- Fabrication, characterization and structure activity relationship of Co and Mn encapsulated on magnetic nanocomposite and its application in one-pot tandem synthesis of various tetrazoles and vitamin K3
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Considering the importance of vitamin K3 in commercial pet foods, veterinary medicines, poultry, and some swine feed and also tetrazole derivatives in pharmacy, medicine, chemistry, petroleum, and military industry, design efficient catalytic systems are desirable. Herein, four magnetic nanocomposites (MNCs) of cobalt and manganese using metformin, 3-aminopropyltrimethoxysilane (L1) and 2-aminoethyl-3-aminopropyltrimethoxysilane (L2) were designed and constructed as an efficient and controllable catalytic system. The synthesized nanocomposites fully characterized by FT-IR, AAS, ICP-OES, BET, CHN elemental analysis, SEM, TEM, DLS, EDX, TGA, VSM, and XPS spectroscopy. The well-prepared magnetically recoverable nanocomposites were used in the synthesis of a wide derivatives of α-hydrazino tetrazoles (α-HyT), ferrocenyltetrazoles (FcT), arylaminotetrazoles (ArAT) and also vitamin K3. Besides, the effect of operating parameters, such as the amount of catalyst, nature of solvent, temperature and reaction time, metal nature, chain length and hydrophobicity properties of linkers, was studied in the catalytic efficiency of synthesized nanocatalysts. The best catalytic results were obtained in the following order: FS-L2-Met@Co(II) > FS-L2-Met@Mn(II) > FS-L1-Met@Co(II) > FS-L1-Met@Mn(II) due to their structural characteristics. In addition to high TOF, these magnetic nanocomposites are superior in easy, inexpensive, and commercially preparation, keeping the structural and magnetic characteristics, easy magnetically separation from the reaction medium, short reaction time, mild reaction condition, easy work-up, and reusability without any metal leaching in six runs. Graphical abstract: [Figure not available: see fulltext.]
- Ashouri, Fatemeh,Farahanipour, Alireza,Faraji, Ali Reza,Hekmatian, Zahra
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- Selective oxidation of pseudocumene and 2-methylnaphthalene with aqueous hydrogen peroxide catalyzed by γ-Keggin divanadium-substituted polyoxotungstate
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The catalytic performance of a γ-Keggin divanadium-substituted phosphotungstate, (Bu4N)4[γ-PW10O38V2(μ-O)(μ-OH)], has been evaluated in the selective oxidation of 1,2,4-trimethylbenzene (pseudocumene, PC) and 2-methylnaphthalene with the green oxidant, 35% aqueous hydrogen peroxide. Under conditions of H2O2 deficiency ([PC]/[H2O2] = 17-22), PC oxidation proceeded with unusually high chemo- and regioselectivity, producing exclusively 2,4,5-trimethylphenol (2,4,5-TMP) and 2,3,5-TMP in a molar ratio of 7.3/1 and a yield of 73% based on the oxidant. Isomeric 2,3,6-trimethylphenol was found in trace amounts. Under conditions of H2O2 excess ([H2O2]/[PC] = 8), 2,3,5-trimethyl-1,4-benzoquinone (TMBQ, vitamin E key intermediate) formed with 41% selectivity at 41% substrate conversion. Atypical regioselectivity was also found in the oxidation of 2-methylnaphthalene which gave predominantly 6-methyl-1,4-naphthoquinone (6-MNQ) rather than isomeric 2-MNQ. The ratio between the isomers could be altered by varying the catalyst and oxidant amounts.
- Zalomaeva, Olga V.,Evtushok, Vasiliy Yu.,Maksimov, Gennadii M.,Kholdeeva, Oxana A.
