EP0988287A1 - Method for producing nitroguanidine derivatives - Google Patents

Method for producing nitroguanidine derivatives

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Publication number
EP0988287A1
EP0988287A1 EP98934916A EP98934916A EP0988287A1 EP 0988287 A1 EP0988287 A1 EP 0988287A1 EP 98934916 A EP98934916 A EP 98934916A EP 98934916 A EP98934916 A EP 98934916A EP 0988287 A1 EP0988287 A1 EP 0988287A1
Authority
EP
European Patent Office
Prior art keywords
formula
alkyl
compound
preparation
cyclopropyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP98934916A
Other languages
German (de)
French (fr)
Inventor
Peter Maienfisch
Hansjürg Widmer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Participations AG
Original Assignee
Novartis Erfindungen Verwaltungs GmbH
Novartis AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Novartis Erfindungen Verwaltungs GmbH, Novartis AG filed Critical Novartis Erfindungen Verwaltungs GmbH
Publication of EP0988287A1 publication Critical patent/EP0988287A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • 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
    • C07D213/60—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
    • C—CHEMISTRY; METALLURGY
    • 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
    • C07D213/89—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
    • 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
    • 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
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the invention relates to a method for producing a compound of the formula
  • R hydrogen or -CC 4 alkyl
  • R 2 is hydrogen, -CC 6 alkyl, C 3 -C 6 cycloalkyl or a radical -CH 2 B;
  • A is an unsubstituted or - depending on the possibilities of substitution of the ring system - one to five times with substituents selected from the group consisting of halogen, C 1 -C 3 -alkyl, d-Cs-alkoxy, halogen-C C3-alkyl, C 1 -C 3 - Haiogenalkoxy, cyclopropyl propyl, halogenocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl and C 2 - C 3 haloalkynyl, CrC 3 alkylthio, -C 3 haloalkylthio, Allyloxy, propargyloxy, allylthio, propargylthio, haiogenallyloxy, haloallylthio, cyano and nitro-substituted aromatic or non-aromatic, monocyclic or bicyclic heterocycl
  • B phenyl, 3-pyridyl or thiazolyl, which are optionally substituted by one to three substituents from the group consisting of CrC alkyl, CrC 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, d-Cs-alkoxy, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, CrC 3 -Halogenaikoxy, C Cs alkylthio, C Cs haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, Haiogenallyloxy, haloallylthio, halogen , Cyano and nitro are substituted; and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in
  • R 1 f R 2 and A have the same meaning as indicated in formula (I) and
  • R 3 is unsubstituted or substituted C ⁇ C 0 alkyl, C 3 -C 6 cycloalkyl, phenyl or benzyl; characterized in that the reaction is carried out at a pH between 7 and 14.
  • the compounds of formula (I) can exist as E / Z isomers, e.g. B. 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 formula (I) which have at least one basic center can e.g. B. Form acid addition salts. These are, for example, with strong inorganic acids such as mineral acids, e.g. B. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as, if necessary, for. B. by halogen, substituted -CC 4 alkane carboxylic acids, for. B. acetic acid, such as unsaturated dicarboxylic acids, e.g. B.
  • oxalic, malonic, maleic, fumaric or phthalic acid such as hydroxycarboxylic acids, e.g. B. ascorbic, milk, apple, wine or citric acid, or like benzoic acid, or with organic sulfonic acids, such as optionally, e.g. B. by halogen, substituted CC alkane or aryl sulfonic acids, for. B. methane or p-toluenesulfonic acid.
  • Salts of compounds of formula (I) with acids of the type mentioned are preferably obtained in the working up of the reaction mixtures.
  • 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. As 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. B. ethyl, diethyl, triethyl or dimethyl propyl amine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. B. 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, haiogenallyloxy 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. If the alkyl, alkoxy, alkenyl, alkynyl or cycloalkyl groups which are suitable as substituents are substituted by halogen, they can only be partially or also 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 , CF 2 CHF 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.
  • EP-A-0.483.062 describes a process for the preparation of the compounds of the formula (I), in which a compound of the above formula (II) is hydrolyzed.
  • the hydrolysis process according to the invention is preferably carried out at a pH greater than 7 to 12, particularly 8 to 12, in particular 8 to 10, likewise preferably 7 to 10; 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.
  • solvents are alcohols, such as methanol, ethanol, propanol and isopropanol, and especially water.
  • suitable solvents are e.g. Ethers such as tetrahydrofuran and dioxane, as well as other solvents that 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 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, Na 2 HPO 4 , alcoholates such as sodium methoxide, sodium ethoxide and K-tert-butoxide, organic amines such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. B. ethyl, diethyl, triethyl or dimethyl propyl amine, or a mono-, di- or trihydroxy-lower alkylamine, e.g.
  • B mono-, di- or triethanolamine, or dialkylaniline, such as N, N-dimethyl or N, N-diethylaniline; as well as salts of organic acids such as sodium acetate, potassium acetate or sodium benzoate; or mixtures thereof, such as acetate or phosphate buffers.
  • the process according to the invention is preferably used to prepare compounds of the formula (I) in which the heterocyclic radical A is unsaturated and is bonded to the base body via a carbon atom as a ring member.
  • Particularly preferred radicals A are pyridyl, Thiazolyl, tetrahydrofuranyl, dihydrofuranyl, furanyl, N-oxidopyridinio, oxazolyl, isoxazolyl, thienyl, morpholinyl, piperidinyl, pyridinyl and pyrazinyl; very particularly pyridyl, thiazolyl, tetrahydrofuranyl and N-oxidopyridinio, especially 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-halothiazol-5-yl, tetrahydrofuran-3-yl , 5-methyl-tetrahydrofuran-3-
  • the heterocycles A carry from one to three substituents from the group halogen, CC 3 alkyl, -C 3 haloalkyl and -C 3 haloalkoxy, each with 1 to 7 halogen atoms, and dC 3 alkoxy.
  • radical B represents a phenyl, pyridyl or thiazolyl, which is unsubstituted or substituted by a 3 haloalkyl or two radicals from the group halogen, -C 3 alkyl, CrC and CrC 3 -Halogenalkoxy with 1 to 7 halogen atoms and CrC 3 -alkoxy may be substituted.
  • R 1 is hydrogen
  • R 2 is hydrogen, methyl, ethyl or cyclopropyl
  • A are pyridyl, 1 -oxopyridyl, tetrahydrofuranyl, thiazolyl or in each case by one to three substituents from the group halogen , C r C 3 -alkyl, C 3 haloalkyl and C 1 -C 3 - mean halogenoalkoxy having 1 to 7 halogen atoms, and dC 3 alkoxy substituted pyridyl, 1-oxidopyridinio, thiazolyl or tetrahydrofuranyl.
  • Ri is hydrogen
  • R 2 is hydrogen, CrC 3 alkyl or cyclopropyl, especially methyl
  • A is 2-chloropyrid-5-yl, tetrahydrofuran-3-yl, 5-methyl-tetrahydrofuran-3-yl or 2-chlorothiazol-5-yl
  • R 3 is C 1 -C 3 -alkyl, cyclopropyl, cyclohexyl, phenyl or benzyl.
  • formula (II) come as substituents for the radical R 3 in particular halogen, dC 4 - alkyl, halo -CC alkyl, nitro, -C -alkoxy and halogen-dC 4 alkoxy in question.
  • the compounds of the formula (I) prepared according to the invention are valuable active ingredients in pest control, while being well tolerated by warm-blooded animals, fish and plants.
  • the compounds of the formula (I) are suitable for controlling insects and arachnids which are found in useful and ornamental plants in agriculture, in particular re in cotton, vegetable and fruit plantations, in the forest, in the protection of stored goods and materials as well as in the hygiene sector, particularly in domestic and farm animals.
  • the compounds are particularly effective against sucking insect pests, especially against aphids and cicadas.
  • Substituted pesticidal 2-nitroguanidines of the type which can be prepared according to the invention are described, for example, in EP patent applications 376.279, 375.907 and 383.091.
