids, epoxides, chromic acid/or
calcium hypochlorite.
Waste Disposal
Consult with environmental
regulatory agencies for guidance on acceptable disposal
practices. Generators of waste containing this contaminant
(≥100 kg/mo) must conform with EPA regulations governing
storage, transportation, treatment, and waste disposal.
Incineration.
Check Digit Verification of cas no
The CAS Registry Mumber 120-12-7 includes 6 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 3 digits, 1,2 and 0 respectively; the second part has 2 digits, 1 and 2 respectively.
Calculate Digit Verification of CAS Registry Number 120-12:
(5*1)+(4*2)+(3*0)+(2*1)+(1*2)=17
17 % 10 = 7
So 120-12-7 is a valid CAS Registry Number.
InChI:InChI=1/C14H10/c1-2-6-12-10-14-8-4-3-7-13(14)9-11(12)5-1/h1-10H
120-12-7Relevant articles and documents
In situelectrosynthesis of anthraquinone electrolytes in aqueous flow batteries
Aziz, Michael J.,Fell, Eric M.,Gordon, Roy G.,Jin, Shijian,Jing, Yan,Kerr, Emily F.,Pollack, Daniel A.,Wong, Andrew A.,Wu, Min
, p. 6084 - 6092 (2020)
We demonstrate the electrochemical oxidation of an anthracene derivative to a redox-active anthraquinone at room temperature in a flow cell without the use of hazardous oxidants or noble metal catalysts. The anthraquinone, generatedin situ, was used as the active species in a flow battery electrolyte without further modification or purification. This potentially scalable, safe, green, and economical electrosynthetic method is also applied to another anthracene-based derivative and may be extended to other redox-active aromatics.
Organocatalytic oxidative dehydrogenation of dihydroarenes by dioxygen using 2,3-dichloro-5,6-dicyano-benzoquinone (DDQ) and NaNO2
Zhang, Wei,Ma, Hong,Zhou, Lipeng,Sun, Zhiqiang,Du, Zhongtian,Miao, Hong,Xu, Jie
, p. 3236 - 3245 (2008)
The oxidative dehydrogenation of dihydroarenes catalyzed by 2,3-dichloro-5,6-dicyano-benzoquinone(DDQ) and NaNO2 with dioxygen is reported. The combination of DDQ and NaNO2 showed high efficiency and high selectivity, compared with other benzoquinones and anthraquinones, e.g., >99% conversion of 9,10-dihydroanthracene with 99% selectivity for anthracene can be obtained at 120 °C under 1.3 MPa O2 for 8 h. Excellent results were achieved in the oxidative dehydrogenation of variety of dihydroarenes.
Photochemistry of 9-Benzoylanthracene
Becker, Hans-Dieter,Langer, Vratislav,Becker, Hans-Christian
, p. 6394 - 6396 (1993)
Photoexcitation of 9-benzoylanthracene (1) in toluene solution under argon results in head-to-tail dimerization by 4? + 4? cycloaddition to give dibenzoyl-substituted dianthracene in about 60percent yield.The concomitant formation of both anthracene and 9,10-dibenzoylanthracene (ca. 4percent yield) suggests that intermolecular benzoyl group/hydrogen exchange may be an inefficient mode of deactivation the intermediate excimer.Irradiation of crystalline 1 gave the head-to-tail dimer, without byproducts, in a maximal yield of 50percent.It was established by X-ray diffraction that theasymmetric unit of 1 consists of two molecules, 1A and 1B, in which the carbonyl group is twisted out of the plane of the anthracene by 67.4 deg and 86.5 deg, respectively.Investigation of the packing pattern revealed that only parallel overlapping head-to-tail oriented molecules of 1A, characterized by an interplanar spacing of 3.35 Angstroem, can undergo photochemical dimerization by 4? + 4? cycloaddition.The spatial relation of adjacent molecules of 1B is such as to preclude their involvement in the photochemical dimerization.
