The crystal structure of (dimorpholinophosphoryl)carbonitrile oxide

An X-ray diffraction study of (dimorpholinophosphoryl)carbonitrile oxide (1) was carried out. The structure of the nitrile oxide group in compound1 is more similar to that in fulminic acid (HCNO) than to those in aryl- and hetarylcarbonitrile oxides. The NO bond in1 is shorter than those in the latter compounds, and the nitrile oxide fragment is more linear due to an increase in the XCN angle.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1245–1247, July, 1994.This work has been financially supported by the Russian Foundation for Basic Research, project No. 93-03-5069.     

Podand-porphyrins with peripheral chelates

Alkylation of 5-(3-nitro-4-hydroxyphenyl)-10,15,20-triphenylporphyrin with chloropyridines[2,6-dichloromethyl-and 2-chloromethyl-6-(2-nitrophenoxymethylpyridine)] as well as condensation by a mixed-aldehyde method starting with formylpyridines [2-(2-nitro-4-formylphenoxymethyl)-6-(2-nitrophenoxy-methyl-) or 2,6-di(2-nitro-4-formylphenoxymethyl)pyridine], benzaldehyde, and pyrrole are used to synthesize previously unknown podand-porphyrins containing from one to four peripheral chelates.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 475–481, April, 1991.     

Spectrophotometric determination of vanadium with 4-(1′H-1′,2′,4′-Triazolyl-3′-azo)-2-methylresorcinol

Summary 4-(1H-1,2,4-Triazolyl-3-azo)-2-methylresorcinol reacts with vanadium(V) at pH 8.10 (Tris-HClO₄ buffer solution) to produce a pink-violet 11 complex ( _max=525 nm,=2.55×10⁴l·mol^–1· cm^–1) in a 50% (v/v) methanol-water medium, which allows the spectrophotometric determination of 0.1 to 1.51 ppm of vanadium. The method has been applied for the determination of the vanadium content in low alloy steels.

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Spectrophotometriscbe Bestimmung von Vanadin mit 4-(1H-1,2,4-triazo-lyl-3-azo)-2-methylresorcin

Zusammenfassung Vanadin bildet bei pH 8,10 (Tris-HClO₄-buffer) mit 4-(1H-1,2,4-tri-azolyl-3-azo)-2-methylresorcin ein rosenrot-violettes Chelat, dessen Absorptionsmaximum bei 525 nm in Gegenwart von 50% Methylalkohol gemessen wird. Dieser 11-Komplex entspricht bei einer Vanadin-Konzentration von 0,1–1,51g/ml dem Beerschen Gesetz; seine molare Absorptivität ist 2,55×10⁴l·mol^–1·cm^–1. Das Verfahren wurde zur Bestimmung des Vanadins in Stahl verwendet.

     

Zur Mannich-Reaktion von Dihydro-6-methyl-2(1H)-pyrimidinonen

Zusammenfassung Dihydro-4,4,6-trimethyl-2(1H)-pyrimidinone reagieren mit Formaldehyd und sekundären bzw. primären Aminen zu 6-Dialkylaminoäthylidentetrahydro-2(1H)-pyrimidinonen bzw. Hexahydro-2(1H)-pyrido[4,3-d]Pyrimidinonen. Mit Succindialdehyd bzw. Glutardialdehyd und primären Aminen entstehen 5,7-Äthanohexahydro-2(1H)-pyrido[4,3-d]pyrimidinone bzw. Tetrahydro-6,8-propano-6H-pyrimido[1,6-c]pyrimidin-1(2H)-one. Die 6-Dialkylaminoäthylidentetrahydro-2(1H)-pyrimidinone geben mit Phenolen Tetrahydrospiro([1]benzopyran-2,4(1H)-pyrimidin)-2(3H)-one, mit cycl. -Dicarbonylverbindungen Hexahydrospiro([1]benzopyran-2,4(1H)-pyrimidin)-2,5(3H, 6H)-dione bzw. Tetrahydrospiro(2H,5H-pyrano[3,2-c][1]benzopyran-2,4(1H)-pyrimidin)-2(3H),5-dione bzw. mit Malonestern -(Tetrahydro-4,4-dimethyl-2-oxo-6-pyrimidyl)-äthylmalonester.Zusammenfassung Dihydro-4.4.6-trimethyl-2(1H)-pyrimidinones react with formaldehyde and sec. and prim. amines resp. to 6-dialkylaminoethylidentetrahydro-2(1H)-pyrimidinones and hexahydro-2(1H)-pyrido[4.3-d]pyrimidinones, resp. succindialdehyde and glutaraldehyde with primary amines give 5.7-ethanohexahydro-2(1H)-pyrido[4.3-d]pyrimidinones and tetrahydro6.8-propano-6H-pyrimido[1.6-c]pyrimidin-1(2H)-ones, resp. 6-Dialkylaminoethylidentetrahydro-2(1H)-pyrimidinones react with phenols to tetrahydrospiro([1]benzopyran-2.4(1H)-pyrimidin)-2(3H)-ones, with cyclic -dicarbonyl compounds to hexahydrospiro([1]benzopyran-2.4 (1H)-pyrimidin)-2,5 (3H), 6H)-diones and tetrahydrospiro(2H,5H-pyrano[3.2-c][1]benzopyran-2.4(1H)-pyrimidin)-2(3H),5-diones, resp., with malonates -(tetrahydro-4.4-dimethyl-2-oxopyrimidyl-6)-ethylmalonates.

