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
作者: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
日期:2017.1
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
研究了夹心钨磷酸盐B-α-[M 4(H 2 O)2(PW 9 O 34)2 ] n-(M = Co II,Mn II,Fe III)的四丁基铵盐在(- )的氧化中的催化效率R)-(+)-柠檬烯,香叶醇,芳樟醇,乙酸芳樟酯,香芹酚和顺式-环辛烯与过氧化氢的乙腈溶液。(R的氧化)-(+)-柠檬烯得到柠檬烯-1,2-二醇作为主要产物。芳樟醇的环氧化反应优先发生在取代度更高的6,7-双键上,相应的6,7-环氧化物进一步反应,通过分子内环化反应生成呋喃-和吡喃氧化物。乙酸芳樟酯的氧化优先发生在Mn 4(PW 9)2的更取代的6,7-双键处,以82%的选择性提供6,7-环氧。乙酸芳基酯1,2-环氧化物是主要产物,对Co 4(PW 9)2和Fe 4(PW 9)2的选择性分别为51%和77%。在锰的存在下,香芹酚的氧化转化率很高4(PW 9)2,Co 4(PW 9)2和Fe 4(PW 9)2产生类似量的香芹酮和香芹酚1