832-69-9

Usage

Uses

Used in Environmental Research:
1-Methylphenanthrene is used as a biomarker for [identifying the presence of particulate matter from small-scale biomass combustion] in environmental studies. Its presence in samples can indicate exposure to pollutants from combustion processes.
Used in Toxicological Studies:
1-Methylphenanthrene is used as a test compound for [studying the effects of polycyclic aromatic hydrocarbons on biological systems] in toxicological research. It has been found to cause acute systemic and lung inflammation in mice after intratracheal aspiration, providing valuable insights into the potential health risks associated with exposure to PAHs.

Synthesis Reference(s)

The Journal of Organic Chemistry, 45, p. 2009, 1980 DOI: 10.1021/jo01298a054Tetrahedron Letters, 6, p. 359, 1965

Air & Water Reactions

Insoluble in water.

Reactivity Profile

Vigorous reactions, sometimes amounting to explosions, can result from the contact between aromatic hydrocarbons, such as 1-METHYLPHENANTHRENE, and strong oxidizing agents. They can react exothermically with bases and with diazo compounds. Substitution at the benzene nucleus occurs by halogenation (acid catalyst), nitration, sulfonation, and the Friedel-Crafts reaction. 1-METHYLPHENANTHRENE is sensitive to excessive heat and light.

Fire Hazard

Flash point data for 1-METHYLPHENANTHRENE are not available. 1-METHYLPHENANTHRENE is probably combustible.

Source

Detected in 8 diesel fuels at concentrations ranging from 0.10 to 210 mg/L with a mean value of 44.33 mg/L (Westerholm and Li, 1994). Identified in a South Louisiana crude oil at a concentration of 111 ppm (Pancirov and Brown, 1975). Schauer et al. (1999) reported 1- methylphenanthrene in diesel fuel at a concentration of 28 μg/g and in a diesel-powered mediumduty truck exhaust at an emission rate of 17.0 μg/km. California Phase II reformulated gasoline contained 1-methylphenathrene at a concentration of 3.91 g/kg. Gas-phase tailpipe emission rates from gasoline-powered automobiles with and without catalytic converters were approximately 1.63 and 122 μg/km, respectively (Schauer et al., 2002). 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 1-methylphenanthrene were 2.22 and 0.579 mg/kg of pine burned and 1.04 and 0.050 mg/kg of oak burned. The gas-phase emission rate was 0.720 mg/kg of eucalyptus burned.

InChI:InChI=1/C15H12/c1-11-5-4-8-15-13(11)10-9-12-6-2-3-7-14(12)15/h2-10H,1H3

Upstream product

• 917-64-6 methyl magnesium iodide 
• 107620-55-3 1,2,3,4,4a,9,10,10a-octahydro-1-oxo-phenanthren 
• 483-65-8 Retene 
• 6314-07-4 2-Isopropyl-8-methyl-[3]phenanthrol 
• 5947-49-9 podocarpic acid 
• 514-10-3 abietic acid 
• 93987-66-7 1-methyl-1,2,3,4,4a,10a-hexahydro-phenanthrene 
• 111589-13-0 8-methylphenanthren-3-ol 
• 854649-66-4 1-cyclohexyl-3-(2-methyl-cyclopentyl)-propane 
• 132649-61-7 1,1-dimethyl-1,2,3,4,4a,9,10,10a-octahydro-phenanthrene 
• 35831-91-5 8-methylphenylphenanthrene-9-carboxylic acid 
• 131081-82-8 8-methyl-5,6,7,8-tetrahydro-phenanthrene-9-carboxylic acid 
• 63523-46-6 2-(1-Hydroxy-2-phenylethyl)-1-methyl-cyclohexanol 
• 110148-70-4 1-<2,4-Dinitro-phenylhydrazono>-1,2,3,4,5,6,7,8-octahydro-phenanthren 

Downstream Products

• 2531-84-2 2-methylphenathrene 
• 832-71-3 3-methylphenathrene 
• 883-20-5 9-methylphenanthrene 
• 85-01-8 phenanthrene 
• 217-37-8 benzo[c]picene 
• 42155-49-7 1-Phenanthreneacetonitrile 
• 42050-08-8 5(4H)-Acephenanthrylenone 

Relevant academic research and scientific papers

Palladium-Catalyzed Sequential Vinyl C–H Activation/Dual Decarboxylation: Regioselective Synthesis of Phenanthrenes and Cyclohepta[1,2,3-de]naphthalenes

The application of a C(vinyl), C(aryl)-palladacycle from vinyl-containing substrates is challenging due to the interference of a reactive double bond in palladium catalysis. This Letter describes a [4 + 2] or [4 + 3] cyclization based on a C(vinyl), C(aryl)-palladacycle by employing α-oxocarboxylic acids as the insertion units under a palladium/air system. The reaction proceeded through the key vinyl C–H activation and dual decarboxylation sequence, forming phenanthrenes and cyclohepta[1,2,3-de]naphthalenes regioselectively in good yields. The synthetic versatility of this protocol is highlighted by the gram-scale synthesis and synthesizing functional material molecule.

Alumina-Mediated π-Activation of Alkynes

The ability to induce powerful atom-economic transformation of alkynes is the key feature of carbophilic π-Lewis acids such as gold- and platinum-based catalysts. The unique catalytic activity of these compounds in electrophilic activations of alkynes is explained through relativistic effects, enabling efficient orbital overlapping with π-systems. For this reason, it is believed that noble metals are indispensable components in the catalysis of such reactions. In this study, we report that thermally activated γ-Al2O3activates enynes, diynes, and arene-ynes in a manner enabling reactions that were typically assigned to the softest π-Lewis acids, while some were known to be triggered exclusively by gold catalysts. We demonstrate the scope of these transformations and suggest a qualitative explanation of this phenomenon based on the Dewar-Chatt-Duncanson model confirmed by density functional theory calculations.

