- Substitution of Quinizarin and 5-Hydroxyquinizarin at C-2
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Carbanions derived from ethyl acetoacetate, acetylacetone, and alkyl nitro-compounds add to C-2 of quinizarin and its 5-hydroxy-derivative.
- Sutherland, James K.,Towers, Patrick,Greenhalgh, Colin W.
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- Synthesis of functionalized 1,4-dihydro-9,10-anthraquinones and anthraquinones by ring closing metathesis using Grubbs' catalyst
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A general and straightforward synthesis of anthraquinones was developed, in which diallylation of 1,4-naphthoquinones, followed by Ring Closing Metathesis (RCM) of the resulting diallylnaphthoquinones with Grubbs' catalyst and subsequent dehydrogenation using Pd/C afforded the desired anthraquinones with regiocontrol of substituents and in good yields.
- Van Nguyen, Tuyen,D'Hooghe, Matthias,Pattyn, Siegfried,De Kimpe, Norbert
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- Novel Oxidative Transformation: Regiospecific Preparation of Naturally Occurring 1-Hydroxyanthraquinones
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A brief reaction sequence for synthesis of the naturally occurring anthraquinones 1-hydroxyanthraquinone (4a), 1-hydroxy-2-methylanthraquinone (4b), pachybasin (4c), chrysophanol (5a), and rhein (5c) has been developed.
- Hauser, Frank M.,Prasanna, Subbarao
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- Preparation of 3,4-Dihydroanthracen-1(2H)-ones. A Synthetic Approach to Islandicin and Digitopurpone via Difluoro1,O9>boron Chelates
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Three 9,10-dihydroxyanthracen-1(2H)-one derivatives (2a-c) have been obtained by the catalytic hydrogenation of quinizarin, 1-hydroxy-5-methoxyanthraquinone, and 1-hydroxy-8-methoxyanthraquinone, respectively; in the last two reactions, monohydroxyanthracen-1(2H)-ones (4a) and (4b) are formed as by-products.The anthracenone derivatives (2a-c) were O-methylated by methyl toluene-p-sulphonate and the selective demethylation of the dimethoxy derivative (2d) to the monomethoxy derivative (2e) was effected by AlCl3.The silyl enolate (5) was unreactive toward C-methylation but the lithium enolate of the anthracenone (2d) reacted with methyl iodide to give a mixture of C-mono (2f) and C-di (6a) alkylated derivatives; in contrast, the boron enolate of (2d) reacted with methyl iodide to give exclusively the C-monomethylated derivative (2f) and this procedure was extended to the synthesis of 5-methoxy (2g) and 8-methoxy (2h) analogues of (2f).Whereas the dimethoxyanthracenone derivative (2d) is brominated (Br2-CHCl3, 0 deg C) in separate reactions to give monobromo (2i) and dibromo (6b) derivatives, the difluoroboron chelate (9a) was converted by photochemical bromination into a product (9g) of benzylic substitution; the analogue (9h) was similarly obtained from the difluoroboron chelate (9b).The boron derivatives (9g) and (9h) were transformed by methanol into hydroxydimethoxyanthracenone derivatives (2l) and (2m), and (9g) was also converted by wet alumina into the dihydroxymethoxyanthracenone (2n).The hydroxydimethoxyanthracenone (2l) and (2m) were transformed by 2,3-dichloro-5,6-dicyanobenzoquinone and selenium dioxide into 1-hydroxy-4-methoxyanthraquinone and 1-hydroxy-4-methoxy-2-methylanthraquinone, respectively.
- Preston, Peter N.,Will, Stephen G.,Winwick Thomas,Morley, John O.
