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  • Organic Chemistry  (1,360)
  • 1980-1984  (1,360)
  • 1984  (646)
  • 1981  (714)
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 67 (1984), S. 616-624 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structural modifications of multifidene (1), viridiene (2) and ectocarpene (5) led to the synthesis of eleven new pheromone components or imitatin substances mostly by Grignard alkylation of cyclopentene and cycloheptadiene synthons. A new lactone α,ω dienol conversion is reported.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 67 (1984), S. 640-653 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The He(Ia) photoelectron (PE) spectra of the (E,E)-, (E,Z)- and (Z,Z)-isomers of the title compound have been recorded to obtain information about their conformation in the gas phase. For a valid correlation with the PE data of other dienes it is necessary to take the potentials V(ϕ) for internal rotation and the corresponding conformer population densities P (ϕ) into account, as well as the rather complicated way wy in which the π-1 ionization energy gap ΔI(ϕ) depends on the direct π-orbital interaction and the long-range ‘through-space’ interaction between the semi-localized methyl-group orbitals and the π-orbitals. These factors being taken into account, the mean twist angles, ϕ, compatible with the PE-spectroscopic results are ϕ (E,E) ≍ O° ± 30°, ϕ (E,Z) ≍ 80° or 110° within ± 15°, and ϕ (Z,Z) ≍ 85° to 105°. These results are in rough agreement with electron diffraction data by Traetteberg [15], other spectroscopic results and, for the (E, E)- and (Z,Z)-isomers, internal rotation potentials V(ϕ) previously calculated by Roth [17]. On the other hand the potential V (ϕ) proposed for the (E,Z)-isomer does not seem to be compatible with our findings.
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  • 3
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The olefins 2, 7, 11, and 19, have been reduced using catalytic amounts of cob(I)alamin(I(I)). During a slow saturation, the catalyst is able to differentiate the two diastereotopic faces of the endocyclic double bonds in 11 (t1/2 4 h,. cf. Scheme 3) are reduced much faster. A rationalization of the data can be obtained formulating tertiary alkylcobalamins as intermediates. Of the oxime 6 (cf. Scheme 2) and the p- bromobenzoate 23 (cf. Scheme 5) the structures have been determined by X-ray analysis.
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  • 4
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Structural Elucidation of Niphimycin, Part 3. Identity of Scopafungin and Niphimycin I. Position of the Malonyl Residue of Niphimycin and CopiamycinThe identity of scopafungin with niphimycin I was proven by spectroscopic and chromatographic methods and by common degradation products. The position of the malonyl residue in niphimycin I (9) and in copiamycin (14) was deduced by 1H-NMR spin-decoupling experiments of a degradation product (10).
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  • 5
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Syntheses, Chemical and Electrical Properties of Tetrathiafulvalene with a 1,6-Methano[10]annulene Moiety and of Chalcogendiimide-DerivativesThe synthesis of the tetrathiafulvalene 6 has been described: the reaction of 1 with the benzenedithoil 2 yielded the bis-dithioacetal 3 of 1,6-methano[10]annulene-dicarbaldehyde 1. The oxidation of 3 in the presence of HBF4 in Et2O yielded the salt 4, elimination of a hydride anion with triphenylmethylium tetrafluoroborate the salt 5, and elimination of a proton in 5 with Et3N the tetrathiafulvalene 6 with a 1,6-methano[10]annulene moiety. The spectroscopic and electrochemical properties of 6 are described, and also the syntheses and properties of charge-trasnfer complexes 7 and 8, including the properties of electric conductivity of 7 and 8. the syntheses of 9-13 are reported and also their spectroscopic properties.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 67 (1984), S. 765-769 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Voltammetric Investigations on the Oxidation Step of Symmetrical Triazacarbocyanine Dyes in Acetonitrile SolutionThe oxidation behaviour of twelve symmetrical triazacarbocyanine dyes with different heterocycles in MeCN (containing tetrabutylammonium perchlorate) has been investigated by means of dc-, ac- and cyclic triangular wave voltammetry. The oxidation mechanism has been found to be of the type ec, with the electrochemical step being reversible to irreversible. Oxidation potentials and transfer coefficients have been measured (E1/2 1.60 to 2.12 V vs. Ag/AgCl) and compared with known properties of carbocyanines. The effect of substituents X has been studied on the compounds 1,3-diethyl-2-[3-(1,3-diethyl-5-X-benzimidazolin-2-ylidene)-1-triazeno]-5-X-benzimidazolium tetrafluoroborate ((1a(X)) and 3-ethyl-2-[3-ethyl-5-X-Δ4-1,3-thiazolin-2-ylidene)-1-triazeno]-5-X-1,3-thiazolium tetrafluoroborate (1g(X)), and ρ-values of 0.425 and 0.565 V, respectively, have been found.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 67 (1984), S. 947-952 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The enantioselective synthesis of (+)- and (-)-cis-2-methyl-4-propyl-1,3-oxathine 8 and 9 form (E)-2-hezen-1-ol (1) as common starting material is described. The two enantiomeric forms exhibit different organoleptic properties.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 67 (1984), S. 1003-1011 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Plectranthons A, B, C, and D. Diterpenoid Phenanthrene-1,4-diones from Leaf-glands a Plectranthus sp. (Labiatae)The following structures of four new 1,4-phenanthraquionones, isolated in minute amounts from the coloured leaf-glands of a Plectranthus sp. obtained from the borders of Lake Kiwu2, Rwanda, are proposed: plectranthon A (1; 3-hydroxy-5, 7,8-trimethyl-2-(2-propenyl)phenanthrene-1, 4-dione), plectranthon B (2; 2-(2ξ-acetoxypropyl)-3-hydroxy-5,7,8-trimethylphenanthrene-1,4-dione), plextranthon C (3; 3-hydroxy- 7,8-diemethyl-2-(2-propenyl)phenanthrene-1,4-dione), and plectranthon D (4; 3-hydroxy-7,8,10-trimethyl-2-(2-propenyl)phenanthrene-1,4-dione). 2-(2ξ-Hydroxypropyl)-3,6-dihydroxy-5,7,8-trimethylphenanthrene-1,4-dione (11), a compound very similar to 1-4, was prepared by a Wagner-Meerwein, rearrangement of coleon E (5). Biogenetically, the plectranthons are derived from abietanoic precursors. The compounds 1, 2 and 4 are the first natural C20-phenanthrenes of diterpenoid origin.
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  • 9
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Building Units of Oligosaccharides, XXXVI.  -  Investigation of Reactivity in Tri- and Pentasaccharide Syntheses. Improved Synthesis of the Pentasaccharide Chain of the Forssman AntigenThe dependence of selectivity and yield upon the initial saccharide′s reactivity is shown for the syntheses of the trisaccharides 7, 8, 9, and 12. From 8 comes the trisaccharide halide 15 which, together with 22 in a block synthesis, yields the pentasaccharide 23 which in turn, after deprotection, gives the pentasaccharide chain of the Forssman hapten 25. This improved synthesis of 25 only uses 2-azido sugars and avoids the use of 2-phthalimido sugars.
    Notes: Die Abhängigkeit der Selektivität und der Ausbeute von den Reaktivitäten der Ausgangssaccharide bei der Synthese der Trisaccharide 7, 8, 9 und 12 wird gezeigt. Aus 8 ist der Trisaccharidhalogenid-Baustein 15 darstellbar, der in einer Blocksynthese mit 22 das Pentasaccharid 23 liefert, dessen Entblockierung zur Pentasaccharidkette des Forssman-Haptens 25 führt. Diese verbesserte Synthese von 25 verwendet nur 2-Azido-Zucker und vermeidet 2-Phthalimido-Zucker.
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  • 10
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemistry at Rigid Surfaces, 6.  -  Photochemically Induced Reactions with Surface-bound SensitizersAerosil® reacts with 3-triethoxysilylpropylamine to give Aminoaerosil(1) which can be converted into aerosils2a-f by means of sensitizers containing carboxyl groups. The density of the functional groups on the surface which was determined by several methods clearly effects the reaction. On irradiation in 2-propanol, acetone was produced as well as the surface-bound pinacol, e. g.4, which could be reoxidized by lead tetraacetate to give2b. Hydrodimerization on the surface of2b
    Notes: Aerosil® wird mit 3-Triethoxysilylpropylamin zu Aminoaerosil(1) umgesetzt und dieses mit carboxylgruppenhaltigen Sensibilisatoren in die grenzflächenmodifizierten Aerosile2a-f übergeführt. Die Beladungsdichte mit funktionellen Gruppen, die nach unterschiedlichen Methoden bestimmt wird, beeinflußt maβgebend das Reaktionsergebnis. Bei der Bestrahlung der grenzflächenmodifizierten Aerosile2a - c in Isopropylalkohol entstehen Aceton sowie das grenzflächengebundene Pinakol, z. B.4, das mit Bleitetraacetat wieder zu2b rückoxidiert werden kann. Die Hydrodimerisierung an der Grenzfläche von2b läuft 3mal langsamer als mit der Analogverbindung im Homogensystem. Bei der Photoreduktion von2b geringer Beladungsdichte entstehen neben dem Pinakol4 das grenzflächenfixierte Carbinol8 sowie das gemischte Pinakol9. An Aerosil grenzflächengebundene p-Acetylbenzoesäure (modifiziertes Aerosil2b) wird  -  in Analogie zu früher im Homogensystem durchgeführten Versuchen  -  in (S)-Milchsäure-(p-menth-3-ylester) und (R, S)-Milchsäure-(p-menth-3-ylester) bestrahlt. In beiden Fällen bildet sich grenzflächengebundenes Pinakol4, im zweiten Fall auch eine geringe Menge an optisch aktivem Lactat. Mit grenzflächengebundenen Sensibilisatoren werden folgende photochemisch induzierte Reaktionen studiert: a) die photosensibilisierte Addition von Isopropylalkohol an Maleinsäure und Maleinsäure-diethylester zu Terebinsäure(12a) bzw. deren Ethylester; b) die sensibilisierte cis/trans-Isomerisierung von Maleinsäure- bzw. Fumarsäure-diethylester; c) die sensibilisierte cis/trans-Isomerisierung von 1,2-Diphenylcyclopropan; d) die sensibilisierte Autoxidation von 2,5-Dimethylfuran. Bei allen vier Reaktionstypen entstehen  -  wenn auch langsamer  -  die gleichen Reaktionsprodukte wie mit analog strukturierten Sensibilisatoren im Homogensystem. Bei den Reaktionen b), c) und d) wurden der Wirkungsfaktor WF (Quotient der Reaktionsgeschwindigkeiten im Homogen- und Heterogensystem) sowie die Wiederverwendbarkeit SF (Quotient der Umsätze nach gleichen Zeiten im Zweit- und Erstversuch) der heterogen gebundenen Sensibilisatoren bestimmt.
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  • 11
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 1015-1017 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A Simple Synthesis of TetramethyloxamideTetramethyloxamide has been prepared by a new and simple procedure from dimethylformamide, iron(II) sulfate heptahydrate, and tert-butyl hydroperoxide (yield 43%) or 30% aqueous hydroperoxide (yield 77%).
    Notes: Es wird eine neue, einfache Synthese von Tetramethyloxamid aus Dimethylformamid, Eisen(II)-sulfat-heptahydrat und tert-Butylhydroperoxid (Ausb. 43%) oder 30proz. Wasserstoffperoxid (Ausb. 77%) beschrieben.
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  • 12
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 1025-1034 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis, Thermal and Photochemical Reactions of New Mesoionic 1,3,2-OxathiazolonesThe synthesis and spectroscopic data of the new mesoionic 1,3,2-oxathiazolones 3b, c, e are described. As cyclic thiocarbonyl imine, 3e reacts with dimethyl acetylenedicarboxylate at 80°C with evolution of carbon dioxide to produce the 5-arylisothiazole derivative 6e (80%). On the other hand, the visible light-induced fragmentation of 3e leads to a nitrile sulfide intermediate of type 10 which suffers unimolecular decay with formation of sulfur and the arylnitrile 11e or which can be partially trapped with dimethyl acetylenedicarboxylate to form the isomeric 3-arylisothiazole derivative 13e (29-21%). The analogous photochemical decay of 3c in the presence of dimethyl acetylenedicarboxylate proceeds with formation of the isothiazole derivative 13c besides sulfur and the nitrile 11c, whereas the nitrile sulfide 10b  -  photochemically generated from 3b  -  does not more react with formation of an isothiazole derivative.
    Notes: Die Synthese und spektroskopischen Daten der neuen mesoionischen 1,3,2-Oxathiazolone 3b, c, e werden beschrieben. Als cyclisches Thiocarbonylimin reagiert 3e mit Acetylendicarbonsäuredimethylester bei 80°C unter Kohlendioxid-Freisetzung zum 5-Arylisothiazol-Derivat 6e (Ausb. 80%). Demgegenüber führt die mit sichtbarem Licht induzierte Fragmentierung von 3e zu einer Nitrilsulfid-Zwischenstufe vom Typ 10, die unimolekularen Eigenzerfall in Schwefel und das Arylnitril 11e erleidet oder mit Acetylendicarbonsäure-dimethylester teilweise als isomerer 3-Aryl-isothiazol-Abkömmling 13e (Ausb. 29-21%) abgefangen werden kann. Der analoge photochemische Zerfall von 3c liefert in Gegenwart von Acetylendicarbonsäure-dimethylester neben Schwefel und dem Nitril 11c das Isothiazol-Derivat 13c, während das aus 3b photochemisch entstandene Nitrilsulfid 10b nicht mehr zur Isothiazol-Bildung befähigt ist.
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  • 13
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Structure and Reactions of 2,2′-Oxybis[2,2-dimethyl-4,4,5,5-tetrakis(trifluoromethyl)-1,3,2λ5-dioxaphospholane]The structure of the title compound 3 has been determined by X-ray diffraction. 3 was found to crystallize in the monoclinic system (space group P21/c). Two crystallographically independent molecules are observed in the crystal lattice which differ with regard to the P - O - P angle [147.3(3)° and 150.8(3)°, respectively]. Formation of 3 has been observed in the reaction of the chlorophosphorane Me2P(pfp)Cl (2; pfp = perfluoropinacolyl) with NaHCO3, and of the siloxyphosphorane Me2P(pfp)OSiMe3 (1) with Me2P(= O)Cl. Cleavage of 3 with methanol furnishes the previously known compound Me2P(pfp)OMe (5) and the acyclic phosphinic acid ester Me2P(= O)OC(CF3)2C(CF3)2OH (4b). Reaction of 3 with water leads to exclusive formation of 4b; the isomeric hydroxyphosphorane Me2P(pfp)OH (4a) has not been observed.
    Notes: Die Struktur der monoklin (Raumgruppe P21/c) kristallisierenden Titelverbindung 3 wurde durch Röntgenstrukturanalyse bestimmt (Abb. 1-3). Im Kristallgitter werden zwei kristallographisch unabhängige Moleküle beobachtet, die sich in der Groβe des P - O - P-Winkels unterscheiden [147.3(3)° bzw. 150.8(3)°]. 3 bildet sich bei der Umsetzung des Chlorphosphorans Me2P(pfp)Cl (2; pfp = perfluorpinakolyl) mit NaHCO3 sowie aus dem Siloxyphosphoran Me2P(pfp)OSiMe3 (1) mit Me2P(= O)Cl. Die Spaltung von 3 mit Methanol liefert die bereits bekannte Verbindung Me2P(pfp)OMe (5) und den acyclischen Phosphinsäureester Me2P(= O)OC(CF3)2C(CF3)2OH (4b). Die Umsetzung von 3 mit H2O führt ausschließlich zu 4b; die Bildung des isomeren Hydroxyphosphorans Me2P(pfp)OH (4a) wird nicht beobachtet.
