CA2382432A1 - Novel herbicides - Google Patents

Novel herbicides Download PDF

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CA2382432A1
CA2382432A1 CA002382432A CA2382432A CA2382432A1 CA 2382432 A1 CA2382432 A1 CA 2382432A1 CA 002382432 A CA002382432 A CA 002382432A CA 2382432 A CA2382432 A CA 2382432A CA 2382432 A1 CA2382432 A1 CA 2382432A1
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substituted
halo
c6alkyl
c6alkoxy
formula
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Thomas Maetzke
Sebastian Wendeborn
Andre Stoller
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Syngenta Participations AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/62—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
    • C07C69/616—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety polycyclic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/62—Halogen-containing esters
    • C07C69/65—Halogen-containing esters of unsaturated acids
    • 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
    • C07D231/28—Two oxygen or sulfur atoms
    • C07D231/30—Two oxygen or sulfur atoms attached in positions 3 and 5
    • C07D231/32—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

The invention relates to compounds of formula (I), wherein the substituents have the meaning cited in Claim (1). Said compounds are suitable for utilization as herbicides.

Description

The present invention relates to novel, herbicidally active pyrazolinone derivatives, to a process for their preparation, to compositions comprising such compounds, and to the use thereof in controlling weeds, ~;:~i:;;;~ially in crops of useful plants, or in inhibiting plant growth.
Pyrazolinone derivatives having herbicidal action are described, for example, in f,,., W092116510 and W096/21652.
Novel 4-arylpyrazolinones having herbicidal and growth-inhibiting properties have now been found.
The present invention accordingly relates to compounds of formula I

N~Ra R2 ~ ~ ~ N
Rs R3 O, G
I
wherein R, and R3 are each independently of the other hydrogen, halogen, nitro, cyano, C,-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, tri(C,-C4alkylsilyl)-C2-C4alkynyl, C,-C4haloalkyl, C2-Cshaloalkenyl, C3-Cscycloalkyl, halo-substituted C3-Cscycloalkyl, benzyl, C2-Csalkoxyalkyl, C2-Csalkylthio-alkyl, hydroxy, mercapto, C,-Csalkoxy, C3-Csalkenyloxy, C3-Csalkynyloxy, C,-C4alkyl-carbonyl, C,-C4alkoxycarbonyl, C,-C4alkylthio, C,-C4alkylsulfinyl, C,-C4alkylsulfonyl, amino, C,-C4alkylamino, di(C,-C4alkyl)amino, C,-C4hydroxyalkyl, formyl, C,-C4alkylcarbonylamino or C,-C4alkylsulfonylamino, R2 is phenyl, naphthyl or a 5- or 6-membered aromatic ring that may contain 1 or 2 hetero atoms selected from the group nitrogen, oxygen and sulfur, it being possible far the phenyl ring, the naphthyl ring and the 5- or 6-membered aromatic ring to be substituted by halogen, C3-C8cycloalkyl, hydroxy, mercapto, amino, amino-C,-Csalkyl, carboxyl-C,-Csalkyl, cyano, nitro or by formyl; andlor for the phenyl ring, the naphthyl ring and the 5- or 6-membered aromatic ring to be substituted by C,-Csalkyl, C,-Csalkoxy, hydroxy-C,-Csalkyl, C,-Csalkoxy-C,-Csalkyl, C,-C6-alkoxy-C,-Csalkoxy, C,-Csalkylcarbonyl, C,-Csalkylthio, C,-Csalkylsulfinyl, C,-Csalkylsulfonyl, mono-C,-Csalkylamino, di-C,-Cfialkylamino, C,-Csalkylcarbonylamino, C,-Csalkylcarbonyl-(C,-Csalkyl)amino, C2-Csalkenyl, C3-Csalkenyloxy, hydroxy-C3-Csalkenyl, C,-Cfialkoxy-C3-C6-alkenyl, C,-Csalkoxy-C3-Csalkenyloxy, C2-Csalkenylcarbonyl, C2-Csalkenylthio, C2-Csalkenyl-sulfinyl, C2-Csalkenylsulfonyl, mono- or di-C2-Csalkenylamino, C,-Csalkyl-(C3-Csalkenyl)-amino, C2-Cealkenylcarbonylamino, C2-Csalkenylcarbonyl-(C,-Csalkyl)amino, C2-Csalkynyl, C3-Csalkynyloxy, hydroxy-C3-Csalkynyl, C,-Csalkoxy-C3-Csalkynyl, C,-Csalkoxy-alkynyloxy, C2-Csalkynylcarbonyl, C2-Csalkynylthio, C2-Csalkynylsulfinyl, C2-Csalkynylsulfonyl, mono- or di-C3-Csalkynylamino, C,-Csalkyl-(C3-Csalkynyl)amino, C2-Csalkynylcarbonylamino or by C2-Csalkynylcarbonyl-(C,-Csalkyl)amino; andlor for the phenyl ring, the naphthyl ring and the 5- or 6-membered aromatic ring to be substituted by halo-substituted C,-Csalkyl, halo-substituted C,-Csalkoxy, halo-substituted hydroxy-C,-Cfialkyl, halo-substituted C,-Csalkoxy-C,-Csalkyl, halo-substituted C,-Csalkoxy-C,-Csalkoxy, halo-substituted C,-Csalkylcarbonyl, halo-substituted C,-Csalkylthio, halo-substituted C,-Csalkylsulfinyl, halo-substituted C,-Cgalkylsulfonyl, halo-substituted mono-C,-Csalkylamino, halo-substituted di-C,-Csalkylamino, halo-substituted C,-Csalkylcarbonyl-amino, halo-substituted C,-Csalkylcarbonyl-(C,-Csalkyl)amino, halo-substituted C2-Csalkenyl, halo-substituted C3-Csalkenyloxy, halo-substituted hydroxy-C3-Csalkenyl, halo-substituted C,-Csalkoxy-C2-Csalkenyl, halo-substituted C,-Csalkoxy-C3-Csalkenyloxy, halo-substituted C2-Csalkenylcarbonyl, halo-substituted C2-Csalkenylthio, halo-substituted C2-Csalkenylsulfinyl, halo-substituted C2-Csalkenylsulfonyl, halo-substituted mono- or di-C3-Csalkenylamino, halo-substituted C,-Csalkyl-(C3-Csalkenyl)amino, halo-substituted C2-Csalkenylcarbonylamino, halo-substituted C2-Csalkenylcarbonyl-(C,-Csalkyl)amino, halo-substituted C2-Csalkynyl, halo-substituted C3-Csalkynyloxy, halo-substituted hydroxy-C3-Csalkynyl, halo-substituted C,-Cs-alkoxy-C3-Csalkynyl, halo-substituted C,-Csalkoxy-C4-Csalkynyloxy, halo-substituted C2-Cs-alkynylcarbonyl, halo-substituted C2-Csalkynylthio, halo-substituted C2-Csalkynylsulfinyl, halo-substituted C2-Csalkynylsulfonyl, halo-substituted mono- or di-C3-Csalkynylamino, halo-substituted C,-Csalkyl-(C3-Csalkynyl)amino, halo-substituted C2-Csalkynylcarbonylamino or by halo-substituted C2-Csalkynylcarbonyl-(C,-Csalkyl)amino; andlor for the phenyl ring, the naphthyl ring and the 5- or 6-membered aromatic ring to be substituted by a radical of formula COORS, CONRS,, S02NR53R~or S020R55, wherein Rte, Rs,, Rs2. Rsa. R~ and R55 are each independently of the others hydrogen, C,-Csalkyl, C2-Cs-alkenyl or C3-Csalkynyl, or C,-Csalkyl, C2-Csalkenyl or C3-Csalkynyl each substituted by halogen, hydroxy, alkoxy, mercapto, amino, cyano, vitro, alkylthio, alkylsulfinyl or by alkylsulfonyl, R4 and R5 are each independently of the other hydrogen, C,-C,zalkyl, C,-C,2haloalkyl, C,-C,2-hydroxyalkyl, C3-CBalkenyl, C3-Cealkynyl, C,-C,oalkoxy-C,-CBalkyl, or C3-Cealkyl that may contain one or two oxygen atoms, C,-C,oalkylthio-C,-Csalkyl, C3-Cscycloalkyl, C3-Cecyclo-alkyl that contains 1 or 2 hetero atoms selected from the group oxygen and sulfur, C3-C8-halocycloalkyl, C3-CBhalocycloalkyl that contains 1 or 2 hetero atoms selected from the group oxygen and sulfur, phenyl, or phenyl substituted by halogen, C,-Csalkyl, C,-Cshaloalkyl, C,-Csalkoxy, C,-Cshaloalkoxy, vitro or by cyano, or R4 and R5 are each independently of the other a 5- or 6-membered ring that may contain hetero atoms selected from the group oxygen, sulfur and nitrogen, or R4 and R5, together with the atoms to which they are bonded, form a 5- to 8-membered ring, which may contain 1 or 2 oxygen atoms, sulfur atoms or NRs groups, wherein Rs is hydrogen, C,-C4alkyl, C,-CBalkylcarbonyl, C,-Cgalkylsulfonyl, C3-Csalkenyl or C3-C6-alkynyl, and which may be substituted by halogen, hydroxy, C,-C,oalkyl, C,-C,oalkoxy, C,-C,ohaloalkyl, C3-Cecycloalkyl, phenyl or by benzyl; or which may be substituted by phenyl substituted by halogen, C,-Csalkyl, C,-Cshaloalkyl, C3-Cscycloalkyl, hydroxy, C,-Csalkoxy, C,-Csalkoxy-C,-Csalkoxy, C,-Cshaloalkoxy or by vitro, or by benzyl substituted by halogen, C,-Csalkyl, C,-Cehaloalkyl, C3-Cscycloalkyl, hydroxy, C,-Csalkoxy, C,-Cshaloalkoxy or by vitro; or which may be substituted by CH2-heteroaryl, wherein the aryl moiety has 5 or 6 members, or by halo-, C,-Csalkyl-, C,-Cshaloalkyl-, C,-Cscycloalkyl-, hydroxy-, C,-Csalkoxy-, C,-Cshalo-alkoxy- or vitro-substituted CH2-heteroaryl, wherein the aryl moiety has 5 or 6 members; or which may be substituted by heteroaryl, wherein the aryl moiety has 5 or 6 members, or by halo-, C,-Csalkyl-, C,-Cshaloalkyl-, hydroxy-, C,-Csalkoxy-, C,-Cshaloalkoxy-, cycloalkyl- or vitro-substituted heteroaryl, wherein the aryl moiety has 5 or 6 members; and which may contain a fused or spiro-bound alkylene or alkenylene chain containing from 2 to 6 carbon atoms, which chain may be interrupted by oxygen or sulfur atoms, G is hydrogen, -C(X,)-R3o, -C(X2)-X3-R3,, -C(X4)-N(R~)-R33, -S02-Rte, an alkali metal cation, alkaline earth metal cation, sulfonium cation or ammonium cation, -P(Xs)(R35)-R3s or -CH2XsC(X~)-R3,, -CH2X8C(X9)-X,o-Rte, -CH2X"C(X,2)-N(R39)-R,~ or -CH2X,3SO2-R4,, wherein X,, X2, X3, X4, X5, Xs, X,, Xs X9, X,o, X", X,2 and X,3 are each independently of the others oxygen or sulfur, and R3o, R3,, R32, R33, R34~ R35~ Ras~ Ra>> Rya, Rss, Rao and R4, are each independently of the others hydrogen, C,-C,zalkyl or C,-C,2alkyl substituted by halogen, formyl, cyano, vitro, tri-C,-Csalkylsilyl, hydroxy, C,-Csalkoxy, C,-Csalkoxycarbonyl, amino, C,-Csalkylamino, di-C,-Csalkylamino, mercapto, C,-Csalkylthio, C,-Csalkylcarbonyl, C,-Cs-alkylcarbvnylthio, C,-Csalkylcarbonylamino, C,-Csalkoxycarbonylamino, C,-Csalkylamino-carbonylamino, C,-Csalkylthiocarbonyloxy, C,-Csalkylthiocarbonylamino, C,-Csalkoxythio-carbonyl, aminothiocarbonyl, C,-Csalkylthiocarbonyloxy, C,-Csalkylthiocarbonylamino, C,-Cs-alkoxythiocarbonylamino, C,-Csalkylsulfinyl, C,-Csalkylsulfonyl, C,-Csalkylsulfonyloxy, C,-Cs-alkylsulfonylamino, C,-Csalkoxyimino, hydroxyimino, heteroaryl, benzyloxy, phenoxy or by halophenoxy; or C2-C,zalkenyl, C3-C,2cycloalkyl, C3-Cscyclvalkyl substituted by halogen, C,-Cshaloalkyl, C,-Csalkyl, C,-Csalkoxy, C,-Csalkylcarbonyloxy, C,-Csthioalkyl, C,-Csalkylcarbonylthio, C,-Csalkylamino, C,-Csalkylcarbonylamino, tri-C,-Csalkylsilyl or by tri-C,-Csalkylsilyloxy;
phenyl or phenyl substituted by alkoxy, halogen, C,-Cshaloalkyl, vitro, cyano, C,-Csalkyl, C,-Csalkylcarbonyloxy, C,-Csthioalkyl, C,-Csalkylcarbonylthio, C,-Csalkylamino, C,-Csalkyl-carbonylamino, tri-C,-Csalkylsilyl or by tri-C,-Csalkylsilyloxy; heteroaryl or heteroaryl substituted by halogen, C,-Cshaloalkyl, vitro, cyano, C,-Csalkyl, C,-Csalkoxy, C,-Csalkyl-carbonyloxy, C,-Csthioalkyl, C,-Csalkylcarbonylthio, C,-Csalkylamino, C,-Csalkylcarbonyl-amino, tri-C,-Csalkylsilyl or by tri-C,-Csalkylsilyloxy; and R~ is additionally C2-C~alkenyl or C2-C~alkenyl substituted by halogen, C,-Csalkylcarbonyl, C,-Csalkoxycarbonyl, C,-Csalkylcarbonyloxy, C,-Csalkoxy, C,-Csthioalkyl, C,-Csalkylthio-carbonyl, C,-Csalkylcarbonylthio, C,-Csalkylsulfonyl, C,-Csalkylsulfinyl, C,-Csalkylamino-sulfonyl, di-C,-Csalkylaminosulfonyl, C,-Csalkylsulfonyloxy, C,-Csalkylsulfonylamino, C,-Cs-alkylamino, di-C,-Csalkylamino, C,-Csalkylcarbonylamino, di-C,-Csalkylcarbonylamino, cyano, C3-Cecycloalkyl, C3-Csheterocyclyl, tri-C,-Csalkylsilyl, tri-C,-Csalkylsilyloxy, phenyl, substituted phenyl, heteroaryl or by substituted heteroaryl; or C2-C~alkynyl or C2-C~alkynyl substituted by halogen, C,-Csalkylcarbonyl, C,-Csalkoxy-carbonyl, C,-Csalkylcarbonyloxy, C,-Csalkoxy, C,-Csthioalkyl, C,-Csalkylthiocarbonyl, C,-Csalkylcarbonylthio, C,-Csalkylsulfonyl, C,-Csalkylsulfinyl, C,-Csalkylaminosulfonyl, di-C,-Csalkylaminosulfonyl, C,-Csalkylsulfonyloxy, C,-Csalkylsulfonylamino, C,-Csalkylamino, di-C,-Csalkylamino, C,-Csalkylcarbonylamino, di-C,-Csalkylcarbonylamino, cyano, C3-C,-cycloalkyl, C3-C,heterocyclyl, tri-C,-Cfialkylsilyl, tri-C,-Csalkylsilyloxy, phenyl, substituted phenyl, heteroaryl or by substituted heteroaryl; or C3-CBcycloalkyl or C3-CBcycloalkyl substituted by halogen, C,-Cshaloalkyl, C,-Csalkyl, C,-C6-alkoxy, C,-Csalkylcarbonyloxy, C,-Csthioalkyl, C,-Csalkylcarbonylthio, C,-Csalkylamino, ,.....
C,-Csalkylcarbonylamino, tri-C,-Csalkylsilyl or by tri-C,-Csalkylsilyloxy; or heteroaryl or heteroaryl substituted by halogen, C,-Cshaloalkyl, nitro, cyano, C,-Csalkyl, C,-Csalkoxy, C,-Csalkylcarbonyloxy, C,-Csthioalkyl, C,-Csalkylcarbonylthio, C,-Csalkylamino, C,-Csalkylcarbonylamino, tri-C,-Csalkylsilyl or by tri-C,-Csalkylsilyloxy; or heteroaryloxy, substituted heteroaryloxy, heteroarylthio, substituted heteroarylthio, heteroarylamino, substituted heteroarylamino, diheteroarylamino, substituted diheteroarylamino, phenylamino, substituted phenylamino, diphenylamino, substituted diphenylamino, cycloalkylamino, substituted cycloalkylarnino, dicycloalkylamino, substituted dicycloalkylamino, cycloalkoxy or substituted cycloalkoxy, and to salts and diastereoisomers of the compounds of formula I.
The alkyl groups occurring in the definitions of the substituents may be straight-chained or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, pentyl and hexyl and branched isomers thereof. Suitable alkenyl and alkynyl groups and alkoxy and alkylthio groups and other groups containing an alkyl unit are derived from the mentioned alkyl groups. Examples of suitable cycloalkyl groups according to the invention are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
Halogen substituents are preferably fluorine, chlorine or bromine. Examples of 5- and 6-membered aromatic rings having hetero atoms are thienyl, furyl and pyridyl. As 5- to 8-membered heteroaryls and heterocycloalkyls there may be mentioned, for example, pyrazolidine, 1,2,3,6-tetrahydropyridazine, hexahydropyridazine, 1,4,5-oxadiazepane, 1,4,5-thiadiazepane and 1,4,5-oxadiazoxane.
The invention relates also to the salts that the compounds of formula I can form preferably with amines, alkali metal and alkaline earth metal bases or with quaternary ammonium bases. Suitable salt formers are described, for example, in WO 98141089.
The invention relates also to the salts that the compounds of formula I can form with amines, alkali metal and alkaline earth metal bases or with quaternary ammonium bases.
Among the alkali metal and alkaline earth metal hydroxides as salt formers, special mention may be made of the hydroxides of lithium, sodium, potassium, magnesium or calcium, but especially those of sodium or potassium.
As examples of amines suitable for ammonium salt formation there come into consideration both ammonia and primary, secondary and tertiary C,-C,salkylamines, C,-C4hydroxy-alkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylarnine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-iso-propylamine, methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethyl-propanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, di-butenyl-2-amine, n-hexenyl-2-amine, propylenediarnine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triiso-butylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine;
heterocyclic amines, such as pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, such as anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
Preferred quarternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(Re RbR~Rd )]OH, wherein R~, Rb, R~ and Rd are each independently of the _7_ ,..
others C,-C4alkyl. Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
Preferred compounds of formula I are those wherein R, and R3 are each independently of the other C,-C4alkyl, especially methyl or ethyl, C2-C4alkynyl, especially ethynyl, C,-Csalkoxy, especially methoxy, C,-C4alkylthio, especially methylthio, C,-C4haloalkyl, especially chloro-methyl and chloroethyl, formyl, C,-C4alkylcarbonyl, especially acetyl, or C,-C4alkylamino or di(C,-C4)alkylamino. Special preference is given to methyl, ethyl, ethynyl and methoxy.
In a further group of preferred compounds of formula I, R2 is phenyl, 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 2-pyridyl, 3-pyridyl or 4-pyridyl, with phenyl being especially preferred.
Preference is given also to the corresponding substituted ring systems, with halogen, hydroxy, mercapto, amino, cyano, nitro, formyl, C,-Csalkyl, C,-Cshaloalkyl and C3-C$-cycloalkyl coming into consideration as substituents.
Other preferred compounds of formula I are those wherein R4 and RS are each independently of the other C,-C,zalkyl, C,-C,oalkoxy-C,-CBalkyl or C3-Csalkyl that may contain one or two oxygen atoms, or R4 and R5, together with the atoms to which they are bonded, form a saturated 5- to 8-membered, especially 6- or 7-membered, ring.
Especially preferably R4 and R5 together form a radical -CH2CH2-O-CH2CH2- or -(CH2)4-, it being possible for those radicals to be substituted by C,-C,oalkyl, C,-C,oalkoxy , C,-Cealkoxy-C,-Csalkoxy or by hydroxyl and to carry an alkylene or alkenylene chain containing from 2 to 6 carbon atoms, which chain may be interrupted by oxygen.
Further preferred compounds of formula I have as substituent G hydrogen or COR3o, especially pivaloyl, C(O)X3R3, or S02R~, wherein X3 is oxygen or sulfur, R3, is C,-C,2alkyl, C,-C,2haloalkyl, C2-C,2alkenyl, C,-C,2alkoxyalkyl, C3-C,2cycloalkyl or phenyl, and R~, is C,-C6-alkyl, C,-Cshaloalkyl, phenyl, chloro-, cyano- or methyl-substituted phenyl;
or heteroaryl or chloro-, cyano- or methyl-substituted heteroaryl.
In a further preferred group of compounds of formula I, R, and R3 are each independently of the other C,-C4alkyl, especially methyl or ethyl, C2-C4alkynyl, especially ethynyl, C,-Cs-alkoxy, especially methoxy, or C,-C4alkylthio, especially methylthio, R2 is phenyl, 2-thienyl, 3-thienyl, 2-furyl or 3-furyl, R4 and Rs are each independently of the other C,-C,2alkyl, or R4 and Rs, together with the atoms to which they are bonded, form a radical -CH2CH2-O-CH2CH2- or -(CH2)4-, it being possible for those radicals to be substituted by C,-C,oalkyl or by C,-Csalkoxy-C,-Csalkoxy, and G is hydrogen or COR3o, especially pivalyl, or C(O)X3R3,, wherein X3 is oxygen and R3, is C,-C,2alkyl, C3-C,2cycloalkyl or phenyl.
The compounds of formula I can be prepared by processes known per se, for example processes described in WO 97/02243 or in the literature references cited below, by, for example, introducing the aromatic ring R2 by Pd(0)-catalysed cross-coupling of aromatic tin compounds, for example phenyl-trialkyltin compounds, (Stille, J.K. Angew.
Chem. Int.Ed.
Engl. 1986, 25, 508. Kwon, H.B.; McKee, B.H.; Stille, J.K. J. Org. Chem. 1990, 55, 3114), or zinc compounds, such as phenyl-zinc halides (Negishi, E.; Valente, L.F.;
Kobayashi, M. J.
Am. Chem. Soc. 1980. 102, 3298. Knochel, P.; Singer, R. Chem. Rev. 1993, 93, 2117), or aromatic boric acids, such as furyl-boric acids (Miyaura; N.; Yanagi, T.;
Suzuki, A. Synth.
Common. 1981, 11, 513), or aromatic boric acid esters, such as phenyl-boric acid dialkyl esters (Sato, M.; Miyaura, N.; Suzuki, A. Chem. Lett. 1989, 1405. Watanabe, T.; Miyaura, N.; Suzuki, A. Synlett 1992, 3, 207), or aromatic Grignard compounds, such as phenyl-magnesium bromide (Jendrella, H.; Chen, I. J., Synthesis 1990, 827; Widdowson, D. A.;
Zhang, Y. Z., Tetrahedron 1986, 42, 2111 ) with the halogen compounds II (Hal = chlorine, bromine or iodine).
R~ O R~ O
N~Ra N~Ra Hal ~ / ~ N R2 ~ / ~ N
R3 O ~R5 R3 O wRs ,G ,G
The compound of formula II can be prepared analogously as described in WO
97102243 or, for example, according to the following Scheme for II wherein R,, R2 = CH2CH3 (Hal = CI, Br, _g_ a NHz Ci ~Ci home home t. NaOMe Br Br ~ Br Br 2. H O Br 8r CHzaCHSnBu3 \ TS 4 \ Pd (0) _ / \ \
tBuO-NO ~ ~ ~ CH~CHz, Pd(~
CuClz Oz Z NOz 3 NOz y NOz Hz, PdIC
O O
HN~R~
O HN~ Me home home R
- ,R, III 5 - O (Me0)zC0 \ 1. diazotisation \
Hal N ~- Hal "-- .,.
O NaH ~ / 2. Sandmeyer ~ ,R ~ ~
O M Hal NHz II (R"R3 - CHZCH3) ~ 8 5 The corresponding dimethyl compound (II wherein R,, R2 = CH3) can be prepared, for example, according to the following Scheme:

