84-11-7

Basic information

• Product Name: Phenanthrenequinone
• Synonyms: 9,10-dihydro-9,10-dioxo-phenanthren;9,10-phenanthraquinone[qr];9,10-phenanthrenequinone[qr];phenanthraquinone[qr];Phenanthrene, 9,10-dihydro-9,10-dioxo-;phenanthrene,9,10-dihydro-9,10-dioxo-[qr];phenanthrenequinone[qr];Phenanthroquinone
• CAS NO: 84-11-7
• Molecular Formula: C₁₄H₈O₂
• Molecular Weight: 208.21
• EINECS: 201-515-5
• Product Categories: Intermediates of Dyes and Pigments;Aromatic Compounds;FINE Chemical & INTERMEDIATES;Anthraquinones, Hydroquinones and Quinones
• Mol File: 84-11-7.mol
• Article Data: 130

Chemical Properties

• Melting Point: 209-212 °C(lit.)
• Boiling Point: 360 °C
• Flash Point: 245 °C
• Appearance: Orange-brownish/Powder
• Density: 1.405
• Vapor Pressure: 2.29E-05mmHg at 25°C
• Refractive Index: 1.5681 (estimate)
• Storage Temp.: 2-8°C
• Solubility: 7.5mg/l
• Water Solubility: Insoluble in water.
• Stability: Stable. Incompatible with strong oxidizing agents.
• Merck: 14,7213
• BRN: 608838
• CAS DataBase Reference: Phenanthrenequinone(CAS DataBase Reference)
• NIST Chemistry Reference: Phenanthrenequinone(84-11-7)
• EPA Substance Registry System: Phenanthrenequinone(84-11-7)

Safety Data

• Hazard Codes: Xi
• Statements: 36/37/38
• Safety Statements: 26-36-24/25-22
• RIDADR: UN3077
• WGK Germany: 3
• RTECS: SF7875000
• TSCA: Yes
• HazardClass: 9
• PackingGroup: III
• Hazardous Substances Data: 84-11-7(Hazardous Substances Data)

Usage

Description

9,10-Phenanthrenequinone (9,10-PQ) is a quinone molecule that is abundantly found in air pollution, particularly in diesel exhaust particles (DEP). It is a burnt-orange powder and has been extensively studied for its cytotoxic effects both in vitro and in vivo. 9,10-PQ is known to generate reactive oxygen species (ROS) through redox cycling, leading to the development of cytotoxicity. Additionally, it reduces the expression of glutathione (GSH), which plays a critical role in Phase II detoxification reactions.

Uses

Used in Semiconductor Industry:
9,10-Phenanthrenequinone is used as a high-quality passivation agent on silicon (100) surfaces. It reacts with the dangling bonds on the surface via a heteroatomic Diels-Alder reaction, preserving the semiconducting nature of the silicon due to the Π-electron conjugation.
Used in Enzyme Substrates:
Quinones, including 9,10-Phenanthrenequinone, serve as substrates for a variety of flavoenzymes, which are essential for various biological processes.
Used in Chemical Synthesis:
9,10-Phenanthrenequinone is used in the formation of spirophosphoranes containing acyclic 5-methyl-2-phenyl-2H-1,2,3-diazaphosphol-4-yl substituent, which can be utilized in various chemical applications.

Preparation

Phenanthrenequinone is obtained by the oxidation of the hydrocarbon phenanthrene C14H10. Upon reduction with sulphur dioxide, it yields phenanthrenehydroquinone which absorbs oxygen from the air forming a black quinhydrone. Upon further oxidation the phenanthrenequinone is again formed. 9,10-Phenanthrenequinone is prepared by oxidation of phenanthrene with dihydroxy phenylselenonium benzenesulfonate in boiling dioxane-water. 9-methoxyphenanthrene is obtained when the reaction is carried out in methanol. https://www.tandfonline.com/doi/abs/10.1080/00397919708004809

Reactions

9,10-Phenanthrenequinone (PQ) reacts with ketones under FeCl3 catalysis to furnish a variety of structurally diverse furan annulated products. While the reaction of PQ with acetone and cyclopentanone furnishes furan annulated ketals, its reaction with ethyl alkyl ketones provides 3-furaldehyde annulated products. In contrast to the reaction of PQ with cyclopentanone, its reaction with cyclohexanone furnishes a tetrahydrobenzofuran annulated secondary alcohol. The reactions of PQ with cycloheptanone and cyclooctanone take a different course to provide 7,8-dihydro-6H-cyclohepta[b]furan and 6,7,8,9-tetrahydrocycloocta[b]furan annulated products, respectively. Mechanistically, the above reactions go through aldol condensation, dehydration and cyclization to form furan-phenanthrene annulated products where in each step FeCl3 catalysis is involved. https://pubs.rsc.org/en/content/articlelanding/2012/ra/c2ra20499a

Synthesis Reference(s)

The Journal of Organic Chemistry, 52, p. 3472, 1987 DOI: 10.1021/jo00391a065

Safety Profile

Poison by acute intraperitoneal route. Questionable carcinogen with experimental tumorigenic data by skin contact. Mutation data reported. When heated to decomposition it emits acrid smoke and irritating fumes.

