Synthesis of functionally substituted benzo[c]pyrylium salts

Benzo[c]pyrylium salts that contain an acetyl, cyano, or ethoxycarbonyl group in the 4 position of the pyrylium ring were synthesized by the reaction of 3-(3,4-dimethoxyphenyl)pentane-2,4-dione and -(3,4-dimethoxyphenyl)acetoacetonitrile and ethyl -(3,4-dimethoxyphenyl)acetoacetate, as well as ethyl -(3,4-dimethoxyphenyl)benzoylacetate, with acyl perchlorates. It is shown that -(3,4-dimethoxyphenyl)acetoacetonitrile ethyleneketal is converted to 3-amino-4-acetylbenzo(c)pyrylium salts under these conditions.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 465–470, April, 1990.     

Mechanism of rearrangement with cyclopropyl involvement in acetylosis of β-3,4-epoxycarane

Conclusions The theory was expressed that the acetolysis of 3,4-caranediol monotosylate proceeds via the intermediate formation of the protonated form of -3,4-epoxycarane and a mechanism was proposed for rearrangement of the carane structure with 1,3-trans-annular cyclopropyl involvement in the acetolysis of -3,4-epoxycarane and 3,4-caranediol monotosylate, and also the hydration of -3,4-epoxycarane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2778–2780, December, 1980.     

Steroid compounds from the Pacific starfish Lysastrosoma anthosticta

Two new steroid compounds, 3,6-dihydroxy-5-cholesta-9(11),24-dien-23-one 3-sulfate and 3,6-dihydroxy-5-cholest-9(11)-en-23-one 3-sulfate, were isolated from the Pacific starfish Lysastrosoma anthosticta as the corresponding sodium salts and identified. Two previously known glycosides of 24(S)-5-cholestane-3,6,8,15,24-pentol were also isolated and identified as sodium 24-O--d-glucopyranoside 6"-sulfate (pycnopodioside C) and sodium 24-O--d-xylopyranoside 4"-sulfate (luridoside A).     

Acid-catalyzed opening of 3,4-epoxycaranones

Conclusions -3,4-Epoxy-2-caranone and-3,4-epoxy-5-caranone when treated with MeOH in acid medium undergo rearrangement of the bicyclo[4.1.0]heptane structure to the menthane structure, which was observed previously in the reactions with HCl. The mechanism of the acid-catalyzed opening of 3,4-epoxycaranones is discussed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 698–700, March, 1982.     

<Superscript>1</Superscript>H and <Superscript>13</Superscript>C NMR spectra of some drimanic sesquiterpenoids

One- and two-dimensional homo- and heteronuclear correlation proton, carbon, proton—proton, and proton—carbon NMR spectra of fifteen drimanic sesquiterpenoids: 11,12-dibromodrima-5,8-dien-7-one, drim-8-en-7-one, 11-hydroxydrim-8-en-7-one, 11,12-dihydroxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 11-hydroxy-11,12-epoxydrim-8-en-7-one, 8,9-epoxydriman-7-one, 8,9-epoxydriman-7-ol, 11,12-diacetoxydrim-8-en-7-ol, drimane-7,8,11-triol, 7,8-isopropylidenedioxydriman-11-al, 9, 11-dihydroxydrim-7-en-6-one, drimane-7,8,9-triol, drimane-7,8,11-triol, and drim-8-ene-7,11,12-triol were studied. The proton and carbon chemical shifts were assigned.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2589–2594, December, 2004.     

Transformed steroids

Conclusions The addition of thioacetic acid to the ⁵ bonds of 16- and 16-mercapto-3-hydroxypregn-5-en-20-one 3,16-diacetates (II) and (III) under radical conditions gives not only trans-diaxial addition products-6,16- and 6,16-dimercapto-3-hydroxy-5o;-pregnan-20-one 3,6,16-triacetates (IV) and (V) -but also cis-addition products-6,16- and 6,16-dimercapto-3-hydroxy-5-pregnan-20-one 3,6,16-triacetates (VI) and (VII).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 405–411, February, 1969.     

