New method for the synthesis of 8-azasteroids: Synthesis of benzo[a]cyclohexa[f]furo[2,3-g]-quinolizines from 2-cinnamoylcyclohexa[b]oxirane

The reaction of 2-cinnamoylcyclohexa[b]oxirane with allylamine gave cis-2(),3,4a,5,6,7,8,8a()-octahydro-1-allyl-4a()-hydroxy-(2)-phenylquinolin-4-one, which upon subsequent reaction with dimethyl malonate, peroxide epoxidation, and heating with hydrochloric acid gave cis-4,5,6a(),7,8,9,10a-octa-hydro-6-allyl-20-oxo-5()phenyl-3-chlorofuro[3,2-d]quinoline. Heating of this intermediate in 96% sulfuric acid gavetrans-3a(a),7a(a),9,10(),14b(),15-hexahydro-10()-methyl-2-oxo-1-chlorobenzo[a]cyclo-hexa[f]furo[2,3-g]quitiolizine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 30, No. 3, pp. 411–414, March, 1994.     

Synthesis of 2-[β-(5′-halogenofur-2′-yl)vikyl]benzimidazoles

2-[-(5-halogenofur-2-yl)vinyl]benzimidazoles (I) have been synthesized by the condensation of o-phenylenediamine with 5-halogeno-fur-2-ylacroleins or of 2-methylbenzimidazole with 5-halogenofurfurals. The methiodides of the 1-methyl-substituted derivatives ofI readily react with secondary amines (piperidine, dimethylamine)giving methiodides of 2-[-(5-dialkylaminofur-2-yl)vinyl]-1-methylbenzimidazoles.     

3-[ω-(2-Benzimidazolyl)alkyl]benzoxazolones

A new method for the preparation of -(3-benzoxazolonyl) butyric acids from sodium salts of benzoxazolones and -butyrolactone was developed. 3-[-(2-benzimidazolyl)alkyl]benzoxazolones were synthesized by the reaction of these acids and also (3-benzoxazolonyl)acetic and -(3-benzoxazolonyl)propionic acids with o-phenylenediamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 464–466, April, 1973.     

Photoinduced Acylotropic Rearrangement of Crown-Containing 2-[N-Acetyl-N-(4-aminobenzo-15-crown-5)methylene]-2,3-dihydrobenzo[b]thiophen-3-one

2-N-(4-Aminobenzo-15-crown-5)methylene-2,3-dihydrobenzo[b]thiophen-3-one and its acetyl derivative were synthesized. Their treatment with lithium, sodium, or potassium iodide in acetonitrile solution leads to formation of the corresponding crown-metal complexes. Irradiation of the acylated compounds at 436 nm induces NO migration of the acetyl group to give O-acyl isomer which is characterized by a considerable blue shift of the long-wave absorption band ( = 70 nm). The quantum yields of the photo- induced acylotropic reaction for the free ligand and its complexes with alkali metal cations change in the series: _L > K⁺ > Na⁺ > Li⁺.     

Synthesis of some substituted 2- and 4-[2′-(5″-nitro-2″-furyl)vinyl]-quinolines

A series of 2- and 4-[2-(5-nitro-2-furyl)vinyl]quinolines were synthesized by catalytic condensation of 5-nitrofurfural with 2- and 4-methylquinolines. 2-Methylquinoline (quinaldine) and its substituted derivatives also react when the starting reagents are fused directly.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 253–255, February, 1976.     

2-Amino-4-[2-(5-nitro-furyl)vinyl]thiazole and its derivatives

The reactions of 4-bromo-1-(5-nitro-2-furyl)but-1-en-3-one and its 2-methyl and 2-chloro derivatives with thiourea and its N-allyl and N-phenyl derivatives have yielded 2-amino-4-[-5-nitro-2-furyl)-vinyl]thiazole and its - and N-substituted derivatives. 2-Amino-4-[-(5-nitro-2-furyl)vinyl]thiazole and its -methyl derivative have also been prepared by the direct reaction of the corresponding , -unsaturated ketones with bromine and an excess of thiourea in chloroform, as was shown by a comparison of UV spectra. A series of N-acyl derivatives of the aminothiazoles has been obtained. UV and IR spectra are given.     

