WO2005013696A1 - Method of controlling weeds in transgenic crops - Google Patents
Method of controlling weeds in transgenic crops Download PDFInfo
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- WO2005013696A1 WO2005013696A1 PCT/EP2004/008443 EP2004008443W WO2005013696A1 WO 2005013696 A1 WO2005013696 A1 WO 2005013696A1 EP 2004008443 W EP2004008443 W EP 2004008443W WO 2005013696 A1 WO2005013696 A1 WO 2005013696A1
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- Prior art keywords
- crc
- alkyl
- alkoxy
- substituted
- halogen
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- 0 COc1cc(*)ccc1 Chemical compound COc1cc(*)ccc1 0.000 description 7
- DHXVGJBLRPWPCS-UHFFFAOYSA-N C1CCOCC1 Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- FNKSTXGVEUSZJJ-UHFFFAOYSA-N CN1COCC1 Chemical compound CN1COCC1 FNKSTXGVEUSZJJ-UHFFFAOYSA-N 0.000 description 1
- MVKDNXIKAWKCCS-UHFFFAOYSA-N Cc(cccn1)c1O Chemical compound Cc(cccn1)c1O MVKDNXIKAWKCCS-UHFFFAOYSA-N 0.000 description 1
- DVGNYVVFWIWKON-UHFFFAOYSA-N Cc(cccn1)c1OC Chemical compound Cc(cccn1)c1OC DVGNYVVFWIWKON-UHFFFAOYSA-N 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N Cc1cc(O)ccc1 Chemical compound Cc1cc(O)ccc1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- SJZAUIVYZWPNAS-UHFFFAOYSA-N Cc1ccc(C)c(OC)c1 Chemical compound Cc1ccc(C)c(OC)c1 SJZAUIVYZWPNAS-UHFFFAOYSA-N 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N Cc1ccccc1O Chemical compound Cc1ccccc1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- CUMCMYMKECWGHO-UHFFFAOYSA-N Cc1n[o]cc1 Chemical compound Cc1n[o]cc1 CUMCMYMKECWGHO-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N O=C1OCCN1 Chemical compound O=C1OCCN1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action
-
- 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
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/10—Sulfones; Sulfoxides
-
- 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
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
-
- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
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- 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
Definitions
- the present invention relates to the use of herbicidally active compounds from the class of HPPD (4-hydroxyphenylpyruvate-dioxygenase) inhibitors in specific pest-resistant and/or fungus-resistant fransgenic useful plant crops, especially in pest-resistant fransgenic maize crops.
- HPPD 4-hydroxyphenylpyruvate-dioxygenase
- herbicides can result in considerable damage also being caused to the crop plants, for example in dependence upon the concentration of the herbicide and the mode of its application, the crop plant, the nature of the soil and the climatic conditions, such as period of exposure to light, temperature and amounts of precipitation.
- Selective weed control can be achieved, however, by using the herbicide in crops in which the useful plant has been rendered more or less resistant to the phytotoxic action of the herbicide by means of breeding methods or genetic techniques.
- Bt maize resistant to European corn borer
- Bt cotton resistant to cotton boll weevil
- Bt potatoes resistant to Colorado beetle
- Bt toxins are proteins formed naturally by Bacillus thuringiensis soil bacteria (Bt soil bacteria).
- Bt soil bacteria Bacillus thuringiensis soil bacteria
- the present invention relates also to a herbicidal and plant-growth-inhibiting composition for controlling undesirable plant growth in pest-resistant and/or fungus-resistant transgenic useful plant crops, which comprises a herbicidally effective amount of at least one herbicide selected from the class of HPPD inhibitors, on an inert carrier.
- Herbicides from the class of HPPD inhibitors that are preferred for the method according to the invention and for the composition according to the invention are compounds of formula I
- Q is an organic substituent which is so chosen that the compound of formula I has a pK value of from 1 to 5;
- D is hydrogen or R 3 ;
- E is hydrogen or R 4 ;
- D and E together are C 2 -C 3 alkylene which can be mono- or poly-substituted by R 6 ;
- A is C C 2 alkylene which can be mono- or poly-substituted by R 5 ; or A may additionally be carbonyl, oxygen or -N-R 7 - when D and E are other than C 2 -C 3 alkylene;
- R t , R 2 , R 3 , R 4 , R 5 and R 6 are each independently of the others hydrogen, C 1 -C 4 alkyl, phenyl,
- R 2 and R 4 together form a C 2 -C 4 alkylene chain which can be interrupted by oxygen and/or carbonyl and/or sulfur, with the proviso that the oxygen and sulfur atoms are separated by at least one methylene group;
- R 7 is CrC alkyl, alkoxycarbonyl or C-
- Ro 36 is hydroxy, O " M + , wherein M + is an alkali metal cation or ammonium cation, halogen,
- Ro 36 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy, benzoyloxy or benzoyl-d-C 6 alkoxy, wherein the phenyl groups can in turn be substituted one or more times by halogen, nitro, cyano, d-C 4 alkyl, d-C- 4 haloalkyl, C- ⁇ -C - alkoxy and/or C ⁇ -C haloalkoxy, or R 036 is a group Het 07 -thio, Het 08 -sulfinyl, Het 09 -sulfonyl, Het 0 ⁇ 0 -(CO)O or Het 0 n-N(R 047 ); wherein
- Het 07 , Het 08 , Het 09 , Het 0 ⁇ 0 and Het 011 are each independently of the others a five- to ten- membered monocyclic or annellated bicyclic ring system which may be aromatic or partially saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, and each ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system itself can be substituted by d-C 6 alkyl, d-C 6 - haloalkyl, d-C 6 alkoxy, C C 6 haloalkoxy, d-C 6 alkylthio, d-C 6 alkylsulfinyl, d-C 6 alkylsulfonyl, di(d-C 4 alkyl)aminosulfonyl, di(d-C 4 alkyl)amino, halogen, cyano, nitro or by phenyl, and the
- R 037 and R 038 together or R 039 and R 04 o together or R 0 ⁇ and R 042 together or R 0 3 and R 0 4 together are pyrrolidino, piperidino, morpholino or thiomorpholino, which can be mono- or poly-substituted by methyl groups; or T is T 2 wherein
- R 34 is hydrogen, C C 4 alkyl, C ⁇ -C 4 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl or benzyl, it being possible for the phenyl group to be substituted one or more times by d-C 6 alkyl, C ⁇ -C 6 haloalkyl, C C 6 alkoxy, C C 6 haloalkoxy, halogen, cyano, hydroxy and/or nitro;
- R 35 is hydrogen, d-C alkyl, d-C 4 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl or benzyl, it being possible for the phenyl group to be substituted one or more times by d-C- 6 alkyl, d-C 6 haloalkyl, d-C 6 alkoxy, d-C- 6 haloalkoxy, halogen, cyano, hydroxy and/or nitro;
- R 36 is hydroxy, O " M + , wherein M + is an alkali metal cation or ammonium cation, halogen, d-C ⁇ 2 alkylsulfonyloxy, amino, d-C 4 alkylthio, d-C 12 alkylsulfinyl, d-C 12 alkylsulfonyl, C 1 -C 12 - haloalkylthio, d-C ⁇ 2 haloalkylsulfinyl, CrC 12 haloalkylsulfonyl, CrC 6 alkoxy-C ⁇ -C 6 alkylthio, CrC ⁇ alkoxy-d-Cealkylsulfinyl, d-C 6 alkoxy-C ⁇ -C 6 alkylsulfonyl, C 3 -C 12 alkenylthio, C 3 -C 12 - alkenylsulfinyl, C 3 -C 12 alkenyl
- R 37 and R 38 together or R 39 and R 40 together or R 41 and R 2 together or R 43 and R ⁇ together are pyrrolidino, piperidino, morpholino or thiomorpholino, which can be mono- or poly- substituted by methyl groups; or T is T 3
- R 49 is C C 4 alkyl, d-C 4 haloalkyl, C 3 -C 6 cycloalkyl or halo-substituted C 3 -C 6 cycloalkyl;
- Z 01 is a chemical bond, S, SO or SO 2 ;
- R 50 is hydrogen or d-C 3 alkylene which can be substituted by the following substituents: halogen, hydroxy, d-C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, d-C 6 alkoxy-
- R 045 is d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 cycloalkyl or halo-substituted C 3 -C 6 cycloalkyl; and their agronomically acceptable salts, isomers and enantiomers.
- the compounds of formula I also include the salts which such compounds are able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
- alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium.
- amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C C 18 aIkylamines, d-C hydroxyalkylamines and C 2 -C 4 - alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octyl- amine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonyl- amine, methylpentadecylamine, methyloctadecylamine, methyl
- formula I also includes the enolised forms of formulae la, lb, lc and Id wherein M is hydrogen or a metal ion or an ammonium ion.
- compounds of formula I may also contain asymmetric carbon atoms, for example in the case of the carbon atom carrying R-i, D and A, all stereoisomeric forms are also included.
- Q is especially an organic substituent which is so chosen that the compound of formula I has a pK value of from 2.5 to 4.
- the organic substituent Q may be an inert substituent of any desired structure, provided that the compounds of formula I retain their action as HPPD inhibitors.
- Q is preferably a mono- or poly-substituted phenyl, pyridyl or heteroaryl group, especially 2- benzoyl, 2-isonicotinoyl and 2-nicotinoyl derivatives, the substitution pattern of those groups being freely selectable provided that the compounds of formula I retain their action as HPPD inhibitors.
- HPPD inhibitors are compounds of formula I wherein Q is Q 1
- Ai is methine, C(Ra ⁇ ) or N(O) p ; p is O or 1 ;
- Ra ! is hydrogen, d-C 6 alkyl, hydroxy, C ⁇ -C 6 alkoxy, d-C-ehaloalkoxy, C 3 -C 6 alkenyloxy, C 3 -
- Rai is a three- to ten-membered monocyclic ring system or, together with Ra 2 or Ra 5 , annellated mono- or bi-cyclic ring system which may be interrupted by oxygen, sulfur, SO,
- -CH CH-, -C ⁇ C-, -CH 2 O-.
- -CH 2 N(d-C 4 alkyl)-, -CH 2 S-, -CH 2 SO- or -CH 2 SO 2 - group and the ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system can itself be mono-, di- or tri-substituted by C ⁇ -C 6 alkyl, d-C- 6 - haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, d-C 6 alkoxy,
- X 6 is a d-C 6 alkylene, C 3 -C 6 alkenylene or C 3 -C 6 alkynylene chain which can be mono- or poly-substituted by halogen and/or by X 8 , the unsaturated bonds of the chain not being bonded directly to the substituent X 5 ;
- X 8 is hydroxy, d-C 6 alkoxy, C 3 -C 6 cycloalkyloxy, d-Cealkoxy-Cj-Cealkoxy, C C 6 alkoxy-d-C 6 - alkoxy-d-C 6 alkoxy or C ⁇ -C 2 alkylsulfonyloxy;
- X 5 is oxygen, -O(CO)-, -(CO)O-, -O(CO)O-, -N(d-C 4 alkyl)-O-, -O-N(d-C 4 alkyl)-, thio, sulfinyl, sulfonyl, -SO 2 N(C C 4 alkyl)-, -N(C C 4 alkoxy)SO 2 -, -N(C 1 -C 4 alkyl)SO 2 -,
- Ra 6 is hydrogen, d-C 4 alkyl, d-C 4 alkylthio-d-C 4 carbonyl, C ⁇ -C 4 alkylsulfinyl-d-C 4 carbonyl, C ⁇ -C 4 alkylsulfonyl-d-C 4 carbonyl, C ⁇ -C 4 alkoxycarbonyl, C-j-C 4 alkylcarbonyl, phenylcarbonyl or phenyl, it being possible for the phenyl groups in turn to be substituted by d-C 4 alkyl.
