卤素功能化靛红的合成及其烃基化、还原和酰基化反应研究有机化学.pdfVIP

DOI: 10.6023/cjoc201307020 研究论文 有机化学 Chinese Journal of Organic Chemistry ARTICLE 卤素功能化靛红的合成及其烃基化、还原和酰基化反应研究 高文涛* 赵鹏波 赵宾宾 李 阳 (渤海大学超精细化学品研究所 锦州 121000) 摘要 报道了以 4- 卤代苯胺为原料经Sandmeyer 反应得到卤素功能化靛红 3a～3c, 进一步烃基化反应得到氮上烃基化 产物 4a～4o. 4a～4o 用水合肼还原得到了吲哚酮产物 5a～5o, 5a～5o 用乙酸酐作酰化试剂在 4-二甲氨基吡啶为催化剂 的条件下反应生成2, 3 位酰基化的中间体, 此中间体不经提纯, 而使酯基在四氢呋喃为溶剂、5%氢氧化钠为碱的条件 下水解得到 3 位酰基化产物 6a～6o. 部分化合物未见文献报道, 其结构经红外光谱、质谱、核磁氢谱(碳谱)和元素分析 确认. 关键词 卤素功能化靛红; 还原; 烃基化; 乙酰化 Synthesis, Alkylation, Reduction and Acylation of Halo-functionalized Isatins Gao, Wentao* Zhao, Pengbo Zhao, Binbin Li, Yang (Institute of Superfine Chemicals, Bohai University, Jinzhou 121000) Abstract In this paper, 4-haloanilines were first underwent the Sandmeyer reaction to give the corresponding halo-functionalized isatins 3a～3c, which were further alkylated at the nitrogen atom to give 4a～4o followed by in situ re- duction using hydrazine hydrate to obtain the oxindole products 5a～5o. 5a～5o were subjected to the acetylation reaction by the treatment with acetic anhydride in the presence of a catalytic amount of N,N-dimethylaminopyridine to afford the interme- diates of 2-acetoxy-3-acetylindoles, which were used in next step without further purifucation. Subsequently, the hydrolysis reaction of the arising ester functions of the intermediates was carried out in tetrahydrofuran (THF) with the presence of 5% aq. NaOH at room temperature to give the targeted compounds 6a～6o. Some compounds synthesized are novel. Their struc- tures were confirmed by 1H NMR, 13C NMR, IR, MS and elemental analysis.