负载型Ni催化剂高效催化2-羟基四氢吡喃还原胺化制备5-氨基-1-戊醇

doi:10.1016/S1872-2067(19)63471-6

催化学报 ›› 2020, Vol. 41 ›› Issue (4): 631-641.DOI: 10.1016/S1872-2067(19)63471-6

• 中国科学院青年创新促进会专栏 • 上一篇下一篇

负载型Ni催化剂高效催化2-羟基四氢吡喃还原胺化制备5-氨基-1-戊醇

李雪梅, 田俊英, 刘海龙, 唐从奎, 夏春谷, 陈静, 黄志威

中国科学院兰州化学物理研究所, 羰基合成与选择氧化国家重点实验室, 苏州研究院, 甘肃兰州 730000

收稿日期:2019-09-01 修回日期:2019-10-10 出版日期:2020-04-18 发布日期:2019-12-12
通讯作者: 陈静, 黄志威
基金资助:
国家自然科学基金（21872155，21473224）；中国科学院洁净能源创新研究院合作基金（DNL 180303）；中国科学院前沿科学重点研究项目（QYZDJ-SSW-SLH051）；中国科学院青年创新促进会（2016371）；苏州科技发展计划项目（SYG201626）.

Effective synthesis of 5-amino-1-pentanol by reductive amination of biomass-derived 2-hydroxytetrahydropyran over supported Ni catalysts

Xuemei Li, Junying Tian, Hailong Liu, Congkui Tang, Chungu Xia, Jing Chen, Zhiwei Huang

State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, Gansu, China

Received:2019-09-01 Revised:2019-10-10 Online:2020-04-18 Published:2019-12-12
Supported by:
This work was supported by the National Natural Science Foundation of China (21872155, 21473224), Cooperation Foundation of Dalian National Laboratory for Clean Energy (DNL 180303),Key Research Project of Frontier Science of Chinese Academy of Sciences (QYZDJ-SSW-SLH051), the Youth Innovation Promotion Association, CAS (2016371), and the Suzhou Science and Technology Development Plan (SYG201626).

摘要/Abstract

摘要： 伯胺等含氮化合物是最重要的化工中间体之一，被广泛应用于聚合物、医药、农药、染料和表面活性剂等产品的生产.当前，商业化伯胺主要通过卤代烃或环氧化合物直接胺化以及腈类或酰胺类化合物加氢制备，这些过程受具有特定官能团的有机原料短缺以及产生较多废物等问题的限制，导致其生产成本较高.因此，高效可持续生产伯胺化合物路径的开发得到了广泛关注.醛和酮类化合物直接与氨还原胺化反应所需温度一般较低（≤120℃），为伯胺的高选择性合成提供了一个重要途径.基于此，本文利用2-羟基四氢吡喃能够原位转化为其互变异构体5-羟基戊醛，而5-羟基戊醛中醛基具有较高还原胺化活性的特征，发展了一种以生物糠醛衍生二氢吡喃为原料，通过先水合得到2-羟基四氢吡喃再在温和条件下还原胺化合成5-氨基-1-戊醇的新方法.5-氨基-1-戊醇是一种分子中同时含有羟基和氨基的重要双官能团化合物，广泛用于医药和农药合成，也常被用作有机合成砌块，目前其主要用途是合成具有很高药用价值的生物碱Manzamine A.5-氨基-1-戊醇的一条传统合成路线是以石化基1，5-戊二醇经浓盐酸进行单氯取代制备5-氯戊醇中间体，该中间体经分离后再与氨气反应制得5-氨基-1-戊醇的方法.该方法原料成本高，产生大量废弃物，且只取得中等目标产物收率（66.6%）.
本文重点研究了不同氧化物载体包括SiO₂，TiO₂，γ-Al₂O₃，ZrO₂和MgO负载Ni催化剂的2-羟基四氢吡喃还原胺化性能，并对比考察了CuCr₂O₄，雷尼Ni，Ru/C，Pd/C，Pt/C和Rh/C等商业加氢催化剂的性能.研究发现，ZrO₂负载Ni催化剂的活性高于其他氧化物载体负载Ni催化剂的活性，也明显优于所对比的系列商业加氢催化剂.系列物理化学表征结果显示，Ni/ZrO₂催化剂同时表现出较高的还原性和表面酸密度，这可能是该催化剂表现出最高5-氨基-1-戊醇收率的原因.以Ni/ZrO₂为催化剂，于80℃，2MPa H₂条件下在间歇式反应器中催化2-羟基四氢吡喃水溶液还原胺化可取得90.8%的5-氨基-1-戊醇收率.通过固定床反应器研究了Ni/ZrO₂催化剂稳定性，发现5-氨基-1-戊醇初始收率可达83%，反应90h活性缓慢下降至初活性的81%.Ni流失和表面氧化可能是催化剂的失活的主要原因.通过对反应温度、H₂压力、2-羟基四氢吡喃/NH₃摩尔比等因素对反应活性调变规律的探究，推测2-羟基四氢吡喃催化还原胺化制备5-氨基-1-戊醇反应机理如下：首先，受化学平衡作用，2-羟基四氢吡喃逐渐转化为其互变异构体5-羟基戊醛；然后，5-羟基戊醛中醛基迅速与NH₃反应生成亚胺中间体；最后，亚胺中间体在金属催化剂上加氢得到5-氨基-1-戊醇.