Stoichiometric Formation of an Oxoiron(IV) Complex by a Soluble Methane Monooxygenase Type Activation of O2 at an Iron(II)-Cyclam Center
Kass, Dustin,Corona, Teresa,Warm, Katrin,Braun-Cula, Beatrice,Kuhlmann, Uwe,Bill, Eckhard,Mebs, Stefan,Swart, Marcel,Dau, Holger,Haumann, Michael,Hildebrandt, Peter,Ray, Kallol
, p. 5924 - 5928 (2020)
In soluble methane monooxygenase enzymes (sMMO), dioxygen (O2) is activated at a diiron(II) center to form an oxodiiron(IV) intermediate Q that performs the challenging oxidation of methane to methanol. An analogous mechanism of O2 activation at mono-or dinuclear iron centers is rare in the synthetic chemistry. Herein, we report a mononuclear non-heme iron(II)-cyclam complex, 1-trans, that activates O2 to form the corresponding iron(IV)-oxo complex, 2-trans, via a mechanism reminiscent of the O2 activation process in sMMO. The conversion of 1-trans to 2-trans proceeds via the intermediate formation of an iron(III)-superoxide species 3, which could be trapped and spectroscopically characterized at-50 °C. Surprisingly, 3 is a stronger oxygen atom transfer (OAT) agent than 2-trans; 3 performs OAT to 1-trans or PPh3 to yield 2-trans quantitatively. Furthermore, 2-trans oxidizes the aromatic C-H bonds of 2,6-di-tert-butylphenol, which, together with the strong OAT ability of 3, represents new domains of oxoiron(IV) and superoxoiron(III) reactivities.
Investigation of the formation reaction and structural characterization of the 'platinum Grignard reagent' [Pt(MgCl)2(THF)(x)] by extended X-ray absorption fine structure (EXAFS) and other methods
Aleandri, Lorraine E.,Bogdanovic, Borislav,Duerr, Christine,Huckett, Sara C.,Jones, Deborah J.,Kolb, Uwe,Lagarden, Martin,Roziere, Jacques,Wilczok, Ursula
, p. 1710 - 1718 (1997)
The 'platinum Grignard reagent' [Pt(MgCl)2(THF)(x)] (2), obtained by the reaction of PtCl2 and Et2Mg in a 1:2 molar ratio, as well as finely divided platinum (Pt*) a possible intermediate formed during the preparation of 2-have been investigated by EXAFS spectroscopy at the Pt L(III) edge. Parallel investigations were carried out on Pt* obtained from PtCl2 and (9,10-dihydro-9,10-anthracenediyl)tris(tettrahydrofuran)magnesium (MgA), and on 2 obtained from Pt* MgA, and MgCl2. The EXAFS results suggest that Pt* consists of extremely small particles (? 5-11 A) with strongly reduced Pt-Pt distances compared to bulk Pt (?0.09 A). The EXAFS spectra of 2 indicate the presence of Mg shells in addition to Pt shells in the Pt environment; Mg atoms are at a bonding distance from Pt atoms (2.78-2.80 A). These results suggest that 2 consists of very small Pt-Mg clusters and confirm their formation from organomagnesium reagents and PtCl2 or Pt*.
Indium-catalyzed construction of polycyclic aromatic hydrocarbon skeletons via dehydration
Kuninobu, Yoichiro,Tatsuzaki, Tomohiro,Matsuki, Takashi,Takai, Kazuhiko
, p. 7005 - 7009 (2011)
Polycyclic aromatic compounds can be synthesized from 2-benzylic- or 2-allylbenzaldehydes using a catalytic amount of In(III) or Re(I) complexes. By using this method, polycyclic aza-aromatic compounds can also be prepared efficiently. In these reactions, only water is formed as a side product.
Transition metal-free regioselective access to 9,10-dihydroanthracenes via the reaction of anthracenes with elemental phosphorus in the KOH/DMSO system
Kuimov, Vladimir A.,Gusarova, Nina K.,Malysheva, Svetlana F.,Trofimov, Boris A.
, p. 4533 - 4536 (2018)
Anthracene and its 9- or 9,10-substituted (Me, Ph, Cl, Br) derivatives react with red phosphorus (Pn) in the KOH/DMSO superbase system at 85–120 °C to afford 9,10-dihydroanthracenes in good to excellent yields, thus providing simple and clean access to these extensively used dihydroaromatics.
