Classifications

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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
  • C07D213/40—Acylated substituent nitrogen atom
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  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
  • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/61—Halogen atoms or nitro radicals
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/08—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
  • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
  • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
  • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
  • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
  • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
  • C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
  • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
  • C07D277/28—Radicals substituted by nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
  • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
  • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/14—Radicals substituted by nitrogen atoms not forming part of a nitro radical
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
  • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
  • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

• the present invention relates to a novel process for the preparation of substituted 2-nitroguanidine derivatives.
• EP patent applications mentioned describe the preparation of 1,3-disubstituted 2-nitroguanidines by reacting monosubstituted nitroisothioureas with primary amines with elimination of mercapto.
• these nitroisothiourea compounds containing alkylthio leaving groups, which are proposed as starting compounds in the known processes, are difficult to obtain.
• EP-A-0.483.062 describes a process for the preparation of the compounds of the formula (I) by hydrolysis of hexahydrotriazines.
• the aim of the present invention is an improved process for the preparation of 1 -monosubstituted and 1, 3-disubstituted 2-nitroguanidines from readily available starting compounds, which allows targeted 1, 3-disubstitution without the formation of large amounts of undesirable by-products.
• the subject of the invention is a) a process for the preparation of a compound of formula
• R 2 is hydrogen, d-Ce-alkyl, C 3 -C 6 cycloalkyl or a radical -CH 2 B;
• Het is an unsubstituted or - depending on the substitution possibilities of the ring system - mono- to pentasubstituted with substituents selected from the group consisting of halogen, -C 3 -alkyl, C 3 alkoxy, halogen CRCS alkyl, C ⁇ -C 3 haloalkoxy, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl and C 2 -C 3 haloalkynyl, C ⁇ -C 3 alkylthio, CC 3 haloalkylthio, allyloxy, Propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro substituted aromatic or non-aromatic, monocyclic or bicyclic heterocyclic radical; and
• R 1, R 2 and Het have the meanings given above for formula (I), and if appropriate their E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form, are hydrolyzed.
• the compounds of formula (I) may exist as E / Z isomers, e.g. in the following two isomeric forms
• the compounds of formula (I) and optionally their E / Z isomers and tautomers can be present as salts.
• Compounds of the formula (I) which have at least one basic center can form, for example, acid addition salts. These are, for example, with strong inorganic acids, such as mineral acids, for example sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as optionally, for example, halogen-substituted CrC -alkanecarboxylic acids, for example acetic acid, such as unsaturated dicarboxylic acids, for example oxalic or malonic acid -, Maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as optionally substituted, for example by halogen, C 1 -C 4 -alkane-
• compounds of the formula (I) with at least one acidic group can form salts with bases.
• Suitable salts with bases are, for example, metal salts such as alkali or alkaline earth metal salts, e.g. Sodium, potassium or magnesium salts, or salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. Ethyl, diethyl, triethyl or dimethyl propyl amine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. Mono-, di- or triethanolamine.
• Corresponding internal salts can optionally also be formed.
• halogen atoms which are suitable as substituents are both fluorine and chlorine and also bromine and iodine, fluorine, chlorine and bromine, especially chlorine, being preferred.
• Halogen is to be understood as an independent substituent or as part of a substituent as in haloalkyl, haloalkylthio, haloalkoxy, halocycloalkyl, haloalkenyl, haloalkynyl, haloallyloxy or haloallylthio.
• the alkyl, alkylthio, alkenyl, alkynyl and alkoxy radicals which are suitable as substituents can be straight-chain or branched.
• alkyls examples are methyl, ethyl, propyl, isopropyl, butyl, i-butyl, sec-butyl or tert-butyl.
• Suitable alkoxy radicals include: methoxy, ethoxy, propoxy, isopropoxy or butoxy and their isomers.
• Alkylthio stands for example for methylthio, ethylthio, isopropylthio, propylthio or the isomeric butylthio. Are they considered as substituents coming alkyl, alkoxy, alkenyl, alkynyl or cycloalkyl groups substituted by halogen, they can only be partially or perhalogenated.
