- Novel covalently linked pyrene-aryl azide systems: synthesis of 1-(4-azidobenzoyloxy)pyrene
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Lead tetraacetate oxidation of pyrene followed by hydrolysis affords 1-hydroxypyrene whose esterification with 4-azidobenzoic acid gives a new bifunctional luminophore characterized by UV and luminescence spectroscopy.
- Barabanov, Igor I.,Polukhin, Alexander V.,Korolev, Valerii V.,Kuibida, Leonid V.,Nefedov, Andrey A.
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Read Online
- Preparation method of N-acylpyrene amine and preparation method of 1-hydroxypyrene
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The invention provides a preparation method of N-acylpyrene amine and a preparation method of 1-hydroxypyrene. The preparation method comprises the steps: reacting C2-C10 nitro compounds containing alpha-H with pyrene in solid superacid and a first solvent to obtain the N-acyl pyrene amine. According to the method, under the catalytic action of the solid superacid, the alpha-H of the C2-C10 nitro compound containing alpha-H is easier to pull out, so that the alpha-C of the C2-C10 nitro compound containing alpha-H is connected with the C on the 1 position of pyrene, and then the N-acetyl pyrene amine is obtained through one-step reaction; and the 1-hydroxypyrene is synthesized by taking the N-acetyl pyrene amine obtained by the preparation method as a raw material. According to the preparation method, the reaction steps are reduced, the reaction conditions are mild, the raw material source is wide, and the use of a polluting acylation reagent is avoided, so that the environmental pollution is reduced, and the production cost is reduced on the whole.
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Paragraph 0077; 0078
(2021/04/21)
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- Preparation method of 1-pyrenol
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The invention discloses a preparation method of 1-pyrenol. The method comprises the following steps: 1) using 1-bromopyrene as a starting compound, mixing the 1-bromopyrene, a copper catalyst, a baseand a solvent, and performing coupling by a Ullmann reaction to obtain 1-pyrenol in one step; 2) performing acylation on the 1-pyrenol to convert the 1-pyrenol into 1-acetoxypyrene, adding a 1-acetoxypyrene seed crystal to induce recrystallization, and performing hydrolysis on the 1-acetoxypyrene obtained by recrystallization under alkaline conditions to obtain 1-pyrenol; and 3) adding a 1-pyrenolseed crystal into the 1-pyrenol obtained by hydrolysis to induce recrystallization to obtain the high-purity 1-pyrenol. The method provided by the invention is different from a conventional preparation method of 1-pyrenol and relates to coupling of aromatic compounds, the raw materials and catalysts are economical and easy to obtain, and the reaction method is simple and easy to implement, and has a high yield, small pollution to the environment, and very high application value.
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Paragraph 0034; 0045; 0048
(2019/11/28)
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- Enhanced Out-of-Plane Conductivity and Photovoltaic Performance in n = 1 Layered Perovskites through Organic Cation Design
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Layered perovskites with the formula (R-NH3)2PbI4 have excellent environmental stability but poor photovoltaic function due to the preferential orientation of the semiconducting layer parallel to the substrate and the typically insulating nature of the R-NH3+ cation. Here, we report a series of these n = 1 layered perovskites with the form (aromatic-O-linker-NH3)2PbI4 where the aromatic moiety is naphthalene, pyrene, or perylene and the linker is ethyl, propyl, or butyl. These materials achieve enhanced conductivity perpendicular to the inorganic layers due to better energy level matching between the inorganic layers and organic galleries. The enhanced conductivity and visible absorption of these materials led to a champion power conversion efficiency of 1.38%, which is the highest value reported for any n = 1 layered perovskite, and it is an order of magnitude higher efficiency than any other n = 1 layered perovskite oriented with layers parallel to the substrate. These findings demonstrate the importance of leveraging the electronic character of the organic cation to improve optoelectronic properties and thus the photovoltaic performance of these chemically stable low n layered perovskites.
- Passarelli, James V.,Fairfield, Daniel J.,Sather, Nicholas A.,Hendricks, Mark P.,Sai, Hiroaki,Stern, Charlotte L.,Stupp, Samuel I.
