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High-energy chemistry: Part A. Isomeric transition activation in 5-bromouridine. Part B. Molecular mechanics calculations and stereochemical reactions for dihalogenated hydrocarbons
Abstract
A. Reaction of $\sp{80}$Br activated by thermal neutron capture and $\sp{82}$Br generated by the $\sp{\rm 82m}$Br(I.T.) $\sp{82}$Br nuclear transformation was studied in aqueous solutions of 5-bromouridine. The $\sp{80}$Br total organic product yield decreased with decreasing solute concentration. This was as expected for a high energy recoil atom in a system with decreasing aggregate size. The $\sp{82}$Br total organic product yield showed no concentration dependence. The later data indicates that the Auger effect Coulombic explosion model does not apply in this system. B. The conformational energies in 2,3-dihalogenated butanes, 2,3-dihalogenated pentanes and 3,4-dihalogenated hexanes were calculated using molecular mechanics techniques. The rotational isomer populations in the gas, liquid and solid phases were determined from the conformational energies. The results were in agreement with previously reported data which was available for the 2,3-dichlorobutanes. The steric hinderance was also calculated for each chiral carbon. Substitution reactions of $\sp{38}$Cl-for-X and $\sp{\rm 82m}$Br-for-X (X = halogen) in dihalobutanes and dihalopentanes were examined and interpreted in light of the molecular mechanics calculations. These results indicate that retention of configuration is the dominant pathway. However, significant inversion of configuration product was measured indicating that a two-channel mechanism is present.
Subject Area
Chemistry|Nuclear chemistry|Radiation
Recommended Citation
Meyer, Richard Jonathan, "High-energy chemistry: Part A. Isomeric transition activation in 5-bromouridine. Part B. Molecular mechanics calculations and stereochemical reactions for dihalogenated hydrocarbons" (1989). ETD collection for University of Nebraska-Lincoln. AAI9013615.
https://digitalcommons.unl.edu/dissertations/AAI9013615