EP2061770A1 - Piperazinverbindungen mit herbizider wirkung - Google Patents

Piperazinverbindungen mit herbizider wirkung

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Publication number
EP2061770A1
EP2061770A1 EP08774158A EP08774158A EP2061770A1 EP 2061770 A1 EP2061770 A1 EP 2061770A1 EP 08774158 A EP08774158 A EP 08774158A EP 08774158 A EP08774158 A EP 08774158A EP 2061770 A1 EP2061770 A1 EP 2061770A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
alkoxy
hydrogen
alkenyl
carry
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Withdrawn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
EP08774158A
Other languages
German (de)
English (en)
French (fr)
Inventor
Eike Hupe
Thomas Seitz
Matthias Witschel
Dschun Song
William Karl Moberg
Liliana Parra Rapado
Frank Stelzer
Andrea Vescovi
Trevor William Newton
Robert Reinhard
Klaus Grossmann
Thomas Ehrhardt
Michael Rack
Elmar Kibler
Bernd Sievernich
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.)
BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP08774158A priority Critical patent/EP2061770A1/de
Publication of EP2061770A1 publication Critical patent/EP2061770A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/20—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D239/22—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/48—Two nitrogen atoms
    • C07D239/49—Two nitrogen atoms with an aralkyl radical, or substituted aralkyl radical, attached in position 5, e.g. trimethoprim
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/58—Two sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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
    • C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic 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
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic 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
    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems

Definitions

  • the present invention relates to piperazine compounds of the general formula I defined below and their use as herbicides.
  • the invention also relates to crop protection agents and to a method of controlling undesired plant growth.
  • the thaxtomines A and B produced by the plant pathogen S. scabies are natural substances with a central piperazine-2, 5-dione ring which carries a 4-nitro-indol-3-ylmethyl radical in the 3-position and a benzyl radical optionally substituted by OH in the 2-position. Because of their plant-damaging effect, the possibility of using this class of compounds as herbicides was also investigated (King R.R. et al., J. Agric. Food Chem. (2001) 49, 2298-2301).
  • EP-A 181 152 and EP-A 243122 describe structurally similar piperazine compounds and their use as antagonists of the platelet activating factor.
  • WO 99/48889, WO 01/53290 and WO 2005/011699 describe 2,5-diketopiperazine compounds which have, in the 3- or 6-position, a 4-imidazolyl radical bonded via a methylene or methine group and in the another 3- or 6-position benzyl or Benzylidenrest have. These compounds are antitumor agents.
  • R is H or methyl, as an anti-inflammatory drug in medicine.
  • R y is hydrogen or benzyl and R x is hydrogen, acetyl or Isopro- pyloxycarbonyl, as precursors for the preparation of Ecteinascidinen.
  • An object of the present invention is to provide compounds having herbicidal activity.
  • compounds are to be made available which have a high herbicidal action, in particular even at low application rates, and their compatibility with crop plants for commercial exploitation is sufficient.
  • the present invention thus provides piperazine compounds of the general formula I.
  • a 1 , A 2 independently of one another are aryl or heteroaryl, where R a is bonded in the ortho position to the point of attachment of A 1 to a C atom or N atom of A 1 ,
  • Y 1 is oxygen, sulfur or a group NR y1 , wherein R ⁇ 1 is selected from hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, Cs-Ce cycloalkyl, C 3 -C 6 -CyCl oa I kyl methyl, OH, Ci-C 6 alkoxy, C 3 -C 6 -alkenyl oxy, C 3 -C 6 alkynyloxy, C 3 -C 6 cycloalkoxy, and C 3 -C 6 cycloalkylmethoxy;
  • Y 2 is oxygen, sulfur or a group NR ⁇ 2, wherein R ⁇ 2 is selected from hydrogen, Ci-C 6 -alkyl, C 3 -C 6 alkenyl, C 3 -C 6 -alkyl kinyl, C 3 -C 6 cycloalkyl, C 3 -C 6 -CyCl oa I kyl methyl, OH, Ci-C 6 alkoxy, C 3 -C 6 -alkenyl oxy, C 3 -C 6 alkynyloxy, C 3 -C 6 Cycloalkoxy and C 3 -C 6 cycloalkylmethoxy; wherein said aliphatic or cyclic portions of the substituents Y 1 and Y 2 are unsubstituted, may be partially or fully halogenated and / or may carry one to three of the following groups: cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -alkyl halo
  • R a is selected from halogen, cyano, nitro, SF 5 , C 1 -C 6 -alkyl, C 5 -C 6 -cycloalkyl, C 2 -C 6 -alkynyl, C 5 -C 8 -cycloalkenyl, C 5 -C 8 -CyCl oa I kinyl, C 3 -C 6 -CyCIo- alkyl- (Ci-C 6) alkyl, C 5 -C 8 cycloalkenyl (Ci-C 6) alkyl, C 5 -C 8 -Cycloalkinyl- (Ci-C 6) alkyl, C 3 -C 6 cycloalkyl, (C2-C6) alkenyl, C 5 -C 8 cycloalkenyl (C 2 -C 6) alkenyl, C 5 -C 8 cycloalkynyl - (C 2 -C 6) alkenyl
  • Z 5 CH NOR 14 , Z 6 OR 15 , Z 7 SR 16 , Z 7 S (O) R 16 and Z 7 SO 2 R 16 ;
  • R b , R c , R d , R e and R f are each independently hydrogen or have one of the meanings given for R a ;
  • R e or R f can also be linear C 3 -C 6 -alkylene, which can be partially or completely halogenated and which can carry one to three of the following groups: cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -Haloalkyl, Cs-Ce-cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, di- (C 1 -C 4 -alkyl) -amino, C 1 -C 4 -alkylcarbonyl, hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, aminocarbonyl, C 1 -C 4 -alkylaminocarbonyl, di- (C 1 -C 4 -alkyl) aminocarbonyl or C 1 -C 4 -alkylcarbonyloxy, in which a CH 2 group in C 3 -C 6 alkylene may be replaced by
  • R 1 and R 2 are independently selected from:
  • R 1 may additionally denote hydrogen
  • aliphatic, cyclic or aromatic portions of the substituents R 1 and R 2 may be partially or fully halogenated and / or may carry one to three of the following groups: cyano, hydroxy, C 1 -C 4 alkyl, C i C 4 -haloalkyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, di- (C 1 -C 4 -alkyl) amino, C 1 -C 4 -alkylcarbonyl, hydroxycarbonyl, d- C 4 alkoxycarbonyl, aminocarbonyl, C 1 -C 4 -alkylaminocarbonyl, di- (C 1 -C 4 -alkyl) amino carbonyl or C 1 -C 4 -alkylcarbonyloxy;
  • R 3 is halogen, cyano, nitro or a radical R 26 , OR 27 , SR 28 , S (O) R 28 , SO 2 R 28 ,
  • R 4 is hydrogen, halogen, cyano, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkynyl, C 5 -C 8 -cycloalkenyl, C 2 -C 6 -alkynyl, C 5 - C 8 -cycloalkynyl, phenyl, phenyl- (C 1 -C 6 ) -alkyl, heterocyclyl, heterocyclyl- (C 1 -C 6 ) -alkyl, phenyl- [C 1 -C 6 -alkoxycarbonyl] - (C 1 -C 6 ) -alkyl or a radical COR 21 , OR 27 , SR 28 , S (O) R 28 , SO 2 R 28 , NR 29 R 30 or N (OR 31 ) R 32 , wherein said aliphatic, cyclic or aromatic portions of the substituent R 4 are
  • R 5 is hydrogen, halogen, cyano, nitro, hydroxy, C 1 -C 8 -alkyl, C 2 -C 8 -alkenyl, C 3 -C 8 -cycloalkyl, C 5 -C 8 -cycloalkenyl, C 2 -C 8 - al kinyl, C 4 -C 8 - alkadienyl, C 7 -C 8 -CyCl oa I kinyl, C 5 -C 8 cycloalkenyl (Ci-C 6) alkyl, C 5 -C 8 - cycloalkynyl (Ci- C 6) alkyl, C 3 -C 6 cycloalkyl, (C2-C6) alkenyl, C 5 -C 8 - cycloalkenyl (C 2 -C 6) alkenyl, C 5 -C 8 -Cycloalkinyl- (C 2 -C 6 ) -alken
  • R 3 together with R 5 represents a chemical bond
  • R 6 is halogen, cyano, nitro, C 2 -C 8 -alkenyl, C 3 -C 8 -cycloalkyl, C 5 -C 8 -
  • Z 11 CH NOR 64 , OR 65 , Z 9 SR 65a , Z 9 S (O) R 66 , Z 9 S (O) 2 R 66 or Z 10 P (O) (OR 67 ) 2 ; wherein said aliphatic, cyclic or aromatic portions of the substituents R 4 , R 5 and R 6 may be independently or partially halogenated and / or may carry one to three of the following groups: cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, di- (C 1 -C 4 -alkyl) -amino, d-
  • R 7 is halogen, cyano, nitro or a radical R 26 , OR 27 , SR 28 , S (O) R 28 , SO 2 R 28 ,
  • R 8 has one of the meanings given for R 4 ;
  • R 9 , R 10 and R 67 are each independently of one another hydrogen or C 1 -C 6 -alkyl and R 10 in Z 2 B (OR 10 ) 2 can together form a C 2 -C 4 -alkylene chain; or
  • R 9a is C 1 -C 6 alkyl
  • R 11, R 61 are independently hydrogen, C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 - Ce alkenyl, C 5 -C 8 cycloalkenyl, C 2 -C 6 alkynyl, C 7 - C 8 cycloalkynyl, hydroxy, d-Ce-alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 -alkynyloxy, amino, C r C 6 alkyl amino, di- (CrC 6 alkyl) amino, C 1 -C 6 -alkoxyamino, di- (C 1 -C 6 -alkoxy) amino, C 1 -C 6 -alkylsulfonylamino, C 1 -C 6 -alkylaminosulfonylamino, [di (C 1 -C 6 -alkyl) -amino] sulfonylamino, C 3
  • R 12 and R 62 independently of one another are hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyloxy, C 3 -C 6 -alkynyl, C 3 -C 6 - Alkenyloxy, Cs-Cs-cycloalkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -alkynyloxy, C 7 -C 8 -cycloalkyl, C 1 -C 6 -alkylcarbonyl, C 3 -C 6 -cycloalkylcarbonyl, Di- (C 1 -C 6 -alkyl) amino carbonyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -alkoxycarbonyl- (C 1 -C 6 ) -alkyl, C 1 -C 6
  • R 14 , R 64 independently of one another are hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl or
  • R 15, R 65a are independently hydrogen, Ci-C 6 alkyl, C 3 -C 6 cycloalkyl,
  • R 65 is d-Ce-alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkynyl, C 5 -C 8 -cycloalkenyl, C 3 -C 6 -alkynyl, C 7 -C 8 -cycloalkynyl, C 3 -C 6 cycloalkyl (Ci-C 6) alkyl, C 5 -C 8 - cycloalkenyl (Ci-C 6) alkyl, C 5 -C 8 -Cycloalkinyl- (Ci-C 6) alkyl, C 3 -C 6 -
  • R 16, R 66 are independently -C 6 alkyl, -C 6 alkoxy, phenyl or pheno- xy;
  • Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 , Z 8 , Z 9 , Z 10 and Z 11 independently of one another a bond, -CH 2 -, -CH 2 -CH 2 -, -O-CH (R 17 ) -, -S-CH (R 18 ) -, -S (O) -CH (R 19 ) - or - SO 2 CH (R 20 ) -, wherein R 17 , R 18 R 19 and R 20 independently of one another are hydrogen or C 1 -C 6 -alkyl; R 21 is hydrogen, Ci -C 6 -alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 -alkenyl, C 5 -C 8 -
  • R 22 and R 23 are independently hydrogen, Ci-C6 alkyl, C3-C6 cycloalkyl, Cs-Ce alkenyl, C 5 -C 8 cycloalkenyl, C 3 -C 6 -alkyl kinyl, C 7 -C 8 -cycloalkynyl or C 1 -C 6 -alkylcarbonyl; or
  • R 24 is hydrogen, Ci-C 6 alkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 -alkenyl, C 5 -C 8 -
  • R 25 is C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, phenyl or phenoxy;
  • R 25a is C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkynyl, C 5 -C 8 -cycloalkenyl, C 3 -C 6 -
  • R 26 , R 27 , R 28 , R 29 and R 32 independently of one another are hydrogen, C 1 -C 6 -alkyl,
  • Cs-Ce-cycloalkyl C 3 -C 6 alkenyl, C 3 -C 6 kinyl -alkyl, formyl, Ci-C6 alkylcarbonyl, C3-C6-cycloalkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6-alkynylcarbonyl, Ci-C 6 alkoxy (Ci-C 6) alkyl, Ci-Ce-alkoxycarbonyl, C 2 -C 6 alkenyloxy carbonyl, Cs-C ⁇ -alkynyloxycarbonyl, Ci-C ⁇ -alkylaminocarbonyl,
  • Ci-C ⁇ -alkyl heterocyclyloxycarbonyl, heterocyclylaminocarbonyl, heterocyclylsulfonylaminocarbonyl, N- (Ci-C6-alkyl) -N- (heterocyclyl) - aminocarbonyl, or heterocyclyl-Ci-C ⁇ -alkylcarbonyl, wherein the phenyl or heterocyclyl parts of the substituents partially may be or fully halogenated and / or may carry one to three of the following groups: nitro, cyano, Ci-C 4 alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy; or
  • R 30 and R 31 independently of one another are hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl,
  • R 33 is C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl or phenyl, and where the phenyl substituent may be partially or completely halogenated and / or may carry one to three of the following groups: nitro, cyano, C 1 -C 4 - alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy; and
  • R 1 taken together with the radical R 2 or the radical R 5 is a 1-, 2-, 3- or 4-membered carbon chain, in which a carbon atom may be replaced by O, S or a group NR A , wherein one of Carbon atoms can carry a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Ci C 4 haloalkoxy can carry selected radicals;
  • R 1 together with a radical R d , which is bonded in the ortho position to the point of attachment of A 2 to a C atom or N atom of A 2 , a covalent bond or a 1, 2, 3 - or 4-membered carbon chain, wherein a carbon atom may be replaced by O, S or a group NR B , wherein one of the carbon atoms can carry a carbonyl oxygen atom and / or wherein the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano , hydroxy, Ci-C4-alkyl, Ci-C can carry 4 -haloalkoxy radicals selected 4 haloalkyl, Ci-C4-alkoxy, Ci-C;
  • R 1 together with the radical R 6 denotes a 3-, 4- or 5-membered carbon chain, in which a carbon atom can be replaced by O, S or a group NR D , where one of the carbon atoms carries a carbonyl oxygen atom can and / or wherein the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy selected Res- te can carry;
  • R 2 together with the radical R 6 denotes a 1-, 2-, 3- or 4-membered carbon chain in which a carbon atom can be replaced by O, S or a group NR E , where one of the carbon atoms is a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy carry selected radicals can;
