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US 5,849,910 AGranted
Process for the preparation of unsymmetrical 4,6-bis aryloxy-pyrimidine compounds
AssigneeAmerican Cyanamid Company
InventorVenkataraman Kameswaran
Life of this patent
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Abstract
This invention provides an improved process for the preparation of unsymmetrical 4,6-bis(aryloxy)pyrimidine compounds having the structural formula I ##STR1## The unsymmetrical 4,6-bis(aryloxy)pyrimidine compounds are useful as pesticidal agents.
Claims24
In a process for the preparation of an unsymmetrical 4,6-bis(aryloxy)pyrimidine compound having the structural formula I ##STR22## 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, haloalkyl, alkoxy, alkylthio, amino, alkylamino, dialkylamino, alkoxyalkyl, haloalkoxyalkyl or alkoxycarbonyl;
- R.sub.2 and R.sub.6 are each independently hydrogen, halogen, alkyl, haloalkyl, haloalkoxy, haloalkylthio, 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, haloalkyl, 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;
- the improvement comprises reacting a 4-halo-6-(aryloxy)pyrimidine compound having the structural formula II ##STR23## wherein R, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as described above and X is Cl, Br or I 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 solvent selected from the group consisting of an aromatic hydrocarbon and a halogenated aromatic hydrocarbon and mixtures thereof to form an ammonium halide compound having the structural formula III ##STR24## wherein R, R.sub.1, R.sub.2, R.sub.3, R.sub.4 and X are as described above,
- Q.sup.+ is ##STR25## 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 in situ with at least about one molar equivalent of a phenol compound having the structural formula IV ##STR26## wherein R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are as described above and a base.
12 more elements
In a process for the preparation of an unsymmetrical 4,6-bis(aryloxy)pyrimidine compound having the structural formula I ##STR29## 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, haloalkyl, alkoxy, alkylthio, amino, alkylamino, dialkylamino, alkoxyalkyl, haloalkoxyalkyl or alkoxycarbonyl;
- R.sub.2 and R.sub.6 are each independently hydrogen, halogen, alkyl, haloalkyl, haloalkoxy, haloalkylthio, 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, haloalkyl, 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;
- the improvement comprises reacting a 4,6-dihalopyrimidine compound having the structural formula V ##STR30## wherein R.sub.4 is as described above and X is Cl, Br or I with up to one molar equivalent of a first phenol compound having the structural formula VI ##STR31## 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 II ##STR32## 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 selected from the group consisting of an aromatic hydrocarbon and a halogenated aromatic hydrocarbon and mixtures thereof to form an ammonium halide compound having the structural formula III ##STR33## wherein R, R.sub.1, R.sub.2, R.sub.3, R.sub.4 and X are as described above,
- Q.sup.+ is ##STR34## 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 in situ with at least about one molar equivalent of a second phenol compound having the structural formula IV ##STR35## wherein R.sub.5, R.sub.6, R.sub.7 and R.sub.8 are as described above and a second base.
12 more elements
Dependencies are inferred from the claim text.