EP0763018A2 - Derives imino heterocycliques - Google Patents

Derives imino heterocycliques

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Publication number
EP0763018A2
EP0763018A2 EP95920853A EP95920853A EP0763018A2 EP 0763018 A2 EP0763018 A2 EP 0763018A2 EP 95920853 A EP95920853 A EP 95920853A EP 95920853 A EP95920853 A EP 95920853A EP 0763018 A2 EP0763018 A2 EP 0763018A2
Authority
EP
European Patent Office
Prior art keywords
chr
alkyl
halogen
methyl
alkoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP95920853A
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German (de)
English (en)
Inventor
Lutz Assmann
Thomas Seitz
Ralf Tiemann
Heinz-Wilhelm Dehne
Klaus Stenzel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
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Filing date
Publication date
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Publication of EP0763018A2 publication Critical patent/EP0763018A2/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D263/28—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D277/18—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • C07D417/06—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 carbon chain containing only aliphatic carbon atoms
    • 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 invention relates to new heterocyclic imino derivatives, several processes for their preparation and their use for controlling pests.
  • ⁇ represents oxygen, sulfur or the CH 2 group
  • B represents the CH 2 or the CH 2 CH 2 group
  • R 1 represents in each case optionally substituted by halogen, cyano or alkoxy alkyl, alkoxy, alkylthio, alkylamino and dialkylamino and R 2 represents amino or alkyl, alkoxy, alkylamino and dialkylamino which are each optionally substituted by halogen, cyano or alkoxy,
  • R 3 represents hydrogen or alkyl
  • R 4 represents hydrogen or an easily removable group
  • D represents optionally substituted alkanediyl
  • Alkenylene and alkynylene and for the groupings - (CHR 5 ) n -O-, - (CHR 5 ) n -S-, - (CHR 5 ) n -NH-, - (CHR 5 ) n -NR 6 -, - (CHR 5 ) n -S O-,
  • R, R and R independently of one another represent hydrogen, cyano and in each case optionally substituted alkyl, alkenyl, alkynyl or aryl;
  • R for hydrogen; Halogen; for each optionally substituted alkyl,
  • R 5 and R 6 have the meaning given above and
  • n represents the numbers 1, 2, 3 or 4, it being possible for the radicals R 5 to be different if m is greater than 1.
  • R and Z have the meaning given above, in the presence of a diluent and, if appropriate, in the presence of a reaction auxiliary;
  • Y 1 represents the groupings -CO-alkyl or -COOalkyl
  • Y 1 represents the groupings -CO-alkyl or -COOalkyl
  • R 1 has the meaning given above
  • R 2 has the meaning given above
  • R 3 and R 4 have the meaning given above
  • A, B, R, X and Z have the meaning given above, in a first stage with hydroxylamine (or a hydrogen halide thereof), optionally in the presence of an acid acceptor and, if appropriate, in the presence of a diluent, and in situ in a second stage with disubstituted alkanes of the general formula (XIV)
  • E represents halogen, alkylsulfonyloxy or arylsulfonyloxy
  • the compounds according to the invention can optionally be present as mixtures of various possible isomeric forms, in particular of E and Z isomers, but if appropriate also of optical isomers and diastereomers. Both the E and the Z isomers as well as any mixtures of the other possible isomers are claimed.
  • the invention preferably relates to compounds of the formula (I) in which
  • A represents oxygen, sulfur or the CH 2 group.
  • B represents the CH 2 or the CH 2 CH 2 group.
  • R 1 stands for alkyl, alkoxy, alkylthio, alkylamino and dialkylamino, each optionally substituted by halogen, cyano or C ] -C - alkoxy, each having 1 to 4 carbon atoms in the alkyl radicals and
  • R 2 represents amino or alkyl, alkoxy, alkylamino and dialkylamino, each of which has 1 to 4 carbon atoms in the alkyl radicals, optionally substituted by halogen, cyano or C 1 -C 4 -alkoxy.
  • R 3 represents hydrogen or C r C 4 alkyl
  • R 4 for hydrogen, each optionally by halogen, CJ-J-alkoxy-C r C 4 -alkoxy, N, N-di- (C r C 4 -alkyl) -amino, N- (C r C 4 - alkyl -carbonyl) -amino, N- (C 1 -C 4 -alkyl) -N- (C 1 -C 4 -alkyl-carbonyl-amino; N- (C ] -C 4 -alkoxy-carbonyl) -amino or N - (C 1 -C 4 alkyl) -N-
  • D represents alkanediyl which has 1 to 3 carbon atoms and is optionally substituted by halogen, C ] -C 4 -alkyl or halogen- C - * - C 4 - alkyl.
  • Z represents a direct bond
  • n represents the numbers 0, 1, 2, 3 or 4, it being possible for the radicals R 5 to be different if n is greater than 1;
