吡咯并[1,2-a:3,4-c′]二喹啉衍生物的合成及缓蚀构效关系研究  

Preparation and Structure-activity Relation on Anti-corrosive Inhibition of Pyrrolo[1,2-a:3,4-c′]Diquinoline Derivatives

作　　者：杨正兴 杨震 胡华友[3] 杨秋雯 王业飞[2] 王超[1] YANG Zhengxing;YANG Zhen;HU Huayou;YANG Qiuwen;WANG Yefei;WANG Chao(School of Materials and Chemistry,Southwest University of Science and Technology,Mianyang 621010,Sichuan,China;School of Petroleum Engineering,China University of Petroleum,Qingdao 266580,Shandong,China;School of Chemistry and Chemical Engineering,Huaiyin Normal University,Huaian 223300,Jiangsu,China)

机构地区：[1]西南科技大学材料与化学学院,四川绵阳621010 [2]中国石油大学(华东)石油工程学院,山东青岛266580 [3]淮阴师范学院化学化工学院,江苏淮安223300

出　　处：《材料导报》2024年第S02期579-588,共10页Materials Reports

基　　金：国家重点研发计划政府间国际科技创新合作重点专项(2021YFE0107000);国家自然科学基金(52074339);青岛市博士后应用研究项目资助(QDBSH_(2)0230101022)。

摘　　要：以取代氯化苄与取代喹啉为原料,在制备出氯化苄基喹啉季铵盐后,通过1,3-偶极环加成反应成功合成18种吡咯并[1,2-a:3,4-c′]二喹啉鎓盐衍生物。通过单因素变量法探究了1,3-偶极环加成过程中的酸钠加量、底物浓度、反应温度以及反应时间对最终产率的影响。确定了最佳反应条件为:在140℃下密闭反应6~8 h,底物浓度为0.4~0.5 mol·L^(-1)且n(季铵盐)∶n(硝酸钠)=1∶3,目标产品收率为62%~81%。产物分子结构经IR、1H NMR和质谱进行了确认。通过失重法在温度为90℃的15%(质量分数)盐酸中对比评价了系列目标产物对N80钢试片的缓蚀效果,并结合量子化学计算分析了这类衍生物的结构特点。结果显示:分子所连取代基的给电子效应能够增强吡咯并[1,2-a:3,4-c′]二喹啉鎓盐衍生物的缓蚀效率,而取代基的吸电子效应会使其缓蚀作用减弱。Using substituted benzyl chloride and substituted quinoline as raw materials,18 pyrrolo[1,2-a:3,4-c′]diquinolinium salt derivatives were successfully synthesized through the preparation of benzyl chloride-based quinolinium quaternary salts and a subsequent 1,3-dipolar cycloaddition reaction.The impact of sodium nitrate dosage,substrate concentration,reaction temperature,and reaction time on the final yield during the 1,3-dipolar cycloaddition process was investigated using a single-factor variable method.The optimal reaction conditions were determined as follows:the ratio of quaternary ammonium salt to sodium nitrate was 1∶3,substrate concentration ranged from 0.4-0.5 mol·L^(-1),closed reaction at 140℃for 6-8 hours.Under these conditions,the final product yield could reach 62%-81%.The product structure was confirmed by IR,1H NMR and mass spectrometry.The corrosion inhibition properties of the target products on N80 steel specimens were evaluated by the weight loss method in 15%(mass fraction)hydrochloric acid at 90℃,and combined with quantum chemical calculations,the structural characteristics of these derivatives were analyzed.The results showed that the electron-donating effect of the substituent groups attached to the molecules enhances the efficiency of the corrosion inhibition of the pyrrolo[1,2-a:3,4-c′]diquinoline salt derivatives,whereas the electron-absorbing effect of the substituents leads to the diminution of the corrosion inhibition effect of such derivatives.

关 键 词：1 3-偶极环加成 氧化脱氢芳构化 吡咯并[1 2-a:3 4-c′]二喹啉 酸化缓蚀剂 构效关系 

分 类 号：TE357[石油与天然气工程—油气田开发工程]