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Lithiation and silylation of 7-amino-3-tert-butyl-4-oxopyrazolo[5,1-c][1,2,4]triazines
Russian Chemical Bulletin ( IF 1.7 ) Pub Date : 2020-05-01 , DOI: 10.1007/s11172-020-2862-z
S. M. Ivanov , L. M. Mironovich , E. D. Daeva , M. E. Minyaev

The treatment of 7-amino-8-bromo-3-tert-butylpyrazolo[5,1-c][1,2,4]triazin-4(6H)-one with an excess of NaH in THF and AlkLi (Alk = Bun, But) at -97 °C produced disodium (8-lithio-3-tert-butyl-4-oxopyrazolo[5,1-c][1,2,4]triazin-1-id-7-yl)amide unstable under ambient conditions. The chemical properties of the newly synthesized compound were studied. The electrophilic attack occurs at the N(1), C(7)—N, or C(8) ring positions depending on the nature of the electrophilic agent (PhCHO, ButCOCl, TMSBr). The treatment of the N(1)-Boc-protected derivative with BuLi resulted in the C(8)-metalation accompanied by the addition of alkyl at the carbonyl groups or at the N(2) atom. The low-temperature reaction with pivaloyl chloride was studied using deuterium labeling of the amino group, which confirmed the hydrogen atom transfer from the C(7)—NH group to the C(8) position of the heterocycle. The structures of the synthesized compounds were established by IR spectroscopy, 1H, 2H, 13C, and 2D 1H—29Si HMBC NMR spectroscopy, high-resolution mass spectrometry, and single-crystal X-ray dif raction.

中文翻译:

7-氨基-3-叔丁基-4-氧代吡唑并[5,1-c][1,2,4]三嗪的锂化和硅烷化

7-amino-8-bromo-3-tert-butylpyrazolo[5,1-c][1,2,4]triazin-4(6H)-one 在 THF 和 AlkLi 中用过量的 NaH 处理 (Alk = Bun, But) 在 -97 °C 下产生(8-lithio-3-tert-butyl-4-oxopyrazolo[5,1-c][1,2,4]triazin-1-id-7-yl)酰胺二钠在环境条件下不稳定。研究了新合成化合物的化学性质。亲电攻击发生在 N(1)、C(7)-N 或 C(8) 环位置,具体取决于亲电剂(PhCHO、ButCOCl、TMSBr)的性质。用 BuLi 处理 N(1)-Boc-保护的衍生物导致 C(8)-金属化,伴随着在羰基或 N(2) 原子处添加烷基。使用氨基的氘标记研究了与新戊酰氯的低温反应,这证实了氢原子从 C(7)-NH 基团转移到杂环的 C(8) 位置。通过红外光谱、1H、2H、13C和2D 1H-29Si HMBC NMR光谱、高分辨率质谱和单晶X射线衍射确定了合成化合物的结构。
更新日期:2020-05-01
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