On Cyanine Dyes. X. Conformation of the Structures of the Tri-nuclear Cyanine Dyes

Terutaro Ogata
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Abstract

In continuation of studies of Cyanine dyes which have been prepared previously1•2>, the new method of preparation of Krypto·cyanine OA 1 (KCOA 1)> and of Thiazolocyanine OA 1 (TCOA 1) is herein described. As to the question of the structures of the trinuclear cyanine dyes, which is of interest, the ,8-methyl-trimethine · type (1)> is conceivable on basis of the formation of the tri-mesomethyl-acridylmethane tri-iodide, which was obtained by the reaction -of 9-methyl-acridine-alkyl-iodide and orthoformic acid ethylester>. In this paper I report on the new preparative methods for TCOA 1 as an additional example. The tri-nuclear dyes have been indicated to have the structure of the a-vinyl-trimethine type (II)>. The a'vinyl-trimethine type (IIIf> may be tautometric isomer of type {II). I suppose that the ,8-vinyl-trimethine type (IV)8> may be obtainable when the hydrogen of aand of a'-position are replaced by less :active radicals.
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关于菁染料。三核菁染料结构的构象
在前人研究的基础上,提出了Krypto·Cyanine oa1 (kcoa1)>和Thiazolocyanine oa1 (tcoa1)的制备新方法。对于令人感兴趣的三核菁染料的结构问题,根据9-甲基吖啶烷-烷基碘化物与原甲酸乙酯>反应得到的三中甲基吖啶甲烷三碘化物的形成,可以推测出8-甲基三甲基·(1)>。在本文中,我报告了新的制备方法tcoa1作为一个额外的例子。三核染料具有a-乙烯基三甲基型(II)>的结构。a'乙烯基三甲基型(IIIf>可能是{II型的互变异构体)。我猜想,当a -位的氢被活性较低的自由基取代时,8-乙烯基三甲基(IV)8>可能是可得的。
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