Condensed heterocycles with a thiazole ring. 13. Azinothiazoloquinoxalinium salts

The condensation of 2,3-dichloroquinoxaline with 2-mercaptopyridines and 2-mercaptoquinolines gave the corresponding derivatives of new heterocyclic systems, viz., azino[1,23,2]thaizolo[4,5-b]quinoxalinium salts, which can be used for the synthesis of cyanine dyes.See [1] for Communication 12.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 551–553, April, 1987.     

Investigation of furan compounds XXX. Intramolecular alkoxylation of furfuryl-substituted mono- and bicyclic alcohols

On electrolysis mono- and bicyclic furfuryl-substituted alcohols undergo intramolecular alkoxylation, giving polycyclic spirans. Spiro[perhydrobenzofuran-2, 2-(5-methoxy, 5H)furan] and spiro[4H, 5H, 6H, 11H-naphtho-(,)-furan-2(3H)] [2-(5-methoxy, 5H)furan], hitherto not described, are prepared in this way. On catalytic hydrogenation they give the previously unknown spiro[perhydrobenzofuran-2, 2-tetrahydrofuran] and spiro[4H, 5H, 6H, 11H-naphtho-(,)-furan-2(3H)][2-tetrahydrofuran].For Part XXIX see [1].     

Glycosides of marine invertebrates. XII. Structure of a new triterpene oligoglycoside from holothurians of familyStichopodidae

From an ethanolic extract of the holothuriansStichopus chloronotus by column chromatography on silica gel a new triterpene oligoside has been isolated the structure of which has been established as 23(S)-acetoxy-3-{4-O-[O-(3-O-methyl--D-glucopyranosyl)-(13)--D-glucopyranosyl]-2-O-[O-(3-O-methyl--D-glucopyranosyl(-(13)-O--D-xylopyranosyl-(14)--D-glucopyranosyl]--D-xylopyranosyloxy}holost-7-ene. A hypothesis has been put forward concerning the biosynthesis of the carbohydrate chains in the glycosides of holothurians of the orderAspidochirota from bioside blocks.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 200–204, March–April, 1982.     

Benzindoles. 21. Structures of the products of the wittig reaction in the angular benzindole series

-Phenyl--(1H-benzo[g] indol-3-yl)ethylene and -phenyl--(3H-benzo[e] indol-l-yl)-ethylene were obtained in the form of two geometrical isomers by reaction of 3-formyl-1H-benzo[g]- and 1-formyl-3H-benzo[e] indoles with benzylidenetriphenylphosphorane in tert-butyl alcohol containing potassium tert-butoxide. The configurations of the compounds obtained were established on the basis of data from the PMR spectra.See [1] for Communication 20.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1380–1382, October, 1980.     

Porphyrins. 9. New data on the polyformylation of metal complexes of etioporphyrin I

The structures of the products of the polyformylation of Cu, Ni, and Co complexes of etioporphyrin (EP) as monoformyl-, ,-diformyl-, ,-diformyl-, and ,,-triformyl-EP were established by electronic, IR, and PMR spectroscopy and mass spectrometry. -Formyl--(N-methylformaldimine)-EP and porphyrins that contain a cyclopentane ring can be formed by alkaline treatment of the Vilsmeier formylation products.See [1] for communication 8.See [2] for our preliminary communication.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 767–775, June, 1979.     

Coumarin glycosides ofHaplophyllum performatum. structures of haploperosides C,D, and E

New coumarin glycosides — haploperosides C, D, and E — have been isolated from the epigeal part of theHaplophyllum performatum (MB) Kar et Kir. On the basis of chemical transformations and spectral characteristics, haploperoside D has the structure of 6-methoxy-7-[0--L-rhamnopyranosyl-(1 2)--D-glucopyranosyloxy]-2H-benzopyran-2-one, and haploperoside C that of 6-methoxy-7-[0--L-rhamnopyranosyl-(1 6)-(2-0-acetyl--D-glucopyranosyloxy)]-2H-benzopyran-2-one. The structure of haploperoside E has been established as 7-[0--L-rhamnopyranosyl-(1 2)-0--L-rhamnopyranosyl-(1 6)--D-glucopyranosyloxy]-2H-benzopyran-2-one. The structures of haploperosides A and B have been refined. An assignment has been made of the carbon signals in the¹³C NMR spectra of haploperosides A, D, C, and E.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 27–35, January–February, 1985.     

