Abstract
A series of saturated linear dimethyl diesters [MeO2C·[CH2]n·CO2Me, n= 1–8 or 12], hitherto only examined by low resolution mass spectroscopy, have been examined using a high resolution instrument. An important decomposition mode for M– CO2Me and M– CH2CO2Me ions is loss of keten with associated methoxy-migration. In this manner, ions with compositions corresponding to those normally derived from saturated aliphatic ether groupings are generated. Carbonium ion-stabilising substitutents in substituted dimethyl succinates and glutarates in general enhance the abundance of the rearrangement ions, which frequently are among the most abundant in the spectra.

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