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  

Synthesis, Alkylation, Reduction and Acylation of Halo-functionalized Isatins

作　　者：高文涛[1] 赵鹏波 赵宾宾[1] 李阳[1] 

机构地区：[1]渤海大学超精细化学品研究所,锦州121000

出　　处：《有机化学》2014年第1期126-136,共11页Chinese Journal of Organic Chemistry

基　　金：辽宁省自然科学基金(No.20120001)资助项目~~

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.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 reduction 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 intermediates 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 structures were confirmed by ^1H NMR, ^13C NMR, IR, MS and elemental analysis.

关 键 词：卤素功能化靛红 还原 烃基化 乙酰化 

分 类 号：O621.25[理学—有机化学] TQ460.1[理学—化学]