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  • 1
    Digitale Medien
    Digitale Medien
    Ion structural studies by ion kinetic energy spectrometry: [C7H7]+, [C7H8]+·, [C7H7OCH3]+· (1973)
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 7 (1973), S. 1303-1312 
    Details
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The use of kinetic energy release measurements in the structural characterization of ions formed in the mass spectrometer and in the determination of fragmentation mechanisms is demonstrated. In combination with information on the mode of energy partitioning in some of these reactions this allows the following conclusions: (i) The metastable [C7H8]8· ions formed from toluene, cyclohepatatriene, n-butylbenzene, the three methyl anisoles, methyl tropyl ether and benzyl methyl ether all undergo loss of H· from a common structure. (ii) The metastable [C7H7]+ ions generated from the same sources and from benzyl bromide, benzyl alcohol, p-xylene and ethylbenzene appear to undergo loss of acetylene from both the benzylic and the tropylium structures. (iii) The metastable [C7H7OCH3]+· ether molecular ions undergo loss of CH3· by two types of mechanism, simple cleavage to give the aryloxy cation (not observed for benzyl methyl ether) and a rearrangement process which appears to lead to protonated tropone as the product. (iv) Loss of formaldehyde from the metastable [C7H7OCH3]+· molecular ions involves hydrogen transfer via competitive 4- and 5-membered cyclic transition states in the case of the anisoles and in the case of methyl tropyl ether, while for benzyl methyl ether, hydrogen transfer in the nonisomerized molecular ion occurs via a 4-membered cyclic transition state to yield the cycloheptatriene molecular ion.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/oms.1210071110
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  • 2
    Digitale Medien
    Digitale Medien
    The reactive states of ions: Octatrienes and dimethyl substituted cyclohexadienes (1975)
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 10 (1975), S. 1075-1083 
    Details
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The principal decomposition routes of molecular ions of cis, cis, cis-2,4,6-octatriene, cis, cis, trans-2,4,6-octatriene, trans, cis, trans-2,4,6-octatriene, trans-5,6-dimethyl-1,3-cyclohexadiene and cis-5,6-dimethyl-1,3-cyclohexadiene were studied using ion kinetic spectroscopy. The loss of radicals from [M]+· appears to proceed via a ground state, while loss of a neutral molecule appears to involve either complete equilibration of structure within the system or both ground state and excited state pathways.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/oms.1210101205
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  • 3
    Digitale Medien
    Digitale Medien
    Ionic dehydration reactions: The effect of location of the activated complex on kinetic energy release (1977)
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 12 (1977), S. 258-260 
    Details
    ISSN: 0030-493X
    Schlagwort(e): Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A broad range of kinetic energy release has been found for the 1,4 elimination of water in a series of ortho substituted benzyl alcohols and benzoic acids. It is suggested that the trend reflects, in part, the position of the activated complex on the reaction coordinate. More specifically, reactions which proceed via an ‘early’ transition state release only small quantities of energy, whereas those processes occurring ‘later’ release a larger fraction of the available energy. Consequently, the o- methyl derivatives give large kinetic energy release compared to o- amino or hydroxy substituted compounds. Father verification is obtained from the small kinetic energy release observed for the 1,4 ionic dehydration in simple,acyclic alcohols.
    Zusätzliches Material: 2 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/oms.1210120415
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