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- Copper-catalyzed one-pot relay synthesis of anthraquinone based pyrimidine derivative as a probe for antioxidant and antidiabetic activity
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Synthetic compounds have modernized the globe due to its vast applicable fields. Anthraquinones, as well as pyrimidine derivatives, are used as essential pharmacophores in the field of medicine. Maintenance of a green disease-free environment by using these derivatives is being acknowledged in developed as well as developing countries of the world. Considering the use of active catalysts in the synthesis of anthraquinone based derivatives are the era of concern for researchers due to their distinctive properties. Owing to the remarkable activities of anthraquinone and pyrimidine derivative, we synthesize compounds having both functionalities with the utilization of novel synergically active copper catalysts. This study explores the application of synthesized compounds using fast, ecofriendly and cost-effective approaches.1H and 13C NMR, antioxidant, antidiabetic, molecular docking and QSAR studies were used for characterization and evaluation of newly synthesized anthraquinone based pyrimidine derivatives. The result of these techniques shows that our desired compounds were successfully synthesized and have potent applications. Among all synthesized compounds, G2 and G3 showed a remarkable antioxidant activity with IC50 of 15.09 and 21.88 μg/ml respectively. While the compound G2 and G4 showed a strong inhibitory antidiabetic activity with the IC50 value of 24.23 and 28.94 μg/ml respectively. Furthermore, molecular docking results for both of the proteins assist the experimental data and confirms the different interactions between binding domains and substituent moieties. SAR study also relates to the experimental facts by giving us positive results of synthesized compounds. According to the QSAR study, G4 and G2 emerged as the most stable and most reactive compound among other compounds respectively. While MEP shows moderate to good nucleophilic and electrophilic reactivity of all four compounds.
- Ahmad, Zaheer,Arshad, Uzma,Parveen, Shagufta,Rafiq, Naila,Shafiq, Nusrat,Zarren, Gul
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- TARGETED BIFUNCTIONAL DEGRADERS
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The present invention provides, in one aspect, bifunctional compounds that can be used to promote or enhance degradation of certain circulating proteins. In another aspect, the present invention provides bifunctional compounds that can be used to promote or enhance degradation of certain autoantibodies. In certain embodiments, treatment or management of a disease and/or disorder requires degradation, removal, or reduction in concentration of the circulating protein or the autoantibody in the subject. Thus, in certain embodiments, administration of a compound of the invention to the subject removes or reduces the circulation concentration of the circulating protein or the autoantibody, thus treating, ameliorating, or preventing the disease and/or disorder. In certain embodiments, the circulating protein is TNF.
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Page/Page column 34; 164; 165
(2021/04/17)
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- BIFUNCTIONAL SMALL MOLECULES TO TARGET THE SELECTIVE DEGRADATION OF CIRCULATING PROTEINS
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The present invention is directed to bifunctional small molecules which contain a circulating protein binding moiety (CPBM) linked through a linker group to a cellular receptor binding moiety (CRBM) which is a membrane receptor of degrading cell such as a hepatocyte or other degrading cell. In embodiments, the (CRBM) is a moiety which binds to asialoglycoprotein receptor (an asialoglycoprotein receptor binding moiety, or ASGPRBM) of a hepatocyte. In additional embodiments, the (CRBM) is a moiety which binds to a receptor of other cells which can degrade proteins, such as a LRP1, LDLR, FcyRI, FcRN, Transferrin or Macrophage Scavenger receptor. Pharmaceutical compositions based upon these bifunctional small molecules represent an additional aspect of the present invention. These compounds and/or compositions may be used to treat disease states and conditions by removing circulating proteins through degradation in the hepatocytes or macrophages of a patient or subject in need of therapy. Methods of treating disease states and/or conditions in which circulating proteins are associated with the disease state and/or condition are also described herein.
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Page/Page column 32
(2019/11/04)
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- Efficient reductive Claisen rearrangement of prop-2’-enyloxyanthraquinones and 2’-chloroprop-2’-enyloxyanthraquinones with iron powder in ionic liquids
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A rapid and selective iron-mediated reductive Claisen rearrangement of various prop-2’-enyloxyanthraquinones and 2’-chloroprop-2’-enyloxyanthraquinones to 1-hydroxy-2-(prop-2’-enyl)anthraquinones and anthrafurandiones is presented. All reactions are carried out in a mixture of ionic liquids, [Bzmim]Cl (1-benzyl-3-methylimidazolium chloride) and [Hmim]BF4 (1-methylimidazolium tetrafluoroborate), in short reaction times (5–35 min). Our study showed that 1-(prop-2’-enyloxy)anthraquinone is more active than 1-(2’-chloroprop-2’-enyloxy)anthraquinone to perform this rearrangement.
