Calculation of Acidity Constants of Protonated Weak Organic Bases by a New Method, III* Ethers

Chemistry Department, College of Science, University of Texas, El Paso, T X 79968, USA Z. Naturforsch. 84b, 614-620 (1979); received September 11, 1978 Relative Basicity Parameter, Conductivity of Protonated Ethers, Calculation of PKA'S for R20H+ It is shown in this paper that a consistent set of values of pKBH+ for 24 ethers, in good agreement with the few which have been obtained b y other methods, can be calculated from a correlation of the HCl solubility in the ethers with La\ of the R groups, and also with the gas phase I .P . ' s of the ethers. W e find that in solution the order of basicity is R 0 H > R 2 0 > H 2 0 whereas in the gas phase it is R 2 0 > R 0 H > H 2 0 . Evidence for complete H+ transfer to R2O is deduced for most cases, but a H-bonding "bas i c i ty " occurs for the less basic ethers. A brief review of previously obtained pKBH+'s for some ethers, MeOH, and H2O is also presented.