Synthesis Of Phenanthrene Research Articles

Diazene-Catalyzed Oxidative Alkyl Halide-Olefin Metathesis.

The first platform for oxidative alkyl halide-olefin metathesis is described. The procedure employs diazenes as catalysts, which effect the cyclization of alkenyl alkyl halides to generate cyclic olefins and carbonyl products. The synthesis of phenanthrene, coumarin, and quinolone derivatives is demonstrated as well as the potential to apply this strategy to other electrophiles.

Exploring the chemical dynamics of phenanthrene (C14H10) formation via the bimolecular gas-phase reaction of the phenylethynyl radical (C6H5CC) with benzene (C6H6).

The exploration of the fundamental formation mechanisms of polycyclic aromatic hydrocarbons (PAHs) is crucial for the understanding of molecular mass growth processes leading to two- and three-dimensional carbonaceous nanostructures (nanosheets, graphenes, nanotubes, buckyballs) in extraterrestrial environments (circumstellar envelopes, planetary nebulae, molecular clouds) and combustion systems. While key studies have been conducted exploiting traditional, high-temperature mechanisms such as the hydrogen abstraction-acetylene addition (HACA) and phenyl addition-dehydrocyclization (PAC) pathways, the complexity of extreme environments highlights the necessity of investigating chemically diverse mass growth reaction mechanisms leading to PAHs. Employing the crossed molecular beams technique coupled with electronic structure calculations, we report on the gas-phase synthesis of phenanthrene (C14H10)-a three-ring, 14π benzenoid PAH-via a phenylethynyl addition-cyclization-aromatization mechanism, featuring bimolecular reactions of the phenylethynyl radical (C6H5CC, X2A1) with benzene (C6H6) under single collision conditions. The dynamics involve a phenylethynyl radical addition to benzene without entrance barrier leading eventually to phenanthrene via indirect scattering dynamics through C14H11 intermediates. The barrierless nature of reaction allows rapid access to phenanthrene in low-temperature environments such as cold molecular clouds which can reach temperatures as low as 10 K. This mechanism constitutes a unique, low-temperature framework for the formation of PAHs as building blocks in molecular mass growth processes to carbonaceous nanostructures in extraterrestrial environments thus affording critical insight into the low-temperature hydrocarbon chemistry in our universe.

Catalytic Cycloisomerization of Enyne Diesters Derived from Biaryls and Related Substrates

AbstractEnyne diesters derived from biaryls and related substrates undergo intramolecular [2+2]‐cycloaddition and concomitant cyclo‐reversion when treated with 10 mol% In(OTf)3 in 1,2‐dichloroethane. This enyne metathesis type cycloisomerization reaction enables the synthesis of phenanthrene, benzophenanthrene, benzotetraphene and other polycyclic (hetero)aromatic compounds bearing a synthetically useful diethyl β‐(hetero)arylidene malonate moiety in a step‐ and atom‐economic manner. In(OTf)3‐catalyzed two independent intramolecular cycloisomerization on substrates 5 a and 5 b provides direct access to benzotetraphenes 6 a and 6 b containing bis(diethyl β‐phenylmethylene malonate) moiety. Tetrasubstituted vinylidene malonate 4 a, substiututed by two different aromatic groups, is stereoselectively converted into E‐ and Z‐isomer of triaryl group containing all carbon tetrasubstituted olefins (8 a, 8 a′ and 8 b) via Pd‐catalyzed stereoselective decarboxylative arylation reaction.

PHENANTHRENE: A VERSATILE MOLECULE; A REVIEW

Phenanthrene is a nucleus of the poly aromatic hydrocarbon family consisting of three fused benzene rings. They are of great importance in the field of medicine. They are mainly synthesized through Bardhan-Sengupta synthesis, Haworth synthesis and Pschorr synthesis of phenanthrene. Presently, many naturally existing drugs such as morphine, codeine halofantrine, among others bear the phenanthrene nucleus. Synthetic derivatives including dextromethorphan and other drugs also possess this nucleus. Phenanthrene derivates have many distinct therapeutic benefits including analgesic, antitussive, antimalarial, cytotoxic, and anticonstipation. This study was performed to highlight the various pharmacological uses of phenanthrene derivatives by reviewing experiments performed on its derivatives.