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Mannich reaction with dihydro-6-methyl-2(1H)-pyrimidinones

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Herrn Prof. Dr.F. Kuffner zum 65. Geburtstag gewidmet.     

Investigations in the field of the chemistry of 2-hetarylbenzimidazoles. 6. Synthesis and properties of 1-methyl-2-(2′-selenienyl)benzimidazole

2-(2-Selenienyl)benzimidazole has been synthesized by a Weidenhagen reaction and converted into the N-methylated derivative. Electrophilic-substitution reactions (nitration, sulfonation, bromination, chloromethylation, and acylation) in the selenophene ring have been studied. It has been shown that the substituent enters the position of the selenophene ring in most cases. The bromination of 1-methyl-2-(2-selenienyl)benzimidazole in acetic acid produces the 3,5-dibromo derivative, whereas 1-methyl-5(or 6)-bromo-2-(3,5-dibromo-2-selenienyl)benzimidazole is obtained in polyphosphoric acid.For Report 5, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1531–1534, November, 1983.     

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.     

Mono and dinuclear cationic rhodium(I) and iridium(I) complexes with sulphur donor and group Vb ligands

Summary Rhodium(I) and iridium(I) mixed complexes of the formulae [M(diolefin)LL]ClO₄, [M(diolefin)L₂L]ClO₄, [(diolefin)LIr(-L)₂IrL(diolefin)](ClO₄)₂, [(diolefin)LM(-L-L)ML'(diolefin)](ClO₄)₂, [(diolefin)Rh{-(L-L)}₂Rh(PPh₃)₂](ClO₄)₂ and [(diolefin)LIr{-(L-L)}₂IrL (diolefin)](C1O₄)₂, (L=monodentate sulphur ligand, L-L=bidentate sulphur ligand, L=group Vb ligand; M=Rh, diolefin=1,5-cyclooctadiene (COD) or 2,5-norbornadiene (NBD); M=Ir, diolefin=COD) are described.Author to whom all correspondence should be directed.     

Cobalt(II) and nickel(II) chloride and bromide complexes of 2-(2′-methyl-8′-quinolyl)benzoxazole and 2-(2′ or 4′-methyl 8′-quinolyl)benzimidazole

Summary Cobalt(II) and nickel(II) halide complexes of the ligands 2-(2-methyl-8-quinolyl)benzoxazole (mqbo), 2-(2-methyl8quinolyl)benzimidazole (mqbi) and 2-(4-methyl-8-quinolyl)benzimidazole (mqbi) were synthesized and characterized by analytical, thermogravimetric, conductivity and magnetic data, and i.r. and electronic spectra.The ligands are bidentate N-donors yielding complexes where the coordination geometry depends on the metal ion and steric hindrance. All the cobalt complexes have formula [CoL₂X₂] and distorted tetrahedral geometry. Different types of nickel compounds were obtained: i) complexes of formula NiLX₂ · n H₂O (or EtOH) (L = mqbo or mqbi; n=0–1.5) which arepseudo-tetrahedral or five-coordinate and ii) complexes NiL₂X₂ · n H₂O (L = mqbi, n=3 or 4) where the metal is bound to four nitrogen atoms and the overall coordination geometry is tetragonal. The structural changes occurring after removal of water or alcohol from the complexes are also reported.     

