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  • 1985-1989  (4)
  • 1980-1984  (10)
Material
Years
Year
  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Journal of chemical & engineering data 33 (1988), S. 540-541 
    ISSN: 1520-5134
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 72 (1989), S. 744-755 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Condensation reactions of the 5-amino-6-(subst. amino)-2,4-dithiouracils 12 and 13 with diacetyl or benzil led to the 6,7,8-trisubstituted 2,4-dithiolumazines 14-16. Methylation of these compounds affected both thio functions forming various types of 2,4-bis(methylthio)lumazine derivatives depending on the nature of the substituents at C(7) and N(8). The 6,7,8-trimethyl-2,4-dithiolumazine (14) was converted into 7,8-dihydro-6,8-dimethyl-7-methylidene-2,4-bis(methylthio)pteridine (17), whereas the 8-methyl-6,7-diphenyl-(15) and the 8-(2-hydroxyethyl)-6,7-diphenyl-2,4-dithiolumazine (16) yielded the corresponding covalent inter- or intramolecular 7,8-adducts 18-21. The unusual structures were proven by spectroscopic means and those of the alcohol adducts 20 and 21, furthermore, confirmed by X-ray analysis.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 118 (1985), S. 1876-1886 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Reaktion von 1-Oxa-3-azabutatrienium-Salzen mit tertiären CarbonsäureamidenDie α-Chlorisocyanate 1 reagieren mit tertiären Carbonsäureamiden oder Acyliminen 3 in Gegenwart von Lewis-Säuren (SbCl5, FeCl3) unter milden Bedingungen zu den aminosubstituierten 2-Azaallenium-Salzen 5a - t. Die nur mäßig starken Elektrophile 5 setzen sich mit Methanol zu den Acetalen 8 und 10 um. Eine Röntgenstrukturanlyse von 5a zeigt, daß die -Einheit dieses Moleküls gewinkelt ist (128°). Es besteht eine Proportionalität zwischen der Wellenzahl der antisymmetrischen Valenzschwingung von 2-Azaallenium-Salzen und dem -Bindungswinkel. Die durch die sp2-Kohlenstoffe der -Einheit von 5a definierten Ebenen stehen nahezu senkrecht (84°) aufeinander.
    Notes: α-Chloro isocyanates 1 react with tertiary carboxamides or acylimines 3 in the presence of Lewis acids (SbCl5, FeCl3) to give the amino-substituted 2-azaallenium salts 5a - t under mild conditions. With methanol the moderately strong electrophiles 5 afford the acetals 8 and 10. According to an X-ray structural analysis, the C = N = C unit of 5a is bent by 128°. There exists a linear relationship between the wave number of the antisymmetric stretching vibration of 2-azaallenium salts and the bond angle. The planes defined by the sp2 carbons of the moiety of 5a are almost perpendicular (84°) with respect to each other.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1695-1706 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Degradation of (PhP)5 by Cyanide: Formation, Structure, and Reactions of the Phenyl Cyanophosphide Ion1)Phenyl cyanophosphide PhPCN- is formed in the reactions of P(CN)2- with phenyllithium and of PhP(CN)2 with CN-, and it may best be prepared by nucleophilic degradation of (PhP)5 with ammonium or phosphonium cyanides. With sulfur it yields phenyl cyanodithiophosphinates 4, by alkylation alkyl(phenyl)cyanophosphanes 6 and by hydrolysis of the latter alkyl(phenyl)phosphine oxides 7. - The molecular structure of [Ph3PNPPh3]PhPCN (3c) as determined by X-ray analysis shows an almost planar anion with a 102° CPC angle. A long PC and short CN bond in the PCN group make PhPCN- appear as “cyanide complex of phenylphosphinidene”.
    Notes: Phenyl-cyanphosphid PhPCN- entsteht bei den Reaktionen von P(CN)2- mit Phenyllithium und von PhP(CN)2 mit CN-, sowie präparativ verwertbar durch nucleophilen Abbau von (PhP)5 mit Ammonium- oder Phosphoniumcyaniden. Mit Schwefel kann es weiter zu Phenyl-cyandithiophosphinat 4, durch Alkylieren zu Alkyl(phenyl)-cyanphosphanen 6 und durch deren Hydrolyse zu Alkyl(phenyl)phosphanoxiden 7 umgesetzt werden. - Die röntgenographisch bestimmte Struktur von [Ph3PNPPh3]PhPCN (3c) zeigt ein fast planares Anion mit einem CPC-Winkel von 102°. Der lange PC- und kurze CN-Abstand der PCN-Gruppe läßt PhPCN- als „Cyanidkomplex des Phenylphosphinidens“ erscheinen.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 1900-1912 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Aminosubstituierte 2-AzaalleniumsalzeNitriliumsalze (14a - i) reagieren mit Iminen (15a - e) in guten Ausbeuten zu den mono- bis tetra-azasubstituierten 2-Azzalleniumsalzen 16a - w. Für die Verbindungen 16 wird eine Allengeometrie (A) oder alternativ eine planare 1,3-Diaza-1,3-butadienium-Struktur (B) diskutiert. Nach den IR-, 1H- und 13C-NMR-Spektren zu schließen, müssen die Salze 16 um das zentrale Stickstoffatom recht flexibel sein. Zumindest die Verbindungen 16a - d liegen in Lösung in einer chiralen Allenkonformation vor. Für die Rotationsbarrieren um die C=N+=C-Achse werden durch DNMR-Messungen Werte zwischen δG173† = 36 · 1 kJmol-1 für 16a und mehr als 90 kJmol-1 für 16c gefunden. Nach einer Röntgenstrukturanalyse liegt 16 o im Kristall in einer weitgehend idealen Allengeometrie (A) vor. - Es werden einige interessante 13C-14N-Kopplungen der Nitriliumsalze 14 beschrieben.
