HYDRIDE TRANSFER AND OXYANION ADDITION EQUILIBRIA OF NAD+ ANALOGS

HYDRIDE TRANSFER AND OXYANION ADDITION EQUILIBRIA OF NAD+ ANALOGS
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DOI:
10.1021/jo00222a006
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发表时间:
1985-01-01
影响因子:
3.6
通讯作者:
KREEVOY, MM
KREEVOY, MM
中科院分区:
化学2区
文献类型:
--
作者:
OSTOVIC, D;LEE, ISH;KREEVOY, MM

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已经确定了15个n -杂环氢化物供体(吖啶、喹啉、吡啶和菲苯啶衍生物)还原10-甲基吖啶离子的平衡常数K。溶剂为2-丙醇和水的混合物,体积比为4:1。通过假设K′s相同,并接受-361 mV作为3-(氨基羰基)-1-苄基吡啶离子的还原电位,估计了水溶液中相应阳离子的还原电位。这些还原电位跨越430 mV。pKR的值也被确定为六个阳离子在同一溶剂。对于同一环系的导数,-。delta。log K近似等于。pKR,但当菲蒽啶衍生物与9-甲基吖啶离子比较时,出现4个对数单位的差异。
Equilibrium constants, K, have been determined for the reduction of 10-methylacridinium ion by 15 N-heterocyclic hydride donors: acridine, quinoline, pyridine, and phenanthridine derivatives. The solvent was a mixture of 2-propanol and water in the ratio 4:1 by volume. Reduction potentials have been estimated for the corresponding cations in aqueous solution by assuming that the K''s would be the same and accepting -361 mV as the reduction potential of the 3-(aminocarbonyl)-1-benzylpyridinium ion. These reduction potentials span 430 mV. Values of pKR have also been determined for six of the cations in the same solvent. For derivatives of the same ring system, -.DELTA. log K is approximately equal to .DELTA.pKR, but a 4 log unit discrepancy appears when phenanthridine derivatives are compared with the 9-methylacridinium ion.