EP1121357A1 - 2-hetaryl-3,4-dihydro-2h-pyrrol-derivate - Google Patents

2-hetaryl-3,4-dihydro-2h-pyrrol-derivate

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Publication number
EP1121357A1
EP1121357A1 EP99948915A EP99948915A EP1121357A1 EP 1121357 A1 EP1121357 A1 EP 1121357A1 EP 99948915 A EP99948915 A EP 99948915A EP 99948915 A EP99948915 A EP 99948915A EP 1121357 A1 EP1121357 A1 EP 1121357A1
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EP
European Patent Office
Prior art keywords
formula
alkyl
compounds
haloalkyl
optionally
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP99948915A
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German (de)
English (en)
French (fr)
Inventor
Andrew Plant
Bernd Alig
Alan Graff
Udo Kraatz
Wolfgang Krämer
Christoph Erdelen
Andreas Turberg
Norbert Mencke
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 CropScience AG
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Bayer AG
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Publication date
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Publication of EP1121357A1 publication Critical patent/EP1121357A1/de
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—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
    • C07D417/04—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 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
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the invention relates to new 2-hetaryl-3,4-dihydro-2H-pyrrole derivatives, several processes for their preparation and their use as pesticides.
  • WO 98/22438 reports on new substituted ⁇ , ⁇ '-diphenylimines and their suitability for use as pesticides. So far, however, nothing has been known about substituted ⁇ -hetaryl- ⁇ '-phenylimines and their suitability for use as pesticides.
  • Hetaryl represents unsaturated 5 to 10-membered, mono- or bicyclic heterocyclic compounds which are optionally mono- or polysubstituted by radicals from the list H 1 , for example 5 or 6-membered monocyclyls with one or more heteroatoms from the series N, O and S.
  • H 1 represents hydrogen, halogen, cyano, formyl, nitro, alkyl, trialkylsilyl, alkoxy, haloalkyl, haloalkoxy, haloalkenyloxy, alkylcarbonyl, alkoxycarbonyl, pentafluorothio, carbamoyl, thiocarbamoyl, alkoximino or -S (O) 0 R3,
  • n 0, 1, 2, 3 or 4
  • R2 represents hydrogen, halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxyalkoxy or -S (O) 0 R3,
  • o 0, 1 or 2
  • R ⁇ represents alkyl or haloalkyl, X for a direct bond, oxygen, sulfur, carbonyl, carbonyloxy,
  • Wl substituted phenyl, naphthyl or tetrahydronaphthyl or for each 5- or 10-membered, containing 1 or 2 aromatic rings containing heterocyclicl with one or more heteroatoms from the series nitrogen, oxygen and optionally mono- or polysubstituted by radicals from the list W ⁇ Sulfur stands,
  • B represents p-phenylene which is optionally mono- or disubstituted by radicals from the list W,
  • Z represents oxygen or sulfur
  • Y for a direct bond, oxygen, sulfur, carbonyl, carbonyloxy, oxycarbonyl, alkylene, alkenylene, alkynylene, alkyleneoxy, oxyalkylene,
  • Thioalkylene, alkylenedioxy or p-phenylene which is optionally mono- or disubstituted by radicals from the list W ⁇ ,
  • E represents hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, in each case optionally by halogen, alkyl, alkenyl, haloalkenyl,
  • R5 represents hydrogen or alkyl
  • p, q and r independently of one another represent 0, 1, 2 or 3, the sum of which is less than 6,
  • R ⁇ and R8 independently of one another represent hydrogen or alkyl
  • R 9 represents hydrogen, alkyl, alkenyl, haloalkyl, haloalkenyl, cycloalkyl which is optionally substituted by halogen, alkyl or haloalkyl or represents phenyl which is optionally monosubstituted to fivefold by alkylcarbonylamino, alkylcarbonylalkylamino and / or radicals from the list W ⁇ ,
  • R 10 represents hydrogen, alkyl, alkenyl, haloalkyl, haloalkenyl, in each case cycloalkyl or cycloalkylalkyl which is optionally substituted by halogen, alkyl or haloalkyl or represents arylalkyl which is optionally monosubstituted to fivefold by radicals from the list W->
  • R 1! and R 12 independently of one another for hydrogen, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, in each case optionally substituted by halogen, alkyl or haloalkyl cycloalkyl or cycloalkylalkyl, for in each case optionally up to five times substituted by radicals from the list W ⁇ aryl or arylalkyl, for -OR 10 or -NR 9 R 10 or together represent an alkylene chain with 2 to 6 links, in which a methylene group is optionally replaced by oxygen,
  • R 13 stands for -OR 10 , -NR9R 10 or -N (R 9 ) -COOR '°
  • R 14 , R 15 and R 16 independently of one another represent alkyl
  • Wl represents hydrogen, halogen, cyano, formyl, nitro, alkyl, trialkylsilyl, alkoxy, haloalkyl, haloalkoxy, haloalkenyloxy, alkylcarbonyl, alkoxycarbonyl, pentafluorothio or -S (O) 0 R 3 ,
  • W ⁇ represents halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, dialkylamino, -S (O) 0 R 3 , -COOR 17 or -CONR 18 R 19 ,
  • R 17 represents hydrogen, alkyl, haloalkyl, cycloalkyl optionally substituted by halogen, alkyl or haloalkyl or phenyl optionally substituted up to five times by radicals from the list W 4 ,
  • R 18 and R 19 independently of one another for hydrogen, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, in each case optionally through halogen, alkyl or
  • W 4 represents halogen, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, dialkylamino, alkoxycarbonyl, dialkylaminocarbonyl or -S (O) 0 R 3 .
  • the compounds of formula (I) can, depending on the type of
  • Cyclic imines of the formula (I) can also be prepared by cyclic O-methylsulfonyloximes of the formula (III)
  • Hetaryl has the meanings given above, m has the meanings given above,
  • R 2_1 represents hydrogen, fluorine, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, alkoxyalkoxy or -SR 3 , where
  • R 3 has the meanings given above
  • R 2 " 1 and m have the meanings given above and X 1 represents bromine, iodine, -OH or -OSO 2 CF 3
  • R 1 " 1 has the meanings given above,
  • R 2 and m have the meanings given above,
  • ⁇ l represents oxygen or sulfur
  • R 7 , R 8 , G, p, q and r have the meanings given above,
  • R 2 and m have the meanings given above and
  • R 7 , R 8 , G, p, q and r have the meanings given above and
  • R 2 and m have the meanings given above and
  • Rl stands for a group containing the radical G from the description of the compounds of the formula (I) according to the invention, wherein
  • G represents one of the above-mentioned groupings (e) to (k),
  • R 1 and hetaryl have the meanings given above, derivatized, and this in a final step ⁇ ) by reaction with PIFA (l, l-bis (trifluoroacetoxy) iodobenzene) of the formula (F-VII), or other compounds known to have a comparable effect, such as NaOBr or iodosobenzene,
  • Method G can be varied in step ⁇ ).
  • the amino function of the arylbutyrolactam (X) is then protected with a dialkylaminomethyl function or a vinyl function instead of a hetarylcarbonyl flashing.
  • the dialkylaminomethyl function is then generated by reacting the lactam (X) with dialkylamine and formaldehyde, the vinylation can e.g. with acetylene (see e.g. textbooks of heterocycle chemistry).
  • the course of steps ß) and ⁇ ) remains unchanged (see e.g. Jr. Org. Chem. 1998, 63, p. 1109 ff, J. Org. Chem. 1982, 47, p. 4165 ff and Oppi Briefs, 1995, 27, P. 510 ff).
  • Hetaryl preferably represents optionally mono- or polysubstituted, unsaturated 5- or 6-membered heterocyclyls, for example thienyl, furanyl, thiazolyl, pyridyl, imidazolyl and triazolyl, which contain one or more heteroatoms from the series N, O or S and their substituents, for example from the series H, alkyl, alkoxy, halogen, cyano, haloalkyl, haloalkoxy, S (O) 0 R 3 , carbamoyl, thiocarbamoyl, alkoximino and
  • Haloalkylthio can be selected.
  • Ar preferably represents the rest
  • m preferably represents 0, 1, 2, 3.
  • R 1 preferably represents a substituent in the meta or para position from the series hydrogen, halogen or one of the following groups
  • R 2 preferably represents hydrogen, halogen, cyano, nitro, C ⁇ -C ⁇ - alkyl, C ⁇ - C iß-alkoxy, Ci-Cg-haloalkyl, Cj-Cg-haloalkoxy, C -Cg-alkoxy-q-Cs -alkoxy or -SOD ⁇ R 3 .
  • o is preferably 0, 1 or 2.
  • R ⁇ preferably represents C ⁇ - C0-alkyl optionally substituted by fluorine or chlorine.
