Synthesis of N-Unprotected Diaryl Ketimines and Alkyl Ketimines from Ketones and Ammonia Using Porous Solid Acids with Analysis of Their Adsorption Behavior

Author:

Shibata Shintaro1,Masui Yoichi1,Narukawa Naoki2,Shiroshita Takuya2,Miya Haruhiko2,Sato Rintaro2,Tokutake Shunta2,Tanaka Yoshiki2,Onaka Makoto2

Affiliation:

1. Graduate School of Arts and Sciences, The University of Tokyo, 8-3-1 Komaba, Meguro-ku, Tokyo 153-8902 , Japan

2. Faculty of Life Sciences, Tokyo University of Agriculture, 1-1-1 Sakuragaoka, Setagaya-ku, Tokyo 156-8502 , Japan

Abstract

Abstract The most atom-efficient synthetic method for N-unprotected ketimines (N-H ketimines) from ketones is the dehydration condensation reaction with ammonia (NH3). However, until now, few synthetic methods for N-H ketimines with high versatility have been known. In this study, we examined various solid acids and found that N-H diaryl ketimines with various functional groups on the aryl groups could be synthesized in high yields from diaryl ketones and NH3 under solvent-free conditions using silica-alumina (SiO2-Al2O3) or proton-exchanged Y-type zeolite (H-Y). Solid-state 13C and 15N NMR measurements indicated that the N-H ketimine formed in the pores of acidic zeolite was coordinated to NH4+ species on the pore surface. By quantum chemical calculations we also discussed the reason why the dehydration-condensation reaction between ketone and NH3, which is an endothermic reaction in a vacuum, was biased toward the product side in the actual experiment. In addition, this synthetic method can be applied to synthesize N-H alkyl ketimines with α-acidic hydrogens, which are less stable and more sensitive to hydrolysis and oligomerization than diaryl ketimines.

Publisher

Oxford University Press (OUP)

Subject

General Chemistry

Cited by 1 articles. 订阅此论文施引文献 订阅此论文施引文献,注册后可以免费订阅5篇论文的施引文献,订阅后可以查看论文全部施引文献

同舟云学术

1.学者识别学者识别

2.学术分析学术分析

3.人才评估人才评估

"同舟云学术"是以全球学者为主线,采集、加工和组织学术论文而形成的新型学术文献查询和分析系统,可以对全球学者进行文献检索和人才价值评估。用户可以通过关注某些学科领域的顶尖人物而持续追踪该领域的学科进展和研究前沿。经过近期的数据扩容,当前同舟云学术共收录了国内外主流学术期刊6万余种,收集的期刊论文及会议论文总量共计约1.5亿篇,并以每天添加12000余篇中外论文的速度递增。我们也可以为用户提供个性化、定制化的学者数据。欢迎来电咨询!咨询电话:010-8811{复制后删除}0370

www.globalauthorid.com

TOP

Copyright © 2019-2024 北京同舟云网络信息技术有限公司
京公网安备11010802033243号  京ICP备18003416号-3