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Clinical Chemistry, Vol 23, 1669-1678, Copyright © 1977 by American Association for Clinical Chemistry
KR Johnson, G Ellis and C Toothill
New evidence is presented for the mechanism of this reaction, which is used in estimating lipids. The reaction occurs in two stages: (a) Stage 1 evidently involves an oxidation step, forming a specific type of carbonium ion called an alkenyl cation of the general formula R--C+-- C==C--R' (previous evidence had indicated that a carbonium ion of general formula R--C+--R' was formed by protonation only.) (b) Stage 2 of the reaction was examined by nuclear magnetic resonance studies and by partition experiments, which have indicated that a vanillin phosphate ester is not formed as previously suggested. Comparative data from other acid-aldehyde reactions indicate that in this reaction 1,1- di(4-hydroxy-3-methoxy phenyl)ethylene ion is formed, a product compatible with the formation of an alkenyl cation at stage 1.
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