  • R 4 halogen, dC 3 alkyl, dC 3 alkoxy, halogen-CrC alkyl, dC 3 haloalkoxy, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 -Halogenalkenyl and C 2 -C 3 -haloalkynyl, dC 3 -alkylthio, C ⁇ -C 3 -haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, Haiogenallyloxy, haloallylthio, cyano and nitro, preferably dC 3 -alkyl, and n , 2 or 3, preferably 0 or 1; and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)

Abstract

The invention relates to a method for producing compounds of formula (I), wherein R1 = hydrogen or C1-C4-alkyl; R2 = hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl or a CH2-B radical; A = an unsubstituted or mono or penta-substituted aromatic or non-aromatic monocyclic or bicyclic or heterocyclic radical and B = phenyl, 3-pyridyl or thiazolyl which are optionally substituted by one to three substituents, by hydrolyzing a compound of formula (II), wherein R1, R2 and A have the same meaning as in formula (I) and R3 stands for an unsubstituted or substituted C1-C10-alkyl, C3-C6-cycloalkyl, phenyl or benzyl. The invention is characterized in that the reaction is carried out at a pH value ranging from 7 to 14. The invention further relates to starting materials to implement said method. The compounds of formula (I) are suitable as intermediate products for the production of pesticide mixtures.

Description

VERFAHREN ZUR HERSTELLUNG VON NITROGUANIDINDERIVATEN METHOD FOR PRODUCING NITROGUANIDINE DERIVATIVES
Die Erfindung betrifft ein Verfahren zur Herstellung einer Verbindung der FormelThe invention relates to a method for producing a compound of the formula
worin wherein
R. Wasserstoff oder Cι-C4-Alkyl;R. hydrogen or -CC 4 alkyl;
R2 Wasserstoff, Cι-C6-Alkyl, C3-C6-Cycloalkyl oder einen Rest -CH2B;R 2 is hydrogen, -CC 6 alkyl, C 3 -C 6 cycloalkyl or a radical -CH 2 B;
A einen unsubstituierten oder - je nach Substitutionsmöglichkeiten des Ringsystems - ein- bis fünffach mit Substituenten ausgewählt aus der Gruppe bestehend aus Halogen, Cι-C3-Alkyl, d-Cs-Alkoxy, Halogen-C C3-alkyl, Cι-C3-Haiogenalkoxy, Cyclopro- pyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, C2-C3-Halogenalkenyl und C2- C3-Halogenalkinyl, CrC3-Alkylthio, CrC3-Halogenalkylthio, Allyloxy, Propargyloxy, Al- lylthio, Propargylthio, Haiogenallyloxy, Halogenallylthio, Cyan und Nitro substituierten aromatischen oder nichtaromatischen, monocyciischen oder bicyclischen heterocy- clischen Rest; undA is an unsubstituted or - depending on the possibilities of substitution of the ring system - one to five times with substituents selected from the group consisting of halogen, C 1 -C 3 -alkyl, d-Cs-alkoxy, halogen-C C3-alkyl, C 1 -C 3 - Haiogenalkoxy, cyclopropyl propyl, halogenocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 haloalkenyl and C 2 - C 3 haloalkynyl, CrC 3 alkylthio, -C 3 haloalkylthio, Allyloxy, propargyloxy, allylthio, propargylthio, haiogenallyloxy, haloallylthio, cyano and nitro-substituted aromatic or non-aromatic, monocyclic or bicyclic heterocyclic radical; and
B Phenyl, 3-Pyridyl oder Thiazolyl, welche gegebenenfalls durch ein bis drei Substituenten aus der Gruppe bestehend aus CrC -Alkyl, CrC3-Halogenalkyl, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, d-Cs-Alkoxy, C2-C3-Halogenalkenyl, C2-C3-Halogenalkinyl, CrC3-Halogenaikoxy, C Cs-Alkylthio, C Cs-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Haiogenallyloxy, Halogenallylthio, Halogen, Cyano und Nitro substituiert sind; und gegebenenfalls ihrer möglichen E/Z-Isomeren, E/Z-Isomerengemische und/oder Tautomeren, jeweils in freier Form oder in Salzform; durch Hydrolyse einer Verbindung der FormelB phenyl, 3-pyridyl or thiazolyl, which are optionally substituted by one to three substituents from the group consisting of CrC alkyl, CrC 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, d-Cs-alkoxy, C 2 -C 3 haloalkenyl, C 2 -C 3 haloalkynyl, CrC 3 -Halogenaikoxy, C Cs alkylthio, C Cs haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, Haiogenallyloxy, haloallylthio, halogen , Cyano and nitro are substituted; and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form; by hydrolysis of a compound of the formula
worin R1 f R2 und A die gleiche Bedeutung haben wie in Formel (I) angegeben und wherein R 1 f R 2 and A have the same meaning as indicated in formula (I) and
R3 unsubstituiertes oder substituiertes C Cι0-Alkyl, C3-C6-Cycloalkyl, Phenyl oder Benzyl bedeutet; dadurch gekennzeichnet, dass man die Reaktion bei einem pH-Wert zwischen 7 und 14 durchführt.R 3 is unsubstituted or substituted Cι C 0 alkyl, C 3 -C 6 cycloalkyl, phenyl or benzyl; characterized in that the reaction is carried out at a pH between 7 and 14.
Die Verbindungen der Formel (I) können als E/Z-Isomere vorliegen, z. B. in den folgenden zwei isomeren FormenThe compounds of formula (I) can exist as E / Z isomers, e.g. B. in the following two isomeric forms
Demgemäss sind unter den Verbindungen der Formel (I) nachstehend gegebenenfalls auch entsprechende E/Z-Isomere zu verstehen, auch wenn letztere nicht in jedem Fall speziell erwähnt werden.Accordingly, the compounds of the formula (I) below are also to be understood as meaning corresponding E / Z isomers, even if the latter are not specifically mentioned in every case.
Die Verbindungen der Formel (I) können teilweise als Tautomere vorliegen, beispielsweise in den FormenSome of the compounds of the formula (I) can be present as tautomers, for example in the forms
Demgemäss sind unter den Verbindungen der Formel (I) vor- und nachstehend gegebenenfalls auch entsprechende Tautomere zu verstehen, auch wenn letztere nicht in jedem Fall speziell erwähnt werden.Accordingly, the compounds of the formula (I) above and below may also be understood to mean corresponding tautomers, even if the latter are not specifically mentioned in every case.
Die Verbindungen der Formel (I) und gegebenenfalls ihre E/Z-Isomeren und Tautomeren können als Salze vorliegen. Verbindungen der Formel (I), welche mindestens ein basisches Zentrum aufweisen, können z. B. Säureadditionssalze bilden. Diese werden beispielsweise mit starken anorganischen Säuren, wie Mineralsäuren, z. B. Schwefelsäure, einer Phosphorsäure oder einer Halogenwasserstoffsäure, mit starken organischen Carbonsäuren, wie gegebenenfalls, z. B. durch Halogen, substituierten Cι-C4-Alkancarbonsäuren, z. B. Essigsäure, wie gegebenenfalls ungesättigten Dicarbonsäuren, z. B. Oxal-, Malon-, Malein-, Fumar- oder Phthalsäure, wie Hydroxycarbonsäuren, z. B. Ascorbin-, Milch-, Äpfel-, Wein- oder Zitronensäure, oder wie Benzoesäure, oder mit organischen Sulfonsäuren, wie gegebenenfalls, z. B. durch Halogen, substituierten C C -Alkan- oder Aryl-sulfonsäuren, z. B. Methan- oder p-Toluolsulfonsäure, gebildet. Salze von Verbindungen der Formel (I) mit Säuren der genannten Art werden vorzugweise bei der Aufarbeitung der Reaktionsgemische gewonnen.The compounds of formula (I) and optionally their E / Z isomers and tautomers can be present as salts. Compounds of formula (I) which have at least one basic center can e.g. B. Form acid addition salts. These are, for example, with strong inorganic acids such as mineral acids, e.g. B. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as, if necessary, for. B. by halogen, substituted -CC 4 alkane carboxylic acids, for. B. acetic acid, such as unsaturated dicarboxylic acids, e.g. B. oxalic, malonic, maleic, fumaric or phthalic acid, such as hydroxycarboxylic acids, e.g. B. ascorbic, milk, apple, wine or citric acid, or like benzoic acid, or with organic sulfonic acids, such as optionally, e.g. B. by halogen, substituted CC alkane or aryl sulfonic acids, for. B. methane or p-toluenesulfonic acid. Salts of compounds of formula (I) with acids of the type mentioned are preferably obtained in the working up of the reaction mixtures.
