- Clean process for synthesizing 1, 4-dihydroxy anthraquinone
-
The invention relates to the technical field of dye intermediates, and especially relates to a clean process for synthesizing 1, 4-dihydroxy anthraquinone. The process comprises the following steps: sequentially adding 98% sulfuric acid, boric anhydride, phthalic anhydride and hydroquinone into a dry reaction container according to a stoichiometric ratio, uniformly stirring, heating to 100-180 DEG C, and carrying out heat preservation reaction for 2-24 hours; after the heat preservation reaction is finished, cooling the materials, and transferring the materials into another reaction container for hydrolysis; and after hydrolysis is completed, cooling, filtering and washing to obtain the 1, 4-dihydroxy anthraquinone. According to the clean process for synthesizing the 1, 4-dihydroxy anthraquinone, provided by the invention, the dosage of the raw material phthalic anhydride can be reduced, the wastewater treatment difficulty is greatly reduced, and the production cost is also reduced; and meanwhile, the yield of the 1, 4-dihydroxy anthraquinone is also improved to a certain extent.
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Paragraph 0020-0023
(2021/07/08)
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- Synthesis method of orange intermediate
-
The invention discloses a synthesis method of an orange intermediate, and belongs to the field of orange intermediates. The synthesis method of the orange intermediate comprises the following steps: 1, preparing 106-110% sulfuric acid as a solvent; 2, adding p-chlorophenol and excessive phthalic anhydride into a clean reaction container, adding a catalyst boric anhydride, and pouring the sulfuricacid solvent obtained in step 1 into the reaction container; 3, heating the reaction container to 190-200 DEG C, and reacting the p-chlorophenol and phthalic anhydride added in step 2 under the actionof a catalyst; and 4, after the reaction is finished, cooling, diluting, separating out upper wastewater, and filtering to obtain the orange intermediate. According to the scheme, 106-110% sulfuric acid is adopted as the solvent, boric anhydride is adopted as the catalyst, and hydrolysis of phthalic anhydride can be greatly reduced, so the use amount of phthalic anhydride is reduced, the yield isgreatly increased, phthalic anhydride is recycled, and COD of three wastes is greatly reduced.
- -
-
Paragraph 0029-0039
(2020/10/21)
-
- Evaluation of a series of 9,10-anthraquinones as antiplasmodial agents
-
Background: A phytochemical study on medicinal plants used for the treatment of fever and malaria in Africa yielded metabolites with potential antiplasmodial activity, many of which are Anthraquinones (AQ). AQs have similar sub-structure as naphthoquinones and xanthones, which were previously reported as novel antiplasmodial agents. Objective: The present study aimed to investigate the structural requirements of 9,10-anthraquinones with hydroxy, methoxy and methyl substituents to exert strong antiplasmodial activity and to investigate their possible mode of action. Methods: Thirty-one AQs were synthesized through Friedel-Crafts reaction and assayed for antiplasmodial activity in vitro against Plasmodium falciparum (3D7). The selected compounds were tested for toxicity and probed for their mode of action against β-hematin dimerization through HRP2 and lipid catalyses. The most active compounds were subjected to a docking study using AutoDock 4.2. Results: The active AQs have similar common structural characteristics. However, it is difficult to establish a structure-activity relationship as certain compounds are active despite the absence of the structural features exhibited by other active AQs. They have either ortho- or meta-arranged substituents and one free hydroxyl and/or carbonyl groups. When C-6 is substituted with a methyl group, the activity of AQs generally increased. 1,3-DihydroxyAQ (15) showed good antiplasmodial activity with an IC50 value of 1.08 μM, and when C-6 was substituted with a methyl group, 1,3-dihydroxy-6-methylAQ (24) showed stronger antiplasmodial activity with an IC50 value of 0.02μM, with better selectivity index. Compounds 15 and 24 showed strong HRP2 activity and mild toxicity against hepatocyte cells. Molecular docking studies showed that the hydroxyl groups at the ortho (23) and meta (24) positions are able to form hydrogen bonds with heme, of 3.49 A and 3.02 A, respectively. Conclusion: The activity of 1,3-dihydroxy-6-methylAQ (24) could be due to their inhibition against the free heme dimerization by inhibiting the HRP2 protein. It was further observed that the anthraquinone moiety of compound 24 bind in parallel to the heme ring through hydrophobic interactions, thus preventing crystallization of heme into hemozoin.