- Nadali, Samaneh,Khoshroo, Ali,Aghapour, Ghasem
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p. 883 - 895
(2018/06/07)
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- Preparation method of 4-hydroxyindole
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The invention discloses a preparation method of 4-hydroxyindole, comprising the steps of (1) dissolving 3-methoxyphenylhydrazine hydrochloride in DMF (dimethylformamide), adding concentrated sulfuricacid and a catalyst, mixing well, adding acetaldehyde, allowing reflux reaction at controlled temperature of 60-80 DEG C for 90-120 min, filtering after reaction is over to obtain 4-methoxyindole; (2)dissolving 4-methoxyindole in dichloromethane, adding the obtained solution in a reactor, introducing nitrogen, controlling the temperature to 50-70 DEG C, and introducing HBr into the solution, allowing reflux reaction for 45-90 min, lowering the temperature to room temperature, performing reduced pressure removal of a solvent, and recrystallizing to obtain 4-hydroxyindole. The preparation method according to the application is simple to perform and has mild conditions and few byproducts, the product is high in purity, and the yield of the product is high.
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Paragraph 0018-0021; 0025-0028; 0032-0035; 0039-0049
(2018/05/16)
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- Tautomeric chromoionophores derived from 1-aryloxyanthraquinones and 4′-aminobenzo-15-crown-5 ether: Sandwich complex formation enhanced by interchromophoric interactions
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A series of tautomeric chromoionophores were prepared photochemically from 1-aryloxyanthraquinones and 4′-aminobenzo-15-crown-5 ether. All the synthesized dyes can bind strontium and barium cations as sandwich-type 2:1 ligand–metal complexes that show higher stability constants (K2:1) than the corresponding 1:1 complexes (K1:1), the K2:1/K1:1ratio reaching a value of 10 (in MeCN). The inverse relation, i.e. K2:1?1:1, is observed for the related complexes of unsubstituted benzo-15-crown-5 ether. The sandwich complexes were studied by spectrophotometry,1H NMR spectroscopy, mass spectrometry, and density functional theory calculations. A correlation was found between the K2:1/K1:1ratio and the number of short stacking contacts in the sandwich complex.
- Martyanov, Timofey P.,Klimenko, Lubov S.,Kozlovskiy, Viacheslav I.,Ushakov, Evgeny N.
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p. 681 - 691
(2017/01/16)
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- Synthesis method of anthraquinone derivatives and tetracenedione derivatives through benzannulation reaction
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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; 0044
(2017/08/09)
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- Efficient and selective iron-mediated reductive Claisen rearrangement of propargyloxyanthraquinones to anthrafurandiones in ionic liquids
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An efficient and rapid method is described for the reductive Claisen rearrangement of different propargyloxyanthraquinones to anthra[1,2-b]furan-6,11-diones for first time using iron powder in a mixture of two ionic liquids, namely 1-methylimidazolium tetrafluoroborate [Hmim]BF4 and 1-benzyl-3-methylimidazolium chloride [Bzmim]Cl. The present method is able to execute single or double Claisen rearrangements of 1,4-or 1,5-bispropargyloxyanthraquinones selectively, so that the desired anthra(mono)furandiones or anthra(bis)furandiones are produced, respectively, as the major product.
- Nadali, Samaneh,Aghapour, Ghasem,Rafieepour, Zahra
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p. 1045 - 1051
(2017/10/03)
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- SMALL MOLECULE BASED ANTIBODY-RECRUITING COMPOUNDS FOR CANCER TREATMENT
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The present invention relates to chimeric (including bifunctional) compounds, compositions comprising those compounds and methods of treating cancer in a patient or subject, especially including metastatic cancer where cancer cells exhibit overexpression (heightened expression) of cell surface urokinase-type plasminogen activator receptor (urokinase receptor) compared to normal (non-cancerous) cells. The compounds bind to the urokinase-type plasminogen activator receptor (uPAR) on the surface of a cancer cell, including a metastatic cancer cell, and consequently recruit native antibodies of the patient or subject where the antibodies can selectively degrade and/or deactivate targeted cancer cells through antibody-dependent cellular phagocytosis and antibody-dependent cellular cytotoxicity (ADCC) and/or complement dependent cytotoxicity (CDC) against a large number and variety of cancers, thus providing cancer cell death and an inhibition of growth, elaboration and/or metastasis of the cancer, including remission and cure of the patient's cancer.
