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EP1322607A1 - Optisch aktive 2,5-bisaryl-delta1-pyrroline und deren verwendung als schädlingsbekämpfungsmittel - Google Patents

Optisch aktive 2,5-bisaryl-delta1-pyrroline und deren verwendung als schädlingsbekämpfungsmittel

Info

Publication number
EP1322607A1
EP1322607A1 EP01982267A EP01982267A EP1322607A1 EP 1322607 A1 EP1322607 A1 EP 1322607A1 EP 01982267 A EP01982267 A EP 01982267A EP 01982267 A EP01982267 A EP 01982267A EP 1322607 A1 EP1322607 A1 EP 1322607A1
Authority
EP
European Patent Office
Prior art keywords
formula
alkyl
spp
chlorine
fluorine
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Withdrawn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
EP01982267A
Other languages
German (de)
English (en)
French (fr)
Inventor
Andrew Plant
Thomas Geller
Bernd Gallenkamp
Rolf Grosser
Albrecht Marhold
Christoph Erdelen
Andreas Turberg
Olaf Hansen
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
Original Assignee
Bayer CropScience AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer CropScience AG filed Critical Bayer CropScience AG
Publication of EP1322607A1 publication Critical patent/EP1322607A1/de
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
    • C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/18—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by doubly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • 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
    • C07D207/20—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • C07D207/24—Oxygen or sulfur atoms
    • C07D207/26—2-Pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Definitions

  • the invention relates to new optically active 2,5-bisaryl- ⁇ 1 -pyrrolines, ner processes for their preparation and their use as pesticides.
  • WO 00/21958, WO 99/59968, WO 99/59967 and WO 98/22438 already describe racing ⁇ 1 -pyrrolines as pesticides.
  • the object of the present invention is to provide optically active compounds of the general formula (I). This allows the application rate to be reduced when used as a pesticide.
  • n 0, 1, 2, 3 or 4
  • R represents halogen or methyl
  • R 2 represents hydrogen or halogen
  • R 3 for hydrogen, halogen, hydroxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkenyl, alkoxy, -S (O) 0 R 6 , -OSO 2 R 6 , bisalkoxyborane, -B (OH) 2 or for optionally one or more times substituted phenyl from the list W 1 ,
  • R 4 represents halogen, alkyl, alkoxy, haloalkyl, haloalkoxy or -S (O) 0 R 6 ,
  • o 0, 1 or 2
  • R 6 represents hydrogen, alkyl or haloalkyl
  • R 7 and R 8 independently of one another represent hydrogen, alkyl, haloalkyl or together represent alkylene or alkoxyalkylene.
  • an asterisk (*) in the formulas denotes a chiral carbon atom on which the ⁇ configuration is present.
  • optically active compounds of the formula (I) can be obtained by
  • R, R, R, R and m have the meanings given above,
  • R, R, R and m have the meanings given above and X 1 represents Cl, Br, I, -OSO 2 CF 3 , -OSO 2 (CF 2 ) 3 CF 3 ,
  • A represents phenyl which is optionally mono- or polysubstituted from the list W 1 ,
  • M represents -B (OH) 2 , Sn ( n Bu) 3 or ZnCl
  • M also stands for MgCl
  • R, R, R and m have the meanings given above, X 2 for -B (OH) 2 , (4,4,5,5-tetramethyl-l, 3,2-dioxoborolane) -2-yl, (5,5-dimethyl-l, 3,2-dioxoborinane) - 2-yl, (4,4,6-trimethyl-1, 3,2-dioxoborinan) -2-yl, 1, 3,2-benzodioxaborol-2-yl,
  • A represents phenyl which is optionally mono- or polysubstituted from the list W ",
  • T stands for Cl, Br, I, -OSO 2 CF 3 , -OSO 2 (CF 2 ) 3 CF 3 ,
  • R .1, ü R 2 , ⁇ R3, R n and m have the meanings given above, deprotected by treatment with a Lewis acid or protonic acid and the amine formed in situ can be cyclized in the presence of an acid.
  • the compounds of the formula (I) according to the invention have very good insecticidal properties and can be used both in crop protection and in material protection to control unwanted pests, such as insects.
  • column material used in process (A) selected from a large number of tested, commercially available solid phases, provides column material
  • n preferably represents 0, 1, 2 or 3.
  • R 1 preferably represents fluorine, chlorine, bromine or methyl.
  • R 2 preferably represents hydrogen, fluorine, chlorine or bromine.
  • R 3 preferably represents hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, C r C 6 - alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C r C 6 haloalkyl, C 2 - C 6 haloalkenyl, C r C 6 alkoxy, -S (O) 0 R 6 , -OSO 2 R 6 , bis (C 4 -C 8 alkoxy) borane, -B (OH) 2 or for phenyl which is optionally mono- or polysubstituted from the list W 1 .
  • R 4 is preferably halogen, C, -C6 alkyl, C, -C6 alkoxy, C, -C 6 halo-alkyl, C, -C 6 haloalkoxy or -S (O) R 0. 6
  • W 1 preferably represents cyano, halogen, hydroxyl, C, -C 6 -alkyl, C j - -alkoxy, C r C 6 -haloalkyl, CC 6 -haloalkoxy, C 2 -C 6 -haloalkenyloxy, C r C 6 - Alkoxycarbonyl, tri (C r C 4 alkyl) silyl, tri (C r C 4 alkyl) silyloxy, -S (O) 0 R 6 or -SO 2 NR 7 R 8 .
  • o is preferably 0, 1 or 2.
  • R 6 preferably represents hydrogen, C, -C 6 alkyl or C, -C 6 haloalkyl.
