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Characterization and Reactivity of the [N,N-Dimethyl(thioformamidyl)]-9-fluorenyl Cation(1).

Authors :
Lew CS
Wong DF
Johnston LJ
Bertone M
Hopkinson AC
Lee-Ruff E
Source :
The Journal of organic chemistry [J Org Chem] 1996 Oct 04; Vol. 61 (20), pp. 6805-6808.
Publication Year :
1996

Abstract

The 9-[N,N-dimethyl(thioformamidyl)]-9-fluorenyl cation was generated under stable ion conditions and characterized by UV/visible and NMR spectroscopy and methanol trapping reactions. The same cation was generated by laser excitation of the appropriate chloride precursor in 2,2,2-trifluoroethanol, and rate constants for nucleophilic quenching by alcohols and several anions were measured. The quenching data for this and other 9-fluorenyl cations demonstrate that the reactivity decreases for 9-substituents in the order H > carbomethoxy > N,N-dimethyl(thioformamidyl), demonstrating that the thioamidyl group imparts substantial kinetic stabilization to an adjacent cationic center. Both steric and electronic factors are suggested to be important in determining this reactivity order.

Details

Language :
English
ISSN :
1520-6904
Volume :
61
Issue :
20
Database :
MEDLINE
Journal :
The Journal of organic chemistry
Publication Type :
Academic Journal
Accession number :
11667572
Full Text :
https://doi.org/10.1021/jo941685m