Aromatic nitration with ion radical pairs (ArH/sup +/,NO/sub 2/) as reactive intermediates. Time-resolved studies of charge-transfer activation of dialkoxybenzenes
Journal Article
·
· J. Am. Chem. Soc.; (United States)
Aromatic nitrations carried out both under electrophilic conditions and by charge-transfer activation afford the same yields and isomer distributions of nitration products from a common series of aromatic ethers (ArH). Time-resolved spectroscopy establishes the charge-transfer nitration to proceed via the ion radical pair (ArH/sup +/,NO/sub 2/), generated by the deliberate excitation of the electron donor-acceptor or ..pi.. complex of the arene with C(NO/sub 2/)/sub 4/. Laser flash photolysis of the charge-transfer band defines the evolution of the arene cation radical ArH/sup +/ and allows its decay kinetics to be delineated in various solvents and with added salts. The internal trapping of ArH/sup +/ is examined in the substituted p-dimethoxybenzenes CH/sub 3/OC/sub 6/H/sub 4/OCH/sub 2/X with X = CO/sub 2/H, CO/sub 2//sup -/, CO/sub 2/Et, and CH/sub 2/OH as the pendant functional groups. The mechanistic relevance of the collapse of (ArH/sup +/, NO/sub 2/) to the Wheland intermediate is discussed in the context of electrophilic aromatic nitrations.
- Research Organization:
- Univ. of Houston, University Park, TX
- OSTI ID:
- 6091046
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:17; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Effect of the complex-forming characteristics of aromatic solvents on the selectivity of free-radical chlorination. Chlorination of 2-chloropropane
Photochemisty of low-spin iron(III) complexes with macrocyclic ligands
Arene complexes of transition metals in reactions with nucleophilic reagents. XVIII. Effect of substituents in chlorobenzene derivatives coordinated with the Cr(CO)/sub 3/ fragment on substitution rate of the chlorine atom by action of sodium methoxide in methanol
Journal Article
·
Thu Nov 19 23:00:00 EST 1987
· J. Org. Chem. USSR (Engl. Transl.); (United States)
·
OSTI ID:7160053
Photochemisty of low-spin iron(III) complexes with macrocyclic ligands
Journal Article
·
Fri Oct 31 23:00:00 EST 1980
· Inorg. Chem.; (United States)
·
OSTI ID:6535736
Arene complexes of transition metals in reactions with nucleophilic reagents. XVIII. Effect of substituents in chlorobenzene derivatives coordinated with the Cr(CO)/sub 3/ fragment on substitution rate of the chlorine atom by action of sodium methoxide in methanol
Journal Article
·
Mon Oct 10 00:00:00 EDT 1988
· J. Org. Chem. USSR (Engl. Transl.); (United States)
·
OSTI ID:6008648
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ARGON COMPOUNDS
ARGON HYDRIDES
CATIONS
CHARGED PARTICLES
CHEMICAL REACTIONS
DATA
DEUTERIUM
DEUTERIUM COMPOUNDS
ELECTRON TRANSFER
EXPERIMENTAL DATA
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
IONS
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
NITRATION
NITROXYL RADICALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
RADICALS
RARE GAS COMPOUNDS
REACTION INTERMEDIATES
STABLE ISOTOPES
TIME DEPENDENCE
400201* -- Chemical & Physicochemical Properties
400202 -- Isotope Effects
Isotope Exchange
& Isotope Separation
ARGON COMPOUNDS
ARGON HYDRIDES
CATIONS
CHARGED PARTICLES
CHEMICAL REACTIONS
DATA
DEUTERIUM
DEUTERIUM COMPOUNDS
ELECTRON TRANSFER
EXPERIMENTAL DATA
HYDRIDES
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INFORMATION
IONS
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
NITRATION
NITROXYL RADICALS
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
RADICALS
RARE GAS COMPOUNDS
REACTION INTERMEDIATES
STABLE ISOTOPES
TIME DEPENDENCE