130-15-4Relevant articles and documents
The Formation of 1,4-Quinones by Oxovanadium(IV)-Complexes Catalyzed Aerobic Oxygenation of Fused Aromatic Compounds
Takai, Toshihiro,Hata, Eiichiro,Mukaiyama, Teruaki
, p. 885 - 888 (1994)
In the presence of a catalytic amount of oxovanadium(IV) complexes coordinated with 1,3-diketone ligands, fused aromatic compounds such as naphthalenes and naphthol derivatives are smoothly oxygenated into the corresponding 1,4-naphthoquinones by combined use of molecular oxygen and crotonaldehyde under an atmospheric pressure.
2-Pyridyldimethylsilyl Group as a Removable Hydrophilic Group in Aqueous Organic Reactions: Formation of Molecular Aggregates and Dramatic Rate Enhancement in Diels-Alder Reactions
Itami, Kenichiro,Nokami, Toshiki,Yoshida, Jun-Ichi
, p. 441 - 451 (2002)
A novel methodology for aqueous organic reactions utilizing a 2-pyridyldimethylsilyl (2-PyMe2Si) group as a removable hydrophilic group has been developed. It was found that 1,3-dienes bearing the 2-PyMe2Si group form molecular aggregates in water when 1.0 equivalent of HCl was added, as evidenced by dynamic light-scattering experiments. The Diels-Alder reaction of 2-PyMe2Si-substituted 1,3-dienes with various dienophiles took place in water at room temperature. The Diels-Alder reaction in organic solvents (Et2O/toluene) under the same reaction temperature and time gave the cycloadduct in much lower yield, indicating the dramatic rate acceleration in water. The removal of the 2-PyMe2Si group was accomplished by desilylation, oxidation, and electrophilic substitution.
Sodium hypochlorite/Dowex 1X8-200: An effective oxidant for the oxidation of aromatic amines to quinones
Hashemi, Mohammed M.,Beni, Yousef A.
, p. 672 - 673 (1999)
Polymer supported hypochlorite ion is a useful oxidant for the oxidation of aromatic amines to the corresponding quinones.
Influence of the sulfinyl group on the chemoselectivity and π-facial selectivity of diels-alder reactions of (S)-2-(p Tolylsulfinyl)-1,4-benzoquinone
Carreno, M. Carmen,Garcia Ruano, José L.,Toledo, Miguel A.,Urbano, Antonio,Remor, Cynthia Z.,Stefani, Valter,Fischer, Jean
, p. 503 - 509 (1996)
Diels-Alder reactions of (S)-2-(p-tolylsulfmyl)-1,4-benzoquinone (1a) with cyclic (cyclopentadiene and cyelohexadiene) and acyclic dienes (1-[(trimethylsilyl)oxy]-1,3-butadiene and trans-piperylene) under different thermal and Lewis acid conditions are reported. Chemoselectivity (reactions on C2-C3 versus C5-C6 double bonds) is mainly related to the cyclic (on C5-C6) or acyclic (on C2-C3) structure of the diene. The high π-facial selectivity observed could be controlled by choosing adequate experimental conditions.
Preparation and photocatalytic activity of WO3-MWCNT nanocomposite for degradation of naphthalene under visible light irradiation
Farhadian, Mousa,Sangpour, Parvaneh,Hosseinzadeh, Ghader
, p. 39063 - 39073 (2016)
In this study, a WO3-multiwalled carbon nanotube nanocomposite has been prepared for the first time by in situ liquid phase process. The prepared nanocomposite was used for photodegradation of dilute solution of naphthalene under visible light irradiation. Based on our results, comparing photocatalytic activity of WO3 nanoparticle with WO3-multiwalled carbon nanotube nanocomposite showed that the photodegradation of naphthalene is negligible by using pure WO3 nanoparticles while, composition of WO3 nanoparticles with multi walled carbon nanotubes could improve significantly their photocatalytic activity under visible light. Due to its high electrical conductivity, carbon nanotube can transfer photogenerated electron on its surface and in this way decreases electron-hole recombination rate and increases photocatalytic activity. After the reaction, the irradiated solution has been analyzed by gas chromatography and mass spectrometry techniques for identification of the naphthalene photodegradation intermediates and products. 1-Naphthol, 1,4-naphthalenedione and 1,2-benzendicarboxilic acid have been determined as intermediates and based on these intermediates a suitable mechanism for photodegradation of naphthalene was suggested.