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Page/Page column 53; 54
(2017/03/08)
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- Re-engineering the Immune Response to Metastatic Cancer: Antibody-Recruiting Small Molecules Targeting the Urokinase Receptor
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Developing selective strategies to treat metastatic cancers remains a significant challenge. Herein, we report the first antibody-recruiting small molecule (ARM) that is capable of recognizing the urokinase-type plasminogen activator receptor (uPAR), a uniquely overexpressed cancer cell-surface marker, and facilitating the immune-mediated destruction of cancer cells. A co-crystal structure of the ARM-U2/uPAR complex was obtained, representing the first crystal structure of uPAR complexed with a non-peptide ligand. Finally, we demonstrated that ARM-U2 substantially suppresses tumor growth in vivo with no evidence of weight loss, unlike the standard-of-care agent doxorubicin. This work underscores the promise of antibody-recruiting molecules as immunotherapeutics for treating cancer.
- Rullo, Anthony F.,Fitzgerald, Kelly J.,Muthusamy, Viswanathan,Liu, Min,Yuan, Cai,Huang, Mingdong,Kim, Minsup,Cho, Art E.,Spiegel, David A.
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supporting information
p. 3642 - 3646
(2016/03/23)
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- Organocatalyzed benzannulation for the construction of diverse anthraquinones and tetracenediones
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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
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supporting information
p. 8592 - 8595
(2015/05/20)
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- Total synthesis, cytotoxic effects of damnacanthal, nordamnacanthal and related anthraquinone analogues
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Naturally occurring anthraquinones, damnacanthal (1) and nordamnacanthal (2) were synthesized with modified reaction steps and investigated for their cytotoxicity against the MCF-7 and K-562 cancer cell lines, respectively. Intermediate analogues 2-bromomethyl-1,3-dimethoxyanthraquinone (5, IC 50 = 5.70 ± 0.21 and 8.50 ± 1.18 μg/mL), 2-hydroxymethyl-1,3-dimethoxyanthraquinone (6, IC50 = 12.10 ± 0.14 and 14.00 ± 2.13), 2-formyl-1,3-dimethoxyantharquinone (7, IC 50 = 13.10 ± 1.02 and 14.80 ± 0.74), 1,3-dimethoxy-2-methylanthraquinone (4, IC50 = 9.40 ± 3.51 and 28.40 ± 2.33), and 1,3-dihydroxy-2-methylanthraquinone (3, IC 50 = 25.60 ± 0.42 and 28.40 ± 0.79) also exhibited moderate cytotoxicity against MCF-7 and K-562 cancer cell lines, respectively. Other structurally related compounds like 1,3-dihydroxyanthraquinone (13a, IC50 = 19.70 ± 0.35 and 14.50 ± 1.28), 1,3-dimethoxyanthraquinone (13b, IC50 = 6.50 ± 0.66 and 5.90 ± 0.95) were also showed good cytotoxicity. The target compound damnacanthal (1) was found to be the most cytotoxic against the MCF-7 and K-562 cancer cell lines, with IC50 values of 3.80 ± 0.57 and 5.50 ± 1.26, respectively. The structures of all compounds were elucidated with the help of detailed spectroscopic techniques.
- Akhtar, Muhammad Nadeem,Zareen, Seema,Yeap, Swee Keong,Ho, Wan Yong,Lo, Kong Mun,Hasan, Aurangzeb,Alitheen, Noorjahan Banu
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p. 10042 - 10055
(2013/09/23)
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- Synthesis of damnacanthal, a naturally occurring 9,10-anthraquinone and its analogues, and its biological evaluation against five cancer cell lines
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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.
