Chemical ionization and collisional activation spectra of α,β-unsaturated nitriles |
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Authors: | K. P. Madhusudanan V. S. Murthy D. Fraisse |
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Abstract: | A study of the chemical ionization (CI) and collisional activation (CA) spectra of a number of α, β-unsaturated nitriles has revealed that the even-electron ions such as [MH]+ and [MNH4]+ produced under chemical ionization undergo decomposition by radical losses also. This results in the formation of M +˙ ions from both [MH]+ and [MNH4]+ ions. In the halogenated molecules losses of X˙ and HX compete with losses of H˙ and HCN. Elimination of X˙ from [MH]+ is highly favoured in the bromoderivative. The dinitriles undergo a substitution reaction in which one of the CN groups is replaced with a hydrogen radical and the resulting mononitrile is ionized leading to [M ? CN + 2H]+ under CI(CH4) or [M ? CN + H + NH4] and [M ? CN + H + N2H7]+ under CI(NH3) conditions. |
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