WO1997000246A1 - Nouveaux herbicides - Google Patents

Nouveaux herbicides Download PDF

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Publication number
WO1997000246A1
WO1997000246A1 PCT/EP1996/002417 EP9602417W WO9700246A1 WO 1997000246 A1 WO1997000246 A1 WO 1997000246A1 EP 9602417 W EP9602417 W EP 9602417W WO 9700246 A1 WO9700246 A1 WO 9700246A1
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WIPO (PCT)
Prior art keywords
alkyl
halogen
substituted
tri
benzyl
Prior art date
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PCT/EP1996/002417
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English (en)
Inventor
Hans-Georg Brunner
Milan Karvas
Kurt Nebel
Georg Pissiotas
Original Assignee
Novartis Ag
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Filing date
Publication date
Application filed by Novartis Ag filed Critical Novartis Ag
Priority to US08/765,161 priority Critical patent/US6103667A/en
Priority to MX9710042A priority patent/MX9710042A/es
Priority to AU62217/96A priority patent/AU6221796A/en
Priority to EP96920785A priority patent/EP0832070A1/fr
Publication of WO1997000246A1 publication Critical patent/WO1997000246A1/fr

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    • 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
    • C07D405/12—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 linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom

Definitions

  • the present invention relates to novel, herbicidally active phenylpyrazole derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants or in the inhibition of plant growth.
  • Pyrazole compounds having herbicidal action are known and are disclosed, for example, in EP-A-0 361 114, JP-A-03 093 774, JP-A-02 300 173 and JP-A-03 163 063.
  • the present invention therefore relates to compounds of formula I
  • R is C r C 4 alkyl
  • R 2 is C r C 4 alkyl, C,-C 4 haloalkyl, C 3 - or C 4 -alkenyl, C 3 - or C 4 -haloalkenyl or C 3 - or C 4 -alkynyl; n is 0, 1 or 2;
  • R 3 is hydrogen, C r C 4 alkyl, C r C 4 haloalkyl, C 3 - or C 4 -alkenyl, C 3 - or C 4 -haloalkenyl, C 3 - or C 4 -alkynyl, -CH 2 COOH, -CH 2 COO-C r C 4 alkyl or -CH 2 CN;
  • R 4 is hydrogen, fluorine, chlorine or bromine
  • R 5 is hydrogen, halogen, methyl, trifluoromethyl, cyano, nitro, amino or C r C 4 halo- alkoxy;
  • R 6 is hydrogen, halogen, cyano, NHR 10 , NR 10 R j j or SO 2 Cl;
  • R 10 and R ⁇ are each independently of the other C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 cycloalkyl, C,-C 8 haloalkyl, C 3 -C 8 haloalkenyl, C r C 4 alkylcarbonyl, C r C 4 haloalkylcarbonyl, C r C 4 alkylsulfonyl, C r C 4 haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by C r C 4 alkyl, C,-C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C,-C 4 alkyl, C,-C 4 haloalkyl or by halogen; or
  • R 6 is OR 20 ;
  • R 20 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl,
  • R 20 is C r Cgalkyl-COXR 21 or CH(C 6 H 5 )COXR 2 . ;
  • X is oxygen, sulfur or NR 22 ;
  • R 21 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C r C 4 alkylthio-C r C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by Cj-C 4 alkyl or by halogen; and
  • R 22 is hydrogen, C r C 8 alkyl or C 3 -C 8 alkenyl
  • R 6 is S(O) m R 30 ; m is 0, 1 or 2;
  • R 30 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C g haloalkyl, C 3 -C 8 halo- alkenyl, C 3 -C 6 cycloalkyl, C r C 4 alkoxy-C r C 4 alkyl, C 1 -C 4 alkylthio-C 1 -C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, or C r C 4 alkyl-CONR 31 ;
  • N is oxygen, sulfur or ⁇ R 32 ;
  • R 31 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C r C 4 alkoxy-C r C 4 alkyl, C r C 4 alkylthio-C r C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen; and
  • R 32 is hydrogen, C r C 8 alkyl or C 3 -C 8 alkenyl
  • R 6 is COR 40 ;
  • R 40 is hydrogen, chlorine, C,-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C,-C 8 haloalkyl, C 3 -C 8 haloalkenyl, C 3 -C 6 cycloalkyl, C r C 4 alkoxy-C r C 4 alkyl, C,-C 4 alkylthio- C,-C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C,-C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C r C 4 alkyl, C,-C 4 halo- alkyl or by halogen; or R 6 is COYR 50 ;
  • Y is oxygen, sulfur, NR 51 or NOR 54 ;
  • R 50 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl,
  • Z is oxygen, sulfur, NR 53 or NOR 55 ;
  • R 52 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, O
  • R 51 and R 53 are each independently of the other C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r Cghaloalkyl, C r C 4 alkylcarbonyl, C r C 4 haloalkylcarbonyl, C r C 4 alkylsulfonyl, C r C 4 haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C r C alkyl, C r C 4 haloalkyl or by halogen;
  • R 54 and R 55 are each independently of the other C r C 4 alkyl; or
  • R 56 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl;
  • R 57 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl or C r C 4 alkylcarbonyl; or
  • R 6 is C r C 8 alkyl-B, C r C 8 haloalkyl-B, C 2 -C 8 alkenyl-B, C 2 -C 8 alkynyl-B, C 2 -C 8 halo- alkenyl-B, C r C 4 alkoxy-C,-C 4 alkyl-B or C r C 4 alkylthio-C,-C 4 alkyl-B; and
  • B is hydrogen, -COZR 52 , cyano or C r C 4 alkyl-C(O)-, and the salts and stereoisomers of the compound of formula I.
  • the present invention relates also to compounds of formula I wherein
  • R j is C r C 4 alkyl
  • R 2 is C r C 4 alkyl, C r C 4 haloalkyl, C 3 - or C 4 -alkenyl or C 3 - or C 4 -alkynyl; n is 0, 1 or 2;
  • R 3 is hydrogen, C r C 4 alkyl, C r C 4 haloalkyl, C 3 - or C 4 -alkenyl or C 3 - or C 4 -alkynyl;
  • R 4 is hydrogen, fluorine or chlorine
  • R 5 is hydrogen, halogen, methyl, trifluoromethyl, cyano, nitro, amino or C ⁇ -C 4 haloalkoxy;
  • R 6 is hydrogen, halogen, C r C 5 alkyl, C r C 5 haloalkyl, C 2 -C 5 alkenyl, C 2 -C 5 haloalkenyl, C 2 -C 5 alkynyl, C 2 -C 5 haloalkynyl, cyano, NHR 10 or NR 10 R ⁇ ;
