TY - JOUR
T1 - Do deprotonated amidoximes undergo the Tiemann rearrangement in the gas phase?
AU - Adams, Gregory W.
AU - Bowie, John H.
AU - Hayes, Roger N.
AU - Gross, Michael L.
PY - 1992
Y1 - 1992
N2 - The Tiemann rearrangement in the condensed phase involves base-catalysed transformation of suitably substituted amidoximes to ureas, e.g. R 1(NH2)C=NOR2 →base NH=C=NR 1 →H2O R1NHCONH2 In contrast, deprotonated amidoximes, in the gas phase, undergo only minor reaction through Tiemann intermediates. Instead, they decompose by loss of hydroxylamine, e.g. -NHC(Me)=NOH ←→ NH=C(Me) - N̄OH ←→ [(MeCN)-NHOH] → -CH2CN + NH2OH a process substantiated by 15N and 2H labelling and product-ion studies.
AB - The Tiemann rearrangement in the condensed phase involves base-catalysed transformation of suitably substituted amidoximes to ureas, e.g. R 1(NH2)C=NOR2 →base NH=C=NR 1 →H2O R1NHCONH2 In contrast, deprotonated amidoximes, in the gas phase, undergo only minor reaction through Tiemann intermediates. Instead, they decompose by loss of hydroxylamine, e.g. -NHC(Me)=NOH ←→ NH=C(Me) - N̄OH ←→ [(MeCN)-NHOH] → -CH2CN + NH2OH a process substantiated by 15N and 2H labelling and product-ion studies.
UR - https://www.scopus.com/pages/publications/37049090282
U2 - 10.1039/p29920000897
DO - 10.1039/p29920000897
M3 - Article
AN - SCOPUS:37049090282
SN - 1472-779X
SP - 897
EP - 901
JO - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
IS - 6
ER -