  • Bond or a 1-, 2-, 3- or 4-membered carbon chain, wherein a carbon atom may be replaced by O, S or a group NR F , wherein one of the carbon atoms may carry a carbonyl oxygen atom and / or wherein the carbon atoms in addition to hydrogen , 2, 3 or 4 under halogen, cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl,
  • Ci-C4-alkoxy, Ci-C4-haloalkoxy can carry selected radicals
  • R 2 together with the radical R 4 or the radical R ⁇ 2 , if present, denotes a 2-, 3- or 4-membered carbon chain, in which a carbon atom may be replaced by O, S or a group NR G , where one of the
  • Carbon atoms can carry a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Ci C 4 -haloalkoxy can carry selected radicals;
  • R 2 together with the radical R 5 is a 3-, 4- or 5-membered carbon chain, in which a carbon atom can be replaced by O, S or a group NR H , where one of the carbon atoms can carry a carbonyl oxygen atom and / or wherein the carbon atoms next to water hydrogen 1, 2, 3 or 4 may be halogen, cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy;
  • R 3 together with the radical R 5 is a 1-, 2-, 3- or 4-membered carbon chain, in which a carbon atom is represented by O, S or a group
  • NR 1 may be replaced, where one of the carbon atoms can carry a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 are halogen, cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy may carry selected radicals;
  • R 3 together with the radical R 4 signifies a 2-, 3-, 4- or 5-membered carbon chain, in which a carbon atom can be replaced by O, S or a group NR K , where one of the carbon atoms is a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy carry selected radicals can;
  • R 4 together with the radical R a is a 2-, 3-, 4- or 5-membered
  • R 5 together with the radical R a denotes a 2-, 3-, 4- or 5-membered carbon chain in which a carbon atom can be replaced by O, S or a group NR M , where one of the carbon atoms is a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy carry selected radicals can;
  • R 5 together with the radical R 6 represents a 1-, 2-, 3-, 4- or 5-membered carbon chain, in which a carbon atom may be replaced by O, S or a group NR N , where one of the carbon atoms Carbonyl oxygen atom and / or wherein the carbon atoms next to water hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy may carry selected radicals;
  • Cyano, hydroxy, Ci -C4 -alkyl, Ci-C 4 haloalkyl, Ci-C can carry radicals selected 4 alkoxy, Ci-C4-haloalkoxy;
  • R 6 taken together with a radical R ⁇ 2 , if present, a 2-, 3-, 4- or 5-membered carbon chain, wherein a carbon atom may be replaced by O, S or a group NR P , wherein one of Carbon atoms can carry a carbonyl oxygen atom and / or wherein the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy can carry selected radicals;
  • R 6 together with the radical R 7 denotes a 1-, 2-, 3- or 4-membered carbon chain, in which a carbon atom can be replaced by O, S or a group NR Q , where one of the carbon atoms is a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy carry selected radicals can;
  • R 8 together with a radical R d , which in the ortho position to the point of attachment of A 2 to a C atom or N atom of A 2 bound is a 2-, 3-, 4- or 5-membered carbon chain in which a carbon atom may be replaced by O, S or a group NR S , wherein one of the carbon atoms may carry a carbonyl oxygen atom and / or wherein the carbon atoms in addition to hydrogen , 2, 3 or 4 halo, Cy ano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C 4 -
  • Halogenoalkoxy can carry selected radicals
  • R 8 taken together with a radical R ⁇ 2 , if present, a 2-, 3-, 4- or 5-membered carbon chain, wherein a carbon atom may be replaced by O, S or a group NR T , wherein one of Carbon atoms can carry a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Ci C 4 haloalkoxy can carry selected radicals;
  • R A , R B , R c , R D , R E , R F , R G , R H , R ", R ⁇ , R L , R M , R N , R °, R p , R Q , R R, R ⁇ s and R are independently selected from hydrogen, cyano, Ci-C 4 alkyl, Ci-C 4 haloalkyl, phenyl and benzyl, wherein the phenyl ring in phenyl or benzyl may be partially or fully halogenated and / or one to three of the following groups: Nitro, Cyano,
  • R 3 and R 4 together form a keto group or a group NR 3a, wherein R 3a is selected from hydrogen, Ci-C 6 -alkyl, halo-C 6 alkyl, C 3 -C 6 -alkenyl Al, C 3 -C 6 -alkyl kinyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl, methyl, OH, Ci-C 6 alkoxy, Ci-C 6 haloalkoxy, C 3 -C 6 alkenyloxy C 3 -C 6 alkynyloxy, C 3 -C 6 cycloalkoxy, and C 3 -C 6 cycloalkylmethoxy;
  • R 7 and R 8 together form a keto group or a group NR 7a wherein R 7a is selected from hydrogen, Ci-C 6 -alkyl, halo-C 6 alkyl, C 3 -C 6 -alkenyl Al, C 3 -C 6 -alkyl kinyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl, methyl, OH, Ci-C 6 alkoxy, Ci-C 6 haloalkoxy, C 3 -C 6 alkenyloxy C 3 -C 6 alkynyloxy, C 3 -C 6 cycloalkoxy, and C 3 -C 6 cycloalkylmethoxy;
  • R 6 may also be hydrogen 6 alkyl, OH or C, which may be partially or fully halogenated and / or may carry one to three of the following groups:
  • Ci-C ⁇ -alkyl, Ci-C ⁇ -alkoxy different radical wherein Ci-C ⁇ -alkyl and Ci-C ⁇ -alkoxy may be unsubstituted or partially or completely halogenated and / or may carry one to three of the following groups:
  • R 6 is not C 1 -C 6 -alkoxy which may be partially or completely halogenated and / or may carry one to three of the following groups:
  • the present invention also provides the use of piperazine compounds of general formula I or the agriculturally useful salts of piperazine compounds of formula I as herbicides, i. for controlling harmful plants.
  • the present invention also relates to compositions which contain at least one piperazine compound of the formula I or an agriculturally useful salt of I and auxiliaries customary for the formulation of crop protection agents.
  • the present invention also relates to a method for controlling undesired plant growth, which comprises allowing a herbicidally effective amount of at least one piperazine compound of the formula I or an agriculturally useful salt of I to act on plants, their seeds and / or their habitat.
  • the compounds of the formula I can contain one or more chiral centers and are then present as enantiomer or diastereomer mixtures.
  • the invention relates to both the pure enantiomers or diastereomers and mixtures thereof.
  • compounds of formula I may exist as E-isomer or Z-isomer with respect to the exocyclic double bond formed thereby.
  • the invention relates to both the pure E isomers and Z isomers and their mixtures.
  • the compounds of the formula I can also be in the form of their agriculturally useful salts, whereby the type of salt generally does not matter.
  • the salts of those cations or the acid addition salts of those acids come into consideration whose cations, or anions, do not adversely affect the herbicidal activity of the compounds I.
  • ions of the alkali metals preferably lithium, sodium or potassium, the alkaline earth metals, preferably calcium or magnesium, and the transition metals, preferably manganese, copper, zinc or iron are suitable as cations.
  • ammonium as cation, in which case one to four hydrogen atoms are optionally substituted by C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkoxy-Ci-C 4 alkyl, phenyl or benzyl may be replaced, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-1-oxy) eth-1 -ylammonium, di (2-hydroxyeth -1-yl) ammonium, di (2-hydroxye
  • Phosphonium ions sulfonium ions, preferably tri (C 1 -C 4 -alkyl) sulfonium or sulfonoxonium ions, preferably tri (C 1 -C 4 -alkyl) sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate or butyrate.
  • halogenated substituents preferably carry one to five identical or different halogen atoms, in particular fluorine atoms or chlorine atoms.
  • halogen in each case represents fluorine, chlorine, bromine or iodine. Furthermore, for example:
  • Alkyl and the alkyl moieties for example, in alkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl, alkylcarbonyl, alkylamino, trialkylsilyl, phenylalkyl, phenylsulfonylalkyl, heterocyclylalkyl: saturated, straight-chain or branched hydrocarbon radicals having one or more carbon atoms, eg 1 to 2, 1 to 4, or 1 to 6 carbon atoms, eg.
  • d-Ce-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methyl-propyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- Methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethyl-1-methyl
  • Haloalkyl an alkyl radical as mentioned above, the hydrogen atoms of which are partially or fully substituted by halogen atoms such as fluorine, chlorine, bromine and / or iodine, e.g. Chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2- Chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropy
  • Cycloalkyl and the cycloalkyl moieties for example, in cycloalkoxy or cycloalkylcarbonyl: monocyclic, saturated hydrocarbon groups having three or more C atoms, e.g. 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Alkenyl and alkenyl for example, in phenyl (C2-C6) alkenyl or alkenylamino: monounsaturated, straight-chain or branched hydrocarbon radicals having two or more carbon atoms, eg. B.
  • C2-C6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl , 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2- Methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl 3-butenyl, 3-methyl-3-butenyl, 1, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-butenyl
  • alkenyl groups such as C2-C6 alkenyl are used. In another embodiment of the invention, alkenyl groups such as Cs-C ⁇ -alkenyl are used.
  • Cycloalkenyl and cycloalkenyl moieties in cycloalkenylalkyl, cycloalkenylalkenyl and cycloalkenylalkynyl monocyclic monounsaturated hydrocarbon groups having three or more C atoms, e.g. B. 5 to 8, preferably 5 to 6 carbon ring members such as cyclopenten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl.
  • Alkynyl and alkynyl moieties for example, in [tri (Ci-C6) alkylsilyl (C2-C6) alkynyl or alkynylamino: straight-chain or branched hydrocarbon groups having two or more carbon atoms, for. B. 2 to 4, 2 to 6, or 3 to 6 carbon atoms and one or two triple bonds in any, but not adjacent position, for.
  • C 2 -C 6 alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2 propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl 4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentyn
  • Cycloalkynyl and Cycloalkinyl maschine in Cycloalkinylalkyl, Cycloalkinylalkenyl and Cycloalkinylalkinyl: monocyclic hydrocarbon groups having three or more carbon atoms, eg. B. 7 to 8 carbon ring members and a triple bond such as cycloheptin-1-yl, cycloheptin-3-yl, cycloheptin-4-yl.
  • C4-Cio-alkadienyl diunsaturated, straight-chain or branched hydrocarbon radicals having four or more carbon atoms and two double bonds in any but not adjacent position, eg. B. 4 to 10 carbon atoms and two double bonds in any, but not adjacent position, for. B.
  • Alkoxy or alkoxy for example, in phenylalkoxy, alkoxyamino, alkoxycarbonyl: alkyl, as defined above, which is bonded via an O atom: z.
  • small alkoxy groups such as C 1 -C 4 alkoxy are used.
  • larger alkoxy groups such as Cs-C ⁇ -alkoxy are used.
  • Alkenyloxy Alkenyl as mentioned above, which is bonded via an oxygen atom, for. B.
  • C3-C6 alkenyloxy such as 1-propenyloxy, 2-propenyloxy, 1-methylethenyloxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy, 1-methyl-1-propenyloxy, 2-methyl-1-propenyloxy, 1 - Methyl 2-propenyloxy, 2-methyl-2-propenyloxy, 1-pentenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 1-methyl-1-butenyloxy, 2-methyl-1-butenyloxy, 3-methyl 1-butenyloxy, 1-methyl-2-butenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy, 1-methyl-3-butenyloxy, 2-methyl-3-butenyloxy, 3-methyl-3 butenyloxy, 1, 1-dimethyl-2-propenyloxy, 1, 2-dimethyl-1-propenyloxy, 1, 2-dimethyl-2-propenyloxy
  • Alkynyloxy alkynyl as mentioned above, which is bonded via an oxygen atom, for. Cs-C ⁇ -alkynyloxy such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 1-methyl-2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-methyl-2-butynyloxy, 1 Methyl-3-butynyloxy, 2-methyl-3-butynyloxy, 1-ethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynyloxy, 4-hexynyloxy, 5-hexynyloxy, 1-methyl-2-pentynyloxy, 1-methyl 3-pentynyloxy.
  • small alkynyloxy groups such as C3-C4 alkynyloxy are used.
  • larger alkynyloxy groups such as C3-C
  • Alkylthio Alkyl as defined above attached via an S atom.
  • Alkylsulfinyl alkyl as defined above bonded through an SO group.
  • Alkylsulfonyl Alkyl as defined above attached via an S (O) 2 group.
  • Heterocyclyl a mono- or bicyclic, saturated, partially unsaturated or aromatic heterocyclic ring having three or more, e.g. 3 to 10 ring atoms:
  • z. B a monocyclic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring containing one to four identical or different heteroatoms selected from the group consisting of oxygen, sulfur or nitrogen, and may be bonded via C or N. , z. B.
