3-甲氧基二苯胺的合成工艺研究
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摘要
3-甲氧基二苯胺是生产阴图PS版感光剂、2-甲氧基吩噻嗪和荧烷类热敏染料的重要中间体,广泛应用于医药、染料、印刷等工业。
本文在文献基础上采用一条新的合成路线:以间二硝基苯为原料,经过甲氧基化、加氢还原、N-酰化、Ullmann缩合再水解得到最终产物,总收率为70.2%。
在甲氧基化反应中,用甲醇代替了高毒、价高、后处理困难的强极性溶剂。研究了影响反应的重要因素,优化的工艺条件为:甲醇作为溶剂,18-冠-6-醚作为相转移催化剂(用量为间二硝基苯质量的0.2%),反应时间6h,间二硝基苯与甲醇钠的摩尔比1∶1.2,反应温度120℃,反应压力0.65MPa,产品收率89.9%。
在还原反应中,采用Pd/C作催化剂,使用催化加氢的方法合成3-甲氧基苯胺,工艺简单清洁,收率较高。较适宜的工艺条件为:甲醇作为溶剂,催化剂10%wtPd/C用量为原料3-甲氧基硝基苯质量的0.5%,反应温度80℃,反应压力2.0MPa,反应时间8h,收率93.5%。在每次反应后补加20%(质量分数)新鲜催化剂的条件下,催化剂至少可循环使用5次,产品收率变化不大,溶剂甲醇可套用。
在N-酰化反应中,用三光气作为3-甲氧基苯胺的酰化剂,得到的3,3'-二甲氧基二苯脲可以在较温和的条件下与氯苯发生反应Ullmann缩合反应。并且酰化过程中没有水生成,避免了Ullmann缩合反应中的水解副反应。较适宜的工艺条件为:甲苯作为溶剂,3-甲氧基二苯胺与三光气的摩尔比为4.0∶1,反应温度30℃,催化剂三乙胺的用量为3-甲氧基苯胺质量的4.0%,反应时间7h,收率92.7%。
在Ullmann缩合反应中,以碘化亚铜和N,N'-二甲基乙二胺的配合物作为催化剂,碳酸钾为缚酸剂,采用缩合后直接水解的方法,简化了操作步骤。合适的工艺条件为:氯苯与3,3'-二甲氧基二苯脲的摩尔比为3.0∶1,过量的氯苯在缩合后经水蒸汽蒸馏基本可以完全回收,碘化亚铜用量为3,3'-二甲氧基二苯脲质量的0.2%,N,N'-二甲基乙二胺用量为3,3'-二甲氧基二苯脲质量的2.0%,碳酸钾与3,3'-二甲氧基二苯脲的摩尔比为2.2∶1,反应温度130℃,反应时间4h,3,3'-二甲氧基二苯脲的转化率达98.7%,直接加入氢氧化钠(用量为3,3'-二甲氧基二苯脲摩尔量的2.5倍)溶液水解5h后,收率90.9%(以3-甲氧基苯胺计)。
各步产品经熔点法、GC-MS、ESI-MS、IR、H-NMR等方法检测证明结构正确。
新的生产工艺降低了生产成本,简化了操作过程,减少了污染产生量,易实现工业化生产。
3-Methoxy-N-phenyl-benzenamine is an important intermediate for producing negative PS photosensitizer,2-methoxylphenothiazine and fluorane heat sensitive dyes,and is widely used in medicine,dye and printing industry.
3-Methoxy-N-phenyl-benzenamine was synthesized from the methoxylation of m-dinitrobenzene,followed by reduction,N-acylation,Ullmann condensation and hydrolysis. The overall yield was 70.2%.
In the methoxylation of m-dinitrobenzene,methanol was used as solvent instead of the toxicant,expensive and polar ones.The optimized conditions were:the mole ratio of m-dinitrobenzene and sodium methoxide of 1:1.2,the 0.2%wt 18-crown-6-ether as the phase transfer catalyst to m-dinitrobenzene,reaction temperature of 120℃,reaction pressure of 0.65MPa,reaction time of 6h.With these conditions,the product was obtained with a yield of 89.9%.