  • R 7 and R s independently of one another preferably represent hydrogen, CC 6 alkyl,
  • n particularly preferably stands for 0. 1. or 2.
  • R 1 particularly preferably represents fluorine, chlorine or methyl.
  • R 2 is particularly preferably hydrogen, fluorine or chlorine.
  • R 3 particularly preferably represents hydrogen, fluorine, chlorine, bromine, hydroxy, C, -
  • -OSO 2 R 6 (5,5-dimethyl-l, 3,2-dioxoborinane) -2-yl, (4,4,5,5-tetramethyl-l, 3,2-dioxoborolane) -2-yl, (4,4,6-trimethyl-l, 3,2-dioxoborinan) -2-yl, 1,3,2- Benzodioxaborol-2-yl, -B (OH) 2 or for phenyl which is optionally monosubstituted to trisubstituted from the list W 1 .
  • R 4 particularly preferably represents fluorine, chlorine, bromine, C r C 6 -alkyl, Cj- - alkoxy, in each case C, -C 6 -alkyl or C, - substituted by fluorine or chlorine.
  • W 1 particularly preferably represents cyano, fluorine, chlorine, bromine, iodine, hydroxy, CC 4 alkyl, C r C 4 alkoxy, in each case fluorine- or chlorine-substituted C, -C 4 - alkyl, C r C 4 - alkoxy, , C 2 -C 6 alkenyloxy, for C r C 4 alkoxycarbonyl,
  • o particularly preferably represents 0, 1 or 2.
  • R 6 particularly preferably represents hydrogen, C, -C 6 -alkyl or C ] -C 4 -alkyl substituted by fluorine or chlorine.
  • R 7 and R 8 independently of one another are particularly preferably hydrogen, C 1 -C 6 -alkyl, C r C 6 -alkyl substituted by fluorine or chlorine, or together are C 4 -C 5 -alkylene.
  • n very particularly preferably represents 0, 1 or 2.
  • R very particularly preferably represents fluorine, chlorine or methyl.
  • R very particularly preferably represents hydrogen, fluorine or chlorine.
  • R 3 very particularly preferably represents hydrogen, chlorine, bromine, hydroxyl
  • R 3 also very particularly preferably represents isopropoxy.
  • R 4 very particularly preferably represents fluorine, chlorine, bromine, methyl, ethyl, methoxy, ethoxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy or
  • W 1 very particularly preferably represents cyano, fluorine, chlorine, bromine, hydroxy, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, methoxy, ethoxy, n-propoxy , n-butoxy, isobutoxy, sec.-butoxy, tert.-
  • W 1 also very particularly preferably represents isopropoxy.
  • R 3 has the meanings given above and
  • R represents hydrogen, methoxy or ethoxy.
  • W 1 has the meanings given above.
  • oxyalkylene or thioalkylene stand for -O- alkyl- or -S-alkyl- and alkyleneoxy or alkylene thio for -alkyl-O- or
  • -Alkyl-S-, oxyalkyleneoxy stands for -O-alkyl-O.
  • Preferred, particularly preferred or very particularly preferred are compounds which carry the substituents mentioned under preferred, particularly preferred or very particularly preferred.
  • Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl
  • 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 4 for m> 1, can be the same or different.
  • the formula (I-rac) provides a general definition of the racemic compounds required as starting materials when carrying out process A according to the invention.
  • R 1, R 2, R 3, R 4 and m are preferred, particularly preferred and very particularly preferably has those meanings already in connection with the description of the compounds of formula (I) according to the invention as being preferred for these radicals the , particularly preferred, etc. were mentioned.
  • racemic compounds of the formula (I-rac) used in carrying out process A according to the invention are known and can be prepared by known processes (WO 00/21958, WO 99/59968, WO 99/59967 and WO 98/22438).
  • the preparative chromatography method is used, preferably the high performance liquid chromatography (HPLC) method.
  • HPLC high performance liquid chromatography
  • a chiral stationary silica gel phase is used.
  • process B (i) are illustrated by the following formula scheme.
  • process B (iii) according to the invention can be illustrated by the following formula.
  • R 1 , R 2 , R 4 and m are preferably, particularly preferably or very particularly preferably those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred for these radicals, particularly preferred etc. were mentioned.
  • X 1 preferably represents Cl, Br, -OSO 2 CF 3 or -OSO 2 (CF 2 ) 3 CF 3 .
  • X 1 particularly preferably represents Cl, Br or -OSO 2 CF 3 .
  • X 1 very particularly preferably represents Cl, Br or -OSO 2 CF 3 .
  • X 2 preferably represents -B (OH) 2 , (4,4,5,5-tetramethyl-l, 3,2-dioxoborolane) -2-yl,
  • X 2 particularly preferably represents -B (OH) 2 , (4,4,5,5-tetramethyl-l, 3,2-dioxoboronane) -2-yl, (5,5-dimethyl-1,3, 2-dioxoborinan) -2-yl, (4,4,6-trimethyl-l, 3,2-dioxoborinan) -2-yl or l, 3,2-benzodioxaborol-2-yl.
  • X 2 very particularly preferably represents -B (OH) 2 , (4,4,5,5-tetramethyl-l, 3,2-dioxoborolan) -2-yl or (4,4,6-trimethyl-1 , 3, 2-dioxoborinan) -2-yl.
  • radicals R 6 , R 7 and R 8 have preferred, particularly preferably or very particularly preferably those meanings which have already been associated with the Description of the compounds of formula (I) according to the invention for these radicals as being preferred, particularly preferred etc.
  • Optically active cyclic imines of the formulas (I-a) and (I-b) are new and are prepared analogously to process A or C.
  • Formula (II) provides a general definition of the organometallic compounds required as starting materials when carrying out process B (i) according to the invention.
