Pulse radiolysis and 77 K matrix. gamma. irradiation of dimethyl truxinates and trans-methyl cinnamate in 2-methyltetrahydrofuran
One-electron reduction of dimethyl ..mu..-truxinate (..mu..-DMT), dimethyl ..beta..-truxinate (..beta..-DMT), and dimethyl ..cap alpha..-truxillate (..cap alpha..-DMT) has been investigated by pulse radiolysis and 77 K matrix ..gamma.. irradiation of the 2-methyltetrahydrofuran solutions. Cycloreversion of the radical anions formed by an electron attachment to these cyclobutanes was observed in all cases, even at 77 K. The orientation of the cycloreversion was dependent on the stereochemistry of the cyclobutanes, and the selectivity was reasonably explained by a so-called cis effect; the best possible release of steric hindrance decides the primary step of the reaction. In 77 K matrix ..gamma.. irradiation of ..cap alpha..-DMT, an intense IR absorption was found after the photobleaching of trapped electrons with light > 690 nm. In other DMTs, the IR absorption band was not observed while the cycloreversion of DMT by mobile electrons occurred. Thus, the IR band in the case of ..cap alpha..-DMT was assigned to an associated dimer anion due to the interaction between the radical anion and the neutral molecule pair of trans-methyl cinnamate orginally formed by the cycloreversion of ..cap alpha..-DMT. The dimer anion was presumed to be oriented in a head-to-tail structure in a solvent cage on the basis of the original configuration of ..cap alpha..-DMT.
- Research Organization:
- Osaka Univ., Japan
- OSTI ID:
- 6592193
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 86:10
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CYCLOALKANES
RADIOLYSIS
STEREOCHEMISTRY
ABSORPTION SPECTRA
CHEMICAL REACTIONS
ELECTRON BEAMS
ELECTRON CAPTURE
EXPERIMENTAL DATA
GAMMA RADIATION
LOW TEMPERATURE
MTHF
PULSED IRRADIATION
RADICALS
REDUCTION
ALKANES
BEAMS
CAPTURE
CHEMICAL RADIATION EFFECTS
CHEMISTRY
DATA
DECOMPOSITION
ELECTROMAGNETIC RADIATION
FURANS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INFORMATION
IONIZING RADIATIONS
IRRADIATION
LEPTON BEAMS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PARTICLE BEAMS
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIATIONS
SPECTRA
TETRAHYDROFURAN
400600* - Radiation Chemistry
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)
400200 - Inorganic
Organic
& Physical Chemistry