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WO1997000246A1 - Novel herbicides - Google Patents

Novel 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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WO
WIPO (PCT)
Prior art keywords
alkyl
halogen
substituted
tri
benzyl
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.)
Ceased
Application number
PCT/EP1996/002417
Other languages
French (fr)
Inventor
Hans-Georg Brunner
Milan Karvas
Kurt Nebel
Georg Pissiotas
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.)
Novartis AG
Original Assignee
Ciba Geigy AG
Novartis AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG, Novartis AG filed Critical Ciba Geigy AG
Priority to AU62217/96A priority Critical patent/AU6221796A/en
Priority to MX9710042A priority patent/MX9710042A/en
Priority to US08/765,161 priority patent/US6103667A/en
Priority to EP96920785A priority patent/EP0832070A1/en
Publication of WO1997000246A1 publication Critical patent/WO1997000246A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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

Compounds of formula (I), wherein the substituents R1 to R6 and n are as defined in claim 1, and the salts and stereoisomers of the compounds of formula (I) have good pre- and post-emergence selective herbicidal properties. The preparation of those compounds and their use as herbicidal active ingredients are described.

Description

Novel herbicides
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.
Novel phenylpyrazole derivatives having herbicidal and growth-inhibiting properties have now been found.
The present invention therefore relates to compounds of formula I
Figure imgf000003_0001
wherein
R, is CrC4alkyl;
R2 is CrC4alkyl, C,-C4haloalkyl, C3- or C4-alkenyl, C3- or C4-haloalkenyl or C3- or C4-alkynyl; n is 0, 1 or 2;
R3 is hydrogen, CrC4alkyl, CrC4haloalkyl, C3- or C4-alkenyl, C3- or C4-haloalkenyl, C3- or C4-alkynyl, -CH2COOH, -CH2COO-CrC4alkyl or -CH2CN;
R4 is hydrogen, fluorine, chlorine or bromine;
R5 is hydrogen, halogen, methyl, trifluoromethyl, cyano, nitro, amino or CrC4halo- alkoxy;
R6 is hydrogen, halogen, cyano, NHR10, NR10Rj j or SO2Cl;
R10 and Rπ are each independently of the other CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, C3-C6cycloalkyl, C,-C8haloalkyl, C3-C8haloalkenyl, CrC4alkylcarbonyl, CrC4haloalkylcarbonyl, CrC4alkylsulfonyl, CrC4haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by CrC4alkyl, C,-C4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C,-C4alkyl, C,-C4haloalkyl or by halogen; or
R6 is OR20;
R20 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl,
O
/ \ ^1
— CH2— CH- CH2 , C3-C8haloalkenyl, C3-C6cycloalkyl, - CH2-<J ,
Cj -C4alkoxy-C, -C4alkyl, Ci -C4alkylamino-C j -C4alkyl, di-C , - alkylamino- CI-C4alkyl, C1-C4alkoxy-CrC4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, phenyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, those aromatic and heteroaromatic rings being unsubstituted or mono- to tri-substituted by CrC4alkyl, Cj-C4haloalkyl or by halogen; or
R20 is CrCgalkyl-COXR21 or CH(C6H5)COXR2. ;
X is oxygen, sulfur or NR22;
R21 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, C1-C4alkoxy-C1-C4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by Cj-C4alkyl or by halogen; and
R22 is hydrogen, CrC8alkyl or C3-C8alkenyl; or
R6 is S(O)mR30; m is 0, 1 or 2;
R30 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrCghaloalkyl, C3-C8halo- alkenyl, C3-C6cycloalkyl, CrC4alkoxy-CrC4alkyl, C1-C4alkylthio-C1-C4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, or CrC4alkyl-CONR31;
N is oxygen, sulfur or ΝR32;
R31 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen; and
R32 is hydrogen, CrC8alkyl or C3-C8alkenyl; or
R6 is COR40;
R40 is hydrogen, chlorine, C,-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C,-C8haloalkyl, C3-C8haloalkenyl, C3-C6cycloalkyl, CrC4alkoxy-CrC4alkyl, C,-C4alkylthio- C,-C4alkyl, phenyl, phenyl mono- to tri-substituted by C,-C4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, C,-C4halo- alkyl or by halogen; or R6 is COYR50;
Y is oxygen, sulfur, NR51 or NOR54;
R50 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl,
Figure imgf000005_0001
, C3-C8haloalkenyl, C3-C6cycloalkyl,
Figure imgf000005_0002
,
CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri- substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, CrC4alkyl-COZR52, C3-C6cycloalkyl-COZR52, CrC4alkyl-CO-CrC4alkyl or CrC4cyanoalkyl;
Z is oxygen, sulfur, NR53 or NOR55;
R52 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, O
— CH2— CH- CH2 , C3-C8haloalkenyl, C3-C6cycloalkyl, - CH2-<ζJ ,
C j -C4alkoxy-C , -C4alky 1 , C * -C4alkoxy-C , -C4alkoxy-C • -C4alkyl, C , - alkylthio- CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, Cj-C4halo- alkyl or by halogen;
R51 and R53 are each independently of the other CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrCghaloalkyl, CrC4alkylcarbonyl, CrC4haloalkylcarbonyl, CrC4alkylsulfonyl, CrC4haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC alkyl, CrC4haloalkyl or by halogen;
R54 and R55 are each independently of the other CrC4alkyl; or
Figure imgf000005_0003
R56 is hydrogen, CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl;
R57 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl or CrC4alkylcarbonyl; or
R6 is CrC8alkyl-B, CrC8haloalkyl-B, C2-C8alkenyl-B, C2-C8alkynyl-B, C2-C8halo- alkenyl-B, CrC4alkoxy-C,-C4alkyl-B or CrC4alkylthio-C,-C4alkyl-B; and
B is hydrogen, -COZR52, cyano or CrC4alkyl-C(O)-, and the salts and stereoisomers of the compound of formula I. The present invention relates also to compounds of formula I wherein
Rj is CrC4alkyl;
R2 is CrC4alkyl, CrC4haloalkyl, C3- or C4-alkenyl or C3- or C4-alkynyl; n is 0, 1 or 2;
R3 is hydrogen, CrC4alkyl, CrC4haloalkyl, C3- or C4-alkenyl or C3- or C4-alkynyl;
R4 is hydrogen, fluorine or chlorine;
R5 is hydrogen, halogen, methyl, trifluoromethyl, cyano, nitro, amino or Cι-C4haloalkoxy;
R6 is hydrogen, halogen, CrC5alkyl, CrC5haloalkyl, C2-C5alkenyl, C2-C5haloalkenyl, C2-C5alkynyl, C2-C5haloalkynyl, cyano, NHR10 or NR10Rπ;
R10 and Rπ are each independently of the other CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, CrC4alkylcarbonyl, Cj- haloalkylcarbonyl, CrC4alkylsulfonyl, CrC4haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by C1-C4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, C1-C4haloalkyl or by halogen; or
R^ is OR2u;
R20 is hydrogen, C,-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, CrC4alkoxy-CrC4alkyl, CI-C4alkylthio-C1-C4alkyl, phenyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, those aromatic and heteroaromatic rings being unsubstituted or mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, or CrC8alkyl-COXR21;
X is oxygen, sulfur or NR22;
R2ι is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl or by halogen; and
R22 is hydrogen, CrC8alkyl or C3-C8alkenyl; or
R6 is S(O)mR30; m is 0, 1 or 2;
R30 is hydrogen, chlorine, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cycloalkyl, CrC4alkoxy-CrC4alkyl, C,-C4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, C,-C4haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by C,-C4alkyl, CrC4haloalkyl or by halogen, or C,-C4alkyl-COVR3I;
V is oxygen, sulfur or NR32; R3] is hydrogen, C,-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen; and
R32 is hydrogen, CrC8alkyl or C3-C8alkenyl; or
R6 is COR40;
R40 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, C,-C4haloalkyl or by halogen; or
R6 is COYR50;
Y is oxygen, sulfur, NR51 or NOR54;
R50 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, or CrC4alkyl- COZR52;
Z is oxygen, sulfur, NR53 or NOR55;
R52 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, CI-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen;
R5] and R53 are each independently of the other CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, CrC4alkylcarbonyl, CrC4haloalkylcarbonyl, CrC4alkylsulfonyl, CrC4haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by Cj-C4alkyl, CrC4haloalkyl or by halogen; and
R54 and R55 are each independently of the other CrC4alkyl; or
R6 is CrC4alkylCOZR52, CrC4haloalkylCOZR52, C2-C4alkenylCOZR52, C2-C4alkynylCOZR52 or C2-C4haloalkenylCOZR52, and the salts and stereoisomers of the compound of formula I.