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supporting information
p. 7313 - 7323
(2018/06/26)
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- Photo-Fries rearrangement of 1-pyrenyl esters
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Photo-Fries rearrangement reactions of 1-pyrenyl esters were investigated. Photoreaction of 1-pyrenyl benzoate in benzene generates 1-hydroxy-2-pyrenyl phenyl ketone along with 1-pyrenol. The exceptionally down field 1H NMR chemical shift of OH proton in the photoproduct indicates the existence of intramolecular hydrogen bonding. Photorearrangements of analogs that have electron-withdrawing or electron-releasing group on the phenyl ring, and related heteroaromatic carboxylates also take place to form the corresponding ketones. However, photoreactions of 1-pyrenyl aliphatic carboxylate esters do not occur. The results of spectroscopic and theoretical studies suggest the mechanistic pathway for this process is initiated by homolytic C–O bond cleavage in an aroyl group localized 1(π → π?) excited state of the 1-pyrenyl esters. The radical pair generated in this fashion then undergoes in-solvent-cage coupling to yield the 1-hydroxy-2-pyrenyl aryl ketone selectively.
- Maeda, Hajime,Akai, Tomomi,Segi, Masahito
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supporting information
p. 4377 - 4380
(2017/10/23)
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- Polymer-Supported Palladium(II) Carbene Complexes: Catalytic Activity, Recyclability, and Selectivity in C?H Acetoxylation of Arenes
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Heterogeneous catalysts for selective oxidation of C?H bonds were synthesized by co-polymerization of new N-heterocyclic carbene-palladium(II) (NHC-PdII) monomers with divinylbenzene. The polymer-supported NHC-PdII-catalysed undirect
- Majeed, Maitham H.,Shayesteh, Payam,Wallenberg, L. Reine,Persson, Axel R.,Johansson, Niclas,Ye, Lei,Schnadt, Joachim,Wendt, Ola F.
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supporting information
p. 8457 - 8465
(2017/06/28)
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- Synthesis method of 1-pyrenol and intermediates thereof
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The invention discloses a synthesis method of 1-pyrenol and intermediates thereof.The synthesis method includes firstly, preparing an intermediate, namely acetylpyrene by subjecting pyrene and acetyl chloride to Friedel-Crafts reaction; secondly, preparing an intermediate, namely acetoxypyrene by Baeyer-Villiger oxidation rearrangement; thirdly, preparing the 1-pyrenol by saponification.The synthesis method has the advantages that the 1-pyrenol and the intermediates thereof are prepared from the pyrene and the acetyl chloride, and accordingly the synthesis method is economic, easy to operate, little in environmental pollution, capable of saving production cost for enterprises and high in reaction yield rate of the 1-pyrenol and the intermediates thereof.
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Paragraph 0019
(2017/03/23)
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- Photodegradation mechanisms of 1-nitropyrene, an environmental pollutant: The effect of organic solvents, water, oxygen, phenols, and polycyclic aromatics on the destruction and product yields
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This work describes studies of the photodegradation mechanism of 1-nitropyrene (1-NO2Py) in a chemical model system consisting of an organic solvent and known constituents of an aerosol particle. Photoproducts such as 1-hydroxypyrene (1-OHPy),
- Garcia-Berrios, Zulma I.,Arce, Rafael
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experimental part
p. 3662 - 3664
(2012/06/30)
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- Role of O-acetyltransferase in activation of oxidised metabolites of the genotoxic environmental pollutant 1-nitropyrene
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The genotoxic environmental contaminant 1-nitropyrene is metabolised in mammalian systems by pathways more complex than the straightforward nitroreduction which accounts for most of its biological activity in bacteria. In order to evaluate the role of O-acetyltransferase (OAT) activity in generation of genotoxic intermediates from 1-nitropyrene, the mutagenicity of the major primary oxidised metabolites of 1-nitropyrene was characterised in the Ames Salmonella typhimurium plate incorporation assay with strain TA98, and with variants of TA98 deficient (TA98/1,8-DNP6) or enhanced (YG1024) in O-acetyltransferase. 1-Nitropyren-3-ol was more mutagenic in the absence than in the presence of S9, while 1-nitropyren-4-ol, 1-nitropyren-6-ol and 1-nitropyren-8-ol required S9 for maximum expression of mutagenicity. 1-Nitropyren-4-ol (176 rev/nmol without S9, 467 rev/nmol with S9 in TA98) and 1-nitropyren-6-ol (13 rev/nmol without S9, 266 rev/nmol with S9 in TA98) were overall the most potent nitropyrenol isomers assayed. 1-Acetamidopyren-8-ol and 1-acetamidopyrene 4,5-quinone were only minimally active. 1-Acetamidopyren-3-ol exhibited direct-acting mutagenicity. 1-Acetamidopyren-6-ol, previously shown to be a major contributor to mutagenicity in the urines of rats dosed with 1-nitropyrene (Ball et al., 1984b), was confirmed as a potent (359 rev/nmol) S9-dependent mutagen. Both the direct-acting and the S9-dependent mutagenicity of all the compounds studied was enhanced in the OAT-overproducing strain and much diminished (though not always entirely lost) in the OAT-deficient strain, showing that OAT amplifies expression of the genotoxicity of these compounds. 1-Acetamidopyren-6-ol required both S9 and OAT activity in order to exhibit any mutagenicity; this finding strongly implicates N-hydroxylation followed by O-esterification, as opposed to further S9-catalyzed ring oxidation, as a major route of activation for urinary metabolites of 1-nitropyrene.