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p. 2093 - 2104
(2013/07/26)
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- 1,4-Dihydroxyanthraquinone-copper(II) nanoparticles immobilized on silica gel: A highly efficient, copper scavenger and recyclable heterogeneous nanocatalyst for a click approach to the three-component synthesis of 1,2,3-triazole derivatives in water
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High yielding preparation of structurally different β-hydroxy 1,4-disubstituted 1,2,3-triazole from the regio-selective reaction of epoxides 2a-2c with wide range of terminal alkynes 1a-1j, and sodium azide in the presence of catalytic amount, complexed form of homogeneous catalyst [bis 1,4-mono ester hydroxy anthraquinone copper(II)] (5.0 mol%), [AQ 2Cu(II)] 7 at 25 °C in water has been described. To benefit from the recovery and reuse of the catalyst, a novel heterogeneous nanoparticles of catalyst [bis 1,4-mono ester hydroxy anthraquinone copper(II) aminopropyl silica gel] (5.0 mol%), [AQ2Cu(II)-APSiO2] 13 bearing oxygen anthraquinone ligands with strong copper(II) affinity was easily prepared by using silica gel as a suitable support. The heterogeneous catalyst was fully characterized by XRD, SEM, AFM, ICP, TG methods for analysis of nitrogen adsorption, and FT-IR techniques. The remarkable features of this protocol are high yields, short reaction times, a cleaner reaction profile in an environmentally benign solvent (H2O), one-pot procedure and the method is applicable to large-scale operation without any problem. Furthermore, the catalyst could be recovered and easily removed by simple filtration of the reaction mixture and it was recycled ten times showing negligible copper leaching. In their uncomplexed form of homogeneous catalyst [AQ 2Cu(II)] 7 and heterogeneous catalyst [AQ2Cu(II)- APSiO2] 13, the anthraquinone ligand 6 and [AQ-APSiO2] 12 are very efficient copper scavengers able to catalyze the 1,3-dipolar cycloaddition reaction of azides with alkynes (CuAAC) without pre-synthesis of catalysts.
- Sharghi, Hashem,Khoshnood, Abbas,Doroodmand, Mohammad Mahdi,Khalifeh, Reza
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experimental part
p. 231 - 250
(2012/09/11)
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- Photochemistry of 1, n -Dibenzyloxy-9,10-anthraquinones
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Figure presented The photochemistry of a series of 9,10-anthraquinones with multiple benzyloxy substituents was investigated. In polar solvent, the expected Blankespoor oxidative cleavage reaction is the major reaction pathway, but in most cases, several minor products were observed. In nonpolar solvents, the abundance of these minor products increases dramatically. Four types of product were observed with the favored reaction pathway shifting with minor changes in substitution on the anthraquinone. Several types of product require cleavage of the C-O bond on the benzyloxy group and, apparently, follow a photo-Claisen-type mechanism. Others involve the expected 1,5-diradical but do not exhibit the single-electron transfer usually observed in the Blankespoor-type reaction. The results indicate the importance of considering the medium and photoredox behavior in anthraquinone photochemistry.
- Sarma, Saurav J.,Jones, Paul B.
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supporting information; experimental part
p. 3806 - 3813
(2010/08/20)
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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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- Observation of heavy atom effects in the development of water soluble caged 4-hydroxy-trans-2-nonenal
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During the course of our study on the photochemistry of 1-alkoxy-9,10-anthraquinones, we have developed a second generation of a caged 4-hydroxy-trans-2-nonenal (4-HNE). As we optimized the anthraquinonyl chromophore to achieve water solubility, we studied the photochemistry of various substituents to understand their effect on the photochemistry. We observed a significant heavy atom effect that severely reduced the rate of oxidative cleavage of the alkoxy group. Based on the results of our substituent study, we designed a new caged 4-HNE that is soluble under physiological conditions, and that releases 4-HNE photochemically in high yield.
- Jones, Paul B.,Brinson, Robert G.,Sarma, Saurav J.,Elkazaz, Salwa
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scheme or table
p. 4204 - 4211
(2009/02/07)
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- Halophenol rearrangement in Lewis acid-catalyzed Friedel-Crafts conditions: Evidence of competitive initial protonation and acylation
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Halogen rearrangement was observed during the Lewis acid-catalyzed Friedel-Crafts reaction of phthalic anhydride with bromophenols or bromoanisole. Further investigation revealed that 2-, 3-, and 4-bromophenols undergo rearrangement into other isomers under these reaction conditions. Product distribution from these reactions suggested that halogen rearrangement takes place during the s-complex intermediate of the condensation step. Furthermore, iodophenol undergoes hydrodeiodination rapidly rather than rearrangement, whereas chlorophenol does not undergo rearrangement at all. CSIRO 2008.
- Saha, Koushik,Lajis, Nordin H.,Abas, Faridah,Naji, Nabil Ali,Hamzah, A. Sazali,Shaari, Khozirah
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p. 821 - 825
(2008/12/22)
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- Synthesis of anthraquinone derivatives: Tandem Diels-Alder-decarboxylation- oxidation reaction of 3-hydroxy-2-pyrone with 1,4-naphthoquinone
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In the presence of triethylamine, the Diels-Alder reaction of 3-hydroxy-2-pyrones with 1,4-naphthoquinones by a decarboxylation-oxidation process gave anthraquinone derivatives in good to excellent yields. Georg Thieme Verlag Stuttgart.
