Acetals of lactams and acid amides. 51. Cyclization of α-cyano-Β-phenylamino-N-dimethylaminomethyleneacrylamide to pyrimido[5,4-c]quinol-4-one

Cyclization of -cyano--phenylamino-N-dimethylaminomethyleneacrylamide to pyrimido[5,4-c]quinol-4-one proceeds via the intermediate formation of 1-phenyl-5-cyano-1,4-dihydropyrimidin-4-one and -cyano--phenyl-amino-N-formylacrylamide.For Communication 50, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 88–90, January, 1988.     

Kinetics of oxidation of carbonyl compounds by peroxomonosulfate. Formaldehyde, formic acid and formate anion

Kinetics of oxidation of formaldehyde, formic acid and formate anion by peroxomonosulfate (PMS) were studied. Formaldehyde is oxidized both by HSO ₅ ^– and SO ₅ ^2– , whereas formic acid and formate ion are oxidized by SO ₅ ^2– alone. The kinetic results show that the formaldehyde is 10³ times more reactive than formic acid, which in turn reacts 10² times faster than formate anion. Mechanisms are discussed in terms of the kinetic results.

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, . HSO ₅ ^– , SO ₅ ^2– , SO ₅ ^2– . , . 10³ , , , , . 10² , . .

     

Some methoxy derivatives of 9-amino-6-nitroacridine

The reaction of the 2-, 3-, and 4-methoxy derivatives of 9-chloro-6-nitroacridine with-diethylamino--methylbutylamine and with-diethylamino--hydroxypropylainine in phenol has given the 2-, 3-, and 4-methoxy derivatives of 9-(-diethylamino--methylbutylamino)-6-nitroacridine and of 9-(-diethylamino--hydroxypropylamino)6-nitroacridine, respectively.     

Formation of 3,4-dihydro-α-carbolines from 2-aminoindole

In the condensation of 2-aminoindole with ,-unsaturated oxo compounds, in contrast to ordinary aromatic amines and a number of heterocyclic amines, the direction of cyclization is reversed. The general scheme of the reaction includes the reaction of the position of 2-aminoindole with the activated double bond of the oxo compound via a mechanism of the Michael type and condensation of the carbonyl group of the unsaturated carboline structure, which subsequently undergoes aromatization. The intermediate 3,4-dihydro--carbolines were produced and isolated; this made it possible in a number of cases to establish the structures of the final -carbolines. The structures of the 3,4-dihydro compounds were confirmed by the set of spectral characteristics. Data from the UV, IR, PMR, and mass spectra are presented.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 945–951, pp. 945–951, July, 1977.     

Electronic spectra of α, Β-unsaturated diketone derivatives of thiophene

The electronic absorption spectra of ,-unsaturated diketone derivatives of thiophene of the p-dichalcone type have been studied. As a rule, these compounds have deeper colors than the monoketone thiophene analogs of the chalcones corresponding to them. Electron-donating substituents in the aromatic nucleus of 2,5-dicinnamoylthiophene and also the replacement of the phenyl radicals in them by heterocyclic radicals cause a bathochromic shift of the long-wave absorption maximum (frequency) which correlates satisfactorily with Hammett's constants. Some ketones with strong electron-donating groupings fluoresce under UV irradiation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 744–749, June, 1970.     

Reaction mechanism for formation of condensed thienopyrans and thienothiopyrans

The formation of 2-amino-3-cyanothiophenes has been studied. It has been shown that the intermediates in the synthesis are the Knoevenagel type ,-unsaturated nitriles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 395–397, March, 1987.     

Transformed steroids. 180. Stereospecific transformation of 17Β-hydroxy-17α-ethynylsteroids into various 17α-substituted 17Β-ethynylsteroids

The use of a dicobalt hexacarbonyl protective group permitted us to carry out the stereospecific conversion of 17-hydroxy-17-ethynylsteroids into branched 17-R-substituted 17-ethynylsteroids (R-OH, OAc, OMe, NCS, and F).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 675–681, March, 1990.     

The dimer of trifluoromethylthiirene

Conclusion The action of the hexaethyltriamide of phosphorous acid on disulfides containing an ,-dichloro-,,-trifluoroisopropyl group gives the dimer of trifluoromethylthiirene, namely, 2,5-bis(trifluoromethyl)p-dithiine. Oxidation of this dimer by the action of sulfuric acid gives a stable radical-cation.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1160–1162, May, 1987.     

Mass spectrometric decomposition of Β-phenyloxiranecarboxylic esters

The electron-impact mass spectra of the E- and Z-isomers of the ,-methyl substituted esters of -phenyloxiranecarboxylic acids have been studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1310–1314, October, 1986.     