Ferner können Verbindungen der Formel (I) mit mindestens einer aciden Gruppe Salze mit Basen bilden. Geeignete Salze mit Basen sind beispielsweise Metallsalze, wie Alkali- oder Erdalkalimetallsalze, z. B. Natrium-, Kalium- oder Magnesiumsalze, oder Salze mit Ammoniak oder einem organischen Amin, wie Morpholin, Piperidin, Pyrrolidin, einem Mono-, Dioder Triniederalkylamin, z. B. Ethyl-, Diethyl-, Triethyl- oder Dimethyl-propyl-amin, oder einem Mono-, Di- oder Trihydroxyniederalkylamin, z. B. Mono-, Di- oder Triethanolamin. Weiterhin können gegebenenfalls entsprechende innere Salze gebildet werden. Bevorzugt sind im Rahmen der Erfindung agrochemisch vorteilhafte Salze. Vorstehend und nachfolgend sind unter den freien Verbindungen der Formel (I) bzw. ihren Salzen sinngemäss gegebenenfalls auch die entsprechenden Salze bzw. die freien Verbindungen der Formel (I) zu verstehen. Entsprechendes gilt für E/Z-Isomere und Tautomere von Verbindungen der Formel (I) und deren Salze. Bevorzugt ist die freie Form.Furthermore, 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. As 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. B. ethyl, diethyl, triethyl or dimethyl propyl amine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. B. mono-, di- or triethanolamine. Corresponding internal salts can optionally also be formed. Preferred in the context of the invention are agrochemically advantageous salts. Above and below, the free compounds of the formula (I) or their salts are also to be understood as meaning, where appropriate, the corresponding salts or the free compounds of the formula (I). The same applies to E / Z isomers and tautomers of compounds of formula (I) and their salts. The free form is preferred.
In der Definition der vorstehenden Formeln (I) und (II) sollen die einzelnen generischen Begriffe wie folgt verstanden werden:In the definition of formulas (I) and (II) above, the individual generic terms should be understood as follows:
Bei den als Substituenten in Betracht kommenden Halogenatomen handelt es sich sowohl um Fluor und Chlor als auch um Brom und Jod, wobei Fluor, Chlor und Brom, besonders Chlor, bevorzugt sind. Halogen ist dabei als selbständiger Substituent oder als Teil eines Substituenten zu verstehen wie im Halogenalkyl, Halogenalkylthio, Halogenalkoxy, Halo- gencycloalkyl, Halogenalkenyl, Halogenalkinyl, Haiogenallyloxy oder Halogenallylthio. Die als Substituenten in Betracht kommenden Alkyl-, Alkylthio-, Alkenyl-, Alkinyl- und Alkoxyre- ste können geradkettig oder verzweigt sein. Als Beispiele solcher Alkyle seien Methyl, Ae- thyl, Propyl, Isopropyl, Butyl, i-Butyl, sek.-Butyl oder tert.-Butyl genannt. Als geeignete Al- koxyreste seien unter anderem genannt: Methoxy, Aethoxy, Propoxy, Isopropoxy oder Bu- toxy und ihre Isomeren. Alkylthio steht beispielsweise für Methylthio, Aethylthio, Isopropyl- thio, Propylthio oder die isomeren Butylthio. Sind die als Substituenten in Betracht kommenden Alkyl-, Alkoxy-, Alkenyl-, Alkinyl- oder Cycloalkylgruppen durch Halogen substituiert, so können sie nur teilweise oder auch perhalogeniert sein. Dabei gelten für Halogen, Alkyl und Alkoxy die oben gegebenen Definitionen. Beispiele der Alkylelemente dieser Gruppen sind das ein- bis dreifach durch Fluor, Chlor und/oder Brom substituierte Methyl wie beispielsweise CHF2 oder CF3; das ein- bis fünffach durch Fluor, Chlor und/oder Brom substituierte Aethyl wie zum Beispiel CH2CF3, CF2CF3, CF2CCI3, CF2CHCI2, CF2CHF2. CF2CFCI2, CF2CHBr2, CF2CHCIF, CF2CHBrF oder CCIFCHCIF; das ein- bis siebenfach durch Fluor, Chlor und/oder Brom substituierte Propyl oder Isopropyl wie beispielsweise CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 oder CH(CF3)2; das ein- bis neunfach durch Fluor, Chlor und/oder Brom substituierte Butyl oder eines seiner Isomeren wie zum Beispiel CF(CF3)CHFCF3 oder CH2(CF2)2CF3; 2-Chlorcyclopropyl oder 2,2-Difluorcyclopropyl; 2,2-Di- fluorvinyl, 2,2-Dichlorvinyl, 2-Chloralkyl, 2,3-Dichlorvinyl oder 2,3-Dibromvinyl.The 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, haiogenallyloxy or haloallylthio. The alkyl, alkylthio, alkenyl, alkynyl and alkoxy radicals which are suitable as substituents can be straight-chain or branched. Examples of such alkyls 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. If the alkyl, alkoxy, alkenyl, alkynyl or cycloalkyl groups which are suitable as substituents are substituted by halogen, they can only be partially or also perhalogenated. The definitions given above apply to halogen, alkyl and alkoxy. Examples of the 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 , CF 2 CHF 2 . CF 2 CFCI 2 , CF 2 CHBr 2 , CF 2 CHCIF, CF 2 CHBrF or CCIFCHCIF; the one to seven times substituted by fluorine, chlorine and / or bromine, propyl or isopropyl such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH2CF2CF3 or CH (CF 3 ) 2 ; the one to nine times substituted by fluorine, chlorine and / or bromine butyl or one of its isomers such as CF (CF 3 ) CHFCF 3 or CH 2 (CF 2 ) 2 CF 3 ; 2-chlorocyclopropyl or 2,2-difluorocyclopropyl; 2,2-di-fluorovinyl, 2,2-dichlorovinyl, 2-chloroalkyl, 2,3-dichlorovinyl or 2,3-dibromovinyl.
Sind die definierten Alkyl-, Alkoxy- oder Cycloalkylgruppen durch andere Substituenten substituiert, so können sie ein- oder mehrfach durch den gleichen oder verschiedene der aufgezählten Substituenten substituiert sein. Vorzugsweise sind in den substituierten Gruppen ein oder zwei weitere Substituenten vorhanden. Bei den als Substituenten in Betracht kommenden Cycloalkylresten handelt es sich beispielsweise um Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl. Alkenyl- und Alkinylgruppen enthalten eine ungesättigte Kohlenstoff-Kohlenstoff-Bindung. Typische Vertreter sind Allyl, Methallyl oder Propargyl, aber auch Vinyl und Äthinyl. Die Doppel- oder Dreifachbindungen in Allyloxy, Propargyloxy, Al- lylthio oder Propargylthio sind von der Verknüpfungsstelle zum Heteroatom (O oder S) vorzugsweise durch ein gesättigtes Kohlenstoffatom getrennt.If the defined 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.
