METHOD FOR PRODUCING A CROSS-COUPLING PRODUCT OF A BENZENOID DIAZONIUM SALT

摘要

The invention relates to a method for producing a cross-coupling product of a benzenoid dizonium salt according to the general formula (I), wherein the groups R₁, R₂, R₃, R₄, and R₅ represent hydrogen, halogen, an alkyl, alkenyl, aryl, alkoxy, aryloxy, nitro, cyano, hydroxy, acetyl, and/or diazo groups independently of each, and X represents BF₄, Cl, F, SO₃CH₃, CO₂CH₃, PF₆, ClO₂CH₃, or CIO₄, comprising the following steps: (a) providing a benzenoid amide, which with the exception of the diazo function has the same substituents R₁, R₂, R₃, R₄, and R₅ as the benzenoid diazonium salt of the general formula (I), and hydrolytically cleaving the amide to form an amine or providing a corresponding amine, (b) diazotizing the amine thus obtained or provided with a nitrite, and (c) subsequently reacting the benzenoid diazonium salt with a coupling partner in the presence of a catalyst to form a cross-coupling product, wherein the coupling parter is represented by the general formula (II), R₆, R₇, and R₈ are the same or different and represent hydrogen, carboxyalkyl groups, carboxyaryl groups, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, wherein the groups can each contain Si, N, S, O, and or halogen atoms, or R₆ and R₇ with the double bound form an aromatic ring, which can be provided with R₈ and one to four further substituents, independently of each other, selected from the group comprising a straight-chain or branched (C₁-C₆) alkyl group, a (C₃-C₇) cycloalkyl group, a straight-chain or branched (C₁-C₆) alkenyl group, a straight-chain or branched (C₁-C₆) alkyoxy group, halogen, the hydroxy group, an amino, di(C₁-C₆) alkylamino, nitro, acetyl, cyan, benzyl, 4-methoxybenzyl, 4-nitrobenzyl, phenyl, and 4-methoxyphenyl group and represents Y=H, —B(OR)₂, —SnR₃, —ZnR, —SiR₃, or Mg (halogen), and wherein at least the steps (b) and (c) are performed without intermediate isolation of an intermediate product. According to said method, cross-couplings can be performed more simply and with improved yield without the hydroxyl group in aromatic reactants containing hydroxyl groups having to be provided with a protective group.;