Synthesis, Table of Contents Synthesis 2022; 54(07): 1793-1802DOI: 10.1055/a-1684-0308 paper Halogenations of 3-Aryl-1H-pyrazol-5-amines Authors Jing He Yueting Wei Yijiao Feng Chuntian Li Bin Dai∗ Ping Liu∗ Recommend Article Abstract Buy Article(opens in new window) All articles of this category(opens in new window) Abstract A direct C–H halogenation of 3-aryl-1H-pyrazol-5-amines using N-halogenosuccinimides (NXS; X = Br, I, Cl) in dimethyl sulfoxide at room temperature has been developed. This transformation provides an effective metal-free protocol for the synthesis of novel 4-halogenated pyrazole derivatives with moderate to excellent yields. The method utilizes NXS reagents as cheap and safe halogenating reagents under simple and mild reaction conditions, it has broad substrate scope, and can be used for gram-scale synthesis. The utility of this procedure is established by further transformations of the 4-halogenated products. Mechanism studies show that DMSO plays a dual role of catalyst and solvent. Key words Key wordshalogenation - metal-free - pyrazol-5-amine - synthesis - 4-halogenopyrazole - N-halogenosuccinimides - dimethyl sulfoxide Full Text References References 1 Taylor RD, MacCoss M, Lawson AD. G. J. Med. Chem. 2014; 57: 5845 2 MacBean C. The Pesticide Manual, 16th ed. British Crop Production Council; Alton: 2012 3a Janin YL. Chem. Rev. 2012; 112: 3924 3b Jedinák L, Cankař P. Eur. J. Org. Chem. 2016; 2016: 2013 3c Jedinák L, Zátopková R, Zemánková H, Šustková A, Cankař P. J. Org. Chem. 2017; 82: 157 3d Fu L, Xu Z, Wan JP, Liu Y. Org. Lett. 2020; 22: 9518 3e Pan Y, Gong Y, Song Y, Tong W, Gong H. Org. Biomol. Chem. 2019; 17: 4230 3f Xiong J, Zhong G, Liu Y. Adv. Synth. Catal. 2019; 361: 550 4 Lamberth C. Heterocycles 2007; 71: 1467 5 Clarke ED, Mallon LJ. In Modern Methods in Crop Protection Research . Jeschke P, Krämer W, Schirmer U, Witschel M. 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