Diazabicycloalkanes with nitrogen atoms in bridgehead positions. 16. Synthesis and properties of benzo[b]-1,4-diazabicyclo[2.2.2]octene and dibenzo[b,e]-1,4-diazabicyclo[2.2.2]octadiene,containing primary aromatic amino acids

4-Aminobenzo[1,2-b]-1,4-diazabicyclo[2.2.2]octene and 4-aminodibenzo[1,2-b, e]-1,4-diazabicyclo[2.2.2]octadiene have been prepared by cyclization reactions of N--chloroethyl derivatives of 1,2,4-triaminobenzene and aminophenazine, and subsequent catalytic hydrogenation of the corresponding 4-nitrobenzo[1,2-b]-1,4-diazabicyclo[2.2.2]octene and 4-benzylaminodibenzo[1,2-b,e]-1,4-diazabicyclo[2.2.2]-octadiene. Using the conversion of these compounds to azides as an example, we have demonstrated the feasibility of applying these primary aromatic amines for the synthesis of derivatives of these heterocycles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 831–837, June, 1988.     

Über die SystemeABr/VBr2 (A=Na-Cs,Tl) [1]

Zusammenfassung Die Systeme ABr/VBr₂(A= Na, K, Tl, Rb, Cs) wurden mit der Differenzthermoanalyse untersucht. Das System mit NaBr ist rein eutektisch, in den übrigen Systemen existieren VerbindungenAVBr₃. Sie kristallisieren im CsNiCl₃-Typ: Säulen flächenverknüpfter Oktaeder werden durch die Alkaliionen zusammengehalten. Dies bedingt durch antiferromagnetische Kopplung reduzierte magnetische Momente. Das Fehlen von Verbindungen mit tetraedrisch koordiniertem V²⁺ wird mit der site-preference-energy der Ligandenfeldtheorie erklärt.

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The systemsABr/VBr₂ (A= Na, K, Tl, Rb, Cs) were investigated by means of differential thermal analysis. The system with NaBr is purely eutectic, in all other systems a compoundAVBr₃ exists. The compounds crystallize with the CsNiCl₃-structure: columns of face-shared octahedra are held together by the alkali ions. This involves reduced magnetic moments (antiferromagnetism). The lack of compounds with tetrahedral coordination of the V²⁺-ion is explained by the site-preferenceenergy according to ligand field theory.

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Résumé On a étudié par analyse thermique différentielle les systèmes ABr/VBr₂ (A=Na, K, Tl, Rb, Cs). Le système contenant NaBr est purement eutectique; dans tous les autres systèmes, il existe un composéAVBr₃. Les composés cristallisent avec la structure CsNiCl₃: les colonnes d'octaèdres ayant des surfaces communes sont maintenues par les ions alcalins. Cela implique des moments magnétiques réduits (antiferromagnétisme). L'absence de composés a coordination tétraédrique de l'ion V²⁺ s'explique par l'énergie de site préférentielle d'après la théorie de champ de ligand.

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Ar/Vr₂, =Na, K, Tl, Rb, Cs. NaBr , AVBr₃. CsNiCl₃:: - , . ( ). V²⁺ , , .

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Wir danken Herrn Prof. Hoppe, Universität Gießen, für die Berechnung von Madelung-faktoren, Herrn Prof. Babel, Universität Marburg, für die Erlaubnis, eine Hochtemperatur-DTA-Apparatur zu benutzen. Die Arbeit wurde von der Deutschen Forschungsgemeinschaft und dem Fonds der Chemischen Industrie mit Sachmitteln unterstützt.     

Preparative synthesis of benzo[b]thio-(seleno,telluro)phene derivatives

A preparative synthesis of aminomethyl derivatives of benzo[b]thio(seleno,telluro)phenes and their hydrohalides by the reaction of sulfur, selenium, and tellurium halides with 1-phenylpropynamines was developed.Communication 12 from the series Electrophilic reactions of halides of group VI elements. See [1] for Communication 11.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1331–1334, October, 1990.     

Synthesis of derivatives of pyrido[3,4-b]- and azepino[3,4-b]pyrrolo[2,3-d]pyrimidines from enamines of α-oxo lactams

The reaction of enamines of some -oxo lactams with 1,3-dimethyl- and 1,3-dibenzyl-4-hydrazinouracils gave the uracilyl-4-hydrazones of these lactams, the catalytic and thermal indolization of which yielded derivatives of pyrido[3,4-b]- and azepino[3,4-b]pyrrolo[2,3-d]pyrimidines. Some reactions of the latter were studied.Communication XXVIII from the series Investigation of Lactams. See [1] for communication XXVII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1398–1403, October, 1977.     

Pyridinium 1-phenyl-3,5,8-tris(trichloromethyl)-1-boronata-2, 6,7-trioxa-4-phosphabicyclo[2.2.2]octane

Conclusions The reaction of tris(-hydraxy-,,-trichloroethyl)phosphine with phenylboric anhydride in the presence of pyridine gives pyridinium 1-phenyl-3.5.8-tris(trichloromethyl)-1-boronato-2,6,7-trioxa-4-phosphabicyclo [2.2.2]octane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimieheskaya, No. 2, pp. 469–471, February, 1985.     

