Synthesis and calculated properties of some 1,4-bis(amino)anthracene-9,10-diones

The synthesis of a number of 1,4-bis(amino)anthracene-9,10-diones containing chlorine or sulfur which are related to the anti-cancer drugs Ametantrone and Mitoxantrone are reported. 1,4-Dichloro-2,3-dihydro-5,8-dihydroxyanthracene-9,10-dione reacts readily with a series of alkylamines to yield the corresponding 1,4-bis(alkylamino)-5,8-dichloroanthracene-9,10-dione after oxidation. The subsequent reaction of the products with ethanethiol or thiophenol gives the corresponding 1,4-bis(alkylamino)-5,8-bis(sulfanyl)anthracene-9,10-dione in good yield. Theoretical calculations at the RHF 6-31G** level indicate that the introduction of either chlorine or the phenylsulfanyl group into the 5- and 8-positions of 1,4-bis(alkylamino)anthracene-9,10-diones results in a lowering of the LUMO energies suggesting that related functionalised derivatives might have lower cardiotoxicities than Mitoxantrone.     

Synthesis of lomazarin and norlomazarin, pigments from Lomandra hastilis

5,8-Dihydroxy-2,3,6-trimethoxy-7-ethyl-1,4-naphthoquinone (1) was used to synthesize in high yield 5,8-dihydroxy-7(1′-hydroxyethyl)-2,3,6-trimethoxy-1,4-naphthoquinone (lomazarin, 3), a pigment from Lomandra hastilis. Alkaline hydrolysis of lomazarin produced mainly 5,6,8-trihydroxy-2,3-dimethoxy-1,4-naphthoquinone (9) through a retro-aldol decomposition of the 6-keto-form of 5,6,8-trihydroxy-7(1′-hydroxyethyl)-2,3-dimethoxy-1,4-naphthoquinone (13b) formed during the reaction. 2,5,8-Trihydroxy-7(1′-hydroxyethyl)-3,6-dimethoxy-1,4-naphthoquinone (norlomazarin, 4a), a pigment of L. hastilis, and its 3,5,8-trihydroxy-7(1′-hydroxyethyl)-2,6-dimethoxy isomer 4b were formed as a difficultly separable mixture in addition to quinone 9. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 581–584, November–December, 2008.     

New NH-substituted 1,4-naphtho- and 1,4-benzo- quinones: Synthesis,characterization and potential antiproliferative effect against MDA-MB-231 cells

Abstract

Eleven new alkyl and aryl amino quinones were synthesized from quinones (2,3-dibromo-1,4-naphthoquinone 1, 2-bromo-1,4-naphthoquinone 2, p-benzoquinone 3 or 2,6-dichloro-1,4-benzoquinone 8) with primary amines. The structures of all compounds were characterized by spectroscopic technics and elemental analysis. The structure of 2-((6,6-Dimethylbicyclo[3.1.1]heptan-2-yl)methylamino)-3-bromonaphthalene-1,4-dione (5a) was established by single crystal diffraction. 2-(2-(Ethylthio)ethylamino)naphthalene-1,4-dione (6b) was found to have noteworthy antiproliferative effect against MDA-MB-231 cells.     

Ring closure of diethyl 2-methoxy-2-[N-(5-amino-1-benzylimidazolyl-4-carbonyl)amino]malonate: Product structures and pathways of product formation

Ring closure of the title compound (1) with sodium methoxide in methanol yielded three products, one 56-fused and two 57-fused heterocyclic systems: 9-benzyl-2-methoxycarbonylhypoxanthine (2), 3-benzyl-4,5,7,8-tetrahydro-6-methoxy-6-methoxycarbonyl-6H-imidazo[4,5-e][1,4]-diazepine-5,8-dione (3), and 3-benzyl-4,5,7,8-tetrahydro-6-methoxy-6H-imidazo[4,5-e][1,4]-diazepine-5,8-dione (4). Structures and pathways of formation of all three products have been described. Structures of2 and3 were confirmed by single-crystal X-ray diffraction analyses.     

