影像科学与光化学 ›› 2000, Vol. 18 ›› Issue (4): 348-356.DOI: 10.7517/j.issn.1674-0475.2000.04.348

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微反应器控制的化学反应的选择性

吴骊珠, 张丽萍, 李红茹, 仪修禹, 宋恺, 徐明苑振宇, 官景渠, 应允明, 王红伟, 佟振合   

  1. 中国科学院感光化学研究所, 北京100101
  • 收稿日期:2000-06-20 修回日期:2000-07-03 出版日期:2000-11-20 发布日期:2000-11-20
  • 通讯作者: 佟振合(1937- ),男,中国科学院院士,主要从事有机光化学研究;通讯联系人.

MICROREACTOR-CONTROLLED SELECTIVITY IN ORGANIC PHOTOCHEMICAL REACTIONS

WU Li-zhu, ZHANG Li-ping, LI Hong-ru, YI Xiu-yu, SONG Kai, XU Ming, YUAN Zhen-yu, GUAN Jing-qu, YING Yun-ming, WANG Hong-wei, TONG Zhen-he(TUNG Chen-ho)   

  1. Institute of Photographic Chemistry, Chinese Academy of Sciences, Beijing 100101, P. R. China
  • Received:2000-06-20 Revised:2000-07-03 Online:2000-11-20 Published:2000-11-20

摘要: 研究利用分子筛、Nafion薄膜、低密度聚乙烯薄膜和囊泡作为微反应器控制有机光化学反应的方向,提高反应的选择性和可能性.在NaY沸石或低密度聚乙烯薄膜中,带有长烷基链或醚链的二芳基化合物光二聚只生成分子内的加成产物,而不生成分子间的加成产物,从而在底物浓度很大的情况下,高选择性地合成了大环化合物.通过控制底物和敏化剂分子在ZSM-5沸石、Nafion薄膜和囊泡中的分布高选择性地控制烯烃光敏氧化反应的方向,单一地生成单重态氧的氧化产物或超氧负离子的氧化产物.利用Nafion薄膜作为介质进行光诱导电子转移,得到超长寿命的电荷分离态.

关键词: 微反应器, 大环化合物的合成, 烯烃光敏氧化, 长寿命电荷分离态

Abstract: Molecular-sieves zeolites, Nafion membranes, low-density polyethylene films and mixed surfactant vesicles have been used as microreactors to control the product selectivity in organic photochemical reactions. The photocycloadditions of diaryl compounds with long flexible chains included in NaY zeolite or low-density polyethylene films yield intramolecular photocyclomers to the exclusion of intermolecular products. The photosensitized oxidation of alkenes included in pentasil zeolite or Nafion membrane or vesicles can be directed selectively towards either the singlet oxygen mediated or the superoxide radical anion mediated products by controlling the status and location of the substrate and sensitizer molecules in the reaction media. Long lived photoinduced charge separation in Ru(bpy)32+/viologen system at Nafion membrane solution interface was achieved.

Key words: microreactors, synthesis of large-ring compounds, photosensitized oxidation of alkenes, long-lived photo-induced charge-separation

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