- Osman, Che Puteh,Ismail, Nor Hadiani,Widyawaruyanti, Aty,Imran, Syahrul,Tumewu, Lidya,Choo, Chee Yan,Ideris, Sharinah
-
p. 353 - 363
(2019/06/20)
-
- Fluorescent molecule for recognizing copper ions, preparation method and application
-
The invention discloses a fluorescent molecule for recognizing copper ions, a preparation method and application. Polycyclic aromatic hydrocarbons such as naphthalene rings or anthracene rings are used as initial raw materials; through a series of optimized organic synthesis reaction (substitution and addition), after the connection with different recognition sites, molecular clamp body tweezer host compounds with different recognition performance can be obtained. The fluorescent molecule can be used for copper ion detection and solves the problems that the existing molecule device is difficult to effectively recognize object molecules.
- -
-
Paragraph 0078; 0079; 0080; 0081
(2019/02/04)
-
- Synthesis method of anthraquinone derivatives and tetracenedione derivatives through benzannulation reaction
-
The present invention relates to a method for synthesizing anthraquinone derivatives and tetracene dione derivatives through a benzannulation reaction, which presents a novel synthesis method, capable of processing synthesis easily, conveniently, and efficiently under mild conditions by an organic catalyst. The synthesis method uses an L-proline catalyst which is nontoxic, economical and easily available, compared to conventional production methods, thereby providing the anthraquinone derivatives and the tetracene dione derivatives through the one-pot benzannulation reaction of an α, β-unsaturated aldehyde compound, various 1,4-naphthoquinone compounds or 1,4-anthracenedione compounds. Various forms of anthraquinone derivatives or tetracene dione derivatives prepared by the synthesis method can be widely used for synthesis of natural products, dyes, and pharmaceutical products.COPYRIGHT KIPO 2017
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-
Paragraph 0029-0030; 0045
(2017/08/09)
-
- Monitoring the activity of immobilized lipase with quinizarin diester fluoro-chromogenic probe
-
Ouinizarin diester is used as a fluoro-chromogenic substrate of the activity of lipase supported in poly(methylmetacrylate) beads (CALB, Novozymfi 435) dispersed in organic solvents. The monoester and diester of quinizarin are both non-fluorescent species contrasting with the enzymatic product quinizarin that shows optical absorption in the visible region and strong fluorescence signal. The enzymatic conversion is accomplished by spectroscopic measurements and it follows a sigmoid curve from which the mean reaction time of the enzymatic process can be determined. This parameter indicates the enzyme activity of the immobilized lipase. Its dependency with the amount of lipase allowed the determination of the ratio of the catalytic rate and the Michaelis constant (kc/Km) and the experimental value found was (1.0 ± 0.1) × 10?2 mg?1/min in the case of quinizarin diacetate.
- Sabatini, Carolina Aparecida,dos Santos, Denis Massucatto,da Silva, Sabrina Matos de Oliveira,Gehlen, Marcelo Henrique
-
-
- Visible-light photocatalytic activity of chitosan/polyaniline/CdS nanocomposite: Kinetic studies and artificial neural network modeling
-
Chitosan/polyaniline (CS/PAni), chitosan/CdS (CS/CdS) and chitosan/polyaniline/CdS nanocomposite were synthesized and characterized using X-ray diffraction pattern analysis, FT-IR spectroscopy and scanning electronic microscopy. The adsorption performance and photocatalytic activity of CS/PAni/CdS was compared with CS/PAni and CS/CdS in the removal of Reactive Blue 19 (RB19) dye. After five cycles of experiments under visible light irradiation, CS/PAni/CdS retained high photocatalytic activity which confirmed good stability of nanocomposite. Moreover, the kinetics of decolorization was investigated and novel equation rate for dye removal was established by considering two parallel mechanisms including adsorption and surface photocatalytic degradation of dye by CS/PAni/CdS. Artificial neural network was employed to develop a model for predicting the decolorization efficiency and determining the relative importance of operational parameters. A 3-layer perceptron network with optimized 5:10:1 topology could provide adequate predictive performance (R2 = 0.983). Moreover, the photocatalytic degradation of RB19 was monitored by measuring the total organic carbon (TOC) and GC-MS analysis, enabling the evaluating the mineralization and identifying the intermediates. During 120 min of experiment, more than 80% of TOC was removed.
- Rasoulifard,Seyed Dorraji,Amani-Ghadim,Keshavarz-Babaeinezhad
-
-
- Organocatalyzed benzannulation for the construction of diverse anthraquinones and tetracenediones
-
An efficient one-pot synthesis of anthraquinones and tetracenediones was achieved vial-proline catalyzed [4+2] cycloaddition of in situ generated azadiene from α,β-unsaturated aldehydes and 1,4-naphthoquinones or 1,4-anthracenedione in good to excellent yield. This protocol constitutes an unprecedented tandem benzannulation that allows one-pot construction of diverse anthraquinones and tetracenediones in the presence of organocatalysts. This methodology was applied successfully to the synthesis of naturally occurring molecules and photochemically interesting phenanthrenequinone derivatives.