  • A preferably represents unsubstituted or monosubstituted to tetrasubstituted from the list W 1 .
  • A is particularly preferably phenyl which is unsubstituted or monosubstituted or disubstituted from the list W 1 .
  • W 1 here is preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. in connection with the description of the compounds of the formula (I) according to the invention for these radicals.
  • M preferably represents -B (OH) 2 , Sn ( n Bu) 3 or ZnCl.
  • M also preferably represents MgCl.
  • M particularly preferably represents -B (OH) 2 or Sn ( n Bu) 3 .
  • M very particularly preferably represents -B (OH) 2 .
  • Organometallic compounds of the formula (II) are known in some cases.
  • M -B (OH) 2
  • Mg Br-Li (Mg) exchange
  • tris-alkoxyboron compounds cf. e.g. Tetrahedron Lett. 1993, 34, 8237-8240.
  • Formula (III) provides a general definition of the aromatics required as starting materials when carrying out processes B (ii) and B (iii) according to the invention.
  • A is preferably, particularly preferably or very particularly preferably those radicals which have already been mentioned as preferred, particularly preferred or very particularly preferred in the description of the compounds of the formula (II).
  • T preferably represents Cl, Br, -OSO 2 CF 3 or -OSO 2 (CF 2 ) 3 CF 3 .
  • T particularly preferably stands for Cl, Br or -OSO 2 CF 3 .
  • T very particularly preferably represents Br or -OSO 2 CF 3 .
  • Aromatics of the formula (III) are generally known or are commercially available.
  • a palladium catalyst is generally used, which in turn can be used with or without the addition of further ligands.
  • PdCl 2 (dppf), Pd (PPh 3 ) 4 or Pd (OAc) 2 are particularly preferably used.
  • Pd 2 (dba) 3 is particularly preferably used.
  • PdCl 2 (dppf) in the first step PdCl 2 (dppf), Pd (PPh 3 ) 4 or Pd (OAc) 2 are particularly preferably used in the second step of the tandem reaction ,
  • Triarylphosphines, trialkylphosphines or arsines are suitable as ligands.
  • Dppf, PPh 3 , P (t-Bu) 3 , Pcy 3 or AsPh 3 are preferably used, particularly preferably dppf.
  • Formula (IV) provides a general definition of the aminoketones required as starting materials when carrying out process C according to the invention.
  • R 1, R 2, R 3, R 4 and m are preferred, particularly preferred and very particularly preferably has those meanings already in connection with the description of the compounds of formula (I) according to the invention as being preferred for these radicals the , particularly preferred, etc. were mentioned.
  • R 1 , R 2 , R 3 , R 4 and m have the meanings given above,
  • R 3 , R 4 and m have the meanings given above,
  • R 1 and R 2 have the meanings given above and
  • M 1 represents Li, MgCl, MgBr, Mgl, ZnCl,
  • Formula (VI) provides a general definition of the metallated aromatics required as starting materials when carrying out process ⁇ .
  • R 1 and R 2 are preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned as preferred, particularly preferred, etc. in connection with the description of the compounds of the formula (I) according to the invention for these radicals.
  • M 1 preferably represents Li, MgCl, MgBr, Mgl, ZnCl, particularly preferably Li, MgCl, MgBr, Mgl, very particularly preferably Li, MgCl, MgBr.
  • Metallized aromatics of the formula (VI) are known in some cases or can be prepared from the corresponding aromatics or halogen aromatics by known methods, such as, for example, lithiation or Grignard reaction.
  • Formula (V) provides a general definition of the N-Boc lactams required as starting materials when carrying out process ⁇ .
  • R 3 , R 4 and m are preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the compounds of the formula (I) according to the invention were.
  • R, R and m have the meanings given above,
  • Formula (VII) provides a general definition of the lactams required as starting materials when carrying out process ⁇ .
  • R 3 , R 4 and m are preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the compounds of the formula (I) according to the invention were.
  • Optically active lactams of formula (VII) are new. They can be made by ⁇ ) racemic lactams of the formula (VH-rac)
  • R 3 , R 4 and m have the meanings given above,
  • R 3 , R 4 and m have the meanings given above,
  • R represents alkyl
  • R 3 , R 4 and m have the meanings given above,
  • racemic lactams required as starting materials when carrying out the process ⁇ are generally defined by the formula (VH-rac).
  • R 3 , R 4 and m are preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the compounds of the formula (I) according to the invention were.
  • Racemic lactams of the formula (VH-rac) are known and can be prepared by known processes (WO 99/59968, WO 99/59967 and WO 98/22438).
  • the racemic lactams of the formula (VH-rac) can be separated on relatively small columns [450 mm ⁇ 75 mm, (ID)] in a short time (gradients shorter than 20 min) by repeated chromatography on a kg scale, which results in this process can also be used on an industrial scale.
  • the multistage process ⁇ according to the invention can be represented by the following film scheme.
  • ⁇ -Ketocarboxylic acids of the formula (VIII) are condensed with 2 (S) -2-amino-2-phenylethanol to give bicyclic lactams of the formula (IX), which are obtained predominantly as a diastereomer.
  • ⁇ -lactams of formula (X) can e.g. by treatment with a base (for example LiOH) in a suitable solvent (for example DMSO) at temperatures between 60 ° C. and 140 ° C. can also be converted directly into the N-nyllactams of the formula (XII) (cf. J. Org. 1996, 61, 5813).
  • a base for example LiOH
  • a suitable solvent for example DMSO
  • the ⁇ -ketocarboxylic acids required as starting materials when carrying out the process ⁇ according to the invention are generally defined by the formula (VIII), the intermediates by the formulas (IX), (X), (XI) and (XII).
