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  • 1
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to study the structure dependence of the 13C,H coupling constants in polycyclic conjugated π electron systems with 5-and 7-membered rings, the 1H coupled 13C NMR spectra of aceheptylene, azulene and 5-azaazulene have been analysed. The results are discussed, including published data of monocyclic reference compounds, and are compared to theoretical values calculated by the FPT-INDO method. It is shown that, first, the geminal 13C,H couplings in the unsaturated 5-membered carbocycles are predominantly dependent on CC bond lengths. Second, the vicinal 13C,H coupling constants in 5- as well as in 7-membered unsaturated carbocyclic rings can be linearly related to the lengths of the central CC bonds. Third, the vicinal inter-ring couplings show a large variation and give information on ring junction, thus being of special value in structure determination and are governed mainly by the bond angles. Fourth, the calculated 13C,H couplings across one and two bonds are totally useless for practical purposes; those across three bonds, however, at least reflect the experimental trends.
    Additional Material: 1 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 7 (1975), S. 199-205 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Using the pulse Fourier transform technique, the undecoupled carbon-13 NMR spectra of the products obtained in the reaction of methyltriazines with 1-(dimethylamino)-1-ethoxyethylene have been recorded and completely assigned. A comparison of the observed 13C chemical shifts and 13C—H coupling constants with those in the starting triazines and in 2-dimethylamino-2-penten-4-one confirms the (2-dimethylamino-1-propenyl) triazine structure. The data are discussed in terms of steric effects and of the configuration and conformation of the sidechain.
    Notes: Die unentkoppelten 13C-NMR-Spektren der bei der Reaktion von Methyltriazinen mit 1-Äthoxy-1-(dimethylamino)-äthylen entstandenen Produkte wurden mit Hilfe der Puls-Fourier-Transform-Technik aufgenommen und analysiert. Der Vergleich der beobachteten 13C-chemischen Verschiebungen und 13C—H-Kopplungskonstanten mit denen der Ausgangstriazine und des 2-Dimethylamino-2-penten-4-ons bestätigt die (2-Dimethylamino-1-propenyl)triazin-Struktur. Die Daten werden im Hinblick auf sterische Effekte sowie die Konfiguration und Konformation der Seitenkette diskutiert.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 7 (1975), S. 194-198 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Using the pulse Fourier transform technique, the high resolution carbon-13 NMR spectra of 1,2,4- and 1,3,5-triazine and their methyl derivatives as well as the 1H noise decoupled spectra of phenyl- and methylphenyl substituted triazines, have been recorded and analysed. The chemical shifts of the polysubstituted 1,2,4-triazines normally show additivity; deviations observed with phenyl derivatives are ascribed to steric effects. The 13C—H coupling constants are compared to those of benzene, pyridine, the diazines and disubstituted ethylenes. The strong influence on the coupling constants exerted by number and position of the nitrogen atoms is revealed by the observation that geminal couplings in 1,2,4-triazine are larger than vicinal ones, in contrast to the usual sequence.
    Notes: Mit Hilfe der Puls-Fourier-Transform-Technik wurden die Hochauflösungs-13C-NMR-Spektren des 1,2,4- und 1,3,5-Triazins sowie ihrer Methylderivate aufgenommen, ferner auch die 1H-breitbandentkoppelten 13C-Spektren von phenyl- und methyl-phenyl-substituierten Triazinen. Die chemischen Verschiebungen der mehrfach substituierten 1,2,4-Triazine verhalten sich weitgehend additiv; Abweichungen bei Phenylderivaten werden sterischen Ursachen zugeschrieben. Die 13C—H-Kopplungskonstanten werden mit denen im Benzol, im Pyridin, in den Diazinen sowie in disubstituierten Äthylenen verglichen. Der starke Einfluß von Anzahl und Position der Stickstoffatome auf die Kopplungskonstanten läßt sich daran erkennen, daß im 1,2,4-Triazin, entgegen der üblichen Reihenfolge, geminale Kopplungen größer als vicinale sind.
    Additional Material: 1 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 8 (1976), S. 273-274 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 13C,15N coupling constants in three 1,2,4-triazine-4-15N derivatives and in a substituted pyrimidine-1-15N have been determined and are compared with those in pyridine and quinoline. Of special interest are the data of the 5-(2-dimethylamino-1-propenyl)-3,6-dimethyl-1,2,4-triazine-4-15N, since one observes a characteristic alternation of the absolute value of J(13C,15N) along the sidechain and a hitherto unobserved very large 13C,15N coupling constant through four bonds of 3·9 Hz, the origin of which is attributed to the influence of the lone pair orbital on the 15N at position 4.
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 11 (1978), S. 197-203 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Vicinal 13C, H coupling constants 3J(CO, H) for butenedioic acids and 3J(CH3, H) for 3-pentene-2-ones have been determined and are correlated with the configuration of the corresponding C=C double bond. For both types the relationship 3J(CH) trans 〉 3J(CH)cis holds; in the case of the CH3, H couplings, however, the 3J(CH3, H) trans values are reduced because of steric reasons, so that configurational assignments seem possible only when both isomers are present. Additionally, the coupling constants 3J(COCH3,H) and the chemical shifts δCOCH3 have been evaluated for the pentenones and it is shown that these parameters give information about the predominating conformation of α, β-unsaturated methyl ketones.
    Additional Material: 2 Ill.
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