铜基固体废弃物促进的末端炔烃交叉偶联反应

doi:10.6023/cjoc202401012

有机化学 ›› 2024, Vol. 44 ›› Issue (7): 2341-2349.DOI: 10.6023/cjoc202401012 上一篇下一篇

研究论文

铜基固体废弃物促进的末端炔烃交叉偶联反应

徐童^a, 张宁^a, 张永红^a, 王斌^a, 夏昱^a, 金伟伟^b^,^*(), 金聘入^c^,^*(), 刘晨江^a^,^*()

a 新疆大学化学学院乌鲁木齐 830046
b 中国计量大学生命科学学院杭州 310018
c 光大城乡再生能源(柘城)有限公司河南商丘 476200

收稿日期:2024-01-12 修回日期:2024-03-07 发布日期:2024-03-28
基金资助:
国家自然科学基金(21961037); 国家自然科学基金(22161044); 国家自然科学基金(22201241); 国家自然科学基金(22361044); 天山科技创新领军人才计划(2022TSYCLJ0016); 新疆维吾尔自治区自然科学基金重点(2022D01D06)

Copper-Based Solid Wastes Promoted Cross-Coupling Reactions of Terminal Alkynes

Tong Xu^a, Ning Zhang^a, Yonghong Zhang^a, Bin Wang^a, Yu Xia^a, Weiwei Jin^b(), Pinru Jin^c(), Chenjiang Liu^a()

a College of Chemistry, Xinjiang University, Urumqi 830046
b College of Life Sciences, China Jiliang University, Hangzhou 310018
c Everbright Urban Rural Renewable Energy (Zhecheng) Co., LTD., Shangqiu, Henan 476200

Received:2024-01-12 Revised:2024-03-07 Published:2024-03-28
Contact: * E-mail: wwjin0722@163.com;jinpinru@cebenvironment.com.cn;pxylcj@126.com
Supported by:
National Natural Science Foundation of China(21961037); National Natural Science Foundation of China(22161044); National Natural Science Foundation of China(22201241); National Natural Science Foundation of China(22361044); Tianshan Talents Program for Leading Talents in Science and Technology Innovation(2022TSYCLJ0016); Key Program of Natural Science Foundation of Xinjiang Uygur Autonomous Region(2022D01D06)

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摘要/Abstract

开发了一种使用铜基固体废弃物代替传统铜盐参与Sonogashira和Glaser-Hay偶联反应的方法, 在较为温和的条件下, 高效地合成了多种二取代炔烃. 对于Sonogashira偶联反应, 各种取代的苯乙炔和碘代芳烃反应效果良好, 以57%~97%的产率生成二芳基乙炔类化合物. 对于Glaser-Hay偶联反应, 多种末端炔烃既能以优秀的产率生成对称二取代1,3-丁二炔衍生物, 也能以中等的产率合成交叉偶联产物. 克级规模实验和循环实验表明该固体废弃物在有机合成中有潜在的应用前景.

关键词: 铜基固体废弃物, 末端炔烃, Sonogashira偶联反应, Glaser-Hay偶联反应

An approach to the Sonogashira and Glaser-Hay coupling reactions utilizing copper-based solid wastes instead of traditional copper salts has been developed. This method enables the efficient synthesis of various disubstituted alkynes under relatively mild conditions. For the Sonogashira coupling reaction, diverse substituted phenylacetylenes and aryl iodides exhibit excellent reactivity, resulting in diaryl acetylene compounds with yields ranging from 57% to 97%. The Glaser-Hay coupling reaction allows for the high-yield production of symmetrically disubstituted 1,3-butadiyne derivatives using a variety of terminal alkynes. Additionally, moderate yields can be achieved for cross-coupling products. Gram-scale and cycling experiments demonstrate promising prospects for the application of solid waste in organic synthesis.

Key words: copper based solid waste, terminal alkyne, Sonogashira coupling reaction, Glaser-Hay coupling reaction

引用此文

徐童, 张宁, 张永红, 王斌, 夏昱, 金伟伟, 金聘入, 刘晨江. 铜基固体废弃物促进的末端炔烃交叉偶联反应[J]. 有机化学, 2024, 44(7): 2341-2349.