1. NaOMe H3C ~ CH3 ~ 2. H2S04 tBuO-NO
CuCl2 Br (Me0)2C0 NaH
HN~R' CH3 O HN~R
NiR4 III
Br ~ ~ N \ .~---Rs II (R,, R3 s CHI o ~
Another method of preparing the compounds according to the invention is based on coupling the malonic acid ester IV or malonodiamide V with a substituted hydrazine II1.
R, to R,o can then be hydrogen andlor alkyl, especially Ct-Csalkyl, andlor aryl, preferably phenyl and naphthyl.

Rt O
OMe OMe R O
IV R3 0 HN~Ra t N~Ra or 'f- HN ~ R2 ~ ~ ~ N
~R
Rt O III Rs R3 O'G s NR~R9 I
r"° R2 NR$Rto V
The malonic acid ester IV or the malonodiamide V can be prepared, for example, by Pd(0)-catalysed cross-coupling according to the following Scheme:
NHz NHz Hal R R Suzuki R R R, Rs ' \ ' Stille coupling ' \ 3 1. diazotisation \
Negishi coupling ~ '~ 2.Sandmeyer Hah Rz Rz VI VII VIII
NC~CN o 0 Rry Q.R.
NC CN pd(0), base Pd(0), base R' \ R3 ~Re IX R
z HZSO" HZO
for R~ Rio = H ~ R~R9NH
RaR~oNH
O V
IV
R~R9N ~NRBR~o R1 \ R3 Rz V

The Suzuki, Stille or Negishi coupling of VI to form VII can be carried out according to the above-mentioned procedures (Hal, = Br or I); diazotisation and Sandmeyer reaction (Vogel's Textbook of Practical Organic Chemistry, 5'" Edition, B.S. Furniss, A.J. Hannaford, P.W.G. Smith, A.R. Tatchell; Longman Scientific & Technical 1989, page 923) result in halogen compounds VIII (Hale = CI, Br or I) which can be converted directly to the phenyl malonates IV by Pd(0) cross-couplings (Kawatsura, M.; Hartwig, J.F. J. Am.
Chem. Soc.
1999, i2i, 1473). Starting from VIII by means of analogous Pd(0) cross-couplings, there are obtainable malonodinitriles IX, from which amides V are obtainable.
Compounds of formula I wherein G is hydrogen can also be prepared by reacting a compound of formula XXX
O
~N.~R4 N

(XXX) wherein R4 and R5 are as defined above, with a compound of formula VIII
R~
Hal ~ ~ R2 (VIII) wherein R~, R2 and R3 are as defined for formula I and Hal is chlorine, bromine or iodine, in the presence of an inert solvent, a base and a palladium catalyst at temperatures of from 30 to 250 °C. The reaction is preferably carried out under an inert gas atmosphere.
The compounds of formula XXX are known or can be prepared according to known processes, as described, for example, in J. Chem. Soc. Perkin Trans. 1 (1987), (4), 877-884.
The compounds of formula VIII can be prepared, for example, according to known methods, by way of the diazonium salts e.g. Sandmeyer reaction, from the corresponding anilines of formula VI

H N ~ ~ R2 (VI), z wherein R, and R3 are as defined for formula I. Such reactions are described, for example, in Vogel's Textbook of Practical Organic Chemistry, 5th Edition, B.S. Furniss, A.J. Hannaford, "~ P.W.G. Smith, A.R. Tatchell; Longman Scientific & Technical 1989, page 923.
The compounds of formula VI are known, some of them are commercially available or they can be prepared analogously to known compounds.
Suitable for that reaction are bases, such as tri-alkali metal phosphates, alkali metal and alkaline earth metal hydrides, alkali metal and alkaline earth metal amides or alkali metal alcoholates, for example tripotassium phosphate, sodium hydride, lithium diisopropylamide (LDA), sodium tert-butanolate or potassium tert-butanolate. Special preference is given to sodium tert-butanolate, potassium tert-butanolate and tripotassium phosphate.
Suitable solvents are, for example, aromatic hydrocarbons, such as xylene or toluene, ,.., ethers, such as tetrahydrofuran, dioxane or ethylene glycol dimethyl ether, dimethyl sulfoxide or tertiary amides, such as dimethylformamide, N-methylpyrrolidinone or dimethylacetamide or acyclic ureas, such as N,N'-dimethylpropyleneurea.
The palladium catalysts suitable for the C-C linkage reaction of a compound of formula XXX
with a compound of formula VIII are generally palladium(II) or palladium(0) complexes, such as palladium(II) dihalides, palladium(II) acetate, palladium(II) sulfate, bis(triphenyl-phosphine)palladium(II) dichloride, bis(tricyclopentylphosphine)palladium(II) dichloride, bis(tricyclohexylphosphine)palladium(II) dichloride, bis(dibenzylideneacetone)palladium(0) or tetrakis(triphenylphosphine)palladium(0). The palladium catalyst can also be prepared from palladium(Ip or palladium(t)) compounds by complexing with the desired ligands in situ, for example by placing the palladium(II) salt to be complexed, for example palladium(II) dichloride (PdCl2) or palladium(II) acetate (Pd(OAc)2), together with the desired ligand, for example triphenylphosphine (PPh3), tricyclopentylphosphine or tricyclohexylphosphine, together with the selected solvent, a compound of formula VIII, a compound of formula XXX
and base. Bidendate ligands are also suitable, for example 1,1'-bis(diphenylphosphino)-ferrocene or 1,2-bis(diphenylphosphino)ethane. By heating the reaction mixture, the palladium(II) or palladium(0) complex desired for the C-C coupling reaction is formed in situ, and said complex then initiates the C-C coupling reaction.
The palladium catalysts are used in an amount of from 0.001 to 50 mol %, preferably in an amount of from 0.1 to 15 mol %, based on the compound of formula VIII.
The reaction temperatures are selected in dependence upon the solvent used and, where applicable, the pressure. The reaction is preferably carried out at atmospheric pressure.
A further synthesis variant involves the ortho-functionalisation of a bi-aromatic compound: in that process, it is to be noted that any ortho-position CH2 that is present must be protected against competitive metallisation before the introduction of the second ortho substituent (R~.
o c1 O N~
\ TMEDA, s-BuLi diethylamine '~ THF, R,CHZX
/ .. ~ R1 n-Buli, THF
Me3SiCl \ ./

TMEDA, s-BuLi CsF, DMF THF, R3X
R ~-l.iAlH,, toluene XI
XIII XII

R~
KCN, MeC
AcOH, HCI

XIV XV XVI
OH
e~~.. ~-O
Ra (Me0) CO SOC12, toluene Rr NaH 2 R~ MeOH
XVIII XVII
IV (R~.CHZ = R~, R3 = CeH~
Compounds of the If type can be cyclised by aminal formation with aldehydes (in this case with formaldehyde). lc is accessible by the reaction of hydrazine alcohols, e.g. Illa, with IV

N xylene, 140°C / \ N
IV + ~ R2 OH
Illa R3 O
Ic (R4 = (CH2)30H; R5 = H) 3096 HCHO in H20, THF, 80°C

~N~O

If The following intermediates of formula XIX, which are used in the above-mentioned syntheses and were developed specifically therefor, are novel and also form part of the present invention:

R~ ~ R 3 /

XIX
wherein Ro is COOR,, COORe, CONR,R9, CONRBR,o or cyano, and R~ is hydrogen, COOR,, COORs, CONR,R9, CONReR,o or cyano, and R,, Rs, R9 and R,o and R,, R2 and R3 are as defined above, but R, and R3 are not simultaneously hydrogen.
Preferred intermediates correspond to the formulae /j Rw Rs ~Rs I
Rio R~ \ R3 ,.~
Rz R2 R2 IV V IX
wherein the substituents are as defined above.
The following intermediates of formula VIII, which are used in the syntheses described above and were developed specifically therefor, are novel and also form part of the present invention:

Hal R1 ~ R 3 R2 VIII, wherein R,, R2 and R3 are as defined above, and Hal is chlorine, bromine or iodine, Hal being other than iodine when R, and R3 are methyl and R2 is phenyl.
Hydrazine components required for the compounds according to the invention can be prepared according to a novel process. That process accordingly also forms part of the present invention. That process is characterised in that the last step is carried out in anhydrous alcohol directly with anhydrous hydrohalic acid or with hydrohalic acid prepared in situ, e.g. from the action of methanol on acetyl chloride.
O
~ O
HN' \ R ~ (C~m (C ) R ~ ~ R ~N~ ~ , ~ m NH anhydrous HN
Hal-(CI-~ -X-(CI~ -Hal ~ N ~ alcohol HN~ ~ H I
n m H, O o ~ ~C~n ac I halide (CH-1 (H a ) r K2C03, DMF, 130 C O y XXI XXII
m= 2, 3 r= 1 - 2 n= 2, 3 X= chemical bond, O, S
R~ C1-C4alkyl Hal= halogen The hydrohalic acid can be produced by reacting anhydrous alcohol, such as methanol, with an acyl halide, such as acetyl halide, in situ, which is preferred. A
preferred hydrohalic acid is hydrochloric acid.
The substituent G can be introduced by the reaction of compounds of type I
with organic or inorganic acids under water-removing conditions or in the presence of a coupling reagent.
Acid chlorides and acid anhydrides are also very suitable for that purpose. It is to be noted that, in dependence on the type of substituents R,, R3, R4 and RS - R,o, the compound of formula I may be in the form of a geometric andlor optical isomeric mixture or in the form of a tautomeric mixture. When G = H, for example, compound I may be present as the following three tautomers in equilibrium:
Ra R, ~R
~H
I keto-enol form Nina R
N\R5 I annl-katn fnrm NiR4 R.
N~

I keto-keto form For that reason, when R4 ~ R5 the introduction of G can result in the formation of two ,".. additional geometric isomers:
G
rRa R;
~R

~G
I keto-enol isomer A I keto-enol isomer B
The reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitrites, such as _ 18-acetonitrile or propionitrile, amides, such as N,N-dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably from -20°C to +120°C. The reactions are generally slightly exothermic and can usually be carried out at room temperature. To reduce the reaction time or to initiate the reaction, the reaction mixture may also optionally be heated to boiling point for a short time. The reaction times can also be shortened by the addition of a few drops of base as reaction catalyst.
Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1,4-diaza-bicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo[5.4.0]undec-7-ene. As bases it is also possible, however, to use inorganic bases, e.g.
hydrides, such as sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium and potassium carbonate, or hydrogen carbonates, such as potassium and sodium hydrogen carbonate. The compounds of formula I can be isolated in customary manner by concentration andlor evaporation of the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
For the use of the compounds of formula I according to the invention or compositions comprising them, there are suitable any of the methods of application customary in agriculture, such as preemergence application, postemergence application and seed dressing, as well as various methods and techniques, such as the controlled release of active ingredient. In that method the active ingredient is applied in solution to mineral granule carriers or polymerised granules (urealformaldehyde) and dried. Where appropriate, 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.
The compounds of formula I can be used as herbicides in unmodified form, i.e.
as obtained during synthesis, but are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules and microcapsules. Such formulations are described, for example, in WO 97134485 on pages 9 to 13. 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 circumstances.

r-.
The formulations, i.e. the compositions, preparations or mixtures comprising the active ingredient of formula I or at least one active ingredient of formula I and generally one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g.
by intimately mixing and/or grinding the active ingredients with the formulation adjuvants, e.g. solvents or solid carriers. Surface-active compounds (surfactants) may additionally be used in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, in WO 97134485 on page 6.
Depending on the nature of the active ingredient of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic andlor anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, in WO 97134485 on pages 7 and 8. The surfactants customarily employed in formulation technology, which are described inter alia in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, MunichlVienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol I-III, Chemical Publishing Co., New York, 1980-81, are also suitable for the preparation of the herbicidal compositions according to the invention.
The herbicidal formulations usually comprise from 0.1 to 99 °~b by weight, especially from 0.1 to 95 °~ by weight, herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 °~ by weight, of a solid or liquid formulation adjuvant and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products are preferably formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients such as stabilisers, e.g.
vegetable oils and epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, as well as fertilisers or other active ingredients.
The active ingredients of formula I are generally used on the plant or on the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kglha. 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 crop plant and of the weed, and also upon the application (place, time, method) and, in dependence on those parameters, can vary within wide ranges.
The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties that make 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 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 by genetic engineering techniques, e.g. IMI Maize, Poast Protected Maize, Liberty Link Maize, B.t.ILiberty Link Maize, IMIILiberty Link Maize, IMIILiberty LinkIB.t.
Maize, Roundup Ready Maize and Roundup ReadyIB.t. Maize. The weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The compound of formula I can be mixed advantageously with a number of further known herbicides, preferably selected from the groups of sulfonylureas, areas, chloroacetanilides, ,,...,. chloroacetamides, diphenyl ethers, nitroanilines, oxadiazolones, pyrazoles, triazines, (hetero)aryloxypropionic acids, carbamates, thiocarbamates, thiatriazines, cyclohexane-diones, imidazolinones, triazolopyrimidinesulfonamides, pyrimidinyloxypyridinecarboxylic acids and pyrimidinyloxybenzoic acids. As a result, for example, a substantial widening of the weed spectrum and in many cases also an increase in selectivity towards the useful plants is obtained. The mixing partners of the compound of formula I may also optionally be present in the form of esters or salts, as mentioned, for example, in The Pesticide Manual, Eleventh Edition, 1997, BCPC.
The compound of formula I and mixtures thereof with the further herbicides mentioned above can also be used in combination with safeners. Preference is given to the following suitable safeners:
a compound of formula S-I

Rs~
~N ~ (S-I) O-CH2~0-Rs2 IO
wherein Rs, is hydrogen or chlorine, and Rs2 is hydrogen, C,-Caalkyl or C,-Cealkyl substituted by C,-Cfialkoxy or by C3-Csalkenyloxy, or a compound of formula S-II
Rss E~ ~
N
Rs3 N ~ (S-I I), Rs4 Rs5 wherein E, is nitrogen or methine;
Rs3 is -CCI3, phenyl or halo-substituted phenyl;
Rs4 and Rs5 are each independently of the other hydrogen or halogen; and ,,...< Rss is C,-C4alkyl;
or a compound of formula S-III
C02Rs~ 1 Rs~o02C ~N
Rs9 N . (S-I I I), Rsa Rsl wherein Rs, and Rse are each independently of the other hydrogen or halogen and Rs9, Rs,o and Rs" are each independently of the others C,-C4alkyl, or a compound of formula S-IV

Rsis N-CO - N ~ (S-IV), Rs1 ~ ~ S02 N H -C 0-Rsl2 Rsl~
wherein Rs,2 is a group RS2~ Rsao Rs3s > > I ' / / , Rs45 RSV or ,RS28 Ss~
RS2s ~J38 RS4t Rs~
Rs4s S
Rs,3 is hydrogen, halogen, cyano, trifluoromethyl, vitro, C,-C4alkyl, C,-C4alkoxy, C,-C4-alkylthio, C,-C4 alkylsulfinyl, C,-C4alkylsulfonyl, -COOH, -COO-C,-C4alkyl, -CONRs,eRs,9, -C(O)-C,-C4alkyl, C(O)-phenyl, or phenyl substituted by halogen, C,-C,alkyl, methoxy, vitro or by trifluoromethyl, or -S02NRs~Rs2, or -OS02-C,-C4alkyl;
Rs,s, Rs,9, Rs2o and Rs2, are each independently of the others hydrogen or C,-C4alkyl, or Rs,$ and Rs,9 or Rs~ and Rs2, together form a C4-Csalkylene bridge which may be interrupted by oxygen, NH or by -N(C,-C4alkyl)-;
Rs,4 is hydrogen, halogen, C,-C4alkyl, trifluoromethyl, C,-Csalkoxy, C,-Csalkylthio, -COOH or -COO-C,-C4alkyl;
or Rs,3 and Rs,4 together form a C3-C4alkylene bridge which may be substituted by halogen or by C,-C4alkyl, or Rs,3 and Rs,4 together form a C3-C4alkenylene bridge which may be substituted by halogen or by C,-C4alkyl, or Rs,3 and Rs,4 together form a C4alkadienylene bridge which may be substituted by halogen or by C,-C4alkyl;
Rs,S and Rs,s are each independently of the other hydrogen, C,-Cealkyl, C3-CBcycloalkyl, C3-Csalkenyl, C3-Csalkynyl, , or C,-C4alkyl substituted by C,-C4-Rs2a alkoxy or by \' ; or Rs,s and Rs,s together form a C4-Csalkylene bridge Rs2s which may be interrupted by oxygen, sulfur, SO, S02, NH or by -N(C,-C4alkyl)-;
''~'' Rs~, Rs23, Rs24 and Rs25 are each independently of the others hydrogen, halogen, C,-C4-alkyl, C,-C4alkoxy, C,-C4alkylthio, -COORs~, trifluoromethyl, vitro or cyano, wherein Rs~ is in each case hydrogen, C,-C,oalkyl, C,-C4alkoxy-C,-C4alkyl, C,-C4alkylthio-C,-C4alkyl, di-C,-C4alkylamino-C,-C4alkyl, halo-C,-CBalkyl, C2-CSalkenyl, halo-C2-Cealkenyl, C3-CBalkynyl, C3-C,cycloalkyl, halo-C3-C,cycloalkyl, C,-C$alkylcarbonyl, allylcarbonyl, C3-C,cycloalkyl-carbonyl, benzoyl that is unsubstituted or substituted on the phenyl ring identically or differently up to three times by halogen, C,-C4alkyl, halo-C,-C4alkyl, halo-C,-C4alkoxy or C,-C4alkoxy; or furyl or thienyl; or C,-C4alkyl substituted by phenyl, halophenyl, C,-C4-alkylphenyl, C,-C4alkoxyphenyl, halo-C,-C4alkylphenyl, halo-C,-C4alkoxyphenyl, C,-C6-alkoxycarbonyl, C,-C4alkoxy-C,-C8alkoxycarbonyl, C3-Cealkenyloxycarbonyl, C3-CBalkynyl-oxycarbonyl, C,-Cealkylthiocarbonyl, C3-Cealkenylthiocarbonyl, C3-CBalkynylthiocarbonyl, carbamoyl, mono-C,-C4alkylaminocarbonyl or by di-C,-C4alkylaminocarbonyl; or phenyl-aminocarbonyl which may itself be substituted on the phenyl identically or differently up to three times by halogen, C,-C4alkyl, halo-C,-C4alkyl, halo-C,-C4alkoxy or C,-C4alkoxy or once by cyano or vitro; or dioxolan-2-yl which may itself be substituted by one or two C,-C4alkyl groups, or dioxan-2-yl which may itself be substituted by one or two C,-C4alkyl groups; or C,-C4alkyl substituted by cyano, vitro, carboxyl or by C,-C8-alkylthio-C,-Cealkoxycarbonyl;
Rs" is hydrogen or C,-C4alkyl;
Rs2, is hydrogen, halogen, vitro, C,-C4alkyl or methoxy;
Rs2$ is hydrogen, halogen, C,-C4alkyl, trifluoromethyl, C,-Csalkoxy, C,-Csalkylthio, -COOH or -COO-C,-C4al kyl;
Rs~ is hydrogen, halogen, cyano, vitro, C,-C4alkyl, C,-C4haloalkyl, C,-C4alkylthio, C,-C4-alkylsulfinyl, C,-C,alkylsulfonyl, -COOH, -COO-C,-C4alkyl, -CONRs~Rs3,, C(O)-phenyl, or phenyl substituted by halogen, C,-C,alkyl, methoxy, vitro or by trifluoromethyl, or Rs2s -S02NRs32Rs33, -OS02-C,-C4alkyl, C,-Csalkoxy, or C,-Csalkoxy substituted by C,-C4alkoxy or by halogen; or C3 Csalkenyloxy or C3-Csalkenyloxy substituted by halogen; or C3-Csalkynyl-oxy; wherein Rs~ and Rs3, are each independently of the other hydrogen or C,-C4alkyl; or Rs3o and Rs3, together form a C4-Csalkylene bridge which may be interrupted by oxygen, NH
or by -N(C,-C4aIky0-, and Rs32 and Rs33 are each independently of the other hydrogen or C,-C4alkyl, or Rs32 and Rs33 together form a C4-Csalkylene bridge which may be interrupted by oxygen, NH or by -N(C,-C4alkyl)-;
RS34 is hydrogen, halogen, vitro, C,-C4alkyl, C,-C4alkoxy, C,-C4alkylthio, C,-C4alkylsulfinyl, C,-C4alkylsulfonyl, -COOH, -COO-C,-C4alkyl or CONRs35Rs~, wherein Rs35 and Rs36 are each independently of the other hydrogen or C,-C4alkyl, or RS35 and Rs36 together form a C4-Csalkylene bridge which may be interrupted by oxygen, NH or by -N(C,-C4alkyl)-;
Rs3, is hydrogen, halogen, C,-C4alkyl, -COOH, -COO-C,-C4alkyl, trifluoromethyl or methoxy, or Rs~ and Rs3, together form a C3-C4alkylene bridge;
Rs~ is hydrogen, halogen or C,-C4alkyl;
RSgg is hydrogen, halogen, C,-C4alkyl, -COOH, -COO-C,-C4alkyl, trifluoromethyl or methoxy;
Rs,~ is hydrogen, halogen, vitro, C,-C4alkyl, C,-C4alkoxy, C,-C4alkylthio, C,-C4alkylsulfinyl, C,-C4alkylsulfonyl, -COOH, -COO-C,-C4alkyl or CONRs42Rs,~;
Rs4, is hydrogen, halogen or C,-C4alkyl; or Rs~ and Rs4, together form a C3-C4alkylene bridge;
RS42 and Rs,~ are each independently of the other hydrogen or C,-C4alkyl, or Rs42 and Rs,~
together form a C4-Csalkylene bridge which may be interrupted by oxygen, NH or by -N(C,-C4alkyl)-;
Rs~ is hydrogen, halogen, C,-C4alkyl, -COOH, -COO-C,-C4alkyl, trifluoromethyl or methoxy;
Rs,~ is hydrogen, halogen, vitro, C,-C4alkyl, C,-C4alkoxy, C,-C4alkylthio, C,-C4alkylsulfinyl, C,-C4alkylsulfonyl, -COOH, -COO-C,-C4alkyl or CONRs~Rs4,;
Rs,~ and Rs4, are each independently of the other hydrogen or C,-C4alkyl, or Rs,~ and Rs4, together form a C4-Csalkylene bridge which may be interrupted by oxygen, NH or by -N(C,-C4alkyl)-;
Rs~ is hydrogen, halogen, C,-C4alkyl, -COOH, -COO-C,-C,alkyl, trifluoromethyl or methoxy;
Rs,~ is hydrogen, halogen, vitro, C,-C4alkyl, C,-C4alkoxy, C,-C4alkylthio, C,-C4alkylsulfinyl, C,-C4alkylsulfonyl, -COOH, -COO-C,-C4alkyl or CONRs~RsS,;
Rss, and Rs~ are each independently of the other hydrogen or C,-C4alkyl, or Rss, and Rs52 together form a C4-Csalkylene bridge which may be interrupted by oxygen, NH or by -N(C,-C4alkyl)-;
or a compound of formula S-V
Rsss\ Q (S-V), Rs /~
wherein Rss3 and Rss4 are each independently of the other C,-Csalkyl or C2-Csalkenyl; or Rs~ Rs~
Rss3 and Rss4 together are p ; Rsss and Rsss are each independently of the Rss~
other hydrogen or C,-Csalkyl; or Rss3 and Rss4 together are ~ ; wherein Rsss Rsss Rsss and Rsss are each independently of the other C,-C4alkyl, or Rsss and Rsss together are -(CH2)s- ;
Rss, is hydrogen, C,-C4alkyl or I I ;

Rsss Rsss Rsso or Rss3 and Rss4 together are Rs63 Rss, or Rs ;
Rssa _~N~Rss2 RssS Rsss wherein Rsse, Rsse, Rsso, Rss,, Rs62, Rs~, Rss,,, Rsss, Rsss, Rss,, Rsss, Rss9, Rs,o, Rs", Rs,2 and Rs,3 are each independently of the others hydrogen or C,-C,alkyl;
or a compound of formula S-VI