  • R 5 , R 6 and R 7 independently of one another for hydrogen and for in each case optionally by halogen, C ] -C 4 -alkyl, halogen-C r C 4 -alkyl, nitro, cyano, C r C 4 -alkoxy, halogen -C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and / or C j -C 4 haloalkylthio substituted C -.- C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 -alkynyl or phenyl.
  • benzannilated heteroaryl with 5 or 6 ring members, one of which is oxygen, sulfur or nitrogen and optionally one or two more are nitrogen, the substituents which are possible in each case preferably being selected from the list below: Oxygen (as a substitute for two geminal hydrogen atoms), halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, each straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each with 1 to 6 carbon atoms, each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1
  • the saturated or unsaturated hydrocarbon chains such as alkyl, alkanediyl, alkenyl or alkynyl, are in each case straight-chain or branched, also in combination with heteroatoms, such as in alkoxy, alkylthio or alkylamino.
  • Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
  • the invention relates in particular to compounds of the formula (I) in which
  • A represents oxygen, sulfur or the CH 2 group.
  • B represents the CH 2 or the CH 2 CH 2 group.
  • R 1 represents methyl, ethyl, propyl, methoxy, ethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, each optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy,
  • R 2 represents amino or methyl, ethyl, methoxy, ethoxy, methylamino, ethylamino or dimethylamino which is optionally substituted by fluorine, chlorine, cyano, methoxy or ethoxy.
  • N is (CH 3 ) C 3 H 7 -i, -CO-NR 3 -OR 4 and & ⁇ , where 95/33717
  • R 3 represents hydrogen, methyl, ethyl, n- or i-propyl
  • R 4 for hydrogen, for optionally by fluorine, chlorine, methoxy, ethoxy, n- or i-propoxy, methoxy-ethoxy, ethoxy-ethoxy, dimethylamino, diethylamino, acetylamino, propionyl amino, N-
  • Trifluoromethyl substituted methylene or ethane-l, 2-diyl Trifluoromethyl substituted methylene or ethane-l, 2-diyl.
  • R for hydrogen; for chlorine or bromine; represents in each case optionally substituted by fluorine, chlorine or trifluoromethyl methyl, ethyl and ethenyl;
  • Piperidinyl or morpholinyl where the possible substituents are preferably selected from the list below: oxygen (as a replacement for two geminal hydrogen atoms), fluorine, chlorine, bromine, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl , Methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy,
  • A, R and Z represent the general, preferred and particularly preferred meanings mentioned above.
  • A, R and Z represent the general, preferred and particularly preferred meanings mentioned above and
  • A, R and Z represent the general, preferred and particularly preferred meanings mentioned above and
  • Substance groups of the general formulas (IA-1) to (IA-3) and (IB-1) to (IB-3) are also very particularly preferred:
  • Ar represents phenyl or naphthyl which is optionally monosubstituted to trisubstituted by identical or different substituents, the substituents above under (R) phenyl substituents mentioned as preferred and particularly preferred come into question.
  • Q represents hydrogen, methyl or cyano
  • Ph represents phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, the phenyl substituents mentioned above under (R) being preferred and particularly preferred being suitable as substituents.
  • heteroaryl which is optionally monosubstituted to trisubstituted by identical or different substituents, such as, in particular, thiazolyl, thiadiazolyl, oxazolyl, oxadiazolyl, pyridinyl, pyrimidinyl or 1,3,5-
  • Ar represents phenyl or naphthyl which is optionally monosubstituted to trisubstituted by identical or different substituents, the substituents which may be mentioned as preferred and particularly preferred phenyl substituents above under (R).
  • Ph represents phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents, the phenyl substituents mentioned above as preferred and particularly preferred under (R) being suitable as substituents.
  • Het represents in each case mono- to trisubstituted, identically or differently substituted 5- or 6-membered heteroaryl, such as, in particular, thiazolyl, thiadiazolyl, oxazolyl, oxadiazolyl, pyridinyl, pyrimidinyl or 1,3,5-triazinyl, where the substituents described above under ( R) are preferred and particularly preferred heteroaryl substituents.
  • reaction sequence of process (a) according to the invention can be outlined using the following formula:
  • reaction sequence of process (b) according to the invention can be outlined using the following formula:
  • reaction sequence of process (c) according to the invention can be outlined using the following formula:
  • reaction sequence of process (d) according to the invention can be outlined using the following formula:
  • reaction sequence of process (e) according to the invention can be outlined using the following formula:
  • reaction sequence of process (f) according to the invention can be outlined by the following formula:
  • reaction sequence of process (g) according to the invention can be outlined by the following formula: 95/33717
  • reaction sequence of process (h) according to the invention can be outlined using the following formula:
  • Formula (II) provides a general definition of the heterocyclic keto derivatives required as starting materials for carrying out processes (a) and (b) according to the invention.
  • A, B, X and Y preferably or in particular have those meanings which have already been mentioned above in connection with the
  • heterocyclic keto derivatives of the formula (II) are not yet known. However, they can be obtained by generally customary standard methods by using known heterocyclic ketones of the general formula (XV)
  • formulas (III) and (IV) generally define the amines or isocyanates required as starting materials for carrying out processes (a) and (b) according to the invention.
  • Z and R preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for these substituents.
  • the amines of the formula (III) or the isocyanates of the formula (IV) are generally known compounds of organic chemistry or can be obtained by standard methods described in the literature.
  • Formula (V) provides a general definition of the heterocyclic imino derivatives required as starting materials for carrying out process (c) according to the invention.
  • A, B, X and Y preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of formula (I) as preferred or as particularly preferred for these substituents.
  • heterocyclic imino derivatives of the formula (V) are not yet known. However, they can be obtained in a generally known manner by refluxing heterocyclic keto derivatives of the general formula (II) with chlorosulfonyl isocyanate in the presence of a diluent, such as chloroform (see also the preparation examples).
  • Halogen derivatives required as starting materials are generally defined by the formula (VI).
  • R and Z preferably or in particular have those meanings which have already been mentioned above in connection with the meaning of the compounds of the formula (I) as preferred or as particularly preferred for the substituents.
  • Shark 1 is preferably chlorine or
  • halogen derivatives of the formula (VT) are generally known compounds of organic chemistry.
  • Formula (VII) provides a general definition of the heterocyclic imino derivatives required as starting materials for carrying out processes (d) and (e) according to the invention.
  • A, B, R and Z preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for these substituents.
  • Y 1 preferably or in particular stands for those meanings of the groupings -CO- alkyl and -COOalkyl which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for these groupings.
  • heterocyclic imino derivatives of the formula (VII) are not yet known. However, they can be obtained by generally customary standard methods by using imino derivatives of the general formula (XVTH)
  • halides of the formula (XVI) optionally in the presence of a diluent, such as, for example, tetrahydrofuran and optionally in
  • reaction auxiliary such as potassium tert-butoxide
  • Suitable alkylating agents for carrying out processes (d) and (f) are customary reagents, such as, for example, alkyl halides, in particular methyl chloride, methyl bromide and methyl iodide, and also di alkyl sulfates, such as, in particular, dimethyl sulfate.
  • the alkylating agents are generally known compounds of the organic radicals
  • Formula (IX) provides a general definition of the aldehydes also required as starting materials for carrying out process (e) according to the invention.
  • R 1 preferably or in particular has those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for these substituents.
  • the aldehydes of the formula (IX) are generally known compounds of organic chemistry.
  • Formula (VTII) provides a general definition of the heterocyclic imino derivatives required as starting materials for carrying out process (f) according to the invention.
  • A, B, R and Z preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for these substituents.