- Somai Magar, Krishna Bahadur,Xia, Likai,Lee, Yong Rok
-
supporting information
p. 8592 - 8595
(2015/05/20)
-
- Synthesis of damnacanthal, a naturally occurring 9,10-anthraquinone and its analogues, and its biological evaluation against five cancer cell lines
-
Damnacanthal and nordamnacanthal, two naturally occurring 9,10-anthraquinones, and their analogues were synthesized. Cytotoxic activity against five cancer cell lines was evaluated using MTT assay. 2-Bromomethyl-1,3-dimethoxyanthraquinone was found to display the highest activity against all cell lines with IC50 range of 2-8 μM. Structure-activity relationship (SAR) assessment was considered to rationalise the cytotoxic effect. Bromomethyl group at position C-2 of the anthraquinone was found to be important in exerting cytotoxic activity of this class of compounds. The presence of the flanking methoxyl or hydroxyl groups at C-1 and C-3 also contributes to this activity. Finally, the antioxidant effect of these compounds was evaluated. MTT assay was used to measure the cytotoxicity against different cancer cell lines. Antioxidant activity was measured by FTC and TBA methods. Only two anthraquinones, damnacanthal and nordamnacanthal, were found to be antioxidative.
- Saha, Koushik,Lam, Kok Wai,Abas, Faridah,Sazali Hamzah,Stanslas, Johnson,Hui, Lim Siang,Lajis, Nordin H.
-
p. 2093 - 2104
(2013/07/26)
-
- Combined spectral experiment and theoretical calculation to study the interaction of 1,4-dihydroxyanthraquinone for metal ions in solution
-
The interaction between 1,4-dihydroxyanthraquinone (1,4-DHA) and metal ions was studied by UV-Visible and fluorescence spectroscopies in solution. Time-dependent density functional theory calculations confirmed complex structures. The investigation results showed 1,4-DHA can selectively respond some metal ions and can be monitored by UV-Vis, fluorescence spectra and naked-eye. So 1,4-DHA has a potential application in the design of metal ions probe. More, as typical metal ions, Hg2+ and Er3+, their reaction abilities for 1,4-DHA were studied in detailed. Experimental results showed they have better response for 1,4-DHA. And theoretical calculation concluded that Er3+ easily reacts with 1,4-DHA over Hg2+ attributed to the low reaction energy of Er3+-1,4-DHA than Hg 2+-1,4-DHA.
- Yin, Caixia,Zhang, Jingjing,Huo, Fangjun
-
supporting information
p. 772 - 777
(2013/11/06)
-
- Tetraanthraquinonoporphyrazines: III.1 Synthesis and physicochemical properties of metal complexes of hydroxy-substituted tetraanthraquinonoporphyrazines
-
Methods have been developed for the synthesis of metal complexes of hydroxy-substituted tetraanthraquinonoporphyrazines. The yield of the target products has been improved via complexation with the corresponding methoxy derivatives and subsequent hydrolysis of the methoxy groups. Some physicochemical properties of substituted 9,10-dioxo-9,10-dihydroanthracene-2,3- dicarboxylic acids and tetraanthraporphyrazine metal complexes derived therefrom have been studied. Pleiades Publishing, Ltd., 2012.
- Borisov,Maizlish,Shaposhnikov,Korzhenevskii,Shikova,Sokolova,Koifman
-
p. 1740 - 1747
(2013/02/23)
-
- Comparative synthetic study of 1,4-dihydroxy anthraquinone (quinizarin) dye intermediate
-
1,4-Dihydroxy anthraquinone (quinizarin) has been synthesised with two different precursors' p-chlorophenol and hydroquinone by condensation of phthalic anhydride. It has been noticed that p-chlorophenol gave higher yield as compared to hydroquinone on reaction with phthalic anhydride at 200°C within 3:30 hours in a mixture of concentrated H2SO4 and boric acid. Three disperse dyes have been prepared from the quinizarin. The physical properties of three different colored dyes have also been discussed.
- Bhatti, Khalid Pervez,Zuber, Muhammad
-
experimental part
p. 758 - 763
(2012/07/28)
-
- Direct access to 1,4-dihydroxyanthraquinones: The Hauser annulation reexamined with p-quinones
-
(Chemical Equation Presented) 3-Phenylsulfanylphthalides (e.g. 8a) readily react with p-benzoquinones in the presence of LiOtBu in THF to furnish 1,4-dihydroxyanthraquinones in good yields and one-pot operations.
