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Selective N-acetylation with concurrent S-oxidation of o-amino thiol at ambient conditions over Ce doped ZnO composite nanocrystallites
Molecular Catalysis ( IF 3.9 ) Pub Date : 2018-03-14 , DOI: 10.1016/j.mcat.2018.03.007
Rohidas Jagtap , Sachin Sakate , Satish Pardeshi

The oxidative SS coupling of thiol to disulfide is an imperative chemical transformation in the domain of biological processes and also finds numerous chemical applications. The CeO2 and ZnO are significant catalysts for oxidation of thiol to disulfide and N-acetylation of amines respectively. Dithiobis(phenylene)bis(benzyldeneimine) moiety containing N-acetyl and disulfide functional groups is a potential antimicrobial agent with Leishmanicidal and antihyperlipidemic activities. Herein, we report a synchronized catalytic application of Ce doped ZnO (Ce-ZnO) and CeO2-Ce-ZnO composites for selective synthesis of Dithiobis(phenylene)bis(benzyldeneimine) from o-amino thiol. The Ce-ZnO samples were synthesized by simple co precipitation method by calcination of hydroxide precursors at 400 °C to get 0–10% Ce-ZnO nanocrystallites. The formation of CeO2-Ce-ZnO composite material was observed beyond 1.5% Ce concentration. The synthesized materials were well characterized by IR, XRD, DRS spectroscopy and SEM-EDS analysis. The application of Ce doped ZnO as an efficient catalyst towards the selective N-acetylation and concurrent S-oxidation of o-amino thiol to afford Dithiobis(phenylene)bis(benzyldeneimine) at ambient temperature in acetonitrile was deliberated. Among all screened catalysts, the maximum selectivity was found for 7.5% Ce-ZnO as CeO2-Ce-ZnO composite catalyst. Lewis acidic property of catalyst supported probable mechanism for achieved dual transformations. Also, the 7.5% Ce-ZnO catalyst has demonstrated a versatile SS coupling ability for variety of thiol substrates with excellent stability.



中文翻译:

Ce掺杂的ZnO复合纳米微晶在环境条件下选择性N-乙酰化和氨基硫醇的S-氧化

硫醇与二硫键的氧化S S偶联是生物过程领域中必不可少的化学转化,并且也发现了许多化学应用。CeO 2和ZnO分别是硫醇氧化为二硫化物和胺的N-乙酰化的重要催化剂。含有N-乙酰基和二硫键官能团的二硫代双(亚苯基)双(苄基亚胺)部分是一种潜在的具有杀菌作用和降血脂活性的抗菌剂。本文中,我们报道了Ce掺杂的ZnO(Ce-ZnO)和CeO 2 -Ce-ZnO复合材料的同步催化应用,用于从邻位选择性合成二硫代双(亚苯基)双(苄基亚胺)-氨基硫醇。通过简单的共沉淀法,在400°C下煅烧氢氧化物前体,合成Ce-ZnO样品,得到0-10%的Ce-ZnO纳米微晶。超过1.5%的Ce浓度观察到CeO 2 -Ce-ZnO复合材料的形成。通过IR,XRD,DRS光谱和SEM-EDS分析对合成的材料进行了很好的表征。研究了Ce掺杂的ZnO作为有效催化剂对氨基硫醇的选择性N-乙酰化和同时S-氧化的反应,从而在环境温度下在乙腈中提供二硫代双(亚苯基)双(苄基亚胺)。在所有筛选的催化剂中,发现7.5%的Ce-ZnO作为CeO 2的最大选择性-Ce-ZnO复合催化剂。催化剂的路易斯酸性质支持了实现双重转化的可能机理。同样,7.5%的Ce-ZnO催化剂对多种硫醇底物表现出广泛的S S偶联能力,并具有出色的稳定性。

更新日期:2018-03-14
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