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p. 210 - 216
(2015/09/01)
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- Bio-inspired dimerisation of prenylated quinones directed towards the synthesis of the meroterpenoid natural products, the scabellones
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Stirring 2-geranyl-6-methoxy-1,4-hydroquinone in pyridine/O2 or 2-geranyl-6-methoxy-1,4-benzoquinone in pyridine/N2 affords the dimeric meroterpenoid natural products, scabellones A-C in modest to low yields and also identifies 2-methoxy-6-(4-methylpent-3-en-1-yl)-1,4-naphthoquinone (scabellone E) as a new natural product. The corresponding reaction of the des-methoxy analogue, 2-geranyl-1,4-benzoquinone in degassed pyridine for three days afforded the natural product cordiachromene A (15% yield) and 6-(4-methylpent-3-en-1-yl)-1,4-naphthoquinone (12%), the latter being a likely biosynthetic precursor to the marine meroterpenoid alkaloids, conicaquinones A and B.
- Chan, Susanna T.S.,Pullar, Michael A.,Khalil, Iman M.,Allouche, Emmanuelle,Barker, David,Copp, Brent R.
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p. 1486 - 1488
(2015/03/14)
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- Binuclear iron(III) octakis(perfluorophenyl)tetraazaporphyrin μ-oxodimer: A highly efficient catalyst for biomimetic oxygenation reactions
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Binuclear iron(III) octakis(perfluorophenyl)tetraazaporphyrin μ-oxodimer complex was prepared by the reaction of bis(perfluorophenyl)maleonitrile and Fe(CO)5and tested in catalytic oxygenation reactions of several hydrocarbons in comparison with the analogous non-fluorinated phthalocyanine complexes. Results of the study demonstrate that this complex is a highly efficient catalyst for the oxygenation of anthracene, 2-tert-butylanthracene, naphthalene, 2-methylnaphthalene, phenanthrene, adamantane, and toluene using iodosylbenzene, oligomeric iodosylbenzene sulfate, or Oxone as stoichiometric oxidants.
- Yusubov, Mekhman S.,Celik, Cumali,Geraskina, Margarita R.,Yoshimura, Akira,Zhdankin, Viktor V.,Nemykin, Victor N.
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supporting information
p. 5687 - 5690
(2014/12/11)
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- Efficient oxidation of polycyclic aromatic hydrocarbons with H 2O2 catalyzed by 5,10,15-triarylcorrolatoiron (IV) chloride in ionic liquids
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A simple and efficient oxidative system has been developed for the oxidation of polycyclic aromatic hydrocarbons with H2O2 catalyzed by 5,10,15-triarylcorrolatoiron (IV) chloride in mixed reaction media using imidazolium ionic liquids and organic solvents. The coordination effects of different organic solvents as well as anions of ionic liquids on the oxidation reactions have been examined.
- Kumari, Pratibha,Nagpal, Ritika,Chauhan, Shive M.S.
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supporting information
p. 15 - 20
(2013/01/15)
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- Oxidation of 1,2,4-trimethylbenzene (TMB), 2,3,6-trimethylphenol (TMP) and 2-methylnaphthalene to 2,3,5-trimethylbenzoquinone (TMBQ) and menadione (vitamin K3)
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The synthesis of industrially important quinones as intermediates for vitamin syntheses is reviewed with special emphasis on recent developments in our own group.
- M?ller, Konstanze,Wienh?fer, Gerrit,Westerhaus, Felix,Junge, Kathrin,Beller, Matthias
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scheme or table
p. 68 - 75
(2012/06/18)
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- YIELD-EFFICIENT PROCESS FOR THE PRODUCTION OF HIGHLY PURE 2-METHYL-1,4-NAPHTHOQUINONE AND ITS DERIVATIVES
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The present invention discloses a process for the production of 2-methyl-1,4-naphthoquinone and its bisulfite adducts, comprising the following steps: a) oxidizing 2-methyl-naphthalene (2-MNA) to achieve an organic phase containing 2-methyl-naphthoquinone (2-MNQ) and 6-methyl-naphthoquinone (6-MNQ); b) subjecting said organic phase to treatment with an aqueous solution of a bisulfite salt to extract preferentially the 6-MNQ isomer from the organic phase; c) separating said organic phase from the aqueous phase; d) subjecting the organic phase of process step c) to a second bisulfitation step with an aqueous solution of a bisulfite salt, resulting in an organic phase containing 2-MNA and trace amounts of 2-MNQ and an aqueous phase containing 2-MSB and trace amounts of 6-MSB; e) optionally removing interfering bisulfite ions from the aqueous phase of process step c); f) raising the pH of the aqueous phase from step c) or e) to higher than 8,5 in the presence of a solvent resulting in an organic phase containing 2-MNQ; g) combining the organic phase from step f) with the organic phase being treated in the process step d); h) recycling the organic phase from step d) back to step a) to be used as solvent for the oxidation reaction of 2-MNA.
