4-hydroxy-2-quinolones. 40. Synthesis and biological properties of anilides of 1H-2-oxo-4-hydroxyquinoline-3-carboxylic acid

An improved method for the synthesis of anilides of 1H-2-oxo-4-hydroxyquinoline-3-carboxylic acid was proposed. Results of the study of antithyroid and anti-tuberculosis activity of the compounds synthesized are presented.For the Communication 39, see [1].National Pharmaceutical Academy of Ukraine, Kharkov 31002. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 203–206, February, 2000.     

4-hydroxy-2-quinolones. 42. Synthesis and biological activity of 1-R-2-oxo-3-(2H-1,2,4-benzothiadiazine-1,1-dioxid-3-yl)-4-hydroxyquinolines

A preparative method for the synthesis of 1-R-2-oxo-3-(2H-1,2,4-benzothiadiazine-1,1-dioxid-3-yl)-4-hydroxyquinolines has been developed. The diuretic and antitubercular activity of the obtained compounds have been studied.For Communication 41 see [1].National Pharmaceutical Academy of Ukraine, Khar'kov 310002; e-mail: igor@uiv.kharkov.ua. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 409–414, March, 2000.     

4-Hydroxy-2-quinolones. 44. Synthesis of 2-R-3-oxomorpholino[5,6-c]-6-R'-Quinolin-5-ones

Treatment of 1-R-2-oxo-4-hydroxyquinolin-3-ylamides of -halogen-substituted carboxylic acids with sodium methoxide leads to the formation of 2-R-3-oxomorpholino-[5,6-c]-6-R-quinolin-5-ones. The antituberculosis activity of the compounds synthesized was studied.For Communication 43, see [1].National Pharmaceutical Academy of Ukraine, Kharkov 310002; e-mail: igor@uiv.kharkov.ua. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1080–1083, August, 2000.     

Dehydration of 4-hydroxy-4-methyl-3-phenylamino-oxazolidin-2-ones

The dehydration of two 5,5-disubstituted 4-hydroxy-4-methyl-3-phenylaminooxazolidin-2-ones into the corresponding 4-methylene-3-phenylaminooxazolidin-2-ones has been carried out. The structure of the products was confirmed by X-ray diffraction analysis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1512–1517, October, 2004.     

4-hydroxy-2-quinolones. 41. Reaction of hydrazides of 1-R-2-oxo-4-hydroxyquinoline-3-carboxylic acids with ethyl orthoformate

The boiling of hydrazides of 1-R-2-oxo-4-hydroxyquinoline-3-carboxylic acids in an excess of ethyl orthoformate leads to the formation of ethyl esters of the corresponding quinoline-3-carboxylic acids, the structure of which was confirmed by X-ray diffraction analysis.For the Communication 40, see [1].National Pharmaceutical Academy of Ukraine, Kharkov 310002. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 207–211, February, 2000.     

Synthesis of some schiff bases of 3-aroyl-6-aryl-4-hydroxy-2H-pyran-2-ones

Summary The reaction of 3-aroyl-6-aryl-4-hydroxy-2H-pyran-2-ones (Ar=p-tolyl, 1,1-biphenyl-4-yl or thienyl) with aniline and substitutedo-phenylenediamine (R=H, CH₃ or Cl) yields a series of new Schiff bases2a–f in 51–72% yield. Bromination of1a gave the 5-bromo derivative1c, while the compounds1a,1b,2b,2e, and2f were converted into 2,6-diaryl-4H-pyran-4-ones3a–c. All products have been fully characterized.

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Synthese von Schiff'schen Basen von 3-Aroyl-6-aryl-4-hydroxy-2H-pyran-2-onen

Zusammenfassung Die Reaktion von 3-Aroyl-6-aryl-4-hydroxy-2H-pyran-2-onen (Ar=p-Tolyl, 1,1-Biphenyl-4-yl oder Thienyl) mit Anilin und substituierteno-Phenylendiaminen liefert neue Schiff'sche Basen2a–f/bd in 51–72% Ausbeute. Bromierung von1a gab das 5-Bromderivate1c, während die Verbindungen1a,1b,2b,2e und2f in 2,6-Diaryl-4H-pyran-4-onen3a–c übergeführt wurden. Alle Produkte wurden voll charakterisiert.

     

4-hydroxy-2-quinolones. 43. Thermolysis of ethyl esters of 1-R-2-oxo-4-hydroxy-quinoline-3-carboxylic acids

Ethyl esters of 1-R-2-oxo-4-hydroxyquinoline-3-carboxylic acids under thermolysis conditions are converted to 5,9-di-R-6,7,8-trioxodiquinolino[3,4-b;3,4-e]-4H-pyrans. One of the synthesized compounds was studied by X-ray diffraction.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 516–522, April, 2000.     

