- Carbon-13 NMR Spectra of Anthraquinone-Derived Dyes
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The 13C NMR spectra of six anthraquinone-derived dyes, namely benzanthrone, 1-(methylamino)anthraquinone, 1,4-di-p-toluidinoanthraquinone, 1,4-diamino-2,3-dihydroanthraquinone, 1,4-diaminonanthraquinone and dibenzochrysenedione, have been measured.The chemical shift assignments were achieved by elucidation of the coupling patterns of the fully coupled spectra and by comparison with the chemical shifts of other anthraquinone derivatives and other model compounds.One- and three-bond carbon-hydrogen coupling constants are also reported.
- Rubin, I. B.,Buchanan, M. V.
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- A new Synthesis of 1-Amino-4-butylaminoanthraquinone from 1-Aminoanthraquinone Promoted by Metal Ions
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In the presence of some metal ions and atmospheric oxygen, 1-aminoanthraquinone (1) reacts readily with butylamine to give 1-amino-4-butylaminoanthraquinone(2a), along with a small amount of 1,4-diaminoanthraquinone, which is produced by the dealkylation of 2a.The activity of the metal ions decreased in the following order: Co(II) >> Ni(II) above Cu(II) above Al(III).The reaction is remarkably affected by the substitution of an alkyl group into the amino group of 1, the addition of a chelating agent, the counter anion of metal ions, and the reaction temperature.By the use of cobalt(II) chloride, the reaction proceeds most smoothly at about 30 deg C.Both anthraquinone and 2-aminoanthraquinone show no sign of the reaction under the same conditions.A possible mechanism involving the formation of a metal complex, followed by the nucleophilic attack of amine at the 4-position and the oxidative abstraction of the hydride anion by atmospheric oxygen is proposed.
- Yoshida, Katsuhira,Matsuoka, Masaru,Yamashita, Yoshio,Kitao, Teijiro
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- Reaction of 5-chloroanthra[1,9-cd]-6-isoxazolone with pyridine bases
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In the reaction of 5-chloroanthra[1,9-cd]-6-isoxazolone with pyridine bases the chlorine atom is substituted to give the corresponding pyridinium salts. The pyridine ring of the synthesized anthra[1,9-cd]isoxazol-6-one-5-pyridinium chloride was cleaved by the Zincke method. The reduction of the cleavage product, viz., N-(anthra[1′,9′-cd]isoxazol-6-on-5-yl)-5-amino-2,4-pentadienal, under various conditions was investigated.
- Gornostaev,Zolotareva,Verkhovodova
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- Structure-activity relationships of novel P2-receptor antagonists structurally related to Reactive Blue 2
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P2 membrane receptors for nucleotides represent significant targets for experimental pharmacology and drug research. In earlier publications, we have shown that Reactive Blue 2 (RB 2), one of the most widely used P2-receptor antagonists, displays only moderate affinity and does not discriminate between native P2X- and P2Y-receptor subtypes. In the present study we have pharmacologically evaluated a series of 15 synthesized and re-evaluated four commercially obtained and chromatographically purified RB 2 type anthraquinone derivatives on contractions of the rat vas deferens (RVD) elicited by α,β-methylene ATP (α,β-meATP), mediated by P2X 1-receptors, and relaxations of the carbachol-precontracted guinea-pig taenia coli (GPTC) elicited by adenosine 5′-O-(2- thiodiphosphate) (ADPβS), mediated by P2Y1-like receptors. Based on the structure-activity relationships (SAR) it is concluded that hydrophobic interactions of aromatic π-electron systems, hydrogen bonds with nitrogen as donor and acceptor atoms, and, particularly, position, conformational distance and number of anionic sulfonate groups are of great importance for the blockade of the two native P2-receptor subtypes. We have also identified novel, for the most part reversible antagonists that bind with higher affinity and improved subtype selectivity in comparison to RB 2. In particular, 1-amino-4-{4-[4- chloro-6-(2-sulfonatophenylamino)-[1,3,5]triazine-2-ylamino]-2- sulfonatophenylamino}-9,10-dioxo-9,10-dihydroanthracene-2-sulfonic acid trisodium salt (MG 50-3-1) is the most potent antagonist at the P2Y 1-like-receptors of the GPTC reported so far (IC50 = 4.6:nM). It is significantly less potent as reversible antagonist at the P2X1-receptors of the RVD (IC50 = 2.8 μM). Thus, MG 50-3-1 represents a selective pharmacological tool and may be a lead compound for future investigations.
- Gl?nzel, Markus,Bültmann, Ralph,Starke, Klaus,Frahm, August W.
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p. 1262 - 1276
(2007/10/03)
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- Synthesis and cytotoxic evaluation of two novel anthraquinone derivatives
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The antitumor activity of dihydroxyanthracenediones such as mitoxantrone on a panel of cancer cell lines during the last 30 years, led investigators to synthesize thousands of anthracycline analogs and test their cytotoxicity to identify compounds superior to the parent drugs in terms of increased therapeutic effectiveness, reduced toxicity or both. To achieve this, new synthesized congeners either have different side arms or have extra rings on their skeletons. Following these studies, we proposed total synthesis of 2-amino-N-[4-(2-amino-3-hydroxy-propionylamino)-9,10-dioxo-9, 10-dihydroanthracene-1-yl]-3-hydroxy-propionamide (V) and 6-amino-hexanoic acid [4-(5-amino-pentanoylamino)-9,10-dioxo-9,10-dihydro-anthracen-1-yl]-amide (VI). Acetylation of 1,4-diaminobenzene using acetyl chloride and reaction with phthalic anhydride under a Friedel-Crafts reaction and then cyclization gave 1, 4-diamino-anthraquinone. This compound was reacted with two amino acids (L-serine and 6-amino hexanoic acid) in their ester forms, using ethyl chloroformate as a coupling agent. Hydrolyzing esterified compounds gave their amino substituted derivatives. These compounds with diamine side arms are supposed to provide better intercalation with DNA. Synthesized novel ametantrone derivatives were tested against a panel of cancer cells (KB, Hela, MDA-MB-468 and K562), using MTT assay. The results showed that tested compounds inhibited the growth of cancer cells at micromolar concentrations. However, compound (VI) was more cytotoxic than compound (V) probably because of its longer side chains and better intercalation with DNA.
