AU7514600A - Novel herbicides - Google Patents

Novel herbicides Download PDF

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Publication number
AU7514600A
AU7514600A AU75146/00A AU7514600A AU7514600A AU 7514600 A AU7514600 A AU 7514600A AU 75146/00 A AU75146/00 A AU 75146/00A AU 7514600 A AU7514600 A AU 7514600A AU 7514600 A AU7514600 A AU 7514600A
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Australia
Prior art keywords
substituted
alkyl
halo
alkoxy
formula
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AU75146/00A
Inventor
Thomas Maetzke
Andre Stoller
Sebastian Wendeborn
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Syngenta Participations AG
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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)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Description

-1 Novel herbicides 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, especially in crops of useful plants, or in inhibiting plant growth. Pyrazolinone derivatives having herbicidal action are described, for example, in W092/16510 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 R, 0 N R4
R
2
R
5
R
3 0, G * I, wherein
R
1 and R 3 are each independently of the other hydrogen, halogen, nitro, cyano, C-C 4 alkyl,
C
2
-C
4 alkenyl, C 2
-C
4 alkynyl, tri(C-C 4 alkylsilyl)-C 2
-C
4 alkynyl, C-C 4 haloalkyl, C 2
-C
6 haloalkenyl,
C
3
-C
6 cycloalkyl, halo-substituted C 3
-C
6 cycloalkyl, benzyl, C 2
-C
6 alkoxyalkyl, C 2
-C
6 alkylthio alkyl, hydroxy, mercapto, C-C 6 alkoxy, C 3
-C
6 alkenyloxy, C 3
-C
6 alkynyloxy, C-C 4 alkyl carbonyl, C-C 4 alkoxycarbonyl, C-C 4 alkylthio, C-C 4 alkylsulfinyl, C-C 4 alkylsulfonyl, amino,
C-C
4 alkylamino, di(C-C 4 alkyl)amino, C-C 4 hydroxyalkyl, formyl, C-C 4 alkylcarbonylamino or
C-C
4 alkylsulfonylamino,
R
2 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, -2
C
3
-C
8 cycloalkyl, hydroxy, mercapto, amino, amino-C-C 6 alkyl, carboxyl-C-C 6 alkyl, 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 C 1
C
6 alkyl, C 1
C
6 alkoxy, hydroxy-C-C 6 alkyl, C-C 6 alkoxy-C-C 6 alkyl, C-C 6 alkoxy-C-C 6 alkoxy, C-C 6 alkylcarbonyl, C-C 6 alkylthio, C-C 6 alkylsulfinyl, C-C 6 alkylsulfonyl, mono-C-C 6 alkylamino, di-C-C 6 alkylamino, C-C 6 alkylcarbonylamino, C-C 6 alkylcarbonyl
(C-C
6 alkyl)amino, C 2
-C
6 alkenyl, C 3
-C
6 alkenyloxy, hydroxy-C 3
-C
6 alkenyl, C-C 6 alkoxy-C 3
-C
6 alkenyl, C-C 6 alkoxy-C 3 -Cealkenyloxy, C 2
-C
6 alkenylcarbonyl, C 2
-C
6 alkenylthio, C 2
-C
6 alkenyl sulfinyl, C 2
-C
6 alkenylsulfonyl, mono- or di-C 2
-C
6 alkenylamino, C-C 6 alkyl-(C 3
-C
6 alkenyl) amino, C 2
-C
6 alkenylcarbonylamino, C 2
-C
6 alkenylcarbonyl-(C-C 6 alkyl)amino, C 2
-C
6 alkynyl,
C
3
C
6 alkynyloxy, hydroxy-C 3 rC 6 alkynyl, C-C 6 alkoxy-C 3
-C
6 alkynyl, C-C 6 alkoxy-C 4
-C
6 alkynyloxy, C 2
-C
6 alkynylcarbonyl, C 2 -Calkynylthio, C 2
-C
6 alkynylsulfinyl, C 2
-C
6 alkynylsulfonyl, mono- or di-C 3
-C
6 alkynylamino, C-C 6 alkyl-(C 3
-C
6 alkynyl)amino, C 2
-C
6 alkynylcarbonylamino or by C 2
-C
6 alkynylcarbonyl-(C-C 6 alkyl)amino; and/or for the phenyl ring, the naphthyl ring and the 5- or 6-membered aromatic ring to be substituted by halo-substituted C-C 6 alkyl, halo-substituted C-C 6 alkoxy, halo-substituted hydroxy-C-C 6 alkyl, halo-substituted C-C 6 alkoxy-C-C 6 alkyl, halo-substituted C-Cealkoxy Cr-C 6 alkoxy, halo-substituted C-C 6 alkylcarbonyl, halo-substituted C-C 6 alkylthio, halo substituted C-C 6 alkylsulfinyl, halo-substituted C-Calkylsulfonyl, halo-substituted mono
C
1
-C
6 alkylamino, halo-substituted di-C-C 6 alkylamino, halo-substituted C-C 6 alkylcarbonyl amino, halo-substituted C-C 6 alkylcarbonyl-(C-C 6 alkyl)amino, halo-substituted C 2
-C
6 alkenyl, halo-substituted C 3
-C
6 alkenyloxy, halo-substituted hydroxy-C 3
C
6 alkenyl, halo-substituted
C
1 rC 6 alkoxy-C 2
C
6 alkenyl, halo-substituted C-C 6 alkoxy-C 3
-C
6 alkenyloxy, halo-substituted
C
2
-C
6 alkenylcarbonyl, halo-substituted C 2
-C
6 alkenylthio, halo-substituted C 2
-C
6 alkenylsulfinyl, halo-substituted C 2
-C
6 alkenylsulfonyl, halo-substituted mono- or di-C 3
-C
6 alkenylamino, halo substituted C-C 6 alkyl-(C 3
-C
6 alkenyl)amino, halo-substituted C 2
-C
6 alkenylcarbonylamino, halo-substituted C 2
-C
6 alkenylcarbonyl-(C-C 6 alkyl)amino, halo-substituted C 2
-C
6 alkynyl, halo substituted C 3
-C
6 alkynyloxy, halo-substituted hydroxy-C 3
-C
6 alkynyl, halo-substituted C-C 6 alkoxy-C 3
-C
6 alkynyl, halo-substituted C-Cealkoxy-C 4
-C
6 alkynyloxy, halo-substituted C 2
-C
6 alkynylcarbonyl, halo-substituted C 2
-C
6 alkynylthio, halo-substituted C 2
-C
6 alkynylsulfinyl, halo substituted C 2
-C
6 alkynylsulfonyl, halo-substituted mono- or di-C 3
-C
6 alkynylamino, halo substituted C-C 6 alkyl-(C 3
-C
6 alkynyl)amino, halo-substituted C 2
-C
6 alkynylcarbonylamino or by halo-substituted C 2
-C
6 alkynylcarbonyl-(C-C 6 alkyl)amino; and/or -3 for the phenyl ring, the naphthyl ring and the 5- or 6-membered aromatic ring to be substituted by a radical of formula COOR5o, CONR 51 , SO 2
NR
53 R54or S0 2 0R 5 ., wherein R 50 ,
R
51 , R 52 , R 53 , R54and R5sare each independently of the others hydrogen, C-C 6 alkyl, C 2
C
6 alkenyl or C 3
C
6 alkynyl, or C-C 6 alkyl, C 2
C
6 alkenyl or C 3
-C
6 alkynyl each substituted by halogen, hydroxy, alkoxy, mercapto, amino, cyano, nitro, alkylthio, alkylsulfinyl or by alkylsulfonyl,
R
4 and R, are each independently of the other hydrogen, C-Cl 2 alkyl, C-Cl 2 haloalkyl, C 1 C1 2 hydroxyakyl, C 3
C
8 alkenyl, C 3
C
8 alkynyl, C-C 1 oalkoxy-C-C 8 alkyl, or C 3
-C
8 alkyl that may contain one or two oxygen atoms, C-C 1 oalkylthio-C-C 8 alkyl, C 3
-C
8 cycloalkyl, C 3
-C
8 cyclo alkyl that contains 1 or 2 hetero atoms selected from the group oxygen and sulfur, C 3
C
8 halocycloalkyl, C 3
-C
8 halocycloalkyl that contains 1 or 2 hetero atoms selected from the group oxygen and sulfur, phenyl, or phenyl substituted by halogen, C-C 6 alkyl, C-C 6 haloalkyl, Cr-C 6 alkoxy, C-C 6 haloalkoxy, nitro or by cyano, or R 4 and R 5 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
R
4 and R,, 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 NR 6 groups, wherein
R
6 is hydrogen, C-C 4 alkyl, C-C 6 alkylcarbonyl, C-C 6 alkylsulfonyl, C 3
C
6 alkenyl or C 3
C
6 alkynyl, and which may be substituted by halogen, hydroxy, C-C 1 oalkyl, C-C 1 oalkoxy,
C-C
1 ohaloalkyl, C 3
C
8 cycloalkyl, phenyl or by benzyl; or which may be substituted by phenyl substituted by halogen, Cr-C 6 alkyl, 0 1
-C
6 haloalkyl, 0 3
-C
6 cycloalkyl, hydroxy, Cr-C 6 alkoxy, C-C 6 alkoxy-Cr-C 6 alkoxy, Cr-C 6 haloalkoxy or by nitro, or by benzyl substituted by halogen, C-Cealkyl, C-C 6 haloalkyl, C 3
-C
6 cycloalkyl, hydroxy,
C
1
C
6 alkoxy, 0 1
-C
6 haloalkoxy or by nitro; or which may be substituted by CH 2 -heteroaryl, wherein the aryl moiety has 5 or 6 members, or by halo-, C-C 6 alkyl-, C-C 6 haloalkyl-, C-C 6 cycloalkyl-, hydroxy-, C-C 6 alkoxy-, C 1 rC 6 halo alkoxy- or nitro-substituted CH 2 -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-C 6 alkyl-, C-C 6 haloalkyl-, hydroxy-, C-C 6 alkoxy-, C-C 6 haloalkoxy-, cycloalkyl- or nitro-substituted heteroaryl, wherein the aryl moiety has 5 or 6 members; and -4 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 1
)-R
30 , -C(X 2
)-X
3
-R
3 1 , -C(X 4
)-N(R
32
)-R
33 , -SO 2
-R
3 4 , an alkali metal cation, alkaline earth metal cation, sulfonium cation or ammonium cation, -P(X 5
)(R
35
)-R
36 or
-CH
2
X
6
C(X
7
)-R
37 , -CH 2
X
8
C(X
9
)-X
10 -R38, -CH 2
X
11
C(X
1 2
)-N(R
39 )-R4o or -CH 2
X
1 3
SO
2
-R
41 , wherein
X
1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8
X
9 , X 10 , X 11 , X 1 2 and X 1 3 are each independently of the others oxygen or sulfur, and R 3 0 , R 31 , R 32 , R 33 , R 34 , R 3 5 , R 36 , R 37 , R 38 , R 39 , R40 and R 41 are each independently of the others hydrogen, C-C 2 alkyl or C-C 2 alkyl substituted by halogen, formyl, cyano, nitro, tri-C-C 6 alkylsilyl, hydroxy, C-C 6 alkoxy, C-C 6 alkoxycarbonyl, amino,
C
1
-C
6 alkylamino, di-C-C 6 alkylamino, mercapto, C-C 6 alkylthio, C-C 6 alkylcarbonyl, C-C 6 alkylcarbonylthio, C-C 6 alkylcarbonylamino, C-C 6 alkoxycarbonylamino, C-C 6 alkylamino carbonylamino, C-C 6 alkylthiocarbonyloxy, C-C 6 alkylthiocarbonylamino, C-C 6 alkoxythio carbonyl, aminothiocarbonyl,
C-C
6 alkylthiocarbonyloxy,
C-C
6 alkylthiocarbonylamino, CrC6 alkoxythiocarbonylamino,
C-C
6 alkylsulfinyl, C-C 6 alkylsulfonyl, C-C 6 alkylsulfonyloxy, C-C 6 alkylsulfonylamino, C-C 6 alkoxyimino, hydroxyimino, heteroaryl, benzyloxy, phenoxy or by halophenoxy; or
C
2 -Cl 2 alkenyl, C 3 -Cl 2 cycloalkyl, C 3
-C
8 cycloalkyl substituted by halogen, C-C 6 haloalkyl,
C
1
-C
6 alkyl, C-C 6 alkoxy, C-C 6 alkylcarbonyloxy, C-C 6 thioalkyl, C-C 6 alkylcarbonylthio,
C
1
-C
6 alkylamino, C-C 6 alkylcarbonylamino, tri-C-C 6 alkylsilyl or by tri-C-C 6 alkylsilyloxy; phenyl or phenyl substituted by alkoxy, halogen, C-C 6 haloalkyl, nitro, cyano, C-C 6 alkyl,
C,-C
6 alkylcarbonyloxy, C-C 6 thioalkyl, C-C 6 alkylcarbonylthio, C-C 6 alkylamino, C-C 6 alkyl carbonylamino, tri-C-C 6 alkylsilyl or by tri-C-C 6 alkylsilyloxy; heteroaryl or heteroaryl substituted by halogen, C-C 6 haloalkyl, nitro, cyano, C-C 6 alkyl, C-C 6 alkoxy, C-C 6 alkyl carbonyloxy, C-C 6 thioalkyl, C-C 6 alkylcarbonylthio, C-C 6 alkylamino, C-C 6 alkylcarbonyl amino, tri-C-C 6 alkylsilyl or by tri-C-C 6 alkylsilyloxy; and
R
34 is additionally C 2 -C2alkenyl or C 2 -C2alkenyl substituted by halogen, C-C 6 alkylcarbonyl,
C,-C
6 alkoxycarbonyl, C-C 6 alkylcarbonyloxy, C-C 6 alkoxy, C-C 6 thioalkyl, C-C 6 alkylthio carbonyl, C-C 6 alkylcarbonylthio, C-C 6 alkylsulfonyl, C-C 6 alkylsulfinyl, C-C 6 alkylamino sulfonyl, di-C-C 6 alkylaminosulfonyl,
C-C
6 alkylsulfonyloxy, C-C 6 alkylsulfonylamino, CrC6 alkylamino, di-C-C 6 alkylamino, C-C 6 alkylcarbonylamino, di-C-C 6 alkylcarbonylamino, cyano,
C
3
-C
8 cycloalkyl, C 3
-C
8 heterocyclyl, tri-C-C 6 alkylsilyl, tri-C-C 6 alkylsilyloxy, phenyl, substituted phenyl, heteroaryl or by substituted heteroaryl; or -5
C
2
C
2 0 alkynyl or C 2
-C
20 alkynyl substituted by halogen, C-C 6 alkylcarbonyl, C 1
C
6 alkoxy carbonyl, C-C 6 alkylcarbonyloxy, C 1 rC 6 alkoxy, C-C 6 thioalkyl, C-C 6 alkylthiocarbonyl,
C
1
-C
6 alkylcarbonylthio, C-C 6 alkylsulfonyl, C-C 6 alkylsulfinyl, C-C 6 alkylaminosulfonyl, di-C-C 6 alkylaminosulfonyl, C-C 6 alkylsulfonyloxy, C-C 6 alkylsulfonylamino, C-C 6 alkylamino, di-C-C 6 alkylamino, C-C 6 alkylcarbonylamino, di-C-C 6 alkylcarbonylamino, cyano, C 3
-C
7 cycloalkyl, C 3
-C
7 heterocyclyl, tri-C-C 6 alkylsilyl, tri-C-C 6 alkylsilyloxy, phenyl, substituted phenyl, heteroaryl or by substituted heteroaryl; or
C
3 -Cscycloalkyl or C 3
-C
8 cycloalkyl substituted by halogen, C-C 6 haloalkyl, C 1
C
6 alkyl, Cr-C 6 alkoxy, C-C 6 alkylcarbonyloxy, C-C 6 thioalkyl, C-C 6 alkylcarbonylthio, C-C 6 alkylamino, Cl-C 6 alkylcarbonylamino, tri-C-C 6 alkylsilyl or by tri-C-C 6 alkylsilyloxy; or heteroaryl or heteroaryl substituted by halogen, C-C 6 haloalkyl, nitro, cyano, C,-C 6 alkyl,
C
1 rC 6 alkoxy, C-C 6 alkylcarbonyloxy, C-C 6 thioalkyl, C-C 6 alkylcarbonylthio, C-C 6 alkylamino,
C.-C
6 alkylcarbonylamino, tri-C-C 6 alkylsilyl or by tri-C-C 6 alkylsilyloxy; 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, and to salts and diastereoisomers of the compounds of formula 1. 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.
