Premium
Substitution of 9‐(α‐bromo‐α‐arylmethylene)fluorenes by thiolate ions in aqueous acetonitrile
Author(s) -
Rappoport Zvi,
Shainyan Bagrat A.
Publication year - 1997
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(199712)10:12<871::aid-poc952>3.0.co;2-r
Subject(s) - chemistry , substituent , acetonitrile , sn1 reaction , nucleophilic substitution , aryl , aqueous solution , nucleophile , medicinal chemistry , leaving group , solvent , ion , substitution reaction , nucleophilic aromatic substitution , computational chemistry , solvent effects , organic chemistry , alkyl , catalysis
The substitution of 9‐(α‐bromo‐α‐arylmethylene fluorenes by MeS − and p ‐TolS − ions in 80% MeCN–20% H 2 O is a second‐order reaction. With MeS − , for the change of the α‐aryl group, Hammett's ρ=1·07 in MeCN. The reaction rate decreases on increasing the water content of the medium. The reactions proceed by the Ad N – E route and no competitive S N 1 reaction was observed. The expected influence of the changes in the substituent, solvent, nucleophile and nucleofuge on the competition between the Ad N – E and S N 1 reactions was analyzed. © 1997 John Wiley & Sons, Ltd.