Construction of Phenanthrenes and Chrysenes from β-Bromovinylarenes via Aryne Diels-Alder Reaction/Aromatization

A highly efficient transition-metal-free general method for the synthesis of polycyclic aromatic hydrocarbons like phenanthrenes and chrysenes (and tetraphene) from β-bromovinylarenes and arynes has been developed. The reactions proceed via an aryne Diels-Alder (ADA) reaction, followed by a facile aromatization. This is the first report on direct construction of chrysenes (and tetraphene) using the ADA approach. Unlike the literature method which is limited to only 9/10-substituted derivatives, this method gives access to a wide variety of functionalized phenanthrenes.

A novel and efficient synthesis of phenanthrene derivatives via palladium/norbornadiene-catalyzed domino one-pot reaction

Herein we report a novel palladium-catalyzed reaction that results in phenanthrene derivatives using aryl iodides, ortho-bromoben-zoyl chlorides and norbornadiene in one pot. This dramatic transformation undergoes ortho-C–H activation, decarbonylation and subsequent a retro-Diels–Alder process. Pleasantly, this protocol has a wider substrate range, shorter reaction times and higher yields of products than previously reported methods.

Systematic investigations on fused π-system compounds of seven benzene rings prepared by photocyclization of diphenanthrylethenes

We studied the photoproducts of 1-(n-phenanthryl)-2-(m-phenanthryl)ethenes (nEm; n, m = 1, 3 and 9) for understanding photocyclization patterns based on NMR spectroscopy. The crystal structures of the photoproducts were analyzed by X-ray crystallography, and the photophysical features of the photocyclized molecules were investigated based on emission and transient absorption measurements. Phenanthrene derivatives substituted at the 1- and 3-positions were prepared for synthesizing nEm by photocyclization of stilbene derivatives. We obtained four types of primary photoproducts (n@m) from the corresponding nEm. Two of them were found to have racemic molecular structures in the single crystal determined by X-ray crystallography. Besides the primary photoproducts, two types of secondary photoproducts (n@mPP) were isolated. Fluorescence quantum yields and lifetimes of the obtained photoproducts were determined in solution whereas the definite fluorescence quantum yields were obtained in the powder. Observation of the triplet-triplet absorption spectra in solution by laser photolysis techniques showed that intersystem crossing to the triplet state competes with the fluorescence process.

Regioselective Synthesis of Polycyclic and Heptagon-embedded Aromatic Compounds through a Versatile π-Extension of Aryl Halides

A versatile π-extension reaction was developed based on the three-component cross-coupling of aryl halides, 2-haloarylcarboxylic acids, and norbornadiene. The transformation is driven by the direction and subsequent decarboxylation of the carboxyl group, while norbornadiene serves as an ortho-C?H activator and ethylene synthon via a retro-Diels–Alder reaction. Comprehensive DFT calculations were performed to account for the catalytic intermediates.

Further insight into the photochemical behavior of 3-aryl-N-(arylsulfonyl)propiolamides: tunable synthetic route to phenanthrenes

Reported herein is further insight into the photochemical behaviour of 3-aryl-N-(arylsulfonyl)-propiolamides, which provides a straightforward way to access meaningful phenanthrenes. Mechanistic investigation indicated that aryl migration, C-C coupling, 1,3-hydrogen shift, desulfonylation and elimination were involved in the process. Moreover, this protocol allowed for scale-up using a flow reactor.

Synthesis, Properties, and Two-Dimensional Adsorption Characteristics of [6]Hexahelicene-7-carboxylic acid

A convergent synthesis of racemic [6]hexahelicene-7-carboxylic acid by cross-coupling of a bicyclic and a tricyclic component is described. A metal-catalyzed ring-closure is also a fundamental component of the synthetic approach. Scanning tunneling microscopy (STM) measurements of the racemate self-assembled on Au(111) at liquid–solid interface revealed the formation of ordered racemic 2D crystals.

Directed Metalation-Suzuki-Miyaura Cross-Coupling Strategies: Regioselective Synthesis of Hydroxylated 1-Methyl-phenanthrenes

A general, efficient, and regioselective synthesis of a series of hydroxylated 1-methylphenanthrenes 9 by a combined directed ortho metalation (DoM)-Suzuki-Miyaura cross-coupling-directed remote metalation (DreM) sequence is reported. Diversity to this methodology was achieved by a regioselective DoM rather than DreM reaction, affording more highly substituted phenanthrols (Table 2). Application of the turbo-Grignard reagent (i-PrMgCl·LiCl) in the Ni-catalyzed Corriu-Kumada reaction gave efficient decarbamoylation (Tables 3and 4). Additional features are the TMS protecting group and halo-induced ipso-desilylation tactics applied to the regioselective synthesis of phenanthrenes (Scheme 2).

Efficient synthetic photocyclization for phenacenes using a continuous flow reactor

The continuous flow reaction technique has been applied to the photocyclization of 1,2-diarylethenes, the so-called Mallory reaction, to afford phenacenes in high chemical yields and efficiencies (114-288mg h-1). The present technique will allow us to produce several grams of phenacenes at a time.