Study of nitrogen- and sulfur-containing heterocycles. 46. New heterocyclic systems — Derivatives of pyrido[3′,2′∶5,6][1,4]thiazino[3,4-c]- and pyrimido-[5′,4′∶5,6][1,4]thiazino[3,4-c][1,2,4]triazines. Synthesis,properties

Representatives of new heterocyclic systems were obtained — pyrido[3,25,6][1,4]thiazino[3,4-c]- and pyrimido[5,45,6][1,4]thiazino[3,4-c][1,2, 4]triazines. Hydrazides of N-(pyrid-3-yl)- and N-(pyrimid-5-yl)oxamic acids were isolated and characterized. Their acylation products were investigated.For communication 45, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 559–562, April, 1993.     

Studies in the imidazole series

Methods were developed for the synthesis of dihydro and tetrahydro derivatives of imidazo-[1,2-a]- and imidazo[1,2-c]pyrimidine and imidazo[2,1-b]-5-quinazolone from 2-amino- and 4-aminopyrimidines, 2-amino-4-quinazolones, and -haloethanols or 1,2-dihaloethanes. Dihydroimidazo[1,2-c]quinazoline, which was also obtained by cyclization of 4-(-hydroxyethylamino)-quinazoline, was synthesized by reaction of 4-chloroquinazoline with -haloethylamines.See [1] for communication LXXXV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 834–836, June, 1976.     

Synthesen in der Pyridazin-Reihe, 31. Mitt.: Über einige neue polycyclische Azolo- und Azinopyridazine

Zusammenfassung Synthesen von verschiedenen neuen polyazaheterocyclischen Systemen, wie 11H-Imidazo[1,22,3]pyridazino[6,1-b]-chinazolin-11-on (3), 11H-s-Triazolo[4,32,3]pyridazino[6,1-b]chinazolin-11-on (4), der Isomeren 4H-Pyrido[2,34,5]-pyridazino[6,1-c]-as-triazin (6) und 4H-Pyrido[3,24,5]-pyridazino[6,1-c]-as-triazin (9), Pyrido[3,24,5]pyridazino[1,6-b]benzimidazol (14) sowie Pyrido[3,24,5]-s-triazolo[4,32,3]pyridazino[1,6-a]benzimidazol (15) werden beschrieben.

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Syntheses of pyridazines, XXXI: Some new polycyclic azolo and azino-pyridazines

Syntheses of several new polyazaheterocyclic systems are described, i.e. 11H-Imidazo[1,22,3]pyridazino[6,1-b]quinazolin-11-one (3), 11H-s-Triazolo[4,32,3]pyridazino[6,1-b]quinazolin-11-one (4), the isomeric 4H-Pyrido[2,34,5]pyridazino[6,1-c]-as-triazine (6) and 4H-Pyrido[3,24,5]pyridazino[6,1-c]-as-triazine (9), Pyrido[3,24,5]pyridazino[1,6-b]-benzimidazole (14) and Pyrido[3,24,5]-s-triazolo[4,32,3]pyridazino[1,6-a]benzimidazole (15).

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Heterocyclen, 69. Mitt.     

Acetals of lactams and acid amides. 35. Synthesis of condensed two- and three-ring pyridine systems on the basis of enamino amides

The synthesis of 2,3,5,6-tetrahydropyrrolo[3,2-c]pyrid-6-one was accomplished by rearrangement of 8H,1-cyano-8-dimethylaminomethylene-2,5,6,7-tetrahydropyrrolo[1, 2-c]pyrimidine. Pyrrolo[3,2-c]pyrimidine, 1,6-naphthyridine, and pyrimido[4,3-b]-azepine derivatives were synthesized on the basis of enamino dinitriles. The hydrolysis of 8H,1-cyano-8-dimethylaminomethylene-2,5,6,7-tetrahydropyrrolo[1,2-c]-pyrimidine in 50% CH₃COOH leads to a pyrrolo[1,2-c]pyrido[4,3-d]pyrimidine derivative. A similar dipyrido[4,3-d-1,2-c]pyrimidine derivative was obtained from 1-cyano-9-dimethylaminomethylene-2,5,6,7,8,9-hexahydropyrido[1,2-c]pyrimidine under these conditions, and 3,4-dioxo-3,4,7,8,9,10-hexahydropyrido[1,2-c]pyrano[4,3-d]-pyrimidine was synthesized bytreatment with a 1 N solution of HCl.See [1] for Communication 34.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 518–522, April, 1982.     

