224-41-9

Usage

Synthesis Reference(s)

The Journal of Organic Chemistry, 46, p. 2601, 1981 DOI: 10.1021/jo00325a041

Health Hazard

Dibenz[a,j]anthracene has shown to causeskin cancer in animals, producing tumor atthe site of application. There is no report ofits toxicity. It tested positive in a histidinereversion–Ames test.

InChI:InChI=1/C22H14/c1-3-7-19-15(5-1)9-11-17-13-18-12-10-16-6-2-4-8-20(16)22(18)14-21(17)19/h1-14H

Synthetic route

2,4',6',2''-tetravinyl-[1,1';3',1'']terphenyl (868847-77-2) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
With Grubbs catalyst first generation In dichloromethane at 35℃; for 23h; ring-closing olefin metathesis;	98%

1,2,3,4,10,11,12,13-Octahydrodibenzanthracene (130799-92-7) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
palladium on activated charcoal In various solvent(s) Heating;	93%

14-acetoxydibenzanthracene (81205-71-2) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
With potassium hydroxide; zinc In 1,4-dioxane; water Heating;	90%

2-(Naphthalene-2-carbonyl)-naphthalene-1-carboxylic acid (77321-42-7) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
With phosphorus; hydrogen iodide In acetic acid for 120h; Heating;	84%

3-Naphthalen-2-yl-3H-naphtho[1,2-c]furan-1-one (73540-68-8) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
With hydrogen iodide; hypophosphorous acid In acetic acid for 240h; Heating;	80%

7-(Methylthio)-dibenzanthracene (134576-19-5) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
With nickel In methanol for 6h; Ambient temperature;	78%

(E,E)-1,3-distyrylbenzene (1725-76-4) → benzo[c]chrysene (194-69-4) + dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
With iodine In benzene for 1h; Irradiation;	A 70% B 8%
With iodine In benzene Irradiation;	A 70% B 8%

7,14-dihydro-14-ethoxy-7-(trimrthylsilyl)-7,14-epoxydibenzanthracene (103224-51-7) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
With acetic acid; zinc for 14h; Heating;	55%

C28H22 (80992-42-3) → dibenz[a,j]anthracene (224-41-9) + C28H22 (82344-75-0) + C28H22 (80992-41-2)

Conditions	Yield
In benzene Irradiation; Yields of byproduct given;	A 39% B n/a C n/a
In benzene Irradiation; Yield given. Yields of byproduct given;

(2-methylnaphthalen-1-yl)(naphthalen-1-yl)methanone (41774-28-1) → dibenzo[a,h]anthracene (53-70-3) + dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
at 420℃; for 0.75h;	A 20% B 2%

1-Methylnaphthalene (90-12-0) → picene (213-46-7) + dibenzo[a,h]anthracene (53-70-3) + Benzo[b]chrysene (214-17-5) + dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
at 750℃;

5,6,8,9-Tetrahydrodibenzoanthracene (19399-64-5) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
With carbon dioxide; palladium on activated charcoal at 300℃;

14H-dibenz[a,j]anthracen-7-one (41774-36-1) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
With sodium hydroxide; zinc

1,2-dihydrocyclobutene[α]naphthalene (32277-35-3) → dibenzo[a,h]anthracene (53-70-3) + dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
at 890℃;

C22H30O2 (130800-12-3) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
With methanesulfonic acid; 2,3-dicyano-5,6-dichloro-p-benzoquinone 1.) CHCl3, r.t., 2.) benzene, reflux; Yield given. Multistep reaction;
Multi-step reaction with 2 steps 1: 1.) methanesulfonic acid, 2.) o-chloranil / 1.) CHCl3, r.t., 2.) benzene, reflux, 48 h 2: 93 percent / 10 percent Pd/C / various solvent(s) / Heating View Scheme