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  • 14
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electron Donor-Acceptor Compounds, XXVII.  -  Quinhydrones of the [4.4]Paracyclophane SeriesIn the context of the determination of the distance and orientation dependence of charge-transfer interactions the diastereomeric quinhydrones 5 and 6 of the [4.4]paracyclophane series were prepared. Cyclisation of 1,4-bis(3-bromopropyl)-2,5-dimethoxybenzene with 2,5-dimethoxy-1,4-benzenedimethanethiol yielded the diastereomeric dithia[5.5]paracyclophanes 9/10 which, via the corresponding disulfones 11/12, were converted into the 6,9,16,19-tetramethoxy-[4.4]paracyclophanes 7/8. The stereoisomers 7/8, as well as the pairs of diastereomers 9/10 and 11/12. have been separated; experiments on thermal isomerisation are reported. The assignment of 7/8 to the pseudoortho and pseudogeminal constitution was established by an X-ray structure analysis of 7 the molecular structure of which is discussed. Oxidative demethylation of 7 and 8 yielded the diastereomeric quinhydrones 5 and 6. Charge-transfer absorptions of these compounds are compared with those of the corresponding [3.3]paracyclophane quinhydrones 3b and 4b and are discussed under the aspect of the specific conformational situation present in the [4.4]paracyclophane system.
    Notes: Zur Untersuchung der Abstands- und Orientierungsabhängigkeit der Charge-Transfer-Wechsel-wirkungen wurden die diastereomeren Chinhydrone 5 und 6 der [4.4]Paracyclophan-Rehe synthetisiert. Die Cyclisierung von 1,4-Bis(3-brompropyl)-2,5-dimethoxybenzol mit 2,5-Dimethoxy-1,4-benzoldimethanthiol ergab die diastereomeren Dithia[5.5]paracyclophane 9/10, die über die entsprechenden Disulfone 11/12 in die 6,9,16,19-Tetramethoxy[4.4]paracyclophane 7/8 über-führt wurden. Ebenso wie die Diastereomeren-Paare 9/10 und 11/12 lieβen sich auch 7/8 in die Stereoisomeren trennen; über Isomerisierungsversuche wird berichtet. Die Zuordnung von 7/8 zur pseudoortho- und pseudogeminalen Reihe geschah durch Röntgen-Strukturanalyse von 7, für das die Molekülstruktur diskutiert wird. Oxidative Demethylierung von 7 und 8 diastereomeren Chinhydrone 5 und 6. Die Charge-Transfer-Absorptionen dieser Verbindungen werden mit denen der entsprechenden [3.3]Paracyclophan-Chinhydrone 3b und 4b verglichen und unter dem Gesichtspunkt der im [4.4]Paracyclophan-System vorliegenden besonderen Konformationsverhältnisse diskutiert.
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  • 15
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 1065-1072 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Electron Donor-Acceptor Compounds, XXVIII.  -  Synthesis and Charge-Transfer Properties of 4,7-Diaza[2.2]paracyclophanes
    Notes: 2,5-Bis(brommethyl)pyrazin (3) wurde dargestellt und mit 1,4-Benzoldimethanthiol und 2,5-Dimethoxy-1,4-benzoldimethanthiol zu den entsprechenden 5,8-Diaza-2,11-dithia[3.3]paracyclophanen cyclisiert. Photochemische Schwefel-Extrusion ergab 4,7-Diaza[2.2]paracyclophan (1) und die stereoisomeren 12,15-Dimethoxy-4,7-diaza[2.2]paracyclophane 5 und 6, die chromatographisch getrennt wurden.  -  Absorptions- und Emissionsspektren von 5 und 6 beweisen die π-Acceptor-Eigenschaft eines Pyrazins, das im [2.2]Paracyclophan-System einem starken Elektron-Donor gegenübersteht. Die beobachtete Lösungsmittelabhängigkeit der Charge-Transfer-Absorptionen von 5 und 6 (Abb.) wird auf eine Änderung der Elektronenaffinität des Pyrazin-Teils durch Solvatation und Protonierung zurückgeführt. Der Vergleich von Charge-Transfer-Eigenschaften der Stereoisomeren 5 und 6 zeigt die Orientierungsabhängigkeit der Donor-Acceptor-Wechselwirkung.2,5-Bis(bromomethyl)pyrazine (3) was prepared and cyclized with 1,4-benzenedimethanethiol and 2,5-dimethoxy-1,4-benzenedimethanethiol to give the corresponding 5,8-diaza-2,11-dithia[3.3]-paracyclophanes. Photochemical sulfur extrusion yielded 4,7-diaza[2.2]paracyclophane (1) and the stereoisomeric 12,15-dimethoxy-4,7-diaza[2.2]paracyclophanes 5 and 6 which were separated by chromatography.  -  Absorption and emission spectra of 5 and 6 demonstrate the π-acceptor quality of pyrazine when linked in a [2.2]paracyclophane system vis-a-vis to a strong electron donor. The solvent dependence of charge-transfer absorptions observed for 5 and 6 (Fig.) is ascribed to the change in electron affinity of the pyrazine moiety by solvation and protonation. By comparing charge-transfer properties of the stereoisomers 5 and 6 the orientation dependence of electron donor-acceptor interactions is shown.
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  • 16
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 1207-1214 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of 2-Aminomethylene-5-halo-2H-pyrroles and 5-Halo-2-pyrrolecarbaldehydes, II.  -  Cyclotetramerizations of Suitable Pyrroles into Octamethylporphyrins without Acid CatalysisCyclotetramerizations of 2-aminomethyl- and 2-dimethylaminomethyl-3,4-dimethylpyrrole with dimethyl sulfate, methyl iodide, copper(II) acetate, zinc acetate, magnesium chloride, hydroperoxide, formaldehyde, benzaldehyde, and ethylmagnesium bromide have been investigated. The syntheses of the pyrroles 4-6, 8, and 9 are described.
    Notes: Die Cyclotetramerisierungen von 2-Aminomethyl- und 2-Dimethylaminomethyl-3,4-dimethylpyrrol mit Dimethylsulfat, Methyliodid, Kupfer(II)-acetat, Zinkacetat, Magnesiumchlorid, Wasserstoffperoxid, Formaldehyd, Benzaldehyd und Ethylmagnesiumbromid werden untersucht. Die Synthese der Pyrrole 4-6, 8 und 9 wird beschrieben.
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  • 17
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 1223-1233 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Some β-Mycaminose GlycosidesStarting from derivatives of 3-azido-3,6-dideoxy-α-α-glucofuranose 5 or 3-azidoglucofuranose 10 the 1-bromides 7, 14 and 30, suitable for glycoside synthesis under Koenigs-Knorr conditions, have been prepared. By reaction of 14 with methanol, cyclohexanol, benzyl alcohol, 2,2,2-trichloroethanol, and 1,2;3,4-di-O-isopropyliden-α-galactose the β-glycosides 16-20 are obtained in high yields. Reductive alkylation of 16, 17, and 20 with palladium on charcoal/formaldehyde gave the 3-dimethylamino compounds 21, 22, and 23. After their dehalogenation with tributyltin hydride, the corresponding β-glycosides 24, 25, and 26 of D-Mycaminose are received in high yields.
    Notes: Ausgehend von Derivaten der 3-Azido-3,6-didesoxy-α-D-glucofuranose 5 oder 3-Azidoglucofuranose 10 werden die für die Glycosidsynthesen unter Koenigs-Knorr-Bedingungen geeigneten 1-Bromhalogenosen 7, 14 und 30 dargestellt. Die Umsetzung von 14 mit Methanol, Cyclohexylalkohol, Benzylalkohol, 2,2,2-Trichlorethanol und 1,2;3,4-Di-O-isopropyliden-α-D-galactose führt in hohen Ausbeuten zu den β-Glycosiden 16-20. Die reduktive Alkylierung von 16, 17 und 20 mittels Palladiums auf Kohle/Formaldehyd-führt zu den 3-Dimethylaminoverbindungen 21, 22 und 23. Deren Enthalogenierung mit Tri-n-butylzinnhydrid verläuft in hohen Ausbeuten zu den entsprechenden β-Glycosiden 24, 25 und 26 der D-Mycaminose.
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  • 18
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Theoretical and Spectroscopical Investigations of Indigo Dyes, XXII.  -  Preparations of 5,5′-and 6,6′-Dialkylated Indigo DyesThe manifolded applicabilities of indigo dyes are strongly restricted by the low solubility of most of their representatives. We describe in this paper the preparation of a series of dialkylated indigos 1, thioindigos 2, dyes of the cibaviolett-type 3, and of the corresponding vinylogues 4, 5, and 6 by different synthetic methods. Some of the prepared compounds show a remarkable solubility and can be used for spectroscopic measurements even in non-polar solvents.
    Notes: Die vielseitigen Verwendungsmöglichkeiten der Indigoide werden durch die geringe Löslichkeit der meisten Vertreter dieser Farbstoffklasse stark eingeschränkt. Wir berichten hier über die Darstellung einer Reihe dialkylierter Indigos 1, Thioindigos 2, Cibaviolett-Farbstoffe 3 sowie ihrer Vinylogen 4, 5 und 6 auf unterschiedlichen Wegen. Einige der Verbindungen zeigen eine sehr gute Löslichkeit und können in unpolaren Lösungsmitteln für spektroskopische Zwecke genutzt werden.
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  • 19
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 1354-1360 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Sugar Tosylates via p-Toluenesulfinic Acid Esters.  -  p-Toluenesulfinimidazolide  -  A Reagent for Formation of Sulfinic Acid Esters without Using HalidesThe reaction of the protected sugar derivatives 1, 4, 7, 10, 13, 16, 19 and 20 with p-toluenesulfin-imidazolide prepared from p-toluenesulfinic acid and N,N'-carbonyldiimidazole yields the corresponding p-toluenesulfinic esters 2, 5, 8, 11, 14, 17, 20 and 22. With the exception of 20 and 22, these products can be oxidized with m-chloroperbenzoic acid in high yields and short overall reaction times to the tosylates 3, 6, 9, 12, 15 and 18.
    Notes: Durch Umsetzung der blockierten Zuckerderivate 1, 4, 7, 10, 13, 16, 19 und 21 mit dem aus p-Toluolsulfinsäure und N,N'-Carbonyldiimidazol intermediär gebildeten p-Toluolsulfinimidazolid werden die p-Toluolsulfinsäureester 2, 5, 8, 11, 14, 17, 20 und 22 erhalten. Daraus lassen sich mit Ausnahme von 20 und 22 in hohen Ausbeuten und insgesamt kurzer Reaktionszeit die entsprechenden Tosylate 3, 6, 9, 12, 15 und 18 durch Oxidation mit m-Chlorperbenzoesäure darstellen.
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  • 20
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 1361-1366 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Condensed Azoles with Two Bridgehead Nitrogen AtomsThe pyrazolo[1,2-a][1,2,4]triazoles 4, 1,2,4-triazolo[1,2-b]phthalazine 7, 1,2,4-triazolo[1,2-a]-[1,2,4]triazine 9, 1,2,4-triazolo[1,2-a]indazoles 16, 1,2,3,5-thiatriazolo[2,3-a]indazole 17 and 1,2,4-triazino[1,2-a]indazole 18 are prepared by the cycloreaction of the triazoles 1 or the triazole and indazole carboxamides 5, 6, 13, and 14 with 1,1-, 1,2-, 1,3-, and 1,4-dielectrophiles.
    Notes: Die Pyrazolo[1,2-a][1,2,4]triazole4, das 1,2,4-Triazolo[1,2-b]phthalazin 7, 1,2,4-Triazolo[1,2-a]-[1,2,4]triazin 9, die 1,2,4-Triazolo[1,2-a]indazole 16, das 1,2,3,5-Thiatriazolo[2,3-a]indazol 17 und 1,2,4-Triazino[1,2-a]indazol 18 werden durch Cycloreaktion der Triazole 1 bzw. der Triazol-und Indazolcarboxamide 5, 6, 13 und 14 mit 1,1-, 1,2-, 1,3- und 1,4-Dielektrophilen dargestellt.
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  • 21
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 1415-1418 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stable Carbenium Ions, 271). - Diarylchlorocarbenium IonsDiarylchlorocarbenium hexachloroantimonates have been prepared as crystalline salts and are characterised.
    Notes: Diarylchlorcarbenium-hexachloroantimonate werden als kristalline Salze dargestellt und charakterisiert.
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  • 22
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stable Carbenium Ions, 281). - α,α′-Dihalogen-α,α′-diphenyl-m-phenylenedicarbenium Ionsα,α′-Difluoro-α,α′-diphenyl-m-phenylenedicarbenium hexafluoroantimonate and α,α′-dichloro-α,α′-diphenyl-m-phenylenedicarbenium hexachloroantimonate are prepared as crystalline salts and are characterised.
    Notes: α,α′-Difluor-α,α′-diphenyl-m-phenylendicarbenium-hexafluoroantimonat und α,α′-Dichlor-α,α′-diphenyl-m-phenylendicarbenium-hexachloroantimonat werden als kristalline Salze dargestellt und charakterisiert.
    Additional Material: 2 Tab.
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  • 23
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of Bile Pigments, XIII1).  -  Preparation of 3,4-Dihydro-5(1H)-pyrromethenones from 5(1H)-Pyrromethenones and from 5(2H)-Dipyrrylmethanones5(2H)-Dipyrrylmethanones 2 which are usually obtained by catalytical hydrogenation of 5(1H)-pyrromethenones 1, are only formed as the main product (ca. 80%) in alkaline solutions. In the absence of base, the obtained mixture contains up to 40% of the cis-configurated (Z)-3,4-dihydro-5(1H)-pyrromethenones (rac-3). On the other hand, the corresponding trans-isomers (rac-7) are available by base-catalyzed, irreversible rearrangement of 2 in boiling methanol in max. 40% yield. Under the same conditions (Z)-cis-3,4-dihydro-5(1H)-pyrromethenones (rac-3) are converted into the corresponding trans-isomers (rac-7), which can be isolated in 80% yield from the reaction mixture. In H3COD the products are deuterated at C-4 and at the methine bridge. (Z)-trans-3,4-Dihydro-5(1H)-pyrromethenones (rac-7) exchange only the H-atom at the methine bridge. Both cis- (rac-3) and trans-(Z)-3,4-dihydro-5(1H)-pyrromethenones (rac-7) can be transformed into the corresponding E-isomers rac-10 and rac-11, respectively, by photoisomerization at the exocyclic double bond.
    Notes: 5(2H)-Dipyrrylmethanone 2, die bekanntlich durch katalytische Hydrierung von 5(1H)-Pyrromethenonen 1 zugänglich sind, werden nur in alkalischem Medium als Hauptprodukte (ca. 80%) gebildet. In Abwesenheit von Base enthält das Produktgemisch bis zu 40% cis-konfigurierte (Z)-3,4-Dihydro-5(1H)-pyrromethenone (rac-3). Ihre trans-konfigurierten Z-Isomeren (rac-7) sind durch basenkatalysierte irreversible Umlagerung von 2 in siedendem Methanol in max. 40proz. Ausbeute zugänglich. Unter denselben Bedingungen isomerisieren cis-konfigurierte (Z)-3,4-Dihydro-5(1H)-pyrromethenone (rac-3) zu den entsprechenden (Z)-trans-Isomeren (rac-7), die in 80proz. Ausbeute isoliert werden können. In H3COD findet dabei H/D-Austausch an C-4 und an der Methin-Brücke statt. (Z)-trans-3,4-Dihydro-5(1H)-pyrromethenone (rac-7) tauschen dagegen nur das methinständige H-Atom aus. Sowohl cis- (rac-3) als auch trans-konfigurierte (Z)-3,4-Dihydro-5(1H)-pyrromethenone (rac-7) lassen sich in die entsprechenden E-Stereo-isomeren rac-10 bzw. rac-11 durch Photoisomerisierung der exocyclischen Doppelbindung über-führen.
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  • 24
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 1513-1514 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Cyclisation of Salicylamides and Salicylohydroxamic Acids with 1,1′-CarbonyldiimidazoleCyclisation of salicylamides 1a, b and salicylohydroxamic acids 1c, d with 1,1′-carbonyldiimid-azole (2) causes formation of 2H-1,3-benzoxazine-2,4(3H)-diones 4a-d. In contrast to statements in the literature isoimides 3 or isoxazoles 5 could not be isolated.
    Notes: Salicylsäureamide 1a, b und Salicylohydroxamsäuren 1c, d cyclisieren mit 1,1′-Carbonyldiimid-azol (2) zu 2H-1,3-Benzoxazin-2,4(3H)-dionen 4a-d. Isoimide 3 oder Isoxazole 5 konnten entgegen Literaturangaben nicht isoliert werden.
