摘要
报道了一种安全、绿色、高效合成N,N,N-三甲基-1-金刚烷基季铵碱的方法。首先,以1-金刚烷胺为原料,碳酸二甲酯(DMC)为甲基化试剂,合成中间体N,N,N-三甲基-1-金刚烷基季铵盐。然后,中间体与氢氧化钙反应,得到最终产物N,N,N-三甲基-1-金刚烷基季铵碱。通过^(1)HNMR和^(13)CNMR对季铵盐和季铵碱的结构进行了表征。分别考察了催化剂、反应物物质的量比[n(1-金刚烷胺)∶n(DMC)]、反应温度和时间对N,N,N-三甲基-1-金刚烷基季铵盐收率的影响。得到的最佳反应条件为:N,N-二甲基甲酰胺(DMF)作为催化剂,且m(DMF)/m(1-金刚烷胺)=0.25,n(1-金刚烷胺)∶n(DMC)=1∶8,反应温度和时间分别为140℃和5h。在该条件下,N,N,N-三甲基-1-金刚烷基季铵盐的收率可达97.3%。
A safe, green and effective method to synthesize N,N,N-trimethyladamantan-1-aminium hydroxide was reported. Firstly, intermediate N,N,N-trimethyladamantan-1-aminium salt was obtained by using 1-adamantanamine as raw material, dimethyl carbonate(DMC) as methylation reagent. Then, the intermediate reacted with calcium hydroxide to give final product N,N,N-trimethyladamantan-1-aminium hydroxide. The structures of quaternary ammonium salt and quaternary ammonium hydroxide were characterized by ^(1)HNMR and ^(13)CNMR. The effects of catalyst, molar ratio of reactants [n(1-adamantanamine)∶n(DMC)], reaction temperature and reaction time on the yield of N,N,N-trimethyladamantan-1-aminium salt were investigated. The optimum reaction conditions were obtained as follows: N,N-dimethyl formamide(DMF) as catalyst, m(DMF)/m(1-adamantanamine)=0.25, n(1-adamantanamine)∶n(DMC)=1∶8, reaction temperature and time were 140 ℃ and 5 h, respectively. Under these conditions, the yield of N,N,N-trimethyladamantan-1-aminium salt could be up to 97.3%..
作者
杨丰科
周林
张永富
袁世申
高巍伟
YANG Fengke;ZHOU Lin;ZHANG Yongfu;YUAN Shishen;GAO Weiwei(College of Chemical Engineering,Qingdao University of Science and Technology,Qingdao 266042,Shandong,China)
出处
《精细化工》
EI
CAS
CSCD
北大核心
2021年第9期1935-1939,共5页
Fine Chemicals
基金
山东省重点研究发展计划(特殊社会公益专项)(2017GSF17106)
山东省自然科学青年基金(ZR2020QB168)。
关键词
季铵盐
碳酸二甲酯
甲基化
季铵碱
绿色合成
精细化工中间体
quaternary ammonium salt
dimethyl carbonate
methylation
quaternary ammonium hydroxide
green synthesis
fine chemical intermediates
