WO1999009009A1 - Method for producing organic compounds - Google Patents

Method for producing organic compounds Download PDF

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Publication number
WO1999009009A1
WO1999009009A1 PCT/EP1998/005248 EP9805248W WO9909009A1 WO 1999009009 A1 WO1999009009 A1 WO 1999009009A1 EP 9805248 W EP9805248 W EP 9805248W WO 9909009 A1 WO9909009 A1 WO 9909009A1
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WO
WIPO (PCT)
Prior art keywords
formula
compound
alkyl
substituted
preparation
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PCT/EP1998/005248
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German (de)
French (fr)
Inventor
Peter Maienfisch
Original Assignee
Novartis Ag
Novartis-Erfindungen Verwaltungsgesellschaft Mbh
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 Ag, Novartis-Erfindungen Verwaltungsgesellschaft Mbh filed Critical Novartis Ag
Priority to IL13450298A priority Critical patent/IL134502A0/en
Priority to CA002301172A priority patent/CA2301172A1/en
Priority to AU93442/98A priority patent/AU741658B2/en
Priority to EP98946375A priority patent/EP1005456A1/en
Priority to KR1020007001670A priority patent/KR20010023053A/en
Priority to BR9811966-4A priority patent/BR9811966A/en
Priority to PL98338778A priority patent/PL338778A1/en
Priority to JP2000509693A priority patent/JP2001515066A/en
Publication of WO1999009009A1 publication Critical patent/WO1999009009A1/en

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    • 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
    • C07D401/02—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 two hetero rings
    • C07D401/04—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 two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • 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
    • 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
    • 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
    • C07D401/02—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 two hetero rings
    • C07D401/06—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 two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • C07D405/02—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 two hetero rings
    • C07D405/04—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 two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D417/02—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 two hetero rings
    • C07D417/12—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 two hetero rings linked by a chain containing hetero atoms as chain links

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 mercaptan.
  • 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 hexahydro-triazines.
  • 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 invention relates a) a process for the preparation of a compound of formula
  • R T is hydrogen or CC alkyl
  • R 2 is hydrogen, CrC 6 alkyl, C 3 -C 6 cycloalkyl or a radical -CH 2 B;
  • A 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, C 1 -C 3 -alkyl, CC 3 -alkoxy, halogen-CrC 3 -alkyl, d-0 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, CrCs-alkylthio, CC 3 -haloalkylthio, allyloxy, propargyloxy, Allylthio, propargylthio, haloallyloxy, haloallylthio, cyano and nitro substituted aromatic or non-aromatic, monocyclic or bicyclic heterocyclic radical; and
  • Substituents selected from the group consisting of -C 3 -alkyl, C 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, C ⁇ -C 3 alkoxy, C 2 -C 3 - Halogenalkenyl, C 2 -C 3 -haloalkynyl, -C-C 3 -haloalkoxy, C Cs-alkylthio, -C-C 3 -haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, 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; characterized in that a compound of
  • R 3 is unsubstituted or substituted C ⁇ C 22 alkyl, C 7 -C ⁇ 6 cycloalkyl, C 3 -C 20 alkenyl, C 3 -C 2 o-alkynyl, N (R) R, optionally substituted aryl with the exception of unsubstituted and substituted phenyl; or an optionally substituted, aromatic or non-aromatic, monocyclic or bicyclic, heterocyclic radical;
  • R 4 is hydrogen or CC ⁇ alkyl
  • R 5 is hydrogen, CrC 12 alkyl, CrC ⁇ 2 alkyl carbonyl or CrC 12 alkoxy carbonyl; means 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, for example, CC-alkane-carboxylic acids substituted by halogen, for example acetic acid, such as optionally unsaturated dicarboxylic acids, for example Oxal, malon, malein, 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, for example, dC 4 -alkane or arylsulfonic acids substituted by halogen, for example methan
  • 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 substitute 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.
  • alkyl groups have up to 6 carbon atoms. 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.
  • 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 , CH 2 CF 2 CF 3 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 )
  • 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 (N, O or S) by a saturated carbon atom.
  • alkyl, alkoxy, alkenyl, alkynyl 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.
  • the cycloalkyl radicals which are suitable as substituents R 3 are, for example, cyclodecyl, cyclohexadecyl, cyclododecyl or cyclooctadecyl.
  • Aryl means phenyl, naphthyl, phenanthrenyl or anthracenyl, in connection with the substituent R 3 in the compounds of the formulas (II) and (III) especially naphthyl, in connection with the other substituents listed especially phenyl.
  • a heterocyclic radical preferably means a 5- to 7-membered aromatic or non-aromatic ring with one to three heteroatoms, which are selected from the group consisting of N, O and S.
  • Aromatic 5- and 6- are preferred. Rings, which have a nitrogen atom as hetero atom and optionally have 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, in particular in a strongly acidic, and in a basic medium.
  • acidic range pH values of less than 5 to 1, particularly less than 3 to 1, 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.
  • Mineral acids such as e.g. Sulfuric acid, a phosphoric acid or a hydrohalic acid, an organic carboxylic acid such as, e.g., e.g. halogen, substituted C C alkane carboxylic acids, e.g. Acetic acid such as optionally unsaturated dicarboxylic acids e.g. Oxalic, maionic, maleic, fumaric or phthalic acid such as hydroxycarboxylic acids e.g. Ascorbic, lactic, malic, tartaric or citric acid, or such as benzoic acid, or an organic sulfonic acid, such as optionally e.g. halogen, substituted CrC - alkane or aryl sulfonic acids, e.g. Methane or p-toluenesulfonic acid.
  • an organic carboxylic acid such as, e.g., e.g. halogen, substituted C C alkane carboxylic acids,
  • 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 4 , 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
  • 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-oxido-pyridinio, 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-yI, tetrahydrofuran-3-yl , 5-methyl-tetrahydrofuran
  • the heterocycles A also preferably carry one to three substituents from the group halogen, C 1 -C 3 -alkyl, dC 3 -haloalkyl and CC 3 -haloalkoxy, each having 1 to 7 halogen atoms and dC 3 -alkoxy.
  • 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 halogen, C 1 -C 3 -alkyl, dC 3 -haloalkyl and dC can be 3 haloalkoxy, each with 1 to 7 halogen atoms, and dC substituted 3 alkoxy.
  • the radical B is a phenyl, pyridyl or thiazolyl radical which is unsubstituted or by one or two radicals from the group halogen, C 1 -C 3 -alkyl, dC 3 -haloalkyl and dC can be 3 haloalkoxy, each with 1 to 7 halogen atoms, and dC substituted 3 alkoxy.
  • R 2 are hydrogen, methyl, ethyl or cyclopropyl and A are pyridyl, 1 -oxopyridyl, tetrahydrofuranyl, thiazolyl or in each case by one to three substituents from the halogen group , dC 3 -alkyl, dC 3 -haloalkyl and CC 3 - haloalkoxy with 1 to 7 halogen atoms and CC 3 -alkoxy substituted pyridyl, 1 -oxidopyridinio, tetrahydrofuranyl or thiazolyl.
  • R T is hydrogen
  • R 2 is hydrogen, dC 3 alkyl or cyclopropyl, especially methyl
  • A is 2-chloropyrid-5-yl, tetrahydrofuran-3-yl, 2-methyl-tetrahydrofuran-4-yl or 2-chlorothiazol-5-yl.
  • the substituents for the radical R 3 are in particular Cn-Cie-alkyl, Cn-C ⁇ - 8 alkyl substituted by hydroxy or -COO-d-de-alkyl , optionally with phenyl or hydroxy substituted C 3 -C 18 alkenyl, optionally substituted with phenyl C 3 -Ci 8 alkynyl, cyclooctyl, cyclodecyl, cycloheptyl, cyclododecyl, thiazolyl, pyridyl, pyridinyl, pyrazinyl or optionally substituted naphthyl.
  • the invention further relates to b) a process for the preparation of a compound of the formula (II) and, if appropriate, its E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form, characterized in that that you have a compound of the formula
  • R 2 and R 3 have the same meaning as defined above for the formula (II); and optionally their E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form, with a compound of the formula
  • R 1 and A have the meanings given above for the formula (I) and Y denotes a leaving group, preferably halogen, preferably in the presence of a base.