lithium salt of N,N-diethyl-1-naphthtamide (81194-74-3) + β-naphthaldehyde (66-99-9) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
1.) diethyl ether, THF, -60 deg C 2.) Zn, KOH, pyridine, H2O, MeOH, reflux, 2.5 h 3.) ZnCl2, acetic acid, 30 min 4.) HI, hypophosphoric acid, 30 min; Yield given. Multistep reaction;

trans-9,10-dihydro-2-styrylphenanthrene (89988-22-7) → benzo[c]chrysene (194-69-4) + dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
With iodine; 2,3-dicyano-5,6-dichloro-p-benzoquinone 1) benzene, irradiation, 7 h, 2) benzene, reflux, 14 h; Yield given. Multistep reaction. Yields of byproduct given;

carbon disulfide (75-15-0) + aluminium trichloride (7446-70-0) + 1-Chloromethylnaphthalene (86-52-2) + 1-chloromethylnaphthalene (2506-41-4) → dibenzo[a,h]anthracene (53-70-3) + benzo[a]naphthacene (226-88-0) + dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
Erhitzen des Reaktionsprodukts mit Kupfer-Pulver, neben groessren Mengen makromolekularer Substanzen;

carbon disulfide (75-15-0) + aluminium trichloride (7446-70-0) + 1-Chloromethylnaphthalene (86-52-2) + 2-Methylnaphthalene (91-57-6) → dibenzo[a,h]anthracene (53-70-3) + benzo[a]naphthacene (226-88-0) + dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
Erhitzen des Reaktionsprodukts mit Kupfer-Pulver;

7-oxo-7.14-dihydro-dibenzanthracene → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
With sodium hydroxide; zinc

dibenzanthracene-dicarboxylic acid-(6.8) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
at 340 - 350℃; under 3 - 4 Torr;

1,5-dibromo-2,4-divinylbenzene (868847-74-9) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: 93 percent / tetrakis(triphenylphosphine)palladium(0); sodium carbonate / 1,2-dimethoxy-ethane; ethanol; H2O / 16 h / Heating 2: 98 percent / bis(tricyclohexylphosphine)(benzylidene)ruthenium dichloride / CH2Cl2 / 23 h / 35 °C View Scheme

1,5-dibromo-2,4-bis(dibromomethyl)benzene (58997-70-9) → dibenz[a,j]anthracene (224-41-9)

Conditions

Yield

Multi-step reaction with 4 steps 1.1: 96 percent / silver nitrate / ethanol; H2O / 0.5 h / Heating 2.1: potassium tert-butoxide / tetrahydrofuran / 0.08 h 2.2: 61 percent / tetrahydrofuran / 25 °C 3.1: 93 percent / tetrakis(triphenylphosphine)palladium(0); sodium carbonate / 1,2-dimethoxy-ethane; ethanol; H2O / 16 h / Heating 4.1: 98 percent / bis(tricyclohexylphosphine)(benzylidene)ruthenium dichloride / CH2Cl2 / 23 h / 35 °C View Scheme

1,5-dibromo-2,4-dimethylbenzene (615-87-2) → dibenz[a,j]anthracene (224-41-9)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: 88 percent / N-bromosuccinimide / CCl4 / 9 h / Heating; irradiation 2.1: 96 percent / silver nitrate / ethanol; H2O / 0.5 h / Heating 3.1: potassium tert-butoxide / tetrahydrofuran / 0.08 h 3.2: 61 percent / tetrahydrofuran / 25 °C 4.1: 93 percent / tetrakis(triphenylphosphine)palladium(0); sodium carbonate / 1,2-dimethoxy-ethane; ethanol; H2O / 16 h / Heating 5.1: 98 percent / bis(tricyclohexylphosphine)(benzylidene)ruthenium dichloride / CH2Cl2 / 23 h / 35 °C View Scheme