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Page/Page column 9
(2011/08/04)
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- Yield-efficient process for the production of highly pure 2-methyl-1,4-naphthoquinone and its derivatives
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The present invention concerns a process for the production of 2-methyl-1,4-naphthoquinone and its derivatives, comprising the following steps: a) oxidizing 2-methyl-naphthalene (2-MNA) to achieve an organic phase containing 2-methyl-naphthoquinone (2-MNQ) and 6-methyl-naphthoquinone (6-MNQ); b) subjecting said organic phase to treatment with an aqueous solution of a bisulfite salt to extract preferentially the 6-MNQ isomer from the organic phase; c) separating said organic phase from the aqueous phase: d) optionally removing interfering bisulfite ions from said aqueous phase e) raising the pH of said aqueous phase to higher than 8.5 in the presence of a solvent resulting in an organic phase containing 2-MNQ; f) isolating said 2-MNQ from said organic phase.
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Page/Page column 7
(2011/08/04)
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- A novel process for selective Ruthenium-Catalyzed oxidation of naphthalenes and phenols
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Arenes are selectively oxidized to the corresponding quinones employing ruthenium(2,2′,6′:2″-terpyridine)(2,6-pyridinedicarboxylate) [Ru(tpy)(pydic] as catalyst and hydrogen peroxide as the terminal oxidant. Applying alkylated naphthalenes and phenols, benzo- and naphthoquinones are obtained in up to 93% yield. The industrially interesting oxidation of 2-methylnaphthalene gave 74% of the corresponding quinones and 60% of menadione (vitamin K3). 2,3,5-Trimethylbenzoquinone which constitutes the key intermediate for vitamin E is obtained in 83% yield.
- Wienhoefer, Gerrit,Schroeder, Kristin,Moeller, Konstanze,Junge, Kathrin,Beller, Matthias
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experimental part
p. 1615 - 1620
(2010/09/05)
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- Selective iron-catalyzed oxidation of phenols and arenes with hydrogen peroxide: Synthesis of vitamin e intermediates and vitamin k3
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(Figure Presented). Pumping iron! Convenient iron-based catalyst systems for the selective oxidation of arenes and phenols with hydrogen peroxide to give 1, 4-quinones have been developed. This selective oxidation reaction takes place under mild conditions (room temperature, alcoholic solvents) with H 2O2 as the terminal oxidant.
- Moeller, Konstanze,Wienhoefer, Gerrit,Schroeder, Kristin,Join, Benoit,Junge, Kathrin,Beller, Matthias
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experimental part
p. 10300 - 10303
(2010/10/21)
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- Binuclear iron(III) phthalocyanine(μ-oxodimer)/tetrabutylammonium oxone: A powerful catalytic system for oxidation of hydrocarbons in organic solution
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Binuclear iron(III) phthalocyanine-(μ-oxodimer) complex was tested in catalytic oxygenation reactions of several hydrocarbons using tetrabutylammonium oxone as the oxidant in dichloromethane solution at room temperature. Results of the study demonstrate that this is an extremely powerful catalytic system for oxidative conversion of aromatic hydrocarbons (anthracene, 2-tert- butylanthracene, 2-methylnaphthalene, 9, 10-dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, indane, ethylbenzene, toluene, and benzene) to the respective p-quinones in high yields in 5-30 min. Under these conditions, adamantane is oxidized with 71% conversion after 10 min affording a mixture of 1 -adamantanol, 2-adamantanone, 1-hydroxy-2-adamantanone, and 4-protoadamantanone.