The present invention relates also to compounds of formula I wherein R, is Cj- alkyl;
R2 is CrC4alkyl, CrC4haloalkyl, C3- or alkenyl or C3- or C4alkynyl; n is 0, 1 or 2; R3 is C]-C4alkyl, CrC4haloalkyl, C3- or C4-alkenyl or C3- or C4-alkynyl;
R4 is hydrogen, fluorine or chlorine;
R5 is hydrogen, halogen, methyl, trifluoromethyl, cyano, nitro, amino or CrC4halo- alkoxy;
R6 is hydrogen, halogen, cyano, NHR< 0 or NR* 0Rι X ;
R10 and Rπ are each independently of the other CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, CrC4alkylcarbonyl, CrC4haloalkylcarbonyl, CrC4alkylsulfonyl, CrC4haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by Cj-C4alkyl, CrC4haloalkyl or by halogen; or
R6 is OR20;
R20 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, C1-C4alkoxy-C1-C4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, those aromatic and heteroaromatic rings being unsubstituted or mono- to tri-substituted by CrC alkyl, CrC4haloalkyl or by halogen, or CrC8alkyl-COXR2ι;
X is oxygen, sulfur or NR22Ϊ
R2ι is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, CrC4alkoxy-Cj-C4alkyl,
Figure imgf000008_0001
phenyl, phenyl mono- to tri-substituted by Cι-C4alkyl, CrC4haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by Cι-C alkyl or by halogen; and
R22 is hydrogen, CrC8alkyl or C3-C8alkenyl; or
R6 is SCO)^; m is 0, 1 or 2;
R30 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by Cj- afkyl, CrC4haloalkyl or by halogen, or CrC4alkyl- COVR31;
V is oxygen, sulfur or NR32;
R3 I is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, C,-C4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen; and R32 is hydrogen, CrC8alkyl or C3-C8alkenyl; or R6 is COR40; R40 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CpCghaloalkyl, C3-C6cyclo- alkyl, CrC4alkoxy-CrC4alkyl, CrC4aIkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen; or
R6 is COYR50;
Y is oxygen, sulfur, NR51 or NOR5 ;
R50 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, or C,-C4alkyl-COZR52;
Z is oxygen, sulfur, NR53 or NOR55;
R52 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, C1-C8haloalkyl, C3-C6cyclo- alkyl, Cι-C4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C1-C alkyl, CrC4haloalkyl or by halogen;
R51 and R53 are each independently of the other C*-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrCghaloalkyl, Cj-C4alkylcarbonyl, CrC4haloalkylcarbonyl, C]-C4alkylsulfonyl, CrC4haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by Cι-C4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC alkyl, CrC4haloalkyl or by halogen; and
R54 and R55 are each independently of the other CrC4alkyl; or
R6 is CrC4alkylCOZR52, CrC4haloalkylCOZR52, C2-C4alkenylCOZR52, C2-C4alkynylCOZR52 or C2-C4haloalkenylCOZR52, and the salts and stereoisomers of the compound of formula I.
In the above definitions, unless otherwise indicated halogen is to be understood as being fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
The 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, alkylthio-alkyl, alkyl- thio-alkoxycarbonyl, alkylthiocarbonyl-alkyl, alkenylthiocarbonyl, alkynylthiocarbonyl, haloalkoxycarbonyl-alkyl, alkylcarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl and alkoxycarbonyl-alkyl groups.
Examples of alkyl groups that may be mentioned are 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.
Examples of alkenyls that may be mentioned are 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.
Example of 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-fluoroρropenyl, 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. Of the C2-C5alkenyl 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 R6 as haloalkenylCOZR52 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, CrC4alkyl, halogen, CrC4haloalkyl, cyano, nitro, hydroxy, CrC4alkoxy, CrC4haloalkoxy, amino, CrC4alkylamino, di-CrC4alkylamino, carboxyl, CrC4alkoxy- carbonyl, carbamoyl, CrC4alkylaminocarbonyl or di-CrC4alkylaminocarbonyl.
Corresponding meanings can be assigned also to the substituents in combined definitions, for example cycloalkyl-oxy, cycloalkyl-thio, cycloalkylcarbonyl, cycloalkyl-oxycarbonyl- alkyl, phenylalkyl, phenylalkenyl, alkoxycarbonylalkyl, alkenyloxycarbonylalkyl, alkynyl- oxycarbonyl-alkyl, haloalkoxycarbonyl-alkyl, alkylaminocarbonyl-alkyl, alkenylamino- carbonyl-alkyl, alkynylaminocarbonyl-alkyl, dialkylaminocarbonyl-alkyl, alkoxyalkyl- amino, alkoxyalkylaminocarbonyl-alkyl, dialkoxyalkylamino, alkoxy alkoxycarbonyl, alkoxyalkoxycarbonyl-alkyl, alkylaminocarbonyl, alkylaminocarbonyl-alkyl, dialkyl¬ aminocarbonyl-alkyl, alkylthio-alkoxycarbonyl, alkylthiocarbonyl, alkylthio-alkyl, alkyl- thiocarbonyl-alkyl and haloalkoxycarbonyl-alkyl, and also for the combined definitions of the hydroxamic acid derivatives, such as, for example, for R6=CON(R50)OR54 or R6=COY-CrC4alkyl-CON(R52)OR55.
Salts of the compounds of formula I with acidic hydrogen, especially the derivatives with carboxylic acid groups (for example carboxy-substituted alkyl and phenyl groups) 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.
Of the 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 CrC18alkylamines, CrC4hydroxyalkylamines and C2-C4alkoxy- 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-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethyl- amine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amyl- amine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethyl- butenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethyl- amine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutyl- amine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, thio- mo holine, N-methylmorpholine, N-methyl-thiomoφholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxy- anilines, ethoxyanilines, o,m,p-toluidines, phenylenediamines, benzidines, naphthylamines and o,m,p-chloroanilines; but especially triethylamine, isopropylamine and diisopropyl- amine.
Salts of the compounds of formula I with basic groups, especially the derivatives with amino groups, for example alkylamino, dialkylamino or alkenylamino, 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.
The possible presence of at least one asymmetric carbon or sulfur atom in the compounds of formula I, for example in the substituent R6=OR20 wherein R2Q is a branched alkyl, alkenyl, haloalkyl or alkoxyalkyl group, or R6=S(O)mR30 wherein, for example, m=l and/or R30 is a branched alkyl, alkenyl, haloalkyl or alkoxyalkyl group, means that the compounds can occur both as optically active individual isomers and in the form of racemic mixtures. In the present invention, the compounds of formula I are to be under¬ stood as including both the pure optical antipodes and the racemates or diastereoisomers.
If an aliphatic C=C double bond is present, geometric isomerism may occur. The present invention relates also to those isomers.
Preference is given to compounds of formula I wherein R5 is chlorine, bromine, methyl, trifluoromethyl or cyano.
Preference is given also to compounds of formula I wherein R6 is hydrogen, halogen, OR2o, S(O)mR30 or COYR5o.
Compounds of formula I wherein n is 0 or 2 are also preferred.
Compounds of formula I wherein R> is methyl are also preferred. Preference is also given to compounds of formula I wherein R2 is methyl.
Also preferred are compounds of formula I wherein R3 is methyl or ethyl.
Compounds of formula I wherein R3 is methyl are especially preferred.
In a group of very especially preferred compounds of formula I, R4 is fluorine.
In a further very especially preferred group of compounds of formula I, R4 is hydrogen.
In another very especially preferred group of compounds of formula I, R4 is chlorine.
In a further group of very especially preferred compounds of formula I, R4 is chlorine; and R6 is OR2υ wherein R υ is as defined for formula I.
A group of very especially preferred compounds of formula I comprises compounds wherein R4 is fluorine; and R6 is OR2υ wherein R20 is as defined for formula I.
Further groups of very especially preferred compounds of formula I comprise compounds wherein R4 is chlorine; and Rg is S(O)mR30 wherein R30 and m are as defined for formula I.
In other groups of very especially preferred compounds of formula I, R4 is fluorine; and R6 is S(O)mR30 wherein R30 and m are as defined for formula I.
A further group of very especially preferred compounds of formula I comprises compounds wherein R4 is chlorine; and R6 is COR40, COYR50, CrC4alkylCOZR52, CrC4haloalkylCOZR52, C2-C4alkenylCOZR52, C2-C4alkynylCOZR52 or C2-C4halo- alkenylCOZR52 wherein R40, R50, R52, Y and Z are as defined for formula I.
A further group of very especially preferred compounds of formula I comprises compounds wherein R4 is fluorine; and R6 is COR40, COYR50, CrC4alkylCOZR52, CrC4haloalkylCOZR52, C2-C4alkenylCOZR52, C2-C4alkynylCOZR52 or C2-C4halo- alkenylCOZR52 wherein R40, R50, Rs2, Y and Z are as defined for formula I.
In a further group of compounds of formula I that are likewise very especially preferred, R5 is chlorine; and R6 is -COYR50.
Another group of likewise very especially preferred compounds of formula I comprises compounds wherein R5 is chlorine; and R6 is CrC4alkyl-B or CrC4haloalkyl-B.
The compounds of formula I
Figure imgf000016_0001
wherein Ri to R6 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
Figure imgf000016_0004
Figure imgf000016_0002
wherein Rj, R2 and R4 to R6 are as defined,
a) with hydrazine optionally in the presence of a suitable solvent to form a compound of formula lla
Figure imgf000016_0003
and then reacting that compound in the presence of a compound of formula Xa containing a corresponding CrC4alkyl, C,-C4haloalkyl, C3- or C4-alkenyl or C3- or C4-alkynyl group
Figure imgf000017_0001
the radical R3 in the compounds of formula Xa being as defined for formula I and L* being a leaving group, preferably chlorine, bromine, iodine, CH3SO2O- or
H C - S020- , optionally in the presence of a suitable solvent to form a compound of formula I
Figure imgf000017_0002
wherein n is 0, and then oxidising that compound; or
b) with a compound of formula XI
NH2-NH-R3 (XI),
wherein R3 is as defined, optionally in the presence of a suitable solvent, to form a compound of formula I
Figure imgf000017_0003
wherein R- to R6 are as defined, and n is 0, and then oxidising that compound.
