Matea Bačić, Maria Tejeda–Serrano, Yongkun Zheng, Judit Oliver–Meseguer, Antonio Leyva–Pérez
{"title":"HY zeolite catalyzes the ortho–methylation of 1–naphthol","authors":"Matea Bačić, Maria Tejeda–Serrano, Yongkun Zheng, Judit Oliver–Meseguer, Antonio Leyva–Pérez","doi":"10.1016/j.apsadv.2024.100598","DOIUrl":null,"url":null,"abstract":"<div><p>The selective <em>ortho</em>–alkylation of 1–naphthol with methanol is carried out over various commercially available acid solid catalysts under relatively mild reaction conditions (<300 ºC), in batch, and anhydrous zeolite HY shows the best catalytic activity. Removal of the strongly adsorbed water in the zeolite is key for the alkylation reaction. Mechanistic studies based on isotopically labelled experiments reveal the transformation of <em>O</em>–methylated 1–naphthol into the desired <em>ortho</em>–<em>C</em>–methylation product after intramolecular rearrangement of the methyl group. These results open the way to design a new synthesis of <em>ortho</em>–methyl 1–naphthol and, consequently, of vitamin K3, based on a commercially available, inexpensive and non–toxic solid catalyst such as HY zeolite.</p></div>","PeriodicalId":34303,"journal":{"name":"Applied Surface Science Advances","volume":null,"pages":null},"PeriodicalIF":7.5000,"publicationDate":"2024-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666523924000266/pdfft?md5=da32f7b2673a88de04427f0b61cee119&pid=1-s2.0-S2666523924000266-main.pdf","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Surface Science Advances","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2666523924000266","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The selective ortho–alkylation of 1–naphthol with methanol is carried out over various commercially available acid solid catalysts under relatively mild reaction conditions (<300 ºC), in batch, and anhydrous zeolite HY shows the best catalytic activity. Removal of the strongly adsorbed water in the zeolite is key for the alkylation reaction. Mechanistic studies based on isotopically labelled experiments reveal the transformation of O–methylated 1–naphthol into the desired ortho–C–methylation product after intramolecular rearrangement of the methyl group. These results open the way to design a new synthesis of ortho–methyl 1–naphthol and, consequently, of vitamin K3, based on a commercially available, inexpensive and non–toxic solid catalyst such as HY zeolite.
在相对温和的反应条件下(<300 ºC),采用多种市售酸性固体催化剂,分批进行了 1-萘酚与甲醇的选择性正烷基化反应,其中无水沸石 HY 的催化活性最好。去除沸石中的强吸附水是烷基化反应的关键。基于同位素标记实验的机理研究表明,O-甲基化的 1-萘酚在经过甲基的分子内重排后会转化为所需的正交-C-甲基化产物。这些结果为设计一种新的 1-萘酚原甲基合成方法开辟了道路,这种合成方法基于 HY 沸石等市售、廉价和无毒的固体催化剂。