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  • 25
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981) 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 26
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 1523-1533 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Dihydropyridines, VI1).  -  Derivatives of Diimido Malonic Acid in the Hantzsch Pyridine SynthesisOne-pot-condensation of aldehydes 6, 2,2′-methylenediimidazoline hydrochloride (7) and β-dicarbonyl compounds 10 leads to 1,2,3,7-tetrahydro-8-(2-imidazoline-2-yl)imidazo[1,2-a]pyridine hydrochloride 11. Michael addition of 7 to α,β-unsaturated ketones is followed by ring closure to give 16, 17, and 18. Condensation of the free base 8a with aldehydes 6 and 1,3-cyclohexanedione yields the fused imidazopyridines 19a-d. Compounds 20 and 21 are prepared by use of a second enamine in the one-pot-synthesis, thus furnishing another basic centre. 2,2′-Methylenedi(2-thiazoline) hydrochloride (22) is prepared by condensation of diethyl malonodiimidate and 2-amino
    Notes: Die Dreikomponenten-Kondensation von Aldehyden 6, 2,2′-Methylendiimidazolin-hydrochlorid (7) und β-Dicarbonylverbindungen 10 führt zu 1,2,3,7-Tetrahydro-8-(2-imidazolin-2-yl)imidazo-[1,2-a]pyridin-hydrochloriden 11. Die Verbindungen 16, 17 und 18 werden durch cyclisierende Michael-Addition von 7 an α,β-ungesättigte Ketone erhalten. Die freie Base 8a kondensiert mit 1,3-Cyclohexandion und den Aldehyden 6 zu den anellierten Imidazopyridinen 19a-d. Einsatz eines zweiten Enamins in der Dreikomponenten-Reaktion liefert die Verbindungen 20 und 21 mit einem weiteren basischen Zentrum. 2,2′-Methylendi(2-thiazolin)-hydrochlorid (22) wird durch Kondensation von Malondiimidsäure-diethylester und 2-Aminoethanthiol-hydrochlorid erhalten. Natronlauge liefert die freie Base 8b. Die 2,3-Dihydro-8-(2-thiazolin-2-yl) 7H-thiazolo[3,2-a]-pyridine 23, 25, 26, 28 und 29 sind durch cyclisierende Michael-Addition von 8b an verschiedene α,β-ungesättigte Carbonylverbindungen in Ethanol oder Eisessig zugänglich.
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  • 27
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 1545-1549 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Malonodiamidines, III.  -  Synthesis and Condensation Reactions of 1,2,3,4,6,7-Hexahydro-7 imino-1,4-dimethyl-5H -1,4-diazepin-5-oneDiethyl malonodiimidate dihydrochloride (I) and N-methylethylenediamine yield in ethanol the N,N'-bridged malonodiamidine salt 2b, whereas 1 and N,N'-dimethylethylenediamine fail to give the 2b analogous salt 4. Instead the 1 H-1,4-diazepine-5,7-diimine hydrochloride 5 is obtained in low yield. Under hydrolytic reaction conditions the hydrochloride of the title compound is obtained in 56% yield. [3 + 3]-Condensations of the corresponding base 7 with 2,4-pentanedione and α,β-unsaturated carbonyl compounds lead to the diazepines 8, 9, and 10. 1 H-[1,4]diazepino-[5,6-b]quinolines 12a- f are obtained by condensation of 6 with the isatines 11.
    Notes: Malondiimidsäure-diethylester-dihydrochlorid (1) liefert mit N-Methylethylendiamin in Ethanol das N,N'-verbrückte Malondiamidiniumsalz 2b. Umsetzung von 1 mit N,N'-Dimethylethylendiamin führt wider Erwarten nicht zum 2b analogen Salz 4, sondern in geringer Ausbeute zum 1 H-1,4-Diazepin-5,7-diiminsalz 5. Unter hydrolytischen Reaktionsbedingungen wird das Hydrochlorid der Titelverbindung mit 56% Ausbeute erhalten. Die zugrundeliegende Base 7 geht mit 2,4-Pentandion und α,β-ungesättigten Carbonylverbindungen [3 + 3]-Kondensationen zu den Diazepinen 8, 9 und 10 ein. Die Isatine 11 kondensieren mit 7 zu den 1 H-[1,4]Diazepino[5,6-b]-chinolinen 12a- f.
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  • 28
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Condensations with Oxime O-Sulfonates, I.  -  Synthesis of 2-Amino-4,5-dihydro-4,5-diimino-1 H-pyrrole-3-carboxylatesThe reaction of the oxime O-tosylates 1 with the amidinoacetic acid esters 2 does not lead to the expected pyrazines 4, but rather to the novel 4,5-dihydro-1 H-pyrrole-3-carboxylates 8 (= 2-pyrroline-3-carboxylates) by rearrangement via 7. The hydrolysis of the pyrroles 8 and their reactions with amines have been studied.
    Notes: Die Reaktion der Oxim-O-tosylate 1 mit den Amidinoessigestern 2 führt nicht zu den erwarteten Pyrazinen 4, sondern unter Umlagerung über 7 zu den neuartigen 4,5-Dihydro-1 H-pyrrol-3-carbonsäureestern 8 (= 2-Pyrrolin-3-carbonsäureester). Die Hydrolyse der Pyrrole 8 sowie deren Umsetzung mit Aminen wird untersucht.
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  • 29
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Branched Sugars, XXVII1).  -  Synthesis of Long Chain Saccharides by Chain Elongation with the Dianion of 1,3-Dithiane-2-methanol and Related DianionsThe dianions 3, 4, and 16, which are suitable for nucleophilic addition to aldehydo-saccharides, can be obtained by reaction of 1,3-dithiane-2-methanol, or the appropriate side chain-elongated derivatives, with 2 molar equivalents of butyllithium. With these dianions, chain elongated saccharides can be made and, in one step, various potential chiral centres may be introduced. The octose 18, the decose 21, and the undecose 22 are obtainable from 17. With 23, the elongation of the chain leads to the septose 25, the nonose 27, and the decose 28. A 2-septulose 35 and 5-deculose 37 were also made.
    Notes: Durch Umsetzung von 1,3-Dithian-2-methanol und entsprechenden an der Seitenkette verlängerten Derivaten mit 2 Moläquivalenten Butyllithium lassen sich Dianionen 3, 4 und 16 darstellen, die zur nucleophilen Addition an aldehydo-Saccharide geeignet sind. Dabei werden kettenverlängerte Saccharide erhalten, bei denen in einem Schritt mehrere vorgegebene chirale Zentren eingeführt werden können. Aus 17 sind so die Octose 18, die Decose 21 und die Undecose 22 zu erhalten. Mit 23 führt die Kettenverlängerung zur Septose 25, zur Nonose 27 und Decose 28. Auch eine 2-Septulose 35 und 5-Deculose 37 sind darstellbar.
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  • 30
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    Liebigs Annalen 1981 (1981), S. 2057-2060 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On the Configuration of NardosinoneX-ray analysis of nardosinone (1) shows cis position of the 1,2-dioxolane ring. Therefore, the formation of nardofuran (3) from isonardosinone (2) takes place by retention of the configuration at C-4.
    Notes: Die Röntgenstrukturanalyse zeigt, daß im Nardosinon (1) der 1,2-Dioxolan-Ring in cis-Stellung steht. Die Bildung des Nardofurans (3) aus Isonardosinon (2) verläuft daher unter Retention der Konfiguration an C-4.
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  • 31
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    Liebigs Annalen 1981 (1981), S. 2090-2092 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Experiments Concerning the Reduction of Dichloromethanedisulfonyl DichlorideMild reducing agents, including methanol, reduce dichloromethanedisulfonyl dichloride (2) to give dichloro(chlorosulfonyl)methanesulfinic acid (6) which desulfinylates spontaneously to form dichloromethanesulfonyl chloride (9). Chloromethanedisulfonyl dichloride (12) ist not reduced under these conditions and can be derivatized „normally“, for instance with morpholine.
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  • 32
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    Liebigs Annalen 1981 (1981), S. 2097-2097 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 33
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stellvertretende nucleophile Substitution von Wasserstoff in Nitropyridinen durch α-Chloralkylphenylsulfon-CarbanionenNitropyridine und Chlornitropyridine reagieren mit Carbanionen von α-Chloralkylphenylsulfonen unter „stellvertretender nucleophiler Substitution“ von Wasserstoff in o- und p-Stellung zur Nitrogruppe. Als allgemeine Regel wurde beobachtet, daß die „stellvertretende Substitution“ des Wasserstoffs rascher als die nucleophile Substitution von entsprechend aktiviertem Halogen erfolgt. Die Orientierung der Wasserstoff-Substitution wird diskutiert.
    Notes: Nitropyridines and chloronitropyridines react with carbanions of α-chloroalkyl phenyl sulfones yielding products of the vicarious nucleophilic substitution of hydrogen at positions ortho and para to the nitro group. A general rule that the vicarious substitution of hydrogen proceeds faster than the nucleophilic substitution of equally activated halogen is observed. The orientation of the hydrogen substitution is discussed.
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  • 34
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 2384-2391 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on Natural γ- and δ-Lactones, XI.  -  Synthesis of Psilotin and 6-EpipsilotinThe glucoside psilotin (1) and its 6-epi isomer were synthesized. From CD measurements the 6S-configuration can be assigned to 1.
    Notes: Psilotin (1) und 6-Epipsilotin wurden synthetisiert. CD-Messungen an diesen Verbindungen legen für natürliches Psilotin die 6S-Konfiguration fest.
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  • 35
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    Liebigs Annalen 1981 (1981), S. 2407-2418 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Asymmetric Syntheses via Heterocyclic Intermediates, X.  -  Enantioselective Synthesis of (2R)-2-MethylserinesAldehydes and ketones react with the lithiated bislactim ether 3 of cyclo-(L-Ala-L-Ala) with 81 to 〉 95% asymmetric induction (d. e. = diastereomeric excess) at C-3; (R) configuration is formed predominantly.  -  A model concept for the asymmetric induction is proposed.  -  With aldehydes or unsymmetrical ketones C-7 of the adducts 6 becomes a chiral center, too. (R) configuration is induced here [for the (3R)-isomers] with d. e. 47-73%. Hydrolysis of the addition products 6 (0.25 N HCl, room temperature) gives L-Ala-OCH3 and (2R)-2-methylserine methyl esters 7. Both compounds can be separated either at the ester stage by distillation or  -  if 7 is thermolabile  -  after further hydrolysis at the amino acid stage.
    Notes: Die Umsetzung des lithiierten Bislactimethers 3 von cyclo-(L-Ala-L-Ala) mit Aldehyden und Ketonen vollzieht sich mit 81 bis 〉 95% asymmetrischer Induktion (d. e. = diastereomeric excess) an C-3, wobei die (R)-Konfiguration induziert wird.  -  Eine Modellvorstellung zur Deutung dieser ungewöhnlich hohen Induktion wird diskutiert.  -  Bei Aldehyden oder unsymmetrischen Ketonen wird auch C-7 der Addukte 6 zu einem Chiralitätszentrum; hier wird [bei den (3R)-Isomeren] mit 47-73% d. e. ebenfalls (R)-Konfiguration induziert.  -  Hydrolyse der Addukte 6 (0.25 N HCl, Raumtemperatur) liefert neben L-Ala-OCH3 die (2R)-2-Methylserin-methylester 7. Die bei-den Verbindungen lassen sich entweder auf der Stufe der Ester destillativ trennen oder  -  wenn 7 thermolabil ist  -  nach weiterer Hydrolyse auf der Stufe der Aminosäuren.
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  • 36
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Carbonyl und Thiocarbonylverbindungen: Reaktionen von 4-Chlorxanthion mit Diazoalkanen und Ch-aciden verbindungenWährend 4-Chlorxanthion 1 mit Diazomethan das Dithiolan 2 ergibt, entstehen mit anderen Diazoalkanen die Episulfide 3-5, deren Entschwefelung zu den entsprechenden Ethylenen 6-7 führt. Malononitril und Cyanessigsäure-ethylester reagieren mit 1 zu den Cyanderivaten 8a, b. Mit Hydrazinen und p-Toluidin ergibt 4-Chlorxanthion (1) die Hydrazone 9a, b und die Schiff-Base 9c. In Abhängigkeit von den Reaktionsbedingungen liefert die Oxidation des Hydrazons 9a die Diazoverbindung 10 oder das Ketazin 11. Hydroxylamin reagiert mit 1 zum Oxim 9d, das mit Phenylisocynat zum N-Phenylcarbamat 9e reagiert.
    Notes: While 4-chloroxanthione 1 gives with diazomethane the dithiol 2, it reacts with other diazoalkanes to give the episulfides 3-5, desulfurization of which forms the ethylenes 6 and 7. Malononitrile and ethyl cyanoacetate react with 1 to give the cyano derivatives 8a, b. With hydrazines and p-toluidine, 4-chloroxanthione (1) give the hydrazones 9a, b and the Schiff's base 9c, respectively. The hydrazone 9a on oxidation may give either the corresponding diazo compound 10 or the ketazine 11 according to the reaction conditions. The title compound 1 reacts with hydroxylamine to yield the oxime 9d which forms the N-phenylcarbamate 9e when treated with phenyl isocyanate.
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  • 37
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1984 (1984), S. 196-198 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaktionen von 4-Chlor-9H-xanthen-9-thion mit Tetrachlor-O-benzochinon4-Chlor-9H-xanthen-9-thion (1) reagiert mit Tetrachlor-o-benzochinon zu dem cyclischen Acetal 2. Zur Struktursicherung wurde 2 auf unabhängigen Wegen aus Tetrachlor-o-benzochinon und 4-Chlor-9-diazo-9H-xanthen oder 4-Chlor-9H-xanthen-9-on-hydrazon sowie aus Tetrachlorbrenzcatechin und 4,9,9-Trichlor-9H-xanthen synthetisiert. Die Spaltung der Acetalgruppe in 2 mit Salzsäure, Malononitril, Cyanessigsäure-ethylester und Hydrazinhydrat wurde studiert.
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  • 38
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Polyhydroxyamino Compounds via Diene Synthesis with Nitroso compounds, IX.  -  trans-6-Azido-1,3-cyclohexadien-5-ol as educt for the Synthesis of Kondurodiamine and Streptamine IsomersThe diaminodideoxykonduritols 8a, 8b, and 9 as well as the analogs 10 and 11 of Streptamine have been synthesized starting with O,N-5,6-disubstituted cyclohexadienes.
    Notes: Die Diaminodidesoxykondurite 8a, 8b und 9 sowie die Streptaminanalogen 10 und 11 werden ausgehend von O,N-5,6-disubstituierten Cyclohexadienen synthetisiert.
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  • 39
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1984 (1984), S. 1-7 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thiophosphatidic Acid Esters Containing a C—S—P BondThiophosphatidic acid and the following thiophosphatidic acid esters containing a C—S—P bond were synthesized: O,O-dimethyl S-(2,3-distearoyloxypropyl) thiophosphate (4). O-methyl S-(2,3-distearoyloxypropyl) thiophosphoric acid (4a), and O,O-bis(trimethylsilyl) S-(2,3-distearoyloxypropyl) thiophosphate (6). The structures were proved by NMR and IR spectra. It was demonstrated that O,O-dimethyl S-(2,3-isopropylidenedioxypropyl) thiophosphate (3) can be obtained from 2,3-isopropylidenedioxy-1-propanethiol (1) in good yield and acylated to yield 4.
    Notes: Thiophosphatidsäure und folgende Thiophosphatidsäureester mit C—S—P-Bindung wurden synthetisiert: Thiophosphorsäure-O,O-dimethyl-S-(2,3-distearoyloxypropyl)ester (4), Thiophosphorsäure-O-methyl-S-(2,3-distearoyloxypropyl)ester (4a) und Thiophosphorsäure-O,O-bis(trimethylsilyl)-S-(2,3-distearoyloxypropyl)ester (6). Die Strukturen wurden durch NMR- und IR-Spektren bestätigt. Es wurde gezeigt, daß Thiophosphorsäure-O,O-dimethyl-S-(2,3-isopropylidendioxypropyl)ester (3) mit guter Ausbeute aus 2,3-Isopropylidendioxy-1-propanthiol (1) erhalten und zu 4 acyliert werden kann.
