2,3,5-三取代咪唑衍生物的高效合成方法

兰州理工大学学报 ›› 2025, Vol. 51 ›› Issue (1): 66-71.

2,3,5-三取代咪唑衍生物的高效合成方法

杨峥^1,2,3, 丛兴顺^*3, 陈益武¹, 张刚^1,2, 解恒参¹

1.江苏建筑职业技术学院建筑智能学院, 江苏徐州 221116;
2.江苏建筑节能与建造技术协同创新中心, 江苏徐州 221116;
3.枣庄学院化学化工与材料科学学院, 山东枣庄 277160

收稿日期:2023-03-01 出版日期:2025-02-28 发布日期:2025-03-03
通讯作者: 丛兴顺(1980-),男,山东枣庄人,博士,教授.Email:cong_xingshun@126.com
基金资助:
山东省自然科学基金(ZR2022QB093,ZR2022MB027),江苏省高等学校自然科学研究面上项目(24KJB530008),江苏建筑节能与建造技术协同创新中心博士专项课题(SJXTBS2120,SJXTBZ2114),江苏省教育科学“十四五”规划课题(C-c/2021/03/24,B/2021/03/17),江苏省高等教育教改研究立项课题(2021JSJG467,2021JSJG168)

An efficient protocol for the synthesis of 2,3,5-trisubstituted imidazole derivatives

YANG Zheng^1,2,3, CONG Xing-shun³, CHEN Yi-wu¹, ZHANG Gang^1,2, XIE Heng-shen¹

1. School of Architectural Intelligence, Jiangsu Vocational Institute of Architectural Technology, Xuzhou 221116, China;
2. Jiangsu Collaborative Innovation Center for Building Energy Saving and Construct Technology, Xuzhou 221116, China;
3. College of Chemistry, Chemical Engineering and Materials Science, Zaozhuang University, Zaozhuang 277160, China

Received:2023-03-01 Online:2025-02-28 Published:2025-03-03

摘要/Abstract

摘要： 以芳甲酰甲醛、芳基脒和乙酸酐为起始原料,在80 ℃的醋酸溶剂中,经分子内环化/分子间亲电加成反应,合成了一系列2,3,5-三取代咪唑衍生物,优化收率在63%~82%之间.所有产物的结构均经核磁共振氢谱、红外光谱和高分辨率质谱证实,并且化合物4c的结构得到了X-单晶衍射的确认.

关键词: 芳甲酰甲醛, 芳基脒, 咪唑

Abstract: By using arylglyoxal monohydrate, aromatic amidine, and acetic anhydride as starting materials, a series of 2,3,5-trisubstituted imidazole derivatives were synthesized via intramolecular cyclization/intermolecular electrophilic addition reaction in acetic acid solvent at 80 ℃. The optimized yields ranged from 63% to 82%. The structures of all products were confirmed by ¹H NMR, IR, and HRMS.Additionally, the structure of compound 4c was also confirmed by X-ray single crystal diffraction.

Key words: arylglyoxal monohydrate, aromatic amidine, imidazole

中图分类号:

O626

杨峥, 丛兴顺, 陈益武, 张刚, 解恒参. 2,3,5-三取代咪唑衍生物的高效合成方法[J]. 兰州理工大学学报, 2025, 51(1): 66-71.

YANG Zheng, CONG Xing-shun, CHEN Yi-wu, ZHANG Gang, XIE Heng-shen. An efficient protocol for the synthesis of 2,3,5-trisubstituted imidazole derivatives[J]. Journal of Lanzhou University of Technology, 2025, 51(1): 66-71.

参考文献

[1] 赵咪娜,杨梓墨,杨得锁,等.通过环化反应构建多取代咪唑的最新研究进展[J].有机化学,2022,42:111-128.
[2] 杨峥,解恒参,丁维华,等.1,3,5-三芳基吡唑衍生物的高效合成方法[J].兰州理工大学学报,2021,47(5):65-69.
[3] 徐鑫明,陈德茂,王祖利.无过渡金属催化的吲哚C—H键的巯基化反应研究进展[J].有机化学,2020,40:886-898.
[4] 朱彦荣,陈明凯,王进贤,等.微波促进无溶剂无催化条件下2,4,5-三芳基取代咪唑衍生物的合成[J].化学研究与应用,2008,2:10-16.
[5] 邱志鹏,谭继华,蔡宁,等.菲并咪唑类衍生物蓝光材料的研究进展[J].有机化学,2019,39:679-696.
[6] WANG Y,ZHOU Y,SONG Q L.[3+1+1] type cyclization of ClCF₂COONa for the assembly of imidazoles and tetrazoles via in situ generated isocyanides[J].Chemical Communications,2020,56:6106-6109.
[7] HINDI K M,PANZNER M J,TESSIER C A,et al.The medicinal applications of imidazolium carbene-metal complexes[J].Chemical Reviews,2009,109:3859-3884.
[8] VUILLERMET F,BOURRET J,PELLETIER G.Synthesis of Imidazo [1,2-a]pyridines:triflic anhydride-mediated annulation of 2H-azirines with 2-chloropyridines[J].The Journal of Organic Chemistry,2021,86:388-402.
[9] HUANG H,JI X,TANG X,et al.Conversion of pyridine to imidazo [1,2-a] pyridines by copper-catalyzed aerobic dehydrogenative cyclization with oxime esters[J].Organic Letters,2013,15:6254-6257.
[10] QU Z,ZHANG F,DENG G J,et al.Regioselectivity control in the oxidative formal [3+2] annulations of ketoxime acetates and tetrohydroisoquinolines[J].Organic Letters,2019,21:8239-8243.
[11] LI G,HE R,LIU Q,et al.Formation of amidinyl radicals via visible-light-promoted reduction of N-phenyl amidoxime esters and application to the synthesis of 2-substituted benzimidazoles[J].The Journal of Organic Chemistry,2019,84:8646-8660.
[12] MIAO C,HOU Q,WEN Y,et al.Long-chained acidic ionic liquids-catalyzed cyclization of 2-substituted aminoaromatics with β-diketones:a metal-free strategy to construct benzoazoles[J].ACS Sustainable Chemistry & Engineering,2019,7:12008-12013.
[13] PAN Z,SONG C,ZHOU W,et al.Synthesis of imidazo [1,2-a][1,3,5] triazines by NBS-mediated coupling of 2-amino-1,3,5-triazines with 1,3-dicarbonyl compounds[J].New Journal of Chemistry,2020,44:6182-6185.
[14] REDDY N N K,RAO S N,RAVI C.Catalyst-free synthesis of 2,4-disubstituted-1H-imidazoles through [3+2] cyclization of vinyl azides with amidines[J].ACS Omega,2017,2:5235-5241.
[15] WANG C,YU Y,SU Z,et al.Metal-free C-B bond cleavage:an acid catalyzed three-component reaction construction of imidazole-containing triarylmethanes[J].Organic Letters,2019,21:4420-4423.