- d-C 4 haloalkyl d-C 4 alkoxy, d-C 4 haloalkoxy, d-C 4 alkylcarbonyl, C ⁇ -C 4 alkoxycarbonyl, d-C 4 alkylamino, di-d-C 4 alkylamino, d-C 4 alkyl-S-, d-C 4 alkyl-SO-, d-C 4 alkyl-SO 2 , d-C 4 alkyl-S(O) 2 O, d-C 4 haloalkyl-S-, C C 4 haloalkyl-SO, C 1 -C 4 haloalkyl-SO 2 , C C 4 halo- alkyl-S(O) 2 O, d-C 4 alkyl-S(O) 2 NH, d-C 4 alkyl-S(O) 2 N(d-C 4 alkyl), halogen, nitro or by cyano; Ra 7 is CrC 4 al
- Ra 2 is hydrogen, C C 6 alkyl, d-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, vinyl substituted by d-C 2 alkoxycarbonyl or by phenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, ethynyl substituted by trimethylsilyl, hydroxy, C 1 -C 2 alkoxy, d-C 2 alkoxycarbonyl or by phenyl, C 3 -C 6 allenyl, C 3 -C 6 - cycloalkyl, halo-substituted C 3 -C 6 cycloalkyl, C C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, CrC 6 haloalkoxy, C 3 -C 6 haloalkenyloxy, cyano-d
- X 2 is a d-C 6 alkylene, C 3 -C 6 alkenylene or C 3 -C 6 alkynylene chain which can be mono- or poly-substituted by halogen or by X 4 , the unsaturated bonds of the chain not being bonded directly to the substituent Xi;
- X is hydroxy, C C 6 alkoxy, C 3 -C 6 cycloalkyloxy, C ⁇ -C 6 alkoxy-C ⁇ -Cealkoxy, C ⁇ -C 6 alkoxy-d-C 6 - alkoxy-C ⁇ -C 6 alkoxy or C ⁇ -C 2 alkylsulfonyloxy;
- Xi is oxygen, -O(CO)-, -(CO)O-, -O(CO)O-, -N(C C 4 alkyl)-O-, -O-N(C ⁇ -C 4 alkyl)-, thio, sulfinyl, sulfonyl, -SO 2 N(C ⁇ -C 4 alkyl)-, -N(d-C 4 alkyl)SO 2 -, -N(Ci-C 2 alkoxy-Ci-C 2 alkyl)SO2- or -N(C ⁇ -C 4 alkyl)-;
- X 3 and X 7 are each independently of the other a C ⁇ -C 8 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group which is mono- or poly-substituted by the following substituents: halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, d-C 6 alkoxy, d-C 6 alkoxycarbonyl, C 2 -C 6 - alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, halo-substituted C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C ⁇ -C 6 haloalkoxy, C 3 -C 6 haloal
- X 3 and X 7 are each independently of the other phenyl which can be substituted one or more times by CrC 6 alkyl, CrC 6 haloalkyl, d-C 6 alkoxy, CrC 6 haloalkoxy, halogen, cyano, hydroxy and/or nitro; or
- X 3 and X 7 are each independently of the other C 3 -C 6 cycloalkyl, C C 6 alkoxy- or d-C 6 alkyl- substituted C 3 -C 6 cycioalkyl, 3-oxetanyl or d-C 6 alkyl-substituted 3-oxetanyl; or X 3 and X 7 are each independently of the other a five- to ten-membered monocyclic or annellated bicyclic ring system which may be aromatic or saturated or partially saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system being bonded to the substituent Xi or X 5 directly or by way of a C C 4 alkylene, C 2 -C 4 alkenyl-d-C 4 alkylene, C 2 -C 4 alkynyl-CrC 4 alkylene, -N(C 1 -C 4 al yl)-C 1 -C 4 alkylene,
- Ra 3 is hydrogen, CrC 6 alkyl, CrC 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, d-C 6 alkoxy, CrC 6 haloalkoxy, CrC 6 alkylthio, d-C 6 alkyl- sulfinyl, CrC 6 alkylsulfonyl, CrC 6 haloalkylthio, CrC 6 haloalkylsulfinyl, CrC 6 haloalkylsulfonyl, CrC 6 alkylamino, di-C 2 -C 6 alkylamino, CrC 6 alkylaminosulfonyl, di-C 2 -C 6 alkylaminosulfonyl, phenyl, phenyl
- Ra 5 is hydrogen, CrC 6 alkyl, CrC 6 haloalkyl, C 2 -Cealkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, CrC 6 alkoxy, CrC 6 haloalkoxy, CrC 6 alkylthio, d-C 6 alkyl- sulfinyl, CrC 6 alkylsulfonyl, CrCehaloalkylthio, CrC 6 haloalkylsulfinyl, d-C-ehaloalkylsulfonyl, CrC 6 alkylamino, di-C 2 -C 6 alkylamino, CrC 6 alkylaminosulfonyl, di-C 2 -C 6 alkylaminosulfonyl, phenyl, phenylthi
- Q is an organic substituent which is so chosen that the compound of formula I has a pK value of from 1 to 5;
- D is hydrogen or R 3 ;
- E is hydrogen or R 4 ;
- D and E together are C 2 -C 3 alkylene which can be mono- or poly-substituted by R 6 ;
- A is d-C 2 alkylene which can be mono- or poly-substituted by R 5 ; or A may additionally be carbonyl, oxygen or -N-R 7 - when D and E are other than C 2 -C 3 alkylene; i. R 2 , R 3 , R 4 , R 5 and R 6 are each independently of the others hydrogen, CrC alkyl, phenyl, d-C 4 alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl or C C 4 alkoxycarbonyl; and
- R 7 is CrC 4 alkyl, alkoxycarbonyl or d-C 4 alkylcarbonyl, and their agronomically acceptable salts, isomers and enantiomers.
- alkyl groups appearing in the above substituent definitions may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
- Alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals.
- the alkenyl and alkynyl groups may be mono- or poly-unsaturated.
- Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert- butoxy.
- Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxy- carbonyl; preferably methoxycarbonyl or ethoxycarbonyl.
- Halogen is generally fluorine, chlorine, bromine or iodine. The same is also true of halogen in conjunction with other meanings, such as haloalkyl or halophenyl.
- Haloalkyl groups having a chain length of from 1 to 6 carbon atoms are, for example, fluoro- methyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2- trifluoroethyl, 1-fluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-fluoroprop-2-yl, pentafluoroethyl, 1 ,1 -difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, pentafluoro- ethyl, heptafluoro-n-propyl and perfluoro-n-hexyl.
- Alkenyl and alkynyl groups can be mono- or poly-unsaturated, so that alkyl, alkenyl and alkynyl chains having one or more double or triple bonds are also included.
- An alkylene chain can also be substituted by one or more CrC 3 alkyl groups, especially by methyl groups. Such alkylene chains and alkylene groups are preferably unsubstituted. The same applies also to all groups containing C 3 -C 6 cycloalkyl, C 3 -C 5 oxacycloalkyl, C 3 -C 5 thia- cycloalkyl, C 3 -C 4 dioxacycloalkyl, C 3 -C dithiacycloalkyl or C 3 -C oxathiacycloalkyl which occur, for example, also as part of oxygen- and sulfur-containing heterocyclic ring systems of the radicals Rai and Ra 2 .
- a d-C 4 alkylene, d-C 4 alkenylene or C 2 -C alkynylene bridge which may be interrupted by oxygen, -N(d-C alkyl)-, sulfur, sulfinyl and/or sulfonyl, or in X 2 or X 6 in the meaning of a d- C 6 alkylene, C 3 -C 6 alkenylene or C 3 -C 6 alkynylene chain which can be mono- or poly- substituted by halogen and/or by X 4 or X 8 , and wherein the unsaturated bonds of the chain are not bonded directly to the substituent Xi or X 5 , is to be understood as being, for example, — CH 2 -, -CH2CH 2 -, -CH 2 CH2CH 2 -, -CH 2 CH 2 CH2CH2-, -CH(CH 3 )-, -CH 2 CH(CH 3 )-, - CH 2 CH(CH 3 )
- each R 26 is methyl
- each R 27 independently is hydrogen, CrC 3 alkyl, CrC 3 alkoxy, d-C 3 alkylthio or trifluoromethyl
- X 9 is oxygen or sulfur
- R 46 is hydrogen, halogen, d-C 4 alkyl. d-C haloalkyl, C C 4 alkoxy or CrC 4 alkylthio; R 47 is hydrogen, halogen, d-C 4 alkyl or d-C 4 alkoxy; and R 50 , R 51> R 52 , Rss, Rs 4 , R55, se, R57, Rss and R 59 are hydrogen or d-C 4 alkyl; and X 10 is oxygen or NOR 59 .
- HPPD inhibitors of formula I are described, for example, in WO/0015615, WO 00/37437, WO 01/66522 and WO 01/94339.
- Ri and R 2 are hydrogen; A is CrC 2 alkylene; D and E together are C 2 -C 3 alkylene; Q is Qi, wherein
- Rai is hydrogen, d-C 6 alkyl, hydroxy, CrC 6 alkoxy, CrC 6 haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 haIoalkenyloxy, C 3 -C 6 alkynyloxy, d-C alkylcarbonyloxy, d-C 4 alkylsulfonyIoxy, tosyloxy, CrC 4 alkylthio, d-C 4 alkylsulfinyl, d-C 4 alkylsulfonyl, CrC 4 alkylamino, di-d- C 4 alkylamino, d-C 4 alkoxycarbonyl, CrC 4 haloalkyl, formyl, cyano, halogen, phenyl or phenoxy; it being possible for phenyl in turn to be substituted by d-C 3 alkyl, d-C 3 haloalkyl, CrC 3 alkoxy,
- Ra 2 is hydrogen, CrC 6 alkyl, d-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, vinyl substituted by d-C 2 alkoxycarbonyl or by phenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, ethynyl substituted by trimethylsilyl, hydroxy, d-C 2 alkoxy, CrC 2 alkoxycarbonyl or by phenyl, C 3 -C 6 allenyl, C 3 -C 6 - cycloalkyl, halo-substituted C 3 -C 6 cycloalkyl, d-C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, CrC 6 haloalkoxy, C 3 -C 6 haloalkenyloxy, cyano-d-
- Q is Qi
- Ra 3 and Ra 4 are hydrogen
- Ra 5 is d-C 3 haloalkyl, especially trifluoromethyl
- Ra 2 is C ⁇ -C 4 alkoxy-C ⁇ -C 4 alkoxy-CrC 4 alkyl, especially methoxyethoxymethyl.
- CCH is the ethynyl group
- Ph is the phenyl group
- Me is the methyl group.
- A422 CH CHCH 2 CH, H CF 3 O 0
- A423 CH CHCH 2 CH, H CF 3 O 0 O
- A425 CH CHCH 2 CH, H CF 3 O o-
- A432 CH CHCH 2 CH, H CF 3 O 0 OCH,
- A436 CH CHCH 2 CH 2 H CF 3 O 0
- the ring linkage site for the substituent A in the case of rings is located at the carbon atom labelled "C", for example O ⁇ ; and in the case of open-chain structures, for
- Radicals in which the substituent C-R 2 is a ring, for example (B16), are formed by combination of the substituent R 2 with the substituent E in the meaning of R . together form a C 2 -C 4 alkylene chain which can be interrupted by oxygen and/or carbonyl and/or sulfur, with the proviso that the oxygen and sulfur atoms are separated by at least one methylene group;
- Q is Q 2 and Q 2 is the radical B52:
- Q is Q 2 and Q 2 is the radical B39:
- Q is Q 3 and Q 3 is the radical C2: C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 ⁇ C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12
- Q is Q 3 and Q 3 denotes the radicals D1, D2 or D3:
- R-i, R 2 , R 3 , R 4 , X 1 and p are as defined for the radical A, and n is 0, 1 or 2:
- B1 B2 B4 B5 B6 B7 B8 B9 B10 B11 B12 B13 B14 B15 B16 B17 B18 B19 B20 B21 B22 B23 B24 B25 B26 B27 B28 B29 B30 B31 B32 B33 B34 B35 B36 B37 B38 - B40 B41 B42 B43 B44 B45 B46 B47 B48 B49 B50 B51 - B53 B54 B55 B56 B57 B58 B59 B60 B61 B62 B63 B64 B65 B66 B67 B68 B69 B70 B71 B72 A10 A10 A10 A10 A10 A10 A10 A10 A10 A/jo Ajjj AjO A ⁇ O ATO A ⁇ O A10 B73 B74 B75 B76 B77 B78 B79 B80 B8 ⁇ B82 B83 B84 B85 B86 B87 B88 B89 B90 B91 B92 B93 B94 B96 B97 B98 B99 B100 B101 B102 B103 B104 B105 B106 B107 B108 B109 B
- A is A10:
- A is A10:
- A is A646:
- A is A646:
- A is A646:
- Compound No. 2.01 is known from The Pesticide Manual 12 th ed., Entry No.: 467.
- Compound No. 2.02 (4-chloro-2-mesylphenyl-5-cyclopropyl-1 ,2-oxazol-4-yl ketone) is registered under Chemical Abstracts No. 141112-06-3.
- Compound No. 2.03 is known from The Pesticide Manual 12 th ed., Entry No.: 710, and compound No. 2.04 is described under Entry No. 500.
- Compound No. 2.05 is known from The Pesticide Manual 12 th ed., under Entry No.: 71 ; compound No. 2.06 under Entry No. 663; compound No. 2.07 under Entry No. 666; and compound No. 2.08 under Entry No. 70.
- Compound No. 2.12 is described in WO 98/42677 A1 and US 6,211 ,403 B1 and has the Chemical Abstracts registration number 128133-27-7.
- Compounds Nos. 2.13 and 2.14 and their preparation are known from WO/0015615.
- Compound No. 2.15 is described in EP-A-0 496 631 , and compound No. 2.16 is described in WO 03/092380.
- Compound No. 2.17 is known from WO 02/085118, and compound No. 2.18 from WO 00/021924.
- the compounds of formula I can be used as herbicides in unmodified form, that is to say as obtained in the synthesis, but they 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, suspensions, mixtures of a suspension and an emulsion (suspoemulsions), wettable powders, soluble powders, dusts, granules or microcapsules.