Es ist bereits bekannt, dass zur Herstellung von 1 ,3-disubstituierten 2-Nitroguanidinen in monosubstituierte 2-Nitroguanidine ein weiterer Substituent (z.B. durch Alkylierung) eingeführt werden kann (vgl. z.B. die EP-Patentanmeldungen 0.375.907, 0.376.279 und 0.383.091 ). Aufgrund des Vorliegens von drei reaktionsfähigen Wasserstoffatomen in den bei diesen Umsetzungen als Ausgangsmaterial verwendeten monosubstituierten 2-Nitro- guanidinen verlaufen die bisher vorgeschlagenen Substitutionsreaktionen dieser Art oftmals unselektiv und führen zu unerwünschten Substitutionsprodukten. In den erwähnten EP- Patentanmeldungen wird die Herstellung von 1 ,3-disubstituierten 2-Nitroguanidinen durch Umsetzung von monosubstituierten Nitroisothioharnstoffen mit primären Aminen unter Mer- captan-Abspaltung beschrieben. Diese bei den bekannten Verfahren als Ausgangsverbindungen vorgeschlagenen Alkylthio-Abgangsgruppen enthaltenden Nitroisothioharnstoffver- bindungen sind aber nur schwer zugänglich.It is already known that for the preparation of 1,3-disubstituted 2-nitroguanidines in monosubstituted 2-nitroguanidines, a further substituent can be introduced (for example by alkylation) (see, for example, EP patent applications 0.375.907, 0.376.279 and 0.383 .091). Due to the presence of three reactive hydrogen atoms in the monosubstituted 2-nitroguanidines used as starting material in these reactions, the previously proposed substitution reactions of this type are often unselective and lead to undesired substitution products. The EP patent applications mentioned describe the preparation of 1,3-disubstituted 2-nitroguanidines by reacting monosubstituted nitroisothioureas with primary amines with release of mercaptan. However, these nitroisothiourea compounds containing alkylthio leaving groups, which are proposed as starting compounds in the known processes, are difficult to obtain.
Weiterhin wird in EP-A-0.483.062 ein Verfahren zur Herstellung der Verbindungen der Formel (I) beschrieben, worin eine Verbindung der obigen Formel (II) hydrolysiert wird. Die dort angeführten Beispiele zeigen, dass die Hydrolyse unter sauren Bedingungen durchgeführt werden muss. Beispiele für die Möglichkeit einer Hydrolyse im basischen Bereich fehlen in der genannten Schrift vollständig.Furthermore, EP-A-0.483.062 describes a process for the preparation of the compounds of the formula (I), in which a compound of the above formula (II) is hydrolyzed. These The examples given show that the hydrolysis must be carried out under acidic conditions. Examples of the possibility of hydrolysis in the basic range are completely missing in the cited document.
Es zeigt sich nun, dass die oben beschriebenen Verfahren zur Herstllung von Verbindungen der Formel (I) den Anforderungen bezüglich Reinheit und Ausbeute nicht genügen, weshalb weiterhin das Bedürfnis besteht, verbesserte Verfahren zur Herstellung dieser Verbindungen aus leicht erhältlichen Ausgangsverbindungen zur Verfügung zu stellen.It now turns out that the processes described above for the preparation of compounds of the formula (I) do not meet the requirements with regard to purity and yield, which is why there is still a need to provide improved processes for the preparation of these compounds from readily available starting compounds.
Es wurde nun überraschenderweise gefunden, dass das erfindungsgemässe Verfahren diese Anforderungen zu befriedigen vermag.It has now surprisingly been found that the method according to the invention is able to meet these requirements.
Das erfindungsgemässe Hydrolyseverfahren wird vorzugsweise bei einem pH-Wert grösser als 7 bis 12, besonders von 8 bis 12, insbesondere 8 bis 10, ebenfalls bevorzugt 7 bis 10; unter Normaldruck und bei einer Temperatur von 0 bis 120°C, vorzugsweise 20 bis 80°C durchgeführt.The hydrolysis process according to the invention is preferably carried out at a pH greater than 7 to 12, particularly 8 to 12, in particular 8 to 10, likewise preferably 7 to 10; carried out under normal pressure and at a temperature of 0 to 120 ° C, preferably 20 to 80 ° C.
Die Reaktion wird in einem gegenüber den Reaktionsteilnehmern inerten Lösungsmittel oder Verdünnungsmittel durchgeführt. Als Lösungsmittel eignen sich in besonderer Weise Alkohole, wie Methanol, Aethanol, Propanol und iso-Propanol, sowie speziell Wasser. Weitere geeignete Lösungsmittel sind z.B. Aether, wie Tetrahydrofuran und Dioxan, sowie andere Lösungsmittel, die die Reaktion nicht beeinträchtigen. Die Lösungsmittel können auch als Gemische verwendet werden. Bevorzugt hydroiysiert man eine Verbindung der Formel (II) in einem wässrigen Milieu oder einem Gemisch von Wasser mit einem Alkohol.The reaction is carried out in a solvent or diluent which is inert to the reactants. Particularly suitable solvents are alcohols, such as methanol, ethanol, propanol and isopropanol, and especially water. Other suitable solvents are e.g. Ethers such as tetrahydrofuran and dioxane, as well as other solvents that 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.
Als Base zur Durchführung des Verfahrens eigenen sich vorzugsweise Hydroxide von Alkali- und Erdalkalimetallen, wie NaOH und KOH; Carbonate wie Na2CO3, NaHCO3, K2CO3; Phosphate wie Na3PO , Na2HPO4, Alkoholate wie Natriummethanolat, Natriumethanolat und K-tert.-butanolat, organische Amine wie Morpholin, Piperidin, Pyrrolidin, einem Mono-, Di- oder Triniederalkylamin, z. B. Ethyl-, Diethyl-, Triethyl- oder Dimethyl-propyl-amin, oder einem Mono-, Di- oder Trihydroxyniederalkylamin, z. B. Mono-, Di- oder Triethanolamin, oder Dialkylanilin, wie beispielsweise N,N-Dimethyl- oder N,N-Diethylanilin; sowie Salze von organischen Säuren wie etwa Natrium-acetat, Kaliumacetat oder Natriumbenzoat; oder Mischungen davon, wie beispielsweise Acetat- oder Phosphatpuffer.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, Na 2 HPO 4 , alcoholates such as sodium methoxide, sodium ethoxide and K-tert-butoxide, organic amines such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. B. ethyl, diethyl, triethyl or dimethyl propyl amine, or a mono-, di- or trihydroxy-lower alkylamine, e.g. B. mono-, di- or triethanolamine, or dialkylaniline, such as N, N-dimethyl or N, N-diethylaniline; as well as salts of organic acids such as sodium acetate, potassium acetate or sodium benzoate; or mixtures thereof, such as acetate or phosphate buffers.
Das erfindungsgemässe Verfahren dient bevorzugt zur Herstellung von Verbindungen der Formel (I), worin der heterocyclische Rest A ungesättigt und über ein Kohlenstoffatom als Ringglied an den Grundkörper gebunden ist. Besonders bevorzugte Reste A sind Pyridyl, Thiazolyl, Tetrahydrofuranyl, Dihydrofuranyl, Furanyl, N-Oxido-pyridinio, Oxazolyl, Isoxazo- lyl, Thienyl, Morpholinyl, Piperidinyl, Pyridinyl und Pyrazinyl; ganz besonders Pyridyl, Thiazolyl, Tetrahydrofuranyl und N-Oxido-pyridinio, besonders 3-Pyridyl, 2-Halogenpyrid-5-yl, 2,3-Dihalogenpyrid-5-yl, 2-Halogenthiazol-5-yl, Tetrahydrofuran-3-yl, 5-Methyl- tetrahydrofuran-3-yl, 1 -Oxopyrid-3-yl, 1 -Oxo-2-halogen-pyrid-5-yl und 1-Oxo-2,3- dihalogenpyrid-5-yl.The process according to the invention is preferably used to prepare compounds of the formula (I) in which the heterocyclic radical A is unsaturated and is bonded to the base body via a carbon atom as a ring member. Particularly preferred radicals A are pyridyl, Thiazolyl, tetrahydrofuranyl, dihydrofuranyl, furanyl, N-oxidopyridinio, oxazolyl, isoxazolyl, thienyl, morpholinyl, piperidinyl, pyridinyl and pyrazinyl; very particularly pyridyl, thiazolyl, tetrahydrofuranyl and N-oxidopyridinio, especially 3-pyridyl, 2-halopyrid-5-yl, 2,3-dihalopyrid-5-yl, 2-halothiazol-5-yl, tetrahydrofuran-3-yl , 5-methyl-tetrahydrofuran-3-yl, 1-oxopyrid-3-yl, 1-oxo-2-halogenopyrid-5-yl and 1-oxo-2,3-dihalopyrid-5-yl.