  • heterocyclic imino derivatives of the formula (VIII) are not yet known. However, they can be obtained by generally customary standard methods, by imino derivatives of the general formula (XVIII) with known keto-halides of the general formula (XIX)
  • Y 1 has the meaning given above, if appropriate in the presence of a diluent, such as, for example, tetrahydrofuran and, if appropriate, in the presence of a reaction auxiliary, such as, for example, potassium carbonate, at temperatures between 0 and 100 ° C. (cf. also the preparation examples).
  • a diluent such as, for example, tetrahydrofuran
  • a reaction auxiliary such as, for example, potassium carbonate
  • Formula (X) provides a general definition of the heterocyclic imino derivatives required as starting materials for carrying out process (g) according to the invention.
  • A, B, R and Z preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for these substituents.
  • Y 1 preferably or in particular represents those meanings of the -CO-alkyl and -COOalkyl groups which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for these groupings were.
  • heterocyclic imino derivatives of the formula (X) are not yet known. However, they can be obtained according to standard methods described in the literature, for example by using the corresponding keto derivatives of the general formula (VIII) with a sulfurizing agent, such as P 4 S 10 or Lawesson's reagent [2,4-bis (4-methoxyphenyl) -l, 3,2,4-dithiadiphosphetane-2,4-dithione], optionally in a diluent, such as xylene or toluene, at temperatures between 80 and 200 ° C.
  • a sulfurizing agent such as P 4 S 10 or Lawesson's reagent [2,4-bis (4-methoxyphenyl) -l, 3,2,4-dithiadiphosphetane-2,4-dithione]
  • a diluent such as xylene or toluene
  • Formula (XI) provides a general definition of the amines also required as starting materials for carrying out process (g) according to the invention.
  • R 1 preferably or in particular has those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for these substituents.
  • the amines of the formula (XI) are generally known compounds of organic chemistry.
  • heterocyclic imino derivatives required as starting materials for carrying out processes (h) and (i) according to the invention are represented by the formula (XII) generally defined.
  • A, B, R, X and Z preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of formula (I) as preferred or as particularly preferred for these substituents .
  • heterocyclic imino derivatives of the formula (XII) are according to the invention.
  • R 3 and R 4 preferably or in particular have those
  • the amines of the formulas (Xffla), (Xlllb) and (XIIIc) are generally known compounds of organic chemistry.
  • Formula (XIV) provides a general definition of disubstituted alkanes required as starting materials.
  • D has preferably or in particular those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) as preferred or as particularly preferred for these substituents.
  • E preferably represents chlorine, bromine, iodine, methanesulfonyloxy or p-toluenesulfinyloxy.
  • the disubstituted alkanes of the formula (XIV) are generally known compounds of organic chemistry.
  • Inert organic solvents are suitable as diluents for carrying out processes (a) to (i) according to the invention.
  • Aliphatic, alicyclic or aromatic, optionally halogenated can preferably be used
  • Hydrocarbons such as gasoline, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, nitriles, such as Acetonitrile or propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid amide, esters such as ethyl acetate or sulfoxides such as dimethyl sulfoxide, alcohols such as methanol or ethanol or basic solvents such as pyridine or triethylamine.
  • ethers such as diethyl ether, dioxane, tetrahydrofuran or
  • Process (a) according to the invention is preferably carried out in the presence of a dehydrating agent as reaction auxiliary.
  • a dehydrating agent as reaction auxiliary.
  • Phosphorus oxychloride is preferably usable (see e.g. J. Med. Chem. 18 (1975) 90-99)
  • Processes (c) and (i) according to the invention are preferably carried out in the presence of a suitable reaction auxiliary.
  • All commonly used inorganic and organic bases are suitable as such.
  • Alkali metal hydrides, hydroxides, alcoholates, carbonates or hydrogen carbonates such as, for example, sodium hydroxide, sodium methylate, sodium ethylate, potassium t-butoxide, sodium carbonate, potassium carbonate or sodium hydrogen carbonate or also tertiary amines, such as, for example, triethylamine, are preferably used , N, N-deimethylaniline, pyridine, N, N-dimethylaminopyridine, diazabicyclo-octane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