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  • 40
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1984 (1984), S. 15-30 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of 4-Penten-4-olides (γ-Methylene-γ-butyrolactones) vis 4-Pentenoic Acids4-Penten-4-olides (γ-Methylene-γ-butyrolactones) 7 are easily accessible starting from allylic alcohols 1, which on ortho ester Claisen rearrangement and hydrolytic work-up furnish 4-pentenoic acids 5. The latter on iodolactonization and hydrogen iodide elimination by means of 1,8-diaza-bicyclo[5.4.0]undec-7-ene (DBU) furnish 7, in good over-all yield and with variable substitution patterns.  -  Iodolactonization under kinetic control shows moderate 1,2- or 1,3-asymmetric induction (≳ 3:1 and ca. 2:1, respectively). The composition of the iodolactone mixtures 6 as well as the individual relative configurations are deduced from 1H and 13C NMR data.  -  Similarly, the spirobipentenolide 13 is obtained starting from diethyl diallylmalonate (9) via 11 resulting from ester iodocyclization.
    Notes: 4-Penten-4-olide (γ-Methylen-γ-butyrolactone) 7 sind aus Allylalkoholen 1 durch Orthoester-Claisenumlagerung und Hydrolyse zu 4-Pentensäuren 5, anschließende Iodlactonisierung und HI-Abspaltung mit 1,8-Diazabicyclo[5.4.0]undec-7-en (DBU) in guter Gesamtausbeute und variablem Substitutionsmuster leicht zugänglich.  -  Die Iodlactonisierung unter kinetischer Kontrolle zeigt mäßige 1,2- oder 1,3-asymmetrische Induktion (≳ 3:1 bzw. ca. 2:1). Die Zusammensetzungen der Iodlactongemische 6 sowie die relativen Konfigurationen werden aus 1H- und 13C-NMR-Daten abgeleitet.  -  Das Spirobipentenolid 13 wird in ähnlicher Weise aus Diallylmalonsäure-diethylester (9) über 11 (durch Ester-Iodlactonisierung) erhalten.
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  • 41
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on the Chemistry of Natural Organic Materials, 89.  -  halogenation Reactions of 1,3-Dihydroxy-10methyl-9(10H)-acridinone and its Ethers  -  A Simple Regiospecific Synthesis of AcroyncineIodination of 1,3-dihydroxy-10-methyl-9-acridone (2c) and its ethers 2a and 2b gave the corresponding 2-iodo derivatives 3a-c. Bromination of 2a with NBS yielded 2-bromo-(10), 4-bromo- (11), as well as small amounts of 2,4-dibromo-1,3-dimethoxy-10-methyl-9-acridone (12). Under the same conditions from 2c 2-bromo-1,3-dihydroxy-10-methyl-9-acridone (13) has been obtained. Chlorination of 2a with SO2Cl2 in CHCl3 gave-4-chloro- (14) and 2,4-dichloro-1-hydroxy-3-methoxy-10-methyl-9-acridone (15). The reaction of 3b with copper(I) phenyl- and copper(I) isopropenylacetylide yielded the corresponding 2-substituted 4-methoxy-6-methylfuro[2,3-α]acridin-11(6H)-ones 6a and 6b, respectively. From the condensation reaction of 3c with 3-chloro-3-methyl-1-butyne noracronycine (8) has been obtained.
    Notes: Die I2/HIO4-Iodierung von 1,3-Dihydroxy-10-methyl-9-acridon (2c) und seiner Ether 2a und 2b ergab die entsprechenden 2-Iod-Derivate 3a-c. Bromierung von 2a mit NBS führte zu 2-Brom-(10), 4-Brom-(11) sowie geringen Mengen von 2,4-Dibrom-1,3-dimethoxy-10-methyl-9-acridon (12). Unter denselben Bedingungen lieferte 2c 2-Brom-1,3-dihydroxy-10-methyl-9-acridon (13). Chlorierung von 2a mit SO2Cl2 in CHCl3 ergab 4-Chlor-(14) und 2,4-Dichlor-1-hydroxy-3-methoxy-10-methyl-9-acridon (15). Umsetzen von 3b mit Kupfer(I)-phenyl- bzw. Kupfer(I)-isopropenylacetylid führte zu den 2-substituierten 4-Methoxy-6-methylfuro[2,3-α]acridin-11(6H)-onen 6a und 6b. Die Reaktion von 3c mit 3-Chlor-3-methyl-1-butin ergab Noracronycin (8).
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  • 42
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1984 (1984), S. 66-77 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of the Methyl Ether of “Herzgift-Methylreduktinsäure” Starting from D-GlucoseThe methyl ether 5 of „Herzgift-Methylreduktinsäure“ (2), a degradation product of the Calotropis cardenolides, has been synthesized starting from D-glucose as the chiral pool. The configuration of 2, previously based on the results of degradation, is confirmed by the synthesis of 5.
    Notes: Der Methylether 5 der „Herzgift-Methylreduktinsäure“ (2), eines Abbauproduktes der Calotropis-Cardenolide, wird in einer mehrstufigen Synthese aus D-Glucose als chiralem Ausgangsmaterial hergestellt. Damit wird die durch Abbaureaktionen getroffene Konfigurationszuordnung für 2 durch Synthese von 5 bestätigt.
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  • 43
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1984 (1984), S. 85-97 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aminoethynyl Metallations, 313.  -  Synthesis and Reactions of 3-AminopropiolamidinesThe lithium aminoacetylides 1 react with the carbodiimides 2 to give the lithium propiolamidinates 3, which are hydrolyzed to yield the 3-aminopropiolamidines 4. 3 can directly be converted into the persubstituted ynamine carboxamidines 5 by adding methyl iodide. The amidines 4 with less activated C/C-triple bonds (NR1R2 = N(Me)Ph or NPh2) react with thioformaldehyde dioxide or with diphenyl ketene exclusively at the NH group with formation of the sulfonamides 6 or of an carboxamide 7. The more reactive (diethylaminoacetylene)carboxamidine 4h adds a second molecule of ketene to furnish the cyclobutenone derivative 8. The propiolamidine 4b with a diphenylamino group at the triple bond reacts with concentrated hydrochloric acid under formation of the amidinium salt 9 and partly by addition of a second molecule of hydrochloride to the triple bond to give 10. Adding tosyl azide to 4 we obtained via the triazole 11 by two successive 1,5-cyclizations the 4-amidino-1,2,3-triazoles 12. The 3-aminopropiolamidines 4 bearing at least one aryl group in the amidine moiety cyclize to give the 2,4-diaminoquinolines 17 if they are chromatographed on silica gel. The same or analogously substituted quinolines 17 are obtained by the reaction of the simple ynamines 15(H, Me, or Ph in the β-position) with the corresponding carbodiimides 2 2-Anilino-4-diethylamino-3-methylquinoline (17e) is hydrolyzed in acidic solution to give the 4-quinolone derivative 19.
    Notes: Die Lithium(aminoacetylide) 1 reagieren mit den Carbodiimiden 2 zu den Lithiumpropiolamidinaten 3, deren Hydrolyse die 3-Aminopropiolamidine 4 liefert. Mit Methyliodid entstehen aus 3 die persubstituierten Inamincarboxamidine 5. Die Amidine 4 reagieren bei geringer Aktivierung der Dreifachbindung [NR1R2 = N(Me)Ph oder NPh2] mit Sulfen oder mit Diphenylketen ausschließlich an der NH-Gruppe unter Sulfonamid- bzw. Carboxamidbildung (s. 6 und 7). Das reaktivere (Diethylaminoacetylen)carboxamidin 4h addiert bei der Umsetzung mit Diphenylketen zusätzlich ein Ketenmolekül an der Dreifachbindung zum Cyclobutenonderivat 8. Der Propiolamidinvertreter 4b mit Diphenylaminogruppe an der Dreifachbindung reagiert mit konz. Salzsäure unter Bildung des Amidiniumsalzes 9, und unter Addition von Chlorwasserstoff an die Dreifachbindung zu 10, Mit Tosylazid erhält man nach der Triazolbildung 11 in zwei aufeinanderfolgenden 1,5-Cyclisierungen die 4-Amidino-1,2,3-triazole 12. Die 3-Aminopropiolamidine 4 mit mindestens einer Arylgruppe im Amidinteil cyclisieren im Kontakt mit Silicagel zu den 2,4-Diaminochinolinen 17. Die gleichen oder analog substituierten Chinoline 17 erhält man auch durch Umsetzung der einfachen Inamine 15 (Wasserstoff, Methyl- oder Phenylgruppen in β-Position) mit den entsprechenden Carbodiimiden 2. 2-Anilino-4-diethylamino-3-methylchinolin (17e) wird in saurem Medium zum 4-Chinolonderivat 19 hydrolysiert.
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  • 44
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    Liebigs Annalen 1984 (1984), S. 127-132 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of Pterocarpan Constituents of Swartzia laevicarpaThe synthesis of 2,8-dihydroxy-3,4-dimethoxy- (1), 2,8-dihydroxy-3,9,10-trimethoxy- (2), 8-hydroxy-3,4,9,10-tetramethoxy- (3), and 2,8-dihydroxy-3,4,9,10-tetramethoxypterocarpan (4)  -  each of them as racemate  -  confirmed the constitution of four new pterocarpans isolated from Swartzia laevicarpa.
    Notes: Durch die eindeutige Synthese von jeweils racemischem 2,8-Dihydroxy-3,9-dimethoxy- (1), 2,8-Dihydroxy-3,9,10-trimethoxy-(2), 8-Hydroxy-3,4,9,10-tetramethoxy-(3) und 2,8-Dihydroxy-3,4,9,10-tetramethoxypterocarpan (4) wurde die Konstitution von vier neuen, aus Swartzia laevicarpa isolierten Pterocarpanen bestätigt.
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  • 45
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    Liebigs Annalen 1984 (1984), S. 147-156 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Diastereoselective Synthesis of (1RS)-endo-Brevicomin(1RS-endo-Brevicomin (1) is synthesized starting from trans-1-bromo-2-pentene. Synthetic key step is the diastereoselective linkage of erythro-2,3-butanediol to 3,3-dimethoxy-1-(phenylsulfonyl)-butane or methyl 4,4-dimethoxypentanoate.
    Notes: (1RS)-endo-Brevicomin (1) wird ausgehend von trans-1-Brom-2-penten synthetisiert. Schlüsselreaktion ist die diastereoselektive Verknüpfung von erythro-2,3-Butandiol mit 3,3-Dimethoxy-1-(phenylsulfonyl)butan oder 4,4-Dimethoxypentansäure-methylester.
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  • 46
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Cycloarenes, a New Class of Aromatic Compounds, IV. - Attempts to Synthesize cyclo-[d.e.e.d.e.e.d.e.e]nonakisbenzene and cyclo[d.e.d.e.d.e.d.e.d.e]decakisbenzeneWith the aim to synthesize 3 the dithiaphane 5 was prepared from which via 6 the [2]anthraceno[2]benzo[c]phenanthrenophane 10 was obtained. The corresponding [2.2]phane-diene 11 was prepared from 5 via 12 and 13. The conformations of 5, 10, and 11 yielded 14 which was dehydrogenated to yield the new aromatic system 15. The second internal ring closure to 3 so far did not succeed. - As precursors for the synthesis of 4 the [2]dibenzo[a, j]anthraceno[2]anthraceno[2]phenanthrenophanes 19 and 20 as well as the corresponding [2.2]phane-dienes 23 and 24 were prepared via 18.Attempts to cyclodehydrogenate to 4 failed. In this context the conformations of 19, 20, 23, and 24 are discussed based on 1H NMR spectra.
    Notes: Mit dem Ziel der Synthese von 3 wurde das Dithiaphan 5 dargestellt, das über 6 in das [2]Anthraceno[2]benzo[c]phenanthrenophan 10 übergeführt wurde. Das entsprechende Phandien 11 wurde aus 5 über 12 und 13 erhalten. Die Konformationsverhältnisse von 5, 10 und 11 werden anhand der 1H-NMR-Spektren diskutiert. - Aus 11 entstand durch nicht-oxidative Photocyclisierung 14, das zu dem neuen aromatischen Bindungssystem 15 dehydriert wurde. Der zweite innere Ringschluß zu 3 gelang bisher nicht. - Als Vorstufen für die Synthese von 4 wurden über 18 die [2]Dibenz[a, j]anthraceno[2]phenanthrenophane 19 und 20 sowie die entsprechenden [2.2]Phandiene 23 und 24 dargestellt. Versuche der Cyclodehydrierung zu 4 schlugen fehl. In diesem Zusammenhang werden die Konformationsverhältnisse von 19, 20, 23 und 24 auf der Basis von 1H-NMR-Daten diskutiert.
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  • 47
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    Liebigs Annalen 1984 (1984), S. 773-782 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Selective Reactions of Hydroazulenes: Chiral Norcarane Derivatives by the Reaction of a Dihydroazulene with Singlet OxygenPhotosensitized oxygenation of the dihydroazulene 6 affords the two peroxides 7 and 8 in good overall yield. The major product is derived from the “norcaradiene” of 6. The cycloaddition with singlet oxygen occurs stereospecifically. Consecutive reaction of 7 yield chiral norcarane derivatives in stereospecific ways. Thus, by thermolysis of 7 the bisepoxide 10 is formed; reaction of 7 with triethylamine leads to the hydroxyketone 11 with MnO2 the homoquinone 13 is formed. The structures are established by spectroscopic methods.
    Notes: Die Umsetzung des Dihydroazulens 6 mit Singulettsauerstoff ergibt die beiden Peroxide 7 und 8. Das Hauptprodukt 7 leitet sich vom “Norcaradien” des Hydroazulens 6 ab. Die 1O2-Addition erfolgt stereoselektiv. Folgereaktionen von 7 ergeben chirale Norcaranderivate: Thermolyse führt zum Bisepoxid 10, mit Triethylamin entsteht das Hydroxyketon 11 und Triphenylphosphan führt unter Sauerstoffabspaltung zu den Vinyloxiranen 12a und 12b. Bei diesen Reaktionen wird jeweils nur ein Diastereomeres gebildet. Die Oxidation von 11 mit Mangandioxid ergibt das Homochinon 13. Für sämtliche Reaktionsprodukte sind spektroskopische Daten angegeben.
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  • 48
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    Liebigs Annalen 1984 (1984), S. 791-801 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses of (+)-Oudemansin and (+)-Epioudemansin Starting from Enantiomerically Pure Precursors; Absolute configuration of the Naturally Occurring (-)OudemansinThe syntheses of the four optically pure methyl (E)-3-hydroxy-2-methyl-5-phenyl-4-pentenoates (+)- and (-)-5 as well as (+)- and (-)-6 were achieved by consecutive methylation and protonation of enolates, starting from (+)- and (-)-4. The esters (+)-6 and (-)-5 are used as starting materials to synthesize (+)-oudemansin [(+)-3] and (+)-epioudemansin [(+)-9].
    Notes: Die Darstellung der vier optisch reinen (E)-3-hydroxy-2-methyl-5-phenyl-4-pentensäure-methylester (+)- und (-)-6 gelingt durch aufeinanderfolgende Methylierung und Protonierung von Esterenolaten, ausgehend von (+)- und (-)-4. Die Ester (+)-6 und (-)-5 werden für Synthesen von (+)-Oudemansin [(+)-3] und (+)-Epioudemansin [(+)=9] eingesetzt.
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  • 49
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    Liebigs Annalen 1984 (1984), S. 820-827 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A Flexible and efficient Synthesis of Methyl 4-Oxo-2-alkenoatesThe title compounds E are obtained in good yield by low temperature ring cleavage of the easily available methyl 2-siloxycyclopropanecarboxylates C with bromine and subsequent elimination of hydrogen bromide. Due to the variability of C a high flexibility concerning substituents R1-R4 in products E is guaranteed. 2-Alkyl- and 2-methylthio-substituted olefins are thus effectively synthesized. In several cases the initally formed methyl 2-bromo-4-oxoalkanoates F are stable enough to be isolated in high yield.
