Studies in organic mass spectrometry. VI [1]. Influence of alkylsubstituents on the fragmentation of 1,3‐dioxane

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Abstract
The mass spectra of 1,3‐dioxane and its 2,4,5‐ and 6‐alkyl substituted derivatives are discussed. Two main degradation patterns result respectively from initial elimination of a 2‐hydrogen atom or alkyl substituent and from the expulsion of a formaldehyde molecule. Subsequent fragmentations are highly influenced by the presence of substituents.4,6‐Disubstituted 1,3‐dioxanes exhibit a distinct and typical fragmentation, starting with the expulsion of a substituent.Some of the mechanisms proposed are sustained by deuterium labeling.