- Ionic liquids as novel and recyclable reaction media for N-alkylation of amino-9,10-anthraquinones by trialkyl phosphites
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Ionic liquids such as 1,3-dialkylimidazolium bromides make excellent catalysts and solvents for N-alkylation of amino-9,10-anthraquinones in the presence of trialkyl phosphites. For triethyl phosphite, [bpim][Br] gave better results. The ionic liquids are successfully regenerated and reused.
- Yavari, Issa,Kowsari, Elaheh
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- Perfluoroalkylquinones. Synthesis Using Bis(perfluoroalkanoyl) Peroxides, Absorption Bands, and Solubility
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The reactions of 1,4-benzo-, naphtho-, and 9,10-anthraquinones with bis(perfluoroalkanoyl) peroxides gave the corresponding perfluoroalkylated derivatives.Those of 2-methyl- and 2--1,4-naphthoquinones with bis(oxaperfluoroalkanoyl) peroxides afforded the dichloromethyl and trifluoromethyl derivatives, respectively.Absorption bands of the perfluoroalkylated naphtho- and anthraquinone dyes showed a slight hypsochromic shift.The solubilities of the perfluoroalkylated anthraquinone dyes into hexane were much more higher than those of the non-perfluoroalkylated ones.
- Matsui, Masaki,Kondoh, Shigeru,Shibata, Katsuyoshi,Muramatsu, Hiroshige
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- Method for synthesizing solvent dye intermediate
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The invention discloses a method for synthesizing a solvent dye intermediate. The dye intermediate is 1-methylaminoanthraquinone, and the method comprises the following steps: 1-aminoanthraquinone andchloromethane are used as the raw materials, and the target product is obtained by the condensation reaction under the action of a catalyst and an acid binding agent in a polar solvent. The route that 1-methylaminoanthraquinone is synthesized by using 1-aminoanthraquinone and chloromethane as the raw materials does not have nitrosamine formation, the high quality solvent dye intermediate is produced, and the quality of downstream products is improved. Moreover, the method uses ammonium chloride, ammonium acetate or ammonium nitrate as the reaction catalyst, the selectivity of the main productsecondary amine is improved, and the side reaction tertiary amine production is reduced.
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Paragraph 0026-0035
(2019/07/16)
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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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- Process for preparing substituted aminoanthraquinones
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Substituted aminoanthraquinone compounds, which are used for dye stuffs or intermediate thereof, represented by the formula (II) STR1 wherein R3 represents a C1 -C6 alkyl group which may be substituted, X represents a hydrogen atom, --COR1 or --SO2 R2 wherein R1 and R2 each represents a substituted or unsubstituted C1 -C4 alkyl or C6 -C12 aryl group, and Y and Z represent independently a hydrogen atom, a halogen atom, a nitro group or a C1 -C4 alkyl group, is prepared by allowing anthraquinone compounds represented by the formula STR2 wherein X, Y and Z are as defined above, to react with alkylating agents in organic solvents in the presence of organic quaternary ammonium salts and alkalies.
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- Facile synthesis of substituted n-monoalkylaromatic amines under PTC conditions
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Substituted aromatic amides were alkylated under PTC conditions. Compounds with ortho electron withdrawing substituents furnished exclusively monoalkyl amines. A plausible mechanism has been suggested.
- Kalkote,Choudhary,Natu,Lahoti,Ayyangar
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p. 1889 - 1900
(2007/10/02)
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- Phase transfer catalysed N-monoalkylation of amino anthraquinones
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1-Alkylaminoanthraquinones (2a-f) and 1,4-bisalkylaminoanthraquinones (4a-c) were prepared from aminoanthraquinones (1,3) by alkylation with alkyl sulphate/alkyl halide in presence of powdered sodium hydroxide, potassium carbonate and phase transfer catalyst.
- Ramrao,Ramkumar,Anant,Ramanuja
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p. 1129 - 1135
(2007/10/02)
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- Formation of N-N and N-C Bond-Cleavage Products in Displacements with N,N-Disubstituted Hydrazines on 1-Halo- or 1,4-Dihaloanthracene-9,10-diones
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The displacements of 1-halo- and 1,4-dihaloanthracene-9,10-diones by N,N-disubstituted hydrazines have been studied.These reactions proceed via N-N bond cleavages of the hydrazine to yield products with the regiospecific incorporation of an N,N-disubstituted amino group.In addition, pyrazoles which arise from intermediates which undergo N-C bond cleavage are also formed.The ratio of the N-N to N-C cleavage products is dependent on the reaction solvent, temperature, structure of the hydrazine, and the nature of the leaving group being displaced from the anthracene-9,10-dione.For example, treatment of 1a with N,N-dimethylhydrazine in pyridine or dimethyl sulfoxide (DMSO) leads to 3a:2c ratios of 6 and 3, respectively.Compound 1e under comparable reaction conditions gives 3a:2c product ratios of 49 and 4, respectively.The dichloro dione 1c with N,N-dimethylhydrazine in pyridine or DMSO leads predominantly to 3b in 76percent and 72percent yields, respectively, with relatively little pyrazole 2d.The more reactive difluoro dione 1h on reaction with N,N-dimethylhydrazine in pyridine leads to N-N bond-cleavage products 3c (48percent) and 3d (40percent).Treatment of 1e with 1-piperidinamine in pyridine yields 3f.The results will be discussed.
- Krapcho, A. Paul,Avery, Kenneth L.
