Part I. Solid-state and Solvent-Free Synthesis of Azines, Pyrazoles, and Pyridazinones using Solid Hydrazine Part II. Solvent-Free Reductive Amination of aldehydes with a Solidified Amine
- 주제(키워드) 도움말 Solvent-Free , Reductive Amination , Azine , Pyrazole , Pyridazinone , solid hydrazine , solidified amine
- 발행기관 서강대학교 일반대학원
- 지도교수 이원구
- 발행년도 2014
- 학위수여년월 2014. 2
- 학위명 석사
- 학과 및 전공 도움말 일반대학원 화학과
- 실제URI http://www.dcollection.net/handler/sogang/000000053223
- 본문언어 영어
- 저작권 서강대학교 논문은 저작권 보호를 받습니다.
초록/요약 도움말
Azines, pyrazoles, and pyridazinones were isolated as the sole products in high yields (>97%) by grinding a solid hydrazine (H3N+NHCO2-) with di-carbonyl compounds or by their reaction in the absence of solvent. Neither catalysts nor additives were needed to promote the reactions. The solid-state and solvent-free reactions proceeded under ambient conditions and did not produce any wastes other than water and carbon dioxide. They are operationally easy, environmentally safe, and readily scalable, allowing for highly selective synthesis of compounds containing the hydrazine motif.
more초록/요약 도움말
Many of the amines are liquid at room temperature and have unpleasant odors, leading to difficulty in handling them. We converted a liquid (S)-(-)-1-phenylethylamine 1 to the corresponding solid form of the carbamate ammonium salt 2 by reacting with carbon dioxide in the absence of solvents. We performed one-pot solvent-free reductive amination between 2 and various aldehydes 3 by 1:2 molar ratio. Imines 4 were formed by reaction of the solidified amine 2 and a wide range of aldehydes 3 at 60 oC without any solvent as well. Then the imines 4 were catalytic hydrogenated with Platinum oxide, known as Adams’ catalyst, under 1 atm of H2 as well as solvent-free conditions, which gives secondary amines 5 in almost quantitative yields. This one-pot solvent-free reductive amination is appealing from both environmental and economic perspectives.
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