- Comparison of spin density calculation methods for various alkyl-substituted 9,10-anthraquinone anion radicals in the solution phase
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EPR and ENDOR spectra were recorded for 2-methyl-9,10-anthraquinone (2-methylAQ), 2-ethylAQ, 2-tertbutylAQ and 2,3-dimethylAQ anion radicals in the solution phase. The EPR spectra were simulated with the help of ENDOR data. The experimental isotropic hyperfine coupling constants (IHFCs) were compared with calculated values from semi-empirical INDO, spin-restricted AM1/CI and B3PW91 density-functional methods. The best computational methods for the IHFCs were the semi-empirical AM1/CI method and the B3PW91 density-functional method with a large basis set.
- Eloranta, Jussi,Vatanen, Virpi,Groenroos, Antti,Vuolle, Mikko,Maekelae, Reijo,Heikkilae, Hilkka
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- Friedel - gram acylating reaction method based on phthalic anhydride and aromatic alkyl compound
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A part of a substituted alkylbenzene is used as a solvent and a reaction raw material for - gram acylating reaction, a part of a substituted alkylbenzene is dissolved in a reaction raw material phthalic anhydride and a chloroaluminate ionic liquid catalyst, and a residual part of a substituted alkylbenzene is added dropwise - to obtain - (2 - 4' - alkylbenzoyl) benzoic acid intermediate. 2 -position positioning selectivity of the method is higher, and the reaction production cost is low.
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Paragraph 0085-0087
(2021/09/08)
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- Preparation method of anthraquinone and alkyl derivatives thereof
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The invention relates to the field of organic matter preparation, and discloses a preparation method of anthraquinone and alkyl derivatives thereof, and the method comprises the following steps: underacidic conditions, carrying out contact reaction on anthracene and alkyl derivatives thereof, an oxidant and a catalyst. The anthraquinone and the alkyl derivative thereof have a structure as shown in a formula (I) which is described in the specification. The catalyst comprises a carrier and metal elements loaded on the carrier, wherein the metal elements comprise molybdenum and tungsten, in theformula (I), R1 and R2 are each independently selected from hydrogen and substituted or unsubstituted C1-C10 hydrocarbon groups. The method provided by the invention has the characteristics of mild operation conditions and high product yield.
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Page/Page column 0139-0142; 0145-0154
(2020/08/18)
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- Method for synthesizing 2-alkylanthraquinone
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The invention discloses a method for synthesizing 2-alkylanthraquinone. The method comprises the following steps: preparing a tert-butylanthraquinone intermediate BE acid from phthalic anhydride and alkylbenzene in the presence of a Lewis acid, carrying out dehydration ring closure by adopting a combined dehydrating agent composed of polyphosphoric acid and phosphorus pentoxide, pouring the obtained solution into ice water after the end of the ring closure I order to dilute the polyphosphoric acid to a certain concentration, adding xylene for extraction after water precipitation is finished, washing and concentrating the obtained extract to obtain a brown yellow block solid, and recrystallizing the solid to obtain the 2-alkylanthraquinone. The method of the invention the advantages of avoiding of using of fuming sulfuric acid and production of a large amount of dilute sulfuric acid in the phthalic anhydride method production process of anthraquinone, easily available raw materials, mild reaction conditions, easiness in application in industrial production, realization of continuous using of the byproduct phosphoric acid as the dehydrating agent after addition of phosphorus pentoxide, and good environmental protection meaning.
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Paragraph 0023; 0025
(2019/10/04)
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- Method for preparing 2-alkyl anthraquinone by taking solid super acids as catalysts
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The invention provides a method for preparing 2-alkyl anthraquinone by taking solid super acids as catalysts. The 2-alkyl anthraquinone (alkyl is straight or branched alkyl with the number of carbon atoms of 1-6) is obtained by adopting the solid super acids like perfluorinated sulfonic acid resin and heteropoly acid as the catalysts, taking 2-(4'-alkyl benzoyl) benzoic acid as a raw material andperforming acylated dewatering closed loop through Friedel-Crafts reaction. The method provided by the invention is characterized in that traditional smoking sulfuric acid catalysts are replaced by the solid super acids, so that the environment is friendly, and no waste acid is discharged; the operation process is simple, and the solid catalysts are easy to recover; therefore, the method is a green pollution-free new process.