-6 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 98/41089. 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-Clalkylamines, C-C 4 hydroxy alkylamines and C 2
-C
4 alkoxyalkylamines, for example methylamine, ethylamine, n propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, 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, propylenediamine, 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(Ra RbRRd )]OH, wherein Ra, Rb, Rc and Rd are each independently of the -7 others C-C 4 alkyl. 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 1 and R 3 are each independently of the other C-C 4 alkyl, especially methyl or ethyl, C 2
-C
4 alkynyl, especially ethynyl, C-C 6 alkoxy, especially methoxy, C-C 4 alkylthio, especially methylthio, C-C 4 haloalkyl, especially chloro methyl and chloroethyl, formyl, C-C 4 alkylcarbonyl, especially acetyl, or Cl-C 4 alkylamino or di(C-C 4 )alkylamino. Special preference is given to methyl, ethyl, ethynyl and methoxy. In a further group of preferred compounds of formula I, R 2 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-C 6 alkyl, C-C 6 haloalkyl and C 3
-C
8 cycloalkyl coming into consideration as substituents. Other preferred compounds of formula I are those wherein R 4 and R, are each independently of the other C-Cl 2 alkyl, C-C 1 oalkoxy-C-C 8 alkyl or C 3 -Cealkyl that may contain one or two oxygen atoms, or R 4 and R 5 , together with the atoms to which they are bonded, form a saturated 5- to 8-membered, especially 6- or 7-membered, ring. Especially preferably
R
4 and R 5 together form a radical -CH 2
CH
2
-O-CH
2
CH
2 - or -(CH 2
)
4 -, it being possible for those radicals to be substituted tiy C-C 1 oalkyl, C-C 1 oalkoxy , 0-C 6 alkoxy-C-C 6 alkoxy 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 CORo, especially pivaloyl, C(O)X 3
R
3 1 or SO 2 R34, wherein X 3 is oxygen or sulfur, R 31 is C-Cl 2 alkyl, Cl-C 2 haloalkyl, C 2 -Cl 2 alkenyl, C-Cl 2 alkoxyalkyl, C 3
-C
12 cycloalkyl or phenyl, and R34 is C 1
-C
6 alkyl, C-C 6 haloalkyl, 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 1 and R 3 are each independently of the other C-C 4 alkyl, especially methyl or ethyl, C 2
-C
4 alkynyl, especially ethynyl, C 1
-C
6
-
-8 alkoxy, especially methoxy, or C 1
-C
4 alkylthio, especially methylthio, R 2 is phenyl, 2-thienyl, 3 thienyl, 2-furyl or 3-furyl, R 4 and R 5 are each independently of the other C 1
-C
12 alkyl, or R 4 and R 5 , together with the atoms to which they are bonded, form a radical
-CH
2
CH
2 -0-CH 2
CH
2 - or -(CH 2
)
4 -, it being possible for those radicals to be substituted by
C-C
1 oalkyl or by C 1
-C
6 alkoxy-C 1
-C
6 alkoxy, and G is hydrogen or COR 30 , especially pivalyl, or
C(O)XR
1 , wherein X 3 is oxygen and R 3 1 is C 1
C
1 2 alkyl, C 3
-C
1 2 cycloalkyl 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 R 2 by Pd(O)-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. Commun. 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 I| (Hal = chlorine, bromine or iodine).
R
1 O R 0 ~ N, R 4 _ N IR 4 Hal 1 R R 2 C \ I
R
3 0,
R
3 0, G G II 1 The compound of formula Il can be prepared analogously as described in WO 97/02243 or, for example, according to the following Scheme for 11 wherein R 1 , R 2 = CH 2
CH
3 (Hal = Cl, Br,
I)
-9 C1 C1 0 O
NH
2 C1 Cl OMe OMe Br NBr C 1. NaOMe 0e0MMe Br Br 2. H Br Br CH 2 CHSnBu3 Ci Pd (0) .~N N tBuO-NO or
CU
2
CH
2
=CH
2 , Pd() NO 2 2 NO 2 4 NO 2 2 3 H2, Pd/C
HN'R
4 0 0 O H MeO OMe OMe N - 0 (MeO) 2 CO 1. diazotisation Hal /a O/NaH 2. Sandmeyer O MeO Hal
NH
2 Il (R 1 ,R, = CH 2
CH
3 ) 7 6 5 The corresponding dimethyl compound (I wherein R 1 , R 2 = CH 3 ) can be prepared, for example, according to the following Scheme: ci 0 ci
NH
2 cl cl OMe H3C CH3 H3C CH NaOMe H3C CH tBuO-NO Br Cul 2 Br Br 8 9 10 (MeO) 2 CO NaH R HN CH CH3 0 HN-R CH30 N "R40 Br i I Br N~ N/
CH
3 O CH30 11 (R 1 , R 3 = CH 3 ) 11 CH3 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 Ill. R 7 to R 1 0 can then be hydrogen and/or alkyl, especially 0 1
-C
6 alkyl, and/or aryl, preferably phenyl and naphthyl.
-10 R 0 R OMe
R
2 R OOMe ~vHN'
R
4
NR
1 0 or + H
R
2 /
R
1 O R 3
-NR
7
R
9 I G
R
2 RR R2
NR
8
R
1 0
R
3 0 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:
NH
2
NH
2 Hal R R Suzuki, R R3 R R3 Stille coupling RN 1. diazotisation or12 Negishi coupling 2.Sandmeyer Hal R 2
R
2 VI Vil Vill NC CN o o NC CN Pd(O), base Pd(O), base R, R 3 0 0 ix R2 R O0 R RI R
H
2
SO
4 , H 2 0 for R 7
-R
1 O = H R 7 RNH / R 8 Rj 0 NH 0 O R2 IV RRN
NR
8
R
0 R1
R
3 R2 - 11 The Suzuki, Stille or Negishi coupling of VI to form VII can be carried out according to the above-mentioned procedures (Hal 1 = Br or 1); diazotisation and Sandmeyer reaction (Vogel's Textbook of Practical Organic Chemistry, 5 th Edition, B.S. Furniss, A.J. Hannaford, P.W.G. Smith, A.R. Tatchell; Longman Scientific & Technical 1989, page 923) result in halogen compounds Vill (Hal 2 = Cl, Br or 1) which can be converted directly to the phenyl malonates IV by Pd(O) cross-couplings (Kawatsura, M.; Hartwig, J.F. J. Am. Chem. Soc. 1999, 121, 1473). Starting from VIII by means of analogous Pd(O) 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 0
N'R
4 N 0 R5 (XXX) wherein R4 and R5 are as defined above, with a compound of formula Vill R , Hal R2 (ViII) R 3 wherein R 1 , R 2 and R 3 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 -12 formula VI R ,
H
2 N / \ R 2 VI), R 3 wherein R 1 and R 3 are as defined for formula 1. 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(O) complexes, such as palladium(II) dihalides, palladium(lI) acetate, palladium(II) sulfate, bis(triphenyl phosphine)palladium(lI) 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(lI) or palladium(0) compounds by complexing with the desired ligands in situ, for example by placing the palladium(lI) salt to be complexed, for example palladium(II) dichloride (PdCl 2 ) or palladium(ll) acetate (Pd(OAc) 2 ), together with the desired ligand, for -13 example triphenylphosphine (PPh 3 ), 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(Il) 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 CH 2 that is present must be protected against competitive metallisation before the introduction of the second ortho substituent (R 3 ). o ci r 0 N O N, 0 0 TMEDA, s-BuU diethylamine THF, R 1
CH
2 X R1 n-BuLi, THF Me 3 SicI 12 13 x 0 O Si / / TMEDA, s-BuLii
R
3 CsF, DMF R THFD, RX R HAI-, tolueneX X1 XIII XI11 -14 ci R1 R 3 EtOC(O)Cr1 R 3
R
1 \ R 3 toluene KCN, MeCN AcOH, HCI XIV XV XVI O O- OfOH 0 O 0 0 R R 3 (MeO) 2 CO R 3 sOC12, toluene R 1 . NaH R. MeOH XVIll XVil IV (RICH 2 = R 1 , R 3 = CH) Compounds of the If type can be cyclised by aminal formation with aldehydes (in this case with formaldehyde). Ic is accessible by the reaction of hydrazine alcohols, e.g. Ilia, with IV R1 0 N xylene, 140C H IV + I- . 2
NH
2 OR2_Rn NH~jO OH OH lila R3 0 Ic (R 4 = (CH 2
)
3 0H; R 5 = H) 30% HCHO in H 2 0, THF, 800C R1 0 N R2 R3 0 If -15 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: 0 R00 R 1 R3 wherein Ro is COOR 7 , COOR 8 , CONRR 9 , CONRAR 10 or cyano, and Roo is hydrogen, COOR 7 ,
COOR
8 , CONR 7
R
9 , CONR 8
R
1 O or cyano, and R 7 , R 8 , R 9 and RIO and R 1 , R 2 and R 3 are as defined above, but R, and R 3 are not simultaneously hydrogen. Preferred intermediates correspond to the formulae N N R7,O O .1Ra R7', N N "R8 RR 7 -~~~NR R1 R 3 R, R3 10 R R3 R2
R
2 R 2 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: -16 Hal R1 R3 R2 VIll, wherein R 1
R
2 and R 3 are as defined above, and Hal is chlorine, bromine or iodine, Hal being other than iodine when R 1 and R 3 are methyl and R 2 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. 0 HN R (CH2 m (CH) m R NH R N 0000 1-~.. ,X anhydrous H N Hal-(CF9 -(C H9 -Hal CHXNho u ( (
K
2
CO
3 , DMF, 130*C O n acyl halide (CHn r XX XXI XXII m= 2,3 r= 1 - 2 n= 2, 3 X= chemical bond, 0, S R = C -Cgalkyl 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 1 , R 3 , R 4 and R. - Rj,, the compound of -17 formula I may be in the form of a geometric and/or 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: R, 0 R
R
2 R2 N
R
5
R
3 0 H H I keto-enol form R 0 O R2 R4 II - N
R
3 R , OI enol-keto form R 2
-
H N R5
R
3 0 I keto-keto form For that reason, when R 4 + R 5 the introduction of G can result in the formation of two additional geometric isomers: R, 0 R, 0 R R
R
2 N 7 + .N Rs R 5
R
3 O R 3 0 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, nitriles, 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 +1 20*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 and/or 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 (urea/formaldehyde) 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 97/34485 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.
