Catalytic rearrangement of the chloroallyl ethers of p-cresol
The rearrangement of a series of p-cresol ethers (..beta..- and ..gamma..-chloro-, ..beta gamma..- and ..beta gamma..,..gamma..-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 (3,3)-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 ..beta.. position of the allyl unit promotes rearrangement by a concerted intramolecular mechanism, while a chlorine atom at the ..gamma.. position promotes rearrangement by an intermolecular stage mechanism. Two chlorine atoms at the ..gamma.. position give rise mainly to the intermolecular rearrangement path.
- Research Organization:
- Lensovet Leningrad Technological Institute, USSR
- OSTI ID:
- 6035898
- Journal Information:
- J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 22:2; ISSN JOCYA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400201* -- Chemical & Physicochemical Properties
640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
AROMATICS
BENZENE
BORON COMPOUNDS
BORON FLUORIDES
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL REACTIONS
CHLORINATED AROMATIC HYDROCARBONS
CHROMATOGRAPHY
CONFORMATIONAL CHANGES
COUPLING
COUPLING CONSTANTS
CRESOLS
DEHYDROCYCLIZATION
ETHERS
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HALOGENATED AROMATIC HYDROCARBONS
HYDROCARBONS
HYDROXY COMPOUNDS
INFRARED SPECTRA
INTERMEDIATE COUPLING
J-J COUPLING
MOLECULAR STRUCTURE
NMR SPECTRA
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PHENOLS
SEPARATION PROCESSES
SPECTRA