5-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile5-amino-4-trifluoromethylsulfinyl-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-thi°Carbamoylpyrazolesulfur dioxide5-amino-3-bromo-1-(2,6-dichloro-4-trifluoromethylphenyl)-4-trifluoromethylthiopyrazoleMB 465135-amino-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitriletriethylamine salt of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoromethylsulfinyl-5-(ethoxyacetamido)pyrazole5-amino-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-trifluoromethylsulfinyl-1H-pyrazole-3-carboximidic acid methyl ester
合成工艺路线路线简述
合成目标产物 Fipronil 主要起始原料 Trifluoromethyl Sulfinyl Chloride And 5-Amino-3-Cyano-1-(2,6-Dichloro-4-Trifluoromethylphenyl)Pyrazole
专利号:US-12221421-B2 优先权日:2019-03-19 标题:Process for synthesis of Fipronil 发明人:GHARDA KEKI HORMUSJI; SHENOY DIWAKAR; SHET LAXMINARAYAN; SAMANGADKAR YATIN; KAWADE ABHIJEET SURESH 权利人:GHARDA CHEMICALS LTD 摘要:A process for the synthesis of fipronil, which is a broad spectrum insecticide of the following chemical structure, is provided.The process provides fipronil with a yield in the range of 75% to 90% and purity in the range of 95% to 97%. By the process, the observed amount of sulfone impurity i.e., 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-cyano-4-trifluoro methylsulfonyl pyrazole in fipronil is in the range of 0% to 0.5%.
专利号:US-2015239796-A1 优先权日:2014-02-19 标题:One pot synthesis of 18f labeledtrifluoromethylated compounds with difluoro(iodo)methane 发明人:RüHL THOMAS; RISS PATRICK; RAFIQUE WAQAS 权利人:UNIV OSLO 摘要:The present invention relates to compositions and methods for the synthesis of 18 F labeled compounds. In particular, the present invention relates to a copper (I) mediated one pot method for 18 F-trifluoromethylation of aromatic- or heteroaromatic halides with difluoro(iodo)methane (e.g., for use at PET imaging agents).
专利号:WO-2010049789-A1 优先权日:2008-10-27 标 题 :Process for the synthesis of fipronil 发明人:JUELICH ALEXANDER; TILLICH JOACHIM 权利人:DYNAMIT NOBEL AG; JUELICH ALEXANDER; TILLICH JOACHIM 摘要:This invention relates to a process for the continuous synthesis of 5-amino-1-[2,6- dichloro-4-(rifluoromethyl)phenyl]-4-(rifluoromethylsulfinyl)-1H-pyrazole-3-carbonitrile comprising the step of reacting in a solvent 5-amino-1-[2,6-dichloro-4- (trifluoromethyl)phenyl]-4-(trifluoromethylthio)-1H-pyrazole-3-carbonitrile with an oxidizing agent. The process provides a more efficient and more robust process than the existing processes.
专利号:US-RE48674-E 优先权日:2010-07-07 标题 :Method for the synthesis of 5-amino-1-phenyl-3-cyano-4-trifluoromethyl sulfinyl 发明人:PASTORIO ANDREA; BETTI PAOLO 权利人:PASTORIO ANDREA; BETTI PAOLO; FINCHIMICA SRL 摘要:The present invention relates to a method for the preparation of the 5-amino-1-phenyl-3-cyano-4-trifluoromethyl sulfinyl pyrazole having the described general formula (I), particularly preferred for the synthesis of Fipronil I, through oxidation of a compound having the general formula (II) as follows:wherein R1 and R2 are independently hydrogen or halogen, and wherein the oxidizing agent is dichloroperacetic acid.
专利号:US-6747175-B2 优先权日:2000-03-01 标 题:Chlorination of an aniline in a hydrofluoric medium 发明人:KEMPF HUBERT; GUIDOT GILBERT; SAINT-JALMES LAURENT 权利人:RHODIA CHIMIE SA 摘要:The invention concerns a method for the synthesis of chlorinated aniline on the ring and comprising at least a sp3 hybridization carbon atom both perhalogenated and bearing a fluorine atom. Said method is characterized in that it comprises a step which consists in chlorinating a precursor aniline of said chlorinated aniline, said chlorination being carried out in a hydrofluoric medium capable of exchanging chlorine and fluorine in benzyl position. The invention is useful for the synthesis of organofluorinated and/or chlorinated compounds.
