纳米氧化铜催化单质硒与芳基碘“一锅法”合成对称二硒化物

doi:10.6023/cjoc202411011

有机化学 ›› 2025, Vol. 45 ›› Issue (7): 2425-2434.DOI: 10.6023/cjoc202411011 上一篇下一篇

研究论文

纳米氧化铜催化单质硒与芳基碘“一锅法”合成对称二硒化物

冯书晓^a^,^*(), 钟轩^a, 陈嘉豪^a, 张宗洛^a, 谷广娜^a, 王俊岭^a, 郭亚菲^a, 马军营^a, 张守仁^b^,^*()

^a 河南科技大学化学化工学院河南洛阳 471023
^b 黄河科技学院纳米功能材料研究所河南省纳米复合材料与应用重点实验室郑州 450006

收稿日期:2025-01-16 修回日期:2025-02-08 发布日期:2025-02-27
通讯作者: 冯书晓, 张守仁
基金资助:
河南省科技攻关基金(242102311203)

One-Pot Synthesis of Symmetrical Diselenides via Nano-CuO Catalysis through Aryl Iodides with Se⁰

Shuxiao Feng^a^,^*(), Xuan Zhong^a, Jiahao Chen^a, Zongluo Zhang^a, Guangna Gu^a, Junling Wang^a, Yafei Guo^a, Junying Ma^a, Shouren Zhang^b^,^*()

^a School of Chemistry & Chemical Engineering, Henan University of Science and Technology, Luoyang, Henan 471023
^b Henan Key Laboratory of Nanocomposites and Applications, Institute of Nanostructured Functional Materials, Huanghe Science and Technology College, Zhengzhou 450006

Received:2025-01-16 Revised:2025-02-08 Published:2025-02-27
Contact: Shuxiao Feng, Shouren Zhang
Supported by:
Henan Scientific and Technological Research Projects(242102311203)

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1. cjoc202411011辅助材料.pdf(3332KB)

摘要/Abstract

含硒化合物具有独特的化学特性、酶学特性和生物学活性. 近年, 二硒化物作为高反应活性硒物种的前体已成为一类生物活性明显和化学用途广泛的重要分子. 单质硒的高效转化策略是无机硒转向有机硒的有效途径. 报道了一种纳米氧化铜催化单质硒与芳基碘“一锅法”合成对称二硒化物的通用合成方法, 该方法适用于邻位、间位及对位不同官能团取代产物, 具有反应方法简单、反应条件温和、收率高、反应过程无硫系异味气体产生、硒原料可回收可再用及适合百克级制备等特点.

关键词: 单质硒, 纳米氧化铜, 芳基碘代物, 含硒化合物, 对称二硒化物

Selenium-containing compounds have unique chemical, enzymatic and biological properties. In recent years, diselenides, as the precursors of highly reactive selenium species, have become a class of important molecules with obvious biological activities and wide chemical applications. The efficient conversion strategy of elemental selenium is an effective way for inorganic selenium to organic selenium. A general synthesis method of symmetrical diselenides from elemental selenium and aryl iodine catalyzed by nano-CuO is reported. The method is suitable for substituting products with different functional groups at ortho-, meta- and para-site. Moreover, this method has the characteristics of simple reaction method, mild reaction conditions, high yield, no production of sulfur based odor gases during the reaction process, recyclable and reusable selenium raw materials, and suitable for the preparation of hundreds of grams.

Key words: elemental selenium, nano-copper oxide, aryl iodide, selenium-containing compound, symmetrical diselenide

引用此文

冯书晓, 钟轩, 陈嘉豪, 张宗洛, 谷广娜, 王俊岭, 郭亚菲, 马军营, 张守仁. 纳米氧化铜催化单质硒与芳基碘“一锅法”合成对称二硒化物[J]. 有机化学, 2025, 45(7): 2425-2434.

Shuxiao Feng, Xuan Zhong, Jiahao Chen, Zongluo Zhang, Guangna Gu, Junling Wang, Yafei Guo, Junying Ma, Shouren Zhang. One-Pot Synthesis of Symmetrical Diselenides via Nano-CuO Catalysis through Aryl Iodides with Se⁰[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2425-2434.