  • DABCO diazabicyclo-octane
  • DBU diazabicyclonones
  • DBU diazabicycloundecene
  • Acidic reaction aids such as p-toluenesulfonic acid may also be advantageous.
  • reaction temperatures can be varied within a substantial range when carrying out processes (a) to (i) according to the invention. In general, temperatures between 0 ° C and + 200 ° C, preferably at
  • the corresponding alkylated hydroxylamine derivative can also be used directly.
  • 1 to 4 mol, preferably 1 to 2 mol of amine or the corresponding hydrohalide and optionally 1 to 3 mol, preferably 1, are generally employed per mol of heterocyclic imino derivative of the formula (X) to 2 moles of reaction aids.
  • 1 to 3 mol, preferably 1 to 1.5 mol, of amine of the formulas (Xllla), (Xi ⁇ b) and (XIIIc.) are generally employed per mole of heterocyclic imino derivative of the formula (VII) ) and optionally OJ to 3 mol, preferably 0.5 to 1.5 mol, of reaction auxiliary.
  • 1 to 5 mol, preferably 1 to 2.5 mol, of hydroxylamine or the corresponding hydrohalide and in general 1 to 1 mol are generally employed per mol of heterocyclic imino derivative of the formula (XII) 10 moles, preferably 1 to 5 moles of disubstituted alkane of the formula (XTV) and optionally 1 to 5 moles, preferably 1 to 2.5 moles, of reaction auxiliaries.
  • reaction is carried out, worked up and isolated in all of the processes by generally customary and known methods.
  • the active compounds according to the invention have a strong microbicidal action and can be used practically to combat unwanted microorganisms.
  • the active ingredients are suitable for use as crop protection agents, in particular as fungicides.
  • Fungicidal agents in crop protection are used to combat plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.
  • Pythium species such as, for example, Pythium ultimum; Phytophthora species, such as, for example, Phytophthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubense; Plasmopara species, such as, for example, Plasmopara viticola;
  • Peronospora species such as, for example, Peronospora pisi or Peronospora brassicae;
  • Erysiphe species such as, for example, Erysiphe graminis
  • Sphaerotheca species such as, for example, Sphaerotheca fuliginea
  • Podosphaera species such as, for example, Podosphaera leucotricha
  • Venturia species such as, for example, Venturia inaequalis
  • Pyrenophora species such as, for example, Pyrenophora teres or Pyrenophora graminea (conidia form: Drechslera, synonym: Helminthosporium); Cochliobolus species, such as, for example, Cochliobolus sativus (conical form:.
  • Drechslera synonym: Helminthosporium
  • Uromyces species such as, for example, Uromyces appendiculatus
  • Puccinia species such as, for example, Puccinia recondita
  • Tilletia species such as, for example, Tilletia caries
  • Ustilago species such as, for example, Ustilago nuda or Ustilago avenae
  • Pellicularia species such as, for example, Pellicularia sasakii;
  • Pyricularia species such as, for example, Pyricularia oryzae
  • Fusarium species such as, for example, Fusarium culmorum
  • Botrytis species such as, for example, Botrytis cinerea; Septoria species, such as, for example, Septoria nodorum;
  • Leptosphaeria species such as, for example, Leptosphaeria nodorum;
  • Cercospora species such as, for example, Cercospora canescens
  • Alternaria species such as, for example, Alternaria brassicae;
  • Pseudocercosporella species such as, for example, Pseudocercosporella herpotrichoides.
  • the active compounds according to the invention can be used with particularly good success for combating diseases in fruit and vegetable cultivation, for example against Podosphaera species, or for combating rice diseases, for example against Pyricularia oryzae.
  • the active compounds can be converted into customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV cold and warm mist formulations.
  • formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents, under
  • Pressurized liquefied gases and / or solid carriers optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.
  • water e.g. organic solvents can also be used as auxiliary solvents.
  • organic solvents can also be used as auxiliary solvents.
  • the following are essentially suitable as liquid solvents: aromatics such as xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide or dimethyl sulfoxide, and water;
  • liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; solid carriers are possible: e.g.
  • natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates
  • Solid carriers for granules are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; emulsifying and / or foaming agents are possible: e.g. non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ether,
  • Adhesives such as carboxymethyl cellulose, natural and synthetic, powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural ones, can be used in the formulations Phospholipids such as cephalins and lecithins and synthetic phospholipids.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron,
  • Copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0J and 95% by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can be used as such or in their formulations, also in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance.
  • Tebuconazole Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thiophanate-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin,
  • Azinphos M Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin,
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157
  • Fenamiphos fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,
  • Fenoxycarb fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron, flucythrinate, flufenoxuron, flufenprox,
  • Lamda-cyhalothrin Lamda-cyhalothrin, Lufenuron, Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyd, Methacrifosj
  • Methamidophos methidathione, methiocarb, methomyl, metolcarb, milbemectin,
  • Tebufenozid Tebufenpyrad
  • Tebupirimphos Teflubenzuron
  • Tefluthrin Temephos
  • Terbam Terbufos
  • Tetrachlorvinphos Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenethriazonium, Triomenethriazonium, Tri
  • the active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated.
  • the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.
  • amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.
  • reaction mixture was then poured onto 300 ml of water, made alkaline with potassium carbonate solution, extracted twice with 100 ml of ether each time, and the combined organic extracts were dried over sodium sulfate and concentrated in vacuo. After trituration with a mixture of 10 ml of ether and 10 ml of n-pentane, a yellow solid was obtained.
  • reaction mixture was poured onto 250 ml of water, with dilute
  • the suspension was then poured onto 600 ml of water, 3 times with
  • the suspension was then poured onto 600 ml of water, extracted 3 times with 200 ml of ether each time, the water phase was acidified with dilute hydrochloric acid, extracted 3 times with 200 ml of methylene chloride each time and the combined extracts were dried over sodium sulfate and concentrated in vacuo. The mixture was then stirred with ether to give a yellow solid.
  • the suspension was then poured onto 100 ml of water, extracted 3 times with 30 ml of ethyl acetate each time, and the organic extracts were dried and concentrated.
  • the suspension was then poured onto 200 ml of water, extracted 3 times with 40 ml of ethyl acetate each time, and the organic extracts were dried and concentrated.
  • the suspension was then concentrated in vacuo, the residue was partitioned between 400 ml of methylene chloride and 300 ml of water, the water phase was extracted twice with 100 ml of methylene chloride each time, and the organic extracts were dried and concentrated in vacuo.
  • reaction mixture was poured onto 3 l of water, extracted 3 times with 500 ml of ether each time, the ether extracts were discarded, the water phase was acidified with dilute hydrochloric acid, extracted 4 times with 500 ml of methylene chloride each time, the organic phase was dried over sodium sulfate and in Vacuum concentrated.
  • the suspension was then poured onto 100 ml of water, extracted 3 times with 70 ml of methylene chloride each time, and the organic extracts were dried and concentrated.
  • - ⁇ -ci 3.68 (t, 2H, CH 2 ), 3.77 (s, 3H, OCH 3 ), 4J5 (s, 2H, CH 2 CO), 4.40 (t, 2H, CH 2 ), 6.84-6.90 ( m, 1H, Ar-H), 7J7-7.40 (m, 1H, Ar-H).
  • the suspension was then added to 250 ml of water, extracted 3 times with 70 ml of ethyl acetate, the organic extracts dried over sodium sulfate and concentrated in vacuo. The residue was then stirred in 30 ml of n-pentane and the solid obtained was filtered off and dried.
  • Solvent 4.7 parts by weight of acetone emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at 23 and at a relative humidity of approx. 70%.
  • Evaluation is carried out 10 days after the inoculation.
  • the compound according to Preparation Example 9 shows an efficiency of 86% at an active ingredient concentration of 10 ppm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

