Evolved gas analysis for examination of surface oxides on alloys

Temperature programmed reduction in a hydrogen flow with simultaneous evolved gas analysis was employed to determine surface oxides on oxide dispersion strengthened (ODS) nickel containing TiO₂, A1₂O₃ or Cr₂O₃ particles, and on a Ni-2OCr alloy, after exposure to air at elevated temperatures. Oxides on particles of water-atomized (WA) Ni-2OCr powder were analysed similarly. Significant differences in starting temperatures of the reaction between hydrogen and phases present in oxide layers made identification of the phases possible. NiO or NiO doped with Ti, Al or Cr are the major constituents of the scale formed on ODS Ni. NiTiO₃, NiCr₂O₄ and NiAl₂O₄ are formed as a result of a reaction between TiO₂, A1₂O₃ or Cr₂O₃ particles in the scale with NiO. The oxide layer formed on Ni-2OCr alloy consists of Cr₂O₃ and of NiO doped with Cr. Surface oxides on WA Ni-2OCr contain Cr₂O₃ and a small amount of NiO.

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Zusammenfassung Temperaturprogrammierte Reduktion im Wasserstoffstrom wurde zusammen mit gleichzeitiger Analyse des in Freiheit gesetzten Gases dazu benutzt, um Oberflächenoxide an Nickel enthaltenden TiO₂-, A1₂O₃- oder Cr₂O₃-Partikeln mit verstärkter Oxiddispersion (ODS) und an einer Ni-2OCr-Legierung nach Behandlung in Luft bei erhöhten Temperaturen zu bestimmen. Oxide auf Partikeln von wasser-zerstäubtem (WA) Ni-2OCr-Pulver wurden auf ähnliche Weise analysiert. Signifikante Unterschiede in der Starttemperatur der Reaktionen zwischen Wasserstoff und der in den Oxidschichten vorliegenden Phasen ermöglichen die Identifikation der Phasen. NiO oder mit Ti, Al oder Cr gedoptes NiO sind die Hauptbestandteile des auf ODS-Ni gebildeten Belags. NiTiO₃, NiCr₂O₄ und NiAl₂O₄ treten als Produkte der Reaktion von TiO₂-, Al₂O₃- oder Cr₂O₃-Partikeln mit NiO im Belag auf. Die auf der Ni-2OCr-Legierung gebildete Oxidschicht besteht aus Cr₂O₃ und aus mit Cr gedoptem NiO. Oberflächenoxide auf WA-Ni2OCr enthalten Cr₂O₂ und geringe Mengen an NiO.

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- , , , , , , Ni-2r, . Ni-2OCr. , , . , , , , . NiTiO₃, NiCr₂O₄ NiAl₂O₄ , , . , Ni-2r, , . Ni-2r .

     

1,4-bis(4′-hydroxy-1′,2′,5′-trimethyl-4-piperidyl)-1,3-butadiyne and its derivatives

1.4-Bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)-1.3-butadiyne has been synthesized from the individual isomers of 4-ethynyl-1,2,5-trimethyl-4-piperidol. Hydrogenation, bromination, and cleavage have given, respectively, 1,4-bis(4-hydroxy-1,2,5-trimethyl-4-piperidyl)butane, 1,4-bis(4-nydroxy-1,2,5-trimethyl-4-piperidyl)-1,2,3,4-tetrabromo-1, 3-butadiene, and 4-(1,3-butadiynyl)-1,2,5-trimethyl-4-piperidol.     

Coumarins of Smyrniopsis aucheri

Chemical transformations and spectral characteristics have enabled us to establish the structure and configurations of three coumarins: (+)-2,2-dimethyl-3-hydroxy-3,4-dihydropyrano(5,6:6,7)coumarin (I); (+)-4-hydroxy-5-(1-hydroxy-1-methylethyl)-4,5-dihydrofuro(2,3:6,7)coumarin (II); and (+)-4-hydroxy-5-(1-glucopyranosyloxy-1-methylethyl)-4,5-dihydrofuro(2,3:6,7)-coumarin (III) isolated from the roots ofSmyrnopsis aucheri Karjag. This is the first time that these compounds, which have been called smyrinol, smyrindiol, and smyrindioloside, have been detected in nature.Institute of Chemistry of Plant Substances, Uzbekistan Republic Academy of Sciences, Tashkent. Azerbaidzhan State University, Baku. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 36–40, January–February, 1992.     

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.     