- Sadeghi-Aliabadi, Hojjat,Tabarzadi, Maryam,Zarghi, Afshin
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p. 645 - 649
(2007/10/03)
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- Experimental and theoretical study of tautomerism in 1,4-bisanthracene-9,10-diones and their reduced forms
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Treatment of leucoquinizarin 4a with methoxylamine hydrochloride (O-methylhydroxylamine hydrochloride) in oyridine led to tautomer 4e.Oxidation of 4e in refluxing nitrobenzene led to 1,4-diaminoanthracene-9,10-dione 1e while oxidation with manganese dioxide yielded 1,4-bis(methoxyimino)-2,3-dihydroanthracene-9,10-dione 6.Attempted diplacement of the fluorides from 1,4-difluroanthracene-9,10-dione by methoxylamine in dimethyl sulfoxide led to 9,10-dihydroxy-1,4-bis(methoxyimino)anthracene 2h instead of the anticipated bis(methoxyamino) tautomer 1h.Calculations have been carried out on some of these derivatives using the 3-21G basis set and the results for 2h compared with X-ray data from a single crystal.The calculated results show that that 1h is marginally preferred over 2h by 0.68 kcal mol-1.The reduced forms show the opposite trend with 4e preferred by 11.3 kcal mol-1 over 3e in line with NMR data recorded in chloroform.The presence of an oxygen atom adjacent to the nitrogen atom in the methoxyimine substituent forces a tetrahedral conformation at nitrogen resulting in a destabilization of the anthracene-9,10-dione tautomers 1h and 3e.
- Morley, John. O.,Krapcho, A. Paul,Cummings, Douglas S.
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p. 287 - 292
(2007/10/03)
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- A facile method for preparing substituted 1-aminoanthraquinones
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An efficient and simple preparation of α-substituted aminoanthraquinones using 2,2,-dialkoxyethylamines is described.
- Wormser,Sardessai,Abramson
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p. 3211 - 3222
(2007/10/02)
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- 1,4-Diamino- and 1,4-Dibutylamino-anthraquinones: Reduction and/or Deprotonation-initiated Elimination of the Butyl Groups in Dipolar Aprotic Media
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The standard redox potentials of the one- and two-electron reductions of the title compounds have been determined.The deprotonated form of the dibutylamino compound underwent a base-initiated elimination of the butyl groups and the basicity of the radical anion resulting from one-electron reduction was sufficient to provoke the same type of cleavage through an initial father-son reaction.A multi-step mechanism is proposed for the elimination on the basis of the identification of intermediates.
- Anne, Agnes
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p. 311 - 318
(2007/10/02)
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- NUCLEOPHILIC SUBSTITUTION OF HYDROGEN IN AROMATIC SYSTEMS. II. MECHANISM OF AMINATION IN ANTHRAISOXAZOL-6-ONES
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The nucleophilic substitution of the C5-H hydrogen atom in anthraisoxazol-6-ones by amines in acetonitrile in the absence of Cu2+, Ag+, Co2+, or Ni2+ cations takes place with the formation of strong hydrogen bond in the sixmembered chelate ring of the product from 1,4-addition of the amine to the isoxazolone at the C5 and =O atoms.The structure of the reaction product is determined by the character of the amine, and (with the absence of readily eliminated groups) substitution of C5-H is suppressed by the competing amination of C3-H and reduction of the heterocycle.The substitution of C5-Hlg by amines under analogous conditions leads to trivial reaction products.In nitromethane C3-H or C3-Hlg is mainly substituted, and C5-H or C5-Hlg is partly substituted, leading to products with trivial structures.In the presence of Cu2+, Ag+, Co2+, Ni2+ cations in acetonitrile only C3-H or C3-Hlg is substituted through the formation of mixed complex of amine and isoxazolone on the cation.
- Galushko, A. M.,Dokunikhin, N. S.
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p. 1347 - 1357
(2007/10/02)
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- The Direct Alkylamination of 1-Aminoanthraquinone Promoted by Cobalt(II) Chloride
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The reaction of 1-aminoanthraquinone with primary aliphatic amines in the presence of cobalt(II) chloride under atmospheric oxygen preferentially gave the corresponding 1-amino-4-(alkylamino)anthraquinones.The reaction did not proceed with aqueous ammonia, bidentate amines, secondary aliphatic amines, and primary arylamines.While, with alicyclic amines the reaction mainly afforded 1-amino-2,4-bis(alkylamino)anthraquinones.
- Yoshida, Katsuhira,Matsuoka, Masaru,Yamashita, Yoshio,Nagamori, Shoichi,Kitao, Teijiro
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p. 3725 - 3726
(2007/10/02)
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- Process for the production of aminoanthraquinone compounds
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The present invention concerns a novel process for the reduction of a nitro-anthraquinone compound of formula I: STR1 wherein M IS AN INTEGER 1, 2 OR 3, AND n is an integer 1, 2 or 3, The sum of m + n being 3, 4 or 5, and the rings A and B are either further substituted or unsubstituted, To the corresponding amino-anthraquinone compound which comprises reacting the compound of formula I with hydrazine in aqueous medium. The resulting amino-anthraquinone compounds are in general known and are useful intermediates in the production of anthraquinone dyestuffs.
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