Cobalt(II) and nickel(II) chloride complexes with some 2-(4′-Methyl-2′-pyridyl and 2′- or 8′-quinolyl)benz-X-azoles

Summary Complexes of general formula ML_mCl₂ · nH₂O, where M=cobalt(II) or nickel(II); L=2-(4-methyl, 2-pyridyl)-benzimidazole (mpbi), 2-(4-methyl, 2-pyridyl)benzothiazole (mpbt), 2-(4-methyl, 2-pyridyl)benzoxazole (mpbo), 2-(4-methyl, 2-quinolyl)benzoxazole (mqbo), or 2-(4-methyl, 8-quinolyl)benzoxazole (mqbo); m=1,2; n=0–3, were prepared and characterized by t.g.a., conductance and magnetic measurements, i.r. and diffuse-reflectance electronic spectra.All the ligands behave as bidentate and coordinate through the pyridine- and isoxazole-nitrogen atoms.The nickel complexes have distorted octahedral or fivecoordinate structures. The cobalt complexes arepseudo-tet- rahedral except Co(mpbo)₂Cl₂·2H₂O where the metal is six-coordinate.     

Indolobenzo[b]furans. 3. Synthesis of unsubstituted indolo[7′,6′∶2,3]- and indolo[6′,7′∶2,3]benzo[b]pyrans

Indolo[7,62,3]- and indolo[6,72,3]benzo[b]furans have been synthesized with the aid of the Fischer reaction. The physicochemical characteristics of the compounds synthesized are considered.For communication 2, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 631–634, May, 1985.     

Kinetics of the catalytic transformation of isobutene into methacrylonitrile with NO on supported nickel oxide aerogel

Kinetic studies of the nitroxidation of isobutene by NO show that the reaction follows a redox mechanism in the temperature range of 300–400°C. This mechanism implies an interaction between dehydrogenated isobutene -allyl radical and atomic nitrogen due to the decomposition of NO by the reduced catalyst, which is then reoxidized.

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NO , 300–400°C. - , NO , .

     

1,2-bis(2',6'-dimethyl-i',3'-dioxa-6'-aza-2'-silacyclooctyl-2')ethane and the corresponding ethylene and acetylene derivatives

Conclusions The reaction of 1,2-bis(methyldimethoxysilyl)ethane and the corresponding ethylene and acetylene derivatives with bis(2-hydroxyethyl)methylamine gives 1,2-bis(2,6-dimethyl-1,3-dioxa-6-aza-2-silacyclooctyl-2)ethane and the corresponding ethylene and acetylene derivatives. Analogously, 1,2-bis(vinyldimethoxysilyl)acetylene gave 1,2-bis(2-vinyl-6-methyl-1,3-dioxa-6-aza-2-silacyclooctyl-2)acetylene.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1420–1421, June, 1988.     

Liquid phase CO+H2 reactions in presence of ruthenium catalysts

Several effects on the hydrogenation of carbon monoxide in propanol in presence of ruthenium catalysts are examined. The homologation reaction is not observed, only propyl formate and propyl acetate are produced with any ruthenium catalyst. The pH-value is an important parameter: in acid media, the yield of propyl formate is noticeably increased indicating different catalytic active species. The addition of cesium salts is also benefitial for formate formation. This is not the case when water is associated with propanol as solvent. Finally, no ethylene glycol is detected. The process is found to be homogeneous and methanol seems to be the precursor of methyl formate.

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, . , . : , . . , . . , -, .

     

Localization of gallium in erionite type Ga?Al zeolites by71Ga,27Al and29Si NMR

The state of Al³⁺, Ga³⁺ and Si⁴⁺ in erionites obtained by hydrothermal crystallization from Ga–Al–Si gels has been examined. The results suggest that gallium cations can isomorphously substitute a part of silicon cations in the zeolite framework, to a notable extent in the sites having no aluminium cations in the second coordination sphere of silicon.

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Al³⁺, Ga³⁺ Si⁴⁺ , . , , .

     

Differential thermal analysis of potassium perchlorate

A study has been made of the differential thermal analysis of (i) potassium perchlorate in powdered form, (ii) potassium perchlorate in pelletized form, (iii) potassium perchlorate recrystallized from liquid NH₃, and (iv) potassium perchlorate preheated for 24 hours at 375°. Pretreatment of potassium perchlorate leads to a desensitization of both endothermic and exothermic processes. Additionally, the pretreatment tends to convert the symmetric exotherm into an asymmetric exotherm due to merging of the two exotherms. An analysis of the factors causing asymmetry in the exotherm has thrown fresh light on the mechanism of thermal decomposition of potassium perchlorate.