Synthesis and Pyrolysis of a Triafulvene Precursor
Muehlebach, Michel,Neuenschwander, Markus,Engel, Peter
, p. 2089 - 2110 (1993)
In view of retro-Diels-Alder reactions (RDA reactions), the triafulvene precursor 3 has been prepared in a simple three-step synthesis by dibromocarbene addition at dibenzo-barralene (11-->12; 44percent), halogen-Li exchange followed by methylation (12-->14, 100percent) and HBr elimination (14-->3, 62percent) Scheme 3).Reactivity of the so far unknown bridged 1,1-dibromocyclopropane 12 has been explored, including reductions, allylic rearrangements, and "carbene dimerizations" (Scheme 4).First experiments with respect to the thermal behaviour of 3 show that RDA reaction, although occuring in most cases, is not the predominant pathway.When 3 is heated in a sealed tube without solvent, two dimers 26 and 27 are isolated in a total yield of 55percent (Scheme 6).On the other hand, gas-phase pyrolysis of 3 at 400 deg mainly produces rearranged 28 (56percent; Scheme 7).It is assumed that bridged trimethylenemethane 29 is an essential intermediate in thermal rearrangements of 3 (Scheme 8).
Evaluation of the Transferability of the “Flexible Steric Bulk” Concept from N-Heterocyclic Carbenes to Planar-Chiral Phosphinoferrocenes and their Electronic Modification
Korb, Marcus,Schaarschmidt, Dieter,Grumbt, Martin,K?nig, Matthias,Lang, Heinrich
, p. 2968 - 2982 (2020)
The concept of “flexible steric bulk” is discussed at 2-phenylvinyl-1-phosphinoferrocenes. The introduction of freely rotatable 1'-silyl groups increases the catalytic productivity within the synthesis of tri-ortho-substituted biaryls by Suzuki–Miyaura C,C cross-coupling reactions, giving higher yields with 1/4 of catalyst concentration than for the non-silylated derivatives. Electronic modification of the P and the vinyl donor functionalities was investigated by introducing substituents in the para positions of both groups. Therein, electron-withdrawing phosphines increased the yield from 78 to 91 percent for a given biaryl, by changing from a diphenylphosphino to the P(p-CN-C6H4)2 unit. Opposite results, obtained from electron-donating and sterically demanding phosphines, were in accordance with the 1J(31P,77Se) values. However, the electron density of the ferrocenyl backbone, expressed by the redox potential of the first ferrocenyl-related redox process, cannot be correlated with the donor-properties at the P atom. Changing from a PPh2-substituted ferrocene to a (RA)-1,1'-binaphthyl-containing phosphonite, a complex interaction between the axial- and the planar-chiral motifs occurs, resulting a change of the absolute biaryl configuration.
Aerobic Oxidation Catalysis by a Molecular Barium Vanadium Oxide
Lechner, Manuel,Kastner, Katharina,Chan, Chee Jian,Güttel, Robert,Streb, Carsten
, p. 4952 - 4956 (2018)
Aerobic catalytic oxidations are promising routes to replace environmentally harmful oxidants with O2 in organic syntheses. Here, we report a molecular barium vanadium oxide, [Ba4(dmso)14V14O38(NO3)] (={Ba4V14}) as viable homogeneous catalyst for a series of oxidation reactions in N,N-dimethyl formamide solution under oxygen (8 bar). Starting from the model compound 9,10-dihydroanthracene, we report initial dehydrogenation/ aromatization leading to anthracene formation; this intermediate is subsequently oxidized by stepwise oxygen transfer, first giving the mono-oxygenated anthrone and then the di-oxygenated target product, anthraquinone. Comparative reaction analyses using the Neumann catalyst [PV2Mo10O40]5? as reference show that oxygen diffusion into the reaction mixture is the rate-limiting step, resulting in accumulation of the reduced catalyst species. This allows us to propose improved reactor designs to overcome this fundamental challenge for aerobic oxidation catalysis.
