Triazolopyrimidine derivatives

Abstract: This invention relates to certain triazolopyrimidine derivatives of the general formula in which R 3 represents an optionally substituted aryl group and Hal represents a chlorine or bromine atom, and processes for their preparation.

Description: This invention relates to certain triazolopyrimidine derivatives, and a process for their preparation. According to the invention there is therefore provided a compound of the general formula in which R 3 represents an optionally substituted phenyl or naphthyl group, wherein optional substituents are selected from halogen atoms, nitro, cyano, thiocyanato, cyanato, hydroxyl, C 1-12 alkyl, C 1-12 haloalkyl, C 1-12 alkoxy, C 1-12 haloalkoxy, amino, C 1-12 alkylamino, di-C 1-12 alkylamino, formyl, C 1-12 alkoxycarbonyl, carboxyl, C 1-12 alkanoyl, C 1-12 alkylthio, C 1-12 alkylsulphinyl, C 1-12 alkylsulphonyl, carbamoyl, C 1-12 alkylamido and 3- to 6-membered heterocyclyl groups and optionally substituted phenyl, phenoxy, benzyl, benzyloxy and C 3-8 cycloalkyl groups each optionally substituted by one or more halogen atoms, nitro, cyano, C 1-12 alkyl, C 1-12 haloalkyl, C 1-12 alkoxy or C 1-12 haloalkoxy groups; and Hal represents a chlorine or bromine atom. It is preferred that R 3 represents a phenyl or naphthyl group, each group being optionally substituted by one or more substituents selected from halogen atoms, nitro, cyano, hydroxyl, C 1-12 alkyl, C 1-12 haloalkyl, C 1-12 alkoxy, C 1-12 haloalkoxy, amino, C 1-4 alkylamino, di-C 1-4 alkylamino, formyl, C 1-4 alkoxycarbonyl, carboxyl, phenyl, phenoxy and benzyloxy groups. More preferably, R 3 represents a phenyl group optionally substituted by up to three substituents selected from halogen atoms, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, C 1-4 haloalkoxy, phenyl, phenoxy and benzyloxy groups, or a naphthyl group. A particularly preferred sub-group of compounds of formula II is that in which R 3 represents a phenyl, fluorophenyl, chlorophenyl, bromophenyl, chloro-fluorophenyl, methylphenyl, propylphenyl, trifluoromethylphenyl, methoxyphenyl, ethoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, trifluoromethoxyphenyl, biphenylyl, phenoxyphenyl, benzyloxyphenyl or naphthyl group, It is especially preferred that the compound of formula II is selected from 5,7-dichloro-6-(4-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dibromo-6-phenyl-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-methoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(2-methoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(3-methoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-ethoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-phenyl-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(3-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(3-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]-pyrimidine, 5,7-dichloro-6-(4-isopropylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-trifluoromethoxyphenyl)-1,2,4-triazolo[1,5-a]-pyrimidine, 5,7-dichloro-6-naphth-2-yl-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(3,4-dimethoxyphenyl)-1,2,4-triazolo[1,5-a]-pyrimidine, 5,7-dichloro-6-(2-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-biphenylyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(2-bromophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(2-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-phenoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-benzyloxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-bromophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(3-bromophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(3-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(2-benzyloxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(2,3-dimethoxyphenyl)-1,2,4-triazolo[1,5-a]-pyrimidine, 5,7-dichloro-6-(3,4,5-trimethoxyphenyl)-1,2,4-triazolo[1,5-a]-pyrimidine, and 5,7-dichloro-6-(2-chloro-6-fluorophenyl)-1,2,4-triazolo[1,5-a]-pyrimidine, The present invention also provides a process for the preparation of a compound of formula II as defined above which comprises reacting a compound of the general formula in which R 3 is as defined above, with a chlorinating or brominating agent, such as phosphorus oxychloride or phosphorus oxybromide. Compounds of formula V can be prepared by reacting 3-amino-1,2,4-triazole with an appropriate malonic acid ester under alkaline conditions according to the method of Y. Makisumi, Chem. Pharm. Bull., 9 , 801, (1961). The compounds of formula II are useful as intermediates in the preparation of certain fungicidal triazolopyrimidine derivatives which form the subject of EP-B-0 550 113 from which the present application is divided.

