The hydrolysis of geminal ethers: A kinetic appraisal of orthoesters and ketals

Repetto, Sonia L.; Lam, Joseph K.W.; Repetto, Sonia; Costello, James F.; Lam, Joseph K W; Butts, Craig P.; Ratcliffe, Norman M.

Abstract

© 2016 Repetto et al. A novel approach to protecting jet fuel against the effects of water contamination is predicated upon the coupling of the rapid hydrolysis reactions of lipophilic cyclic geminal ethers, with the concomitant production of a hydrophilic acyclic hydroxyester with de-icing properties (Fuel Dehydrating Icing Inhibitors - FDII). To this end, a kinetic appraisal of the hydrolysis reactions of representative geminal ethers was undertaken using a convenient surrogate for the fuel-water interface (D2 O/CD3 CN 1:4). We present here a library of acyclic and five/six-membered cyclic geminal ethers arranged according to their hydroxonium catalytic coefficients for hydrolysis, providing for the first time a framework for the development of FDII. A combination of 1H NMR, labelling and computational studies was used to assess the effects that may govern the observed relative rates of hydrolyses.

Citation

Lam, J. K., Repetto, S. L., Repetto, S., Costello, J. F., Butts, C. P., Lam, J. K. W., & Ratcliffe, N. M. (2016). The hydrolysis of geminal ethers: A kinetic appraisal of orthoesters and ketals. Beilstein Journal of Organic Chemistry, 12, 1467-1475. https://doi.org/10.3762/bjoc.12.143

• Journal Article Type: Article
• Acceptance Date: Jun 23, 2016
• Publication Date: Jul 15, 2016
• Deposit Date: Jun 9, 2016
• Publicly Available Date: Jul 15, 2016
• Journal: Beilstein Journal of Organic Chemistry
• Print ISSN: 1860-5397
• Electronic ISSN: 1860-5397
• Publisher: Beilstein-Institut
• Peer Reviewed: Peer Reviewed
• Volume: 12
• Pages: 1467-1475
• DOI: https://doi.org/10.3762/bjoc.12.143
• Keywords: FDII, geminal ethers, kinetics
• Public URL: https://uwe-repository.worktribe.com/output/922595
• Publisher URL: http://dx.doi.org/10.3762/bjoc.12.143