- Neu, Heather M.,Zhdankin, Viktor V.,Nemykin, Victor N.
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scheme or table
p. 6545 - 6548
(2011/02/22)
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- Binuclear iron(III) phthalocyanine(μ-oxodimer)-catalyzed oxygenation of aromatic hydrocarbons with iodosylbenzene sulfate and iodosylbenzene as the oxidants
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Two binuclear iron(III) phthalocyanine-(μ-oxodimer) complexes were tested in catalytic oxygenation reactions of several aromatic hydrocarbons using iodosylbenzene (PhIO)n or oligomeric iodosylbenzene sulfate [(PhIO)3SO3]n as the oxidants. Results of this study demonstrate that [(PhIO)3SO3]n is the most reactive oxygenating reagent that can be used as a safe and convenient alternative to the thermally unstable and potentially explosive iodosylbenzene. The pyridine-containing binuclear μ-oxobis-{iron(III)-pyridino[3,4]-9(10), 16(17),23(24)-tri-tertbutyltribenzoporphyrazine} is significantly more active as compared to the traditional μ-oxobis[iron-(III)-2,9(10),16(17),23(24)-tetra- tert-butylphthalocyanine].
- Neu, Heather M.,Yusubov, Mekhman S.,Zhdankin, Viktor V.,Nemykin, Victor N.
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scheme or table
p. 3168 - 3174
(2010/04/28)
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- A novel and convenient process for the selective oxidation of naphthalenes with hydrogen peroxide
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A practical ruthenium phase-transfer catalyst (Ru-PTC) system for the oxidation of naphthalene derivatives has been developed. Substituted 1,4-quinones are obtained in good selectivity and yield in water without the addition of any organic solvent and acid. By applying the optimized conditions the feed additive menadione (vitamin K3) is obtained from 2-methylnaphthalene with 64 % yield and 73 % selectivity.
- Shi, Feng,Tse, Man Kin,Beller, Matthias
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p. 303 - 308
(2008/02/05)
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- A new metal-free access to vitamin K3
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2-Methylnaphthalene is oxidized in about 80% yield with 7-9/1 regioselectivity to 2-methyl-1,4-naphthoquinone by hydrogen peroxide with a strong mineral acid as the catalyst. No (transition) metal catalyst is required for this transformation.
- Bohle, Anne,Schubert, Anett,Sun, Yu,Thiel, Werner R.
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p. 1011 - 1015
(2007/10/03)
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- METHOD FOR PRODUCING 2-METHYL-1,4-NAPHTHOQUINONE
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The invention relates to a method for producing 2-methyl-1,4-naphthoquinone by the oxidation of 2-methylnaphthalene. 2-methyl-1,4-naphthoquinone, also known as menandione or vitamin K3, is used in the field of animal nutrition as a food supplement and is thus produced in large quantities. To facilitate large-scale production, the oxidation of the 2-methylnaphthalene takes place without a metallic catalyst, using hydrogen peroxide in carboxylic acids, their respective anhydride and a strong mineral acid as a catalyst for the formation of the percarboxylic acid in a thermal treatment process.