Purification Methods

Crystallise the quinone from dioxane or 95% EtOH and dry it under vacuum. [Beilstein 7 IV 2565.]

InChI:InChI=1/C14H8O2/c15-13-11-7-3-1-5-9(11)10-6-2-4-8-12(10)14(13)16/h1-8H

Upstream product

• 39559-48-3 10-Benzoyloxy-[9]phenanthrol 
• 863305-32-2 diphenic acid 
• 93-89-0 benzoic acid ethyl ester 
• 64440-29-5 (9R,10R)-trans-9,10-dihydroxy-3,4-dihydrophenanthrene 
• 81593-15-9 1-chloro-1a,9b-dihydro-1H-<9,10-b>azirine 
• 67-63-0 isopropyl alcohol 
• 67-56-1 methanol 
• 85-01-8 phenanthrene 
• 7509-44-6 10-diazophenanthren-9(10H)-one 
• 7446-08-4 selenium(IV) oxide 
• 28830-56-0 Phenyl-(10-hydroxy-phenanthryl-⁽⁹⁾)-aether 
• 7697-37-2 nitric acid 
• 7722-84-1 dihydrogen peroxide 
• 64-19-7 acetic acid 

Downstream Products

• 100575-70-0 2-phenyl-phenanthro[9,10-d][1,3]dioxole 
• 111326-43-3 10-chloro-dibenzo[f,h]pyrido[3,4-b]quinoxaline 
• 36939-59-0 2-(2-chlorophenyl)-1H-phenanthro[9,10-d]-imidazole 
• 37053-62-6 2‐(4‐nitrophenyl)‐1H‐phenanthro[9,10‐d]imidazole 
• 6931-31-3 2-phenyl-9,10-phenanthroimidazole 
• 39559-48-3 10-Benzoyloxy-[9]phenanthrol 
• 4410-14-4 2-phenylphenanthro[9,10-d]oxazole 
• 24293-67-2 2-(2-(vinyloxy)phenyl)-1H-phenanthro[9,10-d]imidazole 
• 39559-42-7 9-Acetoxy-10-hydroxyphenanthren 
• 58131-87-6 trans-9,10-dihydro-9,10-diphenyl-9,10-phenanthrenediol 
• 58131-79-6 (+/-)-9r.10t-bis-(4-chloro-phenyl)-9.10-dihydro-phenanthrenediol-(9.10c) 
• 215-64-5 dibenzo[a,c]phenacine 
• 858856-49-2 9,10-di(4-methoxyphenyl)-9,10-dihydro-phenanthrene-9,10-diol 
• 4661-57-8 11-nitrodibenzo[a,c]phenazine 

Relevant articles and documents

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Synthesis, characterization, DNA binding and cleaving properties of photochemically activated phenanthrene dihydrodioxin

Dihydrodioxin compounds are formed upon visible light irradiation of a mixture of an ortho-quinone and a substituted alkene. The reverse photochemical reaction can result in the release of a highly reactive ortho-quinone that can induce oxidative DNA damage. A novel DNA binding and cleaving phenanthrene dihydrodioxin compound (1)was synthesized. The photochemical release of 9,10-phenanthrenequinone was studied under different light irradiation wavelengths. Interaction of 1 with DNA caused an increase in the viscosity of DNA as well as hypochromic effect and a bathochromic shift in the absorption of 1. These results indicated the intercalative mode of binding of 1 to DNA. Binding affinities of 1 to several DNA sequences were evaluated, and slightly preferential binding to AT-rich DNA oligomers was observed. Intercalation of 1 between CT-DNA base pairs induced a partial transition from B-form to Z-form of DNA. Significant stabilization of the DNA duplex was revealed by DNA optical melting experiments with 33 % GC 12-mer (?Tm = 9 oC). ΦX174 photocleavage assay showed that 1 is capable of > 90 % single-strand DNA cleavage and ～ 5 % of double-strand DNA breakage. Therefore, 1 further demonstrates the potential of masked orhto-quinones as efficient photoactivated DNA cleaving agents.