Synthesis of 4-Amino-substituted-6-hydroxy and 11-hydroxynaphtho[2,3-g]quinoline-5,12-diones,and the unexpected formation of disubstituted imidazo[4,5,l-i,j]naphtho[2,3-g]quinolin-7-ones

4-Chloroquinoline-5,8-dione ( 8a ) and 6-bromo-4-chloroquinoline-5,8-dione ( 8b ) were reacted with homophthalic anhydride to give tetracyclic compounds 10 and 11 respectively. The 6,11-dihydroxy derivative 12 was prepared in low yield by photochemical addition of benzocyclobutenedione to 4-chloroquinoline-5,8-dione ( 8a ) and in better yield through a Friedel-Crafts reaction of phthalic anhydride with 4-chloro-5,8-dimethoxyquinoline ( 7a ). Whereas 4-chloro-6-hydroxynaphtho[2,3-g]quinoline-5,12-dione ( 11 ) was substituted by amines in the usual way to the corresponding 4-amino-substituted derivatives, 4-chloro-11-hydroxynaph-tho[2,3-g]quinoline-5,12-dione ( 10 ) led to a mixture of 4-amino derivatives and the unexpected 2,6-disubstituted-imidazo[4,5,l-I-j]naphtho[2,3-g]quinolin-7-ones, 13a-b .     

Synthesis and properties of copper and cobalt phthalocyanine complexes fused with the nitrogen heterocyclic quinones

Copper and cobalt complexes of tetra[4,5]([8,9](benzo[f]quinoline-7,10-dione)phthalocyanine, tetra[4,5]-([6,7]1-acetyl-2H-naphtho[2,3-d][1,2,3]triazole-5,8-dione) phthalocyanine, and tetra[4,5]([6,7]3-methylquinoline-5,8-dione)phthalocyanine were synthesized and their spectral properties were investigated.     

The synthesis of pyridazino[4,5-d] pyridazines,pyrazino [2,3-d] pyridazines and a pyrimido [4,5-d] pyridazine

The synthetic chemistry of the relatively unknown pyridazino [4,5-d]pyridazine ring system has been extended. 1,4-Diaminopyridazino [4,5-d]pyridazine (VIII) has been prepared by two routes, the most interesting of these being the one-step conversion of 4,5-dicyanopyridazine into VIII with hydrazine. Upon nitration VIII gave only the mononitramine (X). Attempts to prepare 1,4-dichloropyridazino [4,5-d]pyridazine gave only 4-chloro-2H-pyridazino [4,5-d]pyridazin-1-one (XII). Pyrimido [4,5-d]pyridazine-1,3-dione (XIV) was prepared from pyridazine-4,5-dicarboxamide (IV). The hydrolysis of 5,8-dichloropyrazino [2,3-d]pyridazine (XV) gave 5-chloropyrazino [2,3-d]pyridazin-8-one (XVII) and likewise the ammonolysis of XV gave 5-amino-8-chloropyrazino [2,3-d]pyridazine (XX). As expected the hydrolysis of 5,8-dibromo-pyrazino [2,3-d]pyridazine (XXI) gave 5-bromopyrazino [2,3-d]pyridazin-8-one (XXII). Attempted catalytic dechlorination of 5-chloropyrazino [2,3-d]pyridazin-8-one (XVII) gave 1,2,3,4-tetrahydropyrazino [2,3-d]pyridazin-5-one (XIX).     