- Mal, Dipakranjan,Ray, Sutapa,Sharma, Indrajeet
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p. 4981 - 4984
(2008/02/05)
-
- Synthesis and activity of substituted anthraquinones against a human filarial parasite, Brugia malayi
-
Lymphatic filariasis (elephantiasis) is a global public health problem caused by the parasitic nematodes Wuchereria bancrofti and Brugia malayi. We have previously reported anthraquinones from daylily roots with potent activity against pathogenic trematode Schistosoma mansoni. Here we report the synthesis of novel anthraquinones A-S and their antifilrarial activity. Anthraquinones A-S were synthesized by a single-step Friedel-Crafts acylation reaction between phthalic anhydrides and substituted benzenes. The antifilarial properties of these synthetic anthraquinones were tested against microfilaria as well as adult male and female worms of B. malayi. The most active anthraquinone was K, which showed 100% mortality within 1, 5, and 3 days, respectively, against microfilaria and adult male and female worms at 5 ppm concentration. Albendazole, an oral drug currently used to treat parasitic infections, was used as a positive control. Methylated products of anthraquinones did not affect the microfilaria. Histological examination of treated adult female parasites showed most of the anthraquinones caused marked effects on intrauterine embryos.
- Dhananjeyan, Mugunthu R.,Milev, Youli P.,Kron, Michael A.,Nair, Muraleedharan G.
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p. 2822 - 2830
(2007/10/03)
-
- Novel anthraquinones and process for the preparation and method of use thereof
-
A process for the preparation of hydroxyl substituted anthraquinones is described. The process couples a phthalic anhydride (substituted or unsubstituted) to benzene ring moiety substituted with at least two hydroxyl groups. Remaining hydroxy groups were converted to methoxy groups in some anthraquinones. The compounds are particularly useful for the treatment of parasitic diseases. Also, a method of treating or preventing malaria, filariasis schistosomiasis and other parasitic diseases using anthraquinones.
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-
Page/Page column 5
(2008/06/13)
-
- Synthesis of quinizarin and its derivatives under conditions of microwave activation
-
In a microwave field, phthalic anhydride reacts with p-chlorophenol to give 1,4-dihydroxyanthraquinone (quinizarin) within 10 min. The reaction with 4-chlorophthalic anhydride occurs similarly. Phthalic and chlorophthalic acids can be used instead of anhydrides. 3-Nitrophthalic acid and 3,4,5,6-tetrabromophthalic anhydride do not react with p-chlorophenol under these conditions.
- El'tsov,Sokolova,Grigor'ev,Dmitrieva,Shtol'vin
-
p. 255 - 258
(2007/10/03)
-
- Parimycin: Isolation and structure elucidation of a novel cytotoxic 2,3-dihydroquinizarin analogue of γ-indomycinone from a marine Streptomycete isolate
-
In our screening of actinomycetes from the marine environment for bioactive components, a new antibiotic with a novel structure designated as parimycin was obtained from the culture broth of Streptomyces sp. isolate B8652. The structure of the new antibiotic was determined by spectroscopic methods and by comparison of the NMR data with those of the structurally related γ-indomycinone.
- Maskey, Rajendra P.,Helmke, Elisabeth,Fiebig, Heinz-Herbert,Laatsch, Hartmut
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p. 1031 - 1035
(2007/10/03)
-
- Rapid, one-pot conversion of aryl fluorides into phenols with 2-butyn-1-ol and potassium t-butoxide in DMSO
-
Aryl fluorides react rapidly with 2-butyn-1-ol and potassium t-butoxide in DMSO under microwave irradiation to give propargylic ethers. These ethers isomerize in situ to the corresponding allenyl ethers, which hydrolyze on work-up to give phenols in good yield.
- Levin, Jeremy I.,Du, Mila T.
-
p. 1401 - 1406
(2007/10/03)
-
- The synthesis of ventilone A
-
2-Amino-3,6-dimethoxy-4,5-methylenedioxybenzoic acid (12) was prepared from 1,4-dimethoxy-2,3-methylenedioxybenzene (8) via the isatin (11). The benzyne generated from (12) was intercepted with 3-acetyl-2-ethoxy-4-[(4-methoxyphenoxy)methyl]furan (4) to give the naphthol (27), which on treatment with ceric ammonium nitrate gave the dimethyl ether of ventilone A (29). Demethylation with boron tribromide then afforded ventilone A (1). CSIRO 2000.
- Piggott, Matthew J.,Wege, Dieter
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p. 749 - 754
(2007/10/03)
-
- Reaction of hydroquinones with supported oxidizing reagents in solvent- free conditions
-
Supported MnO2 or HNO3 on bentonitic clay cleanly oxidize some hydroquinones under infrared or microwave irradiation to the corresponding quinones with excellent conversion in short reaction times, using an easy and solvent-free approach.