A Simple Synthesis of Phenanthrene

In continuation of polycyclic aromatic hydrocarbons (PAH) synthesis via an aryne Diels-Alder cycloaddition and bridge extrusion methodology,1–5 we now describe a simple phenanthrene (1) synthesis u...

Effective synthesis of fluorine-containing phenanthrene bearing hydroxyl group using Mallory reaction and its application for fluorinated polyesters

Mallory reaction of 1,2-bis(4-hydroxyphenyl)-3,3,4,4,5,5-hexafluorocyclopentene under light irradiation (λ = 356 nm) in the presence of iodine as an oxidant proceeded to give fluorine-containing phenanthrene bearing hydroxyl groups, 6,9-bis(4-hydroxyphenyl)-1,1,2,2,3,3-hexafluoro-2,3-dihydro-1H-cyclopenta[l]phenanthrene. Polycondensation of the prepared fluorine-containing phenanthrene with various acid dichlorides afforded the phenanthrene-type polyesters. For comparison, diarylethene-type polyesters were also prepared analogously. Diarylethene-type polyesters consisting m-phenylene unit showed good solubility in typical organic solvents such as CHCl3. Tetramethylene-linked diarylethene-type polyesters with Mn = 4100 (Mn = number average molecular weight) was isolated as oil. Other diarylethene-type and all phenanthrene-type polyesters were insoluble in organic solvents. The phenanthrene-type polyesters had high thermal stability revealed by TGA analysis.

Microwave-assisted one-pot synthesis of new phenanthrene fused-tetrahydrodibenzo-acridinones as potential cytotoxic and apoptosis inducing agents

An expeditious microwave-assisted one-pot synthesis of new cytotoxic phenanthrene fused-tetrahydrodibenzo-acridinones has been successfully accomplished. This protocol offers wide substrate scope, catalyst-free synthesis, atom-economy, simple recrystallization, high yields, and ethanol was used as green solvent. These new compounds were tested for their in vitro cytotoxicity against cervical (HeLa), prostate (PC-3), fibrosarcoma (HT-1080), ovarian (SKOV-3) cancer cells, and were safer to normal (Hek-293T) kidney cell line. All the compounds have displayed significant cytotoxicity profile, among them 8m being the most potent compound with an IC50 0.24 ± 0.05 μM against SKOV-3 ovarian cancer cells. Flow cytometry analysis revealed that cells were blocked at the G2/M phase of the cell cycle. The effect of 8m on F-actin polymerisation was also studied. Hoechst staining clearly showed the decreased number of viable cells and indicated apoptosis progression. Compound 8m caused the collapse of mitochondrial membrane potential as observed via JC-1 staining and also enhanced the generation of reactive oxygen species. The increase of caspase-3 activation by 3.7 folds supported the strong apoptosis induction. In addition, an in vitro 3D-spheroid progression assay was performed with 8m that significantly suppressed the tumor cells.

Sulfamic acid promoted one-pot synthesis of phenanthrene fused-dihydrodibenzo-quinolinones: Anticancer activity, tubulin polymerization inhibition and apoptosis inducing studies