  • R 10 and R ⁇ are each independently of the other C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C r C 4 alkylcarbonyl, Cj- haloalkylcarbonyl, C r C 4 alkylsulfonyl, C r C 4 haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by C 1 -C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C r C 4 alkyl, C 1 -C 4 haloalkyl or by halogen; or
  • R ⁇ is OR 2u ;
  • R 20 is hydrogen, C,-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C r C 4 alkoxy-C r C 4 alkyl, C I -C 4 alkylthio-C 1 -C 4 alkyl, phenyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, those aromatic and heteroaromatic rings being unsubstituted or mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, or C r C 8 alkyl-COXR 21 ;
  • X is oxygen, sulfur or NR 22 ;
  • R 2 ⁇ is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C r C 4 alkoxy-C r C 4 alkyl, C r C 4 alkylthio-C r C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C r C 4 alkyl or by halogen; and
  • R 22 is hydrogen, C r C 8 alkyl or C 3 -C 8 alkenyl
  • R 6 is S(O) m R 30 ; m is 0, 1 or 2;
  • R 30 is hydrogen, chlorine, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cycloalkyl, C r C 4 alkoxy-C r C 4 alkyl, C,-C 4 alkylthio-C r C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C,-C 4 haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by C,-C 4 alkyl, C r C 4 haloalkyl or by halogen, or C,-C 4 alkyl-COVR 3I ;
  • V is oxygen, sulfur or NR 32 ;
  • R 3] is hydrogen, C,-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C r C 4 alkoxy-C r C 4 alkyl, C r C 4 alkylthio-C r C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen; and
  • R 32 is hydrogen, C r C 8 alkyl or C 3 -C 8 alkenyl
  • R 6 is COR 40 ;
  • R 40 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C r C 4 alkoxy-C r C 4 alkyl, C r C 4 alkylthio-C r C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C r C 4 alkyl, C,-C 4 haloalkyl or by halogen; or
  • R 6 is COYR 50 ;
  • Y is oxygen, sulfur, NR 51 or NOR 54 ;
  • R 50 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C r C 4 alkoxy-C r C 4 alkyl, C r C 4 alkylthio-C r C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, or C r C 4 alkyl- COZR 52 ;
  • Z is oxygen, sulfur, NR 53 or NOR 55 ;
  • R 52 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C I -C 4 alkoxy-C 1 -C 4 alkyl, C 1 -C 4 alkylthio-C 1 -C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen;
  • R 5] and R 53 are each independently of the other C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C r C 4 alkylcarbonyl, C r C 4 haloalkylcarbonyl, C r C 4 alkylsulfonyl, C r C 4 haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C j -C 4 alkyl, C r C 4 haloalkyl or by halogen; and
  • R 54 and R 55 are each independently of the other C r C 4 alkyl; or
  • R 6 is C r C 4 alkylCOZR 52 , C r C 4 haloalkylCOZR 52 , C 2 -C 4 alkenylCOZR 52 , C 2 -C 4 alkynylCOZR 52 or C 2 -C 4 haloalkenylCOZR 52 , and the salts and stereoisomers of the compound of formula I.
  • the present invention relates also to compounds of formula I wherein R, is C j - alkyl;
  • R 2 is C r C 4 alkyl, C r C 4 haloalkyl, C 3 - or alkenyl or C 3 - or C 4 alkynyl; n is 0, 1 or 2; R 3 is C]-C 4 alkyl, C r C 4 haloalkyl, C 3 - or C 4 -alkenyl or C 3 - or C 4 -alkynyl;
  • R 4 is hydrogen, fluorine or chlorine
  • R 5 is hydrogen, halogen, methyl, trifluoromethyl, cyano, nitro, amino or C r C 4 halo- alkoxy;
  • R 6 is hydrogen, halogen, cyano, NHR ⁇ 0 or NR* 0 R ⁇ X ;
  • R 10 and R ⁇ are each independently of the other C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C r C 4 alkylcarbonyl, C r C 4 haloalkylcarbonyl, C r C 4 alkylsulfonyl, C r C 4 haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C j -C 4 alkyl, C r C 4 haloalkyl or by halogen; or
  • R 6 is OR 20 ;
  • R 20 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C r C 4 alkylthio-C r C 4 alkyl, phenyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, those aromatic and heteroaromatic rings being unsubstituted or mono- to tri-substituted by C r C alkyl, C r C 4 haloalkyl or by halogen, or C r C 8 alkyl-COXR 2 ⁇ ;
  • X is oxygen, sulfur or NR 22 ⁇
  • R 2 ⁇ is hydrogen, C C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C r C 4 alkoxy-Cj-C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C ⁇ -C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by C ⁇ -C alkyl or by halogen; and
  • R 22 is hydrogen, C r C 8 alkyl or C 3 -C 8 alkenyl
  • R 6 is SCO) ⁇ ; m is 0, 1 or 2;
  • R 30 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C r C 4 alkoxy-C r C 4 alkyl, C r C 4 alkylthio-C r C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by Cj- afkyl, C r C 4 haloalkyl or by halogen, or C r C 4 alkyl- COVR 31 ;
  • V is oxygen, sulfur or NR 32 ;
  • R 3 I is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C,-C 4 alkoxy-C r C 4 alkyl, C r C 4 alkylthio-C r C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen; and R 32 is hydrogen, C r C 8 alkyl or C 3 -C 8 alkenyl; or R 6 is COR 40 ; R 40 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl
  • R 6 is COYR 50 ;
  • Y is oxygen, sulfur, NR 51 or NOR 5 ;
  • R 50 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C r C 4 alkoxy-C r C 4 alkyl, C r C 4 alkylthio-C r C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, or C,-C 4 alkyl-COZR 52 ;
  • Z is oxygen, sulfur, NR 53 or NOR 55 ;
  • R 52 is hydrogen, C r C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 1 -C 8 haloalkyl, C 3 -C 6 cyclo- alkyl, C ⁇ -C 4 alkoxy-C r C 4 alkyl, C r C 4 alkylthio-C r C 4 alkyl, phenyl, phenyl mono- to tri-substituted by C r C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C 1 -C alkyl, C r C 4 haloalkyl or by halogen;