The process according to the invention for the preparation of a compound of formula II
Figure imgf000018_0001
wherein R-, R2, R4 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
Figure imgf000018_0002
optionally in the presence of a solvent and a base, for example acetic acid and sodium acetate, to form a compound of formula XII
Figure imgf000018_0003
Ri and R4 to R6 in the compounds of formulae IV and XII being as defined and Hal being halogen, especially chlorine and bromine, and cyclising that compound of formula XII with a compound of formula Xm
H2Ν-ΝH-C(S)S-R2 (xm),
wherein R2 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
Figure imgf000019_0001
which is not isolated, and then subjecting that compound to a ring contraction (extrusion reaction) (n=0) thermally or by acid catalysis, for example with 2N hydrochloric acid, and then oxidising the product (n=l or 2).
The formation of the pyrazole rings of the compounds of formula I wherein n is 0, 1 or 2 is illustrated in more detail in Reaction Schemes 1, 2 and 10 below.
Reaction Scheme 1
Route a):
Figure imgf000019_0002
base l (n=0) I (n=l or 2) Route b):
Figure imgf000020_0001
oxidation e.g. m-chloroper- benzoic acid, solvent
Figure imgf000020_0002
I(n=lor2)
Reaction Scheme 2
Hal / " CH-R
Figure imgf000020_0003
IN xπ
Figure imgf000020_0004
oxidation e.g. m-chloroperbenzoic acid
Figure imgf000020_0006
Figure imgf000020_0005
lla II (n= lor 2) 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.
For the formation of the pyrazole rings that are substituted at the nitrogen atom (Reaction Scheme 1, Route b)), the procedure is analogous to that indicated under Reaction Scheme 1, Route a), with a compound of formula XI, for example N-alkylhydrazine, preferably N-methylhydrazine, being used as reagent.
The formation of the pyrazole rings of formulae π 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.
In certain cases it is advantageous to prepare the Ν-alkyl-substituted pyrazole derivatives, especially the Ν-methyl-substituted pyrazole derivatives, via Ν-alkylation of the corres¬ ponding unsubstituted pyrazoles of formula II (or Ha). Reaction Scheme 3 illustrates this.
Reaction Scheme 3
R2
Figure imgf000021_0001
In Reaction Schemes 1, Route b), and 3, the radical R3 in the hydrazine derivative of formula XI and in the alkylating agents of formulae Xa and Xb is as defined for formula I, and Lj is a leaving group, for example chlorine, bromine, iodine, CH3SO2O- or
Figure imgf000022_0001
The 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.
The selection of the suitable preparation method and the corresponding reaction conditions is made in accordance with the properties (reactivities) of the substituents in the inter¬ mediates in question.
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. 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 starting compound of formula HI in Reaction Scheme 1 can be prepared analogously to known procedures, for example in accordance with the method given in Reaction Scheme 4 below: Reaction Scheme 4
1) base, e.g. NaH, CS2, solvent
2) alkylating agent, e.g. R2-I, solvent
Figure imgf000023_0002
Figure imgf000023_0001
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 R2-Hal or R2OSO2OR2 wherein R2 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.
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 R2OSO2OR2 wherein R2 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, and suitable bases are, for example, alcoholates, for example sodium methanolate or sodium ethanolate, or potassium or sodium hydroxide.
The starting compound of formula IV in Reaction Scheme 4 can be prepared analogously to known procedures, for example in accordance with Methods a), b), c) and d) given in Reaction Scheme 5 below. Reaction Scheme 5
Method a):
Figure imgf000024_0001
Method b):
Figure imgf000024_0002
(X*=-OH or -N(CH3)OCH3)
Method c):
Figure imgf000024_0003
Method d):
Figure imgf000024_0004
In Reaction Scheme 5, the radicals Rj, R4, R5 and R6 are as defined for formula I, it being necessary to note that not all substituent definitions are compatible with all the procedures indicated. The selection of the suitable preparation method is made in accordance with the properties (reactivities) of the substituents in the intermediates in question.
The 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. In that reaction the 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(CH3)OCH3 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 reaction according to Method c) in Reaction Scheme 5 is carried out analogously to 'Advanced Organic Chemistry', Editor J. March, McGraw-Hill Book Company, New York, 1985, pages 816 ff. and 1057 ff., starting from an aldehyde of formula Vc by means of a Grignard reagent of formula VHI, for example alkylmagnesium chloride or bromide, or by means of alkyllithium in an inert solvent, preferably diethyl ether, at temperatures of from -80°C to 25°C and subsequent oxidation of the alcohol to the ketone. Suitable oxidising agents are, for example, potassium permanganate, pyridinium dichromate and sodium dichromate.
The reaction according to Method d) in Reaction Scheme 5 is carried out analogously to J. Chem. Soc. 1954, 1297. The amines of formula Vb are accordingly first diazotised to form the corresponding diazonium salts and allowed to react with an aldehydeoxime of formula LX. Subsequent hydrolysis, for example with aqueous sodium acetate and copper sulfate, yields the corresponding methyl ketone of formula IV.
The starting compounds of formulae V, Va, Vb, Vc, VI, VII, VIII, LX and XI in Reaction Schemes 1 , Route b), and 5 are known or can be prepared in accordance with known procedures.
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-ρosition of the phenyl ring (R6), the selection of the suitable preparation processes being made in accordance with the properties (reactivities) of the substituents in the intermediates in question. Some examples are given in Reaction Schemes 6 to 9.
The preparation of the phenylpyrazole derivatives of formula I that are O-substituted in the 5-position of the phenyl ring, wherein R6= OR 0, starting from the methoxy- or benzyloxy-substituted derivatives of formula Ij or I2, respectively, is illustrated in Reaction Scheme 6.
Reaction Scheme 6
Figure imgf000026_0001
The phenolpyrazole derivatives of formula I3 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 I2 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. 93, 746 (1971). The derivatisation of the phenolpyrazoles of formula I3 in Reaction Scheme 6 to form the compounds of formula I can be carried out in accordance with standard procedures, for example via alkylation with R20-Hal wherein R20 is as defined for formula I and Hal is halogen, especially chlorine, bromine or iodine.
The preparation of the phenylpyrazole derivatives of formula I that are S-substituted in the 5-position of the phenyl ring, wherein R6=S(O)mR30, starting from the derivatives of formula I4 that are unsubstituted in the 5-position, is illustrated in Reaction Scheme 7.
Reaction Scheme 7
Figure imgf000027_0001
The preparation of the thiophenolpyrazoles of formula I6 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 I4 is then chlorosulfonylated with chlorosulfonic acid or sulfur trioxide in sulfuric acid to form the compound of formula I5 and then reduced with tin chloride or zinc chloride to the thiophenol derivative of formula I6. The derivatisation of the thiophenolpyrazoles of formula I6 to form the compounds of formula I in Reaction Scheme 7 can be carried out in accordance with standard procedures, for example via alkylation with R30-Hal wherein R30 is as defined for formula I and Hal is halogen, especially chlorine, bromine or iodine (m=0). The subsequent oxidation to the sulfine or sulfone derivatives of formula I (m= 1 or 2, respectively) can likewise be carried out in accordance with standard procedures, for example with peracids, for example m-chloroperbenzoic acid.
The preparation of the phenylpyrazole derivatives of formula I that are carboxy- substituted in the 5-position of the phenyl ring, wherein R6 is halogen, cyano, nitro, amino, NHR10, NR10Rn, COR40 or COYR50, starting from the derivatives of formula I4 or Iπ that are unsubstituted in the 5-position or triflate-substituted in the 5-position, respectively, is illustrated in Reaction Scheme 8.
Reaction Scheme 8
Figure imgf000028_0001
R<
,S(O^ R2
In Reaction Scheme 8, W is the radical wherein R2 to R3 and n are as
N-N
R, defined for formula I. In accordance with Reaction Scheme 8, the phenylpyrazole of formula I4 can be converted into an aniline derivative of formula I8 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 I7 with hydrogen in the presence of a catalyst or according to Bechamps. The aniline derivative of formula I8 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 I9 by means of diazotisation and Sandmeyer reaction. The benzoic acid ester of formula I10 in Reaction Scheme 8 can be obtained, for example, analogously to J. Org. Chem. 39, 3318 (1974) or ibid. 40, 532 (1975) from the compound of formula l9 by means of carbon monoxide and a catalyst, for example palladium chloride-triphenylphosphine (PdCl2(TPP)2) in the presence of a solvent, for example ethanol, optionally under pressure at elevated temperature. A further possible method of preparing the intermediate of formula I10 is carried out analogously to Tetrahedron Letters 25, 2271 (1984) and ibid. 27, 3931 (1986). According to that method, the compound of formula Iπ is carbonylated in the presence of a catalyst, for example palladium. The subsequent hydrolysis of the benzoic acid ester of formula I10 yields the benzoic acid derivative of formula I12, which can be converted into the corresponding compounds of formula I in accordance with standard procedures, for example esterification or amidation.
