Synthesen von kernsubstituierten N,N-Diphenyl-β-alaninen

Zusammenfassung N,N-Diphenyl--alanine mit Substituenten in einem oder in beiden Phenylresten wurden durch Umsetzung von entsprechenden Diphenylaminderivaten mit -Propiolacton erhalten. In ähnlicher Weise reagierte Diphenylamin mit -Butyrolacton zu -(N,N-Diphenylamino)-buttersäure. 4,4-Diäthyldiphenylamin und 2-Chlor-6-methyl-diphenylamin wurden als Ausgangsmaterialien für die entsprechenden -Alanine hergestellt.

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N.N-Diphenyl--alanines with substituents in one or in both of the phenyl groups were synthesized by reactions of the corresponding diphenylamine derivatives with -propiolactone. Similarly diphenylamine reacted with -butyrolactone to give -(N.N-diphenylamino)-butyric acid. 4.4-Diethyldiphenylamine and 2-chloro-6-methyldiphenylamine were prepared as starting materials for the corresponding -alanines.

     

Cephalosporins containing carbonate functions at positions 3 and 7

Sulfones of 7-alkoxycarbonyloxy-substituted cephalosporanic acid tert-butyl esters were synthesized by reduction of 7-oxocephalosporanic acid tert-butyl ester, acylation of the intermediate 7-hydroxycephalosporanate with 2,2,2-trichloroethyl chloroformate or di-tert-butyl pyrocarbonate, and oxidation of the sulfur atom. Sulfones of 7-chloro- and 7-alkylidene-substituted 3-alkoxycarbonyloxymethylcephalosporanic acid tert-butyl esters were obtained by replacement of the bromine atom in tert-butyl 3-bromomethylcephalosporanates with hydroxy group and acylation of the latter with chlorocarbonic esters. The cytotoxic activity of the synthesized substances was studied in vitro and also their ability to inhibit elastase.Latvian Institute of Organic Synthesis, Riga LV-1006Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 847–853, June, 2000.     

Synthesis and some properties of the methyl ester and N,N-diethylamide of 2-azido-5-phenyl-4-thiazolecarboxylic acid

The methyl ester and N,N-diethylamide of 2-azido-5-phenyl-4-thiazolecarboxylic acid were obtained by the reaction of the corresponding 4-substituted 2-hydrazino-5-phenylthiazole with NaNO₂ in acid media. IR and UV spectroscopy were used to show that the compounds synthesized retain azide form in both the crystalline state and in solution. The reaction of azides with dicarbonyl compounds gave derivatives of 2-[5-methyl-4-acetyl-or 2-[5-methyl-4-ethoxycarbonyl-1,2,3-triazol-1-yl]-5-phenylthiazole-4-carboxylic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 710–714, May, 1993.     

MO LCAO calculations and the electronic spectra of the anions of cyclopent-4-ene-1,3-diones and indane-1,3-diones

The Hückel approximation in MO LCAO is used to show that the anion system of cyclopent-4-ene-1,3-dione should have two ^* transitions: a weak one at long wavelengths, NV₁, and a strong one at short wavelengths, C=C(1,3)V₁. An ethylene, phenyl, or acyl group at position 2 gives rise to a new strong band, NC=C(2), Nbenz, or NC=O (2). A p-nitrophenyl group at position 2 gives rise to a strong NNO₂ band, which overlaps the weak NV₁ band, while the Nbenz band becomes weak and is virtually lost from the spectrum.     

Self organization of fluorescent molecular necklaces in aqueous solution

N-Fluoresceinyl-N-(mono-6-desoxy-6--cyclodextrinyl)-thiourea2 was synthesized from mono-6-amino-6-desoxy--CD1 and fluorescein isothiocyanate. The fluorescent CD derivative2 was threaded on a water soluble polymer, poly(N,N-dimethylammoniumhexamethylene-N,N-dimethyl-ammoniumdecamethylene dibromide)3. The existence of the molecular necklace was visualized by gel electrophoresis.     

Investigation of thermooxidative stability of oils by thermal analysis methods

Two base oils, obtained on a laboratory scale, were investigated with a derivatograph and by means of DSC. The sensitivities of the oils to some antioxidants were also examined. The high thermooxidative stability of the oil obtained from a preoxidized atmospheric crude residue was confirmed.