- Gomez-Lara,Gutierrez-Perez,Penieres-Carrillo,Lopez-Cortes,Escudero-Salas,Alvarez-Toledano
-
p. 2713 - 2720
(2007/10/03)
-
- Pathway of anthracene modification under simulated solar radiation
-
Exposure of polycyclic aromatic hydrocarbons (PAHs) to sunlight results in rapid structural photomodification generally via oxidation reactions. These PAH modification products are in many cases more toxic than their parent compounds. In this study, anthracene (ANT), a rapidly photooxidized PAH, was irradiated with simulated solar radiation (SSR, 100 μmol m-2 s- 1) in aqueous solution to examine the photomodification pathway. The photoproducts formed were identified by HPLC. The ANT product profile after 9 h in SSR was very complex, with more than 20 compounds detected. The photoproducts formed were anthraquinones, benzoic acids, benzaldehydes and phenols showing the process to be oxidative in nature. Some of the anthraquinones were themselves subject to photooxidation, and were thus intermediates in the product pathway. The kinetics of ANT photooxidation revealed a pseudo first-order reaction with a half-life of 2 h under the SSR source used. The kinetics of product formation allowed deduction of a probable photomodification pathway. This study indicates that PAH photooxidation products are likely to exist as complex, dynamically changing mixtures in PAH contaminated aquatic environments.
- Mallakin, Ali,George Dixon,Greenberg, Bruce M.
-
p. 1435 - 1441
(2007/10/03)
-
- A powerful o-quinone dimethide strategy for intermolecular Diels-Alder cycloadditions
-
Conrotatory thermal fragmentation of trans-1,2- disilyloxybenzocyclobutenes generates o-quinone dimethides at remarkably low temperatures. Smooth stereoselective Diels-Alder cycloaddition with a range of dienophiles provides hydronaphthalene derivatives in excellent yield. Direct oxidative desilylation of the adducts affords the corresponding naphthoquinones. Substitution of the benzene nucleus with an electron- releasing methoxyl group directs the cycloaddition to give good control of regioselectivity in the expected direction. A short synthesis of the aglycon of the anticancer antibiotic idarubicin is presented.
- Allen, John G.,Hentemann, Martin F.,Danishefsky, Samuel J.
-
p. 571 - 575
(2007/10/03)
-
- The reductive dehalogenation of halosubstituted naphthazarins and quinizarins as a simple route to parent compounds
-
By the reaction of 2-chloro-3-alkyl-, 2,3-dichloro(dibromo)-, trichloro(tribromo)-and tetrachloro(tetrabromo)-naphthazarins and 2,3- dichloroquinizarin with Fe/HOAc followed by oxidation with an air in a mild basic conditions the corresponding naphthazarins and quinizarin were obtained in good to excellent yields.
- Anufriev, Victor Ph.,Malinovskaya, Galina V.,Novikov, Vyacheslav L.,Balanyova, Nadezhda N.,Polonik, Sergey G.
-
p. 2149 - 2157
(2007/10/03)
-
- Sodium trimethyl silanoate. A hydroxyl synthon for fluoride S(n)Ar type displacements from anthracene-9,10-diones, benz[g]isoquinoline-5-10-diones and nitrobenzenes
-
Treatment of fluoroanthracene-9,10-diones, fluorobenz[g]isoquinoline- 5,10-diones and 1- or 4-fluoronitrobenzenes with sodium trimethylsilanoate in THF followed by acidification readily yields the corresponding hydroxyl analogues.
- Krapcho, A. Paul,Waterhouse, David
-
p. 3415 - 3422
(2007/10/03)
-
- Thermodynamics of semiquinone disproportionation in aqueous buffer
-
The thermodynamic parameters, Kdisp, ΔH° and ΔS°, controlling the disproportionation of semiquinones derived from 1,4-benzoquinone (BQ), 1,4-naphthoquinone (NQ), 2-methylbenzoquinone (MBQ), menadione (MNQ), naphthazarin (NZQ) and quinizarin (QNZ), have been determined. Smaller disproportionation constants, Kdisp, are observed upon addition of a fused benzene ring to the semiquinone structure. Negative enthalpies and positive entropies of disproportionation govern the disproportionation equilibria. Addition of OH groups to the 5 and 8 positions in NQ?- displaces the disproportionation equilibrium to the semiquinone probably due to intramolecular hydrogen bonding.
- Alegria, Antonio E.,Lopez, Marcos,Guevara, Norberto
-
p. 4965 - 4968
(2007/10/03)
-
- Control of the ring selectivity in Diels-Alder reactions of naphthazarins mediated by sulfur functions
-
Ring selectivity of Diels-Alder reactions of naphthazarin thioderivatives with cyclopentadiene is controlled by choosing the adequate sulfur substituent: p-tolylsulfonyl and p-tolylsulfinyl (under BF3·OEt2 catalysis) derivatives give cycloaddition only on the C-6 substituted tautomer. The opposite ring selectivity (exclusive reaction on the C-2 substituted tautomer) is achieved in the reaction of the p-tolylsulfonyl derivative at -78°C.
