- Photoinduced electron transfer from excited [tris(2,2'- bipyridine)ruthenium(II)]2+ to a series of anthraquinones with small positive or negative Gibbs energy of reaction. Marcus behavior and negative activation enthalpies
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In the electron transfer (ET) quenching reactions of electronically excited *Ru(bpy)32+ in acetonitrile an increase of the rate constant k(q) is observed in the series of 2-methyl-, 1-chloro-, and 1-nitro-anthraquinone as quenchers. If alkali salts are used as supporting electrolytes the AQ·- radical anions are found to form specific associates with the alkali cations. In the presence of non-associating tetraalkylammonium salts the system follows the predictions of Marcus theory. Numerical methods are developed which allow the determination of the rate constants of the conventional reaction scheme. This analysis shows that the quantum yield of free AQ*- radical anion formation is governed by the interplay of forward, reverse and back ET. Negative activation enthalpies are found for the activation controlled quenching reactions. From the numerical analysis of the system of rate constants it is inferred that this phenomenon is due to the elementary ET step in the reaction sequence. We discuss the pre-equilibrium and elementary reaction models for reactions with negative activation enthalpy and present, to our knowledge, the first example of successful discrimination between them.
- Frank, Rudolf,Greiner, Gerhard,Rau, Hermann
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Read Online
- Clamping device anthraquinone compound in the preparation of antineoplastic application
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The invention relates to application of dianthraquinonyl, in particular to application of dianthraquinonyl compounds to preparing anti-tumor medicine. Radioactive therapeutic nuclides are labeled on dianthraquinonyl medicine, and accordingly the labeled medicine with excellent tumor targeting can be obtained. The application has the advantages that the compounds can be gathered on dead cells and tissues in tumors and are provided with instable chemical elements or isotopes, accordingly, radiation can occur, surrounding cells and tissues can be destroyed, and the purpose of treating tumors can be achieved.
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Paragraph 0072; 0073; 0074
(2019/01/14)
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- The invention relates to a pyrrolidone ionic liquid as catalyst preparation 1 - nitroanthraquinone method
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The invention belongs to the technical field of anthraquinone dye intermediate synthesis, and particularly relates to a method for preparing 1-nitroanthraquinone through location nitration by using pyrrolidinone ionic liquid as a catalyst. The method comprises the step of preparing the 1-nitroanthraquinone by using anthraquinone and a nitration agent as raw materials and using the pyrrolidinone ionic liquid as the catalyst. The method has the advantages that the purity of the crude 1-nitroanthraquinone product obtained in a catalytic nitration process is increased to 90% or more, the catalyst preparation is simple, the cost is reduced, and the quantity of solid waste residues generated in a refinement process is reduced.
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Paragraph 0028; 0029; 0030; 0031; 0032; 0033; 0034-0040
(2018/03/26)
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- A 1-aminoanthraquinone method for the synthesis of
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The invention relates to a method for synthesizing 1-aminoanthraquinone. According to the method, the dosage of anthraquinone and nitric acid is adjusted in a mixed solvent in the presence of a catalyst, the depth of nitrification is controlled, anthraquinone is subjected to partial nitrification by using a mixed-acid nitrification method, so as to produce 1-nitroanthraquinone, and then, 1-aminoanthraquinone is synthesized through reduction reaction; the solvent used is one or more of dichloroethane, dimethyl formamide, xylene, chlorobenzene and toluene; mixed acid used means a mixture prepared from fuming nitric acid and fuming sulfuric acid; the catalyst used is para-toluenesulfonic acid and salt thereof; during the nitrification of the method, 1-nitroanthraquinone is mainly produced, and 1,8-dinitroanthraquinone, 1,5-dinitroanthraquinone, 1,7-dinitroanthraquinone, 1,6-dinitroanthraquinone and 2-nitroanthraquinone are not produced; the yield of the product, namely 1-aminoanthraquinone, is 95-99%, the purity is high (over 99%), refining is not required, the production cost is low, the operation is simple and convenient, and the industrial production is convenient to realize.