  • X preferably represents a direct bond, oxygen, sulfur, carbonyl
  • A preferably represents phenyl, naphthyl or tetrahydronaphthyl which is optionally monosubstituted to tetrasubstituted by radicals from the list W ⁇ or for 5- to 10-membered, 1 to 2 aromatic ring-containing heterocyclyls with 1 to 4 heteroatoms which have 0 to 4 nitrogen atoms, 0 to 2 oxygen atoms and 0 to 2 sulfur atoms and are optionally substituted up to four times by radicals from the list W 2 contain, (especially furyl, benzofuryl, thienyl, benzothienyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, pyrrolyl, pyridyl, pyrimidyl, 1,3,5-triazinyl, quinolinyl, isoquinoline, indolyl, purinyl, benzodioxolyl, indanyl, Benzo
  • B preferably represents optionally single or double by residues from the
  • Z preferably represents oxygen or sulfur.
  • D preferably represents hydrogen, Cj-Cig-alkyl, C 2 -C ig-alkenyl, C 2 -Cg-
  • C5-Cg-Cycloalkenyl-C ⁇ -C4-alkyl for each optionally substituted by nitro, halogen, Cj-Cg-alkyl, Ci-Cg-alkoxy, Cj-Cö-haloalkyl or Ci-Cg-haloalkoxy substituted phenyl-Ci-Cg- alkyl, naphthyl-Cj-Cö-alkyl, tetrahydronaphthyl-Ci-Cg-alkyl or 5- to 6-membered hetaryl-C -Cg-alkyl with 1 or 2 heteroatoms from the series nitrogen, oxygen and
  • D also preferably together represent phenoxy-C 1 -C 4 -alkyl which is optionally substituted by nitro, halogen, Ci-Cg-alkyl, Ci-Cg-alkoxy, C j -Cg-haloalkyl or Ci-Cg-haloalkoxy.
  • Y preferably represents a direct bond, oxygen, sulfur, carbonyl
  • E preferably represents hydrogen, C1 -C ⁇ alkyl, C 2 -Cj6 alkenyl, C 2 -Cö-
  • Cg-cycloalkenyl for phenyl which is optionally monosubstituted to tetrasubstituted by radicals from the list Wl or for in each case optionally monosubstituted to quadrupled by radicals from the list W 2, 5- to 6-membered hetaryl having 1 or 2 heteroatoms from the series nitrogen, oxygen and sulfur (especially furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl,
  • R 4 preferably represents C 1 -C 4 alkyl, C 1 -C 2 alkoxy, C 2 -C 2 alkenyl, C 2 -
  • R ⁇ preferably represents hydrogen or C i -C ⁇ 2 alkyl.
  • R6 preferably represents C ⁇ -C 2 - alkyl, C i -C 2 -haloalkyl 1, j in each case optionally substituted by halogen, C ⁇ -C4-alkyl, C 2 -C 4 alkenyl, C ⁇ -C4-haloalkyl or C 2 -C 4 -Halogenalkenyl substituted C 3 -Cg cycloalkyl or C 3 -Cg cycloalkyl-Ci-Cg-alkyl or for each optionally up to four times by halogen, -CC 2 alkyl, -C 2 -C alkoxy, C - C ⁇ 2 -haloalkyl or C ⁇ - C ⁇ 2 -haloalkoxy substituted phenyl or phenyl-Ci-Cg-alkyl.
  • p, q and r are preferably independently of one another 0, 1, 2 or 3, the sum of which is less than 6.
  • R7 and R8 are each independently preferably represents hydrogen or C j -C4- alkyl.
  • G preferably represents cyano, a 5- or 6-membered heterocycle with 1 to 3 of the same or with 1 to 3 substituents which is optionally monosubstituted to trisubstituted by halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl and optionally at the point of attachment by the R 4 radical various heteroatoms from the series nitrogen, oxygen and sulfur (in particular 5,6-dihydrodioxazin-2-yl, 3-pyridyl, 3-furyl, 3-thienyl, 2-thiazolyl, 5-thiazolyl, 2-dioxolanyl, l, 3- Dioxan-2-yl, 2-dithiolanyl, l, 3-dithian-2-yl or l, 3-thioxan-2-yl) or one of the following groups:
  • R 9 preferably represents hydrogen, Cj-Cg alkyl, C 2 -Cö- alkenyl, C ⁇ -Halo- genalkyl, C 2 -C 6 haloalkenyl, optionally substituted by halogen, C1-C4 alkyl or C ⁇ -C4-halogenoalkyl C 3 -Cg-Cycloalkyl or for phenyl optionally substituted up to five times by C -C4-alkylcarbonylamino, C1-C4-alkylcarbonyl-C ⁇ -C4-alkylamino and / or radicals from the list W ⁇ .
  • R 10 preferably represents hydrogen, C1-C4-alkyl, C 2 -C6-alkenyl, -C4-haloalkyl, C 2 -Cg-haloalkenyl, in each case optionally substituted by halogen, C1-C4-alkyl or Cj-C4-haloalkyl -Cö-cycloalkyl or C 3 -C6-Cycloalkyl-C -C4-alkyl or for optionally up to four times substituted by radicals from the list W 3 (In particular phenyl -CC4-alkyl or naphthyl -CC4-alkyl).
  • R ⁇ and Rl2 independently of one another preferably represent hydrogen, C1-C4-
  • R 1 preferably represents -OR 1 °, -NR 9 R ⁇ ° or -N (R 9 ) -COOR 1 °.
  • R.4, R15 and R16 independently of one another preferably represent Ci-Cg-alkyl.
  • W * preferably represents hydrogen, halogen, cyano, formyl, nitro, Cj-Cg-alkyl, tri-C 1 -C4-alkylsilyl, C ⁇ C ⁇ - alkoxy, Ci-Cg-haloalkyl, C1-C6-haloalkoxy, C. 2 -Cg-haloalkenyloxy, Ci-Cg-alkylcarbonyl, CJ-CI ⁇ -
  • W 2 preferably represents halogen, cyano, formyl, nitro, C j -Cg alkyl, tri-C-C4 alkylsilyl, CJ -CJ ⁇ - alkoxy, Ci-Cg-haloalkyl, Ci-Cg-haloalkoxy, C ⁇ - Cg -Alkylcarbonyl, Cj-C 15 -alkoxycarbonyl, pentafluorothio, -S (O) 0 R 3 or
  • W 3 preferably represents halogen, cyano, nitro, C 4 -C 4 alkyl, C 4 -C 4 alkoxy, C 4 C 4 haloalkyl, C 4 -C 4 haloalkoxy, di-C 4 -C 4 alkylamino, -S (O) 0 R 3 , -COOR 17 or -CONR 1 8 R19.
  • Rl7 preferably represents hydrogen, C1-C4-alkyl, -C-C4-haloalkyl, C 3 -C7-cycloalkyl optionally substituted by halogen, -C-C4-alkyl or C ⁇ -C4-haloalkyl or optionally up to five times by radicals from the List W 4 substituted phenyl.
  • R * 8 and R 19 independently of one another preferably represent hydrogen, C1-C4-alkyl, C -Cö-alkenyl, C ⁇ -C4-haloalkyl, C 3 -C6-haloalkenyl, C1-C4- alkoxy, in each case optionally by halogen, C1 -C4- alkyl or C1-C4- haloalkyl substituted C 3 -Cg-cycloalkyl or C ⁇ Cg-cycloalkyl-Cj- C4-alkyl or for phenyl or phenyl-C ⁇ -substituted in each case optionally up to five times by radicals from the list W 4 - C4-alkyl, for -OR 14 or -NR15R16 oc ⁇ er together for an alkylene chain with 4 to 6 links, in which a methylene group is optionally replaced by oxygen.
  • W 4 preferably represents halogen, cyano, nitro, C ⁇ -Cg alkyl, C ⁇ -Cg alkoxy, C ⁇ -
  • Cg-haloalkyl Cj-Cg-haloalkoxy, Di-C ⁇ -C4-alkylamino, Ci -Cg-alkoxycarbonyl, Di-Ci -Cg-alkylaminocarbonyl or -S (O) 0 R 3 .
  • Halogen in the preferred areas is, for example, Cl, F. Br and iodine, in particular F, Cl and Br.
  • Ar particularly preferably represents the rest
  • n particularly preferably represents 0, 1 or 2.
  • R 1 particularly preferably represents a substituent in the meta or para position from the series hydrogen, fluorine, chlorine, bromine, iodine or one of the following groups
  • R 2 particularly preferably represents hydrogen, fluorine, chlorine, bromine, iodine, cyano,
  • o particularly preferably represents 0, 1 or 2.