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Zusammenfassung Eine differentialthermoanalytische Untersuchung wurde an, (i) Kaliumperchlorat in Pulverform, (ii) Kaliumperchlorat in pelletisierter Form, (iii) Kaliumperchlorat, umkristallisiert aus flüssigem Ammoniak und (iv) Kaliumperchlorat, 24 Stunden bei 375° vorgeheizt, durchgeführt. Die Vorbehandlung von Kaliumperchlorat führt zu einer Verdichtung sowohl der endothermen als auch der exotherman Vorgänge. Ausserdem führt die Vorbehandlung zur Umwandlung der symmetrischen Exotherme in eine asymmetrische Exotherme durch Vereinigung der zwei Exothermen. Die Analyse der die Asymetrie der Exothermen verursachenden Faktoren zeigte den Mechanismus der thermischen Zersetzung des Kaliumperchlorats unter neuen Gesichtspunkten.

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Résumé On a effectué l'étude par analyse thermique différentielle du perchlorate de potassium: (i) en poudre, (ii) sous forme comprimée, (iii) recristallisé dans NH₃ liquide, (iv) préchauffé à 375° pendant 24 heures. Le traitement préalable du perchlorate de potassium entraîne la désensibilisation des processus endothermiques et exothermiques. De plus, le traitement préalable tend à convertir l'exotherme symétrique en un exotherme asymétrique, du fait de la fusion des deux exothermes. Une analyse des facteurs causant l'asymétrie de l'exotherme a donné une vue nouvelle du mécanisme de la décomposition thermique du perchlorate de potassium.

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, , , 375° 24 . . , , . , , .

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This work has been supported by a grant from the Indian Space Research Organization (I.S.R.O). It also includes financial support to one of the authors (D. S.). This support is gratefully acknowledged.     

1,1′,2,2′,6,6′-Hexaphenyl-4,4′-bipyridinium cation radical

Aniline reacts with 2,2,6,6-tetraphenyl-4,4-bipyrilium perchlorate to form 1,1,2,2,6,6-hexaphenyl-4,4-bipyridine perchlorate. A relatively stable cation radical is formed in the first stage of electrochemical reduction of this compound, which has been examined by ESR, where there are splittings from two nitrogen nuclei and the four protons in the 3,3,5,5 positions: a_N=0.38; a_H=0.14 mT.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, No. 1, pp. 61–64, January–February 1992.     

Synthesis and structure of o-bis(2-fluoro-2,2-dinitroethyl)-nitromethyl ester of 2′-fluoro-2′, 2′-dinitroethyl-2″-fluoro-2″-nitroethylenecarboxime

Conclusions The product of conversion of O-bis(2-fluoro-2,2-dinitroethyl)nitromethylbis(2-fluoro-2,2-dinitroethyl)carboxime in methanol or ether is O-bis(2-fluoro-2,2-dinitroethyl)nitromethyl-2-fluoro-2,2-dinitroethyl-2'-fluoro-2-nitroethylenecarboxinie, the structure of which has been established by x-ray diffraction analysis.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2019–2021, September, 1987.     

Investigations in the field of oxygen-containing heterocycles

2-(4-Chloro-2-methyl-2-butenyl)tetrahydropyran and 2-(4-chloro2, 3-dimethyl-2-butenyl)tetrahydropyran react with organomagnesium compounds and also with sodium amalgam with the formation of mixtures of the 2-(2-alkenyl)tetrahydropyrans corresponding to the initial chlorides and the 2-(3-alkenyl)tetrahydropyrans corresponding to the allyl isomers of the initial chlorides. The structure and composition of the products have been established by IR and NMR spectroscopy and by gas-liquid chromatography.For part V, see [1].     

Nitration,amination, and halogenation of Di-O-methylphloracetophenone

Chlorination of the title compound gave 5- and 3-chloro-2-hydroxy-4,6-dimethoxyacetophenone. The nitration of its acetate, followed successively by reduction, diazotization, and reaction with cuprous chloride, gave the 3-substituted series, 2-acetoxy-4,6-dimethoxy-3-nitroacetophenone, 3-amino-2-hydroxy-4,6-dimethoxyacetophenone, and 3-chloro-2-hydroxy-4,6-methoxyacetophenone, respectively. The orientation of substituents in the products was proved. The amino and chloro members of the isomeric 5-substituted series were availablevia 2-hydroxy-4,6-dimethoxy-5-phenylazoacetophenone, the product of the reaction of the title compound with benzenediazonium chloride.

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Nitrierung, Aminierung und Halogenierung von Di-O-methylphloracetophenon

Zusammenfassung Chlorierung der Titelverbindung gab 5- und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Nitrierung des Acetats, gefolgt von Reduktion, Diazotierung und Reaktion mit CuCl ergab die 3-substituierte Reihe: 2-Acetoxy-4,6-dimethoxy-3-nitroacetophenon, 3-Amino-2-hydroxy-4,6-dimethoxyacetophenon und 3-Chlor-2-hydroxy-4,6-dimethoxyacetophenon. Die Orientierung der Substituenten wird diskutiert. Die Amino- und Chlorderivate der isomeren 5-substituierten Reihe sind über 2-Hydroxy-4,6-dimethoxy-5-phenylacetophenon zugängig, dem Produkt der Reaktion der Titelverbindung mit Phenyldiazoniumchlorid.

