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Rate and product studies with 2‐adamantyl fluoroformate under solvolytic conditions
Author(s) -
Kyong Jin Burm,
Rhu Chan Joo,
Kim YongGun,
Kevill Dennis N.
Publication year - 2007
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/poc.1194
Subject(s) - chemistry , solvolysis , nucleophile , chloroformate , solvent , aqueous solution , medicinal chemistry , solvent effects , selectivity , organic chemistry , computational chemistry , hydrolysis , catalysis
The specific rates of solvolysis of 2‐adamantyl fluoroformate have been measured at 25.0 °C in 20 pure and binary solvents. These are well correlated using the extended Grunwald–Winstein equation, with incorporation of the N T solvent nucleophilicity scale and the Y Cl solvent ionizing power scale. The sensitivities ( l = 2.15 ± 0.17 and m = 0.95 ± 0.07) toward the changes in solvent nucleophilicity and solvent ionizing power, and the k F / k Cl values are very similar to those previously observed for solvolyses of n‐octyl fluoroformate, consistent with the addition step of an addition‐elimination pathway being rate‐determining. For aqueous ethanol, measurement of the product ratio allowed selectivity values ( S ) to be determined. The results are compared with those reported earlier for 2‐adamantyl chloroformate and mechanistic conclusions are drawn. Copyright © 2007 John Wiley & Sons, Ltd.