4-三氟甲基烟酸的合成
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摘要
4-三氟甲基烟酸是高效杀虫剂氟啶虫酰胺的重要中间体。以三氟乙酰乙酸乙酯和氰基乙酰胺为原料,经环合、氯代、氢化还原、水解反应得到目标产物。经优化反应条件,以三氟乙酰乙酸乙酯计4-三氟甲基烟酸的总收率达到38.6%。该路线原料易得、收率高,适合工业化生产。
4-(Trifluoromethyl)nicotinic acid was an important intermediate for the preparation of flonicamid. With ethyl 4,4,4-trifluoroacetoacetate and cyanoacetamide as starting materials, the desired product was prepared via optimized cyclization, chlorination, hydrogenolysis, hydrolysis. The total yield was 38.6% based on ethyl 4,4,4-trifluoroacetoacetate. The method benefited from readily available materials, satisfactory yield, and was suitable for industrial production.
4-(Trifluoromethyl)nicotinic acid was an important intermediate for the preparation of flonicamid. With ethyl 4,4,4-trifluoroacetoacetate and cyanoacetamide as starting materials, the desired product was prepared via optimized cyclization, chlorination, hydrogenolysis, hydrolysis. The total yield was 38.6% based on ethyl 4,4,4-trifluoroacetoacetate. The method benefited from readily available materials, satisfactory yield, and was suitable for industrial production.
引文
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[2]刘振香,蔡春.2-氯-3-氰基吡啶的合成[J].精细化工中间体,2005,30(3):28–29.
[3]杨吉春,吴峤,刘允萍,等.含氟农药开发的新进展[J].农药,2011,50(4):289–295.
[4]张亦冰.新颖杀虫剂——氟啶虫酰胺[J].世界农药,2010,32(1):54–56.
[5]李杰,陈浩,周勋,等.3-氨甲基-4-三氟甲基吡啶的合成研究[J].有机化学,2008,28(9):1637–1640.
[6]Bobbitt J M,Scola D A.Synthesis of Isoquinoline Alkaloids.Ⅱ.The Synthesis and Reactions of 4-Methyl-3-pyridinecarboxaldehyde and Other 4-Methyl-3-substituted Pyridines[J].J Org Chem,1960,25:560–564.
[7]Holland G F,Pereira J N.Heterocyclic Tetrazoles,a New Class of Lipolysis Inhibitors[J].J Med Chem,1967,10(2):149–154.
[8]马梦林.一种4-三氟甲基烟酸的制备方法:ZL,200910167945.1[P].2010–10–06.
[9]Ueda G,Wakabayashi T.Method for Producing 4-Trifluoromethylnicotinic Acid or Its Salt:JP,2007210923 A[P].2007–08–23.
[10]Cottet F,Marull M,Lefebvre O,et al.Recommendable Routes to Trifluoromethyl-substituted Pyridine and Quinolinecarboxylic Acids[J].Eur J Org Chem,2003(8):1559–1568.