Claims
- 1. A process for the preparation of an unsymmetrical 4,6-bis(aryloxy)pyrimidine compound having the structural formula ##STR24## wherein R and R.sub.8 are each independently hydrogen or halogen;
- R.sub.1 and R.sub.7 are each independently hydrogen, halogen, cyano, nitro, alkyl, trifluoromethyl, pentafluoroethyl, alkoxy, alkylthio, amino, alkylamino, dialkylamino, alkoxyalkyl, haloalkoxyalkyl or alkoxycarbonyl;
- R.sub.2 and R.sub.3 are each independently hydrogen, halogen, alkyl, trifluoromethyl, pentafluoroethyl, haloalkoxy, haloalkenyl, haloalkynyl, haloalkoxyalkyl, alkoxycarbonyl, haloalkoxycarbonyl, haloalkylsulfinyl, haloalkylsulfonyl, nitro or cyano;
- R.sub.3 and R.sub.5 are each independently hydrogen, halogen, alkyl or alkoxy; and
- R.sub.4 is hydrogen, cyano, alkyl, alkoxy, alkylthio, alkylsulfinyl or phenyl;
- provided that at least one of R.sub.2 and R.sub.6 is other than hydrogen, and that the aryloxy groups are not the same; which comprises reacting a 4,6-dihalopyrimidine compound having the structural formula ##STR25## wherein R.sub.4 is as described above and X is Cl, Br or I with one molar equivalent or less of a first phenol compound having the structural formula ##STR26## wherein R, R.sub.1, R.sub.2 and R.sub.3 are as described above and a first base in the presence of a first solvent to form a 4-halo-6-(aryloxy)pyrimidine compound having the structural formula ##STR27## wherein R, R.sub.1, R.sub.2, R.sub.3, R.sub.4 and X are as described above, reacting the 4-halo-6-(aryloxy)pyrimidine compound with at least about one molar equivalent of a C.sub.1 -C.sub.4 trialkylamine, a 5- to 6-membered saturated or 5- to 14-membered unsaturated heterocyclic amine optionally substituted with one to three C.sub.1 -C.sub.4 alkyl groups or C.sub.1 -C.sub.4 alkoxy groups in the presence of a second solvent to form an ammonium halide compound having the structural formula ##STR28## wherein R, R.sub.1, R.sub.2, R.sub.3, R.sub.4 and X are as described above, Q.sup.+ is ##STR29## R.sub.9, R.sub.10 and R.sub.11 are each independently C.sub.1 -C.sub.4 alkyl, and when taken together, R.sub.9 and R.sub.10 may form a 5- or 6-membered ring in which R.sub.9 R.sub.10 is represented by the structure: --(CH.sub.2).sub.n --, optionally interrupted by O, S or NR.sub.14, where n is an integer of 3, 4 or 5, provided R.sub.11 is C.sub.1 -C.sub.4 alkyl;
- Z is O, S or NR.sub.14,
- R.sub.12 and R.sub.13 are each independently hydrogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy, and when taken together, R.sub.12 and R.sub.13 may form a 5- or 6-membered saturated or unsaturated ring optionally interrupted by O, S or NR.sub.14 and optionally substituted with one to three C.sub.1 -C.sub.4 alkyl groups or C.sub.1 -C.sub.4 alkoxy groups; and
- R.sub.14 is C.sub.1 -C.sub.4 alkyl; and
- reacting the ammonium halide compound with at least about one molar equivalent of a second phenol compound having the structural formula ##STR30## wherein R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are as described above and a second base in the presence of a third solvent.
- 2. The process according to claim 1 wherein the first and second bases are selected from the group consisting of an alkali metal carbonate, an alkaline earth metal carbonate, an alkali metal hydride, an alkali metal hydroxide and an alkaline earth metal hydroxide.
- 3. The process according to claim 2 wherein the first and second bases are an alkali metal carbonate.
- 4. The process according to claim 1 wherein the first solvent is selected from the group consisting of an ether, a carboxylic acid amide, a halogenated hydrocarbon, a sulfoxide and a ketone; the second solvent is selected from the group consisting of an aromatic hydrocarbon and a chlorinated aromatic hydrocarbon; and the third solvent is selected from the group consisting of a carboxylic acid amide and a sulfoxide.
- 5. The process according to claim 4 wherein the first solvent is selected from the group consisting of a carboxylic acid amide and a ketone, the second solvent is an aromatic hydrocarbon, and the third solvent is a carboxylic acid amide.
- 6. The process according to claim 1 wherein X is Cl.
- 7. The process according to claim 1 wherein Q.sup.+ is ##STR31##
- 8. The process according to claim 7 wherein Q.sup.+ is (CH.sub.3).sub.3 N.sup.+ --.
- 9. The process according to claim 1 wherein the 4,6-dihalopyrimidine compound is reacted with the first phenol compound and the first base at a temperature of about 0.degree. C. to 100.degree. C., the 4-halo-6-(aryloxy)pyrimidine compound is reacted with the amine at a temperature of about 0.degree. C. to 100.degree. C., and the ammonium halide compound is reacted with the second phenol compound and the second base at a temperature of about 0.degree. C. to 100.degree. C.
- 10. The process according to claim 1 wherein R and R.sub.8 are the same and each represents hydrogen or fluorine;
- R.sub.1 and R.sub.7 are each independently hydrogen, halogen, cyano, nitro or C.sub.1 -C.sub.4 alkyl;
- R.sub.2 and R.sub.6 are each independently hydrogen, fluorine, chlorine, C.sub.1 -C.sub.4 alkyl, trifluoromethyl, pentafluoroethyl, C.sub.1 -C.sub.4 haloalkoxy, C.sub.2 -C.sub.4 haloalkenyl, C.sub.1 -C.sub.4 alkoxycarbonyl or nitro;
- R.sub.3 and R.sub.5 are each independently hydrogen, halogen or C.sub.1 -C.sub.4 alkyl; and
- R.sub.4 is hydrogen, C.sub.1 -C.sub.4 alkylthio, C.sub.1 -C.sub.4 alkylsulfinyl or phenyl.
- 11. The process according to claim 10 wherein
- R, R.sub.3, R.sub.4, R.sub.5, and R.sub.8 are hydrogen;
- one of R.sub.1 and R.sub.7 is hydrogen, chlorine or cyano and the other is fluorine; and
- R.sub.2 and R.sub.6 are trifluoromethyl.
Parent Case Info
This is a divisional of application Ser. No. 09/076,435 filed on May 12, 1998 which is now a U.S. Pat. No. 5,977,363 which claims benefit of U.S. provisional application No. 60/013,019 filed on Mar. 7, 1996 and the entire disclosure of the application is hereby incorporated by reference.
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Divisions (1)
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Number |
Date |
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Parent |
076435 |
May 1998 |
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