Stereochemistry of the bromine for chlorine exchange following /sup 79/Br(n,. gamma. )/sup 80m/Br and /sup 82m(80m)/Br(IT)/sup 82(80)/Br in diastereomeric 2,3-dichlorobutanes
The stereochemistry of bromine for chlorine substitution at asymmetric carbon atoms was studied in the pure liquid diastereomeric 2,3-dichlorobutanes and in organic solutions of these compounds. The reactive bromine species were either energetic (hot) /sup 80m/Br atoms generated via the /sup 79/Br(n,..gamma..)/sup 80m/Br nuclear process or bromine species formed as a result of Coulomb fragmentation of /sup 80m/Br- or /sup 82m/Br-labeled molecules. Distinct differences in the sterospecificity of the Br for Cl exchange have been observed depending on the type of nuclear process by which the reactive bromine species are formed and on the amount and nature of the additives present. In the case of the decay induced /sup 80/Br for Cl exchange the observed results can be explained in terms of a model in which the neutralization time for the Br/sup +/ and the time for radical recombination are the determining factors for the stereochemical course of the exchange process. The Br for Cl exchange initiated by ''hot'' /sup 80m/Br atoms appears to be primarily the result of a ''hot'' one-step replacement reaction, as indicated by the presence of a strong conformational effect on the stereochemical course of the reaction.
- Research Organization:
- Virginia Polytechnic Inst. and State Univ., Blacksburg
- OSTI ID:
- 7351146
- Journal Information:
- J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 80:7; ISSN JPCHA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400701* -- Radiochemistry & Nuclear Chemistry-- Hot-Atom Chemistry
400702 -- Radiochemistry & Nuclear Chemistry-- Properties of Radioactive Materials
ALKANES
BETA DECAY RADIOISOTOPES
BETA-MINUS DECAY RADIOISOTOPES
BETA-PLUS DECAY RADIOISOTOPES
BROMINE 80
BROMINE 82
BROMINE ISOTOPES
CHEMICAL REACTION KINETICS
CHEMISTRY
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINE
DAYS LIVING RADIOISOTOPES
DECAY
ELECTRON CAPTURE RADIOISOTOPES
ELEMENTS
ENERGY-LEVEL TRANSITIONS
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENS
HOT ATOM CHEMISTRY
HOURS LIVING RADIOISOTOPES
HYDROCARBONS
INTERMEDIATE MASS NUCLEI
INTERNAL CONVERSION RADIOISOTOPES
ION EXCHANGE
ISOMERIC NUCLEI
ISOMERIC TRANSITIONS
ISOTOPES
KINETICS
LIQUID SCINTILLATION DETECTORS
MEASURING INSTRUMENTS
MINUTES LIVING RADIOISOTOPES
NONMETALS
NUCLEI
ODD-ODD NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RADIATION DETECTORS
RADIOCHEMISTRY
RADIOISOTOPES
REACTION KINETICS
SCINTILLATION COUNTERS
STEREOCHEMISTRY