Synthesis of new pyridazino[4′,3′:4,5]-thieno[3,2-d]-1,2,3-triazine and pyrimido[4′,5′:4,5]thieno[2,3-c]pyridazine derivatives

Summary 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (2), 3-substituted 8,9-diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-ones (3a–c), 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (4), 8-chloro-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (5), 8-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazines (6a–h) and 7-substituted 3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-ones(7a–c) were synthesized from 5-amino-3,4-diphenylthieno[2,3-c]pyridazine-6-carboxamide (1).

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Synthese neuer Pyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-und Pyrimido[4,5:4,5]thieno[2,3-c]pyridazin-Derivate

Zusammenfassung Folgende Verbindungen wurden ausgehend von 5-Amino-3,4-diphenylthieno[2,3-c]pyridazin-6-carboxamid (1) synthetisiert: 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-on (2), 3-substituierte 8,9-Diphenylpyridazino[4,3:4,5]thieno[3,2-d]-1,2,3-triazin-4(3H)-one (3a–c), 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8[7H]-on (4), 8-Chlor-3,4-diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin (5), 8-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazine (6a–h) und 7-substituierte 3,4-Diphenylpyrimido[4,5:4,5]thieno[2,3-c]pyridazin-8(7H)-one (7a–c).

     

Synthetic studies in the field of chlorobium chlorophyll

By the condensation of -halogenomethyl derivatives of pyrroles with -unsubstituted pyrroles the synthesis of the following unsymmetrical dipyrrolylmethanes has been effected: 5-benzyloxycarbonyl-5-ethoxycarbonyl-3, 3-di(-methoxycarbonylethyl)-4,4-dimethyl-2,2-dipyrrolylmethane (IIIa), 5-benzyloxycarbonyl-5-ethoxycarbonyl-3-(-methoxycarbonylethyl)-4, 4-diniethyl-3-n-propyl-2,2-dipyrrolylmethane(IIIb), 3-acetyl-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIIc), and 3-bromo-5-benzyloxycarbonyl-4-ethyl-5-methoxycarbonyl-3, 4-dimethyl-2,2-dipyrrolylmethane (IIId). Hydrogenation of the unsymmetrical dipyrrolylmethanes IIIa, b, c, and d has given the corresponding monocarboxylic acids IVa, b, c, and d. The formylation of the dipyrrolylmethanemonocarboxylic acid IVa has given 5-ethoxycarbonyl-5-formyl-3,3-di(-methoxycarbonylethyl)-4, 4-dimethyl-2,2-dipyrrolylmethane (V).For communication II, see [1].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 8, pp. 1045–1047, August, 1970.     

Über Tetrahydrospiro [cyclohexan-1,4′(1′H)-chinazolin]-2′(3′H)-one

Zusammenfassung Cyclohexanon bzw. Cyclopentanon sowie ihre durch Aldolreaktion entstehenden Dimeren reagieren mit Harnstoff im sauren Medium zu 5,6,7,8-Tetrahydrospiro[cyclohexan-1,4(1H)-chinazolin]-3(2H)-onen (2) bzw. zum Dihydrospiro-(cyclopentan-1,4(1H)-5H-cyclopenta[d]pyrimidin)-2(3H)-on (10). Substituierte Harnsotoffe geben Gemische der isomeren 5,6,7,8-Tetrahydro- und 4a,5,6,7-Tetrahydroverbindungen (2, 3) bzw. 6,7-Dihydro-tH- und 5,6-Dihydro-4aH-verbindungen (10, 11). Charakteristisch für2 (3),10 (11) ist die Reaktivität der Kernstellen 8 bzw. 7 gegenüber elektrophilen Agentien (2f-v, 3f-j, 9 a-i, 10 d-f). Äthylmalonsäurebis-trichlorphenylester bzw. Formaldehyd und prim. Amine führen2 in ein partiell hydriertes 1H-Pyrido[3,2,1-ij]chinazolintrion (6) bzw. 1H-Pyrimido[5,6,1-ij]chinazolinon (7) über. Die 1-Alkylverbindungen (2) geben mit Formaldehyd und primären Aminen Hexahydro-8a-hydroxy-4a,8-propanospiro-(cyclohexan-1,4(1H)-pyrido[4,3-d]pyrimidin)-2(3H)-one (8).

