The gas phase reactivity of chloronium ions by high pressure mass spectroscopy

The reactions of CH3ClCH3+ (I) and CH3ClCH2Cl+ (II) with a range of bases have been studied in a high pressure ion source. Reactant ion monitoring has been used to obtain the relative reactivities. Transfer of CH3+ from I and CH2Cl+ from II are the only reactions observed with N- and O-containing bases. Following addition of CH2Cl+ from II, the lower alkyl aromatics (ArH) yield either ArHCH2Cl+ or the benzyl ions ArCH2+ and ArCHCl+ while CH3+ transfer leads only to ArHCH3+. The reactivities of the alkyl aromatics increase with increasing exothermicity (benzene → mesitylene) and there is an increasingly negative temperature coefficient of reactivity in the same order.