ANODIC CYANATION OF TERTIARY ALIPHATIC AND HETEROCYCLIC AMINES
ANODIC CYANATION OF TERTIARY ALIPHATIC AND HETEROCYCLIC AMINES
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DOI：
10.1021/jo00438a005
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发表时间：
1977-01-01
影响因子：
3.6
通讯作者：
TAKATA, Y
中科院分区：
文献类型：
--
作者：
CHIBA, T;TAKATA, Y
结果在铂阳极上，用三乙胺和α-二乙氨基丙腈在0.5M氰化钠-甲醇水溶液中进行了电流-电位测量。如图1所示，三乙胺在约0.7 V（SCE）下开始放电，然后电流在0.9 V或更高时急剧上升，而α-二乙氨基丙腈在比三乙胺更阳极化的约0.3 V下氧化。通常，氰化产物的氧化电位显著高于相应结合胺的值。在不含三乙胺的甲醇氰化钠水溶液中，在1.0 V附近观察到偏离欧姆电流，并且电解电流通过1.7 V的电势逐渐增加。6-8尽管氰离子浓度高，电流增加的程度非常低。因此，在胺的存在下，胺本身的氧化在1.4V以下将不受显著影响。
ResultsPrior to the preparativestudies, current-potential mea-surements were carried out with triethylamine and a-diethylaminopropionitrile in 0.5 M sodium cyanide-aqueous methanol solution at a platinum anode. As shown in Figure 1, triethylamine initiated a discharge at approximately 0.7 V (SCE) and then the current rose steeply at 0.9 V or over, whereas a-diethylaminopropionitrile was oxidized at about 0.3 V more anodic thantriethylamine. Generally, oxidation potentials of the cyanated products are substantially higher than the values for the correspbnding amines. In aqueous methanolic sodium cyanide without tri-ethylamine, a deviation from the ohmic current was observed in the vicinity of 1.0 V, and the electrolytic current gradually increased through the potential of 1.7 V. 6-8 Despite the high concentration of cyanide ion, the degree of increase in the current was very low. Therefore, in the presence of amine, the oxidation of amine itself would be insignificantly affected below 1.4 V.