53299-64-2Relevant academic research and scientific papers
CATALYTIC REARRANGEMENT OF THE CHLOROALLYL ETHERS OF p-CRESOL
Andreev, N. A.,Bunina-Krivorukova, L. I.,Levashova, V. I.
, p. 345 - 351 (2007/10/02)
The rearrangement of a series of p-cresol ethers (β- and γ-chloro-, β,γ- and β,γ,γ-trichloroallyl), catalyzed by boron trifluoride etherate, was studied.Increase in the number of chlorine atoms in the allyl unit of the ether hinders the rearrangement, and its mechanism changes in the investigated series of ethers from intramolecular -sigmatropic (with inversion of the allyl unit) to intermolecular, which corresponds to electrophilic substitution in the aromatic ring (without inversion).The presence of the chlorine atom at the β position of the allyl unitpromotes rearrangement by a concerted intramolecular mechanism, while a chlorine atom at the γ position promotes rearrangement by an intermolecular stage mechanism.Two chlorine atoms at the γ position give rise mainly to the intermolecular rearrangement path.
THERMAL REARRANGEMENT OF CHLORINE-CONTAINING ALLYL ETHERS OF p-CRESOL. FORMATION OF 2H-CHROMENE
Andreev, N. A.,Levashova, V. I.,Bunina-Krivorukova, L. I.
, p. 966 - 970 (2007/10/02)
The thermal rearrangement of β- and γ-chloro- and β,γ-dichloroallyl ethers of p-cresol takes place by an intramolecular mechanism with inversion of the allyl unit of the initial ether.The final product from the rearrangement of γ-chlorine-containing ethers are 2H-chromenes, which are formed in parallel by two paths involving a -sigmatropic shift either with the formation of a classical Claisen phenol at the first stage or with the formation of propargyl ether (as a result of the elimination of HCl).In the presence of two chlorine atoms at the γ position the alkenyl aryl ethers do not change when heated under the adopted conditions.