- formulations are described, for example, on pages 9 to 13 of WO 97/34485.
- the methods of application such as spraying, atomising, dusting, wetting, scattering or pouring, are selected in accordance with the intended objectives and the prevailing circumstances.
- compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers.
- formulation adjuvants for example solvents or solid carriers.
- Surface-active compounds surfactants
- solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
- suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
- suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485.
- surfactants conventionally employed in formulation technology which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Kunststoff/Vienna 1981 , and M.
- the active ingredient can also be contained in very fine microcapsules consisting of a polymer.
- Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredient to be released into the surroundings in controlled amounts.
- Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredient in an amount of about from 25 to 95 % by weight of the capsule weight.
- the active ingredients can be present in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
- the encapsulating membranes comprise, for example, natural and synthetic gums, cellulose, styrene-butadiene copolymers, polyacrylo- nitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers known to the person skilled in the art.
- cellulose styrene-butadiene copolymers
- polyacrylo- nitrile polyacrylate
- polyester polyamides
- polyureas polyurethane or chemically modified polymers and starch xanthates or other polymers known to the person skilled in the art.
- compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters thereof or mixtures of such oils and oil derivatives.
- the amount of oil additive in the composition according to the invention is generally from 0.01 to 2 %, based on the spray mixture.
- the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared.
- Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® obtainable from Rh ⁇ ne-Poulenc Canada Inc., alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
- a preferred additive contains as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers.
- Especially preferred oil additives comprise alkyl esters of higher fatty acids (C 8 -C 22 ), especially the methyl derivatives of C 12 -C 18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9).
- a preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Henkel subsidiary Cognis GMBH, DE).
- the application and action of the oil additives can be improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants.
- surface-active substances such as non-ionic, anionic or cationic surfactants.
- suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485.
- Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C 12 -C 22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available, preferred surfactants are the Genapol types (Clariant AG, Muttenz, Switzerland). Also preferred for use as surface-active substances are silicone surfactants, especially polyalkyl-oxide- modified heptamethyltrisiloxanes, such as are commercially available as e.g. Silwet L-77®, and also perfluorinated surfactants. The concentration of surface-active substances in relation to the total additive is generally from 1 to 30 % by weight.
- oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, CA) and Actipron® (BP Oil UK Limited, GB).
- an organic solvent to the oil additive/surfactant mixture can also bring about a further enhancement of action.
- Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation) types.
- the concentration of such solvents can be from 10 to 80 % by weight of the total weight.
- oil additives which are also described, for example, in US-A-4 834 908, are suitable for the composition according to the invention.
- a commercially available oil additive is known by the name MERGE®, is obtainable from the BASF Corporation and is essentially described, for example, in US-A-4 834 908 in col. 5, as Example COC-1.
- a further oil additive that is suitable according to the invention is SCORE® (Novartis Crop Protection Canada.) ln addition to the oil additives listed above, in order to enhance the action of the compositions according to the invention it is also possible for formulations of alkyl pyrrolidones, such as are commercially available e.g. as Agrimax®, to be added to the spray mixture.
- Formulations of synthetic latices such as, for example, polyacrylamide, polyvinyl compounds or poly-1 -p-menthene, such as are commercially available as e.g. Bond®, Courier® or Emerald®, can also be used to enhance action.
- Solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, can also be added as action-enhancing agent to the spray mixture.
- the herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of 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.
- a surfactant especially from 0.1 to 25 % by weight
- compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
- stabilisers for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
- HPPD inhibitors especially the compounds of formula I, are generally applied to the plant or to the locus thereof at rates of application of from 0.001 to 2 kg/ha, especially from 0.005 to 1 kg/ha.
- concentration required to achieve the desired effect can be determined by experiment. It is dependent upon the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
- HPPD inhibitors according to the invention are distinguished by herbicidal and growth- inhibiting properties and/or by properties improving on the existing pest- and/or fungus- resistance of the useful plants, allowing them to be used in pest-resistant and/or fungus- resistant transgenic crops of useful plants, especially in cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops (for example citrus fruit, coffee, bananas), rape, maize and rice. Preference is given to the use of the HPPD inhibitors according to the invention in pest-resistant transgenic crops of maize and cotton, especially in maize.
- pest-resistant and/or fungus-resistant transgenic useful plants include expressly those useful plants which, in addition to pest-resistance and/or fungus-resistance, additionally possess herbicide tolerance.
- herbicide-tolerant useful plants preference is given to those having tolerance to glyphosate, glufosinate ammonium, ALS (acetolactate synthase) inhibitors, e.g. sulfonylureas, for example primisulfuron, prosulfuron and trifloxysulfuron, or bromoxynil, such as Bt11 maize or Herculex I® maize.
- pest-resistant transgenic crop plants are to be understood as being those which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus ' .
- Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, Cry ⁇ IIB(bl ) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp.
- insecticidal proteins for example insecticidal proteins from Bacillus cereus or Bacillus popliae
- Bacillus thuringiensis such as ⁇ -endotoxins, e.g. CrylA(b), CrylA(c), CrylF, Cryl
- Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
- toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
- toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
- agglutinins proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
- ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
- steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
- ⁇ -endotoxins for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c, or vegetative insecticidal proteins (VIP), for example VIP1 , VIP2, VIP3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins.
- Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
- a truncated toxin is a truncated CrylA(b), which is expressed in the Bt11 maize from Syngenta Seed SAS, as described below.
- modified toxins one or more amino acids of the naturally occurring toxin are replaced.
- non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylllA055, a cathepsin-D- recognition sequence is inserted into a CrylllA toxin (see WO 03/018810).
- Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
- Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
- the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
- insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
- insects from different taxonomic groups are especially common in maize crops: Ostrinia nubilalis, European corn borer Agrotis ipsilon, black cutworm Helicoverpa zea, corn earworm Spodoptera frugiperda, fall armyworm Diatraea grandiosella, soiled corn borer Elasmopalpus lignosellus, lesser cornstalk borer Diatraea saccharalis, sugarcane borer Diabrotica virgifera virgifera, western corn rootworm Diabrotica longicornis barberi, northern corn rootworm Diabrotica undecimpunctata howardi, southern corn rootworm Melanotus spp., wireworms Cyclocephala borealis, northern masked chafer (white grub) Cyclocephala immaculata, southern masked chafer (white grub) Popillia japonica, Japanese beetle Chaetocnema pulicaria, corn flea beet
- Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) tox
- transgenic crops are: 1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR 96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylA(b) toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
- MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified CrylllA toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
- MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a CrylllB(bl) toxin and has resistance to certain Coleoptera insects.
- NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
- NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacte um sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
- fungus-resistant transgenic crop plants are to be understood as being those which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225).
- PRPs pathogenesis-related proteins
- Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191.
- the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
- Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A- 0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
- ion channel blockers such as blockers for sodium and calcium channels
- the viral KP1 , KP4 or KP6 toxins for example the viral KP1 , KP4 or KP6 toxins
- stilbene synthases such as the viral K
- the method according to the invention is suitable especially in transgenic insect-resistant useful plant crops.
- the method according to the invention is suitable very especially in transgenic useful plant crops that contain a coding sequence which codes for a ⁇ -endotoxin or a vegetative insecticidal protein (VIP) toxin.
- VIP vegetative insecticidal protein
- the method according to the invention is very especially suitable in transgenic useful plant crops that contain a coding sequence which codes for a toxin selected from the group CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ), Cry9c, VIP1 , VIP2, VIP3 and VIP3A.
- the method according to the invention is especially suitable in Bt11 maize and Bt176 maize from Syngenta Crop Protection AG; in YieldGard®, YieldGard Plus® and YieldGard Rootworm® from the Monsanto Company; in Starlink® from Bayer AG and in Herculex I®; more especially in Bt11 maize.
- the method according to the invention is very especially suitable in transgenic useful plant crops that contain a coding sequence which codes for a toxin selected from the group CrylA(b), CrylllA and VIP3A.
- the method according to the invention is more especially suitable in transgenic useful plant crops that express a CrylllA toxin modified by insertion of a non-naturally present protease recognition sequence, such as, for example, CrylllA055.
- a non-naturally present protease recognition sequence such as, for example, CrylllA055.
- Toxins of that kind are described specifically in WO 03/018810, which is incorporated by this reference in the present application.
- the use of the method according to the invention in transgenic useful plant crops that express CrylllA055 is very especially preferred.
- the weeds to be controlled may be both monocotyledonous and dicotyledenous weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
- Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida,
- compositions according to the invention may additionally also comprise growth regulators, for example trinexapac (744), chlormequat chloride (129), clofencet (148), cyclanilide (170), ethephon (281 ), flurprimidol (355), gibberellic acid (379), inabenfide (421), maleic hydrazide (449), mefluidide (463), mepiquat chloride (465), paclobutrazol (548), prohexadione-calcium (595), uniconazole (746) or thidiazuron (703).
- growth regulators for example trinexapac (744), chlormequat chloride (129), clofencet (148), cyclanilide (170), ethephon (281 ), flurprimidol (355), gibberellic acid (379), inabenfide (421), maleic hydrazide (449), mefluidide (463), mepiquat chloride (465), paclobu
- composition according to the invention may also comprise fungicides, for example azoxystrobin (43), epoxiconazole (48), benomyl (60), bromuconazole (89), bitertanol (77), carbendazim (107), cyproconazole (189), cyprodinil (190), diclomezine (220), difenoconazole (228), diniconazole (247), epoxiconazole (48), ethirimol (284), etridiazole (294), fenarimol (300), fenbuconazole (302), fenpiclonil (311), fenpropidin (313), fenpropimorph (314), ferimzone (321), fludioxonil (334), fluquinconazole (349), flutolanil (360), flutriafol (361), imazalil (410), ipconazole (426), iprodione (428
- test plants Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastic pots.
- the test compounds in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying in an optimum concentration (500 litres of water/ha).
- the test plants are then grown on in a greenhouse under optimum conditions.
- the present invention therefore relates also to a method of controlling undesirable plant growth in pest-resistant and/or fungus-resistant transgenic useful plant crops, which process comprises applying to the plants or to the locus thereof a herbicidally effective amount of at least one herbicide selected from the class of HPPD inhibitors together with an amount, effective for herbicide antagonism, of at least one safener.
- the present invention relates also to a herbicidal and plant-growth-inhibiting composition for controlling undesirable plant growth in pest-resistant and/or fungus-resistant transgenic useful plant crops, which comprises a herbicidally effective amount of at least one herbicide selected from the class of HPPD inhibitors together with an amount, effective for herbicide antagonism, of at least one safener, on an inert carrier.
- composition according to the invention is suitable especially for controlling undesirable plant growth in transgenic pest-resistant useful plant crops.
- compounds especially suitable as safeners are: a compound selected from the compound formula 3.1
Abstract
The present invention relates to a method of controlling undesirable plant growth in pest-resistant and/or fungusresistant transgenic useful plant crops, which process comprises applying at least one herbicide selected from the class of HPPD inhibitors in a herbicidally effective amount to the plants or to the locus thereof.
Description
METHOD OF CONTROLLING WEEDS IN TRANSGENIC CROPS
The present invention relates to the use of herbicidally active compounds from the class of HPPD (4-hydroxyphenylpyruvate-dioxygenase) inhibitors in specific pest-resistant and/or fungus-resistant fransgenic useful plant crops, especially in pest-resistant fransgenic maize crops.
The use of herbicides can result in considerable damage also being caused to the crop plants, for example in dependence upon the concentration of the herbicide and the mode of its application, the crop plant, the nature of the soil and the climatic conditions, such as period of exposure to light, temperature and amounts of precipitation. Selective weed control can be achieved, however, by using the herbicide in crops in which the useful plant has been rendered more or less resistant to the phytotoxic action of the herbicide by means of breeding methods or genetic techniques.
In addition to herbicide-tolerant useful plant crops, increasing use is being made commercially of fransgenic useful plant crops which have been rendered resistant to harmful insects and/or fungal infestation, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Bt maize, Bt cotton and Bt potatoes transgenically express Bt toxins. Bt toxins are proteins formed naturally by Bacillus thuringiensis soil bacteria (Bt soil bacteria). Such pest-resistant fransgenic useful plant crops generally do not exhibit enhanced resistance to the phytotoxic action of herbicides.
It has now been found that specific herbicides from the class of HPPD inhibitors are especially suitable for the selective control of weeds in pest-resistant and/or fungus-resistant fransgenic maize crops and/or that the use of specific herbicides from the class of HPPD inhibitors for the selective control of weeds in pest-resistant and/or fungus-resistant transgenic maize crops gives rise to unexpectedly positive effects in the pest-resistant and/or fungus-resistant properties of the transgenic maize crops. There is therefore proposed according to the invention a method of controlling undesirable plant growth in pest- resistant and/or fungus-resistant transgenic useful plant crops, which process comprises applying at least one herbicide selected from the class of HPPD inhibitors in a herbicidally effective amount to the plants or to the locus thereof. The present invention relates also to a herbicidal and plant-growth-inhibiting composition for controlling undesirable plant growth in
pest-resistant and/or fungus-resistant transgenic useful plant crops, which comprises a herbicidally effective amount of at least one herbicide selected from the class of HPPD inhibitors, on an inert carrier.