  • the invention further provides c) a process for the preparation of the compounds of the formula (III) and, if appropriate, their E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form, characterized in that that you have a compound of the formula
  • Another object of the invention is d) a process for the preparation of a compound of formula (I), and optionally its E / Z isomers, E / Z isomer mixtures and / or tautomers, each in free form or in salt form, characterized in that that a compound of formula (V) is converted into a compound of formula (III) by reaction with a compound of formula (VI) and formaldehyde or paraformaldehyde; converting this compound of formula (III) with a compound of (IV) into a compound of formula (II), and hydrolyzing this compound of formula (II).
  • Another object of the invention is e) the use of the compounds of formula (II) for the preparation of the compounds of formula (I).
  • the compounds of the formula (I) prepared in accordance with the invention are valuable active ingredients in pest control with favorable warm-blood tolerance, 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 occurrence.
  • 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.
  • Table 2 Compounds of the general formula (Ila), in which A means and R 3 corresponds to one row of Table A.
  • Connection 2.A.5 Smpt .: 119-121 ° C Connection 2.A.37: Smpt .: 137-139 ° C Connection 2.A.38: Smpt .: 76-78 ° C Connection 2.A. 39: Smpt .: 90-92 ° C
  • Table 3 Compounds of the general formula (Ila), in which A denotes and R 3 corresponds to one row of Table A.
  • Table 4 Compounds of the general formula (Ila), in which A denotes and R 3 corresponds to one row of Table A.
  • Table 5 Compounds of the general formula (Ila), in which A denotes and R 3 corresponds to one row of Table A.
  • Table 6 Compounds of the general formula (Ila), in which A denotes and R 3 corresponds to one row of Table A.
  • R 3 corresponds in each case to one row of table A.
  • N-0 and R 3 each correspond to one row of Table A.
  • Table 9 Compounds of the general formula (IIIa), in which A means and R 3 corresponds to one row of Table A.
  • R 3 corresponds in each case to one row of table A.
  • R 3 corresponds to one row of Table A.
  • Table 12 Compounds of the general formula (IIIa), in which A denotes and R 3 corresponds to one row of Table A.
  • Table 13 Compounds of the general formula (IIIa), in which A denotes and R 3 corresponds to one row of Table A.
  • Example 3.1 Preparation of the compound of the formula
  • Another object of the invention is f) a method for controlling pests, especially animal pests, in particular insects and representatives of the order Akarina, with the compounds of formula (II).
  • the 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.

Abstract

The invention relates to a method for producing compounds of formula (I), wherein R1 is hydrogen or C1-C4 alkyl, R2 is hydrogen, C1-C6alkyl, C3-C6 cycloalkyl or a radical -CH2B, A is an unsubstituted or substituted, aromatic or non-aromatic, monocyclic or bicyclic heterocyclic radical and B is phenyl, 3-pyridyl or thiazolyl, these being substituted. The inventive method is characterised in that a compound of formula (II) wherein R1, R2 and A have the same meanings as in formula (I) and R3 is unsubstituted or substituted C11-C22 alkyl, C7-C16 cycloalkyl, C3-C20 alkenyl, C3-C20 alkinyl, N(R4)R5, optionally substituted aryl with the exception of unsubstituted and substituted phenyl, or an optionally substituted heterocyclic radical, R4 is hydrogen or C1-C12 alkyl and R5 is hydrogen, C1-C12 alkyl, C1-C12 alkyl carbonyl or C1-C12 alkoxy carbonyl is hydrolysed. The invention also relates to a method for producing compounds of formulae (II) and (III), and to a method for combating pests using compounds of formula (II). The compounds of formula (I) are suitable for producing pesticide mixtures.

Description

VERFAHREN ZUR HERSTELLUNG VON SUBSTITUIERTEN 2-NITROGUANIDINDERIVATENMETHOD FOR PRODUCING SUBSTITUTED 2-NITROGUANIDINE DERIVATIVES
Die vorliegende Erfindung betrifft ein neuartiges Verfahren zur Herstellung von substituierten 2-Nitroguanidinderivaten.The present invention relates to a novel process for the preparation of substituted 2-nitroguanidine derivatives.
Es ist 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 unselektive 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 Mercaptan-Abspaltung beschrieben. Diese bei den bekannten Verfahren als Ausgangsverbindungen vorgeschlagenen Alkylthio-Abgangsgruppen enthaltenden Nitroisothioharnstoffverbindungen sind aber nur schwer zugänglich. Weiterhin wird in EP-A- 0.483.062 ein Verfahren zur Herstellung der Verbindungen der Formel (I) durch Hydrolyse von Hexahydro-triazinen beschrieben.It is 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 elimination of mercaptan. However, these nitroisothiourea compounds containing alkylthio leaving groups, which are proposed as starting compounds in the known processes, are difficult to obtain. Furthermore, EP-A-0.483.062 describes a process for the preparation of the compounds of the formula (I) by hydrolysis of hexahydro-triazines.
Es zeigt sich nun, dass die oben beschriebenen Verfahren zur Herstellung von Verbindungen der Formel (I) den Anforderungen, welche an ein chemisches Produktionsverfahren gestellt werden, wie beispielsweise Verfügbarkeit, Toxizität, Lagerstabilität und Reinheit der Ausgangmaterialien und Hilfsstoffe, Reaktionszeit, Energieverbrauch und Volumenausbeute des Prozesses, Menge und Zurückgewinnung der anfallenden Nebenprodukte und Abfälle sowie Reinheit und Ausbeute des Endproduktes nicht genügen. Deshalb besteht weiterhin das Bedürfnis, verbesserte Verfahren zur Herstellung dieser Verbindungen zur Verfügung zu stellen. Es wurde nun überraschenderweise gefunden, dass das erfindungs- gemässe Verfahren diese Anforderungen in hohem Masse zu befriedigen vermag.It can now be seen that the processes described above for the preparation of compounds of the formula (I) meet the requirements placed on a chemical production process, such as, for example, availability, toxicity, storage stability and purity of the starting materials and auxiliaries, reaction time, energy consumption and volume yield of the The process, quantity and recovery of the by-products and waste produced, as well as the purity and yield of the end product are not sufficient. Therefore, there continues to be a need to provide improved methods of making these compounds. It has now surprisingly been found that the method according to the invention is able to meet these requirements to a high degree.
Demgemäss ist das Ziel der vorliegenden Erfindung ein verbessertes Verfahren zur Herstellung von 1 -monosubstituierten und 1 ,3-disubstituierten 2-Nitroguanidinen aus leicht erhältlichen Ausgangsverbindungen, welche eine gezielte 1 ,3-Disubstitution ohne Entstehung grösserer Mengen unerwünschter Nebenprodukte gestattet.Accordingly, 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.