Tong Xu, Ning Zhang, Yonghong Zhang, Bin Wang, Yu Xia, Weiwei Jin, Pinru Jin, Chenjiang Liu. Copper-Based Solid Wastes Promoted Cross-Coupling Reactions of Terminal Alkynes[J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2341-2349.

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图/表 12

Entry	Pd catalyst	Solid waste/mg	Base	Solvent	1a∶2a	T/℃	Atmosphere	Yield^b/%
1	Pd(OAc)₂	200	Et₃N	DMSO	1∶2	60	N₂	66
2	PdCl₂	200	Et₃N	DMSO	1∶2	60	N₂	76
3	Pd(PPh₃)₄	200	Et₃N	DMSO	1∶2	60	N₂	93
4	Pd(PPh₃)₄	200	Et₃N	H₂O	1∶2	60	N₂	32
5	Pd(PPh₃)₄	200	Et₃N	EtOH	1∶2	60	N₂	39
6	Pd(PPh₃)₄	200	Et₃N	EG	1∶2	60	N₂	60
7	Pd(PPh₃)₄	200	Et₃N	PEG-400	1∶2	60	N₂	64
8	Pd(PPh₃)₄	200	Et₃N	PEG-400	2∶1	60	N₂	90
9	Pd(PPh₃)₄	200	Et₃N	PEG-400	2∶1	30	N₂	15
10	Pd(PPh₃)₄	200	Et₃N	PEG-400	2∶1	60	Air	96
11	—	200	Et₃N	PEG-400	2∶1	60	Air	N.R.
12	Pd(PPh₃)₄	0	Et₃N	PEG-400	2∶1	60	Air	60
13	Pd(PPh₃)₄	200	—	PEG-400	2∶1	60	Air	16

表1. Sonogashira偶联反应条件优化a

Table 1. Optimization conditions of Sonogashira coupling reaction

表2. 芳基碘化物的底物范围a

Table 2. Substrate scope of aryl iodides

表3. 芳基乙炔的底物范围a

Table 3. Substrate scope of aryl acetylenes

图1. 克级规模Sonogashira偶联反应

Figure 1. Gram scale of Sonogashira coupling reaction

Entry	Variation from the standard conditions	Yield^b/%
1	None	98
2	DEEDA instead of TMEDA	N.R.
3	DMEDA instead of TMEDA	N.R.
4	20 mol% Et₃N instead of TMEDA	40
5	40 mol% Et₃N instead of TMEDA	Trace
6	EtOH instead of CH₃CN	69
7	PEG-400 instead of CH₃CN	57
8	Without solid Waste	Trace
9	Without TMEDA	Trace

表4. Glaser-Hay偶联反应条件优化a

Table 4. Optimization conditions of Glaser-Hay coupling reaction

表5. 末端炔烃的底物范围a

Table 5. Substrate scope of terminal alkynes

图2. 克级规模Glaser-Hay偶联反应

Figure 2. Gram scale of Glaser-Hay coupling reaction

图3. Glaser-Hay偶联反应前后固体废弃物的XPS表征

Figure 3. XPS characterization of solid waste before and after the Glaser-Hay coupling reaction

图4. Glaser-Hay偶联反应前后固体废弃物铜的XPS精细谱表征

Figure 4. XPS fine characterization of solid waste copper before and after the Glaser-Hay coupling reaction

图5. Glaser-Hay偶联反应前后固体废弃物的XRD表征

Figure 5. XRD characterization of solid waste before and after the Glaser-Hay coupling reaction

图6. Glaser-Hay偶联反应前后固体废弃物的扫描电子显微镜(SEM)表征

Figure 6. Scanning electron microscope (SEM) characterization of solid waste before and after the Glaser-Hay coupling reaction

Entry	Cu content of solid waste/(μg•g^–1)
Before reaction	50253
After reaction	5173

表6. ICP法测定固体废弃物中的铜含量

Table 6. Determination of copper content in solid waste by ICP

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铜基固体废弃物促进的末端炔烃交叉偶联反应

Copper-Based Solid Wastes Promoted Cross-Coupling Reactions of Terminal Alkynes

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