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Zusammenfassung Zwei im Labormaßstab hergestellte Rohöle wurden mit einem Derivatographen und mittels DSC untersucht. Die Empfindlichkeit der Öle gegenüber Antioxidanten wurde ebenfalls geprüft. Es wurde eine hohe thermooxidative Stabilität des aus einem präoxidierten atmosphärischen Rohstoffrestes erhaltenen Öls nachgewiesen.

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, . . , .

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The authors are grateful to the Institute of Petroleum Technology for the DSC measurements.     

Synthesis and properties of indolo-3,3′-trimethinecyanines substituted in the polymethine chain and heterorings

New 8-chloro-, 9-cyano-, and 8-methyl-9-carboxy-substituted (in the outer polymethine chain), indolo-3,3-trimethinecyanines containing substituents in the 2, 5, or 7 position of the indole heteroresidues were synthesized, and their spectral, polarographic, and photographic properties were studied. It is shown that electron-acceptor substituents in the 2 and 2 positions of the indole heteroresidues and the 8 and/or 9 positions of the polymethine chain of the dye molecules that do not have steric hindrance give rise to a bathochromic shift of their absorption maxima. 8-Chloro-, 9-cyano- and 8-methyl-9-carbethoxyindolo-3,3-trimethinecyanines with electron-acceptor groups in the 2 and 2 positions are ineffective sensitizers of direct positive silver halide emulsions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 897–901, July, 1988.     

Vitreous phases of the Ag2O∶B22O3∶P2O5 system

Most optimized vitreous electrolytes are obtained by doping an oxide glass with a salt (MX); the resulting substance has an increased ionic conductivity, but a reduced thermal stability. On the other hand, this paper shows that it is possible to obtain vitreous electrolytes with enhanced electrical and thermal performances by mixing two glass formers. This phenomenon may be called the mixed anion effect. The Ag₂OB₂O₃P₂O₅ system is shown to offer a very interesting example of such a phenomenon.

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Zusammenfassung Optimale glasartige Elektrolyte werden durch Dopen eines Oxydglases mit einem Salz (MX) erhalten; die Produkte weisen eine erhöhte ionische Leitfähigkeit, jedoch auch eine verminderte thermische Stabilität auf. Andererseits wird gezeigt, daß glasartige Elektrolyte mit besseren elektrischen und thermischen Eigenschaften durch Mischen von zwei Glasbildnern erhalten werden können. Für dieses Phänomen wird die Bezeichnung mixed anion effect in Vorschlag gebracht. Es wird gezeigt, daß das System Ag₂OB₂O₃P₂O₅ ein sehr interessantes Beispiel dieses Phänomens bietet.

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MX. , . . . , Ag₂O₂₃₂₅ .

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The NMR data were collected at the Regional NMR Center of the Colorado State University (Fort Collins, Co, USA), funded by NSF Grant CHE-8208821). This research was funded in part by the Italian Department of Education (MPI 40%).     

Influence of physically adsorbed oxygen on the separation of electron-hole pairs on anatase irradiated by visible light

ESR studies on the formation and properties of O ₂ ^– and [O^–·O₂] ion-radicals under photo-irradiation of oxidized anatase have been performed. The role of physically adsorbed oxygen in the separation of electrone-hole pairs is shown.

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- O ₂ ^– [O^–·O₂], . - .

     

Nature of the pentamethyldisilanyl group in organosilicon compounds

Summary The positige inductive effect of the pentamethyldisilanyl group (CH₃)₃SiSi(CH₃)₂ and the election-acceptor effect of its p-d bond with an aromatic ring are appreciably greater than the analogous effects of the trimethylsilyl group (CH_{3 3}Si, which gives ground for the postulation of the presence of a p-d-d¹ bond in the fragment C_sp ²-Si-Si.     