Die Erfindung betrifft a) ein Verfahren zur Herstellung einer Verbindung der FormelThe invention relates a) a process for the preparation of a compound of formula
H ?■ H ? ■
N02 worinN0 2 where
RT Wasserstoff oder C C -Alkyl;R T is hydrogen or CC alkyl;
R2 Wasserstoff, CrC6-Alkyl, C3-C6-Cycloalkyl oder einen Rest -CH2B;R 2 is hydrogen, CrC 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, C C3-Alkoxy, Halogen-CrC3-alkyl, d-03-Halogenalkoxy, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, C2-C3-Halogenalkenyl und C2-C3-Halogenalkinyl, CrCs-Alkylthio, C C3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Halogenallyloxy, Halogenallylthio, Cyan und Nitro substituierten aromatischen oder nichtaromatischen, monocyclischen oder bicyclischen heterocyclischen 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, C 1 -C 3 -alkyl, CC 3 -alkoxy, halogen-CrC 3 -alkyl, d-0 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, CrCs-alkylthio, CC 3 -haloalkylthio, allyloxy, propargyloxy, Allylthio, propargylthio, haloallyloxy, 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 dreiB phenyl, 3-pyridyl or thiazolyl, which are optionally by one to three
Substituenten aus der Gruppe bestehend aus CrC3-Alkyl, Cι-C3-Halogenalkyl, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, Cι-C3-Alkoxy, C2-C3- Halogenalkenyl, C2-C3-Halogenalkinyl, Cι-C3-Halogenalkoxy, C Cs-Alkylthio, Cι-C3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Halogenallyloxy, 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; dadurch gekennzeichnet, dass man eine Verbindung der FormelSubstituents selected from the group consisting of -C 3 -alkyl, C 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, Cι-C 3 alkoxy, C 2 -C 3 - Halogenalkenyl, C 2 -C 3 -haloalkynyl, -C-C 3 -haloalkoxy, C Cs-alkylthio, -C-C 3 -haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, 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; characterized in that a compound of the formula
Figure imgf000004_0001
worin R1 t R2 und A die gleiche Bedeutung haben wie in Formel (I) angegeben und
Figure imgf000004_0001
wherein R 1 t R 2 and A have the same meaning as indicated in formula (I) and
R3 unsubstituiertes oder substituiertes Cι C22-Alkyl, C7-Cι6-Cycloalkyl, C3-C20-Alkenyl, C3-C2o-Alkinyl, N(R )Rs, gegebenenfalls substituiertes Aryl mit Ausnahme von unsubstituiertem und substituiertem Phenyl; oder einen gegebenenfalls substituierten, aromatischen oder nichtaromatischen, monocyclischen oder bicyclischen, heterocyclischen Rest;R 3 is unsubstituted or substituted C ι C 22 alkyl, C 7 -Cι 6 cycloalkyl, C 3 -C 20 alkenyl, C 3 -C 2 o-alkynyl, N (R) R, optionally substituted aryl with the exception of unsubstituted and substituted phenyl; or an optionally substituted, aromatic or non-aromatic, monocyclic or bicyclic, heterocyclic radical;
R4 Wasserstoff oder C C^-Alkyl;R 4 is hydrogen or CC ^ alkyl;
R5 Wasserstoff, CrC12-Alkyl, CrCι2-Alkyl-carbonyl oder CrC12-Alkoxy-carbonyl; bedeutet, hydrolysiert.R 5 is hydrogen, CrC 12 alkyl, CrCι 2 alkyl carbonyl or CrC 12 alkoxy carbonyl; means hydrolyzed.
Die Verbindungen der Formel (I) können als E/Z-Isomere vorliegen, z.B. in den folgenden zwei isomeren FormenThe compounds of formula (I) may exist as E / Z isomers, e.g. in the following two isomeric forms
Figure imgf000005_0001
Figure imgf000005_0001
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
Figure imgf000005_0002
Figure imgf000005_0002
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 Carbon-säuren, wie gegebenenfalls, z.B. durch Halogen, substituierten C C -Alkan-carbonsäuren, z.B. Essigsäure, wie gegebenenfalls ungesättigten Dicarbonsäuren, z.B. Oxal-, Malon-, Malein-, Fumar- oder Phthalsäure, wie Hydroxycarbonsäuren, z.B. Ascorbin-, Milch-, Äpfel-, Weinoder Zitronensäure, oder wie Benzoesäure, oder mit organischen Sulfonsäuren, wie gegebenenfalls, z.B. durch Halogen, substituierten d-C4-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 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, for example, CC-alkane-carboxylic acids substituted by halogen, for example acetic acid, such as optionally unsaturated dicarboxylic acids, for example Oxal, malon, malein, 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, for example, dC 4 -alkane or arylsulfonic acids substituted by halogen, for example 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-, Di- oder 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 sinngemäss unter den freien Verbindungen der Formel (I) gegebenenfalls auch die entsprechenden Salze, und unter den Salzen auch 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. 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. Preferred in the context of the invention are agrochemically advantageous salts. Above and below, the free compounds of the formula (I) are also to be understood as meaning, where appropriate, the corresponding salts, and the salts also include 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 vor- und nachstehenden Formeln (I) bis (VI) sollen die einzelnen generischen Begriffe wie folgt verstanden werden:In the definition of the formulas (I) to (VI) above and below, 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 Substitueήt oder als Teil eines Substituenten zu verstehen wie im Halogenalkyl, Halogenalkylthio, Halogenalkoxy, Halogencycloalkyl, Halogenalkenyl, Halogenalkinyl, Halogenallyloxy oder Halogenallylthio. Die als Substituenten in Betracht kommenden Alkyl-, Alkylthio-, Alkenyl-, Alkinyl- und Alkoxyreste können geradkettig oder verzweigt sein. Alkylgruppen haben, wenn nicht anders definiert, bis zu 6 Kohlenstoffatome. Als Beispiele solcher Alkyle seien Methyl, Ethyl, Propyl, Isopropyl, Butyl, i-Butyl, sek.-Butyl oder tert.-Butyl genannt. Als geeignete Alkoxyreste seien unter anderem genannt: Methoxy, Ethoxy, Propoxy, Isopropoxy oder Butoxy und ihre Isomeren. Alkylthio steht beispielsweise für Methylthio, Ethylthio, 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 perhaiogeniert 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 Ethyl 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, CH2CF2CF3oder 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 substitute 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. Unless otherwise defined, alkyl groups have up to 6 carbon atoms. 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. Are the possible substituents alkyl, alkoxy, alkenyl, alkynyl or cycloalkyl groups by halogen substituted, so they can only be partially or perhaogenized. 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 , CH 2 CF 2 CF 3 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.
Alkenyl- und Alkinylgruppen enthalten eine ungesättigte Kohlenstoff-Kohlenstoff-Bindung. Typische Vertreter sind Allyl, Methallyl oder Propargyl, aber auch Vinyl und Ethinyl. Die Doppel- oder Dreifachbindungen in Allyloxy, Propargyloxy, Allylthio oder Propargylthio sind von der Verknüpfungsstelle zum Heteroatom (N, O oder S) vorzugsweise durch ein gesättigtes Kohlenstoffatom getrennt.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 (N, O or S) by a saturated carbon atom.
Sind die definierten Alkyl-, Alkoxy-, Alkenyl-, Alkinyl- 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. Bei den als Substituenten R3 in Betracht kommenden Cycloalkylresten handelt es sich beispielsweise um Cyclodecyl, Cyclo- hexadecyl, Cyclododecyl oder Cyclooctadecyl.If the defined alkyl, alkoxy, alkenyl, alkynyl 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. The cycloalkyl radicals which are suitable as substituents R 3 are, for example, cyclodecyl, cyclohexadecyl, cyclododecyl or cyclooctadecyl.
Aryl bedeutet Phenyl, Naphthyl, Phenanthrenyl oder Anthracenyl, im Zusammenhang mit dem Substituenten R3 in den Verbindungen der Formeln (II) und (III) besonders Naphthyl, im Zusammenhang mit den übrigen aufgeführten Substituenten besonders Phenyl.Aryl means phenyl, naphthyl, phenanthrenyl or anthracenyl, in connection with the substituent R 3 in the compounds of the formulas (II) and (III) especially naphthyl, in connection with the other substituents listed especially phenyl.
Ein heterocyclischer Rest bedeutet im Rahmen der vorliegenden Erfindung vorzugsweise einen 5- bis 7-gliedrigen aromatischen oder nichtaromatischen Ring mit einem bis drei Heteroatomen, welche ausgewählt sind aus der Gruppe, bestehend aus N, O und S. Bevorzugt sind aromatische 5- und 6-Ringe, welche ein Stickstoffatom als Heteroatom und gegebenenfalls ein weiteres Heteroatom, vorzugsweise Stickstoff, Sauerstoff oder Schwefel, besonders Stickstoff, aufweisen.In the context of the present invention, a heterocyclic radical preferably means a 5- to 7-membered aromatic or non-aromatic ring with one to three heteroatoms, which are selected from the group consisting of N, O and S. Aromatic 5- and 6- are preferred. Rings, which have a nitrogen atom as hetero atom and optionally have a further heteroatom, preferably nitrogen, oxygen or sulfur, especially nitrogen.
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 kann sowohl im sauren, besonders im stark sauren, als auch im basischen Milieu durchgeführt werden. Im sauren Bereich sind pH- Werte von kleiner 5 bis 1 , besonders kleiner 3 bis 1 , bevorzugt. Im basischen Bereich ist ein pH-Wert grösser als 7 bis 12, besonders von 8 bis 12, insbesondere 8 bis 10 bevorzugt. Die Reaktion wird unter Normaldruck und bei einer Temperatur von 0 bis 120°C, vorzugs-weise 20 bis 80°C durchgeführt.The hydrolysis process according to the invention can be carried out both in an acidic, in particular in a strongly acidic, and in a basic medium. In the acidic range, pH values of less than 5 to 1, particularly less than 3 to 1, are preferred. In the 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.