Rs~4 (S-VI), -O\ ~~
RS75 , N
O
wherein Rs,S is hydrogen or chlorine and Rs,4 is cyano or trifluoromethyl, or a compound of formula S-VII
CI
Rs~s ~ ~ N (S-VII) N
CI
wherein Rs,s is hydrogen or methyl, or of formula S-VIII
~E3~ r E4 (S-VIII), .~~~s wherein ris0orl;
Rs" is hydrogen or C,-C4alkyl which may be substituted by C,-C4alkoxy, C,-C4alkylthio, C,-C4alkylsulfinyl, C,-C4alkylsulfonyl, C,-C4haloalkyl, C,-C4haloalkoxy, C,-C4haloalkylthio, C,-C4haloalkylsulfinyl, C,-C4haloalkylsulfonyl, vitro, cyano, -COOH, COO-C,-C4alkyl, -NRs~Rse,, -S02NRs82Rse3 or by -CONRs84Rs~;
Rs,$ is hydrogen, halogen, C,-C4alkyl, trifluoromethyl, C,-C4alkoxy or C,-C4haloalkoxy;
Rs,9 is hydrogen, halogen or C,-C4alkyl;
Rs~ is hydrogen, C,-C4alkyl or C,-C4alkylcarbonyl;
Rse, is hydrogen or C,-C4alkyl; or Rs~ and Rse, together form a C4- or C5-alkylene group;
Rs~, Rse3, Rs~ and RsaS are each independently of the others hydrogen or C,-C4alkyl; or Rs~ together with Rse3, or Rs~ together with Rs~, are each independently of the other C4- or CS-alkylene, it being possible for one carbon atom to be replaced by oxygen or sulfur, or for one or two carbon atoms to be replaced by -NH- or by -N(C,-C4alkyl)-;
E2 , E3 , E4 and ES are each independently of the others oxygen, sulfur, C(Rs~)Rse,, _27_ H O H
carbonyl, -NH-, -N(C,-Cealkyl)-, a group C~ Rs~ or C~ Rs9~ , O
Rs~ Rsa9 RS95/ 'Rs~
Rs~ and Rse, are each independently of the other hydrogen or C,-CSalkyl; or Rses and Rse, together are C2-Csalkylene;
Rs~ and Rsa9 are each independently of the other hydrogen or C,-CBalkyl; or Rs~ and Rsa9 together form a C2-Csalkylene group;
Rs~ is Rs9,-O-, RSg2-S- or -NRs93Rs9,;
"~ Rs9, and Rs~ are each independently of the other hydrogen, C,-CBalkyl, C,-Cehaloalkyl, C,-C4alkoxy-C,-Cealkyl, C3-Csalkenyloxy-C,-Cealkyl or phenyl-C,-Csalkyl, it being possible for the phenyl ring to be substituted by halogen, C,-C4alkyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl or by methylsulfonyl, or are C3-Csalkenyl, C3-Cshaloalkenyl, phenyl-C3-C6-alkenyl, C3-Csalkynyl, phenyl-C3-Csalkynyl, oxetanyl, furyl or tetrahydrofuryl;
RSg3 is hydrogen, C,-CBalkyl, phenyl, phenyl-C,-Cealkyl, it being possible for the phenyl rings to be substituted by fluorine, chlorine, bromine, nitro, cyano, -OCH3, C,-C4alkyl or by CH3S02-, or is C,-C4alkoxy-C,-CBalkyl, C3-Csalkenyl or C3-Csalkynyl;
Rs~ is hydrogen, C,-CBalkyl, C3-Csalkenyl or C3-Csalkynyl; or Rs93 and Rs~ together are C4- or C5-alkylene, it being possible for one carbon atom to be replaced by oxygen or sulfur, or for one or two carbon atoms to be replaced by -NH- or by ,.., -N(C,-C4alkyp- ; ' Rs95 and Rs~ are each independently of the other hydrogen or C,-CBalkyl; or RSgS and Rs~ together form a C2-Csalkylene group; and Rse, is C2-C4alkenyl or C2-C4alkynyl; with the provisos that a) at least one of the ring members E2, E3, E4 and E5 is carbonyl, and one ring member that H O
is adjacent to thatlthose ring members) is the group C~ Rs~ or O
Rs~ Rs$s H
C
Rs9~ , such a group occurring only once; and O
R~Rs b) two adjacent ring members E2 and E3, E3 and E4, and E4 and E5 cannot simultaneously be oxygen;
or a compound of formula S-IX
RSSs I I NHSOz -~N~ \ Rsi~ (S-IX), S~ ~COORssa wherein Rs98 is hydrogen, C,-Csalkyl, C3-Cscycloalkyl, C3-Csalkenyl or C3-Csalkynyl; and Rs~, Rs,~ and Rs,o, are each independently of the others hydrogen, C,-Csalkyl, C3-Cscycloalkyl or C,-Csalkoxy, with the proviso that one of the substituents Rs99, Rs,~ and Rs,o, is other than hydrogen;
or a compound of formula S-X
RSino ~RS102~ (S-X) RSi~
wherein E6 is nitrogen or methine, n is 0, 1, 2 or 3 when Es is nitrogen and 0, 1, 2, 3 or 4 ''~ when Es is methine, Rs,o2 is halogen, C,-C4alkyl, C,-C4haloalkyl, C,-C4alkoxy, C,-C4halo-alkoxy, vitro, C,-C4alkylthio, C,-C4alkylsulfonyl, C,-C4alkoxycarbonyl, phenyl or phenoxy, or phenyl or phenoxy each substituted by C,-C3alkyl, C,-C3haloalkyl, C,-C3alkoxy, C,-C3-haloalkoxy, halogen, cyano or by vitro;
Rs,o3 is hydrogen or C,-C4alkyl;
Rs,~, is hydrogen, C,-C4alkyl, C3-Cscycloalkyl, C2-Csalkenyl, C2-Csalkynyl, C,-C4haloalkyl, C2-Cshaloalkenyl, C2-Cshaloalkynyl, C,-C4alkylthio-C,-C4alkyl, C,-C4alkylsulfonyl-C,-C4alkyl, C,-C4alkoxy-C,-C4alkyl, C,-C4alkenyloxy-C,-C4alkyl or C,-C4alkynyloxy-C,-C4alkyl;
or a compound of formula S-XI

_29_ / /
\ \ ~ (S-XI) wherein E, is oxygen or N-Rs,os and Rs,oS is a group of formula Hz Rslos 'C
O~N~Rs '"' O
wherein Rs,~ and Rs,o, are each independently of the other cyano, hydrogen, C,-C4alkyl, C3-Cscycloalkyl, C2-Csalkenyl, aryl, phenyl or heteroaryl, or phenyl, aryl or heteroaryl each substituted by C,-C3alkyl, C,-C3haloalkyl, C,-C3alkoxy, C,-C3haloalkoxy, halogen, cyano or by nitro;
or a compound of formula S-XII
Rsloav i ~slos / (S-XII) Rsllo Rs111 wherein Ee is oxygen, sulfur, sulfinyl, sulfonyl or methine, Rs,oe and Rs,~ are each independently of the other CH2COORs"2 or COORs"3 or together are a group of formula -(CH2)C(O)-O-C(O)-(CH2)-, and Rs"2 and Rs"3 are each independently of the other hydrogen, C,-C4alkyl, C2-C4alkenyl, C2-Csalkynyl, C3-Cscycloalkyl, C,-C4haloalkyl, or a metal cation or ammonium cation; and Rs"o and Rs", are each independently of the other hydrogen, halogen or C,-C4alkyl;
or a compound of formula S-XIII

(S-Xlll), / I O / ORslls \ Es \

wherein Rs"4 and Rs"5 are each independently of the other hydrogen, halogen or C,-C4-haloalkyl, Rs"s is hydrogen, C,-C4alkyl, C3-C4alkenyl, C3-C4alkynyl, C,-C4haloalkyl, C3-Cs-cycloalkyl, a metal cation or an ammonium cation;
,.,, E9 is nitrogen, methine, C-F or C-CI and E,o is a group of formula RS119 Or RS122 Rslla ORsll~

O
O Rs121 O , wherein Rs Rs Rs and »e, »s, ~2~
Rs,~ are each independently of the others hydrogen or C,-C4alkyl;
Rs", and Rs,~ are each independently of the other hydrogen, C,-C4alkyl, C3-C4alkenyl, C3-C4alkynyl, C,-C4haloalkyl, C3-Cscycloalkyl, a metal cation or an ammonium cation;
or a compound of formula S-XIV
O
/ RSl2a (S-XIV), wherein Rs,23 is hydrogen, cyano, halogen, C,-C4alkyl, C3-Cscycloalkyl, C,-C4alkoxy, C,-C4-alkoxycarbonyl, C,-C4alkylthiocarbonyl, -NH-Rs,25 -C(O)NH-Rs,~, aryl or heteroaryl, or aryl or heteroaryl each substituted by C,-C3alkyl, C,-C3haloalkyl, C,-C3alkoxy, C,-C3haloalkoxy, halogen, cyano or by vitro;
Rs,24 is hydrogen, cyano, vitro, halogen, C,-C4alkyl, C,-C4haloalkyl, C,-C4alkoxy, C,-C4-thioalkyl; and Rs,25 and Rs,~ are each independently of the other C,-C4alkyl, C,-C4haloalkyl, C3-C4alkenyl, C3-C4alkynyl, C3-C4cycloalkyl, C,-C4alkylcarbonyl, C,-C4alkylsulfonyl, aryl or heteroaryl, or aryl or heteroaryl each substituted by C,-C3alkyl, C,-C3haloalkyl, C,-C3alkoxy, C,-C3halo-alkoxy, halogen, cyano or by nitro;
or a compound of formula S-XV
Rsl2s Rsl2e Rsl3o / / N (S-XV), Rs \N"N"Rs wherein Rs,2, and Rs,2$ are each independently of the other hydrogen, C,-C4alkyl, C,-C4-haloalkyl, C,-C4alkoxy, mono-C,-C8- or di-C,-C$-alkylamino, C3-Cscycloalkyl, C,-C4thioalkyl, phenyl or heteroaryl;
Rs,~ is hydrogen, C,-C4alkyl, C,-C4haloalkyl, C,-C4alkoxy, mono-C,-CB- or di-C,-CB-alkyl-amino, C3-Cscycloalkyl, C,-C4thioalkyl, phenyl, heteroaryl, OH, NH2, halogen, di-C,-C4-aminoalkyl, C,-C4alkylthio, C,-C4alkylsulfonyl or C,-C4alkoxycarbonyl;
Rs,~ is hydrogen, C,-C4alkyl, C,-C4haloalkyl, C,-C4alkoxy, mono-C,-C8- or di-C,-CB-alkylamino, C3-Cscycloalkyl, C,-C4thioalkyl, phenyl, heteroaryl, cyano, nitro, carboxyl, C,-C4-alkoxycarbonyl, di-C,-C4aminoalkyl, C,-C4alkylthio, C,-C4alkylsulfonyl, S02-OH, I-C,-C4-aminoalkylsulfonyl or C,-C4alkoxysulfonyl;
Rs,3, is hydrogen, C,-C4alkyl, C,-C4haloalkyl, C,-C4alkoxy, mono-C,-C8- or di-C,-Cs-alkyl-amino, C3-Cscycloalkyl, C,-C4thioalkyl, phenyl, heteroaryl, OH, NH2, halogen, di-C,-C4-aminoalkyl, pyrrolidin-1-yl, piperid-1-yl, morpholin-1-yl, C,-C4alkylthio, C,-C4alkylsulfonyl, C,-C4alkoxycarbonyl, phenoxy, naphthoxy, phenylamino, benzoyloxy or phenylsulfonyloxy;
or a compound of formula S-XVI
O O'Rs132 Rsl~ O
(S-XVI), N
wherein Rs,~ is hydrogen, C4alkyl, C,-C4haloalkyl, C2-C4alkenyl, C2-C4alkynyl or C,-C4-alkoxy-C,-C4alkyl;
Rs,~ is hydrogen, halogen, C,-C4alkyl, C,-C4haloalkyl or C,-C4alkoxy and Rs,~is hydrogen, halogen, C,-C4alkyl, C,-C4haloalkyl or C,-C4alkoxy; with the proviso that Rs,~
and Rs,~ are not simultaneously hydrogen.
Especially preferred safeners for the composition according to the invention are selected from the group of compounds of formula S1.1 N Me (S1.1 ), CI
O
CI
and of the compound of formula S1.2 CI
-N
(S1.2), CI
and of the compound of formula SS1.3 ''~'' (S1.3), (CH3)CSH~ ~-n and of the compound of formula S1.4 CI Me COOCH2CH3 CI ~ ~ N ~ (S1.4), \N

and of the compound of formula S1.5 O CI
N Me CI (S1.5), O
O Me and of the compound of formula S1.6 H
,~. (S1.6), and of the compound of formula S1.7 CI
O
CI
Me N (S1.7), Me N
Me O
and of the compound of formula S1.8 ',....
CI
\ ~ j ~ O (S1.8), O
CF O

and of formula S1.9 CI2CHCON(CH2CH=CH2) (S1.9), and of formula S1.10 S O
CI~ / O-CH 2 ~ ~ (S1.10), 1,N

and of formula S1.11 CI
O
,,~-.. CI (S1.11 O
and of formula S1.12 (S1.12) and of formula S1.13 ~CH2CH3 CI
O
CI ~ ~ (S1.13).
CI
CI
The compounds of formulae S1.1 to S1.13 are known and are described, for example in The Pesticide Manual, eleventh ed., British Crop Protection Council, 1997 under entry numbers 61 (formula S1.1, benoxacor), 304 (formula S1.2, fenclorim), 154 (formula S1.3, cloquintocet), 462 (formula S1.4, mefenpyr-diethyl), 377 (formula S1.5, furilazole), 363 (formula S1.8, fluxofenim), 213 (formula S1.9, dichlormid) and 350 (formula S1.10, flurazole). The compound of formula S1.11 is known by the name MON 4660 (Monsanto) and is described, for example, in EP-A-0 436 483.
The compound of formula S1.6 (AC 304415) is described, for example, in EP-A-0 613 618, and the compound of formula S1.7 is described in DE-A-2948535. The compound of formula S1.12 is described in DE-A-4331448, and the compound of formula S1.13 is described in DE-A-3525205.
The following Examples illustrate the invention further but do not limit it.
Preparation Exam Ip es:

Br ~ Br .. Br Vinylidene chloride (84 ml, 1.05 M), tert-butyl nitrite (12.5 ml, 0.105 M) and copper(II) chloride were placed in acetonitrile (70 ml). At 10°C, 2,6-dibromo-4-nitroaniline 1 was added in portions thereto. The reaction mixture was then stirred at room temperature for 16 hours r and filtered, and the filtrate was washed with tert-butyl methyl ether. The organic phase was washed with 150 ml of 1096 HCI and 2 x 150 ml of water, and dried over Na2S04.
The organic phase was concentrated and chromatographed over silica gel. 13.2 g of 2 were obtained.'H-NMR (300 MHz, CDCI3): 8 = 4.69 (s, 2H).
Br Br 2 (10.9 g, 26.4 mmol) was suspended in methanol and an NaOMe solution (30°~ in methanol, 27.8 ml) was added at room temperature. The reaction mixture was then refluxed for 1 hour, cooled, rendered acidic with H2S04 (3.7 ml) and refluxed for a further 0.5 hour.
The reaction mixture was cooled, diluted with water and extracted with CH2CI2 (3 x 100 ml).
The combined organic phases were dried using Na2S04, filtered and concentrated. 3 (9.1 g) was obtained in the form of a crude product.'H-NMR (300 MHz, CDCI3): b = 8.4 (s, 2H); 4.2 (s, 2H); 3.7 (s, 3H).
Br 3 (9.1, 25.7 mmol) and vinyl tributyl tin (18 ml, 61.7 mmol) were placed in toluene. The reaction mixture was degassed for 0.33 hour by the introduction of argon.
Tetrakis-triphenylphosphine-Pd(0) (1.46 g, 1.28 mmol) was then added thereto. The reaction mixture was heated at 100°C for 16 hours and cooled, and an NaOH solution (1 N, 100 ml) was added. The two-phase mixture was stirred rapidly for 0.5 hour. The organic phase was separated off and washed with water and brine, dried over Na2S04, concentrated and ..-. chromatographed over silica gel (EtOAC:hexane (1:10)). 4 (4.13 g) was obtained. 'H-NMR
(300 MHz, CDCI3): b = 8.2 (s, 2H); 6.9 (dd, 1 H); 5.8 (d, 1 H); 5.5 (d, 1 H);
3.8 (s, 2H); 3.7 (s, 3H).
4 (4 g, 16.2 mmol) was dissolved in MeOH (100 ml), and PdIC (596, 2 g) was added thereto.
The reaction mixture was stirred rapidly for 2.5 hours under a hydrogen atmosphere (normal pressure). The reaction mixture was filtered and concentrated. 5 (3.25 g) was obtained.
'H-NMR (300 MHz, CDCI3): 8 = 6.4 (s, 2H); 3.7 (s, 3H); 3.6 (s, 2H); 2.6 (q, 4H); 1.2 (t, 6H) Tert-butyl nitrite (5.96 ml, 50 mmop and methylene iodide (4.15 ml, 50 mmoQ
were placed in acetonitrile (30 ml) and, at 0°C, 5 (5.52 g, 25 mmol) dissolved in acetonitrile (20 ml), was added thereto. The reaction mixture was illuminated for 1 hour (200 W), during which the temperature rose to 70°C. The reaction mixture was cooled, water was added, and extraction was carried out with ethyl acetate (2 x 20 ml). The combined organic phases were washed with 1 N HCI and brine, dried over Na2S04, filtered, concentrated and chromatographed over silica gel (ethyl acetate:hex = 1:5). 6 (Hal = I) (1.6 g) was obtained.
'H-NMR (300 MHz, CDCI3): b = 7.4 (s, 2H); 3.7 (2s, 5H); 2.6 (q, 4H); 1.2 (t, 6H).
MeO~ Y home 8 (Hal = I) 7 (Hal = I) Diisopropylamine (565 mg, 5.59 mmol) was placed in THF (15 ml) and, at -30°C, n-BuLi (2M
in cyclohexane, 2.67 ml, 5.34 mmol) was added. The reaction mixture was stirred at 0°C for 0.25 hour and cooled to -78°C. 6 (Hal = I) was dissolved in THF (15 ml) and added dropwise to the reaction mixture. After stirring for 0.5 hour at -78°C, cyanoformic acid methyl ester was added, and the reaction mixture was slowly heated to 0°C. The reaction mixture was added to NH4CI (aq) (100 ml) and extracted with ethyl acetate (2 x 70 ml). The combined organic phases were washed with H20 (3 x 70 ml) and brine (70 ml), dried over Na2S04, filterad and concentrated. The crude product was chromatographed over silica gel.
7 (Hal = I, 1.125 g) was obtained.'H-NMR (300 MHz, CDCI3): 8 = 7.4 (s, 2H);
5.0 (s, 1 H); 3.8 (s, 6H); 2.6 (m, 4H) 1.2 (m, 6H).
Tert-butyl nitrite (355 ml, 3 mol) and copper(II) chloride (337.4 g, 2.5 mol) were placed in acetonitrile (1200 ml). First, at < 30°C, vinylidene chloride (2385 ml, 29.9 mol) was added dropwise and then, at 10°C, a solution of 4-bromo-2,6-dimethylaniline 8 (398 g, 2 mol) in acetonitrile (2000 ml) was added dropwise. The reaction mixture was then stirred at room temperature for 16 hours, stirred into 2096 HCI (9000 ml) and extracted with tert-butyl methyl ether (3 x 3000 ml). The organic phase was washed with 20°6 HCI and water and dried over Na2S04. The organic phase was concentrated. 470 g of 9 were obtained.'H-NMR
(300 MHz, CDCI3): 8 = 4.13 (s, 2H).

9 (257 g, 0.813 mol) was dissolved in methanol (400 ml) and, at < 30°C, NaOMe (3096 in methanol, 640 ml, 3.53 mol) was added. The reaction mixture was stirred at reflux for 15 hours. The reaction mixture was cooled to room temperature, and concentrated sulfuric acid (95 ml, 1.75 mol) was added. The reaction mixture was stirred at reflux for 10 hours, concentrated and stirred with water. The suspension was extracted with methylene chloride (3x) and the combined organic phases were dried over Na2S04, concentrated and distilled.
(198 g, b.p.:95-100°CI0.2) was obtained. 'H-NMR (300 MHz, CDCI3): 8 =
3.67 (s, 3H);
3.62 (s, 2H); 2.28 (s, 6H).
Sodium hydride (60 g, 1.6 mol) was suspended in dimethyl carbonate (1500 ml, 17.7 mol) and heated to 90°C. 10 (198 g, 0.77 mol) dissolved in dimethyl carbonate (1200 ml, 14.2 M) was added dropwise to the reaction mixture. The reaction mixture was stirred at 90°C for hours and cooled, and excess sodium hydride was destroyed with methanol. The reaction mixture was poured into icelwater, adjusted to pH = 5 with HCI, and extracted with methylene chloride (4x). The combined organic phases were washed with brine, dried over Na2S04, concentrated and recrystallised from ethyl acetatelhexane (1:10). 11 (161.33 g, m.p.: 69-71°C) was obtained.'H-NMR (300 MHz, CDCI3): b = 7.21 (s, 2H);
4.98 (s, 1H); 3.76 (s, 6H) 2.31 (s, 6H).
11 (40 g, 0.129 mol) and hydrazine 16 (27.15, 0.155 mol) were suspended in xylene ,.-.. (500 ml) and degassed for 0.3 hour by the introduction of argon into the reaction mixture.
Triethylamine (43 ml, 0.1552 mol) was added to the reaction mixture, which was stirred for 4 hours at 140°C. The reaction mixture was cooled to room temperature and concentrated, and the residue was stirred with 10°~ HCI and extracted 3 times with ethyl acetate. The combined organic phases were washed with brine, dried over Na2S04 and concentrated.
17 was obtained (42.87 g, m.p: 299-301 °C). 'H-NMR (300 MHz, CDCI3): 8 = 7.26 and 7.18 (2s, 2H); 4.70 (s, 1 H); 4.20 - 3.75 (m, 8H); 2.41 (s, 3H) 2.08 (s, 3H).

NEt2 ---~ B O
I' /

17 (42.87 g, 0.12 mol) was suspended in acetonitrile (400 ml), and triethylamine (29 ml, 0.206 mol) was added. The solution, which was now clear, was cooled to 10°C, and diethylcarbamoyl chloride (26.2 ml, 0.206 mol) was added. The reaction mixture was heated at reflux for 10 hours, cooled to room temperature, poured into icelwater and adjusted to pH = 5 with concentrated HCI. The reaction mixture was extracted several times with ethyl acetate. The combined organic phases were washed with brine, dried over Na2S04 and concentrated. The resulting resin was stirred with ether. The crystals obtained 18 (47 g, m.p.
122°C) were filtered off.'H-NMR (300 MHz, CDCI3): b = 7.21 (s, 2H);
4.28 (m, 2H); 3.92 (m, 6H); 3.2 (m, 4H); 2.22 (s, 6H), 1.0 (m, 6H).
18 (2.76 g, 6.1 mmol), sodium carbonate (2.5 ml of a 2M solution in water, 9.98 mmop and phenylboric acid (0.18 g, 8.88 mmol) were suspended in 1,2-diethoxyethane and degassed by the introduction of argon into the reaction mixture. After the addition of tetrakis--. (triphenylphosphine)palladium (0.36 g, 0.312 mmol), the reaction mixture was stirred at reflux for 8 hours, cooled, poured into water and adjusted to pH = 5 with concentrated HCI.
Extraction was carried out 3 times with ethyl acetate, and the combined organic phases were washed with brine, dried over Na2S04, concentrated and chromatographed over silica gel (ethyl acetate:methanol = 5:1). 19 (2.7 g) was obtained.'H-NMR (300 MHz, CDCI3): b = 7.7-7.25 (m, 7H); 4.3 (m, 2H); 3.92 (m, 6H); 3.2 (m, 4H); 2.29 (s, 6H), 0.95 (m, 6H).
19 (~.0 g, 8.9 mmol) was dissolved in methanol (50 ml), and sodium hydroxide solution (2N, 17.6 ml, 17.8 mmol) was added. The reaction mixture was stirred at reflux for 12 hours, cooled and concentrated. The residue was stirred with water and adjusted to a pH of 3 with concentrated HCI. The substance that precipitated was filtered off and dried.
20 (3.1 g, m.p.:
260-261°C) was obtained.'H-NMR (300 MHz, CDCI~: 8 = 7.6-7.25 (m, 7H);
4.26 (m, 2H);
4.0 (m, 4H); 3.85 (m, 2H); 2.50 (s, 3H), 2.16 (s, 3H).

20 (1.04 g, 2.96 mmol) was placed in acetonitrile (25 ml), and triethylamine (0.49 ml, 3.55 mmol) and pivalic acid chloride (0.45 ml, 3.55 mmol) were added. The reaction mixture was stirred at room temperature for 1 hour, concentrated, stirred with water and adjusted to a pH of 0.5 with concentrated HCI. Extraction was carried out three times with ethyl acetate, and the combined organic phases were washed with brine, dried over Na2S04, concentrated and chromatographed over silica gel (ethyl acetate: methanol = 5:1 ). 21 (0.93 g, m.p. 159°C) was obtained. 'H-NMR (300 MHz, CDCI3): 8 = 7.6-7.25 (m, 7H); 4.3 (m, 2H); 3.94 (m, 2H);
3.85 (m, 4H); 2.28 (s, 6H), 1.05 (s, 9H).
4-Biphenylcarbonyl chloride 12 (25 g, 0.115 mol) was dissolved in acetonitrile (150 ml), cooled to 0°C, and diethylamine (18.6 g, 0.254 mol) was added. The reaction mixture was stirred at room temperature for 0.5 hour, concentrated, taken up in ethyl acetate (200 m0 and washed with water (2 x 100 ml) and aqueous NaHC03 solution (100 ml), dried over Na2S04 and concentrated. The crude product (28.5 g) was crystallised from Et201hexane.
13 (24.5 g) was obtained. 'H-NMR (300 MHz, CDCI3): 8 = 7.6-7.35 (m, 9H); 3.7-3.2 (2bs, 4H); 1.2 (m, 6H).
TMEDA (17.1 g, 0.147 mol) was dissolved in THF (distilled over Na, 500 ml), cooled to -78°C, and s-BuLi (113 ml of a 1.3M solution in cyclohexane, 0.147 mol) was added. The reaction mixture was stirred at -78°C for 0.25 hour, and a solution of 13 133.9 g, 0.134 mol) in THF (100 ml) was added dropwise thereto, and the mixture was stirred at -78°C for a further 0.25 hour. The reaction mixture was treated dropwise with iodoethane (45.2 g, 0.29 mol) and heated to 0°C. An aqueous, saturated NH4CI solution (200 ml) was added to the reaction mixture. The organic phase was separated off, washed with brine, dried over Na2S04, concentrated and chromatographed over silica gel (Et201hexane = 1:1 ).
22 (29.5 g) was obtained.

'H-NMR (300 MHz, CDCI3): b = 7.6-7.2 (m, 9H); 3.9-3.1 (m, 4H); 2.7 (q, 2H), 1.25 (t, 6H); 1.1 (t, 3H) Diisopropylamine (13.36 g, 0.132 mol) was dissolved in THF (distilled over Na, 400 ml), cooled to -30°C and n-BuLi (79 ml of a 1.6M solution in hexane, 0.126 mol) was added.
After 0.25 hour, the reaction mixture was cooled to -78°C, and TMEDA
(15.3 g, 0.132 mol) and 22 (29.5 g, 0.105 mol) dissolved in THF (75 ml) were slowly added. After 0.3 hour, chlorotrimethylsilylane was added to the reaction mixture, which was heated to 0°C.
Aqueous, saturated NH4CI solution (200 ml) was added to the reaction mixture, and the organic phase was separated off. The organic phase was washed with brine, dried over Na2S04 and concentrated. 23 (38.2) was obtained in the form of a crude product. 'H-NMR
(300 MHz, CDCI3): b = 7.6-7.1 (m, 8H); 3.75 (m, 1 H); 3.4-3-0 (m, 3H); 2.3 and 2.1 (2m, 1 H);
1.35 (d,3H); 1.25 (m, 6H); 0.0 (s, 9H).
TMEDA (8.9 g, 0.077 mol) was dissolved in THF (distilled over Na, 400 ml), the reaction mixture was cooled to -78°C, and s-BuLi (59 ml of a 1.3M solution in cyclohexane, 0.077 mol) and then a solution of 23 (24.8 g, 0.07 mol) in THF (75 ml) were added dropwise.
After 0.5 hour at -78°C, iodomethane (13.3 g, 0.085 mol) was added to the reaction mixture, which was heated to 0°C. Aqueous, saturated NH4CI solution (200 ml) was added to the reaction mixture, and the organic phase was separated off. The organic phase was washed with brine, dried over Na2S04 and concentrated. The crude product was chromatographed over silica gel (ethyl acetatelhexane = 1:7). 24 (18.5) was obtained.
'H-NMR (300 MHz, CDCI3): 8 = 7.6-7.2 (m, 7H); 3.6 (m, 2H); 3.1 (m, 2H); 2.6 (m, 2H); 2.1 (m, 1 H); 1.4 (d, 3H); 1.2 (m, 6H); 0.0 (s, 9H).
24 (18.5 g, 0.059 mop was dissolved in DMF (100 ml) and water (10 ml), and CsF
(11.2 g, 0.074 mol) was added at room temperature. The reaction mixture was stirred at 75°C for 8 hours, poured into water (300 ml) and extracted with ethyl acetate (2 x 100 ml). The combined organic phases were washed with brine, dried over Na2S04 and concentrated.
25 (15.7 g) was obtained in the form of a crude product.'H-NMR (300 MHz, CDCI3): 8 = 7.6-7.3 (m, 7H); 3.6 (m, 2H); 3.15 (m, 2H); 2.6 (m, 2H); 1.3 (m, 9H); 1.05 (t, 3H).
25 (15.7 g, 0.051 mol) was dissolved in toluene, and LiAIH4 (1.92 g, 0.051 mol) was added.
The reaction mixture was stirred at reflux for 20 hours and cooled to 0°C, HCI solution (1 N, 150 ml) was added cautiously, and extraction was carried out with ethyl acetate (2 x 100 ml).
The combined organic phases were extracted with 1 N HCI solution (1 x 75 ml).
The combined aqueous phases were adjusted to a pH of 11 with 2N NaOH solution, and extracted with ethyl acetate (2 x 100 ml). The combined organic phases were dried over Na2S04 and concentrated. 26 (8.6 g) was obtained in the form of a crude product. 'H-NMR
(300 MHz, CDCI3): b = 7.8-7.25 (m, 7H); 3.6 (s, 2H); 3.35 (q, 4H); 2.5 (q, 4H); 1.25 (t, 6H);
1.05 (t, 6H).
,..~-26 (8.6 g, 0.029 mol) was dissolved in toluene (50 ml), and chloroformic acid ethyl ester (12.6 g, 0.116 mol) was added. The reaction mixture was stirred at 75°C
for 3 hours, and concentrated. 27 (11 g) was obtained in the form of a crude product. 'H-NMR
(300 MHz, CDCI3): b = 7.6-7.3 (m, 7H); 4.75 (s, 2H); 2.9 (q, 4H); 1.3 (t, 6H).