L'invention concerne de nouveaux dérivés imino hétérocycliques, plusieurs procédés de préparation de ces nouveaux dérivés et leur utilisation comme pesticides.
EP95920853A 1994-06-03 1995-05-22 Derives imino heterocycliques Withdrawn EP0763018A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4419587A DE4419587A1 (de) 1994-06-03 1994-06-03 Heterocyclische Imino-Derivate
DE4419587 1994-06-03
PCT/EP1995/001933 WO1995033717A2 (fr) 1994-06-03 1995-05-22 Derives imino heterocycliques

Publications (1)

Publication Number Publication Date
EP0763018A2 true EP0763018A2 (fr) 1997-03-19

Family

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Application Number Title Priority Date Filing Date
EP95920853A Withdrawn EP0763018A2 (fr) 1994-06-03 1995-05-22 Derives imino heterocycliques

Country Status (6)

Country Link
US (1) US5922881A (fr)
EP (1) EP0763018A2 (fr)
JP (1) JPH10500961A (fr)
AU (1) AU2615095A (fr)
DE (1) DE4419587A1 (fr)
WO (1) WO1995033717A2 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6353006B1 (en) 1999-01-14 2002-03-05 Bayer Corporation Substituted 2-arylimino heterocycles and compositions containing them, for use as progesterone receptor binding agents
JP2001261652A (ja) * 2000-03-21 2001-09-26 Suntory Ltd 二置換イミノヘテロサイクリック化合物
CN101346374A (zh) * 2005-12-22 2009-01-14 巴斯夫欧洲公司 农业组合物

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1488270A (fr) * 1966-03-21 1967-07-13 Chimetron Sarl Benzimidazoles portant un substituant bicyclique
AT294798B (de) * 1968-04-26 1971-12-10 Egyt Gyogyszervegyeszeti Gyar Verfahren zur Herstellung von Formamidinderivaten
GB1571826A (en) * 1976-03-09 1980-07-23 Shell Int Research Method of combating pests and pesticidal compositions and thiazoline derivatives useful therefor
GB1595412A (en) * 1976-12-14 1981-08-12 Boots Co Ltd Method for control of pests attacking animals
US4559357A (en) * 1982-06-11 1985-12-17 Ciba-Geigy Corporation Insecticidal and acaricidal phenylhydrazono- and phenylhydrazino-pyrrolidines
JPH02250874A (ja) * 1989-03-23 1990-10-08 Hodogaya Chem Co Ltd チアゾール誘導体
DE69029334T2 (de) * 1989-05-17 1997-04-30 Shionogi Seiyaku Kk Verfahren zur Herstellung von Alkoxyiminoacetamid-Derivaten und ein Zwischenproduckt dafür
JPH0725727B2 (ja) * 1990-07-26 1995-03-22 塩野義製薬株式会社 メトキシイミノアセトアミド化合物の製造法
JPH06504538A (ja) * 1991-01-30 1994-05-26 ゼネカ・リミテッド 殺菌剤
JP3217191B2 (ja) * 1992-07-16 2001-10-09 ビーエーエスエフ アクチェンゲゼルシャフト ヘテロ芳香族化合物およびこれを含有する植物保護剤

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9533717A2 *

Also Published As

Publication number Publication date
AU2615095A (en) 1996-01-04
US5922881A (en) 1999-07-13
WO1995033717A3 (fr) 1996-02-15
JPH10500961A (ja) 1998-01-27
WO1995033717A2 (fr) 1995-12-14
DE4419587A1 (de) 1995-12-07

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