Theoretical studies of eliminations. 5. Intermolecular vs intramolecular eliminations: An ab initio study of the gas-phase reaction of NH2- with CH3CH2SCH3

Journal of Organic Chemistry

Volumn 61, Issue 26, 1996, Pages 9430-9433

  Gronert, Scott ^a   Freed, Peter ^a  

^a SAN FRANCISCO STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0005984443     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo961482t     Document Type: Article

References (23)

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4. This mechanism has also been noted in the reactions of ethers with strong bases in solution: Maercker, A.; Demuth, D. Liebigs Ann. Chem. 1977, 1909.
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20. The reaction of free VII has a negative activation barrier, and the presence of the ammonia should further stabilize transition state VIII (via ion-dipole interactions) relative to the separated reactants.
21. 3, VII may not have enough internal energy to reach VIII.
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23. Zero-point energy differences do not suggest any unusual isotope effects in these transition states. However, a very low primary isotope effect is observed because the transition state is late and has a nearly fully formed H-F bond.