Peroxide chemistry of triaryl-substituted imidazoles. Fenflumizole, a non-steroidal, anti-inflammatory agent.

Fenflumizole, [2-(2,4-difluorophenyl)4,5-bis(4-methoxyphenyl)imidazole] is a nonsteroidal, anti-inflammatory analgesic. It reacts quantitatively with 1O2 forming 2-(2,4-difluorophenyl)-4-hydroperoxy-4,5-bis(4-methoxyphenyl)imidazole in a reversible reaction. In ethanol solution at ambient temperatures, the peroxide regenerates parent fenflumizole and 1O2 together with minor quantities of other products. The structures of those products point to the intermediacy of a 1,3-endoperoxide and a dioxetane. These observations may be relevant to the biological activity of fenflumizole.     

Polyimidines,a new class of polymers. II. Polyhexamethylenetetraphenyldithiopyromellitimidine

Polyimidines have been shown to be soluble, thermally stable polymers. In searching for an alternate synthetic method the thio analog of this system has been discovered. The brightly colored (red-orange) perthio derivatives of 3,3-diphenylphthalide and 3,3,5,5-tetraphenyipyromellitide were synthesized from their oxo analogs with P₂S₅. The model compound thioimidines were synthesized by reacting 3,3-diphenyldithiophthalide with aniline and with 1,6-hexane diamine and by reacting 3,3,5,5-tetraphenyltetrathiopyromellitide with aniline and n-hexylamine. The polymerization of tetraphenyltetrathiopyromellitide occurred readily with 1,6-hexanediamine in boiling carbon tetrachloride with complete cyclization. This reaction gave an 80% yield with inherent viscosities up to 0.89 and molecular weights up to approximately 11,000. Thermogravimetric analysis showed a 2% weight loss at 200°C and 10% weight loss at 300°C with rapid decomposition above 300°C. Although the polythioimidine was less thermally stable than its oxo analog, it was much more soluble in common solvents (aromatic and chlorinated aliphatic hydrocarbons) and more readily synthesized in higher yield.     

Alizarin-s,a reagent for thorium. a gravimetric,colorimetric, and spectrophotometric study

The claim of Beck in the use of alizarin-S for separating cerite earths from thorium could not be substantiated. Detailed conditions for estimating from 0.0095 to 6.3 mg of thorium dioxide in 50 ml of solution by the method of Rao and Murthy are described. The absorption characteristics of alizarin-S and its-thorium complex have been studied in their dependance on pH. The thorium complex has been shown by adopting different optical methods to correspond to Th-Al-S (a stoichiometric ratio of 1:1) which is also confirmed from gravimetric analyses. The dissociation coefficient of the complex at pH 2.7 has been computed to be less than 1.10^-8.     

Oxidative coupling in 4a,9-diaza-1,2,4a,9a-tetrahydrofluorene derivatives. 2. Synthesis of methylenequinoneimines

The oxidative coupling of 4a,9-diaza-1,2,4a,9a-tetrahydro-9H-fluorene derivatives with methylene-active compounds in the presence of MnO₂ leads to substituted (at the methylene group) 6-methylene-4a,9-diaza-1,2,4a,9a-tetrahydro-6H-fluorene derivatives. The corresponding 2,2-disubstituted 5-dicyanomethylene-3,5-dihydrobenzimidozoles were obtained in the reaction of 2,2-disubstituted benzimidazolines with malonitrile in the presence of MnO₂.See [1] for Communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 779–785, June, 1990.     

Oxidative coupling of 4a,9-diaza-1,2,4a,9a-tetrahydrofluorenes. 1. Synthesis of mononuclear heterocyclic quinonediimines

Oxidative coupling of 4a,9-diaza-1,2,4a,9a-tetrahydro-9H-fluorene with primary amines and ammonia in the presence of MnO₂ gives the corresponding 6-aryl (or alkyl)imino-4a,9-diaza-1,2,4a,9a-tetrahydro-6H-fluorenes. Coupling with thiourea under these conditions affords 6-cyanoimino-4a,9-diaza-1,2,4a,9a-tetrahydro-6H-fluorenes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1500–1504, November, 1989.     

Oxidative Coupling in a Series of Derivatives of 4a,9-Diaza-1,2,4a,9a-tetrahydrofluorene. 6. Reactions with Substituted 2-Aminoethanols

Oxidative coupling of derivatives of 4a,9-diaza-1,2,4a,9a-tetrahydro-9H-fluorene with 2-ethyl-, 2,2-dimethyl-, and 2-hydroxymethyl-2-methylaminoethanol in the presence of MnO₂ led to the selective formation of the corresponding mono- and di(hydroxymethyl)quinonediimines, subsequent cyclization of which gave the products of 6,7-annelation. Coupling with 2,2-di(hydroxymethyl)aminoethanol gave the annelation products directly.     

