| 摘要 |
#CMT# #/CMT# Preparation of alkyl- or arylether compound (III) comprises reaction of a phenyl-halogen compound (II) with an alcoholate compound or an alcohol compound and a base in presence of a copper-containing catalyst and a ligand. #CMT# : #/CMT# Preparation of alkyl- or arylether compound of formula (III) comprises reaction of a phenyl-halogen compound of formula (II) with an alcoholate compound of formula (R1-O ->) or an alcohol compound of formula (R1-OH) and a base in presence of a copper-containing catalyst and a ligand. R1 : methyl, primary, secondary or tertiary, cyclic or acyclic 1-12C alkylradical, substituted cyclic or acyclic 1-12C alkylradical or a phenyl- or heteroaryl radical (both substituted), when R6 and X1-X5 are hal; either R2-R5 : H, methyl, primary, secondary or tertiary cyclic or acyclic alkyl radical, in which optionally one or more hydrogen atoms are substituted by F or Cl, substituted cyclic or acyclic alkyl radical, alkoxy-, dialkylamino-, alkyl-amino-arylamino-, diarylamino-, phenyl-, substituted phenyl-, heteroaryl-, substituted heteroaryl-, alkylthio-, arylthio-, diarylphosphino-, dialkylphosphino-, dlkylarylphosphino-, dialkyl-, arylalkyl- or diarylaminocarbonyl-, monoalkyl- or monoarylaminocarbonyl-, CO 2 ->, alkyl- or aryloxycarbonyl-, hydroxyalkyl-, alkoxyalkyl-, nitro- or cyano residue; or two adjacent residues of R2-R5 : an aromatic, heteroaromatic or aliphatic condensation ring; Hal : Cl, Br, I, alkylsulfonate or arylsulfonate; and X1-X5 : carbon or nitrogen, or two adjacent residues XiRi = a double bond, O, S, NRH or connected over a double bond, where i is 1-6, O, S, NRH or NRi. #CMT#[Image]#/CMT# #CMT#USE : #/CMT# (III) is useful in pharmaceutical and agrochemical industries. #CMT#ADVANTAGE : #/CMT# The product obtained from the process exhibits high purity. The process provides (III) in high yield, preferably 85-99%. The process exhibits high space-time yield. The ligand and the copper compounds are separated without the interference of the respective coupling products. The process prevents the contamination of the coupling product. #CMT#INORGANIC CHEMISTRY : #/CMT# Preferred Components: The oxidation state of the copper catalyst is 0, +1 or +2. The catalyst is copper(I) chloride, copper(I) bromide, copper(I) iodide, copper(I) oxide, copper(II) acetylacetonate, copper(II) bromide, copper(II) iodide or copper powder. The amount of copper catalyst is 20-0.01 mol.%. #CMT#ORGANIC CHEMISTRY : #/CMT# Preferred Components: The ligand is acyclic and/or cyclic oligo- and polyglycol, oligo- and polyamine or oligo- and polyaminoglycol of formula (R7-[X-[-C(R) 2-] k] n-Y1R8); hexadecyloxypropanol, octadecyloxyethanol, hexadecyl-oxypropylmethylether, octadecyloxyethyl-methylether, polyethyleneglycol 200, polyethyleneglycol 300, polyethyleneglycol 600, polyethyleneglycol 1000, polyethyleneglycol 20000, polyethyleneglycol 35000, polyethyleneglycoldimethylether 250, polyethyleneglycoldimethylether 500, polyethyleneglycoldimethylether 2000, 1,4,10-trioxa-7,13-diazacyclopentadecane, 2-(2-aminoethoxy)ethanol, tetraethylene pentamine or crown ether. The amount of ligand is 40-0.02 mol. (II) is benzol, pyridine, pyrimidine, pyrazine, pyridazine, furane, thiophene or optionally substituted pyrrole or naphthalene. Either R7, R8 : H, methyl, primary, secondary or tertiary, cyclic or acyclic alkyl radical, in which optionally one or more hydrogen atoms are substituted by F or Cl, or substituted cyclic or acyclic alkyl radical; or R7Y1R8 : a ring form; X, Y1 : O, NH or NRi; either R : H, methyl, primary, secondary or tertiary, cyclic or acyclic alkyl radical, in which optionally one or more hydrogen atoms are substituted by F or Cl, or substituted cyclic or acyclic alkyl radical; or R[CR 2]-unit : a double bond, an alkenyl radical or a part of an aromatic ring; k : greater than 0; and n : greater than 1. Preferred Process: The process is carried out in the presence of a solvent such as tetrahydrofuran, dioxane, diethylether, di-n-butylether, diisopropylether, methanol, ethanol, 2-propanol or n-butanol. The process is carried out at 25-200[deg]C. #CMT#EXAMPLE : #/CMT# 2-Bromo-3-(trifluoromethyl)pyridine (45 g) was reacted with a mixture of copper(I) bromide (574 mg), polyethylene glycoldimethyl-ether 250 (2 g) and sodiumethanolate solution (136 g) in 20% ethanol and heated to 100[deg]C. The reaction mixture was worked up to give 2-ethoxy-3-(trifluoromethyl)pyridine (greater than 99%). |