  • R 3 particularly preferably represents C 1 -C 4 -alkyl or methyl or ethyl substituted in each case by fluorine or chlorine.
  • X particularly preferably represents a direct bond, oxygen, sulfur,
  • Ring-containing heterocyclyls with 1 to 4 heteroatoms which contain 0 to 4 nitrogen atoms, 0 to 2 oxygen atoms and 0 to 2 sulfur atoms (in particular furyl, benzofuryl, thienyl, benzothienyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, pyrrolyl, pyridyl, pyrimidyl, 1,3,5-triazinyl, quinolinyl, isoquinolinyl, indolyl, purinyl, benzodioxolyl, indanyl,
  • B particularly preferably stands for single or double if necessary
  • Residues from the list W * substituted p-phenylene.
  • D particularly preferably represents hydrogen, C 1 -C 7 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, in each case C 1 -C 4 -alkyl or C 2 -C 4 -alkenyl substituted by fluorine or chlorine, for each optionally by fluorine, chlorine, bromine,
  • C1 -C4 alkyl C 2 -C4 alkenyl, fluorine or chlorine substituted C 2 -C4 alkenyl, phenyl, styryl, fluorine, chlorine or bromo substituted phenyl or styryl substituted C 3 -Cg cycloalkyl or C 3 -Cg-Cycloalkyl-C -C4-alkyl, for each optionally substituted by fluorine, chlorine, bromine or C -C4-alkyl substituted C5-Cg-cycloalkenyl or C5-Cg-cycloalkenyl -CC-C4-alkyl, for each optionally substituted by nitro, fluorine, chlorine, bromine, -Cg-alkyl, -C ⁇ Cg-alkoxy, fluorine or chlorine-substituted Cj-C ⁇ alkyl or C ⁇ -C4-alkoxy phenyl-C
  • Z and D also particularly preferably together represent phenoxy-C which is optionally substituted by nitro, fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, fluorine- or chlorine-substituted C -C4-alkyl or C -C4-alkoxy - C 3 alkyl.
  • Y particularly preferably represents a direct bond, oxygen, sulfur,
  • Thioalkylene, -C-C4-alkylenedioxy or for p-phenylene which is optionally mono- or disubstituted by radicals from the list W ⁇ .
  • E particularly preferably represents hydrogen, C -C g-alkyl, C 2 -C ⁇ g-alkenyl,
  • C 2 -CG-alkynyl in each case substituted by fluorine or chlorine, C1-C4 alkyl or C 2 -C 4 -alkenyl which is optionally substituted by fluorine, chlorine, bromine, C1-C4 alkyl, C 2 -C 4 alkenyl, fluoro- or chlorine-substituted C -C4 alkenyl,
  • W 2 substituted 5- or 6-membered heterocyclyls with 1 or 2 heteroatoms from the series nitrogen, oxygen and sulfur (in particular furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl or pyridyl) or for the grouping
  • R 4 particularly preferably represents C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 2 -Cg-alkenyl, C 2 -Cg-alkenyloxy, in each case optionally fluorine- or chlorine-substituted by fluorine, chlorine, C1-C3-alkyl C ⁇ -C 2 - alkyl or C 2 -C 3 alkenyl substitutability tes C3 -CG-cycloalkyl, C3-Cg-cycloalkyloxy or C3-Cg-cycloalkyl-C ⁇ -C 2 - simply alkyloxy or optionally mono- or disubstituted by fluorine, Chlorine, bromine, iodine, C1-C4-alkyl, -C-C4-alkoxy, fluorine or chlorine-substituted C - C
  • R5 particularly preferably represents hydrogen or C 4 -C 4 alkyl.
  • R6 particularly preferably represents C -C4-alkyl or phenyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, C 1 -C 4 -alkyl, fluorine- or chlorine-substituted C 1 -C 4 -alkyl or C -C4-alkoxy Benzyl.
  • p, q and r are particularly preferably independently of one another 0, 1, 2 or 3, the sum of which is less than 6.
  • R 7 " and R independently of one another are particularly preferably hydrogen or
  • G particularly preferably represents cyano, optionally mono- to trisubstituted by fluorine, chlorine, bromine, C1-C4-alkyl or fluorine- or chlorine-substituted C -C4-alkyl and optionally 5- substituted at the point of attachment by the radical R 9 or 6-membered heterocyclyl with 1 to 3 identical or different heteroatoms from the series nitrogen, oxygen and sulfur (in particular 5,6-dihydrodioxazin-2-yl, 3-pyridyl, 3-furyl, 3-thienyl, 2-thiazolyl, 5 -Thiazolyl, 2-dioxolanyl, l, 3-dioxan-2-yl, 2-dithiolanyl, l, 3-dithian-2-yl or l, 3-thioxan-2-yl) or one of the following
  • Alkenyl optionally substituted by fluorine, chlorine, C1-C4-alkyl, fluorine or chlorine-substituted C -C4-alkyl C3-Cg-cycloalkyl or for optionally mono- to trisubstituted by C -C4-alkylcarbonylamino, C ⁇ - C4-alkylcarbonyl-C ⁇ -C4-alkylamino and / or radicals from the list W 3 substituted phenyl.
  • RIO particularly preferably represents hydrogen, C -C4-alkyl, C3-Cg-alkenyl, in each case C -C4-alkyl or C3-Cg-alkenyl substituted by fluorine or chlorine, in each case optionally by fluorine, chlorine, C 1 -C 4 -alkyl, fluorine- or chlorine-substituted C -C4-alkyl substituted C3-Cg-cycloalkyl or C3- Cg-cycloalkyl-C ⁇ -C4-alkyl or for each phenyl-C-substituted by radicals from the list W 3, which is optionally mono- to triple-substituted C4-alkyl or
  • R 1 and R 12 independently of one another particularly preferably represent hydrogen, C -C4-alkyl, C3-Cg-alkenyl, in each case fluorine or chlorine-substituted C -C4-alkyl or C3-Cg-alkenyl, for C ⁇ -C4-alkoxy , in each case optionally substituted by fluorine, chlorine, C 1 -C 4 -alkyl, fluorine- or chlorine-substituted C1-C4-alkyl C3-Cg-cycloalkyl or C3-Cg-cycloalkyl-C -C4-alkyl, for each in each case simply until phenyl or phenyl-Ci-Ct-alkyl substituted three times by radicals from the list W 3 , for -OR 10 or -NR 9 R 10 or together for - (CH 2 ) 5 -, - (CH 2 ) g- or - ( CH 2 ) 2 -O
  • R particularly preferably represents -OR 1 °, -NR ⁇ 1 ° or -N (R 9 ) -COOR 1 °.
  • R 14 , R ⁇ and R ⁇ independently of one another are particularly preferably C -C4-alkyl.
  • W 1 particularly preferably represents hydrogen, fluorine, chlorine, bromine, iodine, cyano, formyl, nitro, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, in each case C 1 -C 4 -alkyl or C 1 -C 4- substituted by fluorine or chlorine.
  • W 3 particularly preferably represents fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, in each case fluorine or chlorine-substituted C1-C4-alkyl or C1-C4-alkoxy, for di-C 1 -C 4 alkylamino, -S (O) 0 R 3 , -COOR 17 or -CONR 18 R 19 .
  • R 7 particularly preferably represents hydrogen, -CC-alkyl, by fluorine or
  • Chlorine-substituted C -C4-alkyl optionally by fluorine, chlorine, C1-C4-
  • Cycloalkyl or phenyl which is optionally monosubstituted to trisubstituted by radicals from the list W 4 .
  • R 1 * and R 9 independently of one another particularly preferably represent hydrogen, C 4 -C 4 -alkyl, C 3 -Cg-alkenyl, in each case substituted by fluorine or chlorine, C -C 4 -alkyl or C 3 -Cg-alkenyl, for CJ-C4 - Alkoxy, each optionally substituted by fluorine, chlorine, C1-C4-alkyl, fluorine or chlorine-substituted C1-C4-
  • W 4 particularly preferably represents fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, Cj-C4-alkoxy, in each case substituted by fluorine or chlorine, C1-C4-alkyl or C 1 -C 4 -alkoxy, di-C j -C4-alkylamino, C] -C4-alkoxycarbonyl, di-C 1 -Cg-alkylaminocarbonyl or -S (O) 0 R 3 .
  • Hetaryl very particularly preferably represents thienyl-, pyridyl which is optionally mono- to disubstituted by substituents from the series H, F, Cl, Br, cyano, CH 3 , OCH 3 OCF 3 SCF 3 , S (O) 0 R 3 and CF 3 -, thiazolyl or furanyl groups.