  • R 3 , R 4 and m are preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the compounds of the formula (I) according to the invention were.
  • ⁇ -ketocarboxylic acids of the formula (VIII) are known. They can be produced using methods that are known in some cases. One obtains ⁇ -ketocarboxylic acids of formula (VIII) e.g. by reacting corresponding aromatics with succinic anhydride or succinic acid monoester chloride in the presence of a Lewis acid (for example aluminum chloride) and if appropriate in the presence of a diluent (for example 1,2-dichloroethane) (cf. for example Org. Prep. Proced. Int. 1995, 27,
  • an alternative organometallic derivative such as a Grignard reagent can be used as an alternative (cf. Syn. Commun. 1996, 26, 3897).
  • ⁇ -Ketocarboxylic acids of formula (VIII) can also be prepared by using ⁇ , ⁇ -unsaturated carbonyl compounds of formula (XIII) e.g. reduced by using Zn dust in glacial acetic acid according to the following reaction scheme (cf. Chem. Pharm. Bull. 1988, 36, 2050).
  • the carbonyl compounds are generally defined by the formula (XIII).
  • R 3 , R 4 and m are preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the compounds of the formula (I) according to the invention were.
  • ⁇ -unsaturated carbonyl compounds of the formula (XIII) are known in some cases and / or can be e.g. by condensation of acetophenones of the formula (XIV) with glyoxalic acid in the presence of a base (e.g. NaOH) and optionally in
  • the formula (XIV) generally defines the acetophenones.
  • R 3 , R 4 and m are preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. in connection with the description of the compounds of the formula (I) according to the invention for these radicals were.
  • Acetophenones of the formula (XIV) are known.
  • the multi-stage process ⁇ can be represented by the following formula.
  • keto functionality in compounds of the formula (XV) can, according to the Corey, Bakshi & Shibata-PxoX koW (CßS reduction) in the presence of a catalyst ⁇ e.g. (3aR) -l-methyl-3,3,6-triphenyltetrahydro-3H-pyrrolo [1,2-c] [1,2,2] oxazaborole, commercially available ⁇ can be reduced enantioselectively (cf. Angew. Chem. 1998 , 110, 2093 and references cited herein).
  • Lactams of the formula (XVII) can be obtained by double deprotonation with KOtBu and reaction with tosyl chloride (cf. Synth. Commun. 1988, 18, 1159) without any noticeable loss of stereochemical information.
  • HMPT carcinogenic hexamethylphosphoric triamide
  • the allyl protecting group is split off in an aqueous THF solution in the presence of toluenesulfonic acid with the addition of 10 mol% of Pd (Ph 3 P) 4 (cf.Heterocycles 1997, 44, 213 and references cited therein), whereupon the lactams of the formula ( VII) receives.
  • the desired enantiomer can be enriched by recrystallization from petroleum ether (40/60) / toluene.
  • the ⁇ -ketocarboxylic acid esters required as starting materials when carrying out the process ⁇ according to the invention are generally defined by the formula (VHI-a), the intermediates are generally defined by the formulas (XV), (XVI) and (XVII).
  • R 3 , R 4 and m are preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the compounds of the formula (I) according to the invention were.
  • ⁇ -ketocarboxylic acid esters of the formula (VHI-a) can be prepared from the corresponding acids of the formula (NIII) by known esterification processes.
  • Alkaline earth metal or alkali metal metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide, or also ammonium hydroxide
  • alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate
  • alkali metal or alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate, alkali metal fluorides
  • tertiary amines such as trimethylamine , Triethylamine, tributylamine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).
  • DABCO diazabicyclooctane
  • DBU diazabicyclonones
  • DBU diazabicycloundecene
  • Tripotassium phosphate cesium carbonate, potassium carbonate, sodium carbonate, potassium acetate, triethylamine, KOtBu, cesium fluoride or potassium fluoride.
  • Suitable diluents for carrying out processes (B) and (C) according to the invention are all customary inert, organic solvents.
  • Halogenated aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, may preferably be used.
  • Dichloromethane chloroform, carbon tetrachloride, dichloroethane or trichloroethane
  • Ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether,
  • Nitriles such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-
  • Methylpyrrolidone or hexamethylphosphoric triamide Esters such as methyl acetate or ethyl acetate, sulfoxides such as dimethyl sulfoxide or sulfones such as sulfolane.
  • Halogenated aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane; Dichloromethane, chloroform; Alcohols, such as methanol, ethanol, propanol; Nitriles such as acetonitrile; Esters such as methyl acetate or ethyl acetate.
  • aliphatic hydrocarbons such as hexane or heptane
  • alcohols such as methanol or propanol, very particularly preferably n-heptane and isopropanol or mixtures of these.
  • the diluent used in carrying out process (B) according to the invention is particularly preferably acetone, dimethoxyethane, dioxane, THF, DMF, dimethylacetamide, DMSO, ethanol, toluene or, if appropriate, mixtures of these diluents with water.
  • the diluent used in carrying out process (C) according to the invention is particularly preferably methylene chloride, chloroform, toluene, methanol or ethanol.
  • reaction temperatures can in each case be varied within a substantial range. In general, temperatures between 10 ° C and 60 ° C, preferably between
  • reaction temperatures can be varied within a substantial range when carrying out process (B) according to the invention. In general, temperatures between 0 ° C and 140 ° C, preferably between
  • an approximately 1% strength solution of the racemic compound (I-rac) is generally used for the chromatographic separation.
  • concentrations it is also possible to use other concentrations.
