Glinyanaya Nataliya V, Rayenko Gennady F, Korotkikh Nikolai I, Rusanov Eduard B, Ryabitsky Alexey B, Shvaika Oles P
The L. M. Litvinenko Institute of Physical Organic and Coal Chemistry, Ukrainian Academy of Sciences Kyiv 02160 Ukraine.
Institute of Organic Chemistry, Ukrainian Academy of Sciences Kyiv 02660 Ukraine
RSC Adv. 2021 Sep 16;11(49):30841-30848. doi: 10.1039/d1ra04337d. eCollection 2021 Sep 14.
A series of new stable halogenated carbenes, 1--butyl-3,4-diaryl-1,2,4-triazol-5-ylidenes, has been synthesized. According to quantum chemical calculations, 4-(2,3,4-trifluorophenyl)-substituted 1--butyl-3,4-diaryl-1,2,4-triazol-5-ylidene is the least basic in comparison with the known sterically open stable heteroaromatic carbenes. Upon heating in organic solvents these carbenes undergo a tandem induced reaction thereby forming 5-amidino-1,2,4-triazoles. The interaction of carbenes with benzylidenemalononitrile, propanesultone and phenyl isothiocyanate results in zwitterionic compounds of the 1,2,4-triazole series. The data for X-ray diffraction study of 1--butyl-3-phenyl-4-(2,4-difluorophenyl)-1,2,4-triazol-5-ylidene, its protonated salt, complex with copper(i) iodide, related complex of 1--butyl-3-phenyl-4-(2-trifluoromethylphenyl)-1,2,4-triazol-5-ylidene, and adduct of 1--butyl-3-phenyl-4-(4-bromophenyl)-1,2,4-triazol-5-ylidene and propansultone are given.
已经合成了一系列新型稳定的卤代卡宾，即1-丁基-3,4-二芳基-1,2,4-三唑-5-亚基。根据量子化学计算，与已知的空间开放稳定杂芳基卡宾相比，4-(2,3,4-三氟苯基)取代的1-丁基-3,4-二芳基-1,2,4-三唑-5-亚基碱性最弱。在有机溶剂中加热时，这些卡宾会发生串联诱导反应，从而形成5-脒基-1,2,4-三唑。卡宾与亚苄基丙二腈、丙烷磺内酯和苯基异硫氰酸酯的相互作用会生成1,2,4-三唑系列的两性离子化合物。给出了1-丁基-3-苯基-4-(2,4-二氟苯基)-1,2,4-三唑-5-亚基、其质子化盐、与碘化亚铜的配合物、1-丁基-3-苯基-4-(2-三氟甲基苯基)-1,2,4-三唑-5-亚基的相关配合物以及1-丁基-3-苯基-4-(4-溴苯基)-1,2,4-三唑-5-亚基与丙烷磺内酯加合物的X射线衍射研究数据。
