芳氧基取代的邻苯二腈衍生物的合成研究

doi:10.3969/j.issn.2095-2198.2022.06.003

下载:

PDF (405KB)
输出: BibTeX | EndNote (RIS)

摘要

芳氧基取代的邻苯二腈衍生物是制备金属酞菁的重要前体.以硝基取代的邻苯二腈和对叔丁基苯酚的芳香族亲核取代反应为模型反应，研究芳氧基取代的邻苯二腈衍生物的合成方法.重点考察溶剂、碱、温度、反应物物质的量的比和时间对芳香族亲核取代反应的影响，优选条件为：3-硝基邻苯二腈为底物时，DMF为溶剂，K2CO3作碱，n（3-硝基邻苯二腈）∶n（对叔丁基苯酚）∶n（K2CO3）=1∶11∶2，65 ℃，反应时间为6 h；4-硝基邻苯二腈为底物时，DMF为溶剂，K2CO3作碱，n（4-硝基邻苯二腈）∶n（对叔丁基苯酚）∶n(K2CO3）=1∶105∶2，55 ℃，反应时间为6 h.通过上述优选条件，高收率地合成了6个邻苯二腈衍生物，并通过核磁氢谱进行表征.此外，讨论了芳香族亲核取代反应的机理.

	服务
	把本文推荐给朋友
	加入引用管理器
	E-mail Alert
	RSS
	（）
	作者相关文章

关键词: 邻苯二腈')" href="#">

邻苯二腈金属酞菁芳香族亲核取代反应

Abstract:

Aryloxy-substituted phthalonitrile derivatives are important precursors for the preparation of metal phthalocyanines.The nucleophilic aromatic substitution of nitro-substituted phthalonitriles and p-tert-butylphenol were employed as a model reaction to study the synthesis of aryloxy-substituted phthalonitrile derivatives.The effects of solvent，base，temperature，mole ratio of reagents and time on aromatic nucleophilic substitution reaction were investigated.The optimal conditions were:when 3-nitrophthalonitrile was used as substrate，DMF was used as solvent，K2CO3 was used as base，n(3-nitrophthalonitrile)∶n(p-tert-butylphenol)∶n(K2CO3)=1∶11∶2，65 ℃，and the reaction time was 6 h.When 4-nitrophthalonitrile was used as substrate，DMF was used as solvent，K2CO3 was used as base，n(4-nitrophthalonitrile):n(p-tert-butylphenol)∶n(K2CO3)=1∶105∶2，55 ℃，and the reaction time was 6 h.Six phthalonitrile derivatives were obtained with high yield by the above optimal conditions，and these phthalonitriles were characterized by 1H-NMR.In addition，the mechanism of nucleophilic aromatic substitution was discussed.

Key words: phthalonitrile')" href="#">

phthalonitrile metal phthalocyanine nucleophilic aromatic substitution

出版日期: 2022-12-31 发布日期: 2024-03-12 整期出版日期: 2022-12-31

ZTFLH:

O625 67

基金资助:

沈阳化工大学青年“育苗”项目（XXLQ2019001）

通讯作者: 王康军

作者简介: 丁茯（1974—），女，辽宁营口人，教授，博士，主要从事金属配合物的合成和应用研究.

引用本文:

丁茯, 姚佳, 陈伟楠, 陈卓, 姚美任, 王东平, 王康军.

芳氧基取代的邻苯二腈衍生物的合成研究 [J]. 沈阳化工大学学报, 2022, 36(6): 489-494.
DING Fu, YAO Jia, CHEN Wei-nan, CHEN Zhuo, YAO Mei-ren, WANG Dong-ping, WANG Kang-jun.

Synthesis of Aryloxy-Substituted Phthalonitrile Derivatives . Journal of Shenyang University of Chemical Technology, 2022, 36(6): 489-494.

链接本文:

https://xuebao.syuct.edu.cn/CN/10.3969/j.issn.2095-2198.2022.06.003 或 https://xuebao.syuct.edu.cn/CN/Y2022/V36/I6/489

［1］YU Z，HAGFELDT A，SUN L.The Application of Transition Metal Complexes in Hole-Transporting Layers for Perovskite Solar Cells:Recent Progress and Future Perspectives［J］.Coordination Chemistry Reviews，2020，406:213143.

［2］URBANI M，TORRE G，NAZEERUDDIN M K，et al.Phthalocyanines and Porphyrinoid Analogues as Hole-and Electron-Transporting Materials for Perovskite Solar Cells［J］.Chemical Society Reviews，2019，48(10):2738-2766.

［3］王远越，杨红，周治国，等.酞菁配合物的合成及在肿瘤诊断与治疗中的研究进展［J］.上海师范大学学报(自然科学版)，2018，47(1):100-112.

［4］丁翔，王瑞，徐磊，等.酞菁铜及其衍生物在气体传感器中的应用研究进展［J］.化工新型材料，2018，46(6):61-64.

［5］蔡捷，李艳丽，贺旭，等.金属酞菁配合物催化的咪唑N-芳基化反应［J］.沈阳化工大学学报，2019，33(2):132-136.

［6］GUO J J，SUN M M，MENG X F，et al.Impact of Peripheral Groups on Novel Asymmetric Phthalocyanine-Based Hole-Transporting Materials for Perovskite Solar Cells［J］.Dyes and Pigments，2020，177:108301.

［7］FENG Y M，HU Q K，REZAEE E，et al.High-Performance and Stable Perovskite Solar Cells Based on Dopant-Free Arylamine-Substituted Copper(Ⅱ) Phthalocyanine Hole-Transporting Materials［J］.Advanced Energy Materials，2019，9(26):1901019.

［8］JIANG X Q，WANG D P，YU Z，et al.Molecular Engineering of Copper Phthalocyanines:A Strategy in Developing Dopant-Free Hole-Transporting Materials for Efficient and Ambient-Stable Perovskite Solar Cells［J］.Advanced Energy Materials，2019，9(4):1803287.

［9］GUO J J，MENG X F，ZHU H W，et al.Boosting the Performance and Stability of Perovskite Solar Cells with Phthalocyanine-Based Dopant-Free Hole Transporting Materials through Core Metal and Peripheral Groups Engineering［J］.Organic Electronics，2019，64:71-78.

［10］TANIGUCHI N.Alkyl-or Arylthiolation of Aryl Iodide via Cleavage of the S-S Bond of Disulfide Compound by Nickel Catalyst and Zinc［J］.The Journal of Organic Chemistry，2004，69(20):6904-6906.