McLafferty Rearrangement
A carbonyl-containing ion with a gamma hydrogen transfers that hydrogen to the carbonyl oxygen through a six-membered cyclic transition state, then cleaves the beta bond to expel a neutral alkene. The surviving enol radical cation appears at an even-mass m/z, a strong clue for aldehydes, ketones, esters and acids with a chain of at least three carbons.
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A carbonyl-containing ion with a gamma hydrogen transfers that hydrogen to the carbonyl oxygen through a six-membered cyclic transition state, then cleaves the beta bond to expel a neutral alkene. The surviving enol radical cation appears at an even-mass m/z, a strong clue for aldehydes, ketones, esters and acids with a chain of at least three carbons.
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