Five-membered 2,3-dioxo heterocycles: XLIX. Reaction of methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrole-2-carboxylates with N-substituted 3-amino-5,5-dimethyl-2-cyclohexenones

Methyl 1-aryl-3-aroyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates react with N-substituted 3-amino-5,5-dimethyl-2-cyclohexenones to give 4-hydroxy-1-aryl-3-aroyl-6,6-dimethyl-1, 2,3,4,5,5,6,7-octahydro-1H,2H-indole-3-spiro-2-pyrrole-2,4,5-triones. The structure of the products was proved by the X-ray diffraction data for the 1-cyclohexyl derivative.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 12, 2004, pp. 1840–1845.Original Russian Text Copyright © 2004 by Bannikova, Maslivets, Aliev.For communication XLVIII, see [1].     

2-Spiroanellated 1,3-Benzodioxoles from the Reaction of 2,3-Dihydro-1<Emphasis Type="Italic">H</Emphasis>-pyrrol-3-ones with Tetrachloro-1,2-benzoquinone

Summary. Novel spiro[1,3-benzodioxole-2,2-(2,3-dihydro-1H-pyrrol-3-ones)] were obtained from 2-aminomethylene-2,3-dihydropyrrol-3(1H)-ones and tetrachloro-1,2-benzoquinone in ethanol at room temperature. However, in addition, 3,4-dichloro-7-methoxy-5-(4-methoxyphenyl)-5,10-dihydrophenazine-1,2-dione was formed in the reaction of 1-(4-methoxyphenyl)-2-(4-methoxyphenylaminomethylene)-4,5-diphenyl-1,2-dihydropyrrol-3-one with tetrachloro-1,2-benzoquinone.     

Enantioselective Catalysis. Part 156 [1]. Ruthenium Procatalysts and 2-Pyridinealdehyde/(<Emphasis Type="Italic">S</Emphasis>)-<Emphasis Type="Italic">NOBIN</Emphasis>-Derived Cocatalysts in the Transfer Hydrogenation of Acetophenone with 2-Propanol

Summary. Several ruthenium procatalysts were tested in the transfer hydrogenation of acetophenone with 2-propanol using the chiral imine ligand (S)-2-(2-pyridinylmethyleneamino)-2-hydroxy-1,1-binaphthyl and the corresponding amine (S)-2-(2-pyridinylmethylamino)-2-hydroxy-1,1-binaphthyl. Ru(PPh ₃)₃Cl₂ was the best procatalyst. Its triphenylphosphane ligands were crucial for the catalytic activity and take part in the chirality transfer. Triphenylphosphane removing reagents such as copper(I) chloride, TEMPO, or TMAO improved the catalytic performance to enantioselectivities up to 99% ee. The findings led to a mechanistic proposal including dissociation equilibria of triphenylphosphane and chelate ring opening of the tridentate chiral binaphthyl ligand. New ligands with an additional chiral center were synthesized and tested as cocatalysts. The nature of catalytically active intermediates was examined by MS and NMR spectroscopy.     

Synthesis of Side Chain Substituted 3-Butylisocoumarins and Absolute Configurations of Natural Isocoumarins from <Emphasis Type="Italic">Artemisia dracunculus</Emphasis>

Summary. A series of 3-hydroxy- and 3-bromobutyl-substituted isocoumarins was synthesized. The absolute configurations of three isocoumarin derivatives from Artemisia dracunculus, namely (–)-epoxyartemidin, (–)-2-methoxydihydroartemidin, and (+)-3-hydroxyartemidin were determined by chemical means via derivatization, kinetic racemate resolution (Horeau method), and comparison of the circular dichroism (CD) spectra.DeceasedReceived March 17, 2003; accepted March 19, 2003 Published online August 18, 2003     

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.     

A new steroidal glycoside phrygioside A and its aglycone from the starfish <Emphasis Type="Italic">Hippasteria phrygiana</Emphasis>

Three polyhydroxylated steroids were isolated from the Far-Eastern starfish Hippasteria phrygiana collected from the Sea of Okhotsk and were characterized as a new glycoside phrygioside A, viz., sodium (20R, 24S)-3,4,7,8,15,24-hexahydroxy-24-O-[3-O-methyl--D-xylopyranosyl-(12)--L-arabinofuranosyl]-5-cholestan-6-yl sulfate, its aglycone, and the already known marthasterone sulfate.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2526–2529, November, 2004.     

Synthesis of Spiro and Fused Five Membered <Emphasis Type="Italic">N</Emphasis>-Heterocycles from Alkylidenephosphoranes

Summary. Triketoindan-2-oxime reacted readily with ethoxycarbonylmethylene triphenylphosphorane to give mainly the corresponding spiro-pyrrole (38%) along with the fused 1-hydroxydihydropyrrole (14%), whereas the spiro-dimer (29%) was obtained from the reaction of the oxime with methoxycarbonylmethylenetriphenyl phosphorane in addition to the corresponding 1-hydroxydihydropyrrole (31%). Conversely, Wittig products, mono-olefin (52%) and diolefin (<7%) along with the reduced substrate (10%), were observed when the oxime was treated with a cyano ylide. The reactions of the oxime with allyl- and vinyl phosphonium salts proceeded under phase-transfer catalysis to afford fused oxazole (46%) and spiro[2]oxazole (17%), while with the latter the fused 1-hydroxypyrrole (55%) was produced.Received February 26, 2003; accepted (revised) March 19, 2003 Published online August 28, 2003     

Error analysis of surface area determinations by the chromatographic technique

The systematic and random errors in the determination of the surface area of adsorbents and catalysts by argon thermodesorption chromatography are analyzed.

