84-11-7

Usage

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

• 64-17-5 ethanol 
• 67888-37-3 10-hydroxy-10-(2-oxopropyl)-9,10-dihydrophenanthren-9-one 
• 5412-84-0 9,10-dihydro-10,10-dichlorophenanthren-9-one 
• 139-02-6 sodium phenoxide 
• 121476-09-3 phenanthrene-9,10-dione; compound with phenanthrene-9,10-diol 
• 85-01-8 phenanthrene 
• 39559-48-3 10-Benzoyloxy-[9]phenanthrol 
• 776-35-2 9,10-dihydrophenanthrene 
• 5085-74-5 9-methoxyphenanthrene 
• 863305-32-2 diphenic acid 
• 3674-75-7 9-ethylphenanthrene 
• 1139-82-8 5,7-dihydro-dibenzo[a,c]cyclohepten-6-one 
• 14140-04-6 phenanthrene-9,10-dione oxime 
• 69882-78-6 2-(10-oxo-10H-phenanthren-9-ylidene)-benzo[b]thiophen-3-one 

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 
• 5768-84-3 phenanthro[9,10-g]pteridine-11,13(10H,12H)-dione 
• 3712-95-6 9a-phenyl-9a,15b-dihydro-phenanthro[9',10';5,6][1,4]dioxino[2,3-c]isochromen-11-one 
• 107278-96-6 3-methyl-5,6-phenanthreno-1-phenylpyrazolo<3,4-b>pyrazine 
• 24344-71-6 10,15-Diphenyl-10,15-dihydro-10,15-epoxido-benzo[f]phenanthro[9,10-b][1,4]dioxocin 
• 236-02-2 9,10-Phenanthroimidazol 
• 120499-81-2 4,3'-diphenyl-spiro[naphtho[2,3-c]furan-1,2'-phenanthro[9,10-b][1,4]dioxin]-3-one 
• 72471-15-9 ethyl 3,3a-dihydro-3a-hydroxy-2-oxo-2H-cyclopentaphenanthrene-1-carboxylate 
• 36939-59-0 2-(2-chlorophenyl)-1H-phenanthro[9,10-d]-imidazole 
• 36939-57-8 2-(3-nitrophenyl)phenanthroimidazole 
• 61587-89-1 2-(4-nitrophenyl)phenanthro<9,10-d>oxazole 
• 37053-62-6 2‐(4‐nitrophenyl)‐1H‐phenanthro[9,10‐d]imidazole 
• 131574-16-8 3-(4-nitro-phenyl)-spiro[oxirane-2,9'-phenanthren]-10'-one 

Relevant academic research and scientific papers

N-Aryl-9,10-phenanthreneimines as Scaffolds for Exploring Noncovalent Interactions: A Structural and Computational Study

A series of 10-[(4-halo-2,6-diisopropylphenyl)imino]phenanthren-9-ones and derivatives of the phenanthrene-9,10-dione ligand have been synthesised and structurally characterised to explore two types of noncovalent interactions, namely the influence of the steric bulk upon the resulting C–H···π and π-stacking interactions and halogen bonding. Selected noncovalent interactions have additionally been analysed by DFT and AIM techniques. No halogen bonding has been observed in these systems, but X lone pair···π, C–H···O=C and C–H···π interactions are the prevalent ones in the halogenated systems. Removal of the steric bulk in N-(2,4,6-trimethylphenyl)-9,10-iminophenanthrenequinone affords different noncovalent interactions, but the C–H···O=C hydrogen bonds are observed. Surprisingly, in N-(2,6-dimethylphenyl)-9,10-iminophenanthrenequinone and N-(phenyl)-9,10-iminophenanthrenequinone these C–H···O=C hydrogen bonds are not observed. However, they are observed in the related 2,6-di-tert-butylphenanthrene-9,10-dione. The π-interactions in dimers extracted from the crystal structures have been analysed by DFT and AIM. Spectroscopic investigations are also presented and these show only small perturbations to the O=C–C=N fragment.

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.