Thermal decomposition of [Co(NH3)6]Cl3

The thermal decomposition reactions of [Co(NH₃)₆]Cl₃ were determined in dynamic argon and air atmospheres. The investigations were carried out with simultaneous TG-DTG-DTA measurements under non-isothermal conditions, thermogravimetry under quasi-isothermal conditions, reflectance spectroscopy, absorption spectroscopy, X-ray diffraction and chemical analysis. The data show that the thermal decomposition of [Co(NH₃)₆]Cl₃ occurs in three and four stages in argon and air atmospheres, respectively. The determined sequences are in agreement with that proposed by Simons and Wendlandt [2, 5].The changes in the morphology of the studied complex crystalline powder in the course of thermal decomposition in air were followed by scanning electron microscopy.

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Zusammenfassung In bewegter Argon- und Luftatmosphäre wurden die Zersetzungsreaktionen für [Co(NH₃)₆]Cl₃ bestimmt. Zu den Untersuchungen wurden folgende Methoden zu Hilfe gezogen: simultane TG-DTG-DTA-Messungen unter nichtisothermen Bedingungen, Thermogravimetrie unter quasi-isothermen Bedingungen, Remissionsspektroskopie, Absorptionsspektroskopie, Röntgendiffraktion und chemische Analyse. Die Ergebnisse zeigen, daß sich [Co(NH₃)₆]Cl₃ in Argon in drei und in Luft in vier Schritten thermisch zersetzt. Die festgestellten Sequenzen stehen in Übereinstimmung mit den von Simon und Wendlandt [2, 5] vorgeschlagenen. Veränderungen in der Morphologie des untersuchten Komplexkristallpulvers wurden über die thermische Zersetzung in Luft mittels Scanning-Elektronen-Mikroskopie beobachtet.

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[Co(NH₃)₆]Cl₃. , , - , , , . , , , , , , .

     

Catalytic activity of perovskite-type oxides LaMeO3

Catalytic activities for CO oxidation of a series of LaMeO₃(Me³⁺=V³⁺, Cr³⁺, Mn³⁺, Fe³⁺, Co³⁺, Ni³⁺) perovskite-type oxides were measured. Maxima for Mn³⁺ and Co³⁺ were found. The relation between local symmetry of solid surfaces and chemisorption and catalysis is discussed.

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, LaMeO₃ (Me⁺³=V⁺³, Cr⁺³, Mn⁺³, Fe⁺³, Co⁺³, Ni⁺³) CO. Mn⁺³ Co⁺³. , .

     

Synthesis of a Diterpene 1,3,4-Oxadiazolin-2′-one from Dimethylcyclopentenonepimarate

A diterpene 1,3,4-oxadiazolin-2-one was synthesized by lead-tetraacetate oxidation of 16,17- epoxydimethylcyclpentenonepimarate. The structures of the synthesized compounds were confirmed by IR and NMR spectroscopies.     

Inclusion of Nonopiate Analgesic Drugs in Cyclodextrins. I. X-Ray Structure of a 1 : 1 β-Cyclodextrin-p-bromoacetanilide Complex

The preparation and X-ray crystal structure of a 1 : 1 complex between -cyclodextrin (-CD) and the analgesic p-bromoacetanilide are reported. Thermogravimetric and UV spectrophotometric analyses of single crystals grown from an aqueous solution containing host and guest in 1 : 1 molar ratio yielded the composition -CD p-bromoacetanilide $ 13.5H2O. Crystals of the complex are triclinic, space group P1, with a = 15.197(3), b = 15.613(2), c = 15.743(4) Å, = 87.16(2), = 98.29(2), = 103.39(1)° and Z = 2 crystallographically independent complex units per unit cell. The -CD molecules form head-to-head dimers which pack in the channel-mode. Each dimer contains two guest molecules whose acetylamino substituents are located at the dimer interface while the bromine atoms protrude from the -CD primary faces. The acetyl residues of both guest molecules were found to be disordered but the X-ray data permitted     

Effect of cross-conjugation on properties of α-mercurated carbonyl compounds

Conclusions The polarographic data and the data of the IR spectra of the-mercurated esters of the cinnamic and crotonic acids show that in these compounds the- conjugation of the C-Hg bond with the C=O group is weakly expressed, and may be completely absent.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1912–1913, August, 1973.     