  • the processing takes place according to usual methods. In general, the procedure is such that the eluate is largely concentrated, solid constituents are filtered off and dried after washing with n-heptane. The residue is optionally chromatographically freed of any impurities that may still be present. Mixtures of n-hexane or cyclohexane and ethyl acetate are used as eluents, the composition of which must be adapted to the particular compound to be purified.
  • Refurbishment is carried out using customary methods.
  • the procedure is such that the reaction mixture is taken up in ethyl acetate and the organic phase is washed with water, dried over sodium sulfate, filtered and concentrated.
  • the residue is optionally freed of any impurities that may still be present, using customary methods, such as chromium atography or recrystallization.
  • the refurbishment takes place according to usual methods.
  • the procedure is such that the reaction mixture is taken up in ethyl acetate and the organic phase is washed with water, dried over sodium sulfate, filtered and concentrated.
  • the residue is optionally freed of any impurities that may still be present, using customary methods, such as chromatography or recrystallization.
  • Phase is washed with water, dried over sodium sulfate, filtered and concentrated.
  • the residue is optionally freed of any impurities that may still be present, using customary methods, such as chromatography or recrystallization.
  • the active compounds according to the invention are suitable, with good plant tolerance and favorable warm-blood toxicity, 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 can preferably be used as pesticides. 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.
  • Thysanura e.g. Lepisma saccharina.
  • Collembola e.g. Onychiurus armatus.
  • Orthoptera e.g. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.
  • Phthiraptera e.g. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp ..
  • Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
  • From the order of the Homoptera for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastpp, Pemphigusum spp ., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
  • Feltia spp. Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonellella, Galleria mellonellaella, Galleria mellonellaella, Galleria mellonellaella, Galleria mellonellaella Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.
  • Leptinotarsa decemlineata Phaedon cochleariae, Diabrotica spp., Psylliodes chryso- cephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus suleutordhidishppm.
  • Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Tipula paludosa Hylemyia spp., Liriomyza spp ..
  • Siphonaptera for example Xenopsylla cheopis, Ceratophyllus spp.
  • Scorpio maurus Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllo-coptruta oleivora.
  • Rhipicephalus spp. Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp.,
  • Bryobia praetiosa Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevi-palpus spp ..
  • the compounds of the formula (I) according to the invention are distinguished in particular by an excellent action against caterpillars, beetle larvae, spider mites, aphids and leaf miners.
  • plants and parts of plants can be treated.
  • Plants are understood here to mean all plants and plant populations, such as desired and undesirable wild plants or crop plants (including naturally occurring crop plants).
  • Cultivated plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including those by
  • Plant variety rights of protectable or non-protectable plant varieties Under plant All parts above and below ground and organs of the plants, such as sprout, leaf, flower and root, should be understood to mean parts, leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes being listed as examples.
  • the plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
  • the treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space using the customary treatment methods, e.g. by dipping, spraying,
  • the active compounds according to the invention can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances ,
  • organic solvents can, for example, also be used as auxiliary solvents.
  • auxiliary solvents include 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 acetone, 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 such as chlorobenzene
  • Possible solid carriers are: e.g. -Amonium 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 silica, 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;
  • nonionic 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 waste liquors 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, 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 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used in a mixture with other, also known active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance.
  • active compounds such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides, in order, for example, to broaden the spectrum of activity or to prevent the development of resistance.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.
  • Flusilazole Flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminum, fosetyl
  • Iodocarb Ipconazole, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan,
  • Mancopper Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl,
  • Metconazole methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,
  • Oxadixyl Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
  • Paclobutrazole pefurazoate, penconazole, pencycuron, phosdiphen, picoxystrobin,
  • Tebuconazole Tecloftalam, Tecnazen, Tetcyclacis, Tetraconazole, Thiabendazole, Thicyofen, Thifluzamide, Thiophanate-methyl, Thiram, Tioxymid, Tolclofos-methyl,
  • Tricyclazole tridemo h
  • trifloxystrobin triflumizole
  • triforin triticonazole
  • Dagger G OK-8705, OK-8801, ⁇ - (1, 1-Dimethylethy 1) - ß - (2-phenoxyethy 1) - 1 H- 1, 2,4-triazole-1-ethanol, ⁇ - (2,4-dichlorophenyl) -ß-fluoro-ß -propyl-lH-l, 2,4-triazole-l-ethanol, ⁇ - (2,4-dichlorophenyl) -ß-methoxy- ⁇ -methyl-lH-l, 2,4-triazole-l-ethanol, ⁇ - (5-methyl-1,3-dioxan-5-yl) -ß- [[4- (trifluoromethyl) phenyl] methylene] - 1 H-1, 2,4-triazol-1-ethanol,
  • N-formyl-N-hydroxy-DL-alanine sodium salt O, O-diethyl- [2- (dipropylamino) -2-oxoethyl] ethylphosphoramidothioate, O-methyl-S-phenyl-phenylpropylphosphoramidothioate, S-methyl-1, 2,3-benzothiadiazole-7-carbothioate, spiro [2H] - 1 -Benzopyran-2, 1 '(3 ⁇ ) -isobenzofuran] -3' -one, 4- [3,4-dimethoxyphenyl) -3- (4-fluo ⁇ henyl) acryloyl] -mo ⁇ holin
  • Halofenozide HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene, Imidacloprid, Indoxacarb, Isazofos, Isofenphos, Isoxathion, Ivermectin, Ke polyederviren Lambda-cyhalothrin, Lufenuron
  • Paecilomyces fumosoroseus Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propargite, Propoxur, Prothiofos, Prothrohrinos, Pothrohrinos, Pothrohrinate, Pothrohrinate , Pyridaben, Pyridathione, Pyrimidifen, Pyriproxyfen, Quinalphos, Ribavirin Salithion, Sebufos, Silafluofen, Spinosad, Spirodiclofen, Sulfotep, Sulprofos, Tau-fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimiphon, Teflubenzur
  • Tefluthrin Tefluthrin, temephos, temivinphos, terbufos, tetrachlorvinphos, tetradifon, theta-cypermethrin, thiacloprid, thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen oxalate, triodicarb, thiofanox, thuringienshrin, tri Triflumuron, trimethacarb,
  • the active compounds according to the invention can also be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists.