关键词: Ni催化剂, 还原胺化, 二氢吡喃, 5-氨基-1-戊醇, 构效关系

Abstract: A highly efficient and green process was developed for the synthesis of useful 5-amino-1-pentanol (5-AP) from biomass-derived dihydropyran by coupling the in situ generation of 5-hydroxypentanal (5-HP, via the ring-opening tautomerization of 2-hydroxytetrahydropyran (2-HTHP)) and its reductive amination over supported Ni catalysts. The catalytic performances of the supported Ni catalysts on different oxides including SiO₂, TiO₂, ZrO₂, γ-Al₂O₃, and MgO as well as several commercial hydrogenation catalysts were investigated. The Ni/ZrO₂ catalyst presented the highest 5-AP yield. The characterization results of the oxide-supported Ni catalysts showed that the Ni/ZrO₂ catalyst possessed high reducibility and a high surface acid density, which lead to the enhanced activity and selectivity of the catalyst. The effect of reaction parameters on the catalytic performance of the Ni/ZrO₂ catalyst was studied, and a high 5-AP yield of 90.8% was achieved in the reductive amination of 2-HTHP aqueous solution under mild conditions of 80℃ and 2 MPa H₂. The stability of the Ni/ZrO₂ catalyst was studied using a continuous flow reactor, and only a slight decrease in the 5-AP yield was observed after a 90-h time-on-stream. Additionally, the reaction pathways for the reductive amination of 2-HTHP to synthesize 5-AP were proposed.

Key words: Ni catalyst, Reductive amination, Dihydropyran, 5-Amino-1-pentanol, Structure-performance relationship

中图分类号:

李雪梅, 田俊英, 刘海龙, 唐从奎, 夏春谷, 陈静, 黄志威. 负载型Ni催化剂高效催化2-羟基四氢吡喃还原胺化制备5-氨基-1-戊醇[J]. 催化学报, 2020, 41(4): 631-641.

Xuemei Li, Junying Tian, Hailong Liu, Congkui Tang, Chungu Xia, Jing Chen, Zhiwei Huang. Effective synthesis of 5-amino-1-pentanol by reductive amination of biomass-derived 2-hydroxytetrahydropyran over supported Ni catalysts[J]. Chinese Journal of Catalysis, 2020, 41(4): 631-641.

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负载型Ni催化剂高效催化2-羟基四氢吡喃还原胺化制备5-氨基-1-戊醇

Effective synthesis of 5-amino-1-pentanol by reductive amination of biomass-derived 2-hydroxytetrahydropyran over supported Ni catalysts

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