Herbicides from the class of HPPD inhibitors that are preferred for the method according to the invention and for the composition according to the invention are compounds of formula I
T ΪS TT
D is hydrogen or R3;
E is hydrogen or R4; or
D and E together are C2-C3alkylene which can be mono- or poly-substituted by R6;
A is C C2alkylene which can be mono- or poly-substituted by R5; or A may additionally be carbonyl, oxygen or -N-R7- when D and E are other than C2-C3alkylene;
Rt, R2, R3, R4, R5 and R6 are each independently of the others hydrogen, C1-C4alkyl, phenyl,
CrC alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl or d-C^lkoxycarbonyl; or R2 and R4 together form a C2-C4alkylene chain which can be interrupted by oxygen and/or carbonyl and/or sulfur, with the proviso that the oxygen and sulfur atoms are separated by at least one methylene group;
R7 is CrC alkyl, alkoxycarbonyl or C-|-C4alkylcarbonyl;
Ro36 is hydroxy, O"M+, wherein M+ is an alkali metal cation or ammonium cation, halogen,
C-ι-C12alkylsulfonyloxy, amino, CrC4alkylthio, CrC12alkylsulfinyl, C C12alkylsulfonyl, C~ι-C12- haloalkylthio, CrCι2haloalkylsulfinyl, d-Cjahaloalkylsulfonyl, C-i-Cealkoxy-CrCealkylthio,
Cι-C6alkoxy-C-ι-C6alkylsulfinyl, d-Cealkoxy-d-dalkylsulfonyl, C3-Cι2alkenylthio, C3-C 2- alkenylsulfinyl, C3-Cι2alkenylsulfonyl, C3-Cι2alkynylthio, C3-C12alkynylsulfinyl, C3-Cι2alkynyl- sulfonyl, d-dalkoxycarbonyl-d-dalkylthio, Cι-C4alkoxycarbonyl-d-C4alkylsulfinyl, Cι-C4alkoxycarbonyl-Cι-C4alkylsulfonyl, (d-C4alkoxy)2P(O)O, d-C4alkyl-(d-C4alkoxy)- P(O)O, H(d-C4alkoxy)P(O)O, R037Ro38N, R039R040NNH, R041R042NC(O)O-, Ro43Ro 4NC(O)NH-, CrCjsalkylcarbonyloxy, C2-C 8alkenylcarbonyloxy, C2-Cι8alkynyl- carbonyloxy, C3-C6cycloalkylcarbonyloxy, d-C12alkoxycarbonyloxy, d-d2alkylthiocarbonyl- oxy or d-daalkylthiocarbamoyl, wherein the alkyl, alkenyl and alkynyl groups can be substituted by halogen, d-C6alkoxy, d-C6alkylthio, d-C6alkylsulfinyl, d-C6alkylsulfonyl or by cyano; or
Ro36 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy, benzoyloxy or benzoyl-d-C6alkoxy, wherein the phenyl groups can in turn be substituted one or more times by halogen, nitro, cyano, d-C4alkyl, d-C-4haloalkyl, C-ι-C - alkoxy and/or Cι-C haloalkoxy, or R036 is a group Het07-thio, Het08-sulfinyl, Het09-sulfonyl, Het0ι0-(CO)O or Het0n-N(R047); wherein
Het07, Het08, Het09, Het0ι0 and Het011 are each independently of the others a five- to ten- membered monocyclic or annellated bicyclic ring system which may be aromatic or partially saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, and each ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system itself can be substituted by d-C6alkyl, d-C6- haloalkyl, d-C6alkoxy, C C6haloalkoxy, d-C6alkylthio, d-C6alkylsulfinyl, d-C6alkylsulfonyl, di(d-C4alkyl)aminosulfonyl, di(d-C4alkyl)amino, halogen, cyano, nitro or by phenyl, and the substituents on the nitrogen atom in the heterocyclic ring are other than halogen; R037, Ro38, R039, Ro o, Ron, Ro 2, Ro^, c and R047 are each independently of the others hydrogen or d-C6alkyl; or
R037 and R038 together or R039 and R04o together or R0 ι and R042 together or R0 3 and R0 4 together are pyrrolidino, piperidino, morpholino or thiomorpholino, which can be mono- or poly-substituted by methyl groups; or T is T2
wherein
R34 is hydrogen, C C4alkyl, Cι-C4haloalkyl, C3-C6cycloalkyl, C2-C4alkenyl, C2-C4alkynyl or benzyl, it being possible for the phenyl group to be substituted one or more times by d-C6alkyl, Cι-C6haloalkyl, C C6alkoxy, C C6haloalkoxy, halogen, cyano, hydroxy and/or nitro;
R35 is hydrogen, d-C alkyl, d-C4haloalkyl, C3-C6cycloalkyl, C3-C4alkenyl, C3-C4alkynyl or benzyl, it being possible for the phenyl group to be substituted one or more times by d-C-6alkyl, d-C6haloalkyl, d-C6alkoxy, d-C-6haloalkoxy, halogen, cyano, hydroxy and/or nitro;
R36 is hydroxy, O"M+, wherein M+ is an alkali metal cation or ammonium cation, halogen, d-Cι2alkylsulfonyloxy, amino, d-C4alkylthio, d-C12alkylsulfinyl, d-C12alkylsulfonyl, C1-C12- haloalkylthio, d-Cι2haloalkylsulfinyl, CrC12haloalkylsulfonyl, CrC6alkoxy-Cι-C6alkylthio, CrCβalkoxy-d-Cealkylsulfinyl, d-C6alkoxy-Cι-C6alkylsulfonyl, C3-C12alkenylthio, C3-C12- alkenylsulfinyl, C3-C12alkenylsulfonyl, C3-C12alkynylthio, C3-C12alkynylsulfinyl, C3-C12alkynyl- sulfonyl, CrC4alkoxycarbonyl-CrC4alkylthio, Cι-C4alkoxycarbonyl-Cι-C4alkylsulfinyl, d-C4alkoxycarbonyl-d-C4alkylsulfonyl, (C1-C4alkoxy)2P(O)O, d-C4alkyl-(d-C4alkoxy)- P(O)O, H(d-C4alkoxy)P(O)O, R37R38N, R39R40NNH, R41R42NC(O)O-, R43R44NC(O)NH-, CrC18alkylcarbonyloxy, C2-C18alkenylcarbonyloxy, C2-C18alkynylcarbonyloxy, C3-C6- cycloalkylcarbonyloxy, Cι-C12alkoxycarbonyloxy, d-Cι2alkylthiocarbonyloxy or Cι-C12- alkylthiocarbamoyl, wherein the alkyl, alkenyl and alkynyl groups can be substituted by halogen, d-C6alkoxy, d-C6alkylthio, d-C6alkylsulfinyl, d-C6alkylsulfonyl or by cyano; or R36 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy, benzoyloxy or benzoyl-d-C6alkoxy, it being possible for the phenyl groups in turn to be substituted one or more times by halogen, nitro, cyano, C C4alkyl, C1-C4haloalkyl, C C4alkoxy and/or d-C4haloalkoxy, or R36 is a group Het7-thio, Het8-sulfinyl, Het9-sulfonyl, Het10-(CO)O or Het1-ι-N(R47); wherein Het7> Het8, Het9, Het 0 and Hetjj are each independently of the others a five- to ten- membered monocyclic or annellated bicyclic ring system which may be aromatic or partially saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and
sulfur, and each ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system itself can be substituted by d-C6alkyl, C C6- haloalkyl, C C6alkoxy, d-C6haloalkoxy, d-C-6aikylthio, d-C6alkylsulfinyl, Cι-C6alkylsulfonyl, di(d-C4alkyl)aminosulfonyl, di(d-C4alkyl)amino, halogen, cyano, nitro or by phenyl, and the substituents on the nitrogen atom in the heterocyclic ring are other than halogen; R37, 38, 39, R4o, R4ι, R42, R^, R4 and R47 are each independently of the others hydrogen or d-C6alkyl; or
R37 and R38 together or R39 and R40 together or R41 and R 2 together or R43 and R^ together are pyrrolidino, piperidino, morpholino or thiomorpholino, which can be mono- or poly- substituted by methyl groups; or T is T3
wherein
R49 is C C4alkyl, d-C4haloalkyl, C3-C6cycloalkyl or halo-substituted C3-C6cycloalkyl;
Z01 is a chemical bond, S, SO or SO2;
R50 is hydrogen or d-C3alkylene which can be substituted by the following substituents: halogen, hydroxy, d-C6alkoxy, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, d-C6alkoxy-
Cι-C6alkoxy, d-Cealkoxy-C Cealkoxy-d-Cβalkoxy, (3-oxetanyl)-oxy, CrC6alkyl-substituted
(3-oxetanyl)-oxy, benzylthio, benzylsulfinyl, benzylsulfonyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, it being possible for the phenyl- and benzyl-containing groups in turn to be substituted by one or more d-C6alkyl, CrC6haloalkyl, d-C6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy and/or nitro groups; or R50 is phenyl, it being possible for the phenyl-containing group in turn to be substituted by one or more C C6alkyl, d-C6haloalkyl, d-C6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy and/or nitro groups, or R50 is C3-C6cycloalkyl, C C6alkoxy- or d-C6alkyl-subst.tuted C3-C6cycloalkyl, 3-oxetanyl or Cι-C6alkyl-substituted 3-oxetanyl; or T is T
wherein
R045 is d-C6alkyl, d-C6haloalkyl, C3-C6cycloalkyl or halo-substituted C3-C6cycloalkyl; and their agronomically acceptable salts, isomers and enantiomers.
The compounds of formula I also include the salts which such compounds are able to form with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium.
Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C C18aIkylamines, d-C hydroxyalkylamines and C2-C4- alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octyl- amine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonyl- amine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n- propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexyl- amine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2- amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2- amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuciidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylene- diamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
Because the compounds of formula I wherein T is T-\ are preferably in enolised forms or in the form of salts, formula I also includes the enolised forms of formulae la, lb, lc and Id wherein M is hydrogen or a metal ion or an ammonium ion.
Since compounds of formula I may also contain asymmetric carbon atoms, for example in the case of the carbon atom carrying R-i, D and A, all stereoisomeric forms are also included.
Q is especially an organic substituent which is so chosen that the compound of formula I has a pK value of from 2.5 to 4.
The organic substituent Q may be an inert substituent of any desired structure, provided that the compounds of formula I retain their action as HPPD inhibitors.
Q is preferably a mono- or poly-substituted phenyl, pyridyl or heteroaryl group, especially 2- benzoyl, 2-isonicotinoyl and 2-nicotinoyl derivatives, the substitution pattern of those groups being freely selectable provided that the compounds of formula I retain their action as HPPD inhibitors.
