Combination of near-infrared spectroscopy and a transient flow method for efficient kinetic analysis of the Claisen rearrangement†

IF 3.4 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Reaction Chemistry & Engineering Pub Date : 2024-08-11 DOI:10.1039/D4RE00301B
Yoshihiro Takebayashi, Kiwamu Sue and Sho Kataoka
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Abstract

Kinetic analysis of the Claisen rearrangement of allyl phenyl ether (APE) to 2-allylphenol was conducted in pressurized N-methylpyrrolidone (NMP) at various temperatures from 240 to 280 °C using an automated flow reactor. Rapid inline analysis using a compact near-infrared (NIR) spectrometer coupled with a flow rate ramp as a reciprocal function of the experimental time allowed high-density data acquisition (900 points in 15 min) of the conversion of APE over residence times ranging from 0.8 to 10.3 min. Inline NIR monitoring was also employed to measure the residence time of the NMP solution in the reactor. The residence time was shown to decrease by 26% with increasing temperature from 20 to 300 °C due to the thermal expansion of the solution. The APE conversion exhibited first-order kinetics with an activation energy of 137 ± 1 kJ mol−1 and a pre-exponential factor of 7.3 × 1010 s−1. The result of the flow rate ramp experiment was consistent with that of the temperature ramp experiment, while the latter gave a continuous Arrhenius plot in a wider temperature range from 230 to 290 °C. The rate constant in NMP was found to be 10 and 1.5 times smaller than those reported in subcritical water and alcohol solvents, respectively.

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结合近红外光谱仪和瞬态流动法对克莱森重排进行高效动力学分析
在加压的 N-甲基吡咯烷酮(NMP)中,使用自动流动反应器在 240 至 280°C 的不同温度下对烯丙基苯基醚(APE)到 2-烯丙基苯酚的克莱森重排反应进行了动力学分析。通过紧凑型近红外光谱仪进行快速在线分析,并将流速斜坡与实验时间互为函数关系,可以高密度地获取 APE 在 0.8 至 10.3 分钟停留时间内的转化数据(15 分钟内 900 个点)。在线近红外监测还用于测量 NMP 溶液在反应器中的停留时间。结果表明,由于溶液的热膨胀,停留时间随着温度从 20°C 升至 300°C 减少了 26%。APE 转化呈现一阶动力学,活化能为 137 ± 1 kJ mol-1,前指数为 7.3×1010 s-1。流速斜坡实验的结果与温度斜坡实验的结果一致,而后者在 230 至 290°C 较宽的温度范围内给出了连续的阿伦尼乌斯曲线图。在 NMP 中的速率常数分别比在亚临界水和酒精溶剂中的速率常数小 10 倍和 1.5 倍。
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来源期刊
Reaction Chemistry & Engineering
Reaction Chemistry & Engineering Chemistry-Chemistry (miscellaneous)
CiteScore
6.60
自引率
7.70%
发文量
227
期刊介绍: Reaction Chemistry & Engineering is a new journal reporting cutting edge research into all aspects of making molecules for the benefit of fundamental research, applied processes and wider society. From fundamental, molecular-level chemistry to large scale chemical production, Reaction Chemistry & Engineering brings together communities of chemists and chemical engineers working to ensure the crucial role of reaction chemistry in today’s world.
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