Continuous formation of N-chloro-N,N-dialkylamine solutions in well-mixed meso-scale flow reactors.
Continuous formation of N-chloro-N,N-dialkylamine solutions in well-mixed meso-scale flow reactors.
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DOI：
10.3762/bjoc.11.262
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发表时间：
2015
影响因子：
2.7
通讯作者：
Jolley KE
中科院分区：
文献类型：
--
作者：
Blacker AJ;Jolley KE
本文描述了一系列N，N-二烷基-N-氯胺有机溶液的连续流动合成方法，该方法采用自制的带静态混合器的介观管式反应器或连续搅拌釜式反应器。这两个反应器都促进了N，N-二烷胺在有机溶剂中的两相溶液和次氯酸钠的有效混合，以实现接近定量的转化率，原位产率为72-100%，有效产率约为0.05mol/h，停留时间为3-20分钟。已经进行了初步的量热研究，以了解反应放热、速率和安全操作。主要在有机相中分配的胺需要更长的反应时间，由CSTR提供，以弥补两相体系中较低的传质速率。对反应的绿色指标进行了评估，并与现有程序进行了比较，结果表明，连续过程比以前的程序有所改进。连续生产的N，N-二烷基-N-氯胺的有机溶液将使它们能够与一系列亲核底物进行串联流动反应。
The continuous flow synthesis of a range of organic solutions of N,N-dialkyl-N-chloramines is described using either a bespoke meso-scale tubular reactor with static mixers or a continuous stirred tank reactor. Both reactors promote the efficient mixing of a biphasic solution of N,N-dialkylamine in organic solvent, and aqueous sodium hypochlorite to achieve near quantitative conversions, in 72–100% in situ yields, and useful productivities of around 0.05 mol/h with residence times from 3 to 20 minutes. Initial calorimetric studies have been carried out to inform on reaction exotherms, rates and safe operation. Amines which partition mainly in the organic phase require longer reaction times, provided by the CSTR, to compensate for low mass transfer rates in the biphasic system. The green metrics of the reaction have been assessed and compared to existing procedures and have shown the continuous process is improved over previous procedures. The organic solutions of N,N-dialkyl-N-chloramines produced continuously will enable their use in tandem flow reactions with a range of nucleophilic substrates.