  • Synergists are compounds which increase the activity of the active compounds according to the invention 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.
  • Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention.
  • Plant cultivars are understood to mean plants with certain properties (“traits”) which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- and genotypes.
  • the preferred transgenic (genetically engineered) plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic engineering modification, which gives these plants particularly advantageous valuable properties (“traits”). Examples of such properties are better Plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripening, higher harvest yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life vmd / or processability of the harvested products. Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses, and an increased tolerance of the plants to certain herbicides
  • transgenic plants are the important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes and cotton and rapeseed are highlighted.
  • the properties (“traits”) which are particularly emphasized are the plants' increased defense against insects by toxins arising in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (for example by the genes Cry ⁇ A (a), Cry ⁇ A (b), Cry ⁇ A (c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter "Bt plants”).
  • Bt plants The increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins are also particularly emphasized as properties (“traits").
  • traits are also particularly emphasized the increased tolerance of the plants to certain herbicidal active ingredients, for example imidazoline, sulfonylureas, glyphosate or phosphinotricin (for example "PAT” gene).
  • herbicidal active ingredients for example imidazoline, sulfonylureas, glyphosate or phosphinotricin (for example "PAT” gene).
  • the genes which confer the desired properties (“traits”) can also be found in Combinations with each other occur in the transgenic plants.
  • Examples of “Bt plants” are corn varieties, cotton varieties, soy varieties and potato varieties that are sold under the trade names YIELD GARD ® (e.g.
  • Phosphinotricin eg rape
  • IMI tolerance to imidazolinones
  • STS ® Tole- ranz against sulfonylureas such as corn.
  • Herbicide-resistant plants (bred conventionally for herbicide tolerance) plants also sold under the name Clearfield ® varieties (eg maize) are mentioned. Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or those developed in the future
  • plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention.
  • the preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants. Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.
  • the active compounds according to the invention act not only against plant, hygiene and
  • animal parasites ectoparasites
  • tortoise ticks leather ticks, space mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, featherlings, featherlings and fleas.
  • parasites include:
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes 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 ..
  • Siphonaptrida e.g. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp ..
  • Pterolichus spp. Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes 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 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 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
  • dermal application in the form of, for example, diving or bathing (dipping), spraying (spray), pouring on (pour-on and spot-on), washing, powdering and with the help of shaped articles containing active ingredients, such as collars, ear tags, tail tags , Limb straps, holsters, marking devices etc.
  • active ingredients such as collars, ear tags, tail tags , Limb straps, holsters, marking devices etc.
  • 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, wood processing products and paints.
  • the material to be protected against insect infestation is very particularly preferably wood and wood processing products.
  • 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: Lumber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood, chipboard, carpentry or wooden products that are generally used in house construction or joinery.
  • the formulations mentioned can be prepared in a manner known per se, e.g. by mixing the active compounds according to the invention with at least one solvent or diluent, emulsifier, dispersant and / or binder or fixative, water repellants, 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 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 their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene, are used as such low-volatility, water-insoluble, oily and oily solvents.
  • Mineral oils with a boiling range of 170 to 220 ° C, white spirit 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.
  • the organic low-volatility oily or oily solvents with an evaporation number above 35 and a flash point above 30 ° C., preferably above 45 ° C. can be partially replaced by slightly or medium-volatile organic chemical solvents, with the proviso that the solvent mixture is also a 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 or an aliphatic polar organic chemical solvent or solvent mixture is replaced.
  • Aliphatic hydroxyl and / or ester and / or ether groups are preferably used organic chemical solvents such as glycol ether, ester or the like. For use.
  • organic water-borne synthetic resins and / or synthetic oils which are soluble or dispersible or emulsifiable and / or binding drying oils, in particular binders consisting of or containing, are used as organic-chemical binders Acrylate 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 used.
  • 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
  • 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 or higher molecular glycerol ether, glycerol ether, glycerol ether, glycerol ether, glycerol ether, glycerol ether, glycerol ether, glycerol ether, glycerol ether, glycerol ether, glycerol ether - ether, glycerol ester and p-toluenesulfonic acid ester.
  • phthalic acid esters such as dibut
  • 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 process.
  • 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, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthronid, as well as thifloxiduron, and methifluorideuron, fifluorideuron, and methifluorideuron, as well as thifluorideuron, as well as fungloxidonuron, as well as fungloxidonuron, as well as fungloxidonuron, as well as fungalidium clonid, as well as Funglumidopuron, as well Epoxyconazole,
  • Ledamo ⁇ ha barnacles
  • Balanomo ⁇ ha barnacles
  • Baianus or Pollicipes species increases the frictional resistance of Ships and subsequently leads to a significant increase in operating costs due to increased energy consumption and, moreover, frequent dry dock stays.
  • heavy metals such as e.g. in bis (trialkyltin) sulfides, tri - «- butyltin laurate, tri - « - butyltin chloride, copper (I) oxide, triethyltin chloride, tri - «- butyl (2-phenyl-4-chl ⁇ henoxy) tin, tributyltin oxide,
  • the ready-to-use antifouling paints can optionally contain other active ingredients, preferably algicides, fungicides, herbicides, molluscicides or others
  • Suitable combination partners for the antifouling agents according to the invention are preferably:
  • the antifouling agents used contain the active compound according to the invention of the compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular of 0.01 to 20% by weight.
