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島根農科大学研究報告 Volume 12
published_at 1964-01-10
アミンオキシド類のポーラログラムの非可逆理論による解析
Application of a Theory of Irreversible Polarographic Waves to the Reduction of Amine Oxides
Date Yoshio
Yamamoto Harumi
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The theory of irreversible polarographic waves was applied to the reduction of a series of aliphatic amino oxides such as trimethyl-, dimethylbenzyl-, dibenzylmethyl- and tribenzyl-amine oxides, and of a series of substituted N, N-dimethylaniline oxides such as dimethyl-p-toluidine-, dimethyl-p-chloraniline-, dimethyl-m-chloraniline-, dimethyl-o-toluidine- and dimethyl-o-chloraniline oxides. In every case, a well-defined straight line was obtained in the relation between logk and E (vs. SHE). In aliphatic amine oxides the plot log ^<k^0_f> vs. E_<1/2> for the first three yielded a straight line, while the one for the last deviated somewhat from the line. On the other hand, the plot for N, N-dimethylaniline oxides substituted in para or meta position fell into a straight line a little different in its slope from that for those substituted in ortho position.
In spite of the above fact, those deviations are rather small, and the relation between log ^<k^0_f> values for the oxides and pK_a values for the parent amines in both groups agrees at least qualitatively with that between E_<1/2> and pK_a shown formerly. Therefore we may say that the above E_<1/2> values used in the comparison between the molecular structure and the electrode process roughly show the characters of the structure of each amine oxide.
In spite of the above fact, those deviations are rather small, and the relation between log ^<k^0_f> values for the oxides and pK_a values for the parent amines in both groups agrees at least qualitatively with that between E_<1/2> and pK_a shown formerly. Therefore we may say that the above E_<1/2> values used in the comparison between the molecular structure and the electrode process roughly show the characters of the structure of each amine oxide.
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