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Paragraph 0016; 0032-0033; 0036-0037; 0040-0041
(2019/02/02)
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- Non-reductive conversion of 1-nitro-9,10-anthraquinone to 1-amino-9,10-anthraquinones
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Heating 1-nitro-9,10-anthraquinone 2 with ureas 4 in N,N,N',N'-tetramethylurea (TMU) at around 130 °C resulted in the displacement of the nitro group by the amino groups, leading to the corresponding aminoanthraquinones 5 in good yields.
- Suzuki,Kawakami,Maeda
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p. 9217 - 9220
(2007/10/02)
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- An efficient procedure for the preparation of 1-nitroanthraquinone
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A novel and efficient method is developed for the selective mono nitration of anthraquinone (1). A mixture of fuming nitric acid, sulfuric acid and phosphoric acid in carbon tetrachloride is introduced as a new nitrating system for the high yield preparation of 1-nitroanthraquinone.
- Sharghi,Tamaddon
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p. 2349 - 2359
(2007/10/02)
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- Process for the preparation of 1-nitroanthraquinone
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A process for the preparation of 1-nitroanthraquinone by oxidising 1-nitro-5,8,11,12-tetrahydroanthraquinone with oxygen, inorganic peroxo compounds or metal oxides.
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- NITRATION OF AROMATIC COMPOUNDS CATALYZED BY ZrO2/SO42-
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Catalytic activity was demonstrated for zirconium dioxide, which is a solid acid, modified by sulfate ions in the nitration of inactive aromatic compounds.
- Nagi, Sh. M.,Zubkov, E. A.,Shubin, V. G.
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p. 1500 - 1502
(2007/10/02)
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- Nitrodienamines: An Easy Synthesis and Cycloaddition Reactions with α,β-Unsaturated Carbonyl Compounds and Quinones
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The nitrodienamine 6 was synthesized through the vinamidinium salt 7.The reactivity of 6 was investigated with the α,β-unsaturated carbonyls and styrene 8-14, and the quinones 15, 16, 25, 29, 31, 33, 37, and 41.Keywords: nitrodienamine; synthesis; cycloaddition; α,β-unsaturated carbonyl; quinone; vinamidinium salt
- Takeuchi, Naoki,Ohki, Junji,Tobinaga, Seisho
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p. 481 - 487
(2007/10/02)
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- Method for producing 1-nitroanthraquinone
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Anthraquinone is nitrated using a mixed acid comprising sulfuric acid and nitric acid, the concentration of sulfuric acid being 70 to 76% by weight and the amount of nitric acid being 33 to 55% by weight based on the total weight of sulfuric acid and nitric acid, whereby 1-nitroanthraquinone is obtained in a high yield and a high purity.
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- Process for the mononitration of anthraquinone
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A process has been developed for the mononitration of anthraquinone to 1-nitroanthraquinone with nitric acid/sulphuric acid mixtures wherein anthraquinone is nitrated in a nitric acid/sulphuric acid mixture, in which the weight ratio of nitric acid to sulphuric acid is about 1:1 to about 2:1, in which the weight ratio of sulphuric acid to anthraquinone is about 0.5:1 to about 1:1 and in which the weight ratio of sulphuric acid to water is about 2.5:1 to about 5.5:1, the weight ratios relating to the sum of the materials employed, at temperatures in the range from about 45° to 70° C. until the anthraquinone content is less than 3% by weight, relative to the sum of the anthraquinone compounds.
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- Continuous reduction process
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A process for the reduction of aromatic nitro compounds to amino compounds in the liquid phase using iron as reducing agent, which comprises carrying out the reduction continuously such that the reducing iron, based on the amount of nitro compound present in the reactor, is present in an amount substantially in excess of the stoichiometric amount, and effecting the continuous removal of the reaction products such that the substantial excess of reducing iron is also constantly present in the reactor during the reduction.
