Solvolysis−Decomposition of 2-Adamantyl Chloroformate:  Evidence for Two Reaction Pathways

• Published in: Journal of organic chemistry Vol. 68; no. 9; pp. 3425 - 3432
• Main Authors: Kyong, Jin Burm, Yoo, Jung-Suk, Kevill, Dennis N.
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 02.05.2003
• Subjects: Chemistry; Exact sciences and technology; Kinetics and mechanisms; Organic chemistry; Reactivity and mechanisms; Solvent effect; Solvolysis; Decomposition; Kinetics; Reaction rate; Chlorine Organic compounds
• ISSN: 0022-3263; 1520-6904
• DOI: 10.1021/jo0207426

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 CO2 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 CO2, 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.