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Page/Page column 4-5
(2008/06/13)
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- Dichlororuthenium(IV) complex of meso-Tetrakis(2,6-dichlorophenyl) porphyrin: Active and robust catalyst for highly selective oxidation of arenes, Unsaturated steroids, and electron-deficient alkenes by using 2,6-dichloropyridine N-oxide
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[RuIV(2,6-Cl2tpp)Cl2], prepared in 90% yield from the reaction of [RuVI(2,6-Cl2tpp)O2] with Me3SiCl and structurally characterized by X-ray crystallography, is markedly superior to [RuIv(tmp)Cl2], [RuIV(ttp)Cl2], and [RuII(por)(CO)] (por = 2,6-Cl2tpp, F20-tpp, F28-tpp) as a catalyst for alkene epoxidation with 2,6-Cl2pyNO (2,6Cl2tpp = meso-tetrakis(2,6-dichlorophenyl)porphyrinato dianion; tmp = meso-tetramesitylporphyrinato dianion; ttp = meso-tetrakis(p-tolyl)porphyrinato dianion; F20-tpp = meso-tetrakis(pentafluorophenyl)porphyrinato dianion; F28-tpp = 2,3,7,8,12,13,17,18-octafluoro-5,10,15,20- tetrakis(pentafluorophenyl)-porphyrinato dianion). The "[Ru IV(2,6-Cl2tpp)Cl2] + 2,6-Cl 2pyNO" protocol oxidized, under acid-free conditions, a wide variety of hydrocarbons including 1) cycloalkenes, conjugated enynes, electron-deficient alkenes (to afford epoxides), 2) arenes (to afford quinones), and 3) Δ5-unsaturated steroids, Δ4-3- ketosteroids, and estratetraene derivatives (to afford epoxide/ketone derivatives of steroids) in up to 99% product yield within several hours with up to 100% substrate conversion and excellent regio- or diastereoselectivity. Catalyst [RuIv(2,6-Cl2tpp)Cl2] is remarkably active and robust toward the above oxidation reactions, and turnover numbers of up to 6.4 × 103, 2.0 × 104, and 1.6 × 104 were obtained for the oxidation of α,β-unsaturated ketones, arenes, and Δ5-unsaturated steroids, respectively.
- Zhang, Jun-Long,Che, Chi-Ming
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p. 3899 - 3914
(2007/10/03)
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- Bis(trifluoroacetoxyiodo)benzene-induced activation of tert-butyl hydroperoxide for the direct oxyfunctionalization of arenes to quinones
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Various aromatic hydrocarbons were oxidized with bis(trifluoroacetoxyiodo) benzene (PIFA)/tert-butyl hydroperoxide system to afford the corresponding quinones. The reaction conditions and scope have been discussed in detail.
- Catir, Mustafa,Kilic, Hamdullah
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p. 2151 - 2154
(2007/10/03)
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- Chromium(VI) oxide-catalyzed oxidation of arenes with periodic acid
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Chromium(VI) oxide was found to catalyze the oxidation of arenes such as naphthalenes and anthrathene to the corresponding quinones with periodic acid as the terminal oxidant in acetonitrile. 2-Methylnaphthalene was oxidized smoothly to 2-methyl-1,4-naphthoquinone (vitamin K3) by the catalytic system in high yield and regioselectivity.
- Yamazaki, Shigekazu
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p. 3355 - 3357
(2007/10/03)
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- Metalloporphyrin-catalyzed oxidation of 2-methylnaphthalene to vitamin K3 and 6-methyl-1,4-naphthoquinone by potassium monopersulfate in aqueous solution
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The metalloporphyrin-catalyzed oxidation of 2-methylnaphthalene (1) by potassium monopersulfate produced mainly two naphthoquinones: 2-methyl-1,4-naphthoquinone (2) (menadione or vitamin K3) and 6-methyl-1,4-naphthoquinone (3). In aqueous solution and at room temperature in the presence of 5 mol % of the water-soluble metalloporphyrins MnTPPS or FeTMPS, 2-methylnaphthalene was quantitatively oxidized to quinones 2 and 3. Based on experiments performed in 18O-labeled water and according to the 'redox tautomerism' mechanism previously described for such catalysts, the oxidation to quinones is proposed to be mainly due to a cytochrome P-450-type oxygenation reaction (oxygen atom transfer), rather than a peroxidase-type oxidation (electron transfer).
