Sitko Magdalena, Szelwicka Anna, Wojewódka Andrzej, Skwarek Andrzej, Tadasiewicz Dariusz, Schimmelpfennig Lech, Dziuba Krzysztof, Morawiec-Witczak Magdalena, Chrobok Anna
Department of Chemical Organic Technology and Petrochemistry, Silesian University of Technology Krzywoustego 4 44-100 Gliwice Poland
Department of Inorganic Chemistry, Analytical Chemistry and Electrochemistry, Silesian University of Technology Krzywoustego 6 44-100 Gliwice Poland.
RSC Adv. 2019 Sep 23;9(51):30012-30018. doi: 10.1039/c9ra06087a. eCollection 2019 Sep 18.
Stability studies dedicated to high-energy compounds for a series of linear peracids (C-C), including sensitivity to mechanical impulse (shock and friction), as well as electrical (spark) and thermal sensitivity (temperature and heat of decomposition), were presented in this work for the first time. Studies revealed that all peracids were insensitive to shock, while in the case of the other sensitivity tests sharp differences between results for C and C peracids were observed. Taking into account the relatively high initial temperature of decomposition (above 64 °C) perdecanoic acid was selected as a safe alternative to commonly used hazardous short-chain peracids. Next, a new method for the Baeyer-Villiger oxidation was presented. Oxidation of 2-adamantanone was chosen as a model reaction. Peroctanoic, perdecanoic and perdodecanoic acids were tested as oxidants. Peroctanoic acid was the most reactive but taking into account both safety and kinetic issues, perdecanoic acid was selected for the further studies. The influence of reaction conditions on reaction rate was investigated. Optimized reaction conditions were suggested (two-fold molar excess of peracid with respect to the ketone, toluene as a solvent, 35 °C). This exploratory study offers promise with regard to the development of safer alternatives to peracetic acid in industrial oxidation.
本工作首次对一系列直链过氧酸（C-C）这类高能化合物进行了稳定性研究，包括对机械冲击（撞击和摩擦）、电（火花）以及热敏感性（温度和分解热）的研究。研究表明，所有过氧酸对撞击均不敏感，而在其他敏感性测试中，观察到C和C过氧酸的结果存在显著差异。考虑到过癸酸相对较高的初始分解温度（高于64°C），它被选为常用危险短链过氧酸的安全替代品。接下来，提出了一种新的拜耳-维利格氧化方法。选择2-金刚烷酮的氧化作为模型反应。测试了过辛酸、过癸酸和过十二酸作为氧化剂。过辛酸反应活性最高，但综合考虑安全性和动力学问题，选择过癸酸进行进一步研究。研究了反应条件对反应速率的影响。提出了优化的反应条件（过酸相对于酮为两倍摩尔过量，甲苯为溶剂，35°C）。这项探索性研究为工业氧化中开发比过氧乙酸更安全的替代品带来了希望。