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.     

Complexes of metallochromic substances. VI

Summary Two new simple spectrophotometric methods are developed, which are based on the estimation of one or two pairs of absorptivities in given conditions. The first extrapolation method is convenient for the determination of formation constants of complexes 11, 21, and 22 (LM). The second calculating method is suitable for the classification of complexes 11 and 22.

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Zusammenfassung Zwei neue, einfache spektralphotometrische Methoden wurden entwickelt, die auf der Bestimmung von einem oder zwei Extinktionspaaren unter gegebenen Bedingungen beruhen. Die erste Extrapolationsmethode ist für die Bestimmung der Bildungskonstanten von Komplexen 11, 21 und 22 (LM) geeignet. Die zweite Rechnungsmethode eignet sich für die Klassifikation der Komplexe 11 und 22.

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Part V, see: Z. analyt. Chem. 207, 247 (1965).     

N-acetylindoxyl in the synthesis of new condensed heterocycles

Derivatives of a new heterocyclic system thieno[2,35,6]pyrimido[3,4-a]indole, were obtained by the reaction of substituted N,O-diacetylindoxyls with excess N-(2-methyl-3-ethoxycarbonyl-4-thienyl)hydrazine. The reaction of N-acetylindoxyl and 4-hydrazinouracil forms 12-amino-1,3-dioxo-2,4,6-trimethylpyrimido[5,45,6]pyrimido[3,4-a]indole.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, 1343–1345, October, 1987.     

Thiolactame als Reagenzien in der quantitativen Analyse. IX

Zusammenfassung Thiocaprolactam (T) eignet sich zur Goldbestimmung im Konzentrationsbereich 10 bis 130 g Au/ml mit einem Fehler von ±0,5g. Thiocaprolactam bildet mit [AuCl₄]^– eine Verbindung im molaren Verhältnis TAuCl=112, mit [AuJ₄]^– im molaren Verhältnis TAuJ=213. Dagegen bilden sich im System T:Au:Br zwei verschiedene Verbindungen: Ein Bromidkomplex mit höherem Goldgehalt TAu=12, der mit Chloroform extrahierbar ist, und eine sich als Niederschlag ausscheidende Verbindung mit dem Verhältnis TAuBr=112.

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Thiolactams as reagents in quantitative analysis. IX

Summary Thiocaprolactam (T) is suitable for the determination of gold in the concentration range 10–130g Au/ml with an error of ±0.5g. Thiocaprolactam yields with [AuCl₄]^– a compound in the molar ratio TAuCl=112, with [Aul₄]^– in the molar ratio TAuI=213. On the other hand various compounds result in the system TAu Br. The molar ratio in the case of the bromide complex has a higher gold content, namely TAu=12; this product is extractable with chloroform and a compound that comes down as a precipitate shows the ratioT Au Br=112.

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Herrn Dr.K. Czerepko möchte ich hiermit meinen Dank für die Diskussion der Ergebnisse aussprechen.     

Synthesis of isomeric benzodipyrrolenines and their derivatives

The Fischer reaction was used to synthesize 2,3,3,5,5,6-hexamethyl-3H,5H-benzo[1,2-b5,4-b]dipyrrole and 2,3,3,7,8,8-hexamethyl-3H,8H-benzo[1,2-b3,4-b]dipyrrole from the dihydrazone obtained by the action of methyl isopropyl ketone on m-phenylenedihydrazine. Centrosymmetrical 2,3,3,6,7,7-hexamethyl-3H,7H-benzo[1,2-b4,5-b]dipyrrole was synthesized from p-phenylenediamine and methyl bromoisopropyl ketone. Mono- and diquaternary salts were obtained from the new bases. The diquaternary salts were converted to bismethylene bases.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 614–617, May, 1971.     

