铜催化异噁唑还原开环清洁高效合成1-氨基-2-乙酰基蒽醌

doi:10.1016/S1872-2067(12)60743-8

催化学报 ›› 2014, Vol. 35 ›› Issue (3): 319-323.DOI: 10.1016/S1872-2067(12)60743-8

铜催化异噁唑还原开环清洁高效合成1-氨基-2-乙酰基蒽醌

赵忠奎, 李仁志, 李宇

大连理工大学精细化工国家重点实验室, 化工学院催化化学与工程系, 辽宁大连116024

收稿日期:2013-10-10 修回日期:2013-11-04 出版日期:2014-02-26 发布日期:2014-02-26
通讯作者: 赵忠奎
基金资助:
教育部新世纪优秀人才支持计划（NCET-12-0079）；中央高校基本科研业务费专项资金（DUT12LK51）.

Highly efficient and clean synthesis of 1-amino-2-acetylanthraquinone by copper-catalyzed reductive cleavage of isoxazole motif

Zhongkui Zhao, Renzhi Li, Yu Li

State Key Laboratory of Fine Chemicals, Department of Catalysis Chemistry and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China

Received:2013-10-10 Revised:2013-11-04 Online:2014-02-26 Published:2014-02-26
Supported by:
This work was supported by the Chinese Ministry of Education via the Program for New Century Excellent Talents in University (NCET-12-0079) and the Fundamental Research Funds for the Central Universities (DUT12LK51).

摘要/Abstract

摘要：

以水为反应介质，水合肼为还原剂，研究了痕量铜催化3-甲基蒽醌-[1，2-c]-异噁唑还原开环反应以清洁高效合成1-氨基-2-乙酰基蒽醌，考察了不同种类过渡金属硝酸盐的催化性能，发现Cu（NO₃）₂性能最好. 加入 2.6% 的催化剂和1.3倍的水合肼，在室温反应 2 h，底物转化率和目标产物选择性分别可达到 97.2%和 95%，TON达到38. 产品结构经氢核磁谱和质谱得以确证，主要副产为羟基取代的1-氨基-2-乙酰基蒽醌. 此外，提出了铜催化 3-甲基蒽醌-[1，2-c]-异噁唑还原开环反应合成 1-氨基-2-乙酰基蒽醌的可能反应机理.

关键词: 铜催化剂, 还原开环, 1-氨基-2-乙酰基蒽醌, 3-甲基蒽醌-[1,2-c]-异噁唑, 清洁合成

Abstract:

A clean and highly efficient synthesis of 1-amino-2-acetylanthraquinone via reductive isoxazole ring cleavage of 3-methylanthra[1,2-c]isoxazole-6,11-dione catalyzed by trace copper using hydrazine hydrate as a clean reducing agent and water as a green reaction medium under mild reaction conditions was investigated. Various transition-metal catalysts were screened for the reductive ring-opening reaction, and Cu(NO₃)₂ was shown to be an excellent catalyst. A conversion of 97.2% and 1-amino-2-acetylanthraquinone selectivity greater than 95% were obtained in the presence of 2.6 mol% Cu(NO₃)₂ (turnover number 38) with 1.3 equiv. of hydrazine hydrate for 2 h in water. The structure of the product was confirmed by ¹H nuclear magnetic resonance spectroscopy and mass spectrometry; the main byproduct was hydroxyl-substituted 1-amino-2-acetylanthraquinone. A possible reaction mechanism for the copper-catalyzed ring cleavage of 3-methylanthra[1,2-c]isoxazole-6,11-dione with hydrazine hydrate was proposed.

Key words: Copper catalyst, Reductive ring-cleavage, 1-Amino-2-acetyl anthraquinone, 3-Methylanthra[1,2-c]isoxazol-6,11-dione, Clean synthesis

赵忠奎, 李仁志, 李宇. 铜催化异噁唑还原开环清洁高效合成1-氨基-2-乙酰基蒽醌[J]. 催化学报, 2014, 35(3): 319-323.

Zhongkui Zhao, Renzhi Li, Yu Li. Highly efficient and clean synthesis of 1-amino-2-acetylanthraquinone by copper-catalyzed reductive cleavage of isoxazole motif[J]. Chinese Journal of Catalysis, 2014, 35(3): 319-323.

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铜催化异噁唑还原开环清洁高效合成1-氨基-2-乙酰基蒽醌

Highly efficient and clean synthesis of 1-amino-2-acetylanthraquinone by copper-catalyzed reductive cleavage of isoxazole motif

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