1-萘甲醇置于caesium Fluoroxysulphate体系中,用 乙腈 用作溶剂,化学反应生成1-氟萘 参考文献:Nucleophilic Catalysis In The Reactions Of Polyfluorocarbonyl Compounds With Phenols 标题:Nucleophilic Catalysis In The Reactions Of Polyfluorocarbonyl Compounds With Phenols 摘要: Doi:10.1016/s0022-1139(00)83777-X
专利号:US-2010016607-A1 优先权日:2006-12-11 标题:Process for the Synthesis of Highly Active Binary Metal Fluoride as a Fluorinating Agent for Aromatics 发明人:DOLBIER JR WILLIAM R; JANMANCHI KRISHNA MURTHY 权利人:UNIV FLORIDA 摘要:The subject invention relates to a process for the synthesis of highly active binary metal fluoride system for the fluorination of aromatic compounds. Fluorinated aromatic compounds are valuable synthons for the chemical synthesis of pharmaceutical drugs and novel polymers. Fluorobenzene is used to control carbon content in steel manufacturing, is an intermediate for pharmaceuticals, pesticides and other organic compounds. Fluorobenzene is typically produced by the reaction of aniline and sodium nitrite in the presence of hydrogen fluoride. The present invention relates to a process for the synthesis of highly active binary metal fluoride system consists of copper (II) fluoride and aluminum (III) fluoride for the fluorination of aromatic compounds in gas phase and recycling of the reagent, in situ, using O 2 and HF.
专利号:US-5491243-A 优先权日:1993-10-12 标题 :Intermediate useful for the asymmetric synthesis of duloxetine 发明人:BERGLUND RICHARD A 权利人:LILLY CO ELI 摘要:This invention provides a stereospecific process for the synthesis of (S)-(+)-N,N-dimethyl-3-(1-naphthalenyloxy)-3-(2-thienyl)propanamine, a key intermediate in the synthesis of duloxetine.
专利号:US-7538232-B2 优先权日:2006-01-19 标 题 :Process for the asymmetric synthesis of duloxetine 发明人:BUTCHKO MARK ANTHONY; MERSCHAERT ALAIN; MODER KENNETH PHILIP 权利人:LILLY CO ELI 摘要:This invention provides an improved asymmetric process for the synthesis of duloxetine involving arylation of Compounds of Formula I.
专利号:US-8269023-B2 优先权日:2007-03-05 标题 :Process for preparation of duloxetine hydrochloride 发明人:SIYAN RAJINDER SINGH; GOHEL SUNIL KUMAR VINUBHAI; SINGH GIRIJ PAL 权利人:SIYAN RAJINDER SINGH; GOHEL SUNIL KUMAR VINUBHAI; SINGH GIRIJ PAL; LUPIN LTD 摘要:An improved process for synthesis of duloxetine hydrochloride (1) having chiral purity greater than 99.9% that is characterized by the following:n (i) preparation of racemic condensed compound (RS)—N,N-di methyl-3-(1-naphthyloxy)-3-(2-thienyl)propanamine (4) by reaction of racemic hydroxy compound (2) with 1-fluoronaphthalene (3) in presence of a base such as sodamide, potassium amide or potassium bis(trimethylsilyl)amide (KHDMS) in polar aprotic solvent, (ii) optical resolution of racemic condensed compound (5a+5b) with di-benzoyl-L-tartaric acid (7, DBTA, R=H) or di-para-anisoyl-L-tartaric acid (7, DATA, R=OCH 3 ) to obtain crude (S)—N.N-dimethyl-3-(1-naphthyloxy)-3-(2-thienyl)propanamine dibenzoyl tartarate salt (8a) or (S)—N.N-dimethyl-3-(1-naphthyloxy)-3-(2-thienyl)propanamine di-p-anisoyl tartarate salt (9a) respectively, (iii) optionally purification of crude tartarate salts (8a or 9a) by crystallization, (iv) optionally purification of duloxetine hydrochloride (1) by crystallization and (v) racemization of undesired (R)—N,N-di methyl-3-(1-naphthyloxy)-3-(2-thienyl)propanamine (5b) by treatment with base potassium bis(trimethylsilyl)amide (KHDMS) to obtain racemic mixture of condensed compounds (5a and 5b).
专利号:US-2004110228-A1 优先权日:2002-04-01 标 题:Combinatorial organic synthesis of unique biologically active compounds 发明人:MCALPINE SHELLI R; TAYLOR RACHEL E; BOLLA MEGAN L; SEGALL ANCA M 摘要:The invention provides a method for making a combinatorial library of cyclic compounds, such as Holliday junction-trapping compounds, comprising the steps of (a) obtaining a plurality of trimers according to the generic structure X 1- X 2- X 3 , wherein X 1 , X 2 and X 3 can be independently any naturally or nonnaturally occurring amino acids or peptidomimetics thereof; (b) optionally coupling a spacer S to the trimer at either end; (c) cyclizing two trimers or trimer-spacer conjugates in a head-to-tail orientation; thereby obtaining a combinatorial library of compounds, wherein the library does not include an unmodifed or naturally occurring Holliday Junction-trapping compounds. The invention additionally provides methods macrocyclic compounds that are synergimycin derivatives.
专利号:US-2005171360-A1 优先权日:2002-02-22 标题:Preparation of n-methyl-3-hydroxy- 3-(2-thienyl)propylamine via novel thiophene derivatives containing carbamate groups as intermediates 发明人:REICHERT DIETMAR; ALMENA PEREA JUAN J; SCHWARM MICHAEL; DRAUZ KARLHEINZ; KRIMMER HANS-PETER 摘要:A novel route is described for the synthesis of N-methyl-3-hydroxy-3-(2-thienyl)propylamine IV, which can be used as a starting compound for the preparation of duloxetine. N-methyl-3-hydroxy-3-(2-thienyl)propylamine is synthesized via novel thiophene derivatives containing carbamate groups, I and IIa, as intermediates.
[参考文献]: C E Cerniglia, Et Al. Effects Of A Fluoro Substituent On The Fungal Metabolism Of 1-Fluoronaphthalene. Appl Environ Microbiol. 1984 Aug;48(2):294-300. [参考文献]: C E Cerniglia, Et Al. Effects Of A Fluoro Substituent On The Fungal Metabolism Of 1-Fluoronaphthalene. Appl Environ Microbiol. 1984 Aug;48(2):294-300. [参考文献]: Peter Wipf, Et Al. Synthesis Of Highly Oxygenated Dinaphthyl Ethers Via Snar Reactions Promoted By Barton'S Base. Org Lett. 2003 Apr 3;5(7):1155-8.
合成参考文献
摘要:Yoshida, H., Science of Synthesis Knowledge Updates, (2022) 3, 16. 摘要:Song, Z.; Takahashi, T., Science of Synthesis Knowledge Updates, (2013) 1, 107. 摘要:Wolf, C., Science of Synthesis: Cross Coupling and Heck-Type Reactions, (2012) 1, 863. 摘要:McMurtrey, K. B.; Sanford, M. S., Science of Synthesis: Cross Coupling and Heck-Type Reactions, (2012) 2, 553. 摘要:McMurtrey, K. B.; Sanford, M. S., Science of Synthesis: Cross Coupling and Heck-Type Reactions, (2012) 2, 555.