18062-78-7Relevant academic research and scientific papers
EFFECT OF NUCLEOPHILIC ADDITIONS ON THE VARIATION OF THE ORTHO-PARA ORIENTATION DURING THE CATALYTIC REARRANGEMENT OF ALKENYL ARYL ETHERS
Feoktistov, V. M.,Bunina-Krivorukova, L. I.,Aleksandrova, E. K.
, p. 1977 - 1984 (2007/10/02)
The catalytic rearrangement of γ-chloro-γ-methyl- and γ,γ-dimethylallyl ethers of o- and p-cresols in the presence of various amounts (0.25-10 moles) of the related nucleophiles (o- and p-cresol) was investigated.The contribution from intermolecular alkenylation of the related nucleohile increases substantially with increase in its amount from 0.25 to 4 moles.Further increase (to 10 moles) gives a small increase in the degree of alkenylation.Comparison of the products from ortho-para-alkenylation during rearrangement and during direct alkenylation of the mixtureof cresols by allyl halides makes it possible to suppose that the catalytic rearrangement of the ethers can take place both by an intermolecular mechanism and, in parallel, by an intramolecular (non-Claissen) mechanism with the formation of the same products - with retention of the structure of the allyl unit in the initial ether.
EFFECT OF STRONG NUCLEOPHILE ON THE DIRECTION OF TRANSFORMATION IN ALKENYL ARYL ETHERS DURING CATALYTIC REARRANGEMENT
Bunina-Krivorukova, L. I.,Feoktistov, V. M.,Aleksandrova, E. K.,Bal'yan, Kh. V.
, p. 745 - 750 (2007/10/02)
The results from the introduction of tetrahydrothiophene into the reaction zone during the catalytic rearrangements of alkenyl aryl ethers demonstrate the possibility of a change in the direction of transformation of the ether from -sigmatropic rearrangement to intermolecular alkenylation of a concurrent strong nucleophile.The heterolytic character of the catalytic intermolecular rearrangement (alkenylation) was confirmed by the formation of alkenylsulfonium salts, the structure of the allyl unit which corresponded to the most thermodynamically stable isomer.