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Paragraph 0038-0039
(2020/03/28)
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- A 2 - alkyl anthraquinone synthetic method (by machine translation)
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The invention provides a 2 - alkyl anthraquinone synthetic method, the 2 - alkyl anthraquinone synthetic method comprises the following steps: the 2 - (4' - alkyl benzoyl) benzoic acid in the presence of a solvent through the acyl acyl; under the action of the promoter, using anhydrous aluminum ring to carry out the dehydrochlorination; reactant through hydrolysis, liquid separation, pressure reducing desolventizing, drying, to obtain 2 - alkyl anthraquinone. The beneficial effect of the present invention is: not the use of fuming sulfuric acid, mild reaction conditions, acid-free, simple process operation, the product quality is stable, and the yield of the product than the existing production process to improve the 5 - 10%. (by machine translation)
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Paragraph 0058
(2017/05/26)
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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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- Metalloporphyrin/Iodine(III)-Cocatalyzed oxygenation of aromatic hydrocarbons asc.wiley-vch.de
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Hypervalent iodine species have a pronounced catalytic effect on the metalloporphyrinmediated oxygenations of aromatic hydrocarbons. In particular, the oxidation of anthracene to anthraquinone with Oxone readily occurs at room temperature in aqueous acetonitrile in the presence of 5-20 mol% of iodobenzene and 5 mol% of a water-soluble iron(III)-porphyrin complex. 2-tert-Butylan- thracene and phenanthrene also can be oxygenated under similar conditions in the presence of 50 mol% of iodobenzene. The oxidation of styrene in the presence of 20 mol% of iodobenzene leads to a mixture of products of epoxidation and cleavage of the double bond. Partially hydrogenated aromatic hydrocarbons (e.g., 9,10-dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, and 2,3-dihydro-1H- indene) afford under these conditions products of oxidation at the benzylic position in moderate yields. The proposed mechanism for these catalytic oxidations includes two catalytic redox cycles: 1) initial oxidation of iodobenzene with Oxone producing the hydroxy(phenyl)iodonium ion and hydrated iodosylbenzene, and 2) the oxidation of iron(III)-porphyrin to the oxoiron(IV)-porphyrin cation-radical complex by the intermediate iodine(III) species. The oxoiron(IV)-porphyrin cation-radical complex acts as the actual oxygenating agent toward aromatic hydrocarbons.
- Yoshimura, Akira,Neu, Heather M.,Nemykin, Victor N.,Zhdankin, Viktor V.
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experimental part
p. 1455 - 1460
(2010/08/20)
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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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- Comparative reactivity of hypervalent iodine oxidants in metalloporphyrin-catalyzed oxygenation of hydrocarbons: Iodosylbenzene sulfate and 2-iodylbenzoic acid ester as safe and convenient alternatives to iodosylbenzene
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A comparative study of the reactivity of 2-iodylbenzoic acid isopropyl ester (IBX-ester), oligomeric iodosylbenzene sulfate [(PhIO)3· SO3]u, and iodosylbenzene in the oxygenation of anthracene in the presence of metal porphyrin or phthalocyanine complexes is reported. Results of this study demonstrate that oligomeric iodosylbenzene sulfate and the IBX-ester are the most reactive oxygenating reagents that can be used as a safe and convenient alternative to the thermally unstable and potentially explosive iodosylbenzene.
- Geraskin, Ivan M.,Pavlova, Olga,Neu, Heather M.,Yusubov, Mekhman S.,Nemykin, Victor N.,Zhdankin, Viktor V.
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experimental part
p. 733 - 737
(2010/03/01)
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- Ru(II)-catalyzed [2 + 2 + 2] cycloaddition of 1,2-bis(propiolyl)benzenes with monoalkynes leading to substituted anthraquinones
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[2 + 2 + 2] cycloadditions of 1,2-bis(propiolyl)benzenes with monoalkynes were effectively catalysed by Cp*RuCl(cod) under mild conditions to give substituted anthraquinones in moderate to high yields.
- Yamamoto, Yoshihiko,Hata, Koichi,Arakawa, Takayasu,Itoh, Kenji
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p. 1290 - 1291
(2007/10/03)
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- Photophysical and photochemical processes of 2-methyl, 2-ethyl, and 2-tert-butylanthracenes on silica gel. A substituent effect study
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PAH are organic pollutants formed and released into the environment by the incomplete combustion of fossil fuel, coal, wood, gas, oil, garbage, tobacco, and charbroiled meat. The photophysics and photochemistry of 2-methylanthracene (2MA), 2-ethylanthracene (2EA), and 2-tert-butylanthracene (2TBA) adsorbed on silica were studied at a silica/air interface. 2MA, 2EA, and 2TBA showed no evidence of ground state pairing even at high surface coverages, and crystallized on the surface at higher surface coverages. The photolysis of 2MA, 2EA, and 2TBA at a silica/air interface proceeded more efficiently than the photolysis of anthracene, to produce the corresponding 9,10-endoperoxides formed by the addition of singlet molecular oxygen (type II) to the ground state molecules. At low surface coverages, no evidence of any dimer was observed in photolyzed 2MA, 2EA, and 2TBA samples. A small amount of dimers (isomeric) were observed at higher surface coverages, suggesting that the crystal forms of these molecules may be involved in the dimerization process. The photolysis rate decreased with increasing surface coverage, due to an inner effect induced by crystal formation. Photolysis rate decreased by an order of magnitude in the presence of 1 monolayer of physisorbed water. Time-resolved transient studies of excited triplet states of 2MA, 2EA, and 2TBA showed that triplet lifetimes were shortened on wet silica. The efficiency of singlet molecular oxygen formation significantly decreased on wet silica. These results indicated that decreased photolysis rate was caused by reduced singlet quantum yield in the presence of physisorbed water.