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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.     

Arjunolic acid derivative glycoside from the stems of <Emphasis Type="Italic">Hedera colchica</Emphasis>

Five triterpenoid saponins were isolated from the stems of Hedera colchica K. Koch, Araliaceae. Two of them are new natural substances. HCSt-A (1): 3-O--D-arabinopyranoside; 28-O--L-rhamnopyranosyl-(1 4)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl-arjunolic acid. HCSt-B (2): 3-O--D-xylopyranoside; 28-O--L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl-hederagenin. The derivative of arjunolic acid is described for the first time in Araliaceae family. The chemical structures of isolated compounds were established on the base of chemical and 1D and 2D NMR experiments.Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 461–463, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Kinetics and mechanism of monomolecular heterolysis of commercial organohalogen compounds: XXXVIII. Correlation analysis of solvent effects on the activation parameters of heterolysis of <Emphasis Type="Italic">t</Emphasis>-BuBr and <Emphasis Type="Italic">t</Emphasis>-BuI

Heterolysis of t-BuBr and t-BuI in aprotic solvents involves a H - S compensation effect. The G of t-BuBr heterolysis in aprotic solvents decreases with increasing solvent polarity and cohesion, whereas the respective value for t-BuI heterolysis decreases with increasing solvent polarity, nucleophilicity, and polarizability. In protic solvents, a negative effect of nucleophilic solvation is observed.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1476–1483.Original Russian Text Copyright © 2004 by Ponomarev, Zaliznyi, Dvorko.This revised version was published online in April 2005 with a corrected cover date.     

Über Tetrahydrospiro [cyclohexan-1,4′(1′H)-chinazolin]-2′(3′H)-one

Zusammenfassung Cyclohexanon bzw. Cyclopentanon sowie ihre durch Aldolreaktion entstehenden Dimeren reagieren mit Harnstoff im sauren Medium zu 5,6,7,8-Tetrahydrospiro[cyclohexan-1,4(1H)-chinazolin]-3(2H)-onen (2) bzw. zum Dihydrospiro-(cyclopentan-1,4(1H)-5H-cyclopenta[d]pyrimidin)-2(3H)-on (10). Substituierte Harnsotoffe geben Gemische der isomeren 5,6,7,8-Tetrahydro- und 4a,5,6,7-Tetrahydroverbindungen (2, 3) bzw. 6,7-Dihydro-tH- und 5,6-Dihydro-4aH-verbindungen (10, 11). Charakteristisch für2 (3),10 (11) ist die Reaktivität der Kernstellen 8 bzw. 7 gegenüber elektrophilen Agentien (2f-v, 3f-j, 9 a-i, 10 d-f). Äthylmalonsäurebis-trichlorphenylester bzw. Formaldehyd und prim. Amine führen2 in ein partiell hydriertes 1H-Pyrido[3,2,1-ij]chinazolintrion (6) bzw. 1H-Pyrimido[5,6,1-ij]chinazolinon (7) über. Die 1-Alkylverbindungen (2) geben mit Formaldehyd und primären Aminen Hexahydro-8a-hydroxy-4a,8-propanospiro-(cyclohexan-1,4(1H)-pyrido[4,3-d]pyrimidin)-2(3H)-one (8).

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Heterocycles, XXV: tetrahydrospiro [cyclohexane-1,4(1H)-quinazoline]-2(3H)-ones

Cyclohexanone and cyclopentanone, resp., as well as their dimers (formed by aldol reaction) react with urea in the presence of acids to 5,6,7,8-tetrahydrospiro[cyclohexane-1,4-(1H)-quinazoline]-3(2H)-ones (2) and to the dihydrospiro-(cyclopentane-1,4(2H)-5H-cyclopenta[d]pyrimidine)-2(3H)-one (10), resp. Substituted ureas give the isomeric 5,6,7,8-tetrahydro- and 4a,5,6,7-tetrahydro compounds (2, 3), and 6,7-dihydro-5H- and 5,6-dihydro-4aH-compounds (10, 11), resp. Characteristic for2 (3),10 (11) is the reactivity of the nuclear places 8 and 7 with electrophilic agents (2f-v, 3f-j, 9a-i, 10d-f). Ethylmalonic acid bistrichlorophenylester resp. formaldehyde and primary amines react with2 to the partially-hydrogenated 1H-pyrido[3,2,1-ij]-quinazolinetrione (6) and 1H-pyrimido[5,6,1-ij]-quinazolinone (7), resp. The 1-alkyl compounds (2) give with formaldehyde and primary amines hexahydro-8a-hydroxy-4a, 8-propanospiro(cyclohexane-1,4-(1H)-pyrido[4,3-d]pyrimidine)-2(3H)-ones (8).