Results of thermal analysis for investigation of salt hydrates as latent heat-storage materials

DTA and DSC methods and quasi-isothermal and quasi-isobaric thermogravimetry are of great importance in the investigation of salt hydrates as latent heat-storage materials. However, the transferability of the DTA and DSC results is given only for application in static latent heatstorage units. Special calorimetric methods adapted to the storage principle are preferred for the study of salt hydrates under dynamic storage conditions. The findings are discussed in connection with the examples of Na₂SO₄·10H₂O, CH₃COONa·3H₂O, Na₂S·9H₂O, Na₂S·5H₂O, Mg(NO₃)₂·6H₂O, MgCl₂·6H₂O and the eutectic mixture of Mg(NO₃)₂·6H₂O-MgCl₂·6H₂O.

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Zusammenfassung Bei der Untersuchung von Salzhydraten als Latentwärmespeichermaterialien besitzen DTA-, DSC-Methoden und die quasi-isotherme und quasi-isobare Thermogravimetrie eine wesentliche Bedeutung. Die Übertragbarkeit der DTA- und DSC-Ergebnisse ist jedoch nur für den Einsatz in statischen latentwärmespeichern gegeben. Für das Studium der Salzhydrate under dynamischen Speicherbedingungen werden spezielle, dem Speicherprinzip angepaßte kalorimetrische Methoden bevorzugt. Die Aussagen werden an den Beispielen Na₂SO₄·10H₂O, CH₃COONa·3H₂O, Na₂S·9H₂O, Na₂S·5H₂O, Mg(NO₃)₂·6H₂O, MgCl₂·6H₂O und der eutektischen Mischung von Mg(NO₃)₂·6H₂O-MgCl₂·6H₂O diskutiert.

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, . , . , . Na₂SO₄·10H₂O, CH₃COONa·3H₂O, Na₂S·5H₂O, Na₂S·9H₂O, Mg(NO₃)₂·6H₂O, MgCl₂·6H₂O Mg(NO₃)₂·6H₂O·MgCl₂·6H₂O.

     

Transformed steroids. 121. Synthesis of the δ-lactone of 3β-acetoxy-16α-hydroxy-6-oxo-24-nor-5α-chol-17(20)-en-23-oic acid

The synthesis of the ¹⁷⁽²⁰⁾-16 analog of natural chiogralactone is described. Attempts to introduce a 6-oxo group directly into the -lactone proved unsuccessful, since the first stage — saponification — took place with the formation of three products: the 3-hydroxy--lactone, the 3-hydroxy-²⁰⁽²²⁾-lactone, and the 15,17(20)-dienoic acid. The synthesis of the desired compound was effected from the ethyl ester of the 5,16-dienoic acid by the scheme 3-acetate3-tosylate6-hydroxy-3,5-cyclosteroid6-oxo-3,5-cyclosteroid6-oxo-5H--lactone. It has been shown that the cyclopropane ring in the 3,5-cyclosteroid -lactone is extremely stable under the conditions of acid treatments.N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 184–187, March–April, 1981.     

Effect of free phosphine on the reactivity of phosphine-containing rhodium(I) complexes

The photolysis products of SO₂-pentane-NO mixtures are N₂O, H₂O and a compound designated as RNO. Kinetic data obtained by OC method confirm the previously proposed scheme of photolysis. Also studied was the photolysis of SO₂, NO and cyclohexane mixtures. From comparison of spectral characteristics of RNO and its analog 2-methyl-2-nitrosopropane, the probable structure of RNO is suggested.

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SO₂--NO N₂O, H₂O , RNO. , , . SO₂ NO . RNO 2--2- RNO.

     

Dispersity and reducibility of the molybdenum oxide phase in SiO2, SiO2?Al2O3 and γ-Al2O3 supported molybdena catalysts

XRD, isothermal and temperature-programmed reduction (TPR) experiments were carried out with SiO₂, SiO₂–Al₂O₃ and -Al₂O₃ supported catalysts. Molybdena is in a more disperse state on supports containing more alumina and it is more reducible on SiO₂–Al₂O₃ than on SiO₂ or -Al₂O₃. TPR curves were shown to reflect connections between reduction kinetics and dispersity.

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-, , SiO₂, SiO₂–Al₂O₃ -Al₂O₃. , , SiO₂–Al₂O₃ SiO₂ -Al₂O₃. .