• alkyl elements of these groups are methyl which is mono- to trisubstituted by fluorine, chlorine and / or bromine, for example CHF 2 or CF 3 ; the one to five times substituted by fluorine, chlorine and / or bromine ethyl such as CH 2 CF 3 , CF 2 CF 3> CF 2 CCI 3 , CF 2 CHCI 2 .
• alkyl, alkoxy or cycloalkyl groups are substituted by other substituents, they can be substituted one or more times by the same or different of the substituents listed.
• One or two further substituents are preferably present in the substituted groups.
• the cycloalkyl radicals which are suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
• Alkenyl and alkynyl groups contain an unsaturated carbon-carbon bond. Typical representatives are allyl, methallyl or propargyl, but also vinyl and ethynyl. The double or triple bonds in allyloxy, propargyloxy, allylthio or propargylthio are preferably separated from the point of attachment to the heteroatom (O or S) by a saturated carbon atom.
• alkylene, alkenylene and alkynylene groups defined below can also be straight-chain or branched. Examples are -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -, -CH 2 -CH2-CH 2 -CH 2 -, -CH 2 -C (CH 3 ) H- and -C (CH 3 ) HC (CH 3 ) H-.
• the alkylene, alkenylene, alkynylene, cycloalkylene, arylene or heterocyclylene groups listed below are optionally substituted in the same way as the alkyl, alkenyl and alkynyl groups mentioned above.
• Aryl or arylene means phenyl or naphthyl, or phenylene or naphthylene, especially phenyl or phenylene.
• heteroaryl radical referred to as het preferably means a 5- to 7-membered aromatic or non-aromatic ring one to three heteroatoms which are selected from the group consisting of N, O and S.
• Aromatic 5- and 6-rings are preferred which have a nitrogen atom as a heteroatom and optionally a further heteroatom, preferably nitrogen, oxygen or sulfur, especially nitrogen.
• the hydrolysis process according to the invention can be carried out both in an acidic and in a basic medium.
• pH values of 6 or less, particularly 1 to 3, are preferred.
• basic range a pH greater than 7 to 12, particularly 8 to 12, especially 8 to 10 is preferred.
• the reaction is carried out under normal pressure and at a temperature of 0 to 120 ° C., preferably 20 to 80 ° C.
• the reaction is carried out in a solvent or diluent which is inert to the reactants.
• Alcohols such as methanol, ethanol, propanol and isopropanol, and especially water, are particularly suitable as solvents.
• Other suitable solvents are e.g. Ethers such as tetrahydrofuran and dioxane, as well as other solvents, do not affect the reaction.
• the solvents can also be used as mixtures.
• a compound of formula (II) is preferably hydrolyzed in an aqueous medium or a mixture of water with an alcohol.
• Suitable acids for carrying out the process are preferably mineral acids, such as, for example, sulfuric acid, a phosphoric acid or a hydrohalic acid, an organic carboxylic acid, such as CC-AI-carboxylic acids, for example acetic acid, such as optionally substituted by halogen, for example acetic acid, such as unsaturated dicarboxylic acids, for example oxalic acid.
• mineral acids such as, for example, sulfuric acid, a phosphoric acid or a hydrohalic acid
• an organic carboxylic acid such as CC-AI-carboxylic acids
• acetic acid such as optionally substituted by halogen
• acetic acid such as unsaturated dicarboxylic acids, for example oxalic acid.
• Malonic, maleic, fumaric or phthalic acid such as hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or such as benzoic acid, or an organic sulfonic acid, such as dC which is optionally substituted, for example, by halogen 4 -alkane or aryl sulfonic acids, for example methane or p-toluenesulfonic acid.