- Carmen Carreno,Garcia Ruano, Jose L.,Urbano, Antonio
-
p. 3789 - 3792
(2007/10/02)
-
- Method for dyeing keratinous fibres using a monohydroxyindole or dihydroxyindole and a non-oxidizing aromatic carbonyl derivative and dyeing agent
-
The present invention relates to a method for dyeing keratinous fibers, characterized in that the following are applied to the fibers: a) a composition (A) containing, in a medium appropriate for dyeing, at least one monohydroxyindole or dihydroxyindole, this application being preceded or followed by the application of b) a composition (B) containing, in a medium appropriate for dyeing, at least one aromatic carbonyl derivative chosen from hydroxyacetophenones, hydroxybenzophenones, 2-hydroxy-1,4-benzoquinones, hydroxy-1,4-naphthoquinones,amino-1,4-naphthoquinones,hydroxy-9,10-anthraquinones and amino-9,10-anthraquinones. It also relates to the dyeing agents for carrying it out.
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-
-
- Transformation of dyes and related compounds in anoxic sediment: kinetics and products
-
The reactions of several azo, anthraquinone, and quinoline dyes were studied in settled sediments. Both the anthrone from Disperse Red 9 and the demethylation product of Disperse Red 11 reacted with half-lives of a few months, but other major products were not detected. An azo dye (Solvent Red 1) and a quinoline dye (Solvent Yellow 33) were transformed with half-lives of a few days andmonths, respectively. -from Authors
- Baughman,Weber
-
p. 267 - 276
(2007/10/03)
-
- Vicarious Nucleophilic Hydroxylation of Aromatic Nitro Compounds with Organic Hydroperoxides
-
Nitrobenzene, α-nitronaphthalene, m-dinitrobenzene, 1,3,5-trinitrobenzene, m-nitrobenzophenone, m-nitrobenzonitrile, methyl m-nitrobenzoate and m-nitro diphenylsulphone can be hydroxylated with cumene or tert-butyl hydroperoxide in dipolar aprotic solvents in the presence of strong bases.The hydroxyl group is introduced preferably in p-position to the nitro group.Attempts to hydroxylate benzophenone, anthraquinone, 2-ethyl anthraquinone, anthraquinone 2-sulphonate, benzonitrile and diphenyl sulphone under the same conditions failed. 1-Nitroanthraquinone delivered 1-hydroxy, 1,2-dihydroxy and 1,4-dihydroxy anthraquinone.
- Brose, Thomas,Holzscheiter, Felix,Mattersteig, Gunter,Pritzkow, Wilhelm,Voerckel, Volkmar
-
p. 497 - 504
(2007/10/02)
-
- Absorption Spectra of the Radical Ions of Quinones: A Pulse Radiolysis Study
-
The formation of quinone radical ions was observed at room temperature using pulse radiolysis.The following quinones were investigated: p-benzoquinone, p-naphthoquinone, 5,8-dihydroxy-1,4-naphthoquinone, anthraquinone and 1,4-dihydroxyanthraquinone.The radial cations were produced in freon-113 solutions and the radical anions were produced in methanol solutions.Th absorption spectra of the radical ions were found in the near -UV-VIS range.The spectra of the radical cations were blue shifted compared with the spectra of the corresponding radical anions.
- Mayer, Jozef,Krasiukianis, Roman
-
p. 2943 - 2947
(2007/10/02)
-
- A NEW METHODOLOGICAL APPROACH TO ANTHRAQUINONE AND ANTHRACYCLINONE SYNTHESIS
-
A new general methodology for the anthraquinone and anthracyclinone synthesis has been developed.In contrast to the data reported in the previous literature, anthraquinones can be obtained under mild conditions from ortho dicarboxylic acid chlorides and suitable aromatic substrates via a Friedel-Crafts process.In this context the classic Wong synthesis of anthracyclinones has been greatly improved.The study of the reaction mechanism permitted the unexpected results to be rationalized and to account for the "ortho template bisacylation" of the phenol substrates.
- Sartori, Giovanni,Casnati, Giuseppe,Bigi, Franca,Foglio, Federica
-
-
- Production process of quinizarin
-
Quinizarin, an intermediate for dyestuffs, is prepared in high yield and in high purity by reacting p-chlorophenol and phthalic anhydride in a small amount of a specific sulfuric acid in the presence of boric acid or boric anhydride.