- Komiyama, Takuzo,Takaguchi, Yutaka,Tsuboi, Sadao
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p. 124 - 126
(2007/10/03)
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- Pathway of anthracene modification under simulated solar radiation
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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.
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p. 1435 - 1441
(2007/10/03)
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- 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
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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
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p. 3415 - 3422
(2007/10/03)
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- Synthesis of 9-chloro-1,10-anthraquinone and its reactions with amines
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1-Dichlorophosphoryloxy-9,9-dichloroanthrone, a product of the reaction between 1-hydroxyanthraquinone and PCl5, reacts with primary amines in benzene to give first 1-(diaminophosphoryloxy)-9,9-dichloroanthrones and then the corresponding 9-imines. The reaction in DMF occurs with elimination of the phosphoryloxy group and generation of 9-chloro-1,10-anthraquinone that undergoes amination followed by substitution of the hydrogen atom in position 4 rather than a chlorine atom in position 9, which is the most active position in 2,4,9-trichloro-1,10-anthraquinone. The second step of amination results in 4,9-di(alkylamino)-1,10-anthraquinone. The literature data on obtaining individual 9-chloro-1,10-anthraquinone under the action of bases on 1-dichorophosphoryloxy-9,9-dichloroanthrone were not experimentally supported.
- Gorelik,Titova,Gladysheva
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p. 1141 - 1146
(2007/10/03)
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- Photochemistry of 1-Alkoxy- and 1-(Benzyloxy)-9,10-anthraquinones in Methanol: A Facile Process for the Preparation of Aldehydes and Ketones
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The facile production of acid sensitive aldehydes and ketones via photochemical intramolecular δ-hydrogen atom transfer in 1-alkoxy- and 1-(benzyloxy)-9,10-anthraquinones (1) was investigated.Irradiation of 1 in argon purged methanol generates the primary photoproducts, 1-(RCH(OMe)O)- and 1-(ArCH(OMe)O)-9,10-anthrahydroquinones (2), respectively.Upon exposure to air, the intermediate anthrahydroquinone is rapidly converted to the corresponding aldehyde and 1-hydroxy-9,10-anthraquinone (3), which can be recycled.Aldehydes containing an acetal or ketal were prepared in high yields using this photoprocess.Apparent rate constants for the photodemethylation of 1-methoxy-2-X-9,10-anthraquinones (X = H, Me, Et, Pr, i-Bu, and benzyl) were measured and found to vary by a factor of 10 separating the slowest anthraquinone (X = H) and the fastest (X = benzyl), indicating a strong dependency upon the size of the substituent at the 2-position.These rate constants are ascribed to equilibrium populations of conformers in the geometry required for the reaction in the n,?* triplet state.
- Blankespoor, Ronald L.,Smart, Robert P.,Batts, Eric D.,Kiste, Alan A.,Lew, Rebecca E.,Vliet, Marc E. Vander
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p. 6852 - 6859
(2007/10/03)
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- Experimental and quantum chemical study of the reactions of 1,10-anthraquinones with alcohols and amines
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The primary stage of the reaction between 9-aryloxy-1,10-anthraquinones and methanol is the nucleophilic 1,4-addition which gives rise to the adduct, corresponding to 1-hydroxy-9-methoxy-9-aryloxy-10-anthrone. The reaction of 9-aryloxy-1,10-anthraquinones with the primary aliphatic and aromatic amines results in the formation of 9-alkyl(aryl)amino-1,10-anthraquinones that are in a tautomeric equilibrium with 1-hydroxy-9,10-anthraquinone-9-alkyl(aryl)imines. The quantum chemical calculations of the enthalpy of 9-amine-1,10-anthraquinone isomerization are in agreement with the experimentally recorded influence on the tautomeric equilibrium of the nature of amine, solvent, and substituent in the anthraquinone nucleus. The data of quantum chemical calculations confirm the addition-elimination mechanism of the reaction of 1,10-anthraquinones with amines.
- Gritsan, Nina P.,Klimenko, Lubov S.,Leonenko, Zoya V.,Mainagashev, Iiya Ya.,Mamatyuk, Victor I.,Vetchinov, Valerii P.
