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1. (WO2010122105) METHOD FOR PRODUCING A CROSS-COUPLING PRODUCT OF A BENZENOID DIAZONIUM SALT

Pub. No.:    WO/2010/122105    International Application No.:    PCT/EP2010/055347
Publication Date: Fri Oct 29 01:59:59 CEST 2010 International Filing Date: Fri Apr 23 01:59:59 CEST 2010
IPC: C07C 245/20
C07C 37/14
C07C 39/15
C07C 39/19
Applicants: ZYLUM BETEILIGUNGSGESELLSCHAFT MBH & CO. PATENTE II KG
BOEGE, Nicolas
KREIPL, Andreas
SCHMIDT, Bernd
HOELTER, Frank
BERGER, René
Inventors: BOEGE, Nicolas
KREIPL, Andreas
SCHMIDT, Bernd
HOELTER, Frank
BERGER, René
Title: METHOD FOR PRODUCING A CROSS-COUPLING PRODUCT OF A BENZENOID DIAZONIUM SALT
Abstract:
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.