  • the antifouling agents according to the invention further contain the usual ingredients such as e.g. in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.
  • antifouling paints contain in particular binders.
  • Examples of recognized binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, acrylic resins in a solvent system, in particular in an aqueous system, vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / styrene / acrylonitrile rubbers, drying oils, such as linseed oil, resin esters or modified hard resins in combination with tar or bitumen, asphalt and epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.
  • Paints may also contain inorganic pigments, organic pigments or dyes, which are preferably insoluble in sea water. Paints may also contain materials such as rosin to enable controlled release of the active ingredients. The paints may also contain plasticizers, modifiers that affect the rheological properties, and other conventional ingredients. The compounds according to the invention or the abovementioned mixtures can also be incorporated into self-polishing antifouling systems.
  • the active compounds according to the invention are also suitable for controlling animal
  • Pests especially insects, arachnids and mites, which live in closed rooms such as apartments, factories, offices, vehicle cabins, etc.
  • they can be used alone or in combination with other active ingredients and auxiliaries in household insecticide products. They are effective against sensitive and resistant species and against all stages of development.
  • These pests include:
  • Sco ⁇ ionidea e.g. Buthus occitanus.
  • Dermanyssus gallinae Glyciphagus domesticus, Ornithodorus moubat, Rhipice- phalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophosphides pteronissimus, Dermatophagoides forinae.
  • Opiliones e.g. Pseudosco ⁇ iones chelifer, Pseudosco ⁇ iones cheiridium, Opiliones phalangium.
  • Isopoda e.g. Oniscus asellus, Porcellio scaber.
  • Diplopoda e.g. Blaniulus guttulatus, Polydesmus spp ..
  • Lepismodes inquilinus From the order of the Blattaria e.g. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta austral-asiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.
  • the Blattaria e.g. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta austral-asiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.
  • Saltatoria e.g. Acheta domesticus.
  • Dermaptera e.g. Forficula auricularia.
  • From the order of the Diptera for example Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora eryfhrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Frosannia sppis.
  • Lepidoptera e.g. Achroia grisella, Galleria mellonella, Plodia inte ⁇ unctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
  • Ctenocephalides canis From the order of the Siphonaptera e.g. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis. From the order of the Hymenoptera e.g. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp.,
  • Rhodinus prolixus Triatoma infestans.
  • (+/-) - 5- (2,6-Difluo ⁇ henyl) -2- [4 '- (trifluoromethoxy) -l, l'-biphenyl-4-yl] -3,4-dihydro-2H-pyrrole (1- 3) (8 g) is dissolved in 1 1 n-heptane / isopropanol 9: 1 (v / v volume / volume).
  • 1,3-difluorobenzene (0.29 g, 2.55 mmol) is placed in THF (30 ml) at -78 ° C under an argon atmosphere.
  • N-BuLi 1.6 M in hexane, 2.55 mmol, 1.59 ml
  • tetramethylethylenediamine (2.55 mmol, 0.38 ml) are added dropwise to this solution.
  • the mixture is stirred at -78 ° C for 20 min and then compound (V-1) (1.70 mmol, 0.72 g) in THF (2 ml) is added dropwise at this temperature.
  • compound (V-1) (1.70 mmol, 0.72 g) in THF (2 ml) is added dropwise at this temperature.
  • reaction mixture is allowed to come to room temperature overnight and then poured onto water (10 ml).
  • the aqueous phase is extracted with ethyl acetate (100 ml) and the organic phase is washed with brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure.
  • 1,3-difluorobenzene (0.31 g, 2.7 mmol) is placed in THF (20 ml) at -78 ° C under an argon atmosphere. N-BuLi (1.6 M in hexane, 2.7 mmol, 1.69 ml) is added dropwise to this solution. The mixture is stirred at -78 ° C. for 15 min and then compound V-2 (1.80 mmol, 0.60 g) in THF (2 ml) is added dropwise at this temperature. The reaction mixture is allowed to come to room temperature overnight and then poured onto water (10 ml). The aqueous phase is extracted with ethyl acetate (100 ml) and the organic phase is washed with brine, dried over magnesium sulfate, filtered and concentrated under reduced pressure.
  • Ethyl acetate as eluent and photometric detection.
  • the chiral phase used is based on the monomer N-methacryloyl-L-leucine-d-menthylamide, which after free-radical polymerization is covalently bound to a modified silica gel.
  • Such phases are e.g. in EP-A 0 379 917. Under the conditions given above, the right-handed enantiomer elutes first.
  • the chromatographic separation conditions are set so that the elution of the second enantiomer is accelerated by a short gradient with 100% methanol and the total elution time can thereby be shortened considerably.
  • Residues filtered off and dried after washing with n-heptane.
  • a chromatographically purified sample of the lactam was recrystallized from petroleum ether (40/60) / toluene.
  • Enantiomeric excess (ee value): 99% (according to method 2 for lactams)
  • the logP values given in the tables and manufacturing examples above are determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). Temperature: 43 ° C.
  • the determination is carried out in the acidic range at pH 2.3 with 0.1% aqueous phosphoric acid and acetonitrile as eluents; linear gradient from 10% acetonitrile to 90% acetonitrile.
  • the calibration is carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values based on the retention times by linear interpolation between two successive alkanones).
  • the lambda max values were determined using the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals.