Fluorinated Β-hydroxy-Β-carbomethoxy acids and photoreduction of their copper salts

Conclusions The methyl esters of fluorinated -keto acids enter into the Knoevenagel condensation with malonic acid and give fluorinated -hydroxy--carbomethoxy acids, which form copper salts with a ligand:copper composition=1:1. The Cu salts of fluorinated -hydroxy--carbomethoxy acids are photoreduced by alcohols in the presence of UV light to give -hydroxy--carbomethoxy acids and metallic Cu.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1896–1900, August, 1982.     

Synthesis of 1-β-D-ribopyranosyl- and ribofuranosyl-6-nitroindole and indoline for the phosphotriester oligonucleotide synthesis

The glycosylation reaction of 6-nitroindoline with 5-tritylribose led to the synthesis of the 1--D-ribofuranoside and 1--D-ribopyranoside of 6-nitroindoline, the dehydrogenation of which resulted in the isolation of the corresponding 1--D-ribopyranoside and 1--D-ribofuranoside of 6-nitroindole; the last with protecting groups are suitable for utilization in oligonucleotide synthesis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1500–1506, November, 1990.     

Thermal and some other properties of the complexes crystallizing from the system Ni(II)-en-[Ni(CN)4]2−-H2O

Seven complex compounds exhibiting the compositions Ni(en)₃Ni(CN)₄·H₂O (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄·2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2.5H₂O (VI) and-Ni(en)₂Ni(CN)₄ (VII) were prepared from the system Ni-en-[Ni(CN)₄]^2–-H₂O. These compounds were examined by the methods of infrared spectroscopy, X-ray powder diffractometry, UV-VIS reflectance spectroscopy, and also by the measurement of magnetic moments. The thermal stability, the stoichiometry of thermal decomposition and the mutual transformations were investigated with a derivatograph. The reactions proceeding according to the following schemes were observed if the system was heated to appropriate temperature: (I)(II)(III)(V)(IV) and (VI)(VII)(III)(V)(IV) Process (VII)(III) represents isomerization. The reversibility of the process (V)(IV) is due to the high hygroscopicity of the anhydrous complex. The changes in structure in the course of the individual processes are discussed.

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Zusammenfassung Aus einem System Ni-en-[Ni(CN)₄]^2–-H₂O wurden sieben Komplexe der Formeln Ni(en)₃Ni(CN)₄·H₂O (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄·2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2.5H₂O (VI) und-Ni(en)₂Ni(CN)₄ (VII) hergestellt. Diese Verbindungen wurden mittels IR-Spektroskopie, Röntgenpulverdiffraktometrie, UV-Reflexionsspektroskopie und durch Messungen des magnetischen Momentes untersucht. Die Wärmestabilität, die Stöchiometrie des thermischen Zerfalles und die gegenseitigen Umwandlungen wurden mittels eines Derivatographen untersucht. Wird das System auf geeignete Temperaturen erhitzt, kann der Reaktionsverlauf durch folgendes Schema dargestellt werden: (I)(II)(III)(V)(IV) und (VI)(VII)(III)(V)(IV).Der Prozeß (VII)(III) verkörpert eine Isomerisierung. Die Umkehrbarkeit von Prozeß (V)(IV) ist auf die ausgeprägten Hygroskopieeigenschaften des wasserfreien Komplexes zurückzuführen. Es werden die im Ablaufe der einzelnen Prozesse vorgehenden Strukturveränderungen besprochen.

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Ni- -[No(N)]² -₂ Ni(en)₃Ni(CN)₄ · ₂ (I), Ni(en)₃Ni(CN)₄ (II),-Ni(en)₂Ni(CN)₄ (III), Ni(en)Ni(CN)₄-2H₂O (IV), Ni(en)Ni(CN)₄ (V), Ni(en)₂Ni(CN)₄ · 2,5H₂O (VI) -Ni(en)₂Ni(CN)₄ (VII). , , - , . , . (I)(II)(III)(V)(IV) (VI)(VII)(III)(V)(IV). (VII)(III) . (V)(IV) . .

     

Untersuchung von Werken der Kunst- und Kulturgeschichte mit Hilfe der Differentialthermoanalyse

Zusammenfassung Farbproben aus Gemälden wurden unter Stickstoff und Sauerstoff differentialthermoanalytisch untersucht. Die unter Sauerstoff erhaltenen Thermogramme von Proben aus Ölgemälden zeigten eine deutliche Abhängigkeit des thermischen Verhaltens einer Farbprobe von ihrem Alter innerhalb eines Zeitraums von etwa 100 Jahren. Die Ergebnisse werden in Form einer halblogarithmischen Auftragung dargestellt und diskutiert.Unser Dank gilt der Stiftung Volkswagenwerk für die großzügige Förderung dieses Forschungsprogramms mit Sach- und Personalmitteln.