Tautomerism of Representative Aromatic α-Hydroxy Carbaldehyde Anils as Studied by Spectroscopic Methods and AM1 Calculations. Synthesis of 10-Hydroxyphenanthrene-9-carbaldehyde

The synthesis of 10-hydroxyphenanthrene-9-carbaldehyde and its anil are described.The structure of the latter compound has been thoroughly studied by 1H and 13C NMR, UV-visible absorption, fluorescence and IR spectroscopies.All the experimental results support the existence of this anil mainly in the keto-enamine tautomeric form.A comparison is presented with previously studied anils derived from salicylaldehyde and 2-hydroxynaphthalene-1-carbaldehyde.Semiempirical calculations (AM1) concerning the relative stability of tautomers as well as the optimized molecular geometries are in good agreement with the experimental findings.

Synthetic models for catechol 1,2-dioxygenases. Interception of a metal catecholate - dioxygen adduct

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Substituted imidazole-pyrazole clubbed scaffolds: Microwave assisted synthesis and examined their in-vitro antimicrobial and antituberculosis effects

A series of substituted imidazole-pyrazole fused compounds were designed & fused synthesized by employing Debus-Radziszewski one-pot synthesis reaction. Azoles are an extensive and comparatively new class of synthetic compounds including imidazoles and pyrazoles. The current clinical treatment uses compounds of azole framework. Azoles act by inhibiting ergosterol synthesis pathway (a principal component of the fungal cell wall). In addition, a literature review shows that the compounds that include imidazoles and pyrazoles have significant anti-bacterial and anti-mycobacterial effects. In light of the above findings, a series of compounds with imidazole and pyrazole scaffolds were sketched and developed to examine anti-bacterial, antifungal and anti-mycobacterial activities. The structures of the synthesized compounds were characterized using1HNMR,13CNMR, elemental analysis, and MS spectral data. The target compounds were screened for their in-vitro antimicrobial activity against gram-positive and gram-negative bacterial species by disc diffusion method according to the NCCLS (National Committee for Clinical Laboratory Standards) and anti-mycobacterial activity against the Mycobacterium tuberculosis H37Rv strain. The results revealed that imidazole-pyrazole fused scaffold compounds have potential anti-bacterial, antifungal and anti-mycobacterial activities which can be further optimized to get a lead compound.

Rhodium-Catalyzed Aerobic Decomposition of 1,3-Diaryl-2-diazo-1,3-diketones: Mechanistic Investigation and Application to the Synthesis of Benzils

The conversion of 1,3-diaryl-2-diazo-1,3-diketones to 1,2-daryl-1,2-diketones (benzils) is reported based on a rhodium(II)-catalyzed aerobic decomposition process. The reaction occurs at ambient temperatures and can be catalyzed by a few dirhodium carboxylates (5 mol %) under a balloon pressure of oxygen. Moreover, an oxygen atom from the O2 reagent is shown to be incorporated into the product, and this is accompanied by the extrusion of a carbonyl unit from the starting materials. Mechanistically, it is proposed that the decomposition may proceed via the interaction of a ketene intermediate resulting from a Wolff rearrangement of the carbenoid, with a rhodium peroxide or peroxy radical species generated upon the activation of molecular oxygen. The proposed mechanism has been supported by the results from a set of controlled experiments. By using this newly developed strategy, a large array of benzil derivatives as well as 9,10-phenanthrenequinone were synthesized from the corresponding diazo substrates in varying yields. On the other hand, the method did not allow the generation of benzocyclobutene-1,2-dione from 2-diazo-1,3-indandione because of the difficulty of inducing the initial rearrangement.

Aerobic Dehydrogenation of N-Heterocycles with Grubbs Catalyst: Its Application to Assisted-Tandem Catalysis to Construct N-Containing Fused Heteroarenes

An aerobic dehydrogenation of nitrogen-containing heterocycles catalyzed by Grubbs catalyst is developed. The reaction is applicable to various nitrogen-containing heterocycles. The exceptionally high functional group compatibility of this method was confirmed by the oxidation of an unprotected dihydroindolactam V to indolactam V. Furthermore, by taking advantage of the oxygen-mediated structural change of the Grubbs catalyst, we integrated ring-closing metathesis and subsequent aerobic dehydrogenation to develop the novel assisted-tandem catalysis using molecular oxygen as a chemical trigger. The utility of the assisted-tandem catalysis was demonstrated by the concise synthesis of N-containing fused heteroarenes including a natural antibiotic, pyocyanine.