The preparation of the phenylpyrazole derivatives of formula I that are substituted in the 5-position of the phenyl ring, wherein Rβ is CrC4alkylCOZR52, CrC4haloalkylCOZR52, C2-C4alkenylCOZR52, C2-C4alkynylCOZR52 or C2-C4haloalkenylCOZR52, starting from the derivatives of formula I9 that are substituted in the 5-position of the phenyl ring by halogen, especially by chlorine, bromine or iodine, via Heck reaction (Route a)), or starting from the derivatives of formula I8 that are substituted in the 5-position of the phenyl ring by amino via diazotisation and subsequent Meerwein reaction, is illustrated in Reaction Scheme 9.
Reaction Scheme 9 Route a):
Figure imgf000029_0001
I9 I 13 Route b):
D diazotisation
2) Meerwein reaction
Figure imgf000029_0002
Figure imgf000029_0003
In Reaction Scheme 9, W is the radical wherein Rj to R3 and n are as
Figure imgf000029_0004
defined for formula I. In accordance with Reaction Scheme 9, Route a), the alkynyl ester derivatives of formula Il 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-COZR52 derivatives, respectively, or via halogenation the corresponding haloalkenyl- or haloalkyl-COZR52 derivatives of formula I.
In accordance with Reaction Scheme 9, Route b), the haloalkylCOZR52 derivatives of formula I14 can be produced from the aniline derivatives of formula I8 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-COZR52 derivatives of formula I.
Reaction scheme 10
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000031_0002
Figure imgf000031_0004
Figure imgf000031_0003
The formation of the pyrazole rings of the compounds of formula I according to Reaction Scheme 10 is carried out
a) starting from the ketone derivative of formula IV wherein R* and R4 to R6 are as defined for formula I, by reaction with a carbonate of formula XVI wherein R7 is C]-C4alkyl, phenyl or benzyl, in the presence of a base, especially the corresponding sodium alcoholate R7O" +Na, in a solvent, for example the corresponding alcohol R7OH together with a second solvent, for example an ether or hydrocarbon, at temperatures of from 0°C to the boiling point of the solvent in question, or
b) starting from the α-haloketone of formula XII wherein R* and R4 to R6 are as defined and Hal is halogen, especially chlorine or bromine, by carbonylation in the presence of the palladium(II) chloride.bis-triphenylphosphine complex PdCl2[(PH)3P]2 as catalyst, carbon monoxide and a phase transfer catalyst in a suitable solvent, for example the alcohol R7OH wherein R7 is as defined, together with a second solvent, for example N,N-di- methylformamide, analogously to Indian J. Chem. B 31, 363 (1982).
In Reaction Scheme 10 the preparation of the pyrazolinone rings of formula XVII that are unsubstituted at the nitrogen atom is carried out by reaction of the above-prepared keto ester of formula XVI with hydrazine or hydrazine hydrate optionally in the presence of a suitable solvent at elevated temperature, preferably hydrazine hydrate in alcoholic solution at elevated temperature.
For the preparation of the pyrazolinone rings of formula XVHI that are substituted at the nitrogen atom, the reagent used is the compound of formula XI, for example N-alkyl- hydrazine, preferably N-methylhydrazine.
If desired, the 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 conversion of the pyrazolinone derivatives of formula XVIII into the corresponding mercapto analogues of formula XV is carried out in accordance with standard methods, for example with the aid of Lawesson reagent in a suitable solvent at elevated temperatures. The subsequent S-alkylation yields compounds of formula I (n=0) and is carried out in accordance with standard methods with the aid of an alkylating agent, for example R2-Hal wherein R is as defined for formula I and Hal is halogen, especially chlorine or bromine, optionally in the presence of a solvent and a base.
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.
For the use according to the invention of the compounds of formula I, or compositions comprising them, there come into consideration all the methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques, for example the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is also possible to apply a coating (coated granules) which allows the active ingredient to be released in metered amounts over a specific period of time.
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. As with the nature of the compositions, 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.
The formulations, i.e. the 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, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, e.g. solvents or solid carriers. It is also possible to use surface- active compounds (surfactants) in the preparation of the formulations.
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.
The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. 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. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.
Depending upon the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "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.
More frequently, however, 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 C8-C22alkyl 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. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalene- sulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.
Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-noήylphenol 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.
Further suitable 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.
Examples of 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 C8-C22alkyl 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 surfactants customarily employed in formulation technology, which may also be used in the compositions according to the invention, are described inter alia in "Mc Cutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Ridgewood, New Jersey, 1981; Stache, H., "Tensid-Taschenbuch" (Surfactant Handbook), Carl Hanser Verlag, Munich/Vienna 1981 ; and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-HJ, Chemical Publishing Co., New York, 1980-1981.
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.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
The 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.
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. The 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.
The following Examples further illustrate, but do not limit, the invention. Preparation examples
Example PI : 1 -(2,4-Dichlorophenyl)-3,3-bis(methylthio)-2-methyl-2-propen-l-one
Figure imgf000038_0001
1.07 g (0.005 mol) of l-(2,4-dichlorophenyl)-l-propanone (95 %) are added to an emulsion of 0.24 g (0.01 mol) of sodium hydride in 8 ml of dry tetrahydrofuran and the mixture is stirred at 40°C for one hour. The reaction mixture is cooled to 0°C and 0.381 g (0.05 mol) of carbon disulfide is added at 0-5°C. Immediately after the addition of carbon disulfide is complete, 1.42 g (0.01 mol) of methyl iodide are added dropwise at 0-5°C and the reaction mixture is stirred for one hour, then poured into 25 ml of a mixture of ice/water and stirred for a further 30 minutes. The crude product is extracted with ether and the organic phase is separated off, dried over sodium sulfate and concentrated by evaporation. The resulting residue is purified by column chromatography using 10 % ethyl acetate in hexane as eluant. The desired product is obtained in a yield of 1.38 g (89.8 %) in the form of a yellow oil.
Example P2: 3-(2,4-Dichlorophenyl)-4-methyl-5-(methylthio)-l-methyl-riH1-pyrazole
Figure imgf000038_0002
0.138 g (0.003 mol) of methyl hydrazine is added to a solution of 0.614 g (0.002 mol) of l-(2,4-dichlorophenyl)-3,3-bis(methylthio)-2-methyl-2-propen-l-one in 10 ml of aceto¬ nitrile and the reaction mixture is heated at 80°C for 8 hours. The mixture is then concen¬ trated in vacuo and the residue is taken up in ether, washed with water and dried over sodium sulfate. After the ether phase has been concentrated by evaporation, the residue is purified by column chromatography over silica gel with hexane/ethyl acetate 2/1 as eluant. The desired product is obtained in a yield of 0.425 g (74.0 ) in the form of a white solid having a melting point of 65-66°C (recrystallised from hexane). Example P3: 3-(2,4-Dichlorophenyl)-4-methyl-5-(methylsuIfonyl)-l-methyl-riH1- pyrazole
Figure imgf000039_0001
0.515 g (0.0015 mol) of m-chloroperbenzoic acid (50-60 %) is added to a solution of 0.214 g (0.00075 mol) of 3-(2,4-dichlorophenyl)-4-methyl-5-(methylthio)-l-methyl-[lH]- pyrazole in 10 ml of dichlormethane and the reaction mixture is stirred at 22°C overnight. The mixture is then washed with a saturated sodium hydrogen carbonate solution that contains 5 % sodium thiosulfate and then with water, dried over sodium sulfate and concentrated by evaporation. The resulting residue is purified by column chromatography over silica gel with hexane/ethyl acetate 1/1. The desired product is obtained in a yield of 0.206 g (86.2 %) in the form of a white solid having a melting point of 110-112°C.
Example P4: 3-(4-Chloro-2-fluorophenyl)-4-methyl-5-(methylthio)-r 1 Hl-pyrazole
Figure imgf000039_0002
0.6 ml (0.01 mol) of carbon disulfide in 2 ml of ethanol is added dropwise at 20-28°C to 3.35 ml (0.01 mol) of a 21 % ethanolic sodium ethanolate solution and 0.49 ml (0.01 mol) of hydrazine hydrate in 10 ml of ethanol. After 0.5 hour's stirring at 22°C, 0.62 ml (0.01 mol) of methyl iodide is added dropwise at 20-22°C to the suspension that has formed. After 1 hour's stirring at 22°C, 3.35 ml (0.01 mol) of 21 % ethanolic sodium ethanolate solution are added to the resulting suspension and stirring is continued for a further 10 minutes. The resulting solution is then cooled to 5-10°C and 2.7 g (0.01 mol) of α-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. As residue there is obtained 2.5 g of an oil which is chromatographed over 50 g of silica gel with ethyl acetate/hexane 1/2 as eluant. 1.4 g (54.6%) of the desired compound are obtained in the form of colourless crystals having a melting point of 88-90°C.
Example P5: -Bromo-4-chloro-2-fluoropropiophenone
Figure imgf000040_0001
2.2 ml (0.42 mol) of bromine are added dropwise at 20-25°C to a solution of 8.5 g (0.04 mol) of 4-chloro-2-fluoropropiophenone and 0.1 ml of 33 % hydrobromic acid in 20 ml of acetic acid. After being stirred for 1 hour at 22°C, the mixture is poured into ice- water, extracted with tert-butyl methyl ether and washed neutral with dilute sodium hydrogen carbonate solution. The reaction mixture is then concentrated by evaporation using a rotary evaporator and then dried at 22°C for 1 hour under a high vacuum. 10.4 g of 95 % α-bromo-4-chloro-2-fluoropropiophenone are obtained in the form of a light- yellow oil.
