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以水为氧化剂,通过负载在 Merrifield 树脂上的钼(Ⅵ)配合物对伯醇、仲醇和苄醇进行无溶剂、选择性催化氧化。

Solventless, selective and catalytic oxidation of primary, secondary and benzylic alcohols by a Merrifield resin supported molybdenum(vi) complex with HO as an oxidant.

作者信息

Boruah Jeena Jyoti, Das Siva Prasad

机构信息

Department of Chemistry, School of Science, RK University Bhavnagar Highway, Kasturbadham Rajkot-360020 Gujarat India

Department of Chemistry, Moridhal College Moridhal, Dhemaji-787057 Assam India.

出版信息

RSC Adv. 2018 Oct 8;8(60):34491-34504. doi: 10.1039/c8ra05969a. eCollection 2018 Oct 4.

Abstract

Here, we have described the synthesis, characterization and catalytic activity of a dioxo-molybdenum(vi) complex supported on functionalized Merrifield resin (MR-SB-Mo). The functionalization of Merrifield resin (MR) was achieved in two-steps carbonylation (MR-C) and Schiff base formation (MR-SB). The compounds, MR-C, MR-SB and MR-SB-Mo, were characterized at each step of the synthesis by elemental, SEM, EDX, thermal, BET and different spectroscopic analysis. The catalyst, MR-SB-Mo, efficiently and selectively oxidized a wide variety of alcohols to aldehydes or ketones using 30% HO as an oxidant with reasonably good TOF (660 h in case of benzyl alcohol). The catalyst acted heterogeneously under solventless reaction conditions and did not lead to over oxidized products under optimized conditions. The catalyst afforded regeneration and can be reused for at least five reaction cycles without loss of efficiency and product selectivity. A reaction mechanism for the catalytic activity of MR-SB-Mo was proposed and a probable reactive intermediate species isolated.

摘要

在此,我们描述了负载在功能化 Merrifield 树脂(MR-SB-Mo)上的二氧代钼(VI)配合物的合成、表征及催化活性。Merrifield 树脂(MR)的功能化通过两步实现:羰基化(MR-C)和席夫碱形成(MR-SB)。在合成的每个步骤中,通过元素分析、扫描电子显微镜(SEM)、能量色散X射线光谱(EDX)、热分析、比表面积分析(BET)以及不同的光谱分析对化合物 MR-C、MR-SB 和 MR-SB-Mo 进行了表征。催化剂 MR-SB-Mo 以 30% 的过氧化氢(H₂O₂)作为氧化剂,高效且选择性地将多种醇氧化为醛或酮,具有相当不错的转化频率(以苯甲醇为例,TOF 为 660 h⁻¹)。该催化剂在无溶剂反应条件下表现为非均相催化,在优化条件下不会导致过度氧化产物的生成。该催化剂能够再生,并且可以重复使用至少五个反应循环而不会损失效率和产物选择性。我们提出了 MR-SB-Mo 催化活性的反应机理,并分离出了一种可能的反应中间体物种。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/82c6/9086892/e1c3ae5366a9/c8ra05969a-s1.jpg

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