Rate and product studies with 2‐adamantyl fluoroformate under solvolytic conditions |
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| Authors: | Jin Burm Kyong Chan Joo Rhu Yong‐Gun Kim Dennis N Kevill |
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| Institution: | 1. Department of Chemistry and Applied Chemistry, Hanyang University, Ansan‐si, Gyeonggi‐do 426‐791, KoreaDepartment of Chemistry and Applied Chemistry, Hanyang University, Ansan‐si, Gyeonggi‐do 426‐791, Korea.===;2. Department of Chemistry and Applied Chemistry, Hanyang University, Ansan‐si, Gyeonggi‐do 426‐791, Korea |
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| Abstract: | 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 NT solvent nucleophilicity scale and the YCl 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 kF/kCl 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. |
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| Keywords: | 2‐adamantyl fluoroformate addition– elimination Grunwald– Winstein equation product selectivity |
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