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Arnold,Larson
, p. 250 (1940)
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Direct photooxidation and xanthene-sensitized oxidation of naphthols: Quantum yields and mechanism
Oelgemoeller, Michael,Mattay, Jochen,Goerner, Helmut
, p. 280 - 285 (2011)
The photoinduced oxidation of 1-naphthol to 1,4-naphthoquinone and of 5-hydroxy-1-naphthol to 5-hydroxy-1,4-naphthoquinone was studied by steady-state and time-resolved techniques. The direct photooxidation of naphthols in methanol or water takes place by reaction of the naphoxyl radical ( ·ONaph) with the superoxide ion radical (O2 ·-), the latter of which results from the reaction of the solvated electron with oxygen after photoionization. The sensitized oxidation takes place by energy transfer from the xanthene triplet state to oxygen. From the two oxygen atoms, which are consumed, one is incorporated into the naphthol molecule giving naphthoquinone and the second gives rise to water. The effects of eosin, erythrosin, and rose bengal in aqueous solution, pH, and the oxygen and naphthol concentrations were studied. The quantum yield of the photosensitized transformation was determined, which increases with the naphthol concentration and is largest at pH > 10. The quantum yield of oxygen uptake is similar. The pathway involving singlet molecular oxygen is suggested to operate for the three sensitizers. The alternative pathway via electron transfer from the naphthol to the xanthene triplet state and subsequent reaction of ·ONaph with O2·-, the latter of which is formed by scavenging of the xanthene radical anion by oxygen, does also contribute.
Polymer incarcerated gold catalyzed aerobic oxidation of hydroquinones and their derivatives
Miyamura, Hiroyuki,Shiramizu, Mika,Matsubara, Ryosuke,Kobayashi, Shu
, p. 360 - 361 (2008)
Polymer-incarcerated gold (PI Au) cluster catalysts mediated aerobic oxidation of hydroquinones and catechols to quinones very efficiently under mild conditions. The characteristic role of water in the reaction system was also observed. Copyright
Oxidation of Methoxy- and/or Methyl-Substituted Benzenes and Naphthalenes to Quinones and Phenols by H2O2 in HCOOH
Orita, Hideo,Shimizu, Masao,Hayakawa, Takashi,Takehira, Katsuomi
, p. 1652 - 1657 (1989)
The oxidation of a number of arenes (methoxybenzenes, methylbenzenes, and naphthalenes) to quinones and phenols by H2O2 in HCOOH has been examined.Methoxybenzenes were much more easily oxidized to p-benzoquinones than methylbenzenes (e.g., 1,3,5-trimethoxybenzene was oxidized to 2,6-dimethoxy-p-benzoquinone in a 75percent yield and 1,2,4-trimethylbenzene to 2,3,5-trimethyl-p-benzoquinone in a 16percent yield).Electron-withdrawing substituents, such as nitro, cyano, and chloro groups, lowered the conversion of reactants and changed the product selectivity from quinones to phenols.Methoxybenzonitriles were oxidized to corresponding phenols in a moder ate yield (e.g., 2,6-dimethoxybenzonitrile to 3-hydroxy-2,6-dimethoxybenzonitrile in a 39percent yield and a 64percent selectivity).
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Periasamy,M.,Bhatt,M.V.
