116467-75-5Relevant academic research and scientific papers
Decoupling deprotonation from metalation: Thia-fries rearrangement
Dyke, Alan M.,Gill, Duncan M.,Harvey, Jeremy N.,Hester, Alison J.,Lloyd-Jones, Guy C.,Munoz, M. Paz,Shepperson, Ian R.
supporting information; experimental part, p. 5067 - 5070 (2009/03/11)
(Chemical Equation Presented) Label-enabled: Studies with 2H-, 18O-, and 34S-labeled aryl triflates show that lithium diisopropylamide-mediated thia-Fries rearrangement proceeds through an irreversible ortho deprotonation (see scheme; DIPA = diisopropylamine, LDA = lithium diisopropylamide). In contrast, ortho metalation results exclusively in the generation of a benzyne.
Gas-phase oxygenation of benzene derivatives around 300 K with O(3P) atoms produced by microwave discharge of N2O. Part 2. Kinetic H/D isotope effects.
Sol, Veronica M.,Louw, Robert,Mulder, Peter
, p. 346 - 352 (2007/10/02)
The possible pathways for the formation of (chloro)phenol, following the addition of O(3P) to (chloro)benzene, have been examined using deuterated substrates: C6D6 (also in admixture with C6H6) and p-deuterochlorobenzene.Whereas with O-C6H6 adduct biradicals, loss of H* to give phenoxy radicals predominates, only one-third of the O-C5D6 intermediates undergo the corresponding reaction.Phenoxy radicals lead to phenol by transfer of an H(D) atom from cyclohexadienyl-type radicals, formed from H* (D*) and substrate.Analogously, in reactions of p-deuterochlorobenzene, loss of H is a major reaction after addition of an oxygen atom to a meta position, whereas loss of D (to give p-chlorophenol) occurs only with 35percent of the corresponding O(3P) adduct biradicals.The isotopic composition of phenol formed from p-DC6H4Cl (via p-DC6H4O*; generated by ipso substitution) revealed that H transfer to phenoxy radicals primarily gives the keto tautomers as major products.Isomerization of (chloro)benzene-O(3P) adduct biradicals to the corresponding phenols also appears to involve mainly, keto tautomers.The reaction of O(3P) with p-deuterochlorobenzene showed a slight change in the o/m/p distribution; this can be explained by the absence of a net secondary H/D isotope effect for O(3P) addition to the para site and a normal secondary isotope effect for meta addition.