  • Ar very particularly preferably stands for the rest
  • R 1 very particularly preferably represents a substituent in the meta or para position from the series hydrogen, fluorine, chlorine, bromine, iodine or one of the following groups
  • R 2 very particularly preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, trifluoromethyl, difluoromethoxy, trifluoromethoxy or trifluoromethylthio.
  • o very particularly preferably represents 0, 1 or 2, in particular 0 or 2.
  • R 3 very particularly preferably represents methyl, ethyl, n-propyl, isopropyl, difluoromethyl or trifluoromethyl.
  • X very particularly preferably represents a direct bond, oxygen,
  • Z very particularly preferably represents oxygen or sulfur.
  • D very particularly preferably represents hydrogen, methyl, ethyl, n-propyl,
  • Dimethylethenyl, -CH CC1 2 , phenyl, styryl, fluorine, chlorine or bromine-substituted phenyl or 4-chlorostyryl substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally with fluorine, chlorine, methyl, in each case , Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl substituted cyclopentenyl, cyclohexenyl, cyclohexenyl methyl or cyclopentenylmethyl, each optionally mono- or disubstituted by nitro, fluorine, chlorine, bromine, methyl, ethyl, n-prop
  • Z and D also very particularly preferably together represent, optionally, single or double by nitro, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, n-propoxy, i-propoxy, trifluoromethyl,
  • E very particularly preferably represents hydrogen, methyl, ethyl, n-propyl,
  • Residues from the list W 2 substituted furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl or pyridyl, or for the grouping
  • R 4 very particularly preferably represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, isobutoxy , sec.-butoxy, tert.-butoxy, cyclopropyl, cyclohexyl, cyclohexyloxy, cyclohexylmethyloxy, phenyl, 2-chlorophenyl, 3-chlorophenyl, 2,6-difluorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2-
  • Trifluoromethoxyphenyl or 4-trifluoromethoxyphenyl Trifluoromethoxyphenyl or 4-trifluoromethoxyphenyl.
  • R5 very particularly preferably represents hydrogen.
  • R ⁇ very particularly preferably represents methyl, ethyl or phenyl which is optionally monosubstituted by chlorine.
  • R 7 and R8 independently of one another very particularly preferably represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.
  • G very particularly preferably represents cyano, each optionally monosubstituted to trisubstituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl or trifluoromethyl and 5,6-dihydrodioxazin-2 optionally substituted at the point of attachment by the radical R 9 -yl, 3-pyridyl, 3-furyl, 3-thienyl, 2-thiazolyl, 5-thiazolyl, 2-dioxolanyl, l, 3-dioxan-2-yl, 2-dithiolanyl, l, 3-dithian-2-yl or l, 3-thioxan-2-yl or one of the following
  • R 9 very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, the isomeric pentyls, the isomeric hexyls, -CF 3 , -CHF, -CC1F 2 , -CF 2 CHFC1, -CF CH 2 F,
  • R 1 ⁇ very particularly preferably represents hydrogen, methyl, ethyl, n-propyl,
  • R 1 1 and R 2 independently of one another very particularly preferably represent
  • Hydrogen methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, -CH 2 CF 3 , methoxy, ethoxy, allyl, for each optionally optionally or twice by fluorine, chlorine , Methyl, ethyl, n-propyl, Isopropyl or trifluoromethyl-substituted cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclopentylme hyl or cyclohexylmethyl, for phenyl, benzyl or phenethyl optionally substituted once or twice by radicals from the list W 3 , for -OR 10 or -NR 9 R 10 .
  • R 13 very particularly preferably represents -OR 10 , -NR 9 R 10 or -N (R 9 ) -COOR 10 .
  • R 4 , R 1 ⁇ and R 1 ⁇ independently of one another are particularly preferably methyl, ethyl, n-propyl or isopropyl.
  • W 1 very particularly preferably represents hydrogen, fluorine, chlorine, bromine, cyano, formyl, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, methoxy, ethoxy , n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec.-butoxy, tert.-butoxy, -CF 3 , -CHF 2 , -CC1F 2 , -CF 2 CHFC1, -CF 2 CH 2 F, -CF 2 CHF 2 , -CF 2 CC1 3 , -CH 2 CF 3 , -CF 2 CHFCF 3 ,
  • -C (CH 3 ) N-OC 3 H 7
  • -C (C 2 H 5 ) N-OCH 3
  • W 3 very particularly preferably represents fluorine, chlorine, cyano, nitro, methyl, ethyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, dimethylamino, diethylamino, -COOR 17 or -CONR 18 R 19 .
  • R 17 very particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, tert-butyl, -CH 2 CF 3 , each in each case optionally once or twice by fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl or -CF 3 substituted cyclopropyl, cyclopentyl or cyclohexyl or for phenyl optionally substituted once or twice by radicals from the list W 4 .
  • R 1 * and R 19 independently of one another very particularly preferably represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-
  • W 4 very particularly preferably represents fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio.
  • Hetaryl has the abovementioned general, preferred, particularly preferred or very particularly preferred meanings
  • R 2 has the general, preferred, particularly preferred or very particularly preferred meanings mentioned above
  • R 1 is hydrogen or phenyl which is monosubstituted or disubstituted by radicals from the list W 1 or one of the following groups
  • R 9 and R 13 have the abovementioned general, preferred, particularly preferred or very particularly preferred meanings and
  • W has the general, preferred, particularly preferred or very particularly preferred meaning given above.
  • o 0, 1 or 2
  • R 1 for hydrogen or a) phenyl, phenoxy or benzyloxy which is substituted once or twice by radicals from the lists W 2 or W 1 , b) hetaryl which is substituted once or twice by radicals from the list W 2 (in particular furyl, thienyl, pyrrolyl, oxazolyl , Isoxazolyl, thiazolyl or pyridyl, especially thienyl), c) alkyloxy, alkenyloxy,
  • W 1 and W 2 have the very particularly preferred meanings given above, and
  • R 3 stands for CH 3 , CHF 2 , CF 3 .
  • Compounds of the formula (Ig) are furthermore preferred.
  • Hetaryl represents thienyl, thiazolyl, pyridyl or furanyl groups which are optionally monosubstituted or disubstituted by substituents from the group H, F, Cl, cyano, OCF 3 , SCF 3 , CH 3 , OCH 3 and CF 3 , and
  • Trifluoromethyl trifluoromethoxy, difluoromethoxy, chlorodifluoromethoxy
  • Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl can also be used in connection with heteroatoms, e.g. in alkoxy, where possible, be straight-chain or branched.
  • Optionally substituted radicals can be mono- or polysubstituted, whereby in the case of multiple substitutions the substituents can be the same or different.
  • residues with the same indices such as m residues R 2 for m> 1, can be the same or different.
  • reaction sequence of process (E) according to the invention can be represented by the following formula:
  • Formula (II) provides a general definition of the amino ketone derivatives required for carrying out process (A) according to the invention.
  • Ar and hetaryl preferably have those meanings which have already been mentioned as preferred in connection with the description of the cyclic imines of the formula (I).
  • Aminoketone derivatives of formula (II) can be e.g. prepared by reacting BOC-protected lactams of the formula (VIII) with metalated heteroaromatics of the formula (IX) at temperatures between 0 ° C and 80 ° C according to the following reaction scheme:
  • Met represents a monovalent metal radical such as Li, Mgl, MgBr or MgCl.
  • Metallized hetaryls of formula (IX) are known in some cases or can be prepared by known methods such as e.g. Lithiation or Grignard reaction can be prepared from the corresponding hetarylene or halogenated hetarylene.
  • Protected lactams of the formula (VIII) are obtained, for example, by lactams of the formula (X) by customary methods, such as Metalation with butyl lithium and implementation with di-tert-butyl dicarbonate BOC-protecting (see e.g. T. W. Greene, P. G. M. Wuts, Protective Groups in Organic Synthesis, 2nd Ed., John Wiley & Sons, New York 1991).
  • Lactams of formula (X) can e.g. Starting from ⁇ - alkoxy lactams of the formula (XI) using two methods. These can be reacted with aromatics of the formula (XII) in the presence of an acidic catalyst, such as, for example, sulfuric acid, acetic acid or aluminum chloride and, if appropriate, in the presence of a diluent, such as, for example, dichloromethane or acetonitrile, in accordance with the following reaction scheme [see also WO 98/22 438]:
  • an acidic catalyst such as, for example, sulfuric acid, acetic acid or aluminum chloride
  • a diluent such as, for example, dichloromethane or acetonitrile
  • aryl-Grignard compounds of the formula (XIII) in the presence of a diluent such as, for example, tetrahydrofuran according to the following reaction scheme [cf. Org. Prep. Proced. Int. 25, 255 (1993)]: Ar-MgHal
  • R 20 represents methyl or ethyl.
  • shark represents chlorine, bromine or iodine.