, p. 330 - 332 (1977)
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Discovery of juglone and its derivatives as potent SARS-CoV-2 main proteinase inhibitors
Cui, Jiahua,Jia, Jinping
, (2021)
SARS-CoV-2 as a positive-sense single-stranded RNA coronavirus caused the global outbreak of COVID-19. The main protease (Mpro) of the virus as the major enzyme processing viral polyproteins contributed to the replication and transcription of SARS-CoV-2 in host cells, and has been characterized as an attractive target in drug discovery. Herein, a set of 1,4-naphthoquinones with juglone skeleton were prepared and evaluated for the inhibitory efficacy against SARS-CoV-2 Mpro. More than half of the tested naphthoquinones could effectively inhibit the target enzyme with an inhibition rate of more than 90% at the concentration of 10 μM. In the structure-activity relationships (SARs) analysis, the characteristics of substituents and their position on juglone core scaffold were recognized as key ingredients for enzyme inhibitory activity. The most active compound, 2-acetyl-8-methoxy-1,4-naphthoquinone (15), which exhibited much higher potency in enzyme inhibitions than shikonin as the positive control, displayed an IC50 value of 72.07 ± 4.84 nM towards Mpro-mediated hydrolysis of the fluorescently labeled peptide. It fit well into the active site cavity of the enzyme by forming hydrogen bonds with adjacent amino acid residues in molecular docking studies. The results from in vitro antiviral activity evaluation demonstrated that the most potent Mpro inhibitor could significantly suppress the replication of SARS-CoV-2 in Vero E6 cells within the low micromolar concentrations, with its EC50 value of about 4.55 μM. It was non-toxic towards the host Vero E6 cells under tested concentrations. The present research work implied that juglone skeleton could be a primary template for the development of potent Mpro inhibitors.
Visible-light induced solvent-free photooxygenations of organic substrates by using [60]fullerene-linked silica gels as heterogeneous catalysts and as solid-phase reaction fields
Hino, Tetsuo,Anzai, Takahiro,Kuramoto, Noriyuki
, p. 1429 - 1432 (2006)
Novel recyclable heterogeneous catalysts generating singlet-oxygen under visible-light irradiation have been prepared by linking [60]fullerene to amino-functionalized silica gels. The catalysts facilitate various types of photooxygenerations including Diels-Alder reaction, ene reaction, and oxidations of phenol and sulfide in a solid-solvent system and even in a solvent-free system.
Convenient Synthesis of 1,4-Naphthoquinones from Polymethoxynaphthalenes. Oxidative Demethylation with Silver-Catalyzed Ammonium Peroxodisulfate
Tanoue, Yasuhiro,Sakata, Kazunori,Hashimoto, Mamoru,Morishita, Shin-ichi,Hamada, Moritsugu
, p. 2593 - 2595 (1994)
The oxidative demethylation of polymethoxynaphthalenes such as 1,4-di, 1,4,5-tri, 1,4,5,8-tetra-, and 1,2,4,5,8-pentamethoxynaphthalenes with silver-catalyzed ammonium peroxodisulfate gave the corresponding 1,4-naphthoquinones in good yield under mild reaction conditions.
Immobilization of a Metal Complex in Y-Zeolite Matrix: Synthesis, X-ray Single-Crystal, and Catalytic Activities of a Copper (Schiff-Base)-Y Zeolite Based Hybrid Catalyst
Saha, Pratap Kumar,Banerjee, Surajit,Saha, Sandip,Mukherjee, Alok Kumar,Sivasanker, Subramanian,Koner, Subratanath
, p. 709 - 714 (2004)
A new zeolite-immobilized copper(II) complex catalyst has been prepared by entrapping [CuL] [LH2 = N,N′ -(1,1-dimethylethylene)bis(salicylaldiimine)] on NaY zeolite matrix. The reaction of Cu-NaY and molten LH2 affords a green mass of crude catalyst that upon a treatment with CH3CN gives a gray-colored hybrid catalyst (CuL-NaY). The prepared catalyst has been characterized by IR and UV-vis spectroscopic and EPR spectrometric measurements, TG-DTA analysis, powder X-ray diffraction, and surface-area measurements. To ascertain the structure of the immobilized complex, a single-crystal X-ray diffraction analysis of [CuL] was performed. Spectroscopic measurements showed that the green crude of CuL-NaY contains a penta- or hexa-coordinated copper(II) moiety, while the CuL-NaY catalyst contains a distorted square-planar [CuL] complex moiety. A remarkable catalytic activity of the prepared hybrid catalyst has been observed in oxidation reactions of 1-naphthol and norbornene.
