Process for preparing chlorinated biphenylanilides and biphenylanilines

A process for preparing a halogenated biphenylanilide of formula (I)

• in which
• X is selected from the group consisting of hydrogen, fluorine and chlorine;
• R1 is selected from the group consisting of —NH(CO)R3, —N═CR4R5, NO2, NH2 and NHR3;
• R2 is chlorine;
• R3, R4, R5 are each independently selected from the group consisting of hydrogen, —CH2—(C═O)CH3, C1-C8-alkyl, C1-C8-alkenyl, C1-C8-alkynyl and C6-C18-aryl;
• or
• R4, R5, together with the carbon atom to which they are bonded, may form a 5- or 6-membered ring containing 1, 2 or 3 heteroatoms selected from N, O and S;
• n is selected from 1, 2 and 3,
• by reacting a compound of the formula (II)
• in which
• Hal is selected from the group consisting of bromine and iodine;
• and R1 and X are each as defined above, in the presence of a base and a palladium catalyst selected from the group consisting of:
• a) a complex consisting of palladium in the 0 oxidation state and a phosphine ligand of the formula (V) or a salt thereof,
• b) a palladium salt in the presence of a phosphine ligand of the formula (V) or a salt thereof and
• c) metallic palladium, optionally applied to a support, in the presence of a phosphine ligand of the formula (V) or a salt thereof,
• where the phosphine ligand of the formula (V) is defined as follows:
• wherein
• R6 is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 haloalkyl, phenyl, and NR72 and
• R7 is a C1-C4 alkyl,
• or a salt thereof,
• wherein the phosphine ligand of formula (V) is di(tert-butyl)phenylphosphine, di-tert-butyl-p-[4-(trifluoromethyl)phenyl]phosphine, 4-(di-tert-butylphosphino)-p-N,N-dimethylaniline or di-tert-butyl-p-(4-methylphenyl)phosphine, or a salt thereof,
• in a solvent, with an organoboron compound of the formula (III)
• selected from the group consisting of:
• (i) boronic acids of the formula (III) in which
• m is 2,
• p is 1,
• Q1 and Q2 are each hydroxyl groups,
• R2 and n are each as defined above,
• or the anhydrides, dimers or trimers formed from the boronic acids of the formula (III);
• (ii) boronic acid derivatives of the formula (III) in which
• m is 2,
• p is 1,
• Q1 and Q2 are each independently selected from the group consisting of F, Cl, Br, I, C1-4-alkyl-, C6-10-aryl-, C1-4-alkoxy- and C6-10-aryloxy,
• R2 and n are each as defined above;
• (iii) borinic acids of the formula (III) in which
• m is 1,
• p is 2,
• Q is selected from the group consisting of OH, F, Cl, Br, I, C1-4-alkyl, C6-10-aryl, C1-4-alkoxy and C6-10-aryloxy radicals,
• R2 and n are each as defined above;
• (iv) cyclic boronic esters of the formula (III) in which
• m is 2,
• p is 1,
• Q1 and Q2 are each independently a C1-4-alkoxy radical, which,
• R2 and n are each as defined above;
• (v) boronates of the formula (III) in which
• m is 3,
• p is 1,
• R2 and n are each as defined above,
• Q1 to Q3 are each independently selected from the group consisting of OH, F, Cl, Br, I, C1-4-alkyl, C6-10-aryl, C1-4-alkoxy and C6-10-aryloxy radicals,
• and in which the negative charge of the boronate anion is compensated for by a cation;
• (vi) triarylboranes of the formula (III) in which
• m is 0,
• p is 3,
• R2 and n are each as defined above;
• and
• (vii) tetraarylborates of the formula (III) in which
• m is 0,
• p is 4,
• R2 and n are each as defined above,
• and in which the negative charge of the boronate anion is compensated for by a cation.