  • R 51 and R 53 are each independently of the other C*-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r Cghaloalkyl, Cj-C 4 alkylcarbonyl, C r C 4 haloalkylcarbonyl, C ] -C 4 alkylsulfonyl, C r C 4 haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by C ⁇ -C 4 alkyl, C r C 4 haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C r C alkyl, C r C 4 haloalkyl or by halogen; and
  • R 54 and R 55 are each independently of the other C r C 4 alkyl; or
  • R 6 is C r C 4 alkylCOZR 52 , C r C 4 haloalkylCOZR 52 , C 2 -C 4 alkenylCOZR 52 , C 2 -C 4 alkynylCOZR 52 or C 2 -C 4 haloalkenylCOZR 52 , and the salts and stereoisomers of the compound of formula I.
  • halogen is to be understood as being fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • alkyl, alkenyl and alkynyl groups may be straight-chained or branched, and this applies also to the alkyl, alkenyl and alkynyl moiety of alkylcarbonyl, haloalkyl, halo ⁇ alkoxy, haloalkylcarbonyl, haloalkylphenyl, alkoxyalkyl, alkoxyalkoxyalkyl, alkylthio, alkenylthio, alkynylthio, alkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, alkylphenyl, alkylamino, dialkylamino, alkylaminocarbonyl-alkyl, halo- alkylamino, di(haloalkyl)amino, alkoxyalkylamino, carboxyalkyl
  • alkyl groups examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and the various isomeric pentyl, hexyl, heptyl and octyl radicals, preferably alkyl groups having from 1 to 4 carbon atoms.
  • alkenyls examples include vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-l-yl, pentenyl, 2-hexenyl, 3-heptenyl and 4-octenyl, preferably alkenyl radicals having a chain length of from 3 to 5 carbon atoms.
  • alkynyls that may be mentioned are ethynyl, propargyl, 1-methylpropargyl, 3-butynyl, but-2-yn-l-yl, 2-methylbutyn-2-yl, but-3-yn-2-yl, 1-pentynyl, pent-4-yn-l-yl and 2-hexynyl, preferably alkynyl radicals having a chain length of from 2 to 4 carbon atoms.
  • Suitable as haloalkyl are alkyl groups mono- or poly-substituted, especially mono- to tri- substituted, by halogen, with halogen being in particular iodine and especially fluorine, chlorine and bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloro- methyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl and 2,2,2-trichloroethyl.
  • Suitable as haloalkenyl are alkenyl groups mono- or poly-substituted by halogen, with halogen being in particular bromine, iodine and especially fluorine and chlorine, for example 3-fluoro ⁇ ropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluoro-but-2-en-l-yl and 4,4,4-trichloro-but-2-en-l-yl.
  • alkenyl radicals mono-, di- or tri-substituted by halogen, preference is given to those having a chain length of 3 or 4 carbon atoms.
  • the alkenyl groups may be substituted with halogen at saturated or unsaturated carbon atoms.
  • Haloalkenyl in the definition of R 6 as haloalkenylCOZR 52 is, for example, 1 ,2-dichloro- ethenyl or 1,2-dibromoethenyl.
  • Suitable as haloalkynyl are, for example, alkynyl groups mono- or poly-substituted by halogen, with halogen being bromine, iodine and especially fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn- 1 -yl.
  • Carboxyalkyl is, for example, carboxymethyl, carboxyethyl, carboxyeth-1-yl and carboxy- propyl.
  • Alkoxyalkyl is, for example, methoxymethyl, ethoxymethyl, propoxymethyl, methoxy- ethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, ethoxypropyl or propoxy- propyl.
  • Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.
  • Alkenyloxy is, for example, allyloxy, methallyloxy and but-2-en-l-yloxy.
  • Alkynyloxy is, for example, propargyloxy and 1-methylpropargyloxy.
  • Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl and n-butoxycarbonyl, preferably methoxycarbonyl and ethoxy ⁇ carbonyl.
  • Alkenyloxycarbonyl is, for example, allyloxycarbonyl, methallyloxycarbonyl, but-2-en- 1-yl-oxycarbonyl, pentenyloxycarbonyl, 2-hexenyloxycarbonyl and 3-heptenyloxy- carbonyl.
  • Alkynyloxycarbonyl is, for example, propargyloxycarbonyl, 3-butynyloxycarbonyl, but-2-yn-l-yl-oxycarbonyl and 2-methylbutyn-2-yl-oxycarbonyl.
  • Alkylamino is, for example, methylamino, ethylamino and the isomeric propylamino and butylamino.
  • Dialkylamino is, for example, dimethylamino, diethylamino and the isomeric dipropyl- amino and dibutylamino.
  • Alkenylamino is, for example, allylamino, methallylamino and but-2-en-l-yl-amino.
  • Alkynylamino is, for example, propargylamino and 1-methylpropargylamino.
  • Cycloalkyl radicals that come into consideration as substituents are, for example, cyclo ⁇ propyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Alkoxyalkoxycarbonyl is, for example, methoxymethoxycarbonyl, ethoxymethoxy- carbonyl, ethoxyethoxycarbonyl, propoxymethoxycarbonyl, propoxyethoxycarbonyl, propoxypropoxycarbonyl, butoxyethoxycarbonyl and butoxybutoxycarbonyl.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-tri- fluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2-tri- chloroethoxy.
  • Haloalkylamino is, for example, chloroethylamino, trifluoroethylamino and 3-chloro- propylamino.
  • Di(haloalkyl)amino is, for example, di(chloroethyl)amino.
  • Alkylthioalkyl is, for example, methylthioethyl, ethylthioethyl, methylthiopropyl and ethylthiopropyl.
  • Alkenylthiocarbonyl is, for example, allylthiocarbonyl, methallylthiocarbonyl, but-2-en-l-yl-thiocarbonyl, pentenylthiocarbonyl and 2-hexenylthiocarbonyl.
  • Alkynylthiocarbonyl is, for example, propargylthiocarbonyl, 1-methylpropargylthio- carbonyl and but-2-yn-l-yl-thiocarbonyl.
  • Phenyl, benzyl or benzoyl as part of a substituent such as phenoxy, phenoxycarbonyl, phenoxycarbonylalkyl, benzoylamino or benzylamino is unsubstituted or substituted.
  • the substituents may then be in the ortho-, meta- or para-position.
  • Substituents are, for example, C r C 4 alkyl, halogen, C r C 4 haloalkyl, cyano, nitro, hydroxy, C r C 4 alkoxy, C r C 4 haloalkoxy, amino, C r C 4 alkylamino, di-C r C 4 alkylamino, carboxyl, C r C 4 alkoxy- carbonyl, carbamoyl, C r C 4 alkylaminocarbonyl or di-C r C 4 alkylaminocarbonyl.