Die Reaktion wird in einem gegenüber den Reaktionsteilnehmern inerten Lösungsmittel oder Verdünnungsmittel durchgeführt. Als Lösungsmittel eignen sich in besonderer Weise Alkohole, wie Methanol, Ethanol, Propanol und iso-Propanol, sowie speziell Wasser. Weitere geeignete Lösungsmittel sind z.B. Ether, wie Tetrahydrofuran und Dioxan, sowie andere Lösungsmittel, die Reaktion nicht beeinträchtigen. Die Lösungsmittel können auch als Gemische verwendet werden. Bevorzugt hydrolysiert 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. 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.
Als Säuren zur Durchführung des Verfahrens eigenen sich vorzugsweise Mineralsäuren, wie z.B. Schwefelsäure, eine Phosphorsäure oder eine Halogenwasserstoffsäure, eine organische Carbonsäure, wie gegebenenfalls, z.B. durch Halogen, substituierten C C - Alkancarbonsäuren, z.B. Essigsäure, wie gegebenenfalls ungesättigten Dicarbonsäuren, z.B. Oxal-, Maion-, Malein-, Fumar- oder Phthalsäure, wie Hydroxycarbonsäuren, z.B. Ascorbin-, Milch-, Äpfel-, Wein- oder Zitronensäure, oder wie Benzoesäure, oder eine organische Sulfonsäure, wie gegebenenfalls, z.B. durch Halogen, substituierten CrC - Alkan- oder Aryl-sulfonsäuren, z.B. Methan- oder p-Toluolsulfonsäure.Mineral acids, such as e.g. Sulfuric acid, a phosphoric acid or a hydrohalic acid, an organic carboxylic acid such as, e.g., e.g. halogen, substituted C C alkane carboxylic acids, e.g. Acetic acid such as optionally unsaturated dicarboxylic acids e.g. Oxalic, maionic, maleic, fumaric or phthalic acid such as hydroxycarboxylic acids e.g. Ascorbic, lactic, malic, tartaric or citric acid, or such as benzoic acid, or an organic sulfonic acid, such as optionally e.g. halogen, substituted CrC - alkane or aryl sulfonic acids, e.g. Methane or p-toluenesulfonic acid.
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 Na3PO4, Na2HPO4, Alkoholate wie Natriummethanolat, Natrium- ethanolat 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 Natrium- benzoat; 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 4 , Na 2 HPO 4 , 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 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, Isoxa- zolyl, 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-yI, Tetrahydrofuran-3-yl, 5-Methyl-tetrahydro- furan-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-oxido-pyridinio, 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-yI, tetrahydrofuran-3-yl , 5-methyl-tetrahydrofuran-3-yl, 1-oxopyrid-3-yl, 1-oxo-2-halopyrid-5-yl and 1-oxo-2,3-dihalopyrid-5-yl.
Ebenfalls bevorzugt tragen die Heterocyclen A ein bis drei Substituenten aus der Gruppe Halogen, Cι-C3-Alkyl, d-C3-Halogenalkyl und C C3-Halogenalkoxy mit je 1 bis 7 Halogenatomen und d-C3-Alkoxy.The heterocycles A also preferably carry one to three substituents from the group halogen, C 1 -C 3 -alkyl, dC 3 -haloalkyl and CC 3 -haloalkoxy, each having 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, Cι-C3-Alkyl, d-C3-Halogenalkyl sowie d-C3-Halogenalkoxy mit je 1 bis 7 Halogenatomen und d-C3-Alkoxy substituiert sein kann.Furthermore, 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 halogen, C 1 -C 3 -alkyl, dC 3 -haloalkyl and dC can be 3 haloalkoxy, each with 1 to 7 halogen atoms, and dC substituted 3 alkoxy.
Unter den erfindungsgemäss herzustellenden Verbindungen der Formel (I) sind solche herauszuheben, in denen ^ Wasserstoff, R2 Wasserstoff, Methyl, Ethyl oder Cyclopropyl und A Pyridyl, 1 -Oxopyridyl, Tetrahydrofuranyl, Thiazolyl oder jeweils durch ein bis drei Substituenten aus der Gruppe Halogen, d-C3-Alkyl, d-C3-Halogenalkyl sowie C C3- Halogenalkoxy mit 1 bis 7 Halogenatomen und C C3-Alkoxy substituiertes Pyridyl, 1 -Oxidopyridinio, Tetrahydrofuranyl oder Thiazolyl bedeuten. In diesem Sinne ist vor allem die Herstellung von Verbindungen der Formel (I) von Interesse, worin a) RT für Wasserstoff steht; b) R2 Wasserstoff, d-C3-Alkyl oder Cyclopropyl, besonders Methyl, bedeutet; c) A 2-Chlorpyrid-5-yl, Tetrahydrofuran-3-yl, 2-Methyl-tetrahydrofuran-4-yl oder 2-Chlorthiazol-5-yl bedeutet.Among the compounds of the formula (I) to be prepared according to the invention, those in which ^ hydrogen, R 2 are hydrogen, methyl, ethyl or cyclopropyl and A are pyridyl, 1 -oxopyridyl, tetrahydrofuranyl, thiazolyl or in each case by one to three substituents from the halogen group , dC 3 -alkyl, dC 3 -haloalkyl and CC 3 - haloalkoxy with 1 to 7 halogen atoms and CC 3 -alkoxy substituted pyridyl, 1 -oxidopyridinio, tetrahydrofuranyl or thiazolyl. In this sense, the preparation of compounds of the formula (I) is of particular interest, in which a) R T is hydrogen; b) R 2 is hydrogen, dC 3 alkyl or cyclopropyl, especially methyl; c) A is 2-chloropyrid-5-yl, tetrahydrofuran-3-yl, 2-methyl-tetrahydrofuran-4-yl or 2-chlorothiazol-5-yl.
In den vor- und nachstehend aufgeführten Verbindungen der Formeln (II) und (III) kommen als Substituenten für den Rest R3 insbesondere Cn-Cie-Alkyl, mit Hydroxy oder -COO-d-de-alkyl substituiertes Cn-Cι8-Alkyl, gegebenenfalls mit Phenyl oder Hydroxy substituiertes C3-C18-Alkenyl, gegebenenfalls mit Phenyl substituiertes C3-Ci8-Alkinyl, Cyclooctyl, Cyclodecyl, Cycloheptyl, Cyclododecyl, Thiazolyl, Pyridyl, Pyridinyl, Pyrazinyl oder gegebenenfalls substituiertes Naphthyl in Frage.In the compounds of the formulas (II) and (III) listed above and below, the substituents for the radical R 3 are in particular Cn-Cie-alkyl, Cn-Cι- 8 alkyl substituted by hydroxy or -COO-d-de-alkyl , optionally with phenyl or hydroxy substituted C 3 -C 18 alkenyl, optionally substituted with phenyl C 3 -Ci 8 alkynyl, cyclooctyl, cyclodecyl, cycloheptyl, cyclododecyl, thiazolyl, pyridyl, pyridinyl, pyrazinyl or optionally substituted naphthyl.
Ein weiterer Gegenstand der Erfindung ist b) ein Verfahren zur Herstellung einer Verbindung der Formel (II), und gegebenenfalls ihrer E/Z-Isomeren, E/Z-Isomerengemische und/oder Tautomeren, jeweils in freier Form oder in Salzform, dadurch gekennzeichnet, dass man eine Verbindung der FormelThe invention further relates to b) a process for the preparation of a compound of the formula (II) and, if appropriate, its E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form, characterized in that that you have a compound of the formula
Figure imgf000010_0001
worin R2 und R3 die gleiche Bedeutung haben wie vorstehend für die Formel (II) definiert; und gegebenenfalls ihrer E/Z-Isomeren, E/Z-Isomerengemische und/oder Tautomeren, jeweils in freier Form oder in Salzform, mit einer Verbindung der Formel
Figure imgf000010_0001
wherein R 2 and R 3 have the same meaning as defined above for the formula (II); and optionally their E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form, with a compound of the formula
AA
(IV),(IV),
R,R,
welche bekannt ist oder in Analogie zu an sich bekannten Methoden hergestellt werden kann, worin Ri und A die vorstehend für die Formel (I) angegebenen Bedeutungen haben und Y eine Abgangsgruppe, vorzugsweise Halogen, bedeutet, vorzugsweise in Gegenwart einer Base umsetzt.which is known or can be prepared analogously to methods known per se, in which R 1 and A have the meanings given above for the formula (I) and Y denotes a leaving group, preferably halogen, preferably in the presence of a base.
