Microfluidic continuous flow synthesis of 1,5-ditosyl-1,5-diazocane-3,7-dione using response surface methodology
Microfluidic continuous flow synthesis of 1,5-ditosyl-1,5-diazocane-3,7-dione using response surface methodology
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使用响应面法微流控连续流动合成 1,5-二甲苯磺酰-1,5-重氮烷-3,7-二酮
DOI：
10.1016/j.jiec.2019.10.002
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发表时间：
2020-02
影响因子：
6.1
通讯作者：
Liu Xinghai
中科院分区：
文献类型：
--
作者：
Zou Yang;Zhang Tao;Wang Guannan;Zhou Mengwen;Xiong Yabo;Huang Shaoyun;Li Houbin;Liu Xinghai
3，3，7，7-四（二氟氨基）八氢-1，5-二硝基-1，5-二氮杂环辛（HNFX）是一种高密度高能氧化剂，具有四个二氟氨基（-NF 2）。本研究分别在传统间歇式反应器和连续流动微反装置中，采用Swern氧化法成功合成了HNFX的重要中间体1，5-二甲磺酰基-1，5-重氮辛烷-3，7-二酮。通过HPLC、FTIR、1H NMR、13 C NMR、质谱和X-射线晶体衍射对1，5-对甲苯磺酰基-1，5-重氮辛烷-3，7-二酮进行了表征。与传统的间歇式反应器相比，该反应器具有反应时间短、反应温度低、收率高、选择性高等优点。该微反应器为1，5-二甲苯磺酰基-1，5-重氮辛烷-3，7-二酮的安全、大规模工业化生产提供了保障。然而，在Swern氧化中产生的一些固体可能堵塞微反应器中的通道（直径为0.3mm）。为了克服这些困难，我们对实验装置进行了改进，使之适合于Swern氧化反应，为微反应器的广泛应用做出了贡献。此外，还引入了响应面法，建立了相应的数学模型，对实验条件进行了优化。最佳实验条件为反应温度7.8 ℃，流速7.7mL/min，草酰氯浓度6%。1，5-二甲苯磺酰基-1，5-重氮辛烷-3，7-二酮的实际收率为89.7%，与最高预测收率（90.1%）基本一致。
3,3,7,7-tetrakis(difluoroamino) octahydro-1,5-dinitro-1,5-diazocine (HNFX) is a high-density energetic oxidizer with four difluoroamino groups (-NF2). In this study, 1,5-ditosyl-1,5-diazocane-3,7-dione, as an important intermediate for synthesis of HNFX, was successfully synthesized using Swern oxidation in a traditional batch reactor and a continuous flow microreactor, respectively. 1,5-dotosyl-1,5-diazocane-3,7-dione was characterized by HPLC, FTIR,1H NMR,13C NMR, Mass spectrometry, and X-ray crystal diffraction. Compared with the traditional batch reactor, the microreactor showed several advantages, including less reaction time, milder reaction temperature, higher yield and selectivity for 1,5-ditosyl-1,5-diazocane-3,7-dione. Moreover, the microreactor could ensure the safer and large-scale industrial production of 1,5-ditosyl-1,5-diazocane-3,7-dione. However, some solids produced in Swern oxidation which might block the channels (diameter of 0.3 mm) in the microreactor. To overcome the challenges, the experimental device was modified to suit for Swern oxidation, contributing to wider application of the microreactor. Besides, response surface methodology (RSM) was introduced and an appropriate mathematical model was built to optimize experimental conditions. The optimum experimental parameters were recommended as 7.8 ℃ for the reaction temperature, 7.7 mL/min for the flow rate, and 6% for the concentration of oxalyl chloride. The actual yield of 1,5-ditosyl-1,5-diazocane-3,7-dione was 89.7%, which was in great agreement with the highest predicted yield (90.1%).
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影响因子：
2.1
作者：
Z. Peralta-Inga;N. Deǧirmenbaşı;U. Olgun;H. Gocmez;D. Kalyon
通讯作者：
Z. Peralta-Inga;N. Deǧirmenbaşı;U. Olgun;H. Gocmez;D. Kalyon
影响因子：
2.5
作者：
P. Weck;Cedric L. Gobin;Eunja Kim;M. Pravica
通讯作者：
P. Weck;Cedric L. Gobin;Eunja Kim;M. Pravica
DOI：
10.1021/jo9819640
发表时间：
1999-01
期刊：
The Journal of organic chemistry
影响因子：
--
作者：
R. Chapman;R. Gilardi;Mark F. Welker;Charles B. Kreutzberger
通讯作者：
R. Chapman;R. Gilardi;Mark F. Welker;Charles B. Kreutzberger
影响因子：
3.6
作者：
R. Chapman;Mark F. Welker;Charles B. Kreutzberger
通讯作者：
R. Chapman;Mark F. Welker;Charles B. Kreutzberger
DOI：
10.1016/j.jiec.2018.05.006
发表时间：
2018-09-25
影响因子：
6.1
作者：
Sadeghfar, Fardin;Ghaedi, Mehrorang;Pezeshkpour, Vahid
通讯作者：
Pezeshkpour, Vahid