Yoshihiro Kon , Takuya Nakashima , Yoshiki Makino , Shun-ya Onozawa , Hiroyuki Miyamura , Shū Kobayashi , Kazuhiko Sato
{"title":"用铂和二氧化硅催化过氧化氢氧化法从醇连续流合成羧酸。","authors":"Yoshihiro Kon , Takuya Nakashima , Yoshiki Makino , Shun-ya Onozawa , Hiroyuki Miyamura , Shū Kobayashi , Kazuhiko Sato","doi":"10.1039/d4ob01668h","DOIUrl":null,"url":null,"abstract":"<div><div>A continuous-flow method for the direct oxidation of alcohols to carboxylic acids is reported, employing hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) and a platinum (Pt) catalyst within a flow reactor system. This approach allows for precise control over the contact time between the reactants and the catalyst, enabling optimization of reaction conditions. By analyzing the yields of both aldehydes and carboxylic acids as a function of weight hourly space velocity (WHSV), selective synthesis of carboxylic acids was achieved without the formation of corresponding aldehydes. The Pt catalyst exhibited excellent stability, producing 25.2 g of octanoic acid from 1-octanol with a yield exceeding 96% over 210 h at a WHSV of 1.3 h<sup>−1</sup> using a 5 mm inner diameter × 100 mm column. This Pt-catalyzed continuous-flow H<sub>2</sub>O<sub>2</sub> oxidation method demonstrates good reactivity for a variety of alcohols, including aliphatic, aromatic, allylic, and heteroaromatic, affording the corresponding carboxylic acids in 19–98% isolated yields with water as the sole byproduct. X-ray photoelectron spectroscopy (XPS) analysis confirmed the preservation of metallic zero-valent Pt (Pt(0)) throughout the reaction.</div></div>","PeriodicalId":96,"journal":{"name":"Organic & Biomolecular Chemistry","volume":"23 9","pages":"Pages 2125-2132"},"PeriodicalIF":2.9000,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Continuous-flow synthesis of carboxylic acids from alcohols via platinum and silicon dioxide-catalyzed hydrogen peroxide oxidation†\",\"authors\":\"Yoshihiro Kon , Takuya Nakashima , Yoshiki Makino , Shun-ya Onozawa , Hiroyuki Miyamura , Shū Kobayashi , Kazuhiko Sato\",\"doi\":\"10.1039/d4ob01668h\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>A continuous-flow method for the direct oxidation of alcohols to carboxylic acids is reported, employing hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) and a platinum (Pt) catalyst within a flow reactor system. This approach allows for precise control over the contact time between the reactants and the catalyst, enabling optimization of reaction conditions. By analyzing the yields of both aldehydes and carboxylic acids as a function of weight hourly space velocity (WHSV), selective synthesis of carboxylic acids was achieved without the formation of corresponding aldehydes. The Pt catalyst exhibited excellent stability, producing 25.2 g of octanoic acid from 1-octanol with a yield exceeding 96% over 210 h at a WHSV of 1.3 h<sup>−1</sup> using a 5 mm inner diameter × 100 mm column. This Pt-catalyzed continuous-flow H<sub>2</sub>O<sub>2</sub> oxidation method demonstrates good reactivity for a variety of alcohols, including aliphatic, aromatic, allylic, and heteroaromatic, affording the corresponding carboxylic acids in 19–98% isolated yields with water as the sole byproduct. X-ray photoelectron spectroscopy (XPS) analysis confirmed the preservation of metallic zero-valent Pt (Pt(0)) throughout the reaction.</div></div>\",\"PeriodicalId\":96,\"journal\":{\"name\":\"Organic & Biomolecular Chemistry\",\"volume\":\"23 9\",\"pages\":\"Pages 2125-2132\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2025-01-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organic & Biomolecular Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S1477052024011352\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, ORGANIC\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Organic & Biomolecular Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S1477052024011352","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, ORGANIC","Score":null,"Total":0}
Continuous-flow synthesis of carboxylic acids from alcohols via platinum and silicon dioxide-catalyzed hydrogen peroxide oxidation†
A continuous-flow method for the direct oxidation of alcohols to carboxylic acids is reported, employing hydrogen peroxide (H2O2) and a platinum (Pt) catalyst within a flow reactor system. This approach allows for precise control over the contact time between the reactants and the catalyst, enabling optimization of reaction conditions. By analyzing the yields of both aldehydes and carboxylic acids as a function of weight hourly space velocity (WHSV), selective synthesis of carboxylic acids was achieved without the formation of corresponding aldehydes. The Pt catalyst exhibited excellent stability, producing 25.2 g of octanoic acid from 1-octanol with a yield exceeding 96% over 210 h at a WHSV of 1.3 h−1 using a 5 mm inner diameter × 100 mm column. This Pt-catalyzed continuous-flow H2O2 oxidation method demonstrates good reactivity for a variety of alcohols, including aliphatic, aromatic, allylic, and heteroaromatic, affording the corresponding carboxylic acids in 19–98% isolated yields with water as the sole byproduct. X-ray photoelectron spectroscopy (XPS) analysis confirmed the preservation of metallic zero-valent Pt (Pt(0)) throughout the reaction.
期刊介绍:
Organic & Biomolecular Chemistry is an international journal using integrated research in chemistry-organic chemistry. Founded in 2003 by the Royal Society of Chemistry, the journal is published in Semimonthly issues and has been indexed by SCIE, a leading international database. The journal focuses on the key research and cutting-edge progress in the field of chemistry-organic chemistry, publishes and reports the research results in this field in a timely manner, and is committed to becoming a window and platform for rapid academic exchanges among peers in this field. The journal's impact factor in 2023 is 2.9, and its CiteScore is 5.5.