Sayed Abdelwahed R, Ahmed Mohamed S M, Gomha Sobhi M
Department of Chemistry, Faculty of Science, King Faisal University, Al-Hofuf, Al-Ahsa, 31982, Saudi Arabia.
Department of Chemistry, Faculty of Science, Cairo University, Giza 12613, Egypt.
Curr Org Synth. 2020;17(4):282-287. doi: 10.2174/1570179417666200226091711.
Hydrazonoyl halides are convenient for the synthesis of arylazothiazoles.
A series of novel arylazothiazoles were efficiently synthesized from the reaction of hydrazonoyl chlorides with 2-(adamantan-2-ylidene)hydrazinecarbothioamide or 2-(ferrocenyl-1-ylidene)hydrazinecarbo-- thioamide in dioxane used as an aprotic solvent because of its lower toxicity and higher boiling point (101 °C) and triethylamine at reflux. The reaction mechanistic pathway proceeded by the nucleophilic substitution reaction by the elimination of hydrogen chloride to give thiohydrazonates as intermediate, which in situ undergo intramolecular cyclization and loss of water molecule to afford the final product of novel arylazothiazoles. This method is simple with good yield and excellent purities.
The synthetic schemes for the final products are proposed and discussed. The chemical structures of the final products were identified by different techniques, such as elemental analysis, Fourier-transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), and mass spectrometry (MS).
In this article, we prepared arylazothiazoles from the reaction of 2-(adamantan-2-ylidene)hydrazinecarbothioamide or 2-(ferrocenyl-1-ylidene)hydrazinecarbothioamide with hydrazonoyl halides.
卤代肼基酰卤便于用于芳基偶氮噻唑的合成。
以二氧六环作为非质子溶剂（因其毒性较低且沸点较高（101℃）），在回流条件下，使肼基酰氯与2 -（金刚烷 - 2 - 亚基）肼基硫代甲酰胺或2 -（二茂铁 - 1 - 亚基）肼基硫代甲酰胺反应，高效合成了一系列新型芳基偶氮噻唑。反应机理途径是通过亲核取代反应消除氯化氢生成硫代腙酸酯作为中间体，该中间体原位进行分子内环化并失去水分子，从而得到新型芳基偶氮噻唑的最终产物。此方法简单，产率高且纯度优异。
提出并讨论了最终产物的合成方案。通过元素分析、傅里叶变换红外光谱（FT - IR）、核磁共振（NMR）和质谱（MS）等不同技术对最终产物的化学结构进行了鉴定。
在本文中，我们通过2 -（金刚烷 - 2 - 亚基）肼基硫代甲酰胺或2 -（二茂铁 - 1 - 亚基）肼基硫代甲酰胺与卤代肼基酰卤的反应制备了芳基偶氮噻唑。