Strategies for cleaner oxidations using photochemically generated singlet oxygen in supercritical carbon dioxide
Han, Xue,Bourne, Richard A.,Poliakoff, Martyn,George, Michael W.
, p. 1787 - 1792 (2009)
Photochemically generated singlet oxygen, 1O2, has been reacted with four different substrates in supercritical carbon dioxide. By using fluorous surfactants and a co-solvent to solubilise more polar photosensitisers and reactants respectively, the applicability of the system is greatly enhanced. The Royal Society of Chemistry 2009.
Molecular growth of PAH-like systems induced by oxygen species: Experimental and theoretical study of the reaction of naphthalene with HO (2Π3/2), O (3P), and O2 (3Σ - G)
Scapinello, Marco,Martini, Luca Matteo,Tosi, Paolo,Maranzana, Andrea,Tonachini, Glauco
, p. 38581 - 38590 (2015)
To assess if reactions with oxygen species can induce a mass increase of polycyclic aromatic hydrocarbons, we exposed naphthalene molecules to an oxidative gas flow containing the radicals H and HO (2Π3/2) and the diradicals O (3P) and O2 (3Σ-g). We observed the formation of 1- and 2-naphtol, 1,4-naphthoquinone, naphthalene-derived cyclic ethers, an ester from ring opening, and ether adducts containing two naphthalene units. We investigated the possible reaction pathways as a function of temperature by density functional calculations. We found that the reactivity is characterized by HO, O and H addition to naphthalene, or by H abstraction from it, with roles depending on temperature. In conclusion, oxygen species can promote, under the experimental conditions, mainly naphthalene oxidation and, to a lesser extent, substantial molecular growth, with an efficiency that the calculations indicate to depend on the system temperature. Future experiments should try to quantify key species to allow defining the relative importance of the various reaction mechanisms uncovered by ab initio calculations.
2-Geranyl-1,4-naphthoquinone, a possible intermediate of anthraquinones in a Sesamum indicum hairy root culture
Furumoto, Toshio,Ohara, Tomoko,Kubo, Tetsuya,Kawanami, Yasuhiro,Fukui, Hiroshi
, p. 2600 - 2602 (2007)
2-Geranyl-1,4-naphthoquinone was isolated from the hairy root culture of Sesamum indicum. The structure was determined to be 2-[(E)-3,7-dimethylocta-2,6- dienyl]-1,4-naphthoquinone on the basis of spectroscopic evidence and chemical synthesis. The production of anthrasesamones A, B and C by the hairy root culture was also confirmed for the first time.
Copper-mediated addition of ethanolamine affording 2-hydroxymethyl naphtho[2,1-d]oxazoles from 2-naphthols
Wang, Xiuzhen,Yang, Baoyun,Li, Rui
, p. 846 - 849 (2014)
A new and mild synthetic approach was presented for the synthesis of naphtho[2,1-d]oxazoles. In the presence of copper (II)-ethanolamine, 2-hydroxymethyl naphtho[2,1-d]oxazoles were one-pot synthesized in moderate to good yields through copper-mediated oxidation of 2-naphthols followed with the addition of ethanolamine in acetonitrile.
Anodic oxidation of 4-methoxy-1-naphthol
El-Seedi, Hesham R.,Yamamura, Shosuke,Nishiyama, Shigeru
, p. 3301 - 3304 (2002)
Anodic oxidation of 4-methoxy-1-naphthol 1 in the presence of nucleophiles provided the corresponding products 8-12 and the dimers 13 and 17 were also produced. The reaction mechanism of the oxidation reaction including the [3+2] cycloaddition was investigated.