Ebenfalls bevorzugt tragen die Heterocyclen A ein bis drei Substituenten aus der Gruppe Halogen, C C3-Alkyl, CrC3-Halogenalkyl und CrC3-Halogenalkoxy mit je 1 bis 7 Halogenatomen und d-C3-Alkoxy.Also preferably, the heterocycles A carry from one to three substituents from the group halogen, CC 3 alkyl, -C 3 haloalkyl and -C 3 haloalkoxy, each with 1 to 7 halogen atoms, and dC 3 alkoxy.
Weiterhin werden erfindungsgemäss vorzugsweise Verbindungen der Formel (I) hergestellt, worin der Rest B für einen Phenyl-, Pyridyl- oder Thiazolylrest, welcher unsubstituiert oder durch ein bis zwei Reste aus der Gruppe Halogen, CrC3-Alkyl, CrC3-Halogenalkyl sowie CrC3-Halogenalkoxy mit je 1 bis 7 Halogenatomen und CrC3-Alkoxy substituiert sein kann.Furthermore, according to the invention are preferably compounds of formula (I) are prepared in which the radical B represents a phenyl, pyridyl or thiazolyl, which is unsubstituted or substituted by a 3 haloalkyl or two radicals from the group halogen, -C 3 alkyl, CrC and CrC 3 -Halogenalkoxy with 1 to 7 halogen atoms and CrC 3 -alkoxy may be substituted.
Unter den erfindungsgemäss herzustellenden Verbindungen der Formel (I) sind solche herauszuheben, in denen Ri Wasserstoff, R2 Wasserstoff, Methyl, Äthyl oder Cyclopropyl und A Pyridyl, 1 -Oxopyridyl, Tetrahydrofuranyl, Thiazolyl oder jeweils durch ein bis drei Substituenten aus der Gruppe Halogen, CrC3-Alkyl, Cι-C3-Halogenalkyl sowie C1-C3- Halogenalkoxy mit 1 bis 7 Halogenatomen und d-C3-Alkoxy substituiertes Pyridyl, 1- Oxidopyridinio, Tetrahydrofuranyl oder Thiazolyl bedeuten. In diesem Sinne ist auch die Herstellung solcher Verbindungen der Formel (I) von Interesse, worin a) Ri für Wasserstoff steht; b) R2 Wasserstoff, CrC3-Alkyl oder Cyclopropyl, besonders Methyl, bedeutet; c) A 2-Chlorpyrid-5-yl, Tetrahydrofuran-3-yl, 5-Methyl-tetrahydrofuran-3-yl oder 2- Chlorthiazol-5-yl bedeutet; d) R3 Cι-C-3-Aikyl, Cyclopropyl, Cyclohexyl, Phenyl oder Benzyl bedeutet.Among the compounds of the formula (I) to be prepared according to the invention, those in which R 1 is hydrogen, R 2 is hydrogen, methyl, ethyl or cyclopropyl and A are pyridyl, 1 -oxopyridyl, tetrahydrofuranyl, thiazolyl or in each case by one to three substituents from the group halogen , C r C 3 -alkyl, C 3 haloalkyl and C 1 -C 3 - mean halogenoalkoxy having 1 to 7 halogen atoms, and dC 3 alkoxy substituted pyridyl, 1-oxidopyridinio, thiazolyl or tetrahydrofuranyl. In this sense, the preparation of such compounds of formula (I) is also of interest, in which a) Ri is hydrogen; b) R 2 is hydrogen, CrC 3 alkyl or cyclopropyl, especially methyl; c) A is 2-chloropyrid-5-yl, tetrahydrofuran-3-yl, 5-methyl-tetrahydrofuran-3-yl or 2-chlorothiazol-5-yl; d) R 3 is C 1 -C 3 -alkyl, cyclopropyl, cyclohexyl, phenyl or benzyl.
In Formel (II) kommen als Substituenten für den Rest R3 insbesondere Halogen, d-C4- Alkyl, Halogen-Cι-C alkyl, Nitro, Cι-C -Alkoxy und Halogen-d-C4alkoxy in Frage.In formula (II) come as substituents for the radical R 3 in particular halogen, dC 4 - alkyl, halo -CC alkyl, nitro, -C -alkoxy and halogen-dC 4 alkoxy in question.
Die erfindungsgemäss hergestellten Verbindungen der Formel (I) sind bei günstiger Warmblüter-, Fisch- und Pflanzenverträglichkeit wertvolle Wirkstoffe in der Schädlingsbekämpfung. Insbesondere sind die Verbindungen der Formel (I) geeignet zur Bekämpfung von Insekten und Spinnentieren, die in Nutz- und Zierpflanzen in der Landwirtschaft, insbesonde- re in Baumwoll-, Gemüse- und Obstpflanzungen, im Forst, im Vorrats- und Materialschutz sowie im Hygienesektor insbesondere an Haus- und Nutztieren vorkommen. Die Verbindungen sind vor allem wirksam gegen saugende pflanzenschädigende Insekten, insbesondere gegen Aphiden und Zikaden. Pestizid wirksame substituierte 2-Nitroguanidine vom erfindungsgemäss herstellbaren Typ werden z.B. in den EP-Patentanmeldungen 376.279, 375.907 und 383.091 beschrieben.The compounds of the formula (I) prepared according to the invention are valuable active ingredients in pest control, while being well tolerated by warm-blooded animals, fish and plants. In particular, the compounds of the formula (I) are suitable for controlling insects and arachnids which are found in useful and ornamental plants in agriculture, in particular re in cotton, vegetable and fruit plantations, in the forest, in the protection of stored goods and materials as well as in the hygiene sector, particularly in domestic and farm animals. The compounds are particularly effective against sucking insect pests, especially against aphids and cicadas. Substituted pesticidal 2-nitroguanidines of the type which can be prepared according to the invention are described, for example, in EP patent applications 376.279, 375.907 and 383.091.
Die für das erfindungsgemässe Verfahren in Betracht kommenden Ausgangsverbindungen bzw. Ausgangsprodukte der Formel (II) sind teilweise bekannt oder können nach an sich bekannten Verfahren hergestellt werden. Soweit sie neu sind, sind sie ebenfalls ein Gegenstand der Erfindung. Es handelt sich dabei insbesondere um die Verbindungen der FormelSome of the starting compounds or starting products of the formula (II) which are suitable for the process according to the invention are known or can be prepared by processes known per se. As far as they are new, they are also an object of the invention. These are in particular the compounds of the formula
worin R^ R2 und R3 die in Formel (I) angegebenen Bedeutungen haben, wherein R ^ R 2 and R 3 have the meanings given in formula (I),
R4 Halogen, d-C3-Alkyl, d-C3-Alkoxy, Halogen-CrC -alkyl, d-C3-Halogenalkoxy, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, C2-C3-Halogenalkenyl und C2-C3-Halogenalkinyl, d-C3-Alkylthio, Cι-C3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Haiogenallyloxy, Halogenallylthio, Cyan und Nitro, vorzugsweise d-C3-Alkyl, und n 0, 1 , 2 oder 3, vorzugsweise 0 oder 1 , bedeutet; und gegebenenfalls ihrer möglichen E/Z-Isomeren, E/Z-Isomerengemische und/oder Tautomeren, jeweils in freier Form oder in Salzform.R 4 halogen, dC 3 alkyl, dC 3 alkoxy, halogen-CrC alkyl, dC 3 haloalkoxy, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C 2 -C 3 -Halogenalkenyl and C 2 -C 3 -haloalkynyl, dC 3 -alkylthio, Cι-C 3 -haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, Haiogenallyloxy, haloallylthio, cyano and nitro, preferably dC 3 -alkyl, and n , 2 or 3, preferably 0 or 1; and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form.