Example P6: -Bromo-4-chloro-2-fluoro-5-methoxypropiophenone
Figure imgf000040_0002
54 ml (1.05 mol) of bromine are added dropwise at 20-25°C to a suspension of 217 g (1 mol) of 4-chloro-2-fluoro-5-methoxypropiophenone and 10 ml of 33 % hydrobromic acid in glacial acetic acid in 0.5 litre of acetic acid. After being stirred for 1 hour to complete the reaction, the solution that has formed is poured into 2 litres of ice-water, extracted with tert-butyl methyl ether (MTBE), washed four times with water, dried over magnesium sulfate and concentrated by evaporation. 284 g of the desired compound are obtained in the form of a 95 % oil. Example P7: 3-(4-Chloro-2-fluoro-5-methoxyphenvπ-4-methyl-5-(methylthioV[lH1- pyrazole
Figure imgf000041_0001
At 0-5°C, 37 g (0.3 mol) of methyl dithiocarbazate are added in portions to a solution of 120 ml (0.32 mol) of 21 % sodium ethanolate solution in ethanol. 95 g (0.3 mol) of α-bromo-4-chloro-2-fluoro-5-methoxypropiophenone (90 %) are added dropwise at -5-0°C to the resulting solution. After being stirred for 30 minutes at 0-5°C, the suspension that has formed is diluted with 250 ml of ethanol and stirred at 0-5°C for a further 2 hours. Then, after 1 hour's stirring at 22°C, 25 ml of 37 % hydrochloric acid are added dropwise at 25-30°C and stirring is continued for a further 3 hours. Then 30 ml of 30 % sodium hydroxide solution are added dropwise and the resulting mixture is concentrated by evaporation. After the addition of about 1 litre of tert-butyl methyl ether, the reaction mixture is washed with water and the organic phase is dried and concentrated by evapora¬ tion. The crude product is purified by silica gel chromatography. 60 g (70 % of the theoretical yield) of the desired compound are obtained in the form of brown crystals having a melting point of 95-100°C.
Example P8: 3-(4-Chloro-2-fluorophenyl)-4-methyl-5-(methylthio)-l-methyl-riHl- pyrazole
Figure imgf000041_0002
1.4 ml (0.022 mol) of methyl iodide are added to a mixture of 5.4 g (0.02 mol) of 3-(4-chloro-2-fluorophenyl)-4-methyl-5-(methylthio)-[lH]-pyrazole (Example P4) and 4.2 g (0.030 mol) of potassium carbonate in 25 ml of l-methyl-2-pyrrolidone (NMP). After stirring overnight at 22°C, approximately 200 ml of tert-butyl methyl ether (MTBE) are added, and the mixture is washed three times with water and concentrated by evapora¬ tion. The crude product is purified by means of silica gel chromatography. 3.2 g (59 % of the theoretical yield) of the desired compound are obtained in the form of an oil.
Example P9: 3-(4-Chloro-2-fluoro-5-hydroxyphenyl)-4-methyl-5-(methylthio)- 1 -methyl- riHI-pyrazole
Figure imgf000042_0001
A mixture of 15 g (0.05 mol) of 3-(4-chloro-2-fluoro-5-methoxyphenyl)-4-methyl-5- (methylthio)-l-methyl-[lH]-pyrazole (Example P7) and 10.6 g (0.25 mol) of lithium chloride in 100 ml of N,N-dimethylformamide is stirred at 22°C in an argon atmosphere for 2.5 days. The solution is cooled and poured into 0.5 litre of ice-water and 15 ml of 37 % hydrochloric acid and extracted with tert-butyl methyl ether (MTBE). 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. After concentration by evaporation and recrystallisation in diethyl ether, 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
Figure imgf000042_0002
65 ml (0.8 mol) of pyridine and then 80 ml (0.48 mol) of trifluoromethanesulfonic acid anhydride are added dropwise at 0-5°C to a solution of 129 g (0.3 mol) of 3-(4-chloro-2- fluoro-5-hydroxyphenyl)-4-methyl-5-(methylthio)-l-methyl-[lH]-pyrazole (approx. 70 %) (Example P9) in 1.2 litres of 1,4-dioxane. 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
Figure imgf000043_0001
A mixture of 40.7 g (0.1 mol) of 3-(4-chloro-2-fluoro-5-trifluoromethylsulfonyloxy- phenyl)-4-methyl-5-(methylthio)-l-methyl-[lH]-pyrazole (Example P10), 31 ml (0.22 mol) of triethylamine, 1.12 g (0.005 mol) of palladium(U) acetate and 2.06 g (0.005 mol) of l,3-bis(diphenylphosphino)propane (Ph2P(CH2)3PPh2) in 300 ml of NJSf-dimethylformamide and 215 ml of methanol is stirred at 70°C at a pressure of 5 bar of carbon monoxide for 2 hours. The solution is then concentrated by evaporation, the resulting residue is dissolved in tert-butyl methyl ether (MTBE), washed with 0.2N hydro¬ chloric acid and water, concentrated by evaporation and purified by means of silica gel column chromatography. 23.4 g (71.3 % of the theoretical yield) of the desired compound are obtained in the form of crystals having a melting point of 82-83°C. Example P 12: 3-(4-Chloro-2-fluoro-5-propargyloxyphenyl)-4-methyl-5-(methylthio)- 1 ■ ethy 1- r 1 HI - yrazole
Figure imgf000044_0001
1 ml (0.0132 mol) of propargyl bromide are added dropwise at 20-25°C to a mixture of 3.15 g (0.011 mol) of 3-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-methyl-5-(methylthio)- l-methyl-[lH]-pyrazole (Example P9) and 2.5 g (0.018 mol) of potassium carbonate in 30 ml of N,N-dimethylformamide. After being stirred for 18 hours at 22°C, the mixture is poured into water, extracted with tert-butyl methyl ether (MTBE), washed with water and concentrated by evaporation. After recrystallisation in petroleum ether, 2.84 g (81.1% of the theoretical yield) of the desired compound are obtained in the form of crystals having a melting point of 76-78°C.
Example P13: 3-(4-Chloro-2-fluoro-5-propargyloxyphenyl)-4-methyl-5-(methylsulfinyl)- 1 -methyl- 1" 1 Hl-pyrazole
Figure imgf000044_0002
A solution of 1.57 g (0.005 mol) of 50-60 % 3-chloroperbenzoic acid in 30 ml of dichloro¬ methane is added dropwise at 0-5°C to a solution of 1.7 g (0.005 mol) of 3-(4-chloro-2- fluoro-5-proρargyloxyphenyl)-4-methyl-5-(methylthio)-l-methyl-[lH]-pyrazole (Example PI 2) in 20 ml of dichloromethane. After being stirred overnight at 22°C, the reaction mixture is washed with, a dilute sodium hydrogen carbonate solution, then with water and concentrated by evaporation, and the resulting residue is recrystallised in petroleum ether/- diethyl ether. 1.5 g (88.2 % of the theoretical yield) of the desired compound are isolated in the form of crystals having a melting point of 93-96°C. Example PI 4: 3-(4-Chloro-2-fluoro-5-propargyloxyphenyl)-4-methyl-5-(methylsulfonyl)- 1 -methyl- 1" 1 Hl-pyrazole
Figure imgf000045_0001
A solution of 3.45 g (0.011 mol) of 50-60 % 3-chloroperbenzoic acid in 60 ml of dichloro¬ methane is added dropwise at 0-5°C to a solution of 1.7 g (0.005 mol) of 3-(4-chloro-2- fluoro-5-propargyloxyphenyl)-4-methyl-5-(methylthio)-l-methyl-[lH]-pyrazole (Example PI 2) in 20 ml of dichloromethane. After being stirred overnight at 22°C, the reaction mixture is washed with a dilute sodium hydrogen carbonate solution, then with water and concentrated by evaporation, and the resulting residue is recrystallised in diethyl ether. 1.4 g (78.6 % of the theoretical yield) of the desired compound are obtained in the form of crystals having a melting point of 123-124°C.
In an analogous manner or by means of known methods it is also possible to prepare the compounds listed in the Tables which follow.