Especially preferred HPPD inhibitors according to the present invention are compounds of formula I wherein Q is Q1
Ra! is hydrogen, d-C6alkyl, hydroxy, Cι-C6alkoxy, d-C-ehaloalkoxy, C3-C6alkenyloxy, C3-
C6haloalkenyloxy, C3-C6alkynyloxy, d-C4alkylcarbonyloxy, Cι-C4alkylsulfonyloxy, tosyloxy,
Cι-C4alkylthio, C1-C4alkylsulfinyl, d-C4alkylsulfonyl, C C4alkylamino, di-Cι-C4alkylamino, d-
C4alkoxycarbonyl, d-C4haloalkyl, formyl, cyano, halogen, phenyl or phenoxy; it being possible for phenyl in turn to be substituted by Cι-C alkyl, d-C3haloalkyl, d-C3alkoxy, d-
C3haloalkoxy, halogen, cyano or by nitro; or Rai is a three- to ten-membered monocyclic ring system or, together with Ra2 or Ra5, annellated mono- or bi-cyclic ring system which may be interrupted by oxygen, sulfur, SO,
SO2, NRa6, carbonyl and/or by =NORa7, the ring system, unless it is annellated, being bonded to the carbon atom of the substituent Ai directly or by way of a d-C alkylene,
-CH=CH-, -C≡C-, -CH2O-. -CH2N(d-C4alkyl)-, -CH2S-, -CH2SO- or -CH2SO2- group, and the ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system can itself be mono-, di- or tri-substituted by Cι-C6alkyl, d-C-6- haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, d-C6alkoxy,
C C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, d-C6alkylthio, Cι-C6haloalkylthio,
C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, d-C4alkoxy-Cι-C2alkylthio, d-C4alkylcarbonyl-d-C2alkylthio, d-C alkoxycarbonyl-d-C2alkylthio, cyano-d-C4alkylthio, d-C6alkylsulfinyl, d-C6haloalkylsulfinyl, Cι-C6alkylsulfonyl, d-C6haloalkylsulfonyl, amino- sulfonyl, Cι-C2alkylaminosulfonyl, di(C C2alkyl)aminosulfonyl, di(C C4alkyl)amino, halogen, cyano, nitro, phenyl and/or benzylthio, it being possible for phenyl and benzylthio in turn to be substituted on the phenyl ring by C C3alkyl, d-C3haloalkyl, d-C3alkoxy, d-C3- haloalkoxy, halogen, cyano or by nitro, and substituents on the nitrogen atom in the heterocyclic ring are other than halogen; or Ra! is the group -X5-X7 or the group -X6-X5-X7; wherein
X6 is a d-C6alkylene, C3-C6alkenylene or C3-C6alkynylene chain which can be mono- or poly-substituted by halogen and/or by X8, the unsaturated bonds of the chain not being bonded directly to the substituent X5;
X8 is hydroxy, d-C6alkoxy, C3-C6cycloalkyloxy, d-Cealkoxy-Cj-Cealkoxy, C C6alkoxy-d-C6- alkoxy-d-C6alkoxy or Cι-C2alkylsulfonyloxy;
X5 is oxygen, -O(CO)-, -(CO)O-, -O(CO)O-, -N(d-C4alkyl)-O-, -O-N(d-C4alkyl)-, thio, sulfinyl, sulfonyl, -SO2N(C C4alkyl)-, -N(C C4alkoxy)SO2-, -N(C1-C4alkyl)SO2-,
-N(C1-C2alkoxy-C1-C2alkyl)SO2- or -N(C C4alkyl)-;
Ra6 is hydrogen, d-C4alkyl, d-C4alkylthio-d-C4carbonyl, Cι-C4alkylsulfinyl-d-C4carbonyl, Cι-C4alkylsulfonyl-d-C4carbonyl, Cι-C4alkoxycarbonyl, C-j-C4alkylcarbonyl, phenylcarbonyl or phenyl, it being possible for the phenyl groups in turn to be substituted by d-C4alkyl. d-C4haloalkyl, d-C4alkoxy, d-C4haloalkoxy, d-C4alkylcarbonyl, Cι-C4alkoxycarbonyl, d-C4alkylamino, di-d-C4alkylamino, d-C4alkyl-S-, d-C4alkyl-SO-, d-C4alkyl-SO2, d-C4alkyl-S(O)2O, d-C4haloalkyl-S-, C C4haloalkyl-SO, C1-C4haloalkyl-SO2, C C4halo- alkyl-S(O)2O, d-C4alkyl-S(O)2NH, d-C4alkyl-S(O)2N(d-C4alkyl), halogen, nitro or by cyano; Ra7 is CrC4alkyl;
Ra2 is hydrogen, C C6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, vinyl substituted by d-C2alkoxycarbonyl or by phenyl, C2-C6alkynyl, C2-C6haloalkynyl, ethynyl substituted by trimethylsilyl, hydroxy, C1-C2alkoxy, d-C2alkoxycarbonyl or by phenyl, C3-C6allenyl, C3-C6- cycloalkyl, halo-substituted C3-C6cycloalkyl, C C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, CrC6haloalkoxy, C3-C6haloalkenyloxy, cyano-d-C4alkoxy, d-C alkoxy-CrC4alkoxy, Cι-C - alkylthio-C C4alkoxy, d-C4alkylsulfinyl-Cι-C4alkoxy, d-C4alkylsulfonyl-Cι-C4alkoxy, d-C4- alkoxycarbonyl-d-C4alkoxy, d-C6alkylthio, d-C6alkylsulfinyl, d-C6alkylsulfonyl, d-C6halo- alkylthio, d-C6haloalkylsulfinyl, d-C6haloalkylsulfonyl, d-C4alkoxycarbonyl-Cι-C4alkylthio, d-C4alkoxycarbonyl-d-C4alkylsulfinyl, C C alkoxycarbonyl-Cι-C alkylsulfonyl, benzyl-S-, benzyl-SO-, benzyl-SO -, C-ι-C6alkylamino, di-C2-C6alkylamino, d-C6alkylaminosulfonyl, di(Cι-C6alkylamino)sulfonyl, benzyloxy, benzyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, it being possible for the phenyl-containing groups in turn to be substituted by d-C3alkyl, d-C3haloalkyl, d-C3alkoxy, d-C-3haloalkoxy, halogen, cyano or by nitro, or Ra2 is OS-C C4alkyl, OSO-d-C4alkyl, OSO2-d-C4alkyl, OS-d-C4haloalkyl, OSO-C C4- haloalkyl, OSO2-C C4haloalkyl, N(d-C4alkyl)-S-d-C4alkyl, N(d-C4aIkyl)-SO-d-C4alkyl, N(CrC alkyl)-SO2-Cι-C4alkyl, cyano, carbamoyl, d-C4alkoxycarbonyl, formyl, halogen, rhodano, amino, hydroxy-C C4alkyl, CrC4alkoxy-d-C4alkyl, Cι-C4alkyl-S-d-C4alkyl, d-dalkyl-SO-d-dalkyl, d-C4aIkyl-SO2-d-C4alkyl, cyano-d-C4alkyl, C C6alkyl- carbonyloxy-d-C4alkyl, CrC4alkoxycarbonyl-d-C alkyl, d-C4alkoxycarbonyloxy-d-C4alkyl, d-C4rhodano-d-C4alkyl, benzoyloxy-C C4alkyl, C2-C6oxiranyl, Cι-C4aIkylamino-d-C4alkyl, di(Cι-C4alkyl)amino-Cι-C4alkyl, d-Cι2alkylthiocarbonyl-Cι-C4alkyl or formyl-d-C4alkyl, or Ra2 is a five- to ten-membered monocyclic or annellated bicyclic ring system which may be aromatic or partially saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system being bonded to the pyridine ring by way of a d-C4alkylene, -CH=CH-, -C≡C-, -CH2O-, -CH2N(d-C4alkyl)-, -CH2SO- or -CH2SO2- group, and each ring system may contain not more than two oxygen atoms and not more than two
sulfur atoms, and the ring system itself can be mono-, di- or tri-substituted by d-C6alkyl, Cι-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, d-C6alkoxy, C C6haloalkoxy, C3-C6alkenyioxy, C3-C6alkynyloxy, mercapto, Cι-C6alkylthio, CrC6haloalkyl- thio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5- acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, d-C6alkylsulfinyl, d-C6- haloalkylsulfinyl, d-C6alkylsulfonyl, CrC6haloalkylsulfonyl, aminosulfonyl, d-C2alkylamino- sulfonyl, di(C C2alkyl)aminosulfonyl, di(Cι-C4alkyl)amino, halogen, cyano, nitro, phenyl and/or by benzylthio, it being possible for phenyl and benzylthio in turn to be substituted on the phenyl ring by d-C3alkyl, Cι-C3haloalkyl. Cι-C3alkoxy. Cι-C3haloalkoxy, halogen, cyano or by nitro, and substituents on the nitrogen atom in the heterocyclic ring are other than halogen; or Ra2 is the group -X X3 or the group -X2-XrX3; wherein
X2 is a d-C6alkylene, C3-C6alkenylene or C3-C6alkynylene chain which can be mono- or poly-substituted by halogen or by X4, the unsaturated bonds of the chain not being bonded directly to the substituent Xi;
X is hydroxy, C C6alkoxy, C3-C6cycloalkyloxy, Cι-C6alkoxy-Cι-Cealkoxy, Cι-C6alkoxy-d-C6- alkoxy-Cι-C6alkoxy or Cι-C2alkylsulfonyloxy;
Xi is oxygen, -O(CO)-, -(CO)O-, -O(CO)O-, -N(C C4alkyl)-O-, -O-N(Cι-C4alkyl)-, thio, sulfinyl, sulfonyl, -SO2N(Cι-C4alkyl)-, -N(d-C4alkyl)SO2-, -N(Ci-C2alkoxy-Ci-C2alkyl)SO2- or -N(Cι-C4alkyl)-;
X3 and X7 are each independently of the other a Cι-C8alkyl, C3-C6alkenyl or C3-C6alkynyl group which is mono- or poly-substituted by the following substituents: halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, d-C6alkoxy, d-C6alkoxycarbonyl, C2-C6- alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, halo-substituted C3-C6cycloalkyl, C3-C6alkenyloxy, C3-C6alkynyloxy, Cι-C6haloalkoxy, C3-C6haloalkenyloxy, cyano-CrC6alkoxy, Cι-C6alkoxy-Cι-C6alkoxy, Cι-C6alkoxy-Cι-C6alkoxy-Cι-C6alkoxy, Cι-C6- alkylthio-Cι-C6alkoxy, d-C6alkylsulfinyl-Cι-C6alkoxy, CrC6alkylsulfonyl-CrC6alkoxy, d-C6- alkoxycarbonyl-d-C6alkoxy, Cι-C6alkoxycarbonyl, d-C6alkylcarbonyl, Cι-C6alkylthio, CrC6alkylsulfinyl, CrC6alkylsulfonyl, Cι-C6haloalkylthio, d-C6haloalkylsulfinyl, CrCehaloalkylsulfonyl, oxiranyl, which can in turn be substituted by CrC6alkyl, (3-oxetanyl)-oxy, which can in turn be substituted by d-C6alkyl, benzylthio, benzylsulfinyl, benzylsulfonyl, d-C6alkyl- amino, di(C C6alkyl)amino, d-C4alkyl-S(O)2O, CrC4alkyl-N(CrC4alkyl)SO2-, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl and/or phenylsulfonyl;
it being possible for the phenyl- or benzyl-containing groups in turn to be substituted by one or more CrC6alkyl, CrC6haloalkyl, CrC6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy and/or nitro groups, or
X3 and X7 are each independently of the other phenyl which can be substituted one or more times by CrC6alkyl, CrC6haloalkyl, d-C6alkoxy, CrC6haloalkoxy, halogen, cyano, hydroxy and/or nitro; or
X3 and X7 are each independently of the other C3-C6cycloalkyl, C C6alkoxy- or d-C6alkyl- substituted C3-C6cycioalkyl, 3-oxetanyl or d-C6alkyl-substituted 3-oxetanyl; or X3 and X7 are each independently of the other a five- to ten-membered monocyclic or annellated bicyclic ring system which may be aromatic or saturated or partially saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system being bonded to the substituent Xi or X5 directly or by way of a C C4alkylene, C2-C4alkenyl-d-C4alkylene, C2-C4alkynyl-CrC4alkylene, -N(C1-C4al yl)-C1-C4alkylene, -SO- CrC4alkylene or -SO2-CrC alkylene group, and each ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system can itself be mono-, di- or tri-substituted by CrC6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, CrC6alkoxy, hydroxy, CrC6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, CrC6alkylthio, d-C6haloalkylthio, C3-C6alkenylthio, C3-C6halo- alkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonyl- alkylthio, C2-C4cyanoalkylthio, CrC6alkylsulfinyl, d-C6haloalkylsulfinyl, d-C6alkylsulfonyl, CrC6haIoalkylsulfonyl, aminosulfonyl, Cι-C alkylaminosulfonyl, di(CrC2alkyl)aminosulfonyl, di(CrC4alkyl)amino, halogen, cyano, nitro, phenyl and/or by benzylthio, it being possible for phenyl and benzylthio in turn to be substituted on the phenyl ring by Cι-C3alkyl, CrC3halo- alkyl, CrC3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro, and the substituents on the nitrogen atom in the heterocyclic ring are other than halogen;
Ra3 is hydrogen, CrC6alkyl, CrC6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, d-C6alkoxy, CrC6haloalkoxy, CrC6alkylthio, d-C6alkyl- sulfinyl, CrC6alkylsulfonyl, CrC6haloalkylthio, CrC6haloalkylsulfinyl, CrC6haloalkylsulfonyl, CrC6alkylamino, di-C2-C6alkylamino, CrC6alkylaminosulfonyl, di-C2-C6alkylaminosulfonyl, phenyl, phenylthio, phenylsulfinyl, phenylsulfonyl or phenoxy, it being possible for phenyl in turn to be substituted by d-C3alkyl, d-C3haloalkyl, CrC3alkoxy, CrC3haloalkoxy, halogen, cyano or by nitro, or Ra3 is -N(C1-C alkyl)-S-C -C4alkyl, -N(CrC4alkyl)-SO-C C4alkyl, -N(Cι-C4alkyl)-SO2-Cι-C4alkyl, cyano, halogen, amino, d-C alkoxy-CrC4alkyl, CrC4alkyl-S- d-C4alkyl, CrC4alkyl-SO-Cι-C4alkyl or Cι-C4alkyl-SO2-CrC4alkyl;
Ra4 is hydrogen, d-C6alkyl, hydroxy, CrC6alkoxy, CrC6haloalkoxy, C3-C6alkenyloxy, C3-C6haloalkenyloxy, C3-C6alkynyloxy, CrC4alkylcarbonyloxy, CrC4alkylsulfonyloxy, tosyloxy, CrC4alkylthio, d-C4alkylsulfinyl, CrC4alkylsulfonyl, CrC4alkylamino, di-Cr C4alkylamino, CrC4alkoxycarbonyl, d-C4haloalkyl, formyl, cyano, halogen, phenyl or phenoxy, it being possible for phenyl in turn to be substituted by CrC3alkyl, d-C3haloalkyl, d-C3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro; or Ra4 is a five- to ten-membered monocyclic ring system or, with Ra3, annellated bicyclic ring system which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system, unless it is annellated, being bonded to the ring containing the substituent A directly or by way of a d-C4alkylene, -CH=CH-, -C≡C-, -CH2O-, -CH2N(d-C alkyl)-, -CH2S-, -CH2SO- or -CH2SO2- group, and the ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system can itself be mono-, di- or tri-substituted by d-C6alkyl, CrC6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C -C6alkynyl, C2-C6haloalkynyl, CrC6alkoxy, CrC6haloalkoxy, C3-C6alk- enyloxy, C3-C6alkynyloxy, CrC6alkylthio, CrCehaloalkylthio, C3-C6alkenylthio, C3-C6halo- alkenylthio, C3-C6alkynylthio, C C4alkoxy-CrC2alkylthio, CrC4alkylcarbonyl-CrC2alkylthio, Cι-C4alkoxycarbonyl-CrC2alkylthio, cyano-CrC4alkylthio, CrC6alkylsulfinyl, CrCehaloalkylsulfinyl, CrC6alkylsulfonyl, CrC6haloalkylsulfonyl, aminosulfonyl, CrC2alkylamino- sulfonyl, di(CrC2alkyl)aminosulfonyl, di(d-C alkyl)amino, halogen, cyano, nitro, phenyl and/or by benzylthio, it being possible for phenyl and benzylthio in turn to be substituted on the phenyl ring by d-C3alkyl, CrC3haloalkyl, CrC3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro, and substituents on the nitrogen atom in the heterocyclic ring are other than halogen;
Ra5 is hydrogen, CrC6alkyl, CrC6haloalkyl, C2-Cealkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, CrC6alkoxy, CrC6haloalkoxy, CrC6alkylthio, d-C6alkyl- sulfinyl, CrC6alkylsulfonyl, CrCehaloalkylthio, CrC6haloalkylsulfinyl, d-C-ehaloalkylsulfonyl, CrC6alkylamino, di-C2-C6alkylamino, CrC6alkylaminosulfonyl, di-C2-C6alkylaminosulfonyl, phenyl, phenylthio, phenylsulfinyl, phenylsulfonyl or phenoxy, it being possible for phenyl in turn to be substituted by C C3alkyl, d-C3haloalkyl, CrC3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro, or Ra5 is -N(Cι-C4alkyl)-S-C C4alkyl, -N(CrC4alkyl)-SO-CrC4alkyl, -N(CrC4alkyl)-SO2-Ci-C4alkyl, cyano, halogen, amino, CrC4alkoxy-d-C4alkyl, d-C4alkyl-S- d-C4alkyl, CrC4alkyl-SO-C C4alkyl or Cι-C4alkyI-SO2-CrC4alkyl, and agronomically acceptable salts/N-oxides/isomers/enantiomers of those compounds.
