铁掺杂硒/碳催化β-紫罗兰酮的选择性环氧化

doi:10.6023/cjoc202205005

有机化学 ›› 2022, Vol. 42 ›› Issue (11): 3890-3895.DOI: 10.6023/cjoc202205005 上一篇下一篇

研究简报

铁掺杂硒/碳催化β-紫罗兰酮的选择性环氧化

曹洪恩^a^,^b^,^*(), 李培梓^c^,^d, 景崤壁^d, 周宏伟^c^,^*()

^a扬州大学园艺与植物保护学院江苏扬州 225009
^b贵州大学绿色农药与农业生物工程教育部重点实验室贵阳 550025
^c嘉兴学院生物与化学工程学院浙江嘉兴 314001
^d扬州大学化学化工学院江苏扬州 225002

收稿日期:2022-05-04 修回日期:2022-06-26 发布日期:2022-07-13
通讯作者: 曹洪恩, 周宏伟
基金资助:
浙江省自然科学基金(LY19B020004); 贵州大学绿色农药与农业生物工程国家重点实验室培育基地/教育部重点实验室开放基金(2020GDGP0101); 嘉兴市动物模型创建与新药先导的精准合成重点实验室开放课题(jxsz21006); 江苏高校优势学科建设工程资助项目

Selective Epoxidation of β-Ionone Catalyzed by Iron-Doped Se/C

Hong'en Cao^a^,^b(), Peizi Li^c^,^d, Xiaobi Jing^d, Hongwei Zhou^c()

^aSchool of Horticulture and Plant Protection, Yangzhou University, Yangzhou, Jiangsu 225009
^bKey Laboratory of Green Pesticide and Agriculture Bioengineering of Ministry of Education, Guizhou University, Guiyang 550025
^cCollege of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing, Zhejiang 314001
^dSchool of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, Jiangsu 225002

Received:2022-05-04 Revised:2022-06-26 Published:2022-07-13
Contact: Hong'en Cao, Hongwei Zhou
Supported by:
Natural Science Foundation of Zhejiang Province(LY19B020004); Open Fund of the State Key Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering/Key Laboratory of Ministry of Education(2020GDGP0101); Open Project of Jiaxing Key Laboratory for Creation of Animal Models & Synthesis of Lead Compounds of New Drug(jxsz21006); Priority Academic Program Development of Jiangsu Higher Education Institutions

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摘要/Abstract

5,6-环氧-β-紫罗兰酮作为药物合成中的重要中间体, 具有独特的工业应用价值. 最近, 我们将甲硒化葡萄糖和氯化铁混合煅烧, 设计制备了一种铁掺杂的硒/碳催化剂. 该材料可活化分子氧, 从而选择性氧化β-紫罗兰酮, 合成得到5,6-环氧-β-紫罗兰酮. 该催化剂性能稳定, 可循环套用, 且催化反应过程无需额外添加助催化剂, 从而显著降低了生产成本. 这一利用分子氧为氧化剂的廉价、安全的催化氧化技术有很好的工业应用价值.

关键词: 5,6-环氧-β-紫罗兰酮, β-紫罗兰酮, 硒, 分子氧, 绿色催化

As an important intermediate in pharmaceutical synthesis, 5,6-epoxy-β-ionone has unique industrial application value. Recently, an iron-doped Se/C catalyst has been designed and prepared by calcining a mixture of methylselenized glucose with FeCl₃. The material could activate the molecular oxygen to achieve the selective epoxidation of β-ionone affording 5,6-epoxy-β-ionone. The catalyst is stable and recyclable, and the catalytic reaction process did not require any additive, so that the production cost could be obviously reduced. This cheap and safe catalytic oxidation technology using molecular oxygen as oxidant is of good industrial application values.

Key words: 5,6-epoxy-β-ionone, β-ionone, selenium, molecular oxygen, green catalysis

引用此文

曹洪恩, 李培梓, 景崤壁, 周宏伟. 铁掺杂硒/碳催化β-紫罗兰酮的选择性环氧化[J]. 有机化学, 2022, 42(11): 3890-3895.

Hong'en Cao, Peizi Li, Xiaobi Jing, Hongwei Zhou. Selective Epoxidation of β-Ionone Catalyzed by Iron-Doped Se/C[J]. Chinese Journal of Organic Chemistry, 2022, 42(11): 3890-3895.

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图/表 8

图式1. Se/C-Fe材料的合成

Scheme 1. Synthesis of Se/C-Fe materials

图1. (a) Se/C-Fe的扫描电镜图; (b) Se/C-Fe的透射电镜图; (c-d) Se/C-Fe的高倍透射电镜图; (e) Se/C-Fe的能量色散X射线光谱图; (f) Se/C-Fe的X射线衍射图

Figure 1. (a) SEM image of Se/C-Fe; (b) TEM image of Se/C-Fe; (c-d) HR-TEM image of Se/C-Fe (e) EDX spectrum of Se/C-Fe; (f) XRD image of Se/C-Fe

图2. (a)高角环形暗场-扫描透射电子像和(b~f)元素分布映像

Figure 2. (a) HAADF-STEM image, and (b~f) element mapping

图3. Se/C-Fe材料中硒和铁的X射线光电子能谱图

Figure 3. XPS of Se and Fe in Se/C-Fe

Entry	Solvent	Cat.	Oxidant	T/℃	t/h	Yield^b/%
1	1,4-Dioxane	Se/C-Fe	O₂	80	24	52
2	1,4-Dioxane	FeCl₃	O₂	80	24	46
3	1,4-Dioxane	FeCl₂	O₂	80	24	12
4	1,4-Dioxane	Fe₂O₃	O₂	80	24	17
5	DMF	Se/C-Fe	O₂	80	24	50
6	MeCN	Se/C-Fe	O₂	80	24	50
7	EtOAc	Se/C-Fe	O₂	80	24	45
8	EtOH	Se/C-Fe	O₂	80	24	21
9	THF	Se/C-Fe	O₂	80	24	18
10	1,4-Dioxane	Se/C-Fe	Air	80	24	19
11	1,4-Dioxane	Se/C-Fe	H₂O₂	80	24	23
12	1,4-Dioxane	Se/C-Fe	O₂	60	24	10
13	1,4-Dioxane	Se/C-Fe	O₂	100	24	57
14	1,4-Dioxane	Se/C-Fe	O₂	110^c	24	48
15	1,4-Dioxane	Se/C-Fe	O₂	100	12	42
16	1,4-Dioxane	Se/C-Fe	O₂	100	36	40

表1. Se/C-Fe催化β-紫罗兰酮环氧化反应的条件筛选a

Table 1. Screening of Se/C-Fe-catalyzed β-ionone epoxidation reaction conditions

图4. 催化剂回收与循环使用

Figure 4. Catalyst recovery and recycling

图式2. 对比实验

Scheme 2. Control experiments

图式3. Se/C-Fe催化β-紫罗兰酮环氧化反应的可能机理

Scheme 3. Possible mechanism for Se/C-Fe-catalyzed epoxidation of β-ionone

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铁掺杂硒/碳催化β-紫罗兰酮的选择性环氧化

Selective Epoxidation of β-Ionone Catalyzed by Iron-Doped Se/C

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