• Suitable bases for carrying out the process are preferably hydroxides of alkali and alkaline earth metals, such as NaOH and KOH; Carbonates such as Na 2 CO 3 , NaHCO 3 , K 2 CO 3 ; Phosphates such as Na 3 PO 4 , Na 2 HPO, alcoholates such as sodium methoxide, sodium ethanolate and K-tert-butoxide, organic amines such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethyl, diethyl , Triethyl or dimethyl propyl amine, or a mono-, di- or trihydroxy-lower alkylamine, for example mono-, di- or Triethanolamine, or dialkylaniline, such as N, N-dimethyl- or N, N-diethylaniline; and salts of organic acids such as sodium acetate, potassium acetate or sodium benzoate; or mixtures thereof, such as a
• the process according to the invention is preferably used to prepare compounds of the formula (I) in which the heterocyclic radical Het is unsaturated and is bonded to the base body via a carbon atom as a ring member.
• Particularly preferred radicals Het are pyridyl, thiazolyl, tetrahydrofuranyl, dihydrofuranyl, furanyl, N-oxidopyridinio, oxazolyl, isoxazolyl, thienyl, morpholinyl, piperidinyl, pyridinyl and pyrazinyl; especially pyridyl, thiazolyl, tetrahydrofuranyl and N-oxidopyridinio; very particularly 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-halothiazol-5-yl, tetrahydrofuran-3-yl, 2-methyl-tetrahydrofuran
• the heterocycles Het also preferably carry one to three substituents from the group halogen, CC 3 alkyl, C 1 -C 3 -haloalkyl and C 1 -C 3 -haloalkoxy, each with 1 to 7 halogen atoms and CrC 3 alkoxy, particularly preferably chlorine or methyl .
• compounds of the formula (I) are preferably prepared according to the invention in which the radical B is a phenyl, pyridyl or thiazolyl radical which is unsubstituted or by one or two radicals from the group consisting of halogen, CrC 3 alkyl, CrCs haloalkyl and CrC 3 -Halogenalkoxy can be substituted with 1 to 7 halogen atoms and CrC 3 alkoxy.
• R 2 is hydrogen, CrC 3 alkyl or cyclopropyl; especially hydrogen, methyl, ethyl or cyclopropyl; especially methyl; and
• Het is pyridyl, 1 -Oxopyridyl, tetrahydrofuranyl, thiazolyl, or in each case by one to three substituents from the group halogen, -C 3 alkyl, -C 3 haloalkyl and dC 3 -haloalkoxy having 1 to 7 halogen atoms and CC 3 alkoxy substituted pyridyl, 1 -Oxidopyridinio, tetrahydrofuranyl or thiazolyl; in particular 2-chloropyrid-5-yl, tetrahydrofuran-3-yl, 2-methyl-tetrahydrofuran-4-yl or 2-chlorothiazol-5-yl.
• D. and D 3 independently of one another optionally substituted C 3 -C 12 cycloalkylene or arylene and DC 2 -C 20 alkylene, C 2 -C 20 alkenylene, C 2 -C 20 alkynylene, O, NH or Nd-C ⁇ 2 - Mean alkyl.
• Very particularly preferred bridging members A are C 2 -C 12 alkylene, by one or two phenylene, Cyciohexylen- Piperazinylenreste or interrupted C 2 -C ⁇ 2 alkylene; Cyclohexylene or phenylene; or a group -DD 2 -D 3 -, where di and D 3 are phenylene or dicyclohexylene and D 2 O or C 2 -C 4 alkylene; in particular means AC 2 -C 4 alkylene.
• compounds of the formula (IIb) are preferably used as starting material for carrying out the process according to the invention, wherein U is aryl, heterocyclyl, C 3 -C 2 -cycloalkyl or a group
• X represents N or CH.
• Heterocyclyl A and U in the compounds of the formulas (Ila) and (Ilb) is preferably an aromatic or non-aromatic, three to ten-membered ring. If the rings A and U are aromatic, they are preferably the same rings as defined for Het above. In the case of non-aromatic heterocyclic rings for A and U, piperidinyl, piperazinyl, morpholinyl, pyrrolidinyl, tetrahydrofuranyl and dioxolanyl are particularly preferred.
• the radicals A ⁇ A and A 3 are very particularly preferably independently of one another C 2 -C alkylene, in particular ethylene.