ln preferred compounds of formula I, T is Tι. Those compounds correspond to formula Iz
D is hydrogen or R3;
E is hydrogen or R4; or
D and E together are C2-C3alkylene which can be mono- or poly-substituted by R6;
A is d-C2alkylene which can be mono- or poly-substituted by R5; or A may additionally be carbonyl, oxygen or -N-R7- when D and E are other than C2-C3alkylene; i. R2, R3, R4, R5 and R6 are each independently of the others hydrogen, CrC alkyl, phenyl, d-C4alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl or C C4alkoxycarbonyl; and
R7 is CrC4alkyl, alkoxycarbonyl or d-C4alkylcarbonyl, and their agronomically acceptable salts, isomers and enantiomers.
The alkyl groups appearing in the above substituent definitions may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. Alkoxy, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups may be mono- or poly-unsaturated. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert- butoxy. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl or tert-butoxy- carbonyl; preferably methoxycarbonyl or ethoxycarbonyl.
Halogen is generally fluorine, chlorine, bromine or iodine. The same is also true of halogen in conjunction with other meanings, such as haloalkyl or halophenyl.
Haloalkyl groups having a chain length of from 1 to 6 carbon atoms are, for example, fluoro- methyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2- trifluoroethyl, 1-fluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-fluoroprop-2-yl, pentafluoroethyl,
1 ,1 -difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl, pentafluoro- ethyl, heptafluoro-n-propyl and perfluoro-n-hexyl.
Alkenyl and alkynyl groups can be mono- or poly-unsaturated, so that alkyl, alkenyl and alkynyl chains having one or more double or triple bonds are also included. Alkenyl is, for example, vinyl, allyl, isobuten-3-yl, CH2=CH-CH2-CH=CH-, CH2=CH-CH2-CH2-CH=CH- or CH3-CH=CH-CH2-CH=CH-. A preferred alkynyl is, for example, propargyl, and a preferred allenyl is CH2=C=CH2-.
An alkylene chain can also be substituted by one or more CrC3alkyl groups, especially by methyl groups. Such alkylene chains and alkylene groups are preferably unsubstituted. The same applies also to all groups containing C3-C6cycloalkyl, C3-C5oxacycloalkyl, C3-C5thia- cycloalkyl, C3-C4dioxacycloalkyl, C3-C dithiacycloalkyl or C3-C oxathiacycloalkyl which occur, for example, also as part of oxygen- and sulfur-containing heterocyclic ring systems of the radicals Rai and Ra2.
A d-C4alkylene, d-C4alkenylene or C2-C alkynylene bridge which may be interrupted by oxygen, -N(d-C alkyl)-, sulfur, sulfinyl and/or sulfonyl, or in X2 or X6 in the meaning of a d- C6alkylene, C3-C6alkenylene or C3-C6alkynylene chain which can be mono- or poly- substituted by halogen and/or by X4 or X8, and wherein the unsaturated bonds of the chain are not bonded directly to the substituent Xi or X5, is to be understood as being, for example, — CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH(CH3)-, -CH2CH(CH3)-, - CH2CH(CH3)CH2-, -CH2CH(CI)CH2-, -CH2CH(OCH3)CH2-, -CH2O-, -OCH2-, -CH2OCH2-, - OCH2CH2-, -OCH2CH2CH2-, -CH2OCH2CH2-, -CH2OCH(CH3)CH2-, -SCH2-, -SCH2CH2-, - SCH2CH2CH2-, -CH2S-, — CH2SCH2-, — CH2S(O)CH2-, —CH2SO2CH2-, — CH2SCH2CH2-, — CH2S(O)CH2CH2-, -CH2SO2CH2CH2-, -CH2SO2NH-, -CH2N(CH3)SO2CH2CH2-, - N(SO2Me)CH2CH2-, -CH2C(O)NH- or -CH2NHC(O)CH2-. A C2-C4alkenylene chain which may be uninterrupted or interrupted by oxygen is accordingly to be understood as being, for example, -CH=CH-CH2-, -CH=CH-CH2CH2- or -CH=CHCH2OCH2-, and a C2-C4alkynylene chain which may be uninterrupted or interrupted by oxygen is to be understood as being, for example, -C≡C-, -C≡CCH2-, -C≡CCH2O-, -C≡CCH2OCH2- or -OC≡CCH2-.
A three- to ten-membered mono- or bi-cyclic ring system Rai or Ra2, which may be interrupted once or up to three times selected from oxygen, sulfur, S(O), SO2, N(Ra6), carbonyl
and C(=NORa7) and which is bonded to the carbon atom of the substituent Ai or to the group Qι or Q2 either directly or by way of a d-C4alkylene, d-C4alkenylene or C2-C4alkynylene bridge which may be interrupted by oxygen, -N(d-C4alkyl)-, sulfur, sulfinyl and/or sulfonyl, is to be understood as being, for example, 1 -methyl-1 H-pyrazol-3-yl, 1 -ethyl-1 H-pyrazol-3-yl, 1- propyl-1 H-pyrazol-3-yl, 1 H-pyrazol-3-yl, 1 ,5-dimethyl-1 H-pyrazol-3-yl, 4-chloro-1 -methyl-1 H- pyrazol-3-yl, 1 H-pyrazol-1-yl, 3-methyl-1 H-pyrazol-1 -yl, 3,5-dimethyl-1 H-pyrazol-1-yl, 3- isoxazolyl, 5-methyl-3-isoxazolyl, 3-methyl-5-isoxazolyl, 5-isoxazolyl, 1 H-pyrrol-2-yl, 1- methyl-1 H-pyrrol-2-yl, 1 H-pyrrol-1-yl, 1 -methyl-1 H-pyrrol-3-yl, 2-furanyl, 5-methyl-2-furanyl, 3-furanyl, 5-methyl-2-thienyl, 2-thienyl, 3-thienyl, 1 -methyl-1 H-imidazol-2-yl, 1 H-imidazol-2-yl, 1 -methyl-1 H-imidazol-4-yl, 1 -methyl-1 H-imidazol-5-yl, 4-methyl-2-oxazolyl, 5-methyl-2- oxazolyl, 2-oxazolyl, 2-methyl-5-oxazolyl, 2-methyl-4-oxazolyl, 4-methyl-2-thiazolyl, 5-methyl- 2-thiazolyl, 2-thiazolyl, 2-methyI-5-thiazolyl, 2-methyl-4-thiazolyl, 3-methyl-4-isothiazolyl, 3- methyl-5-isothiazolyl, 5-methyl-3-isothiazolyl, 1 -methyl-1 H-1 ,2,3-triazol-4-yl, 2-methyl-2H- 1 ,2,3-triazol-4-yl, 4-methyl-2H-1 ,2,3-triazol-2-yl, 1 -methyl-1 H-1 ,2,4-triazol-3-yl, 1 ,5-dimethyl- 1 H-1 ,2,4-triazol-3-yl, 3-methyl-1 H-1 ,2,4-triazol-1-yl, 5-methyl-1 H-1 ,2,4-triazol-1 -yl, 4,5- dimethyl-4H-1 ,2,4-triazol-3-yl, 4-methyl-4H-1 ,2,4-triazol-3-yl, 4H-1 ,2,4-triazol-4-yl, 5-methyl- 1 ,2,3-oxadiazol-4-yl, 1 ,2,3-oxadiazol-4-yl, 3-methyl-1 ,2,4-oxadiazol-5-yl, 5-methyl-1 ,2,4-oxa- diazol-3-yl, 4-methyl-3-furazanyl, 3-furazanyl, 5-methyl-1 ,2,4-oxadiazol-2-yl, 5-methyl-1 ,2,3- thiadiazol-4-yl, 1 ,2,3-thiadiazol-4-yl, 3-methyl-1 ,2,4-thiadiazol-5-yl, 5-methyl-1 ,2,4-thiadiazol- 3-yl, 4-methyl-1 ,2,5-thiadiazol-3-yl, 5-methyl-1 ,3,4-thiadiazol-2-yl, 1 -methyl-1 H-tetrazol-5-yl, 1 H-tetrazol-5-yl, 5-methyl-1 H-tetrazol-1-yl, 2-methyl-2H-tetrazol-5-yl, 2-ethyl-2H-tetrazol-5-yl, 5-methyl-2H-tetrazol-2-yl, 2H-tetrazol-2-yl, 2-pyridinyl, 6-methyl-2-pyridinyl, 4-pyridinyl, 3- pyridinyl, 6-methyl-3-pyridazinyl, 5-methyl-3-pyridazinyl, 3-pyridazinyl, 4,6-dimethyl-2-pyrim- idinyl, 4-methyl-2-pyrimidinyl, 2-pyrimidinyl, 2-methyl-4-pyrimidinyl, 2-chloro-4-pyrimidinyl, 2,6-dimethyl-4-pyπmidinyl, 4-pyrimidinyl, 2-methyl-5-pyrimidinyl, 6-methyl-2-pyrazinyl, 2- pyrazinyl, 4,6-dimethyl-1 ,3,5-triazin-2-yl, 4,6-dichloro-1 ,3,5-triazin-2-yl, 1 ,3,5-triazin-2-yl, 4- Λ methyl-1 ,3,5-triazin-2-yl, 3-methyl-1 ,2,4-triazin-5-yl, 3-methyl-1 ,2,4-triazin-6-yl, CH O , C rHy\> ,
A further annellated (fused-on), monocyclic or bicyclic ring system which is formed, for example, by two adjacent substituents Rai and Ra2 or Rai and Ra5 and which is uninterrupted or interrupted once or up to three times selected from oxygen, sulfur, S(O), SO2, -N(Ra6)-, carbonyl and C(=NORa7) and which may be additionally substituted by one or more substituents is to be understood as being, for example, an annellated, bidentate ring system
of formula
!