     

Investigations of 2,3′-biquinolyl. 8. Reduction of 1-alkyl-3-(2-quinolyl)-quinolinium halides with sodium borohydride

Reduction of 1-alkyl-3-(2-quinolyl)quinolinium halides with sodium borohydride leads to 1-alkyl-1,2-dihydro-2,3-biquinolyls which, except for the ethoxycarbonyl derivative, undergo rearrangement to 1-alkyl-1,4-dihydro-2,3-biquinolyls. The last can be synthesized by the alkylation of the corresponding 1,4-dihydro-2,3-biquinolyls under conditions of interphase catalysis and in the system KOH-DMSO.For Communication 7, see [1].Stavropol' State University, Stavropol' 355009, Russia; nauka@stavsu.ru. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1084–1087, August, 2000.     

Acylation of benzimidazole by the regel-buechel method. 2. Deacylation and dissociation of 1-methyl-3-acyl-2-(1′-methyl-2′-benzimidazolyl)-4-benzimidazolines

With excess acyl halide 1-methyl-3-acyl-2-(1-methyl-2-benzimidazolyl)-4-benzimidazoline is converted to an unstable 1-methyl-3-acyl-2-(1-methyl-3-acyl-4-benzimidazolin-2-yl)benzimidazolium chloride, which undergoes intramolecular redox cleavage with the formation of 1,1-dimethyl-2,2-dibenzimidazolyl and an aldehyde and dissociates at the C-C bond that connects the benzimidazolium and benzimidazoline fragments into a carbene yield and a 1-methyl-3-acylbenzimidazolium chloride.See [1] for communication 1.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 339–342, March, 1987.     

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.     

Polarographic determination of some carcinogenic aminoazobenzenes

Summary The polarographic procedure can be used for the quantitative analysis of all the aminoazobenzenes tested in this study as indicated by proportionality between diffusion current and concentration. There is no significant correlation between the half-wave potential and carcinogenic potency for rat liver for three monosubstituted and seven disubstituted derivatives ofp-dimethylaminoazobenzene. These ring-substituted azocarcinogens rank from weak to very strong for carcinogenic potency against rat liver. Also aminoazobenzenes such as the noncarcinogenic 4-amino-4-dimethylaminoazobenzene and the carcinogenic N,N-dimethyl-4-amino-N-formyl-N-methyl-4-aminoazobenzene and N,N-dimethyl-4-amino-N-acetyl-N-methyl-4-aminobenzene have similar have-wave potentials. On the other hand, the noncarcinogenic 4-aminoazobenzene, 4-amino-N-methyl-4-aminoazobenzene and N-methyl-4-amino-N-methyl-4-aminoazobenzene have half-wave potentials that are about 100 mv more negative than that of all other aminoazobenzenes discussed in this report.

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Zusammenfassung Die Proportionalität zwischen Konzentration und Stromdurchfluß bietet die Grundlage zur polarographischen Bestimmung aller in dieser Arbeit geprüften Aminoazobenzole. Zwischen dem Halbwellenpotential und der carcinogenen Wirkung gegenüber Rattenleber besteht bei drei monosubstituierten und sieben disubstituierten Derivaten desp-Dimethylaminoazobenzols keine signifikante Korrelation. Diese ringsubstituierten Azocarcinogene zweigen schwache bis sehr starke carcinogene Wirkung gegenüber Rattenleber. Aminoazobenzole wie das nicht-carcinogene 4-Amino-4-dimethylaminoazobenzol und die carcinogenen Verbindungen N,N-Dimethyl-4-amino-N-formyl-N-methyl-4-aminoazobenzol und N,N-Dimethyl-4-amino-N-acetyl-N-methyl-4-aminoazobenzol haben ähnliche Halbwellenpotentiale. Andrerseits ist das Halbwellenpotential der nicht-carcinogenen Verbindungen 4-Aminoazobenzol, 4-Amino-N-methyl-4-aminoazobenzol und N-Methyl-4-amino-N-methyl-4-aminoazobenzol ungefähr um 100 mV negativer als das aller anderen hier behandelten Aminoazobenzole.

     

New terpenoid coumarins from Ferula tadshikorum

Summary Two new terpenoid coumarins — tadzhiferin (I) and tadzhikorin (II) — have been isolated from the fruit ofFerula tadshikorum M. Pimen.On the basis of physicochemical and spectral investigations, the structure of 7-(9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin is proposed for (I) and that of 7-(4-acetoxy-9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyloxy)coumarin for (II).All-Union Scientific-Research Institute of Medicinal Plants, Moscow. M. V. Lomonosov State University. Botanical Garden, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 593–599, September–October, 1976.     

Synthesis and photochromic properties of spiroanthrooxazine

1,3,3-Trimethylspiro[indoline-2,3-3H-anthraceno[2,1-b][1,4]oxazine] was synthesized. The compound has photochromic properties in solutions and in polymeric matrices. It was found from the spectral data that the colored form of the spiroanthrooxazine exists in a quinoid form and is characterized by a positive solvatochromic effect.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1521–1525, July, 1990.