Journal ArticleDOI
Reaction of (E)-O-Arylbenzaldoximes with Sodium Methoxide in Methanol. Effect of Leaving Group upon Nitrile-Forming Transition State
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In this article, reactions of (E)-O-arylbenzaldoximes 1-3 with MeONa-MeOH have been studied kinetically, in which the first step is rate-determining.Abstract:
Reactions of (E)-O-arylbenzaldoximes 1-3 with MeONa-MeOH have been studied kinetically. The reactions proceed via competing E2 and S N Ar reactions, in which the first step is rate-determining. Although the reactions were strongly influenced by the electronic effect of the β- and O-aryl substituents, they were insensitive to the steric effect of the O-aryl group, except that the S N Ar reaction was retarded by the CF 3 group of 2. For eliminations from 1-3 promoted by MeONa-MeOH, the k H /k D value increased and the Hammett p value decreased with better leaving groupsread more
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Journal ArticleDOI
Controlled Double-Bond Migration in Palladium-Catalyzed Intramolecular Arylation of Enamidines.
Lena Ripa,Anders Hallberg +1 more
TL;DR: A combination of BINAP and the amidine function was required to obtain the isomers 5a and 5b with the double bond in the homoallylic position relative to the aryl group.
Journal ArticleDOI
Theoretical study on the lithium-halogen exchange reaction of 1,1-dihaloalkenes with methyllithium and the nucleophilic substitution reaction of the resulting α-halo alkenyllithiums
TL;DR: Transition structures for the lithium-bromine exchange reaction of 1,1-dibromoalkenes with methyllithium have been located by both the B3LYP and the MP2 levels of theory with the 6-31+G basis set and predict both the kinetic and the thermodynamic stereoselectivity correctly.
Journal ArticleDOI
Aryl radical endo cyclization of enamidines. Selective preparation of trans and cis fused octahydrobenzo[f]quinolines
Lena Ripa,Anders Hallberg +1 more
TL;DR: In the 7-endo cyclization to N-protected octahydro-1H-benzo[3,4]cyclohepta[1,2-b]pyridine, the trans fused isomer predominates, although the selectivity is low.
Journal ArticleDOI
Mechanism of electrophilic chlorination: experimental determination of a geometrical requirement for chlorine transfer by the endocyclic restriction test.
TL;DR: An endocyclic restriction test for acid-catalyzed transfer of chlorine from a protonated chloroamine to an aromatic ring provides data that are consistent with a transition structure with a large bond angle between the entering and leaving groups around chlorine.
Journal ArticleDOI
Elimination reactions of (E)-O-p-nitrophenyl-2,4-dinitrobenzaldoxime promoted by triethylamine in MeCNH2O
TL;DR: In this paper, the E2 mechanism was used to eliminate (E)-O-p-nitrophenyl-2,4-dinitrobenzaldoxime promoted by triethylamine in MeCNH2O.
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