Ab initio, density functional theory and structural studies of 4-amino-2-methylquinoline

The Fourier transform infrared (FTIR) and FT-Raman spectra of 4-amino-2-methylquinoline (AMQ) have been recorded in the range 4000–400 and 4000–100 cm⁻¹, respectively. The experimental vibrational frequency was compared with the wavenumbers obtained theoretically by ab initio HF and DFT–B3LYP gradient calculations employing the standard 6-31G** and high level 6-311++G** basis sets for optimised geometry of the compound. The complete vibrational assignment and analysis of the fundamental modes of the compounds were carried out using the experimental FTIR and FT-Raman data, and quantum mechanical studies. The geometry and normal modes of vibration obtained from the HF and DFT methods are in good agreement with the experimental data. The potential energy distribution of the fundamental modes was calculated with ab initio force fields utilising Wilson's FG matrix method. The NH-π interactions and the influence of amino and methyl groups on the skeletal modes are investigated.     

A novel synthesis of 4-propyl-2H-1-benzopyran-2-ones

Reaction of 2-hydroxybutyrophenones1–5 with ethoxycarbonylmethylenetriphenylphosphorane furnishes the 4-propyl-2H-1-benzopyran-2-ones6–10.

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Eine neue Synthese von 4-Propyl-2H-1-benzopyran-2-onen

Zusammenfassung Die Reaktion von 2-Hydroxybutyrophenonen1–5 ergab mit Ethoxycarbonylmethylentriphenylphosphoran die 4-Propyl-2H-1-benzopyran-2-one6–10

     

Reaction of benzothiazol-2-one with 4-hydroxy-4-methyl-2-pentynonitrile

Reaction between the title compounds gave the unexpected 3-[5,5-dimethyl-2,5-dihydrofur-4-yl-2-(3-isopropanol-2-propenonitrile)imino]benzothiazol-2-one, as a result of the addition of two cyanoacetylene molecules.Irkutsk Institute of Organic Chemistry, Siberian Branch, Russian Academy of Sciences, Irkutsk 664033. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 1003–1005, April, 1992.     

Ylide von Heterocyclen,VIII Reaktionen von Iodonium-Yliden mit Säuren

The reaction of various organic and inorganic acids (HX) with iodonium ylides2 leads to nucleophilic substitution of the iodobenzene substituent by the anionX ^– to yield the heterocycles5. Some of them are hydrolyzed to the hydroxy compounds3 or reduced to the starting compounds1 under the reaction conditions. Reaction of the iodonium ylide2b with monomethyl sulfate gives the salt9, which with bases undergoes nucleophilic substitution to compounds8 and10–12, respectively, or is converted to2b again.

     

4-Hydroxy-2-quinolones. 32. Synthesis and antithyroid activity of thio analogs of 1H-2-oxo-3-(2-Benzimidazolyl)-4-hydroxyquinoline

We propose preparative synthesis methods for 2-thio-4-hydroxy-, 2-oxo-4-mercapto-, and 2-thio-4-mercapto-1H-3-(2-benzimidazolyl)quinolines. We have studied the antithyroid activity of the synthesized compounds.Ukraine Pharmaceutical Academy, Kharkhov 310002. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 692–696, May, 1997.     

Synthesis of 4-trihalomethyl-2-oxobenz-1,5,3-oxathiazepines and 2-oxo-4-trichloromethylbenz-1,5,3-dithiazepine and their conversion to 2-trihalomethyl-2-isocyanatobenz-1,3-oxathiolanes and 2-isocyanato-2-trichloromethylbenz-1,3-dithiolane

The reaction of perhaloethyl isocyanates with o-mercaptophenol and o-dimercaptobenzene gave 4-trihalomethyl-2-oxobenz-1,5,3-oxathiazepines and 2-oxo-4-trichloromethylbenz-1,5,3-dithiazepine, which at 100–110°C undergo contraction of the heteroring and are converted to the corresponding 2-trihalomethyl-2-isocyanato-1, 3-oxathiolanes and a dithiolane.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1472–1474, November, 1993.We thank the State Committee for Problems of Science and New Technology of Ukraine for financial support of this research.     

ESR study of kinetic acidity of 6-tert-butyl-2-hydroxy-4-triphenylmethylphenoxyl

Thermodynamic and kinetic acidities of 6-tert-butyl-2-hydroxy-4-triphenylmethylphenoxyl during its interaction with triethylamine in toluene have been studied by ESR. It has been shown that the protolysis of this radical is a two-pathway process, since tautomeric transitions, i.e. ammonium ion migration between oxygen atoms of the semiquinone radical anion, have been detected in the reaction products, that is, in contact ion pairs of the corresponding semiquinone radicals.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No 1, pp. 81–84, January, 1993.     