Tabelle 1 : Verbindungen der FormelTable 1: Compounds of the formula
Verb.Nr R4 R2 R3 phys. Daten Verb.Nr R 4 R 2 R 3 physical data
1.1 H H H1.1 H H H
1.2 H H -CH3 1.2 HH -CH 3
1.3 H H -C2H5 1.3 HH -C 2 H 5
1.4 H H cyclo-Propyl1.4 H H cyclopropyl
1.5 H H Benzyl1.5 H H benzyl
1.6 H H 4-CI-Benzyl1.6 H H 4 CI benzyl
1.7 H -CH3 -CH3 1.7 H -CH 3 -CH 3
1.9 H -CH3 -C2Hs1.9 H -CH 3 -C 2 ms
1.10 H -CH3 cyclo-Propyl1.10 H -CH 3 cyclopropyl
1.11 5-CH3 H H 1.11 5-CH 3 HH
1.13 5-CH3 H -C2Hs1.13 5-CH 3 H -C 2 Hs
1.14 5-CH3 H cyclo-Propyl1.14 5-CH3 H cyclopropyl
1.15 5-CH3 H Benzyl1.15 5-CH3 H benzyl
1.16 5-CH3 H 4-CI-Benzyl1.16 5-CH3 H 4-CI benzyl
1.19 5-CH3 -CH3 -C2Hδ 1.19 5-CH 3 -CH 3 -C 2 H δ
1.20 5-CH3 -CH3 cyclo-Propyl1.20 5-CH3 -CH 3 cyclo-propyl
HerstellunαsbeispieleManufacturing examples
Beispiel 1 ; : Herstellung von 1 -(2-Chlorpvrid-5-v!methvl)-2-nitro-3-methvl-αuanidin:Example 1 ; : Preparation of 1 - (2-chloroprid-5-v! Methvl) -2-nitro-3-methvl-αuanidine:
Ein Gemisch von 1 ,5 g 1 -(2-Chlorpyrid-5-ylmethyl)-2-nitroimino-3-methyl-5-n-propyl-1 ,3,5-- triazacyclohexan, 0,5 g festem Natnumhydrogencarbonat, 20 ml Methanol und 10 ml Wasser wird während 24 Stunden bei 50°C gerührt. Das Reaktionsgemisch wird eingedampft und der Rückstand an Kieselgel mit Dichlormethan/Methanol 95:5 als Laufmittel gereinigt. Man erhält so die Titelverbindung mit einem Schmelzpunkt von 149-151 °C (Verbindung 2.2). Beispiel 2: Herstellung von 1-(2-Chlorthiazol-5-ylmethyl)-2-nitro-3-methyl-guanidin:A mixture of 1.5 g of 1 - (2-chloropyrid-5-ylmethyl) -2-nitroimino-3-methyl-5-n-propyl-1,3,5- triazacyclohexane, 0.5 g of solid sodium bicarbonate, 20 ml of methanol and 10 ml of water are stirred at 50 ° C. for 24 hours. The reaction mixture is evaporated and the residue is purified on silica gel with dichloromethane / methanol 95: 5 as the eluent. The title compound is thus obtained with a melting point of 149-151 ° C. (compound 2.2). Example 2: Preparation of 1- (2-chlorothiazol-5-ylmethyl) -2-nitro-3-methyl-guanidine:
Ein Gemisch von 1 ,5 g 1-(2-Chlorthiazol-5-ylmethyl)-2-nitroimino-3,5-dimethyl-1 ,3,5-triaza- cyclohexan, 0,3 g NaHCO3, 20 ml Methanol und 20 ml Wasser wird während 16 Stunden bei 50°C gerührt. Das Reaktionsgemisch wird auf 100 ml Essigsäureethyl-ester gegossen und die wässrige Phase abgetrennt. Die organische Phase wird eingedampft und der Rückstand an Kieselgel mit Dichlormethan/Methanol 95:5 als Laufmittel gereinigt. Man erhält so die Titelverbindung mit einem Schmelzpunkt von 167-169°C (Verbindung 2.45).A mixture of 1.5 g of 1- (2-chlorothiazol-5-ylmethyl) -2-nitroimino-3,5-dimethyl-1,3,5-triazacyclohexane, 0.3 g of NaHCO 3 , 20 ml of methanol and 20 ml of water is stirred at 50 ° C. for 16 hours. The reaction mixture is poured onto 100 ml of ethyl acetate and the aqueous phase is separated off. The organic phase is evaporated and the residue is purified on silica gel with dichloromethane / methanol 95: 5 as the eluent. The title compound is thus obtained with a melting point of 167-169 ° C. (compound 2.45).
Beispiel 3: Herstellung von 1-(2-Chlorpyridyl-5-ylmethyl)-2-nitro-guanidin:Example 3: Preparation of 1- (2-chloropyridyl-5-ylmethyl) -2-nitro-guanidine:
Ein Gemisch von 1 ,5 g 1-(2-Chlorpyridyl-5-ylmethyl)-2-nitroimino-5-n-propyl-1 ,3,5-triaza- cyclohexan, 0,77 g NaHCO3, 20 ml Methanol und 10 ml Wasser wird während 21 Stunden bei 50°C gerührt. Das Reaktionsgemisch wird auf 100 ml Essigsäureethyl-ester gegossen, die wässrige Phase abgetrennt und die organische Phase mit Wasser gewaschen. Die organische Phase wird eingedampft und der Rückstand an Kieselgel mit Dichlormethan/Methanol 10:1 als Lauf mittel gereinigt. Man erhält so die Titelverbindung mit einem Schmelzpunkt von 195-197°C (Verbindung 2.1).A mixture of 1.5 g of 1- (2-chloropyridyl-5-ylmethyl) -2-nitroimino-5-n-propyl-1, 3,5-triazacyclohexane, 0.77 g of NaHCO 3 , 20 ml of methanol and 10 ml of water is stirred at 50 ° C for 21 hours. The reaction mixture is poured onto 100 ml of ethyl acetate, the aqueous phase is separated off and the organic phase is washed with water. The organic phase is evaporated and the residue is purified on silica gel with dichloromethane / methanol 10: 1 as the eluent. The title compound is thus obtained with a melting point of 195-197 ° C. (compound 2.1).
Analog zu den obigen Arbeitsweisen der Beispiele 1 bis 3 können auch die folgenden in Tabelle 2 aufgeführten Verbindungen der Formel (I) erhalten werden. c-Propyl bedeutet cyclo-Propyl.Analogously to the above procedures of Examples 1 to 3, the following compounds of the formula (I) listed in Table 2 can also be obtained. c-Propyl means cyclo-propyl.