  • Salts of the compounds of formula I with acidic hydrogen are, for example, alkali metal salts, for example sodium and potassium salts; alkaline earth metal salts, for example calcium and magnesium salts; ammonium salts, that is to say unsubsti- tuted ammonium salts and mono- or poly-substituted ammonium salts, for example triethylammonium and methylammonium salts; or salts with other organic bases.
  • alkali metal salts for example sodium and potassium salts
  • alkaline earth metal salts for example calcium and magnesium salts
  • ammonium salts that is to say unsubsti- tuted ammonium salts and mono- or poly-substituted ammonium salts, for example triethylammonium and methylammonium salts
  • salts with other organic bases are, for example, alkali metal salts, for example sodium and potassium salts; alkaline earth metal salts, for example calcium and magnesium salts; ammonium salts, that
  • alkali metal and alkaline earth metal hydroxides as salt-forming agents, special mention should be made, for example, of the hydroxides of lithium, sodium, potassium, magnesium or calcium, but especially those of sodium or potassium.
  • Examples of amines suitable for ammonium salt formation are both ammonia and primary, secondary and tertiary C r C 18 alkylamines, C r C 4 hydroxyalkylamines and C 2 -C 4 alkoxy- alkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octyl- amine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadec
  • Salts of the compounds of formula I with basic groups are, for example, salts with inorganic and organic acids, for example hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid, and also sulfuric acid, phosphoric acid, nitric acid and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methane- sulfonic acid and salicylic acid.
  • hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid
  • sulfuric acid phosphoric acid
  • nitric acid and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic
  • the compounds of formula I are to be under ⁇ stood as including both the pure optical antipodes and the racemates or diastereoisomers.
  • R 6 is hydrogen, halogen, OR 2 o, S(O) m R 30 or COYR 5 o.
  • R 4 is fluorine
  • R 4 is hydrogen
  • R 4 is chlorine
  • R 4 is chlorine; and R 6 is OR 2 ⁇ wherein R ⁇ is as defined for formula I.
  • a group of very especially preferred compounds of formula I comprises compounds wherein R 4 is fluorine; and R 6 is OR 2 ⁇ wherein R 20 is as defined for formula I.
  • R 4 is fluorine; and R 6 is S(O) m R 30 wherein R 30 and m are as defined for formula I.
  • a further group of very especially preferred compounds of formula I comprises compounds wherein R 4 is chlorine; and R 6 is COR 40 , COYR 50 , C r C 4 alkylCOZR 52 , C r C 4 haloalkylCOZR 52 , C 2 -C 4 alkenylCOZR 52 , C 2 -C 4 alkynylCOZR 52 or C 2 -C 4 halo- alkenylCOZR 52 wherein R 40 , R 50 , R 52 , Y and Z are as defined for formula I.
  • a further group of very especially preferred compounds of formula I comprises compounds wherein R 4 is fluorine; and R 6 is COR 40 , COYR 50 , C r C 4 alkylCOZR 52 , C r C 4 haloalkylCOZR 52 , C 2 -C 4 alkenylCOZR 52 , C 2 -C 4 alkynylCOZR 52 or C 2 -C 4 halo- alkenylCOZR 52 wherein R 40 , R 50 , Rs 2 , Y and Z are as defined for formula I.
  • R 5 is chlorine; and R 6 is -COYR 50 .
  • Another group of likewise very especially preferred compounds of formula I comprises compounds wherein R 5 is chlorine; and R 6 is C r C 4 alkyl-B or C r C 4 haloalkyl-B.
  • Ri to R 6 and n are as defined for formula I can be prepared by means of processes known per se, for example by cyclising a compound of formula DI
  • R j , R 2 and R 4 to R 6 are as defined,
  • radical R 3 in the compounds of formula Xa being as defined for formula I and L* being a leaving group, preferably chlorine, bromine, iodine, CH 3 SO 2 O- or
  • n 0, and then oxidising that compound
  • R- to R 6 are as defined, and n is 0, and then oxidising that compound.
  • R-, R 2 , R 4 to Rg and n are as defined for formula I, is carried out analogously to known processes and comprises halogenating a compound of formula IV
  • R 2 is as defined, optionally in the presence of a solvent, for example an alcohol, for example ethanol, and a base, for example an alcoholate, for example an ethanolate, to form a compound of formula XIV
  • a solvent for example an alcohol, for example ethanol
  • a base for example an alcoholate, for example an ethanolate
  • reaction Scheme 1, Route a The formation of the pyrazole rings of formula lla that are unsubstituted at the nitrogen atoms (Reaction Scheme 1, Route a)) is carried out by reaction of the compounds of formula III with hydrazine or hydrazine hydrate optionally in the presence of a suitable solvent at elevated temperature, preferably with hydrazine hydrate in alcoholic solution at elevated temperature.
  • reaction Scheme 2 The formation of the pyrazole rings of formulae ⁇ and lla that are unsubstituted at the nitrogen atoms (Reaction Scheme 2) can be carried out, for example, also by halogenation of the compounds of formula IN preferably with chlorine or bromine optionally in the presence of a suitable solvent and a base, for example acetic acid and sodium acetate, subsequent cyclisation with a compound of formula XIII optionally in a solvent, for example an alcohol, preferably ethanol, and in the presence of a base, for example an alcoholate, preferably an ethanolate, and ring contraction (extrusion reaction) analogously to known procedures, as described, for example, in Chem. Ber. 92, 2593 (1959) or Acta Chem. Scand. 16, 2395 (1962). That method, described in Reaction Scheme 2, is suitable for the preparation of derivatives of formulae Ha and II that are substituted by halogen, especially by fluorine and chlorine, at the phenyl ring.
