AbstractThe mass spectral fragmentations of methyl mono‐ and dichlorobutanates have been studied. Deutrium labelling and metastable ion analysis were used to elucidate the fragmentation mechanisms. The molecular ion peaks of the esters are weak and show only in the spectra of the monochloro isomers. A McLafferty rearrangement gives the base peaks in the spectra of methyl 2‐chloro‐, 4‐chloro‐ and 4,4‐dichlorobutanoate; α‐cleavage, [COOCH3]+, in methyl 2,2‐ and 2,4‐dichlorobutanoate; [MCl]+, in methyl 3‐chlorobutanoate; [MClHCl]+, in methyl 3,4‐dichlorobutanoate; [MClCH2CO]+, in methyl 3,3‐dichlorobutanoate and [MClCOOCH3]+˙, in methylerythro‐ andthreo‐2,3‐dichlorobutanoate. The mass spectra of the stereoisomers are nearly identical, the loss of a chlorine atom and the McLafferty rearrangement giving the