Imidazole derivatives, their preparation and their use as intermediates for the preparation of pharmaceutical compositions and pesticides

A process for preparing imidazo[4,5-d]pyridazin-4-ones formula (IV)

• characterised in that a compound of formula I
• is reacted with a hydrazine substituted by R4 or a correspondingly protected hydrazine derivative,
• wherein
• R1 denotes a fluorine, chlorine, bromine or iodine atom,
• R2 denotes a C3-8-alkyl group, or a C1-3-alkyl group substituted by a group Ra, while
• Ra denotes:
• a C3-7-cycloalkyl group optionally substituted by one or two C1-3-alkyl groups,
• a C3-8-cycloalkenyl group optionally substituted by one or two C1-3-alkyl groups, an aryl group or a heteroaryl group
• a C3-8-alkenyl group,
• a C3-6-alkenyl group substituted by a fluorine, chlorine or bromine atom or by a trifluoromethyl group,
• a C3-8-alkynyl group,
• an aryl group or
• an aryl-C2-4-alkenyl group,
• X denotes an oxygen or sulphur atom or a nitrogen atom which is substituted by Rb, while
• Rb denotes:
• a hydrogen atom
• a hydroxy, aryloxy, arylmethyloxy, heteroaryloxy, heteroarylmethyloxy or C1-10-alkyloxy group while the hydrogen atoms of the alkyloxy group may be wholly or partly replaced by fluorine atoms,
• a C1-10alkylcarbonyl arylcarbonyl heteroarylcarbonyl C1-10-alkyloxy-carbonyl C1-10-alkylaminocarbonyl di-(C1-10-alkyl)-aminocarbonyl C1-10-alkylsulphonyl, arylsulphonyl, heteroarylsulphonyl, C1-10-alkylsulphinyl arylsulphinyl or heteroarylsulphinyl group, while the hydrogen atoms of the above-mentioned C1-10-alkyl groups may be wholly or partly replaced by fluorine atoms,
• a C1-10-alkyl, C2-10-alkenyl, C2-10-alkynyl, C3-7-cycloalkyl or C5-8-cycloalkenyl group, while the hydrogen atoms in the above-mentioned groups may each be wholly or partly replaced by fluorine atoms and in the above-mentioned groups 1 to 4 methylene groups may each be replaced by an oxygen or sulphur atom, by an —NH— or —N(C1-3-alkyl)- group or by a carbonyl, sulphinyl or sulphonyl group,
• an aryl group or
• a heteroaryl group,
• or
• Rb and R3 are linked together and are closed up into a ring at the nitrogen atom, while Rb and R3 together denote:
• a C2-7-alkylene group while one or two methylene groups may each be substituted by one or two fluorine atoms or replaced by an oxygen or sulphur atom, by an —NH— or —N(C1-3-alkyl)- group or by a carbonyl sulphinyl or sulphonyl group,
• or a C4-7-alkenylene group while one or two methylene groups may each be substituted by one or two fluorine atoms or replaced by an oxygen or sulphur atom by an —NH— or —N(C1-3-alkyl)- group or by a carbonyl, sulphinyl or sulphonyl group and the double bond may be part of an aryl or heteroaryl group anellated to the ring,
• and
• R3 denotes:
• a hydrogen atom
• a C1-20-alkyl group wherein the hydrogen atoms may be wholly or partly replaced by fluorine atoms and wherein 1 to 6 methylene groups may each be replaced by an oxygen or sulphur atom by an —NH— or —N(C1-3-alkyl)- group or by a carbonyl, sulphinyl or sulphonyl group,
• a C1-12-alkyl group substituted by a group Rc wherein the hydrogen atoms may be wholly or partly replaced by fluorine atoms and wherein 1 to 4 methylene groups may each be replaced by an oxygen or sulphur atom, by an —NH— or —N(C1-3-alkyl- group or by a carbonyl, sulphinyl or sulphonyl group, while
• Rc, denotes:
• a C3-18-cycloalkyl group optionally substituted by one or two C1-3-alkyl groups wherein the hydrogen atoms may be wholly or partly replaced by fluorine atoms and wherein one to two methylene groups may each be replaced by an oxygen or sulphur atom, by an —NH— or —N(C1-3-alkyl)- group or by a carbonyl, sulphinyl or sulphonyl group
• a C5-18-cycloalkenyl optionally substituted by:
• one or two C1-3-alkyl groups wherein the hydrogen atoms may be wholly or partly replaced by fluorine atoms, one to two methylene groups may each be replaced by an oxygen or sulphur atom, by an —NH— or —N(C1-3-alkyl)- group or by a carbonyl sulphinyl or sulphonyl group and the double bond may be part of an aryl or heteroaryl group anellated to the ring;
• an aryl group or a heteroaryl group,