Claims: A compound of the general formula II in which R 3 represents an optionally substituted phenyl or naphthyl group, wherein optional substituents are selected from halogen atoms, nitro, cyano, thiocyanato, cyanato, hydroxyl, C 1-12 alkyl, C 1-12 haloalkyl, C 1-12 alkoxy, C 1-12 haloalkoxy, amino, C 1-12 alkylamino, di-C 1-12 alkylamino, formyl, C 1-12 alkoxycarbonyl, carboxyl, C 1-12 alkanoyl, C 1-12 alkylthio, C 1-12 alkylsulphinyl, C 1-12 alkylsulphonyl, carbamoyl, C 1-12 alkylamido and 3- to 6-membered heterocyclyl groups and optionally substituted phenyl, phenoxy, benzyl, benzyloxy and C 3-8 cycloalkyl groups each optionally substituted by one or more halogen atoms, nitro, cyano, C 1-12 alkyl, C 1-12 haloalkyl, C 1-12 alkoxy or C 1-12 haloalkoxy groups; and Hal represents a chlorine or bromine atom. A compound according to Claim 1 in which R 3 represents a phenyl or naphthyl group, each group being optionally substituted by one or more substituents selected from halogen atoms, nitro, cyano, hydroxyl, C 1-12 alkyl, C 1-12 haloalkyl, C 1-12 alkoxy, C 1-12 haloalkoxy, amino, C 1-4 alkylamino, di-C 1-4 alkylamino, formyl, C 1-4 alkoxycarbonyl, carboxyl, phenyl, phenoxy, benzyl and benzyloxy groups. A compound according to Claim 1 or Claim 2 in which R 3 represents a phenyl group optionally substituted by up to three substituents selected from halogen atoms, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, C 1-4 haloalkoxy, phenyl, phenoxy and benzyloxy groups, or a naphthyl group. A compound according to any one of Claims 1 to 3 in which R 3 represents a phenyl, fluorophenyl, chlorophenyl, bromophenyl, chlorofluorophenyl, methylphenyl, propylphenyl, trifluoromethylphenyl, methoxyphenyl, ethoxyphenyl, dimethoxyphenyl, trimethoxyphenyl, trifluoromethoxyphenyl, biphenylyl, phenoxyphenyl, benzyloxyphenyl or naphthyl group. A compound according to any one of the preceding claims selected from 5,7-dichloro-6-(4-methylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dibromo-6-phenyl-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-methoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(2-methoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(3-methoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-ethoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-phenyl-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(3-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(3-trifluoromethylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-isopropylphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-trifluoromethoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-naphth-2-yl-1,2,4-triazolo[1,5-a]-pyrimidine, 5,7-dichloro-6-(3,4-dimethoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(2-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-biphenylyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(2-bromophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(2-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-phenoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-benzyloxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(4-bromophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(3-bromophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(3-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(2-benzyloxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(2,3-dimethoxyphenyl)-1,2,4-triazolo[1,5-a]pyrimidine, 5,7-dichloro-6-(3,4,5-trimethoxyphenyl)-1,2,4-triazolo [1,5-a] pyrimidine, and 5,7-dichloro-6-(2-chloro-6-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine, A process for the preparation of a compound of formula II as defined in any one of the preceding claims which comprises reacting a compound of the general formula V in which R 3 is as defined in any one of the preceding claims, with a chlorinating or brominating agent. A process according to claim 6 in which the chlorinating or brominating agent is phosphorus oxychloride or phosphorus oxybromide.

Inventors: ALBERT GUIDO, PEES KLAUS-JURGEN, ALBERT, GUIDO, PEES, KLAUS-JURGEN
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH
Application year: 1992
Main classification: C07D487
IPC codes: A01N43, C07D487, A01P3