Selective Decomposition of Cyclohexyl Hydroperoxide using Homogeneous and Heterogeneous Cr        <sup >VIVI        Catalysts: Optimizing the Reaction by Evaluating the Reaction Mechanism

摘要

Abstract > In this study, known homogeneous and heterogeneous chromium(VI) catalyst systems were investigated with respect to the favored formation of cyclohexanone during the decomposition of cyclohexyl hydroperoxide (CHHP). The focus was on mechanistic studies using different spectroscopic methods as well as DFT calculations to further optimize the reaction conditions. As in previous decomposition studies, a mechanism via the formation of a metal alkylperoxido intermediate is probable. In?situ spectroscopic studies revealed that in case of both the soluble and insoluble catalyst, the selective decomposition happens via a non‐radical, non‐redox mechanism at the Cr VI stage through the formation of a cyclohexylperoxychromium(VI) complex. The proposed mechanism is supported by thorough DFT calculations. </abstract> </span> <span class="z_kbtn z_kbtnclass hoverxs" style="display: none;">展开▼</span> </div> <div class="translation abstracttxt"> <span class="zhankaihshouqi fivelineshidden" id="abstract"> <span>机译：</span><Abstract Type =“Main”XML：Lang =“en”> <标题类型=“main”>抽象</ title> > 在该研究中，相对于在环己基氢过氧化物（CHHP）分解期间，研究了已知的均匀和异质铬（VI）催化剂体系。使用不同的光谱方法以及DFT计算来进一步优化反应条件的重点是在机械研究。与先前的分解研究一样，通过形成金属烷基氧基中间体的机理是可能的。在原位光谱研究表明，如果溶于溶解和不溶性催化剂，在CR处通过非基团的非氧化还原机制发生选择性分解 vi </ sup> 阶段通过形成环己基氧基苯甲氧化碳键溴（VI）复合物。通过彻底的DFT计算支持所提出的机制。 </ p> </摘要> </span> <span class="z_kbtn z_kbtnclass hoverxs" style="display: none;">展开▼</span> </div> </div> <div class="record"> <h2 class="all_title" id="enpatent33" >著录项</h2> <ul> <li> <span class="lefttit">来源</span> <div style="width: 86%;vertical-align: text-top;display: inline-block;"> <a href='/journal-foreign-16041/'>《ChemCatChem》</a> <b style="margin: 0 2px;">|</b><span>2018年第13期</span><b style="margin: 0 2px;">|</b><span>共13页</span> </div> </li> <li> <div class="author"> <span class="lefttit">作者</span> <p id="fAuthorthree" class="threelineshidden zhankaihshouqi"> </p> <span class="z_kbtnclass z_kbtnclassall hoverxs" id="zkzz" style="display: none;">展开▼</span> </div> </li> <li> <div style="display: flex;"> <span class="lefttit">作者单位</span> <div style="position: relative;margin-left: 3px;max-width: 639px;"> <div class="threelineshidden zhankaihshouqi" id="fOrgthree"> </div> <span class="z_kbtnclass z_kbtnclassall hoverxs" id="zhdw" style="display: none;">展开▼</span> </div> </div> </li> <li > <span class="lefttit">收录信息</span> <span style="width: 86%;vertical-align: text-top;display: inline-block;"></span> </li> <li> <span class="lefttit">原文格式</span> <span>PDF</span> </li> <li> <span class="lefttit">正文语种</span> <span>eng</span> </li> <li> <span class="lefttit">中图分类</span> <span><a href="https://www.zhangqiaokeyan.com/clc/1186.html" title="物理化学（理论化学）、化学物理学">物理化学（理论化学）、化学物理学;</a></span> </li> <li class="antistop"> <span class="lefttit">关键词</span> <p style="width: 86%;vertical-align: text-top;"> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=chromium&option=203" rel="nofollow">chromium;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=cyclohexane oxidation&option=203" rel="nofollow">cyclohexane oxidation;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=cyclohexyl hydroperoxide&option=203" rel="nofollow">cyclohexyl hydroperoxide;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=homogeneous catalysis&option=203" rel="nofollow">homogeneous catalysis;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=kinetic&option=203" rel="nofollow">kinetic;</a> </p> <div class="translation"> 机译：铬;环己烷氧化;环己基氢过氧化物;均匀催化;动力学; 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A.Pinho</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=K.Maeshiro&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">,K.Maeshiro</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=W.K.Huziwara&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">,W.K.Huziwara</a> <span> <a href="/conference-cn-30825/" target="_blank" rel="nofollow" class="tuijian_authcolor"> . 