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-
-
- One- and Two-electron Reduction of Quinizarin and 5-Methoxyquinizarin: A Pulse Radiolysis Study
-
Absorption characteristics of the semiquinone free radicals formed by one-electron reduction of quinizarin (QH2), 5-methoxyquinizarin (MQH2) and quinizarin 2-sulphonate (QSH2) have been studied by pulse radiolysis in a mixed solvent system consisting of water, isopropyl alcohol and acetone.Second-order rate constants have been determined for the reactions of (CH3)2COH with the quinones, of the semiquinone with O2 and of the semiquinones with each other.The one-electron reduction potentials (vs.NHE) are E17 = -269 mV for QH2, -333 mV for MQH2 and -298 mV for QSH2.They vary with pH in accordance with the pKa values of the parent quinones and the semiquinones.The radicals are stable within the approximate pH range 5-11.The stability constant is highest at pH 8.5 (Ks = 0.09) for QH2, at pH = 9.5 for QSH2 (Ks = 10) and pH = 10.8 for MQH2 (Ks = 4.8), respectively.The one-electron reduction potentials of the semiquinones and the two-electron reduction potentials of the quinones are calculated to be E27 = -188, -192 and -216 mV, and Em7 = -229, -263 and -257 mV for QH2, MQH2 and QSH2, respectively.The effect of solvent on the properties of the semiquinones is discussed.
- Mukherjee, Tulsi,Swallow, A. John,Guyan, Patricia M.,Bruce, J. Malcolm
-
p. 1483 - 1491
(2007/10/02)
-
- Enthalpies of combustion of 1,4-naphthoquinone, 9,10-anthraquinone, 9,10-phenanthraquinone, 1,4,9,10-anthradiquinone, 5,8-dihydroxy-1,4-naphthoquinone, and 1,4-dihydroxy-9,10-anthraquinone
-
The standard (p0 = 0.1 MPa) molar enthalpies of combustion in oxygen at 298.15 K were measured by static-bomb calorimetry for some quinones and dihydroxyquinones.The standard molar enthalpies of sublimation at 298.15 K were measured by microcalorimetry for 1,4-naphthoquinone and 9,10-phenanthraquinone; values were selected from the literature for the remaining compounds in order to derive the standard molar enthalpies of formation in the gaseous state. The energies of the intramolecular hydrogen bonds in the dihydroxyquinones were assessed as (25 +/- 3) kJ*mol-1. 1,4,9,10-Anthradiquinone is apparently considerably strained, and although its reaction with water produces 1,4-dihydroxy-9,10-anthraquinone, a concomitant formation of hydrogen peroxide is shown to be thermodynamically improbable.
- Silva, M. A. V. Ribeiro da,Silva, Maria D. M. C. Ribeiro da,Teixeira, J. A. S.,Bruce, J. M.,Guyan, Patricia M.,Pilcher, G.
-
p. 265 - 274
(2007/10/02)
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- Syntheses Totales d'Oxa-9 anthracyclines
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Racemic 7-hydroxy-9-oxa-anthracyclinone (5a) has been synthetised in seven steps from quinizarin (6) and its resolution achieved after glycosylation with 3,4-di-O-acetyl-2-deoxy-L-fucose.Chiral pool syntheses of (8S)-8-hydroxymethyl-9-oxa-anthracyclinone (5b) and of (8S,10R) and (8S,10S)-8-hydroxymethyl-10-methyl-9-oxa-anthracyclinones (5c and 5d) have been achieved using (R)-2,3-O-isopropylideneglyceraldehyde (12) and leucoquinizarin (13) as starting materials.Glycosylation of aglycones 5b-5d by either 3,4-di-O-acetyl-2-deoxy-L-fucose or various 3-amino-2,3,6-trideoxy-L-hexoses yielded the corresponding anthracyclines.The synthetic glycosides do not show significant cytotoxic activity at a concentration of 1 μg/ml against L 1210 cells.Keywords 9-oxa-anthracyclinone; 9-oxa-anthracycline; glycoside; chiral pool synthesis
- Dufat-Trinh, Hahn van,Seguin, Elisabeth,Tillequin, Francois,Monneret, Claude,Koch, Michel
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p. 3294 - 3300
(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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- METAL TEMPLATE ORTHO-ACYLATION OF PHENOLS; A NEW GENERAL APPROACH TO ANTHRACYCLINONES
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Direct and mild synthesis of dihydroxyanthraquinones including 4-demethoxy-7-deoxydaunomycinone 8 from ortho-phthaloyl dichloride and hydroquinone derivatives is described.
- Sartori, Giovanni,Casnati, Giuseppe,Bigi, Franca,Robles, Pasquale
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p. 1533 - 1536
(2007/10/02)
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- An EPR Study of a Model System for the Initial Oxygen Activation Process Caused by Adriamycin-Iron System
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1,4-Dihydroxyanthraquinone, a model compound for Adriamycin, is reduced by Fe2+-ADP complex to generate semiquinone, while by Fe2+-phosphate complex to hydroquinone.The difference is explained in terms of the higher redox potential of the latter reducing agent.Similar reduction reactions were observed in the case of the drug.