    Notes: Aus den leicht zugänglichen 2-Siloxycyclopropancarbonsäure-methylestern C erhält man durch Ringöffnung mit Brom bei tiefer Temperatur und anschließender Bromwasserstoffeliminierung die Titelverbindungen E in guten Ausbeuten. Aufgrund der Variationsmöglichkeiten bei C ergibt sich bei den Produkten E eine große Flexibilität bezüglich der Reste R1-R4. So sind auch 2-alkyl- und 2-methylthiosubstituierte Olefine effektiv darstellbar. In einigen Fällen sind die primär gebildeten 2-Brom-4-oxoalkansäure-methylester F so stabil, daß sie in hoher Ausbeute isolierbar sind.
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  • 50
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    Liebigs Annalen 1984 (1984), S. 828-830 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ring Opening of Methyl 2-(Trimethylsilylmethyl)cyclopropanecarboxylateThe reactivity of the title compound 5 is compared with that of methyl 2-siloxycyclopropanecarboxylates. 2. Whereas these are cleaved under various conditions, the less activated derivative 5 undergoes ring opening to yield methyl pentenoate (6a) only with sources of “free” flouride-like tetra-n-butylammonium fluoride.
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  • 51
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    Liebigs Annalen 1984 (1984), S. 381-388 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 1-Aza- and 1,9-DiazatriptycenesThe polycyclic 1,5-diketone 4 is synthesized via the enamine 2 from ketone 1 and phenyl vinyl ketone (3). On reacting the 1,5-diketone 4 with hydroxylamine the expected ring closure to the 1-azatriptycene 6 competes with a ring cleavage by an anomalous Beckmann rearrangement of the oxime yielding the intermediate nitrile 10 which cyclizes to afford the β-anthracenyl-α-aminopyridine 7. [4 + 2] Cycloaddition of dehydrobenzene, generated by diazotation of anthranilic acid, with the pyrido[3,2-g]quinolines 13a, b produces the diazatriptycenes 15a, b.
    Notes: Aus dem Keton 1 wird via Enamin 2 mit Phenylvinylketon (3) das polycyclische 1,5-Diketon 4 hergestellt. Bei dessen Umsetzung mit Hydroxylamin konkurriert der erwartete Ringschluß zum 1-Azatriptycen 6 mit einer Ringöffnung durch anomale Beckmann-Umlagerung des Oxims 9 zum intermediären Nitril 10, das zum β-Anthracenyl-α-aminopyridin 7 cyclisiert. [4 + 2]-Cycloaddition von Dehydrobenzol, das durch Diazotierung von Anthranilsäure erzeugt wird, mit den Pyrido[3,2-g]chinolinen 13a, b ergibt die Diazatriptycene 15a, b.
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    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Multistep Reversible Redox Systems, XXXV.  -  Voltammetry of Vinylogous Polyenes with Cross-Conjugated End Groups and UV/VIS Spectroscopy of their Radical Anions and CationsMost of the polyenes 1-5, especially of the vinylogous 2.n(n = 0-4) and 5.n(n = 1-4) are as well reversibly reduced as oxidized in two steps. As expected the large semiquinone formation constants decrease with increasing chain length (2: KSEMc = 1013-107; KSEMa = 1011-101). The UV/VIS spectra of the radical anions and cations of system 2.n, generated in solution, belong to the violene type; Δλmax ≈ 135 nm (SEMc) and Δλmax ≈ 160 nm (SEM). The potentials of 5.n and the UV/VIS spectra of the radicals of 5.1 point towards twisted molecules. The systems 2.n are the first polyenes which can exist in five oxidation levels and which form persistent radical anions and cations. The redox potentials of 2.n and the UV/VIS spectra of the radical ions are in accordance with the predictions of the Hückel theory.
    Notes: Die Mehrzahl der Polyene 1-5, insbesondere der Vinylogen 2.n (n = 0-4) und 5.n (n = 1-4) werden sowohl reversibel zweistufig reduziert als auch oxidiert. Erwartungsgemäß nehmen die großen Semichinonbildungskonstanten mit wachsender Kettenlänge ab (2: KSEMc = 1013-107; KSEMa = 1011-101). Die UV/VIS-Spektren der in Lösung erzeugten Radikalanionen und-kationen des Systems 2 (n = 0-4) sind vom Violentyp mit Δλmax ≈ 135 nm (SEMc) und Δλmax ≈ 160nm (SEM). Die Potentiale des Systems 5.n sowie die UV/VIS-Spektren der Radikal-Ionen aus 5.1 weisen auf Verdrillung hin. Mit 2.n liegen erstmals Polyene vor, die in fünf Oxidationsstufen existieren können und deren Radikal-Ionen persistente Lösungen bilden. Sowohl die Redoxpotentiale von 2.n als auch die UV/VIS-Spektren der Radikal-Ionen entsprechen den Erwartungen der Hückel-Theorie.
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  • 53
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Confomational Analysis, XXIV. - determination of the Conformations of Tri-and Tetrasaccharide Sequences of N-Glycoproteins. The problem of the (1 → 6)-glycosidic BondThe preferred solution conformations of the saccharides α-D-Man(1 → 3)-β-D-Man(1 → 4)-D-GIcNAc (1), α-D-Man(1 → 6)-β-Man(1 → 4)-D-GIcNAc (2), and α-D-Man(1 → 3)[α-D-Man(1 → 6)]lβ-D-Man(1 → 4)-D-GIcNAc3), which are known as parts of the core structure of N-glycoproteins, could be established by use of HSEA calculations (HSEA: Hard-Sphere Exo-Anomeric) with the new program GESA (= Geometry of Saccharides) in connection with 1H NMR investigations like NOE experiments, spin-lattice relaxation-time measurements and the observation of selective deshieldings. (1 → 3)- and (1 → 4)-glycosidic bonds show one strongly preferred conformation. The greater flexibility of the (1 → 6)-glycosidic bonds show one strongly preferred conformation. The greater flexibility of the (1 → 6)-glycosidic bond will be discussed in details. For the spectra analysis various 2-D techniques have been used.
    Notes: Von den Sacchariden α-D-Man(1 → 3)-β-D-Man(1 → 4)-D=-GICNAc (1), α-D-Man(1 → 6)-β-D-Man(1 → 4)-D-GIcNAc(2) und α-D-Man(1 → 3)[α-D-Man(1 → 6)]-β-D-Man(1 → 4)-D-GlcNAc(3), die als Core-Struktur in N-Glycoproteinen vorkommen, wurden durch HSEA-Berechnungen (HSEA: Hard-Sphere Exo-Anomeric) mit dem neuen GESA-Programm (GESA: Geometry of Saccharides) die bevorzugten Konformationen bestimmt. Mit Hilfe von 1H-NMR-Experimenten, nämlich NOE-Experimenten, Spin-Gitter-Relaxationszeitmessungen und der Beobachtung selektiver Entschirmungen, ließen sich diese Konformationen in Lösung bestätigen. (1 → 3)- und (1 → 4)-glycosidische Bindungen weisen eine stark bevorzugte Konformation auf. Die weitaus größere Flexibilität der (1 → 6)-glycosidischen Bindung wird besonders diskutiert. Zur Analyse der Spektren wurden verschiedene 2-D-NMR-Techniken angewandt.
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  • 54
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    Liebigs Annalen 1984 (1984), S. 1003-1012 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions with Isocyanides. - Synthesis of Dark-blue Dyes from 1,4-Quinones and Aryl Isocyanides1,4-Benzoquinone reacts with aryl isocyanides 2a-d in boiling toluene or xylene forming darkblue 1:2 and 1:4 adducts, the 4,7-isoindolediones 3a-d and the 1,5- and 1,7-bis(arylamino)-benzodipyrrolediones 4a-c and 5a-c, respectively, which can be separated by chromatography. The structure of the 4-methylphenyl isocyanide adducts 3b, 4b, and 5b is established by NMR spectroscopy. The 1:2 adduct 3b reacts with two moles of 4-methylphenyl isocyanide (2b) affording the isomeric 1:4 adducts 4b and 5b. However, in a similar reaction with 4-chlorophenyl isocyanide (2c) surprisingly only the 1,5-bis(arylamino) derivative 8 is isolated. 1,4-Naphthoquinone (10) reacts with 4-methylphenyl (2b or 4-nitrophenyl isocyanide (2d) to yield the 4,9-benzo[f]isoindoles 11b and d, respectively.
    Notes: 1,4-Benzochinon reagiert mit den Arylisocyaniden 2a-d in siedendem Toluol oder Xylol zu tiefblauen 1:2- und 1:4-Addukten, den 4,7-Isoindoldionen 3a-d bzw. den 1,5- und 1,7-Bis(arylamino)benzodipyrroldionen 4a-c und 5a-c, die chromatographisch getrennt werden. Die Struktur der (4-Methylphenyl)isocyanid-Addukte 3b, 4b und 5b wird NMR-spektroskopisch bewiesen. Das 1:2-Addukt 3b ergibt mit zwei Molen (4-Methylphenyl)isocyanid (2b) die isomeren 1:4-Addukte 4b und 5b; mit (4-Chlorphenyl)isocyanid (2c) wird jedoch überraschenderweise nur das 1,5-Bis(arylamino) Derivat 8 isoliert. 1,4-Naphthochinon (10) bildet mit (4-Methylphenyl)-(2b) bzw. (4-Nitrophenyl)isocyanid (2d) die 4,9-Benzo[f]isoindoldione 11b und d.
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  • 55
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reactions of 1,4-Pentadien-3-ones, 22. - Synthesis and Structure of the Epimers of 3,5-Diaryl-4-hydroxy-1,4-thiazinane 1,1-DioxidesDistyrylsulfones 1 react with the ambident nucleophile hydroxylamine only by double addition of nitrogen to give 4-hydroxy-1,4-thiazinane derivatives 3. In solution 3 consists of a temperature-dependent equilibrium mixture of two epimers. When heated or when crystallized one of the epimers is depopulated. The above phenomena and structures are elucidated by an X-ray analysis and by NMR spectroscopy.
    Notes: Distyrylsulfone 1 reagieren mit dem ambidenten Nucleophil Hydroxylamin ausschließlich unter doppelter Addition des Stickstoffs zu 4-Hydroxy-1,4-thiazinan-Derivaten 3. Diese bilden in Lösung temperaturabhängige Epimeren-Gleichgewichte. Sowohl beim Erwärmen als auch beim Auskristallisieren erfolgt Depopulation eines Epimers. Strukturen und Phänomene werden durch Röntgenstrukturanalyse und NMR-Spektroskopie geklärt.
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  • 56
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    Liebigs Annalen 1984 (1984), S. 1052-1055 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Iodation of Monosaccharide Derivatives with IodotrimethylsilaneWith iodotrimethylsilane generated in situ, iodine can be introduced into carbohydrate derivatives with high selectivity. The rate of iodination at the anomeric center of the C-1-substituted 2,3,4,6-tetra-O-acetyl-D-glucopyranoses 1a-d decreases in the following series: OAc 〉 OBz ≈ OH » OCH3. - Hydroxy groups or their ethers 3b, c react distinctively to give the trimethylsilyl ethers, whereas the primary react to yield the 6-deoxy-6-iodo derivatives 5. The 1-O-acetyl-6-hydroxy derivative 6a and its 6-O-trityl ether form 2,3,4-tri-O-acetyl-6-deoxy-6-iodo-α-D-glucopyranosyl iodide (7).
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  • 57
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    Liebigs Annalen 1984 (1984), S. 1068-1077 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: An Attempted Synthesis of Polystachin[1′RS(3RS)]-1-(2,3-Dihydro-4-hydroxy-6-methoxy-1-benzofuran-3-yl)-2-methyl-1,2-propandiol (21), a partial structure of the title substance 1 was synthetized in 11 steps from phloroglucinol. The key steps were the oxidative rearrangement of the benzylidenacetone derivative 5 by Tl(NO3)3 in methanol to yield the 2-aryl-1,1-dimethoxythane 8 followed by ring closure involving the hydroxy group of 9 liberated by debenzylation. Conversion of 21 into compounds of structure 1 was just as unsuccessful as the synthesis of rac-polystachin (rac-1) from tachrosin (23 via the flavone derivative 29.
    Notes: [1′RS(3RS)]-1-(2,3-Dihydro-4-hydroxy-6-methoxy-1-benzofuran-3-yl)-2-methyl-1,2-propandiol (21), eine Teilstruktur der Titelsubstanz 1, wurde aus Phloroglucin in 11 Schritten synthetisiert. Als Schlüsselreaktion diente die oxidative Umlagerung des Benzalacetonderivates 5 mit Tl(NO3)3 in Methanol zu dem 2-Aryl-1,1-dimethoxyethan 8 gefolgt vom Ringschluß an der durch Entbenzylierung freigesetzten Hydroxygruppe von 9. Die Überführung von 21 in Verbindungen der Struktur 1 blieb ebenso erfolglos wie die Synthese von rac-Polystachin (rac-1) aus Tachrosin (23) über das Flavonderivat 29.
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  • 58
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    Liebigs Annalen 1984 (1984), S. 1109-1116 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemistry of Dimethyl [1α,2β,5α,6β,7α,8β]-3,4-Dioxotricyclo[4.2.1.02,5]nonane-7,8-dicarboxylateThe reaction of the cyclobutanedione 1 with urea or substituted thioureas provides by double addition the heterocyclic compounds 2a-d. Hydrazines react to give monohydrazones 3 or, by loss of nitrogen, hydrazones of type 4; no formation of osazones was observed. The reaction with o-phenylenediamine yields the quinoxaline 5. Reduction of 1 with sodium tetrahydroborate leads stereoselectively to the glycol 6. Treatment of 1 with sodium methoxide causes benzilic acid rearrangement yielding the annulated cyclopropanecarboxylate 7 with retention of the configuration of the other carbon atoms. Ring enlargement reactions yield either by radiation of 1 via oxacarbenes compound 14 or by oxidation the anhydride 8 which can be reduced to yield the γ-lactone 9.
    Notes: Die Umsetzung des Cyclobutandions 1 mit Harnstoff oder substituierten Thioharnstoffen führt durch zweifache Addition unter Cyclisierung zu den Imidazolidinonen bzw. -thionen 2a-d. Hydrazinabkömmlinge liefern Monohydrazone 3 oder unter Stickstoffabspaltung Hydrazone vom Typ 4; Osazonbildung wurde nicht beobachtet. Mit o-Phenylendiamin entsteht unter Kondensation das Chinoxalin 5. Die Reduktion von 1 mit Natrium-tetrahydroborat liefert stereoselektiv das Glycol 6. Mit Natriummethanolat findet eine Benzilsäure-Umlagerung zum anellierten Cyclopropancarbonsäureester 7 unter Erhaltung der Konfiguration der restlichen C-Atome statt. Ringerweiterungen lassen sich sowohl photochemisch über Oxacarbene zu 14 als auch durch Oxidation zum Anhydrid 8 durchführen, das durch anschließende Reduktion das Norbornan-anellierte γ-Lacton 9 liefert.
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  • 59
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    Liebigs Annalen 1984 (1984), S. 608-611 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Syntheses with α-Metalated Isocyanides, LIII.  -  Synthesis of Methyl 2,3-Epoxy-2-isocyanoalkanoatesThe title compounds were synthesized from methyl α-isocyanoacrylates 2 with H2O2 (in sodium hydroxide solution) or with m-chloroperbenzoic acid (in methanol/sodium methoxide)
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  • 60
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    Liebigs Annalen 1984 (1984), S. 600-607 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese und biologische Aktivität des Antibiotikums B 371 und seiner StrukturvariantenDie Synthesen der Titelverbindung 1 und einer Reihe von Strukturvarianten des Typs 4 werden beschrieben. Die antimikrobiellen Aktivitäten dieser Vinylisocyanide, die in β-Position entweder ein Indolderivat oder eine Aryl- oder 2-Thienylgruppe tragen, wurden im Plattentest gegenüber Escherichia coli, Bacillus subtilis und Mucor muhei TÜ 284 geprüft (Tab. 1). Einige der Verbindungen 4 sind stärker wirksam als die natürlich vorkommende Stammverbindung 1.  -  Eine Serie von Alkyl-2-isocyanacrylaten des Typs 5 wurde in den Test einbezogen. Einige davon sind außerordentlich stark aktiv (Tab. 2). Die Aktivität geht in allen Fällen verloren, wenn man die Isocyangruppe zur Formamidogruppe hydrolysiert (4 → 6).