  • N-alkylation of the pyrazole rings in the compounds of formulae II and lla in Reaction Schemes 1 and 3 is carried out at room temperature or at slightly elevated temperatures in the presence of a solvent, for example acetone, methyl ethyl ketone, N,N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide, a base, for example potassium carbonate, sodium carbonate, sodium hydroxide or potassium hydroxide, and an alkylating agent of formula Xa or Xb, preferably methyl iodide or dimethyl sulfate.
  • a solvent for example acetone, methyl ethyl ketone, N,N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide
  • a base for example potassium carbonate, sodium carbonate, sodium hydroxide or potassium hydroxide
  • an alkylating agent of formula Xa or Xb preferably methyl iodide or dimethyl
  • reaction Schemes 1 and 2 The subsequent oxidation of the compounds of formula I wherein n is 0 (Reaction Schemes 1 and 2) is carried out, for example, with peracids, for example m-chloroper- benzoic acid, or hydrogen peroxide in the presence of a suitable solvent, for example dichloromethane, chloroform or carbon tetrachloride, at temperatures of from -40°C to the reflux temperature of the solvent in question, preferably from 0°C to 35°C.
  • a suitable solvent for example dichloromethane, chloroform or carbon tetrachloride
  • the degree of oxidation at the sulfur atom can be controlled by the amount of oxidising agent: in the case of an equimolar amount of oxidising agent, compounds of formula I wherein n is 1 are obtained and in the case of an excess (at least 2 mol) of oxidising agent, compounds of formula I wherein n is 2 are obtained.
  • the reaction in Reaction Scheme 4 is carried out, for example, analogously to WO 92/02509, according to which the phenylcarbonyl derivative of formula IV is allowed to react in the presence of a base, for example sodium hydride or potassium tert- butanolate, and an aprotic solvent, for example tetrahydrofuran, with carbon disulfide at temperatures of from 0°C to 80°C, and immediately afterwards an alkylating agent, for example R 2 -Hal or R 2 OSO 2 OR 2 wherein R 2 is as defined for formula I and Hal is halogen, especially chlorine, bromine or iodine, is added at temperatures of from 0°C to the reflux temperature of the solvent used.
  • a base for example sodium hydride or potassium tert- butanolate
  • an aprotic solvent for example tetrahydrofuran
  • the compounds of formula XUI in Reaction Scheme 2 can be prepared in accordance with known methods (for example Chem. Ber. 92, 2593 (1959) or Acta Chem. Scand. 16, 2395 (1962)), for example by reaction of hydrazine or hydrazine hydrate with carbon disulfide and subsequent alkylation with the reagent R -Hal or R 2 OSO 2 OR 2 wherein R 2 is as defined for formula I and Hal is halogen, especially chlorine or bromine, in the presence of a base.
  • Suitable solvents are, for example, alcohols, for example ethanol
  • suitable bases are, for example, alcoholates, for example sodium methanolate or sodium ethanolate, or potassium or sodium hydroxide.
  • reaction according to Method a) in Reaction Scheme 5 is carried out analogously to Nogel's Textbook of Practical Organic Chemistry', Longman 1989, page 1006 ff.
  • aromatic compound of formula V is allowed to react in the presence of a carboxylic acid derivative, for example a carboxylic acid chloride of formula VI and an acid, for example a Lewis acid such as aluminium chloride, with or without a solvent at temperatures of from 0°C to 150°C.
  • the reaction according to Method b) in Reaction Scheme 5 is carried out, for example, starting from the carboxylic acid derivatives of formula Va wherein X* is -OH or -N(CH 3 )OCH 3 with an alkyllithium compound of formula VII or a Grignard compound (alkylmagnesium chloride or bromide) of formula VIE in an inert solvent, preferably diethyl ether at temperatures of from -100°C to 50°C, analogously to Organic Reactions 18, 1 (1970), Organic Synthesis 49, 81 (1969) and 'Comprehensive Organic Transformations', Editor R.C. Larock, VCH 1989, page 685.
  • the phenylpyrazole derivatives of formula II are novel and have been developed espe ⁇ cially for the synthesis of the compounds of formula I. They are therefore also a subject of the present invention.
  • a large number of known standard procedures is available for the preparation of the phenylpyrazoles of formula I substituted in the 5- ⁇ osition of the phenyl ring (R 6 ), the selection of the suitable preparation processes being made in accordance with the properties (reactivities) of the substituents in the intermediates in question.
  • the phenolpyrazole derivatives of formula I 3 in Reaction Scheme 6 can be obtained, for example, a) from the compounds of formula I- via ether cleavage by means of lithium chloride in N,N-dimethylformamide (DMF) at elevated temperature, as described, for example, in Synthesis.1989, 287, or by means of boron tribromide in dichloromethane at temperatures of from -80°C to 20°C, as described, for example, in Org. Synth., Collect. Vol. V, 412, 1973; or b) from the compounds of formula I 2 via hydrogenolysis by means of hydrogen in the presence of a catalyst, for example palladium on carbon, as described, for example, in J. Am. Chem. Soc.
  • a catalyst for example palladium on carbon
  • the preparation of the thiophenolpyrazoles of formula I 6 in Reaction Scheme 7 can be carried out analogously to known procedures, as described, for example, in J. Org. Chem. 54, 6096 (1989), EP-A-0 259 265 or in "Sulfonation and Related Reactions", Editor Gilbert, Interscience Publishers, New York 1965.
  • the phenylpyrazole of formula I 4 is then chlorosulfonylated with chlorosulfonic acid or sulfur trioxide in sulfuric acid to form the compound of formula I 5 and then reduced with tin chloride or zinc chloride to the thiophenol derivative of formula I 6 .