  • the ⁇ -alkoxy lactams of the formula (XI) are known, in some cases. commercially available and can e.g. from the corresponding unsubstituted imides by cathodic or sodium boranate reduction or from the unsubstituted lactams by anodic oxidation, in each case in the presence of methanol or ethanol (see, for example, 1st Org. Chem. 56, 1822 (1991); Synthesis 1980 , 315).
  • aromatics of the formula (XII) are benzene derivatives which are generally known or can be prepared by a wide range of generally known methods in organic chemistry.
  • the aryl-Grignard compounds of the formula (XIII) can be prepared in a conventional manner from the corresponding aryl halides and magnesium.
  • Aryl halides are generally known compounds of organic chemistry.
  • Lactams of the formula (X) can also be prepared, for example, by cyclizing substituted ⁇ -benzoylcarboxylic acids of the formula (XIV) with a reagent prepared from ammonium carbonate and formic acid at the boiling point in accordance with the following reaction scheme [cf. Recl. Trav. Chim. Bays-Bas 81, 788 (1962), WO 98/22 438]:
  • the ⁇ -benzoylcarboxylic acids of formula (XIV) required for this can be e.g. prepared by reacting the dicarboxylic anhydrides of the formula (XV) with aromatics of the formula (XII) in the presence of a Lewis acid such as, for example, aluminum chloride and optionally in the presence of a diluent such as, for example, benzene according to the following reaction scheme [cf. Recl. Trav. Chim. Bays-Bas 81, 788 (1962)]:
  • the anhydride required for this (succinic anhydride) is commercially available.
  • the phenyl lactams of the formula (XVI) in which X represents bromine or iodine are a subset of the compounds of the formula (X), the preparation of which is indicated above.
  • the new 2H-pyrrole derivatives of the formula (I) can be e.g. also prepared by reducing in a process (A.b) the nitro group of the nitroketones of the formula (XVII), which are also new, according to the following reaction scheme:
  • An amino ketone of the formula (II 1 ) occurs as an intermediate, but, in particular in an acidic medium, cyclocondenses in situ to (I).
  • the reduction can be accomplished by catalytic hydrogenation or other well known ones
  • Nitroketones of the formula (XVII) can be prepared, for example, by ⁇ -chloroalkylhetaryl ketones of the formula (XX) in the presence of a diluent such as methanol, ethanol, another lower aliphatic alcohol or else tetrahydrofuran and in the presence of an acid binder such as Sodium hydride or an alkali alcoholate, preferably the corresponding alcohol used as diluent, condensed according to the following reaction scheme:
  • the ⁇ -chloroalkylhetaryl ketones of formula (XX) can be prepared in a known manner, e.g. by Friedel-Crafts acylation of hetarylene of the formula (XXI) (see below) with 3-chloropropionic acid chloride.
  • nitromethylbenzenes of the formula (XVIII) are known or can be prepared in a known manner, e.g. by nitrating corresponding toluenes in the side chain or reacting corresponding benzyl halides with silver nitrite [cf. for this e.g. J. Am. Chem. Soc. 77: 6269 (1955); J. Am. Chem. Soc 86, 2681 (1964); Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag Stuttgart,
  • the toluenes or benzyl halides required for this are generally known compounds of organic chemistry.
  • nitroketones of formula (XVII) can be e.g. through Michael additions of
  • the hetaryl vinyl ketones of formula (XIX) can e.g. by preparing hydrogen chloride from ⁇ -chloropropyl ketones of the formula (XX), which are e.g. can be obtained by Friedel-Crafts acylation of hetarylene of the formula (XXI) with 3-chloropropionic acid chloride, in the presence of an acid binder such as, for example, potassium acetate in the presence of a diluent such as, for example, methanol according to the following reaction scheme [cf. e.g. J. Prakt. Chem., Series 4, 1, 57 (1955)]:
  • Hetaryls are commercially available or according to generally known methods of organic chemistry.
  • hetaryl vinyl ketones of the formula (XIX) can also be prepared by reacting O-methyl-methyl-hetaryl hydroxamates of the formula (XXII) with vinyl magnesium bromide according to the following reaction scheme: 2nd
  • O-methyl-methyl-hetarylhydroxamates of the formula (XXII) can be prepared by known methods e.g. are produced from the corresponding carboxylic acid derivatives [cf. e.g. analogous to Tetrahedron Lett. 22: 3815 (1981)].
  • Nitroketones of the formula (XVII) can also be prepared by adding enamines of hetarylmethyl ketones of the formula (XXV) to -nitrostyrenes of the formula (XXVI) in accordance with the reaction scheme below and hydrolyzing the reaction product with acid:
  • R 21 and R 22 together with the nitrogen atom to which they are attached represent a cyclic amino radical, such as, for example, 1-pyrrolidino, 1-piperidino or 4-morpholino.
  • the addition usually proceeds in a [4 + 2] cycloaddition to isolable 1,2-oxazine-N-oxide derivatives of the formula (XXIV) and is optionally in the presence of a non-polar diluent such as e.g. Diethyl ether at for example -80 ° to + 20 ° C.
  • Hydrolysis uses, for example, aqueous mineral acids such as hydrochloric acid, optionally in the presence of methanol or ethanol [cf. e.g. Helv. Chim. Acta 68, 162 (1985); Tetrahedron 45, 2099 (1989)].
  • enamines of the formula (XXV) are known or can be prepared, for example, from the appropriately substituted hetaryl ketones and the cyclic amines by standard processes (e.g. Org. Syntheses Vol. 58, 56, John Wiley & Sons, New York). Some of the hetaryl ketones required for this are commercially available, known or can be prepared by known methods in aromatic chemistry.
  • nitrostyrenes of the formula (XXVI) are known or can be e.g. by formylating the nitromethylbenzenes of the formula (XVIII) given above (see, for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Volume E16, 215).
  • the new 2H-pyrrole derivatives of the formula (I) can also be prepared, for example, by hydrolyzing imines of the formula (XXVII) in a process (Ac) in accordance with the following reaction scheme: - 15th
  • the hydrolysis can be carried out by generally known methods e.g. perform with aqueous hydrochloric acid.
  • the imines of the formula (XXVII) can be e.g. prepared by carrying out Michael additions of N-diphenylmethylene benzylamines of the formula (XVIII) to the hetaryl vinyl ketone of the formula (XIX) according to the following reaction scheme:
  • the addition is carried out in the presence of an acid binder and in the presence of a diluent such as e.g. Acetonitrile or dichloromethane and optionally in the presence of a reaction auxiliary e.g. carried out at room temperature.
  • Aqueous alkali such as 50% sodium hydroxide solution is preferably used as the acid binder in the presence of a phase transfer catalyst such as e.g. Triethylbenzylammonium chloride as reaction aids [cf. e.g. Synth. Commun. 17, 211 (1987)].
  • the preparation of the hetaryl vinyl ketone of the formula (XIX) is described above.
  • the N-diphenylmethylene benzylamines of the formula (XXVIII) are obtained, for example by reacting the corresponding benzylamines with benzophenone (see, for example, Tetrahedron. Lett. 1978, 2641).
  • the benzylamines required for this are known or can be prepared by known methods such as aminolysis of the corresponding benzyl halides (see above).
  • Formula (III) provides a general definition of the cyclic O-methanesulfonyloximes required for carrying out process (B) according to the invention.
  • Ar preferably has those meanings which have already been mentioned as preferred in connection with the description of the cyclic imines of the formula (I).
  • the O-methanesulfonyloximes of the formula (III) are described in WO 98/22438.
  • O-methylsulfonyloximes of formula (III) can be prepared by e.g. According to the reaction scheme below, cyclic ⁇ -aryl ketones of the formula (XXX) are first converted into their oximes of the formula (XXIX) using generally known methods and these are then converted analogously to methanesulfonyl chloride
  • Cyclic ⁇ -aryl ketones of the formula (XXX) can be e.g. prepared by epoxidizing 1-arylcycloalkenes of the formula (XXXII) using conventional methods, for example using m-chloroperbenzoic acid, to give oxiranes of the formula (XXXI) and then isomerizing them by acidic workup [cf. e.g. Tetrahedron 30, 2027 (1974)]:
  • oxiranes of the formula (XXXI) obtained in other ways can also be isomerized to give cyclic ⁇ -aryl ketones of the formula (XXX), for example by shaking a solution in chloroform with 20% sulfuric acid.
  • 1-arylcycloalkenes of formula (XXXII) can be e.g. prepared by reacting aryl Grignard compounds of the formula (XIII) described above with cyclobutanone of the formula (XXXIV) under customary Grignard conditions and Cyclic benzyl alcohols of the formula (XXXIII) obtained in this way are dehydrated:
  • the dehydration can be carried out, for example, by dissolving the alcohol in a slightly polar solvent such as hexane and using e.g. 0 ° C to 20 ° C mixed with semi-concentrated sulfuric acid [cf. e.g. Tetrahedron 30, 2027 (1974)].
