Condensation of Diacetyl with Alkyl Amines: Synthesis and Reactivity of p-Iminobenzoquinones and p-Diiminobenzoquinones
作者:Carlos Espinoza-Hicks、Rafael Bautista、Saúl Frias-Puente、Vanessa Pelayo、Eder Martínez-Mora、Francisco Delgado、Joaquín Tamariz
DOI:10.3390/molecules201119716
日期:——
Condensation reactions between diacetyl and α-branched primary alkylamines under mild and neutral conditions provided a mixture of 2,5-dimethylbenzoquinone(alkylimines), 2,5-dimethylbenzoquinone(bis-alkyldiimines), and N,N′-dialkyl-2,5-dimethylbenzene-1,4-diamines, which were efficiently separated as pure products by column chromatography. Both 2,5-dimethylbenzoquinone(alkylimines) and 2,5-dimethylbenzoquinone(bis-alkyldiimines) underwent an interchange of the alkylimino group when treated with anilines, followed by reductive aromatization, to provide diarylamines and 1,4-dianilinobenzenes, respectively. Evaluation was also made of the reactivity and selectivity of these compounds in the presence of anilines, thiophenols and alkylhalides.
在温和中性条件下,双乙酰与α-支链一级烷基胺的缩合反应生成2,5-二甲基苯醌(烷基亚胺)、2,5-二甲基苯醌(双-烷基二亚胺)和N,N'-二烷基-2,5-二甲基苯-1,4-二胺混合物,通过柱层析有效分离为纯品。2,5-二甲基苯醌(烷基亚胺)和2,5-二甲基苯醌(双-烷基二亚胺)在苯胺处理下发生烷基亚胺基团的交换,随后进行还原芳构化,分别得到二芳基胺和1,4-二苯胺基苯。还评估了这些化合物在存在苯胺、硫酚和烷基卤化物时的反应性和选择性。