  • C-linked 3-4-membered, saturated or unsaturated rings such as 2-oxiranyl, 2-oxetanyl, 3-oxetanyl, 2-aziridinyl, 3-thiethanyl, 1-azetidinyl, 2-azetidinyl;
  • Tetrahydrothiopyran-4-yl 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 1, 3 Dithian-2-yl, 1,3-dithian-4-yl, 1,3-dithian-5-yl, 1,4-dithian-2-yl, 1,3-oxathian-2-yl, 1, 3 Oxathian-4-yl, 1,3-oxathian-5-yl, 1,3-oxathian-6-yl, 1,4-oxathian-2-yl, 1,4-oxathian-3-yl, 1, 2 Dithian-3-yl, 1,2-dithian-4-yl, hexa-hydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidin-5-yl, hexa-hydropyrazine-2-y
  • N-linked, 5-membered, saturated rings such as: tetrahydropyrrol-1-yl, tetrahydropyrazol-1-yl, tetrahydroisoxazol-2-yl, tetrahydroisothiazol-2-yl, tetrahydroimidazol-1-yl, tetrahydrooxazol-3-yl Tetrahydrothiazol-3-yl;
  • N-linked, 6-membered, saturated rings such as: piperidin-1-yl, hexahydropyrimidin-1-yl, hexahydropyrazine-1-yl, hexahydropyridazin-1-yl, tetrahydro-1,3-oxazin-3-yl, Tetrahydro-1,3-thiazin-3-yl, tetrahydro-1,4-thiazin-4-yl, tetrahydro-1,4-oxazin-4-yl, tetrahydro-1,2-oxazin-2-yl;
  • N-linked, 5-membered, partially unsaturated rings such as: 2,3-dihydro-1H-pyrrol-1-yl, 2,5-dihydro-1H-pyrrol-1-yl, 4,5-dihydro-1 H-pyrazol-1-yl, 2,5-dihydro-1H-pyrazol-1-yl, 2,3-dihydro-1H-pyrazol-1-yl, 2,5-dihydroisoxazol-2-yl, 2,3- Dihydroisoxazol-2-yl, 2,5-dihydroisothiazol-2-yl, 2,3-dihydroisoxazol-2-yl, 4,5-dihydro-1H-imidazol-1-yl, 2,5-dihydro-1H-imidazole 1-yl, 2,3-dihydro-1H-imidazol-1-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrothiazol
  • N-linked, 6-membered, partially unsaturated rings such as:
  • N-linked, 5-membered, heteroaromatic rings with usually 1, 2, 3 or
  • bicyclic heterocycle having one of the abovementioned 5- or 6-membered heterocyclic rings and another, saturated, unsaturated or aromatic carbocycle fused thereto, for example a benzene, cyclohexane, cyclohexene or cyclohexadiene ring, or a further 5 fused thereto - or 6-membered heterocyclic ring, the latter may also be saturated, unsaturated or aromatic.
  • hetaryl or heteroaryl is a 5- or 6-membered heteroaromatic radical which has 1, 2, 3 or 4 identical or different heteroatoms selected from the group consisting of oxygen, sulfur or nitrogen as ring members which are bonded via C or N may be bonded, and which can form a bicyclic ring system with a further fused benzene ring or a 5- to 6-membered heteroaromatic.
  • hetaryl examples include the abovementioned C-linked, 5- and 6-membered, heteroaromatic rings, the abovementioned N-linked, 5-membered, heteroaromatic rings, and bicyclic heteroaromatic radicals, such as quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, indolyl, benzothienyl, Benzofuryl, benzoxazolyl, benzthiazolyl, benzimidazolyl, benzpyrazolyl, benzotriazole, indolizinyl, 1,2,4-triazolo [1,5-a] pyrimidinyl, 1,2,4-triazolo [4,3-a] pyridinyl, Pyrazolo [3,4-b] pyridinyl, 1,2,4-triazolo [1,5-a] pyridinyl, imidazo [1,2-a] pyridyl, imidazo [
  • Aryl mononuclear or polynuclear aromatic carbocycle, eg. B. mono- to binuclear or mono- to trinuclear aromatic carbocycle having 6 to 14 ring members, such as. As phenyl, naphthyl or anthracenyl.
  • Arylalkyl an aryl radical bonded via an alkylene group, especially via a methylene, 1,1-ethylene or 1,2-ethylene group, e.g. Benzyl, 1-phenylethyl and 2-phenylethyl.
  • Phenylalkenyl a phenyl radical bound via an alkenylene group, in particular via a 1, 1-ethenylene group (vinylidene) or 1, 2-ethenylene group, for example 1-styryl and 2-styryl.
  • Phenylalkynyl a phenyl radical bonded via an alkynylene group, in particular via a 1, 2-ethynylene group.
  • Heterocyclylalkyl and hetarylalkyl a heterocyclyl or hetaryl radical bonded via an alkylene group, in particular via a methylene, 1, 1-ethylene or 1, 2-ethylene group.
  • Heterocyclylalkenyl and hetarylalkenyl a terocyclyl or hetaryl radical bonded via an alkenylene group, in particular via a 1, 1-ethenylene group (vinylidene) or 1, 2-ethenylene group.
  • Heterocyclylalkinyl and hetarylalkynyl a heterocyclyl or hetaryl radical bonded via an alkynylene group, in particular via a 1, 2-ethynylene group.
  • variables of the compounds of the formula I have the following meanings, these being considered both individually and in combination with one another in particular embodiments of the compounds of the formula I:
  • a 1 and A 2 are independently selected from the group phenyl, furyl, thienyl and pyridinyl.
  • a 1 is phenyl or pyridinyl.
  • a 2 is phenyl or thienyl.
  • Y 1 and Y 2 are in particular O.
  • a particularly preferred embodiment of the invention relates to compounds of the formula I and their salts, in which A 1 and A 2 are each phenyl. Of these, preferred compounds are those in which Y 1 and Y 2 are O. These compounds are also referred to below as compounds of the formula I ':
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R a , R b , R c , R d , R e and R f have one of the abovementioned Meanings and in particular one of the meanings mentioned below as preferred.
  • R 11 is hydrogen, C 1 -C 6 -alkyl, hydroxy, C 1 -C 6 -alkoxy, C 3 -C 6 -alkenyloxy,
  • C 3 -C 6 -alkynyloxy amino, C 1 -C 6 -alkylamino, [di (C 1 -C 6) -alkyl] amino, C 1 -C 6 -alkoxyamino, N-C 1 -C 6 -alkoxy-N-C 1 -C 6 -alkylamino , C 1 -C 6 -alkylsulfonylamino, C 1 -C 6 -alkylaminosulfonylamino, [di (C 1 -C 6) -alkylamino] sulfonylamino, phenyl, phenoxy, phenylamino, naphthyl or heterocyclyl, and
  • the said aliphatic, cyclic or aromatic parts of the substituent R 11 may be partially or completely halogenated.
  • R a is in particular cyano, nitro or a 5- or 6-membered heteroaromatic radical as defined above, which preferably has either 1, 2 or 3 nitrogen atoms or 1 oxygen or 1 sulfur atom and optionally 1 or 2 nitrogen atoms as ring members and which is unsubstituted or may have 1 or 2 of the aforementioned substituents.
  • R a is cyano or nitro.
  • R a is a 5- or 6-membered heteroaromatic radical as defined above, which preferably has either 1, 2, 3 or 4 nitrogen atoms or 1 oxygen or 1 sulfur atom and optionally 1 or 2 nitrogen atoms has as ring members and which is unsubstituted or may have 1 or 2 of the aforementioned substituents.
  • heteroaromatic radicals are pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazine-2-yl, 2-furyl, 3 Furyl, 2-thienyl, 3-thienyl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazole-3 yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, Thiazol-2-yl, thiazol-4-yl and thiazol
  • R a is halogen and in particular chlorine or bromine.
  • R b is selected in the compounds of formula I selected from hydrogen, halogen, nitro, cyano, Ci -C4 -alkyl, Ci-C 4 haloalkyl, C 2 -C 4 alkenyl, Ci-C 4 alkoxy, C 1 -C 4 -haloalkoxy, benzyl or a group S (O) n R 21 , in which R 21 is C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl and n is 0, 1 or 2; and
  • R b is particularly preferably hydrogen, fluorine, chlorine, C 1 -C 2 -alkyl,
  • R b is in particular hydrogen, fluorine or chlorine.
  • R b is halogen, in particular chlorine or fluorine, which is arranged in the ortho position to the binding site of the phenyl ring.
  • R c in the compounds of the formula I is preferably hydrogen or halogen, in particular chlorine or fluorine.
  • R c is hydrogen
  • R d and R e are preferred to the compounds of formula I are independently selected from hydrogen, halogen, CN, NO2, Ci-C4-alkyl, Ci-C4 haloalkyl, C2-C 4 alkenyl, C 4 -alkoxy and Ci-C 4 -haloalkoxy.
  • R d is a radical other than hydrogen
  • R d is a radical different from hydrogen
  • R d is hydrogen.
  • R e in the compounds of general formula I is preferably hydrogen.
  • R f in the compounds of general formula I is preferably hydrogen.
  • a particularly preferred embodiment of the invention relates to compounds of the formula I 'and their salts, in which R b is arranged in the ortho position to the point of attachment of the phenyl ring, R c is arranged in the para position to the group R a , R d in para position to Group CR 7 R 8 is arranged and R e and R f are each hydrogen.
  • R b is arranged in the ortho position to the point of attachment of the phenyl ring
  • R c is arranged in the para position to the group R a
  • R d in para position to Group CR 7 R 8 is arranged and
  • R e and R f are each hydrogen.
  • preferred compounds are those in which Y 1 and Y 2 are O.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R a , R b , R c and R d have one of the meanings mentioned above or below as being preferred.
  • R 1 in the compounds of the formula I is selected from hydrogen, C 1 -C 6 -alkyl and C 1 -C 6 -alkylcarbonyl.
  • R 1 is hydrogen or methyl.
  • R 2 in the compounds of the formula I is preferably selected from C 1 -C 6 -alkyl and C 1 -C 6 -alkylcarbonyl.
  • R 2 is methyl.
  • R 3 in the compounds of formula I is R 26 or OR 27 , wherein R 26 and R 27 are independently selected from hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkylcarbonyl, phenyl-C 1 -C 6 -alkyl, phenylcarbonyl, wherein said aliphatic or aromatic moieties of the substituents may be partially or fully halogenated , or a group SO 2 R 33 , wherein R 33 is C 1 -C 6 -alkyl or phenyl, and wherein the phenyl substituent may be partially or completely halogenated and / or may carry one to three C 1 -C 6 -alkyl groups.
  • R 3 in the compounds of general formula I is hydrogen, C 1 -C 6 -alkyl, phenyl-C 1 -C 6 -alkoxy or C 1 -C 6 -alkylsulfonyl. Most preferably, R 3 is hydrogen.
  • R 4 in the compounds of general formula I is preferably hydrogen.
  • R 5 in the compounds of general formula I is preferably hydrogen, hydroxy or C 1 -C 6 -alkyl and in particular methyl or hydroxy.
  • a preferred embodiment of the invention relates to compounds of the general formula I in which R 3 together with R 5 represents a chemical bond. These compounds are described by the following formula IA:
  • a 1 , A 2 , R 1 , R 2 , R 4 , R 6 , R 7 , R 8 , R a , R b , R c , R d , R e and R f have one of the meanings given above and in particular one of the meanings mentioned above or below as being preferred.
  • compounds having the features of the general formula I ' are particularly preferred (compounds of the formula I'-A).
  • R 1 , R 2 , R 4 , R 6 , R 7 , R 8 , R a , R b , R c , R d , R e and R f have one of the meanings given above and in particular one the meanings mentioned above or below as being preferred.
  • R 1 , R 2 , R 4 , R 6 , R 7 , R 8 , R a , R b , R c and R d preferably have one of the meanings mentioned above or below as being preferred.
  • the 6-position of the piperazine ring ie in the position which carries the radical R 6 , has a center of chirality.
  • the compounds of the formula IS are preferred over their enantiomer IR:
  • a 1 , A 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R a , R b , R c , R d , R have one of the abovementioned meanings and in particular one of the meanings mentioned above or below as being preferred.
  • mixtures of the compound IS with the compound IR in which the compound IS is present in excess, in particular mixtures having an IS to IR ratio of at least 2: 1, in particular at least 5: 1.
  • mixtures with a smaller ratio of IS to IR for example racemic mixtures.
  • Another embodiment of the invention relates to compounds of the formula I in which R 5 is not together with R 3 a chemical bond. These compounds are also referred to below as compounds IB.
  • Preferred among these are those compounds of the formula IB in which the benzylic groups at the 3- and the 6-position have a cis arrangement with respect to the piperazine ring, ie usually the S, S enantiomer (S 1 S) -IB and the R , R-enantiomer (R 1 R) -IB and mixtures thereof. Also preferred are mixtures of the cis compound (s) with the trans compound (s) wherein the cis compound (s) is in excess (s), especially cis / trans mixtures having a cis / trans ratio , of at least 2: 1, in particular at least 5: 1.
  • a particularly preferred embodiment of the invention relates to the enantiomer of the formula (S 1 S) -IB, and enantiomeric mixtures and diastereomeric mixtures of IB in which the enantiomer (S 1 S) -IB is the main constituent and preferably at least 70%, in particular at least 80% and especially at least 90% of compound IB. Also preferred are the agriculturally suitable salts of the enantiomeric mixtures (S 1 S) -IB and mixtures of enantiomers and mixtures of diastereomers of the salts, wherein the enantiomer (S 1 S) -IB is the main constituent and preferably at least 70%, in particular at least 80% and especially at least 90% of compound IB. Another, equally preferred embodiment relates to a racemic mixture of the enantiomer (S 1 S) -IB with the enantiomer (R 1 R) -IB.
  • a preferred embodiment of the compounds I-B are the compounds of the formula I'-B shown below:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R a , R b , R c , R d , R e and R f have one of abovementioned meanings and in particular one of the meanings mentioned above or below as being preferred, wherein R 5 does not signify, together with R 3, a chemical bond.
  • R d and R e are hydrogen and which, with respect to the substituents R b , R c and R d have the substitution pattern given for formula Ia.
  • These compounds are also referred to below as compounds of the formula IB.a:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R a , R b , R c and R d preferably have one of the above or below preferred meanings, wherein R 5 does not mean together with R 3 is a chemical bond.
  • salt of the S, S-enantiomer is a major constituent and preferably constitutes at least 70%, in particular at least 80% and especially at least 90% of the salt of IB.a.
  • Another, equally preferred embodiment relates to a racemic mixture of the S, S-enantiomer (S 1 S) -I-Ba with the R, R-enantiomer (R, R) -IB. a.