  • a slightly polar solvent such as hexane
  • Cyclobutanone of formula (XXXIV) is commercially available.
  • Hetaryl-Grignard compounds of the formula (IV) can be prepared from corresponding hetaryl halides and magnesium by the Grignard reaction.
  • Hetaryl halides are generally known compounds of organic chemistry.
  • Imines of the formula (V), insofar as ⁇ is bromine, hydroxy or iodine, are aliquots of the compounds of the general formula (I) according to the invention and can be prepared, for example, by processes (A) or (B).
  • ⁇ is trifluoromethanesulfonyl
  • the compounds of the formula (Va) by reacting hydroxy compounds of the formula (Ih), which can also be prepared by processes (A) or (B), with trifluoromethanesulfonyl chloride or trifluoromethanesulfonic anhydride in the presence of an acid binder, such as pyridine and, if appropriate, in the presence of a diluent according to the following reaction scheme produce:
  • Formula (VI) provides a general definition of the boronic acids also required for carrying out process (C) ⁇ ) according to the invention.
  • R 1_ 1 preferably has those meanings which have already been mentioned as preferred in connection with the description of the cyclic imines of the formula (Ib).
  • Aromatic boronic acids of the formula (VI) are known or can be prepared according to known ones
  • cyclic imines of the formula (Id) required for carrying out process (D) according to the invention are partial amounts of the compounds of the invention general formula (I) and can be prepared, for example, by processes (A) to (C).
  • G, p, q and r preferably have the meanings which have already been mentioned as preferred in connection with the description of the cyclic imines of the formula (I).
  • Ab stands for a common leaving group such as Halogen, especially chlorine or bromine; Alkylsulfonyloxy, especially methylsulfonyloxy; or optionally substituted arylsulfonyloxy, especially phenylsulfonyloxy, p-chlorophenylsulfonyloxy or p-tolylsulfonyloxy.
  • the compounds of formula (VII) are generally known compounds of organic chemistry.
  • the further compounds of the formulas (F-I), (F-II), (F-IV) and (F-VII) required to carry out process (F) according to the invention are generally known compounds of organic chemistry.
  • hetaryl carboxylic acid chlorides and methyl esters required to carry out process (G) according to the invention are available commercially or by generally known methods of organic chemistry. The same applies to the educts dialkylamine, acetylene and formaldehyde required to carry out the variants.
  • Process (A) according to the invention is optionally carried out in the presence of a suitable acid acceptor.
  • a suitable acid acceptor All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium, potassium or ammonium hydroxide, sodium amide, lithium diisopropylamide, sodium methylate, sodium efhylate, potassium -tert.- butylate, sodium, potassium, calcium or ammonium acetate, sodium, potassium or ammonium carbonate, sodium hydrogen or potassium hydrogen carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine , Pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diaza
  • DBN diazabicycloundecene
  • DBU diazabicycloundecene
  • Process (A) according to the invention is optionally carried out in the presence of a diluent.
  • a diluent Water, organic solvents and mixtures thereof can be used for this. Examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as, for example, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro, trichloroethane or carbon tetrachloride; Ethers, such as diethyl, diisopropyl, methyl t-butyl, methyl t-amyl ether,
  • Dioxane tetrahydrofuran, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, diethylene glycol dimethyl ether or anisole; Ketones such as aeetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as formamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; N-
  • Oxides such as N-methylmorpholine-N-oxide; Esters such as methyl, ethyl or butyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether.
  • reaction temperature in process (A) according to the invention can be varied within a substantial range. In general, temperatures between -50 ° C and + 150 ° C, preferably between -20 ° C and + 100 ° C.
  • Suitable diluents for carrying out process (B) according to the invention are inert organic solvents and mixtures thereof.
  • Examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro, trichloroethane or carbon tetrachloride; Ethers such as diethyl, diisopropyl, methyl t-butyl, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether or anisole.
  • aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane,
  • a solution of the Grignard compound of the formula (IV) in an ether and a solution of the O-methylsulfonyloxime of the formula (III) in a hydrocarbon are preferably used.
  • reaction temperature can be varied within a substantial range in process (B) according to the invention. In general, temperatures between -100 ° C and + 50 ° C, preferably between -80 ° C and + 30 ° C.
  • Grignard compounds of the formula (IV) and O-methylsulfonyloximes of the formula (III) are in the molar range
  • Palladium (0) complexes are suitable as catalysts for carrying out process (C) according to the invention.
  • tetrakis (triphenylphosphine) palladium is preferred.
  • Inorganic or organic bases are suitable as acid acceptors for carrying out process (C) according to the invention.
  • These preferably include alkaline earth metal or alkali metal hydroxides, acetates, carbonates or hydrogen carbonates, such as, for example, sodium, potassium, barium or ammonium hydroxide,
  • alkali fluorides such as, for example, cesium fluoride
  • tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethyl-benzylamine, pyridine
  • Suitable diluents for carrying out process (C) according to the invention are water, organic solvents and mixtures thereof.
  • examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro, trichloroethane or carbon tetrachloride; Ethers such as diethyl, diisopropyl, methyl t-butyl, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether or anisole;
  • Alcohols such as methanol, ethanol, n- or i-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethyl englycol monomethyl ether, diethylene glycol monoethyl ether.
  • reaction temperature can be varied within a substantial range in process (C) according to the invention. In general, temperatures between 0 ° C and + 140 ° C, preferably between 50 ° C and + 110 ° C.
  • boronic acids of the formula (VI) and compounds of the formula (V) are used in a molar ratio of 1: 1 to 3: 1, preferably 1: 1 to 2: 1.
  • the catalyst is generally used from 0.005 to 0.5 mol, preferably from 0.01 mol to 0.1 mol, per mol of the compound of the formula (V).
  • the base is generally used in an excess.
  • Process (D) according to the invention is preferably carried out in the presence of a suitable acid acceptor.
  • a suitable acid acceptor All the usual inorganic ones come as such or organic bases in question.
  • These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium, potassium or ammonium hydroxide, sodium amide, lithium diisopropylamide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium, potassium, calcium or ammonium acetate, sodium, potassium or ammonium carbonate, sodium hydrogen or potassium hydrogen carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tri-butylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-d
  • Process (D) according to the invention can be carried out in the presence of a suitable phase transfer catalyst.
  • suitable phase transfer catalysts are: tetrabutylammonium iodide, bromide or chloride, tributylmethylphosphonium bromide, trimethyl-C 1-4 alkylammonium chloride or bromide,
  • Process (D) according to the invention is preferably carried out in the presence of a diluent.
  • a diluent for this come e.g. all solvents listed in process (A) in question.
  • reaction temperature in process (D) according to the invention can be varied within a substantial range. In general, temperatures between -20 ° C and + 100 ° C, preferably between 0 ° C and 60 ° C.
  • process (D) When carrying out process (D) according to the invention, generally one works with approximately equimolar amounts of the starting materials. However, an excess of the compound of formula (VII) can also be used.
  • the reactions according to process E) according to the invention are derivatization reactions known to the person skilled in the art, in particular of carboxylic esters and ketones (cf., for example, Houben-Weyl, Methods of Organic Chemistry, Georg Thieme Verlag, Stuttgart, Vol. VII / 2b, in particular 1912 ff; Vol VIII on carboxylic acid esters and their derivatives; Volume E5, in particular p. 812 ff and the literature cited therein).
  • the steps of process (F) according to the invention are optionally carried out in the presence of a diluent.
  • Water (not for F. ⁇ ), organic solvents and mixtures thereof can be used for this. Examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro, trichloroethane or carbon tetrachloride; Ethers, such as diethyl, diisopropyl, methyl t-butyl, methyl t-amyl ether, dioxane, tetrahydrofuran, 1, 2-dimethoxyethane,
  • 1,2-diethoxyethane diethylene glycol dimethyl ether or anisole; Ketones such as aeetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides such as formamide, N, N-dimethylformamide, N, N-dimefhylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; N-oxides such as N-methylmorpholine-N-oxide; Esters such as methyl, ethyl or butyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, iso-, sec- or tert-
  • reaction temperature can be varied within a substantial range in the individual steps of process (F) according to the invention. In general, temperatures between -50 ° C and 250 ° C, preferably between -20 ° C and + 100 ° C.
  • FI hetaryl chloromethyl ketone
  • F-II iminium salt
  • the steps of process (G) according to the invention are optionally carried out in the presence of a diluent.
  • a diluent for this water (not for G. ⁇ and ß), organic solvents and mixtures thereof can be considered.