Tabelle 2: Verbindungen der Formel (I)Table 2: Compounds of formula (I)
Verb.Nr. A Ri R2 phys. DatenVerb.Nr. A Ri R 2 physical data
2.1 2-Chlor-pyrid-5-yl H H Smp. 195-197°C2.1 2-chloro-pyrid-5-yl H H mp 195-197 ° C
2.2 2-Chlor-pyrid-5-yl I H -CH3 Smp. 149-151 °C2.2 2-chloro-pyrid-5-yl IH -CH 3 mp 149-151 ° C
2.3 2-Chlor-pyrid-5-yl H -C2H5 Smp. 125-127°C2.3 2-chloro-pyrid-5-yl H -C 2 H 5 mp 125-127 ° C
2.4 2-Chlor-pyrid-5-yl I H -C3H7(n) Smp. 122-123°C2.4 2-chloro-pyrid-5-yl IH -C 3 H 7 (n) mp 122-123 ° C
2.5 2-Chlor-pyrid-5-yl H c-Propyl2.5 2-chloro-pyrid-5-yl H c-propyl
2.6 2-Chlor-pyrid-5-yl I H -C4H9(n) Smp. 88-90°C2.6 2-Chloro-pyrid-5-yl IH -C 4 H 9 (n) mp 88-90 ° C
2.7 2-Chlor-pyrid-5-yl H -CH(CH3)2 2.7 2-chloro-pyrid-5-yl H -CH (CH 3 ) 2
2.8 2-Chlor-pyrid-5-yl I H Benzyl2.8 2-chloro-pyrid-5-yl I H benzyl
2.9 2-Chlor-pyrid-5-yl H Pyrid-3-yl2.9 2-chloro-pyrid-5-yl H pyrid-3-yl
2.10 2-Chlor-pyrid-5-yl I H 4-Chlorbenzyl 2.11 2-Chlor-pyrid-5-yl -CH3 -CH3 2.12 2-Chlor-pyrid-5-yl I -CH3 -C2H5 2.13 2-Chlor-pyrid-5-yl -CH3 c-Propyl 2.14 2-Chlor-pyrid-5-yl I -CH3 -C3H7(n) 2.15 2-Chlor-pyrid-5-yl -C2H5 -CH3 2.16 2-Chlor-pyrid-5-yl I -C2H5 -C2H5 2.17 2-Chlor-pyrid-5-yl -C2Hδ c-Propyl 2.18 2,3-Dichlor-pyrid-5-yl H H Smp. 207-209°C 2.19 2,3-Dichlor-pyrid-5-yl H -CH3 Smp. 173-175°C 2.20 2,3-Dichlor-pyrid-5-yl H -C2H5 Smp. 159-161 °C 2.21 2,3-Dichlor-pyrid-5-yl H c-Propyl 2.22 2,3-Dichlor-pyrid-5-yl H -C3H7(n) 2.23 2,3-Dichlor-pyrid-5-yl H -C4H9(n) Smp. 152-153°C 2.24 2,3-Dichlor-pyrid-5-yl -CH3 -CH3 2.25 2,3-Dichlor-pyrid-5-yl -CH3 -C2H5 2.26 2,3-Dichlor-pyrid-5-yl -CH3 c-Propyl 2.27 2,3-Dichlor-pyrid-5-yl -C2H5 -CH3 2.10 2-chloro-pyrid-5-yl IH 4-chlorobenzyl 2.11 2-chloro-pyrid-5-yl -CH 3 -CH 3 2.12 2-chloro-pyrid-5-yl I -CH 3 -C 2 H 5 2.13 2-chloro-pyrid-5-yl -CH 3 c- Propyl 2.14 2-chloro-pyrid-5-yl I -CH 3 -C 3 H 7 (n) 2.15 2-chloro-pyrid-5-yl -C2H5 -CH 3 2.16 2-chloro-pyrid-5-yl I - C2H5 -C 2 H5 2.17 2-chloro-pyrid-5-yl -C 2 H δ c-propyl 2.18 2,3-dichloro-pyrid-5-yl HH mp 207-209 ° C 2.19 2,3-dichloro pyrid-5-yl H -CH 3 mp 173-175 ° C 2.20 2,3-dichloropyrid-5-yl H -C 2 H 5 mp 159-161 ° C 2.21 2,3-dichloropyrid- 5-yl H c-propyl 2.22 2,3-dichloropyrid-5-yl H -C 3 H 7 (n) 2.23 2,3-dichloropyrid-5-yl H -C 4 H 9 (n) m.p. 152-153 ° C 2.24 2,3-dichloropyrid-5-yl -CH 3 -CH 3 2.25 2,3-dichloropyrid-5-yl -CH 3 -C2H5 2.26 2,3-dichloropyrid- 5-yl -CH 3 c-propyl 2.27 2,3-dichloropyrid-5-yl -C2H5 -CH 3
.31 H c-Propyl .31 H c-propyl
.34 -CH3 c-Propyl .34 -CH 3 c-propyl
.39 H c-Propyl .39 H c-propyl
.41 -CH3 c-Propyl .41 -CH 3 c-propyl
2.44 2-Chlor-thiazol-5-yl H H Smp. 158-160°C 2.44 2-chlorothiazol-5-yl HH mp 158-160 ° C
2.45 2-Chlor-thiazol-5-yl H -CH3 Smp. 167-169°C2.45 2-chlorothiazol-5-yl H -CH 3 mp 167-169 ° C
2.46 2-Chlor-thiazol-5-yl H -C2H5 Smp. 135-136°C2.46 2-chlorothiazol-5-yl H -C 2 H 5 mp 135-136 ° C
2.47 2-Chlor-thiazol-5-yl H c-Propyl2.47 2-chlorothiazol-5-yl H c-propyl
2.48 2-Chlor-thiazol-5-yl H Benzyl2.48 2-chlorothiazol-5-yl H benzyl
2.49 2-Chlor-thiazol-5-yl H 4-CI-Benzyl2.49 2-chlorothiazol-5-yl H 4-CI-benzyl
2.50 2-Chlor-thiazol-5-yl -CH3 -CH3 2.50 2-chlorothiazol-5-yl -CH 3 -CH 3
2.51 2-Chlor-thiazol-5-yl -C2Hs -CH3 2.51 2-chlorothiazol-5-yl -C 2 Hs -CH 3
2.52 2-Chlor-thiazol-5-yl -CH3 -C2Hδ 2.52 2-chlorothiazol-5-yl -CH 3 -C 2 H δ
2.53 2-Chlor-thiazol-5-yl -CH3 c-Propyl2.53 2-chlorothiazol-5-yl -CH 3 c-propyl
2.54 Tetrahydrofuran-3-yl H H2.54 tetrahydrofuran-3-yl H H
2.55 Tetrahydrofuran-3-yl H -CH3 2.55 tetrahydrofuran-3-yl H -CH 3
2.56 Tetrahydrofuran-3-yl H -C2H5 2.56 tetrahydrofuran-3-yl H -C 2 H 5
2.57 Tetrahydrofuran-3-yl H c-Propyl2.57 tetrahydrofuran-3-yl H c-propyl
2.58 Tetrahydrofuran-3-yl H Benzyl2.58 tetrahydrofuran-3-yl H benzyl
2.59 Tetrahydrofuran-3-yl H 4-CI-Benzyl2.59 tetrahydrofuran-3-yl H 4-CI-benzyl
2.60 Tetrahydrofuran-3-yl -CH3 -CH3 2.60 tetrahydrofuran-3-yl -CH 3 -CH 3
2.61 Tetrahydrofuran-3-yl -C2Hδ -CH3 2.61 tetrahydrofuran-3-yl -C 2 H δ -CH 3
2.62 Tetrahydrofuran-3-yl -CH3 -C2Hδ 2.62 tetrahydrofuran-3-yl -CH 3 -C 2 H δ
2.63 Tetrahydrofuran-3-yl -CH3 c-Propyl2.63 tetrahydrofuran-3-yl -CH 3 c-propyl
2.64 5-Methyl-Tetrahydrofuran- •3-yl H H2.64 5-methyl-tetrahydrofuran • 3-yl H H
2.65 5-Methyl-Tetrahyd rof u ran- •3-yl H -CH3 2.65 5-methyl-tetrahydrofuran • 3-yl H -CH 3
2.66 5-Methyl-Tetrahydrofuran- 3-yl H -C2Hs2.66 5-methyl-tetrahydrofuran-3-yl H -C 2 Hs
2.67 5-MethyI-Tetrahyd rof u ran- 3-yl H c-Propyl2.67 5-methyl-tetrahydrofuran-3-yl H c-propyl
2.68 5-Methyl-Tetrahydrofuran- 3-yl H Benzyl2.68 5-methyl-tetrahydrofuran-3-yl H benzyl
2.69 5-Methyl-Tetrahydrofuran- 3-yl H 4-CI-Benzyl2.69 5-methyl-tetrahydrofuran-3-yl H 4-CI-benzyl
2.70 5-Methyl-Tetrahydrofuran- 3-yl -CH3 -CH3 2.70 5-methyl-tetrahydrofuran-3-yl -CH 3 -CH 3
2.71 5-Methyl-Tetrahydrofuran-3-yl -C2H5 -CH3 2.71 5-methyl-tetrahydrofuran-3-yl -C 2 H 5 -CH 3
2.72 5-Methyl-Tetrahydrofuran- 3-yl -CH3 -C2H5 2.72 5-methyl-tetrahydrofuran-3-yl -CH 3 -C 2 H 5
2.73 5-Methyl-Tetrahydrofuran- 3-yl -CH3 c-Propyl 2.73 5-methyl-tetrahydrofuran-3-yl -CH 3 c-propyl

Claims

Patentansprüche claims
1 . Verfahren zur Herstellung einer Verbindung der Formel1 . Process for the preparation of a compound of formula
worin wherein
R. Wasserstoff oder Cι-C4-Alkyl; R. Hydrogen or -CC 4 alkyl;
R2 Wasserstoff, d-drAlkyl, C3-C6-Cycloalkyl oder einen Rest -CH2B;R 2 is hydrogen, d-dr alkyl, C 3 -C 6 cycloalkyl or a radical -CH 2 B;