27 (11 g of crude product, 0.029 mol) was stirred at reflux for 20 hours in acetonitrile (100 ml) together with finely triturated potassium cyanide (2.87 g, 0.044 mol). After the addition of additional potassium cyanide (2.87 g, 0.044 mol), the reaction mixture was stirred at reflux for a further 24 hours, cooled, poured into water (300 ml) and extracted with ethyl acetate (2 x 100 ml). The combined organic phases were washed with brine, dried over Na2S04, and concentrated. 28 (10 g) was obtained in the form of a crude product. 'H-NMR
(300MHz, CDCI3): S = 7.6-7.3 (m, 7H); 3.7 (s, 2H); 2.8 (q, 4H); 1.4 (t, 6H).
28 (4.5 g, 0.018 mol) was stirred in acetic acid (25 ml) and HCI (379 aqueous solution) for 24 hours at reflux. The acetic acid was distilled off, the reaction mixture was diluted with water (100 ml) and extracted with methylene chloride (2 x 100 ml). The combined organic phases were dried over Na2S04 and concentrated. 29 (5 g) was obtained in the form of a crude product.'H-NMR (300 MHz, CDCI3): 8 = 7.6-7.3 (m, 7H); 3.8 (s, 2H); 2.7 (q, 4H); 1.25 (t, 6H).
JV

29 (8.1 g, 0.03 mol) was dissolved in toluene (75 ml), and SOCI2 (8.9 g, 0.075 mol) was added. The reaction mixture was heated to reflux temperature and, after the evolution of gas had ceased, concentrated. The resulting oil was taken up in toluene (50 ml), MeOH (20 ml) was added, and the mixture was stirred at room temperature for 0.5 hour and concentrated.
30 (9.1 g) was obtained in the form of a crude product. 'H-NMR (300 MHz, CDCI3): 8 = 7.6-7.3 (m, 7H), 3.8 (s, 2H); 3.7 (s, 3H); 2.7 (q, 4H); 1.25 (t, 6H).
O
O
30 (9.1 g, 0.032 mol) was dissolved in dimethyl carbonate (75 ml) and the solution was added to a suspension of sodium hydride (3.24 g of a 60°~ dispersion in mineral oil, 0.081 mol). The reaction mixture was stirred at reflux for 20 hours, cooled to room temperature, and 1 N HCI solution (100 ml) was added slowly. After the evolution of gas had ceased, the reaction mixture was extracted with ethyl acetate (2 x 100 mD, and the combined organic phases were washed with brine, dried over Na2S04 and concentrated.
31 (11.3 g) was obtained in the form of a crude product.'H-NMR (300 MHz, CDCI~: 8 = 7.6-7.2 (m, 7H); 5.1 (s, 1 H); 3.7 (s, 6H); 2.7 (q, 4H); 1.2 (t, 6H).
TMEDA (15.1 g, 0.13 mol) was dissolved in THF (500 ml) and cooled to -78°C, and s-BuLi (100 ml of a 1.3M solution in cyclohexane, 0.13 mol) was added dropwise. 13 (30 g, 0.12 mol) was dissolved in THF (100 ml), and the solution was added dropwise to the reaction mixture over the course of 0.5 hour. After a further 0.5 hour at -78°C, trimethyl borate was added to the reaction mixture. The reaction mixture was stirred at -78°C for 0.5 hour, heated to -40°C, and an aqueous NH4CI solution (250 ml) was added thereto. The organic phase was washed with brine, dried over Na2S04 and concentrated. 32 (36.7 g) was obtained in the form of a crude product.
B(OH)2 OH
O ~ ~ ~ O
N ~ ~ N

"""" 32 (35.2 g, 0.12 mol) was in MeOH (300 ml) and, with ice-cooling, H202 (16.1 g of a 30%
solution, 0.142 mop was added, the reaction temperature rising from 20°C to 40°C. After 2 hours, the reaction mixture was concentrated to 213, and seed crystals and water (500 ml) were added. The resulting crystals were filtered off and washed with water. 33 (30 g) was obtained. 'H-NMR (300 MHz, CDCI3): 8 = 7.65-7.2 (m, 7H); 7.05 (dd, 1 H); 3.05 (q, 4H); 1.3 (t, 6H).
3s 33 (3.7 g, 13.7 mmol) was placed in DMF, and NaH (0.55 g of a 60% dispersion, 13.7 mmol) was added. After the evolution of hydrogen had ceased, dimethyl sulfate (2.0 g, 16 mmol) was added to the reaction mixture, which was stirred at room temperature for 1 hour, poured into dilute HCI (300 mD and extracted with ethyl acetate (2 x 100 ml). The combined organic phases were washed with brine, dried over Na2S04, concentrated and chromatographed over silica gel (ethyl acetate:hexane, 1:1). 34 (3.4 g) was obtained. 'H-NMR
(300 MHz, CDCI3): b = 7.6-7.2 (m, 8H); 3.9 (s, 3H); 3.6 (bm, 2H); 3.2 (q, 2H); 1.3 (t, 3H); 1.1 (t, 3H).

34 -' TMEDA (1.49 g, 12.8 mmop was dissolved in THF (50 ml) and cooled to -78°C.
s-BuLi (9.8 ml of a 1.3M solution in cyclohexane, 12.8 mmol) was added to the reaction mixture, which was stirred at -78°C for 0.25 hour, a solution of 34 (3.3 g, 11.6 mmol) in THF
(15 ml) was added dropwise and the mixture was stirred at -78°C for 0.3 hour. Ethyl iodide (2.0 g, 13 mmop was added to the reaction mixture. The reaction mixture was heated to 0°C
and an aqueous NH4CI solution (50 ml) was added. The organic phase was washed with brine, dried over Na2S04 and concentrated. 35 (3.5 g) was obtained in the form of a crude product. 'H-NMR (300 MHz, CDCI3): b = 7.6-7.3 (m, 5H); 7.07 (s, 1 H); 6.9 (s, 1 H); 3.9 (s, 3H); 3.8 (m, 1 H); 3.45 (m, 1 H) 3.2 (m, 2H); 2.6 (m, 2H); 1.3 (m, 6H); 1.1 (t, 3H).
O
O
HN' ~N--NH "' O O

N,N'-Diacetylhydrazine 14 (768 g, 6.62 mol), 2,2'-dichlorodiethyl ether (1141 g, 7.9 mol) and potassium carbonate (1827 g, 13.3 mol) were placed in DMF (8.5 litres) at room temperature. The resulting suspension was heated at 130°C for 3.5 hours, cooled, filtered and concentrated. The residue was taken up in toluene (1000 ml) and stirred at 0°C for 16 hours. After filtration, the product 15 was obtained in the form of white crystals (574 g).
The mother liquor was concentrated by evaporation and recrystallised from a small amount of methanol. Again product 15 (108 g) was obtained in the form of white crystals.

O
~N~ HN \
N~ HN
O (HCI)~

15 (1000 g, 5.38 mop was dissolved in anhydrous methanol (5.4 litres) at 35°C, and acetyl chloride (1688 g, 21.5 mol) was added dropwise. After the addition was complete, the reaction mixture was stirred at 55°C for 16 hours. The reaction mixture was cooled and concentrated to about 1.4 litres, and stirred at from 0°C to 10°C. The crystals that formed in the process were filtered off and washed with ether (1.5 litres). The product 16 was obtained in the form of white crystals (520 g). 'H-NMR (300 MHz, D6-DMSO): 8 = 3.8 (s, 4H); 3.4 (s, 4H).
The compounds listed in the following Tables were obtained in analogous manner.
In the following Tables, "LCIMS: M*" denotes the molecular weight determined by coupled HPLC (High Performance Liquid Chromatography) and MS (Mass Spectrometry) analysis;
the numbers given after "UV" indicate the frequency, in nanometres, of the absorption maxima of the UV spectrum measured in waterlacetonitrile.

Table 1 Compounds of formula R, O

R, R2 R3 G Phys. data Comp.
No.

la-1 CH3 Ph CH3 H m.p. 260-261 C

la-2 CH3 Ph CH3 C(O)C(CH3) m.p. 159-161 la-3 CH3 Ph CH3 C(O)N- resin (CH2CH3) la-4 CH2CH3 Ph CH2CH3 H m.p. >250C

la-5 CH2CH3 Ph CH2CH3 C(O)C(CH3) m.p. 162-164C

la-6 CH2CH3 Ph OCH3 H m.p.205-207C

la-7 CH2CH3 Ph OCH3 C(O)C(CH3) m.p. 57-59C

;..-. la-8 CH2CH3 Ph SCH3 H m.p.200-201C

la-9 CH2CH3. Ph. - SCH3 C(O)C(CH3) m.p. 197-199C

la-10 CH2CH3 Ph S(O)2CH3C(O)C(CH3) m.p. 172-174C

la-11 CH2CH3 Ph CH2Ph H m.p.203-205C

la-12 CH3 4-CH2=CH-PhCH3 H (LCIMS:
M+ = 376) la-13 CH3 2-CI-Ph CH3 H (LCIMS:
M' = 384) la-14 CH3 4-CI-Ph CH3 H (LCIMS:
M~ = 384) la-15 CH3CH2 4-CI-Ph CH3CH2 H (LCIMS:
M~=412) la-16 CH3 3-Br-Ph CHa H

la-17 CH3 2-CH30-Ph CH3 H (LCIMS:

M+= 380) la-18 CH3 4-CH30-Ph CH3 H (LCIMS:

M+= 380) la-19 CH3 3-CH3CH20- CH3 H (LC/MS:

Ph M+= 394) la-20 CH3CH2 3-CH3CH20- CH3CH2 H (LCIMS:

Ph M+= 422) la-2i CH3 4-CH3S-Ph CH3 H (LCIMS:

M+= 396) la-22 CH3 2-CH3-Ph CH3 H (LCIMS:

M+ = 364) la-23 CH3 4-CH3-Ph CH3 H (LCIMS:

M+ = 364) la-24 CH3 \ CH3 H

, o la-25 CH3CH2 \ CH3CH2 H

. o la-26 CH3 CH3 H (LC/MS:
~

M' = 356) s la-27 CH2CH3 CH2CH3 H (LCIMS:

M' = 384) s la-28 CH2CH3 2,4-CI2-Ph CH2CH3 H (LCIMS:

M' = 446) la-29 CH2CH3 4-F-Ph CH2CH3 H (LCIMS:

M+= 396) la-30 CH2CH3 3-CI,4-F-PhCH2CH3 H (LCIMS:

M+ = 430) la-3. CH2CH3 3,5-CI2-Ph CH2CH3 H (LCIMS:

M+ = 446) la-32 CH2CH3 4-CF3-Ph CH2CH3 H (LCIMS:

M+= 446) la-33 CH2CH3 I ~ CH3 C(O)C(CH3) m.p. 139-141 ' o la-34 CH3 4-CH2=CH-PhCH3 C(O)N- (LCIMS:

(CH2CH3) M' = 475) la-35 CH3 2-CI-Ph CH3 C(O)N- (LCIMS:

(CH2CH~ 2 M+= 483) la-36 CH3 CH3 C(O)N- (LCIMS:

i (CH2CH3) M+= 499) la-37 CH3 4-CI-Ph CH3 C(O)N- (LCIMS:

(CH2CH3) M+= 483) la-38 CH3 2-CH30-Ph CH3 C(O)N- (LCIMS:

(CH2CH3) M' = 479) la-39 CH3 4-CH3S-Ph CH3 C(O)N- (LCIMS:

(CH2CH~ 2 M+= 495) la-40 CH3 4-CH30-Ph CH3 C(O)N- (LCIMS:

'"""' (CH2CH3) M+= 479) la-41 CH3 3-CH3CH20- CH3 C(O)N- (LCIMS:

Ph (CH2CH3) M+= 493) la-42 CH3 2-CH3-Ph CH3 C(O)N- (LC/MS:

(CH2CH3) M+= 463) la-43 CH3 4-CH3-Ph CH3 C(O)N- (LCIMS:

(CH2CH3) M+= 463) la-44 CH3 CH3 C(O)N- (LCIMS:

(CH2CH3) M* = 455) s 2 la-45 CH3 ~ CH3 C(O)N- (LCIMS:

.I (CH2CH~ 2 M+=455) . s la-46 CH3 CH3 H (LCIMS:
M+= 400) la-47 CH3 ~ CH3 H (LCIMS:
. M+ = 356) s la-48 CH3CH2 4-CI-Ph CH3CH2 C(O)N- (LCIMS:
(CH2CH3) 2 M' = 511 ) la-49 CH3CH2 3-CH3CH20- CH3CH2 C(O)N- (LCIMS:
Ph (CH2CH3) 2 M+= 521 ) la-50 CH2CH3 4-F-Ph CH2CH3 C(O)N- (LCIMS:
(CH2CH3) 2 M+= 495) la-51 CH3CH2 CH3CH2 C(O)N- (LC/MS:
(CH2CH3) 2 M+= 483) s la-52 CH3CH2 I ~ CH3CH2 C(O)N- (LCIMS:
(CH2CH3) 2 M+= 483) s la-53 CH2CH3 3-C1,4-F-Ph CH2CH3 C(O)N- (LCIMS:
(CH2CH3) 2 M+= 529) la-54 CH3CH2 3,5-CI2-Ph CH3CH2 C(O)N- (LCIMS:
(CH2CH3) 2 M+= 545) la-55 CH3CH2 2,4-CI2-Ph CH3CH2 C(O)N- (LCIMS:
(CH2CH3) 2 M+= 545) la-56 CH2CH3 I ~ CH2CH3 H (LCIMS:
. M'= 384) s la-57 CH3 --- ~ ~ CH3 C(O)N- solid (CH2CH3) 2 N
la-58 CH3 --- ~ ~ CH3 H solid N
la-59 CH3 --- ~ ~ CH3 C(O)C(CH~ 3 solid N

la-60 CH3 -__ /~ ~~ CH3 H solid ~N
la-61 CH3 -_- ~ ~ CH3 C(O)C(CH3) 3 m.p. 99-100°C
~~N
la-62 CH2CH3 --- ~ ~ CH2CH3 C(O)C(CH3) 3 wax N
la-63 CH3 --- ~ ~ CH3 H solid N
la-64 CH2CH3 --- /~ ~~ CH2CH3 C(O)C(CH3) 3 amorphous ~N
la-65 CH2CH3 _-- ~ ~ CH2CH3 C(O)C(CH3) 3 m.p. 146-147°C
N
la-66 CH2CH3 __- ~ ~ CH2CH3 H m.p. 250°C
N
la-67 CH3 --- ~ ~ CH3 H m.p. 250°C
N
v_ O
la-68 CH2CH3 _- ~ ~ CH2CH3 C(O)C(CH3) a N
O_ la-69 CH2CH3 so3H CH2CH3 H crystalline ___ ~ ~ CHs la-70 CH3 --- ~ ~ CH3 C(O)N-~/N (CH2CH3) 2 la-71 CH3 _-- ~ ~ CH3 C(O)N-(CH2CH3) 2 N

la-72 CH3 - ___ / \ CH3 C(O)N-(CH2CH3) 2 N
v O
la-73 CH2CH3 ___ ~ ~ CH2CH3 C(O)N-(CH2CH3) 2 N
la-74 CH2CH3 _-_ ~ ~ CH2CH3 H
N
la-75 CH3 __- ~ ~ CH3 C(O)C(CH3) a N
la-76 CH2CH3 ___ ~ ~ CH2CH3 H m.p.250°C
N_ O
la-77 CH2CH3 __- ~ ~ CH2CH3 C(O)C(CH3) 3 N-CI
la-78 CH3 CH3 H m.p.284-286°C
i ,... (CH2)2COOH
la-79 CH3 ; CH3 H m.p.230°C
w (decomp.) (CH2)2NH2 Ph = phenyl Table 2 Compounds of formula R~ O

R2 ~ ~ ~ N

Ib Comp. R, R2 R3 G Phys. data No.