Isofuranonaphthoquinones from ventilago maderaspatana: Crystal structure of ventilone-C

From the root bark of Ventilago maderaspatana (Rhamnaceae) five isofuranonaphthoquinones have been isolated. Ventilone-A is 4,9-dihydro-5,8-dihydroxy-6,7-methylenedioxy-1-methylnaphtho[2,3-c] furan-4,9-dione and B is the 5-methyl ether. Ventilone-C has the structure 1,3,4,9-tetrahydro-8-hydroxy-5-methoxy-6, 7-methylenedioxy-1-methylnaphtho[2,3-c]furan-4,9-dione, D is the isomeric 8-methyl ether, and E is the 5,8-dimethyl ether. Structures were determined by spectroscopic methods, and X-ray crystallographic analysis of ventilone-C.     

Synthesis and Characterization of Nitrogen and Sulfur Containing 1,4-Naphthoquinones

Abstract

New N,S-disubstituted naphthoquinones were synthesized by reactions of S- and N-nucleophiles with 2,3-dichloro-1,4-naphthoquinone. 2-(Hexadecylthio)-3-(phenylamino)-naphthalene-1,4-dione 5a was synthesized by reaction of 2-chloro-3-(phenylamino)-naphthalene-1,4-dione 3a with hexadecanethiol 4a. The structures of the new synthesized naphthoquinone derivatives were determined by micro analyses and spectroscopic methods (FT-IR, ¹H NMR, ¹³C NMR, MS, and UV/Vis.). Photo- and electrochemical properties of selected compounds were investigated by using fluorescence spectroscopy and the cyclovoltammetry method.     

Effect of structure on the thermal degradation and flame retardancy of hexolic anhydride based polyesters

Based on the anhydrides like hexolic (5,6,7,8,10,10-hexachloro -3a,4,4a,5,8,8a,9,9a-octahydro-5,8-methanonaphtho-[2,3-c]-furan-1,3-dione), maleic and phthalic and diols like 1,4-butanediol, cis-2-butene-1,4-diol and 2,3-dichloro-2-butene-1,4-diol, a family of polyesters has been synthesized using azeotropic condensation technique. The structural characterizations of the polyesters have been carried out using infra-red, 1^H - and ¹³C- nuclear magnetic resonance spectroscopic methods. The thermal properties of the polyesters have been studied using thermogravimetric technique. The off-line pyrolysis of these materials was done. The qualitative and semi-quantitative analyses of the volatiles as well as the heavy mass fractions of the degradation products were carried out using a gas chromatograph coupled to a mass selective detector (GC-MSD). Thermogravimetric data indicate that the thermal stability and the char residue of the polyester resins decrease in the order 1,4-butanediol based>cis-2-butene-1,4-diol based>2,3-dichloro-2-butene-1,4-diol based polyesters. The GC-MSD data indicate that the amount of flame cooling agents (hexa-, isomeric penta-, tetra- and isomeric tri-chlorocyclopentadienes) produced during the pyrolysis of the polyesters increases in the order 2,3-dichloro-2-butene-1,4-diol based<cis-2-butene-1,4-diol based<1,4-butanediol based polyesters. The trends observed in these two parameters which are contributing factors to the flame retardancy of the polyester materials were suitably explained on the basis of the effect of the structural changes in the diol part of the polyesters on the primary degradation mechanism, the β-chain scission process.     

Synthesis of 5,8-dihydroxynaphtho[2,3-c][1,2,5]thiadiazole-6,9-dione and 6,9-dihydroxybenzo[g]quinoxaline-5,10-dione

The synthesis of 5,8-dihydroxynaphtho[2,3-c][1,2,5]thiadiazole-4,9-dione 3 , 6,9-dihydroxybenzo[g]quinoxaline-5,10-dione 4 , and their lesser oxygenated analogs via Friedel-Crafts and Diels-Alder synthesis is reported.     

Untersuchungen von Reaktionsmechanismen durch Isotopenmarkierung,IX Zum Ringverengungsmechanismus von 1,4-Benzthiazin-2,3-4H-dion

By¹⁴C-labeling it is shown that the ring contraction reaction of 1,4-benzothiazin-2,3-4H-dione (1), leading via benzthiazol-2-carbonic acid (2) finally to benzthiazole (3), proceeds via hydrolytic opening of the thiolactone-bond in1, irrespectively of H⁺ or OH^– catalysis.

