Process for the preparation of intermediates

A process for the preparation of a compound of formula I

• wherein
• R0 is, each independently of any other, halogen, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C1-C6haloalkyl, cyano-C1-C6alkyl, C2-C6haloalkenyl, cyano-C2-C6alkenyl, C2-C6haloalkynyl, cyano-C2-C6alkynyl, hydroxy, hydroxy-C1-C6alkyl, C1-C6alkoxy, nitro, amino, C1-C6alkylamino, di(C1-C6alkyl)amino, C1-C6alkylcarbonylamino, C1-C6alkylsulfonylamino, C1-C6alkylaminosulfonyl, C1-C6alkylcarbonyl, C1-C6alkylcarbonyl-C1-C6alkyl, C1-C6alkoxycarbonyl-C1-C6alkyl, C1-C6alkylcarbonyl-C2-C6alkenyl, C1-C6alkoxycarbonyl, C1-C6alkoxycarbonyl-C2-C6alkenyl, C1-C6alkylcarbonyl-C2-C6alkynyl, C1-C6alkoxycarbonyl-C2-C6alkynyl, cyano, carboxyl, phenyl or an aromatic ring that contains 1 or 2 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the latter two aromatic rings may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro;
• or
• R0, together with the adjacent substituents R1, R2 and R3, forms a saturated or unsaturated C3-C6hydrocarbon bridge that may be interrupted by 1 or 2 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur and/or substituted by C1-C4alkyl;
• R1, R2 and R3 are, each independently of the others, hydrogen, halogen, C1-C6alkyl, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, C1-C6haloalkyl, C2-C6haloalkenyl, C1-C6alkoxy-carbonyl-C2-C6alkenyl, C1-C6alkylcarbonyl-C2-C6alkenyl, cyano-C2-C6alkenyl, nitro-C2-C6alkenyl, C2-C6haloalkynyl, C1-C6alkoxycarbonyl-C2-C6alkynyl, C1-C6alkylcarbonyl-C2-C6alkynyl, cyano-C2-C6alkynyl, nitro-C2-C6alkynyl, C3-C6halocycloalkyl, hydroxy-C1-C6alkyl, C1-C6alkoxy-C1-C6alkyl, C1-C6alkylthio-C1-C6alkyl, cyano, C1-C4alkylcarbonyl, C1-C6alkoxycarbonyl, hydroxy, C1-C10alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6haloalkoxy, C3-C6haloalkenyloxy, C1-C6alkoxy-C1-C6alkoxy, mercapto, C1-C6alkylthio, C1-C6haloalkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, nitro, amino, C1-C6alkylamino, di(C1-C6alkyl)amino or phenoxy in which the phenyl ring may be substituted by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro;
• R2 also may be phenyl, naphthyl or a 5- or 6-membered aromatic ring that may contain 1 or 2 hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur, wherein the phenyl ring, the naphthyl ring system and the 5- or 6-membered aromatic ring may be substituted by halogen, C3-C8cycloalkyl, hydroxy, mercapto, amino, cyano, nitro or by formyl;
• and/or
• the phenyl ring, the naphthyl ring system and the 5- or 6-membered aromatic ring may be substituted by C1-C6alkyl, C1-C6alkoxy, hydroxy-C1-C6alkyl, C1-C6alkoxy-C1-C6alkyl, C1-C6alkoxy-C1-C6alkoxy, C1-C6alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, mono-C1-C6alkylamino, di(C1-C6alkyl)amino, C1-C6alkylcarbonylamino, C1-C6alkylcarbonyl-(C1-C6alkyl)amino, C2-C6alkenyl, C3-C6alkenyloxy, hydroxy-C3-C6alkenyl, C1-C6alkoxy-C2-C6alkenyl, C1-C6alkoxy-C3-C6alkenyloxy, C2-C6alkenylcarbonyl, C2-C6alkenylthio, C2-C6alkenyl-sulfinyl, C2-C6alkenylsulfonyl, mono- or di-(C2-C6alkenyl)amino, C1-C6alkyl(C3-C6alkenyl)-amino, C2-C6alkenylcarbonylamino, C2-C6alkenylcarbonyl(C1-C6alkyl)amino, C2-C6alkynyl, C3-C6alkynyloxy, hydroxy-C3-C6alkynyl, C1-C6alkoxy-C3-C6alkynyl, C1-C6alkoxy-C4-C6alkynyloxy, C2-C6alkynylcarbonyl, C2-C6alkynylthio, C2-C6alkynylsulfinyl, C2-C6alkynylsulfonyl, mono- or di-(C3-C6alkynyl)amino, C1-C6alkyl(C3-C6alkynyl)amino, C2-C6alkynylcarbonylamino or by C2-C6alkynylcarbonyl(C1-C6alkyl)amino;
• and/or
• the phenyl ring, the naphthyl ring system and the 5- or 6-membered aromatic ring may be substituted by halo-substituted C1-C6alkyl, C1-C6alkoxy, hydroxy-C1-C6alkyl, C1-C6alkoxy-C1-C6alkyl, C1-C6alkoxy-C1-C6alkoxy, C1-C6alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, mono-C1-C6alkylamino, di(C1-C6alkyl)amino, C1-C6alkylcarbonylamino, C1-C6alkylcarbonyl(C1-C6alkyl)amino, C2-C6alkenyl, C3-C6alkenyloxy, hydroxy-C3-C6alkenyl, C1-C6alkoxy-C2-C6alkenyl, C1-C6alkoxy-C3-C6alkenyloxy, C2-C6alkenylcarbonyl, C2-C6alkenylthio, C2-C6alkenylsulfinyl, C2-C6alkenylsulfonyl, mono- or di-(C2-C6alkenyl)amino, C1-C6-alkyl(C3-C6alkenyl)amino, C2-C6alkenylcarbonylamino, C2-C6alkenylcarbonyl(C1-C6alkyl)amino, C2-C6alkynyl, C3-C6alkynyloxy, hydroxy-C3-C6alkynyl, C1-C6alkoxy-C3-C6alkynyl, C1-C6alkoxy-C4-C6alkynyloxy, C2-C6alkynylcarbonyl, C2-C6alkynylthio, C2-C6alkynylsulfinyl, C2-C6alkynylsulfonyl, mono- or di-(C3-C6alkynyl)amino, C1-C6alkyl(C3-C6alkynyl)amino, C2-C6alkynylcarbonylamino or C2-C6alkynylcarbonyl(C1-C6alkyl)amino;
• and/or
• the phenyl ring, the naphthyl ring system and the 5- or 6-membered aromatic ring may be substituted by a radical of formula COOR50, CONR51, SO2NR53R54 or SO2OR55, wherein R50, R51, R52, R53, R54 and R55 are, each independently of the others, C1-C6alkyl, C2-C6alkenyl or C3-C6alkynyl or halo-, hydroxy-, alkoxy-, mercapto-, amino-, cyano-, nitro-, alkylthio-, alkylsulfinyl- or alkylsulfonyl-substituted C1-C6alkyl, C2-C6alkenyl or C3-C6alkynyl;
• X is halogen;
• and
• n is 0, 1 or 2;
• which comprises
• (a) reacting a compound of formula (II)
• with gaseous or aqueous HX in an organic solvent, wherein X is as defined above for formula (I);
• (b) removing water by azeotropic distillation in case that aqueous HX is used;
• and
• (c) adding an organic nitrite, wherein the process takes place in the absence of copper.