非均相CuMgMn层状双氢氧化物无添加剂条件下高效催化级联反应合成喹唑啉与喹唑啉酮

doi:10.6023/cjoc202601013

摘要/Abstract

提出了一种基于CuMgMn层状双氢氧化物(LDH)高效催化醇与二胺通过级联反应合成喹唑啉和喹唑啉酮的新方法. 该催化体系在无任何添加剂条件下即可有效推动级联转化, 并对多种醇底物表现出良好的适用性与优异的催化性能. 结果表明, Cu与Mn活性位点在反应中表现出协同作用. 基于一系列对照实验, 提出了可能的催化机理. 热过滤和催化剂回收实验验证了催化剂的稳定性. 反应放大10倍, 活性和收率保持稳定.

关键词: 喹唑啉, 级联反应, 氧化偶联, 多相催化, 无添加剂

An efficient catalytic method based on CuMgMn-layered double hydroxide (LDH) is presented for the synthesis of quinazolines and quinazolinones via a cascade reaction between alcohols and diamines. The catalytic system operates without any additives, effectively promoting the cascade reaction and showing excellent performance with a range of alcohol substrates. The results indicate that the Cu and Mn active sites exhibit a synergistic effect in the reaction. Based on a series of control experiments, a plausible catalytic mechanism is proposed. Catalyst stability was confirmed through hot filtration and recycling experiments. When the reaction was scaled up by a factor of 10, both the catalytic activity and product yield remained stable.

Key words: quinazoline, cascade reaction, oxidative coupling, heterogeneous catalysis, additive-free

引用此文

吴曼, 姚杰, 房玉阜, 周维友, 钱俊峰, 戴璇, 何明阳. 非均相CuMgMn层状双氢氧化物无添加剂条件下高效催化级联反应合成喹唑啉与喹唑啉酮[J]. 有机化学, 2026, 46(8): 3268-3275.

Man Wu, Jie Yao, Yufu Fang, Weiyou Zhou, Junfeng Qian, Xuan Dai, Mingyang He. Efficient Synthesis of Quinazolines and Quinazolinones via Cascade Reactions over Heterogeneous CuMgMn Layered Double Hydroxide without Additives[J]. Chinese Journal of Organic Chemistry, 2026, 46(8): 3268-3275.

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图/表 8

Scheme 1. A brief survey of previous works and the present work

Entry	Solvent	T/℃	Yield/%
1	Toluene	80	56
2	Acetonitrile	80	58
3	DCE	80	2
4	Trifluorotoluene	80	42
5	Water	80	0
6	Mesitylene	80	41
7	THF	80	22
8	n-Heptane	80	71
9	n-Heptane	50	49
10	n-Heptane	60	60
11	n-Heptane	70	78

Table 1. Optimization of the reaction conditions

Figure 1. Optimization of reaction time and catalyst loading (a) Reaction conditions: 1a (1 mmol), 2a (1 mmol), CuMgMn-LDH (0.2 g), n-heptane (2 mL), O2 (101 kPa), 70 ℃; (b) Reaction conditions: 1a (1 mmol), 2a (1 mmol), CuMgMn-LDH (catalyst), n-heptane (2 mL), O2 (101 kPa), 70 ℃, 14 h

Table 2. Scope of substratesa,b

Entry	Catalyst	Additives	Conv./%	Sel./%
1	CuMgMn-LDH	—	>99	84
2	—	—	Trace	—
3^b	CuMgMn-LDH	—	66	77
4^c	CuMgMn-LDH	—	18	50
5	CuMgAl-LDH	—	64	58
6	Mg₂Al-LDH	—	Trace	—
7	Ni₂Mn-LDH	—	75	58
8	CuMgMn-LDH	BHT^d	Trace	—
9	CuMgMn-LDH	p-Benzoquinone^d	3	—

Table 3. Catalytic results under varied reaction conditionsa

Scheme 2. Proposed reaction pathway

Figure 2. (a) Hot-filtration experiment; (b) Recyclability of Cu- MgMn-LDH in the cascade reaction

Scheme 3. Scale-up reaction

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