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

IF 5.062

Journal of Molecular Catalysis A: Chemical Pub Date : 2017-01-01 DOI:10.1016/j.molcata.2016.10.021

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

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引用次数: 17

Abstract

Catalytic efficiency of tetrabutylammonium salts of sandwich tungstophosphates B‐α‐[M₄(H₂O)₂(PW₉O₃₄)₂]ⁿ⁻, M = Co^II, Mn^II, Fe^III, 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.

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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

研究了夹心钨磷酸盐B‐α‐[M4(H2O)2(PW9O34)2]n−，M = CoII, MnII, FeIII四丁基铵盐在乙腈中过氧化氢氧化(R)-(+)-柠檬烯、香叶醇、芳樟醇、乙酸芳樟醇、卡维罗和顺式环烯的催化效率。(R)-(+)-柠檬烯氧化得到主要产物柠檬烯-1,2-二醇。芳樟醇的环氧化反应优先发生在更取代的6,7-双键上，相应的6,7-环氧化物进一步反应，通过分子内环化生成呋喃和吡喃氧化物。在Mn4(PW9)2的6,7-双键上，芳樟乙酸酯优先发生氧化，产生6,7-环氧化物，选择性为82%。主要产物乙酸1,2-环氧芳樟醇对Co4(PW9)2和Fe4(PW9)2的选择性分别为51%和77%。在Mn4(PW9)2、Co4(PW9)2和Fe4(PW9)2的存在下，carveol发生了很好的氧化转化，生成了相似量的carveone和carveol 1,2-环氧化物。顺式环烯氧化得到环氧化物，而香叶醇在室温下氧化得到主要产物2,3-环氧香叶醇。

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来源期刊

Journal of Molecular Catalysis A: Chemical 化学-物理化学

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0.00%

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审稿时长

2.8 months

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.