  • R 6 is in the compounds of the formula I, or in the compounds of the formulas La, I'-A, IA.a, I'-B or IB.a, preferably halogen, cyano, nitro, C 2 -C 8- alkenyl, C 2 -C 8 -alkynyl or C (O) R 61 , wherein R 61 has the meanings given above.
  • R 61 is C 1 -C 6 -alkyl or C 1 -C 6 -haloalkyl.
  • R 7 and R 8 are in the compounds of the general formula I, or in the compounds of the formulas la, I'-A, IA.a, I'-B or IB.a, preferably for hydrogen.
  • a specific embodiment of the invention relates to compounds of the general formula I in which R 1, together with the radical R 2 , denotes a 1-, 2-, 3- or 4-membered carbon chain in which a carbon atom is replaced by O, S or a group NR A wherein one of the carbon atoms can carry a carbonyl oxygen atom and / or wherein the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C 4 -AlkVl, Ci-C4-haloalkyl, CrC 4 -Akoxy , Ci-C 4 -Halogen alkoxy can carry selected radicals.
  • R 1 with the radical R 2 is preferably CH 2 or CH 2 CH 2 .
  • R 1 together with the radical R 5 is a 1-, 2-, 3- or 4-membered carbon chain, in which a carbon atom is represented by O, S or a group NR A may be replaced, wherein one of the carbon atoms is a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, CrC 4 -alkoxy, C1-C4-haloalkoxy can carry selected radicals , Preferred herein are compounds according to claim 24, wherein R 1 is the radical R 5 for CH 2 or CH 2 CH 2.
  • Another specific embodiment of the invention relates to compounds of the general formula I in which R 1 is taken together with a radical R d which is bonded in the ortho position to the point of attachment of A 2 to a C atom or N atom of A 2 , a covalent bond or a 1-, 2-, 3- or 4-membered carbon chain, wherein a carbon atom may be replaced by O, S or a group NR B , wherein one of the carbon atoms may carry a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy,
  • Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy can carry selected radicals.
  • R 1 together with the radical R d preferably stands for a covalent bond, CH 2 or CH 2 CH 2 .
  • the groups A 1 , A 2 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R a , R b , R c , R e , R f , Y 1 and Y 2 have herein is one of the meanings given above, in particular one of the meanings given above as being preferred.
  • a further specific embodiment of the invention relates to compounds of the general formula I in which R 1 together with an R 8 radical is a 2-, 3- or 4-membered carbon chain in which a carbon atom may be replaced by O, S or a group NR C in which one of the carbon atoms can carry a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1 -C4 haloalkoxy can carry selected radicals.
  • R 1 together with the radical R 8 is preferably CH 2 CH 2 or CH 2 CH 2 CH 2 .
  • a further specific embodiment of the invention relates to compounds of the general formula I in which R 1 together with an R 6 radical is a 3-, 4- or 5-membered carbon chain in which a carbon atom is replaced by O, S or a group NR D wherein one of the carbon atoms can carry a carbonyl oxygen atom and / or wherein the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy .
  • Ci-C4-haloalkoxy can carry selected radicals.
  • R 1 herein together with the radical R 6 is CH 2 CH 2 CH 2 or CH 2 CH 2 CH 2 CH 2 CH 2 in which 1, 2, 3 or 4 of the hydrogen atoms may be replaced by radicals selected from halogen, cyano, ano, hydroxy, Ci-C 4 -alkyl, Ci-C4-haloalkyl, -C 4 -alkoxy and Ci-C 4 are selected haloalkoxy.
  • a further specific embodiment of the invention relates to compounds of the general formula I in which R 3 together with the radical R 5 denotes a 1-, 2-, 3- or 4-membered carbon chain, in which a carbon atom is represented by O, S or a group may be replaced NR 1, wherein one of the carbon atoms may carry a carbonyl oxygen and / or wherein the carbon atoms in addition to hydrogen is 1, 2, 3 or 4 halo, cyano, hydroxy, Ci-C4-alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy can carry selected radicals.
  • R 3 with the radical R 5 is preferably CH 2 , O or a group NR 1 , in which R 1 is hydrogen or C 1 -C 4 -alkyl.
  • the groups A 1 , A 2 , R 1 , R 2 , R 4 , R 6 , R 7 , R 8 , R a , R b , R c , R d , R e , R f , Y 1 and Y 2 have herein is one of the meanings given above, in particular one of the meanings previously given preference.
  • a further specific embodiment of the invention relates to compounds of the general formula I in which R 3 together with the radical R 4 is a 2-, 3-, 4- or 5-membered carbon chain, in which a carbon atom is represented by O, S or a group NR K may be replaced with one of the carbon atoms may carry a carbonyl oxygen and / or wherein the carbon atoms in addition to hydrogen is 1, 2, 3 or 4 halo, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci- C 4 alkoxy, Ci-C 4 haloalkoxy can carry selected radicals.
  • R 3 with the radical R 4 is preferably CH 2 CH 2 , CH 2 CH 2 CH 2 or CH 2 CH 2 CH 2 CH 2 , in which 1, 2, 3 or 4 of the hydrogen atoms may be replaced by radicals which are substituted under halogen, cyano, hydro- xy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy are selected.
  • a further specific embodiment of the invention relates to compounds of the general formula I in which R 4 together with the radical R a denotes a 2-, 3-, 4- or 5-membered carbon chain, in which a carbon atom is represented by O, S or a group NR L may be substituted, wherein one of the carbon atoms can carry a carbonyl oxygen atom and / or wherein the carbon atoms in addition to hydrogen 1, 2, 3 or 4 below Halogen, cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -halo-genoalkoxy can carry selected radicals.
  • R 4 together with the radical R a is preferably C (O) NR L or C (O) O, where R L is hydrogen or C 1 -C 4 -alkyl.
  • the groups A 1 , A 2 , R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 , R b , R c , R d , R e , R f , Y 1 and Y 2 have here in one of the previously given meanings, in particular one of the meanings given above as preferred on.
  • a further specific embodiment of the invention relates to compounds of general formula I wherein R 5 together with the radical R a is a 2-, 3-, 4- or 5-membered carbon chain in which one carbon atom replaced by O, S or a group NR M wherein one of the carbon atoms can carry a carbonyl oxygen atom and / or wherein the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, CrC 4 -Akoxy , Ci-C 4 haloalkoxy can carry selected radicals.
  • R 5 with the radical R a is preferably CH 2 CH 2 or CH 2 CH 2 CH 2 .
  • Another specific embodiment of the invention relates to compounds of general formula I, wherein R 5 together with the radical R 6 is a 1-, 2-, 3-, 4- or
  • 5-membered carbon chain in which a carbon atom can be replaced by O, S or a group NR N , where one of the carbon atoms can carry a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, can carry 4 -haloalkoxy radicals selected from hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C.
  • R 5 together with the radical R 6 is CH 2 or CH 2 CH 2 .
  • Another specific embodiment of the invention relates to compounds of the general formula I in which R 6, together with a radical R d , which is bonded in the ortho position to the point of attachment of A 2 to a C atom or N atom of A 2 , a 1-, 2-, 3- or 4-membered carbon chain, in which a carbon atom can be replaced by O, S or a group NR °, where one of the carbon atoms can carry a carbonyl oxygen atom and / or wherein the carbon atoms in addition to hydrogen 1 , 2, 3 or 4 can carry 4 haloalkoxy groups selected from halogen, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C.
  • R 6 together with the radical R d is CH 2 or CH 2 CH 2 .
  • the groups A 1 , A 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R a , R b , R c , R e , R f , Y 1 and Y 2 have hereinbefore one of the above Meanings, in particular one of the previously given as preferred meanings on.
  • a further specific embodiment of the invention relates to compounds of the general formula I in which R 6 together with a radical R 7 denotes a 1-, 2-, 3- or 4-membered carbon chain, in which a carbon atom is represented by O, S or a group NR Q can be replaced, wherein one of the carbon atoms can carry a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2,
  • R 6 is the radical R 7 is CH 2, O or a group NR Q , wherein R Q is hydrogen or C 1 -C 4 -alkyl.
  • R 7 together with the radical R 8 is a 2-, 3-, 4- or 5-membered carbon chain, in which a carbon atom is represented by O, S or a group NR R wherein one of the carbon atoms may carry a carbonyl oxygen atom and / or in which the carbon atoms in addition to hydrogen 1, 2, 3 or 4 under halogen, cyano, hydroxy, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4- Alkoxy, C1-C4-haloalkoxy can carry selected radicals.
  • R 7 together with the radical R 8 is preferably CH 2 CH 2 , CH 2 CH 2 CH 2 or CH 2 CH 2 CH 2 CH 2 in which 1, 2, 3 or
  • 4 of the hydrogen atoms may be replaced by radicals selected from halogen, cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy.
  • the groups A 1 , A 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R a , R b , R c , R d , R e , R f , Y 1 and Y 2 have herein is one of the meanings given above, in particular one of the meanings previously given preference.
  • R 8 is in common with a radical R d which is bonded in the ortho position to the point of attachment of A 2 to a C atom or N atom of A 2 represents a 2-, 3-, 4- or 5-membered carbon chain, wherein a carbon atom may be replaced by O, S or a group NR S , wherein one of the carbon atoms may carry a carbonyl oxygen atom and / or wherein the carbon atoms besides hydrogen 1, 2, 3 or 4 under cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy may carry selected radicals.
  • R 8 together with the radical R d here preferably stands for C (O) NR S or C (O) O, in which R s is hydrogen or C 1 -C 4 -alkyl.
  • the groups A 1 , A 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R a , R b , R c , R e , R f , Y 1 and Y 2 herein have any of the meanings given above, in particular one of the above as preferred given meanings on.
  • Table 21 Compounds of the formula IA.a '(Compounds IA.A'.44O1 to IA.A'.462O), in which R a is 4-methyloxazol-2-yl, R d is hydrogen and the combination of R b , R c , R 1 and R 6 for a compound corresponds in each case to one row of Table A.
  • Table 45 Compounds of the formula IB.a '(compounds IB.a'.1 to lB.a'.22O) in which R a is CN, R d is hydrogen and the combination of R b , R c , R 1 and R 6 for a compound corresponds in each case to one row of Table A.
  • Table 85 Compounds of the formula IB.a '(compounds Ib.a'.88O1 to Ib.a'.9O2O), in which R a is pyrazine-2-yl, R d is hydrogen and the combination of R b , R c , R 1 and R 6 for a compound corresponds in each case to one row of Table A.
  • the compounds I according to the invention can be prepared by standard methods of organic chemistry. By way of example, some methods are shown below.
  • R X represents a suitable oxygen-linked leaving group.
  • R x is, for example, C 1 -C 6 -alkyl, in particular methyl, ethyl or phenyl-C 1 -C 6 -alkyl, for example benzyl.
  • the cyclization can be effected, for example, by reacting a dipeptide of the formula II, either in the presence of acid or base (acidic or basic cyclization) or by heating the reaction mixture (thermal cycloaddition).
  • bases or acids are used either in equimolar amounts to dipeptide II or in excess. In a particular embodiment of the method according to the invention, the bases or acids are used in an excess relative to the dipeptide.
  • the reaction of the dipeptide II in the presence of a base is usually carried out at temperatures in the range of 0 0 C and the boiling point of the reaction mixture, preferably from 10 0 C to 50 0 C, particularly preferably from 15 ° C to 35 ° C.
  • the reaction is carried out in a solvent, preferably in an inert organic solvent.
  • Suitable inert organic solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs-alkanes, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n Butanol,
  • reaction is carried out in a tetrahydrofuran / water mixture, for example with a mixing ratio of 1:10 to 10: 1 (parts by volume).
  • Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, aqueous solution of ammonia, alkali metal or alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, for example lithium diisopropylamide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, cesium carbonate and calcium carbonate and alkali metal hydrogen carbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and alkali metal and
  • tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, 2-hydroxypyridine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration.
  • a mixture of different bases can be used.
  • the reaction of II is carried out in the presence of bases, preferably in the presence of the bases potassium tert-butoxide, 2-hydroxypyridine or an aqueous solution of ammonia or a mixture of these bases. Preferably, only one of these bases is used. In a particularly preferred embodiment, the reaction is carried out in the presence of an aqueous solution of ammonia, which may for example be from 10 to 50 w / v%.
  • the reaction of II in the presence of an acid is usually carried out at temperatures in the range of 10 0 C to the boiling point of the reaction mixture, preferably from 50 0 C to the boiling point, particularly preferably at the boiling point under reflux.
  • the reaction is carried out in a solvent, preferably in an inert organic solvent.
  • Suitable solvents are, in principle, those which can also be used for the basic cyclization, in particular alcohols. In a preferred embodiment, the reaction is carried out in n-butanol.
  • acids for the cyclization of Il are in principle both Brönstedt and Lewis acids into consideration.
  • inorganic acids for example hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, inorganic oxo acids such as sulfuric acid and perchloric acid, furthermore inorganic Lewis acids such as boron trifluoride, aluminum trichloride, iron (III) chloride, tin (IV) chloride, titanium (IV) chloride and zinc (II) chloride, and organic acids, for example carboxylic acids and hydroxycarboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid, and organic sulfonic acids such as toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid and the like, find use.
  • hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid
  • inorganic oxo acids such as sulfuric acid and perchloric acid
  • the reaction is carried out in the presence of organic acids, for example in the presence of carboxylic acids such as formic acid, acetic acid or trifluoroacetic acid or a mixture of these acids. Preferably, only one of these acids is used. In a preferred embodiment, the reaction is carried out in acetic acid.
  • a particularly preferred embodiment of the acidic cyclization is carried out in the presence of n-butanol, N-methyl-morpholine and acetic acid under reflux conditions.
  • the reaction is carried out exclusively by heating the reaction mixture (thermal cyclization).
  • the reaction is usually carried out at temperatures in the range of 10 ° C and the boiling point of the reaction mixture, preferably from 50 ° C and the boiling point of the reaction mixture, particularly preferably at the boiling point of the reaction mixture under reflux.
  • the reaction is carried out in a solvent, preferably in an inert organic solvent.