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Heterocycles, XXV: tetrahydrospiro [cyclohexane-1,4(1H)-quinazoline]-2(3H)-ones

Cyclohexanone and cyclopentanone, resp., as well as their dimers (formed by aldol reaction) react with urea in the presence of acids to 5,6,7,8-tetrahydrospiro[cyclohexane-1,4-(1H)-quinazoline]-3(2H)-ones (2) and to the dihydrospiro-(cyclopentane-1,4(2H)-5H-cyclopenta[d]pyrimidine)-2(3H)-one (10), resp. Substituted ureas give the isomeric 5,6,7,8-tetrahydro- and 4a,5,6,7-tetrahydro compounds (2, 3), and 6,7-dihydro-5H- and 5,6-dihydro-4aH-compounds (10, 11), resp. Characteristic for2 (3),10 (11) is the reactivity of the nuclear places 8 and 7 with electrophilic agents (2f-v, 3f-j, 9a-i, 10d-f). Ethylmalonic acid bistrichlorophenylester resp. formaldehyde and primary amines react with2 to the partially-hydrogenated 1H-pyrido[3,2,1-ij]-quinazolinetrione (6) and 1H-pyrimido[5,6,1-ij]-quinazolinone (7), resp. The 1-alkyl compounds (2) give with formaldehyde and primary amines hexahydro-8a-hydroxy-4a, 8-propanospiro(cyclohexane-1,4-(1H)-pyrido[4,3-d]pyrimidine)-2(3H)-ones (8).

     

Synthesis of 2,3,7,8-tetramethyldibenzofuran

3,4,3,4-Tetramethyldiphenyl ether readily forms 2,2-dihalo derivatives on bromination and iodination. Heating 2,2-diiodo-4,5,4,5-tetramethyldiphenyl ether with copper powder or oxidation, of 2,2-dilithio-4,5,4,5-tetramethyldiphenyl ether gives 2,3,7,8-tetramethyldibenzofuran, the structure of which was proved by alternative synthesis from 2,2-dinitroand 2,2-diamino-4,5,4,5-tetramethyldiphenyls.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1597–1599, December, 1972.     

Synthesis of tetracarbocyanines by the scission of the pyrylium ring of benzopyrylocyanines

It has been shown that the reaction of monomethinecyanines containing 4-benzopyrylium residues with quaternary salts of derivatives of 2-[(1, 5, 5-trimethylcyclohex-1-en-3-ylidene)-methyl]benzothiazole leads to the scission of the pyrylium ring and the addition of the quaternary salt to the position of scission. The reaction gives tetracarbocyanines containing an o-hydroxyphenyl or an o-acetoxyphenyl substituent in the polymethine chain in addition to a hydrocarbon ring.     

Study of furan compounds

Research on synthesis of polycyclic spirans of the 1, 6-dioxaspiro-[4, 4]nonane group is continued. Electrolysis of methanol solutions of 2-furylcyclopentanol, 2-(5-methyl-furfuryl)cyclopentanol, and 2-furfuryl-1-indanol, gives, by intramolecular alkoxylation, spiro{perhydrocyclopenta[b]furan-2, 2-(5dihydrofuran)}, spiro{perhydrocyclopenta[b]furan-2, 2-(5-methoxy-5-methyl-2, 5-dihydrofuran)}, and spiro{2, 3, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-(5-methoxy-2, 5-dihydrofuran)}, hitherto undescribed in the literature. Depending on the conditions, catalytic hydrogenation of these gives: spiro{perhydiocyclopenta[b]furan-2, 2-(5-methoxytetrahydrofuran)}, spiro{2, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-(5-methoxytetrahydrofuran)}, spiro{perhydrocyclopenta[b]furan-2, 2-tetrahydrofuran}, and spiro{2, 3, 3a, 8b-tetrahydro-4H-indeno[1, 2-b]furan-2, 2-tetrahydrofuran}.For Part XXXI see [1].     

Dibepin-2: A new color reagent for primary aliphatic amines

3-Chloro-3-[2, 3(CO), 6, 5(CO)dibenzoylene-4-pyridyl]phthalide (Dibepin-2) is an analytical color reagent for primary aliphatic amines and arylalkylamines (with the exception of ethylenediamine and 1, 2-diaminopropane). The reaction is always negative with secondary and tertiary amines.     