-19 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 97/34485 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 and/or 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 97/34485 on pages 7 and 8. The surfactants customarily employed in formulation technology, which are described inter a/ia in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol I-Ill, 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 % 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 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is - 20 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./Liberty Link Maize, IMI/Liberty Link Maize, IMI/Liberty Link/B.t. Maize, Roundup Ready Maize and Roundup Ready/B.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, lpomoea, 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, ureas, 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 - 21 Rs N (S-I), N O-CH2 0 -FRs 2 0 wherein Rs 1 is hydrogen or chlorine, and Rs 2 is hydrogen, C 1
-C
8 alkyI or C 1
-C
8 alkyl substituted by C 1 -Cealkoxy or by C 3
-C
6 alkenyloxy, or a compound of formula S-Il Rs 6 E 1_ N RssA N N
R
3 N (S-Il), Rs 4 Rs wherein E 1 is nitrogen or methine; Rs 3 is -CC1 3 , phenyl or halo-substituted phenyl; Rs 4 and Rs 5 are each independently of the other hydrogen or halogen; and Rs 6 is C 1
-C
4 alkyl; or a compound of formula S-Ill C02Rs 1 Rs 10 0 2 C N Rs 9 N (S-ll), Rs 8 Rs wherein Rs 7 and Rs 8 are each independently of the other hydrogen or halogen and Rs 9 , Rs 1 o and Rsjj are each independently of the others C 1
-C
4 alkyl, or a compound of formula S-IV - 22 Rs 13 Rs 1 Rs 14 N-CO-N / (S-IV), Rs 16 Rs 17 S0 2 -N H-CO-Rs 12 wherein Rs 1 2 is a group Rs 27 Rs34 Rs40 Rs 39 N , Rs 45 Rsor Rs 28 Rs 37 Rs 29 Rs 38 Rs 41 Rs8 Rs 4 S Rs 13 is hydrogen, halogen, cyano, trifluoromethyl, nitro, C-C 4 alkyl, C-C 4 alkoxy, C-C 4 alkylthio, C-C 4 alkylsulfinyl, C-C 4 alkylsulfonyl, -COOH, -COO-C-C 4 alkyl, -CONRs 1 8 Rs 19 ,
-C(O)-C-C
4 alkyl, C(O)-phenyl, or phenyl substituted by halogen, C 1
-C
4 alkyl, methoxy, nitro or by trifluoromethyl, or -SO 2 NRs20Rs 21 or -OS0 2
-C-C
4 alkyl; Rs 18 , Rs 19 , Rs20 and Rs 21 are each independently of the others hydrogen or C-C 4 alkyl, or Rs 18 and Rs 19 or Rs 20 and Rs 2 1 together form a C 4
-C
6 alkylene bridge which may be interrupted by oxygen, NH or by -N(C-C 4 alkyl)-; Rs 14 is hydrogen, halogen, C-C 4 alkyl, trifluoromethyl, C-C 6 alkoxy, C-C 6 alkylthio, -COOH or
-COO-C-C
4 alkyl; or Rs 13 and Rs 14 together form a C 3
-C
4 alkylene bridge which may be substituted by halogen or by C-C 4 alkyl, or Rs 1 3 and Rs 1 4 together form a C 3
-C
4 alkenylene bridge which may be substituted by halogen or by C-C 4 alkyl, or Rs 1 3 and Rs 14 together form a C 4 alkadienylene bridge which may be substituted by halogen or by C-C 4 alkyl; Rs 15 and Rs 1 6 are each independently of the other hydrogen, C-C 8 alkyl, C 3
-C
8 cycloalkyl, - 23 Rs 23
C,-C
6 alkenyl, C 3
-C
6 alkynyl, , or C 1
-C
4 alkyl substituted by C1-C4 Rs 22 Rs 24 alkoxy or by ; or Rs 15 and Rs 1 6 together form a C 4
-C
6 alkylene bridge Rs 25 which may be interrupted by oxygen, sulfur, SO, S02, NH or by -N(C-C 4 alkyl)-; Rs2, Rs 23 , Rs 2 4 and Rs 2 , are each independently of the others hydrogen, halogen, C-C 4 alkyl, C-C 4 alkoxy, C-C 4 alkylthio, -COORs 2 6 , trifluoromethyl, nitro or cyano, wherein Rs 26 is in each case hydrogen, C-C 1 oalkyl, C-C 4 alkoxy-C-C 4 alkyl, C-C 4 alkylthio-C-C 4 alkyl, di
C-C
4 alkylamino-C-C 4 alkyl, halo-C-C 8 alkyl, C 2
-C
8 alkenyl, halo-C 2
-C
8 alkenyl, C 3 -Calkynyl,
C
3
-C
7 cycloalkyl, halo-C 3
-C
7 cycloalkyl, C-C 8 alkylcarbonyl, allylcarbonyl, C 3
-C
7 cycloalkyl carbonyl, benzoyl that is unsubstituted or substituted on the phenyl ring identically or differently up to three times by halogen, C-C 4 alkyl, halo-C-C 4 alkyl, halo-C-C 4 alkoxy or
C-C
4 alkoxy; or furyl or thienyl; or C-C 4 alkyl substituted by phenyl, halophenyl, C-C 4 alkylphenyl, C-C 4 alkoxyphenyl, halo-C-C 4 alkylphenyl, halo-C-C 4 alkoxyphenyl, C1-C6 alkoxycarbonyl, C-C 4 alkoxy-C-C 8 alkoxycarbonyl, C 3 -Calkenyloxycarbonyl, C 3
-C
8 alkynyl oxycarbonyl, C-Cealkylthiocarbonyl, C 3 -Calkenylthiocarbonyl, C 3 -Calkynylthiocarbonyl, carbamoyl, mono-C-C 4 alkylaminocarbonyl or by di-C-C 4 alkylaminocarbonyl; or phenyl aminocarbonyl which may itself be substituted on the phenyl identically or differently up to three times by halogen, C-C 4 alkyl, halo-C-C 4 alkyl, halo-C-C 4 alkoxy or C 1
-C
4 alkoxy or once by cyano or nitro; or dioxolan-2-yl which may itself be substituted by one or two C 1
-C
4 alkyl groups, or dioxan-2-yl which may itself be substituted by one or two C 1
-C
4 alkyl groups; or
C
1
-C
4 alkyl substituted by cyano, nitro, carboxyl or by C-C-alkylthio-C-C 8 alkoxycarbonyl; Rs 17 is hydrogen or C 1
-C
4 alkyl; Rs 27 is hydrogen, halogen, nitro, C-C 4 alkyl or methoxy; Rs 2 , is hydrogen, halogen, C-C 4 alkyl, trifluoromethyl, C-C 6 alkoxy, C-C 6 alkylthio, -COOH or
-COO-C-C
4 alkyl; Rsa is hydrogen, halogen, cyano, nitro, C-C 4 alkyl, C 1
-C
4 haloalkyl, C-C 4 alkylthio, CrC4r alkylsulfinyl, C-C 4 alkylsulfonyl, -COOH, -COO-C-C 4 alkyl, -CONRs3oRs 3 1 , C(O)-phenyl, or phenyl substituted by halogen, C-C 4 alkyl, methoxy, nitro or by trifluoromethyl, or - 24 -SO 2 NRs 3 2 Rs 33 , -OSO 2
-C-C
4 alkyl, C 1
-C
6 alkoxy, or C 1
-C
6 alkoxy substituted by C-C 4 alkoxy or by halogen; or C 3
-C
6 alkenyloxy or C 3
-C
6 alkenyloxy substituted by halogen; or C 3
-C
6 alkynyl oxy; wherein Rs 30 and Rs 3 1 are each independently of the other hydrogen or C 1
-C
4 alkyl; or Rs 3 o and Rs 3 1 together form a C 4
-C
6 alkylene bridge which may be interrupted by oxygen, NH or by -N(C-C 4 alkyl)-, and Rs 32 and Rs 33 are each independently of the other hydrogen or
C-C
4 alkyl, or Rs 32 and Rs 33 together form a C 4
-C
6 alkylene bridge which may be interrupted by oxygen, NH or by -N(C-C 4 alkyl)-; Rs4 is hydrogen, halogen, nitro, C-C 4 alkyl, C-C 4 alkoxy, C-C 4 alkylthio, C-C 4 alkylsulfinyl,
C-C
4 alkylsulfonyl, -COOH, -COO-C-C 4 alkyl or CONRs 35 Rs 36 , wherein Rs 3 5 and Rs 3 6 are each independently of the other hydrogen or C-C 4 alkyl, or Rs 35 and Rs 36 together form a
C
4
-C
6 alkylene bridge which may be interrupted by oxygen, NH or by -N(C-C 4 alkyl)-; Rs 37 is hydrogen, halogen, C-C 4 alkyl, -COOH, -COO-C-C 4 alkyl, trifluoromethyl or methoxy, or Rs 34 and Rs 37 together form a C 3
-C
4 alkylene bridge; Rs 38 is hydrogen, halogen or C-C 4 alkyl; Rs 39 is hydrogen, halogen, C-C 4 alkyl, -COOH, -COO-C-C 4 alkyl, trifluoromethyl or methoxy; Rs4e is hydrogen, halogen, nitro, C-C 4 alkyl, C-C 4 alkoxy, C-C 4 alkylthio, C-C 4 alkylsulfinyl,
C-C
4 alkylsulfonyl, -COOH, -COO-C-C 4 alkyl or CONRs 42 Rs 43 ; Rs 41 is hydrogen, halogen or C-C 4 alkyl; or Rs4o and Rs 4 1 together form a C 3
-C
4 alkylene bridge; Rs 42 and Rs43 are each independently of the other hydrogen or C-C 4 alkyl, or Rs 4 2 and Rs43 together form a C 4
-C
6 alkylene bridge which may be interrupted by oxygen, NH or by
-N(C-C
4 alkyl)-; Rs44 is hydrogen, halogen, C-C 4 alkyl, -COOH, -COO-C-C 4 alkyl, trifluoromethyl or methoxy; Rs 45 is hydrogen, halogen, nitro, C-C 4 alkyl, C-C 4 alkoxy, C-C 4 alkylthio, C-C 4 alkylsulfinyl,
C-C
4 alkylsulfonyl, -COOH, -COO-C-C 4 alkyl or CONsRs4Rs 47 ; Rs4 and Rs 47 are each independently of the other hydrogen or C-C 4 alkyl, or Rs4 and Rs 47 together form a C 4
-C
6 alkylene bridge which may be interrupted by oxygen, NH or by
-N(C-C
4 alkyl)-; Rs48 is hydrogen, halogen, C-C 4 alkyl, -COOH, -COO-C-C 4 alkyl, trifluoromethyl or methoxy; Rs 49 is hydrogen, halogen, nitro, C-C 4 alkyl, C-C 4 alkoxy, C-C 4 alkylthio, C-C 4 alkylsulfinyl,
C-C
4 alkylsulfonyl, -COOH, -COO-C-C 4 alkyl or CONRs5oRs 5 1 ; Rs 5 1 and Rs 52 are each independently of the other hydrogen or C-C 4 alkyl, or Rs 5 1 and Rs 52 together form a C 4
-C
6 alkylene bridge which may be interrupted by oxygen, NH or by - 25 -N(C-C 4 alkyl)-; or a compound of formula S-V Rssa O (S-V), R XN--lCHC2 Rs~ wherein Rs 53 and Rs 54 are each independently of the other C-C 6 alkyl or C 2 -Calkenyl; or Rs ~ Rs~ Rs 3 and Rs.
4 together are O ; Rs 55 and Rsse are each independently of the Rs 57 other hydrogen or Cr-Cealkyl; or Rssa and Rss4 together are O; wherein Rs 55 Rs 5 Rs6 and Rs 56 are each independently of the other C-C 4 alkyl, or Rs, 5 and Rss together are -(CH2)s Rs.