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p. 5927 - 5929
(2007/10/02)
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- REACTION OF 1-CHLORO- AND 1-NITROANTHRAQUINONES WITH 3-ALKYLAMINO- AND 3-DIALKYLAMINOPROPIONITRILES
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The reaction of 1-chloro- and 1-nitroanthraquinones with 3-alkylaminopropionitriles at 130-170 deg C leads to the formation of 1-alkylaminoanthraquinones; the reaction with 3-dialkylaminopropionitriles leads to 1-dialkylaminoanthraquinones, which undergo thermal cleavage under the reaction conditions (isoamyl alcohol, 130 deg C) with the formation of 1-alkylaminoanthraquinone.The nature of the substituted atom affects the reaction rate; the nitro group is substituted 54 times more quickly than the chlorine atom.The initial reaction rates in alcohols are 2-3 orders of magnitude higher than in benzene.
- Vostrova, V. N.,Plakidin, V. L.
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p. 939 - 942
(2007/10/02)
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- SOME RELATIONSHIPS IN THE SYNTHESIS OF BIARYLS FROM HALOGENOANTHRAQUINONES
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The effects of the solvent and the concentration of the reagents on the reaction path and on the results of the synthesis of biaryls from halogenoanthraquinones were investigated for the case of the reaction of 1-chloro-4-benzoylaminoanthraquinone with copper.The use of concentrated reaction mixtures and of donating aprotic dipolar solvents with copper-aryl halide ratios slightly exceeding an equimolar ratio leads to a reduction in the induction period and to an increase in the yield of the biaryls.This explained by interaction between the copmonents of the metal-aryl halide-solvent complex.
- Koshelev, V. I.,Paramonova, L. N.,Filippov, M. P.
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p. 557 - 562
(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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- Reactions of 1,5-Dichloroanthrachinone with Nucleophiles
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Reactions of 1,5-dichloroanthraquinone (1) with various nucleophiles were examined to evaluate possibilities for selective substitution. 1-Amino-5-chloroanthraquinone was obtained from 1 by reaction with (a) sodium azide in dimethyl sulfoxide and (b ammonia in the presence of potassium fluoride, but 1 with potassium in ammonia gave 3-chlorobenzoic acid.Conditions were found for preferential substitution in reactions of 1 with (c) 4-toluidine, (d) hexamethylphosphoric triamide, and (e) N-methylformamide.Reagent e is preferred for making 1-chloro-5-(methylamino)anthraquinone, though this compound predominates in mixtures produced when d is used.Potassium hydroxide in 2-ethoxyethanol converts 1 to the corresponding mono- and diethers of 1,5-dihydroxyanthraquinone, while sodium hydrosulfide and 1 give bis(5-chloroanthraquinonyl)sulfide.
- Ruediger, Edward H.,Kaldas, Magdy L.,Ghandi. Sham S.,Fedryna, Cristi,Gibson, Martin S.
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p. 1974 - 1978
(2007/10/02)
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- USE OF ARYLAMINOANTHRAQUINONES AS AZO COMPONENTS
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1-Phenylaminoanthraquinone enters into azo coupling with diazo compounds of the 2,4-dinitrobenzenediazonium type and, in the presence of an N-methyl group or of electron-donating substituents at position 3 of the phenyl group, with 4-nitrobenzenediazonium salts to form 1-(4-arylazophenyl)anthraquinones.Derivatives of 2-phenylamino- and 1-hydroxy-4-phenylaminoanthraquinones and also 1,5- and 1,8-bis(phenylamino)anthraquinones react similarly, whereas 1-amino-, 1-methylamino-, and 1-phenylamino-4-phenylaminoanthraquinones are only capable of azo coupling in the form of the 1-N-acyl derivatives.
- Kazankov, M. V.,Ginodman, L. G.
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p. 2039 - 2044
(2007/10/02)
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- Photochemical Substitution of Amino- and Hydroxy-anthraquinones
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Irradiation of 1-aminoanthraquinone with visible light in the presence of an excess of either sodium sulphite or sulphide in 50percent aqueous pyridine gives exclusively sodium 1-aminoanthraquinone-2-sulphonate and -2-thiolate, respectively, in good yield.Under similar conditions with sodium sulphite, 1-methylamino-, 1-amino-4-chloro-, and 1-amino-5-chloro-anthraquinone give the respective sodium 2-sulphonate only, while 2-aminoanthraquinone gives the sodium 3-sulphonate.In contrast, 1-hydroxyanthraquinone gives a mixture of the sodium 2- and 4-sulphonates and disodium 2,4-disulphonates.The different substitution pattern observed for 1-amino- and 1-hydroxy-anthraquinone has been rationalised by application of semi-empirical molecular orbital theory.
- Hamilton, Kenneth,Hunter, John A.,Preston, Peter N.,Morley, John O.
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p. 1544 - 1548
(2007/10/02)
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- Process for the manufacture of aminoanthraquinones
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A process for the manufacture of aminoanthraquinones, wherein nitroanthraquinones are reacted in dipolar aprotic solvents which contain --SO2 -- or --SO-- groups and are inert to the reactants, with aliphatic, aliphatic-aromatic, cycloaliphatic, substituted or unsubstituted primary or secondary amines of the formulae R--NH2 or R--R'--NH, in which R and R' are radicals that are the same or different, such as alkyl, aralkyl, cycloalkyl, hydroxyalkyl radicals of 1 to 8 carbon atoms.
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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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