Drochioiu Gabi, Mangalagiu Ionel, Avram Ecaterina, Popa Karin, Dirtu Alin Constantin, Druta Ioan
Organic Chemistry and Biochemistry Department, Al I Cuza University of Iasi, 11 Carol I, Iasi-700506, Romania.
Anal Sci. 2004 Oct;20(10):1443-7. doi: 10.2116/analsci.20.1443.
A new sensitive spectrophotometric method has recently been developed for the trace determination of cyanide with ninhydrin. Cyanide ion was supposed to act as a specific base catalyst. Nevertheless, this paper demonstrates that the reported assay is based on a novel reaction of cyanide with 2,2-dihydroxy-1,3-indanedione, which affords purple or blue colored salts of 2-cyano-1,2,3-trihydroxy-2H indene. Hydrindantin is merely an intermediary of the reaction. The formation of a stable and isolable ninhydrin-cyanide compound has been confirmed by its preparation in crystalline form. Also, it is thoroughly characterized by elemental as well as MS, IR, UV/VIS and 1H NMR analyses. The Ruhemann's sequence of reactions of cyanide with ninhydrin has been reconsidered and an adequate mechanism of the reaction is proposed. As a consequence, the interference of oxidizers as well as copper, silver and mercury ions with the cyanide determination has been elucidated.
最近开发了一种新的灵敏分光光度法，用于用茚三酮痕量测定氰化物。氰离子被认为是一种特殊的碱催化剂。然而，本文证明所报道的测定方法基于氰化物与2,2 - 二羟基 - 1,3 - 茚二酮的一种新反应，该反应生成2 - 氰基 - 1,2,3 - 三羟基 - 2H茚的紫色或蓝色盐。茚二酮只是该反应的中间体。通过以结晶形式制备，已证实形成了稳定且可分离的茚三酮 - 氰化物化合物。此外，通过元素分析以及质谱、红外、紫外/可见光谱和1H核磁共振分析对其进行了全面表征。重新考虑了氰化物与茚三酮反应的鲁赫曼反应序列，并提出了适当的反应机理。因此，阐明了氧化剂以及铜、银和汞离子对氰化物测定的干扰。
