Chemical ionization mass spectrometry (CIMS) is often used for the cha
racterization of thermally stable and electron impact-labile compounds
, and acetone is one of the CI reagent gases used not only to characte
rize the analytes but also to differentiate regio-and stereoisomers. T
he nature of the reagent ions, the factors affecting the reagent plasm
a, and the type of ion-molecule reactions with the substrate molecules
under acetone/CI are briefly discussed in this article. The ion-molec
ule reactions between the reagent ions and a wide variety of organic c
ompounds are reviewed. The mechanisms involved in the formation of cha
racteristic ions studied by using acetone-d(6) as a reagent and also b
y collision-induced dissociation of the respective adduct ions have be
en discussed. The site of acetylation in most of the substrates by the
reagent ions of acetone has been found to depend on the nature and po
sition of the substituents present in the substrate, and in some cases
the acetylation reaction is controlled by the steric factors. (C) 199
8 John Wiley & Sons, Inc.