     

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.     

Detection of <Emphasis Type="Italic">N</Emphasis>-monomethyl-lysine generated by metabolic transmethylation

Administration of radiolabelled deprenyl to rats resulted in the urinary elimination of a ¹⁴C-labelled N-monomethyl-lysine. An increased level of N-monomethyl-lysine was found following an oral dose of another drug, also containing an N-methyl group. The urine sample was treated with 9-fluorenylmethoxycarbonyl chloride and then subjected to high-performance liquid chromatography (HPLC); the radioactive fraction was identified as N-monomethyl-lysine by using HPLC-MS in electrospray mode. Identification of N-monomethyl-lysine in the radioactive fraction gives experimental proof of transmethylation from a well-known drug to an endogenous compound.     

Acid-base and complexation properties of <Emphasis Type="Italic">gem</Emphasis>-diphosphonic and <Emphasis Type="Italic">gem</Emphasis>-diphosphinic acids in aqueous solutions and micellar media of surfactants

Acid-base and complexation properties of gem-disubstituted phosphorus acids, viz., methylenediphosphonic, 1-hydroxyethylidene-1,1-diphosphonic, P,P-diphenylmethylene-diphosphinic, and P, P-diphenyl-1-hydroxyethylidene-1, 1-diphosphinic acids, were studied in aqueous solutions and in the presence of biomimetics (micelles of ionic surfactants). The dissociation constants of the acids and stability constants of complexes with magnesium(II) and copper(II) ions were determined in aqueous solutions and microheterogeneous media containing sodium dodecyl sulfate, cetylpyridinium chloride, or cetylpyridinium nitrate (ionic strength 0.1 mol L^–1, temperature 25°C).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1919–1925, September, 2004.     

Steroid glycosides XXI. The structure of polygonatoside E′ and protopolygonatoside E′ from the leaves ofPolygonatum latifolium

Summary The chemical structures of two new steroid glycosides from the leaves ofPolygonatum latifolium have been shown. Polygonatoside E is 3-[0--D-glucopyranosyl-(1 3)-0--D-glucopyranosyl-(1 4)-0--d-galactopyranosyl-(1 3)--D-glucopyranosyloxy]-(25R)-spirost-5-ene, and protopolygonatoside E is 26--D-galactopyranosyl-(1 3)--D-glucopyranosyloxy]-(25R)-furost-5-en-22-ol.Institute of Chemistry, Academy of Sciences of the Moldavian SSR, Kishenev. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 350–354, May–June, 1978.     

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.     

Anomalous nucleosides

A preparative synthesis of the antimetabolite 6-azacytidine is described which involves the amination under mild conditions without the use of an autoclave of 2, 3, 5-tri-O-acyl-4-thip-6-azauridines with the isolation of the intermediate 2, 3, 5-tri-O-acyl-6-azacytidines and subsequent elimination of the protective groups at room temperature.For communication VI, see [10].     

Synthesis of <Emphasis Type="Italic">N</Emphasis>-(2-vinyloxyethyl)pyrazoles

Alkylation of pyrazoles with 2,2-dichloroethyl ether under conditions of phase-transfer catalysis was studied. The monoalkylation products of 3(5)-methylpyrazoles at 190–200°C undergo intramolecular cyclization to form bicyclic salts. Conditions for dehydrochlorination of N-[2-(2- chloroethoxy)ethyl]pyrazoles into N-(2-vinyloxyethyl)pyrazoles were found.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1365–1367.Original Russian Text Copyright © 2004 by Attaryan, Martirosyan, Panosyan, Matsoyan.This revised version was published online in April 2005 with a corrected cover date.     

Formation of a Hydroxo-bridged Dinuclear Ru(III)/Ru(III) Complex from <Emphasis Type="Italic">N</Emphasis>-Methylimidazole and [Ru<Emphasis Type="Italic">Cp</Emphasis>(CH<Subscript>3</Subscript>CN)<Subscript>3</Subscript>]<Superscript>+</Superscript>

Summary. The reaction of [RuCp(CH₃CN)₃]PF₆ with 1 equiv of N-Me-imidazole results in the quantitative formation of [RuCp(¹N-N-Me-imidazole)(CH₃CN)₂]PF₆ (1) featuring a ¹N rather than a ¹C bound N-Me-imidazole ligand. According to DFT/B3LYP calculations, ¹N coordination of N-Me-imidazole is preferred over ¹C coordination by 25.5kJ/mol. Upon exposure to air 1 reacts with oxygen and water to afford the novel hydroxo-bridged dinuclear complex of [Ru₂Cp₂(¹N-N-Me-imidazole)₂(-OH)₂](PF₆)₂ (2) featuring a metal-metal single bond. The dimeric nature of 2 was confirmed by a single-crystal X-ray structure analysis.