Ein weiterer Gegenstand der Erfindung ist c) ein Verfahren zur Herstellung der Verbindungen der Formel (III), und gegebenenfalls ihrer E/Z-Isomeren, E/Z-Isomerengemische und/oder Tautomeren, jeweils in freier Form oder in Salzform, dadurch gekennzeichnet, dass man eine Verbindung der FormelThe invention further provides c) a process for the preparation of the compounds of the formula (III) and, if appropriate, their E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form, characterized in that that you have a compound of the formula
Figure imgf000010_0002
welche bekannt ist oder in Analogie zu sich bekannten Methoden hergestellt werden kann, und worin R2 die gleiche Bedeutung hat wie für Formel (I) definiert, mit einer Verbindung der Formel
Figure imgf000010_0002
which is known or can be prepared in analogy to methods known per se, and in which R 2 has the same meaning as defined for formula (I), with a compound of the formula
H2N-R3 (VI), worin R3 die gleiche Bedeutung hat wie vorstehend für die Verbindungen der Formeln (II) definiert, und welche bekannt ist oder in Analogie zu an sich bekannten Methoden hergestellt werden kann, in Gegenwart eines Überschusses an Formaldehyd oder Paraformaldehyd umsetzt.H 2 NR 3 (VI), in which R 3 has the same meaning as defined above for the compounds of the formulas (II), and which is known or can be prepared analogously to methods known per se, in the presence of an excess of formaldehyde or Paraformaldehyde implemented.
Ein weiterer Gegenstand der Erfindung ist d) ein Verfahren zur Herstellung einer Verbindung der Formel (I), und gegebenenfalls ihrer E/Z-Isomeren, E/Z-Isomerengemische und/oder Tautomeren, jeweils in freier Form oder in Salzform, dadurch gekennzeichnet, dass man eine Verbindung der Formel (V) durch Umsetzung mit einer Verbindung der Formel (VI) und Formaldehyd bzw. Paraformaldehyd in eine Verbindung der Formel (III) überführt; diese Verbindung der Formel (III) mit einer Verbindung der (IV) in eine Verbindung der Formel (II) überführt, und diese Verbindung der Formel (II) hydrolysiert.Another object of the invention is d) a process for the preparation of a compound of formula (I), and optionally its E / Z isomers, E / Z isomer mixtures and / or tautomers, each in free form or in salt form, characterized in that that a compound of formula (V) is converted into a compound of formula (III) by reaction with a compound of formula (VI) and formaldehyde or paraformaldehyde; converting this compound of formula (III) with a compound of (IV) into a compound of formula (II), and hydrolyzing this compound of formula (II).
Ein weiterer Gegenstand der Erfindung ist e) die Verwendung der Verbindungen der Formel (II) zur Herstellung der Verbindungen der Formel (I).Another object of the invention is e) the use of the compounds of formula (II) for the preparation of the compounds of formula (I).
Bevorzugte Ausführungsformen der Verfahren gemäss den Varianten b) bis d) können den Beispielen entnommen werden.Preferred embodiments of the processes according to variants b) to d) can be found in the examples.
Die für das erfindungsgemässe Verfahren in Betracht kommenden Ausgangsverbindungen bzw. Ausgangsprodukte der Formeln (II) und (III) und gegebenenfalls ihre möglichen E/Z-Isomeren, E/Z-Isomerengemische und/oder Tautomeren, jeweils in freier Form oder in Salzform, sind neu. Sie sind ebenfalls ein Gegenstand der Erfindung.The starting compounds or starting products of the formulas (II) and (III) which are suitable for the process according to the invention and, if appropriate, their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form New. They are also an object of the invention.
Die erfindungsgemäss hergestellten Verbindungen der Formel (I) sind bei günstiger Warmblüter-, Fisch- und Pflanzenverträglichkeit wertvolle Wirkstoffe in der Schäd- lingsbekämp-fung. Insbesondere sind die Verbindungen der Formel (I) geeignet zur Bekämpfung von Insekten und Spinnentieren, die in Nutz- und Zierpflanzen in der Landwirtschaft, insbesondere 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 in accordance with the invention are valuable active ingredients in pest control with favorable warm-blood tolerance, fish and plant tolerance. In particular, 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 occurrence. 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.
HerstellungsbeispieleManufacturing examples
Beispiel H1.1 : Herstellung der Verbindung der FormelExample H1.1: Preparation of the compound of the formula
Figure imgf000012_0001
Figure imgf000012_0001
Ein Gemisch von 2.4 g 1-Methyl-2-nitroguanidin, 5,5 g Octadecylamin, 20 ml Ethanol und 3,2 ml einer 37%igen Lösung von Formaldehyd in Wasser wird auf 50 °C aufgeheizt und während 4 Stunden bei dieser Temperatur gerührt. Dann wird die Mischung am Vakuum zur Trockene eingedampft, der Rückstand mit Diethylether verrührt und die Titelverbindung durch Filtration isoliert (Verbindung 1.10).A mixture of 2.4 g of 1-methyl-2-nitroguanidine, 5.5 g of octadecylamine, 20 ml of ethanol and 3.2 ml of a 37% solution of formaldehyde in water is heated to 50 ° C. and stirred at this temperature for 4 hours . The mixture is then evaporated to dryness in vacuo, the residue is stirred with diethyl ether and the title compound is isolated by filtration (compound 1.10).
Beispiel H1.2: Herstellung der Verbindung der FormelExample H1.2: Preparation of the compound of the formula
Figure imgf000012_0002
Figure imgf000012_0002
Ein Gemisch von 3.54 g 1 -Methyl-2-nitroguanidin, 2,7 ml Allylamin, 50 ml Toluoi und 2,7 g Paraformaldehyd wird mit 3 Tropfen konzentrierter Salzsäure versetzt und 20 Stunden am Wasserabscheider erhitzt. Dann wird die Mischung am Vakuum zur Trockene eingedampft, der Rückstand mit Dichlormethan/Methanol (98:29 aufgenommen, über Kieselgel filtriert und das Filtrat eingedampft. Man erhält die Titelverbindung durch Rekristallisation aus Isopropanol mit einem Schmelzpunkt von 53-55 °C (Verbindung 1.14).A mixture of 3.54 g of 1-methyl-2-nitroguanidine, 2.7 ml of allylamine, 50 ml of toluene and 2.7 g of paraformaldehyde is mixed with 3 drops of concentrated hydrochloric acid and heated on a water separator for 20 hours. The mixture is then evaporated to dryness in vacuo, the residue is taken up in dichloromethane / methanol (98:29, filtered through silica gel and the filtrate is evaporated. The title compound is obtained by recrystallization from isopropanol with a melting point of 53-55 ° C. (compound 1.14 ).
Beispiel H1.3: Herstellung der Verbindung der FormelExample H1.3: Preparation of the compound of the formula
Figure imgf000012_0003
Ein Gemisch von 5.9 g 1-Methyl-2-nitroguanidin, 5.2 g 3-Aminopyridin, 4,5 g Paraformaldehyd, 60 ml Dioxan und 0,24 g p-Toluolsuflonsäure wird 20 Stunden am Wasserabscheider erhitzt. Nach Abkühlung wird die Reaktionsmischung filtriert und der Filterrückstand mit Dimethylformamid und Toluol gewaschen. Man erhält so die Titelverbindung mit einem Schmelzpunkt von 204-208°C (Verbindung 1.26).
