Intramolecular Cyclization of in Situ Generated Adducts Formed between Thioamide Dianions and Thioformamides Leading to Generation of 5-Amino-2-thiazolines and 5-Aminothiazoles, and Their Fluorescence Properties

Murai, Toshiaki; Hori, Fumihiko; Maruyama, Toshifumi

doi:10.1021/ol200231z

Cited by 55 publications

(16 citation statements)

References 44 publications

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“…The 3026,3005,1591,1548,1491,1448,1410,1266,1236,1213,1032,1002,992,963,831,753,728,694 8,121.6,121.9,123.4,124.0,126.2,127.4,128.1,128.8,129.3,129.4,139.2,140.4,145.4,150.3,166.8;MS (EI) According to the general procedure for thiazolines, compound 8 was prepared. The crude material was purified by column chromatography (SiO 2 , hexane:EtOAc = 15:1) to give 8 (0.87 g, 60%) as a brown liquid: IR (KBr) 3059, 3029, 2956, 2926, 1686, 1597, 1491, 1450, 1276, 1241, 1034, 948, 908, 846, 751, 728, 696 cm -1 ; 1 H NMR (400 MHz,…”

Section: General Procedures For the Preparation Of Thiazolines To A Smentioning

confidence: 99%

5-N-Arylaminothiazoles as Highly Twisted Fluorescent Monocyclic Heterocycles: Synthesis and Characterization

et al. 2015

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A series of 5-N-arylaminothiazoles was prepared by reacting thioamide dianions derived from secondary thioamides with thioformamides, followed by sequential oxidation with iodine. X-ray analyses demonstrated that they adopt structures that are highly twisted from planar conformations. Their orientations were tuned by the steric and/or electronic interactions of the substituents at their 2-, 4-, and 5-positions. The 5-aminothiazoles exhibited a range of fluorescent emissions, from blue to orange. Although the absorption spectra were independent of the polarity of the solvent, fluorescent emissions were influenced by the polarity of the solvent: in more polar solvents, the emissions were red-shifted. These phenomena were examined in terms of Lippert-Mataga plots and the change in the dipole moment between the ground and excited states. They also exhibited emissions in the solid state, again from blue to orange. Cyclic voltammetry of the 5-aminothiazoles showed reversible waves of one-electron oxidation. The half-potential of the oxidation was reduced by the introduction of electron-donating groups to the phenyl groups on the nitrogen atom at the 5-position. DFT calculations were carried out to determine the energy levels of the HOMO and LUMO. Finally, the results of TG-DTA showed that they are thermally stable.

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Section: General Procedures For the Preparation Of Thiazolines To A Smentioning

confidence: 99%

5-N-Arylaminothiazoles as Highly Twisted Fluorescent Monocyclic Heterocycles: Synthesis and Characterization

et al. 2015

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“…; H, 0.95 Å and S, 1.85 Å)[82][83][84][85][86][87]. Thus suggesting the existence of non-conventional CeH⋯N and CeH⋯S intramolecular hydrogen bonds[88], similar to those found in most 2-phenylthiazole derivatives[82][83][84][85][86][89][90][91][92].…”

mentioning

confidence: 85%

A study of the properties, reactivity and anticancer activity of novel N-methylated-3-thiazolyl or 3-thienyl carbazoles and their Pd(II) and Pt(II) complexes

Reig¹,

Bosque²,

Font-Bardı́a

et al. 2018

Journal of Inorganic Biochemistry

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The synthesis and characterization of two hybrid N-methylated carbazole derivatives containing a thiazolyl or a thienyl ring is reported. The thiazolyl derivative has been also characterised by X-ray diffraction analysis. The study of its reactivity in front of [MCl2(dmso)2] (M=Pd or Pt) or Na2[PdCl4] in methanol has allowed us to isolate and characterize its complexes. However, for the thienyl analogue, the formation of any Pd(II) or Pt(II) complex was not detected, indicating that it is less prone to bind to the M(II) ions than its thiazolyl analogue. Density Functional Theory (DFT) and Time-Dependent Density Functional Theory (TD-DFT) calculations have also been carried out in order to rationalize the influence of the nature of the thiazolyl or thienyl group on the electronic delocalization. Molecular mechanics calculations show that the free rotation of the thiazolyl in relation to the carbazole requires a greater energy income than for its thienyl analogue. Studies of the cytotoxic activity of the new compounds on colon (HCT116) and breast (MDA-MB231 and MCF7) cancer cell lines show that the thiazolyl carbazole ligand and its Pt(II) complex are the most active agents of the series and in the MCF7 line their potency is higher than that of cisplatin. In the non-tumoral human skin fibroblast BJ cell line, all the compounds were less toxic than cisplatin. Their potential ability to modify the electrophoretic mobility of pBluescript SK+ plasmid DNA and to act as inhibitors of Topoisomerases I and IIα or cathepsin B has also been investigated.

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“…We have previously reported that the fluorescence properties of 5‐ N ‐arylaminothiazole 1 (Scheme ) can be controlled by the substituents, and that the presence of electron‐donating groups on the nitrogen atom at the 5‐position bathochromically shifts the emission . 5‐Aminothiazole 1 contains monocyclic homo‐ and heteroaromatic groups, whereby their conformation is intricately correlated to both solvent and temperature.…”

Section: Methodsmentioning

confidence: 99%

Acid‐Responsive Absorption and Emission of 5‐N‐Arylaminothiazoles: Emission of White Light from a Single Fluorescent Dye and a Lewis Acid

et al. 2016

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Solutions of 5‐N‐arylaminothiazoles containing pyridyl groups exhibited clear halochromism and halofluorism upon addition of Brønsted and Lewis acids. The addition of triflic acid to solutions of 5‐N‐arylaminothiazoles in Et2O induced bathochromic shifts of the absorption and emission bands. DFT calculations suggested that the spectral changes arise from the protonation of the pyridyl group of the thiazoles in Et2O. Single‐crystal X‐ray diffraction analysis of a thiazole and its protonated form revealed the change of the conformation around the thiazole ring. The emission of white light was accomplished from a single fluorescent dye by adjusting the ratio of dye and B(C6F5)3, whereby the International Commission on Illumination coordinates showed a linear change from blue to orange.

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Intramolecular Cyclization of in Situ Generated Adducts Formed between Thioamide Dianions and Thioformamides Leading to Generation of 5-Amino-2-thiazolines and 5-Aminothiazoles, and Their Fluorescence Properties

Cited by 55 publications

References 44 publications

5-N-Arylaminothiazoles as Highly Twisted Fluorescent Monocyclic Heterocycles: Synthesis and Characterization

5-N-Arylaminothiazoles as Highly Twisted Fluorescent Monocyclic Heterocycles: Synthesis and Characterization

A study of the properties, reactivity and anticancer activity of novel N-methylated-3-thiazolyl or 3-thienyl carbazoles and their Pd(II) and Pt(II) complexes

Acid‐Responsive Absorption and Emission of 5‐N‐Arylaminothiazoles: Emission of White Light from a Single Fluorescent Dye and a Lewis Acid

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