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Reactions of two primary aromatic amines in modified supercritical carbon dioxide to synthesize sulfonamides: On-line SFC to perform solubility measurements and method to monitor reaction progress
The Journal of Supercritical Fluids ( IF 3.4 ) Pub Date : 2021-09-20 , DOI: 10.1016/j.supflu.2021.105419
Wei Guo 1 , Ben Li 1 , Haijun Chi 2 , Liu Qing Wei 3 , Edward D. Ramsey 1
Affiliation  

Aniline and phenylethylamine react with 4-nitrobenzenesulfonyl chloride in 4% acetone modified supercritical fluid carbon dioxide (SFsingle bondCO2) to produce nitro-sulfonamide products via Nsingle bondS bond formation. Solubility measurements of reactants and products in pure SFsingle bondCO2 were performed at temperatures 353 K, 363 K, 373 K with pressures ranging from 10 MPa to 20.3 MPa. Aniline exhibits good solubility in SFsingle bondCO2 and unlike phenylethylamine does not form a carbamate. Estimates of free phenylethylamine release efficiency from its pre-formed carbamate in SFsingle bondCO2 were obtained. Synthetic reactions were performed at 16.8 MPa with temperatures 353 K, 363 K, and 373 K. Under such conditions, on-line SFC reaction progress monitoring established phenylethylamine effectively reacted as a free base at approximately four times the rate of aniline. Nitro-sulfonamide product yields were 75–82.6% using phenylethylamine and 53.9–70.2% using aniline. Aniline product yields were lower due to by-product formation. This study involved using two different interchangeable on-line SFC interfaces.



中文翻译:

两种伯芳胺在改性超临界二氧化碳中反应合成磺酰胺:在线 SFC 进行溶解度测量和监测反应进程的方法

苯胺和苯乙胺与4-硝基苯磺酰氯反应在4%丙酮改性的超临界流体二氧化碳(SF 单键CO 2),以产生硝基-磺酰胺产物经由Ñ 单键S键的形成。反应物和产物在纯 SF 单键CO 2中的溶解度测量在 353 K、363 K、373 K 和 10 MPa 至 20.3 MPa 的压力下进行。苯胺在 SF 单键CO 2 中表现出良好的溶解性,并且与苯乙胺不同,不会形成氨基甲酸酯。SF 单键CO 2 中预先形成的氨基甲酸酯的游离苯乙胺释放效率的估计获得了。合成反应在 16.8 MPa 和 353 K、363 K 和 373 K 的温度下进行。在这种条件下,在线 SFC 反应进程监测确定苯乙胺以游离碱的形式有效反应,反应速率约为苯胺的四倍。使用苯乙胺的硝基磺酰胺产品产率为 75-82.6%,使用苯胺的产率为 53.9-70.2%。由于副产物形成,苯胺产物产率较低。该研究涉及使用两种不同的可互换在线 SFC 接口。

更新日期:2021-09-28
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