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  • Analytical Chemistry and Spectroscopy  (332)
  • ddc:330
  • Wiley-Blackwell  (332)
  • 1970-1974  (332)
  • 1972  (332)
  • 1
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 4 (1972), S. 725-732 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: H-NMR investigations using a high resolution 220 MHz spectrometer were performed on methyl, acetyl and benzoyl derivatives of mannan from ivory nuts and Tubera salep, and on the corresponding d-mannopyranose derivatives. With the exception of the C(1) configuration the structure of these polysaccharides may be determined by comparing the coupling constants and chemical shifts of the substituted polysaccharides with those of the corresponding monosaccharide derivatives. The particularly broad signals in the spectra of low as well as high molecular weight acetyl and benzoyl mannans and furthermore, the differences between the chemical shifts of protons in 1,2,3,4,6-penta-O-acetyl-d-mannopyranose and those of the benzoylated mannans, are discussed in terms of relatively small flexibility of the polymer chains or chain segments in solution. In addition studies to determine the type of glycosidic bonds in polysaccharides from a comparison of the δH(1)-values of various polyglycan derivatives are reported.
    Notes: Die PR-Spektren einiger Methyl-, Acetyl- und Benzoylderivate von Mannan aus Steinnuß und Tubera salep sowie der d-Mannopyranose wurden analysiert. Durch einen Vergleich der Kopplungskonstanten und der Signallagen von entsprechend substituierten Polymeren und Monomeren wird, mit Ausnahme der Konfiguration an C(1), die Struktur dieser Polysaccharide bestimmt. Es wird auf charakteristische Unterschiede der Resonanzlagen von H(1) in Polysacchariden mit α-bzw. β-glycosidischen Bindungen hingewiesen. Dieser Befund eröffnet die Möglichkeit, auch in solchen Fällen eine Entscheidung über die Art der glycosidischen Bindung zu treffen, in denen, wie im Falle der Mannoside mit äquatorialständigem H(2), der Wert der Kopplungskonstante J12 keine Aussage erlaubt.Die auffallend große Breite der Signale in den Spektren der nieder- und hochmolekularen Acetyl- und Benzoylmannane wird auf eine geringe Beweglichkeit der Kette oder einzelner Kettensegmente bei Mannanderivaten in Lösung zurückgeführt.
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 4 (1972), S. 737-763 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 4 (1972) 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 4 (1972), S. 767-778 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Solvent effects on compounds of formula (X—CH2—CH2)2O with X = Cl, Br, I have been studied. The rotamer ratios have been determined for each solvent according to Lin's method and it is shown that the three compounds moved to gauche forms when increasing the medium dielectric constant.Additionally, it is shown that geminal couplings of the iodine derivative algebraically decrease on increasing the medium polarity. An attempt to correlate these variations with rotamer populations is made.
    Notes: L'effet de solvant sur les éthers disubstitués de formule (X—CH2—CH2)2O avec X = Cl, Br, I a été étudié. Les pourcentages des différentes formes stables ont été déterminés pour chaque solvant suivant la méthode de Lin et il est montré que ces trois halogénures évoluent vers les formes gauches quand la constante diélectrique de la solution augmente.De plus, il est montré que les couplages géminés dans le cas du dérivé iodé diminuent algébriquement quand la polarité du solvant augmente. Les auteurs pésentent une tentative de corrélation des variations des couplages géminés avec l'évolution conformationnelle.
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 4 (1972), S. 811-823 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: C-13 and F-19 NMR spectra of seventeen para-substituted fluorobenzenes were measured and the chemical shifts as well as coupling constants with respect to substituents were analysed. The chemical shifts of the fluorine, the C1 and the C2 atoms were found to depend on the total electron densities. In the case of the C3 atom, the chemical shifts seem to depend on π-electron densities rather than the total electron densities. The present calculations also indicate that the chemical shift of the C4 atom depends mainly on σ-electron densities due to the inductive effects of substituents. The strongest factor influencing the coupling constant, nJ(C—F), is also considered to be the π-electron densities on the carbon atoms. In the case of the direct couplings, 1J(C—F), the π-bond orders are important.