Ib-1 CH3 Ph CH3 H m.p.239-240C

Ib-2 CH3 Ph CH3 C(O)C(CH3) resin Ib-3 CH3 Ph CH3 C(O)N-(CH2CH~ resin Ib-4 CH3 Ph CH3 C(O)O-CH2CH3 m.p.144-146C

Ib-5 CH3 Ph CH3 C(O)CH3 m.p.198-199C

Ib-6 CH3 Ph CH3 C(O)cyclopropylm.p.104-105 Ib-7 H Ph CH2CH3 H m.p.176-177C

Ib-8 H Ph CH2CH3 C(O)C(CH~ 3 m.p. 128-130C

Ib-9 CH2CH3 Ph CH2CH3 H m.p. >250C

~ Ib-10 CH2CH3 Ph CH2CH3 C(O)C(CH3) m.p. 166-168C

Ib-11 CH2CH3 Ph SCH3 H m.p.170-172C

Ib-12 CH2CH3 Ph SCH3 C(O)C(CH3) m.p. 182-183C

Ib-13 CH2CH3 Ph OCH3 H m.p.148-150C

Ib-14 CH2CH3 Ph OCH3 C(O)C(CH3) m.p. 127-129C

Ib-15 CH2CH3 Ph C-CSi(CH3)3H m.p.150-152C

Ib-16 CH2CH3 Ph C=CSi(CH3)3C(O)C(CH3) m.p. 69-71 1b-17 CHZCH3 Ph C-CSi(CH3)3C(O)N-(CH2CH3)m.p. 134-136C

Ib-18 CH2CH3 Ph C~H H m.p. 108-111 C

Ib-19 CH2CH3 Ph C~H C(O)C(CH3) m.p. 134-136C

Ib-20 CH2CH3 Ph Br H m.p.221-222C

Ib-21 CH2CH3 Ph Br C(O)C(CH3) m.p. 153-154C

Ib-22 CH2CH3 Ph Br C(O)N-(CH2CH3)2m.p.129-131C

Ib-23 CH2CH3 Ph CH2Ph H m.p.247-249C

Ib-24 CH2CH3 Ph CH2Ph C(O)C(CH3) resin Ib-25 CH3 3-CF3-Ph CH3 H m.p.225-226C

Ib-26 CH3 3-CF3-Ph CH3 C(O)C(CH3) m.p. 197-199C

Ib-27 CH3 3-CF3-Ph CH3 C(O)N-(CH2CH3)oil Ib-28 CH3 3-CF3-Ph CH3 C(O)O-CH2CH3 resin Ib-29 CH3 4-F-Ph CH3 H

Ib-30 CH3 4-F-Ph CH3 C(O)C(CH3) Ib-31 CH3 4-F-Ph CH3 C(O)N-(CH2CH3)oil Ib-32 CH3 4-CF3-Ph CH3 H m.p.294-296C

Ib-33 CH3 4-CF3-Ph CH3 C(O)C(CH3) m.p. 160-161 Ib-34 CH3 4-CF3-Ph CH3 C(O)N-(CH2CH3)m.p. 68-70C

Ib-35 CH3 4-CF3-Ph CH3 C(O)OCH2CH3 resin Ib-36 CH3 3-N02-Ph CH3 H m.p. 219-221 C

Ib-37 CH3 3-N02-Ph CH3 C(O)C(CH3) m.p. 180-182C

Ib-38 CH3 3-N02-Ph CH3 C(O)N-(CH2CH3) r..
1b-39 CH3 4-CH2=CH-PhCH3 H (LC/MS:
M* = 360) Ib-40 CH3 2-CI-Ph CH3 H (LC/MS:
M* = 368) Id-41 CH3 4-CI-Ph CH3 H (LCIMS:
M* = 368) Ib-42 CH2CH3 4-CI-Ph CH2CH3 H (LCIMS:
M* = 396) Ib-43 CH3 3-Br-Ph CH3 H (LCIMS:
M* = 412) Ib-44 CH3 2-CH30-Ph CH3 H (LCIMS:
M*= 364) Ib-45 CH3 4-CH30-Ph CH3 H (LCIMS:

M* = 364) Ib-46 CH3 3-CH3CH20-PhCH3 H (LCIMS:

M* = 378) Ib-47 CH3CH2 3-CH3CH20-PhCH3CH2 H (LCIMS:

M* = 406) Ib-48 CH3 4-CH3S-Ph CH3 H (LCIMS:

M* = 380) ,,.,, Ib-49 CH3 2-CH3-Ph CH3 H (LCIMS:

M+= 348) Ib-50 CH3 4-CH3-Ph CH3 H (LCIMS:

M* = 348) Ib-51 CH3 I ~ CH3 H

' o Ib-52 CH3CH2 I ~ CH3CH2 H

' o Ib-53 CH3 CH3 H (LCIMS:

M* = 340) s F,.. 1b-54 CH3CH2 \ CH3 H
s Ib-55 CH3 CH3 H (LCIMS:

M*= 384) Ib-56 CH2CH3 2,4-CI2-Ph CHZCH3 H (LC/MS:

M* = 430) Ib-57 CH2CH3 4-F-Ph CH2CH3 H (LCIMS:

M* = 380) Ib-58 CH2CH3 3-CI,4-F-Ph CH2CH3 H (LCIMS:

M*= 414) Ib-59 CH2CH3 3,5-CI2-Ph CH2CH3 H (LC/MS:

M* = 430) Ib-60 CH2CH3 4-CF3-Ph CH2CH3 H (LCIMS:

M+= 430) Ib-61 CH3 Ph CH3 o I ~ UV:

.' 212.1 nm 270.9 nm Ib-62 CH3 Ph CH3 UV:
OCH

209.7 nm 270.9 nm Ib-63 CH3 Ph CH3 UV:

,,.~OCH3 207.4 nm 270.9 nm Ib-64 CH3 Ph CH3 ~P" UV:

/'.~ 207.4 nm 270.9 nm Ib-65 CH3 Ph CH3 C(O)nC,H,S UV:

205.0 nm 270.9 nm Ib-66 CH3 Ph CH3 UV:

207.4 nm 268.5 nm ".~ Ib-67 CH3 Ph CH3 UV:

~ OCH3 205.0 nm "3 270.9 nm ib-68 CH3 Ph CH3 ,, o UV:

' 270.9 nm I ~

Ib-69 CH3 Ph CH3 '-Ib-70 CH3 2-CI-Ph CH3 C(O)N-(CH2CH~ (LCIMS:

M+= 467) Ib-71 CH3 CH3 C(O)N-(CH2CH3)(LCIMS:

w w M+= 483) Ib-72CH3 4-CI-Ph CH3 C(O)N-(CH2CH3)(LCIMS:

M*= 467) Ib-73CH3 2-CH30-Ph CH3 C(O)N-(CH2CH3)(LCIMS:

M* = 463) Ib-74CH3 4-CH3S-Ph CH3 C(O)N-(CH2CH3)(LCIMS:

M* = 479) Ib-75CH3 4-CH30-Ph CH3 C(O)N-(CH2CH~ {LCIMS:

M* = 463) Ib-76CH3 3-Br-Ph CH3 C(O)N-(CH2CH~ (LCIMS:

M*= 511) ib-77CH3 3-CH2CH30-PhCH3 C(O)N-(CH2CH3)(LC/MS:

M* = 477) Ib-78CH3 2-CH3-Ph CH3 C(O)N-(CH2CH3){LCIMS-M* = 447) ib-79CH3 4-CH3-Ph CH3 C(O)N-(CH2CH3)(LCIMS:

M* = 447) Ib-80CH3 \ CH3 C(O)N-(CH2CH3)(LC/MS:

s M* = 439) Ib-81CH3 ~ CH3 C(O)N-(CH2CH3)(LCIMS:

s M*= 439) Ib-82CH3 ~ CH3 H (LCIMS~

' I M* = 340) s Ib-83CH2CH3 4-CI-Ph CH2CH3 C(O)N-(CH2CH3)(LCIMS:

M* = 495) Ib-84CH2CH3 3-CH3CH20-PhCH2CH3 C(O)N-(CH2CH3)(LCIMS:

M* = 505) Ib-85CH2CH3 4-F-Ph CH2CH3 C(O)N-(CH2CH3)(LCIMS:

M*= 479) Ib-86CH2CH3 CH2CH3 C(O)N-(CH2CH3)(LCIMS:

s M*= 467) Ib-87 CH2CH3 I ~ CH2CH3 C(O)N-(CH2CH3) 2 (LCIMS:
. M' = 467) s Ib-88 CH2CH3 3-C1,4-F-Ph CH2CH3 C(O)N-(CH2CH3) 2 (LCIMS:
M+ = 513) Ib-89 CH2CH3 3,5-CI2-Ph CH2CH3 C(O)N-(CH2CH3) 2 (LCIMS:
M+ = 529) Ib-90 CH2CH3 2,4-CI2-Ph CH2CH3 C(O)N-(CH2CH3) 2 (LCIMS:
M+ = 529) Ib-91 CH2CH3 4-CF3-Ph CH2CH3 C(O)N-(CH2CH3) 2 Ib-92 CH2CH3 CH2CH3 H (LCIMS:
M+= 368) s 1b-93 CH2CH3 ' I ~ CH2CH3 H (LC/MS:
s M+= 368) Ib-94 CH3 CH3 H m.p.224-226°C
i (CH2)2COOH
Ph = phenyl -6~-Table 3 Compounds of formula Nina R, Nw Rs G
.... lc Comp. R, R2 R3 R4 RS G Phys. data No.

Ic-1 CH3 Ph CH3 CH3 CH3 C(O)N- resin (CH2CH3) Ic-2 CH2CH3 Ph OCH3 H (CH2)30H H m.p.91-93C

Ic-3 CH3 Ph CH3 CH3 CH3 H m.p.197C

Ph = phenyl Table 44 Compounds of formula Id Comp. R, R3 Phys.

No. data Id-1 CH3 CH3 m.p.

Id-2 CH2CH3 SCH3 oil Id-3 CH2CH3 OCH3 oil Id-4 CH2CH3 CH2CH3 oil Id-5 CH2CH3 CH2Ph oil Id-6 CH2CH3 Br oil Id-7 CH2CH3 C--__CSi(CH3)3oil Id-8 CH2CH3 H oil ,,.". Ph = phenyl R4o ...

R. I O
' N
~~ n R

-~ R4~
G
1e Comp. R, R2 R3 G R,~ R4, R~ R43 Phys. data No.

'"'~ 1e-1 CH3CH2 Ph CH30 H H H -(CH2)2- m.p.196-197C

1e-2 CH3CH2 Ph CH30 H CH3CH2 H H H m.p.133-135C

1e-3 CH3CH2 Ph CH30 H CH3 CH3 H H m.p.139-145C

1e-4 CH3CH2 Ph CH30 H CH3 CH3 H H m.p.119C

1e-5 CH3CH2 Ph CH30 C(O)- CH3CH2 H H H crystalline C(CH3)3 Ph = phenyl Compounds of formula /''' O
R
G
If Comp. No. R, R2 R3 G Phys. data If-1 CH3CH2 ~ Ph CH30 Fi m.p. 184-188C

Ph = phenyl 'fable 7 Compounds of formula R~ O
N F
R2 ~ ~ ~ N
F

G
Ig Comp. No. R, R2 R3 G Phys. data Ig-1 CH3CH2 Ph CH30 H m.p.147-149C

Ph = phenyl Table 8 Compounds of formula R~ O

R2 ~ ~ ~ N
R

,,.... G I h Comp R, R2 R3 R G Phys. data No.

Ih-1 -OCH3 Ph C2H5 OH C(O)C(CH3)3'H NMR (CDCI3, 300 MHz) 8 =
7.6 (d, 2H); 7.42 (t, 2H); 7.34 (t, 1 H);

7.1 (s, 1 H);
6.88 (s, 1 H); 4.2 -3.14 (m, 6H); 3.8 (2s, 3H);

2.67 (m, 2H);
2.05 (m, 2H); 1.2 (m, 3H); 1.1 (m, 9H) (Mixture of isomers) Ih-2 CH2CH3 Ph OCH3 H3C-O- C(O)C(CH3)3'H NMR (CDCI3, CH2CH2-O- 300 MHz) b =
7.6 (d, 2H); 7.42 (t, 2H); 7.34 (t, 1 H);

7.1 (s, 1 H);
6.88 (s, 1 H); 4.5 (m, 0.26H); 4.2 (m, . -64-0.17H); 4.0 - 3.3 (m, 8H); 3.8 (bs, 3H);, 3.4 (2s, 3H);

3.2 (m, 0.5H);
2.7 (m, 2H), 2.3 - 1.85 (m, 2H), 1.2 (m, 3H), 1.1 (m, 9H) (Mixture of isomers) Ih-3 CH2CH3 Ph CH2- H3C-O- C(O)C(CH3)s Ih-4 CH2CH3 Ph ethynylH3C-O- C(O)C(CH3)s Ih-5 CH2CH3 Ph CH2- H3C-CH2-O-C(O)C(CH~3 Ih-6 CH3 Ph CH3 H3C-O- C(O)C(CH~3 Ph = phenyl Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. At the 2-to 3-leaf stage of the test plants, an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97134485) of the test compound or an emulsion (prepared from an emulsifiable concentrate (Example F1, c) according to WO 97134485) of the test compound is applied by spraying at an optimum concentration (500 litres of waterlha). The test plants are then cultivated further in a greenhouse under optimum conditions.
After a test duration of from 2 to 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.

Compound Rate of applicationAvena Lolium SetariaSinapis (glha) Ib-1 2000 1 2 1 2 -. - _ I b-4 2000 1 3 1 2 I b-2 2000 3 3 1 2 la-33 2000 2 2 1 2 I b-66 2000 1 2 1 2 la-4 2000 1 1 1 2 la-5 2000 1 1 1 2 I b-9 2000 1 1 1 2 Ib-10 2000 1 1 1 2 la-1 2000 1 1 1 2 la-2 2000 1 1 1 2 la-6 2000 1 1 1 2 la-7 2000 1 1 1 2 Ib-13 2000 1 1 1 2 Ib-14 2000 1 1 1 2 I b-28 2000 1 2 1 2 la-8 2000 2 1 1 2 Ib-20 2000 2 2 1 2 I b-21 2000 1 1 1 2 I b-69 2000 2 2 1 2 Ib-18 2000 1 1 1 2 Ib-19 2000 1 1 1 ~ 2 1e-1 2000 1 1 1 2 If-1 2000 1 1 1 3 I I I I I I I

In that test, the compounds of formula 1 exhibit strong herbicidal action.
The same results are obtained when the compounds of formula I are formulated according to the other Examples of WO 97134485.
. -64-0.17H); 4.0 - 3.3 (m, 8H); 3.8 (bs, 3H);, 3.4 (2s, 3H);

3.2 (m, 0.5H)

Claims (10)

