title: Solvolysis-decomposition of 2-adamantyl chloroformate: evidence for two reaction pathways.
abstract: Reaction of 2-adamantyl chloroformate under a variety of solvolytic conditions leads to 2-adamantyl chloride accompanied by solvolysis products, some with and some without retention of the CO(2) unit. For example, in 100% ethanol, only 4.8% 2-adamantyl chloride is formed with the mixed carbonate (88%) being the dominant product, and in 100% 2,2,2-trifluoroethanol, the products are both formed with loss of CO(2), 59% of the chloride and 41% of the ether. With exclusion of the specific rates in 100% and 90% ethanol and methanol, a good Grunwald-Winstein plot against Y(Cl) values (solvent ionizing power) is obtained, with a slope of 0.47 +/- 0.03. The results are compared with those reported earlier for 1-adamantyl chloroformate and isopropyl chloroformate and mechanistic conclusions are drawn.
authors.affiliation: Department of Chemistry, Hanyang University, Ansan, Kyunggi-Do 425-791, South Korea. jbkyong@hanyang.ac.kr
authors.forename: Jin Burm
authors.initials: JB
authors.lastname: Kyong
authors.forename: Jung-Suk
authors.initials: JS
authors.lastname: Yoo
authors.forename: Dennis N
authors.initials: DN
authors.lastname: Kevill