- Rosser,Ramachandran,Sangaiah,Austin,Gold,Ball
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p. 209 - 220
(2007/10/03)
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- Chemical Oxidation of Nitrated Polycyclic Aromatic Hydrocarbons: Hydroxylation with Superoxide Anion Radical
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Nitrated polycyclic aromatic hydrocarbon (nitroPAH) is a potent mutagen which is reductively and/or oxidatively metabolized. Biological oxidation of nitroPAH, such as hydroxylation and epoxidation, is known, but chemical oxidation has been reported in only a few papers. NitroPAH is barely oxidized by various chemical oxidants because of the electron deficient property of the aromatic ring with the nitro substituent. Nucleophilic reactivity of superoxide anion radical is known, and thus the oxidation of nitroPAH with the chemically generated superoxide anion radical was carried out in this study. When 1-nitropyrene was reacted with KO2/18-crown-6 in dimethylformamide, 5-, 6-, 8-, and 9-hydroxy-1-nitropyrenes and 1-hydroxypyrene were obtained in preparative yields. Three isomeric dinitropyrenes, 3-nitrofluoranthene, 6-nitrobenzopyrene, and 6-nitrochrysene, were oxidized to hydroxy derivatives, some of which correspond to the oxidative metabolite of nitroPAH. The oxidation of dinitropyrenes with trifluoroperacetic acid gave K-region oxidized products.
- Fukuhara, Kiyoshi,Miyata, Naoki
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- A New Chromone and Flavone Synthesis and Its Utilization for the Sythesis of Potentially Antitumorigenic Polycyclic Chromones and Flavones
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A new synthesis of chromones and flavones based on the ortho-directed metalation of methoxymethyl aryl ethers with alkyllithium reagents is described.It entails reaction of the ortho-lithiated intermediates with a conjugated unsaturated aldehyde followed by oxidation of the allylic alcohol product with "periodinane" to yield an ortho-allylic ketone.The latter on heating in acetic acid undergoes loss of the methoxymethyl protecting group and cyclization to a chromanone (or flavanone, if a β-phenyl substituent is present).Dehydrogenation by treatment with pyrrolidinehydrotribromide (PHT) in dimethyl sulfoxide yields the corresponding chromones (or flavones).This synthetic approach appears general in its applicability.It has been applied to the synthesis of a series of polycyclic chromone and flavone compounds containing the naphthalene and pyrene ring systems that hold promise as agents for the chemoprevention of cancer.
- Harvey, Ronald G.,Hahn, Jung-Tai,Bukowska, Maria,Jackson, Henry
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p. 6161 - 6166
(2007/10/02)
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- Spectroscopic and photochemical properties of mononitropyrenes
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The influence of the nitro group on the aromatic ?-system of pyrene has been studied by comparing the spectroscopic and photochemical properties of the three mononitropyrenes.Whereas the UV and mass spectra of 1- and 4-nitropyrene show an interaction normal for nitro-aromatic compounds, this is not observed for 2-nitropyrene.The lack of interaction is reflected in a UV spectrum very similar to that of pyrene and a mass spectrum with a very low abundance of M-NO.The photochemical behaviour of the three compounds is governed by the degree of interaction. 1-Nitropyrene shows the nitro-nitrite rearrangement leading to 1-hydroxypyrene (88percent) and 1-hydroxy-2-nitropyrene (7percent).The photoproducts of 4-nitropyrene are pyrene (9percent) and unstable products which react with the solvent. 2-Nitropyrene is very stable under photochemical conditions due to lack of interaction.Similarly, the sterically hindered 1-methyl-2-nitropyrene is also very stable towards light.The photochemical nitro-nitrite rearrangement observed for nitro-aromatic compounds was found to be governed by electronic effects.
- Braken-van Leersum, A. M. van den,Tintel, C.,Zelfde, M. van't,Cornelisse, J.,Lugtenburg, J.
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p. 120 - 128
(2007/10/02)
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