- A facile method for preparing substituted 1-aminoanthraquinones
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An efficient and simple preparation of α-substituted aminoanthraquinones using 2,2,-dialkoxyethylamines is described.
- Wormser,Sardessai,Abramson
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- Kinetic Studies on the Amination of Leucoquinizarin
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Leucoquinizarin reacts with amines to give mono- and diaminoanthraquinones.The amination mechanism of leucoquinizarin was investigated on the basis of the kinetics and structures of leuco compounds.The amination reaction of leucoquinizarin was characterized as follows.This amination proceeded in polar solvent but not in nonpolar solvent at all.The reaction rate was not influenced by the addition of a small amount of water (95percent ethanol) but enhanced largely in 80percent ethanol.This amination reaction has a low activation energy (ΔE=5.7-9.0 kcal mol-1) and an extraordinarily small pre-exponential term (A=103 - 105 mol-1min-1).Leucoquinizarin was proposed to be aminated by the addition of amine to carboynl group at its 1,4-position.The oxidation of leuco monoaminohydroxyanthraquinone was also examined.
- Kikuchi, Masashi,Yamagishi, Takamichi,Hida, Mitsuhiko
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- Antitumor Agents-CLXVII. Synthesis and structure-activity correlations of the cytotoxic anthraquinone 1,4-bis-(2,3-epoxypropylamino)-9,10-anthracenedione, and of related compounds
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1,4-Bis-(2,3-epoxypropylamino)-9,10-anthracenedione (3) was synthesized in this laboratory and was found to be a potent antitumor agent. Derivatives of this compound containing anthraquinone, naphthoquinone, and quinone skeletons were also prepared and evaluated for in vitro cytotoxic activity in several cell lines. These molecules were designed as bifunctional antitumor agents with the potential to act as (1) intercalating agents due to their planar backbones, and (2) alkylating agents due to the presence of alkylating moieties in their side chains. Compounds with an anthraquinone skeleton and propylamino side chains containing epoxides or halohydrins as the alkylating species showed greater activity than similar compounds with naphthoquinone or quinone skeletons. Compounds without these alkylating functionalities (e.g., with alkene or amino groups) were generally inactive. Hydroxy substitution on the planar skeleton in conjunction with alkylating side chains gave compounds with the most potent cytotoxic activity. The position of the hydroxy groups and side chains could be varied without substantially affecting activity. Activity was retained when an epoxypropyloxy side chain was substituted for the epoxypropylamino side chain in the parent compound.
- Johnson, Mary G.,Kiyokawa, Hiroshi,Tani, Shohei,Koyama, Junko,Morris-Natschke, Susan L.,Mauger, Anthony,Bowers-Daines, Margaret M.,Lange, Barry C.,Lee, Kuo-Hsiung
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- COMPOUND, PHOTOSENSITIVE RESIN COMPOSITION COMPRISING THE SAME, PHOTO RESIST, COLOR FILTER, AND DISPLAY DEVICE
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The present specification provides a compound represented 1 by chemical formula I, a, photosensitive, resin composition including the same, a color filter, a color filter, and a display. device including the same. (by machine translation)
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- BROMINATION OF 2-BENZOYLBENZOIC ACIDS
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A new method was developed for the synthesis of bromine-substituted 9,10-anthraquinones by bromination of 2-benzoylbenzoic acid derivatives in the presence of sulfuric and nitric acids followed by cyclization.
- Popov, S.I.,Kopylova, T.M.,Andrievskii, A.M.,Medvedev, S.V.,Yatsenko, A.V.
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p. 279 - 285
(2007/10/02)
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- Selective Photoalkylamination and Photohydroxylation of Aminoantraquinones and their N-Acylated Derivatives
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The selective introduction of hydroxy and alkylamino groups into the anthraquinone nucleus was achieved by the photochemical reaction of some aminoantraquinones and their N-acylated derivatives with alkylamines under aerobic conditions.