专利号:WO-2016118586-A1 优先权日:2015-01-20 标 题 :Lowcost, high yield synthesis of nevirapine 发明人:AHMAD SAEED; GUPTON FRANK; VERGHESES JENSON; MCQUADE TYLER 权利人:UNIV VIRGINIA COMMONWEALTH 摘要:Improved methods of producing the HIV drug substance, nevirapine are provided. The methods employ a cost effective and high yield synthetic methods for preparing the nevirapine building block 2-chloro-3-amino-4-picoline (CAPIC) and 2-cyclopropyl amino nicotinate (Me-CAN), and improvements in other steps of nevirapine synthesis.
1: Wang X, Martínez MA, Wu Q, Ares I, Martínez-Larrañaga MR, Anadón A, Yuan Z. Fipronil insecticide toxicology: oxidative stress and metabolism. Crit Rev Toxicol. 2016 Nov;46(10):876-899. Epub 2016 Sep 19. Review. doi: 10.1016/j.envint.2016.01.009. Epub 2016 Jan 27. Review. doi: 10.1016/j.pestbp.2014.09.010. Epub 2014 Sep 30. Review. doi: 10.11477/mf.1416200085. Review. Japanese. doi: 10.1016/j.ejmech.2014.11.059. Epub 2014 Dec 5. Review. doi: 10.1007/s11356-014-3229-5. Epub 2014 Oct 10. Review. 7: Simon-Delso N, Amaral-Rogers V, Belzunces LP, Bonmatin JM, Chagnon M, Downs C, Furlan L, Gibbons DW, Giorio C, Girolami V, Goulson D, Kreutzweiser DP, Krupke CH, Liess M, Long E, McField M, Mineau P, Mitchell EA, Morrissey CA, Noome DA, Pisa L, Settele J, Stark JD, Tapparo A, Van Dyck H, Van Praagh J, Van der Sluijs JP, Whitehorn PR, Wiemers M. Systemic insecticides (neonicotinoids and fipronil): trends, uses, mode of action and metabolites. Environ Sci Pollut Res Int. 2015 Jan;22(1):5-34. doi: 10.1007/s11356-014-3470-y. Epub 2014 Sep 19. Review. 8: Pisa LW, Amaral-Rogers V, Belzunces LP, Bonmatin JM, Downs CA, Goulson D, Kreutzweiser DP, Krupke C, Liess M, McField M, Morrissey CA, Noome DA, Settele J, Simon-Delso N, Stark JD, Van der Sluijs JP, Van Dyck H, Wiemers M. Effects of neonicotinoids and fipronil on non-target invertebrates. Environ Sci Pollut Res Int. 2015 Jan;22(1):68-102. doi: 10.1007/s11356-014-3471-x. Epub 2014 Sep 17. Review.
合成参考文献
参考文献:10.1002/jemt.21043 摘要:Ferreira M, De Oliveira PR, Denardi SE, Bechara GH, Mathias MIC. Action of the chemical agent fipronil (active ingredient of acaricide Frontline®) on the liver of mice: An ultrastructural analysis. Microscopy Res & Technique. 2011 Jul 14;75(2):197–205. doi: 10.1002/jemt.21043. 参考文献:10.1002/ps.2232 摘要:Peterson CJ. Bifenthrin longevity at the termiticidal application rate. Pest Manag Sci. 2012 Jan;68(1):123–6. doi: 10.1002/ps.2232. 参考文献:10.3390/ijerph8062265 摘要:Mnif W, Hassine AI, Bouaziz A, Bartegi A, Thomas O, Roig B. Effect of endocrine disruptor pesticides: a review. Int J Environ Res Public Health. 2011 Jun;8(6):2265–303. 参考文献:10.4061/2011/476348 摘要:Giadinis ND, Farmaki R, Papaioannou N, Papadopoulos E, Karatzias H, Koutinas AF. Moxidectin Efficacy in a Goat Herd with Chronic and Generalized Sarcoptic Mange. Veterinary Medicine International. 2011;2011():1–4. doi: 10.4061/2011/476348.