Process for preparation of fungicidally active triazole compounds

A process for preparation of 1,2,4-triazole fungicides of general formula (I), their salts, esters or isomers or tautomers thereof,

• wherein R1, R2, and R3 are independently hydrogen, nitrile, nitro, amino, halogen, hydroxyl, alkanoyl, linear or branched (C1-C10) alkyl, haloalkyl, haloalkoxy, cycloalkyl unsubstituted or substituted with halogen or linear or branched alkyl, aryl unsubstituted or substituted with halogen, heteroaryl unsubstituted or substituted with halogen, heterocyclic unsubstituted or substituted with halogen or linear or branched (C1-C10) alkyl, arylalkyl unsubstituted or substituted with halogen, substituted or unsubstituted biaryl, aryloxy unsubstituted or substituted with halogen, aryloxyaryl unsubstituted or substituted with halogen, alkylsilyl, —C(R5 R6 R7) where R5, R6, R7 can be independently selected from hydrogen, nitrile, nitro, amino, halogen, hydroxyl, alkanoyl, linear or branched (C1-C10) alkyl, haloalkyl, haloalkoxy, cycloalkyl unsubstituted or substituted with halogen or linear or branched alkyl, aryl unsubstituted or substituted with halogen, heteroaryl unsubstituted or substituted with halogen, heterocyclic unsubstituted or substituted with halogen or linear or branched (C1-C10) alkyl, arylalkyl unsubstituted or substituted with halogen, substituted or unsubstituted biaryl, aryloxy unsubstituted or substituted with halogen, aryloxyaryl unsubstituted or substituted with halogen, alkylsilyl;
• and R4 is an —SH group or hydrogen;
• said process consisting essentially of reacting a compound of formula (II)
• wherein X is halogen, methylsulphonyloxy, or methylphenylsulphonyloxy, or wherein X and R2 are bonded to a heteroatom to form a heterocyclic ring;
• with a compound of formula (III)
• wherein A is hydrogen, a metal or a trialkylsilyl group and R4 is an —SH group or a hydrogen tautomer thereof;
• in the presence of a homologous cage amine catalyst, wherein said homologous cage amine catalyst is selected from 1,4-diazabicyclo[2.2.2]octane, 1-azabicyclo[2.2.2]octane, azabicyclo(5.2.2)undecanes, azabicyclo(3.3.1)nonanes, azabicyclo(4.3.0)nonanes, azabicyclo(1.1.0)butanes, azabicyclo(2.2.2)octanes and N-methyl-8-azabicyclo[3.2.1]octane, 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,3,6,8-tetraazatricyclo[4.3.1.13,8] undecane, optionally further reacting the product of the reaction of the compound of formula (II) and the compound of formula (III) with sulphur.