Synthesis of 5‐Alkyl‐ and 5‐Phenylamino‐Substituted Azothiazole Dyes with Solvatochromic and DNA‐Binding Properties
Synthesis of 5‐Alkyl‐ and 5‐Phenylamino‐Substituted Azothiazole Dyes with Solvatochromic and DNA‐Binding Properties
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具有溶剂致变色和 DNA 结合特性的 5-烷基和 5-苯氨基取代的偶氮噻唑染料的合成
DOI：
10.1002/chem.201903657
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
H. Ihmels
中科院分区：
文献类型：
--
作者：
P. M. Pithan;C. Kuhlmann;C. Engelhard;H. Ihmels
摘要以偶氮噻唑-4，4 ′-二羧酸二乙酯为原料，合成了一系列新的5-单氨基和5，5 ′-双氨基偶氮噻唑衍生物。该反应最可能包括在底物的碳原子C5处通过相应的伯烷基胺和芳族胺进行的初始迈克尔型加成。随后，所得中间体容易被分子氧氧化，得到氨基取代的偶氮噻唑衍生物。后者表现出显著的红移吸收带（λ abs=507-661 nm），具有高摩尔消光系数，并表现出强的正溶剂化变色性。 如光谱滴定和圆二色性和线性二色性研究所揭示的，水溶性的双（二甲基氨基丙基氨基）取代的偶氮染料通过在高配体-DNA比（LDR）下沿磷酸骨架沿着形成聚集体和通过在低LDR下嵌入而与双链体DNA缔合，这也导致在671 nm处的低发射强度的显著增加。
Abstract A series of new 5‐mono‐ and 5,5′‐bisamino‐substituted azothiazole derivatives was synthesized from the readily available diethyl azothiazole‐4,4′‐dicarboxylate. This reaction most likely comprises an initial Michael‐type addition by the respective primary alkyl and aromatic amines at the carbon atom C5 of the substrate. Subsequently, the resulting intermediates are readily oxidized by molecular oxygen to afford the amino‐substituted azothiazole derivatives. The latter exhibit remarkably red‐shifted absorption bands (λ abs=507–661 nm) with high molar extinction coefficients and show a strong positive solvatochromism. As revealed by spectrometric titrations and circular and linear dichroism studies, the water‐soluble, bis‐(dimethylaminopropylamino)‐substituted azo dye associates with duplex DNA by formation of aggregates along the phosphate backbone at high ligand–DNA ratios (LDR) and by intercalation at low LDR, which also leads to a significant increase of the otherwise low emission intensity at 671 nm.
噻唑菌素聚集及其与 DNA 小沟分子识别的关系。
影响因子：
3.8
作者：
Salvia MV
通讯作者：
Salvia MV