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  • 1
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectrometric behaviour of the 1,3-diaminopropane derivative 4a (3,7-diacetyl-3,7-diazadodecane) was investigated with regard to the fragmentation reactions of N, N′, N″-triacetylspermidine (1), as model for the 1,3-diaminopropane part. It was established that the degradation reactions in 4a and 1 are essentially the same and mainly due to the interaction of two N-acetyl groups. Thereby it is established that the most important mass spectrometric fragmentation reactions of spermidine derivatives take place within the 1,3-diaminopropane unit and are independent of the influence of further N-atoms in the molecule. An ion (m/e 143) was found in the fragmentation pattern of N, N′, N″-triacetylspermidine whose formation can be explained by interaction of all three N-acetyl groups. The corresponding ion was not found, in the spectrum of 4a, with only two N-acetyl groups, thereby confirming the earlier hypothesis.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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  • 2
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mass spectral fragmentation of dimethyl glutamate (1) and its deuterated derivatives 1a, 1b and 1c has been investigated. By loss of a methoxycarbonyl group from the molecular ion an ion of m/e 116 is generated. The latter splits off methanol (m*), the resulting fragment of m/e 84 giving raise to the base peak of the spectrum. Only part of the hydrogen transferred to the leaving group originates from thc amino group, as was suggested earlier [2] [3]. Basing on experiments with deuterated compounds we propose an additional mechanism for the reaction, i.e. hydrogen transfer from C(3) to methoxyl. The fragment generated by both processes is most likely to be a pyrrolinonium ion. Thermal side reactions in the mass spectrometer (formation of pyroglutamic acid ester) followed by fragmentation may lead to the same ion. - The mechanisms discussed are supported by the mass spectral fragmentation of N-acetyl-glutamic acid diesters 3, 3a, 3b and 3d and of the N, N-dimethyl derivatives 4 and 4a. - The fragmentation reactions investigated are similar to some of 1,3-trimethylenediamine derivatives [7]. This means that there are parallels in the mass spectral fragmentation of difunctional compounds irrespective of the nature of the functional groups.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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