Figure imgf000012_0003
A mixture of 5.9 g of 1-methyl-2-nitroguanidine, 5.2 g of 3-aminopyridine, 4.5 g of paraformaldehyde, 60 ml of dioxane and 0.24 g of p-toluenesulfonic acid is heated for 20 hours on a water separator. After cooling, the reaction mixture is filtered and the filter residue is washed with dimethylformamide and toluene. The title compound is thus obtained with a melting point of 204-208 ° C. (compound 1.26).
Analog zu den obigen Arbeitsweisen der Beispiele H1.1 bis H1.3 können auch die folgenden in Tabelle 1 aufgeführten Verbindungen der Formel (III) erhalten werden.The following compounds of the formula (III) listed in Table 1 can also be obtained analogously to the above procedures of Examples H1.1 to H1.3.
Tabelle 1 : Verbindungen der FormelTable 1: Compounds of the formula
Figure imgf000013_0001
Figure imgf000013_0001
Nr. R3 Phys. DatenR 3 Phys. Data
1.1 Cyclooctyl1.1 cyclooctyl
1.2 Cyclodecyl1.2 cyclodecyl
1.3 Cycloheptyl1.3 cycloheptyl
1.4 -(CH2)ιo-CH3 1.4 - (CH 2 ) ιo-CH 3
1.5 -(CH2)l1-CH3 Smpt. 85-87 °C1.5 - (CH 2 ) l 1-CH3 Smpt. 85-87 ° C
1.6 -(CH2)12-CH3
Figure imgf000013_0002
1.6 - (CH 2 ) 12 -CH 3
Figure imgf000013_0002
1.8 "(CH2)ι4-CH3
Figure imgf000013_0003
1.8 "(CH 2 ) ι 4 -CH 3
Figure imgf000013_0003
1.10 -(CH2)ι -CH3 1.10 - (CH 2 ) ι -CH 3
1.11 -(CH2)8-CH=CH-(CH2)7-CH3 (eis)1.11 - (CH 2 ) 8-CH = CH- (CH 2 ) 7 -CH 3 (ice)
1.12 -(CH2)10-COOH1.12 - (CH 2 ) 10 -COOH
1.13 -(CH2)n-COOH Smpt. 93-95 °C1.13 - (CH 2 ) n-COOH Smpt. 93-95 ° C
1.14 -CH -CH=CH2 Smpt. 53-55 °C1.14 -CH -CH = CH 2 smpt. 53-55 ° C
1.15 - CH-(CH2OH)CH(OH)-CH=CH-(CH2)12-CH3 1.15 - CH- (CH 2 OH) CH (OH) -CH = CH- (CH 2 ) 12 -CH 3
1.16 -CH2-CH=CH(CH3)-(CH2)2-CH=C(CH3)2 1.16 -CH 2 -CH = CH (CH 3 ) - (CH2) 2 -CH = C (CH 3 ) 2
1.17 -CH-(CH2OH)CH(OH)-C≡C-(CH2)12-CH3 1.17 -CH- (CH 2 OH) CH (OH) -C≡C- (CH 2 ) 12 -CH 3
1.18 -(CH2)3-C-≡C-CeH5 Nr. R3 Phys. Daten1.18 - (CH 2 ) 3 -C-≡C-CeH 5 R 3 Phys. Data
1.19 -CH2-C=C-CeH5 1.19 -CH 2 -C = C-CeH 5
Figure imgf000014_0001
Figure imgf000014_0001
1.23 Naphth-1-yl1.23 Naphth-1-yl
1.24 Naphth-2-yl1.24 Naphth-2-yl
1.25 Thiazol-2-yl1.25 thiazol-2-yl
1.26 Pyrid-3-yl Smpt. 204-208 °C1.26 Pyrid-3-yl Smpt. 204-208 ° C
1.27 Pyrid-4-yl1.27 pyrid-4-yl
1.28 3-Brom-naphth-2-yl1.28 3-bromo-naphth-2-yl
1.29 1 -Hydroxy-naphth-2-yl1.29 1-Hydroxy-naphth-2-yl
1.30 4-Methoxy-naphth-2-yl1.30 4-methoxy-naphth-2-yl
1.31 5-Hydroxy-naphth-2-yl1.31 5-hydroxy-naphth-2-yl
1.32 1-Chlor-naphth-2-yl1.32 1-chloro-naphth-2-yl
1.33 8-Nitro-napht-2-yl1.33 8-nitro-naphth-2-yl
1.34 -NHCOOC2H5 Smpt. 203-204 °C1.34 -NHCOOC2H5 smpt. 203-204 ° C
Smpt. 156-158 CSmpt. 156-158 C
Figure imgf000014_0002
Nr. R3 Phys. Daten
Figure imgf000014_0002
R 3 Phys. Data
1.37 Cyclododecyl Smpt. 137-139 °C1.37 Cyclododecyl Smpt. 137-139 ° C
1.38 Smpt. 56-57 °C1.38 smpt. 56-57 ° C
Figure imgf000015_0001
Figure imgf000015_0001
1.39 -CH2)n-C(=O)OCH3 Smpt. 91-94 °C1.39 -CH 2 ) nC (= O) OCH 3 smpt. 91-94 ° C
Beispi* 3l H2.1 : Herstellunα der Verbindung der FormelBeispi * 3l H2.1: Preparation of the compound of the formula
Figure imgf000015_0002
Figure imgf000015_0002
Ein Gemisch von 6,0 g der gemäss Beispiel H1.1 erhältlichen Verbindung, 2.8 g 2-Chlor- 5-chlormethylpyridin und 4.8 g Kaliumcarbonat in 20 ml Dimethylformamid wird während 10 Stunden bei 50 °C gerührt. Dann wird die Reaktionsmischung filtriert, das Filtrat im Vakuum eingedampft und der Rückstand aus Ethanol rekristallisiert. Man erhält die Titelverbindung mit einem Schmelzpunkt von 95-97°C (Verbindung 10.B.1).A mixture of 6.0 g of the compound obtainable according to Example H1.1, 2.8 g of 2-chloro-5-chloromethylpyridine and 4.8 g of potassium carbonate in 20 ml of dimethylformamide is stirred at 50 ° C. for 10 hours. The reaction mixture is then filtered, the filtrate is evaporated in vacuo and the residue is recrystallized from ethanol. The title compound is obtained with a melting point of 95-97 ° C (compound 10.B.1).
Analog zu der obigen Arbeitsweise des Beispiels H2.1 können auch die folgenden in den Tabellen 2 bis 13 aufgeführten Verbindungen der Formel (II) erhalten werden.Analogously to the above procedure of Example H2.1, the following compounds of the formula (II) listed in Tables 2 to 13 can also be obtained.
Tabelle A: Verbindungen der FormelTable A: Compounds of the formula
Figure imgf000015_0003
Figure imgf000016_0002
Figure imgf000015_0003
Figure imgf000016_0002
Figure imgf000016_0001
Tabelle 2: Verbindungen der allgemeinen Formel (lla), worin A
Figure imgf000017_0001
bedeutet und R3 jeweils einer Zeile der Tabelle A entspricht.
Figure imgf000016_0001
Table 2: Compounds of the general formula (Ila), in which A
Figure imgf000017_0001
means and R 3 corresponds to one row of Table A.
Verbindung 2.A.5: Smpt.: 119-121 °C Verbindung 2.A.37: Smpt.: 137-139 °C Verbindung 2.A.38: Smpt.: 76-78 °C Verbindung 2.A.39: Smpt.: 90-92 °CConnection 2.A.5: Smpt .: 119-121 ° C Connection 2.A.37: Smpt .: 137-139 ° C Connection 2.A.38: Smpt .: 76-78 ° C Connection 2.A. 39: Smpt .: 90-92 ° C
Tabelle 3: Verbindungen der allgemeinen Formel (lla), worin A bedeutet
Figure imgf000017_0002
und R3 jeweils einer Zeile der Tabelle A entspricht.Table 3: Compounds of the general formula (Ila), in which A denotes
Figure imgf000017_0002
and R 3 corresponds to one row of Table A.
Tabelle 4: Verbindungen der allgemeinen Formel (lla), worin A bedeutet
Figure imgf000017_0003
und R3 jeweils einer Zeile der Tabelle A entspricht.Table 4: Compounds of the general formula (Ila), in which A denotes
Figure imgf000017_0003
and R 3 corresponds to one row of Table A.
