Institute of Chemistry, University of Tartu, Ravila 14a, Tartu, 50411, Estonia.
J Org Chem. 2011 Jan 21;76(2):391-5. doi: 10.1021/jo101409p. Epub 2010 Dec 17.
In this paper, we report the most comprehensive equilibrium superacidity scale that is available to date. Contrary to most of the past works, this scale is set up in a medium of constant composition and the obtained acidity values characterize the acidities of molecules rather than acidities of media. The current scale is thus complementary to the well-known H(0) scale in the information that it provides. The solvent used is 1,2-dichloroethane (DCE). DCE has very weak basic properties (but sufficiently high polarity) and is an appropriate solvent for measuring acidities of very strong acids of diverse chemical nature. DCE acidities of well-known superacids (CF(3)SO(2)OH, (CF(3)SO(2))(2)NH, cyanocarbon acids, etc.) as well as common mineral acids (H(2)SO(4), HI, HBr, etc.) are reported. Acidities of altogether 62 acids have been determined from 176 interlinked relative acidity measurements. The scale spans 15 orders of magnitude (from picric acid to 1,1,2,3,3-pentacyanopropene) and is expected to be a useful tool in design, use, and further acidity measurements of superacidic molecules.
在本文中,我们报告了迄今为止最全面的平衡超酸尺度。与过去的大多数工作不同,该尺度是在恒定组成的介质中建立的,所得的酸度值表征分子的酸度,而不是介质的酸度。因此,该尺度与广为人知的 H(0)尺度在提供的信息上是互补的。所用的溶剂是 1,2-二氯乙烷(DCE)。DCE 具有非常弱的碱性(但极性足够高),是测量各种化学性质的极强酸的酸度的合适溶剂。报告了众所周知的超酸(CF(3)SO(2)OH、(CF(3)SO(2))(2)NH、碳酰卤酸等)以及常见矿物酸(H(2)SO(4)、HI、HBr 等)在 DCE 中的酸度。通过 176 个相互关联的相对酸度测量,总共确定了 62 种酸的酸度。该尺度跨越了 15 个数量级(从苦味酸到 1,1,2,3,3-五氰丙烯),有望成为设计、使用和进一步测量超酸性分子酸度的有用工具。