Table 1 : Compounds of formula la
Figure imgf000046_0001
Figure imgf000046_0002
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Table 2: Compounds of formula lb
Figure imgf000052_0001
Figure imgf000052_0002
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Table 3: Compounds of formula Ic
Figure imgf000058_0001
Figure imgf000058_0002
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Table 4: Compounds of formula Id
Figure imgf000063_0001
Figure imgf000063_0002
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Table 5: Compounds of formula le
Figure imgf000069_0001
Figure imgf000069_0002
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Table 6: Compounds of formula If
Figure imgf000075_0001
Figure imgf000075_0002
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Table 7: Compounds of formula lg
Figure imgf000081_0001
Figure imgf000081_0002
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Table 8: Compounds of formula Ih
Figure imgf000087_0001
Figure imgf000087_0002
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Table 9: Compounds of formula li
Figure imgf000092_0001
Figure imgf000092_0002
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Table 10: Compounds of formula Ij
Figure imgf000098_0001
Figure imgf000098_0002
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Table 11 : Compounds of formula Ik
Figure imgf000103_0001
Figure imgf000103_0002
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Figure imgf000107_0001
Table 12: Compounds of formula Im
Figure imgf000108_0001
Figure imgf000108_0002
Figure imgf000109_0001
108
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Table 13: Compounds of formula In
Figure imgf000113_0001
Figure imgf000113_0002
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Table 14: Compounds of formula lo
Figure imgf000118_0001
Figure imgf000118_0002
Figure imgf000119_0001
Figure imgf000120_0001
Figure imgf000121_0001
Figure imgf000122_0001
Table 15: Compounds of formula Ip
Figure imgf000123_0001
Figure imgf000123_0002
Figure imgf000124_0001
Figure imgf000125_0001
Figure imgf000126_0001
Figure imgf000127_0001
Table 16: Compounds of formula Iq
Figure imgf000128_0001
Figure imgf000128_0002
Figure imgf000129_0001
Figure imgf000130_0001
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000133_0001
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000137_0001
Figure imgf000138_0001
Figure imgf000139_0001
Figure imgf000140_0001
139
Figure imgf000141_0001
Figure imgf000142_0001
Figure imgf000143_0001
Figure imgf000144_0001
Table 17: Compounds of formula Ir
Figure imgf000145_0001
Figure imgf000145_0002
Figure imgf000146_0001
Table 18: Compounds of formula Is
Figure imgf000147_0001
Figure imgf000147_0002
-146-
Table 19: Compounds of formula It
Figure imgf000148_0001
Figure imgf000148_0002
Figure imgf000149_0001
Figure imgf000150_0001
Figure imgf000151_0001
-150-
Figure imgf000152_0001
151
Table 20: Compounds of formula lu
Figure imgf000153_0001
Figure imgf000153_0002
-152
Figure imgf000154_0001
Figure imgf000155_0001
Figure imgf000156_0001
Figure imgf000157_0001
Table 21 : Compounds of formula Iv
Figure imgf000158_0001
Figure imgf000158_0002
Figure imgf000159_0001
Figure imgf000160_0001
Figure imgf000161_0001
Figure imgf000162_0001
Table 22: Compounds of formula Iw
Figure imgf000163_0001
Figure imgf000163_0002
Figure imgf000164_0001
Figure imgf000165_0001
Figure imgf000166_0001
Figure imgf000167_0001
Table 23: Compounds of formula Ix
Figure imgf000168_0001
Figure imgf000168_0002
Figure imgf000169_0001
Figure imgf000170_0001
Figure imgf000171_0001
Figure imgf000172_0001
Table 24: Compounds of formula ly
Figure imgf000173_0001
Figure imgf000173_0002
Figure imgf000174_0001
Figure imgf000175_0001
Figure imgf000176_0001
Figure imgf000177_0001
Table 25: Compounds of formula Iz
Figure imgf000178_0001
Figure imgf000178_0002
Figure imgf000179_0001
Figure imgf000180_0001
Figure imgf000181_0001
Figure imgf000182_0001
Table 26: Compounds of formula Izz
Figure imgf000183_0001
Figure imgf000183_0002
Figure imgf000184_0001
Figure imgf000185_0001
Figure imgf000186_0001
Figure imgf000187_0001
Table 27: Compounds of formula lyy
Figure imgf000188_0001
Figure imgf000188_0002
Figure imgf000189_0001
Figure imgf000190_0001
Figure imgf000191_0001
Figure imgf000192_0001
Table 28: Compounds of formula Iww
Figure imgf000193_0001
Figure imgf000193_0002
Figure imgf000194_0001
Figure imgf000195_0001
Figure imgf000196_0001
Figure imgf000197_0001
Table 29: Compounds of formula Iw
Figure imgf000198_0001
Figure imgf000198_0002
Figure imgf000199_0001
Figure imgf000200_0001
Figure imgf000201_0001
Figure imgf000202_0001
Table 30: Compounds of formula luu
Figure imgf000203_0001
Figure imgf000203_0002
Figure imgf000204_0001
Figure imgf000205_0001
Figure imgf000206_0001
Figure imgf000207_0001
Formulation Examples for active ingredients of formula I (throughout, percentages are by weight)
Fl. Emulsifiable concentrates a) b) c ) d)
a compound of Tables 1-30 5 % 10 % 25 % 50 % calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 % castor oil polyglycol ether 4 % 4 % 4 % (36 mol of ethylene oxide) octylphenol polyglycol ether 4 % 2 % (7-8 mol of ethylene oxide) cyclohexanone 10 % 20 % aromatic hydrocarbon mixture 85 % 78 % 55 % 16 % C9-C12
Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
F2. Solutions a) b) c ) d)
a compound of Tables 1-30 5 % 10 % 50 % 90 % 1 -methoxy-3-(3-methoxy- propoxy)-propane 20 % 20 % polyethylene glycol (mol.wt.400) 20 % 10 % N-methyl-2-pyrrolidone 30 % 10 % aromatic hydrocarbon mixture 75 % 60 %
C 9-Cι2
The solutions are suitable for application in the form of micro-drops. F3. Wettable powders a) b) c ) d)
a compound of Tables 1-30 5 % 25 % 50 % 80 % sodium lignosulfonate 4 % - 3 % sodium laurylsulfate 2 % 3 % - 4 % sodium diisobutylnaphthalene- sulfonate - 6 % 5 % 6 % octylphenol polyglycol ether - l % 2 %
(7-8 mol of ethylene oxide) highly dispersed silicic acid 1 % 3 % 5 % 10 % kaolin 88 % 62 % 35 % -
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.
F4. Coated granules a) b) c)
a compound of Tables 1-30 highly dispersed silicic acid inorganic carrier
Figure imgf000209_0001
(diameter 0.1 - 1 mm) e.g. CaCO3 or SiO2
The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
F5. Coated granules a) b) c )
a compound of Tables 1-30 polyethylene glycol (mol.wt. 200) highly dispersed silicic acid inorganic carrier
Figure imgf000209_0002
(diameter 0.1 - 1 mm) e.g. CaCO3 or SiO2 The finely ground active ingredient is uniformly applied, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
F6. Extruder granules a) b) d)
a compound of Tables 1-30 0 . 1 % 3 % 5 % 15 % sodium lignosulfonate 1 .5 % 2 % 3 % 4 % carboxymethylcellulose 1 .4 % 2 % 2 % 2 % kaolin 97 . 0 % 93 % 90 % 79 %
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.
F7. Dusts a) b) c )
a compound of Tables 1-30 0 .1 % 1 % 5 % talcum 39 .9 % 49 % 35 % kaolin 60 . 0 % 50 % 60 %
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d)
a compound of Tables 1-30 ethylene glycol nonylphenol polyglycol ether
( 15 mol of ethylene oxide) sodium lignosulfonate carboxymethylcellulose
37% aqueous formaldehyde
Figure imgf000210_0001
solution silicone oil emulsion 0 . 8 % 0 . 8 % 0 . 8 % 0 . 8 % water 87 % 79 % 62 % 38 % The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
Biological Examples
Example Bl: Pre-emergence herbicidal action
Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastic pots. Immediately after sowing, 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). The test plants are then cultivated in a greenhouse under optimum conditions. After 3 weeks the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Test plants: Avena, Setaria, Sinapis, Stellaria
The compounds according to the invention exhibit good herbicidal action.
Examples of the good herbicidal action are given in Table B 1.
Table B 1 : Pre-emergence action:
Test plant: Avena Setaria Sinapis Stellaria Compound No.
1.001 1 1 1.007 1 2 1.010 2 2 2.007 2 2 2.035 2 2 2.037 2 1 3.001 1 1 ellaria
Figure imgf000212_0001
The same results are obtained when compounds of formula I are formulated in accordance with Examples F2 and F4 to F8.
Example B2: Post-emergence herbicidal action (contact herbicide) In a greenhouse, 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). The test plants are then grown on in the greenhouse under optimum conditions. After about 18 days the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
In this test too, the compounds of formula I according to the invention exhibit good herbicidal action.
Examples of the good herbicidal activity of the compounds of formula I are given in Table B2. Table B2: Post-emergence action:
Setaria Sinapis Stellaria
3
Figure imgf000213_0001
2
The same results are obtained when compounds of formula I are formulated in accordance with Examples F2 and F4 to F8.