- Dabestani, Reza,Higgin, Jashua,Stephenson, Daniel,Ivanov, Ilia N.,Sigman, Michael E.
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p. 10235 - 10241
(2007/10/03)
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- Perfluoroalkanesulfonic acid catalyzed acylations of alkylbenzenes: Synthesis of alkylanthraquinones
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The acylation of alkylbenzenes 1 with benzoyl chloride 2 and catalytic amounts of perfluorobutanesulfonic acid affords the corresponding 2-, 3-, and 4-alkylbenzophenones 3 with unusually high amounts of ortho products. Surprisingly, even tert-butylbenzene reacts under these reaction conditions without any acid catalyzed dealkylation. The yield of benzoylation of p-xylene 4 with benzoic acid in the presence of 5 mol% C4F9SO3H to give 2,5-dimethylbenzophenone 5 could significantly be improved from 14% to 90% by continuous removal of water formed during the acylation. Also in the preparation of alkylanthraquinones 7 by reaction of alkylbenzenes with phthalic anhydride, water removal is the decisive factor to obtain satisfactory yields for the second acylation, allowing to cyclize 6 with catalytic amounts (10 mol%) of CF3SO3H in organic solvents to the corresponding alkylanthraquinones 7.
- Effenberger,Buckel,Maier,Schmider
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p. 1427 - 1430
(2007/10/03)
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- SYNTHESIS OF SUBSTITUTED tert-BUTYLANTHRAQUINONES
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The oxidation of 2-methyl-5-tert-butyldiphenylmethane and its 4'-methyl-, chloro-, and nitro-substituded derivatives by potassium permangate in a mixture of pyridine and water leads to the formation of the correspoding 2-benzoyl-4-tert-butyl-benzoic acids, which are converted by the action of sulfuric acid with heat into substituted 2-tert-butylanthraquinones.The cyclization of 2-benzoyl-4-tert-butylbenzoic acids containig a tert-butyl group or chlorine atom in the benzoyl ring is accompanied by a Hayashi rearrangement, which leads to the formation of mixtures thecorresponding 2,6- and 2,7-disubstituted anthraquinones.
- Pozdnyakovich, Yu. V.,Savyak, R. P.,Shein, S. M.
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p. 532 - 538
(2007/10/02)
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- N.M.R. Spectra and Conformations of 9,10-Dihydroanthracenes
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The preparation of a series of substituted 9,10-dihydroanthracenes is described and their proton n.m.r. spectra are dicussed.It is suggested that the trans-isomers of 9,10-dialkyl-9,10-dihydroanthracenes, substituted in the 9,10- or peri-positions adopt a polar ring conformation with the 9,10-dialkyl substituents placed over the ring.It is further suggested that the highfield signal of the β-protons of the 9,10-dialkyl substituents is due to partly to the magnetic anisotropy of the aromatic rings, and partly to the magnetic anisotropy of the carbon-carbon bonds from the alkyl groups to the 9- and 10-positions in the central ring.
- Ahmad, Naseer-ud-din,Cloke, Christopher,Hatton, Ian K.,Lewis, Norman J.,MacMillan, Jake
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p. 1849 - 1858
(2007/10/02)
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- Manufacture of alkylanthraquinones
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A process for preparing alkylanthrquinones wherein the alkyl group contains from 2 to 5 carbon atoms such as 2-ethylanthraquinone, 2-t-amylanthraquinone or 2-t-butylanthraquinone by ring closure from the corresponding alkylbenzoylvenzoic acid is disclosed. The process involves adding a solution of the alkylbenzoylbenzoic acid to 100% concentrated sulfuric acid or up to 12% oleum, distilling off the solvent at from 20° to 60° C., heating the remaining solution to from 80° to 95° C. and preferably from 83° to 87° C. for 3 to 5 hours, diluting the remaining reaction mixture with water and separating the alkylanthraquinone product.
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- Process for the production of substituted anthraquinones
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Substituted anthraquinones are obtained by thermal or catalytic dehydrochlorination of the corresponding substituted ortho-benzoylbenzoic acid chloride. They may be used for the production of hydrogen peroxide and the synthesis of dyes.
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