Reaction of heterocyclic betaines. Synthesis of a new heterocyclic system

A new condensed heterocyclic system, viz., 1,3,7,9-tetra-oxo-2,8-diphenyl-6-formylpyrimido [3,4-a]pyrimido[4,5-dloxazine, was synthesized, and its electronic and PMR spectra were recorded. Factors that affect the orientation of nucleophilic substitution in betaines of the pyrimidine series with aliphatic amines are discussed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 993–995, July, 1980.     

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.     

Pseudo-cross-conjugated mesomeric betaines 2. X-Ray crystallographic investigation of betaines based on quinoxaline derivatives

An x-ray crystallographic investigation of 3-methyl-5-cyanoimidazolio[1,21,6]pyrido[2,3 -b]quinoxalin-4-olate, which is a representative of a previously unknown type of polynuclear heterocyclic pseudo-crossconjugated mesomeric betaine, was undertaken.For Communication I, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1534–1538, November, 1992.     

Diazabicycloalkanes with nitrogen atoms in nodal positions. 14. Synthesis of dibenzo[1′,2′-b,e]-1,4-diazabicyclo[2.2.2]octadienes containing a tertiary amino group in the aromatic ring

The corresponding 2-amino derivatives of phenazinium salts were obtained by the action of dimethylamine and morpholine on N-(2-hydroxyethyl)phenazinium chloride. The subsequent exchange of the hydroxyl group for chlorine and the reductive cyclization of 2-amino derivatives of N-(2-chloroethyl)phenazinium salts leads to 4-aminodibenzo[1,2-b,e]-1,4-diazabicyclo[2.2.2]octadienes, together with unsubstituted dibenzo-[b,e]-1,4-diazabicyclo[2.2.2]octadiene and the corresponding 2-aminophenazines.For Communication 13, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1658–1661, December, 1986.     

Acetals of lactams and acid amides. 51. Cyclization of α-cyano-Β-phenylamino-N-dimethylaminomethyleneacrylamide to pyrimido[5,4-c]quinol-4-one

Cyclization of -cyano--phenylamino-N-dimethylaminomethyleneacrylamide to pyrimido[5,4-c]quinol-4-one proceeds via the intermediate formation of 1-phenyl-5-cyano-1,4-dihydropyrimidin-4-one and -cyano--phenyl-amino-N-formylacrylamide.For Communication 50, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 88–90, January, 1988.     

Stereochemie von Metallocenen, 24. Mitt.: Optisch aktive [3] und [3][3]Ferrocenophane, 1. Mitt.: Darstellung,Racematspaltung und absolute Konfiguration (45. Mitt. über Ferrocenderivate)

Zusammenfassung Aus [3] und [3][3](1,3)Ferrocenophan wurden die isomeren Carbonsäuren über ihreN,N-Diphenylamide dargestellt und über die -Phenäthylaminsalze in die Antipoden gespalten. Die absoluten Konfigurationen der Säuren (und damit aller Derivate und Folgeprodukte) wurden sowohl durch chemische Korrelation mit Methylferrocen--und-carbonsäuren bekannter Konfiguration als auch durch kinetische Racematspaltung ihrer Anhydride mit (-)--Phenäthylamin ermittelt.Aus der Methylferrocen-1-carbonsäure wurden durch Kettenverlängerung zur Propionsäure, Cyclisierung und Racematspaltung der Ringketone mit Menthydrazid ebenfalls aktive Ferrocenophane gewonnen, und ihre Konfiguration durch chemische Korrelation bestimmt.Die beschriebenen 45 optisch aktiven Ferrocenophanderivate sind wegen ihrer starren Konformation und der dadurch bedingten Fixierung chromophorer Gruppen-vor allem im Vergleich mit analogenhomoanular überbrückten Ferrocenen-für die Diskussion und Interpretation der Ferrocenchiralität von großem Interesse.From [3] and [3][3](1.3)ferrocenophane the isomeric carboxylic acids were preparedvia theirN,N-diphenylamides and resolvedvia the -phenethylamine salts. The absolute configurations of the acids (and thereby of all derivatives and subsequent products) were established both by chemical correlations with methylferrocene--and--carboxylic acids of known configurations and by kinetic resolutions of their anhydrides with (-)-- phenethylamine.From methylferrocene-1-carboxylic acid by chain lengthening, cyclization of the propionic acid and resolution of the ring ketones with menthydrazide, likewise active ferrocenophanes were obtained and their configurations determined by chemical correlations.The described 45 optically active ferrocenophane derivatives are because of their rigid conformations and the thereby caused fixation of chromophoric groups-mainly in comparison with analogoushomoanular bridged ferrocenes-of great interest for the discussion and interpretation of the ferrocene chirality.