    Notes: The synthesis of the title compound 1 is described as well as the syntheses of a series of structural analogs of type 4. The antimicrobial in vitro activity of these vinyl isocyanides, substituted in β-position either by an indole derivative or by an aryl or 2-thienyl group, was tested against Escherichia Coli, Bacillus subtilis, and Mucor muhei TÜ 284 (Table 1). Some of the compounds 4 display higher activity than the naturally occurring parent compound 1.  -  A variety of alkyl 2-isocyanoacrylates of type 5 were included in the biological test. Some of them display exceptionally high antimicrobial activity (Table 2). Upon conversion of the isocyano group into the formamido group (4 → 6), the biological activity is lost.
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  • 61
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    Liebigs Annalen 1984 (1984), S. 615-617 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: [2.2](2,7)Anthracenophane: Synthesis and Conformational Studies[2.2](2,7)Anthracenophane (3) was synthesized via the dithia[3.3]anthracenophane 6 and the disulfone 7 derived therefrom. From conformational studies based on 1H NMR a rigid anti conformation was assigned to 3, contrary to 6.
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  • 62
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multistep, Reversible Redox Systems, XXXVI.  -  11,11,12,12-Tetracyano-9,10-anthraquinodimethane (TCNAQ) and its Derivatives: Synthesis and Redox PropertiesTitle compounds 3Ba-d are synthesized from the corresponding anthraquinones and malononitrile with titanium tetrachloride/pyridine. By comparison of the potentials and semiquinone formation constants of 1B-3B with those of the corresponding quinones 1A-3A strong distortion of the biscyanomethylene groups in 2B and especially 3B is derived.
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  • 63
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    Liebigs Annalen 1984 (1984), S. 636-640 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stereospezifische Synthesen von D-Ossamin und D-Tolyposamin2,3,4,6-Tetradesoxy-4-(dimethylamino)-D-threo-hexose (D-Ossamin, 7), der Aminozuckerrest des Pilzmetaboliten Ossamycin und 4-Amino-2,3,4,6-tetradesoxy-D-erythro-hexose (D-Tolyposamin, 12), das Enantiomere des Zuckerrestes des antibiotisch wirksamen Tolypomycins wurden aus D-Glucose über Hex-2-enopyranoside synthetisiert.
    Notes: 2,3,4,6-Tetradesoxy-4-(dimethylamino)-D-threo-hexose (D-ossamine, 7), the amino sugar fragment from the fungal metabolite ossamycin, and 4-amino-2,3,4,6-tetradeoxy-D-erythro-hexose (D-tolyposamine, 12), the enantiomeric constituent of the antibiotic tolypomycin, have been synthesized from D-glucose via hex-2-enopyranosides.
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  • 64
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    Liebigs Annalen 1984 (1984), S. 649-679 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses with Aliphatic Dialdehydes, XXXVIII. - Synthesis and Properties of CycloalkylmalonaldehydesVilsmeier formylation cycloalkyl-substituted enol ethers (7, 14a - c, 23) yields the cycloalkylmalonaldehydes 1- 5 for the first time. In solution 1 - 5 with suitable electrophiles and nucleophiles leads to cycloalkyl-substituted open-chain (29, 30), carbocyclic (31) as well as heterocyclic compounds (32-40) with peculiar properties due to the presence of the lipophilic cycloalkyl group.
    Notes: Durch Vilsmeier-Formylierung cycloalkylsubstituierter Enolether (7, 14a - c, 23) werden die Cycloalkylmalonaldehydes 1 - 5 erstmals dargestellt. In Lösung liegen 1 - 5 in der (E)-s-(E)-Enolform als vinyloge Carbonsäuren vor. Reaktion von 1-5 mit geeigneten Elektrophilen und Nucleophilen führt zu cycloalkylsubstituierten offenkettigen (29, 30), carbocyclischen (31) und heterocyclischen Verbindungen (32-40) mit besonderen, durch die lipophile Cycloalkylgruppe hervorgerufenen Eigenschaften.
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  • 65
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (2′→5′) and (3′→′)-Tubercidylyl-tubercidins - Synthesis via Phosphite Triester and Investigation of Secondary StructureThe (2′→ 5′)- and (3′→5′)-linked dinucleoside monophosphates 3e and 2e of tubercidin were synthesized by condensation of the monomers 1c or 1b with dichloromethoxyphosphane. By 1H NMR studies it could be demonstrated that the conformation of these nucleobases is different from that in (3′→ 5′)ApA and (2′→ 5′)ApA. From thermodynamic parameters, as well as from hypochromicity, a stronger base - base interaction in 3e than in 2e was deduced. Single-strand specific nuclease S1 hydrolyses 2e at a much higher rate than (3′→ 5′)ApA demonstrating that the enzyme is sensitive towards modification of the aglycone. Condensation of the 5′-deprotected dimer 3b with the monomer 1c followed by complete deprotection yields (2′→ 5′)TupTuTu (4e), which is an analogue of (2′→ 5′)ApApA, the triphosphate of which is antivirally active.
    Notes: Die (2′→ 5′)- und (3′→ 5′)-verknüpften Dinucleosid-monophosphate 3e und 2e des Tubercidins werden aus den Vorstufen 1b oder 1c und 1a durch Kondensation mit Dichlormethoxyphosphan erhalten. Mit 1H-NMR-Untersuchungen konnte gezeigt werden, daß die Nucleobasen eine andere Konformation als im (2′→ 5′)- oder (3′→ 4′)ApA einnehmen. Aus thermodynamischen Parametern sowie der Hypochromizität ergibt sich für 3e eine größere Basenwechselwirkung als für 2e. Einzelstrang-spezifische Nuclease S1 spaltet 2e deutlich schneller als (3′→ 5′)ApA und reagiert damit empfindlich auf die Aglyconmodifikation. Die Kondensation des 5′-entschützten Dimers 3b mit dem Monomer 1c, gefolgt von der Abspaltung der Schutzgruppen, führt zu (2′→ 5′)-TupTupTu (4e). Dies stellt ein Analogon von (2′→ 5′)ApApA dar, das als Triphosphat antiviral wirksam ist.
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  • 66
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemistry and Stereochemistry of Iridoids, IV. - Synthesis and X-Ray Structure Analysis of 15-Methyl-12-epi-prostaglandin F2βCrystalline(15R)- and (15S)-15-methyl-12-epi-PGF2β [15R)-5b and 5b] are synthesized enantiomerically pure starting from (1S,6R,9R)-(+)-7,9-bis(p-phenylbenzoyloxy)-3-oxabicyclo- [4.3.0]nonan-2-ol (1), which is prepared from catalpol. Contrary to our described synthesis of 12-epi-PGF2β, the intermediate products 2-5a are crystalline by virtue of the introduction of the p-phenylbenzoyl protecting group. Thus, their physical constants could be determined unequivocally. The X-ray structure analysis of (15R)-15-epi-PGF2β proves the correctness of our earlier statements based on analytical and spectroscopical investigations.
    Notes: Ausgehend von dem aus Catalpol hergestellten (1S,6R,7R,9R)-(+)-7,9-Bis(p-phenylbenzoyloxy)-3-oxabicyclo[4.3.0]nonan-2-ol (1) werden (15R)- und (15S)-15-Methyl-12-epi-PGF2β [(15R)-5b und 5b] kristallin und enantiomerenrein synthetisiert. Im Gegensatz zu der von uns beschriebenen Synthese von 12-epi-PGF2β sind durch die Einführung der p-Phenylbenzoyl-Schutzgruppen auch die Zwischenprodukte 2-5a kristallin, so daß ihre physikalischen Konstanten eindeutig bestimmt werden konnten. Die Röntgenstrukturanalyse von (15R)-15-Methyl-12-epi-PGF2β beweist, daß die von uns aus den analytischen und spektroskopischen Untersuchungen gemachten Aussagen richtig sind.
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  • 67
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    Liebigs Annalen 1984 (1984), S. 877-887 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 5,10-Bridged Pyrido[3,2-g]quinolines via [4+2] Cycloaddition of Dienophiles to Pyrido[3,2-g]quinolinesIn a Diels-Alder reaction, (E)-1,2-dichloroethene (5a), α-acetoxyacrylonitrile (5b), and maleic anhydride (8), respectively, add to the medium ring of some pyrido[3,2-g]quinolines to afford the 5,10-bridged pyrido[3,2-g]quinolines 6a - c, e, f, and 9a - c, respectively. The regioisomeric α-acetoxyacrylonitrile adducts of 4b arise in a ration of 6e:6f = 94.6. On hydrolysis of this mixture, only ketone 7 is obtained. The structures of all compounds are proven by their proton and carbon-13 spectra.
    Notes: (E)-1,2-Dichlorethen (5a), α-Acetoxyacrylnitril (5b) bzw. Maleinsäureanhydrid (8) addieren sich in einer Diels-Alder-Reaktion an den mittleren Ring einiger Pyrido[3,2-g]chinoline 4 zu den 5, 10-überbrückten Pyrido[3,2g]chinolinen 6a - c, e, f bzw. 9a - c. Die regioisomeren α-Acetoxyacrylnitril-Addukte von 4b entstehen dabei im Verhältnis 6e:6f = 94:6. Durch Hydrolyse erhält man daraus das einheitliche Keton 7. Die Strukturen aller Verbindungen wurden 1H- und 13C-NMR-spektroskopisch bewiesen.
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  • 68
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemistry of Reactive Cations Derived from Sulfur Dioxide Analogues, X. - Reaction with Aromatic carbodiimides - Synthesis of BenzothiadiazinesDiphenyl- and bis(4-methoxyphenyl)carbodiimide react with N-methyl-N-sulfinylmethanaminium tetrafluoroborate (2) to give benzothiadiazine 1-oxides 3. The structure of the substituted compound 3a was determined, the course of the complex reaction is discussed.
    Notes: Diphenyl- und Bis(4-methoxyphenyl)carbodiimid reagieren mit N-Methyl-N-sulfinylmethanaminium-tetrafluoroborat (2) unter Bildung von Benzothiadiazin-1-oxiden 3. Die Struktur der substituierten Verbindung 3a wurde bestimmt, der Verlauf der komplexen Reaktion wird diskutiert.
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  • 69
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese von Peptiden mit α,β-Dehydroaminosäuren, I. - Synthese von N-(Benzyloxycarbonyl)-und N-(Trifluoracetyl) dipeptiden von Dehydroalanin und DehydrophenylalaninDie Kondensation von Nα-(Benzyloxycarbonyl)- und Nα-(Trifluoracetyl)aminosäureamiden mit Brenztrauben- und Phenylbrenztraubensäure in Gegenwart von p-Toluolsulfonsäure als Katalysator führt zu N-(Benzyloxycarbonyl)- und N-(Trifluoroacetyl)dehydrodipeptiden mit C-ständigem ΔAla bzw. ΔPhe (Tab 2 und 3).
    Notes: Condensation of amides of N-(benzyloxycarbonyl)- and N-(trifluoroacetyl)amino acid with pyruvic and phenylpyruvic acid yields, in the presence of p-toluenesulfonic acid as a catalyst, N-(benzyloxycarbonyl)- and N-(trifluoroacetyl)dehydro dipeptides with C-terminal Δ Ala and ΔPhe, respectively (Table 2 and 3).
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  • 70
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Asymmetric Synthesis via Heterocyclic Intermediates, XXIII. - Studies on the Enantioselective Synthesis of α-Alkyl-α-(2-furyl)glycines by Alkylation of 3-(2-furyl)-3,6-dihydro-2H-1,4-oxazin-2-ones chirally Substituted at C-63-(2-Furyl)-3,6-dihydro-2H-1,4-oxain-2-ones 10 and 11 are synthesized from DL-(2-furyl)glycine and 2-hydroxyalkanoic acids 4. The heterocycles 10 and 11 contain an endocyclic chiral center at C-6. Their potassium derivatives 12 (obtained with potassium tert-butoxide) react with alkyl halides R2 - X in good chemical yields and with d. e. values (d. e. = asymmetric induction) from 50 → 95% to give the adducts 13. These on hydrolysis are cleaved to yield α-alkyl-α-(2-furyl)-glycines 17 and 2-hydroxyalkanoic acids 4.
    Notes: Ausgehend von DL-(2-Furyl)glycin und den 2-Hydroxyalkansäuren 4 werden die 3-(2-Furyl)-3,6-dihydro-2H-1,4-oxazin-2-one 10 und 11 aufgebaut, die an C-6 ein endocyclisches Chiralitätszentrum besitzen. Deren Kaliumverbindungen 12 (erhalten mit Kalium-tert-butylat) reagieren mit Alkylhalogeniden R2 - X an C-3 mit guten chemischen Ausbeuten und mit 50 → 95% d.e.) (d.e. = asymmetrische Induktion). Der Alkylrest R2 tritt trans zu R1 (am induzierenden Zentrum) ein. Bei der Hydrolyse der Addukte 13 werden die 2-Hydroxyalkansäuren 4 und die (optisch aktiven) α-Alkyl-α-(2-furyl)glycine 17 freigesetzt.
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  • 71
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    Liebigs Annalen 1984 (1984), S. 1513-1518 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Investigations on the Origin of 3,6-Epoxyalkanedioic Acids in Human UrineThe 3,6-epoxyalkanedioic acids 1-4 recently found in human urine are obviously metabolic end products of so far unknown precursors produced in the body.
    Notes: Die im Humanurin kürzlich aufgefundenen 3,6-Epoxyalkandisäuren 1-4 sind offenbar Endabbauprodukte im Körper gebildeter bisher unbekannter Vorstufen.
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  • 72
    Electronic Resource
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1984 (1984) 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 73
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metalloporphyrine in polymeren Matrizen. Mizellen und Vesikeln, VI. - Hydrophobe und hydrophile Derivate des 3,8-Diformyldeuteroporphyrin-dimethylesters und ihre Wechselwirkung mit Vesikeln3,8-Diformyldeuteroporphyrin-dimethylester (1a) wurde durch Ozonisierung des diprotonierten Dikations von Protoporphyrin-dimethylester 1b erhalten. Mehrere Derivate wurden dargestellt, die entweder hydrophobe Eigenschaften aufweisen oder hydrophile Substituenten in der “nördlichen Hemisphäre” des Porphyrinliganden oder an beiden Seiten tragen. Die Porphyrine wurden in wäßrigen Medien gelöst, die Vesikel mit elektroneutralen, -negativen oder -positiven Oberflächenladungen enthielten. Der Aufenthaltsort der gelösten Porphyrine wurde durch den spektroskopischen Nachweis von Reaktionen der zentralen Porphyrin-Stickstoffatome oder von peripheren Substituenten mit wasserlöslichen Säuren oder Metall-Ionen bestimmt.
    Notes: 3,8-Diformyldeuteroporphyrin dimethyl ester (1a) was obtained by ozonization of the diprotonated dication of protoporphyrin dimethyl ester 1b. Several derivatives have been prepared, which are either hydrophobic, or bear hydrophilic substituents in the „northern hemisphere“ of the porphyrin ligand or on both sides. The porphyrins have then been dissolved in aqueous media containing vesicles with electroneutral, -negative, or -positive surface charges. The localization of the dissolved porphyrin chromophore was determined spectroscopically following reactions of the central porphyrin nitrogen atoms or of peripheral substituents with water-soluble acids or metal ions.
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  • 74
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    Liebigs Annalen 1984 (1984), S. 1740-1745 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Retinoids and Carotenoids, II. - Synthesis of (13Z)-Retinoic AcidsPhosphonium ylides 3 react with (E)-2-methyl-3-(4-methyl-2-oxo-2H-pyran-6-yl)propenal (2) to give 2-pyrone derivatives 4 which undergo ring opening by treatment with sodium tetrahydroborate/potassium hydroxide/methanol affording (13Z)-retinoic acids.