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- Process for preparing highly pure 1-nitroanthraquinone
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1-Nitroanthraquinone is produced in highly pure form by a process comprising the steps of partially oxidizing 3-nitro-o-xylene (I) to 2-methyl-3-nitrobenzoic acid (II) converting II to 2-methyl-3-nitrobenzoyl halide (III), converting III to the novel intermediate 2-methyl-3-nitrobenzophenone (IV), oxidizing IV to 2-benzoyl-6-nitrobenzoic acid (V) and cyclizing V to 1-nitroanthraquinone.
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- Process for preparing pure 1-nitroanthraquinone
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Pure 1-nitroanthraquinone substantially free of dinitroanthraquinone is prepared by: 1. Nitrating anthraquinone or a mixture which contains anthraquinone with at least 90% nitric acid at a temperature of at least 0° C wherein the mole ratio of nitric acid to anthraquinone is less than 20 to 1; 2. Stopping the reaction when the anthraquinone conversion is at least 50% by cooling the reaction mixture to a temperature of at most 20° C and/or by adjusting the mole fraction of nitric acid in the reaction mixture to a value of at most 0.86; 3. Precipitating 1-nitroanthraquinone by adjusting the mole fraction of nitric acid to a value of from 0.7 to 0.4 and/or by reducing the temperature to at most 20° C; and 4. Separating the precipitated 1-nitroanthraquinone and subjecting it to vacuum distillation.
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- Production of 1-nitroanthraquinone and 1-aminoanthraquinone
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A process for producing 1-nitroanthraquinone with high purity which comprises treating crude 1-nitroanthraquinone containing as the main impurities dinitroanthraquinones and β-nitroanthraquinone with an alkali sulfite in an aqueous medium under heating and which is characterized in that the crystals of the crude 1-nitroanthraquinone are pulverized by the aid of a pulverizer, a fine pulverizer or an ultra-fine pulverizer prior to and/or during the treatment with the aqueous alkali sulfite; and a process for producing 1-aminoanthraquinone which comprises subjecting the reaction mixture obtained by the said treatment with the alkali sulfite solution mentioned above, if necessary after further fine pulverization, to a reaction with a reducing agent, or ammonia or an aliphatic or aromatic amine.
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- Process for the manufacture of 1-nitroanthraquinone
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Preparation of very pure 1-nitroanthraquinone by heating 1-nitroanthraquinone which contains dinitroanthraquinone with the aqueous solution of a salt of sulphurous acid in the presence of an inert organic solvent.
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- Process for the preparation of pure 1-nitroanthraquinone
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Process for the manufacture of pure 1-nitroanthraquinone, characterised in that a nitroanthraquinone mixture obtained by nitration of anthraquinone in the presence of inorganic acids and, optionally, lowering the molar fraction of the acids in the reaction mixture after isolation of the reaction products which have precipitated and, optionally, further measures, is subjected to a rectification.
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- Process for the preparation of 1-nitroanthraquinone
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Process for the preparation of 1-nitroanthraquinone by nitration of anthraquinone in the presence of highly concentrated nitric acid, characterised in that nitration is carried out at temperatures of 20° to 80°C, the reaction is terminated by lowering the nitric acid molar fraction in the reaction mixture to ≤0.85 by distilling off concentrated nitric acid and 1-nitroanthraquinone is precipitated by subsequently adjusting the nitric acid molar fraction to ≤0.7 to 0.4 and is separated off in a manner which is in itself known.
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- Process for the manufacture of 1-nitro-anthraquinone
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Pure 1-nitro-anthraquinone is produced by nitrating anthraquinone in aqueous hydrogen fluoride containing about 5 - 30 weight percent of water with nitric acid as nitrating agent at about 0° - 150°C preferably 20° - 70°C.
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- Process for preparing 1-nitro-anthraquinone
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1-Nitro-anthraquinone is separated from an anthraquinone nitration mixture in concentrated nitric acid by adding to the nitration mixture sulpholan and separating off the insoluble 1-nitro-anthraquinone. The quantity of sulpholan added is such that the mixture contains 10-90% by weight nitric acid and from 90-10% by weight sulpholan.
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