claims
1. A compound of formula I

wherein R1 and R3 are each independently of the other hydrogen, halogen, nitro, cyano, C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, tri(C1-C4alkylsilyl)-C2-C4alkynyl, C1-C4haloalkyl, C2-C6haloalkenyl, C3-C6cycloalkyl, halo-substituted C3-C6cycloalkyl, benzyl, C2-C6alkoxyalkyl, C2-C6alkylthio-alkyl, hydroxy, mercapto, C1-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C4alkyl-carbonyl, C1-C4alkoxycarbonyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, amino, C1-C4alkylamino, di(C1-C4alkyl)amino, C1-C4hydroxyalkyl, formyl, C1-C4alkylcarbonylamino or C1-C4alkylsulfonylamino, R2 is phenyl, naphthyl or a 5- or 6-membered aromatic ring that may contain 1 or 2 hetero atoms selected from the group nitrogen, oxygen and sulfur, it being possible for the phenyl ring, the naphthyl ring and the 5- or 6-membered aromatic ring to be substituted by halogen, C3-C8cycloalkyl, hydroxy, mercapto, amino, amino-C1-C6alkyl, carboxyl-C1-C6alkyl, cyano, nitro or by formyl; and/or for the phenyl ring, the naphthyl ring and the 5- or 6-membered aromatic ring to be substituted by C1-C6alkyl, C1-C6alkoxy, hydroxy-C1-C6alkyl, C1-C6alkoxy-C1-C6alkyl, C1-C6-alkoxy-C1-C6alkoxy, C1-C6alkylcarbonyl, C1-C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, mono-C1-C6alkylamino, di-C1-C6alkylamino, C1-C6alkylcarbonylamino, C1-C6alkylcarbonyl-(C1-C6alkyl)amino, C2-C6alkenyl, C3-C6alkenyloxy, hydroxy-C3-C6alkenyl, C1-C6alkoxy-C3-C6-alkenyl, C1-C6alkoxy-C3-C6alkenyloxy, C2-C6alkenylcarbonyl, C2-C6alkenylthio, C2-C6alkenyl-sulfinyl, C2-C6alkenylsulfonyl, mono- or di-C2-C6alkenylamino, C1-C6alkyl-(C3-C6alkenyl)-amino, C2-C6alkenylcarbonylamino, C2-C6alkenylcarbonyl-(C1-C6alkyl)amino, C2-C6alkynyl, C3-C6alkynyloxy, hydroxy-C3-C6alkynyl, C1-C6alkoxy-C3-C6alkynyl, C1-C6alkoxy-alkynyloxy, C2-C6alkynylcarbonyl, C2-C6alkynylthio, C2-C6alkynylsulfinyl, C2-C6alkynylsulfonyl, mono- or di-C3-C6alkynylamino, C1-C6alkyl-(C3-C6alkynyl)amino, C2-C6alkynylcarbonylamino or by C2-C6alkynylcarbonyl-(C1-C6alkyl)amino; and/or for the phenyl ring, the naphthyl ring and the 5- or 6-membered aromatic ring to be substituted by halo-substituted C1-C6alkyl, halo-substituted C1-C6alkoxy, halo-substituted hydroxy-C1-C6alkyl, halo-substituted C1-C6alkoxy-C1-C6alkyl, halo-substituted C1-C6alkoxy-C1-C6alkoxy, halo-substituted C1-C6alkylcarbonyl, halo-substituted C1-C6alkylthio, halo-substituted C1-C6alkylsulfinyl, halo-substituted C1-C6alkylsulfonyl, halo-substituted mono-C1-C6alkylamino, halo-substituted di-C1-C6alkylamino, halo-substituted C1-C6alkylcarbonyl-amino, halo-substituted C1-C6alkylcarbonyl-(C1-C6alkyl)amino, halo-substituted C2-C6alkenyl, halo-substituted C3-C6alkenyloxy, halo-substituted hydroxy-C3-C6alkenyl, halo-substituted C1-C6alkoxy-C2-C6alkenyl, halo-substituted C1-C6alkoxy-C3-C9alkenyloxy, halo-substituted C2-C6alkenylcarbonyl, halo-substituted C2-C6alkenylthio, halo-substituted C2-C6alkenyl-sulfinyl, halo-substituted C2-C6alkenylsulfonyl, halo-substituted mono- or di-C3-C6alkenyl-amino, halo-substituted C1-C6alkyl-(C3-C6alkenyl)amino, halo-substituted C2-C6alkenyl-carbonylamino, halo-substituted C2-C6alkenylcarbonyl-(C1-C6alkyl)amino, halo-substituted C2-C6alkynyl, halo-substituted C3-C6alkynyloxy, halo-substituted hydroxy-C3-C6-alkynyl, halo-substituted C1-C6alkoxy-C3-C6alkynyl, halo-substituted C1-C6alkoxy-C4-C6alkynyloxy, halo-substituted C2-C6alkynylcarbonyl, halo-substituted C2-C6alkynylthio, halo-substituted C2-C6alkynylsulfinyl, halo-substituted C2-C6alkynylsulfonyl, halo-substituted mono- or di-C3-C6alkynylamino, halo-substituted C1-C6alkyl-(C3-C6alkynyl)amino, halo-substituted C2-C6alkynylcarbonylamino or by halo-substituted C2-C6alkynylcarbonyl(C1-C6alkyl)amino;
and/or for the phenyl ring, the naphthyl ring and the 5- or 6-membered aromatic ring to be substituted by a radical of formula COOR50, CONR51, SO2NR53R54 or SO2OR55, wherein R50, R51, R52, R53. R54 and R55 are each independently of the others hydrogen, C1-C6alkyl, C2-C6-alkenyl or C3-C6alkynyl, or C1-C6alkyl, C2-C6alkenyl or C3-C6alkynyl each substituted by halogen, hydroxy, alkoxy, mercapto, amino, cyano, nitro, alkylthio, alkylsulfinyl or by alkylsulfonyl, R4 and R5 are each independently of the other hydrogen, C1-C12alkyl, C1-C12haloalkyl, C1-C12-hydroxyalkyl, C3-C8alkenyl, C3-C8alkynyl, C1-C10alkoxy-C1-C8alkyl, or C3-C8alkyl that may contain one or two oxygen atoms, C1-C10alkylthio-C1-C8alkyl, C3-C8cycloalkyl, C3-C8cyclo-alkyl that contains 1 or 2 hetero atoms selected from the group oxygen and sulfur, C3-C8halocycloalkyl, C3-C8halocycloalkyl that contains 1 or 2 hetero atoms selected from the group oxygen and sulfur, phenyl, or phenyl substituted by halogen, C1-C6alkyl, C1-C6halo-alkyl, C1-C6alkoxy, C1-C6haloalkoxy, nitro or by cyano, or R4 and R5 are each independently of the other a 5- or 6-membered ring that may contain hetero atoms selected from the group oxygen, sulfur and nitrogen, or R4 and R5, together with the atoms to which they are bonded, form a 5- to 8-membered ring, which may contain 1 or 2 oxygen atoms, sulfur atoms or NR6 groups, wherein R6 is hydrogen, C1-C4alkyl, C1-C6alkylcarbonyl, C1-C6alkylsulfonyl, C3-C6alkenyl or C3-C6-alkynyl, and which may be substituted by halogen, hydroxy, C1-C10alkyl, C1-C10alkoxy, C1-C10haloalkyl, C3-C8cycloalkyl, phenyl or by benzyl; or which may be substituted by phenyl substituted by halogen, C1-C6alkyl, C1-C6haloalkyl, C3-C6cycloalkyl, hydroxy, C1-C6alkoxy, C1-C6alkoxy-C1-C6alkoxy, C1-C6haloalkoxy or by nitro, or by benzyl substituted by halogen, C1-C6alkyl, C1-C6haloalkyl, C3-C6cycloalkyl, hydroxy, C1-C6alkoxy, C1-C6haloalkoxy or by nitro; or which may be substituted by CH2-heteroaryl, wherein the aryl moiety has 5 or 6 members, or by halo-, C1-C6alkyl-, C1-C6haloalkyl-, C1-C6cycloalkyl-, hydroxy-, C1-C6alkoxy-, C1-C6halo-alkoxy- or nitro-substituted CH2-heteroaryl, wherein the aryl moiety has 5 or 6 members; or which may be substituted by heteroaryl, wherein the aryl moiety has 5 or 6 members, or by halo-, C1-C6alkyl-, C1-C6haloalkyl-, hydroxy-, C1-C6alkoxy-, C1-C6haloalkoxy-, cycloalkyl- or nitro-substituted heteroaryl, wherein the aryl moiety has 5 or 6 members; and which may contain a fused or spiro-bound alkylene or alkenylene chain containing from 2 to 6 carbon atoms, which chain may be interrupted by oxygen or sulfur atoms, G is hydrogen, -C(X1)-R30, -C(X2)-X3-R31, -C(X4)-N(R32)-R33, -SO2-R34, an alkali metal cation, alkaline earth metal cation, sulfonium cation or ammonium cation, -P(X5)(R35)-R36 or -CH2X6C(X7)-R37, -CH2X8C(X9)-X10-R38, -CH2X11C(X12)-N(R39)-R40 or -CH2X13SO2-R41, wherein X1, X2, X3, X4, X5, X6, X7, X8 X9, X10, X11, X12 and X13 are each independently of the others oxygen or sulfur, and R30, R31, R32, R33, R34, R35, R36, R37, R38, R39, R40 and R41 are each independently of the others hydrogen, C1-C12alkyl or C1-C12alkyl substituted by halogen, formyl, cyano, nitro, tri-C1-C6alkylsilyl, hydroxy, C1-C6alkoxy, C1-C6alkoxycarbonyl, amino, C1-C6alkylamino, di-C1-C6alkylamino, mercapto, C1-C6alkylthio, C1-C6alkylcarbonyl, C1-C6-alkylcarbonylthio, C1-C6alkylcarbonylamino, C1-C6alkoxycarbonylamino, C1-C6alkyl-aminocarbonylamino, C1-C6alkylthiocarbonyloxy, C1-C6alkylthiocarbonylamino, C1-alkoxythiocarbonyl, aminothiocarbonyl, C1-C6alkylthiocarbonyloxy, C1-C6alkylthiocarbonyl-amino, C1-C6alkoxythiocarbonylamino, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6alkyl-sulfonyloxy, C1-C6alkylsulfonylamino, C1-C6alkoxyimino, hydroxyimino, heteroaryl, benzyloxy, phenoxy or by halophenoxy; or C2-C12alkenyl, C2-C12alkenyl, C3-C12cycloalkyl, C3-C8cycloalkyl substituted by halogen, C1-C6-haloalkyl, C1-C6alkyl, C1-C6alkoxy, C1-C6alkylcarbonyloxy, C1-C6thioalkyl, C1-C6alkylcarbonyl-thio, C1-C6alkylamino, C1-C6alkylcarbonylamino, tri-C1-C6alkylsilyl or by tri-C1-C6alkylsilyloxy;
phenyl or phenyl substituted by alkoxy, halogen, C1-C6haloalkyl, nitro, cyano, C1-C6alkyl, C1-C6alkylcarbonyloxy, C1-C6thioalkyl, C1-C6alkylcarbonylthio, C1-C6alkylamino, C1-C6alkyl-carbonylamino, tri-C1-C6alkylsilyl or by tri-C1-C6alkylsilyloxy; heteroaryl or heteroaryl substituted by halogen, C1-C6haloalkyl, nitro, cyano, C1-C6alkyl, C1-C6alkoxy, C1-C6alkyl-carbonyloxy, C1-C6thioalkyl, C1-C6alkylcarbonylthio, C1-C6alkylamino, C1-C6alkylcarbonyl-amino, tri-C1-C6alkylsilyl or by tri-C1-C6alkylsilyloxy; and R34 is additionally C2-C20alkenyl or C2-C20alkenyl substituted by halogen, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, C1-6alkylcarbonyloxy, C1-C6alkoxy, C1-C6thioalkyl, C1-C6alkylthio-carbonyl, C1-C6alkylcarbonylthio, C1-C6alkylsulfonyl, C1-C6alkylsulfinyl, C1-C6alkylamino-sulfonyl, di-C1-C6alkylaminosulfonyl, C1-C6alkylsulfonyloxy, C1-C6alkylsulfonylamino, C1-C6-alkylamino, di-C1-C6alkylamino, C1-C6alkylcarbonylamino, di-C1-C6alkylcarbonylamino, cyano, C3-C8cycloalkyl, C3-C8heterocyclyl, tri-C1-C6alkylsilyl, tri-C1-C6alkylsilyloxy, phenyl, substituted phenyl, heteroaryl or by substituted heteroaryl; or C2-C20alkynyl or C2-C20alkynyl substituted by halogen, C1-C6alkylcarbonyl, C1-C6alkoxy-carbonyl, C1-C6alkylcarbonyloxy, C1-C6alkoxy, C1-C6thioalkyl, C1-C6alkylthiocarbonyl, C1-C6-alkylcarbonylthio, C1-C6alkylsulfonyl, C1-C6alkylsulfinyl, C1-C6alkylaminosulfonyl, di-C1-C6-alkylaminosulfonyl, C1-C6alkylsulfonyloxy, C1-C6alkylsulfonylamino, C1-C6alkylamino, di-C1-C6alkylamino, C1-C6alkylcarbonylamino, di-C1-C6alkylcarbonylamino, cyano, C3-C7;
cycloalkyl, C3-C7heterocyclyl, tri-C1-C6alkylsilyl, tri-C1-C6alkylsilyloxy, phenyl, substituted phenyl, heteroaryl or by substituted heteroaryl; or C3-C8cycloalkyl or C3-C8cycloalkyl substituted by halogen, C1-C6haloalkyl, C1-C6alkyl, C1-C6-alkoxy, C1-C6alkylcarbonyloxy, C1-C6thioalkyl, C1-C6alkylcarbonylthio, C1-C6alkylamino, C1-C6alkylcarbonylamino, tri-C1-C6alkylsilyl or by tri-C1-C6alkylsilyloxy; or heteroaryl or heteroaryl substituted by halogen, C1-C6haloalkyl, nitro, cyano, C1-C6alkyl, C1-C6alkoxy, C1-C6alkylcarbonyloxy, C1-C6thioalkyl, C1-C6alkylcarbonylthio, C1-C6alkylamino, C1-C6alkylcarbonylamino, tri-C1-C6alkylsilyl or by tri-C1-C6alkylsilyloxy; or heteroaryloxy, substituted heteroaryloxy, heteroarylthio, substituted heteroarylthio, heteroarylamino, substituted heteroarylamino, diheteroarylamino, substituted diheteroarylamino, phenylamino, substituted phenylamino, diphenylamino, substituted diphenylamino, cycloalkylamino, substituted cycloalkylamino, dicycloalkylamino, substituted dicycloalkylamino, cycloalkoxy or substituted cycloalkoxy, or a salt or diastereoisomer of a compound of formula I.
2. A process for the preparation of a compound of formula I according to claim 1, wherein a) a compound of formula II is reacted with an aromatic zinc or tin compound, an aromatic boric acid, an aromatic boric acid ester or an aromatic Grignard compound, or b) a compound of formula IV or V is reacted with a hydrazine of formula III.
3. A herbicidal and plant-growth-inhibiting composition that comprises a herbicidally effective content of a compound of formula I on an inert carrier.
4. A method of controlling undesired plant growth, wherein a herbicidally effective amount of an active ingredient of formula I or of a composition comprising such an active ingredient is applied to the plants or to the locus thereof.
5. A method of inhibiting plant growth, wherein a herbicidally effective amount of an active ingredient of formula I or of a composition comprising such an active ingredient is applied to the plants or to the locus thereof.
6. A composition according to claim 3 that comprises a further herbicide.
7. A composition according to claim 3 that comprises a safener.
8. A compound of formula XIX

wherein R0 is OR7, OR8, NR7R9, NR8R10 or cyano and R00 is hydrogen, OR7, OR8, NR7R9, NR8R10 or cyano, and R1, R2 and R3 and R7 to R10 are as defined in claim 1, but R1 and R3 are not simultaneously hydrogen.
9. A compound of formula VIII

wherein R1, R2 and R3 are as defined in claim 1, and Hal is chlorine, bromine or iodine, Hal being other than iodine when R1 and R3 are methyl and R2 is phenyl.
10. A process for the preparation of a hydrazine of formula 16 wherein n is 2 or 3, m is 2 or 3 and X is a chemical bond, oxygen or sulfur, in which process a compound of formula 15 wherein R000 is C1-C4alkyl and n, m and X are as defined, is reacted in an anhydrous alcohol with an acyl halide or with a hydrohalic acid.
CA002382432A 1999-09-07 2000-09-05 Novel herbicides Abandoned CA2382432A1 (en)

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AU2004265089B2 (en) * 2003-08-14 2011-07-28 Bayer Cropscience Aktiengesellschaft 4-biphenylsubstituted pyrazolidin-3,5-dione derivatives
US7947704B2 (en) 2004-03-25 2011-05-24 Bayer Cropscience Ag 2,4,6-phenyl-substituted cyclic ketoenols
US8202875B2 (en) 2004-07-20 2012-06-19 Bayer Cropscience Ag Selective insecticides based on substituted cyclic ketoenols and safeners
US8629084B2 (en) 2004-09-16 2014-01-14 Bayer Cropscience Ag Iodine-phenyl-substituted cyclic cetoenols
US8247351B2 (en) 2005-12-13 2012-08-21 Bayer Cropscience Ag Insecticidal compositions having improved effect
US8013172B2 (en) 2006-02-21 2011-09-06 Bayer Cropscience Ag Cycloalkylphenyl substituted cyclic ketoenols
US8541617B2 (en) 2006-02-21 2013-09-24 Bayer Cropscience Ag Cycloalkylphenyl substituted cyclic ketoenols
US8680012B2 (en) 2006-12-14 2014-03-25 Syngenta Crop Protection Llc 4-phenyl-pyrane-3,5-diones,4-phenyl-thiopyrane-3,6-diones and cyclohexanetriones as novel herbicides
US9006429B2 (en) 2006-12-14 2015-04-14 Syngenta Crop Protection, Llc Herbicidal pyrandione, thiopyrandione, and cyclohexanetrione derivatives
US8828908B2 (en) 2007-05-29 2014-09-09 Syngenta Limited Herbicidally active bicyclic 1,3-dione compounds
US8956999B2 (en) 2007-06-28 2015-02-17 Syngenta Limited Herbicides
US8754242B2 (en) 2007-08-08 2014-06-17 Syngenta Crop Protection Llc Herbicides
US8940913B2 (en) 2007-08-09 2015-01-27 Syngenta Crop Protection, Llc Herbicides
US8895761B2 (en) 2007-12-13 2014-11-25 Syngenta Limited 4-phenylpyrane-3,5-diones, 4-phenylthiopyrane-3,5-diones and 2-phenylcyclohexane-1,3,5-triones as herbicides
US9096560B2 (en) 2008-07-03 2015-08-04 Syngenta Limited 5-heterocyclylalkyl-3-hydroxy-2-phenylcyclopent-2-enones as herbicides
US8865623B2 (en) 2009-01-15 2014-10-21 Syngenta Limited Herbicidally active cyclic diones and derivatives thereof, processes for their preparation, compositions, and method of controlling weeds
US8895474B2 (en) 2009-01-22 2014-11-25 Syngenta Limited Herbicidally active cyclopentanediones and derivatives thereof, and their use in controlling weeds
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US9102642B2 (en) 2009-02-04 2015-08-11 Syngenta Limited Herbicidally active cyclic diones and derivatives thereof, processes for their preparation, compositions, and methods of controlling weeds
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US9045390B2 (en) 2009-03-11 2015-06-02 Bayer Cropscience Ag Haloalkylmethyleneoxyphenyl-substituted ketoenols

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WO2001017973A2 (en) 2001-03-15
HUP0202844A2 (en) 2002-12-28
CN1377358A (en) 2002-10-30
WO2001017973A3 (en) 2001-05-10
AU7514600A (en) 2001-04-10
PL356456A1 (en) 2004-06-28
EP1230245A2 (en) 2002-08-14

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