2,4-dibromobenzene-1,5-dicarboxaldehyde (97094-37-6) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: potassium tert-butoxide / tetrahydrofuran / 0.08 h 1.2: 61 percent / tetrahydrofuran / 25 °C 2.1: 93 percent / tetrakis(triphenylphosphine)palladium(0); sodium carbonate / 1,2-dimethoxy-ethane; ethanol; H2O / 16 h / Heating 3.1: 98 percent / bis(tricyclohexylphosphine)(benzylidene)ruthenium dichloride / CH2Cl2 / 23 h / 35 °C View Scheme

m-xylene (108-38-3) → dibenz[a,j]anthracene (224-41-9)

Conditions

Yield

Multi-step reaction with 6 steps 1.1: 58 percent / Br2; I2 / 16 h / 20 °C 2.1: 88 percent / N-bromosuccinimide / CCl4 / 9 h / Heating; irradiation 3.1: 96 percent / silver nitrate / ethanol; H2O / 0.5 h / Heating 4.1: potassium tert-butoxide / tetrahydrofuran / 0.08 h 4.2: 61 percent / tetrahydrofuran / 25 °C 5.1: 93 percent / tetrakis(triphenylphosphine)palladium(0); sodium carbonate / 1,2-dimethoxy-ethane; ethanol; H2O / 16 h / Heating 6.1: 98 percent / bis(tricyclohexylphosphine)(benzylidene)ruthenium dichloride / CH2Cl2 / 23 h / 35 °C View Scheme

1-Bromonaphthalene (90-11-9) + soda lime → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
Multi-step reaction with 2 steps 2: 55 percent / Zn, AcOH / 14 h / Heating View Scheme

7-(Methylthio)-5,6-dihydrodibenzanthracene (134576-15-1) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
Multi-step reaction with 2 steps 1: 96 percent / DDQ / dioxane / 24 h / Heating 2: 78 percent / Raney-Nickel / methanol / 6 h / Ambient temperature View Scheme

1-naphthalenecarboxylic acid (86-55-5) → dibenz[a,j]anthracene (224-41-9)

Conditions	Yield
Multi-step reaction with 4 steps 1: SOCl2, dimethyl formamide / benzene / 2 h 2: 18.5 g / diethyl ether / 1 h / 0 °C 3: 1.) TMEDA, triphenylmethyl chloride, sec-BuLi / 1.) ether, cyclohexane, -78 deg C, 1 h, 2.) a) -78 deg, 1 h, b) room temp., 3 h 4: 80 percent / HI, H3PO2 / acetic acid / 240 h / Heating View Scheme

dibenz[a,j]anthracene (224-41-9) + cyclohexa-1,3-diene (1165952-91-9) → C28H22 (80992-42-3) + C28H22 (80992-41-2)

Conditions	Yield
In benzene Irradiation;	A 91% B 9%
In benzene Irradiation;	A 11% B 89%

dibenz[a,j]anthracene (224-41-9) → 7-bromodibenz[a,j]anthracene

Conditions	Yield
With N-Bromosuccinimide; iron(III) chloride In tetrachloromethane Bromination; Heating;	91%

maleic anhydride (108-31-6) + dibenz[a,j]anthracene (224-41-9) → C26H16O3

Conditions	Yield
In various solvent(s) at 91.5℃; Mechanism; Rate constant; analogous reaction of other polycyclic aromatic hydrocarbons; structure/reactivity correlations, application of theoretical models;

dibenz[a,j]anthracene (224-41-9) + acetic acid (64-19-7) + CrO3 → 7.14-dioxo-7.14-dihydro-dibenzanthracene

Upstream product

• 90-12-0 1-Methylnaphthalene 
• 19399-64-5 5,6,8,9-Tetrahydrodibenzoanthracene 
• 1725-76-4 (E,E)-1,3-distyrylbenzene 
• 32277-35-3 1,2-dihydrocyclobuteno[α]naphthalene 
• 130800-12-3 C₂₂H₃₀O₂ 
• 77321-42-7 2-(Naphthalene-2-carbonyl)-naphthalene-1-carboxylic acid 
• 81205-71-2 14-acetoxydibenzanthracene 
• 80992-42-3 C₂₈H₂₂ 
• 81194-74-3 lithium salt of N,N-diethyl-1-naphthtamide 
• 66-99-9 β-naphthaldehyde 
• 89988-22-7 trans-9,10-dihydro-2-styrylphenanthrene 
• 75-15-0 carbon disulfide 
• 7446-70-0 aluminium trichloride 
• 86-52-2 1-Chloromethylnaphthalene 