  • Carrier gas helium
  • Injector temperature 220 ° C
  • Temperatu ⁇ rog. 13 min 120 ° C, 1 ° C / min up to 220 ° C applications
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Soybean shoots (Glycine max) are treated by being dipped into the preparation of active ingredient of the desired concentration and populated with caterpillars of the cotton capsule worm (Heliothis armigera) 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.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Soybean shoots (Glycine max) are treated by immersing them in the active ingredient preparation of the desired concentration and populating them with Heliothis virescens caterpillars 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 kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • 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.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • 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 mites have been killed.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Amount of emulsifier and dilute the concentrate with water to the desired concentration is required.
  • the active ingredient preparation is poured onto the floor.
  • the concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the amount of active ingredient per unit volume of soil, which is given in ppm (mg / 1). You fill the bottom in 0.25 1 pots and let them stand at 20 ° C.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • Soybean shoots (Glycine max) of the Roundup Ready variety (trademark of Monsanto Comp. USA) are treated by dipping into the preparation of active compound of the desired concentration and populated with the tobacco bud caterpillar Heliothis virescens 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.
  • EH Amblyomma hebraeum
  • Test animals sucked nymphs from Amblyomma hebraeum
  • the active ingredient solution is diluted with water to the concentration desired in each case.
  • Amblyomma hebraeum (multi-host tick nymphs / immersion method, ED50 determination)
  • Test animals sucked nymphs from Amblyomma hebraeum
  • the active ingredient solution is diluted with water to the desired concentration.
  • a dose-response curve with the concentration spectrum 1000, 300, 100, 30, 10, 3, 1, 0.3, 0.1, 0.03, 0.01 ppm is used for the ED50 determination.
  • the data are calculated using a 4-parameter logistic curve fitting with XLfit (ID Business Solutions Ltd.). If 50% mortality is not achieved at 1000 ppm, the ED50 is considered indeterminable.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyrrole Compounds (AREA)
EP01982267A 2000-09-22 2001-09-10 Optisch aktive 2,5-bisaryl-delta1-pyrroline und deren verwendung als schädlingsbekämpfungsmittel Withdrawn EP1322607A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10047110 2000-09-22
DE10047110A DE10047110A1 (de) 2000-09-22 2000-09-22 Optisch aktive 2,5-Bisaryl-DELTA·1·-Pyrroline
PCT/EP2001/010424 WO2002024643A1 (de) 2000-09-22 2001-09-10 Optisch aktive 2,5-bisaryl-delta1-pyrroline und deren verwendung als schädlingsbekämpfungsmittel

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DE10113965A1 (de) * 2001-03-22 2002-09-26 Bayer Ag DELTA·1·-Pyrroline
DE10154517A1 (de) * 2001-11-07 2003-05-15 Bayer Cropscience Ag DELTA·1·-Pyrroline
DE10243939A1 (de) * 2002-09-24 2004-04-01 Bayer Cropscience Ag Pyrroline
US7439280B2 (en) * 2004-04-06 2008-10-21 Basf Corporation Lignocellulosic composite material and method for preparing the same
MX2014000104A (es) * 2011-06-30 2014-07-28 Hansen Ab Gmbh Agentes para el control de parasitos en animales.
US8664756B2 (en) 2012-07-24 2014-03-04 Medtronic, Inc. Reconstituted wafer package with high voltage discrete active dice and integrated field plate for high temperature leakage current stability

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DE2737195A1 (de) * 1977-08-18 1979-03-01 Hoechst Ag Benzolsulfonamidderivate und verfahren zu ihrer herstellung
US5274167A (en) 1989-01-26 1993-12-28 Bayer Aktiengesellschaft Polymeriable optically active (meth) acrylic acid derivatives
AU6845094A (en) 1993-06-07 1995-01-03 Bayer Aktiengesellschaft Iodopropargyl carbamates and their use as biocides in the protection of plants and materials
US5883252A (en) 1996-01-26 1999-03-16 Vertex Pharmaceuticals Incorporated Aspartyl protease inhibitors
EP0882022A1 (en) * 1996-01-26 1998-12-09 Vertex Pharmaceuticals Incorporated Aspartyl protease inhibitors
DE19648011A1 (de) * 1996-11-20 1998-05-28 Bayer Ag Cyclische Imine
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DE19822247A1 (de) 1998-05-18 1999-11-25 Bayer Ag 2-(2-Chlorphenyl)-3,4-dihydro-2H-pyrrol-Derivate
DE19822245A1 (de) * 1998-05-18 1999-11-25 Bayer Ag 2-(2-Methylphenyl)-3,4-dihydro-2H-pyrrol- Derivate
DE19847076A1 (de) * 1998-10-14 2000-04-20 Bayer Ag 2-Hetaryl-3,4-dihydro-2H-pyrrol-Derivate
DE10047109A1 (de) * 2000-09-22 2002-04-11 Bayer Ag Verfahren zur Herstellung von DELTA·1·-Pyrrolinen
DE10060412A1 (de) * 2000-12-05 2002-06-06 Bayer Ag DELTA1-Pyrroline
EP1379500A2 (de) * 2001-04-09 2004-01-14 Bayer CropScience AG Verfahren zur herstellung von 2,5-bisaryl-delta1-pyrrolinen aus aroylpyrrolidinonen

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KR20030034176A (ko) 2003-05-01
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MXPA03002364A (es) 2004-10-15
WO2002024643A1 (de) 2002-03-28
JP2004509166A (ja) 2004-03-25
KR100828310B1 (ko) 2008-05-08
CA2422958A1 (en) 2003-03-19
DE10047110A1 (de) 2002-04-18
AR034146A1 (es) 2004-02-04
EG23084A (en) 2004-03-31
AU1389702A (en) 2002-04-02
CN1630634A (zh) 2005-06-22
TWI306853B (en) 2009-03-01
US20090012144A1 (en) 2009-01-08
BR0114062A (pt) 2003-07-01
US20040059129A1 (en) 2004-03-25

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