Green Synthesis of 2-Substituted-2,3-dihydroquinazolin-4(1H)-ones Catalyzed by a Novel Zn(II) Complex

doi:10.6023/cjoc202501004

Abstract

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

Cite this article

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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Fig. & Tab. 12

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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

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