第十七届世界石油大会 </a> <span> <span> . 2002</span> </span> </div> </li> <li> <div> <b>7. </b><a class="enjiyixqcontent" href="/academic-degree-domestic_mphd_thesis/020316057344.html">铈基催化剂催化净化氯苯的反应机制及性能优化研究</a> <b>[A] </b> <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=戴晓霞&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor"> . 戴晓霞</a> <span> . 2020</span> </span> </div> </li> </ul> <ul style="display: none;"> <li> <div> <b>1. </b><a class="enjiyixqcontent" href="/patent-detail/061202268513.html">制备使用至少一种有机添加剂制备的基于第VIII族金属的催化剂的方法、以及使用所述催化剂的选择性加氢方法</a> <b>[P]</b> . <span> 中国专利： CN104053502B </span> <span> . 2016.12.07</span> </div> </li> <li> <div> <b>2. </b><a class="enjiyixqcontent" href="/patent-detail/06120102800838.html">制备使用至少一种有机添加剂制备的基于第VIII族金属的催化剂的方法、以及使用所述催化剂的选择性加氢方法</a> <b>[P]</b> . <span> 中国专利： CN104053502A </span> <span> . 2014-09-17</span> </div> </li> <li> <div> <b>3. </b><a class="enjiyixqcontent" href="/patent-detail/06130443690214.html">Screening of a number of heterogeneous catalysts for their selectivities in gas-phase reaction catalysts uses measurements of heats of reaction in reactions with different feed gas compositions</a> <b>[P]</b> . <span> 外国专利：  DE10201542A1 </span> <span> . 2003-07-31</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：根据在气相反应催化剂中的选择性对多种非均相催化剂进行筛选，方法是使用不同原料气组成的反应中的反应热进行测量 </span> </p> </li> <li> <div> <b>4. </b><a class="enjiyixqcontent" href="/patent-detail/06130448997597.html">METHOD OF SELECTIVELY OXIDATING CYCLOHEXANE SO AS TO OBTAIN CYCLOHEXANOL, CYCLOHEXANONE AND CYCLOHEXYL HYDROPEROXIDE AS WELL AS METHOD DECOMPOSING CYCLOHEXYL HYDROPEROXIDE INTO CYCLOHEXANOL AND CYCLOHEXANONE AND APPARATUS FOR OXIDATING CYCLOHEXANE AND DECOMPOSING CYCLOHEXYL HYDROPEROXIDE</a> <b>[P]</b> . <span> 外国专利：  PL181569B1 </span> <span> . 2001-08-31</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：选择性氧化环己烷以得到环己醇，环己酮和环己氧基过氧化物的方法，以及将环己氧基过氧化物分解成环己酚和环己酮和装置甲O的方法 </span> </p> </li> <li> <div> <b>5. </b><a class="enjiyixqcontent" href="/patent-detail/06130455928842.html">METHOD OF SELECTIVELY OXIDATING CYCLOHEXANE SO AS TO OBTAIN CYCLOHEXANOL, CYCLOHEXANONE AND CYCLOHEXYL HYDROPEROXIDE AS WELL AS METHOD DECOMPOSING CYCLOHEXYL HYDROPEROXIDE INTO CYCLOHEXANOL AND CYCLOHEXANONE AND APPARATUS FOR OXIDATING CYCLOHEXANE AND DECOMPOSING CYCLOHEXYL HYDROPEROXIDE</a> <b>[P]</b> . <span> 外国专利：  PL312339A1 </span> <span> . 1997-07-21</span> </div> <p class="zwjiyix translation" style="max-width: initial;height: auto;word-break: break-all;white-space: initial;text-overflow: initial;overflow: initial;"> <span>机译：选择性氧化环己烷以得到环己醇，环己酮和环己氧基过氧化物的方法，以及将环己氧基过氧化物分解成环己酚和环己酮和装置甲O的方法 </span> </p> </li> </ul> </div> </div> </div> <div class="theme cardcommon" style="overflow: auto;display:none"> <h3 class="all_title" id="enpatent55">相关主题</h3> <ul id="subject"> </ul> </div> </div> </div> </div> <div class="right rightcon"> <div class="details_img cardcommon clearfix" style="margin-bottom: 10px;display:none;" > </div> </div> </div> <div id="thesis_get_original1" class="downloadBth" style="bottom: 19px;z-index: 999;" onclick="ywcd('0704022060115','4',7,2,1,'',this,24)" class="delivery" 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Selective Decomposition of Cyclohexyl Hydroperoxide using Homogeneous and Heterogeneous Cr VIVI Catalysts: Optimizing the Reaction by Evaluating the Reaction Mechanism

摘要

Selective Decomposition of Cyclohexyl Hydroperoxide using Homogeneous and Heterogeneous Cr ^{VIVI Catalysts: Optimizing the Reaction by Evaluating the Reaction Mechanism}