14N NMR Evidence for Initial Production of NH3 Accompanied by Alcohol from the Hydrolysis of Ethylamine and Butylamine in Supercritical Water

• Ken Yoshida

  Department of Applied Chemistry, Graduate School of Technology, Industrial and Social Sciences, Tokushima University, 2-1 Minamijyousanjima-cho, Tokushima 770-8506 , Japan

• Haruka Yoshioka

  Department of Applied Chemistry, Graduate School of Technology, Industrial and Social Sciences, Tokushima University, 2-1 Minamijyousanjima-cho, Tokushima 770-8506 , Japan

• Natsuko Ushigusa

  Department of Applied Chemistry, Graduate School of Technology, Industrial and Social Sciences, Tokushima University, 2-1 Minamijyousanjima-cho, Tokushima 770-8506 , Japan

• Masaru Nakahara

  Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto 611-0011 , Japan

Abstract

A 14N and 1H NMR spectroscopic study was carried out to shed light on microscopic aspects of the reaction of model alkylamines at a supercritical temperature of 400 °C. It is disclosed that NH3 and ROH (R = CH3CH2 and CH3 (CH2)3) are initially produced from the hydrolysis of ethylamine and butylamine, respectively. When the water density is doubled from 0.2 g cm−3, the pseudo-first-order reaction rate is markedly enhanced beyond the linear response. It suggests that the transition state of the C-N bond cleavage is in a dipolar (ionic) state that can be more stabilized due to the many-body solvation by highly polar water molecules at a higher density.

Journal

• Chemistry Letters

  Chemistry Letters 50 (2), 316-319, 2020-11-20

  Oxford University Press (OUP)

Keywords

• General Chemistry

Details

• CRID: 1361131641911397888
• NII Article ID: 130007986369
• DOI: 10.1246/cl.200783
• ISSN: 13480715
• ISSN: 03667022
• Web Site: https://academic.oup.com/chemlett/article-pdf/50/2/316/56297545/cl.200783.pdf
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