Hydrogen/chlorine exchange reactions of gaseous carbanions

  • Hao Chen
  • R. Graham Cooks
  • Eduardo C. Meurer
  • Marcos N. Eberlin


Gas-phase reactions of three typical carbanions CH2NO 2 , CH2CN, and CH2S(O)CH 3 with the chloromethanes CH2Cl2, CHCl3, and CCl4, examined by tandem mass spectrometry, show a novel hydrogen/chlorine exchange reaction. For example, reaction between the nitromethyl anion CH2NO 2 and carbon tetrachloride CCl4 forms the ion CHClNO 2 . The suggested reaction mechanism involves nucleophilic attack by CH2NO 2 at the chlorine of CCl4 followed by proton transfer within the resulting complex [CH2ClNO2 + CCl 3 ] to form CHClNO 2 and CHCl3. Two other carbanions CH2CN and CH2S(O)CH 3 also undergo the novel hydrogen/chlorine exchange reactions with CCl4 but to a much smaller extent, their higher nucleophilicities favoring competitive nucleophilic attack reactions. Proton abstraction is the exclusive pathway in the reactions of these carbanions with CHCl3. While CH2CN and CH2S(O)CH 3 promote mainly proton abstraction and nucleophilic displacement in reactions with CH2Cl2, CH2NO 2 does not react.


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Copyright information

© American Society for Mass Spectrometry 2005

Authors and Affiliations

  • Hao Chen
    • 1
  • R. Graham Cooks
    • 1
  • Eduardo C. Meurer
    • 2
  • Marcos N. Eberlin
    • 2
  1. 1.Department of ChemistryPurdue UniversityWest LafayetteUSA
  2. 2.Institute of ChemistryState University of Campinas, UNICAMPCampinas SPBrazil

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