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Stereochemistry of Metallocenes, 24. (Ferrocenes, 45). Optically Active [3] and [3][3]Ferrocenophanes. 1: Syntheses, Optical Resolution and Absolute Configurations

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23. Mitt. (44. Mitt. über Ferrocenderivate):H. Falk, Christine Krasa undK. Schlögl, Mh. Chem.,100, 254 (1969).     

Triterpene glycosides ofHedera canariensis IV. Structures of glycosides L-F3, L-G0, and L-Gla from the leaves of Algerian ivy

Three minor partially acetylated glycosides have been isolated from the leaves of Algerian ivy, Hedera canariensis Willd. (Araliaceae) — the previously known {3-O-[-L-rhamnopyranosyl-(12)-O--L-arabinopyranoside] 28-O-[-L-rhamnopyranosyl-(14)-O-(6-acetyl--D-glucopyranosyl)-(16)-O--D-glucopyranoside}s of oleanolic acid and of hederagenin (ciwujianoside C₄ and kizuta saponin K₁₁) and the new 3-O-[-L-rhamnopyranosyl-(12)--O-L-arabinopyranoside] 28-O-[-L-rhamnopyranosyl-(14)-O-(6-O-acetyl--D-glucopyranosyl)-(16)-O--D-glucopyranoside of echinocystic acid (glycoside L-G₀). The structures of the glycosides isolated have been established on the basis of chemical transformations and¹H and¹³C NMR spectroscopy.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 81–86, January–February, 1999.     

Über Heterocyclen, 22. Mitt.: 3,4,6,7-Tetrahydro-5H-pyrrolo[3,4-d]pyrimidin-2(1H), 5-dione

Zusammenfassung Tetrahydro-6-brommethyl-2-oxopyrimidin-5-carbonsäureester reagieren mit Ammoniak bzw. Benzylamin zu Tetrahydro-5H-pyrrolo[3,4-d]pyrimidin-2(1H), 5-dionen. Mit 2-Aminopyridin (A) bilden sich Tetrahydro-6-(2-pyridylaminomethyl)-2-oxopyrimidin-5-carbonsäureester, Tetrahydro-5H-pyrrolo[3,4-d]pyrimidin-2(1H), 5-dione sowie 5-Äthoxycarbony]-2,3,5,6-tetrahydro-2-oxospiro(pyrimidin-4(1H), 2(3H)-1H-imidazo[1,2-a]pyridinium)bromide.

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Heterocycles XXII: 3.4.6.7-Tetrahydro-5H-pyrrolo [3.4-d]-pyrimidine-2(1H)-5-diones

Tetrahydro-6-bromomethyl-2-oxopyrimidine-5-carboxylates react with ammonia and benzylamine, resp., to give tetrahydro-5H-pyrrolo[3.4-d]pyrimidin-2(1H), 5-diones. With 2-aminopyridine (A) tetrahydro-6-(2-pyridylaminomethyl)-2-oxopyrimidine-5-carboxylates, tetrahydro-5H-pyrrolo[3.4-d]pyrimidine-2(1H). 5-diones as well as 5-ethoxycarbonyl-2.3.5.6-tetrahydro-2-oxospiro(pyrimidin-4(1H)-2(3H)-1H-imidazo[1.2-a]-pyridinium) bromides are formed.

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Herrn Prof. Dr.O. Hromatka zum 65. Geburtstag gewidmet.     