A einen unsubstituierten oder - je nach Substitutionsmöglichkeiten des Ringsystems - ein- bis fünffach mit Substituenten ausgewählt aus der Gruppe bestehend aus Halogen, d-C3-Alkyl, C C3-Alkoxy, Halogen-C C3-alkyl- d-C3-Halogenalkoxy, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, C2-C3-Halogenalkenyl und C2-C3-Halogenalkinyl, d-C3-Alkylthio, d-C3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Haiogenallyloxy, Halogenallylthio, Cyan und Nitro substituierten aromatischen oder nichtaromatischen, monocyclischen oder bicyclischen he- terocyclischen Rest; undA is an unsubstituted or, depending on the substitution possibilities of the ring system, one to five times with substituents selected from the group consisting of halogen, dC 3 alkyl, CC 3 alkoxy, halogenoC C 3 alkyl dC 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, dC 3 alkylthio, dC 3 haloalkylthio, allyloxy, propargyloxy, allylthio, Propargylthio, haiogenallyloxy, haloallylthio, cyano and nitro substituted aromatic or non-aromatic, monocyclic or bicyclic heterocyclic radical; and
B Phenyl, 3-Pyridyl oder Thiazolyl, welche gegebenenfalls - je nach Substitutionsmöglichkeiten des Ringsystems - durch ein bis drei Substituenten aus der Gruppe bestehend aus d-C3-Alkyl, d-C3-Halogenalkyl, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, d-C3-Alkoxy, C2-C3-Halogenalkenyl, C2-C3-Halo- genalkinyl, d-C3-Halogenalkoxy, d-C3-Alkylthio, CrC3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Haiogenallyloxy, Halogenallylthio, Halogen, Cyano und Nitro substituiert sind; und gegebenenfalls ihrer möglichen E/Z-Isomeren, E/Z-Isomerengemische und/oder Tautomeren, jeweils in freier Form oder in Salzform; durch Hydrolyse einer Verbindung der Formel worin R1 ( R2 und A die gleiche Bedeutung haben wie in Formel (I) angegeben, undB phenyl, 3-pyridyl or thiazolyl, which optionally - depending on the substitution possibilities of the ring system - by one to three substituents from the group consisting of dC 3 alkyl, dC 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, dC 3 alkoxy, C 2 -C 3 haloalkenyl, C 2 -C 3 -Halo- genalkinyl, dC 3 haloalkoxy, dC 3 alkylthio, -C 3 haloalkylthio, allyloxy, propargyloxy, Allylthio, Propargylthio, Haiogenallyloxy, Halogenallylthio, Halogen, Cyano and Nitro are substituted; and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form; by hydrolysis of a compound of the formula wherein R 1 ( R 2 and A have the same meaning as given in formula (I), and
R3 unsubstituiertes oder substituiertes d-do-Alkyl, C3-C6-Cycloalkyl, Phenyl oder Benzyl bedeutet; dadurch gekennzeichnet, dass man die Reaktion bei einem pH-Wert zwischen 7 und 14 durchführt.R 3 represents unsubstituted or substituted d-do alkyl, C 3 -C 6 cycloalkyl, phenyl or benzyl; characterized in that the reaction is carried out at a pH between 7 and 14.
2. Verfahren gemass Anspruch 1 zur Herstellung einer Verbindung der Formel (I) in freier Form.2. The method according to claim 1 for the preparation of a compound of formula (I) in free form.
3. Verfahren gemass Anspruch 1 zur Herstellung einer Verbindung der Formel (I), worin Ri für Wasserstoff steht.3. The method according to claim 1 for the preparation of a compound of formula (I), wherein Ri is hydrogen.
4. Verfahren gemass Anspruch 1 zur Herstellung einer Verbindung der Formel (I), worin R2 Wasserstoff, C C3-Alkyl oder Cyclopropyl bedeutet.4. The method according to claim 1 for the preparation of a compound of formula (I), wherein R 2 is hydrogen, CC 3 alkyl or cyclopropyl.
5. Verfahren gemass Anspruch 1 zur Herstellung einer Verbindung der Formel (I) aus einer Verbindung der Formel (II), worin R3 d-C3-Alkyl, Cyclopropyl, Cyclohexyl, Phenyl oder Benzyl bedeutet.5. The method according to claim 1 for the preparation of a compound of formula (I) from a compound of formula (II), wherein R 3 is dC 3 alkyl, cyclopropyl, cyclohexyl, phenyl or benzyl.
6. Verfahren gemass Anspruch 1 zur Herstellung einer Verbindung der Formel (I), worin A 2-Chlorpyrid-5-yl, Tetrahydrofuran-3-yl, 5-Methyl-tetrahydrofuran-3-yl oder 2-Chlorthiazol-5-yl bedeutet.6. The method according to claim 1 for the preparation of a compound of formula (I), wherein A is 2-chloropyrid-5-yl, tetrahydrofuran-3-yl, 5-methyl-tetrahydrofuran-3-yl or 2-chlorothiazol-5-yl .
7. Verfahren gemass einem der Anspruch 1 bis 6 zur Herstellung einer Verbindung der Formel (I), dadurch gekennzeichnet, dass der pH-Wert zwischen grösser als 7 und 12 liegt.7. The method according to any one of claims 1 to 6 for the preparation of a compound of formula (I), characterized in that the pH is between greater than 7 and 12.
8. Verfahren gemass einem der Ansprüche 1 bis 7 zur Herstellung einer Verbindung der Formel (I), dadurch gekennzeichnet, dass in Wasser, einem Alkohol oder einer Mischung von Wasser mit einem Alkohol gearbeitet wird.8. The method according to any one of claims 1 to 7 for the preparation of a compound of formula (I), characterized in that it is carried out in water, an alcohol or a mixture of water with an alcohol.
9. Verbindung der Formel 9. Compound of the formula
worin R1f R2 und R3 die in Anspruch 1, Formel (I), angegebenen Bedeutungen haben,wherein R 1f R 2 and R 3 have the meanings given in Claim 1, formula (I),
R4 Halogen, d-C3-Alkyl, CrC3-Alkoxy, Halogen-d-C3-alkyl, d-C3-Halogenalkoxy, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, C2-C3-Halogenalkenyl und C2-C3-Halogenalkinyl, d-C3-Alkylthio, d-C3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Haiogenallyloxy, Halogenallylthio, Cyan und Nitro, und n 0, 1 , 2 oder 3 bedeutet; und gegebenenfalls ihrer möglichen E/Z-Isomeren, E/Z-Isomerengemische und/oder Tautomeren, jeweils in freier Form oder in Salzform. R 4 halogen, dC 3 alkyl, CrC 3 alkoxy, halogen dC 3 alkyl, dC 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, dC 3 -alkylthio, dC 3 -haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haiogenallyloxy, haloallylthio, cyano and nitro, and n denotes 0, 1, 2 or 3; and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form.
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