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p. 3061 - 3076
(2007/10/02)
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- Transformation of dyes and related compounds in anoxic sediment: kinetics and products
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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
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p. 267 - 276
(2007/10/03)
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- Vicarious Nucleophilic Hydroxylation of Aromatic Nitro Compounds with Organic Hydroperoxides
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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
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p. 497 - 504
(2007/10/02)
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- Diels-Alder reactions between dienamides and quinones: Stereochemistry of the cycloadditions and cytotoxic activity of the adducts
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Tetrahydronaphthoquinones and tetrahydroanthraquinones bearing an amido group have been prepared by Diels-Alder reactions between (E)-1-(N-carbobenzyloxyamino)-1,3-butadiene (2) or (E)-1-(N-benzoyl-N-benzylamino)-1,3-butadiene (5) and benzoquinone or 5-substituted naphthoquinones. The stereochemistry of the cycloadditions was investigated. A high regioselectivity was observed in the reaction of the diene carbamate 2 with 5-methoxy and 5-acetoxy naphthoquinones. This latter gave the unexpected 1,8-regioisomer 3d. The cycloadditions of the dienamide 5 with naphthoquinones 1 (R = OH, OMe, OAc) are regiospecific. Assignment of the structure of the tetrahydroanthraquinone 6b is in good agreement with the known directing effect of the 5-hydroxy group of juglone 1b in analogous Diels-Alder reactions. With 5-methoxy and 5-acetoxy naphthoquinones, the opposite regiochemistry observed is consistent with the electron-donating influence of the methoxy or acetoxy group, making the C-3 carbon atom more electron deficient. Aromatization of the adducts 6b and 7c was accompanied by an unusual elimination of the amido moiety. Thus, 1-hydroxy and 1-methoxy anthraquinones were obtained. Reactions of the dienes 2 and 5 with benzoquinone gave the tetrahydronaphthoquinones 9 and 10 with an endo stereospecificity. Oxidation of 9 by activated manganese dioxide gave the naphthoquinone 11. These compounds were submitted to in vitro cytotoxic assays towards murine L 1210 leukemia cells and clonogenic human tumor cell line MDA-MB 231. The naphthoquinone derivatives 9, 10 and 11 had significant activities with IC50 ≤ 0.4 μg/ml towards these two tumor cell systems.
- Chigr,Fillion,Rougny,Berlion,Riondel,Beriel
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p. 688 - 691
(2007/10/02)
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- A NEW METHODOLOGICAL APPROACH TO ANTHRAQUINONE AND ANTHRACYCLINONE SYNTHESIS
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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
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- Synthesis of anthraquinone derivatives by palladium-catalyzed coupling of triflates with stannanes
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The palladium-catalyzed coupling of hydroxyanthraquinone triflates with stannanes provides an efficient entry into substituted anthraquinones under neutral conditions.
- Tamayo, Nuria,Echavarren, Antonio M.,Paredes, M. Carmen,Farina, Francisco,Noheda, Pedro
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p. 5189 - 5192
(2007/10/02)
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- KINETIC OF THE REACTION OF 1-BROMOANTRAQUINONE AND ITS AMINO AND SULFO DERIVATIVES WITH ANILINE
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The products and the kinetics of the reaction of 1-bromo- and 1-amino-4-bromo-anthraquinones and sodium 1-bromoanthraquinone-3-sulfonate and 1-amino-4-bromoanthraquinone-2-sulfonate with aniline were studied in a mixture of dioxane and a buffer solution of borax and sodium carbonate with pH 10 (1.3:1 by volume) in the presence of copper sulfate and without a catalyst.The products from substitution of the bromine atom by the phenylamino group and also the debromination products are formed, and their ratio depends on the presence of oxygen and of the catalyst.In thenoncatalytic reaction the NH2 group reduces and the SO3(1-) group increases the mobility of the bromine atom; in the catalytic reaction both groups increase the mobility of the bromine atom.The activating effect of the amino group is probably due to the formation of chelate complex involving the copper ions and the amino and carbonyl groups of the anthraquinone ring.
- Vinokurov, Yu. V.,Nazarova, N. E.,Solodova, K. V.,Shein, S. M.