• Another object of the invention is b) a process for the preparation of a compound of formula (Ila) and (Ilb), characterized in that a compound of formula
• R 2 has the same meaning as defined above for formula (I); and optionally their E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form, in the case of the preparation of a compound of the formula (purple) with two, in the case of the preparation of a compound of the formula ( IIIb) with three equivalents of a compound of the formula y Het
• Rt which is known or can be prepared analogously to methods known per se, in which Ri and Het have the meanings given above for the formula (I) and Y represents a leaving group, preferably in the presence of a base.
• halogen preferably chlorine, bromine or iodine, especially chlorine, or sulfonic acid esters, such as alkyl sulfonic acid residues, mesylate or tosylate.
• the process step according to b) can preferably be carried out under normal or slightly elevated pressure and in the presence of preferably aprotic solvents or diluents.
• Suitable solvents or diluents are, for example, ethers and ethereal compounds, such as diethyl ether, dipropyl ether, dibutyl ether, dioxane, Dimethoxyethane and tetrahydrofuran; aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylene, chloroform, methylene chloride, carbon tetrachloride and chlorobenzene; Nitriles such as acetonitrile or propionitrile; Dimethyl sulfoxide or dimethylformamide and mixtures of these solvents.
• This process step is generally carried out at a temperature of from -20 ° C. to + 140 ° C., preferably between 0 ° C. and + 120 ° C., preferably in the presence of a base.
• bases are, for example, carbonates, such as sodium and potassium carbonate. Hydrides such as sodium hydride, potassium hydride and potassium hydride can also be used as bases. If appropriate, the reaction can also be carried out in the presence of a catalyst, for example cesium chloride.
• Another object of the invention is c) a process for the preparation of the compounds of the formula (purple) and (IIIb), characterized in that either a compound of the formula
• the process according to c) for the preparation of the compounds of the formula (III) is advantageously carried out under normal pressure, if appropriate also under increased pressure in an inert solvent and at temperatures between 0 ° C and + 140 ° C, preferably between + 20 ° C and + 120 ° C.
• Alcohols such as methanol, ethanol and propanol and water are particularly suitable as solvents.
• solvents are, for example, aromatic hydrocarbons, such as benzene, toluene and xylene; Ethers such as tetrahydrofuran, dioxane and diethyl ether; Halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and chlorobenzene and other solvents that do not affect the reaction.
• the solvents can also be used as mixtures.
• an acid catalyst such as HCl, H 2 SO 4
• a sulfonic acid such as p-toluenesulfonic acid
• Another object of the invention is d) a process for the preparation of a compound of formula (I), characterized in that a compound of formula (Va) or (Vb) by reaction with a compound of formula (VI) and formaldehyde or Converting paraformaldehyde into a compound of formula (purple) or (IIIb); converting this compound of the formula (purple) or (IIIb) with a compound of (IV) into a compound of the formula (Ila) or (Ilb) and hydrolyzing this compound of the formula (Ila) or (Ilb).
• the invention further relates to the compounds of the formulas (Ila), (Ilb), (lilac) and (IIIb), and optionally their E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in Salt form and their use for the preparation of compounds of formula (I).
• the compounds of formula (I) prepared according to the invention are known. They are valuable active ingredients in pest control with favorable warm-blood, fish and plant tolerance.
• the compounds of the formula (I) are suitable for controlling insects and arachnids which are particularly useful in crops and ornamental plants in agriculture, in particular in cotton, vegetable and fruit crops, in forestry, in the protection of stored goods and materials, and in the hygiene sector Pets and farm animals occur.
• the compounds are particularly effective against sucking insect pests, especially against aphids and cicadas.
• Example H1.1 Preparation of the compound of the formula
• Example H1.5 Analogously to the above procedures of Examples H1.1 to H1 .4, the following compounds listed in Table 1 can also be obtained.
• Example H2.2 Analogously to the above procedure of Example H2.1, the following compounds listed in Table 2 can also be obtained.
