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Photochemical transformation. 35. Stereochemistry of electron transfer from photoexcited aromatic rings to carbon-chlorine bonds. Syn stereochemistry of migration in photo-Wagner-Meerwein rearrangements

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00363a022· OSTI ID:6855919
; ;
Studies have been conducted on the ground-state and excited-state solvolyses of the isomeric 7,8-dichloro derivatives of benzonaphthobicyclo(2.2.2)octadiene and benzoveratrobicyclo(2.2.2)octadiene. The silver ion assisted ground-state reactions proceed, as anticipated, with clean anti-stereochemistry (inversion at the migration terminus) reflected in the Wagner-Meerwein rearranged solvolysis products. Unlike the previously reported observations that excitation transfer from a photoexcited benzene ring to a ..beta..-carbon-chlorine bond requires anti-stereochemistry, electron transfer from excited naphthalene or veratrole rings occurs to both syn and anti carbon-chlorine bonds, although that to the latter is preferred. The results are consistent with an electron-transfer process to give a zwitterionic biradical and are rationalized by the Weller equation. Separation of chloride ion from the presumed zwitterionic biradical is accompanied by ''Wagner-Meerwein'' rearrangement but is predominately syn, rather than anti as in the ground state. The rearrangement stereochemistry is consistent with the idea that, in the principal photochemical process, migration with retention of configuration is concerted with the loss of chloride ion. 3 tables.
Research Organization:
Univ. of Colorado, Boulder
DOE Contract Number:
AC02-79ER10366
OSTI ID:
6855919
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 105:25; ISSN JACSA
Country of Publication:
United States
Language:
English

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Related Subjects

14 SOLAR ENERGY
140505 -- Solar Energy Conversion-- Photochemical
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& Thermochemical Conversion-- (1980-)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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ACETIC ACID
ACETOLYSIS
ACETONITRILE
ALKANES
ALKENES
AROMATICS
CARBOXYLIC ACIDS
CATALYTIC EFFECTS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHLORINATED AROMATIC HYDROCARBONS
CONDENSED AROMATICS
CYCLOALKANES
CYCLOALKENES
DATA
DECOMPOSITION
DIENES
ELECTRON TRANSFER
ELEMENTS
EXPERIMENTAL DATA
HALOGENATED AROMATIC HYDROCARBONS
HYDROCARBONS
INFORMATION
IONIZATION
KINETICS
METALS
MONOCARBOXYLIC ACIDS
NITRILES
NMR SPECTRA
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC SOLVENTS
PHOTOCHEMICAL REACTIONS
PHOTOIONIZATION
POLYENES
REACTION KINETICS
SILVER
SOLVENTS
SOLVOLYSIS
SPECTRA
STEREOCHEMISTRY
SYNTHESIS
TIME DEPENDENCE
TRANSITION ELEMENTS