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 4 (1972), S. 831-836 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 14N and 35Cl NQR spectra have been investigated for 24 organophosphorus compounds using a pulse technique. The electron populations of the nitrogen lone pair orbital and the N—P bond are calculated according to the Townes and Dailey method. The experimental data are interpreted assuming a partial double bond character of the N—P bond due to the pπ—dπ interaction and pπ—σ conjugation of the lone pair electrons of the nitrogen atoms. The effect of the different nature of substituents X on the N—P bond populations is observed in X = PRn (R2N)3-n molecules (where X is O, S, Se, or lone pair electrons and n = 0, 1, 2). It can be seen from this dependence that the effective electronegativity of the phosphorus atom is largest in selenophosphoramidates and falls in the sequence P=Se 〉 P=S 〉 P=O 〉 P.
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  • 7
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Praseodymium(III) tris(dipivalomethanato) [Pr(DPM)3] reduces the complex overlapping aromatic absorptions in the proton NMR spectrum of a monosubstituted naphthalene, cis-3-(1-naphthyl)-1,3,5,5-tetramethlcyclohexan-1-ol(1) to a virtually first-order pattern, whereas Eu(DPM)3 at the same and higher molar concentrations does not completely resolve the aromatic proton signals. Plots of the Pr(DPM)3-induced shifts measured in carbon tetrachloride solution versus molar equivalents of Pr(DPM)3 added may be extrapolated to provide accurate chemical shifts in the absence of added lanthanide shift reagent (LSR). The qualitative conformational conclusions from the Pr(DPM)3 shifts agree with those from the Eu(DPM)3-induced shifts, but there are detailed differences in the relative lanthanide-induced shifts (LIS) for different proton types in the molecule.
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 4 (1972), S. 847-856 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Fluorine magnetic resonance shifts are reported for substituted 1- and 2-phenyl-fluoro-ethanols. They have been extrapolated at infinite dilution in solute and internal standard. The linear or other type correlations between these chemical shifts and substituent constants σ lead us to discuss the validity of linear free energy relationships extended to NMR data. The limits and possibilities of such relationships are emphasised.
    Notes: Les déplacements chimiques du fluor de différents phényls-1 et 2 fluoro éthanols ont été mesurés; les valeurs obtenues ont été extrapolées à dilution infinie en soluté et référence interne. Les corrélations linéaires ou non, obtenues entre ces déplacements chimiques et les constantes de substituant σ donnent lieu à une discussion générale relative à la validité des relations d'enthalpie libre étendues aux données de la RMN; les limites et les possibilités de telles relations sont précisées.
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 4 (1972), S. 875-883 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The NMR spectra of a spiro oxirane (1) derivative of codeinone, codeine (2), isocodeine (3), 6-methylcodeine (4) and 6-methylisocodeine (5) were compared. NOE and double-resonance experiments were used to confirm the conformation of 1, and the configuration about C-6 of 6-methylcodeine and 6-methylisocodeine. An interchange of the chemical shifts of the olefinic protons in 1 was noted, as compared with those in all of the other compounds. This interchange could be attributed to the bond anisotropies of the oxirane moiety.
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  • 10
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 4 (1972), S. 857-873 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The 13C-NMR-chemical shifts of 19 para- and 5 ortho-cyclohexadienones are determined by 13C-Fourier-transformation spectroscopy and assigned. The effect of substituents on the chemical shift of the ring carbon atoms is discussed. The mutual dependence of the shifts of the olefinic ring carbons and the allylic carbon atom in the para-quinolid ring system is shown by computing regression lines. A frequently observed correlation between 13C-NMR and 1H-NMR is examined in the case of cyclohexadienones.
    Notes: Die 13C-chemischen Verschiebungen von 19 para-und 5 ortho-Cyclohexadienonen werden durch 13C-Fourier-Transform-Spektroskopie ermittelt und zugeordnet. Der Substituenteneinfluß auf die chemische Verschiebung der Signale der Ringkohlenstoffatome wird diskutiert. Durch die Aufstellung von Regressionsgeraden wird gezeigt, daß die Resonanzlagen der olefinischen Ringatome und des allylischen C-Atoms im para-chinoliden Ring wechselseitig voneinander abhängen. Eine Korrelation zwischen 1H-NMR- und 13C-NMR-Daten wird am Beispiel der Cyclohexadienone überprüft.
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