  • Suitable solvents are, in principle, those used in the basic cilsilation. Preferred are polar aprotic solvents, e.g. Dimethyl sulfoxide or dimethylformamide or mixtures thereof. In a preferred embodiment, the reaction is carried out in dimethyl sulfoxide.
  • the reaction mixtures obtained by one of the processes A according to the invention can, for example, be worked up in the customary manner. This can be done, for example, by mixing with water, separating the phases and, if appropriate, chromatographic purification of the Crude products take place.
  • Some of the intermediate and end products are in the form of viscous oils, which can generally be freed or purified from volatile constituents under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.
  • X 1 is halogen or O-SO 2 -R m , in which R m is C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy or aryl, which is optionally substituted by halogen, C 1 -C 4 -alkyl or Ci-C4-haloalkyl are substituted.
  • acylating agents X 2 -R 1 X 2 may be halogen, in particular Cl.
  • R 1 is different from hydrogen and has one of the meanings mentioned above.
  • the reaction is usually carried out at temperatures in the range of -78 ° C to the boiling point of the reaction mixture, preferably from -50 0 C to 65 ° C, particularly preferably from -30 0 C to 65 ° C.
  • the reaction is carried out in a solvent, preferably in an inert organic solvent.
  • Suitable solvents are the compounds cited under process A, inter alia toluene, dichloromethane, tetrahydrofuran or dimethylformamide or mixtures thereof.
  • the reaction is carried out in tetrahydrofuran.
  • compound I wherein R 1 is hydrogen is reacted with the alkylating or acylating agent in the presence of a base.
  • Suitable bases are the compounds mentioned under method A.
  • the bases are generally used equimolar. They can also be used in excess or as a solvent.
  • the base is added in equimolar amount or in substantially equimolar amount.
  • sodium hydride is used as the base.
  • the work-up is generally carried out in analogy to the procedure described under process A.
  • process C compounds of the formula I in which Y 1 and Y 2 are O and R 2 is hydrogen can be reacted with alkylating agents R 2 -X 1 or acylating agents R 2 -X 2 in which compounds of the formula I in which R 2 has a meaning other than hydrogen (process C).
  • the reaction conditions of process C according to the invention correspond to those of process B.
  • the compounds of the formula I can also be modified on the group R a .
  • R a is CN, optionally substituted phenyl or an optionally substituted heterocyclic radical, starting from compounds I in which R a is halogen, such as chlorine, bromine or iodine, by Conversion of the substituent R a are prepared, for example in analogy to those of J. Tsuji, Top. Organomet. Chem. (14) (2005), 332 pp., J. Tsuji, Organic Synthesis with Palladium Compounds, (1980), 207 et seq., Tetrahedron Lett. 42, 2001, p. 7473 or Org. Lett. 5, 2003, 1785.
  • a piperazine compound of the formula I- ⁇ L ⁇ which has a suitable leaving group L instead of the substituent R a , by reaction with a coupling partner containing a group R a (compound R a -X 3 ), in another Piperazinderivat of Formula I transferred.
  • the reaction is usually carried out in the presence of a catalyst, preferably in the presence of a transition metal catalyst. In general, the reaction takes place in the presence of a base.
  • Suitable coupling partners X 3 -R a are, in particular, those compounds in which X 3 in the case of R a in the meaning of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, aryl or heteroaryl represents one of the following groups:
  • Zn-R 1 with R 1 in the meaning of halogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, aryl or heteroaryl;
  • R a is C 2 -C 6 -alkynyl
  • X 3 may also be hydrogen.
  • L or R a in the compounds of the formula I are bonded in the ortho position to the point of attachment of A 1 to a C atom of A 1 .
  • This reaction is usually carried out at temperatures in the range of -78 ° C and the boiling point of the reaction mixture, preferably from -30 0 C to 65 ° C, particularly preferably at temperatures of 30 0 C to 65 ° C.
  • the reaction is carried out in an inert organic solvent in the presence of a base.
  • Suitable solvents are the compounds cited under method A.
  • tetrahydrofuran is used with a catalytic amount of water; In another embodiment, only tetrahydrofuran is used.
  • Suitable bases are the compounds mentioned in the cyclization of dipeptide VIII to piperazine IV.
  • the bases are generally used equimolar. They can also be used in excess or even as a solvent.
  • the base is added in equimolar amount.
  • triethylamine or cesium carbonate are used as the base, particularly preferably cesium carbonate.
  • compounds of the transition metals Ni, Fe, Pd, Pt, Zr or Cu are suitable as catalysts for the process according to the invention. It is possible to use organic or inorganic compounds. Examples include: Pd (PPh 3 ) 2 Cl 2 , Pd (OAc) 2 , PdCl 2 , or Na 2 PdCl 4 . Ph stands for phenyl.
  • the various catalysts can be used both individually and as mixtures.
  • Pd (PPhi3) 2 Cl 2 is used.
  • the compound I in which R a is CN can also be reacted with copper cyanide analogously to known processes (see, for example, Organikum, 21st Edition, 2001, Wiley , S. 404, Tetrahedron Lett. 42, 2001, p. 7473 or Org. Lett. 5, 2003, 1785 and literature cited therein).
  • reaction are usually carried out at temperatures in the range of 100 0 C to the boiling point of the reaction mixture, preferably from 100 0 C to 250 ° C.
  • the reaction is carried out in an inert organic solvent.
  • Suitable solvents are in particular aprotic polar solvents, for example dimethylformamide, N-methylpyrrolidone, N, N'-dimethylimidazolidin-2-one and dimethylacetamide.
  • the conversion of the group R a can alternatively be carried out in the precursors of the compound I.
  • the workup can be carried out analogously to the procedure described in process A.
  • Piperazine compounds of the formula I in which Y 1 and Y 2 are O and one of the groups R a , R b or R c is COOH can furthermore be prepared from piperazine compound of the formula I in which R a , R b or R c for COOR 11b with R 11b in the meaning of alkyl, for example CH 3 , is prepared by saponification of the ester group. Saponification is possible, for example, by reaction with (H3C) 3SnOH, for example according to KC Nicolaou et al., Angew. Chem. Int. Ed. Engl. (44) (2005), 1378.
  • the carboxylic acid thus obtained can then by standard methods of organic synthesis, optionally after conversion into the acid chloride, by reaction with an amine HNR U R V or an alcohol HOR W in the corresponding ester or Amide are transferred Organikum, author collective, Leipzig 1993, 19th edition, p 424, 429.
  • This reaction sequence is shown below the example of the substituent R a and can of course be used in an analogous manner for the conversion of the substituents R b and R c ,
  • Step 1
  • R u and R v are each independently hydrogen, d-Ce-alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkyl kinyl, Ci-C 6 alkoxy, Ci-C 6 alkylsulfonyl, C C 6 -alkylaminosulfonyl, [di- (C 1 -C 6 ) -alkylamino] sulfonyl or optionally substituted phenyl.
  • R w represents Ci -C 6 -alkyl, C 3 -C 6 alkenyl or C 3 -C 6 -alkyl kinyl.
  • the reaction to the free acid is usually carried out with an excess of (H 3 C) 3 SnOH.
  • the reaction is carried out in an inert organic solvent.
  • suitable solvents is especially dichloroethane.
  • the reaction takes place at elevated temperature, for example at about 80 ° C.
  • the conversion to the acid chloride is carried out, usually at temperatures from 10 0 C to 50 ° C, preferably at room temperature, for example 25 ° C.
  • the reaction is carried out in an inert organic solvent.
  • suitable solvents is in particular dichloromethane.
  • the reaction is carried out in dichloromethane and catalytic amounts of dimethylformamide.
  • Suitable for the chlorination a variety of reagents, such as oxalyl chloride or thionyl chloride. It will be preferred in the sentlichen equimolar amounts of the chlorinating reagent, in particular Oxalylchlo- rid used.
  • the reaction with an amine NHR U R V in the subsequent reaction is usually carried out by adding an excess of the respective amine.
  • the reaction may be carried out in a temperature range of 0 0 C to 40 0 C, preferably at room temperature, for example 25 ° C.
  • the reaction with an alcohol HOR W in the subsequent reaction is usually carried out by adding an excess of both the respective alcohol and triethylamine.
  • the reaction may be carried out in a temperature range of 0 0 C to 40 0 C, preferably at room temperature, for example 25 ° C.
  • the workup can be carried out analogously to the procedure described in process A.
  • a 1 , A 2 , R 1 to R 8 , R a , R b , R c R d , R e and R f have one of the meanings given above.
  • L is a suitable leaving group, such as halogen or
  • the reaction takes place at temperatures in the range of -78 ° C to the boiling point of the reaction mixture, preferably in the range of -78 ° C to 40 0 C, particularly preferably in the range of -78 ° C to 30 0 C.
  • reaction is carried out in an inert organic solvent in the presence of a base.
  • Suitable solvents are the compounds cited under method A.
  • tetrahydrofuran is used.
  • Suitable bases are the compounds cited under Method A.
  • lithium diisopropylamide particularly preferably in substantially equimolar amount, in particular equimolar, is used as the base.
  • the work-up can be carried out in analogy to the procedure described in process A.
  • the dipeptide compounds of the formula II can be prepared, for example, from N-protected dipeptides of the general formula VI in analogy to literature processes, for example according to Glenn L. Stahl et al., J. Org. Chem. 43 (11), ( 1978), 2285-6 or AK Ghosh et al., Org. Lett. 3 (4), (2001), 635-638.
  • the reaction is usually carried out at temperatures in the range of -30 0 C and the boiling point of the reaction mixture, preferably from 0 0 C to 50 0 C, particularly preferably from 20 ° C to 35 ° C.
  • reaction can take place in a solvent, especially in an inert organic solvent.
  • Suitable solvents are, in principle, the compounds cited in the basic cyclization, in particular tetrahydrofuran or
  • dichloromethane or mixtures thereof. In a preferred embodiment, the reaction is carried out in dichloromethane.
  • the acids used are the acids cited in process A.
  • the reaction is carried out in the presence of organic acids, for example in the presence of strong organic acids, such as formic acid, acetic acid or trifluoroacetic acid or mixtures thereof.
  • organic acids for example in the presence of strong organic acids, such as formic acid, acetic acid or trifluoroacetic acid or mixtures thereof.
  • the reaction is carried out in the presence of trifluoroacetic acid.
  • the workup can be carried out analogously to the procedure described in process A.
  • the protected dipeptides of the formula VI can be prepared in analogy to literature methods known, for example, according to Wilford L. Mendelson et al., Int. J. Peptide & Protein Research 35 (3), (1990), 249-57.
  • reaction of VII with VIII is carried out at temperatures in a range from -30 0 C to the boiling point of the reaction mixture, preferably from 0 0 C to 50 0 C, particularly preferably from 20 ° C to 35 ° C.
  • the reaction may be carried out in a solvent, preferably in an inert organic solvent. Suitable solvents are those mentioned in process A, in connection with the basic cyclization.
  • activating reagents are condensing agents, e.g. polystyrene- or non-polystyrene-bonded dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide, 1-ethyl-3- (dimethylaminopropyl) carbodiimide (EDAC), carbonyldiimidazole, chloroformate such as methyl chloroformate, ethyl chloroformate, isopropyl chloroformate, isobutyl chloroformate, sec-butyl chloroformate or allyl chloroformate, pivaloyl chloride, polyphosphoric acid, Propanephosphonic anhydride, bis (2-oxo-3-oxazolidinyl) - phosphoryl chloride (BOPCI) or sulfonyl chlorides such as methanesulfonyl chloride,
  • DCC polystyrene- or non-polys
  • HATU O- (7-azabenzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate
  • preferred activating reagents are EDAC or DCC.
  • Suitable bases are the compounds cited under Method A.
  • the base used is triethylamine or N-ethyldiisopropylamine or mixtures thereof, particularly preferably N-ethyldiisopropylamine.
  • the workup can be carried out analogously to the procedure described in process A.
  • the compounds of formula VII can in turn be prepared by deprotection of corresponding protected amino acid compounds IX in analogy to literature methods, for example according to Glenn L. Stahl et al., J. Org. Chem. 43 (11), (1978), 2285- 6th or AK Ghosh et al., Org. Lett. 3 (4), (2001), 635-638.
  • the preparation of VII from a Boc-protected amino acid compound IX is shown in the following scheme. Instead of the Boc group, other amino protecting groups can also be used.
  • the reaction of a compound of the formula IX to the compound VII is carried out typically in the presence of an acid at temperatures in a range from -30 0 C to the boiling point of the reaction mixture, preferably from 0 0 C to 50 0 C, particularly preferably from 20 ° C up to 35 ° C.
  • the reaction may be carried out in a solvent, preferably in an inert organic solvent.
  • Suitable solvents are, in principle, the compounds cited under the basic cyclization, in particular tetrahydrofuran or dichloromethane or mixtures thereof. In a preferred embodiment, the reaction is carried out in dichloromethane.
  • the acids and acid catalysts used are the substances cited in Process A.
  • the reaction is carried out in the presence of organic acids, for example in the presence of strong organic acids, such as formic acid, acetic acid or trifluoroacetic acid or mixtures thereof.
  • organic acids for example in the presence of strong organic acids, such as formic acid, acetic acid or trifluoroacetic acid or mixtures thereof.
  • the reaction is carried out in the presence of trifluoroacetic acid.
  • the workup can be carried out analogously to the procedure described in process A.
  • the compounds of formula IX can be prepared according to the reaction shown in the following scheme.
  • the reaction of compound V with the protected amino acid compound X can be carried out in analogy to literature known methods, for example, according to I. Ojima et al., J. Am. Chem. Soc., 109 (21), (1987), 6537-6538 or JM McIntosh et al., Tetrahedron 48 (30), (1992), 6219-6224.
  • L represents a leaving group, for example one of the leaving groups mentioned in process F.
  • Boc other amino-protecting groups can also be used.
  • the reaction of V with X is usually carried out in the presence of base.
  • bases are the compounds cited under Method A.
  • lithium diisopropylamide particularly preferably in substantially equimolar amount, in particular equimolar, is used as the base.
  • the reaction is carried out at temperatures in the range of -78 ° C and the boiling point of the reaction mixture, preferably from -78 ° C and the boiling point, more preferably from -78 ° C to 30 0 C.