Synthesis and structure of 2-hydroxy-3-formylbenzo[b]thiophene azomethines

A number of 2-hydroxy-3-formylbenzo[b]thiophene azomethines and their derivatives, which model the individual tautomeric forms, were synthesized. As a result of a study of the electronic, vibrational, and PMR spectra, a ketone-amine structure, the stability of which is confirmed by quantum-mechanical calculations of the atomization energies of the individual tautomeric forms calculated by the Pariser-Parr-Pople (PPP) method within the Dewar , parametrization, was assigned to these azomethines.Communication XVIII from the series Benzoid—Quinoid Tautomerism of Azomethines and Their Structural Analogs. See [1] for communication XVII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 635–642, May, 1975.     

Hydrobenz[c]acridines and their analogs based on 1,5-diketones

The reaction of 1,5-diketones containing an -tetralone fragment with ammonia and primary amines gave hydrogenated benz[c]acridine and benzo[h]cyclopenta[b]quinoline derivatives, for which hydrocyanation, oxidation, and disproportionation reactions were studied.Communication XXIX from the series Reactions of 1,5-Diketones. See [1] for communication XXVIII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1361–1364, October, 1977.     

On the dioximine complexes of transition metals. LXXVIII1 TG and DTA study of the thermal decomposition of some complexes M[Co(DH)2XY] and [Co(DH)2(H2O)X]

18 monobasic complex acids of the type H[Co(DH)₂XY] (X, Y=Cl, Br, I, NO₂, N₃, NCS, NCSe, CN), or their alkalimetal and ammonium salts, and 5 aquo-acido-nonelectrolytes, [Co(DH)₂(H₂O)X] (DH=deprotonated dimethylglyoxime), were obtained and their thermal decompositions were studied by means of TG and DTA. The thermolysis processes are discussed. Kinetic parameters have been derived for several decomposition stages and are discussed in terms of the kinetic compensation effect.

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Zusammenfassung 18 monobasische Komplexsäuren des Typs H[Co(DH)₂XY] X, Y=Cl, Br, I, NO₂, N₃, NCS, NCSe, CN) oder deren Alkalimetall- und Ammoniumsalze und 5 Aquoacido-Nichtelektrolyte [Co(DH)₂(H₂O)X] (DH=deprotoniertes Dimethylglyoxim) wurden hergestellt. Die thermische Zersetzung dieser Verbindungen wurde mittels TG und DTA untersucht. Die Thermolyseprozesse werden diskutiert. Kinetische Parameter wurden für verschiedene Zersetzungsstufen ermittelt und werden in Verbindung mit dem kinetischen Kompensationseffekt diskutiert.

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H[Co(H)₂XY], H = , X, Y=Cl, Br, I, NO₂, N₃, NCS, NCSe, CN, , -- [Co(H)₂(H₂O)X]. . , .

     

Synthesis and reactions of pyrrolo[2,3-c]azepine derivatives

The construction of the pyrrolo[2,3-c]azepine system by the reaction of 2-oxo-3-hydroxy-4-cyano-2H, 1,5,6,7-tetrahydroazepine with glycine ester and subsequent cyclization of the resulting N-substituted amino nitrile in an alcohol solution of sodium ethoxide was studied. The pyrrolo[2,3-c]azepine system was converted to the three-ring pyrimido[4,54,5]pyrrolo[2,3-c]azepine system, the alkylation of which gave N,N-dialkyl and N,N,N-trialkyl derivatives. Cyclization of 3-benzyl-4, 6-dioxo-5-(N,N-dimethyl)aminoethyl-6H,3,4,7,8,9,10-hexahydropyrimido[4,54,5]pyrrolo[2,3-c] azepine hydrochloride under the influence of phosphorus oxychloride gave the four-ring pyrazino[3,2,1-b,c]azepino[3,4-b]pyrrolo[3,2-d]-pyrimidine system. The structures of the compounds obtained were confirmed by their IR, UV, and PMR spectra.Communication 34 from the series Research on Lactams. See [1] for communication 33.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1097–1100, August, 1980.     

Condensation of 2-amino-3, 4, 5, 6-tetrahydroimidazo[4,5,1-ij]quinolinium and 2-amino-2-pyrrolinium salts with β- dike tones

The corresponding 12,l,2,3-tetrahydropyrimido[2,12,3]imidazo[4,5,1-ij]quinolinium and 7,8-dihydro-6H-pyrrolo[1,2-a]pyrimidinium salts were obtained by the condensation of 2-amino-3,4,5,6-tetrahydroimidazo[4,5,1-ij]quinoline hydrochloride and 2-amino-2-pyrroline hydrochloride with -diketones. The structures of the products of condensation with unsymmetrical diketones were determined from their PMR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 419–421, March, 1972.     