Über Inhaltstoffe der Iris germanica (Schwertlilie)

Acetovanillon and the known flavonoids irisolidone, irigenin, irisolone, tectorigenin and dihydroquercetin-7.3-dimethylether were detected in the rhizomes of Iris germanica. Also a few unknown compounds could be isolated and their structure elucidated; 9-methoxy-7-(3.4.5-trimethoxyphenyl)-8H-1.3-dioxolo[4.5-g] [1]-benzopyran-8-on (=5.3.4.5-tetramethoxy-6.7-methylenedioxyisoflavone (III A); 9-methoxy-7-(3.4-dimethoxyphenyl)-8H-1.3-dioxolo[4.5-g] [1]-benzopyran-8-on (=5.3.4-trimethoxy-6.7-methylenedioxyisoflavone(III B); 9-hydroxy-7-(p-hydroxyphenyl)-8H-1.3-dioxolo[4.5-g] [1]-benzopyran-8-on (=5.4-dihydroxy-6.7-methylenedioxyiosoflavone (IX); 5.7-dihydroxy-3-(3-hydroxy-4-methoxyphenyl)-6-methoxy-4H-1-benzopyran-4-on (=5.7.3-trihydroxy-6.4-dimethoxyisoflavone (XI B); 5.7-dihydroxy-3-(4-hydroxy-3-methoxyphenyl)-6-methoxy-4H-1-benzopyran-4-on (=5.7.4-trihydroxy-6.3-dimethoxyisoflavone (XI C).The structure determination was effected by combined spectroscopical and chemical methods.

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Herrn Prof. Dr.F. Hecht mit den besten Wünschen zum 70. Geburtstag gewidmet.     

Reactions of the 2,2′,6,6′-tetra-tert-butyl-4,4′-bispyrylium cation with bases

From 2,2,6,6-tetra-tert-buty1-4,4-bispyrylium perchlorate by the action of aqueous solutions of sodium acetate or caustic soda we have obtained a spiran containing pyran and dihydrofuran rings the structure of which has been established by the x-ray structural method. It has been shown that under the same conditions sodium sulfide reduces the bispyrylium salt to 2,2,6,6-tetra-tert-butyl-4,4-bispyranylidene. For the product of the interaction of the bispyrylium salt with aqueous ammonia the structure of an unsaturated tetraketone is suggested. Possible mechanisms of the formation of the compounds mentioned are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 461–467, April, 1980.     

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].     

Synthesis and alkylation of 4,6-diphenyl-3-thiocarbamoyl-3,4,5,6-tetrahydropyridine-2(1H)-one and 4,6-diphenyl-3-thiocarbamoyl-3,4-dihydropyridine-2(1H)-one

Alkylation of 3-thiocarbamoyl-3,4,5,6-tetrahydropyridine-2(1H)-one with methyl iodide has given 5-methylthio-2,6-diazabicyclo[2.2.2]oct-5-en-3-one and 3-methyl-thiocarbonyl-3,4-dihydropyridine-2(1H)-one. Alkylation of 3-thiocarbamoyl-3,4-dihydridine-2(1H)-one with iodoacetamide affords 3-(1-amino-1-carbamoyl-3,4-methyl-thiomethylene)-1,4-dihydropyridine-2-one, which in acidic media is converted into 3-(4-oxo-3,5-dihydro-1,3-thiazol-2-ylidene)-1,4-dihydropyridine-2-one.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 787–794, June, 1989.     

Synthesis of novel heterocycles from thiazolecarbohydrazides

Cyclization of 2-methyl (or -phenyl)-5-phenylthiazole-4-carbohydrazides (1) and (2) under various conditions gives differing oxadiazoles: 2-(2-substituted-5-phenyl-4-thiazolyl)-1,3,4-oxadiazole-5-thiones (7) and (8), and 2-(2-substituted-5-phenyl-4-thiazolyl)-1,3,4-oxadiazoles (9) and (10). Cyclodehydration of thiazolecarbonyl-thiosemicarbazides (3)–(6) with NaOH givesthe 3-(2-substituted-5-phenyl-4-thiazolyl)-4-substituted-4H-5-mercapto-1,2,4-triazoles (11)–(14), while H ₃ PO ₄ gives the 2-(2-substituted-5-phenyl-4-thiazolyl)-5-phenylamino-1,3,4-thiadiazoles (15) and (16).A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan'. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 3, pp. 679–683, March, 1992.     