- Yoshida, Katsuhira,Hikasa, Masahiro,Ishii, Katsutoshi,Kadota, Hisa,Yamashita, Yoshio
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p. 758 - 759
(2007/10/02)
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- Kinetics and product studies on Ullmann amination of 1-halogenoanthraquinones catalysed by copper(I)salts in acetonitrile solution
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The kinetics and products of reactions of some primary amines (RNH2) with 1-halogenoanthraquininone (AQX) promoted by copper salts, particularly tetrakis(acetonitrile)copper(I) tetrafluoroborate, have been investigated in acetonitrile solution at 70 deg C.Provided that oxygen does not come into contact with solutions of the copper(I) salt and amine, the kinetics of the reactions have the simple form v = k, and the products consist almost entirely of the aminated anthraquinone, AQNHR, and dehalogenated material, AQH, their ratio being directly proportional to .The reaction rate is dependent on the identity of the departing halogen X, decreasing in the sequence I > Br > Cl, but the product ratio is little affected.N-Deuteration of the reactant amine gives rise to a small kinetic isotope effect, but the product ratio is unaffected.Conversely deutearation on the α-carbon atom of the amine has little kinetic effect but leads to a four-fold increase in the ratio of aminated to dehalogenated product.The observations are interpreted in terms of (i) formation of a copper(I)-amine complex, (II) activation of this species for attack on AQX by proton abstraction from an amine ligand by a free molecule (stepwise or concerted), and (iii) generation of an arylcopper(III) intermediate which is partitioned between formation of AQNHR by attack of an externel amine molecule and formation of AQH by an intramolecular process involving hydrogen transfer from the α-carbon atom in the amine ligand generated in (ii).Exposure of the initial copper(I)-amine complex to oxygen leads to a new complex, itself capable of reacting with AQX, which on prolonged incubation at 70 deg C in the presence of an excess of amine is transformed back to its original state.
- Bethell, Donald,Jenkins, Iwan L.,Quan, Peter M.
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p. 1789 - 1796
(2007/10/02)
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- Synthesis of 2-Chloro-6,11(5H)-morphanthridinedione and Its Rearrangement to 1-Amino-4-hydroxyanthraquinone
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p-Nitrochlorobenzene (I) condenses with o-carboxyphenylacetonitrile (II) in methanolic potassium hydroxide to produce 3-(2'-carboxyphenyl)-5-chloro-2,1-benzisoxazole (III).Reduction of III leads to a novel synthesis of 2-chloro-6,11(5H)-morphanthridinedione (V) in good yields.The acid catalysed rearrangement of V affords 1-amino-4-hydroxyanthraquinone (VI).
- Prabhu, V. S.,Seshadri, S.
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p. 163 - 164
(2007/10/02)
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- C-FORMYLATION OF α-PHENYLAMINOANTHRAQUINONES WITH FORMALDEHYDE. REACTION OF α-AMINOANTHRAQUINONES WITH FORMALDEHYDE IN SULFURIC ACID
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The reaction of α-phenylaminoanthraquinones with formaldehyde in concentrated sulfuric acid leads to formylation at the para position of the phenyl group.The possibility of extending the reaction to related systems was demonstrated for the case of 6-phenylamino-N-methylanthrapyridone.It is suggested that the intermediate compounds in the C-formylation, N-methylation, and demethylation respectively of α-amino and α-methylaminoanthraquinones are 7H-7-oxoanthra-1,3-oxazinium cations.
- Kazankov, M. V.,Ginodman, L. G.,Mustafina, M. Ya.
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p. 526 - 533
(2007/10/02)
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- The Schmidt reaction of anthraquinones
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Schmidt reaction (sodium azide/sulfuric acid) of 1,5- and of 1,8-dichloroanthraquinones gives, in each case, both of the theoretically possible lactams (2,3,5,6-dibenzoazepin-4,7-diones).Two of the four theoretically possible lactams have been identified from Schmidt reaction of 1- and 2-chloroanthraquinones respectively.Methods used include:(a) preferential hydrolysis of one lactam and identification of the isomeric aminoanthraquinone formed on cyclodehydration of the resulting amino acid; (b) identification of the isomeric aminoanthraquinone(s) formed on direct treatment of a lactam (or mixture of lactams) by sulfuric acid; (c) cleavage by potassium tert-butoxide of the amino acid formed by preferential hydrolysis of one lactam and identification of the resulting benzoic acid as its methyl ester.
- Flemming, Cecily A.,Gandhi, Sham S.,Gibson, Martin S.,Ruediger, Edward H.
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p. 624 - 628
(2007/10/02)
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- PHOTOCHEMICAL HYDROXYLATION OF ANTHRAQUINONE IN SULFURIC ACID
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The photolysis of anthraquinone in sulfuric acid leads to hydroxylation of its ring with the preferential formation of 2-hydroxyanthraquinone in concentrated and 1-hydroxyanthraquinone in dilute sulfuric acid.The second hydroxy group only enters photochemically at position 4 of 1-hydroxyanthraquinone if the latter is activated by complex formation with boric acid.During photolysis in deaerated sulfuric acid the nitroanthraquinones are reduced photochemically to (hydroxyamino)anthraquinones; here 1-(hydroxyamino)anthraquinones with an unoccupied para position in the same condensed benzene ring undergo rearrangement under the reaction conditions to 1-amino-4-hydroxyanthraquinones.The main photochemical stage of hydroxylation in concentrated sulfuric acid is nucleophilic substitution of hydrogen in the monoprotonated anthraquinone by the HSO4(-) ion, while in dilute sulfuric acid it is electron transfer from water to anthraquinone.
