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Generation and chemical properties of (3,4-di-tert-butyl-1,4-dihydropyrazolo[5,1-c][1,2,4]triazin-4-yl)lithiums
Journal of Organometallic Chemistry ( IF 2.1 ) Pub Date : 2019-12-02 , DOI: 10.1016/j.jorganchem.2019.121060
Sergey M. Ivanov , Mikhail E. Minyaev

Interaction of 3,4-di-tert-butyl-8-methylpyrazolo[5,1-c][1,2,4]triazine with RLi (R = n-Bu, t-Bu) at −110° ÷ −25 °C led to generation of (3,4-di-tert-butyl-8-methyl-1-R-1,4-dihydropyrazolo[5,1-c][1,2,4]triazin-4-yl)lithiums, while application of PhLi furnished a mixture of N(1)- and C(4)-addition products. Alkylation of (3,4-di-tert-butyl-8-methyl-1-R-1,4-dihydropyrazolo[5,1-c][1,2,4]triazin-4-yl)lithiums with MeI proceeded at the N(2) atom, but O2 and H3O+ selectively attacked the C(4) ring position. The protonation product could also be synthesized independently from (trans-)3-tert-butyl-8-methyl-3,4-dihydropyrazolo[5,1-c][1,2,4]triazine-3,4-diyl bispivalate and t-BuLi. 3,4-Di-tert-butyl-4-hydroperoxy-8-methyl-1-R-1,4-dihydropyrazolo[5,1-c][1,2,4]triazines underwent Criegee fragmentation at r.t. (for R = t-Bu) or transformed into C(4)-hydroxy derivative (for R = Ph). Structures of four of the isolated reaction products were established by single-crystal X-ray diffraction analyses.



中文翻译:

(3,4-二叔丁基-1,4-二氢吡唑并[5,1- c ] [1,2,4]三嗪-4-基)锂的产生及化学性质

3,4-二叔丁基-8-甲基吡唑并[5,1- c ] [1,2,4]三嗪与RLi(R =  n -Bu,t -Bu)在-110°÷-25相互作用°C导致生成(3,4-二叔丁基-8-甲基-1-R-1,4-二氢吡唑并[5,1- c ] [1,2,4]三嗪-4-基锂,而应用PhLi可提供N(1)-和C(4)加成产物的混合物。(3,4-二叔丁基-8-甲基-1-R-1,4-二氢吡唑并[5,1- c ] [1,2,4]三嗪-4-基)锂与MeI的烷基化反应在N(2)原子上,但O 2和H 3 O +有选择地攻击C(4)环位置。质子化产物也可以独立于(反式)3-丁基-8-甲基-3,4-二氢吡唑并[5,1- c ] [1,2,4]三嗪-3,4-二基双新戊酸酯合成。和t -BuLi。3,4-二叔丁基-4-氢过氧-8-甲基-1-R-1,4-二氢吡唑并[5,1- c ] [1,2,4]三嗪在rt发生Criegee断裂(对于R =  t -Bu)或转化为C(4)-羟基衍生物(对于R = Ph)。通过单晶X射线衍射分析确定了四种分离的反应产物的结构。

更新日期:2019-12-02
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