3-Methoxy-benzenamine was synthesized through the hydrogenation of m-nitroanisole obtained with palladium on carbon(10%wt)as catalyst in methanol solvent.Under the optimized conditions of:0.5%wt of catalyst to m-nitroanisole,reaction temperature of 80℃, pressure of 2.0MPa,reaction time of 8h,the yield for 3-methoxy-benzenamine was 93.5%.The catalyst can be reused for five times without big lose of the hydrogenation yield,i.e.addition 20%wt of the new catalyst after every reaction.The solvent can be used indiscriminately.
Triphosgene was used as the acylating agent of 3-methoxy-benzenamine in N-acylation to obtain 3,3'-dimethoxy-diphenyl urea which could reacted with chlorobenzene under the mild conditions.At the same time,there was not water produced in N-acylation,so it could avoid the hydrolysis reaction in the Ullmann condensation.Under the optimized conditions,4 fold moles of 3-methoxy-benzenamine to triphosgene,4.0%wt of triethylamine to 3-methoxy-benzenamine as catalyst,reaction temperature of 30℃,reaction time of 7h,the yield of 92.7%for the objective product was obtained.
In Ullmann condensation,the coupled compound of iodide copper and N,N'-dimethyl ethylene diamine was employed as the catalyst and potassium carbonate as acid-reacted agent. The effects of various factors were investigated.The optimized conditions were:the mole ratio of chlorobenzene and 3,3'-dimethoxy-carbanilide was 3.0:1,the excess chlorobenzene was recovered by steam distillation after the condensation reaction,reaction temperature of 130℃, the 0.2%wt iodide copper and 2.0%N,N'-dimethyl ethylene diamine to 3,3'-dimethoxy-carbanilide,the mole ratio of potassium carbonate and 3,3'-dimethoxy-carbanilide was 2.2:1,reaction time of 4h.With the conditions above,the conversion of 3,3'-dimethoxy-carbanilide was 98.7%.The solution of sodium hydrate was directly used for hydrolysis.With the mole ratio of sodium hydrate and 3,3'-dimethoxy-carbanilide was 2.5:1,reaction time of 5h,the yield was 90.9%.
The structure of the product and the relative intermediates were confirmed with the melting point,GC-MS,ESI-MS,IR,H-NMR.
The paper successfully got a new route for the synthesis of 3-methoxy-N-phenyl-benzenamine characterized by cheaper and more readily obtainable raw materials,more convenient operation and less pollution.
本文在文献基础上采用一条新的合成路线:以间二硝基苯为原料,经过甲氧基化、加氢还原、N-酰化、Ullmann缩合再水解得到最终产物,总收率为70.2%。
在甲氧基化反应中,用甲醇代替了高毒、价高、后处理困难的强极性溶剂。研究了影响反应的重要因素,优化的工艺条件为:甲醇作为溶剂,18-冠-6-醚作为相转移催化剂(用量为间二硝基苯质量的0.2%),反应时间6h,间二硝基苯与甲醇钠的摩尔比1∶1.2,反应温度120℃,反应压力0.65MPa,产品收率89.9%。
在还原反应中,采用Pd/C作催化剂,使用催化加氢的方法合成3-甲氧基苯胺,工艺简单清洁,收率较高。较适宜的工艺条件为:甲醇作为溶剂,催化剂10%wtPd/C用量为原料3-甲氧基硝基苯质量的0.5%,反应温度80℃,反应压力2.0MPa,反应时间8h,收率93.5%。在每次反应后补加20%(质量分数)新鲜催化剂的条件下,催化剂至少可循环使用5次,产品收率变化不大,溶剂甲醇可套用。
在N-酰化反应中,用三光气作为3-甲氧基苯胺的酰化剂,得到的3,3'-二甲氧基二苯脲可以在较温和的条件下与氯苯发生反应Ullmann缩合反应。并且酰化过程中没有水生成,避免了Ullmann缩合反应中的水解副反应。较适宜的工艺条件为:甲苯作为溶剂,3-甲氧基二苯胺与三光气的摩尔比为4.0∶1,反应温度30℃,催化剂三乙胺的用量为3-甲氧基苯胺质量的4.0%,反应时间7h,收率92.7%。
在Ullmann缩合反应中,以碘化亚铜和N,N'-二甲基乙二胺的配合物作为催化剂,碳酸钾为缚酸剂,采用缩合后直接水解的方法,简化了操作步骤。合适的工艺条件为:氯苯与3,3'-二甲氧基二苯脲的摩尔比为3.0∶1,过量的氯苯在缩合后经水蒸汽蒸馏基本可以完全回收,碘化亚铜用量为3,3'-二甲氧基二苯脲质量的0.2%,N,N'-二甲基乙二胺用量为3,3'-二甲氧基二苯脲质量的2.0%,碳酸钾与3,3'-二甲氧基二苯脲的摩尔比为2.2∶1,反应温度130℃,反应时间4h,3,3'-二甲氧基二苯脲的转化率达98.7%,直接加入氢氧化钠(用量为3,3'-二甲氧基二苯脲摩尔量的2.5倍)溶液水解5h后,收率90.9%(以3-甲氧基苯胺计)。
各步产品经熔点法、GC-MS、ESI-MS、IR、H-NMR等方法检测证明结构正确。
新的生产工艺降低了生产成本,简化了操作过程,减少了污染产生量,易实现工业化生产。
3-Methoxy-N-phenyl-benzenamine is an important intermediate for producing negative PS photosensitizer,2-methoxylphenothiazine and fluorane heat sensitive dyes,and is widely used in medicine,dye and printing industry.