Tabelle 5: Verbindungen der allgemeinen Formel (lla), worin A bedeutet
Figure imgf000017_0004
und R3 jeweils einer Zeile der Tabelle A entspricht.Table 5: Compounds of the general formula (Ila), in which A denotes
Figure imgf000017_0004
and R 3 corresponds to one row of Table A.
Tabelle 6: Verbindungen der allgemeinen Formel (lla), worin A bedeutet
Figure imgf000017_0005
und R3 jeweils einer Zeile der Tabelle A entspricht.Table 6: Compounds of the general formula (Ila), in which A denotes
Figure imgf000017_0005
and R 3 corresponds to one row of Table A.
Tabelle 7: Verbindungen der allgemeinen Formel (lla), worin A bedeutet und
Figure imgf000017_0006
Table 7: Compounds of the general formula (Ila), in which A is and
Figure imgf000017_0006
R3 jeweils einer Zeile der Tabelle A entspricht.R 3 corresponds in each case to one row of table A.
Tabelle 8: Verbindungen der allgemeinen Formel (lla), worin A \\ 7 bedeutetTable 8: Compounds of the general formula (Ila), in which A \\ 7
N-0 und R3 jeweils einer Zeile der Tabelle A entspricht.N-0 and R 3 each correspond to one row of Table A.
Tabelle 9: Verbindungen der allgemeinen Formel (lla), worin A
Figure imgf000017_0007
bedeutet und R3 jeweils einer Zeile der Tabelle A entspricht. Verbindung 9.A.10 Smpt.: 95-97°C. Verbindung 9.A.14 Smpt.: 75-77°C. Verbindung 9.A.26 Smpt.: 222°C. Verbindung 9.A.34 Smpt.: 200°C. Verbindung 9.A.35 Smpt.: 178-180 °C. Verbindung 9.A.36 Smpt.: 214 °C.Table 9: Compounds of the general formula (IIIa), in which A
Figure imgf000017_0007
means and R 3 corresponds to one row of Table A. Compound 9.A.10 Smpt .: 95-97 ° C. Compound 9.A.14 Smpt .: 75-77 ° C. Compound 9.A.26 Smpt .: 222 ° C. Compound 9.A.34 Smpt .: 200 ° C. Compound 9.A.35 m.p .: 178-180 ° C. Compound 9.A.36 m.p .: 214 ° C.
Tabelle 10: Verbindungen der allgemeinen Formel (lla), worin A bedeutet und
Figure imgf000018_0001
Table 10: Compounds of the general formula (IIIa), in which A denotes and
Figure imgf000018_0001
R3 jeweils einer Zeile der Tabelle A entspricht.R 3 corresponds in each case to one row of table A.
Tabelle 1 1 : Verbindungen der allgemeinen Formel (lla), worin A N+ bedeutetTable 1 1: Compounds of the general formula (Ila), wherein A denotes N +
und R3 jeweils einer Zeile der Tabelle A entspricht.and R 3 corresponds to one row of Table A.
Tabelle 12: Verbindungen der allgemeinen Formel (lla), worin A bedeutet
Figure imgf000018_0002
und R3 jeweils einer Zeile der Tabelle A entspricht.Table 12: Compounds of the general formula (IIIa), in which A denotes
Figure imgf000018_0002
and R 3 corresponds to one row of Table A.
Tabelle 13: Verbindungen der allgemeinen Formel (lla), worin A bedeutet
Figure imgf000018_0003
und R3 jeweils einer Zeile der Tabelle A entspricht. Beispiel 3.1 : Herstellung der Verbindung der FormelTable 13: Compounds of the general formula (IIIa), in which A denotes
Figure imgf000018_0003
and R 3 corresponds to one row of Table A. Example 3.1: Preparation of the compound of the formula
Figure imgf000018_0004
Figure imgf000018_0004
4.0 g der gemäss Beispiel H2.1 erhältlichen Verbindung in 20 ml Methanol und 25 ml 1 n Salzsäure werden 16 Stunden bei 50 °C gerührt. Das Reaktionsgemisch wird filtriert und der Filterrückstand mit Methanol gewaschen und getrocknet. Man erhält so das Titelprodukt mit einem Schmelzpunkt von 147-149CC (Verbindung 14.6). Analog zu der obigen Arbeitsweise des Beispiels H3.1 können auch die folgenden in Tabelle 14 aufgeführten Verbindungen der Formel (I) erhalten werden.4.0 g of the compound obtainable according to Example H2.1 in 20 ml of methanol and 25 ml of 1N hydrochloric acid are stirred at 50 ° C. for 16 hours. The reaction mixture is filtered and the filter residue is washed with methanol and dried. This gives the title product with a melting point of 147-149 C C (compound 14.6). Analogously to the above procedure of Example H3.1, the following compounds of the formula (I) listed in Table 14 can also be obtained.
Tabelle 14: Verbindungen der allgemeinen FormelTable 14: Compounds of the general formula
Figure imgf000019_0001
Figure imgf000019_0001
Nr. phys. DatenNo physical data
Smpt: 147-149°CM.p .: 147-149 ° C
Figure imgf000019_0002
Nr. A phys. Daten
Figure imgf000019_0002
No. A physical data
Figure imgf000020_0001
Figure imgf000020_0001
14.11 Cl-14.11 Cl-
N-ON-O
Figure imgf000020_0002
Figure imgf000020_0002
Ein weiterer Gegenstand der Erfindung ist f) ein Verfahren zur Bekämpfung von Schädlingen, besonders von tierischen Schädlingen, insbesondere von Insekten und Vertretern der Ordnung Akarina, mit den Verbindungen der Formel (II). Zu den erwähnten tierischen Schädlingen gehören beispielsweise jene, welche in der Europäischen Patentanmeldung EP-A-736'252 erwähnt sind. Die dort erwähnten Schädlinge sind daher per Referenz im vorliegenden Erfindungsgegenstand miteingeschlossen. Auch die Verfahren zur Bekämpfung der genannten Schädlinge und die Zusammensetzung und die Herstellung der entsprechenden Mittel sind in EP-A-736'252 beschrieben und im vorliegenden Erfindungsgegenstand per Referenz eingeschlossen. Another object of the invention is f) a method for controlling pests, especially animal pests, in particular insects and representatives of the order Akarina, with the compounds of formula (II). The 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.

Claims

Patentansprüche claims
1 . Verfahren zur Herstellung einer Verbindung der Formel1 . Process for the preparation of a compound of formula
Figure imgf000021_0001
worin
Figure imgf000021_0001
wherein
Ri Wasserstoff oder Cι-C4-Alkyl;Ri is hydrogen or -CC 4 alkyl;
R2 Wasserstoff, C 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, d-C3-Alkyl, C C3-Alkoxy, Halogen-Cι-C3-alkyl, CrC3-Halogenalkoxy, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, C2-C3-Halogenalkenyl und C2-C3-Halogenalkinyl, C C3-Alkylthio, C C3-Haiogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Halogenallyloxy, Halogenallylthio, Cyan und Nitro substituierten aromatischen oder nichtaromatischen, monocyclischen oder bicyclischen heterocyclischen Rest; undA 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, CC 3 alkoxy, halo-Cι-C3-alkyl, -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, CC 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
B Phenyl, 3-Pyridyl oder Thiazolyl, welche gegebenenfalls durch ein bis dreiB phenyl, 3-pyridyl or thiazolyl, which are optionally by one to three
Substituenten aus der Gruppe bestehend aus d-C3-Alkyl, d-C3-Halogenalkyl, Cyclopropyl, Halogencyclopropyl, C2-C3-Alkenyl, C2-C3-Alkinyl, Cι-C3-Alkoxy, C2-C3- Halogenalkenyl, C2-C3-Halogenalkinyl, d-C3-Halogenalkoxy, d-C3-Alkylthio, d-C3-Halogenalkylthio, Allyloxy, Propargyloxy, Allylthio, Propargylthio, Halogenallyloxy, 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; dadurch gekennzeichnet, dass man eine Verbindung der FormelSubstituents selected from the group consisting of dC 3 alkyl, dC 3 haloalkyl, cyclopropyl, halocyclopropyl, C 2 -C 3 alkenyl, C 2 -C 3 alkynyl, Cι-C 3 alkoxy, C 2 -C 3 - haloalkenyl , C 2 -C 3 haloalkynyl, dC 3 haloalkoxy, dC 3 alkylthio, dC 3 haloalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, haloallyloxy, haloallylthio, halogen, cyano and nitro; and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form; characterized in that a compound of the formula
Figure imgf000021_0002
worin R1 f R2 und A die gleiche Bedeutung haben wie in Formel (I) angegeben und R3 unsubstituiertes oder substituiertes Cι C22-Alkyl, C7-Cι6-Cycloalkyl, C3-C20-Alkenyl, C3-C20-Alkinyl, N(R4)R5, gegebenenfalls substituiertes Aryl mit Ausnahme von unsubstituiertem und substituiertem Phenyl; oder einen gegebenenfalls substituierten, aromatischen oder nichtaromatischen, monocyclischen oder bicyclischen, heterocyclischen Rest;
Figure imgf000021_0002
wherein R 1 f R 2 and A have the same meaning as indicated in formula (I) and R 3 is unsubstituted or substituted C ι C 22 alkyl, C 7 -Cι 6 cycloalkyl, C 3 -C 20 alkenyl, C 3 -C 20 alkynyl, N (R 4) R 5, optionally substituted aryl with the exception of unsubstituted and substituted phenyl; or an optionally substituted, aromatic or non-aromatic, monocyclic or bicyclic, heterocyclic radical;
R4 Wasserstoff oder d-Cι2-Alkyl;R 4 is hydrogen or C 1 -C 2 alkyl;
R5 Wasserstoff, d-C12-Alkyl, d-Cι2-Alkyl-carbonyl oder d-Cι2-Alkoxy-carbonyl; bedeutet, hydrolysiert.R 5 is hydrogen, dC 12 alkyl, d -CC 2 alkylcarbonyl or d -CC 2 alkoxycarbonyl; means hydrolyzed.