Phenazine, 3. Mitt.: N-(o-Aminophenyl)-benzo[a]phenazin-5-amin,das vermeintliche “Dihydronaphthodiphenazin”Kehrmanns,und seine Derivate

The dihydronaphthodiphenazine ofKehrmann, which is according toBadger andPettit reported to be 14-o-aminophenyl-13,14-dihydro-5,8,13,14-tetraaza-6,7-benzopentaphene, is N-(o-aminophenyl)-benzo[a]phenazin-5-amine. This was proved by chemical and spectroscopic investigations. The structures of the derivatives prepared byBadger andPettit are also corrected and the acetylation processes are cleared up.     

Thermal behaviour of [N(2-ammoniumethyl) piperazinium] pentachlorocuprate(II) dihydrate

The thermal behaviour of single-crystals of the title compound has been investigated by means of thermal methods supported by optical microscopy. A complex change takes place on heating. After the loss of the two water molecules, leading to an amorphous phase, recrystallization takes place. This results in a solid (probably an anhydrous form) which reacts further, through partial liquefaction, to yield a red crystalline product whose structure has been characterized via X-ray powder spectra and electronic and IR spectroscopy.

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Zusammenfassung Das thermische Verhalten von Einkristallen der Titelverbindung wurden mittels thermischer Methoden und optischer Mikroskopie untersucht. Beim Erhitzen verläuft ein komplexer Prozeß. Nach dem zu einer amorphen Phase führenden Verlust von zwei Wassermolekülen findet eine Rekristallisation statt. Dabei wird eine feste Substanz, wahrscheinlich in wasserfreier Form, erhalten, die über partielle Verflüssigung unter Bildung eines roten kristallinen Produktes weiterreagiert, dessen Struktur durch Röntgenpulverspektren sowie Elektronen- und Infrarotspektroskopie charakterisiert wurde.

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, . . . , , , , , , .

     

Study of the tautomerism of 2-ethoxycarbonyl-3-oxoquinuclidine and -benzo[b]quinuclidine by PMR spectroscopy

The tautomeric equilibrium of 2-ethoxycarbonyl-3-oxoquinuclidine in various media was studied by PMR spectroscopy. The conclusion of the predominance of the keto form in nonpolar and dipolar forms in hydroxyl-containing solvents was confirmed. The lifetime of the forms was estimated to be 0.03 sec in CD₃OD at 75°C. In all of the investigated solvents, 2-ethoxycarbonyl-3-oxobenzo[b]quinuclidine exists as a mixture of two diastereomeric keto forms, the ratio between which depends on the solvent. The time required to establish equilibrium between the diastereomers at room temperature is no more than 5 min. The proton in the 2 position is exchanged by deuterium in deuterohydroxyl solvents; the half-exchange period is 2 min in CD₃OD at –24°, and the activation energy of deuterium exchange is 8 kcal/mole.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 978–983, July, 1972.     

Phase diagrams of MgF2-(Y,Ln)F3 systems

By means of thermal and X-ray analyses with oxygen control, 14 phase diagrams of the systems MgF₂-(Y, Ln)F₃ have been obtained, where Ln are all lanthanides except Pm and Eu. All the systems are eutectic. Solid solutions up to 12 mole% MgF₂, which decompose by the eutectoid scheme, were detected based on high-temperature modifications of trifluorides of Y, Er, Tm, Yb and Lu, with a structure of the-YF₃ type.

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Zusammenfassung Durch Einsatz der Thermo- und Röntgenanalyse mit Sauerstoffkontrolle wurden 14 Phasendiagramme der Systeme MgF₂-(Y, Ln)F₃ erhalten, wobei Ln sämtliche Lanthanoide mit Ausnahme von Pm und Eu sind. Alle Systeme zeigten sich eutektisch. Feste, sich nach dem eutektoiden Schema zersetzende Lösungen bis zu 12 Mol% MgF₂ wurden an Hand der Hochtemperatur-Änderungen der Trifluoride von Y, Er, Tm, Yb, Lu mit-YF₃-Struktur nachgewiesen.

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Résumé 14 diagrammes de phases des systèmes MgF₂ — (Y, Ln) F₃, où Ln représente tous les lanthanoïdes à l'exception de Pm et Eu ont été établis par études aux rayons X et analyse thermique, avec contrôle de l'oxygène. Tous ces systèmes présentent un eutectique. Des solutions solides jusqu'à 12 moles % de MgF₂ à décomposition eutectoïde ont été décelées à l'aide des transitions à haute température des trifluorures d'Y, Er, Tm, Yb et Lu du type-YF₃.

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- , 14 MgF₂ — (Y, Ln)F₃, Ln- , u. -. 12 .% MgF₂, , Y, r, Tm, Yb, Lu, -YF₃.