Novel synthesis of (4<Emphasis Type="Italic">R</Emphasis>)-4-methylpentanolide from (L)-(−)-menthol

A novel synthesis of the promising optically pure chiral (4R)-4-methylpentanolide that is based on several regiospecific oxidative transformations of (4R)-2,4-dimethyl-1-(1-methylethyl)-1-cyclohexene, the product of addition of (–)-menthone and methylmagnesium iodide followed by acid dehydration, was proposed.Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 451–453, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

3-Acetyl-2-amino-4-hydroxy-1,3-pentadienecarbonitrile:E,Z-isomerism and the ability to form chelates

The Ni acetylacetonate-catalyzed addition of acetylacetone to malononitrile was shown to afford 3-acetyl-2-amino-4-hydroxy-1,3-pentadienecarbonitrile. The diphenyl boron chelate of the latter with a -diketone-type structure was obtained.E,Z-isomerism of the chelate and the free ligand were investigated. TheZ-isomers were found to dominate in low polarity solvents.The work was supported by the Russian Foundation for Basic Research (Project No. 94-03-08964).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1432–1435, August, 1994.     

Investigation of 2-[(<Emphasis Type="Italic">E</Emphasis>)-2-(4-diethylaminophenyl)-1-ethenyl]-1,3,3-trimethyl-3H-indolium as a new highly sensitive reagent for the spectrophotometric determination of nitrophenols

A new, simple, rapid, and sensitive spectrophotometric method has been developed for the determination of nitrophenols [picric acid (PA); dinitrophenols (DNP)] in wastewater samples. The method is based on the reaction of nitrophenols with 2-[(E)-2-(4-diethylaminophenyl)-1-ethenyl]-1,3,3-trimethyl-3 H-indolium chloride reagent to form the colored ion associates, which are extracted by organic solvents. The molar absorptivity of the ion associates of PA with the investigated reagent ranges from 8.3×10⁴ to 11.3×10⁴ L mol^–1 cm^–1, depending on the extractant. Because only PA is extracted in an acidic medium with the investigated reagent, but both PA and DNP are extracted in an alkaline medium, it is possible to determine both substances in a mixture. Appropriate reaction conditions have been established. The absorbance of the colored extracts obeys Beers law in the range of 0.04–4.58 mg L^–1 PA, 1.0–18.4 mg L^–1 2,4-DNP and 1.2–14.7 mg L^–1 2,6-DNP, respectively. The limit of detections, calculated from a blank test (n=10; P=0.95), are 0.05 mg L^–1 PA, 0.9 mg L^–1 (2,4-DNP), and 1.1 mg L^–1 (2,6-DNP), respectively.     

Complex compounds of tetracycline with WO 4 2− and MoO 4 2− ions. Investigation by pH-metric and conductometric methods

By using pH-metric and conductometric methods it has been found that tetracycline (H₃TC) forms with WO ₄ ^2– and MoO ₄ ^2– ions the following complex compounds: [WO₃HTC]^2–, [WO₃(H₂TC)₂]^2– and [MoO₃(H₂TC)₂]^2–. Stability constants log/gb ₁ ^k =7.86 and log ₁ ^k =7.80 for [WO₃HTC]^2– and [MoO₃HTC]^2–, respectively, have been calculated from pH-metric measurements.     

Synthesis and crystal structure of ethyl 1-benzyl-2-hydroxy-5-methyl-3-oxo-2-phenacyl-2,3-dihydropyrrole-4-carboxylate

Reaction of 5-phenyl-2,3-dihydro-2,3-furandione with ethyl 3-benzylamino-2-butenoate, resulting in ethyl 1-benzyl-2-hydroxy-5-methyl-3-oxo-2-phenacyl-2,3-dihydropyrrole-4-carboxylate and benzylamide ofN-benzoylpyruvic acid, was studied. The structure of the pyrrole derivative was confirmed by X-ray analysis.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1552–1555, August, 1995.     

Polyfunctional pyrazoles. 1. Synthesis of 3-aryl-1-(2-cyanoethyl)-4-formylpyrazoles and their 3-(5-methylfur-2-yl)-substituted analog

Previously unknown substituted pyrazoles were obtained by the reaction of the 2-cyanoethylhydrazones of aryl methyl ketones and 5-methylfur-2-yl methyl ketone with the Vilsmeier-Haack reagent.Bukovina State Medical Academy, Chernovtsy. Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev, Ukraine. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1219–1221, September, 1999.