Thermal properties of thio-and selenocyanatocopper(II) complexes with bipyridine and phenanthroline

The paper deals with the thermal properties of complex compounds of the general formula CuL₂(NCX)₂ (whereL=bipy or phen,X=S or Se). The phenanthroline complexes exhibit a higher thermal stability than those with bipyridine. For the latter complexes thermal decomposition begins with the release of bipyridine molecules, while for the phenanthroline complexes redox reactions of pseudohalogenide ligands with Cu(II) take place. The redox reactions start at a lower temperature for the selenocyanate complexes than for the thiocyanate complexes.

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Zusammenfassung Vorliegende Arbeit behandelt die thermischen Eigenschaften von Komplexverbindungen der allgemeinen Formel CuL₂(NCX)₂ (mitL=Bipyridin oder Phenanthrolin undX=S oder Se). Die Phenanthrolinkomplexe zeigen eine grössere thermische Stabilität als die Bipyridinkomplexe. Die thermiscne Zersetzung letzterer beginnt mit der Abgabe von Bipyridinmolekülen, während bei den Phenanthrolinkomplexen Redoxreaktionen von Pseudohalogenidliganden·mit Cu(II) stattfinden. Diese Redoxreaktionen beginnen bei den Selenozyanatkomplexen bei niedrigeren Temperaturen als bei den Thiozyanatkomplexen.

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CuL₂(NCX)₂, L= , X= . . , — . - , .

     

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.     

Simple and effective method for the synthesis of 3′,5′-substituted 1-β-D-arabinofuranosyluracil

3,5-Substituted arabinofuranosyluracil is a starting compound in 2-modifications. A convenient and effective method is proposed for the synthesis of 1-(3,5-di-o-trityl--D-arabinofuranosyl)uracil by successive reactions of 2,2-cyclization of uridine, 3,5-tritylation of the 2,2-anhydrouridine, and hydrolytic cleavage of the 2,2-anhydro bond.Institute of Organic Synthesis, Riga LV-1006. Odense Universitet, Kemisk Institut, Odense, Denmark. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 975–977, July, 1996. Original article submitted April 25, 1996.     

9-(2′,5′-Dimethyl-4′-pyridyl)fluorene in syntheses of fluorospirodihydrofuropyridine and pyridofluoranthene

1,2,5-Trimethyl-4-(9-fluorenylidene)piperidine, which is formed by condensation of fluorene with 1,2,5-trimethyl-4-piperidone, is converted catalytically to 9(2,5-dimethyl-4-pyridyl)fluorene, from which 2-methylpyrido[4,5-a]fluoranthene and its demethylated analog were obtained by catalytic dehydrocyclization. Oxidation of 9-(2,5-dimethy1-4-pyridyl)fluorene gave 9-(2,5-dimethyl-4-pyridyl)9-fluorenol and fluorene-9-spiro-4-(6-oxo-2-carboxypyrido[4,5-c]-4-6-dihydrofuran). 6-Methyl-2-phenyl-7-(9-fluorenyl)indolizine was synthesized by the Chichibabin method.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1090, August, 1978.     

1,1′-Disubstituted 2,2′-di(n-perfluoropropyl)-5,5′-bibenzimidazolyls

The synthesis of 4,4-di(methylamino)- and 4,4-dianilino-3,3-diaminobiphenyls is described. The condensation of the tetraaminobiphenyls mentioned with phenyl perfluorobutyrate has given, respectively, 1,1-dlmethyl- and 1,1-diphenyl-2,2-(n-perfluoropropyl)-5, 5-bibenzimidazolyls. A study of the thermal stability of the 2-perfluoroalkylbenzimidazoles has shown that the replacement of the hydrogen of the imino group in these compounds by a methyl or a phenyl radical considerably increases their heat stability.     

Thiazolobenzo-1, 2, 3-thiadiazoles and derived cyanine dyes

The following tricyclic heterocyclic compounds are synthesized: 2-methylthiazolov (5, 4-e) benzo-1, 2, 3thiadiazole, 2-methylthiazolo (4, 5-e) benzo-1, 2, 3-thiadiazole, 2-methylthiazolo (4, 5-g) benzo-1, 2, 3-thiadiazole, and 2-methylthiazolo (5, 4-g) benzo-1, 2, 3-thiadiazole. The quaternary salts of these bases are used to prepare symmetrical and unsymmetrical trimethinecyanines and dimethinemercocyanines containing N-ethylrhodanine residues. The absorption maxima of these dyes are shifted toward the long-wave region as compared with the corresponding thiacyanines.     

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.