绿色有效合成N,N,N-三甲基-1-金刚烷基季铵碱

Green and effective synthesis of N,N,N-trimethyladamantan-1-aminium hydroxide

摘要:

本文报道了绿色合成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，以碳酸二甲酯（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1H NMR和13C NMR对季铵盐和季铵碱的结构进行表征。分别考察了催化剂，反应物的摩尔比[n(1-金刚烷胺):n(DMC)]，反应温度和时间对N,N,N-三甲基-1-金刚烷基季铵盐的收率的影响，获得了最佳的反应条件：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5 h。此反应条件下，N,N,N-三甲基-1-金刚烷基季铵盐的收率可达97.3％。与传统工艺中采用硫酸二甲酯（DMS）为甲基化试剂相比，本工艺更安全、绿色、高效。

Abstract:

In this paper, a green process for the synthesis of N,N,N-trimethyladamantan-1-aminium hydroxide was reported. Firstly, the precursor N,N,N-trimethyladamantan-1-aminium salt was obtained by using 1-adamantanamine as raw material, dimethyl carbonate (DMC) as methylating reagent. Then, the precursor was reacted with calcium hydroxide to achieve the final product N,N,N-trimethyladamantan-1-aminium hydroxide. The structures of ammonium salt and hydroxide were characterized by 1H NMR and 13C NMR spectra. After investigating the effects of catalyst, mole ratio of reactants, reaction temperature and time on the yield of N,N,N-trimethyladamantan-1-aminium salt, the optimum reaction conditions were obtained as follows: N,N-dimethyl formamide (DMF) was used as the 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%. Compared with the traditional process using dimethyl sulfate (DMS) as the methylation reagent, this process is more safe, green and efficient.