PROCESS FOR THE PREPARATION OF UNSYMMETRICAL 4,6-BIS (ARYLOXY) PYRIMIDINE COMPOUNDS AND NOVEL INTERMEDIATES THEREOF

摘要

Process for the preparation of an unsymmetrical 4,6-bis (aryloxy) pyrimidine compound of the formula wherein R and R8 are each independently hydrogen or halogen; R1 and R7 are each independently hydrogen, halogen, cyano, nitro, alkyl, haloalkyl, alkoxy, alkylthio, amino, alkylamino, dialkylamino, alkoxyalkyl, haloalkoxyalkyl or alkoxycarbonyl; R2 and R6 are each independently hydrogen, halogen, alkyl, haloalkyl, haloalkoxy, haloalkylthio, haloalkenyl, haloalkynyl, haloalkoxyalkyl, alkoxycarbonyl, haloalkoxycarbonyl, haloalkylsulfinyl, haloalkylsulfonyl, nitro or cyano; R3 and R5 are each independently hydrogen, halogen, alkyl or alkoxy; and R4 is hydrogen, cyano, alkyl, haloalkyl, alkoxy, alkylthio, alkylsulfinyl or phenyl; provided that at least one of R2 and R6 is other than hydrogen, and that the aryloxy groups are not the same; which comprises reacting a 4,6-dihalopyrimidine compound of the formula 892 ל' באב התש" ס - August 31, 2000 wherein R4 is as described above and X is Cl, Br or I with one molar equivalent or less of a first phenol compound of the formula and a first base in the presence of a first solvent to form a 4-halo-6- (aryloxy) pyrimidine compound of the formula reacting the 4-halo-6- (aryloxy) pyrimidine compound with at least about one molar equivalent of a C1-C4 trialkylamine, a 5- to 6-membered saturated or 5- to 14-membered unsaturated heterocyclic amine optionally substituted with one to three C1-C4 alkyl groups or C1-C4 alkoxy groups in the presence of a second solvent to form an ammonium halide compound of the formula 893 ל' באב התש" ס - August 31, 2000 wherein Q+ is R9, R10 and R11 are each independently C1-C4 alkyl, and when taken together, R9 and R10 may form a 5- or 6-membered ring in which R9R10 is represented by the stucture: -(CH2)n-, optionally interrupted by O, S or NR14, where n is an integer of 3, 4 or 5, provided R11 is C1-C4 alkyl; Z is O, S or NR14, R12 and R13 are each independently hydrogen, C1-C4 alkyl or C1-C4 alkoxy, and when taken together, R12 and R13 may form a 5- or 6-membered staturated or unsaturated ring optionally interrupted by O, S or NR14 and optionally substituted with one to three C1-C4 alkyl groups or C1-C4 alkoxy groups; and R14 is C1-C4 alkyl; and reacting the ammonium halide compound with at least about one molar equivalent of a second phenol compound of the formula 894 ל' באב התש" ס - August 31, 2000 Claimed as novel are the intermediates of the formula V.