Downstream Products

• 134273-46-4 3-(2-Formylphenyl)-2-phenanthrenecarboxaldehyde 
• 131407-74-4 dibenz[a,j]anthracene-5,6-oxide 
• 52755-66-5 dibenzanthracene-5,6-dione 
• 41774-33-8 Dibenzoanthrachinone 

Relevant academic research and scientific papers

Reductive Cyclization of Keto Acids to Polycyclic Aromatic Hydrocarbons by Hydroiodic Acid-Red Phosphorus

Hydroiodic acid-red phosphorus in acetic acid causes ring closure of o-naphthoylbenzoic acids and of o-naphthoylnaphthoic acids to yield benzanthracene and dibenzanthracenes

Controlling the regioselectivity of the di-p-methane rearrangements of 1,2-naphtho-annelated barrelene derivatives-Solution versus solid-state photochemistry

The synthesis of 1,2-naphtho-annelated barrelene derivatives, namely dimethyl-7,12-dihydro-7,12-ethenobenzo[a]anthracene-13,14-dicarboxylate (4a) and dimethyl-7,14-dihydro-7,14-ethenodibenzo[a,j]-anthracene-15,16-dicarboxylate (4b), and the investigation

Polycyclic aromatic hydrocarbons by ring-closing metathesis

A strategy for the synthesis of polycyclic aromatic hydrocarbons (PAHs) by the ring-closing olefin metathesis (RCM) of pendant olefins on a phenylene backbone has been developed. RCM of 2,4′,6′,2″-tetravinyl-[1, 1′;3′,1″]terphenyl and 2,2′,5′,2″- tetravinyl-[1,1′;4′,1′]terphenyl affords in high yield the isomeric [a,j] and [a,h] dibenzanthracenes, respectively. In contrast with other intramolecular annulation methods, such as Friedel-Crafts acylations, this reaction is completely regioselective. Since RCM is reversible and PAHs are often thermodynamic sinks, this strategy is an effective and general method for the preparation of PAHs. Density functional theory calculations support these results. Carbon disulfide is a suitable solvent for these reactions.

The Syntheses of 4b,5a-Dihydrodibenzanthraoxirene and 4b,5a-Dihydro-5H-dibenzanthraazirine

The syntheses of the K-oxide and K-imine derivatives of dibenzanthracene (1) are described.The parent hydrocarbon 1 that was obtained as a side product in the Elbs pyrolysis of (2-methyl-1-naphthyl)-1'-naphthylmethanone (10) was oxidized to 3-(2-formylphenyl)-3-phenanthrenecarboxaldehyde (3).Treatment of the dialdehyde with tris(dimethylamino)phosphine gave 4b,5a-dihydrodibenzanthraoxirene (4).Reaction of the oxirane with sodium azide followed by triethyl phosphite cyclization of the mixture of trans azido-alcohols so formed, yielded mainly 4b,5a-dihydrodibenzanthraazirine (5).

A New General Synthesis of Polycyclic Aromatic Compounds Based on Enamine Chemistry

Alkylation of enamines and enamine salts by benzylic and (β-haloethyl)aryl halides, respectively, followed by acidic cyclodehydration and dehydrogenation provides an efficient synthetic approach to a wide range of polycyclic aromatic compounds of diverse structural types.Specific polycyclic hydrocarbons synthesized by this route include benzo- and benzofluorene, 7H-dibenzo-, 13H-dibenzo-, and 13H-dibenzofluorene, 15H-tribenzofluorene, dibenzochrysene, benzopentaphene, indenofluorene, fluorenofluorene, octahydrodibenzanthracene, dibenzanthracene, octahydrodibenzanthracene, dibenzanthracene, picene, benzopicene, 1H-benzaceanthrylene, and 4H-cyclopentachrysene.This method with appropriate modifications appears to be potentially broader in scope than established traditional methods of polycyclic hydrocarbon synthesis.