A facile one-pot method for the synthesis of new phenanthrene fused-dihydrodibenzo-quinolinone derivatives has been successfully accomplished by employing sulfamic acid as catalyst. These new compounds were evaluated for their in vitro cytotoxic potential against human lung (A549), prostate (PC-3 and DU145), breast (MCF-7) and colon (HT-29 and HCT-116) cancer cell lines. Among all the tested compounds, one of the derivatives 8p showed good anti-proliferative activity against A549 lung cancer cell line with an IC50 of 3.17 ± 0.52 µM. Flow cytometric analyses revealed that compound 8p arrested both Sub G1 and G2/M phases of cell cycle in a dose dependent manner. The compound 8p also displayed significant inhibition of tubulin polymerization and disruption of microtubule network (IC50 of 5.15 ± 0.15 µM). Molecular docking studies revealed that compound 8p efficiently interacted with critical amino acid Cys241 of the α/β-tubulin by a hydrogen bond (SH…O = 2.4 Å). Further, the effect of 8p on cell viability was also studied by AO/EB, DCFDA and DAPI staining. The apoptotic characteristic features revealed that 8p inhibited cell proliferation effectively through apoptosis by inducing the ROS generation. Analysis of mitochondrial membrane potential through JC-1 staining and annexin V binding assay indicated the extent of apoptosis in A549 cancer cells.

Synthesis, Photophysical and Aggregation Properties of Novel Phenanthrene and Pyrene Substituted Phthalocyanines

Synthesis, Photophysical and Aggregation Properties of Novel Phenanthrene and Pyrene Substituted Phthalocyanines

HACA's Heritage: A Free‐Radical Pathway to Phenanthrene in Circumstellar Envelopes of Asymptotic Giant Branch Stars

AbstractThe hydrogen‐abstraction/acetylene‐addition (HACA) mechanism has been central for the last decades in attempting to rationalize the formation of polycyclic aromatic hydrocarbons (PAHs) as detected in carbonaceous meteorites such as in Murchison. Nevertheless, the basic reaction mechanisms leading to the formation of even the simplest tricyclic PAHs like anthracene and phenanthrene are still elusive. Here, by exploring the previously unknown chemistry of the ortho‐biphenylyl radical with acetylene, we deliver compelling evidence on the efficient synthesis of phenanthrene in carbon‐rich circumstellar environments. However, the lack of formation of the anthracene isomer implies that HACA alone cannot be responsible for the formation of PAHs in extreme environments. Considering the overall picture, alternative pathways such as vinylacetylene‐mediated reactions are required to play a crucial role in the synthesis of complex PAHs in circumstellar envelopes of dying carbon‐rich stars.

HACA's Heritage: A Free-Radical Pathway to Phenanthrene in Circumstellar Envelopes of Asymptotic Giant Branch Stars.

The hydrogen-abstraction/acetylene-addition (HACA) mechanism has been central for the last decades in attempting to rationalize the formation of polycyclic aromatic hydrocarbons (PAHs) as detected in carbonaceous meteorites such as in Murchison. Nevertheless, the basic reaction mechanisms leading to the formation of even the simplest tricyclic PAHs like anthracene and phenanthrene are still elusive. Here, by exploring the previously unknown chemistry of the ortho-biphenylyl radical with acetylene, we deliver compelling evidence on the efficient synthesis of phenanthrene in carbon-rich circumstellar environments. However, the lack of formation of the anthracene isomer implies that HACA alone cannot be responsible for the formation of PAHs in extreme environments. Considering the overall picture, alternative pathways such as vinylacetylene-mediated reactions are required to play a crucial role in the synthesis of complex PAHs in circumstellar envelopes of dying carbon-rich stars.

Synthesis and characterization of phenanthrene appended bridged morpholines_ESI

Synthesis and characterization of phenanthrene appended bridged morpholines_ESI

ChemInform Abstract: UV Light‐Mediated Difunctionalization of Alkenes with CF3SO2Na: Synthesis of Trifluoromethyl Phenanthrene and Anthrone Derivatives.

AbstractThe benzophenone‐catalyzed photoreaction of α,β‐unsaturated ketones affords trifluoromethyl‐containing phenanthrenes, whilst the analogous anthraquinone‐catalyzed reaction of γ,δ‐unsaturated ketones gives rise to trifluoromethylated anthrone derivatives.

UV light-mediated difunctionalization of alkenes with CF3SO2Na: synthesis of trifluoromethyl phenanthrene and anthrone derivatives.