  • W is the radical wherein R 2 to R 3 and n are as
  • the phenylpyrazole of formula I 4 can be converted into an aniline derivative of formula I 8 in accordance with standard procedures, for example nitration in a nitric acid and sulfuric acid mixture and subsequent reduction of the resulting nitro compound of formula I 7 with hydrogen in the presence of a catalyst or according to Bechamps.
  • the aniline derivative of formula I 8 can then be either derivatised directly to form the corresponding compounds of formula I according to standard procedures, for example alkylation or acylation, or converted into the halogen compound of formula I 9 by means of diazotisation and Sandmeyer reaction.
  • the benzoic acid ester of formula I 10 in Reaction Scheme 8 can be obtained, for example, analogously to J.
  • W is the radical wherein Rj to R 3 and n are as defined for formula I.
  • the alkynyl ester derivatives of formula I l 3 can be prepared, for example, via Heck reaction analogously to R. F. Heck in W. G. Dauben (Edit.), Organic Reactions 27, 345 (1982). It is possible to obtain therefrom by means of standard procedures, for example by means of partial or complete hydrogenation, the corresponding alkenyl- or alkyl-COZR 52 derivatives, respectively, or via halogenation the corresponding haloalkenyl- or haloalkyl-COZR 52 derivatives of formula I.
  • the haloalkylCOZR 52 derivatives of formula I 14 can be produced from the aniline derivatives of formula I 8 analogously to Organic Reactions 11, 189-260 (1960) via diazotisation and Meerwein reaction.
  • Known standard procedures for example hydrogenolysis or halogen removal, yield therefrom the corresponding alkyl- or alkenyl-COZR 52 derivatives of formula I.
  • the reagent used is the compound of formula XI, for example N-alkyl- hydrazine, preferably N-methylhydrazine.
  • substituted pyrazolinone derivative of formula XVIII can be prepared also via N-alkylation of the corresponding unsubstituted pyrazolinones of formula XVII, in a manner analogous to that described in Reaction Scheme 3.
  • the compounds of formula XV are novel and have been developed especially for the synthesis of the compounds of formula I. They are therefore also a subject of the present invention. All further compounds originating from the scope of formula I can easily be prepared from the described compounds of formula I in manner analogous to that described above, or in accordance with methods as described, for example, in "Methoden der Organischen Chemie” (Houben-Weyl), Volume E 8b, Georg Thieme Verlag Stuttgart, 1994, page 399 ff. or in "Pyrazoles, Pyrazolines, Pyrazolidines, Indazoles and Condensed Rings", Editor R. H. Wiley, Interscience Publishers, New York, 1967, page 1 ff., or by derivatisation in accordance with known standard methods, for example alkylation, acylation and amidation.
  • the end products of formula I can be isolated in customary manner by concentration and/or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydro ⁇ carbons or chlorinated hydrocarbons, by distillation or by means of column chromato ⁇ graphy or flash column chromatography and a suitable eluant.
  • the compounds of formula I may be used in unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants customarily employed in formulation technology e.g. into emulsifiable concen ⁇ trates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • the methods of application such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circum ⁇ stances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and generally one or more solid or liquid formulation adjuvants
  • formulation adjuvants e.g. solvents or solid carriers.
  • surfactants surface- active compounds
  • Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, such as mixtures of alkylbenzenes, e.g. xylene mixtures or alkylated naphthalenes; aliphatic and cycloaliphatic hydrocarbons, such as paraffins, cyclohexane or tetrahydronaphthalene; alcohols, such as ethanol, propanol or butanol; glycols and their ethers and esters, such as propylene glycol or dipropylene glycol ether; ketones, such as cyclohexanone, isophorone or diacetone alcohol; strongly polar solvents, such as N- methyl-2-pyrrolidone, dimethyl sulfoxide or water; vegetable oils and esters thereof, such as rape oil, castor oil or soybean oil; and, where appropriate, also silicone oils.
  • aromatic hydrocarbons preferably the fractions containing 8 to 12 carbon atoms,
  • the solid carriers used are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • calcite talcum
  • kaolin kaolin
  • montmorillonite attapulgite
  • highly dispersed silicic acid or highly dispersed absorbent polymers e.g., calcite, talcum, kaolin, montmorillonite or attapulgite.
  • Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite, and suitable nonsorbent carriers are, for example, calcite or sand.
  • pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
  • suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.
  • surfactants will also be under ⁇ stood as comprising mixtures of surfactants.
  • Both water-soluble soaps and water-soluble synthetic surface-active compounds are suitable anionic surfactants.
  • Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C ]0 -C 2 ), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyltaurin salts.
  • so-called synthetic surfactants are used, especially fatty alcohol sulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylaryl- sulfonates.
  • the fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C 8 -C 22 alkyl radical, which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids.
  • These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts.
  • the sulfonated benz ⁇ imidazole derivatives preferably contain two sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalene- sulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