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图/表 11

图1. 对称芳基二硒醚参与的化学反应及其生物活性

Figure 1. Involved reactions and biological activities of symmetric aryl diselenides

图式1. 二硒化物的各种制备方法

Scheme 1. Various ways to prepare diselenides

图式2. 纳米氧化铜催化单质硒与芳基碘“一锅法”合成对称二硒化物

Scheme 2. One-pot synthesis of symmetrical diselenides via nano-CuO catalysis through aryl iodides with Se0

Entry	Cu catalyst	Solvent	Base	Temp./℃	Yield^b/%
1	Cu	DMF	NaOH	90	0
2	CuCl	DMF	NaOH	90	0
3	CuBr	DMF	NaOH	90	0
4	CuI	DMF	NaOH	90	0
5	Cu₂O	DMF	NaOH	90	0
6	CuO	DMF	NaOH	90	6
7	Cu₂Se	DMF	NaOH	90	4
8	Nano CuO	DMF	NaOH	90	10
9	Nano CuO	DMF	NaOH	120	37
10	Nano CuO	DMSO	NaOH	120	61
11	Nano CuO	Toluene	NaOH	Reflux	18
12	Nano CuO	ETOH	NaOH	Reflux	0
13	Nano CuO	THF	NaOH	Reflux	0
14	Nano CuO	H₂O	NaOH	Reflux	0
15	Nano CuO	CH₃CN	NaOH	Reflux	17
16	Nano CuO	DMSO	KOH	120	67
17	Nano CuO	DMSO	K₂CO₃	120	15
18	Nano CuO	DMSO	KBH₄	120	45
19	Nano CuO	DMSO	NH₃•H₂O	120	0

表1. Cu催化剂、溶剂、碱和反应温度的考察a

Table 1. Investigation of Cu catalyst, solvents, bases, and reaction temperatures

Entry	Nano-CuO/mol%	Se/equiv.	KOH/equiv.	t/h	Yield^b/%^b
1	15	2.00	2.00	1	52
2	15	2.00	2.00	2	67
3	15	2.00	2.00	3	86
4	15	2.00	2.00	4	86
5	15	2.00	2.00	5	85
6	15	1.00	2.00	3	18
7	15	1.25	2.00	3	34
8	15	2.50	2.00	3	86
9	15	3.00	2.00	3	85
10	15	2.00	1.00	3	46
11	15	2.00	2.25	3	93
12	15	2.00	2.75	3	54
13	15	2.00	3.00	3	50
14	3	2.00	2.25	3	90
15	5	2.00	2.25	3	92
16	10	2.00	2.25	3	92
17	20	2.00	2.25	3	94
18	30	2.00	2.25	3	93

表2. 反应时间以及各组分投料比的考察a

Table 2. Investigation of reaction time and the ratio of various components

Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65

表3. 底物扩展a

Table 3. Substrate extension

Entry	Se powder/g	Recycling selenium/g	Yield^b/%
1	6.36	3.14	91
2	3.14	1.55	76
3	1.55	0.81	62
4	0.80	0.43	56
5	0.43	0.43	0

表4. 硒粉的回收利用a

Table 4. Recycling and reuse of selenium powder

图2. 材料XRD表征图谱

Figure 2. XRD characterization of material

图3. SEM和mapping分布图

Figure 3. SEM and mapping distribution (a~d) Scanning electron microscopy images of CuO, recycling CuO, selenium powder and recycling selenium powder; (e, f) Element distribution map of Cu in CuO, recycling CuO; (g, h) Element distribution map of O in CuO, recycling CuO; (i~k) Element distribution map of Se in CuO, Se powder and recycling Se powder.

图4. XPS谱图

Figure 4. Spectrum of XPS

图式3. 可能的反应机理

Scheme 3. Plausible reaction mechanism

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纳米氧化铜催化单质硒与芳基碘“一锅法”合成对称二硒化物

One-Pot Synthesis of Symmetrical Diselenides via Nano-CuO Catalysis through Aryl Iodides with Se⁰

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Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65

Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65

Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65

Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65

纳米氧化铜催化单质硒与芳基碘“一锅法”合成对称二硒化物

One-Pot Synthesis of Symmetrical Diselenides via Nano-CuO Catalysis through Aryl Iodides with Se0

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摘要/Abstract

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One-Pot Synthesis of Symmetrical Diselenides via Nano-CuO Catalysis through Aryl Iodides with Se⁰

Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65

Entry	Substrate	Product	Yield^b/%	Entry	Substrate	Product	Yield^b/%
1	1a	2a	94	12	1l	2l	93
2	1b	2b	87	13	1m	2m	88
3	1c	2c	77	14	1n	2n	75
4	1d	2d	85	15	1o	2o	80
5	1e	2e	87	16	1p	2p	76
6	1f	2c	77	17	1q	2q	54
7	1g	2g	64	18	1r	2r	45
8	1h	2h	72	19	1s	2s	75
9	1i	2i	75	20	1t	2t	74
10	1j	2j	63	21	1u	2u	79
11	1k	2k	84	22	1v	2v	65