7 is hydrogen, C-C 4 alkyl or ; Rs 58 Rs 59 s Rs 67 Rs6R RsRR 7R or ar or59 Rs Rs 7 or Rs 53 and Rs 54 together ar e R Rs 6 , or RsN Rs 6 4 0 N Rs 6 2 O Rs 6 ' Rs 6 6 Rs 7 2 Rs 7 , wherein Rsse, Rs 59 , Rseo, Rs6 1 , Rs 62 , Rs63, Rs64, Rs65, Rs66, Rs 67 , Rsee, Rs 69 , Rs 70 , Rs 7 1 , Rs 72 and Rs 7 3 are each independently of the others hydrogen or C-C 4 alkyl; or a compound of formula S-VI -26 Rs7 Rs 7 O O(S-VI), Rs 7 wherein Rs 75 is hydrogen or chlorine and Rs 74 is cyano or trifluoromethyl, or a compound of formula S-VII C
N
/s 6 (S-VII) Rs76 * - N C wherein Rs 76 is hydrogen or methyl, or of formula S-VIII Rs''
E
2 ) Rs 78 EE4 (S-VI), 5 Rs 79 wherein r is 0 or 1; Rsy7 is hydrogen or C-C 4 alkyl which may be substituted by C-C 4 alkoxy, C-C 4 alkylthio,
C-C
4 alkylsulfinyl, C-C 4 alkylsulfonyl, C-C 4 haloalkyl, C-C 4 haloalkoxy, C-C 4 haloalkylthio,
C-C
4 haloalkylsulfinyl, C-C 4 haloalkylsulfonyl, nitro, cyano, -COOH, COO-C-C 4 alkyl, -NRs 8 oRs 81 , -SO 2 NRs 82 Rs 83 or by -CONRs84Rs..; Rs 7 , is hydrogen, halogen, C-C 4 alkyl, trifluoromethyl, C-C 4 alkoxy or C-C 4 haloalkoxy; Rs 7 is hydrogen, halogen or C-C 4 alkyl; Rs 8 o is hydrogen, C-C 4 alkyl or C-C 4 alkylcarbonyl; Rs 8 1 is hydrogen or C-C 4 alkyl; or Rs 80 and Rs 81 together form a C 4 - or C 5 -alkylene group; Rs 82 , Rs 83 , Rs84 and Rs 85 are each independently of the others hydrogen or C-C 4 alkyl; or Rs 82 together with Rs 83 , or Rs84 together with Rs8,, are each independently of the other C 4 - or
C
5 -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-C 4 alkyl)-;
E
2 , E 3 , E 4 and E, are each independently of the others oxygen, sulfur, C(Rs 86 )Rs 87
,
- 27 H O H carbonyl, -NH-, -N(C-C 8 alkyl)-, a group C Rs 9 o or Rs 9 7 , 0~ 0 O O--7 Rs8 Rs 89 Rs 9 Rsg9 Rs,6 and Rs 87 are each independently of the other hydrogen or C-Cealkyl; or Rs 86 and Rs 87 together are C 2
-C
6 alkylene; Rs., and Rs 89 are each independently of the other hydrogen or C-C 8 alkyl; or Rs88 and Rs 89 together form a C 2
-C
6 alkylene group; Rsqo is Rs 91 -O-, Rs 92 -S- or -NRs 93 Rs 94 ; Rs 1 and Rs 92 are each independently of the other hydrogen, C-Cealkyl, C-Cshaloalkyl,
C
1
-C
4 alkoxy-C 1
-C
8 alkyl, C 3
-C
6 alkenyloxy-C-C 8 alkyl or phenyl- 1
-C
8 alkyl, it being possible for the phenyl ring to be substituted by halogen, C-C 4 alkyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl or by methylsulfonyl, or are C 3
-C
6 alkenyl, C 3
-C
6 haloalkenyl, phenyl-C 3
-C
6 alkenyl, C 3
-C
6 alkynyl, phenyl-C 3
-C
6 alkynyl, oxetanyl, furyl or tetrahydrofuryl; Rs 93 is hydrogen, C 1
-C
8 alkyl, phenyl, phenyl-C-C 8 alkyl, it being possible for the phenyl rings to be substituted by fluorine, chlorine, bromine, nitro, cyano, -OCH 3 , C 1
-C
4 alkyl or by
CH
3
SO
2 -, or is C-C 4 alkoxy-C-C 8 alkyl, C 3
-C
6 alkenyl or C 3
-C
6 alkynyl; Rs 94 is hydrogen, C-C 8 alkyl, C 3
-C
6 alkenyl or C 3
-C
6 alkynyl; or Rs 93 and Rs 94 together are C 4 - or C-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-C
4 alkyl) Rs., and Rs96 are each independently of the other hydrogen or C-Cealkyl; or Rs 5 and Rs 96 together form a C 2
-C
6 alkylene group; and Rs 97 is C 2
-C
4 alkenyl or C 2
-C
4 alkynyl; with the provisos that a) at least one of the ring members E 2 , E 3 , E 4 and E. is carbonyl, and one ring member that H 0 is adjacent to that/those ring member(s) is the group C Rsgo or Rs c Rs.
9 H C= Rs 9 7 , such a group occurring only once; and Rs 95 Rs b) two adjacent ring members E 2 and E 3 , E 3 and E 4 , and E 4 and E. cannot simultaneously be - 28 oxygen; or a compound of formula S-IX Rs 99 -NHS('J N I- - -N SN N R s , 1 o (S -IX ) , S COORs 98 N Rsio, wherein Rs 98 is hydrogen, C-C 6 alkyl, C 3 -C6cycloalkyl, C 3
-C
6 alkenyl or C 3
-C
6 alkynyl; and Rs 9 , Rs 1 ao and Rs 101 are each independently of the others hydrogen, C-C 6 alkyl, C 3
-C
6 cycloalky or
CI-C
6 alkoxy, with the proviso that one of the substituents Rs 99 , Rs 1 oo and Rs 1 o 1 is other than hydrogen; or a compound of formula S-X Rs103 0 (Rs 102 ) (S-X) -_ 0 F E6 Rs104 wherein E 6 is nitrogen or methine, n is 0, 1, 2 or 3 when E 6 is nitrogen and 0, 1, 2, 3 or 4 when E 6 is methine, Rs 1 02 is halogen, C-C 4 alkyl, C-C 4 haloalkyl, C-C 4 alkoxy, C 1
-C
4 halo alkoxy, nitro, C-C 4 alkylthio, C-C 4 alkylsulfonyl, C-C 4 alkoxycarbonyl, phenyl or phenoxy, or phenyl or phenoxy each substituted by C-C 3 alkyl, C-C 3 haloalkyl, C-C 3 alkoxy, C-C 3 haloalkoxy, halogen, cyano or by nitro; Rs 103 is hydrogen or C-C 4 alkyl; Rs, 04 is hydrogen, C-C 4 alkyl, C 3
-C
6 cycloalkyl, C 2
-C
6 alkenyl, C 2
-C
6 alkynyl, C-C 4 haloalkyl,
C
2
-C
6 haloalkenyl, C 2
-C
6 haloalkynyl, C-C 4 alkylthio-C-C 4 alkyl, C-C 4 alkylsulfonyl-C-C 4 alkyl,
C-C
4 alkoxy-C-C 4 alkyl, C-C 4 alkenyloxy-C-C 4 alkyl or C-C 4 alkynyloxy-C-C 4 alkyl; or a compound of formula S-XI - 29 (S-XI) 0 E 0 O wherein E 7 is oxygen or N-Rs 1 o 5 and Rs 105 is a group of formula
H
2 Rs 106 C ,N Rs,07 wherein Rso6 and Rs107 are each independently of the other cyano, hydrogen, C1-C4alkyl, C3-C6cycloalkyl, C2-Cealkenyl, aryl, phenyl or heteroaryl, or phenyl, aryl or heteroaryl each substituted by C1-Csalkyl, C1-Cshaloalkyl, C1-Csalkoxy, C1-Cshaloalkoxy, halogen, cyano or by nitro; or a compound of formula S-XII Rs,0 Rs 11 U R1O(S-Xil) E8 Rsml wherein E8 is oxygen, sulfur, sulfinyl, sulfonyl or methine, RS108 and Rs109 are each independently of the other CH2COORs,12 or COORsjjs or together are a group of formula -(CH2)C(O)-O-C(O)-(CH2)-, and Rs,12 and RS113 are each independently of the other hydrogen, C1-C4alkyl, C2-C4alkenyl, C2-Cealkynyl, C3-C6cycloalkyl, C1-C4haloalkyl, or a metal cation or ammonium cation; and Rs,1o and Rsjj1 are each independently of the other hydrogen, halogen or C1-C4alkyl; or a compound of formula S-XIll - 30 30 Rsm O4 0 (S-XIll), 1 1ORs 116 Eg Rs 5
E
1 0 wherein Rs, 1 4 and Rs 15 are each independently of the other hydrogen, halogen or C 1
-C
4 haloalkyl, Rs 16 is hydrogen, C-C 4 alkyl, C 3
-C
4 alkenyl, C 3
-C
4 alkynyl, C-C 4 haloalkyl, C3-C6 cycloalkyl, a metal cation or an ammonium cation;
E
9 is nitrogen, methine, C-F or C-Cl and
E
1 0 is a group of formula SR ORs 117 or 122ORs O R s 120 :0)Y 0 Rs 1 21 wherein Rs 1 1 8 , Rs, 1 9 , Rs 12 1 and Rs 1 2 are each independently of the others hydrogen or C-C 4 alkyl; Rs 17 and Rs 1 o are each independently of the other hydrogen, C-C 4 alkyl, C 3
-C
4 alkenyl,
C
3
-C
4 alkynyl, C-C 4 haloalkyl, C 3
-C
6 cycloalkyl, a metal cation or an ammonium cation; or a compound of formula S-XIV 0 Rs 124 (S-XIV), I) | S Rs 1 23 wherein Rs 123 is hydrogen, cyano, halogen, C-C 4 alkyl, C 3
-C
6 cycloalkyl, C-C 4 alkoxy, C 1
-C
4 alkoxycarbonyl, C-C 4 alkylthiocarbony, -NH-Rs 125 -C(O)NH-Rs 126 , aryl or heteroaryl, or aryl or heteroaryl each substituted by C-C 3 alkyl, C-C 3 haloalkyl, C-C 3 alkoxy, C-C 3 haloalkoxy, halogen, cyano or by nitro; Rs, 24 is hydrogen, cyano, nitro, halogen, C-C 4 alkyl, C-C 4 haloalkyl, C-C 4 alkoxy, C1-C4 thioalkyl; and Rs 125 and Rs, 26 are each independently of the other C-C 4 alkyl, C-C 4 haloalkyl, C 3
-C
4 alkenyl,
C
3
-C
4 alkynyl, C 3
-C
4 cycloalkyl, C-C 4 alkylcarbonyl, C-C 4 alkylsulfonyl, aryl or heteroaryl, or aryl or heteroaryl each substituted by C-C 3 alkyl, C-C 3 haloalkyl, C-C 3 alkoxy, C-C 3 halo- - 31 alkoxy, halogen, cyano or by nitro; or a compound of formula S-XV Rs129 Rs128 Rs130 N (S-XV), Rs 131 N N Rs127 wherein Rs 127 and Rs 12 8 are each independently of the other hydrogen, C-C 4 alkyl, C 1
-C
4 haloalkyl, C-C 4 alkoxy, mono-C-C8- or di-C-C 8 -alkylamino, C 3
-C
6 cycloalkyl, C-C 4 thioalkyl, phenyl or heteroaryl; Rs 1 2 is hydrogen, C-C 4 alkyl, C-C 4 haloalkyl, C-C 4 alkoxy, mono-C-C 8 - or di-C-C 8 -alkyl amino, C 3
-C
6 cycloalkyl, C-C 4 thioalkyl, phenyl, heteroaryl, OH, NH 2 , halogen, di-C-C 4 aminoalkyl, C-C 4 alkylthio, C-C 4 alkylsulfonyl or C-C 4 alkoxycarbonyl; Rs 1 so is hydrogen, C-C 4 alkyl, C-C 4 haloalkyl, Cr-C 4 alkoxy, mono-C-C.- or di-C-C.