Claims

What is claimed is:
1. A compound of formula I
Figure imgf000214_0001
wherein
Rj is CrC4alkyl;
R2 is CrC4alkyl, CrC4haloalkyl, C3- or C4-alkenyl, C3- or C4-haloalkenyl or C3- or C4-alkynyl; n is 0, 1 or 2;
R3 is hydrogen, C1-C alkyl, C1-C4haloalkyl, C3- or C4-alkenyl, C3- or C4-haloalkenyl, C3- or C4-alkynyl, -CH2COOH, -CH2COO-CrC4alkyl or -CH2CN;
R4 is hydrogen, fluorine, chlorine or bromine;
R5 is hydrogen, halogen, methyl, trifluoromethyl, cyano, nitro, amino or C C4halo- alkoxy;
R6 is hydrogen, halogen, cyano, NHR10, NRIQRH or SO2Cl;
R10 and Rπ are each independently of the other CrCgalkyl, C3-C8alkenyl, C3-C8alkynyl, C3-C6cycloalkyl, CrC8haloalkyl, C3-C8haloalkenyl, CrC4alkylcarbonyl, CrC4haloalkylcarbonyl, CrC4alkylsulfonyl, C1-C4haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by CrC4alkyl, CrC haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen; or
R6 is OR20;
R20 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC haloalkyl, O
— CH2— CH- CH2 , C3-C8haloalkenyl, C3-C6cycloalkyl, -CH2-< ,
CrC4alkoxy-CrC4alkyl, CrC4alkylamino-CrC4alkyl, di-C,-C4aIkyl- amino-CrC4alkyl, C1-C4alkoxy-C1-C4aIkoxy-C1-C4alkyl, CrC4alkyl- thio-CrC4alkyl, phenyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, those aromatic and heteroaromatic rings being unsubstituted or mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen; or
R20 is CrC8alkyl-COXR2ι or CH(C6H5)COXR21 ;
X is oxygen, sulfur or NR22;
R21 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrCghaloalkyl, C3-C6cycIo- alkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl or by halogen; and
R22 is hydrogen, CrC8alkyl or C3-C8alkenyl; or
R6 is S(O)mR30; m is 0, 1 or 2;
R30 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C8halo- alkenyl, C3-C6cycloalkyl, CrC4alkoxy-CrC4alkyl, C1-C4alkylthio-C1-C4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by CrC4alkyl, C haloalkyl or by halogen, or CrC4alkyl-COVR31;
V is oxygen, sulfur or NR32;
R31 is hydrogen, C1-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C6cyclo- alkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen; and
R32 is hydrogen, C.-C8alkyl or C3-C8alkenyl; or
Rg COR4o;
R40 is hydrogen, chlorine, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, C3-C8haloalkenyl, C3-C6cycloalkyl, CrC4alkoxy-CrC4alkyl, CrC4alkyl- thio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4halo- alkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen; or
R6 is COYR50;
Y is oxygen, sulfur, NR51 or NOR54;
R50 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CpCghaloalkyl,
— CH2—
Figure imgf000215_0001
, C3-C8haloalkenyl, C3-C6cycloalkyl, -CH2-< /I ,
CrC4alkoxy-CrC4alkyl, CrC4alkylthio-C,-C4alkyl, phenyl, phenyl mono- to tri- substituted by C]-C4alkyl, CrC4haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by C,-C4alkyl, CrC4haloalkyl or by halogen, CrC4alkyl-COZR52, C3-C6cycloalkyl-COZR52, CrC4alkyl-CO-CrC4alkyl or C,-C4cyanoalkyl;
Z is oxygen, sulfur, NR53 or NOR55;
R52 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, O
— CH2— C /H-\CH2 , C3-C8haloalkenyl, C3-C6cycloalkyl,
Figure imgf000216_0001
,
Figure imgf000216_0002
thio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4halo- alkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen;
R51 and R53 are each independently of the other Cj-Cgalkyl, C3-C8alkenyl, C3-C8alkynyl, CrC8haloalkyl, Cι-C4alkylcarbonyl, CrC4haloalkylcarbonyl, C C4alkylsulfonyl, C haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by Cι~C4alkyl, Cι-C4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by C alkyl, C haloalkyl or by halogen;
R54 and R55 are each independently of the other CrC4alkyl; or
Figure imgf000216_0003
R56 is hydrogen, CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl;
R57 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl or CrC4alkylcarbonyl; or
R6 is CrC8alkyl-B, CrC8haloalkyl-B, C2-C8alkenyl-B, C2-C8alkynyl-B, C2-C8halo- alkenyl-B, CrC4alkoxy-CrC4alkyl-B or CrC4alkylthio-Cι-C4alkyl-B; and
B is hydrogen, -COZR52, cyano or C* -C4alkyl-C(O)-, or a salt or stereoisomer of a compound of formula I.
2. A compound of formula I according to claim 1 , wherein
Ri is CrC4alkyl;
R2 is CrC4alkyl, CrC4haloalkyl, C3- or C4-alkenyl or C3- or C4-alkynyl; n is O, 1 or 2;
R3 is hydrogen, C,-C4alkyl, CrC4haloalkyl, C3- or C4-alkenyl or C3- or C4-alkynyl;
R4 is hydrogen, fluorine or chlorine;
R5 is hydrogen, halogen, methyl, ifluoromethyl, cyano, nitro, amino or
CrC4haloalkoxy; R6 is hydrogen, halogen, CrC5alkyl, C,-C5haloalkyl, C2-C5alkenyl, C2-C5haloalkenyl, C2-C5alkynyl, C2-C5haloalkynyl, cyano, NHR10 or NR10Rπ;
R10 and Rπ are each independently of the other CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CpCghaloalkyl, Cp alkylcarbonyl, CrC4haloalkylcarbonyl, CrC4alkylsulfonyl, CrC4haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by CrC4alkyl, CpC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CpQalkyl, CrC4haloalkyl or by halogen; or
Figure imgf000217_0001
R20 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CpCghaloalkyl,
C3-C6cycloalkyl, CrC4alkoxy-CrC4alkyl, C1-C4alkylthio-CrC4alkyl, phenyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, those aromatic and heteroaromatic rings being unsubstituted or mono- to tri-substituted by C1-C4alkyl, CrC4haloalkyl or by halogen, or CrC8alkyl-COXR2I;
X is oxygen, sulfur or NR2 ;
R2ι is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CpCghaloalkyl,
C3-C6cycloalkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CpC4alkyl, phenyl, phenyl mono- to tri-substituted by CpC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl or by halogen; and
R22 is hydrogen, CrC8alkyl or C3-C8alkenyl; or
Rg is S(O)mR30; m is 0, 1 or 2;
R30 is hydrogen, chlorine, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CpCghaloalkyl, C3-C6cycloalkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CpQalkyl, CrC4haloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, or CrC4alkyl-COVR31;
V is oxygen, sulfur or NR32;
R31 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CpCghaloalkyl,
C3-C6cycloalkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CrC4alkyl, CrC4haloalkyl or by halogen; and
R32 is hydrogen, CrC8alkyl or C3-C8alkenyl; or
R6 is COR40;
R40 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CpCghaloalkyl,
C3-C6cycloalkyl, CrC4alkoxy-CrC4alkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CrC4alkyl, CpQhaloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen; or
R6 is COYR50;
Y is oxygen, sulfur, NR51 or NOR54;
R50 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CpCghaloalkyl,
C3-C6cycloalkyl, CrC4alkoxy-CrC4alkyl, CpQalkylthio-CpQalkyl, phenyl, phenyl mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen, or CpC4alkyl-COZR52;
Z is oxygen, sulfur, NR53 or NOR55;
R52 is hydrogen, CpQalkyl, C3-C8alkenyl, C3-C8alkynyl, CpCghaloalkyl,
Q-Qcycloalkyl, Q-Qalkoxy-CpQalkyl, CrC4alkylthio-CrC4alkyl, phenyl, phenyl mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen;
R51 and R53 are each independently of the other CpQalkyl, C3-C8alkenyl, C3-C8alkynyl, CpCghaloalkyl, CpQalkylcarbonyl, CpQhaloalkylcarbonyl, -Qalkylsulfonyl, CpQhaloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen; and
R5 and R55 are each independently of the other CpQalkyl; or
R6 is CpQalkylCOZR52, CpQhaloalkylCOZR52, C2-QalkenylCOZR52, C2-QalkynylCOZR52 or C2-QhaloaIkenylCOZR52, or a salt or stereoisomer of a compound of formula I.