  • the reaction may be carried out in a solvent, preferably in an inert organic solvent.
  • Suitable solvents are, in principle, the solvents mentioned under the basic cyclization, in particular dichloromethane or tetrahydrofuran or mixtures thereof.
  • the reaction is carried out in tetrahydrofuran.
  • the workup can be carried out analogously to the procedure described in process A.
  • Some compounds of the formula V are commercially available or can be prepared by literature-specific transformations of the corresponding commercially available precursors.
  • Amino acid derivatives of the formula VIII, X or the derivative XV described below are also commercially available in part or can be prepared by literature-described transformations of the corresponding commercially available precursors.
  • the compounds of the formula IV in which R 1 has a meaning other than hydrogen can be prepared by reacting a piperazine compound of the formula IV in which R 1 is hydrogen with an alkylating agent or acylating agent which is the radical other than hydrogen R 1 contains, implemented.
  • compounds of the formula IV in which R 2 has a meaning other than hydrogen can be prepared by reacting a piperazine compound of the formula IV in which R 2 is hydrogen with an alkylating agent or acylating agent which is the radical other than hydrogen Contains R 2 , implemented.
  • the compounds of formula IV can also be prepared by intramolecular cyclization of compounds of general formula XIII in analogy to other literature known methods, for example according to T. Kawasaki et al., Org. Lett. 2 (19) (2000), 3027-3029.
  • R x is, for example, C 1 -C 6 -alkyl, in particular methyl, ethyl or phenyl-C 1 -C 6 -alkyl, for example benzyl.
  • the cyclization of the compounds of the formula XIII can be carried out in the presence of a base.
  • the reaction is then usually carried out at temperatures in the range of 0 0 C and the boiling point of the reaction mixture, preferably from 10 0 C to 50 0 C, particularly preferably from 15 ° C to 35 ° C.
  • the reaction can be carried out in a solvent, preferably in an inert organic solvent.
  • Suitable solvents are, in principle, the compounds cited under the thermal cyclization, in particular a tetrahydrofuran / water mixture having a mixing ratio of 1:10 to 10: 1.
  • Suitable bases are the bases mentioned in the basic cyclization according to process A, in particular potassium tert-butoxide, 2-hydroxypyridine or an aqueous solution of ammonia or a mixture of these bases. Preferably, only one of these bases is used. In a particularly preferred embodiment, the reaction is carried out in the presence of an aqueous solution of ammonia, which may for example be from 10 to 50 w / v%.
  • the compounds of formula XIII can themselves be prepared according to the synthesis shown in the following scheme in analogy to literature known methods, for example according to Wilford L. Mendelson et al., Int. J. Peptide & Protein Research 35 (3), (1990), 249-57, Glenn L. Stahl et al., J. Org. Chem. 43 (11), (1978), 2285-6. or AK Ghosh et al., Org. Lett. 3 (4), (2001), 635-638. ⁇
  • the synthesis comprises in a first step the coupling of amino acid compounds XV with Boc-protected amino acids VIII in the presence of an activating reagent.
  • reaction of a compound of the formula XV with a compound of the formula VIII is usually carried out at temperatures in the range from -30 0 C to the boiling point of the reaction mixture, preferably from 0 0 C to 50 0 C, particularly preferably from 20 0 C to 35 ° C.
  • the reaction may be carried out in a solvent, preferably in an inert organic solvent.
  • activating reagents are condensing agents, e.g. polystyrene- or non-polystyrene-bonded dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide, 1-ethyl-3- (dimethylaminopropyl) carbodiimide (EDAC), carbonyldiimidazole (CDI), chloroformates such as methyl chloroformate, ethyl chloroformate, isopropyl chloroformate, isobutyl chloroformate, sec-butyl chloroformate or allyl chloroformate , Polyvinyl chloride, polyphosphoric acid, propanephosphonic anhydride, bis (2-oxo-3-oxazolidinyl) -phosphoryl chloride (BOPCI) or sulfonyl chlorides such as methanesulfonyl chloride
  • DCC polystyrene- or non-polys
  • HATU O- (7-azabenzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate
  • preferred activating reagents are EDAC or DCC.
  • the reaction of XV with VIII takes place in the presence of a base.
  • bases are the compounds cited under Method A.
  • the base used is triethylamine or N-ethyldiisopropylamine or mixtures thereof, particularly preferably N-ethyldiisopropylamine.
  • the workup can be carried out analogously to the procedure described in process A.
  • Deprotection of compound XIV to compound XIII is typically by treatment with an acid.
  • the reaction is usually carried out at temperatures in the range of -30 0 C and the boiling point of the reaction mixture, preferably from 0 0 C to 50 0 C, particularly preferably from 20 ° C to 35 ° C.
  • the reaction can be carried out in a solvent, preferably in an inert organic solvent.
  • Suitable solvents are, in principle, the solvents mentioned under process A in connection with the basic cyclization, in particular tetrahydrofuran or dichloromethane or mixtures thereof. In a preferred embodiment, the reaction is carried out in dichloromethane.
  • reaction conditions mentioned therein are also suitable for deprotecting compounds pelg XIV.
  • the reaction is carried out in the presence of organic acids, in particular strong organic acids, for example in the presence of formic acid, acetic acid or trifluoroacetic acid or mixtures thereof.
  • the reaction is carried out in the presence of trifluoroacetic acid.
  • the compounds of the formula I according to the invention can, for example, also be prepared starting from corresponding precursor compounds in which R 6 is hydrogen and in which preferably R 3 together with R 5 represents a chemical bond.
  • R 6 is hydrogen and in which preferably R 3 together with R 5 represents a chemical bond.
  • the introduction of the radical R 6 can be carried out by common methods of organic chemistry, which depend on the nature of the respective radical R 6 , for example by alkylation, acylation, nitration, reaction with phosphorus halogen compounds, halogenation, cyanation, thionylation or sulfonylation.
  • X 6 is a leaving group.
  • R 6a has one of the meaning given for R 6 or is a protected precursor of the group R 6 .
  • Suitable bases for the deprotonation of the precursor compounds are inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, Sodium hydroxide, potassium hydroxide or calcium hydroxide, aqueous solution of ammonia, alkali metal or alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amides, for example lithium diisopropylamide, sodium amide, potassium amide and Alkali metal silazanes, such as lithium hexamethyldisilazane or potassium hexamethyldisilazane, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, cesium carbonate and calcium carbonate, and alkali metal hydrogencarbonates such as sodium bicarbonate, organometallic compounds, especially alkali
  • the bases are generally used equimolar. They can also be used in excess or even as a solvent. In a preferred embodiment, the base is added in equimolar amount or substantially equimolar amount. Preferred are alkali metal hydrides, alkali metal tallamides or alkali metal silazanes used as the base.
  • X 6 is in particular halogen, especially chlorine, bromine or iodine, a group OC (O) R m or a group
  • the reaction is usually carried out at temperatures in the range of -78 ° C to the boiling point of the reaction mixture, preferably from -50 0 C to 65 ° C, particularly preferably from -30 0 C to 65 ° C.
  • the reaction is carried out in a solvent, preferably in an inert organic solvent.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs alkanes, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and chlorobenzene, ethers such as Diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-but
  • the precursor compound in which R 6 is hydrogen can be converted into its anion in the manner described above and then treated with a halogenating agent such as tetrachlorodibromoethane, N -Bromsuccinimid or N-chlorosuccinimide implement.
  • a halogenating agent such as tetrachlorodibromoethane, N -Bromsuccinimid or N-chlorosuccinimide implement.
  • the precursor compound where R 6 is hydrogen transfer in the manner described above in its anion, and then reacting with cyanogen bromide.
  • the precursor compound wherein R 6 is hydrogen may be first oxidized with an organic peroxide or hydroperoxide such as tertiary butyl hydroperoxide in the presence of transition metal catalysts, eg, ruthenium compounds such as RuCl 2 (P (C 6 H 5 ) 3) 3.
  • transition metal catalysts eg, ruthenium compounds such as RuCl 2 (P (C 6 H 5 ) 3
  • the introduction of the cyano group succeeds by subsequent reaction of the oxidation product with trimethylsilyl cyanide in the presence of titanium tetrachloride (see J. Am. Chem. Soc., 1 12 (21), 1990, pp. 7820-7822).
  • R 1 and R 2 in formula XVI may be a protective group or hydrogen. With regard to the protective groups, this applies to compounds of the formula XIV.
  • R 1 and / or R 2 in formula XVI are a protective group, the protective groups will be removed. In this way, a compound XVI is obtained in which R 1 and optionally R 2 is hydrogen.
  • the compound XVI in which R 1 is hydrogen is then reacted with an alkylating agent of the formula R 1 -X 1 or an acylating agent of the formula R 1 -X 2 , preferably in the presence of a base. If R 2 is hydrogen, the compound XVI is reacted with an alkylating agent of the formula R 2 -X 1 or an acylating agent of the formula R 2 -X 2 , preferably in the presence of a base.
  • a 1 , A 2 , R 1 , R 2 , R 4 , R 7 , R 8 and R a to R f have the abovementioned meanings, in particular one of the meanings mentioned as being preferred.
  • the alcohol function of the compound XVIa can first be converted into a suitable leaving group and then formally eliminated as compound H-LG.
  • the elimination reaction occurs in the presence of a suitable base.
  • the leaving group LG is a common leaving group easily prepared from a hydroxy group.
  • the introduction of such a leaving group is carried out according to conventional methods, for example by reacting the alcohol XVIa with a base and then with the corresponding sulfonic acid chloride, for example with methanesulfonyl chloride or trifluoromethanesulfonyl chloride.
  • Suitable bases are the bases listed below in the elimination.
  • bases which are soluble in organic solvents for example the abovementioned amines or nitrogen heterocycles.
  • pyridine or substituted pyridines such as dimethylaminopyridine, lutidine or collidine, or mixtures thereof.
  • the organic bases are chosen so that they also function as solvents.
  • the bases generally include inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, aqueous solution of ammonia, alkali metal or alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, Potassium hydride and calcium hydride, alkali metal amides such as lithium amide, for example lithium diisopropylamide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, cesium carbonate and calcium carbonate and also alkali metal hydrogen carbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, Alkylmagnesium halides, such as methylmagnesium chloride
  • tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, 2-hydroxypyridine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration.
  • a mixture of different bases can be used.
  • bases which, although having sufficient basicity but substantially no nucleophilicity, for example sterically hindered alkali metal alkoxides, for example alkali tert-butanolates, such as potassium tert-butoxide, and in particular cyclic amidines, such as DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene) and DBN (1, 5-diazabicyclo [3.4.0] non-5-ene).
  • cyclic amidines such as DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene) and DBN (1, 5-diazabicyclo [3.4.0] non-5-ene.
  • DBU 1, 8-diazabicyclo [5.4.0] undec-7-ene
  • DBN 1, 5-diazabicyclo [3.4.0] non-5-ene
  • Suitable inert organic solvents include aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran.
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and chlorobenzene
  • ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran.
  • nitrites such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, water and dimethyl sulfoxide, dimethylformamide and dimethylacetamide and Morpholine and N-methylmorpholine. It is also possible to use mixtures of the solvents mentioned. Preference is given to using tetrahydrofuran.
  • compound XVI is prepared by dehydration of compound XVIa in the presence of a suitable dehydrating agent.
  • DEAD diethyl azodicarboxylate
  • Burgess reagent diethyl azodicarboxylate
  • the combination of triphenylphosphine and DEAD is generally used for targeted inversion at a hydroxy-substituted chiral center (so-called Mitsunobu).
  • the Burgess reagent is the zwitterion of methyl N- (triethylammonium sulfonylcarbamate ((C2H5) 3N + -S ⁇ 2-N "-COOCHs), which is a mild dehydrating agent which can be equimolar with respect to the alcohol XVI or in
  • the reaction with the Burgess reagent is carried out in molar excess usually in an inert organic solvent.
  • Suitable inert organic solvents include aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, Nitriles such as acetonitrile and propionitrile, and ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone are preferably used aromatic hydrocarbons or mixtures thereof and especially toluene.
  • aromatic hydrocarbons such as toluene, o-, m- and p-xylene
  • halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and chloro
  • dehydration of alcohols XVIa using dehydrating agents can be carried out analogously to known processes of the prior art, for example analogously to those described in Synthesis 2003, 201 and J. Indian Sei. 2001, 81, 461, to which reference is hereby made in its entirety.
  • the alcohols of the formula XVIa can be prepared, for example, in analogy to processes known from the literature by cyclization of corresponding dipeptide precursors, for example in analogy to that described by T. Kawasaki et al., Org. Lett. 2 (19) (2000), 3027-3029, Igor L. Rodionov et al., Tetrahedron 58 (42) (2002), 8515-8523 or AL Johnson et al., Tetrahedron 60 (2004), 961-965 ,
  • the alcohols of the formula XVIa in which R 4 is hydrogen can also be prepared by coupling a benzaldehyde of the formula XV with a piperazine compound XVII in an aldol reaction, as shown in the following scheme:
  • the reaction of XV with XVII in the sense of an aldol reaction is generally carried out in the presence of suitable bases.
  • suitable bases are those which are commonly used in aldol reactions.
  • Suitable reaction conditions are known in the art and described, for example, in J. Org. Chem. 2000, 65 (24), 8402-8405, which is hereby incorporated by reference in its entirety.
  • the reaction of compound XV with compound XVII can also lead directly to the corresponding aldol condensation product, ie to compounds of formula XVI.
  • radicals R 1 and R 2 represent an acyl group, for example a group of the formula C (O) R 21 -, where R 21 has one of the meanings given above and in particular C 1 C 4 -AlkVl for example methyl.
  • the aldol condensation is typically carried out in the presence of suitable bases.
  • suitable bases are those which are commonly used in aldol condensations.
  • an alkali metal or alkaline earth metal carbonate is used as the base, e.g. Sodium carbonate, potassium carbonate or cesium carbonate or mixtures thereof.
  • the reaction is carried out in an inert, preferably aprotic organic solvent.
  • suitable solvents are, in particular, dichloromethane, dichloroethane, chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, and also dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone and dimethylacetamide , Preferred solvents are selected in particular from dimethylformamide, N-methylpyrrolidone and dimethylacetamide.
