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醇催化胺化反应的研究

Studies on the Catalytic Amination of Alcohols

【作者】 白国义

【导师】 冯亚青; 陈立功;

【作者基本信息】 天津大学 , 应用化学, 2003, 博士

【摘要】 脂肪胺是一类极其重要的有机化工原料和医药中间体,而醇的催化胺化反应是制备此类化合物最重要的方法之一。本文对分子内、分子间和能同时进行分子内和分子间醇的催化胺化反应进行了系统地研究。1. 以N-β-羟乙基乙二胺合成哌嗪的反应作为分子内醇催化胺化合成环状仲胺的反应模型,我们采用XPS、XRD、SEM等对所用的催化剂进行了表征,采用GC-MS对产物进行了分析,探讨了反应的机理,筛选得到了BL0182催化剂,并发现二氧六环等有机溶剂的加入能大大延长催化剂的使用寿命。通过优化得到此反应的最佳条件,此时原料转化率可达98%以上,哌嗪选择性在95%左右,催化剂连续使用200小时后其活性未发现明显变化。随后,将BL0182催化剂成功地应用于2-甲基哌嗪和2,6-二甲基哌嗪的合成中,也取得了令人满意的结果。2. 以三乙烯二胺的合成为例对分子内醇催化胺化合成环状叔胺的反应进行了研究,筛选出了BL0308催化剂并对反应的条件进行优化,此时原料转化率接近100%,三乙烯二胺的选择性在90%左右,此催化体系通过210小时的寿命实验仍具有较高活性。3. 以正丁醇与氨的反应作为分子间醇催化胺化的反应模型,确立并优化了BL0385催化剂,当反应温度为250℃,氢压为1.5MPa,氨醇比为6:1时,正丁醇的转化率接近100%,正丁胺的选择性达84%以上,催化剂经过100小时的寿命实验后仍具有较高活性。反应中检测到副产物正丁酰胺证明并完善了醇催化胺化的脱氢/加氢机理。 将BL0385催化剂成功地用于正辛胺和N-乙基乙二胺的合成,取得了令人满意的结果。4. 以二乙醇胺和甲胺(乙胺)的反应为模型,对同时进行分子内和分子间醇的催化胺化反应进行了研究,发现此类反应非常复杂,未取得预期的结果。

【Abstract】 Aliphatic amines are important intermediates for the chemical and pharmaceutical industries. Catalytic amination of alcohols is one of the most useful methods for the manufacture of this kind of compounds. Three kinds of catalytic amination of alcohols: intramolecular, intermolecular and both of them occuring at the same time are investigated systematically in this paper. 1. The synthesis of piperazine from N-β-hydroxyethylethylenediamine was taken as a model for the investigation into the intramolecular catalytic amination of alcohols. The used catalysts were characterized by XPS、XRD、SEM. The intermediates and products were analyzed through GC-MS and the mechanism was proposed on the basis of them. The BL0182 catalyst was selected and organic solvents such as dioxane were found benefit to the service life of this catalyst. The conversion of raw material was over 98% and the selectivity to piperazine was about 95% under the optimized reaction conditions. The catalyst showed high activity after 200 hours of experiment. The BL0182 catalyst was successfully used in the synthesis of 2-methylpiperazine and 2,6-dimethylpiperazine, too.2. The synthesis of triethylenediamine was investigated as a model of intramolecular catalytic amination of alcohols to cyclic tertiary amines. A series of catalysts were prepared and examined and BL0308 catalyst was selected. It was found when BL0308 was employed as catalyst, the conversion of the starting material reached almost up to 100% and triethylenediamine was afforded over 90% selectivity under the optimized reaction conditions, and the catalyst worked well within 210 hours .3. The intermolecular catalytic amination of aliphatic alcohols using n-butanol and ammonia as example was studied . The BL0385 catalyst was selected and optimized for this reaction . The conversion of n-butanol was near 100% and the selectivity of n-butylamine was over 84%, while the reaction temperature was 250℃, the ratio of ammonia to alcohol was 6:1 and the hydrogen pressure was 1.5MPa. The catalyst showed high activity after 100 hours of test. The n-butylamide was first detected and the dehydrogenation/hydrogenation mechanism of catalytic amination of alcohols was<WP=7>proved. The catalyst was successfully used in the synthesis of n-octaylamine and N-ethylethylenediamine, too.4. The cyclization of diethanolamine and methylamine(ethylamine) was taken as a model for the investigation into the intramolecular and intermolecular catalytic amination of alcohols. The reaction was found to be very complex and no desired result was obtained.

  • 【网络出版投稿人】 天津大学
  • 【网络出版年期】2003年 03期
  • 【分类号】O643.3
  • 【被引频次】13
  • 【下载频次】1819
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