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Samples of paintings have been studied by differential thermal analysis under nitrogen and oxygen. The thermal curves of samples of oilpaintings under oxygen depend upon the age of the sample within a range of about 100 years. A graphical interpretation of the results is presented and discussed.

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Résumé Des échantillons de peintures prélevés sur des tableaux ont été étudiés par ATD sous azote et sous oxygène. Les courbes ATD obtenues en chauffant sous oxygène les échantillons prélevés sur des peintures à l'huile dépendent nettement de l'âge des tableaux, dans un intervalle d'environ 100 ans. Les résultats sont présentés sur des graphiques en échelle semilogarithmique et discutés.

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. , , , 100 . .

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Auszugsweise vorgetragen auf der GEFTA-Tagung 1977 in Clausthal-Zellerfeld.

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Unser Dank gilt der Stiftung Volkswagenwerk für die großzügige Förderung dieses Forschungsprogramms mit Sach- und Personalmitteln.     

Methyl γ-phenylacetoacetate in the synthesis of derivatives of α-aminoindol-2-yl-acetic acid

The cyclization of the di(phenylhydrazone) of methyl -phenyl-,-dioxobutyrate with hydrazines has given phenylhydrazones of methyl indol-2-ylglyoxylates, which have been reduced to methyl -aminoindol-2-ylacetates. Some reactions of these compounds have been studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1040–1042, August, 1973.     

Synthesis of some esters of α-acetoxy-Β,Β,Β-trichloroethylphosphonic acid

Summary By the reaction of dialkyl esters of -hydroxy, ,-trichloroethylphosphonic acid and acetic anhydride in the presence of a few drops of sulfuric acid, the dialkyl esters of -acetoxy-,,-trichloroethylphosphonic acid were obtained in high yields.     

Thermal properties of elastin-fatty acid complexes

Differential scanning calorimetry has been applied to study the interaction of fibrous or of soluble elastin with fatty acids and their trialanine derivatives. The DSC curves of elastin-fatty acid preparations exhibited an endothermic transition in the temperature range - 10° to + 50°. The peak temperatures and the enthalpy changes were independent of the chain length and of the saturation of the fatty acid. The interaction with the trialanine derivatives was similar to that with the fatty acids.Such interactions between elastin and lipids might take place in vivo as well, resutling in the loss of elasticity of elastin fibres and consequently in the development of arteriosclerotic lesions.

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Zusammenfassung Zur Untersuchung der Wechselwirkung zwischen dem fibrösen oder lösbaren Elastin, und den Fettsäuren und ihren Trialanin-Derivaten wurde die DSC-Methode angewandt. Die DSC-Kurven der Elastin-Fettsäure-Präparate zeigten in dem Temperaturbereich von - 10° bis + 50° einen endothermischen Übergang. Die Peak-Temperaturen und die Änderungen der Enthalpie waren von der Kettenlänge und der Sättigung der Fettsäure unabhängig. Die Wechselwirkung mit den Trialanin-Derivaten war der mit den Fettsäuren ähnlich.Solche Wechselwirkungen zwischen Elastin und den Lipiden können auch in vivo stattfinden, und die Abnahme der Elastizität der Elastin-Fibern, und folglich die Entfaltung der arteriosklerotischen Schädigungen resultieren.

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. - — — 10° - + 50°. , . , . , , .

     

Acetals of lactams and acid amides. 53. Eamidines in the synthesis of pyridine and pyrimidine

The reaction of -cyano--aminocrotonic ester with DMFA diethylacetal gives 1-ethoxycarbonyl-1-cyano-2-(N-dimethylaminomethylene)-amino-4-dimethylaminobutadiene, the reaction of which with ammonium acetate and amines leads to 4-methylenepyrimidine derivatives. Condensation of -cyano--aminocrotonic ester with dimethylacetamide dieethylacetal gave 2-(ethoxycarbonylcyano)methylene-4-dimethylamino-6-methylpyridine. It was found that in an alkaline medium, 1-benzyl-4-(ethoxycarbonylcyano) methylenepyrimidine recyclizes into 1-benzyl-3-cyano-4-amino-2-pyridone.For Communication 52, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1109–1114, August, 1988.     

Kinetic studies of methanethiol disproportionation

Kinetic regularities in catalytic disproportionation of methanethiol to dimethyl sulfide and hydrogen sulfide have been studied in a flow circulation reactor. A kinetic equation is suggested to describe the reaction on inhomogeneous surfaces.

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- - . , .