Page 225 - 《精细化工》2021年第9期

第 9 期 杨丰科，等: 绿色有效合成 N,N,N-三甲基-1-金刚烷基季铵碱
何优势，因此，DMF 为甲基化反应的最佳催化剂。
注：DMF 用量以Ⅰ的质量为基准，下同
图 5 DMF 用量对收率的影响
Fig. 5 Effect of DMF dosage on the yield
此外，DMF 用量是影响选择性和Ⅵ收率的另一
关键因素。由图 5 所示，随着 DMF 用量的增加，甲
基化反应的选择性和Ⅵ的收率均得到改善，甚至减
少或避免了副产物Ⅲ和Ⅳ的生成。当 DMF 用量为
25%时，Ⅵ的收率可达到 97.3%，且没有副产物Ⅲ
和Ⅳ的生成。继续增加 DMF 用量，收率没有明显变
化。因此，DMF 最佳用量是Ⅰ质量的 25%。
2.6 DMF 催化Ⅵ的合成机理探讨
在此反应路线中，DMC 作为亲电试剂，可与亲
核试剂甲基化反应或甲氧羰基化反应
具有极性化作用，在氨基诱导下，DMF 极性化作用
增强，同时高温会增强 DMF 的极性化效果，这都使
得氨基基团周围极性溶剂化膜增强，带有溶剂化膜
的氨基进入空间位阻较小的甲基更有利于产物的形
成，相应地羰基化副产物的生成量就少。DMC 与Ⅰ
的反应机理如下所示：
3 结论
通过单因素实验优化 1-金刚烷胺甲基化反应的
工艺条件，确定了最佳反应条件：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
5 h 时，使得Ⅵ的收率高达 97.3%。采用 DMC 代替
·1939·
有毒有害的 DMS、卤代烷等作为甲基化试剂，以
DMF 作为甲基化反应催化剂，高选择性地合成Ⅵ，
且母液可循环利用。本工艺不仅提高原料的利用率，
降低反应单耗，还实现生产过程中无废水废液排放，
真正实现 N,N,N-三甲基-1-金刚烷基季铵碱的绿色合
成工艺目标。
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