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有机化学
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有机化学 ›› 2004, Vol. 24 ›› Issue (6): 691-696. 上一篇    下一篇

研究简报

4,4′-二甲氧基-5,6,5′,6′-二次甲二氧基-2-烷氧甲酰基-2′-(4-取代苄基哌嗪基-1)-甲酰基联苯的合成

程森祥a,b, 王利敏b, 常俊标*,b, 屈凌波a, 陈晓岚a, 陈荣峰b   

  1. a郑州大学化学系 郑州 450052
    b河南省科学院研究中心 郑州 450002
  • 收稿日期:2003-08-22 修回日期:2003-10-14 接受日期:2003-12-30 发布日期:2022-09-21
  • 通讯作者: *E-mail: chsxchem@371.net
  • 基金资助:
    河南省自然科学基金(No. 0311022100)资助项目.

Synthesis of 4,4′-Dimethoxy-5,6,5′,6′-dimethenedioxy-2-alkyloxycarbonyl-2′-(4-substituted benzyl piperazin-1-yl)carbonyl-biphenyl

CHENG, Sen-Xianga,b, WANG, Li-Minb, CHANG, Jun-Biao*,b, QU, Ling-Boa, CHEN, Xiao-Lana, CHEN, Rong-Fengb   

  1. a Department of Chemistry, Zhengzhou University, Zhengzhou 450052
    b Center of Research, Henan Academy of Sciences, Zhengzhou 450002
  • Received:2003-08-22 Revised:2003-10-14 Accepted:2003-12-30 Published:2022-09-21

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在NiCl2(PPh3)2/NaH/Zn/PPh3作用下,以2-溴-3,4-次甲二氧基-5-甲氧基-苯甲酸甲酯为原料进行Ullmann-type偶合,在温和条件下以较高的收率得到中间体4,4′-二甲氧基-5,6,5′,6′-二次甲二氧基联苯-2,2′-二甲酸二甲酯,经进一步的水解、环化成酸酐、开环酯化等反应得到4,4′-二甲氧基-5,6,5′,6′-二次甲二氧基联苯-2,2′-二甲酸单酯.最后再与取代苄基哌嗪在DMAP及DCC催化下缩合,得到12个新的不对称联苯甲酸酯甲酰哌嗪类化合物,并用1H NMR, IR, ESI-MS等手段进行了结构确认.

关键词: 联苯, Ullmann-type 偶合, 二氯双三苯基膦合镍, 苄基哌嗪

The key intermediate, dimethyl 4,4′-dimethoxy-5,6,5′,6′-dimethenedioxy-biphenyl-2,2′-dicarboxylate (2), was synthesized in excellent yield from methyl 2-bromo-3,4-methenedioxy-5-methoxybenzoate through Ullmann-type coupling reaction in the presence of NiCl2(PPh3)2/NaH/Zn/PPh3, and then it was converted to 4,4′-dimethoxy-5,6,5′,6′-dimethenedioxy-2-alkyloxycarbonyl-biphenyl-2′-carboxylic acids (4a～4c) through hydrolysis, intramolecular dehydrolysisand single-esterification. The reactions of compounds 4a～4c with N-substituted benzyl piperazines afforded target compounds 5a～5n. The structures of these novel compounds were confirmed by 1H NMR, IR, ESI-MS and elemental analysis.

Key words: biphenyl, Ullmann-type coupling, nickel bis(triphenylphosphine) dichloride, N-benzyl piperazine