- Song, Rita,Sorokin, Alexander,Bernadou, Jean,Meunier, Bernard
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p. 673 - 678
(2007/10/03)
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- Oxidation of naphthalene, 2-methylnaphthalene, and α-naphthol with cerium(IV) in chloric acid solutions
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Cerium(IV) perchlorate oxidizes with high yields α-naphthol and naphthalene to 1,4-naphthoquinone and 2-methylnaphthalene to 2-methyl- or 6-methyl-1,4-naphthoquinone in the two-phase system aqueous or aqueous acetonitrile solution of chloric acid-carbon tetrachloride or n-hexane. The consumption of cerium(IV) perchlorate is ~4.5 mmol for oxidation of 1 mmol of α-naphthol and ~6.5-7.5 mmol for oxidation of 1 mmol of naphthalene and 2-methylnaphthalene. The structure of the final oxidation products is determined by the rate of formation of delocalized radical cations via internal electron transfer in the complex between the organic compound and Ce(IV) ion, by the energy of deprotonation of radical cations formed, and by the substrate concentration. Mechanisms of these processes are proposed on the basis of experimental data and quantum-chemical calculations.
- Steglinska,Gzeidziak,Dziegiec
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p. 825 - 831
(2007/10/03)
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- Rearrangements in the Cerium(IV) and Manganese(III) Oxidations of Substituted Naphthalenes and the NIH Shift Mechanism
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Ceric ammonium sulphate oxidation of 1- and 1,4-disubstituted naphthalenes gives 2- and/or 2,3-disubstituted 1,4-naphthoquinones through migration of substituents (D, Br, Ph).Similar rearrangements are also observed in the manganese(III) oxidation and also in the anodic oxidation of these substrates.The results are consistent with the proposal that these oxidations go through the formation of radical cation followed by reaction with H2O and further oxidation of the radical to the carbocationic intermediate on the way to the corresponding 1,4-naphthoquinone.Oxidation of 1,4-diphenylnaphthalene gives 2,3-diphenyl-1,4-naphthoquinone or 4-hydroxy-2,4-diphenyl-1(4)H-naphthalenone.The results are in accordance with the conclusion that such rearrangements do not require prior formation of arene oxide intermediates, originally proposed for the NIH shift mechanism.
- Bhatt, M. Vivekananda,Periasamy, Mariappan
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p. 3575 - 3586
(2007/10/02)
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- Oxidation of arenes to para-quinones with hydrogen peroxide catalyzed by hexafluoroacetone hydrate
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Various aromatic hydrocarbons were oxidized with aqueous hydrogen peroxide in the presence of hexafluoroacetone hydrate as catalyst to give para-quinones and/or the ring cleavage oxidation products. The regioselective oxidation of 2-methylnaphthalene to 2-methyl-1,4-naphthoquinone (vitamin K3) was studied in detail.
- Adam,Ganeshpure
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p. 280 - 282
(2007/10/02)
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- Oxidation of organic compounds using a catalyzed cerium (IV) composition
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A process for oxidizing aromatic and alkyl substituted aromatic compounds to quinonoid compounds by contacting an aromatic and alkyl aromatic compound with an acidic, aqueous solution of ceric oxidant in the presence of a catalytic amount of chromium cations. The present process provides a means of forming the desired quinonoid product in good yields and high selectivity.
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- CERIUM CATALYZED PERSULFATE OXIDATION OF POLYCYCLIC AROMATIC HYDROCARBONS TO QUINONES
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A practical synthesis of polycyclic quinones from the parent hydrocarbons is described.The twophase oxidation of hydrocarbons was accomplished by using ammonium persulfate in the catalytic presence of cerium ammonium sulfate, silver nitrate, and sodium dodecyl sulfate.The reaction conditions and scope have been discussed in detail.
- Skarzewski, Jacek
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p. 4997 - 5000
(2007/10/02)
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