• Table 2 Compounds of the formula
• Example H3.5 Analogously to the above procedure of Examples H3.1 to H3.4, the following compounds listed in Tables 3 to 26 can also be obtained.
• Table 3 Compounds of the general formula (IIc), in which Het means and A corresponds to one row of Table B. Connection 3.B.01: Smpt. 175-178 ° C
• Table 5 Compounds of the general formula (IIc), in which Het means and A corresponds to one row of Table B.
• Table 6 Compounds of the general formula (IIc), in which Het means and A corresponds to one row of Table B.
• Table 7 Compounds of the general formula (IIc), in which Het is 2-methyl-tetrahydrofuran-4-yl and A corresponds in each case to one line of Table B.
• Table 8 Compounds of the general formula (IIc), in which Het is tetrafuran-3-yl and A corresponds in each case to one line of Table B.
• N-0 means and A corresponds to one row of Table B.
• Table 10 Compounds of the general formula (IIc), in which Het means and A corresponds to one row of Table B.
• Table 11 Compounds of the general formula (IIc), in which Het is pyrid-3-yl and A corresponds in each case to one line of Table B.
• Table 12 Compounds of the general formula (IIc), in which Het denotes and A corresponds to one row of Table B.
• Table 13 Compounds of the general formula (IIc), in which Het means and A corresponds to one row of Table B.
• Table 14 Compounds of the general formula (IIc), in which Het is 2,3-dichloropyrid-5-yl, and A corresponds in each case to one line of Table B.
• Table C Compounds of the formula
• Table 15 Compounds of the general formula (III), in which Het means and Ai, A 2 , A 3 and X each correspond to one row of Table C.
• N-J 'and Ai, A 2 , A 3 and X each correspond to one row of Table C.
• Table 17 Compounds of the general formula (III), in which Het means and Ai, A 2 , A 3 and X each correspond to one row of Table C.
• Table 18 Compounds of the general formula (III), in which Het means and Ai, A 2 , A 3 and X each correspond to one row of Table C.
• Table 19 Compounds of the general formula (III), in which Het is 2-methyl-tetrahydrofuran-4-yl and A t A 2> A 3 and X each correspond to one line of Table C.
• Table 20 Compounds of the general formula (III), in which Het is 3-tetrahydrofuranyl and Ai, A 2 , A 3 and X each correspond to one line of Table C.
• N-0 means and Ai, A 2 , A 3 and X each correspond to one row of Table C.
• Table 22 Compounds of the general formula (III), in which Het is 2-chloro-pyrid-5-yl and Ai, A 2 , A 3 and X each correspond to one line of Table C.
• Table 23 Compounds of the general formula (III), in which Het is 3-pyridyl and A 1 f A 2 , A 3 and X each correspond to one line of Table C.
• Table 24 Compounds of the general formula (III), in which Het denotes and A L A 2 , A 3 and X each correspond to one row of Table C.
• Table 25 Compounds of the general formula (lld), in which Het means and Ai, A 2 , A 3 and X each correspond to one row of Table C.
• Table 26 Compounds of the general formula (III), in which Het is 2,3-dichloropyrid-5-yl, and Ai, A 2 , A 3 and X each correspond to one line of Table C.
• Example H4.3 Analogously to the above procedures of Examples 4.1 and 4.2, the following compounds listed in Table 27 can also be obtained.
• Another object of the invention is a method for controlling pests, especially animal pests, in particular insects and representatives of the order Akarina, with the compounds of the formulas (Ila) and (Ilb).
• animal pests mentioned include, for example, those which are mentioned in European patent application EP-A-736'252.
• the pests mentioned there are therefore included by reference in the present subject matter of the invention.
• the methods for controlling the pests mentioned and the composition and preparation of the corresponding agents are also described in EP-A-736'252 and included in the present subject matter of the invention by reference.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Plural Heterocyclic Compounds (AREA)
• Pyridine Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Thiazole And Isothizaole Compounds (AREA)
• Furan Compounds (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

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• 1998
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• 2002
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