Classifications

• • 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.

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

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• 1998
  • 1998-08-18 JP JP2000509693A patent/JP2001515066A/ja active Pending
  • 1998-08-18 BR BR9811966-4A patent/BR9811966A/pt not_active IP Right Cessation
  • 1998-08-18 EP EP98946375A patent/EP1005456A1/de not_active Withdrawn
  • 1998-08-18 ID IDW20000316A patent/ID24319A/id unknown
  • 1998-08-18 IL IL13450298A patent/IL134502A0/xx unknown
  • 1998-08-18 CN CN98809316A patent/CN1271346A/zh active Pending
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  • 1998-08-18 HU HU0003632A patent/HUP0003632A3/hu unknown
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  • 1998-08-18 AU AU93442/98A patent/AU741658B2/en not_active Ceased
  • 1998-08-18 CA CA002301172A patent/CA2301172A1/en not_active Abandoned
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