alkylamino, C 3 -Cecycloalkyl, C-C 4 thioalkyl, phenyl, heteroaryl, cyano, nitro, carboxyl, C 1
-C
4 alkoxycarbonyl, di-C-C 4 aminoalkyl, C-C 4 alkylthio, C-C 4 alkylsulfonyl, S0-OH, i-Cr C4 aminoalkylsulfonyl or C-C 4 alkoxysulfonyl; Rs 1 31 is hydrogen, C-C 4 alkyl, C-C 4 haloalkyl, C-C 4 alkoxy, mono-C-C 8 - or di-C-C 8 -alkyl amino, C 3
-C
6 cycloalkyl, C-C 4 thioalkyl, phenyl, heteroaryl, OH, NH 2 , halogen, di-C-C 4 aminoalkyl, pyrrolidin-1-yl, piperid-1-yl, morpholin-1-yl, C-C 4 alkylthio, C-C 4 alkylsulfonyl, Cr-C 4 alkoxycarbonyl, phenoxy, naphthoxy, phenylamino, benzoyloxy or phenylsulfonyloxy; or a compound of formula S-XVI 0 T o Rs132 Rs 1 3 0 (S-XVI), Rs 133 N wherein Rs 132 is hydrogen, C 4 alkyl, C-C 4 haloalkyl, C 2
-C
4 alkenyl, C 2
-C
4 alkynyl or C 1
-C
4 alkoxy-C-C 4 alkyl; Rs 1 33 is hydrogen, halogen, C-C 4 alkyl, C-C 4 haloalkyl or C 1
-C
4 alkoxy and Rs 1 34 is hydrogen, halogen, C-C 4 alkyl, C-C 4 haloalkyl or C-C 4 alkoxy; with the proviso that Rs 1 33 and Rs 1 34 are - 32 not simultaneously hydrogen. Especially preferred safeners for the composition according to the invention are selected from the group of compounds of formula S1.1 0 N Me (S1.1), Cl O Cl and of the compound of formula S1.2 C1 N - 0- (S1.2), Cl and of the compound of formula SS1.3 Cl (S1.3), N
O-CH
2
-C(O)-O-CH(CH
3 )CHl -n and of the compound of formula S1.4 CI Me COOCH 2
CH
3 CI / N (S1.4), N
COOCH
2
CH
3 and of the compound of formula S1.5 - 33 0 C1 N Me Cl (S1.5), O Me and of the compound of formula S1.6 COOH COOH (S1.6), 0 and of the compound of formula S1.7 Cl 0 CI M Ci
--
I Me N (S1.7), Me Me 0 and of the compound of formula S1.8 CI S0 (S1.8),
CF
3 0 and of formula S1.9
CI
2
CHCON(CH
2
CH=CH
2 ) (S1 .9), and of formula S1.10 - 34 Cl 0-CH 2-0 (S1.10),
N:Z
CF
3 and of formula S1.11 Cl 0 CI N ( 0 and of formula S1.12 COOH ON (S1.12) and of formula S1.13 0 CH2CH 3 CI Cl N N (S1.13). C C Cl Cl 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) - 35 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 Examples: Example P1: Preparation of 3-hydroxy-4-aryl-5-oxo-pyrazolines Cl
NH
2 Cl Br Br Cl N Br Br
NO
2 1 2 NO 2 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 and filtered, and the filtrate was washed with tert-butyl methyl ether. The organic phase was washed with 150 ml of 10% HCI and 2 x 150 ml of water, and dried over Na 2
SO
4 . The organic phase was concentrated and chromatographed over silica gel. 13.2 g of 2 were obtained. 1 H-NMR (300 MHz, CDCI 3 ): 8 = 4.69 (s, 2H). Cl 0 Cl Cl OMe Br Br Br Br
NO
2
NO
2 2 3 - 36 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 H 2
SO
4 (3.7 ml) and refluxed for a further 0.5 hour. The reaction mixture was cooled, diluted with water and extracted with CH 2
CI
2 (3 x 100 ml). The combined organic phases were dried using Na 2
SO
4 , filtered and concentrated. 3 (9.1 g) was obtained in the form of a crude product. 'H-NMR (300 MHz, CDCI 3 ): 6 = 8.4 (s, 2H); 4.2 (s, 2H); 3.7 (s, 3H). 0 0 OMe OMe Br Br 3 NO 2 4 NO 2 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 1000C for 16 hours and cooled, and an NaOH solution (1N, 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 Na 2
SO
4 , concentrated and chromatographed over silica gel (EtOAC:hexane (1:10)). 4 (4.13 g) was obtained. 1 H-NMR (300 MHz, CDCI 3 ): 6 = 8.2 (s, 2H); 6.9 (dd, 1H); 5.8 (d, 1H); 5.5 (d, 1H); 3.8 (s, 2H); 3.7 (s, 3H). 4 (4 g, 16.2 mmol) was dissolved in MeOH (100 ml), and Pd/C (5%, 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. 1 H-NMR (300 MHz, CDCI 3 ): 6 = 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 mmol) and methylene iodide (4.15 ml, 50 mmol) were placed in acetonitrile (30 ml) and, at 00C, 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 - 37 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 Na 2
SO
4 , filtered, concentrated and chromatographed over silica gel (ethyl acetate:hex = 1:5). 6 (Hal = 1) (1.6 g) was obtained. 'H-NMR (300 MHz, CDCI 3 ): 6 = 7.4 (s, 2H); 3.7 (2s, 5H); 2.6 (q, 4H); 1.2 (t, 6H). 0 0 0 OMe MeO OMe 6 (Hal = 1) 7 (Hal 1) 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 0 C. 6 (Hal = 1) was dissolved in THF (15 ml) and added dropwise to the reaction mixture. After stirring for 0.5 hour at -78 0 C, cyanoformic acid methyl ester was added, and the reaction mixture was slowly heated to 0*C. The reaction mixture was added to NH 4 CI (aq) (100 ml) and extracted with ethyl acetate (2 x 70 ml). The combined organic phases were washed with H 2 0 (3 x 70 ml) and brine (70 ml), dried over Na 2
SO
4 , filtered and concentrated. The crude product was chromatographed over silica gel. 7 (Hal = I, 1.125 g) was obtained. 1 H-NMR (300 MHz, CDCI 3 ): 8 = 7.4 (s, 2H); 5.0 (s, 1H); 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 < 300C, vinylidene chloride (2385 ml, 29.9 mol) was added dropwise and then, at 100C, 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 20% HCI (9000 ml) and extracted with tert-butyl methyl ether (3 x 3000 ml). The organic phase was washed with 20% HCI and water and dried over Na 2
SO
4 . The organic phase was concentrated. 470 g of 9 were obtained. 'H-NMR (300 MHz,
CDCI
3 ): 6 = 4.13 (s, 2H).
- 38 9 (257 g, 0.813 mol) was dissolved in methanol (400 ml) and, at < 300C, NaOMe (30% 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 Na 2
SO
4 , concentrated and distilled. 10 (198 g, b.p.:95-100*C/0.2) was obtained. 'H-NMR (300 MHz, CDCI 3 ): 6 = 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 900C. 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 20 hours and cooled, and excess sodium hydride was destroyed with methanol. The reaction mixture was poured into ice/water, adjusted to pH = 5 with HCI, and extracted with methylene chloride (4x). The combined organic phases were washed with brine, dried over Na 2
SO
4 , concentrated and recrystallised from ethyl acetate/hexane (1:10). 11 (161.33 g, m.p.: 69-71*C) was obtained. 'H-NMR (300 MHz, CDCl 3 ): 6 = 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 1400C. 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 Na 2
SO
4 and concentrated. 17 was obtained (42.87 g, m.p: 299-301*C). 1 H-NMR (300 MHz, CDCl 3 ): 6 = 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).
- 39 0 0 N 17 18 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 ice/water 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 Na 2
SO
4 and concentrated. The resulting resin was stirred with ether. The crystals obtained 18 (47 g, m.p. 1220C) were filtered off. 'H-NMR (300 MHz, CDCl 3 ): 8 = 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 mmol) 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 reactiorr 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 Na 2
SO
4 , concentrated and chromatographed over silica gel (ethyl acetate:methanol = 5:1). 19 (2.7 g) was obtained. 'H-NMR (300 MHz, CDCi 3 ): 6 = 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 (4.0 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. 1 H-NMR (300 MHz, CDCl 3 ): 6 = 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).
- 40 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 HCL. Extraction was carried out three times with ethyl acetate, and the combined organic phases were washed with brine, dried over Na 2
SO
4 , concentrated and chromatographed over silica gel (ethyl acetate: methanol = 5:1). 21 (0.93 g, m.p. 159 0 C) was obtained. 'H-NMR (300 MHz, CDCI 3 ): 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 ml) and washed with water (2 x 100 ml) and aqueous NaHCO 3 solution (100 ml), dried over Na 2
SO
4 and concentrated. The crude product (28.5 g) was crystallised from Et 2 0/hexane. 13 (24.5 g) was obtained. 1 H-NMR (300 MHz, CDCI 3 ): 8 = 7.6-7.35 (m, 9H); 3.7-3.2 (2bs, 4H); 1.2 (m, 6H). * - 0 NN 13 22 TMEDA (17.1 g, 0.147 mol) was dissolved in THF (distilled over Na, 500 ml), cooled to -78 0 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 (33.9 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 NH 4 CI solution (200 ml) was added to the reaction mixture. The organic phase was separated off, washed with brine, dried over Na 2
SO
4 , concentrated and chromatographed over silica gel (Et 2 O/hexane = 1:1). 22 (29.5 g) was obtained.
- 41 'H-NMR (300 MHz, CDCI 3 ): 6 = 7.6-7.2 (m, 9H); 3.9-3.1 (m, 4H); 2.7 (q, 2H), 1.25 (t, 6H); 1.1 (t, 3H) Si NH N 22 23 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 0 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 NH 4 CI 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 Na 2
SO
4 and concentrated. 23 (38.2) was obtained in the form of a crude product. 1 H-NMR (300 MHz, CDC 3 ): 8 = 7.6-7.1 (m, 8H); 3.75 (m, 1H); 3.4-3-0 (m, 3H); 2.3 and 2.1 (2m, 1H); 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 0 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 NH 4 CI 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 Na 2
SO
4 and concentrated. The crude product was chromatographed over silica gel (ethyl acetate/hexane = 1:7). 24 (18.5) was obtained. 1 H-NMR (300 MHz, CDCI 3 ): 6 = 7.6-7.2 (m, 7H); 3.6 (m, 2H); 3.1 (m, 2H); 2.6 (m, 2H); 2.1 (m, 1H); 1.4 (d, 3H); 1.2 (m, 6H); 0.0 (s, 9H). 24 (18.5 g, 0.059 mol) 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 0 C for - 42 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 Na 2
SO
4 and concentrated. 25 (15.7 g) was obtained in the form of a crude product. 1 H-NMR (300 MHz, CDCI 3 ): 6 = 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).
NN-
25 26 25 (15.7 g, 0.051 mol) was dissolved in toluene, and LiAIH 4 (1.92 g, 0.051 mol) was added. The reaction mixture was stirred at reflux for 20 hours and cooled to 0 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 1N 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 Na 2
SO
4 and concentrated. 26 (8.6 g) was obtained in the form of a crude product. 1 H-NMR (300 MHz, CDCI 3 ): 6 = 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). C1 26 27 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 0 C for 3 hours, and concentrated. 27 (11 g) was obtained in the form of a crude product. 'H-NMR (300 MHz,
CDC
3 ): 8 = 7.6-7.3 (m, 7H); 4.75 (s, 2H); 2.9 (q, 4H); 1.3 (t, 6H).
- 43 Cl N 27 28 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 Na 2
SO
4 , and concentrated. 28 (10 g) was obtained in the form of a crude product. 1 H-NMR (300MHz, CDCI 3 ): 6 = 7.6-7.3 (m, 7H); 3.7 (s, 2H); 2.8 (q, 4H); 1.4 (t, 6H). \
-
OH IN O 28 29 28 (4.5 g, 0.018 mol) was stirred in acetic acid (25 ml) and HCI (37% 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 Na 2
SO
4 and concentrated. 29 (5 g) was obtained in the form of a crude product. 1 H-NMR (300 MHz, CDCl 3 ): 8 = 7.6-7.3 (m, 7H); 3.8 (s, 2H); 2.7 (q, 4H); 1.25 (t, 6H). OH 3O 29 30 - 44 29 (8.1 g, 0.03 mol) was dissolved in toluene (75 ml), and SOC1 2 (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, CDCI 3 ): 6 = 7.6 7.3 (m, 7H), 3.8 (s, 2H); 3.7 (s, 3H); 2.7 (q, 4H); 1.25 (t, 6H). O O0 O 30 31 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 ml), and the combined organic phases were washed with brine, dried over Na 2
SO
4 and concentrated. 31 (11.3 g) was obtained in the form of a crude product. 'H-NMR (300 MHz, CDCI 3 ): 6 = 7.6 7.2 (m, 7H); 5.1 (s, 1H); 3.7 (s, 6H); 2.7 (q, 4H); 1.2 (t, 6H).
B(OH)
2 - 0 -0 C) N 13 32 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 0 C, trimethyl borate was added to the reaction mixture. The reaction mixture was stirred at -78*C for 0.5 hour, heated to -400C, and an aqueous NH 4 CI solution (250 ml) was added thereto. The - 45 organic phase was washed with brine, dried over Na 2
SO
4 and concentrated. 32 (36.7 g) was obtained in the form of a crude product.
B(OH)
2 OH - 0 -0 32 33 32 (35.2 g, 0.12 mol) was in MeOH (300 ml) and, with ice-cooling, H 2 0 2 (16.1 g of a 30% solution, 0.142 mol) was added, the reaction temperature rising from 20 0 C to 40 0 C. After 2 hours, the reaction mixture was concentrated to 2/3, 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, CDCi 3 ): 6 = 7.65-7.2 (m, 7H); 7.05 (dd, 1H); 3.05 (q, 4H); 1.3 (t, 6H). OH 0 - 0 -0
N-
33 34 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 ml) and extracted with ethyl acetate (2 x 100 ml). The combined organic phases were washed with brine, dried over Na 2
SO
4 , concentrated and chromatographed over silica gel (ethyl acetate:hexane, 1:1). 34 (3.4 g) was obtained. 'H-NMR (300 MHz,
CDCI
3 ): 6 = 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).
- 46 0- 0 0 0 34 35 TMEDA (1.49 g, 12.8 mmol) 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 0 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 0 C for 0.3 hour. Ethyl iodide (2.0 g, 13 mmol) was added to the reaction mixture. The reaction mixture was heated to 0*C and an aqueous NH 4 CI solution (50 ml) was added. The organic phase was washed with brine, dried over Na 2
SO
4 and concentrated. 35 (3.5 g) was obtained in the form of a crude product. 'H-NMR (300 MHz, CDCI 3 ): 8 = 7.6-7.3 (m, 5H); 7.07 (s, 1H); 6.9 (s, 1H); 3.9 (s, 3H); 3.8 (m, 1H); 3.45 (m, 1H) 3.2 (m, 2H); 2.6 (m, 2H); 1.3 (m, 6H); 1.1 (t, 3H). 0 H N NH I O N 0O 14 15 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.
