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CnH2nCl+ ion formation in electron impact MS conditions: a theoretical study

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Abstract

The mass spectral fragmentation of different 1-chloroalkanes (of the 1-chlorohexane-1-chlorooctadecane series) has been investigated, quantifying the relative abundance of the fragment ions. The base peak is dominantly at m/z 91, 93 in each investigated case, although with the increasing chain length, its contribution to the total ion current exhibits some reduction. Among the possible fragmentation products, the five-membered chloronium containing ring is the most stable as measured by an isodesmic reaction, although the six-and seven-membered rings exhibit only slightly reduced stability. The most stable structure of the 1-chlorohexane radical cation has a hydrogen bonded structure with the involvement of chlorine and the HC(δ), pre-forming the five-membered cationic ring. Accordingly, among the reactions leading to alkyl (or H) radical and a chloronium containing ring, this transition structure has the lowest energy, providing explanation for the experimental observations.

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Notes

  1. The 1-fluoroalkanes provide low abundant C2H4F+ (m/z 47), C3H6F+ (m/z 61), and C4H8F+ (m/z 75) (Fig. S4); other CnH2nF+ ions are negligible [4]. This observation could be explained with the higher ionization potential and the resulting increased ion decompositions instead of CnH2nF+ formation. The ion decomposition is a HF elimination reaction that leads to various cyclic hydrocarbons fragments. The structures of cyclic products depend on the place of the eliminating hydrogen. It is noteworthy that 1-chloroalkanes molecular ions can also proceed through 1,3-eliminations of HCl to form ions containing a cyclopropane ring [5].

  2. The C2H5O+ cyclic ions produced only from 2-bromoethanol, 2-nitroethanol, and direct protonation of ethylene oxide. However, other straight chain isomers of C2H5O+ also formed simultaneously from these compounds.

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Acknowledgments

Financial support from New Szechenyi Plan TAMOP-4.2.2/B-10/1-2010-0009 and OTKA K 170356 is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szent Gellért tér 4, Budapest, 1111, Hungary

    Zoltán Benkő, Noémi Göröcs, László Könczöl, László Nyulászi & Dénes Szieberth

  2. B&B Analytics Ltd., Szent Gellért tér 4, Budapest, 1111, Hungary

    József Balla

Authors
  1. Zoltán Benkő
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  2. Noémi Göröcs
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  3. László Könczöl
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  4. László Nyulászi
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  5. Dénes Szieberth
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  6. József Balla
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Correspondence to László Nyulászi.

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Benkő, Z., Göröcs, N., Könczöl, L. et al. CnH2nCl+ ion formation in electron impact MS conditions: a theoretical study. Struct Chem 25, 659–665 (2014). https://doi.org/10.1007/s11224-013-0371-5

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