3. A compound of formula I according to claim 2, wherein
Rj is CpQalkyl;
R2 is CpQalkyl, CpQhaloalkyl, C3- or Qalkenyl or C3- or Qalkynyl; n is 0, 1 or 2;
R3 is CpQalkyl, CpQhaloalkyl, C3- or Q-alkenyl or C3- or Q-alkynyl;
R4 is hydrogen, fluorine or chlorine;
R5 is hydrogen, halogen, methyl, trifluoromethyl, cyano, nitro, amino or
CpQhaloalkoxy; R6 is hydrogen, halogen, cyano, NHR-0 or NR10Rj , ; R10 and R* • are each independently of the other CpQalkyl, C3-C8alkenyl, Q-Qalkynyl,
CpCghaloalkyl, CrC4alkylcarbonyl, CrC4haloalkylcarbonyl, CrC4alkylsulfonyl, CrC4haloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen; or
R6 is OR20;
R20 is hydrogen, CpQalkyl, C3-Qalkenyl, Q-Qalkynyl, CpCghaloalkyl,
C3-C6cycloalkyl, Q-Qalkoxy-CpQalkyl, CpQalkylthio-CpQalkyl, phenyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, those aromatic and hetero¬ aromatic rings being unsubstituted or mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen, or CrC8alkyl-COXR21;
X is oxygen, sulfur or NR22;
R21 is hydrogen, CpQalkyl, C3-Qalkenyl, C3-C8alkynyl, CpCghaloalkyl,
Q-Qcycloalkyl, CpQalkoxy-Q-Qalkyl, -Qalkylthio-CpQalkyl, phenyl, phenyl mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by CpQalkyl or by halogen; and
R22 is hydrogen, CpQalkyl or Q-Qalkenyl; or
R6 is S(O)mR30; m is 0, 1 or 2;
R30 is hydrogen, CpQalkyl, Q-Qalkenyl, Q-Qalkynyl, CpCghaloalkyl,
Q-Qcycloalkyl, Q-Qalkoxy-Q-Qalkyl, CpQalkylthio-CpQalkyl, phenyl, phenyl mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by CpQalkyl, CpQhaloalkyl or by halogen, or CrQalkyl-CONR31;
N is oxygen, sulfur or ΝR32;
R31 is hydrogen, -Qalkyl, Q-Qalkenyl, Q-Qalkynyl, CpCghaloalkyl,
Q-Qcycloalkyl, Q-Qalkoxy-Q-Qalkyl, CpQalkylthio- -Qalkyl, phenyl, phenyl mono- to tri-substituted by Q-Qalkyl, CpQhaloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by Q-Qalkyl, -Qhaloalkyl or by halogen; and
R32 is hydrogen, Q-Qalkyl or Q-Qalkenyl; or
R6 is COR40;
R40 is hydrogen, Q-Qalkyl, Q-Qalkenyl, Q-Qalkynyl, CpCghaloalkyl,
Q-Qcycloalkyl, Q-Qalkoxy-Q-Qalkyl, CpQalkylthio-CpQalkyl, phenyl, phenyl mono- to tri-substituted by Q-Qalkyl, Q-Qhaloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by Q-Qalkyl, Q-Qhaloalkyl or by halogen; or
R6 is COYR50; Y is oxygen, sulfur, NR51 or NOR54;
R50 is hydrogen, CrC8alkyl, Q-Qalkenyl, Q-Qalkynyl, CpCghaloalkyl,
Q-Qcycloalkyl, Q-Qalkoxy-Q-Qalkyl, Q-Qalkylthio-Q-Qalkyl, phenyl, phenyl mono- to tri-substituted by Q-Qalkyl, Q-Qhaloalkyl or by halogen, benzyl, benzyl mono- to tri-substituted by Q-Qalkyl, Q-Qhaloalkyl or by halogen, or CpQalkyl-COZR52;
Z is oxygen, sulfur, NR53 or NOR55;
R52 is hydrogen, Q-Qalkyl, Q-Qalkenyl, Q-Qalkynyl, Q-Qhaloalkyl,
Q-Qcycloalkyl, Q-Qalkoxy-Q-Qalkyl, CpQalkylthio-Q-Qalkyl, phenyl, phenyl mono- to tri-substituted by Q-Qalkyl, Q-Qhaloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by Q-Qalkyl, Q-Qhaloalkyl or by halogen;
R51 and R53 are each independently of the other Q-Qalkyl, Q-Qalkenyl, Q-Qalkynyl, CpCghaloalkyl, Q-Qalkylcarbonyl, Q-Qhaloalkylcarbonyl, Q-Qalkylsulfonyl, Q-Qhaloalkylsulfonyl, benzoyl, benzoyl mono- to tri-substituted by Q-Qalkyl, Q-Qhaloalkyl or by halogen, benzyl, or benzyl mono- to tri-substituted by Q-Qalkyl, Q-Qhaloalkyl or by halogen; and
R54 and R55 are each independently of the other Q-Qalkyl; or
R6 is Q-QalkylCOZR52, Q-QhaloalkylCOZR52, C2-QalkenylCOZR52, C2-QalkynylCOZR52 or C2-QhaloalkenylCOZR52, or a salt or stereoisomer of a compound of formula I.
4. A compound according to claim 1 , wherein R5 is chlorine, bromine, methyl, trifluoromethyl or cyano.
5. A compound according to claim 1, wherein R6 is hydrogen, halogen, OR20, S(O)mR30 or COYR50.
6. A compound according to claim 1, wherein n is 0 or 2.
7. A compound according to claim 1, wherein R* is methyl.
8. A compound according to claim 1, wherein R2 is methyl.
9. A compound according to claim 1, wherein R3 is methyl or ethyl.
10. A compound according to claim 9, wherein R3 is methyl.
11. A compound according to claim 1, wherein R4 is fluorine.
12. A compound according to claim 1, wherein R4 is hydrogen.
13. A compound according to claim 1, wherein R4 is chlorine.
14. A compound according to claim 1, wherein R4 is chlorine; and Rg is OR20 wherein R20 is as defined in claim 1.
15. A compound according to claim 1, wherein R4 is fluorine; and Rg is OR20 wherein R20 is as defined in claim 1.
16. A compound according to claim 1, wherein R4 is chlorine; and Rg is S(O)mR30 wherein R3Q and m are as defined in claim 1.
17. A compound according to claim 1, wherein R4 is fluorine; and Rg is S(O)mR30 wherein R30 and m are as defined in claim 1.
18. A compound according to claim 1, wherein R4 is chlorine; and Rg is COR40, COYR50, Q-QalkylCOZR52, Q-QhaloalkylCOZR52, C2-QalkenylCOZR52, Q-Qalkynyl- COZR52 or C2-QhaloalkenylCOZR52, wherein R^, R50, R52, Y and Z are as defined in claim 1.
19. A compound according to claim 1, wherein R4 is fluorine; and Rg is COR40, COYR50, Q-QalkylCOZR52, CrC4haloalkylCOZR52, C2-C4alkenylCOZR52, Q-Qalkynyl- COZR52 or C2-C4haloalkenylCOZR52, wherein R40, R50, R52, Y and Z are as defined in claim 1.
20. A compound according to claim 1, wherein R5 is chlorine; and R6 is -COYR50.
21. A compound according to claim 1, wherein R5 is chlorine; and R6 is Q-Qalkyl-B or CpQhaloalkyl-B.
22. A process for the preparation of a compound of formula I
Figure imgf000222_0001
wherein Rj to R6 and n are as defined in claim 1, which process comprises cyclising a compound of formula 1TJ
Figure imgf000222_0002
wherein Rj, R2 and R4 to R are as defined,
a) with hydrazine optionally in the presence of a suitable solvent to form a compound of formula Ha
and then reacting that compound in the presence of a compound of formula Xa containing a corresponding Q-Qalkyl, Q-Qhaloalkyl, Q- or Q-alkenyl or Q- or Q-alkynyl group
Figure imgf000222_0004
the radical R3 in the compounds of formula Xa being as defined in claim 1 and L* being a leaving group, to form a compound of formula I
Figure imgf000223_0001
wherein n is 0, and then oxidising that compound; or
b) with a compound of formula XI
NH2-NH-R3 (XI),
wherein R3 is as defined, optionally in the presence of a suitable solvent, to form a compound of formula I
Figure imgf000223_0002
wherein Rj to R6 are as defined, and n is 0, and then oxidising that compound.
23. A process for the preparation of a compound of formula II
Figure imgf000223_0003
wherein Rh R2, R4 to R6 and n are as defined in claim 1, which process comprises halogenating a compound of formula IV
Figure imgf000224_0001
optionally in the presence of a solvent and a base, to form a compound of formula XII
Figure imgf000224_0002
Rj and R to Rg in the compounds of formulae IN and XII being as defined and Hal being halogen, and cyclising that compound of formula XH with a compound of formula XTTT
H2Ν-ΝH-C(S)S-R2 (XΠD,
wherein R2 is as defined, optionally in the presence of a solvent and a base, to form a compound of formula XIN
Figure imgf000224_0003
Figure imgf000224_0004
and then subjecting that compound to a ring contraction (n=0) thermally or by acid catalysis, and then oxidising that compound (n=l or 2).
24. A compound of formula II
Figure imgf000225_0001
wherein R-, R2, R4 to R6 and n are as defined in claim 1.
25. A compound of formula XV
Figure imgf000225_0002
wherein R- and R3 to R6 are as defined in claim 1.
26. A herbicidal and plant growth-inhibiting composition comprising one or more compounds of formula I according to claim 1.
27. A composition according to claim 26, comprising from 0.1 to 95 % of a compound of formula I according to claim 1.
28. A method of controlling undesired plant growth, which comprises applying an effective amount of a compound of formula I, according to claim 1, or of a composition comprising such a compound, to the plants or to the locus thereof.
29. A method according to claim 28, which comprises the application of a compound of formula I in an amount of from 0.001 to 2 kg per hectare.
30. A method of inhibiting plant growth, which comprises applying an effective amount of a compound of formula I, according to claim 1 , or of a composition comprising such a compound, to the plants or to the locus thereof.
31. The use of a composition according to claim 26 in the selective control of weeds in crops of useful plants.
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RU2362772C2 (en) * 2003-04-08 2009-07-27 Басф Акциенгезельшафт Benzenesulphonamide derivatives
US7741485B2 (en) 2003-04-08 2010-06-22 Basf Aktiengesellschaft Benzenesulphonamide derivatives as herbicides or desiccant/defoliant compounds
JP5113531B2 (en) * 2006-01-16 2013-01-09 三井化学アグロ株式会社 (3-Sulfur atom substituted phenyl) pyrazole derivatives

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MX9710042A (en) 1998-03-29
CA2220136A1 (en) 1997-01-03
AU6221796A (en) 1997-01-15
AR002478A1 (en) 1998-03-25

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