2. Verfahren gemäss 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 gemäss einem der Ansprüche 1 oder 2 zur Herstellung einer Verbindung der Formel (I), worin Ri für Wasserstoff steht.3. The method according to any one of claims 1 or 2 for the preparation of a compound of formula (I), wherein Ri is hydrogen.
4. Verfahren gemäss einem der Ansprüche 1 bis 3 zur Herstellung einer Verbindung der Formel (I), worin R2 Wasserstoff, d-C3-Alkyl oder Cyclopropyl bedeutet.4. The method according to any one of claims 1 to 3 for the preparation of a compound of formula (I), wherein R 2 is hydrogen, dC 3 alkyl or cyclopropyl.
5. Verfahren gemäss einem der Ansprüche 1 bis 4 zur Herstellung einer Verbindung der Formel (I) aus einer Verbindung der Formel (II), worin5. The method according to any one of claims 1 to 4 for the preparation of a compound of formula (I) from a compound of formula (II), wherein
R3 Cn-C16-Alkyl, mit Hydroxy oder -COO-d-C16-alkyl substituiertes Cπ-dβ-Alkyl, gegebenenfalls mit Phenyl oder Hydroxy substituiertes C3-Cι8-Alkenyl, gegebenenfalls mit Phenyl substituiertes C3-Ci8-Alkinyl, Cyclooctyl, Cyclodecyl, Cycloheptyl, Cyclododecyl, Thiazolyl, Pyridyl, Pyridinyl, Pyrazinyl oder gegebenenfalls substituiertes Naphthyl bedeutet.R 3 Cn-C16 alkyl, hydroxy, or -COO-dC 16 alkyl substituted Cπ-D.beta alkyl, optionally substituted with phenyl or hydroxyl-substituted C 3 -Cι 8 alkenyl, optionally substituted by phenyl-substituted C 3 -C 8 - Alkynyl, cyclooctyl, cyclodecyl, cycloheptyl, cyclododecyl, thiazolyl, pyridyl, pyridinyl, pyrazinyl or optionally substituted naphthyl.
6. Verfahren gemäss einem der Ansprüche 1 bis 5 zur Herstellung einer Verbindung der Formel (I), worin6. The method according to any one of claims 1 to 5 for the preparation of a compound of formula (I), wherein
A 2-Chlorpyrid-5-yl, Tetrahydrofuran-3-yl, 5-Methyl-tetrahydrofuran-3-yl oder 2-Chlorthiazol- 5-yl bedeutet.A is 2-chloropyrid-5-yl, tetrahydrofuran-3-yl, 5-methyl-tetrahydrofuran-3-yl or 2-chlorothiazol-5-yl.
7. Verfahren gemäss einem der Ansprüche 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 gemäss einem der Ansprüche 1 bis 6 zur Herstellung einer Verbindung der Formel (I), dadurch gekennzeichnet, dass der pH-Wert zwischen kleiner als 5 und 1 liegt.8. 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 less than 5 and 1.
9. Verfahren zur Herstellung einer Verbindung wie in Anspruch 1 , Formel (II), definiert, und gegebenenfalls ihrer E/Z-Isomeren, E/Z-Isomerengemische und/oder Tautomeren, jeweils in freier Form oder in Salzform, dadurch gekennzeichnet, dass man eine Verbindung der Formel9. A process for the preparation of a compound as defined in claim 1, formula (II), and optionally its E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form, characterized in that a compound of the formula
Figure imgf000023_0001
worin R2 und R3 die gleiche Bedeutung haben wie in Anspruch 1 für die Formel (II) definiert; und gegebenenfalls ihrer E/Z-Isomeren, E/Z-Isomerengemische und/oder Tautomeren, jeweils in freier Form oder in Salzform, mit einer Verbindung der Formel
Figure imgf000023_0001
wherein R 2 and R 3 have the same meaning as defined in claim 1 for the formula (II); and optionally their E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form, with a compound of the formula
Figure imgf000023_0002
worin Ri und A die in Anspruch 1 für die Formel (I) angegebenen Bedeutungen haben und Y eine Abgangsgruppe bedeutet, umsetzt.
Figure imgf000023_0002
wherein Ri and A have the meanings given in claim 1 for the formula (I) and Y represents a leaving group.
10. Verfahren zur Herstellung einer Verbindung wie in Anspruch 9, Formel (III), definiert, und gegebenenfalls ihrer E/Z-Isomeren, E/Z-Isomerengemische und/oder Tautomeren, jeweils in freier Form oder in Salzform, dadurch gekennzeichnet, dass man eine Verbindung der Formel10. A process for the preparation of a compound as defined in claim 9, formula (III), and optionally its E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form, characterized in that to get a compound of formula
HH
.N NH2 <V>' Y.N NH 2 < V >'Y
02N0 2 N
worin R2 die gleiche Bedeutung hat wie die in Anspruch 1 für Formel (I) definiert, mit einer Verbindung der Formelwherein R 2 has the same meaning as defined in claim 1 for formula (I), with a compound of formula
H2N-R3 (VI), worin R3 die gleiche Bedeutung hat wie die in Anspruch 1 für die Verbindungen der Formel (II) definiert, in Gegenwart eines Überschusses an Formaldehyd oder Paraformaldehyd umsetzt. H 2 NR 3 (VI), wherein R 3 has the same meaning as defined in claim 1 for the compounds of formula (II), in the presence of an excess of formaldehyde or paraformaldehyde.
PCT/EP1998/005248 1997-08-20 1998-08-18 Method for producing organic compounds WO1999009009A1 (en)

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WO2001046160A1 (en) * 1999-12-21 2001-06-28 Bayer Aktiengesellschaft Method for production of 1,3-disubstituted 2-nitroguanidines
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CN103254171A (en) * 2013-04-16 2013-08-21 中国农业大学 Aromatic heterocyclic triazine (trans)-delta-farnesene analogue and application thereof

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WO1999042437A1 (en) * 1998-02-17 1999-08-26 Bayer Aktiengesellschaft Method for the production of 1,3-disubstituted 2-nitroguanidines
US6518433B1 (en) * 1998-03-19 2003-02-11 Syngenta Crop Protection, Inc. Process for the preparation of nitroguanidine derivatives
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JP2005500392A (en) * 2001-08-23 2005-01-06 バイエル・クロップサイエンス・ソシエテ・アノニム Substituted propargylamine

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