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Nucleophile‐electrophile interactions in the reaction of oxiranes with carboxylic acids in the presence of tertiary amines

机译：在叔胺存在下，羧酸与羧酸反应的亲核试剂亲电相互作用

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Abstract >The nucleophile‐electrophile interactions in the reaction system “N,N‐dimethylaniline – acetic acid – epichlorohydrin” have been investigated using kinetic methods and computer modeling. The observed orders of reactions have been determined for the overall reaction as well as for individual stages. The kinetic equations have been proposed; the activation parameters of the reactions have been evaluated. The behavior of the initial (amine) and intermediate (carboxylate) nucleophiles has been detailed in reaction pathway. Amine reacts with oxirane activated by acidic reagent while carboxylate‐anion—with both activated and nonactivated epichlorohydrin. The mechanism of oxirane ring opening by acid reagent in the presence of tertiary amine has been proposed, which comprise parallel‐consecutive compensation stages of reaction product formation. It has been demonstrated that the observed reaction order with respect to acid reactant depends upon the nature of electrophilic reagent (activated/nonactivated oxirane) and the ratio of the rates of compensation stages. </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”>摘要</标题> >反应系统中的亲核官能亲电相互作用“N，N-二甲基苯胺 - 乙酸 - 已经使用动力学方法和计算机建模进行了研究。观察到的反应令已针对整体反应以及个体阶段确定。已经提出了动力学方程;已经评估了反应的活化参数。在反应途径中详述了初始（胺）和中间体（羧酸盐）亲核试剂的行为。胺与酸性试剂激活的氧化乙烷反应，而羧酸盐 - 阴离子 - 具有活性和非活化的表氯醇。已经提出了酸试剂在叔胺存在下通过酸试剂开口的机制，其包含反应产物形成的平行连续补偿阶段。已经证明，观察到的反应性的反应顺序取决于电泳试剂（活化/非激活的氧化氢）的性质和补偿阶段的率的比例。</ 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-35546/'>《Journal of Physical Organic Chemistry》</a> <b style="margin: 0 2px;">|</b><span>2017年第12期</span><b style="margin: 0 2px;">|</b><span>共9页</span> </div> </li> <li> <div class="author"> <span class="lefttit">作者</span> <p id="fAuthorthree" class="threelineshidden zhankaihshouqi"> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Bakhtin Stanislav&option=202" target="_blank" rel="nofollow">Bakhtin Stanislav;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Shved Elena&option=202" target="_blank" rel="nofollow">Shved Elena;</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=Bespalko Yuliia&option=202" target="_blank" rel="nofollow">Bespalko Yuliia;</a> </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"> <p>Faculty of ChemistryDonetsk National UniversityDonetsk Ukraine;</p> <p>Faculty of ChemistryVasyl' Stus Donetsk National UniversityVinnytsia Ukraine;</p> <p>Faculty of ChemistryVasyl' Stus Donetsk National UniversityVinnytsia Ukraine;</p> </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/4796.html" title="有机化学一般性问题">有机化学一般性问题;</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=base catalysis&option=203" rel="nofollow">base catalysis;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=kinetic methods&option=203" rel="nofollow">kinetic methods;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=nucleophilic catalysis&option=203" rel="nofollow">nucleophilic catalysis;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=oxirane ring‐opening&option=203" rel="nofollow">oxirane ring‐opening;</a> <a style="color: #3E7FEB;" href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=tertiary amine&option=203" rel="nofollow">tertiary amine;</a> </p> <div class="translation"> 机译：基础催化;动力学方法;亲核催化;氧化乙烷环开口;叔胺; </div> </li> </ul> </div> </div> <div class="literature cardcommon"> <div class="similarity "> <h3 class="all_title" id="enpatent66">相似文献</h3> <div 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href="/academic-conference-cn_meeting-29997_thesis/020222301304.html">亲合毛细管电泳研究环糊精与芳香羧酸的相互作用</a> <b>[C]</b> <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=傅崇岗&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor"> . 傅崇岗</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=赵艳芳&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">,赵艳芳</a> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=刘爱林&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor">,刘爱林</a> <span> <a href="/conference-cn-29997/" target="_blank" rel="nofollow" class="tuijian_authcolor"> . 第五届全国毛细管电泳及相关微分离学术报告会 </a> <span> <span> . 2002</span> </span> </div> </li> <li> <div> <b>7. </b><a class="enjiyixqcontent" href="/academic-degree-domestic_mphd_thesis/020315836716.html">SalenCo配合物催化不对称电羧化反应制备手性羧酸研究</a> <b>[A] </b> <span> <a href="/search.html?doctypes=4_5_6_1-0_4-0_1_2_3_7_9&sertext=张敏&option=202" target="_blank" rel="nofollow" class="tuijian_auth tuijian_authcolor"> . 张敏</a> <span> . 2020</span> </span> </div> </li> </ul> <ul style="display: none;"> <li> <div> <b>1. </b><a class="enjiyixqcontent" href="/patent-detail/06120109761198.html">利用羧酸聚氧乙烯醚亲水单体制备的反应型环氧乳化剂</a> <b>[P]</b> . <span> 中国专利： CN107286726A </span> <span> . 2017-10-24</span> </div> </li> <li> <div> <b>2. </b><a class="enjiyixqcontent" href="/patent-detail/061204247592.html">反应性环氧羧酸酯化合物、反应性多元羧酸化合物树脂组合物、硬化物及物品</a> <b>[P]</b> . <span> 中国专利： CN107298753B </span> <span> . 2021.02.19</span> </div> </li> <li> <div> <b>3. </b><a class="enjiyixqcontent" href="/patent-detail/06130419146780.html">Preparing formic acid, comprises e.g. reacting a reaction mixture comprising carbon dioxide, hydrogen, polar solvent and tertiary amine in presence of cationic complex catalyst into hydrogenation mixture including formic acid-amine-adduct</a> <b>[P]</b> . <span> 外国专利：  DE102012016959A1 </span> <span> . 2013-03-14</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：制备甲酸包括例如使包含二氧化碳，氢，极性溶剂和叔胺的反应混合物在阳离子络合物催化剂的存在下反应成包含甲酸-胺-加合物的氢化混合物 </span> </p> </li> <li> <div> <b>4. </b><a class="enjiyixqcontent" href="/patent-detail/06130462856475.html">Prepn. of ester of higher aromatic carboxylic acid and higher alkanol - by reaction of acid or anhydride and alcohol in presence of sulphonic acid or amine with passage of inert gas</a> <b>[P]</b> . <span> 外国专利：  DE4017903A1 </span> <span> . 1991-12-05</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：准备芳族羧酸和高级链烷醇的酯的合成-在惰性气体通过下，在磺酸或胺的存在下，酸或酸酐与醇反应 </span> </p> </li> <li> <div> <b>5. </b><a class="enjiyixqcontent" href="/patent-detail/06130482783385.html">Arylamine preparation - by reaction of naphthols or resorcinol with amines in the presence of carboxylic acids</a> <b>[P]</b> . <span> 外国专利：  DE2509040A1 </span> <span> . 1976-09-02</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：芳胺的制备-在羧酸存在下，萘酚或间苯二酚与胺反应 </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('0704025793641','4',7,2,1,'',this,24)" class="delivery" prompt="010401" title="通过人工服务将文献原文发送至邮箱" >获取原文</div> <div 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