Polyimidines,a new class of polymers. I. Phenylated polypyromellitimidines

Model compounds and polymers containing the imidine functional group have been synthesized from diphenylphthalide and tetraphenylpyromellitide by condensation with mono- and diamines. The diamine monomers included: 1,6-diaminohexane, p-phenylenediamine, and 4,4′-diaminodiphenyl ether. Reactions were run either in biphenyl or with no solvent at 250–300°C to yield up to 57% product with molecular weights up to approximately 16,000 and inherent viscosities to 0.15. All polymers were soluble in chloroform and dimethylformamide and showed thermal stabilities by TGA to range from 225°C (for aliphatic backbones) to 400°C (for aromatic systems).     

Synthesis of a potent rhodomycin, oxaunomycin, and its analogs.

Oxaunomycin (3) and its regioisomer (6) were synthesized by employing regioselective glycosidations of the C-7 hydroxyl group of 10-O-acetyl-beta-rhodomycinone (16) and the C-10 hydroxyl group of the C-7,9-O-phenylboronate (14), respectively, in the presence of trimethylsilyl trifluoromethanesulfonate. Under the K?nigs-Knorr conditions, 16 was also glycosidated to provide a fluoro sugar analog (7).     

The structure of discretamine, a tetrahydroprotoberberine alkaloid.

On the basis of mass spectrometric analysis, including comparison with closely related isomers, discretamine is proposed to have the structure of a 3,10-dihydroxy-2,9-dimethoxytetrahydroprotoberberine.     

Microbial products. II. Granaticinic acid,a new antibiotic from a thermophilic streptomycete

Streptomyces sp. XT-11989 produces a mixture of two antibiotics with litmus-like indicator properties. One of them was shown to be identical with granaticin, the other was identified as [1S,3S,4S,7R,9R,10S,13R]-4,7,9,10-tetrahydro-5,12-dioxo-4, 6,10,11,13-pentahydroxy-1,9-dimethyl-(1H,3H)-7,10-ethanonaphtho[2,3-c: 6,7-c]dipyran-3-acetic acid and termed granaticinic acid. Microbial production and nuclear magnetic resonance data of these antibiotics are discussed and the antibacterial properties of the antibiotics are compared.

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Mikrobielle produkte. II. Granaticinsäure, ein neues Antibiotikum von einem thermophilen Streptomyceten

Zusammenfassung Der Streptomycetenstamm XT-11989 produziert eine Mischung von zwei Antibiotika mit Lakmus-ähnlichen Indikatoreigenschaften. Eines dieser Antibiotika erwies sich als Granaticin, das andere wurde als [1S,3S,4S,7R,9R,10S,13R]-4,7,9,10-tetrahydro-5,12-dioxo-4,6,10,11,13-pentahydroxy-1,9-dimethyl-(1H,3H)-7,10-ethanonaphto[2,3-c: 6,7-c]dipyran-3-essigsäure identifiziert und Granaticinsäure benannt. Mikrobiologische Produktion und Kernresonanzdaten dieser antibiotika werden besprochen und ihre antibakteriellen Eigenschaften verglichen.

     

Crystal structure of a methine dye, C.I. Disperse Blue 354.

Crystals of C.I. Disperse Blue 354, a commercial methine disperse dye, were grown from an ethyl acetate and the crystal structure was determined. Results show that two aromatic planes are effectively coplanar with the dihedral angle of 10.61(11) degrees. The dicyanomethylene group is slightly twisted and two n-hexyl groups tend to be separated with one alkyl group being at the level of the aromatic plane, and another one below it. The intermolecular hydrogen bonds and the interlayer pi-pi stacking stabilize the crystal packing.     

Application of the Prigogine-Flory-Patterson theory part III. Mixtures of a bicyclic compound,benzene, cyclohexane,n-hexane with a cycloalkane,cyclohexene, a cycloalkadiene and benzene

The Prigogine-Flory-Patterson theory of liquid mixtures has been qpplied to the H _m ^E and V _m ^E for binary mixtures of a bicyclic compound, benzene, cyclohexane and n-hexane with a cycloalkane, cyclohexene, a cycloalkadiene and benzene. Furthermore the Prigogine-Flory theory has been used to predict activity coefficients at infinite dilution from the experimentally determined H _m ^E at 25°C for the mixtures cyclohexane, cyclohexene, 1,3-cyclohexadiene, 1,4-cyclohexadiene and benzene with a bicyclic compound. The predictions are compared to experimental results.