A metal-free and cost-effective protocol for UV light-mediated difunctionalization of alkenes with CF3SO2Na was developed. This strategy realized the direct formation of Csp(3)-CF3 and C-C bonds through a proposed tandem radical cyclization process, which produced a variety of phenanthrene and anthrone derivatives in moderate yields.

ChemInform Abstract: Equatorenes: Synthesis and Properties of Chiral Naphthalene, Phenanthrene, Chrysene, and Pyrene Possessing Bis(1‐adamantyl) Groups at the Peri‐position.

AbstractOptical and electrochemical properties of the novel equatorenes are investigated.

Equatorenes: Synthesis and Properties of Chiral Naphthalene, Phenanthrene, Chrysene, and Pyrene Possessing Bis(1-adamantyl) Groups at the Peri-position

Chiral polycyclic aromatic hydrocarbons containing bis(1-adamantyl) groups at the peri-positions, named equatorenes, were synthesized in optically pure form starting from optically pure 4,5-bis(1-adamantyl)-8-methoxy-1-naphthol. A sequential Diels-Alder reaction of furan and arynes generated from 1,2-bromotriflates provided tricyclic and tetracyclic epoxides, and acid-catalyzed aromatization gave phenanthrol and chrysenol. Deoxygenation reactions involving the hydrogenolysis of triflates gave 1,8-bis(1-adamantyl)naphthalene, 1,10-bis(1-adamantyl)phenanthrene, and 1,12-bis(1-adamantyl)chrysene. 3,4-Bis(1-adamantyl)pyrene was synthesized from phenanthrol by Sonogashira coupling and Pt-catalyzed cyclization. Essentially no racemization occurred during the synthesis. X-ray analysis indicated the distorted naphthalene moiety possessing the peri-diadamantyl groups and the flat structure of the other benzene rings. UV-vis analysis of the equatorenes showed considerable redshifts compared with that of the corresponding achiral arenes. Electrochemical analysis of the naphthalene and pyrene indicated that the distortion decreased the highest occupied molecular orbital stability with no marked effect on the lowest unoccupied molecular orbital energy level, and the origin was discussed on the basis of calculation results.

ChemInform Abstract: Palladium-Catalyzed Intermolecular Controlled Insertion of Benzyne-Benzyne-Alkene and Benzyne-Alkyne-Alkene - Synthesis of Phenanthrene and Naphthalene Derivatives.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Synthesis of Phenanthrene and Alkyl Phenanthrenes by Palladium(0)-Catalyzed Pericyclic Reactions

Palladium-catalyzed pericyclic reactions have been developed for the synthesis of phenanthrenes. This method is also useful for the synthesis of monoalkyl and dialkyl phenanthrene derivatives.

Synthesis of Acenaphthyl and Phenanthrene Based Fused-Aromatic Thienopyrazine Co-Polymers for Photovoltaic and Thin Film Transistor Applications

Dithiophene and fluorene co-polymers containing fused aromatic thieno[3,4-b]pyrazine moieties were synthesized for organic thin film transistor (OTFT) and organic photovoltaic (OPV) applications. Suzuki and Stille polycondensation reactions were used for the polymerization. The band gap (Eg) of the polymers was tuned in the range of 1.15−1.6 eV to match the solar spectrum. Density functional theory calculations were carried out to rationalize the low band gaps. These polymers showed field effect mobility (μ) as high as 0.2 cm2/(V·s) with an on/off ratio as high as 106 in OTFT devices. Interestingly, one polymer in this class also showed ambipolar charge transport. Power conversion efficiency (PCE) up to 1.3% was achieved in bulk heterojunction solar cells, indicating that these materials are promising for OPV applications.

ChemInform Abstract: Iron(III) Chloride‐Based Mild Synthesis of Phenanthrene (II) and Its Application to Total Synthesis of Phenanthroindolizidine Alkaloids (V).

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.