- Studzinskii, O.P.,El'tsov, A.V.
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p. 1666 - 1673
(2007/10/02)
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- NUCLEOPHILIC SUBSTITUTION OF HYDROGEN IN AROMATIC SYSTEMS. II. MECHANISM OF AMINATION IN ANTHRAISOXAZOL-6-ONES
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The nucleophilic substitution of the C5-H hydrogen atom in anthraisoxazol-6-ones by amines in acetonitrile in the absence of Cu2+, Ag+, Co2+, or Ni2+ cations takes place with the formation of strong hydrogen bond in the sixmembered chelate ring of the product from 1,4-addition of the amine to the isoxazolone at the C5 and =O atoms.The structure of the reaction product is determined by the character of the amine, and (with the absence of readily eliminated groups) substitution of C5-H is suppressed by the competing amination of C3-H and reduction of the heterocycle.The substitution of C5-Hlg by amines under analogous conditions leads to trivial reaction products.In nitromethane C3-H or C3-Hlg is mainly substituted, and C5-H or C5-Hlg is partly substituted, leading to products with trivial structures.In the presence of Cu2+, Ag+, Co2+, Ni2+ cations in acetonitrile only C3-H or C3-Hlg is substituted through the formation of mixed complex of amine and isoxazolone on the cation.
- Galushko, A. M.,Dokunikhin, N. S.
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p. 1347 - 1357
(2007/10/02)
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- REACTIONS OF 1-ACETOXY-9,10-ANTHRAQUINONES WITH THE FORMATION OF DERIVATIVES OF 1,10-ANTHRAQUINONE AND 10-ANTHRONE
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The action of alkali-metal alkoxides on 1-acetoxy-9,10-anthraquinone and its nitro and amino derivatives under mild conditions leads to the formation of the corresponding 9,9-dialkoxy-1-hydroxy-10-anthrones.For the 4-amino-substituted 1-acetoxyanthraquinones the intermediately formed 4-amino-substituted 9-alkoxy-1,10-anthraquinones were isolated.The structures of the 9,9-dialkoxy-1-hydroxy-10-anthrones were proved by their chemical transformations.
- Popov, S. I.,Volosenko, V. P.
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p. 127 - 131
(2007/10/02)
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- Process for the preparation of 1-aminoanthraquinones
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A selective process for the preparation of 1-aminoanthraquinones from the corresponding 1-aminoanthraquinone-2-carboxylic acid by decarboxylation in basic solution in the presence of iron, tin or zinc as a catalyst.
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- Process for the preparation of 1-aminoanthraquinones
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A selective process for the preparation of 1-aminoanthraquinones from the corresponding 1-aminoanthraquinone-2-carboxylic acid by decarboxylation in an acid solution in the presence of iron or zinc as a catalyst.
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- Process for the manufacture of aminohydroxyanthraquinones
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The invention relates to a process for the manufacture of an aminohydroxyanthraquinone of the formula STR1 wherein both of X are hydrogen or one X is --NH2 and the other is --OH and Z is hydrogen, C1 -C4 alkyl or carboxyl, with the proviso that, if Z is C1 -C4 alkyl or carboxyl, both of X must be hydrogen, which process comprises reacting a nitroanthraquinone of the formula STR2 wherein both of Y are hydrogen or one Y is --NO2 and the other is hydrogen and Z is as defined for formula (1), with the proviso that, if Z is C1 -C4 alkyl or carboxyl, both of Y must be hydrogen, in an aprotic dipolar solvent, with an alkali metal azide or alkaline earth metal azide, in the temperature range between 0° and 30° C. The reaction products are disperse dyes or intermediates for obtaining vat dyes and disperse dyes.
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- Process for the reductive removal of halogen atoms from anthraquinones
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A process for the reductive removal of halogen atoms from amino-, acylamino- or hydroxyanthraquinones, said halogen atoms being bonded in the α-position and/or ortho-position to amino, acylamino or hydroxyl groups, which comprises carrying out the reductive removal in basic medium with hydrazine or hydrazine derivatives.
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- Process for the preparation of 1-aminoanthraquinones
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A selective process for the preparation of 1-aminoanthraquinones by decarboxylation of the corresponding 1-aminoanthraquinone-2-carboxylic acid in an alkaline solution with an alkali metal hydrosulfite.
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