- 47 0 0 N__ HN N HN o (HCO) 15 16 15 (1000 g, 5.38 mol) was dissolved in anhydrous methanol (5.4 litres) at 350C, 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 00C 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). IH-NMR (300 MHz, D 6 -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, "LC/MS: 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 water/acetonitrile.
- 48 Table 1 Compounds of formula 00 ~ N R2 0
R
3 0 G la Comp. R1 R2 R3 G Phys. data No. la-1 CH 3 Ph CH 3 H m.p. 260-261 OC la-2 CH 3 Ph CH 3
C(O)C(CH
3
)
3 m.p. 159-161*C la-3 CH 3 Ph CH 3 C(O)N- resin
(CH
2
CH
3
)
2 la-4 CH 2
CH
3 Ph CH 2
CH
3 H m.p. >2500C la-5 CH 2
CH
3 Ph CH 2
CH
3
C(O)C(CH
3
)
3 m.p. 162-1640C la-6 CH 2
CH
3 Ph OCH 3 H m.p. 205-207*C la-7 CH 2
CH
3 Ph OCH 3
C(O)C(CH
3
)
3 m.p. 57-59*C la-8 CH 2
CH
3 Ph SCH 3 H m.p. 200-201OC la-9 CH 2
CH
3 Ph SCH 3
C(O)C(CH
3
)
3 m.p. 197-199*C la-10 CH 2
CH
3 Ph S(0) 2
CH
3
C(O)C(CH
3
)
3 m.p. 172-174*C la-11 CH 2
CH
3 Ph CH 2 Ph H m.p. 203-205*C la-12 CH 3 4-CH 2 =CH-Ph CH 3 H (LC/MS: M*= 376) la-13 CH 3 2-Cl-Ph CH 3 H (LC/MS: M*= 384) la-14 CH 3 4-Cl-Ph CH 3 H (LC/MS: M*= 384) la-15 CH 3
CH
2 4-Cl-Ph CH 3
CH
2 H (LC/MS: M*= 412) -49 la-16 CH 3 3-Br-Ph CH 3 H la-17 CH 3 2-CH 3 0-Ph CH 3 H (LC/MS: M*= 380) la-18 CH 3 4-CH 3 0-Ph CH 3 H (LC/MS: M*= 380) la-1 9 CH 3 3-CH 3
CH
2 0- CH 3 H (LC/MS: Ph M*= 394) la-20 CH 3
CH
2 3-CH 3
CH
2 0- CH 3
CH
2 H (LC/MS: Ph M*= 422) la-21 CH 3 4-CH 3 S-Ph CH 3 H (LC/MS: M*= 396) la-22 CH 3 2-CH 3 -Ph CH 3 H (LC/MS: M*= 364) la-23 CH 3 4-CH 3 -Ph CH 3 H (LC/MS: M*= 364) [a-24 CH 3
CH
3 H - 0 la-25 CH 3
CH
2
CH
3
CH
2 H la-26 CH 3 CH 3 H (LC/MS: C, ) M*= 356) la-27 CH 2
CH
3
CH
2
CH
3 H (LC/MS: M*= 384) la-28 CH 2
CH
3 2,4-Cl 2 -Ph CH 2
CH
3 H (LC/MS: M*= 446) la-29 CH 2
CH
3 4-F-Ph CH 2
CH
3 H (LC/MS: M*= 396) la-30 CH 2
CH
3 3-C,4-F-Ph CH 2
CH
3 H (LC/MS: M*= 430) -50 la-31 CH 2
CH
3 3,5-Cl 2 -Ph CH 2
CH
3 H (LC/MS: M*= 446) la-32 CH 2
CH
3 4-CF 3 -Ph CH 2
CH
3 H (LC/MS: M*= 446) la-33 CH 2
CH
3
CH
3
C(O)C(CH
3
)
3 m.p. 139-141*C la-34 CH 3 4-CH 2 =CH-Ph CH 3 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 475) la-35 CH 3 2-Cl-Ph CH 3 C(0)N- (LC/MS:
(CH
2
CHS)
2 M'= 483) la-36 CH 3
CH
3 C(O)N- (LC/MS: lo:u N(CH 2
CH
3
)
2 M*= 499) la-37 CH 3 4-Cl-Ph CH 3 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 483) la-38 CH 3 2-CH 3 0-Ph CH 3 C(O)N- (LC/MS:
(CH
2
CHS)
2 M*= 479) la-39 CH 3 4-CH 3 S-Ph CH 3 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 495) la-40 CH 3 4-CH 3 0-Ph CH 3 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 479) la-41 CH, 3-CH 3
CH
2 0- CH 3 C(O)N- (LC/MS: Ph (CH 2
CH
3
)
2 M*= 493) la-42 CH 3 2-CH 3 -Ph CH 3 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 463) la-43 CH 3 4-CH 3 -Ph CH 3 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 463) la-44 CH 3
CH
3 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 455) la-45 CH 3
CH
3 C(O)N- (LC/MS: --- C (CH 2
CH
3
)
2 M* =455) -51 la-46 CH 3
CH
3 H (LC/MS: M*= 400) la-47 CH 3
CH
3 H (LC/MS: s M*= 356) la-48 CH 3
CH
2 4-CI-Ph CH 3
CH
2 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 511) la-49 CH 3
CH
2 3-CH 3
CH
2 0- CH 3
CH
2 C(O)N- (LC/MS: Ph (CH 2
CH
3
)
2 M*= 521) la-50 CH 2
CH
3 4-F-Ph CH 2
CH
3 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 495) la-51 CH 3
CH
2
CH
3
CH
2 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 483) la-52 CH 3
CH
2
CH
3
CH
2 C(O)N- (LC/MS: ,-- (CH 2
CHS)
2 M*= 483) la-53 CH 2
CH
3 3-CI,4-F-Ph CH 2
CH
3 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 529) la-54 CH 3
CH
2 3,5-C 2 -Ph CH 3
CH
2 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 545) la-55 CH 3
CH
2 2,4-Cl 2 -Ph CH 3
CH
2 C(O)N- (LC/MS:
(CH
2
CH
3
)
2 M*= 545) la-56 CH 2
CH
3
CH
2
CH
3 H (LC/MS: s M*= 384) la-57 CH 3
CH
3 C(O)N- solid -N
(CH
2
CH
3
)
2 la-58 CH 3
CH
3 H solid HN la-59 CH3 CH3 C(O)C(CH3) 3 solid -52 la-60 CH 3
CH
3 H solid la-61 CH 3
CH
3
C(O)C(CH
3 ) 3 m.p. 99-100*C la-62 CH 2
CH
3
CH
2
CH
3
C(O)C(CH
3
)
3 wax --- N la-63 CH 3
CH
3 H solid la-64 CH 2
CH
3
CH
2
CH
3
C(O)C(CH
3
)
3 amorphous la-65 CH 2
CH
3
CH
2
CH
3
C(O)C(CH
3
)
3 m.p. 146-147*C Ia-66 CH 2
CH
3 <-- \ - C H 2
CH
3 H m.p. 2500C N-N la-67 CH 3
CHH
3 H m.p. 250*C -N+ la-68 CH 2
CH
3 CH 2
CH
3
C(O)C(CH
3
)
3 N+ 0 la-69 CH 2
CH
3 S0 3 H CH 2
CH
3 H crystalline -- CH 3 la-70 CH 3
CH
3 C(0)N
(CH
2
CH
3
)
2 la-71 CH 3
CH
3
C(O)N
N_
(CH
2
CH
3
)
2 - 53 Ia-72 OH 3 / CH 3
C(O)N
(CH
2
CH
3
)
2 Ia-73 CH 2
CH
3 - - CH 2
CH
3
C(O)N
(CH
2
CH
3
)
2 Ia-74 CH 2
CH
3 - - / CH 2
CH
3 H Ia-75 OH 3 / CH 3
C(O)C(CH
3
)
3 Ia-76 CH 2 CH1 3 / CH 2
CH
3 H m.p. 2500C N 0 Ia-77 cH 2
CH
3 - -/~ CH 2
CH
3
C(O)C(CH
3
)
3 Ia-78 OH 3
OH
3 H m.p. 284-286C
(CH
2
)
2 000H Ia-79 OH 3
CH
3 H m.p. 230 0 C (decomp.)
(CH
2
)
2
NH
2 Ph = phenyl - 54 Table 2 Compounds of formula
R
1 0 N R2
R
3 0 G lb Comp. R 1
R
2 R3 G Phys. data No. lb-1 CH 3 Ph CH 3 H m.p. 239-240*C lb-2 CH 3 Ph CH 3
C(O)C(CH
3
)
3 resin Ib-3 CH 3 Ph CH 3
C(O)N-(CH
2
CH
3
)
2 resin lb-4 CH 3 Ph CH 3
C(O)O-CH
2
CH
3 m.p. 144-1460C lb-5 CH 3 Ph CH 3
C(O)CH
3 m.p. 198-1990C lb-6 CH 3 Ph CH 3 C(O)cyclopropyl m.p. 104-105 lb-7 H Ph CH 2
CH
3 H m.p. 176-177*C lb-8 H Ph CH 2
CH
3
C(O)C(CH
3
)
3 m.p. 128-130*C lb-9 CH 2
CH
3 Ph CH 2
CH
3 H m.p. >2500C lb-10 CH 2
CH
3 Ph CH 2
CH
3
C(O)C(CH
3
)
3 m.p. 166-1680C lb-11 CH 2
CH
3 Ph SCH 3 H m.p. 170-1720C lb-12 CH 2
CH
3 Ph SCH 3
C(O)C(CH
3
)
3 m.p. 182-1830C lb-13 CH 2
CH
3 Ph OCH 3 H m.p. 148-1500C lb-14 CH 2
CH
3 Ph OCH 3
C(O)C(CH
3
)
3 m.p. 127-1290C lb-15 CH 2
CH
3 Ph C=CSi(CH 3
)
3 H m.p. 150-1520C lb-16 CH 2
CH
3 Ph C-CSi(CH 3
)
3
C(O)C(CH
3
)
3 m.p. 69-710C lb-17 CH 2
CH
3 Ph CmCSi(CH 3
)
3
C(O)N-(CH
2
CH
3
)
2 m.p. 134-1360C lb-18 CH 2
CH
3 Ph C-CH H m.p. 108-111*C lb-19 CH 2
CH
3 Ph C-CH C(O)C(CH 3
)
3 m.p. 134-136*C lb-20 CH 2
CH
3 Ph Br H m.p. 221-2220C lb-21 CH 2
CH
3 Ph Br C(O)C(CH 3
)
3 m.p. 153-1540C -55 lb-22 CH 2
CH
3 Ph Br C(O)N-(CH 2
CH
3
)
2 m.p. 129-131 0 C lb-23 CH 2
CH
3 Ph CH 2 Ph H m.p. 247-249*C lb-24 CH 2
CH
3 Ph CH 2 Ph C(O)C(CH 3
)
3 resin lb-25 CH 3 3-CF 3 -Ph CH 3 H m.p. 225-226*C lb-26 CH 3 3-CF 3 -Ph CH 3
C(O)C(CH
3
)
3 m.p. 197-199 0 C lb-27 CH 3 3-CF 3 -Ph CH 3
C(O)N-(CH
2
CH
3
)
2 Oil Ib-28 CH 3 3-CF 3 -Ph CH 3
C(O)O-CH
2
CH
3 resin lb-29 CH 3 4-F-Ph CH 3 H lb-30 CH 3 4-F-Ph
CH
3
C(O)C(CH
3
)
3 Ib-31 CH 3 4-F-Ph CH 3 C(0)N-(CH 2
CH
3
)
2 Oil Ib-32 CH 3 4-CF 3 -Ph CH 3 H m.p. 294-296*C lb-33 CH 3 4-CF 3 -Ph CH 3
C(O)C(CH
3
)
3 m.p. 160-161 *C lb-34 CH 3 4-CF 3 -Ph CH 3
C(O)N-(CH
2
CH
3
)
2 m.p. 68-70*C lb-35 CH 3 4-CF 3 -Ph CH 3
C(O)OCH
2
CH
3 resin lb-36 CH 3 3-NO 2 -Ph CH 3 H m.p. 219-221 0C lb-37 CH 3 3-NO 2 -Ph CH 3
