| 摘要 |
Preparation of fluorinated benzene, pyridine or naphthalene compounds (I) from a chloro analog (II) and an alkali metal fluoride is effected in presence of a (poly)oxyalkylene quaternary ammonium compound (III), while (I) is separated by distillation and further (II) is supplied corresponding to the amount of (I) removed. Preparation of fluorinated (hetero)aromatic compounds of formula (I) involves reacting a chlorinated analog of formula (II) with alkali metal fluoride(s) at 50-250 degrees C, in presence of quaternary ammonium compound(s) of formula (III) and optionally one or more of amidophosphonium salts of formula (IV), quaternary ammonium compounds of formula (V), quaternary phosphonium compounds of formula (VI), polyethers of formula (VII) and crown ethers (VIII). During the reaction (I) is separated by distillation and (II) is supplied to the reaction mixture in an amount corresponding to the amount of (I) removed. Az = F, Cl, Br, NO2, CN, CF3, CCl3, CHO, COQ, COX' or SO2X'; Q = 1-10C alkyl; X' = F, Cl or Br; x = 1-3; Ar = phenyl, pyridyl or naphthyl; w = 1 to y; y = 1-5; R = H, Q or OQ; z = 1-5; (x + y + z) = total number of positions which can be substituted on Ar; R1-R3 = as R4, 1-30C alkyl or Ar'; R4 = -(CmH2mO)p-R5; R5 = H or 1-16C alkyl; m = 1-10; p = 1-15; Ar' = phenyl or naphthyl (both optionally substituted by halo, 1-4C alkyl, 1-4C alkoxy, NO2 or CN); X<-> = monovalent acid residue or 1 equivalent of a polyvalent acid residue; A = 1-12C alkyl, 2-12C alkenyl, 4-8C cycloalkyl, 6-12C aryl or 7-12C aralkyl; or N(A)2 = 3-7 membered ring, optionally interrupted by O or NA'; A' = 1-4C alkyl; R6-R9 = 1-22C alkyl, Ar' or Ar'-(1-4C) alkyl; R11,R12 = 1-16C alkyl; a = 2-6; b = 0-20.
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