Condensation of N-(piperidylidene-4)arylamines with acetylenedicarboxylic esters

The substituted piperidines, N-(piperidin-3-en-4-yl)-N-(1,2-dimethoxycarbonyl-etheno)arylamine and 1-aryl-3,4,5,6-tetramethoxycarbonyl-1,2-dihydrospiro[cyclo-[pyridine-2,4-piperidine], were synthesized by the condensation of acetylenedicarboxylic ester with an azomethine, obtained from a -piperidone. It was found that the amounts of 11 and 12 addition compounds obtained depends on the ratio of starting reagents. Compounds isomeric at the vinyl group were examined in the case of one of the 11 addition compounds. N-(1,2,5-trimethylpiperidin-4-yl)-N-(1,2-dimethoxycarbonyletheno)aniline was prepared by two methods.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 943–946, July, 1986.     

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.     

Study of the complex formation between 4, 6-diamine-1, 2-dihydro-2-thiopyrimidine and cobalt(II), cobalt(III), nickel(II) and copper(II) ions

Summary Reactions of 4, 6-diamine-1, 2-dihydro-2-thiopyrimidine (HDATP) with cobalt(II), nickel(II) and copper(II) ions in 12 metal:ligand ratio in aqueous media at 25°C and 0.1 M ionic strength (KNO₃), lead to the formation of both [M(DATP)]⁺ and [M(DATP)₂] species, whose stability constants were obtained.On the other hand, in aqueous or ethanolic media, solid complexes with 11, 12, or 13 stoichiometries were isolated. These have been characterized by analytical, i.r. and electronic spectral and magnetic measurement studies, and tentative structures are proposed.     

Research in the imidazole series

The synthesis of 9-acyl- and 8-alkyl-9-acyl-substituted naphth[1,24,5]imidazo[2,1-b]thiazoles was accomplished by the reaction of 2-acylmethylthionaphth[1,2-d]imidazole with acylating agents and of 2-mercaptonaphth[1,2-d]imidazole with 3-chloro-2,4-pentanedione.See [1] for communication LXVII.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 30–32, January, 1972.     

Micro reversed phase liquid chromatography of Cd-, Ni-, Zn-, Cu-, Co-, Hg-diethyldithiocarbamates at picogram level

Summary The use of micro reversed phase columns (Polygosil C18) for the separation of metal DDTC chelates was investigated and applied to drinking water analysis.Three different eluents have been tested [702010 (MeOH H₂OCHCl₃); 8020 (MeOHH₂O); 7030 (MeOHH₂O)] at flow rates of 7 to 28gml/min. Eluent composition showed strong influence onk of Co(DDTC)₂.The linear working curves fitted at least 3 decades with detection limit of 40–500 pg. Monitoring at _max instead of 254 nm decreases the detection limits. The consume of eluent is 10 to 20 times less than with analytical columnes.Results of micro LC have been compared with predictible data of theoretical considerations.

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Mikro-Umkehrphasen-Flüssigkeitschromatographie der Cd-, Ni-, Zn-, Cu-, Co-, Hg-Diethyldithiocarbamatchelate im Picogrammbereich

Zusammenfassung Die Anwendung von Mikro-RP-Säulen (Polygosil C18) für die Trennung von Metall-DDTC-Chelaten wurde untersucht und auf die Analyse von Trinkwasser angewendet. Drei verschiedene Eluentien [702010 (MeOH H₂OCHCl₃); 8020 (MeOHH₃O); 7030 (MeOHH₂O)] bei Fließraten von 7 bis 28gml/min wurden untersucht,k von Co(DDTC)₂ wird von der Eluenszusammensetzung erheblich beeinflußt. Der lineare Meßbereich betrug mindestens 3 Dekaden mit einer Nachweisgrenze von 40–500 pg, die durch Detektion bei _max statt bei 254 nm noch weiter gesenkt werden kann.Der Verbrauch an Eluens ist 10–20mal geringer als bei analytischen Säulen.Die Ergebnisse der Mikro-LC wurden anhand theoretischer Überlegungen mit den vorhersagbaren Daten verglichen.