  • organic solvents and mixtures thereof can be considered. Examples include: aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, dichloro, trichloroethane or carbon tetrachloride; Ether like
  • reaction temperature can be varied within a substantial range in the individual steps of process (G) according to the invention. In general, temperatures between -50 ° C and 250 ° C, preferably between -20 ° C and + 100 ° C.
  • Steps ⁇ ) and ⁇ ) of process (G) according to the invention are preferably carried out in the presence of a suitable acid acceptor.
  • a suitable acid acceptor All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates,
  • acetates, carbonates or hydrogen carbonates such as, for example, sodium, potassium, calcium or ammonium acetate, sodium, potassium or ammonium carbonate, sodium hydrogen or potassium hydrogen carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine,
  • Diazabicyclooctane (DABCO), Diazabicyclononen (DBN) or Diazabicycloundecen (DBU). O-chlorobenzoic acid chloride or methyl ester are used in excess.
  • the reactions of the processes according to the invention can be carried out under normal pressure or under elevated pressure, preferably under normal pressure.
  • the processing takes place according to the usual methods of organic chemistry.
  • the end products are preferably purified by crystallization, chromatographic purification or by removal of the volatile constituents, if appropriate in vacuo.
  • the active substances are suitable for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored goods and materials, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the pests mentioned above include:
  • Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber. From the order of the Diplopoda e.g. Blaniulus guttulatus.
  • Thysanura e.g. Lepisma saccharina.
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.
  • Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, LithocoUetis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.
  • Buccu- latrix thurberiella Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambnauellana virana magna, Homona magna From the order of the Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchi
  • Leptinotarsa decemlineata Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatordimidhmpphppm, spp.
  • Anthrenus spp. Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha., Amphimalltra solitus From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Chorioptes spp. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..
  • Plant parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp.
  • the active compounds of the formula (I) according to the invention are notable in particular for outstanding activity against larvae of the horseradish leaf beetle (Phaedon cochleariae), caterpillars of the owl butterfly (Spodoptera frugiperda) and larvae of the greens
  • Rice leafhopper (Nephotettix cincticeps), peach aphids (Myzus persicae) and all stages of the common spider mite (Tetranychus urticae).
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, and soluble ones
  • formulations are prepared in a known manner, e.g. B. and preferably by mixing the active ingredients with extenders, that is liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
  • extenders that is liquid solvents and / or solid carriers
  • surface-active agents ie emulsifiers and / or dispersants and / or foam-generating agents.
  • organic solvents can, for example, also be used as auxiliary solvents.
  • a liquid solvent Men essentially in question: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol and their ethers and esters, ketones such as aeetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons
  • Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silicic acid, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and 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 ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
  • Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, for example 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 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active substance according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active substances, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas
  • Fenarimol, Fenbuconazole, Fen Inenarimol, Fenbuconazole, Fen Nameam, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimo ⁇ h, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolafilil, Folutriafol
  • Tebuconazole Tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, Thicyofen, thio Phanat-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, Tridemo ⁇ h, triflumizole, triforine, triticonazole, validamycin A, vinclozolin, zineb , Ziram.
  • Bactericides Bactericides:
  • Amitraz Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, Bendiocarb, Benfuracarb, Bensultap, Betacyluthrin, Bifenthrin,
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, CGA 157
  • Cyanophos cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin,
  • Fenamiphos fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb,
  • Fenoxycarb Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Flucycloxuron, Flucythrinat, Flufenoxuron, Flufenprox, Fluvalinate,
  • Parathion A parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, Primiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozine, Pyrachlophos, Pyradaphenthion, Pyresmethrin, pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos,
  • Tebufenozid Tebufenpyrad
  • Tebupirimphos Teflubenzuron
  • Tefluthrin Temephos
  • Terbam Terbufos
  • Tetrachlorvinphos Thiafenox, Thiodicarb, Thiofanox, Thiometon, Thionazin, Thuringiensin, Tralomethron, Triaratheniazine, Triaratheniazine
  • the active ingredient according to the invention can also be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.
  • the active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges.
  • the active substance concentration of the use forms can be from 0.0000001 to 95% by weight of active substance, preferably between 0.0001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active ingredient When used against hygiene pests and pests of stored products, the active ingredient is distinguished by an excellent residual action on wood and clay as well as a good stability to alkali on limed substrates.
  • the active compounds according to the invention act not only against plant, hygiene and stored-product pests, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas.
  • animal parasites ectoparasites
  • tick ticks leather ticks
  • mites running mites
  • flies stinging and licking
  • parasitic fly larvae lice, hair lice, Featherlings and fleas.
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
  • Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp.
  • Atylotus spp. Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp. - 1 / o -
  • Siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
  • Mesostigmata e.g. Argas spp., Ornithodorus spp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietssus spp., ., Sternostoma spp., Varroa spp.
  • Actinedida Prostigmata
  • Acaridida e.g. Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodterol spp ., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp.,
  • the active compounds of the formula (I) according to the invention are also suitable for combating arthropods which are agricultural animals, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and Infest mice.
  • arthropods are agricultural animals, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese, bees, other pets such as dogs, cats, house birds, aquarium fish and so-called experimental animals such as hamsters, guinea pigs, rats and Infest mice.
  • the active compounds according to the invention are used in the veterinary sector in a known manner by enteral administration in the form of, for example, tablets, capsules, drinkers, drenches, granules, pastes, boluses, the feed-through method, suppositories, by parenteral administration, for example by Injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, through nasal
  • the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, flowable agents) which contain the active compounds in an amount of 1 to 80% by weight, directly or apply after 100 to 10,000-fold dilution or use it as a chemical bath.
  • formulations for example powders, emulsions, flowable agents
  • insects may be mentioned by way of example and preferably, but without limitation:
  • Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
  • Bristle tails such as Lepisma saccharina.
  • non-living materials such as preferably plastics, adhesives, glues, papers and cartons, leather, wood and wood processing products and paints.
  • the one to be protected against insect attack is very particularly preferably
  • Wood and wood processing products which can be protected by the agent according to the invention or mixtures containing it are to be understood as examples: timber, wooden beams, railway sleepers, bridge parts, boat jetties,
  • the active substances can be used as such, in the form of concentrates or generally customary formulations such as powders, granules, solutions, suspensions, emulsions or pastes.
  • the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active ingredients with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellent, optionally siccatives and UV stabilizers and optionally dyes and pigments and further processing aids.
  • the insecticidal compositions or concentrates used to protect wood and wood-based materials contain the active compound according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.
  • the amount of the agents or concentrates used depends on the type and occurrence of the insects and on the medium. The optimal amount can be determined in each case by test series. In general, however, it is sufficient to use 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active compound, based on the material to be protected.
  • organic-chemical solvent or solvent mixture and / or an oily or oily or low-volatile organic-chemical solvent or solvent mixture and / or a polar organic-chemical solvent or solvent mixture and / or water and optionally an emulsifier and / or wetting agents.
  • the organic chemical solvents used are preferably oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C.
  • Corresponding mineral oils or. are used as such low-volatility, water-insoluble, oily and oily solvents - 1 oU -
  • aromatic fractions or mineral oil-containing solvent mixtures preferably white spirit, petroleum and / or alkylbenzene are used.
  • Mineral oils with a boiling range of 170 to 220 ° C, test gasoline with a boiling range of 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics with a boiling range of 160 to 280 ° C are advantageous , Te ⁇ entinöl and the like. For use.
  • Evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C can be partially replaced by slightly or moderately volatile organic chemical solvents, with the proviso that the solvent mixture also has an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture is soluble or emulsifiable in this solvent mixture.
  • part of the organic chemical solvent or solvent mixture is replaced by a polar aliphatic organic chemical solvent or solvent mixture.
  • Polar aliphatic organic chemical solvents containing hydroxyl and / or ester and / or ether groups are preferably used.
  • binders consisting of or containing an acrylic resin, a vinyl resin, e.g. Polyvinyl acetate, polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-coumarone resin,
  • Silicone resin drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin are used.
  • the synthetic resin used as a binder can be used in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10% by weight can also be used as binders. In addition, known dyes, pigments, water-repellants, odor correctors and inhibitors or anticorrosive agents and the like can be used.
  • At least one alkyd resin or modified alkyd resin and / or a drying vegetable oil is preferably contained in the agent or in the concentrate as the organic chemical binder.
  • Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight, are preferably used according to the invention.
  • binder mentioned can be replaced by a fixing agent (mixture) or a plasticizer (mixture). These additives are intended to prevent volatilization of the active ingredients and crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).
  • the plasticizers come from the chemical classes of phthalic acid esters such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as tributyl phosphate, adipic acid esters such as di- (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, higher glycerol glycol or glycerol ether
  • Fixing agents are chemically based on polyvinyl alkyl ethers such as e.g. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.