C(O)C(CH
3
)
3 m.p. 180-1820C lb-38 CH 3 3-NO 2 -Ph CH 3
C(O)N-(CH
2
CH
3
)
2 lb-39 CH 3 4-CH 2 =CH-Ph CH 3 H (LC/MS: M*= 360) Ib-40 CH 3 2-C-Ph CH 3 H (LC/MS: M*= 368) Id-41 CH 3 4-C-Ph CH 3 H (LC/MS: M*= 368) lb-42 CH 2
CH
3 4-CI-Ph CH 2
CH
3 H (LC/MS: M*= 396) lb-43 CH 3 3-Br-Ph CH 3 H (LC/MS: M*= 412) Ib-44 CH 3 2-CH 3 0-Ph CH 3 H (LC/MS: M*= 364) -56 lb-45 CH 3 4-CH 3 0-Ph CH 3 H (LC/MS: M*= 364) Ib-46 CH 3 3-CH 3
CH
2 0-Ph CH 3 H (LC/MS: M*= 378) Ib-47 CH 3
CH
2 3-CH 3
CH
2 0-Ph CH 3
CH
2 H (LC/MS: M*= 406) lb-48 CH 3 4-CH 3 S-Ph CH 3 H (LC/MS: M*= 380) Ib-49 CH 3 2-CH 3 -Ph CH 3 H (LC/MS: M*= 348) lb-50 CH 3 4-CH 3 -Ph CH 3 H (LC/MS: M*= 348) lb-51 CH 3 CH 3 H lb-52 CH 3
CH
2 N CH 3
CH
2 H ,-o lb-53 CH 3 - CH 3 H (LC/MS: 00 M*= 340) Ib-54 CH 3
CH
2 ' CH 3 H lb-55 CH 3 CH 3 H (LC/MS: M*= 384) lb-56 CH 2
CH
3 2,4-Cl 2 -Ph CH 2
CH
3 H (LC/MS: M*= 430) lb-57 CH 2
CH
3 4-F-Ph CH 2
CH
3 H (LC/MS: M*= 380) Ib-58 CH 2
CH
3 3-CI,4-F-Ph CH 2
CH
3 H (LC/MS: M*= 414) lb-59 CH 2
CH
3 3,5-Cl 2 -Ph CH 2
CH
3 H (LC/MS: M*= 430) -57 Ib-60 CH 2
CH
3 4-CF 3 -Ph CH 2
CH
3 H (LC/MS: M*= 430) Ib-61 CH 3 Ph CH 3 o UV: - ' s 212.1 nm 270.9 nm Ib-62 CH 3 Ph CH 3 0 UV: OCH, 3 209.7 nm 0 270.9 nm Ib-63 CH 3 Ph CH 3 0 UV: -KOCHa 207.4 nm 270.9 nm Ib-64 CH 3 Ph CH 3 Ph UV: - Ko 207.4 nm 270.9 nm Ib-65 CH 3 Ph CH 3 C(O)nC 7
H
1 5 UV: 205.0 nm 270.9 nm Ib-66 CH 3 Ph CH 3 0 UV: 207.4 nm 268.5 nm Ib-67 CH 3 Ph CH 3 0' UV: CHa 205.0 nm 270.9 nm Ib-68 CH 3 Ph CH 3 UV: 270.9 nm Ib-69 CH 3 Ph
CH
3 Ib-70 CH 3 2-C-Ph CH 3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 467) Ib-71 CH 3
CH
3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 483) -58 lb-72 CH 3 4-CI-Ph CH 3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 467) Ib-73 CH 3 2-CH 3 0-Ph CH 3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 463) lb-74 CH 3 4-CH 3 S-Ph CH 3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 479) Ib-75 CH 3 4-CH 3 0-Ph CH 3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 463) Ib-76 CH 3 3-Br-Ph CH 3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 511) Ib-77 CH 3 3-CH 2
CH
3 0-Ph CH 3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 477) Ib-78 CH 3 2-CH 3 -Ph CH 3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 447) Ib-79 CH 3 4-CH 3 -Ph CH 3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 447) Ib-80 CH 3
CH
3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 439) lb-81 CH 3
CH
3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 439) Ib-82 CH 3 nlx\ CH 3 H (LC/MS: M*= 340) lb-83 CH 2
CH
3 4-CI-Ph CH 2
CH
3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 495) Ib-84 CH 2
CH
3 3-CH 3
CH
2 0-Ph CH 2
CH
3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 505) Ib-85 CH 2
CH
3 4-F-Ph CH 2
CH
3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M*= 479) lb-86 CH 2
CH
3 - CH 2
CH
3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: 00~2 M*= 467) - 59 Ib-87 CH 2
CH
3
CH
2
CH
3
C(O)N-(CH
2
CH
3 ) 2 (LC/MS: s ~M+= 467) Ib-88 CH 2
CH
3 3-CI,4-F-Ph CH 2
CH
3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M+ = 513) Ib-89 CH 2
CH
3 3,5-C1 2 -Ph CH 2
CH
3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M+ = 529) Ib-90 CH 2
CH
3 2,4-C1 2 -Ph CH 2
CH
3
C(O)N-(CH
2
CH
3
)
2 (LC/MS: M+ = 529) Ib-91 CH 2
CH
3 4-CF 3 -Ph CH 2
CH
3
C(O)N-(CH
2
CH
3
)
2 Ib-92 CH 2
CH
3
CH
2
CH
3 H (LC/MS: 00~ M+ = 368) Ib-93 CH 2
CH
3 01\ CH 2
CH
3 H (LC/MS: s ~M+= 368) Ib-94 CH 3
CH
3 H m.p. 224-2260C
(CH
2
)
2 COOH * Ph = phenyl - 60 Table 3 Compounds of formula Ri0 R O R2 R5
R
3 0 G Ic Comp. R 1
R
2
R
3 R4 R5 G Phys. data No. Ic-1 CH 3 Ph CH 3
CH
3
CH
3 C(O)N- resin
(CH
2
CH
3
)
2 Ic-2 CH 2
CH
3 Ph OCH 3 H (CH 2
)
3 0H H m.p. 91-93C Ic-3 CH 3 Ph CH 3
CH
3
CH
3 H m.p. 1970C Ph = phenyl Table Compounds of formula R1 O O R3 O Id Comp. R 1
R
3 Phys. No. data Id-1 CH 3
CH
3 m.p. 68 690C -61 Id-2 CH 2
CH
3
SCH
3 oil Id-3 CH 2
CH
3
OCH
3 oil Id-4 CH 2
CH
3
CH
2
CH
3 oil Id-5 CH 2
CH
3
CH
2 Ph oil Id-6 CH 2
CH
3 Br oil Id-7 CH 2
CH
3 C=CSi(CH 3
)
3 oil Id-8 CH 2
CH
3 H oil Ph = phenyl Table 5 Ri O R40 N 'nR42 R2-C R X 1 - N R2 O
RR
3 0 G le Comp. R 1
R
2
R
3 G R4 R4 R 42
R
43 Phys. data No. le-1 CH 3
CH
2 Ph CH 3 O H H H -(CH 2
)
2 - m.p.196-197 0 C le-2 CH 3
CH
2 Ph CH 3 O H CH 3
CH
2 H H H m.p. 133-135 0 C le-3 CH 3
CH
2 Ph CH 3 O H CH 3
CH
3 H H m.p. 139-145 0 C le-4 CH 3
CH
2 Ph CH 3 O H CH 3
CH
3 H H m.p. 119*C le-5 CH 3
CH
2 Ph CH 3 O C(O)- CH 3
CH
2 H H H crystalline
C(CH
3
)
3 Ph = phenyl - 62 Table 6 Compounds of formula R, 0 N R2
R
3 0 G If Comp. No. R 1
R
2 R3G Phys. data If-i CH 3
CH
2 Ph CH 3 0 H m.p. 184-188 0 C Ph = phenyl Table 7 Compounds of formula ~N F R2 F
R
3 0 G Ig Comp. No. R 1 R2 R3 G Phys. data Ig-1 CH 3
CH
2 Ph CH 3 0 H m.p. 147-149*C Ph = phenyl - 63 Table 8 Compounds of formula 1 0 N R2 R Rh1 -C 3 PhC0HCOCC331 M CC3 G lh Comp R 1
R
2
R
3 R G Phys. data No. lh-1 -OCH 3 Ph C 2
H
5 OH C(O)C(CH 3
)
3 1 H NMR (CDCIS, 300 MHz) 8 = 7.6 (d, 2H); 7.42 (t, 2H); 7.34 (t, 1 H); 7.1 (s, 1H); 6.88 (s, 1H); 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) lh-2 CH 2
CH
3 Ph OCH 3
H
3 C-O- C(O)C(CH 3
)
3 1 H NMR (CDCI 3 ,
CH
2
CH
2 -0- 300 MHz) 6 = 7.6 (d, 2H); 7.42 (t, 2H); 7.34 (t, 1 H); 7.1 (s, 1H); 6.88 (s, 1H); 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) lh-3 CH 2
CH
3 Ph CH 2 - H 3 C-0- C(O)C(CH 3
)
3
CH
3
CH
2
CH
2
-O
lh-4 CH 2
CH
3 Ph ethynyl H 3 C-O- C(O)C(CH 3
)
3
CH
2
CH
2
-O
lh-5 CH 2
CH
3 Ph CH 2 - H 3
C-CH
2 -0- C(O)C(CH 3
)
3
CH
3
CH
2
CH
2
-O
lh-6 CH 3 Ph CH 3
H
3 C-O- C(O)C(CH 3
)
3
CH
2
CH
2
-O
Ph = phenyl Example B2: Postemergence herbicidal action 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 97/34485) of the test compound or an emulsion (prepared from an emulsifiable concentrate (Example F1, c) according to WO 97/34485) of the test compound is applied by spraying at an optimum concentration (500 litres of water/ha). 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.
- 65 Table B2: Compound Rate of application Avena Lolium Setaria Sinapis (g/ha) lb-1 2000 1 2 1 2 lb-4 2000 1 3 1 2 lb-2 2000 3 3 1 2 la-33 2000 2 2 1 2 lb-66 2000 1 2 1 2 la-4 2000 1 1 1 2 la-5 2000 1 1 1 2 lb-9 2000 1 1 1 2 lb-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 lb-13 2000 1 1 1 2 lb-14 2000 1 1 1 2 lb-28 2000 1 2 1 2 la-8 2000 2 1 1 2 lb-20 2000 2 2 1 2 lb-21 2000 1 1 1 2 lb-69 2000 2 2 1 2 lb-18 2000 1 1 1 2 lb-19 2000 1 1 1 2 le-1 2000 1 1 1 2 If-1 2000 1 1 1 3 In that test, the compounds of formula I exhibit strong herbicidal action. The same results are obtained when the compounds of formula I are formulated according to the other Examples of WO 97/34485.