  • the temperatures required for the aldol condensation are generally in the range from 0 ° C. up to the boiling point of the solvent used and in particular in the range from 10 to 80 ° C.
  • the radicals R 1 and R 2 are an acyl group, for example a group of the formula C (O) R 21 .
  • the compounds of the formula XVII can be prepared by intramolecular cyclization of compounds of the general formula XVIII in analogy to other processes known from the literature, for example according to T. Kawasaki et al., Org. Lett. 2 (19) (2000), 3027-3029, Gregor Rodionov et al., Tetrahedron 58 (42) (2002), 8515-8523 or AL Johnson et al., Tetrahedron 60 (2004), 961-965 become.
  • R x is, for example, C 1 -C 6 -alkyl, in particular methyl, ethyl or phenyl-C 1 -C 6 -alkyl, for example benzyl.
  • the cyclization of the compounds of formula XVII can be carried out in the presence of a base.
  • the reaction is then generally carried out at temperatures in the range from 0 ° C. to the boiling point of the reaction mixture, preferably from 10 ° C. to 50 ° C., in particular dere preferably from 15 ° C to 35 ° C.
  • the reaction can be carried out in a solvent, preferably in an inert organic solvent.
  • Suitable inert organic solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of Cs-Cs-alkanes, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n- Butanol,
  • Suitable bases are e.g. inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, aqueous solution of ammonia, alkali metal or alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, Al alkali metal amides, such as lithium amide, for example lithium diisopropylamide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate, cesium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, organometallic compounds, in particular
  • Alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and also alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide, potassium tert-pentoxide and dimethoxy magnesium, as well as organic bases, eg tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, 2-hydroxypyridine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine as well as bicyclic amines.
  • alkylmagnesium halides such as methylmagnesium chloride and also alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium
  • a mixture of different bases can be used.
  • Particularly preferred are potassium tert-butoxide, 2-hydroxypyridine or an aqueous solution of ammonia or a mixture of these bases.
  • the reaction is carried out in the presence of an aqueous solution of ammonia, which may for example be from 10 to 50 w / v%.
  • the cyclization is carried out in a mixture comprising butanol, for. For example, n-butanol, 2-butanol and / or Isobutanol or a mixture thereof, and N-methyl morpholine, preferably under reflux conditions.
  • the cyclization of XVIII to XVII can also be carried out under acidic catalysis, in the presence of activating compounds or thermally.
  • the reaction of XVIII in the presence of an acid is usually carried out at temperatures in the range of 10 0 C to the boiling point of the reaction mixture, preferably from 50 0 C to the boiling point, particularly preferably at the boiling point under reflux.
  • the reaction is carried out in a solvent, preferably in an inert organic see solvent.
  • Suitable solvents are, in principle, those which can also be used for the basic cyclization, in particular alcohols.
  • the reaction is carried out in n-butanol or a mixture of different butanol isomers (e.g., a mixture of n-butanol with 2-butanol and / or isobutanol).
  • Suitable acids for the cyclization of XVIII to XVII are in principle both Bronstedt and Lewis acids into consideration.
  • inorganic acids e.g. Hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, inorganic oxo acids such as sulfuric acid and perchloric acid, furthermore inorganic Lewis acids such as boron trifluoride, aluminum trichloride, iron (III) chloride, tin (IV) chloride, titanium (IV) chloride and zinc - (II) chloride, and organic acids, such as carboxylic acids and hydroxycarboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid, and organic sulfonic acids such as toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid and the like, find use.
  • a mixture of different acids can be used
  • the reaction is carried out in the presence of organic acids, for example in the presence of carboxylic acids such as formic acid, acetic acid or trifluoroacetic acid or a mixture of these acids. Preferably, only one of these acids is used. In a preferred embodiment, the reaction is carried out in acetic acid.
  • the acidic cyclization takes place in a mixture comprising n-butanol or a mixture of butanol isomers (for example a mixture of n-butanol with 2-butanol and / or isobutanol), N-methyl-morpholine and acetic acid, preferably under reflux conditions.
  • the reaction of XVIII is carried out by treatment with an activating agent in the presence of a base.
  • R x stands for hydrogen.
  • An example of a suitable activating agent is di- (N-succinimidinyl) carbonate.
  • Suitable activating agents are also polystyrene- or non-polystyrene-bonded dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide, 1-ethyl-3- (dimethylaminopropyl) carbodiimide (EDAC), carbonyldiimidazole (CDI), chloroformates such as methyl chloroformate, ethyl chloroformate, isopropyl chloroformate, isobutyl chloroformate, sec-butyl chloroformate or allyl chloroformate, polyoyl chloride, polyphosphoric acid, propanephosphonic anhydride, bis (2-oxo-3-oxazolidinyl) -phosphoryl chloride (BOPCI) or sulphonyl chlorides such as methanesulphonyl chloride, toluenesulphonyl chloride or benzenesulphonyl chloride.
  • DCC di
  • Suitable bases are the compounds cited for the basic cyclization.
  • the base used is triethylamine or N-ethyldiisopropylamine or mixtures thereof, more preferably N-ethyldiisopropylamine.
  • the reaction of XVIII is carried out exclusively by heating the reaction mixture (thermal cyclization).
  • the reaction is usually carried out at temperatures in the range of 10 ° C to the boiling point of the reaction mixture, preferably from 50 ° C to the boiling point of the reaction mixture, particularly preferably at the boiling point of the reaction mixture under reflux.
  • the reaction is carried out in a solvent, preferably in an inert organic solvent.
  • Suitable solvents are, in principle, those used in the basic cilsilation. Preferred are polar aprotic solvents, e.g. Dimethyl sulfoxide or dimethylformamide or mixtures thereof. In a preferred embodiment, the reaction is carried out in dimethyl sulfoxide.
  • the compounds of the formula XVIII can themselves be prepared according to the scheme shown below in analogy to processes known from the literature, for example according to Wilford L. Mendelson et al., Int. J. Peptide & Protein Research 35 (3), (1990), 249-57, Glenn L. Stahl et al., J. Org. Chem. 43 (11), (1978), 2285-6. or AK Ghosh et al., Org. Lett. 3 (4), (2001), 635-638.
  • the synthesis comprises in a first step the coupling of glycine ester compounds of the formula XIX with Boc-protected compounds of the formula XX in the presence of an activating reagent.
  • Boc instead of Boc, another amino protecting group can also be used.
  • the compounds XVII can also be prepared by intermolecular cyclization of a glycine ester derivative XIXa with a compound XXa according to the following scheme:
  • R x , R 7 , R 8 and R d to R f have one of the meanings given above.
  • R y is alkyl, for example methyl or ethyl.
  • the intermolecular cyclization can be effected, for example, by a base, for example ammonia.
  • the compounds XIXa and / or XXa can also be used in the form of their acid addition salts, for example as hydrochlorides.
  • process G comprises the preparation of compounds I, wherein Y 1 and Y 2 are O and R 3 together with R 5 represents a chemical bond,
  • a 2 , R 7 , R 8 and R d to R f have one of the meanings given above and X is a nucleophilically displaceable leaving group, in the presence of a
  • R 1 is a protecting group, deprotecting.
  • R 1 preferably has the meaning given to R 1 other than hydrogen.
  • the variable X preferably has one of the following meanings: halogen, in particular chlorine, bromine or iodine or O-SO 2 -R m with R m meaning Ci-C 4 -AlkVl or aryl, which is optionally substituted by halogen, CrC 4 -AlkVl or halo-Ci-C 4 alkyl substituted.
  • Suitable protecting groups for the nitrogen atoms of the piperazine ring in XXI are in particular the abovementioned radicals C (O) R 21 , for example the acetyl radical.
  • reaction of compound XXI with compound XXII in step ii) can be carried out analogously e.g. after in J. Am. Chem. Soc. 105, 1983, 3214 described method.
  • the reaction takes place in the presence of sodium hydride as base in N-methylpyrrolidone as solvent.
  • a 1 , R 1 , R 6 and R a to R c have one of the meanings mentioned above.
  • R 2 has one of the meanings given above or is a protective group. Suitable protecting groups for the nitrogen atoms of the piperazine ring in XXIII are, in particular, the abovementioned radicals C (O) R 21 , for example the acetyl radical.
  • R 1 and R 2 represent one of the abovementioned radicals C (O) R 21 , for example acetyl radicals.
  • reaction of XXIII with XXIV can be carried out under the conditions of an aldol condensation, as already described above.
  • aldol condensations can be analogous to those described in J. Org. Chem. 2000, 65 (24), 8402-8405, Synlett 2006, 677, J. Heterocycl. Chem. 1988, 25, 591, to which reference is hereby fully made.
  • the reaction is usually carried out in the presence of a base.
  • a base it is preferable to use an alkali metal or alkaline earth metal carbonate, e.g. Sodium carbonate, potassium carbonate or cesium carbonate or mixtures thereof.
  • the reaction is carried out in an inert, preferably aprotic organic solvent.
  • suitable solvents are, in particular, dichloromethane, dichloroethane, chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, and also dimethyl sulfoxide, dimethylformamide, N-methylpyrrolidone and dimethylacetamide
  • R 1 , R 2 can be carried out in analogy to known methods of protective group chemistry, for example according to the method described in Green, Wuts, Protective Groups in Organic Synthesis, 3rd ed. 1999, John Wiley and Sons, p ,
  • a subsequent alkylation to introduce the radicals R 1 or R 2 can be carried out by the previously given method.
  • the compounds XXIII are known. Their preparation can be carried out in analogy to the preparation of the compounds XVII described above according to the scheme shown below:
  • R 1 , R 2 and R 6 have one of the meanings given above.
  • R x is preferably C 1 -C 4 -alkyl or benzyl.
  • Boc is a tert-butoxycarbonyl radical.
  • R 1 and R 2 are a protective group, for example a radical C (O) R 21
  • the introduction of these protective groups can be carried out in analogy to known methods of protecting group chemistry, for example by reaction with anhydrides of the formula (R 21 C (O)) 2 ⁇ , eg according to the method described in Green, Wuts, Protective Groups in Organic Synthesis, 3rd Ed. 1999, John Wiley and Sons, p. 553.
  • the hydrogenation is carried out by reaction with hydrogen in the presence of transition metal catalysts, for example catalysts containing Pt, Pd, Rh or Ru as active metal species.
  • transition metal catalysts for example catalysts containing Pt, Pd, Rh or Ru as active metal species.
  • Suitable are both heterogeneous catalysts such as Pd or Pt supported catalysts, for example Pd on activated carbon, further PtÜ2, as well as homogeneous catalysts.
  • stereoselective catalysts allows enantioselective hydrogenation of the double bond (see Peptide Chemistry 17, 1980, pp. 59-64, Tetrahedron Lett. 46, 1979, pp. 4483-4486).
  • the hydrogenation can be carried out analogously to compounds of the formula XVI, ie before the introduction of a radical R 6 different from hydrogen.
  • Suitable sulfurizing agents are organophosphorus sulfides, such as Laweson's reagent (2,2-bis- (4-methoxyphenyl) -1,3,2,4-dithiadiphosphetane-2,4-disulfide), organotin sulfides such as bis (tricyclohexyltin) sulfide or phosphorus pentasulfide (see also J. March, Advanced Organic Synthesis, 4th Edition, Wiley Interscience 1992, p 893f and the literature cited therein).
  • the reaction can be carried out in a solvent or in substance. Suitable solvents are inert organic solvents known in the art, and especially pyridine and comparable solvents.
  • the temperature required for the reaction is generally above room temperature and is in particular in the range from 50 to 200 ° C.
  • R 1 together with R 2 is a 1-, 2-, 3- or 4-membered carbon chain, in which a carbon atom is represented by O, S or a group NR A
  • R 1 and R 2 are hydrogen, by reaction with a compound of formula X a -AX a , wherein A is the 1-, 2-, 3 or 4-membered carbon chain, wherein a carbon atom may be replaced by O, S or a group NR A , and X a is a suitable leaving group such as iodine.
  • a 4-membered carbon chain in which a carbon atom may be replaced by O, S or a group NR 1 can be prepared, for example, starting from compounds I in which R 3 together with R 5 represents a chemical bond.
  • Electrophilously a ring can be built up.
  • compounds I in which R 3 together with R 5 represent an oxygen atom are accessible by epoxidation of the corresponding unsaturated compound.
  • compounds I can also be prepared in which R 6 and R 8 are a 1-, 2-, 3- or 4-membered carbon chain in which one carbon atom may be replaced by O, S or a group NR 1 .
  • compounds of the formula I in which R 1 together with R 6 and together with the atoms to which these radicals are bonded may also be prepared from cyclic amino acids.
  • the compounds I and their agriculturally useful salts are suitable - both as mixtures of isomers and in the form of pure isomers - as herbicides. They are suitable as such or as appropriately formulated agent.
  • the herbicidal compositions containing compound I or Ia control plant growth on nonculture areas very well, especially at high application rates. In crops such as wheat, rice, maize, soya and cotton, they act against weeds and weed grasses, without the Appreciable damage to crops. This effect occurs especially at low application rates.
  • the compounds of the formula I or agents which contain compounds I can be used in a further number of crop plants for the removal of undesirable plants.
  • the following cultures may be considered:
  • the compounds of formula I may also be used in cultures tolerant to the action of herbicides by breeding, including genetic engineering.
  • Breeding including genetic engineering methods are tolerant to insects or fungal infestations.
  • the compounds of the formula I are also suitable for defoliation and / or desiccation of plant parts, for which crops such as
  • agents for desiccation and / or defoliation of plants methods of preparation of these agents and methods have been proposed for the desiccation and / or defoliation of plants with the compounds of the formula I.
  • the compounds of the formula I are particularly suitable for drying out the aerial parts of crop plants such as potato, rape, sunflower and soybean, but also cereals. This enables a completely mechanical harvesting of these important crops.
  • the compounds of the formula I or herbicidal compositions which contain compounds of the formula I can be used, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, even high-percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, Spreading agents or granules by spraying, atomizing, dusting, scattering, pouring or treatment of the seed or mixing with the seed can be applied.