DNA-binding and anticancer activity of binuclear gold(I) alkynyl complexes with a phenanthrenyl bridging ligand

3,6-Diethynyl-9,10-diethoxyphenanthrene (4) was synthesized from phenanthrene and employed in the synthesis of the binuclear gold(I) alkynyl complexes (R3P)Au(C≡C–3-[C14H6-9, 10-diethoxy]-6–C≡C)Au(PR3) (R = Ph (5a), Cy (5b)). The diyne 4 and complexes 5a and 5b were characterized by NMR spectroscopy, mass spectrometry, and elemental analysis. UV-Vis spectroscopy studies of the metal complexes and precursor diyne show strong π → π* transitions in the near UV region that red shift by ca. 50 nm upon coordination at the gold centers. The emission spectrum of 4 shows an intense fluorescence band centered at 420 nm which red shifts, slightly upon coordination of 4 to gold. Binding studies of 4, 5a, and 5b against calf thymus DNA were carried out, revealing that 4, 5a, and 5b have ≥40% stronger binding affinities than the commonly used intercalating agent ethidium bromide. The molecular docking scores of 4, 5a, and 5b with B-DNA suggest a similar trend in behavior to that observed in the DNA-binding study. Unlike the ligand 4, promising anticancer properties for 5a and 5b were observed against several cell lines; the DNA binding capability of the precursor alkyne was maintained, and its anticancer efficacy enhanced by the gold centers. Such phenanthrenyl complexes could be promising candidates in certain biological applications because the two components (phenanthrenyl bridge and metal centers) can be altered independently to improve the targeting of the complex, as well as the biological and physicochemical properties.

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.

Unexpected radical mechanism in a [4+1] cycloaddition reaction

9,10-Phenanthrenequinone monoimines (2,7-R-PQI, R = tBu, H, Br, NO2, 1a-d) undergo a [4+1] cycloaddition reaction with triphenylphosphine to give 2,3-dihydro-2,2,2-triphenylphenanthro[9,10-d]-1,3,2λ5-oxazaphospholes (3a-d). During the reaction, highly colored radicals are formed as intermediates, which were characterized by EPR and UV-vis spectroscopy. The formation rate and the rate of decay of these radicals were determined kinetically. These radicals exhibit high persistency and under inert conditions can be handled conveniently. Based on detailed kinetic and spectroscopic studies and DFT calculations, a plausible mechanism has been proposed. This journal is

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.

Suzuki cross coupling followed by cross dehydrogenative coupling: An efficient one pot synthesis of Phenanthrenequinones and analogues

An efficient one pot protocol has been developed towards the synthesis of substituted phenanthrenequinone and analogous derivatives via Suzuki cross coupling followed by copper catalyzed cross dehydrogenative coupling.

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.

Preparation method for constructing hexabenzocoronene by utilizing polycyclic aromatic hydrocarbon phenanthrene in coal tar

The invention discloses a preparation method for constructing hexabenzocoronene by utilizing polycyclic aromatic hydrocarbon phenanthrene in coal tar. According to the method, polycyclic aromatic hydrocarbon phenanthrene in coal tar is used as a raw material and is subjected to an oxidation addition reaction with chromium trioxide to generate phenanthrenequinone, phenanthrenequinone and dibenzyl ketone are subjected to a nucleophilic addition elimination reaction in a potassium hydroxide methanol solution to generate 9, 10-phenanthro 1, 12-diphenyl cyclopentadiene ketone, 9, 10-phenanthro 1, 12-diphenyl cyclopentadiene ketone and diphenyl acetylene are subjected to a Diels-Alder cycloaddition reaction in a diphenyl ether solution to obtain 1, 2, 3, 4-tetraphenyl triphenylene, and finally,1, 2, 3, 4-tetraphenyl triphenylene and anhydrous ferric chloride are subjected to an oxidative cyclization dehydrogenation reaction to generate hexabenzocoronene. According to the invention, hexabenzocoronene is prepared by taking polycyclic aromatic hydrocarbon substance-phenanthrene in coal tar as a raw material. By reasonably planning the synthesis route, the yield of each step is increased, and the yield of hexabenzocoronene is increased. The method can be popularized and applied to the process of synthesizing graphene from other polycyclic aromatic hydrocarbons in the coal tar, so that high-added-value utilization of coal tar resources is improved.