    Notes: Phosphoniumylide 3 reagieren mit (E)-2-Methyl-3-(4-methyl-2-oxo-2H-pyran-6-yl)propenal (2) zu 2-Pyronderivaten 4, bei deren Reduktion mit Natrium-tetrahydroborat/Kaliumhydroxid/Methanol unter Ringöffnung (13Z)-Retinoidsäuren 5 entstehen.
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  • 75
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    Liebigs Annalen 1984 (1984) 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 76
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    Liebigs Annalen 1984 (1984), S. 1759-1777 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Pyrans, 100.  -  5,6-Dihydro-2H-pyran-3(4H)-one as a Building Unit for the Synthesis of Pyran-annulated Heterocyclic CompoundsOnly in a few cases 5,6-dihydro-2H-pyran-3(4H-one (3) reacts regioselectively with ortho-substituted phenylcarbonyl compounds to form pyran-annulated heterocyclic compounds like the pyrano[3,2-b]quinoline 7c. Better results are obtained in reactions involving the enamine 15d derived from 3, the silyl enol ether 18 and the lithium enolate 14 derived from 18. These pyran derivatives with 2,3- or 3,4-double bonds are well suited for successful synthesis of 2- or 4-substituted 3-pyranones such as 2, 21a, 21b, 23a-c, 26a-c, 31a-c, 32, and 35a-c. They also allow to synthesize pyrano[3,2-b]- or -[3,4-b]quinolones, -chromones, and -thiochromones 6a, 30a-c, 38a-d.
    Notes: Während 5,6-Dihydro-2H-pyran-3(4H)-on (3) sich mit ortho-substituierten Phenylcarbonylverbindungen nur in Einzelfällen regioselektiv zu pyrananellierten Heterocyclen umsetzt - z. B. zum Pyrano[2,3-b]chinolin 7c -, gelingt das besser mit dem aus 3 hergestellten Enamin 15d, dem Silylenolether 18 und dem daraus gewonnenen Lithiumenolat 14. Diese Pyranderivate mit 2,3-oder 3,4-Doppelbindungen eignen sich zur gezielten Darstellung von 2- oder 4-substituierten 3-Pyranonen - z.B. 2, 21a, 21b, 23a-c, 26a-c, 31a-c, 32, sowie 35a-c - und von Pyrano[3,2-b]- oder -[3,4-b]chinolinen, -chinolonen, -chromonen und -thiochromonen 6a, 30a-c und 38a-d.
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  • 77
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    Liebigs Annalen 1984 (1984), S. 1785-1790 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of Further Eremophilane DerivativesStarting with suitable octalin derivatives two further eremophilane derivatives (9 and 13) isolated from Euryops species were synthesized via the epoxides 5 and 6 by regiospecific ring opening with isopropenylmagnesium bromide in the presence of copper(I) iodide followed by appropriate transformation of the eremophilanes obtained. While the preparation of the racemic ketone 9 caused no problems, the corresponding 2α-hydroxy derivative in the trans-decalin series could not be obtained in satisfactory yields. The configurations of the natural compounds have now finally been elucidated.
    Notes: Ausgehend von geeigneten Octalin-Derivaten werden zwei aus Euryops-Arten isolierte Eremophilan-Derivate (9 und 13) über die Epoxide 5 und 6 durch regiospezifische Ringöffnung mit Isopropenylmagnesiumbromid in Gegenwart von Kupfer(I)-iodid und entsprechende Umwandlung der erhaltenen Eremophilane synthetisiert. Während die Darstellung des racemischen Ketons 9 keine Probleme bereitet, konnte das entsprechende 2α-Hydroxy-Derivat in der trans-Decalin-Reihe nicht in befriedigenden Ausbeuten erhalten werden. Die Konfigurationen der Naturstoffe sind damit endgültig geklärt.
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  • 78
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    Liebigs Annalen 1984 (1984), S. 1696-1701 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Chemistry of Amino Oximes, XVIII. - The Cyclocondensation of (E)-β-(Chloroacetylamino)propiophenone Oxime DerivativesThe (E)-β-(chloroacetylamino)propiophenone oximes 2a-c cyclocondense by reaction with alkali to form 3,11-diphenyl-1,9-dioxa-2,6,10-14- tetraazacyclohexadeca-2,10-diene-7,15-diones 3a-c. From (E)-β-[(benzyl)(chloroacetyl)amino]propiophenone oximes 5a-c the 6-benzyl-5,6-dihydro-3-phenyl-4H- 1,2,6-oxadiazocin-7(8H)-one derivates 6a-c are formed.
    Notes: Die (E)-β-(Chloracetylamino)propiophenon-oxime 2a-c werden durch Alkali zu 3,11-Diphenyl-1,9-dioxa-2,6,10,14-tetraazacyclohexadeca-2,10-dien-7,15-dionen 3a-c cyclokondensiert. Aus (E)-β-[(Benzyl)(chloracetyl)amino]propiophenon-oximen 5a-c entstehen dagegen die 6-Benzyl-5,6-dihydro-3-phenyl-4H-1,2,6-oxadiazocin-7(8H)-on-Derivate 6a-c.
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  • 79
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    Liebigs Annalen 1984 (1984), S. 1711-1718 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Enehydrazines, 37. - Synthesis of a Pyrazole Analogue of 7-AminomitoseneThe 9-step synthesis of 7-amino-10-azamitosene (2b) from 3a is described. The crystal-structure analysis of the precursor 1b of 3a secures the position of the substituted propyl group at N-1 of compounds 1 and 3-7.
    Notes: Die neunstufige Synthese von 7-Amino-10-azamitosen (2b) aus 3a wird beschrieben. Die Kristallstrukturanalyse des Vorläufers 1b von 3a sichert die Stellung des substituierten Propylrestes an N-1 der Verbindungen 1 und 3-7.
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  • 80
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    Liebigs Annalen 1984 (1984), S. 1719-1730 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of 2′-Deoxyribofuranosides of 7H-Pyrrolo[2,3-d]pyrimidine: Influence of the C-2 Substituents on the Fluorescence7-Deaza-2′-deoxynebularine (2a), its 2-methylthio (2b) and 2-amino derivative (2c) have been synthesized via phase-transfer glycosylation of the nucleobases 3a, 3b, and 3c, respectively, with the 2-deoxyhalogenose 6. Glycosylation of 3a leads to the formation of a 3:1 mixture of the anomers 7a and 8a in 48-% total yield, the corresponding reaction of 3b or 3c gives mainly the β anomers in increased yield. Cleavage of the protecting groups yields 2a-c or the anomers 8a and 8c. The 2-methylthio group, as well as the 2-amino group increase the fluorescence of the parent nucleoside 2a.
    Notes: 7-Desaza-2′-desoxynebularin (2a), sein 2-Methylthio- (2b) und sein 2-Aminoderivat (2c) wurden durch Phasentransferglycosylierung der Aglycone 3a, 3b und 3c mit der Desoxyhalogenose 6 dargestellt. Die Glycosylierung von 3a führt in 48proz. Ausbeute zum 3:1-Anomerengemisch der toluoylierten Nucleoside 7a und 8a; die entsprechende Reaktion von 3b und 3c ergibt bei erhöhter Ausbeute hauptsächlich die β-Anomeren. Abspaltung der Schutzgruppen liefert 2a-c bzw. die Anomeren 8a und 8c. Sowohl die 2-Methylthiogruppe als auch der 2-Aminosubstituent verstärken die Fluoreszenz der Stammverbindung 2a.
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  • 81
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    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Macrocyclic Trichothecenes From Baccharis coridifolia, I. - Miotoxin B and C, two New Macrocyclic Trichothecenes From Baccharis coridifolia DCFrom extracts of the toxic Brazilian plant Baccharis coridifolia, two further macrocyclic trichothecenes were isolated. The structures of these compounds, named by us as miotoxin B and C, were elucidated by application of mass spectrometry and homo- and heteronuclear two-dimensional NMR techniques.
    Notes: Aus Extrakten der brasilianischen Giftpflanze Baccharis coridifolia wurden zwei macrocyclische Trichothecene isoliert. Die Strukturen der von uns als Miotoxin B und C bezeichneten Substanzen wurden durch Massenspektroskopie und durch homo- und heteronucleare zweidimensionale FT-NMR-Techniken aufgeklärt.
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  • 82
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    Liebigs Annalen 1984 (1984), S. 1755-1758 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Contributions to the Chemistry of Tetraketones, III. - Synthesis and Some Reactions of 1,6-Bis(p-hydroxyphenyl)-1,3,4,6-hexanetetroneCondensation of p-hydroxyacetophenone and diethyl oxalate in the presence of sodium ethoxide gave the tetraketone 3 which can be cyclized with o-phenylenediamine, hydrazine, or phenyl-hydrazine to yield the quinoxaline 1 or the 3,3′-bipyrazolyl derivatives 5 and 6, respectively. Transformation of the p-hydroxyphenyl group in compounds 1 and 3 with methyl isocyanate/triethylamine gave the corresponding carbamates 2 and 4. By condensation of 4 with hydrazine or phenylhydrazine the pyrazoles 7 and 8 were prepared. Compounds 4, 7, and 8 showed no progressive inhibitory properties against acetylcholinesterase.
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  • 83
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    Liebigs Annalen 1984 (1984), S. 1778-1784 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: (1α,2α,5α,6α)-3,4-Bis(trimethylsiloxy)tricyclo[4.2.1.02,5]nona-3,7-diene on Treatment with Oxidative Reagents(1α,2α,5α,6α)-3,4-Bis(trimethylsiloxy)tricyclo[4.2.1.02,5]nona-3,7-diene (1) is treated with different oxidative reagents. The reaction with halogens (Br2, Cl2) primarily yields the cyclobutanedione 2 which adds a second mole of halogen at the olefinic double bond. The adduct 3 is stabilized by forming 4a with an intramolecular ether bridge. Addition of chlorine to 2 directly yields 4b.  -  Reaction of 1 with DMSO/Ac2O or Cu(II) acetate in acetic acid causes an oxidative dimerization to yield 5 or 6, respectively. In the case of Cu(II) acetate the anhydride 7 is obtained as a second product.
    Notes: (1α,2α,5α,6α)-3,4-Bis(trimethylsiloxy)tricyclo[4.2.1.02,5]nona-3,7-dien (1) wird mit verschiedenen Oxidationsmitteln behandelt. Die Reaktion mit Halogenen (Br2, Cl2) liefert zunächst das Cyclobutandion 2, das ein weiteres Mol Halogen an die olefinische Doppelbindung addiert. Das Dihalogenaddukt 3 stabilisiert sich durch Ausbildung einer intramolekularen Etherbrücke zu 4a. Addition von Chlor an 2 liefert unmittelbar 4b.  -  Durch Umsetzung von 1 mit DMSO/Ac2O oder mit Cu(II)-acetat/Eisessig findet eine oxidative Dimerisation zu 5 bzw. 6 statt. Im Falle der Oxidation mit Cu(II)-acetat wird als Nebenreaktion eine Ringerweiterung zum Anhydrid 7 beobachtet.
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  • 84
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    Liebigs Annalen 1981 (1981) 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 85
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 8-Amino-5-ethyl-3-oxido-6-phenylphenanthridinium-betain, a New Solvatochromic CompoundSynthesis and some properties of 8-Amino-5-ethyl-3-oxido-6-phenylphenanthridinium betaine (3) are described. The structure is proved by 1H-NMR and mass spectroscopy. In aqueous solutions 3 is in a pH dependent equilibrium with its conjugated aminophenol 2 and the twice protonated dication 4. The pKa value of the prototropic equilibrium between 3 and 2 at 25° C is 7.15. The betaine shows a strong negative solvent effect. Solutions of 3 in aprotonic solvents are blue, in amphiprotonic solvents red to purple.
    Notes: Synthese und einige Eigenschaften von 8-Amino-5-ethyl-3-oxido-6-phenylphenanthridinium-betain (3) werden beschrieben. Die Struktur von 3 wird durch 1H-NMR-Spektrum und Massen-spektrum bewiesen. 3 steht in wäßrigem Medium in einem pH-abhängigen Gleichgewicht mit dem konjugierten Aminophenol 2 und dem zweifach protonierten Dikation 4. Der pKa-Wert des prototropen Gleichgewichts zwischen 3 und 2 beträgt bei 25° C 7.15. Das Betain zeigt eine starke negative Solvatochromie. Lösungen von 3 in aprotonischen Solventien sind blau, in amphiprotonischen rot bis purpurfarben.
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    Liebigs Annalen 1981 (1981), S. 20-27 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: New Transition Metal Nitrido Complexes with M≡N Triple Bonds from Molybdenum, Tungsten, and RheniumSyntheses, some properties, and IR spectra of the transition metal nitrido complexes MNCl3(Bipy) (M = Mo, W, Re; Bipy = 2,2′-bipyridine) (1a-c), MoNBr2(Bipy) (2), ReNCl3(Pyridine)3 (3), [ReNCl4(Pyridine)]⊖ (4), ReNCl3(PPh3)2 (5), [ReNCl4(PPh3)]⊖ (6), (Ph3P)(Cl4)ReNPPh3 (7), and the porphyrinato complex [MoN(TPP)]Br3 (8) are reported. According to the IR spectra all complexes contain terminal M≡N triple bonds which can be detected by characteristic absorptions in the region from 950 to 1100 cm-1
    Notes: Es wird über die Synthesen, einige Eigenschaften und die IR-Spektren der Übergangsmetall-Nitridokomplexe MNCl3(Bipy) (M = Mo, W, Re; Bipy = 2,2′-Bipyridin) (1a-c), MoNBr2(Bipy) (2), ReNCl3(Pyridin)3 (3), [ReNCl4(Pyridin)]⊖ (4), ReNCl3(PPh3)2 (5), [ReNCl4(PPh3)]⊖ (6), (Ph3P)(Cl4)ReNPPh3 (7) sowie des Porphyrinatokomplexes [MoN(TPP)]Br3 (8) berichtet. Nach den IR-Spektren enthalten alle Komplexe terminale M≡N-Dreifachbindungen, die sich durch charakteristische Absorptionen im Bereich von 950 bis 1100 cm-1 nachweisen lassen.
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    Liebigs Annalen 1981 (1981), S. 28-32 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Extraction of Nucleophilic and Non-nucleophilic Bases into Non-polar Media under the Conditions of Phase Transfer CatalysisOH⊖ ions can be extracted by NR4Hal into non-polar media only to a minor extent, even if a more than hundredfold excess of sodium hydroxide in water is present. The anions of solid carbonates and alkali metal hydrides cannot be transferred into organic media. In the presence of acidic compounds H-Sub there are considerable concentrations of ion pairs [catalyst cation⊕] [Sub⊖] in organic media. Therefore, deprotonation of H-Sub must occur on the phase boundary of the solid salts.
    Notes: Selbst in Gegenwart eines mehrhundertfach molaren Überschusses an Natronlauge können OH⊖-Ionen aus wäßriger Phase nur in untergeordnetem Maße durch NR4Hal in unpolare Lösungsmittel transportiert werden. Die Anionen fester Carbonate und Alkalimetallhydride sind durch NR4Hal nicht in organische Medien überführbar. In Gegenwart acider Verbindungen H-Sub befinden sich merkliche Konzentrationen von Ionenpaaren [Katalysator-Kation⊕] [Sub⊖] in organischen Medien. Die Deprotonierung von H-Sub läuft demnach an der Grenzfläche der Salze ab.
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    Liebigs Annalen 1981 (1981), S. 47-51 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stabilization of Thioniumcarbenium Salts by + M SubstituentsIn order to stabilize thioniumcarbenium salts apart from the methylthio group further substituents with a + M effect such as chlorine or phenyl are needed. The (methylthio)phenylmethylium hexachloroantimonate (8) and the (methylthio)diphenylmethylium hexachloroantimonate (12) are described as an illustration for this. Reaction of chloromethyl methyl sulfide (4a) with aluminium or boron trichloride yields only the sulfonium salts 5, with boron tribromide the betain 6a is obtained.
