Controllable synthesis of diazocine - investigation on electroreduction mechanism for intramolecular cyclization of 2,2′- dinitrodibenzyl in the presence of CO2

IF 4.5 3区 化学 Q1 Chemical Engineering
Yan Liu , Feng Li , Dan Li , Wenhui Dong , Baokang Jin
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引用次数: 0

Abstract

11,12-dihydrodibenzo[c,g][1,2]diazocine (Diazocine, 12), a molecular switch capable of reversible interconversion between (at least) two states by light, has been widely used in pharmacology and biochemistry. However, most of the synthetic methods so far have been limited by tedious steps, complicated derivatives, and long reaction times, resulting in poor synthetic yields of 12. Here, we propose a green, effective, and controllable strategy for synthesizing 12. The intramolecular cyclization (8-membered ring) of 2,2′-dinitrodibenzyl (1) was achieved by electrochemical reduction in the presence of CO2, and 12 and its derivatives 11,12-dihydrodibenzo[c,g][1,2]diazocine-N-oxide (DDCG-N, 11) were synthesized. The electrochemical reduction mechanism of 1 in the presence of CO2 was investigated by cyclic voltammetry (CV) and in situ FT-IR spectroelectrochemistry. The molecular structures of the electrolytic product (12) and intermediate (11) were confirmed by single-crystal X-ray diffraction, NMR, and MS. The results show that the electrochemical behavior of 1 in acetonitrile (AN) changes from a reversible two-step 1-electron transfer process (in the absence of CO2) to an irreversible 8-electron transfer process (in the presence of CO2). The 12 and 11 can be obtained by controlling the electrolytic potential and time. Under the optimum conditions, the yields of 12 and 11 were 84% and 71%, respectively.

重氮嘧啶的可控合成——CO2存在下2,2′-二硝基二苄基分子内环化的电还原机理研究
11,12-二氢二苯并[c,g][1,2]重氮辛(diazocine,12)是一种能够在光作用下在(至少)两种状态之间可逆转换的分子开关,已广泛应用于药理学和生物化学。然而,目前大多数合成方法都存在步骤繁琐、衍生物复杂、反应时间长等问题,导致合成产率仅为12。在此,我们提出了一种绿色、有效、可控的合成策略。在CO2存在下,通过电化学还原实现2,2′-二硝基二苄基(1)的分子内环(8元环),合成了12及其衍生物11,12-二氢二苯并[c,g][1,2]重氮辛- n -氧化物(DDCG-N, 11)。采用循环伏安法(CV)和原位红外光谱电化学技术研究了1在CO2存在下的电化学还原机理。结果表明,1在乙腈(AN)中的电化学行为由可逆的两步1电子转移过程(无CO2存在时)转变为不可逆的8电子转移过程(有CO2存在时)。通过控制电解电位和时间可以得到12和11。在最佳条件下,12号和11号的产率分别为84%和71%。
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来源期刊
Journal of Electroanalytical Chemistry
Journal of Electroanalytical Chemistry Chemical Engineering-General Chemical Engineering
CiteScore
7.50
自引率
6.70%
发文量
912
审稿时长
>12 weeks
期刊介绍: The Journal of Electroanalytical Chemistry is the foremost international journal devoted to the interdisciplinary subject of electrochemistry in all its aspects, theoretical as well as applied. Electrochemistry is a wide ranging area that is in a state of continuous evolution. Rather than compiling a long list of topics covered by the Journal, the editors would like to draw particular attention to the key issues of novelty, topicality and quality. Papers should present new and interesting electrochemical science in a way that is accessible to the reader. The presentation and discussion should be at a level that is consistent with the international status of the Journal. Reports describing the application of well-established techniques to problems that are essentially technical will not be accepted. Similarly, papers that report observations but fail to provide adequate interpretation will be rejected by the Editors. Papers dealing with technical electrochemistry should be submitted to other specialist journals unless the authors can show that their work provides substantially new insights into electrochemical processes.
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