Heavy Atom Isotope Effect Studies of Organic Reaction       Mechanisms
{'Code': '03090003', 'Directorate': {'Abbreviation': 'MPS', 'LongName': 'Direct For Mathematical & Physical Scien'}, 'Division': {'Abbreviation': 'CHE', 'LongName': 'Division Of Chemistry'}}
{'SignBlockName': 'Benjamin F. Plummer', 'PO_EMAI': None, 'PO_PHON': None}
This grant in the Organic and Macromolecular Chemistry Program                  supports the research of Professor Authur Fry, which aims at                    studying reaction pathways through the use of isotopes.  When a                 particular element like hydrogen or carbon is replaced by a                     heavier isotope of that element then a difference in the rate                   of the reaction may be noted if the isotope itself is directly                  involved in the slow step of the reaction.  This is an elegant                  method of abstracting mechanistic information from chemical                     reactions.                                                                                                                                                      Chemical compounds which differ only in isotopic composition                    sometimes react at slightly different rates (kinetic isotope                    effects).  By relating the structures of the reacting compounds                 to whether or not isotope effects are observed (and, if so, to                  the size of the isotope effects) much information can be                        deduced about the details of the paths by which these molecules                 react.  Correlation of experimentally measured and                              theoretically calculated isotope effects is believed to be one                  of the best methods for determining details of transition state                 structure, motion through the transition state, and the timing                  of bonding changes in chemical reactions. The method is most                    powerful when used with compounds successively labeled at all                   positions suspected of undergoing bonding changes, and                          especially when substituted phenyl groups are located near the                  reaction centers.                                                                                                                                               This research utilizes these techniques in determining                          mechanistic details for a wide variety of additions,                            elimination, rearrangement, substitution and                                    oxidation/reduction reactions.  Current research is focused on                  carbon-14 isotope effect measurements in elimination, addition                  and substitution reactions.  Specific systems being studied                     include additions of bromine and arylsulfenyl chlorides to                      substituted styrenes and cinnamic acid derivatives; elimination                 reactions of DDT-related compounds and other 2-phenylethyl                      systems (Elcb-like mechanisms); and solvolyses of highly                        deactivated (by triflouromethyl groups, etc.) 1-phenylethyl                     systems (El/SN1 mechanisms).
{'FirstName': 'Arthur', 'LastName': 'Fry', 'PI_MID_INIT': None, 'PI_SUFX_NAME': None, 'PI_FULL_NAME': 'Arthur Fry', 'EmailAddress': None, 'NSF_ID': '000410739', 'StartDate': '07/01/1987', 'EndDate': None, 'RoleCode': 'Principal Investigator'}
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{'Code': '1944', 'Text': 'BIMOLECULAR PROCESSES'}
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