     

Novel one-pot multicomponent synthesis of (E)-2-(benzylideneamino)-5-mercapto-4H-1,2,4-triazol-3-yl)-2,3-dihydrophthalazine-1,4-dione derivatives

Abstract

An expeditious, one-pot multicomponent reaction has been developed for the synthesis of (E)-2-(benzylideneamino)-5-mercapto-4H-1,2,4-triazol-3-yl)-2,3-dihydrophthalazine-1,4-dione derivatives. Condensation of 4-amino-5-hydrazino-4H-1,2,4-triazole-3-thiol with phthalic anhydride and aromatic aldehyde afforded the (E)-2-(benzylideneamino)-5-mercapto-4H-1,2,4-triazol-3-yl)-2,3-dihydrophthalazine-1,4-diones in acetic acid medium with excellent yields. All the synthesized compounds were characterized by their analytical and spectral data.     

Chemical interactions between 2-mercaptobenzazoles and π-acceptors

Summary 2-Mercaptobenzazoles (1a–c) interact with several -acceptors such as tetracyanoethylene (TCNE) 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), 2,3,5,6-tetrachloro-1,4-benzoquinone (CHL) dicyanomethyleneindane-1,3-dione (CNIND), 2,3-dicyano-1,4-naphthoquinone (DCNQ), 9-dicyanomethylene-2,4,7-trinitrofluorene (DTF), and 2,3-dichloro-1,4-naphthoquinone (DCHNQ)via the formation of charge-transfer (CT) complexes to yield various heterocyclic compounds.

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Chemische Wechselwirkungen zwischen 2-Mercaptobenzazolen und -Akzeptoren

Zusammenfassung Die 2-Mercaptobenzazole1a–c reagieren mit verschiedenen -Akzeptoren wie Tetracyanoethylen (TCNE), 2,3-Dichlor-5,6-dicyano-1,4-benzochinon (DDQ), 2,3,5,6-Tetrachlor-1,4-benzochinon (CHL), Dicyanomethylenindan-1,3-dion (CNIND), 2,3-Dicyano-1,4-naphthochinon (DCNQ), 9-Dicyanomethylen-2,4,7-trinitrofluoren (DTF) und 2,3-Dichlor-1,4-naphthochinon (DCHNQ) unter Ausbildung von charge transfer — Komplexen (CT) zu heterocyclischen Verbindungen.

     

The synthesis of 5,8-difluoronaphtho[2,3-c]thiophene-4,9-dione and its facile conversion to 2-[2-(dimethylamino)ethyl]- 5-[2-(dimethylamino)ethylamino]-8-fluoro-naphtho[2,3-c] pyrrole-4,9-dione

The synthesis of 5,8-difluoronaphtho[2,3-c]thiophene-4,9-dione ( 2a ) has been accomplished. Treatment of 2a with 2,2-dimethylaminoethylamine leads to 2-[2-(dimethylamino)ethyl]-5-[2-(dimethylamino)ethylamino]-8-fluoronaphtho[2,3-c]pyrrole-4,9-dione ( 6 ).     

Synthesis of naphtho[2',3':4,5]imidazo[2,1-<Emphasis Type="Italic">b</Emphasis>][1,3]-thiazole-5,10-dione and naphtho[2',3':4,5]imidazo-[2,1-<Emphasis Type="Italic">b</Emphasis>][1,3]benzothiazole-7,12-dione

The reaction of 2,3-dibromo-1,4-naphthoquinone with 2-aminothiazole in MeONa/MeOH at 60oC for 3 h gave naphtho[2',3':4,5]imidazo[2,1-b][1,3]thiazole-5,10-dione in 64% yield. The reaction of 2,3-dibromo-1,4-naphthoquinone with 2-aminobenzothiazole under the above-mentioned conditions gave 2-(benzo[d]thiazol-2-ylamino)-3-bromonaphthalene-1,4-dione in 64% yield, which on treatment with Na/THF or NaN₃/acetone under reflux conditions gave naphtho[2',3':4,5]imidazo[2,1-b][1,3]- benzothiazole-7,12-dione in 69 and 56% yields, respectively.     