    Notes: Nitrilium salts (14a - i) react with imines (15a - e) to afford the mono- to tetraaza-substituted 2-azaallenium salts 16a - w in high yields. The stereochemistry of these compounds is discussed in terms of an allenic geometry (A) and a planar 1,3-diaza-1,3-butadienium structure (B), respectively. According to the IR, 1H and 13C NMR spectra, the azaallenium salts 16 are rather flexible around the central nitrogen atom. In solution at least 16a - d assume chiral conformations similar to those of allenes. By DNMR measurements barriers to hindered rotation around the C=N+=C axis were found to range from δG173† = 36 ± 1 kJmol-1 for 16a to more than 90 kJmol-1 for 16c. According to an X-ray structural analysis, 16o crystallizes in an almost perfect allene geometry (A). - Some interesting 13C-14N couplings of the nitrilium salts 14 are reported.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 3365-3373 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zum Bau von 2-Azaallenium-KationenEntsprechend einer Röntgenstrukturanalyse kristallisiert das 2-Azaallenium-hexachloroantimonat 23 in der Topologie eines Allens (Geometrie 1a) und nicht eines 2-Azaallyl-Kations (1b). Ab-initio-Molekülorbital- (3-21 G Basissatz) und semiempirische MNDO-Rechnungen für das unsubstituierte 2-Azaallenium-Kation und einige mono- und disubstituierte Derivate (24) bestätigen die experimentellen Befunde: In vielen Fällen ist die Allengeometrie 24a stabiler als die 2-Azaallylium-Form 24b. Elektronenspendende Substituenten verringern den Energieunterschied zwischen 24b und 24a. Ein diaminosubstituiertes Allylium-Kation 24b ist energetisch stabiler als die entsprechende Allenium-Form 24a. Ganz allgemein sind substituierte 2-Azaallenium-Kationen um das zentrale Stickstoffatom sterisch flexibel. Verbindung 23 wurde nach einer neuen Synthese hergestellt.
    Notes: According to an X-ray structural analysis, the 2-azaallenium hexachloroantimonate 23 crystallizes with the topology of an allene (geometry 1a) and not of a 2-azaallyl cation (1b). Ab initio molecular orbital calculations (3-21 G basis set) and semiempirical MNDO calculations for the unsubstituted 2-azaallenium cation and for some mono- and disubstituted derivatives (24) confirm the experimental results: In many cases the allenium geometry 24a is more stable than the 2-azaallylium form 24b. Electron-releasing substituents reduce the energy difference between 24b and 24a. With two amino substituents the allylium geometry 24b is energetically preferred to the allenium form 24a. In general, substituted 2-azaallenium salts are sterically flexible around the central nitrogen atom. Compound 23 was synthesized by a new method.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 117 (1984), S. 3211-3221 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Synthese und Molekülstrukturen von Heterokumulenen mit - und -EinheitenEs wird über Synthesen, IR- und NMR-Spektren der 1-Oxa-3-azabutatrienium-hexachloroantimonate 2a-f und des 1-Thia-3-azabutatrienium-hexachloroantimonats 2g berichtet. Nach Röntgenstrukturanalysen von 2b,g kristallisieren diese Verbindungen als Pseudokumulene mit gewinkelten C=N=C= X-Einheiten ( C=N=C 129° für X = O und 139° für X = S). Die extrem feuchtigkeitsempfindlichen Salze 2a-e reagieren mit Wasser zu den Iminiumsalzen 3, Verbindung 2g dagegen zu Benzophenon. Die 1-Oxabutatrienium-Salze 2a-e reagieren mit Carbonsäuren zu deren Anhydriden und den Iminiumsalzen 3a-e. Das α-Naphthylderivat 2c cyclisiert zum Isochinolinium-Salz 5. Mit N,N-Dimethylanilin erhält man aus 2a,e,g die Triarylcarbenium-Farbstoffe 8.
    Notes: Preparations, IR and NMR spectra of 1-oxa-3-azabutatrienium hexachloroantimonates (2a-f) and of 1-thia-3-azabutatrienium hexachloroantimonate 2g are reported. According to an X-ray structure analysis of 2b,g these compounds crystallize as pseudocumulenes with bent C=N=C=X units ( C=N=C 129° for X = O and 139° for X = S). The extremely moisture sensitive salts 2a-e react with water to give the iminium salts 3, while 2g gives benzophenone. With carboxylic acids the 1-oxabutatrienium salts 2a-e afford carboxylic anhydrides (e.g. 4) and the iminium salts 3a-e. The α-naphthyl compound 2c cyclizes to give the isoquinolinium salt 5. With N,N-dimethylaniline 2a,e,g afford triarylcarbenium dyes (8).
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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