Cycloaromatization of α-oxoketene dithioacetals and β-oxodithioacetals with benzyl-,1-(naphthylmethyl) and 2-(naphthylmethyl)magnesium halides: Synthesis of condensed polynuclear aromatic hydrocarbons

An efficient route for the synthesis of substituted naphthalenes, phenanthrenes and other polynuclear aromatic hydrocarbons has been developed. The methodology involves 1,2- (or sequential 1,4- and 1,2-) addition of either benzyl, 1-(naphthylmethyl) or 2-(naphthylmethyl) magnesium halides to α-oxoketene dithioacetals or β-oxodithioacetals followed by borontrifluoride etherate catalyzed cycloaromatization of the resulting carbinols.

Photochemistry of Electron-Rich 1,3-Distyrylbenzenes

The 1,3-distyrylbenzenes 3, containing up to seven alkoxy groups, are subjected to the oxidative photocyclization.Elimination of methanol (3bb -> 7bb, 3bf -> 7bf) and quinone oxidation can occur as competitive or consecutive reactions in the formation of the products 6, 7, and 8.Selfsensitized generation of singlet oxygen by 6bf can lead to endoperoxide formation (6bf -> 11).

Photochemistry of 1,3-Distyrylbenzene - A New Route to syn-(1,3)Cyclophanes

Depending on the reaction conditions the irradiation of the title compound 1 leads to cyclodimerization 1 -> 6, dehydrogenating cyclization 1 -> 11, 12 or a combination of both processes 1 -> 13, 14, 15.The stereoisomeric (1,3)cyclophanes 6a - c as well as the access into the pyrene series 15, 16, 18 are of special synthetic interest.

Cycloadducts of Arynes with 1,3-Bis(trimethylsilyl)naphthofuran: Formation of Novel Polycyclic Aromatic Derivatives and Related Reactions

A recently developed procedure for the preparation of trimethylsilylated isobenzofurans and the use of these materials in cycloaddition reactions has been extended to an isonaphthofuran analogue.The 1,3-bis(trimethylsilyl)naphthofuran (7) has been isolated; its reaction with maleic anhydride in room temperature is rapid and readily reversible as shown by endo to exo cycloadduct interconversion.The failure of 7 to give cycloadduct with 2-butenolide indicates that it is less reactive than the parent naphthofuran.In situ generation and cycloaddition reactions with various arynes (benzyne, 4-methylbenzyne, 3,4-pyridyne, 9,10-phenanthrolyne, 1,2-naphthalyne, 2,3-naphthalyne) are described.The three unsymmetrical arynes all give mixtures of cycloadducts indicative of negligible regioselectivity in Diels-Alder reactions with 7; thus, in spite of possible steric hindrance the reaction with 1,2-naphthalyne gives a 1:1 mixture of dibenz- and dibenzanthracene derivatives.In contrast, the reaction of 1-ethoxy-3-(trimethylsilyl)naphthoanthracene derivative.Various reactions of the cycloadducts are described.

Dibenzanthracene via Photo-cyclodehydrogenation of 9,10-Dihydro-2-styrylphenanthrene

Waehrend aus 2-Styrylphenanthren (1) durch Photocyclodehydrierung Benzochrysen (2) entsteht, laesst sich unter Ausnutzung der "ΣF*-Regel" aus 9,10-Dihydro-2-styrylphenanthren (4) durch Photocyclodehydrierung zu 6 und anschliessende Dehydrierung Dibenzanthracen (3) erhalten.