1,2-Dimethylimidazobenzo-1′, 2′, 3′-thiadiazoles and derived cyanine dyes

New tricylic heterocyclic systems and their methyl derivatives are synthesized. They are 2-methylimidazo[5, 4-e]benzo-1, 2, 3-thiadiazole, 2-methylimidazo[5, 4-g]benzo-1, 2', 3-thiadiazole, 1, 2-dimethylimidazo[5, 4-g]benzo-1, 2, 3-thiadiazole, and 1, 2-dimethylimidazo[5, 4-g]benzo-1, 2, 3-thiadiazole. Quaternary salts of the 1, 2-dimethyl derivatives are used to prepare symmetrical and unsymmetrical trimethinecyanines and dimethinemerocyanines containing rhodanine groups. The absorption maxima of the dyes are displaced towards the long wavelength region compared with imidacarbocyanines. It is shown that when 1, 2-dimetnyl-5-aminobenzoimidazole is thiocyanated, the thiocyano group enters the benzoimidazole ring at position 4, and that 1, 2-dimethylimidazo[5, 4-e] benzo-1, 2, 3-thiadiazole is less basic than its isomer 1, 2-dimethylimidazo[5, 4-g]benzo-1, 2, 3-thiadiazole.     

Convenient synthesis of 5′-methyl-2′-desoxyuridines

A convenient method has been developed for the synthesis of 5-methyl-2-desoxyuridines. Chlorination of 5-O-benzoyl-5-methyluridines with a mixture of Ph₃P and CCl₄ in DMF affords the 2-desoxy-2-chloro-derivatives, which are then reduced with tributyltin hydride. The crystalline 5-O-benzoyl-5-methyl-2-desoxyuridines were obtained in overall yields of 40–60%. In a similar way, 5-O-benzoyluridine has given 5-O-benzoyl-2-desoxyuridine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 246–248, February, 1989.     

Structure of some components of the roots of Prangos ferulacea

Summary From a methanolic extract of the roots ofPrangos ferulacea (L) Lindl., growing in the Nakhichevan ASSR, in addition to the compounds found previously, another six substances (I–VI) have been isolated, of which (I) and (VI) have been identified as, respectively, meransin hydrate monoacetate, found for the first time in nature, and umbelliferone: and in the study of a crystalline mixture obtained from the resin of the roots of the plant under investigation collected in Armenia, two coumarins — (VII) and (VIII) — have been isolated.On the basis of a study of IR, NMR, and mass spectra and chemical properties, the structures of the six new cumarin derivatives (II–V, VII, and VIII) have been established. Compound (II) has the structure of 8-(3-methylbutenyloxy)furo-2,3:7,6-coumarin and has been called feruliden; (III) is 7-hydroxy-8-(3-hydroxy-2-senecioyloxyisopentyl) coumarin and has been called ferudiol; (IV) is 7-hydroxy-8-(3-methoxy-2-senecioyloxyisopentyl) coumarin; (V) is 5-[1-(2,3-dihydroxy-3-methylbutyroyloxy)-1-methylethyl]-4,5-dihydrofuro-2,3:7,6-coumarin and has been called lindiol; (VII) is 8-(2-hydroxy-3-methylbut-3-enyloxy)-7-methoxycoumarin and has been called ferudenol; (VIII) is 7-methoxy-8-(3-methyl-2-oxobut-3-enyl)coumarin and has been called prangone.Leningrad Sanitary-Hygenic Medical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 568–574, September–October, 1974.     

Studies of 2,3′-biquinolyl. 6. Regioselectivity of nucleophilic addition of organometallic compounds to 1-aklyl-3-(2-quinolyl)quinolinium halides

Nucleophilic addition of organometallic lithium and magnesium compounds to 1-alkyl-3-(2-quinolyl)quinolinium cations produces a mixture of the corresponding 1-alkyl-2-R-1,2-dihydro-2,3-biquinolyls and 1-alkyl-4-R-1,4-dihydro-2,3-biquinolyls. The portion of the latter decreases with increasing hardness of the organometallic compound.For No. 5, see [1].Stavropol State University, Stavropol'355009, Russian Russian Chemical Technology University Moscow 125190 Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 919–923, July, 1999.     

Untersuchung des Zerfalls verschiedener Azoinitiatoren in Lösung

The decomposition of various symmetric and unsymmetric azo-initiators (1,1-dichloro-1,1-diphenyl-1,1-azoethane, 2,2-dichloro-2,2-azopropane, 1,1-dichloro-1,1-azocyclohexane, 2,2-diacetoxy-2,2-azopropane, 1,1-diacetoxy-1,1-diphenyl-1,1-azoethane, 1,1-diacetoxy-1,1-azocyclohexane, 2,2-dipropionoxy-2,2-azopropane, 2,2-dicapronoxy-2,2-azopropane, 4,4-dimethyl-1,4-azobutyrolactone, azoisobutyronitrile, 2-t-butylazo-2-cyanobutan, 2-t-bytylazo-1-cyanocyclohexan) in solution was studied in dependence of temperature. Volumetry and differential-scanning-calorimetry (DSC) were used to determine decomposition rates; first order kinetics was found in all cases.