- Tachibana, Masahiko,Tero-Kubota, Shozo,Iwaizumi, Masamoto
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p. 933 - 936
(2007/10/02)
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- REGIOSELECTIVE REACTIONS OF 9-HYDROXY-10-CHLORO-1,4-ANTHRAQUINONE. SYNTHESIS OF DIGITOPURPONE AND ISLANDICIN
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9-Hydroxy-10-chloro-1,4-anthraquinone, obtained in the reaction of 1,4-dihydroxy-9,10-anthraquinone with thionyl chloride, is nitrated selectively at the peri position to the chlorine atom and is converted into 5-nitro-9-hydroxy-10-chloro-1,4-anthraquinone.The isomeric 8-nitro-9-hydroxy-10-chloro-1,4-anthraquinone is formed during the hydrolysis of the nitration product and the subsequent reaction of 5-nitro-1,4-dihydroxy-9,10-anthraquinone with thionyl chloride.The reaction of 9-hydroxy-10-chloro-1,4-anthraquinone and its nitro derivatives with the carbanion generated from malonic ester leads to selective alkylation at position 3.Together, the indicated reactions make it possible to realize the regioselective synthesis of 2-methyl-1,4,8- and 2-methyl-1,4,5-trihydroxy-9,10-anthraquinones.
- Gorelik, M. V.,Arinich, L. V.,Kotlyarevskii, O. I.,Fes'kova, E. A.
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p. 129 - 138
(2007/10/02)
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- ELECTRONIC ABSORPTION SPECTRA AND STRUCTURE OF ISOMERIC DI(p-TOLYLAMINO)ANTHRAQUINONES
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By analysis of the electronic absorption spectra and the data from quantum-chemical calculations it was shown that 1,4- and 9,10-di(p-tolylamino)anthraquinones exist in the 9,10- and 1,4-anthraquinonoid forms respectively.Tautomerism between the 1,10-anthraquinonoid and 9,10-anthraquinone imine structures was detected and proved for 4,9-di(p-tolylamino)-1,10-anthraquinone.
- Volosenko, V. P.,Zaitsev, B. E.,Popov, S. I.
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p. 990 - 995
(2007/10/02)
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- A FACILE SYNTHESIS OF FUNCTIONALIZED 9,10-ANTHRACENEDIONES VIA TOSYLATE AND TRIFLATE PHENOLIC ACTIVATION
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Reaction of 1,4-dihydroxy-9,10-anthracenedione bistosylates and bistriflates with a range of common nucleophiles is discussed.
- Showalter, H.D. Hollis,Berman, Ellen M.,Johnson, Judith L.,Atwood, Jerry L.,Hunter, William E.
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p. 157 - 160
(2007/10/02)
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- 4,9-DISUBSTITUTED 1,10-ANTHRAQUINONES AND THEIR TAUTOMERISM
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The N-alkyl-, N-aryl-, and N-acetyl-substituted 9-imines of 1-hydroxy-4-aminoanthraquinone exist preferentially in the 4,9-diamino-1,10-anthraquinone form.Tautomerism is only observed for diamines with reduced basicity in the nitrogen atom at position 9.
- Popov, S. I.,Volosenko, V. P.
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p. 983 - 989
(2007/10/02)
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- The photochemistry of 9,10-anthracenedione in sulfuric acid solution. The dependence of product yields on reaction conditions
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Irradiation of a sulfuric acid solution of 9,10-anthracenedione with near-uv light generated 2-hydroxy-9,10-anthracenedione as the major product.In addition, the 1-hydroxy and polyhydroxy derivatives and the reduction products anthrone and bianthronyl were also formed.The yields of these minor products were markedly influenced by the concentrations of water and oxygen in the sulfuric acid.At low light intensities, oxygen quenched the efficient formation of the hydroxyanthracenediones and also oxidised the initial quinone reduction products.Photoreduction of the anthracenedione and photooxidation of anthrone occurred simultaneously in the solution.The reaction mechanism is more complex than previous studies indicated.
- Broadbent, A. Douglas,Stewart, John M.
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p. 1965 - 1969
(2007/10/02)
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- Process for the preparation of quinizarin
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A process, which does not pollute the environment, for the preparation of quinizarin consists in reacting a mixture of phthalic anhydride p-chlorophenol, sulphuric acid and boric acid or boric anhydride at elevated temperatures in such a way that, in the reaction mixture, there is sulphuric acid preferably containing 10-20% of free SO3 and the weight ratio of p-chlorophenol to the total amount of H2 SO4 +SO3 is 1:1.5 to 4.0. Yields and purity of the product are outstanding, despite the concentrated procedure.
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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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