6-甲基-8-氨基喹啉是合成5-甲基-1,10-菲罗啉有机螯合配体的关键物种.以4-甲基-2-硝基苯胺为原料,经Skraup反应和还原,两步合成了6-甲基-8-氨基喹啉.Skraup反应中,用碘化钾/浓硫酸代替碘作为氧化剂,通过浓硫酸的强氧化性实现碘的原位氧化还原循环,使氧化剂的用量大大降低;在4-甲基-2-硝基苯胺、甘油、浓硫酸与碘化钾的物质的量之比为1∶3∶3∶0.1,反应时间3 h,反应温度140℃的优化条件下,6-甲基-8-硝基喹啉的收率达73.1%.以水合肼为氢化试剂,在水合肼与6-甲基-8-硝基喹啉的物质的量之比为2∶1,质量分数10%的Pd/C催化剂用量为6-甲基-8-硝基喹啉质量分数10%,反应时间9 h的优化条件下,6-甲基-8-氨基喹啉的收率为73.5%.
6-methyl-8-amino quinoline is the key species in the synthesis of 5-methyl-1,10-phenanthroline organic chelating ligand. 6-methyl-8-amino quinoline was synthesized by two steps after Skraup reaction and reduction with 4-methyl-2-nitro aniline as the material. In the Skraup reaction, the amount of oxidant was greatly reduced using potassium iodine / sulfuric acid instead of iodine as an oxidant because the strong oxidizability of concentrated sulfuric acid resulted in iodine ion in situ redox cycle. The yield of 6-methyl-8-nitro quinoline reaches 73.1% when the reaction was carried out with the molar ratio of 4-methyl-2-nitro aniline, glycerol, concentrated sulfuric acid to potassium iodide of 1∶3∶3∶0.1, reaction time of 3 h and reaction temperature of 140 ℃.The yield of 6-methyl-8-amino quinoline is 73.5% using hydrazine hydrate as a hydrogenation reagent, at the conditions of the molar ratio of hydrazine hydrate to 6-methyl-8-nitroquinoline of 2∶1, the 10% dosage of 1 ∶10 mass fraction of palladium carbon hydrogenation catalyst and 6-methyl-nitroquinoline, and reaction time of 9 h.