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以氧气氧化环己烷/环己酮混合物作为己二酸合成的替代方法。

Oxidation of Cyclohexane/Cyclohexanone Mixture with Oxygen as Alternative Method of Adipic Acid Synthesis.

作者信息

Lisicki Dawid, Orlińska Beata, Marek Adam A, Bińczak Jakub, Dziuba Krzysztof, Martyniuk Tomasz

机构信息

Department of Chemical Organic Technology and Petrochemistry, PhD School, Silesian University of Technology, Akademicka 2A, 44-100 Gliwice, Poland.

Grupa Azoty Zakłady Azotowe, "Puławy" S.A., Al. Tysiąclecia Państwa Polskiego 13, 24-110 Puławy, Poland.

出版信息

Materials (Basel). 2022 Dec 28;16(1):298. doi: 10.3390/ma16010298.

DOI:10.3390/ma16010298
PMID:36614636
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9821978/
Abstract

Herein, an alternative method for adipic acid (AA) synthesis of industrial importance has been reported. The proposed novel method involves the one-step, solvent-free oxidation of a cyclohexane/cyclohexanone (CH/CH=O) mixture, with a cheap oxidizing agent such as O or air under mild conditions in the presence of -hydroxyphtalimide (NHPI) and transition metals as catalysts. It has been showed that CH/CH=O mixture under applied mild conditions oxidized faster than CH and CH=O separately. This was due to the greater oxidizability of CH=O compared to CH. The peroxyl radicals formed by CH=O oxidation initiated the oxidation of the less reactive CH. Additionally, CH=O increased the polarity of the reaction mixture, promoting the solubility of NHPI. The influence of type and amount of catalyst, cyclohexane to cyclohexanone ratio, temperature, time, type of oxidizing agent on the composition of CH/CH=O oxidation products have been reported.

摘要

在此,已报道了一种具有工业重要性的己二酸(AA)合成的替代方法。所提出的新方法涉及在温和条件下,以廉价的氧化剂如氧气或空气,在α-羟基邻苯二甲酰亚胺(NHPI)和过渡金属作为催化剂存在的情况下,对环己烷/环己酮(CH/CH=O)混合物进行一步无溶剂氧化。结果表明,在施加的温和条件下,CH/CH=O混合物的氧化速度比单独的CH和CH=O更快。这是由于CH=O比CH具有更高的氧化能力。由CH=O氧化形成的过氧自由基引发了反应活性较低的CH的氧化。此外,CH=O增加了反应混合物的极性,促进了NHPI的溶解性。已报道了催化剂的类型和用量、环己烷与环己酮的比例、温度、时间、氧化剂类型对CH/CH=O氧化产物组成的影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/999f/9821978/f8c983b01dd1/materials-16-00298-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/999f/9821978/06aec43ce46d/materials-16-00298-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/999f/9821978/01154c53821f/materials-16-00298-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/999f/9821978/256627b5c385/materials-16-00298-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/999f/9821978/f8c983b01dd1/materials-16-00298-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/999f/9821978/06aec43ce46d/materials-16-00298-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/999f/9821978/01154c53821f/materials-16-00298-sch002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/999f/9821978/256627b5c385/materials-16-00298-sch003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/999f/9821978/f8c983b01dd1/materials-16-00298-g001.jpg

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Metal-free aerobic oxidations mediated by N-hydroxyphthalimide. A concise review.
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