Über die Darstellung von 3β, 16α-und 3β, 16β-Diacetoxy-5α-pregnan-20-on

Zusammenfassung Die Synthese von 3, 16-Diacetoxy-5 -pregnan-20-on (VI) aus 3-Acetoxy-5 -pregn-16-en-20-on und eine verbesserte Darstellung von 3, 16-Diacetoxy-5 -pregnan-20-on (III) aus 3-Acetoxy-pregna-5, 16-dien-20-on werden beschrieben.     

Complex polarizability as used to analyze dielectric relaxation measurements

The effect of representing dielectric properties in terms of the complex polarizability ^c = – i is examined. Loss curves ( and tan ) are shifted towards higher frequencies, revealing the existence of new relaxations and allowing the clarifications of ones already known. We have calculated the shift ratios (at maximum or tan )/ (at maximum or tan ) from the more conventional empirical equations representing the dielectric behavior. Some examples are given.     

GC-MS characterization and quantification of sterols and cholesterol oxidation products

Summary A GC-MS method has been studied for characterization and quantification of phytosterols, cholesterol and cholesterol oxidation products. Baseline separations have been achieved between cholesterol, cholesterol 5-6-epoxide, 5-cholestene-3-ol-7one (7-keto-cholesterol), cholestene-3-5-6-triol, 5-cholestene-3-25-diol (25-hydroxycholesterol), 5-cholestene-3-20-diol (20-hydroxycholesterol), 5-cholestene-3-7-diol (7-hydroxycholesterol) and 5-cholestene-3-19-diol (19-hydroxycholesterol) as well as between -cholestane, cholesterol, stigmasterol, campesterol and -sitosterol. Excellent linearity of response has been obtained permitting reliable quantification. The characterization of each derivatized sterol has been performed by mass-spectrometry. The results confirm the utility of combined gas chromatography-mass spectrometry in the analysis and characterization of sterols and cholesterol oxidation products.     

13C NMR spectra of acetylated methyl glycosides of monosaccharides

Summary A comparative discussion of the signals in the¹³C NMR spectra of acetylated methyl - and -D-xylopyranosides, - and -D-glucopyranosides, - and -D-galactopyranosides, - and -L-arabinopyranosides, - and -L-fucopyranosides, and - and -L-rhamnopyranosides and of the corresponding free glycosides has shown a similarity of the effects of substitution at C₅ with a longer-range nature of these effects in the case of the acetylated glycosides.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center of the Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 6–8, January–February, 1979.     

Triterpenoid Glycosides of Fatsia japonica. II. Isolation and Structure of Glycosides from the Leaves

The previously known triterpenoid 3-O--L-arabinopyranosides of oleanolic and echinocystic acids and hederagenin, 3-O--D-glucopyranosyl-(12)-O--L-arabinopyranosides of oleanolic acid and hederagenin, in addition to 28-O--L-rhamnopyranosyl-(14)-O--D-glucopyranosyl-(16)-O--D-glucopyranosyl ethers of the 3-O--L-arabinopyranoside of hederagenin, and 3-O--D-glucopyranosyl-(12)-O--L-arabinopyranosides of oleanolic acid and hederagenin, respectively, are isolated from leaves ofFatsia japonica(Araliaceae). The structures of the glycosides are confirmed by chemical methods and ¹³ C NMR spectroscopy     

Die Acetalgruppe, 1. Mitt. Acetale von Halogenmethyl-arylcarbinolen

Several halomethyl-arylcarbinols were prepared, and the influence of substituents on enantiomer selectivity in the acetalisation reaction with [2S-(2,3a,4,7,7a)]-octahydro-7,8,8-trimethyl-4,7-methanobenzofuran-2-ol was examined.

Unserem sehr verehrten Lehrer, Herrn Prof. Dr.Otto Hromatka, mit den besten Wünschen zum 80. Geburtstag gewidmet.     

