RELATIVELY FAST SOLVOLYTIC REACTIONS OF 1-ADAMANTYL MESYLATE - FURTHER DEVELOPMENT OF THE YOTS SCALE OF SOLVENT IONIZING POWER AND THE NOTS SCALE OF SOLVENT NUCLEOPHILICITY
RELATIVELY FAST SOLVOLYTIC REACTIONS OF 1-ADAMANTYL MESYLATE - FURTHER DEVELOPMENT OF THE YOTS SCALE OF SOLVENT IONIZING POWER AND THE NOTS SCALE OF SOLVENT NUCLEOPHILICITY
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DOI：
10.1021/jo00152a033
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发表时间：
1983-01-01
影响因子：
3.6
通讯作者：
CARTER, GE
中科院分区：
文献类型：
--
作者：
BENTLEY, TW;CARTER, GE
本文报道了甲磺酸金刚烷酯在乙醇、甲醇、丙酮和三氟乙醇二元混合水溶液中的溶剂分解速率常数。反应的半衰期从约。50分钟到。0.3直接在25 ℃下用方便的电导法测定。另外还报道了2-金刚烷磺酸酯在甲醇水溶液中溶剂分解的动力学数据。从甲苯磺酸酯/甲磺酸酯速率比获得的1-金刚烷基甲苯磺酸酯的溶剂分解速率的对数与2-金刚烷基甲苯磺酸酯的溶剂分解速率的对数线性相关（斜率为1.06±0.03）。因此，甲苯磺酸酯（Y 0X 8）的溶剂电离能力的非常相似的标度可以由log（m/m）Ador = mY 0 Ta定义，其中m= 1.0，AdOTs是指甲苯磺酸1-或2-金刚烷酯。将10种纯溶剂（叔丁醇、2-丙醇、乙醇、甲醇、三氟乙醇、六氟异丙醇和水以及乙酸、甲酸和三氟乙酸）的Yox值与（30）、* 和经验溶剂化参数进行比较; Y 0Xs和Ex（30）之间存在令人满意的相关性，但在Y 0Xs与it* 图中存在大量分散。还计算了溶剂亲核性参数N 0 Ts的附加值。
Solvolytic rate constants for 1-adamantyl mesylate in binary aqueous mixtures of ethanol, methanol, acetone, and trifluoroethanol are reported. Reactions with half-lives varying from ca. 50 min to ca. 0.3 s are followed directly at 25 C by convenient conductimetric methods. Additional kinetic data for solvolyses of 2-adamantyl sulfonates in aqueous methanol are also reported. Logarithms of solvolysis rates for 1-adamantyl tosylate, obtained from tosylate/mesylate rate ratios, correlate linearly (slope of 1.06±0.03) with logarithms of solvolysis rates for 2-adamantyl tosylate. Therefore, very similar scales of solvent ionizingpower for tosylates (Y0X8) may be defined by log (&/&o) Ador»= mYOTa, where m= 1.0 and AdOTs refers to either 1-or 2-adamantyl tosylate. Yox, values for ten pure solvents (tert-butyl alcohol, 2-propanol, ethanol, methanol, trifluoroethanol, hexafluoroisopropyl alcohol, and water and acetic, formic, and trifluoroacetic acids) are compared with the (30),*, and a empirical solvation parameters; there is a satisfactory correlation between Y0Xs and Ex (30) but substantial scatter in a Y0Xe vs. it* plot. Additional values of the solvent nucleophilicity parameter N0Ts are also calculated.