     

Derivatives of 3-aminopiperidine-2, 6-dione

Several N-substituted 3-phthalimidopiperidine-2,6-diones and 3-(3phthalimido-2,5-dioxopyrrolid-1-yl)piperidine-2,6-dione have been synthesized.     

The electronic structure of groups of isomeric hetero-aromatic systems

The electronic structure of the configurational isomers of 3-3-, 3-5- and 5-5-bis-oxadiazole, and of trans-,-di-(3-3)-, -(3-5)- and -(5-5)-diazolyl-ethylene, was studied by using the ASMO, SCF, CI procedure developed by Pariser, Parr and Pople. The total -electron energy is taken as the measure for ranging the various isomers and their different configurations in a given order of stability.Predictions based on charge distributions and bond orders are in agreement with the chemical behaviour of the known 3-3 and 5-5 isomers, and are therefore regarded as reliable also for the 3-5 compounds, not described in the literature so far.The calculated value of the lowest singlet transition energy agrees with the observed spectra, with a scatter of ±0.20 eV depending on the particular procedure chosen for calculating the _pqand (App) integrals. The calculated second singlet transition is found to depend on the procedure chosen for those integrals to such an extent as to make the prediction unreliable.

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Zusammenfassung Die Elektronenstruktur der Konfigurationsisomere von 3,3-, 3,5- und 5,5-bis-Oxadiazol und trans-,-di-3,3-, -3,5- und -5,5-Diazolyläthylen wurde mit Hilfe der ASMO-SCF-CI-Methode studiert. Die totale -Elektronenenergie wurde als Maß für die Stabilität der verschiedenen Isomere und ihrer Konfigurationen gewählt.Voraussagen, die auf Ladungsverteilungen und Bindungsordnungen basieren, sind in Übereinstimmung mit dem chemischen Verhalten der bekannten 3,3- und 5,5-Isomere und wurden deshalb auch als zuverlässig für die 3,5-Verbindungen angesehen, die bis jetzt in der Literatur nicht beschrieben sind.Der berechnete Wert für die niedrigste Singulett-Anregungsenergie stimmt mit den beobachteten Spektren bis auf ±0,2 eV überein, abhängig von der Berechnungsart für die _pqund (App). Die Anregungsenergie für den zweiten Singulettübergang läßt sich in diesem Rahmen nicht vorhersagen.

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Résumé La structure électronique des isomères configurationales des 3-3-, 3-5- et 5-5-bis-oxadiazole, et des trans---di-(3-3)-, -(3-5)- et -(5-5)-diazolyl-ethylène a été étudiée par la méthode ASMO, SCF, CI sélon la forme développée par Pariser, Parr et Pople. L'énergie totale des électrons a été prise comme étalon pour classifier les isomères et leurs differentes configurations sélon un ordre de stabilité.Les déductions que l'on peut tirer de la distribution des charges et des ordres de liaison sont en accord avec les observations chimiques des isomères connus, 3-3 et 5-5; par conséquent on peut considérer raisonables les prédictions que ont été faites sur les isomères 3-5, qui ne sont pas décrites dans la literature jusqu'ici.La valeur calculée pour la première transition de singulet est en bon accord avec le spectre d'absorption observé, l'incertitude due à la procedure choisie pour les integrales _pqet (App) étant ±0.20 eV. La deuxième transition de singulet apparait dépendre presque entièrement de la choix faite pour les dites integrales.

     

Spektrophotometrische und fluorometrische Bestimmung von Myricetin (3,3′,4′,5,5′,7-Hexahydroxy-Flavon)

Zusammenfassung Myricetin (3,3,4,5,5,7-Hexahydroxyflavon) wird aus Pflanzenextrakten chromatographisch abgetrennt, mit Methanol eluiert. Das gelbgrüne Fluoreszenzlicht seines Aluminiumchelats wird in Gegenwart von Essigsäure und Ammoniumacetat gemessen. 10^–4% Myricetin lassen sich mit einem relativen Fehler von ±4% bestimmen.

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Spectrophotometric and fluorometric determination of myricetin (3,3,4,5,5,7 -hexahydroxyflavone)

Summary Myricetin (3,3,4,5,5,7-hexahydroxyflavone) is separated chromatographically from plant extracts and eluted with methanol. The yellow-green fluorescent light of its aluminium chelate is measured in the presence of acetic acid and ammonium acetate. 10^–4% Myricetin can be determined with a relative error of ±4%.