Zhu Bolin, Woyciechowski Rouven, Hübner Eike G, Lederle Felix, Schmidt Andreas
Institute of Organic Chemistry, Clausthal University of Technology, Leibnizstraße 6, D-38678 Clausthal-Zellerfeld, Germany.
Fiber Optical Sensor Systems, Fraunhofer Heinrich Hertz Institute (HHI), Am Stollen 19H, D-38640 Goslar, Germany.
Org Lett. 2025 Jun 6;27(22):5572-5577. doi: 10.1021/acs.orglett.5c00775. Epub 2025 May 28.
Deprotonation of 3-methylpyrazolium and 3-methylindazolium salts yielded -heterocyclic olefins (NHOs) in excellent yields, which reacted with isocyanates, halogens, and carbon disulfide. Calculated proton affinities are 261 kcal/mol (indazole NHOs) and 272 kcal/mol (pyrazole NHOs). The calculated p values are between 14.8 and 25.2, and bond lengths of the exocyclic double bond are slightly shorter than those of imidazole NHOs. As expected, the highest occupied molecular orbitals show significant atomic orbital coefficients at the exocyclic carbon atom.
3-甲基吡唑鎓盐和3-甲基吲唑鎓盐去质子化后以优异的产率生成了N-杂环烯烃（NHOs），这些NHOs能与异氰酸酯、卤素和二硫化碳发生反应。计算得到的质子亲合能分别为261千卡/摩尔（吲唑NHOs）和272千卡/摩尔（吡唑NHOs）。计算得到的p值在14.8至25.2之间，环外双键的键长略短于咪唑NHOs的键长。正如预期的那样，最高占据分子轨道在外环碳原子处显示出显著的原子轨道系数。