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p. 1740 - 1744
(2007/10/02)
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- STUDY OF THE MECHANISM OF ACYLOTROPY IN α-ACYLOXYANTHRAQUINONES BY THE LABELED ATOM METHOD
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It was established by isotope exchange that the hydroxide ion adds to the carbonyl group of 9,10-anthraquinone and its 1-acetoxy-substituted derivative under the influence of Na(18)OH in water-dioxane solution.The hydroxylation of 1-acetoxy-9,10-anthraquinone at position 9 leads to the irreversible migration of the acetyl group to the negatively charged oxygen atom of the hemi-diol.The fragmentation of 9,10-anthraquinone and its 1-acetoxy and 1-hydroxy derivatives containing one or two (18)O atoms under electron impact was studied.It was found that 1-hydroxy-9,10-anthraquinone eliminates the CO groups from positions 1, 9, and 10 with equal probability at the first stage of dissociation.
- Popov, S. I.,Volosenko, V. P.,Sharbatyan, P. A.
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p. 1085 - 1089
(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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- A General, Regiospecific Synthesis of Highly Substituted Quinones
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A general route to a wide variety of substituted quinones (furyl, indolo, pyrrolo, quinolino, naphtho, and anthra) has been developed via the thermolysis (160 deg C, xylene) and subsequent oxidation (air or Ce4+) of 4-hydroxy-4-substituted-cyclobutenones (eq. 1) and 2-hydroxy-2-substituted-benzocyclobutenones which were formed by the regioselective addition of an appropriate aryl or heteroaryl (etc.) lithium reagent to the correspnding cyclobutenedione.
- Liebeskind, Lanny S.,Iyer, Suresh,Jewell, Charles F.
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p. 3065 - 3067
(2007/10/02)
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- PHASE-TRANSFER CATALYSIS IN THE REACTION OF ANTHRAQUINONEDIAZONIUM FLUOROBORATE WITH BENZENE IN THE PRESENCE OF BASE
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Phase-transfer catalysis by polyethers and quaternary ammonium salts in the reaction of anthraquinonediazonium fluoroborate with benzene under the influence of O-nucleophiles was investigated.The introduction of the catalysts increase the yield of 1-phenylanthraquinone from 7 to 80-90percent.The investigated catalysts are similar in effectiveness.The reactivity series of the anions was determined: CH3COO- > OH- >C17H35COO- >CCl3COO-.Realization of the reaction in an atmosphere of oxygen leads to the formation of 1-hydroxyanthraquinone with a yield of up to 18percent in addition to 1-phenylanthraquinone.
- Pushkina, L. L.,Ponomareva, L. A.,Shelyapin, O. P.,Shein, S. M.
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p. 1336 - 1340
(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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- Diels-Alder Syntheses with 1,4-Di-tert-butoxy-1,3-butadiene
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The title compound (DTBU) enters into cycloadditions with fumaronitrile, tetracyanoethene, maleic anhydride, diethyl azodicarboxylate, 1,2-dibenzoylethene, dimethyl acetylenedicarboxylate, p-benzoquinone, 2-carbomethoxybenzoquinone, 2-methylbenzoquinone, 1,4-naphthoquinone, 2-methyl-1,4-naphthoquinone, and 5-hydroxy-1,4-naphthoquinone.When prepared the DTBU isomers are present in the ratio E,Z:Z,Z:E,E = 45:45:10.Of these, Z,Z-DTBU appears to be unreactive.In several cases where multible Diels-Alder products were possible, two related to E,Z- or E,E-DTBU were obtained.A connection between 1H NMR data (δ and J) and stereochemical configuration and conformation was elaborated for adducts of DTBU with p-benzoquinones or maleic anhydride.
- Hiranuma, Hidetoshi,Miller, Sidney I.
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p. 3096 - 3102
(2007/10/02)
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- 1-HYDROXY-9,10-ANTHRAQUINONE 9-ALKYLIMINES AND THEIR CONVERSION INTO 1,3-OXAZINOANTHRONES
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A series of previously uninvestigated N-alkyl-substituted 1-hydroxyanthraquinone 9-imines were obtained.In an acidic medium they decompose to hydroxyanthraquinone, but the 4-amino derivatives are stable to acid hydrolysis.In polar solvents in the presence of bases the 1-hydroxy-9,10-anthraquinone 9-alkylimines undergo intramolecular cyclization to derivatives of anthra-1,3-oxazinoanthrones.
- Popov, S.I.,Volosenko, V.P.
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p. 1708 - 1712
(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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