Isabel C.M.S. Santos , José A.F. Gamelas , Tiago A.G. Duarte , Mário M.Q. Simões , M. Graça P.M.S. Neves , José A.S. Cavaleiro , Ana M.V. Cavaleiro
{"title":"在三明治型钨磷酸盐[M4(H2O)2(PW9O34)2]n−，M = CoII, MnII和FeIII存在下，过氧化氢催化单萜烯和环烯的均相氧化","authors":"Isabel C.M.S. Santos , José A.F. Gamelas , Tiago A.G. Duarte , Mário M.Q. Simões , M. Graça P.M.S. Neves , José A.S. Cavaleiro , Ana M.V. Cavaleiro","doi":"10.1016/j.molcata.2016.10.021","DOIUrl":null,"url":null,"abstract":"<div><p>Catalytic efficiency of tetrabutylammonium salts of sandwich tungstophosphates B‐α‐[M<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>(PW<sub>9</sub>O<sub>34</sub>)<sub>2</sub>]<sup>n−</sup>, M<!--> <!-->=<!--> <!-->Co<sup>II</sup>, Mn<sup>II</sup>, Fe<sup>III</sup>, was studied in the oxidation of (<em>R</em>)-(+)-limonene, geraniol, linalool, linalyl acetate, carveol, and <em>cis</em>-cyclooctene with hydrogen peroxide, in acetonitrile. Oxidation of (<em>R</em>)-(+)-limonene gave limonene-1,2-diol as main product. Epoxidation of linalool takes place preferentially at the more substituted 6,7-double bond, the corresponding 6,7-epoxide reacting further, yielding furano- and pyrano-oxides, via intramolecular cyclization. Oxidation of linalyl acetate occurred preferentially at the more substituted 6,7-double bond for Mn<sub>4</sub>(PW<sub>9</sub>)<sub>2</sub>, affording 6,7-epoxide at 82% selectivity. Linalyl acetate 1,2-epoxide was the major product with 51% and 77% selectivity for Co<sub>4</sub>(PW<sub>9</sub>)<sub>2</sub> and Fe<sub>4</sub>(PW<sub>9</sub>)<sub>2</sub>, respectively. Oxidation of carveol occurred with very good conversions in the presence of Mn<sub>4</sub>(PW<sub>9</sub>)<sub>2</sub>, Co<sub>4</sub>(PW<sub>9</sub>)<sub>2</sub> and Fe<sub>4</sub>(PW<sub>9</sub>)<sub>2</sub>, yielding carvone and carveol 1,2-epoxide in similar amounts. Oxidation of <em>cis</em>-cyclooctene gave only the epoxide, while oxidation of geraniol at room temperature afforded 2,3-epoxygeraniol as the major product.</p></div>","PeriodicalId":370,"journal":{"name":"Journal of Molecular Catalysis A: Chemical","volume":"426 ","pages":"Pages 593-599"},"PeriodicalIF":5.0620,"publicationDate":"2017-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.molcata.2016.10.021","citationCount":"17","resultStr":"{\"title\":\"Catalytic homogeneous oxidation of monoterpenes and cyclooctene with hydrogen peroxide in the presence of sandwich-type tungstophosphates [M4(H2O)2(PW9O34)2]n−, M = CoII, MnII and FeIII\",\"authors\":\"Isabel C.M.S. Santos , José A.F. Gamelas , Tiago A.G. Duarte , Mário M.Q. Simões , M. Graça P.M.S. Neves , José A.S. Cavaleiro , Ana M.V. Cavaleiro\",\"doi\":\"10.1016/j.molcata.2016.10.021\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Catalytic efficiency of tetrabutylammonium salts of sandwich tungstophosphates B‐α‐[M<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>(PW<sub>9</sub>O<sub>34</sub>)<sub>2</sub>]<sup>n−</sup>, M<!--> <!-->=<!--> <!