3-Methoxy-N-phenyl-benzenamine was synthesized from the methoxylation of m-dinitrobenzene,followed by reduction,N-acylation,Ullmann condensation and hydrolysis. The overall yield was 70.2%.
In the methoxylation of m-dinitrobenzene,methanol was used as solvent instead of the toxicant,expensive and polar ones.The optimized conditions were:the mole ratio of m-dinitrobenzene and sodium methoxide of 1:1.2,the 0.2%wt 18-crown-6-ether as the phase transfer catalyst to m-dinitrobenzene,reaction temperature of 120℃,reaction pressure of 0.65MPa,reaction time of 6h.With these conditions,the product was obtained with a yield of 89.9%.
3-Methoxy-benzenamine was synthesized through the hydrogenation of m-nitroanisole obtained with palladium on carbon(10%wt)as catalyst in methanol solvent.Under the optimized conditions of:0.5%wt of catalyst to m-nitroanisole,reaction temperature of 80℃, pressure of 2.0MPa,reaction time of 8h,the yield for 3-methoxy-benzenamine was 93.5%.The catalyst can be reused for five times without big lose of the hydrogenation yield,i.e.addition 20%wt of the new catalyst after every reaction.The solvent can be used indiscriminately.
Triphosgene was used as the acylating agent of 3-methoxy-benzenamine in N-acylation to obtain 3,3'-dimethoxy-diphenyl urea which could reacted with chlorobenzene under the mild conditions.At the same time,there was not water produced in N-acylation,so it could avoid the hydrolysis reaction in the Ullmann condensation.Under the optimized conditions,4 fold moles of 3-methoxy-benzenamine to triphosgene,4.0%wt of triethylamine to 3-methoxy-benzenamine as catalyst,reaction temperature of 30℃,reaction time of 7h,the yield of 92.7%for the objective product was obtained.
In Ullmann condensation,the coupled compound of iodide copper and N,N'-dimethyl ethylene diamine was employed as the catalyst and potassium carbonate as acid-reacted agent. The effects of various factors were investigated.The optimized conditions were:the mole ratio of chlorobenzene and 3,3'-dimethoxy-carbanilide was 3.0:1,the excess chlorobenzene was recovered by steam distillation after the condensation reaction,reaction temperature of 130℃, the 0.2%wt iodide copper and 2.0%N,N'-dimethyl ethylene diamine to 3,3'-dimethoxy-carbanilide,the mole ratio of potassium carbonate and 3,3'-dimethoxy-carbanilide was 2.2:1,reaction time of 4h.With the conditions above,the conversion of 3,3'-dimethoxy-carbanilide was 98.7%.The solution of sodium hydrate was directly used for hydrolysis.With the mole ratio of sodium hydrate and 3,3'-dimethoxy-carbanilide was 2.5:1,reaction time of 5h,the yield was 90.9%.
The structure of the product and the relative intermediates were confirmed with the melting point,GC-MS,ESI-MS,IR,H-NMR.
The paper successfully got a new route for the synthesis of 3-methoxy-N-phenyl-benzenamine characterized by cheaper and more readily obtainable raw materials,more convenient operation and less pollution.
引文
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