2-Methyl-4-methoxyaniline （MMA） was synthesized by one-pot method through the hydrogenation and Bamberger rearrangement of o-nitrotoluene in methanol using acidic ionic liquid and 3% Pt/C as catalyst system. The eff...2-Methyl-4-methoxyaniline （MMA） was synthesized by one-pot method through the hydrogenation and Bamberger rearrangement of o-nitrotoluene in methanol using acidic ionic liquid and 3% Pt/C as catalyst system. The effects of ionic liquid type, dosage of ionic liquid and 3% Pt/C, reaction temperature and reaction pressure on o-nitrotoluene conversion and MMA selectivity were investigated. The results indicated that the imidazolium-based acidic ionic liquid which contains SO3H-functionalized cation showed higher selectivity to MMA than other acidic ionic liquids used in this work. Using 1-（propyl-3-sulfonate）-3-methylimidazolium hydrosulfate （[HSO3-pmim][HSO4]） as the acid catalyst, the selectivity to MMA was as high as 67.6% at 97.8% of o-nitrotoluene conversion. As 3% Pt/C increased from 0.01 g to 0.025 g, the selectivity to MMA decreased from 73.4% to 62.5%, because of the hydrogenation of intermediate o-methyl-phenylhydroxylamine to o-toluidine becoming more dominant. An increase in hydrogen pressure also had obviously dramatic effect in lowering the MMA selectivity. After easy separation from the products, the catalyst system could be reused at least 3 times.展开更多
本文介绍了以2,4-二硝基-6-溴苯胺与3-(N,N-二烯丙基)氨基-4-甲氧基乙酰苯胺为原料合成分散蓝WF-PTS的工艺,并用高分辨率质谱对其结构进行了表征。通过对反应温度、氰化亚铜用量、溶剂用量、析出条件等进行单因素实验分析,确定了最佳反...本文介绍了以2,4-二硝基-6-溴苯胺与3-(N,N-二烯丙基)氨基-4-甲氧基乙酰苯胺为原料合成分散蓝WF-PTS的工艺,并用高分辨率质谱对其结构进行了表征。通过对反应温度、氰化亚铜用量、溶剂用量、析出条件等进行单因素实验分析,确定了最佳反应条件:中间体染料∶氰化锌=1∶0.5,氰化亚铜用量为中间体染料投料量的1.1%,溶剂为DMF,用量为80 m L(中间体染料投料量为0.1 mol时),升温到100℃反应2 h,自然降温至60℃时滴加100 m L甲醇,加完后再自然降温至室温,搅拌30 min,过滤,用清水洗涤,得到染料粗品。得到的粗品染料再进行除毒处理后,便得到分散蓝WF-PTS滤饼。得到的产品HPLC在97%左右,收率在88%以上。经性能测试,产品具有优异的耐水洗牢度和耐升华牢度。展开更多
基金Supported by the National Natural Science Foundation of China （21106134） and the Natural Science Foundation of Zlaejlang Province （Y4100671）.
文摘2-Methyl-4-methoxyaniline （MMA） was synthesized by one-pot method through the hydrogenation and Bamberger rearrangement of o-nitrotoluene in methanol using acidic ionic liquid and 3% Pt/C as catalyst system. The effects of ionic liquid type, dosage of ionic liquid and 3% Pt/C, reaction temperature and reaction pressure on o-nitrotoluene conversion and MMA selectivity were investigated. The results indicated that the imidazolium-based acidic ionic liquid which contains SO3H-functionalized cation showed higher selectivity to MMA than other acidic ionic liquids used in this work. Using 1-（propyl-3-sulfonate）-3-methylimidazolium hydrosulfate （[HSO3-pmim][HSO4]） as the acid catalyst, the selectivity to MMA was as high as 67.6% at 97.8% of o-nitrotoluene conversion. As 3% Pt/C increased from 0.01 g to 0.025 g, the selectivity to MMA decreased from 73.4% to 62.5%, because of the hydrogenation of intermediate o-methyl-phenylhydroxylamine to o-toluidine becoming more dominant. An increase in hydrogen pressure also had obviously dramatic effect in lowering the MMA selectivity. After easy separation from the products, the catalyst system could be reused at least 3 times.
文摘本文介绍了以2,4-二硝基-6-溴苯胺与3-(N,N-二烯丙基)氨基-4-甲氧基乙酰苯胺为原料合成分散蓝WF-PTS的工艺,并用高分辨率质谱对其结构进行了表征。通过对反应温度、氰化亚铜用量、溶剂用量、析出条件等进行单因素实验分析,确定了最佳反应条件:中间体染料∶氰化锌=1∶0.5,氰化亚铜用量为中间体染料投料量的1.1%,溶剂为DMF,用量为80 m L(中间体染料投料量为0.1 mol时),升温到100℃反应2 h,自然降温至60℃时滴加100 m L甲醇,加完后再自然降温至室温,搅拌30 min,过滤,用清水洗涤,得到染料粗品。得到的粗品染料再进行除毒处理后,便得到分散蓝WF-PTS滤饼。得到的产品HPLC在97%左右,收率在88%以上。经性能测试,产品具有优异的耐水洗牢度和耐升华牢度。