Thermolysis of 2-Benzylidenebenzocyclobutenols
Bradley, Jean-Claude,Durst, Tony,Williams, A. J.
, p. 6575 - 6579 (1992)
The thermolysis of a series of 2-benzylidenebenzocyclobuten-1-ols has been studied.Whenever comparisons can be made, the rate of opening of the benzocyclobutene ring was slower for these compounds than the corresponding 2-ones.The intermediate vinylallenes underwent a variety of electrocyclization reactions which depended on the nature of the additional substituent at C-1. 10-Benzylideneanthrone and 4-benzylidene-1-tetralones, respectively, were obtained when this substituent was phenyl or vinyl. 1-(Alkynylphenyl)-2-benzylidenebenzocylobuten-1-ols were converted to mixtures of 4-benzylidene-1,4-naphthoquinonemethides, 2,3-dibenzylidene-1-indanones, and 10-phenylbenzofluorenone.
Photooxygenations of 1-naphthols: An environmentally friendly access to 1,4-naphthoquinones
Suchard, Oliver,Kane, Ronan,Roe, Bernard J.,Zimmermann, Elmar,Jung, Christian,Waske, Prashant A.,Mattay, Jochen,Oelgem?ller, Michael
, p. 1467 - 1473 (2006)
Dye sensitized photooxygenations of 1-naphthols were investigated with soluble and solid-supported sensitizers and moderate to excellent yields of the corresponding 1,4-naphthoquinones were achieved in relatively short irradiation times. The mild and environmentally friendly reaction conditions made this application particularly attractive for 'Green Photochemistry'. Consequently, the photooxygenation of 1,5-dihydroxynaphthalene was studied with non-concentrated and moderately concentrated sunlight and 5-hydroxy-1,4- naphthoquinone (Juglone) was obtained in yields up to 71%.
Homogeneous oxidation of aromatics in nucleus with peracetic acid catalyzed by iron and manganese phthalocyanine complexes
Barkanova, Svetlana V.,Derkacheva, Valentina M.,Dolotova, Olga V.,Li, Vladimir D.,Negrimovsky, Vladimir M.,Kaliya, Oleg L.,Luk'yanets, Eugene A.
, p. 1637 - 1640 (1996)
The reaction of naphthalene and methylnaphthalenes with peracetic acid catalyzed by Mn(III) (1) or Fe(II) (2) octanitrophthalocyanines in CH3CN at 20°C produces 1,4-naphthoquinones with 35-62% yields. The corresponding 2,3-epoxide-1,4-endoperoxides are proposed as intermediate in reaction catalyzed by 1.
μ-oxo-bridged hypervalent iodine(III) compound as an extreme oxidant for aqueous oxidations
Dohi, Toshifumi,Nakae, Tomofumi,Takenaga, Naoko,Uchiyama, Teruyoshi,Fukushima, Kei-Ichiro,Fujioka, Hiromichi,Kita, Yasuyuki
, p. 1183 - 1189 (2012)
We have found that in aqueous oxidations the -oxo-bridged hypervalent iodine trifluoroacetate reagent 1 {[(PhI(OCOCF]} is generally more reactive than the corresponding monomeric reagent, especially toward phenolic substrates. -Oxo-bridged 1 in aqueous media thus provided dearomatized quinones 3 in excellent yields in most cases compared to conventional phenyliodine(III) diacetate and bis(trifluoroacetate), as a result of the rapid oxidation of both phenols and naphthols 2. Furthermore, the oxidation reactions proceeded even in water using water-soluble -oxo oxidant 1, which has promise for -oxo-bridged reagent 1 to become the favored reagent over hydrophobic phenyliodine(III) diacetate and bis(trifluoroacetate). Georg Thieme Verlag Stuttgart New York.
