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Manganese porphyrins as efficient catalysts in solvent-free cyclohexane oxidation
Arabian Journal of Chemistry ( IF 5.3 ) Pub Date : 2020-01-01 , DOI: 10.1016/j.arabjc.2017.12.007
Mariana Goes de Araujo Tôrres , Vinicius Santos da Silva , Ynara Marina Idemori , Gilson DeFreitas-Silva

Abstract Novel non-symmetric third-generation manganese metalloporphyrins, chlorido(5-(4-nitrophenyl)-10,15,20-triphenyl-2,3,7,8,12,13,17,18 octobromoporphyrinate)manganese(III) (MnBr8P1) and the mixture of isomers chlorido(5,10-(4-nitrophenyl)-15,20-diphenyl-2,3,7,8,12,13,17,18-octabromoporphyrinate)manganese(III) and chlorido(5,15-(4-nitrophenyl)-10,20-diphenyl-2,3,7,8,12,13,17,18-octabromoporphyrinate)manganese(III) (cis/trans-MnBr8P2) were obtained from their second-generation analogues (MnP1 and cis/trans-MnP2). These four catalysts were used in cyclohexane oxidation reactions with iodosylbenzene (PhIO) or iodobenzene diacetate (PhI(OAc)2) in the presence or absence of solvent (CH2Cl2). Cyclohexanol (Cy-ol) and cyclohexanone (Cy-one) were the sole reaction products. Regardless of the system, third-generation catalysts MnBr8P1 and cis/trans-MnBr8P2 performed better than second-generation catalysts (MnP1 and cis/trans-MnP2, respectively). In solvent systems, cis/trans-MnBr8P2 afforded a greater total yield (%Cy-ol + %Cy-one) than systems using MnBr8P1, with an increase from 80 to 89% in PhIO and from 47 to 57% in PhI(OAc)2. The systems without solvent, showed to be viable and presented significant yields with PhIO as oxidant, with total yield of 30% for MnBr8P1, and 55% for cis/trans-MnBr8P2. Additionally, in systems with third-generation catalysts without solvent, selectivity was close to 100% for Cy-ol.

中文翻译:

锰卟啉作为无溶剂环己烷氧化的有效催化剂

摘要 新型非对称第三代锰金属卟啉,氯化(5-(4-硝基苯基)-10,15,20-三苯基-2,3,7,8,12,13,17,18 八溴卟啉)锰(III) (MnBr8P1) 和异构体氯化物(5,10-(4-硝基苯基)-15,20-二苯基-2,3,7,8,12,13,17,18-八溴卟啉)锰(III)和氯化物的混合物(5,15-(4-硝基苯基)-10,20-二苯基-2,3,7,8,12,13,17,18-八溴卟啉)锰(III) (cis/trans-MnBr8P2) 是从它们的第二代类似物(MnP1 和 cis/trans-MnP2)。在存在或不存在溶剂 (CH2Cl2) 的情况下,这四种催化剂用于与碘代苯 (PhIO) 或碘苯二乙酸酯 (PhI(OAc)2) 的环己烷氧化反应。环己醇 (Cy-ol) 和环己酮 (Cy-one) 是唯一的反应产物。不管系统如何,第三代催化剂 MnBr8P1 和顺式/反式 MnBr8P2 的性能优于第二代催化剂(分别为 MnP1 和顺式/反式 MnP2)。在溶剂系统中,顺式/反式 MnBr8P2 比使用 MnBr8P1 的系统提供更高的总产率(%Cy-ol + %Cy-one),PhIO 从 80% 增加到 89%,PhI(OAc) 从 47% 增加到 57% )2. 没有溶剂的系统表明是可行的,并且以 PhIO 作为氧化剂表现出显着的产率,MnBr8P1 的总产率为 30%,顺式/反式 MnBr8P2 的总产率为 55%。此外,在没有溶剂的第三代催化剂系统中,Cy-ol 的选择性接近 100%。PhIO 从 80% 增加到 89%,PhI(OAc)2 从 47% 增加到 57%。没有溶剂的系统表明是可行的,并且以 PhIO 作为氧化剂表现出显着的产率,MnBr8P1 的总产率为 30%,顺式/反式 MnBr8P2 的总产率为 55%。此外,在没有溶剂的第三代催化剂系统中,Cy-ol 的选择性接近 100%。PhIO 从 80% 增加到 89%,PhI(OAc)2 从 47% 增加到 57%。没有溶剂的系统表明是可行的,并且以 PhIO 作为氧化剂表现出显着的产率,MnBr8P1 的总产率为 30%,顺式/反式 MnBr8P2 的总产率为 55%。此外,在没有溶剂的第三代催化剂系统中,Cy-ol 的选择性接近 100%。
更新日期:2020-01-01
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