Compounds of formula I that are especially suitable for use according to the invention or for the composition according to the invention are those wherein
Ri and R2 are hydrogen; A is CrC2alkylene; D and E together are C2-C3alkylene; Q is Qi, wherein
Ai is methine, CRai or =N-(O)p, but preferably =N-(O)p; p is 0;
Rai is hydrogen, d-C6alkyl, hydroxy, CrC6alkoxy, CrC6haloalkoxy, C3-C6alkenyloxy, C3-C6haIoalkenyloxy, C3-C6alkynyloxy, d-C alkylcarbonyloxy, d-C4alkylsulfonyIoxy, tosyloxy, CrC4alkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl, CrC4alkylamino, di-d- C4alkylamino, d-C4alkoxycarbonyl, CrC4haloalkyl, formyl, cyano, halogen, phenyl or phenoxy; it being possible for phenyl in turn to be substituted by d-C3alkyl, d-C3haloalkyl, CrC3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro;
Ra2 is hydrogen, CrC6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, vinyl substituted by d-C2alkoxycarbonyl or by phenyl, C2-C6alkynyl, C2-C6haloalkynyl, ethynyl substituted by trimethylsilyl, hydroxy, d-C2alkoxy, CrC2alkoxycarbonyl or by phenyl, C3-C6allenyl, C3-C6- cycloalkyl, halo-substituted C3-C6cycloalkyl, d-C6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, CrC6haloalkoxy, C3-C6haloalkenyloxy, cyano-d-C4alkoxy, d-C4alkoxy-Cι-C4alkoxy, d-C4- alkylthio-d-C4alkoxy, d-C4alkylsulfinyl-CrC4alkoxy, Cι-C4alkylsulfonyl-Cι-C4alkoxy, Cι-C4- alkoxycarbonyl-d-C4alkoxy, CrC6alkylthio, CrC6alkylsulfinyl, CrC6alkylsulfonyl, CrCehaloalkylthio, d-Cehaloalkylsulfinyl, CrC6haloalkylsulfonyl, Cι-C4alkoxycarbonyl-CrC4alkylthio, Cι-C4alkoxycarbonyl-CrC4alkylsulfinyl, CrC4alkoxycarbonyl-CrC alkylsulfonyl, benzyl-S-, benzyl-SO-, benzyl-SO2-, CrC6alkylamino, di-C2-C6alkylamino, CrC6alkylaminosulfonyl, di(CrC6alkylamino)sulfonyl, benzyloxy, benzyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, it being possible for the phenyl-containing groups in turn to be substituted by C C3alkyl, d-C3haloalkyl, d-C3alkoxy, Cι-C3haloalkoxy, halogen, cyano or by nitro, or Ra2 is OS-Cι-C4alkyl, OSO-C C4alkyl, OSO2-d-C4alkyl, OS-C C4haloalkyl, OSO-d-C4halo- alkyl, OSO2-d-C4haloalkyl, N(CrC4alkyl)-S-C C4alkyl, N(CrC4alkyl)-SO-Cι-C4alkyl, N(Cι-C4alkyl)-SO2-d-C4alkyl, cyano, carbamoyl, CrC4alkoxycarbonyl, formyl, halogen,
rhodano, amino, hydroxy-d-C4alkyl, CrC4alkoxy-Cι-C4alkyl, Ci-C4alkyl-S-CrC4alkyl, d-C4alkyl-SO-CrC4alkyl, CrC4alkyl-SO2-Cι-C4alkyl, cyano-C C4alkyl, C C6alkylcarbonyl- oxy-CrC4alkyl, CrC4alkoxycarbonyl-CrC4alkyl, Cι-C4alkoxycarbonyloxy-Cι-C4alkyl, CrC4- rhodano-d-C4alkyl, benzoyloxy-d-C alkyl, C2-C6oxiranyl, Cι-C4alkylamino-CrC4alkyl, di(Ci-C4alkyl)amino-CrC alkyl, Cι-Cι2alkylthiocarbonyl-Cι-C4alkyl or formyl-d-C alkyl, or Ra2 is the group -XrX3 or the group -X2-XrX3; wherein Xi, X2 and X3 are as defined above; Ra3 and Ra4 are hydrogen and Ra5 is as defined above.
Compounds of formula I that are especially well suited for use according to the invention or for the composition according to the invention are those wherein
Ri and R2 are hydrogen, A is methylene, D and E together are ethylene, Ai is =N-(O)p; wherein p is 0;
Q is Qi, Ra3 and Ra4 are hydrogen, Ra5 is d-C3haloalkyl, especially trifluoromethyl, and Ra2 is Cι-C4alkoxy-Cι-C4alkoxy-CrC4alkyl, especially methoxyethoxymethyl.
Further compounds of formula I that are especially well suited for use according to the invention or for the composition according to the invention are listed in the following Tables:
In the Tables, CCH is the ethynyl group, Ph is the phenyl group and Me is the methyl group.
Table 1 : Compounds of formula le
1.001 H CF3 H H 0 1.002 F CF3 H H 0 1.003 CI CF3 H H 0
Comp Ra2 Ra5 Ra4 Ra3 P No.
1.004 Br CF3 H H 0
1.005 CHF2 CF3 H H 0
1.006 CCI3 CF3 H H 0
1.007 CCIF2 CF3 H H 0
1.008 CF3 CF3 H H 0
1.009 CH3 CF3 H H 0 1.01 CH2CH3 CF3 H H 0
1.011 CH(CH3)2 CF3 H H 0
1.012 (CH2)2CH3 CF3 H H 0
1.013 C(CH3)3 CF3 H H 0
1.014 Ph CF3 H H 0
1.015 CH2F CF3 H H 0
1.016 CH2CI CF3 H H 0
1.017 CH2Br CF3 H H 0
1.018 CH2OH CF3 H H 0
1.019 CH2OCOCH3 CF3 H H 0 1.02 CH2OCOPh CF3 H H 0
1.021 CH2OCH3 CF3 H H 0
1.022 CH2OCH2CH3 CF3 H H 0
1.023 CH2CH2OCH3 CF3 H H 0
1.024 CH2SMe CF3 H H 0
1.025 CH2SOMe CF3 H H 0
1.026 CH2SO2Me CF3 H H 0
1.027 CH2SO2Ph CF3 H H 0
1 .028 SCH2Ph CF3 H H 0
1.029 SOCH2Ph CF3 H H 0 1.03 SO2CH2Ph CF3 H H 0
1.031 SCH3 CF3 H H 0
1.032 SOCH3 CF3 H H 0
1.033 SO2CH3 CF3 H H 0
1.034 SPh CF3 H H 0
1.035 SOPh CF3 H H 0
o o o o o o o o O O o o O O o o o o o z o en en en en en en Ol Ol Ol Ol en cπ 01 01 en o o o o o o o o O o >. 4i> . 4s> £> -fc> o CO CO CO CO -vi en en 4^ ω ro 2 en CO 4ϊ> CO OD -J en Ol 45* CO ro — * en 4^ 4^ -P C» ^J en en ^ CO ro CO ∞ si 0) P 3 Ό
o TI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI oTI ^oTI oTI ^oTI ^oTI ^oTI ^oTI ^oTI 03
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x 0)
x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x X 03 ω o o o o o o o o o o o o o o o o
Comp Ra2 Ra5 Ra4 Ra3 p No.
1.068 CH2Br CF3 H H 1
1.069 CH2OH CF3 H H 1 1.07 CH2OCOCH3 CF3 H H 1
1.071 CH2OCOPh CF3 H H 1
1.072 CH2OCH3 CF3 H H 1
1.073 CH2OCH2CH3 CF3 H H 1
1.074 CH2CH2OCH3 CF3 H H 1
1.075 CH2SMe CF3 H H 1
1.076 CH2SOMe CF3 H H 1
1.077 CH2SO2Me CF3 H H 1
1.078 CH2SO2Ph CF3 H H 1
1.079 SCH2Ph CF3 H H 1 1.08 SOCH2Ph CF3 H H 1
1.081 SO2CH2Ph CF3 H H 1
1.082 SCH3 CF3 H H 1
1.083 SOCH3 CF3 H H 1
1.084 SO2CH3 CF3 H H 1
1.085 SPh CF3 H H 1
1.086 SOPh CF3 H H 1
1.087 SO2Ph CF3 H H 1
1.088 N(CH3)2 CF3 H H 1
1.089 CH=CH2 CF3 H H 1 1.09 CH2CH=CH2 CF3 H H 1
1.091 SO2N(CH3)2 CF3 H H 1
1.092 Ethynyl CF3 H H 1
1.093 Cyclopropyl CF3 H H 1
1.094 OCH3 CF3 H H 1
1.095 OPh CF3 H H 1
1.096 OCHF2 CF3 H H 1
1.097 CO2Me CF3 H H 1
1.098 2-Furyl CF3 H H 1
1.099 OCH2CCH CF3 H H 1
Comp Ra2 Ra5 Ra4 Ra3 P No. 1.1 2-PyridyI CF3 H H 1
1.101 3-Pyridyl CF3 H H 1
1.102 4-Pyridyl CF3 H H 1
1.103 H CF2CF3 H H 0
1.104 CI CF2CF3 H H 0
1.105 CHF2 CF2CF3 H H 0
1.106 CCI3 CF2CF3 H H 0
1.107 CCIF2 CF2CF3 H H 0
1.108 CF3 CF2CF3 H H 0
1.109 CH3 CF2CF3 H H 0 1.11 CH2CH3 CF2CF3 H H 0
1.111 CH(CH3)2 CF2CF3 H H 0
1.112 (CH2)2CH3 CF2CF3 H H 0
1.113 C(CH3)3 CF2CF3 H H 0
1.114 CH2F CF2CF3 H H 0
1.115 CH2CI CF2CF3 H H 0
1.116 CH2OH CF2CF3 H H 0
1.117 CH2OCOCH3 CF2CF3 H H 0
1.118 CH2OCOPh CF2CF3 H H 0
1.119 CH2OCH3 CF2CF3 H H 0 1.12 CH2OCH2CH3 CF2CF3 H H 0
1.121 CH2SMe CF2CF3 H H 0
1.122 CH2SOMe CF2CF3 H H 0
1.123 CH2SO2Me CF2CF3 H H 0
1.124 CH2SO2Ph CF2CF3 H H 0
1.125 N(CH3)2 CF2CF3 H H 0
1.126 CH=CH2 CF2CF3 H H 0
1.127 CH2CH=CH CF2CF3 H H 0
1.128 SO2N(CH3)2 CF2CF3 H H 0
1.129 CCH CF2CF3 H H 0 1.13 Cyclopropyl CF2CF3 H H 0
1.131 OPh CF2CF3 H H 0
Comp Ra2 Ra5 Ra4 Ra3 No.
1.132 OCH3 CF2CF3 H H 0
1.133 CO2Me CF2CF3 H H 0
1.134 OCH2CCH CF2CF3 H H 0
1.135 2-Pyridyl CF2CF3 H H 0
1.136 3-Pyridyl CF2CF3 H H 0
1.137 4-Pyridyl CF2CF3 H H 0
1.138 H CF2CF3 H H
1.139 CI CF2CF3 H H 1.14 CHF2 CF2CF3 H H
1.141 CCI3 CI-2 r3 H H
1.142 CCIF2 CF2CF3 H H
1.143 CF3 CF2CF3 H H
1.145 CH2CH3 CF2CF3 H H
1.146 CH(CH3)2 CF2CF3 H H
1.147 (CH2)2CH3 CF2CF3 H H
1.148 C(CH3)3 CF2CF3 H H
1.149 CH2F CF2CF3 H H 1.15 CH2CI CF2CF3 H H
1.151 CH2OH CF2CF3 H H
1.152 CH2OCOCH3 CF2CF3 H H
1.153 CH2OCOPh CF2CF3 H H
1.154 CH2OCH3 CF2CF3 H H
1.155 CH2OCH2CH3 CF2CF3 H H
1.156 CH2SMe CF2CF3 H H
1.157 CH2SOMe CF2CF3 H H
1.158 CH2SO2Me CF2CF3 H H
1.159 CH2SO2Ph CF2CF3 H H 1.16 N(CH3)2 CF2CF3 H H
1.161 CH=CH2 CF2CF3 H H
1.162 CH2CH=CH2 CF2CF3 H H
1.163 SO2N(CH3)2 CF2CF3 H H
Comp Ra2 Ra5 Ra Ra3 No.
1.164 CCH CF2CF3 H H
1.165 Cyclopropyl CF2CF3 H H
1.166 OPh CF2CF3 H H
1.167 OCH3 CF2CF3 H H
1.168 CO2Me CF2CF3 H H
1.169 OCH2CCH CF2CF3 H H 1.17 2-Pyridyl CF2CF3 H H
1.171 3-Pyridyl CF2CF3 H H
1.172 4-Pyridyl CF2CF3 H H
1.173 H CF2CF2CF3 H H 0
1.174 CHF2 CF2CF2CF3 H H 0
1.175 CF3 CF2CF2CF3 H H 0
1.176 CH3 CF2CF2CF3 H H 0
1.177 CH2CH3 CF2CF2CF3 H H 0
1.178 (CH2)2CH3 CF2CF2CF3 H H 0
1.179 CH2CI CF2CF2CF3 H H 0 1.18 CH2OCH3 CF CF2CF3 H H 0
1.181 H CF2CF2CF3 H H 1
1.182 CHF2 CF CF2CF3 H H 1
1.183 CF3 CF2CF2CF3 H H 1
1.184 CH3 CF2CF2CF3 H H 1
1.185 CH2CH3 CF2CF2CF3 H H 1
1.186 (CH2)2CH3 CF2CF2CF3 H H 0
1.187 CH2CI CF2CF2CF3 H H 1
1.188 CH2OCH3 CF CF2CF3 H H 1
1.189 H CF2CI H H 0 1.19 CI CF2CI H H 0
1.191 CHF2 CF2CI H H 0
1.192 CCI3 CF2CI H H 0
1.193 CCIF2 CF2CI H H 0
1.194 CF3 CF2CI H H 0
1.195 CH3 CF2CI H H 0
Comp Ra2 Ra5 Ra4 Ra3 P No.