  • the forms of application depend on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the herbicidal compositions contain a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of compounds of the formula I and at least one auxiliaries customary for the formulation of crop protection agents.
  • adjuvants which are customary for the formulation of pesticides are inert auxiliaries, solid carriers, surface-active substances (such as dispersants, protective colloids, emulsifiers, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if appropriate, dyes and for seed formulations Glue.
  • inert auxiliaries solid carriers
  • surface-active substances such as dispersants, protective colloids, emulsifiers, wetting agents and adhesives
  • organic and inorganic thickeners such as bactericides, antifreeze agents, defoamers, if appropriate, dyes and for seed formulations Glue.
  • thickeners ie, compounds which impart modified flowability to the formulation, ie, high-level at low viscosity and low viscosity in the agitated state
  • polysaccharides such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum ® (RT Vanderbilt) and organic and inorganic layer minerals such as Attaclay® (Engelhardt).
  • antifoam agents examples include silicone emulsions (such as, for example, Silikon® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.
  • Bactericides may be added to stabilize the aqueous herbicidal formulation.
  • bactericides are bactericides based on diclorophene and benzyl alcohol hemiformal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) as well as isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide MBS der Fa. Thor Chemie)
  • antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol.
  • colorants are both water-insoluble pigments and water-soluble dyes. Examples which may be mentioned under the names rhodamine B, Cl. Pigment Red 1 12 and Cl. Solvent Red 1 known dyes, as well as pigment blue 15: 4, pigment blue 15: 3, pigment blue 15: 2, pigment blue 15: 1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 1 12, pigment red 48: 2, pigment red 48: 1, pigment red 57: 1, pigment red 53: 1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, aeid red 51, aeid red 52, aeid red 14, aeid blue 9, aeid yellow 23, basic red 10, basic red 108.
  • adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.
  • Suitable inert additives are, for example:
  • Mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol , Propanol, butanol, cyclohexanol, ketones such as cyclohanol exanone or strongly polar solvents, e.g. As amines such as N-methylpyrrolidone or water.
  • amines such as N-methylpyrrolidone or water.
  • Solid carriers are mineral soils such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • mineral soils such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour
  • surfactants adjuvants, wetting agents, tackifiers, dispersants and emulsifiers
  • the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Ligninsulfonklaren (eg Borrespers types, Borregaard), phenolsulfonic acids, naphthalene sulfonic acids (Morwet types, Akzo Nobel) and dibutylnaphthalenesulfonic acid (Nekal types, BASF AG), as well as fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and Salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthal
  • Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
  • Granules e.g. Coating, impregnation and homogeneous granules can be prepared by binding the active compounds to solid carriers.
  • Aqueous application forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • emulsions, pastes or oil dispersions the compounds of the formula I or Ia as such or in an oil or dissolved, be homogenized by means of wetting agents, adhesives, dispersants or emulsifiers in water.
  • concentrates consisting of active substance, wetting, adhesion, dispersing or emulsifying agent and possibly solvent or oil, which are suitable for dilution with water.
  • the concentrations of the compounds of the formula I in the ready-to-use formulations can be varied within wide limits.
  • the formulations generally contain from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight, of at least one active ingredient.
  • the active compounds are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • the compounds I according to the invention can be formulated, for example, as follows:
  • active compound 20 parts by weight are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.
  • a dispersant e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.
  • the active ingredient content is 20% by weight
  • active compound 15 parts by weight of active compound are dissolved in 75 parts by weight of an organic solvent (for example alkylaromatics) with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion.
  • the formulation has 15% by weight active ingredient content.
  • D Emulsions 25 parts by weight of active compound are dissolved in 35 parts by weight of an organic solvent (for example alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • an organic solvent for example alkylaromatics
  • This mixture is added by means of an emulsifying machine (eg Ultraturax) in 30 parts by weight of water and a homogeneous emulsion brought. Dilution in water results in an emulsion.
  • the formulation has an active ingredient content of 25% by weight.
  • E Suspensions 20 parts by weight of active compound are comminuted with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to give a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient.
  • the active ingredient content in the formulation is 20% by weight.
  • Water-dispersible and water-soluble granules 50 parts by weight of active compound are finely ground with the addition of 50 parts by weight of dispersing and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the formulation has an active ingredient content of 50% by weight.
  • active compound 75 parts by weight of active compound are ground with the addition of 25 parts by weight of dispersing and wetting agents and silica gel in a rotor-Strator mill. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the active ingredient content of the formulation is 75% by weight.
  • H Gel Formulations In a ball mill, 20 parts by weight of active ingredient, 10 parts by weight of dispersant, 1 part by weight of gelling agent and 70 parts by weight of water or an organic solvent are ground to a fine suspension. Dilution with water results in a stable suspension with 20% by weight active ingredient content.
  • 0.5 parts by weight of active compound are finely ground and combined with 99.5 parts by weight of carriers. Common processes are the extrusion, the spray-drying or the fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.
  • the application of the compounds of the formula I or of the herbicidal compositions which contain compounds of the formula I can be carried out in preemergence, postemergence or together with the seed of a crop. It is also possible to apply the herbicidal compositions or active ingredients characterized in that with the herbicidal agents or active ingredients pretreated seed of a crop plant is applied. If the active ingredients are less compatible with certain crops, then application techniques may be employed whereby the herbicidal agents are sprayed by the sprayers so as not to strike the leaves of the sensitive crop if possible, while the active ingredients affect the leaves of undesirable plants growing thereunder or the uncovered floor surface (post-directed, lay-by).
  • the application of the compounds of the formula I or of the herbicidal compositions can be carried out by treating seed.
  • the treatment of seed essentially comprises all techniques familiar to the skilled person (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping, and seed pelleting) on the basis of the invention Compounds of the formula I or of herbicidal compositions produced therefrom, in which case the herbicidal compositions can be diluted or applied undiluted.
  • seed includes seeds of all kinds, e.g. Grains, seeds, fruits, tubers, cuttings and similar forms.
  • seed preferably describes grains and seeds here.
  • Seeds of the abovementioned crops but also the seeds of transgenic or obtained by conventional breeding methods plants can be used as seeds.
  • the application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a. S.).
  • the compounds I are usually used in amounts of 0.001 to 10 kg per 100 kg of seed.
  • the compounds of formula I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups or with safeners and applied together.
  • Safeners are chemical compounds that prevent or reduce damage to crops without significantly affecting the herbicidal activity of the compounds of formula I on undesirable plants. They can be used both before sowing (for example, in seed treatments, in cuttings, or in seedlings) as well as in the pre- or post-emergence of the crop.
  • the safeners and the compounds of the formula I can be used simultaneously or in succession be used.
  • Suitable safeners are, for example, (quinoline- ⁇ -oxy) acetic acids, 1-phenyl-5-haloalkyl-1H-1, 2,4-triazole-3-carboxylic acids, 1-phenyl-4,5-dihydro-5- alkyl-1H-pyrazole-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenone oximes, 4,6-dihalo-2-phenylpyrimidines, N- [ [4- (aminocarbonyl) phenyl] sulfonyl] -2-benzamides,
  • HPLC-MS High Performance Liquid Chromatography combined with Mass Spectrometry; Unless otherwise stated: HPLC column: RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany), 50 x 4.6 mm; Eluent: acetonitrile + 0.1% trifluoroacetic acid (TFA) / water + 0.1% TFA, with a gradient of 5:95 to 100: 0 in 5 minutes at 40 ° C., flow rate 1, 8 ml / min; MS: Quadrupole electrospray ionization, 80V (positive mode).]
  • Example 1a / 1 b 2- (5-Benzyl-1,4-dimethyl-5-methylsulfanyl-3,6-dioxo-piperazin-2-ylidenemethyl) -benzonitrile
  • Example 3 2- (5-Benzyl-1,4-dimethyl-5-methylsulfonyl-3,6-dioxo-piperazine- (Z) -2-ylidenemethyl) -benzonitrile 2- (5-Benzyl-1,4-dimethyl-5-methylsulfanyl-3,6-dioxo-piperazin-2-ylidenemethyl) -benzonitrile from Example 1 (Z-isomer, 90 mg, 0.23 mmol) was added Sodium tungstate dihydrate (10 mg, 0.03 mmol) and glacial acetic acid (3 mL). Thereafter, hydrogen peroxide (60 mg, 30% solution, 0.53 mmol) was added dropwise at room temperature and the mixture was stirred
  • Table B Compounds of general formula IA.a ', wherein R c and R d are each hydrogen and R 1 is methyl.
  • HPLC column RP-18 column (XTerra MS 5 mm from Waters) eluent: acetonitrile + 0.1% formic acid (A) / water + 0.1% formic acid (B) with a gradient of 5:95 ( A / B) to 100: 0 (A / B) in 8 minutes at room temperature. MS: quadrupole electrospray ionization, 80V positive mode) m.p.
  • HPLC column RP-18 column (XTerra MS 5 mm from Waters) eluent: acetonitrile + 0.1% formic acid (A) / water + 0.1% formic acid (B) with a gradient of 5:95 (A / B ) to 100: 0 (A / B) in 8 minutes at room temperature.
  • MS quadrupole electrospray ionization, 80 V positive mode
  • Example 17 To the compound of Example 17 (0.32 g) in 5 ml DMF was added under argon at -15 0 C sodium hydride (80 mg, 60%), stirred for 3 h at -15 0 C gradually added, followed with methyl iodide ( 1, 42 g).
  • the reaction mixture was (1 g) (50 ml) placed in water for 3 h at -15 0 C and 18 h at room temperature and then in a solution of citric acid.
  • the aqueous reaction mixture was extracted four times with dichloromethane. The resulting organic phase was washed twice with water, dried over sodium sulfate, filtered and concentrated. Purification by flash chromatography (methyl tert -butyl ether) gave the title compound 18a (130 mg) and the title compound 18b (40 mg).
  • Example 20 To the compound of Example 20 (0.01 mol) in DMF (50 ml) was added at 0 0 C. NaH (60%, 0.02 mol). The mixture was stirred for 1 h at 0 0 C and then treated with methyl iodide (0.1 mol). The reaction mixture was stirred for 18 h at room temperature and then added to a water (500 ml) / citric acid (5 g) solution. It was extracted several times with CH 2 Cl 2. The resulting organic phase was washed with water, dried over Na 2 SO 4, filtered and concentrated. The title compound was obtained after trituration with diisopropyl ether. RT HPLC / MS: 3.447 min., 426.0 [M + H] +
  • HPLC column RP-18 column (XTerra MS 5 mm from Waters) eluent: acetonitrile + 0.1% formic acid (A) / water + 0.1% formic acid (B) with a gradient of 5:95 (A / B ) to 100: 0 (A / B) in 8 minutes at room temperature.
  • MS Quadrupole electrospray ionization, 80V positive mode
  • HPLC column RP-18 column (XTerra MS 5 mm from Waters) eluent: acetonitrile + 0.1% formic acid (A) / water + 0.1% formic acid (B) with a gradient of 5:95 (A / B ) to 100: 0 (A / B) in 8 minutes at room temperature.
  • the isomer mixture obtained was separated by column chromatography (silica gel, hexane / ethyl acetate, 1: 1). This gave 3.10 g (yield 20%) of the cis isomer and 7.1 g (yield 45%) of the trans isomer.
  • Part B Application examples The herbicidal activity of the compounds of the formula I was demonstrated by greenhouse experiments:
  • the culture vessels used were plastic pots with loamy sand with about 3.0% humus as substrate.
  • the seeds of the test plants were sown separately by species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles.
  • the jars were lightly rained to promote germination and growth, and then covered with clear plastic hoods until the plants had grown. This cover causes a uniform germination of the test plants, if it was not affected by the active ingredients.
  • test plants were grown depending on the growth form only to a height of from 3 to 15 cm and then treated with the suspended or emulsified in water agents.
  • the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test tubes a few days before the treatment.
  • the plants were kept species-specific at temperatures of 10 - 25 ° C and 20 - 35 ° C, respectively.
  • the trial period lasted for 2 to 4 weeks. During this time, the plants were cared for, and their response to each treatment was evaluated.
  • the rating was based on a scale of 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts and 0 no damage or normal growth course.
  • a good herbicidal activity is at values of at least 70 and a very good herbicidal activity is given at values of at least 85.
  • the plants used in the greenhouse experiments were composed of the following species:
  • the compound of Example 2 shows at a rate of 1, 0 kg / ha in pre-emergence against APESV a very good herbicidal activity.
  • the compound of Example 2 shows at a rate of 1, 0 kg / ha pre-emergence against SETFA a good herbicidal action.
  • the compound of Example 4 shows at a rate of 0.5 kg / ha in the pre-emergence against SETFA a good herbicidal action.

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EP08774158A 2007-06-22 2008-06-20 Piperazinverbindungen mit herbizider wirkung Withdrawn EP2061770A1 (de)

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EP08774158A EP2061770A1 (de) 2007-06-22 2008-06-20 Piperazinverbindungen mit herbizider wirkung

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EP07110913 2007-06-22
EP08774158A EP2061770A1 (de) 2007-06-22 2008-06-20 Piperazinverbindungen mit herbizider wirkung
PCT/EP2008/057830 WO2009000757A1 (de) 2007-06-22 2008-06-20 Piperazinverbindungen mit herbizider wirkung

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US20100167933A1 (en) 2010-07-01
KR20100028111A (ko) 2010-03-11
EA201000023A1 (ru) 2010-06-30
UY31168A1 (es) 2009-01-05
CR11172A (es) 2010-04-21
BRPI0812084A2 (pt) 2014-11-25
CN101730686A (zh) 2010-06-09
CA2686224A1 (en) 2008-12-31
ECSP109894A (es) 2010-02-26
JP2010530866A (ja) 2010-09-16
TW200906807A (en) 2009-02-16
AR067116A1 (es) 2009-09-30
MX2009011451A (es) 2009-11-10
ZA201000413B (en) 2011-04-28
CL2008001864A1 (es) 2009-09-25
IL201669A0 (en) 2010-05-31
PE20090420A1 (es) 2009-05-08
AU2008267811A1 (en) 2008-12-31
CO6170357A2 (es) 2010-06-18
WO2009000757A1 (de) 2008-12-31

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