一种新型Zn(II)配合物绿色催化合成2-取代-2,3-二氢喹唑啉-4(1H)-酮

doi:10.6023/cjoc202501004

摘要/Abstract

在溶剂热条件下, 以四水合硫酸锌(ZnSO₄•4H₂O)、4-羟基苯磺酸钠二水合物(C₆H₅NaO₄S•2H₂O)、1,6-二(1H-1,2,4-三氮唑)己烷(btx)为原料合成了一种新的锌配合物[Zn(btx)₂(H₂O)₄]•(p-HOC₆H₄SO₃)₄. 通过X射线单晶衍射、红外光谱、X射线粉末衍射、氮气吸附-脱附测试、扫描电镜对其进行了表征. 考察了该配合物催化芳香醛与邻氨基苯甲酰胺合成2-取代-2,3-二氢喹唑啉-4(1H)-酮的性能. 实验结果表明, 使用少量的催化剂, 在短时间内可以得到较高的产率; 芳香醛苯环上取代基位置相同时, 取代基的吸电子能力越强, 产物产率越高. 运用Gaussian 16程序对16种不同结构的芳香醛分子分别进行优化计算, 计算结果可得, 当取代基位置相同时, 取代基的吸电子能力越强, 芳香醛的最低未占据分子轨道(LUMO)能量越低, 反应活性越强, 有助于反应的顺利进行, 与催化实验的结论相吻合. 最后采用密度泛函理论推测出锌配合物的活性位点, 阐述了其作为催化剂催化合成2-取代-2,3-二氢喹唑啉-4(1H)-酮可能的反应机理.

关键词: 2-取代-2,3-二氢喹唑啉-4(1H)-酮, 锌配合物, 理论计算, 催化机理

A new zinc complex [Zn(btx)₂(H₂O)₄]•(p-OHC₆H₄SO₃)₄ was synthesized from zinc sulfate tetrahydrate (ZnSO₄• 4H₂O), sodium 4-hydroxybenzenesulfonate dihydrate (C₆H₅NaO₄S•2H₂O) and 1,6-bis(1H-1,2,4-triazole)hexane (btx) under solvothermal conditions. It was characterized by X-ray single crystal diffraction, infrared spectrum, X-ray powder diffraction, nitrogen adsorption-desorption test and scanning electron microscope. The catalytic performance of the complex in the synthesis of 2-substituted-2,3-dihydroquinazolin-4(1H)-ones from aromatic aldehydes and o-aminobenzamide was investigated. The experimental results showed that high yields could be achieved in a short time by using a small amount of catalyst. When the substituent positions on the benzene rings of aromatic aldehydes are identical, the stronger electron-withdrawing capability of the substituents results the higher yields of the products. The Gaussian 16 program was used to optimize the calculation on 16 different aromatic aldehydes with various structures. The calculation results showed that when the positions of the substituents are same, the stronger electron-withdrawing ability of the substituents, the lower lowest unoccupied molecular orbital (LUMO) energy of the aromatic aldehydes, and the higher reactivity, which contributes to the proceed of the reactions. This is consistent with the conclusion of the catalytic experiments. Finally, the active sites of the zinc complex were deduced by density functional theory, and the possible reaction mechanism of the zinc complex as a catalyst for the synthesis of 2-substituted-2,3-di- hydroquinazolin-4(1H)-one is described.

Key words: 2-substituted-2,3-dihydroquinazolin-4(1H)-one, zinc complex, theoretical calculation, catalytic mechanism

引用此文

杨瑞杰, 王鑫, 朱志慧, 徐一铭, 宋志国, 王敏. 一种新型Zn(II)配合物绿色催化合成2-取代-2,3-二氢喹唑啉-4(1H)-酮[J]. 有机化学, 2025, 45(12): 4375-4383.

Ruijie Yang, Xin Wang, Zhihui Zhu, Yiming Xu, Zhiguo Song, Min Wang. Green Synthesis of 2-Substituted-2,3-dihydroquinazolin-4(1H)-ones Catalyzed by a Novel Zn(II) Complex[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4375-4383.

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Parameter	Value
Formula	C₄₄H₆₈ZnN₁₂O₂₄S₄
Formula weight	1314.5
Crystal system	Triclinic
Space group	P-1
a/nm	0.75461(3)
b/nm	0.91215(3)
c/nm	1.24011(10)
α/(°)	75.1310(10)
β/(°)	89.0470(10)
γ/(°)	78.3130(10)
V/nm³	0.80734(5)
Z	1
D_c/(mg•m^－3)	1.522
Goodness-of-fit F²	1.100
R₁^a, wR₂^b	0.0497, 0.1492
R₁, wR₂ (all data)	0.0522, 0.1520

Parameter	Value
Formula	C₄₄H₆₈ZnN₁₂O₂₄S₄
Formula weight	1314.5
Crystal system	Triclinic
Space group	P-1
a/nm	0.75461(3)
b/nm	0.91215(3)
c/nm	1.24011(10)
α/(°)	75.1310(10)
β/(°)	89.0470(10)
γ/(°)	78.3130(10)
V/nm³	0.80734(5)
Z	1
D_c/(mg•m^－3)	1.522
Goodness-of-fit F²	1.100
R₁^a, wR₂^b	0.0497, 0.1492
R₁, wR₂ (all data)	0.0522, 0.1520

Bond	Length/nm	Bond angle	Angle/(°)
Zn(1)—N(1)	0.2101(3)	O(2W)—Zn(1)—O(1W)	88.82(11)
Zn(1)—N(1)#1	0.2101(3)	O(2W)#1—Zn(1)—O(1W)	91.18(11)
Zn(1)—O(1W)	0.2142(3)	N(1)#1—Zn(1)—O(2W)#1	88.63(10)
Zn(1)—O(1W)#1	0.2142(3)	N(1)#1—Zn(1)—O(1W)#1	91.23(11)
Zn(1)—O(2W)	0.2105(2)	O(2W)—Zn(1)—O(1W)#1	91.18(11)
Zn(1)—O(1W)#1	0.2105(2)	N(1)—Zn(1)—O(2W)	88.63(10)

Bond	Length/nm	Bond angle	Angle/(°)
Zn(1)—N(1)	0.2101(3)	O(2W)—Zn(1)—O(1W)	88.82(11)
Zn(1)—N(1)#1	0.2101(3)	O(2W)#1—Zn(1)—O(1W)	91.18(11)
Zn(1)—O(1W)	0.2142(3)	N(1)#1—Zn(1)—O(2W)#1	88.63(10)
Zn(1)—O(1W)#1	0.2142(3)	N(1)#1—Zn(1)—O(1W)#1	91.23(11)
Zn(1)—O(2W)	0.2105(2)	O(2W)—Zn(1)—O(1W)#1	91.18(11)
Zn(1)—O(1W)#1	0.2105(2)	N(1)—Zn(1)—O(2W)	88.63(10)

D—H…A	Bond length (D—H)/nm	Bond length (H…A)/nm	Bond length (D…A)/nm	∠DHA/(°)
O(1W)—H(1WA)…O(1)	0.085	0.220	0.2793(4)	150.9
O(1W)—H(1WB)…O(1)#4	0.085	0.197	0.2809(4)	167.0
O(2W)—H(2WA)…O(4)#4	0.085	0.196	0.2769(4)	158.9
O(2W)—H(2WB)…N(3)#5	0.085	0.205	0.2870(4)	161.7