Singlet oxygenation of cis,cis-1,5-cyclooctadiene: a convenient synthetic entry into 5,8-difunctionalized oxygen derivatives of 1,3-cyclooctadiene

The 6-hydroperoxy-1,4-cyclooctadiene ($\text{2}$), which is formed in the photosensitized oxygenation of 1,5-cyclooctadiene ($\text{1}$), affords on further singlet oxygenation 5,8-dihydroperoxy-1,3-cyclooctadiene ($\text{3}$), which via triphenylphosphine reduction leads to $\text{cis}$-5,8-dihydroxy-1,3-cyclooctadiene ($\text{4}$) and subsequent pyridinium chlorochromate oxidation to 1,3-cyclooctadien-5,8-dione ($\text{8}$).     

Syntheses,crystal structures,and properties of three two-dimensional complexes constructed by flexible (2,3-pyridylmethyl)amine

Three two-dimensional coordination polymers [Cd(2,3-Pyma)Cl₂] _n (I), {[Cd(2,3-Pyma)(1,4-Chdc)] · 4H₂O}n (II) and {[Zn₂(2,3-Pyma)(1,2,4,5-Bttc)(H₂O)₄] · 6H₂O} _n (III) (2,3-Pyma = (2,3-pyridylmethyl) amine, H₂-1,4-Chdc = 1,4-cyclohexanedicarboxylic acid, and H₄-1,2,4,5-Bttc = 1,2,4,5-benzenetetracarboxylic acid) have been synthesized and structurally characterized by single crystal X-ray crystallography (CIF files CCDC nos. 989461 (I), 1055685 (II) and 1055686 (III)). Three complexes are all twodimensional layer networks bridged by the flexible 2,3-Pyma ligands or the carboxylate ligands. It is noted that the flexible 1,4-Chdc ligands bind the Cd²⁺ ions into a helical chain structure in complex II. The photoluminescence and thermal properties are investigated.     

Synthesis of 1,2-bis(methoxyamino)cycloalkanes from alicyclic 1,2-bis(hydroxyamines)

Derivatives of 1,4-dihydroxypiperazine-2,3-dione were obtained by reaction of cis-1,2-bis(hydroxyamino)cycloalkanes with diethyl oxalate. Their alkylation with CH₂N₂ or Mel afforded 1,4-dimethoxypiperazine-2,3-diones. Hydrolysis of the latter gave 1,2-bis(methoxyamino)cycloalkanes.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 925–929, April, 1996.     

A Convenient Synthesis of 1-Amino-4-methyl-4H-3-thia-4,5a,10-triazacyclopenta[a]fluoren-5-ones and Some New 2,3-Dihydro-1,3,4-thiadiazoles

1-amino-4-methyl-4H-3-thia-4,5a,10-triazacyclopenta-[a]fluoren-5-one and 6-methyl-6H-,9H-thia-4b,6,9,11,12-pentaazaindeno[1,2-a]-fluorene-5,8-dione derivatives were prepared from 2-methyl-1-oxo-3-thioxo-2,4,9b-trihydropyrimidino[1,6-a] benzimidazole-4-carbonitrile. Also, 2,3-dihydro-1,3,4-thidazoles were synthesized via a reaction of hydrazonoyl chlorides with 3-(methylamino)-2-substituted 3-thioxopropanenitrile. Structures of newly synthesized compounds were elucidated on the basis of elemental analyses, spectral data, and alternative methods synthesis whenever possible.