Triterpene Glycosides of Fatsia japonica. VI. Structures of Glycosides D3a and D3b

Seeds of Fatsia japonica (Araliaceae) yielded the new glycosides of gypsogenin: 3-O--D-glucopyranosyl-(12)-O--D-glucopyranoside and 3-O--D-galactopyranosyl-(12)-O--D-glucopyranoside. The structures of these compounds were established by chemical methods and NMR spectroscopy.     

The phenomenon of conglomerate crystallization. XX. Spontaneous resolution in coordination compounds. XVIII.

The title compound, [cis-Co(en)₂(NO₂)₂](NO₂) (1), crystallizes in the polar, nonenantiomorphic, monoclinic space group, Cc, with lattice constants:a=9.198(2) Å,b=12.444(2),c=9.963(3), and=96.76(2)°;V=1132.39 ų andd(calc;Z=4) =1.860 g cm^–3. Thus, with NO_2– as the counteranion, [cis-Co(en)₂(NO₂)₂] crystallizes in a heterochiral lattice containing racemic pairs of cations. A total of 2699 data were collected over the range of 4°270°; of these, 1859 (independent and withI3(I)) were used in the structural analysis. Data were corrected for absorption (=15.465 cm^–1) and the relative transmission coefficients ranged from 0.9934 to 0.7112. Refinement was carried out for both lattice polarities and the finalR(F) andR _w (F) residuals were, respectively, 0.0242 and 0.0202 for (–––) and 0.0264 and 0.0243 for (+++). Thus, the former was selected as correct for our specimen.Unlike all previous X-ray diffraction studies of the structural properties of the cation [cis-Co(en)₂(NO₂)₂]⁺, which are found to have a pair of oppositely configured en rings [i.e., () or ()], we find that in1 the cations are in the lowest energy conformation and configuration; i.e., () or (). We attribute this change in configuration to the formation of strong interionic hydrogen bonds between nitrite anion oxygens and the axial—NH₂ hydrogens, which markedly weaken the intermolecular and intramolecular hydrogen bonds between ligand—NO₂ oxygens and the hydrogens of those same amine moieties. Thus, the nitrite anions behave exactly as nitrate anions, except that the hydrogen bonds found here are stronger than those formed by the latter. This is as expected since the negative charge is delocalized over two, instead of three, oxygens.     

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].     

Oxidative dehydrogenation of n-butane IV. Kinetic and catalytic activity of copper oxide

Copper oxide is moderately active and selective in the oxidative dehydrogenation of n-butane. Selectivity to C₄ olefin is almost constant in the range of 200–520°C. The apparent activation energy determined between 200 and 360°C was 18.8 kcal/mol, and 9.2 kcal/mol at higher temperatures.

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-. C₄ 200–520°C. 200–360°C 18,8 /, 9,2 /.

     

Thermogravimetry. Fast methods for evaluation of kinetic parameters

The paper discusses three fast methods for determination of the reaction order, as follows: the single-point method proposed by Kissinger, Horowitz and Metzger, an original two-point method, and the three-point method suggested by a Gorbachev's paper. These methods cannot elucidate the reaction mechanism, but they can help in the rapid derivation of the apparent kinetic parametersn andE.

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Zusammenfassung Es wurden drei Methoden zur Schnellbestimmung von Reaktionsordnungen ausgewertet: eine Einpunktmethode von Kissinger, Horowitz und Metzger, eine Zweipunktmethode und eine Dreipunktmethode nach einer Anregung von Gorbachev. Mittels dieser Methoden kann man zwar nicht den Reaktionsmechanismus bestimmen, wohl aber eine schnelle Bestimmung der kinetischen Scheinparametern undE durchführen.

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: , , , , . , n .

     

Synthesis of polysaccharides. 11. Synthesis of α-(1 → 3)-L-rhamnan

Conclusions We synthesized the 4-0-acetyl-3-0-trityl-1,2-0-exo-cyanoethylidene--L-rhamnopyranose monomer, the polycondensation of which gave the regular polysaccharide -(1 3)-L-rhamnan.See [1] for Communication 10.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 196–200, January, 1981.