Phenolic Hydroxyl‐Functionalized Covalent–Organic Frameworks for Formal [3+2] Reaction. Issue 6 (12th February 2022)

• Record Type: Journal Article
• Authors: Ma, Baiwei; Xu, Yimeng; Hu, Fujia; Zhang, Guangci; Zheng, Xiaofei; Wang, Zhuo; Qiao, Huijie; Yang, Dehong; Mi, Liwei
• Is Part Of: Macromolecular chemistry and physics. Volume 223:Issue 6(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-02-12
• Subjects: 5‐alkoxyoxazoles -- covalent–organic frameworks -- formal [3+2] reaction -- heterogeneous catalysts -- phenolic and methyl groups; Polymers -- Periodicals; Polymerization -- Periodicals; Synthetic products -- Periodicals; Macromolecules -- Periodicals; 547.7
• DOI: 10.1002/macp.202100462
• Languages: English
• ISSNs: 1022-1352

Abstract

Abstract: Covalent–organic frameworks (COFs) are rarely used as heterogeneous catalysts for cycloaddition reactions, especially in [3+2] reactions. In this study, 4, 4′, 4″, 4‴‐(pyrene‐1, 3, 6, 8‐tetrayl) tetra‐aniline, 2, 5‐dihydroxyterephthalaldehyde, and 2, 5‐dimethylterephthalaldehyde are used to construct COFs with high porosity, crystallinity, and chemical stability. The phenolic and methyl groups on the pore channel of the COFs are precisely tuned to effectively serve as heterogeneous catalysts for the formal [3+2] reaction between 5‐alkoxyoxazoles and azodicarboxylate or nitrosobenzene compounds. The resultant COFs that are assembled from adjustable building unit ratios exhibit excellent catalytic performance for the targeted [3+2] reaction. Abstract : Four covalent–organic frameworks (COFs) are developed. Among them, [OH]75%‐4, 4′, 4″, 4‴‐(pyrene‐1, 3, 6, 8‐tetrayl) tetra‐aniline (PyTTA)‐COF and [OH]50%‐PyTTA‐COF are obtained through three component monomers condensation reaction including both phenolic and methyl groups in channel wall with higher crystallinity and Brunauer–Emmett–Teller surface area. Especially, the [OH]75%‐PyTTA‐COF has exhibited the best performance for formal [3+2] reaction of 5‐alkoxyoxazoles and azodicarboxylate or nitrosobenzene compounds as a heterogeneous catalyst.