• a C3-18-cycloalkyl group wherein the hydrogen atoms may be wholly or partly replaced by fluorine atoms and wherein 1 to 6 methylene groups may each be replaced by an oxygen or sulphur atom, by an —NH— or —N(C1-3-alkyl)- group or by a carbonyl, sulphinyl or sulphonyl group,
• a C3-20-alkenyl group wherein the hydrogen atoms may be wholly or partly replaced by fluorine atoms and wherein 1 to 6 methylene groups may each be replaced by an oxygen or sulphur atom by an —NH— or —N(C1-3-alkyl)- group or by a carbonyl, sulphinyl or sulphonyl group,
• a C5-20-cycloalkenyl group wherein the hydrogen atoms may be wholly or partly replaced by fluorine atoms and wherein 1 to 4 methylene groups may each be replaced by an oxygen or sulphur atom by an —NH— or —N(C1-3-alkyl)- group or by a carbonyl, sulphinyl or sulphonyl group, and wherein the double bond may be part of an aryl or heteroaryl group anellated to the ring,
• a C3-20-alkynyl group wherein the hydrogen atoms may be wholly or partly replaced by fluorine atoms and wherein 1 to 6 methylene groups may each be replaced by an oxygen or sulphur atom, by an —NH— or —N(C1-3-alkyl)- group or by a carbonyl, sulphinyl or sulphonyl group,
• an aryl group,
• a heteroaryl group,
• an aryl-C2-6-alkenyl group
• or, if X does not represent a nitrogen atom which is substituted by a hydroxy, aryloxy, arylmethyloxy, heteroaryloxy, heteroarylmethyloxy or C1-10-alkyloxy group, R3 may also denote an amino group which may be substituted by one or two C1-3-alkyl groups,
• or, if X does not represent a nitrogen atom which is substituted by a hydroxy, aryloxy, arylmethyloxy, heteroaryloxy, heteroarylmethyloxy or C1-10-alkyloxy group, R3 may also denote a 3- to 7-membered cycloalkyleneimino group, while one to two methylene groups of the cycloalkyleneimino group may each be replaced by an oxygen atom or a carbonyl, sulphinyl or sulphonyl group, or
• R3 and X together represent a fluorine or chlorine atom,
• while by the aryl groups mentioned in the definition of the above groups are meant phenyl or naphthyl groups which may be mono- to pentasubstituted independently of one another by fluorine and chlorine atoms and may be mono-, di- or trisubstituted by Rd, while the substituents may be identical or different and Rd denotes a bromine or iodine atom a trifluoromethyl cyano, nitro, amino, aminocarbonyl, aminosulphonyl, methylsulphonyl, acetylamino, methylsulphonylamino, C1-4-alkyl, C1-3-alkyl-carbonyl, cyclopropyl, ethenyl, ethynyl, hydroxy, C1-4-alkyloxy C1-4-alkoxy-carbonyl, methylsulphinyl, phenylsulphinyl, methylsulphonyl, phenylsulphonyl, difluoromethoxy or trifluoromethoxy group,
• by the heteroaryl groups mentioned in the definition of the above-mentioned groups are meant a pyrrolyl, furanyl, thienyl, pyridyl, indolyl, benzofuranyl, benzothiophenyl, quinolinyl or isoquinolinyl group
• or a pyrrolyl, furanyl, thienyl, or pyridyl group wherein one or two methyne groups are replaced by nitrogen atoms,
• or an indolyl, benzofuranyl, benzothiophenyl, quinolinyl or isoquinolinyl group wherein one to three methyne groups are replaced by nitrogen atoms,
• and the above-mentioned heteroaryl groups may be mono- to pentasubstituted by fluorine and chlorine atoms and Rd may be mono-, di- or trisubstituted, while the substituents may be identical or different and Rd is as hereinbefore defined,
• by the cycloalkyl groups mentioned in the above definitions are meant both mono- and polycyclic ring systems which are either bridged spiro-bridged or anellated in construction,
• by the cycloalkenyl groups mentioned in the above definitions are meant both mono- and polycyclic ring systems which are either bridged or anellated in construction and have at least one C═C double bond,
• while unless otherwise stated the above-mentioned alkyl, alkenyl and alkynyl groups may be straight-chain or branched
• with the exclusion of the compound wherein R1 denotes a bromine atom, R2 denotes a 2-butynyl group, X denotes an oxygen atom and R3 denotes a methyl group,
• the tautomers, the enantiomers, the diastereomers, the mixtures thereof and the salts thereof.