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四氟化钛催化二苯甲醇脱水转化为对称和不对称醚。

Titanium tetrafluoride catalysis for the dehydrative conversion of diphenylmethanols to symmetric and unsymmetric ethers.

作者信息

Singh Aman G, Alawaed Abdulkhaliq A, Ramachandran P Veeraraghavan

机构信息

Department of Chemistry, Purdue University West Lafayette IN 47907 USA

出版信息

RSC Adv. 2024 Aug 2;14(33):24236-24239. doi: 10.1039/d4ra04712e. eCollection 2024 Jul 26.

DOI:10.1039/d4ra04712e
PMID:39101069
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11296350/
Abstract

In contrast to the conversion of diphenylmethanol to the corresponding halides with an equivalent of titanium tetrachloride or -bromide, catalytic (50 mol%) titanium tetrafluoride converts benzhydrols in diethyl ether or dichloromethane to bis(benzhydryl) ethers within 0.5-1 h at room temperature. Cross ether formation with diphenylmethanols and primary aryl or aliphatic alcohols is achieved in the presence of 25 mol% TiF in refluxing toluene as solvent. A tentative mechanism involving a carbocation intermediate has been proposed.

摘要

与用等量四氯化钛或四溴化钛将二苯甲醇转化为相应卤化物不同,催化量(50 mol%)的四氟化钛在室温下于0.5 - 1小时内可将二苯甲醇在乙醚或二氯甲烷中转化为双(二苯甲基)醚。在作为溶剂的回流甲苯中,在25 mol% TiF存在下,二苯甲醇与伯芳基或脂肪醇可实现交叉醚化反应。有人提出了一种涉及碳正离子中间体的初步机理。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5a63/11296350/687e3c3e7894/d4ra04712e-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5a63/11296350/d69229c3e4f5/d4ra04712e-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5a63/11296350/8631c4c2d7cd/d4ra04712e-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5a63/11296350/687e3c3e7894/d4ra04712e-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5a63/11296350/d69229c3e4f5/d4ra04712e-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5a63/11296350/8631c4c2d7cd/d4ra04712e-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/5a63/11296350/687e3c3e7894/d4ra04712e-s2.jpg

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本文引用的文献

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RSC Adv. 2024 May 13;14(22):15554-15559. doi: 10.1039/d4ra02213k. eCollection 2024 May 10.
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Catalytic Degradation of Triphenylmethane Dyes with an Iron Porphyrin Complex as a Cytochrome P450 Model.铁卟啉配合物模拟细胞色素 P450 对三苯甲烷染料的催化降解。
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Balancing Lewis Acidity and Carbocation Stability for the Selective Deoxyhalogenation of Aryl Carbonyls and Carbinols.
平衡路易斯酸度和碳正离子稳定性以实现芳基羰基和碳氢键的选择性脱卤。
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Iron-Catalyzed Selective Etherification and Transetherification Reactions Using Alcohols.铁催化的使用醇类的选择性醚化和转醚化反应
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Org Biomol Chem. 2019 Jun 26;17(25):6221-6228. doi: 10.1039/c9ob01093a.
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