  • corresponding phosphates e.g. salts of the phosphoric acid ester of an adduct of p-no ⁇ ylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.
  • Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cyclo ⁇ aliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydro ⁇ carbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
  • non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil poly ⁇ glycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxy- ethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • Fatty acid esters of polyoxyethylene sorbitan e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
  • Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C 8 -C 22 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.
  • the salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
  • the herbicidal compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula I, 1 to 99.9 % of a solid or liquid formulation adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant.
  • compositions may also comprise further auxiliaries, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients.
  • stabilisers e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil)
  • anti- foams e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers, as well as fertilisers or other active ingredients.
  • Preferred formulations have especially the following composition (throughout, percentages are by weight):
  • Emulsifiable concentrates active ingredient: 1 to 90 %, preferably 5 to 50 % surface-active agent: 5 to 30 %, preferably 10 to 20 % solvent: 15 to 94 %, preferably 70 to 85 %
  • Dusts active ingredient: 0.1 to 50 %, preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • the compounds of formula I are generally used successfully when applied to the plant or to the locus thereof at rates of application of from 0.001 to 2 kg/ha, especially from 0.005 to 1 kg/ha.
  • concentration required to achieve the desired effect can be determined by experiment. It is dependent upon the type of action, the stage of development of the cultivated plant and of the weed, and also upon the application (place, time, method) and, in dependence on those parameters, can vary within wide limits.
  • the compounds of formula I are distinguished by herbicidal and growth-inhibiting properties which render them suitable for use in crops of useful plants, especially in cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • Crops are also to be understood as being those which have been rendered tolerant to herbicides or classes of herbicide by conventional methods of breeding or genetic engineering.
  • Example PI 1 -(2,4-Dichlorophenyl)-3,3-bis(methylthio)-2-methyl-2-propen-l-one
  • the resulting solution is then cooled to 5-10°C and 2.7 g (0.01 mol) of ⁇ -bromo-4-chloro-2-fluoropropiophenone in 5 ml of ethanol are added dropwise to the solution and stirring is continued for a further 10 minutes at 40-45°C.
  • 10 ml of 2N hydro ⁇ chloric acid are added dropwise at 22°C to the solution that has formed and stirring is continued for 1 hour at 22°C and then for 15 minutes at 40-45°C.
  • the resulting suspension is dissolved in tert-butyl methyl ether, washed three times with water and concentrated by evaporation using a rotary evaporator.
  • the organic phase is extracted with a dilute sodium hydroxide solution, and the aqueous phase is separated off and again acidified and extracted with MTBE.
  • 4.8 g (33.5 % of the theoretical yield) of the desired product are obtained in the form of crystals having a melting point of 136- 138°C and 7.6 g of crude product of the desired compound in the form of an oil.
  • Example P 10 3-(4-Chloro-2-fluoro-5-trifluoromethylsulfonyloxyphenyl)-4-methvI-5- (methylthio)- 1 -methyl- 1 " 1 HI -pyrazole
  • reaction mixture After being stirred for 30 minutes at 0-5°C and then at 22°C overnight, the reaction mixture is concentrated to approximately 1/3 of its original volume by evaporation, poured into a mixture of ice, water and hydrochloric acid, extracted with MTBE, washed with water and concentrated by evaporation. After purifica ⁇ tion of the crude product by silica gel chromatography, 87.7 g (70% of the theoretical yield) of the desired compound are isolated in the form of crystals having a melting point of 54-56°C.
  • Example PI 1 3-(4-Chloro-2-fluoro-5-methoxycarbonylphenyl)-4-methyl-5-(methylthio)- 1 -methyl- 1 " 1 Hl-pyrazole
  • Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • the active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
  • the active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water.
  • the mixture is extruded and then dried in a stream of air.
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
  • Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastic pots.
  • an aqueous suspension or emulsion of the test compounds prepared from a 25 % wettable powder or emulsifiable concentrate (Example F3, b) or Fl, c)) is applied by spraying at a rate of application corresponding to 2000 g of active ingredient hectare (5001 water/ha).
  • Test plants Avena, Setaria, Sinapis, Stellaria
  • the compounds according to the invention exhibit good herbicidal action.
  • Test plant Avena Setaria Sinapis Stellaria Compound No.
  • Example B2 Post-emergence herbicidal action (contact herbicide)
  • contact herbicide contact herbicide
  • monocotyledonous and dicotyledonous test plants are raised in plastic pots containing standard soil and at the 4- to 6-leaf stage are sprayed with an aqueous suspension or emulsion of the test compounds of formula I prepared from a 25 % wettable powder or emulsifiable concentrate (Example F3, b) or Fl, c)) at a rate of application corresponding to 2000 g of active ingredient ha (5001 water/ha).