Synthesis of (α-substituted α-aminophosphinic and α-aminophosphonic acids

The reaction of ketoximes with hypophosphorous acid resulted in previously unknown -substituted--aminophosphinic acids, which were oxidized into the corresponding -substituted--aminophosphonic acids.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2729–2732, November, 1996.     

α,β-Butenolides

,-Dibromo--('-carbethoxyacetony)-^,-butenolide (I) reacts with amines in diethyl ether solution to give -bromo-amino--('-carbethoxyacetony)-^,-butenolides. Compounds n are converted to -bromo-amino--('-carbethoxyacetony)-^,-butenolides on reaction with amines. The corresponding arylhydrazones (VI and VII) are obtained by the reaction of I and II with p-nitro- and 2,4-dinitrophenylhydrazines. Compound I reacts with phenylhydrazine to give furopyridazine VIII.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 867–871, July, 1972.     

Synthesis of modified amino acids containing nucleic acid purine bases

The reaction of hydrazides of adenylyl- or hypoxanthinyl-9-alkylcarboxylic acids with sodium nitrite in acid media gives reactive azides of purinyl-9-alkylcarboxylic acids which condense with ()-aminocarboxylic and ,-diaminocarboxylic acids to give N(N)-(adenylyl-9-alkanoyl) aminocarboxylic, N-(adenylyl-9-)- and N-(hypoxanthinyl-9-alkanoyl)-,-diaminocarboxylic acids. The deamination of N-(adenyl-yl-9-alkanoyl)aminocarboxylic acids gives N-(hypoxanthinyl-9-alkanoyl)aminocarboxylic acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 126–130, January, 1985.     

Dark and photochemical interactions of N-benzyl-1, 4-dihydronicotineamide with α, α, α′, α′-tetrabromocyclohexanone

The dark and photochemical reactions of N-benzyl-1, 4-dihydronicotineamide (BDN) with , , , -tetrabromocyclohexanone (TBCH) in ethanolic solutions have been investigated as function of temperature and the concentration of the components in air and in the absence of oxygen. A radical-chain mechanism has been proposed that describes the reaction of BDN with TBCH.Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 22, No. 3, pp. 302–309, May–June, 1986.     

Zum Verhalten von Ketenen gegenüber P−N-Yliden Reaktionen mit phosphororganischen verbindungen, 39. Mitt.

1,3-Skeletal rearrangement of N-substituted ketimines via a possible intimate ion pair is discussed. (CH₃)₃SiCH=C=O (1) reacts with N-(aziridinyl)-triphenylphosphinimine (2) to give N-(1-aziridinyl)-2-trimethylsilylketen-1-imines (3). The compounds3 b, c are thermally labile and do not undergo 1,3-rearrangement but a retro-ene type reaction to yield (CH₃)₃SiCH₂CN and 2,3-diphenyl-2H-azirine (4). Diphenylketene (5) reacts with N-(N, N-dialkylamino)-triphenylphosphinimines (6) to yield -(N-disubstituted-amino)-nitriles (7). , -Dimethyl--(triphenylphosphinimino)-acetonitrile (9) reacts with (5) at room temperature to form , -dimethyl--(2, 2-diphenylketen-1-imino)-acetonitrile (10) which rearranges at 80° to dimethyl diphenylsuccinonitrile (11). The reaction of5 with 7-(triphenylphosphinimino)-7-azabicyclo[4.1.0]heptane (12) gives tetraphenylsuccinonitrile13 and 7-(7-azabicyclo[4.1.0]heptane)-, -diphenylacetonitrile (14). Finally the synthesis of N-acylketenimines (16) from (5) and acyltriphenylphosphinimines (15) is reported.

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38. Mitt.:Chr. Ivancsics undE. Zbiral, Mh. Chem.106, 839 (1975).     

A structural investigation of a D-glucan fromYersinia pseudotuberculosis of serotype VI

It has been established that an -D-glucan isolated fromYersinia pseudotuberculosis, serotype VI, is branched and contains -14- and -16-bound D-glucopy-ranose residues in the main chain and the side chains, respectively.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostock. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 151–154, March–April, 1981.