铜催化C—O偶联制备间苯氧基苯甲醛

doi:10.6023/cjoc202502035

摘要/Abstract

制备并筛选了一系列草酰二胺聚合物铜催化剂, 并研究了其催化苯酚和间溴苯甲醛C—O偶联反应. 结果表明2,2-二氨基二苯硫醚草酰二胺聚合物铜催化剂Cu@PSAO表现出优异的催化苯酚和间溴苯甲醛C—O偶联反应的选择性和非常高的反应活性, 间苯氧基苯甲醛的收率可达99%. 通过X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、能量色散X射线(EDX)、透射电子显微镜(TEM)、红外吸收光谱(FTIR)和比表面积测试(BET)等一系列表征, 研究了该催化剂的结构性能关系. 结果显示Cu@PSAO呈现不规则的三维结构, 草酰二胺聚合物和铜的配位促成了该线性聚合物的交叉或者卷曲形成该三维结构. 与现有的工艺相比, Cu@PSAO中的聚合物结构可以使苯酚和间溴苯甲醛C—O偶联反应的选择性大大提升, 很好地避免了间溴苯甲醛在碱性条件下的歧化副反应. 该催化剂制备简单, 反应后易于分离, 多次反应循环后仍具有稳定的催化性能, 具有良好工业应用的前景.

关键词: 间苯氧基苯甲醛, 铜催化剂, C—O偶联反应, 草酰二胺聚合物

A series of copper catalysts based on oxalyl diamide polymers were prepared and screened for the coupling of m-bromobenzaldehyde with phenol. The reaction results demonstrated that the copper catalyst Cu@PSAO of 2,2-diamino- diphenyl sulfide oxalyl diamide polymer exhibited excellent selectivity for the C—O coupling of m-bromobenzaldehyde with phenol with very high selectivity and high activity. The yield of m-phenoxybenzaldehyde can reach 99%. A series of characterizations including X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), transmission electron microscopy (TEM), infrared absorption spectroscopy (FTIR), and specific surface area test (BET) were employed to study the relationship between the structures and chemical properties of the catalyst Cu@PSAO. Through the characterization results, it was observed that Cu@PSAO presented an irregular three-dimensional structure, and the three-dimensional structure was formed by cross linked or rolled through the coordination of copper with the oxalyl diamide polymers. Compared with the existing processes, the Cu catalyst Cu@PSAO can significantly enhance the selectivity of the C—O coupling of m-bromobenzaldehyde with phenol and effectively avoid the disproportionation side reaction of bromobenzaldehyde under the alkaline condition. The catalyst Cu@PSAO was prepared easily and could be separated simply from the reaction mixture after the reaction. It still maintains stable catalytic performance after multiple reaction cycles, thus exhibiting application prospects for industrial processes.

Key words: m-phenoxybenzaldehyde, copper catalyst, C—O coupling reaction, oxalediamine polymer

引用此文

贾晨旭, 安聪好, 黄军. 铜催化C—O偶联制备间苯氧基苯甲醛[J]. 有机化学, 2025, 45(9): 3412-3419.

Chenxu Jia, Conghao An, Jun Huang. Copper Catalyzed C—O Coupling for the Preparation of m-Phenoxybenzaldehyde[J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3412-3419.

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图/表 11

图1. 草酰二胺聚合物铜催化剂的结构

Figure 1. Structures of oxalediamine polymer Cu catalysts

Entry	Catalyst	Yield/%	Selectivity/%
Entry	Catalyst	Yield/%	3-PBD	Others
1	—	95	2	98
2	Cu@PSAO	99	100	—
3	Cu@PBNO	18	100	—
4	Cu@PBAO	65	100	—
5	Cu@PSAO(Cu₂O)	67	100	—

表1. 不同铜催化剂对3-PBD收率的影响a

Table 1. Effect of 3-PBD yields on different copper catalysts

图2. Cu@PSAO的SEM图(A, B)、TEM图(C)和Cu的EDS元素图(D)

Figure 2. SEM diagram (A, B), TEM diagram (C) of Cu@PSAO, and EDS element map (D) of Cu

图3. Cu@PSAO的XPS光谱: 全光谱的XPS光谱(A), Cu 2p (B)

Figure 3. XPS spectra of Cu@PSAO: XPS spectra of the full spectrum (A), Cu 2p( B)

图4. Cu@PSAO的FTIR光谱

Figure 4. FTIR spectra for Cu@PSAO

图5. Cu@PSAO催化剂的N2吸附-脱附等温线(A)和孔径分布(B)

Figure 5. N2 adsorption-desorption isotherm (A) and pore size distribution of the Cu@PSAO catalyst (B)

图6. Cu@PSAO催化3-BBA和PhOH偶联的反应条件的优化

Figure 6. Optimization of the reaction conditions for the coupling of 3-BBA and PhOH catalyzed by Cu@PSAO Reaction conditions: (A) 10 mmol of 3-BBA, 15 mmol of PhOH, 7 mol% Cu@PSAO, 20 mmol of base, 5 mL of 1,4-dioxane, 120 ℃, 5 h; (B) 10 mmol of 3-BBA, 15 mmol of PhOH, 7 mol% Cu@PSAO, 20 mmol of K3PO4, 5 mL of 1,4-dioxane, 5 h; (C) 10 mmol of 3-BBA, 15 mmol of PhOH, 7 mol% Cu@PSAO, 20 mmol of K3PO4, 5 mL of solvent, 120 ℃, 5 h; (D) 10 mmol of 3-BBA, 15 mmol of PhOH, 20 mmol of K3PO4; 5 mL 1,4-dioxane, 120 ℃, 5 h.

图7. 反应时间对3-PBD收率的影响

Figure 7. Effect of reaction time on 3-PBD yield Reaction conditions: 10 mmol of 3-BBA, 15 mmol of PhOH, 7 mol% Cu@PSAO, 20 mmol of K3PO4, 5 mL of 1,4-dioxane, 120 ℃.

图8. Cu@PSAO催化3-BBA和PhOH偶联反应中催化剂的循环实验(A)和Cu@PSAO催化3-BBA和PhOH偶联3-PBD (B)的热过滤实验示意图

Figure 8. Cu@PSAO cycling experiments of catalysts in 3-BBA and PhOH coupling reactions (A) and the schematic diagram of the Cu@PSAO catalytic thermal filtration experiment for the coupling of 3-BBA and PhOH to 3-PBD catalyzed by Cu@PSAO (B)

图式1. 放大反应

Scheme 1. Amplification reaction

Entry	R¹	R²	Yield/%
1	4-CN	H	98
2	3-CH₃	H	38
3	2-CHO	H	78
4	H	4-CN	31
5	H	3-CH₃	94
6	H	2-CHO	44

表2. C—O偶联底物范围的探究

Table 2. Exploration of the range of C—O coupling substrates

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