  • Water is also particularly suitable as a solvent or diluent, if appropriate in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.
  • a particularly effective wood protection is achieved through industrial impregnation processes, e.g. Vacuum, double vacuum or pressure processes.
  • the ready-to-use compositions can optionally contain further insecticides and, if appropriate, one or more fungicides.
  • insecticides and fungicides mentioned in WO 94/29 268 are preferably suitable as additional admixing partners.
  • the compounds mentioned in this document are an integral part of the present application.
  • Insecticides such as Chlo ⁇ yriphos, Phoxim, Silafluofin, Alphamethrin, Cyfluthrin, Cypermethrin, Deltamethrin are very, particularly preferred admixing partners.
  • fungicides such as Epoxyconazole, Hexaconazole, Azaconazole, Propiconazole, Tebuconazole, Cyproconazole, Metconazole, Imazalil, Dichlorfluanidamyl, 3-Chlorodluanuanid
  • Boc-protected amino ketone (11-868) (3.80 g, 7.3 mmol) was placed in CH 2 C1 2 (10 ml). Trifluoroacetic acid (8.37 g, 73 mmol) was added at 0 ° C. and the mixture was then stirred at room temperature for 3 hours. The solution was concentrated in vacuo and the residue was adjusted to pH 14 with 1N NaOH and then extracted with ethyl acetate. The organic phase was dried over MgSO 4 , filtered and concentrated. 3.12 g of crude yield (100% of theory) was isolated. 1.50 g of which was purified by column chromatography (mobile phase cyclohexane: ethyl acetate).
  • ⁇ -phenyl- ⁇ -butyrolactam (e.g. from Example X-1) were placed in 63 ml of tetrahydrofuran (THF) and 9.24 ml of 2.4N butyllithium solution in n-hexane were added at -78 ° C. After stirring for half an hour at this temperature, a solution of 5.04 g of di-tert-butyl dicarbonate in 20 ml of THF was added dropwise with further cooling, the mixture was stirred for a further 3 hours at -78 ° C. and then overnight without cooling.
  • THF tetrahydrofuran
  • ⁇ -4'-trifluoromethoxybiphenyl-4-yl- ⁇ -butyrolactam for example from example Xa-2
  • THF tetrahydrofuran
  • 2.42 ml of 2.4N Butyllithium solution added in n-hexane.
  • a solution of 1.27 g of di-tert-butyl dicarbonate in 10 ml of THF was added dropwise with further cooling. Then the cooling is removed and stirred at room temperature overnight.
  • the 5- (4-fluorophenyl) pyrrolidone-2 (X-3) is analogous to the procedure by catalytic reductive amination of 4-fluorophenyl-4-oxo-butyric acid (J. Med. Chem. 27, 1099 (1984)) von Rappe et al. Liebigs Ann. Chem. 596, p. 221 (1955) as for the
  • Solvent 7 parts by weight of dimethylformamide emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted to the desired concentration with water containing emulsifier.
  • Bean plants Phaseolus vulgaris
  • Tetranychus urticae which are heavily affected by all stages of development of the common spider mite Tetranychus urticae, are immersed in an active ingredient preparation of the desired concentration.
  • the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
  • Example B the compounds according to Preparation Examples 1-7 and 1-148 at an exemplary active ingredient concentration of 0.1% caused a kill of at least 95% after 7 days.
  • Example B the compounds according to Preparation Examples 1-7 and 1-148 at an exemplary active ingredient concentration of 0.1% caused a kill of at least 95% after 7 days.
  • Emulsifier 1 part by weight of alkylaryl 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 to the desired concentration with water containing emulsifier.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with caterpillars of the army worm (Spodoptera frugiperda) while the leaves are still moist.
  • the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
  • the compounds according to the preparation examples 1-774, 1-336, 1-477, 1-289, 1-821 and 1-195 show a killing of at least 85% according to FIG. 7 at an exemplary active compound concentration of 0.1% Days.
  • Emulsifier 1 part by weight of alkylaryl 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 to the desired concentration with water containing emulsifier.
  • Bean plants Phaseolus vulgaris
  • Tetranychus urticae which are heavily infested with all stages of the common spider mite (Tetranychus urticae), are immersed in an active ingredient preparation of the desired concentration.
  • the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mite has been killed.
  • the compounds according to the preparation examples 1-383, 1-289, 1-618, 1-195, 1-727, 1-708 and 1-709 show a kill of at least at an exemplary active compound concentration of 0.1% 90% after 7 days.
  • Emulsifier 1 part by weight of alkylaryl 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 to the desired concentration with water containing emulsifier.
  • Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and populated with larvae of the horseradish beetle (Phaedon cochleariae) while the leaves are still moist.
  • the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae have been killed.

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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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyrrole Compounds (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
EP99948915A 1998-10-14 1999-10-01 2-hetaryl-3,4-dihydro-2h-pyrrol-derivate Withdrawn EP1121357A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19847076A DE19847076A1 (de) 1998-10-14 1998-10-14 2-Hetaryl-3,4-dihydro-2H-pyrrol-Derivate
DE19847076 1998-10-14
PCT/EP1999/007295 WO2000021958A1 (de) 1998-10-14 1999-10-01 2-hetaryl-3,4-dihydro-2h-pyrrol-derivate

Publications (1)

Publication Number Publication Date
EP1121357A1 true EP1121357A1 (de) 2001-08-08

Family

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Application Number Title Priority Date Filing Date
EP99948915A Withdrawn EP1121357A1 (de) 1998-10-14 1999-10-01 2-hetaryl-3,4-dihydro-2h-pyrrol-derivate

Country Status (10)

Country Link
US (1) US6599924B1 (zh)
EP (1) EP1121357A1 (zh)
JP (1) JP2002527437A (zh)
KR (1) KR20010085879A (zh)
CN (1) CN1323304A (zh)
AU (1) AU761113B2 (zh)
BR (1) BR9915544A (zh)
DE (1) DE19847076A1 (zh)
HK (1) HK1040991A1 (zh)
WO (1) WO2000021958A1 (zh)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030220386A1 (en) * 2000-09-22 2003-11-27 Andrew Plant Delta 1-pyrrolines for use as pesticides
DE10047110A1 (de) * 2000-09-22 2002-04-18 Bayer Ag Optisch aktive 2,5-Bisaryl-DELTA·1·-Pyrroline
DE10047116A1 (de) * 2000-09-22 2002-04-18 Bayer Ag DELTA·1·-Pyrroline
DE10060412A1 (de) * 2000-12-05 2002-06-06 Bayer Ag DELTA1-Pyrroline
DE10106457A1 (de) * 2001-02-13 2002-08-14 Bayer Ag DELTA·1·-Pyrroline
DE10106455A1 (de) * 2001-02-13 2002-08-14 Bayer Ag DELTA·1·-Pyrroline
IL158119A0 (en) * 2001-04-09 2004-03-28 Bayer Cropscience Ag Method for the production of delta1-pyrrolines
DE10145772A1 (de) * 2001-09-17 2003-04-10 Bayer Cropscience Ag DELTA·1·-Pyrroline
DE10154515A1 (de) * 2001-11-07 2003-05-15 Bayer Cropscience Ag DELTA·1·-Pyrroline
DE10204115A1 (de) * 2002-02-01 2003-08-07 Bayer Cropscience Ag DELTA·1·-Pyrroline
DE10243939A1 (de) * 2002-09-24 2004-04-01 Bayer Cropscience Ag Pyrroline
CN112521384B (zh) * 2021-01-13 2021-11-02 湖北大学 溶剂热一锅法合成苯并噻嗪并环戊二烯衍生物

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4014940A1 (de) * 1989-09-01 1991-03-07 Bayer Ag Substituierte acrylsaeureester
EP0712393A1 (de) 1993-08-05 1996-05-22 Bayer Ag Substituierte 4-carbamoyl-pyrrolin-2-on- und -dihydrofuran-2-on-derivate und deren verwendung als schädlingsbekämpfungsmittel
DE19648011A1 (de) * 1996-11-20 1998-05-28 Bayer Ag Cyclische Imine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0021958A1 *

Also Published As

Publication number Publication date
US6599924B1 (en) 2003-07-29
AU761113B2 (en) 2003-05-29
CN1323304A (zh) 2001-11-21
DE19847076A1 (de) 2000-04-20
WO2000021958A1 (de) 2000-04-20
AU6198899A (en) 2000-05-01
BR9915544A (pt) 2001-08-14
JP2002527437A (ja) 2002-08-27
KR20010085879A (ko) 2001-09-07
HK1040991A1 (zh) 2002-06-28

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