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Presented in parts at 9th International Symposium on Microchemical Techniques, Amsterdam 1983.     

Polymeric membrane sodium-selective electrodes based on calix[4]arene ionophores

Six kinds of tetra alkylester type calix[4]arene derivatives, (R₁=R₂=CH₃1, C₂H₅2, C₃H₇3,n-C₄H₉4,t-C₄H₉5,n-C₁₀H₂₁6), a diethyl-didecyl mixed ester type (R₁=C₂H₅, R₂ =C₁₀H₂₁7), and three kinds of lower rim bridged types (R₁=C₂H₅, R₂–R₂=(CH₂)₁₀8, (CH₂)₁₂9, (CH₂)₂(OCH₂CH₂)₃10) were characterized by electrochemical measurement to elucidate the effect of the length of the alkyl group of alkoxycarbonyl substituents on Na⁺ selectivity. To obtain excellent Na⁺ selective ionophores, introduction of short chain alkyl groups rather than long chain ones, such as a decyl group, and maintenance of sufficient solubility of the calix[4]arene derivatives in the membrane solvent are required concurrently. Among the calix[4]arenes tested, 25,26,27,28-tetrakis[(ethoxycarbonyl)methoxy]-p-tert-butylcalix[4]arene2, and the diethyl-didecyl mixed ester type derivative7 are the best ionophores for a Na⁺ selective electrode. On the other hand, sodium selectivity of the bridged type derivative9 is comparable or even superior to that of the known bis(12-crown-4).This paper is dedicated to the commemorative issue on the 50th anniversary of calixarenes.     

7-Aryl-6,7-dihydro-8h-indeno[1′,2′∶2,3]pyrano-[5,6-c]benzo[c]pyran-6,8-diones and their thio analogs

The ability of 3-[-(1,3-dioxo-2-indanyl)benzyl]-4-hydroxy-substituted 2H-benzo [b]pyran-2-ones and benzo[b]thiopyran-2-ones to undergo dehydration under the influence of dehydrating agents to give 7-aryl-6,7-dihydro-8H-indeno[1,2-2,3]pyrano[5,6-c]benzo[c]pyran-6,8-diones and their thio analogs was demonstrated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1475–1476, November, 1985.     

Der Nachweis des Cadmiums durch selektive Papierchromatographie

Zusammenfassung Durch die Anwendung eines H₂S-haltigen Laufmittels werden die Ionen Cu²⁺, Pb²⁺, Bi³⁺ und Hg²⁺ am Startpunkt des Chromatogramms als Sulfide fixiert, während Cd²⁺ nach kurzer Laufzeit in scharf begrenzter Zone als Sulfid im Chromatogramm nachgewiesen wird. Als Arbeitsgefäße dienen Reagensgläser. Die Spezifitäten liegen für 5 g Cd bei Cd²⁺Cu²⁺=12000, Cd²⁺Pb²⁺=12000, Cd²⁺Bi³⁺=12000, Cd²⁺Hg²⁺=1100.Herrn Prof. Dr. O. Glemser, Direktor des Anorganisch-chemischen Insituts der Universität Göttingen, danken wir für Unterstützung der Arbeit.     

Composition of 2-(3,5-dibromo-2-pyridylazo) diethylaminophenol chelates by liquid chromatography

Summary The composition of 3,5-diBr-PADAP metal chelates was determined by liquid chromatography employing appropriate eluents and non-polar bonded stationary phase. The metal-to-ligand ratios were 12, 12 and 12 for Cu(II), Co(III) and Cr(III) respectively, and the V(V)-to-ligand ratio found to be 111 in V(V)-3,5-diBr-PADAP-H₂O₂ in the presence of H₂O₂. The results are in agreement with literature data.