-->Co<sup>II</sup>, Mn<sup>II</sup>, Fe<sup>III</sup>, was studied in the oxidation of (<em>R</em>)-(+)-limonene, geraniol, linalool, linalyl acetate, carveol, and <em>cis</em>-cyclooctene with hydrogen peroxide, in acetonitrile. Oxidation of (<em>R</em>)-(+)-limonene gave limonene-1,2-diol as main product. Epoxidation of linalool takes place preferentially at the more substituted 6,7-double bond, the corresponding 6,7-epoxide reacting further, yielding furano- and pyrano-oxides, via intramolecular cyclization. Oxidation of linalyl acetate occurred preferentially at the more substituted 6,7-double bond for Mn<sub>4</sub>(PW<sub>9</sub>)<sub>2</sub>, affording 6,7-epoxide at 82% selectivity. Linalyl acetate 1,2-epoxide was the major product with 51% and 77% selectivity for Co<sub>4</sub>(PW<sub>9</sub>)<sub>2</sub> and Fe<sub>4</sub>(PW<sub>9</sub>)<sub>2</sub>, respectively. Oxidation of carveol occurred with very good conversions in the presence of Mn<sub>4</sub>(PW<sub>9</sub>)<sub>2</sub>, Co<sub>4</sub>(PW<sub>9</sub>)<sub>2</sub> and Fe<sub>4</sub>(PW<sub>9</sub>)<sub>2</sub>, yielding carvone and carveol 1,2-epoxide in similar amounts. Oxidation of <em>cis</em>-cyclooctene gave only the epoxide, while oxidation of geraniol at room temperature afforded 2,3-epoxygeraniol as the major product.</p></div>\",\"PeriodicalId\":370,\"journal\":{\"name\":\"Journal of Molecular Catalysis A: Chemical\",\"volume\":\"426 \",\"pages\":\"Pages 593-599\"},\"PeriodicalIF\":5.0620,\"publicationDate\":\"2017-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://sci-hub-pdf.com/10.1016/j.molcata.2016.10.021\",\"citationCount\":\"17\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Molecular Catalysis A: Chemical\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1381116916304435\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Molecular Catalysis A: Chemical","FirstCategoryId":"1","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1381116916304435","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Catalytic homogeneous oxidation of monoterpenes and cyclooctene with hydrogen peroxide in the presence of sandwich-type tungstophosphates [M4(H2O)2(PW9O34)2]n−, M = CoII, MnII and FeIII
Catalytic efficiency of tetrabutylammonium salts of sandwich tungstophosphates B‐α‐[M4(H2O)2(PW9O34)2]n−, M = CoII, MnII, FeIII, was studied in the oxidation of (R)-(+)-limonene, geraniol, linalool, linalyl acetate, carveol, and cis-cyclooctene with hydrogen peroxide, in acetonitrile. Oxidation of (R)-(+)-limonene gave limonene-1,2-diol as main product. Epoxidation of linalool takes place preferentially at the more substituted 6,7-double bond, the corresponding 6,7-epoxide reacting further, yielding furano- and pyrano-oxides, via intramolecular cyclization. Oxidation of linalyl acetate occurred preferentially at the more substituted 6,7-double bond for Mn4(PW9)2, affording 6,7-epoxide at 82% selectivity. Linalyl acetate 1,2-epoxide was the major product with 51% and 77% selectivity for Co4(PW9)2 and Fe4(PW9)2, respectively. Oxidation of carveol occurred with very good conversions in the presence of Mn4(PW9)2, Co4(PW9)2 and Fe4(PW9)2, yielding carvone and carveol 1,2-epoxide in similar amounts. Oxidation of cis-cyclooctene gave only the epoxide, while oxidation of geraniol at room temperature afforded 2,3-epoxygeraniol as the major product.
期刊介绍：
The Journal of Molecular Catalysis A: Chemical publishes original, rigorous, and scholarly full papers that examine the molecular and atomic aspects of catalytic activation and reaction mechanisms in homogeneous catalysis, heterogeneous catalysis (including supported organometallic catalysis), and computational catalysis.
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