Claims (10)

1. A compound of formula I R, 0 NR4 R 2 \ R5 R 3 0 G wherein R 1 and R 3 are each independently of the other hydrogen, halogen, nitro, cyano, C-C 4 alkyl, C 2 C 4 alkenyl, C 2 C 4 alkynyl, tri(C-C 4 alkylsilyl)-C 2 -C 4 alkynyl, C-C 4 haloalkyl, C 2 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, halo-substituted C 3 -C 6 cycloalkyl, benzyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthio alkyl, hydroxy, mercapto, C-C 6 alkoxy, C 3 -C 6 alkenyloxy, 3 -C 6 alkynyloxy, C-C 4 alkyl carbonyl, C-C 4 alkoxycarbonyl, C-C 4 alkylthio, C-C 4 alkylsulfinyl, C-C 4 alkylsulfonyl, amino, C-C 4 alkylamino, di(C-C 4 alkyl)amino, C-C 4 hydroxyalkyl, formyl, C-C 4 alkylcarbonylamino or C-C 4 alkylsulfonylamino, R 2 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, C 3 -Cecycloalkyl, hydroxy, mercapto, amino, amino-C-C 6 alkyl, carboxyl-C-C 6 alkyl, 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 C 1 C 6 alkyl, CrC 6 alkoxy, hydroxy-C-C 6 alkyl, C-C 6 alkoxy-C-C 6 alkyl, C-C 6 alkoxy-C-C 6 alkoxy, C-C 6 alkylcarbonyl, C-C 6 alkylthio, C-C 6 alkylsulfinyl, C-C 6 alkylsulfonyl, mono-C-C 6 alkylamino, di-C-C 6 alkylamino, C-C 6 alkylcarbonylamino, C-C 6 alkylcarbonyl (C-C 6 alkyl)amino, C 2 -C 6 alkenyl, C 3 -C 6 alkenyloxy, hydroxy-C 3 -C 6 alkenyl, C-C 6 alkoxy-C 3 -C 6 alkenyl, C-C 6 alkoxy-C 3 -C 6 alkenyloxy, C 2 -C 6 alkenylcarbonyl, C 2 -C 6 alkenylthio, C 2 -C 6 alkenyl sulfinyl, C 2 -C 6 alkenylsulfonyl, mono- or di-C 2 -C 6 alkenylamino, C-C 6 alkyl-(C 3 -C 6 alkenyl) amino, C 2 -C 6 alkenylcarbonylamino, C 2 -C 6 alkenylcarbonyl-(C-Cealkyl)amino, C 2 -C 6 alkynyl, C 3 C 6 alkynyloxy, hydroxy-C 3 -C 6 alkynyl, C-C 6 alkoxy-C 3 -C 6 alkynyl, C-C 6 alkoxy-C 4 -C 6 alkynyloxy, C 2 -C 6 alkynylcarbonyl, C 2 -C 6 alkynylthio, C 2 -C 6 alkynylsulfinyl, C 2 -Calkynylsulfonyl, - 67 mono- or di-C 3 C 6 alkynylamino, C 1 -Cealkyl-(C 3 C 6 alkynyl)amino, C 2 -C 6 alkynylcarbonylamino or by C 2 -C 6 alkynylcarbonyl-(C-C 6 alkyl)amino; and/or for the phenyl ring, the naphthyl ring and the 5- or 6-membered aromatic ring to be substituted by halo-substituted Cr-C 6 alkyl, halo-substituted C 1 C 6 alkoxy, halo-substituted hydroxy-C-C 6 alkyl, halo-substituted Cr C 6 alkoxy-Cr-C 6 alkyl, halo-substituted C 1 rC 6 alkoxy C 1 rC 6 alkoxy, halo-substituted C-C 6 alkylcarbonyl, halo-substituted C-C 6 alkylthio, halo substituted C-C 6 alkylsulfinyl, halo-substituted C-C 6 alkylsulfonyl, halo-substituted mono C 1 -C 6 alkylamino, halo-substituted di-C-C 6 alkylamino, halo-substituted C-C 6 alkylcarbonyl amino, halo-substituted C-Cealkylcarbonyl-(C-C 6 alkyl)amino, halo-substituted C 2 -C 6 alkenyl, halo-substituted C 3 C 6 alkenyloxy, halo-substituted hydroxy-C 3 -C 6 alkenyl, halo-substituted Cr C 6 alkoxy-C 2 -C 6 alkenyl, halo-substituted C 1 C 6 alkoxy-C 3 C 6 alkenyloxy, halo-substituted C 2 -C 6 alkenylcarbonyl, halo-substituted C 2 -C 6 alkenylthio, halo-substituted C 2 C 6 alkenyl sulfinyl, halo-substituted C 2 -C 6 alkenylsulfonyl, halo-substituted mono- or di-C 3 C 6 alkenyl amino, halo-substituted C 1 rC 6 alkyl-(C 3 C 6 alkenyl)amino, halo-substituted C 2 C 6 alkenyl carbonylamino, halo-substituted C 2 -C 6 alkenylcarbonyl-(C-C 6 alkyl)amino, halo-substituted C 2 C 6 alkynyl, halo-substituted C 3 C 6 alkynyloxy, halo-substituted hydroxy-C 3 -C 6 -alkynyl, halo substituted C 1 -C 6 alkoxy-C 3 Cealkynyl, halo-substituted C 1 C 6 alkoxy-C 4 -C 6 alkynyloxy, halo substituted C 2 -Cealkynylcarbonyl, halo-substituted C 2 -C 6 alkynylthio, halo-substituted C 2 -C 6 alkynylsulfinyl, halo-substituted C 2 -C 6 alkynylsulfonyl, halo-substituted mono- or di-C 3 -C 6 alkynylamino, halo-substituted C-C 6 alkyl-(C 3 Cealkynyl)amino, halo-substituted C 2 -C 6 alkynylcarbonylamino or by halo-substituted C 2 -C 6 alkynylcarbonyl(C-C 6 alkyl)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 COOR 50 , CONR 51 , SO 2 NR, 3 R. 4 or SO 2 OR.s, wherein R 5 0 , R 5 1 , R 52 , R 5 3 , R 54 and R 5 , are each independently of the others hydrogen, C-C 6 alkyl, C 2 C 6 alkenyl or C-C 6 alkynyl, or C-C 6 alkyl, C 2 C 6 alkenyl or C 3 C 6 alkynyl each substituted by halogen, hydroxy, alkoxy, mercapto, amino, cyano, nitro, alkylthio, alkylsulfinyl or by alkylsulfonyl, R 4 and R 5 are each independently of the other hydrogen, Cr-C 12 alkyl, C-Cl 2 haloalkyl, C 1 rC 1 2 hydroxyalkyl, C 3 -Cealkenyl, C 3 -C 8 alkynyl, C-C 1 oalkoxy-C-C 8 alkyl, or C 3 C 8 alkyl that may contain one or two oxygen atoms, C-C 1 oalkylthio-C-C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cyclo alkyl that contains 1 or 2 hetero atoms selected from the group oxygen and sulfur, - 68 C 3 -Cahalocycloalkyl, C 3 -C 8 halocycloalkyl that contains 1 or 2 hetero atoms selected from the group oxygen and sulfur, phenyl, or phenyl substituted by halogen, C 1 -C 6 alkyl, C 1 -C 6 halo alkyl, C-C 6 alkoxy, C-C 6 haloalkoxy, nitro or by cyano, or R 4 and R 5 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 R 4 and R., 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 NR 6 groups, wherein R 6 is hydrogen, C-C 4 alky, C-C 6 alkylcarbonyl, C 1 C 6 alkylsulfonyl, C 3 -C 6 alkenyl or C3-C6 alkynyl, and which may be substituted by halogen, hydroxy, C-C 1 oalkyl, C-C 1 oalkoxy, C-C 1 ohaloalkyl, C 3 -C 8 cycloalkyl, phenyl or by benzyl; or which may be substituted by phenyl substituted by halogen, C-C 6 alkyl, C-Cehaloalkyl, C 3 -C 6 cycloalkyl, hydroxy, C 1 C 6 alkoxy, C-C 6 alkoxy-Cr-C 6 alkoxy, C 1 C 6 haloalkoxy or by nitro, or by benzyl substituted by halogen, C-C 6 alkyl, C-C 6 haloalkyl, C 3 -C 6 cycloalkyl, hydroxy, C 1 C 6 alkoxy, CrC 6 haloalkoxy or by nitro; or which may be substituted by CH 2 -heteroaryl, wherein the aryl moiety has 5 or 6 members, or by halo-, C-C 6 alkyl-, C-C 6 haloalkyl-, C-C 6 cycloalkyl-, hydroxy-, C-C 6 alkoxy-, C-C 6 halo alkoxy- or nitro-substituted CH 2 -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-C 6 alkyl-, C-C 6 haloalkyl-, hydroxy-, C-C 6 alkoxy-, C-C 6 haloalkoxy-, 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(X 1 )-R 3 0 , -C(X 2 )-X 3 -R 3 1 , -C(X 4 )-N(R 32 )-R 33 , -SO 2 -R4, an alkali metal cation, alkaline earth metal cation, sulfonium cation or ammonium cation, -P(X,)(R 3 ,)-R 36 or -CH 2 XC(X 7 )-R 37 , -CH 2 X 8 C(X 9 )-X 10 -R38, -CH 2 X 11 C(X 12 )-N(R 3 9 )-R4e or -CH 2 X 13 SO 2 -R 41 , wherein X1, X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 X 9 , X1 0 , X1 1 , X1 2 and X 1 3 are each independently of the others oxygen or sulfur, and R 3 0 , R 31 , R 32 , R 33 , R34, R 35 , R 36 , R 37 , R38, R 3 9 , R40 and R 4 1 are each independently of the others hydrogen, C-C 2 alkyl or CrC 12 alkyl substituted by halogen, formyl, cyano, nitro, tri-C-C 6 alkylsilyl, hydroxy, C-C 6 alkoxy, C-C 6 alkoxycarbonyl, amino, C 1 -C 6 alkylamino, di-C-C 6 alkylamino, mercapto, C-C 6 alkylthio, C-C 6 alkylcarbonyl, C-C 6 alkylcarbonylthio, C-C 6 alkylcarbonylamino, C-Calkoxycarbonylamino, C-C 6 alkyl- - 69 aminocarbonylamino, C-C 6 alkylthiocarbonyloxy, C-C 6 alkylthiocarbonylamino, CC6 alkoxythiocarbonyl, aminothiocarbonyl, 01-C 6 alkylthiocarbonyloxy, 0-C 6 alkylthiocarbonyl amino, 1-C 6 alkoxythiocarbonylamino, C-C 6 alkylsulfinyl, C-C 6 alkylsulfonyl, C-C 6 alkyl sulfonyloxy, C-C 6 alkylsulfonylamino, C-C 6 alkoxyimino, hydroxyimino, heteroaryl, benzyloxy, phenoxy or by halophenoxy; or C 2 -Cl 2 alkenyl, C 2 -C 12 alkenyl, C 3 -C 2 cycloalkyl, C 3 -C 8 cycloalkyl substituted by halogen, C-C 6 haloalkyl, C-C 6 alkyl, C-C 6 alkoxy, 1-C 6 alkylcarbonyloxy, 01-C 6 thioalkyl, C-C 6 alkylcarbonyl thio, 0-C 6 alkylamino, 0-C 6 alkylcarbonylamino, tri-C-C 6 alkylsilyl or by tri-C-C 6 alkylsilyloxy; phenyl or phenyl substituted by alkoxy, halogen, C-C 6 haloalkyl, nitro, cyano, C-C 6 ayI, Cl-C 6 alkylcarbonyloxy, C-C 6 thioalkyl, C-C 6 alkylcarbonylthio, C-C 6 alkylamino, C-C 6 alkyl carbonylamino, tri-C-C 6 alkylsilyl or by tri-C-C 6 alkylsilyloxy; heteroaryl or heteroaryl substituted by halogen, C-C 6 haloalkyl, nitro, cyano, C-C 6 alky, C-C 6 alkoxy, C-C 6 alkyl carbonyloxy, C-C 6 thioalkyl, C-C 6 alkylcarbonylthio, C-C 6 alkylamino, C-C 6 alkylcarbonyl amino, tri-C-C 6 alkylsilyl or by tri-C-C 6 alkylsilyloxy; and R 34 is additionally C 2 -C2alkenyl or C 2 -C 20 alkenyl substituted by halogen, C-C 6 alkylcarbonyl, Cl-C 6 alkoxycarbonyl, C-C 6 alkylcarbonyloxy, C-Cealkoxy, Cl-C 6 thioalkyl, C-C 6 alkylthio carbonyl, C,-C 6 alkylcarbonylthio, C-C 6 alkylsulfonyl, C-C 6 alkylsulfinyl, C-C 6 alkylamino sulfonyl, di-C-C 6 alkylaminosulfonyl, C-Calkylsulfonyloxy, C-C 6 alkylsulfonylamino, C-C alkylamino, di-C-C 6 alkylamino, C-C 6 alkylcarbonylamino, di-C-C 6 alkylcarbonylamino, cyano, C 3 -C 8 cycloalkyl, C 3 -Caheterocyclyl, tri-C-C 6 alkylsilyl, tri-C,-C 6 alkylsilyloxy, phenyl, substituted phenyl, heteroaryl or by substituted heteroaryl; or C 2 -Coalkynyl or C 2 -C2alkynyl substituted by halogen, C-C 6 alkylcarbonyl, C-C 6 alkoxy carbonyl, C-C 6 alkylcarbonyloxy, C-C 6 alkoxy, C-C 6 thioalkyl, C-C 6 alkylthiocarbonyl, CrC6 alkylcarbonylthio, C-C 6 alkylsulfonyl, C-C 6 alkylsulfinyl, C-C 6 alkylaminosulfonyl, di-CrC-6 alkylaminosulfonyl, C-C 6 alkylsulfonyloxy, C-C 6 alkylsulfonylamino, C-C 6 alkylamino, di C,-C 6 alkylamino, C-C 6 alkylcarbonylamino, di-C-C 6 alkylcarbonylamino, cyano, C-C7 cycloalkyl, C 3 -C 7 heterocyclyl, tri-C-C 6 alkylsilyl, tri-C-C 6 alkylsilyloxy, phenyl, substituted phenyl, heteroaryl or by substituted heteroaryl; or C 3 -C 8 cycloalkyl or C 3 -Ccycloalkyl substituted by halogen, C-C 6 haloalkyl, C-C 6 alkyl, CrC6 alkoxy, C-C 6 alkylcarbonyloxy, C-C 6 thioalkyl, C-C 6 alkylcarbonylthio, C-C 6 alkylamino, Cl-C 6 alkylcarbonylamino, tri-C-C 6 alkylsilyl or by tri-C,-C 6 alkylsilyloxy; or heteroaryl or heteroaryl substituted by halogen, C-C 6 haloalkyl, nitro, cyano, C-C 6 alkyl, - 70 C 1 -C 6 alkoxy, C 1 -C 6 alkylcarbonyloxy, C1-C 6 thioalkyl, C 1 -C 6 alkylcarbonylthio, C 1 -C 6 alkylamino, C1-C 6 alkylcarbonylamino, tri-C 1 -C 6 alkylsilyl or by tri-C 1 -C 6 alkylsilyloxy; 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 1.
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 Ill.
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 -71 RO Ro0 R R3 2 XIX, wherein Ro is OR 7 , OR 8 , NR 7 R 9 , NR 8 R 1 o or cyano and Roo is hydrogen, OR 7 , OR 8 , NR 7 R 9 , NR 8 R 1 O or cyano, and R 1 , R 2 and R 3 and R 7 to R 1 0 are as defined in claim 1, but R 1 and R. are not simultaneously hydrogen.
9. A compound of formula Vill Hal R1 R3 R2 Vill, wherein R 1 , R 2 and R 3 are as defined in claim 1, and Hal is chlorine, bromine or iodine, Hal being other than iodine when R 1 and R 3 are methyl and R 2 is phenyl.
10. A process for the preparation of a hydrazine of formula 16 H N (CH) I X HN(CHqm" 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 - 72 R CO- N (CH) 000 | x R CO-N,,(C~,,, 000 -- - N C F15 15, wherein Rooo is C 1 -C 4 alkyl and n, m and X are as defined, is reacted in an anhydrous alcohol with an acyl halide or with a hydrohalic acid.
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