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Abstract

La présente invention se rapporte à de nouveaux composés de formule (I), dans laquelle les substituants R1 à R6 et n sont tels que définis dans la revendication 1. Les sels et les stéréoisomères des composés de formule (I) possèdent de bonnes propriétés herbicides sélectives d'avant et d'après émergence. L'invention décrit également la préparation de ces composés ainsi que leur utilisation en tant qu'ingrédients herbicides actifs.
PCT/EP1996/002417 1995-06-15 1996-06-04 Nouveaux herbicides WO1997000246A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US08/765,161 US6103667A (en) 1995-06-15 1996-06-04 Phenylpyrazole herbicides
MX9710042A MX9710042A (es) 1995-06-15 1996-06-04 Nuevos herbicidas.
AU62217/96A AU6221796A (en) 1995-06-15 1996-06-04 Novel herbicides
EP96920785A EP0832070A1 (fr) 1995-06-15 1996-06-04 Nouveaux herbicides

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CH177295 1995-06-15
CH1772/95 1995-06-15
CH342695 1995-12-04
CH3426/95 1995-12-04

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997046535A1 (fr) * 1996-06-03 1997-12-11 Bayer Aktiengesellschaft 3-cyanoaryl-pyrazoles et leur utilisation comme herbicides
EP0839808A1 (fr) * 1996-10-29 1998-05-06 Novartis AG Dérivés de pyrazole, procédés pour leur préparation et leur application comme herbicides
WO1998042698A1 (fr) * 1997-03-21 1998-10-01 Novartis Ag Derives de pyrazole en tant qu'herbicides
US5962694A (en) * 1995-11-15 1999-10-05 Basf Aktiengesellschaft Substituted 1-methyl-3-phenylpyrazoles and the use thereof as herbicides and for the desiccation or defoliation of plants
US6096689A (en) * 1995-07-06 2000-08-01 Basf Aktiengesellschaft 5-pyrazolylbenzoic acid derivatives as herbicides
WO2004089914A1 (fr) * 2003-04-08 2004-10-21 Basf Aktiengesellschaft Derives de benzolsulfonamide constituant des composes herbicides ou dessiccants/defoliants
JP5113531B2 (ja) * 2006-01-16 2013-01-09 三井化学アグロ株式会社 （３−硫黄原子置換フェニル）ピラゾール誘導体

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JPH03163063A (ja) * 1988-08-31 1991-07-15 Nippon Nohyaku Co Ltd ３―置換フェニルピラゾール誘導体又はその塩類及びその製造方法並びに除草剤
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WO1996015115A1 (fr) * 1994-11-10 1996-05-23 Zeneca Limited Composes de pyrazole herbicides

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JPH03163063A (ja) * 1988-08-31 1991-07-15 Nippon Nohyaku Co Ltd ３―置換フェニルピラゾール誘導体又はその塩類及びその製造方法並びに除草剤
WO1992002509A1 (fr) * 1990-08-06 1992-02-20 Monsanto Company Arylpyrazols d'akylsulfonil herbicides a substitutions
WO1996015115A1 (fr) * 1994-11-10 1996-05-23 Zeneca Limited Composes de pyrazole herbicides

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Cited By (12)

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Publication number Priority date Publication date Assignee Title
US6096689A (en) * 1995-07-06 2000-08-01 Basf Aktiengesellschaft 5-pyrazolylbenzoic acid derivatives as herbicides
US5962694A (en) * 1995-11-15 1999-10-05 Basf Aktiengesellschaft Substituted 1-methyl-3-phenylpyrazoles and the use thereof as herbicides and for the desiccation or defoliation of plants
WO1997046535A1 (fr) * 1996-06-03 1997-12-11 Bayer Aktiengesellschaft 3-cyanoaryl-pyrazoles et leur utilisation comme herbicides
EP0839808A1 (fr) * 1996-10-29 1998-05-06 Novartis AG Dérivés de pyrazole, procédés pour leur préparation et leur application comme herbicides
US6339046B1 (en) 1996-10-29 2002-01-15 Syngenta Investment Corporation Pyrazde herbicides
WO1998042698A1 (fr) * 1997-03-21 1998-10-01 Novartis Ag Derives de pyrazole en tant qu'herbicides
US6274536B1 (en) 1997-03-21 2001-08-14 Syngenta Crop Protection, Inc. Pyrazole derivatives as herbicides
WO2004089914A1 (fr) * 2003-04-08 2004-10-21 Basf Aktiengesellschaft Derives de benzolsulfonamide constituant des composes herbicides ou dessiccants/defoliants
JP2006522760A (ja) * 2003-04-08 2006-10-05 ビーエーエスエフ　アクチェンゲゼルシャフト 除草剤又は乾燥性及び／若しくは落葉性化合物としてのベンゼンスルホンアミド誘導体
US7741485B2 (en) 2003-04-08 2010-06-22 Basf Aktiengesellschaft Benzenesulphonamide derivatives as herbicides or desiccant/defoliant compounds
JP4699358B2 (ja) * 2003-04-08 2011-06-08 ビーエーエスエフ ソシエタス・ヨーロピア 除草剤又は乾燥性及び／若しくは落葉性化合物としてのベンゼンスルホンアミド誘導体
JP5113531B2 (ja) * 2006-01-16 2013-01-09 三井化学アグロ株式会社 （３−硫黄原子置換フェニル）ピラゾール誘導体

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MX9710042A (es) 1998-03-29
EP0832070A1 (fr) 1998-04-01

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