Efficient oxidative ipso-fluorination of para-substituted phenols using pyridinium polyhydrogen fluoride in combination with hypervalent iodine(III) reagents
Karam, Omar,Martin-Mingot, Agnès,Jouannetaud, Marie-Paule,Jacquesy, Jean-Claude,Cousson, Alain
, p. 6629 - 6638 (2004)
Diacetoxyiodobenzene (PIDA) and bis(trifluoroacetoxy)iodobenzene (PIFA) in the presence of pyridinium polyhydrogen fluoride (PPHF) are effective for the fluorination of para-substituted phenols to give a variety of 4-fluorocyclohexa-2,5-dienones in a good yield. (R,S)-1,1′-Bi-5,6,7,8- tetrahydro-2-naphthol (and its monoacetate) yields atropoisomeric fluorocyclohexadienones. The 4-substituted carbamate open-chain phenols were readily converted to fluorohydroindolenone and fluorohydroquinolenone derivatives by intramolecular conjugate addition.
Synthesis, properties and singlet oxygen generation of thiazolidinone double bond linked porphyrin at meso and β-position
Ahmad, Sohail,Yadav, Kumar Karitkey,Narang, Uma,Bhattacharya, Soumee,Singh, Sarangthem Joychandra,Chauhan
, p. 36090 - 36095 (2016)
Meso and β-substituted free base and zinc metallated thiazolidinone-porphyrin conjugates were synthesized by one pot four component Knoevenagel condensation by utilizing substituted amines, carbon disulfide, ethyl chloroacetate and porphyrin aldehydes. These newly synthesized conjugates were characterized by IR, 1H NMR, 13C NMR, UV-Vis, fluorescence and HRMS spectroscopy. The singlet oxygen generation behaviors of these porphyrin conjugates were studied and it was observed that these porphyrin conjugates followed type II singlet oxygen. Fluorescence and singlet oxygen quantum yields among meso-substituted (mono-, di, tetra) and β-substituted conjugates were examined. The photocatalytic photooxidation of naphthols and furan by using these new organic photocatalysts were further analysed and it was observed that meso-tetra substituted (Zn3a) and β-substituted (Zn6a) porphyrins are much efficient for generation of singlet oxygen and for photocatalytic photooxidation.
Oxidative Dearomatization of Phenols and Polycyclic Aromatics with Hydrogen Peroxide Triggered by Heterogeneous Sulfonic Acids
Pancrazzi, Francesco,Maestri, Giovanni,Maggi, Raimondo,Viscardi, Rosanna
supporting information, p. 5407 - 5414 (2021/10/25)
We report herein a method for the oxidative dearomatization of phenols and bare polycyclic arenes into the corresponding quinoid derivatives using hydrogen peroxide. The reaction is catalyzed by sulfonic acids and best results were achieved using heterogenized species. The best results using phenols were achieved using a hybrid material, namely a perfluorinated polymer functionalized with sulfonic acid groups supported on silica. The dearomatization of polycyclic aromatic hydrocarbons performed better using the polymeric acid catalyst. These methods operate under mild conditions, using mild and benign oxidants and thus minimizing the formation of waste.
Menadione structure-based novel coronavirus 3CL protease inhibitor
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Paragraph 0040-0043, (2021/04/14)
The invention discloses a menadione derivative capable of resisting novel coronavirus and medical application of the menadione derivative. The structure of the compound is shown as a formula (I), in the formula, R is a hydrogen atom, methyl, acetyl or hydroxyl, and R1 is hydrogen, methoxy, benzyloxy or benzoyloxy. The compound disclosed by the invention can inhibit the 3CL hydrolase of the 2019-nCoV novel coronavirus, and has the activity of resisting the novel coronavirus. In-vitro activity determination experiments show that the enzyme inhibition rate of part of the compounds reaches 90% or above under the concentration of 1 [mu] M, and is significantly superior to that of a positive control drug alkannin. Cell-level toxicity test experiment results show that the toxicity of menadione and the derivative thereof to host normal cells HSF is significantly lower than that of positive drugs alkannin and juglone, and part of the compounds show relatively strong anti-novel coronavirus activity in vitro, and have an important significance for the development of high-efficiency and low-toxicity new anti-novel coronavirus drugs.