    Notes: Zur Stabilisierung von Thioniumcarbenium-Salzen sind außer der Methylthiogruppe weitere Substituenten mit einem + M-Effekt wie Chlor oder Phenyl erforderlich. Als Beispiele hierfür werden das (Methylthio)phenylmethylium-hexachloroantimonat (8) und das (Methylthio)diphenylmethylium-hexachloroantimonat (12) beschrieben. Die Umsetzung von (Chlormethyl)methylsulfid (4a) mit Aluminium- oder Bortrichlorid liefert lediglich die Sulfoniumsalze 5, mit Bortribromid das Betain 6a.
    Additional Material: 1 Tab.
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  • 89
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemistry of Reactive Cations Derived from Sulfur Dioxide Analogues, III1).  -  N-Methyl-N-sulfinylmethanaminium Salts  -  Preparation and Cycloaddition Reactions with Dienes and DiazomethaneN-Sulfinylmethylamine is N-alkylated by oxonium salts. Reaction of the imonium slats (CH3)2)N⊕ = S = O X⊖ (3a and 4) thus prepared with dienes proceeds by 1,4-addition of the N = S group with formation of the thiazinium compounds 6 and 7. Diazomethane reacts with imonium salts 4 to give aziridinium salt 11.
    Notes: N-Sulfinylmethylamin kann mit Oxoniumsalzen am N-Atom alkyliert werden. Die Umsetzung der so dargestellten Imoniumsalze (CH3)2N⊕ S = O X⊖ (3a und 4) mit Dienen erfolgt unter 1,4-Addition der N = S-Gruppierung zu den Thiaziniumverbindungen 6 und 7. Diazomethan reagiert mit dem Imoniumsalz 4 zum Aziridiniumsalz 11.
    Additional Material: 4 Tab.
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  • 90
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 70-84 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Orthoamides, XXXV.  -  Preparation of O,N-Functional Trisubstituted AcetonitrilesTrichloroacetonitrile (7) reacts with molar amounts of alcoholates in alcohols to give mixtures of orthocarbonates 10 and trichloracetimidates 9. The action of 7 on 3 moles of sodium ethoxide in heptane affords triethoxyacetonitrile 3b among other products, such as 9b, 10b and the imidate 12. The nitrile 3a can be obtained from 7 and sodium methoxide in ether in moderate yields.  -  The orthocarbonic acid derivatives 10b, 20a and 21a are transformed by acyl cyanides into the nitriles 3b, 4a, and 5a, respectively. N,N,N′,N′,N″,N″-hexamethylguanidinium cyanide (23a) is formed in the reaction of 22 with acetyl cyanide.  -  The salts 30a-32a react with alkali cyanides to form the nitriles 3b, 4a, and 5a, respectively. The nitrile 2a transfers cyanide ions to the carbenium ions 30a and 31a to yield the nitriles 3b and 4a, respectively.
    Notes: Die Umsetzung von Trichloracetonitril (7) mit Alkoholaten in Alkohol im Molverhältnis 1:1 ergibt Gemische aus Trichloracetimidaten 9 und Orthocarbonaten 10. Triethoxyacetonitril (3b) entsteht neben 9b und 10b, sowie dem Imidat 12 bei der Einwirkung von 7 auf 3 mol alkoholfreies Natriumethylat in Heptan. Mit befriedigenden Ausbeuten läßt sich 3a aus 7 und Natriummethylat in Ether gewinnen.  -  Die Orthokohlensäurederivate 10b, 20a und 21a werden durch Acylcyanide in die Nitrile 3b, 4a bzw. 5a übergeführt. N,N,N′,N′,N″,N″-Hexamethylguanidiniumcyanid (23a) bildet sich aus 22 und Acetylcyanid.  -  Die Nitrile 3b, 4a und 5a sind auch durch Umsetzung der Salze 30a-32a mit Alkalicyaniden zugänglich. Das Nitril 2a reagiert mit den Carbeniumsalzen 30a und 31a unter Cyanidionenübertragung zu den nitrilen 3b bzw. 4a.
    Additional Material: 2 Tab.
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  • 91
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 99-102 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: tert-Butyl (Diphenylphosphinyl)isocyanoacetate and its Use in the Wittig-Horner Reaction with AldehydesThe title compound 2 is synthesized. Its reaction with aromatic and heteroaromatic aldehydes 1 leads to 3-substituted tert-butyl 2-isocyanoacrylates 3.
    Notes: Die Titelverbindung 2 wird synthetisiert und mit aromatischen und heteroaromatischen Aldehyden 1 zu 3-substituierten 2-Isocyanacrylsäure-tert-butylestern 3 umgesetzt.
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  • 92
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 103-106 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Syntheses with α-Metalated Isocyanides, XLVII1).  -  A Reagent for Nucleophilic 1,3-Diaminopropylation1-Tosyltetrahydropyrimidine 3 reacts with butyllithium (or LDA) to give the lithium compound 4 which undergoes ring opening to yield the isocyanide 5. This reacts with a second mole butyllithium to furnish 1-lithio-3-[(lithio)(tosyl)amino]propyl isocyanide (7) which adds electrophils at the metalated carbon atom. The addition products  -  e. g. with alkyl halides (type 8) or carbonyl compounds (type 10)  -  have two masked amino groups which can be converted into free amino groups using known methods.
    Notes: Das 1-Tosyltetrahydropyrimidin 3 reagiert mit Butyllithium (oder LDA) zur Lithiumverbindung 4, die Ringöffnung zum Isocyanid 5 erleidet. Dieses liefert mit einem zweiten Mol Butyllithium 1-Lithio-3-[(lithio)(tosyl)amino]propylisocyanid (7), welches am metalltragenden C-Atom Elektrophile anlagert. Die Addukte z. B. mit Alkylhalogeniden (Typ 8) oder mit Carbonylverbindungen (Typ 10) enthalten zwei maskierte Aminogruppen, die nach bekannten Methoden in freie Aminogruppen überführbar sind.
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  • 93
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 122-137 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthesis of 5- and 6-O-Alkyl substituted Ketohexoses of the L-sorbo-, L-psico-, D-fructo-, and D-tagato-SeriesStarting from methyl 1,3-O-benzyliden-β-D-fructopyranoside 1 the synthesis of 5-O-benzyl-D-fructose 9 and, after inversion of the configuration at C-4 by oxidation and subsequent stereo-selective reduction, the synthesis of 5-O-benzyl- and 5-O-methyl-D-tagatose 17a and 17b is described. Analogously the α-L-sorbopyranoside 2 was used to synthesize 5-O-benzyl-L-sorbose 10 and the 5-O-alkyl-L-psicoses 18a and 18b. The 1H-NMR spectra of the methyl 4-O-acetyl-5-O-alkyl-1,3-O-benzylidene-keto-hexopyranosides with D-fructo-, D-tagato-, D-sorbo-, and L-psico-configuration are compared and discussed. Furthermore, a synthesis of 6-O-methyl- and 6-O-benzyl-D-psicose 23a and 23b is reported.
    Notes: Ausgehend von Methyl-1,3-O-benzyliden-β-D-fructopyranosid 1 wird die Synthese der 5-O-Benzyl-D-fructose 9 und nach Konfigurationsumkehr an C-4 durch Oxidation und stereoselektive Reduktion die Synthese der 5-O-Benzyl- und 5-O-Methyl-D-tagatose 17a und 17b beschrieben. Analog wurden das α-L-Sorbopyranosid 2 zur Synthese der 5-O-Benzyl-L-sorbose 10 und der 5-O-Alkyl-L-psicosen 18a und 18b verwandt. Die 1H-NMR-Spektren der Methyl-4-O-acetyl-5-O-alkyl-1,3-O-benzyliden-keto-hexopyranoside mit D-fructo-, D-tagato-, L-sorbo- und L-psico-Konfiguration werden vergleichend diskutiert. Ferner wird über eine Synthese für die 6-O-Methyl-und 6-O-Benzyl-D-psicose 23a und 23b berichtet.
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  • 94
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    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 152-164 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Rearrangement of the N-(3-Oxo-1-butenyl) Derivatives of Hexahydrocyclohept[b]indole and Hexahydrocyclooct[b]indoleThe N-(3-oxo-1-butenyl) derivatives 1, 2 of hexahydrocyclohept- and-oct[b]indole are rearranged by methanolic hydrochloric acid to give 3a and 4a. Additionally, 3b, 4b, and 5 result. 3a and 4a are transformed into typical derivatives (6, 7) and stereoselectively reduced to the saturated ketone 8a as well as the allylic alcohols 9 and 10. On boranate reduction, 8a yields the stereoisomeric alcohols 8d and e which are also formed by hydrogenation of 3a with Raney nickel and are investigated with regard to their stereochemistry. The reaction pathway is discussed.
    Notes: Die N-(3-Oxo-1-butenyl)-Derivate 1, 2 von Hexahydrocylcohept- und -oct[b]indol werden mit methanolischer Salzsäure zu 3a und 4a umgelagert. Außerdem entstehen 3b, 4b und 5. 3a und 4a werden durch Derivate charakterisiert (6, 7) sowie stereoselektiv zum gesättigten Keton 8a und den Allylalkoholen 9 und 10 reduziert. 8a liefert bei der Boranat-Reduktion die stereoisomeren Alkohole 8d und e, die auch bei der Hydrierung von 3a an Raney-Nickel entstehen und hinsichtlich Konfiguration und Konformation untersucht werden. Der Reaktionsverlauf wird erörtert.
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  • 95
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Mesoionic Six-membered Heterocycles, III.  -  Reactions of o-Quinonoid Compounds with 6-Oxo-6H-1,3-diazin-1-ium-4-olatesMesoionic 6-oxo-6H-1,3-diazin-1-ium-4-olates 9 react with tetrachloro-o-benzoquinone (2, R = Cl) to give 1:1 adducts 12 which can formally be derived from ketene tautomers 13 of 9. The structure of 12f has been clarified by X-ray crystallography.
    Notes: Mesoionische 6-Oxo-6H-1,3-diazin-1-ium-4-olate 9 reagieren mit Tetrachlor-o-benzochinon (2, R = Cl) unter Bildung von 1:1-Addukten 12, die sich formal von den Ketentautomeren 13 von 9 ableiten. Die Struktur von 12f wurde durch eine Röntgenstrukturanalyse geklärt.
    Additional Material: 2 Ill.
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  • 96
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Condensations of α,α'-Dithiobisformamidine with β-DiketonesIn pursuance of attempts to synthesize S-S-analogs of 2,2′-hydrazopyrimidines by condensation of α,α'-dithiobisformamidine (1) with β-diketones, the strong decomposition tendency of 1, accompanied by the deposition of elemental sulfur, becomes apparent. However, in anhydrous ethanol in the presence of potassium carbonate at room temperature, the condensation of 1 with 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione (2) leading to 2,2′-dithiobis[6-(2-furyl)-4-trifluoro-methylpyrimidine] (3) can be accomplished. Additionally, in this reaction cleavage of 1 also occurs, followed by condensation of a fragment with 2, to form 2-amino-4-trifluoromethyl-5-thiazolyl 2-furyl ketone (4). Application of the same reaction conditions to 1 and 1,1,1-trifluoro-2,4-pentanedione (5) results in the formation of 4-methyl-6-trifluoromethyl-2(1 H)-pyrimidinethione (6).
    Notes: Bei Versuchen zur Darstellung von S-S-Analogen der 2,2′-Hydrazopyrimidine durch Kondensation von α,α'-Dithiobisformamidin (1) mit β-Diketonen zeigt sich eine starke Zersetzungstendenz von 1 unter Abscheidung von elementarem Schwefel. Jedoch gelingt in wasserfreiem Ethanol unter Zusatz von Kaliumcarbonat bei Raumtemp. die zu 2,2′-Dithiobis[6-(2-furyl)-4-trifluormethylpyrimidin] (3) führende Kondensation von 1 mit 4,4,4-Trifluor-1-(2-furyl)-1,3-butandion (2). Auch in dieser Reaktion tritt außerdem Spaltung von 1 und nachfolgende Kondensation eines Bruchstückes mit 2 unter Bildung von (2-Amino-4-trifluormethyl-5-thiazolyl)(2-furyl)keton (4) ein. Unter den gleichen Reaktionsbedingungen erfolgt aus 1 und 1,1,1-Trifluor-2,4-pentandion (5) Bildung von 4-Methyl-6-trifluormethyl-2(1 H)-pyrimidinthion (6).
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  • 97
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 546-564 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: 14β-Hydroxysteroids, II.  -  The Prins Reaction of Lumihecogenin AcetatePhotochemical rearrangement of hecogenin acetate (1) into the unsaturated aldehyde 5 followed by a Prins reaction leads efficiently to the 14β-hydroxysteroids 7a and 10a. The configuration of 7a, 10a, and 9a at C-13 and C-14 has been determined by chemical correlation and spectroscopically (1H-NMR, 13C-NMR, CD).
    Notes: Durch photochemische Umlagerung von Hecogeninacetat (1) zum ungesättigten Aldehyd 5 und anschließende Prins-Reaktion sind die 14β-Hydroxysteroide 7a und 10a bequem zugänglich. Die Konfiguration an C-13 und C-14 bei 7a, 10a und 9a wurde chemisch und mit Hilfe spektroskopischer Methoden (1H-NMR, 13C-NMR und CD) abgeleitet.
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  • 98
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 538-545 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: On Substances Isolated from Melochia pyramidata L.Besides the already earlier detected compounds melochinine (1) and cholin chloride the substances melochinone (2), the D-glucoside of melochinine (3), 1-methyluracil (4), frangufoline (6), adouetine Z (8), and integerrenine (7) were isolated from the leaves of Melochia pyramidata L. (Sterculiaceae). Adouetine Z is not a single compound as originally assumed but a mixture of cis/trans isomeres.
    Notes: Aus Blättern von Melochia pyramidata L. (Sterculiaceae) wurden neben den bereits früher beschriebenen Substanzen Melochinin (1) und Cholin-chlorid die Verbindungen Melochinon (2), das D-Glucosid des Melochinins (3), 1-Methyluracil (4), Frangufolin (6), Adouetin Z (8) und Integerrenin (7) isoliert. Adouetin Z ist kein einheitliches Produkt, wie ursprünglich angenommen, sondern ein Gemisch von cis/trans-Isomeren.
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  • 99
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 581-590 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Carbene Reactions, XV1).  -  Attempted Generation of Tricarbonylcycloheptatrienylidene ChromiumFluorodesilylation of trimethylsilyltropylium ion (5b) generated cycloheptatrienylidene (6), which could be trapped by dimethyl fumarate. In the absence of trapping agents 6 dimerized to heptafulvalene (8). The analogous treatment of tricarbonyl(trimethylsilyltropylium) chromium (4b) led to the dihydrodimer 13 of tricarbonylcycloheptatrienylidene chromium (3).
    Notes: Cycloheptatrienyliden (6) konnte aus dem Trimethylsilyltropylium-Ion (5b) durch Fluordesilylierung freigesetzt und durch Addition an Fumarsäureester abgefangen werden. In Abwesenheit von Abfängern dimerisierte 6 zu Heptafulvalen (8). Bei der übertragung dieser Reaktion auf das Tricarbonyl(trimethylsilyltropylium)chrom (4b) entstand das Dihydrodimere 13 von Tricarbonylcycloheptatrienylidenchrom (3).
    Additional Material: 1 Tab.
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  • 100
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Liebigs Annalen 1981 (1981), S. 668-682 
    ISSN: 0170-2041
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: A New and Versatile Synthesis of FuransThe thermal reaction of oxazoles 1 and acetylenic dienophiles 2 provides a synthetic approach to a great variety of furans (Table 1). Scope and mechanism of this reaction are discussed. Biologically active substances of type 7 are described as examples for practical application.
    Notes: Die thermische Reaktion von Oxazolen 1 mit Acetylen-Dienophilen 2 führt unter Abspaltung von Nitrilen in guten bis sehr guten Ausbeuten zu Furanen (Tab. 1). Die Breite der Reaktion und der Reaktionsmechanismus werden diskutiert. Am Beispiel biologisch wirksamer Verbindungen vom Typ 7 wird die praktische Anwendung vorgestellt.
    Additional Material: 1 Ill.
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