1.196 CH2CH3 CF2CI H H 0
1.197 CH(CH3)2 CF2CI H H 0
1.198 (CH2)2CH3 CF2CI H H 0
1.199 C(CH3)3 CF2CI H H 0 1.2 CH2F CF2CI H H 0
1.201 CH2CI CF2CI H H 0
1.202 CH2OH CF2CI H H 0
1.203 CH2OCOCH3 CF2CI H H 0
1.204 CH2OCOPh CF2CI H H 0
1.205 CH2OCH3 CF2CI H H 0
1.206 CH2OCH2CH3 CF2CI H H 0
1.207 CH2SMe CF2CI H H 0
1.208 CH2SOMe CF2CI H H 0
1.209 CH2SO2Me CF2CI H H 0 1.21 CH2SO2Ph CF2CI H H 0
1.211 N(CH3)2 CF2CI H H 0
1.212 CH=CH2 CF2CI H H 0
1.213 CH2CH=CH2 CF2CI H H 0
1.214 SO2N(CH3)2 CF2CI H H 0
1.215 CCH CF2CI H H 0
1.216 Cyclopropyl CF2CI H H 0
1.217 OPh CF2CI H H 0
1.218 OCH3 CF2CI H H 0
1.219 CO2Me CF2CI H H 0 1.22 OCH2CCH CF2CI H H 0
1.221 2-Pyridyl CF2CI H H 0
1.222 3-Pyridyl CF2CI H H 0
1.223 4-Pyridyl CF2CI H H 0
1.224 H CF2CI H H 1
1.225 CI CF2CI H H 1
1.226 CHF2 CF2CI H H 1
1.227 CCI3 CF2CI H H 1
Comp Ra2 Ra5 Ra4 Ra3 No.
1.228 CCIF2 CF2CI H H
1.229 CF3 CF2CI H H 1.23 CH3 CF2CI H H
1.231 CH2CH3 CF2CI H H
1.232 CH(CH3)2 CF2CI H H
1.233 (CH )2CH3 CF2CI H H
1.234 C(CH3)3 CF2CI H H
1.235 CH2F CF2CI H H
1.236 CH2CI CF2CI H H
1.237 CH2OH CF2CI H H
1.238 CH2OCOCH3 CF2CI H H
1.239 CH2OCOPh CF2CI H H 1.24 CH2OCH3 CF2CI H H
1.241 CH2OCH CH3 CF2CI H H
1.242 CH2SMe CF2CI H H
1.243 CH2SOMe CF2CI H H
1.244 CH2SO2Me CF2CI H H
1.245 CH2SO2Ph CF2CI H H
1.246 N(CH3)2 CF2CI H H
1.247 CH=CH2 CF2CI H H
1.248 CH2CH=CH2 CF2CI H H
1.249 SO2N(CH3)2 CF2CI H H 1.25 CCH CF2CI H H
1.251 Cyclopropyl CF2CI H H
1.252 OPh CF2CI H H
1.253 OCH3 CF2CI H H
1.254 CO2Me CF2CI H H
1.255 OCH2CCH CF2CI H H
1.258 CH3 CCI3 H H 0
Comp Ra2 Ra5 Ra4 Ra3 No. 1.26 CH(CH3)2 CCI3 H H 0
1.261 (CH2)2CH3 CCl3 H H 0
1.262 CH2F CCI3 H H 0
1.263 CH2CI CCI3 H H 0
1.264 CH2OH CCI3 H H 0
1.265 CH2OCOCH3 CCI3 H H 0
1.266 CH2OCOPh CCI3 H H 0
1.267 CH2OCH3 CCI3 H H 0
1.268 CH2OCH2CH3 CCI3 H H 0
1.269 CH2SMe CCI3 H H 0 1.27 CH2SOMe CCI3 H H 0
1.271 CH2SO2Me CCI3 H H 0
1.272 CH2SO2Ph CCI3 H H 0
1.273 Cyclopropyl CCI3 H H 0
1.274 OPh CCI3 H H 0
1.275 OCH3 CCI3 H H 0
1.276 CO2Me CCI3 H H 0
1.277 OCHgCCH CCI3 H H 0
1.278 H CCI3 H H
1.279 CI CCI3 H H 1.28 CH3 CCI3 H H
1.281 CH2CH3 CCI3 H H
1.282 CH(CH3)2 CCI3 H H
1.283 (CH2)2CH3 CCI3 H H
1.284 CH2F CCI3 H H
1.285 CH2CI CCI3 H H
1.286 CH2OH CCI3 H H
1.287 CH2OCOCH3 CCI3 H H
1.288 CH2OCOPh CCI3 H H
1.289 CH2OCH3 CCI3 H H 1.29 CH2OCH2CH3 CCI3 H H
1.291 CH2SMe CCI3 H H
Comp Ra2 Ra5 Ra4 Ra3 P No.
1.292 CH2SOMe CCI3 H H
1.293 CH2SO2Me CCI3 H H
1.294 CH2SO2Ph CCI3 H H
1.295 Cyclopropyl CCI3 H H
1.296 OPh CCI3 H H
1.297 OCH3 CCI3 H H
1.298 CO2Me CCI3 H H
1.299 OCH2CCH CCI3 H H 1.3 CF3 CHF2 H H 0
1.301 CH3 CHF2 H H 0
1.302 CH2OCH3 CHF2 H H 0
1.303 CH2CI CHF2 H H 0
1.304 CH2F CHF2 H H 0
1.305 CF3 CHF2 H H
1.306 CH3 CHF2 H H
1.307 CH2OCH3 CHF2 H H
1.308 CH2CI CHF2 H H
1.309 CH2F CHF2 H H 1.31 CH3 CF3 H CH3 0
1.311 CH3 CF3 H CH3 1
1.312 CI CF3 H CH3 0
1.313 CH3 CF3 CH3 H 0
1.314 CH3 CF3 Ph H 0
1.315 CH3 CF3 CI H 0
1.316 CH3 CF3 CO2CH2CH3 H 0
1.317 CH3 CF3 CO2CH2Ph H 0
1.318 CH3 CF3 CH3 H
1.319 CH3 CF3 Ph H 1.32 CH3 CF3 CI H
1.321 CH3 CF3 CO2CH2CH3 H
1.322 CH3 CF3 CO2CH2Ph H
1.323 OCH3 CF3 CH3 H 0
Comp Ra2 Ra5 Ra4 Ra3 P No.
1.324 CH2OCH3 CF3 CH3 H 0
1.325 CH2OCH3 CF3 Ph H 0
1.326 CH2OCH3 CF3 CI H 0
1.327 CH2OCH3 CF3 CO2CH2CH3 H 0
1.328 CH2OCH3 CF3 CO2CH2Ph H 0
1.329 CH2OCH3 CF3 CH3 H 1.33 CH2OCH3 CF3 Ph H
1.331 CH2OCH3 CF3 CI H
1.332 CH2OCH3 CF3 CO2CH2CH8 H
1.333 CH2OCH3 CF3 CO2CH2Ph H
1.334 COOCH3 H H H 0
1.335 CF3 SCH3 H H 0
1.336 CH3 SCH3 H H 0
1.337 CF3 SOCH3 H H 0
1.338 CH3 SOCH3 H H 0
1.339 CF3 SO2CH3 H H 0 1 .34 CH3 SO2CH3 H H 0
1.341 CF3 SCH2CH3 H H 0
1.342 CH3 SCH2CH3 H H 0
1.343 CF3 SOCH2CH3 H H 0
1.344 CH3 SOCH2CH3 H H 0
1.345 CF3 SO2CH2CH3 H H 0
1.346 CH3 SO2CH CH3 H H 0
1.347 CF3 OCH3 H H 0
1.348 CH3 OCH3 H H 0
1.349 CF3 OCH2CF3 H H 0 1.35 CH3 OCH2CF3 H H 0
1.351 CF3 OCH2CCH H H 0
1.352 CH3 OCH2CCH H H 0
1.353 CF3 CN H H 0
1.354 CH3 CN H H 0
1.355 CF3 CI H H 0
Comp Ra2 Ra5 Ra4 Ra3 P No.
1.356 CF3 CI H H 0
1.357 CH3 CI H H 0
1.358 H CI H H 0
1.359 CF3 OCH3 H H 0 1.36 CH3 OCH3 H H 0
1.361 CF3 CH3 H H 0
1.362 H CF3 H CH3 0
1.363 H CF3 H CF3 0
1.364 H CF3 H CH2CH3 0
1.365 H CF3 H CF3 0
1.366 H CF3 H SCH3 0
1.367 H CF3 H SOCH3 0
1.368 H CF3 H SO2CH3 0
1.369 H CF3 H CI 0 1.37 H CF3 H OCH3 0
1.371 H CH3 H CF3 0
1.372 H CI H CF3 0
1.373 H OCH3 H CF3 0
1.374 H SCH3 H CF3 0
1.375 H SOCH3 H CF3 0
1.376 CF2H SOCH2CH3 H H 0
1.377 CF2CI SOCH2CH3 H H 0
1.378 CF2H SO2CH2CH3 H H 0
1.379 CF2CI SO2CH2CH3 H H 0 1.38 CF2H OCH3 H H 0
1.381 CF2CI OCH3 H H 0
1.382 CF2H OCH2CF3 H H 0
1.383 CF2CI OCH2CF3 H H 0
1.384 CF2H OCH2CCH H H 0
1.385 CF2CI OCH2CCH H H 0
1.386 CF2H CN H H 0
1.387 CF2CI CN H H 0
Comp Ra2 Ra5 Ra4 Ra3 P No. 1.388 CF2H CI H H 0 1.389 CF2CI CI H H 0 1.39 CF2H OCH3 H H 0 1.391 CF2CI OCH3 H H 0 1.392 CF3 CH2OCH3 H H 0 1.393 CF3 CH2OCH3 H H 1 1.394 CF2CI CH2OCH3 H H 0 1.395 CF2CI CH2OCH3 H H 1 1.396 CF2H CH2OCH3 H H 0 1.397 CF2H CH2OCH3 H H 1 1.398 CN CF3 H H 0
Table 2: Preferred HPPD inhibitors according to the present invention:
Further preferred compounds of formula I are listed in the following Tables.
In the following Table, the left-hand valency of the radical X2 is linked to the pyπdine ring.
CH
Where no free valency is indicated for the substituent X3, for example as in ° , the linkage site is located at the carbon atom labelled "CH".
In the following Table, the compounds of formula I are represented as follows:
wherein the formula A0
Radical χ2 χ3 Ra4 Ra5 X! P
A1 CH2 CH3 H CF3 O 0
A3 CH2 (CH3)2CH H CF3 O 0 A4 CH2 PhCH2 H CF3 O 0 A5 CH2 CH3 H CF3 s 0 A6 CH2 CH3 H CF3 SO 0 A7 CH2 CH3 H CF3 SO2 0 A8 CH2 CH3OCH2 H CF3 O 0 A9 CH2 CH3CH2OCH2 H CF3 O 0 A10 CH2 CH3OCH2CH2 H CF3 O 0 A11 CH2 CH3CH2OCH2CH2 H CF3 O 0 A12 CH2 CH3OC(CH3)2CH2 H CF3 O 0 A13 CH2 CH3OCH(CH3)CH2 H CF3 O 0 A14 CH2 CH3OCH2CH(CH3) H CF3 O 0
Radical χ2 χ3 Ra4 Ra5 Xi P A15 CH2 CH3OCH2C(CH3)2 H CF3 O 0 A16 CH2 CH3OCH(CH3) H CF3 O 0 A17 CH2 CH3OC(CH3)2 H CF3 O 0 A18 CH2 HC≡CCH2 H CF3 O 0 A19 CH2 H2C=CHCH2 H CF3 O 0 A20 CH2 CH3C≡CCH2 H CF3 O 0 A21 CH2 [ H H CF3 O 0
A22 CH2 ^CH H CF3 O 0
A24 CH2 CH H CF3 O 0
A25 CH2 O" H CF3 O 0
A26 CH2 0" H CF3 O 0
&
A59 CH2 CH, H CF3 O 0 o A60 CH2 CH2 H CF3 O 0
A61 CH2 CH, H CF3 O 0 o-
A113 CH2CH2 Α H CF3 O 0
A114 CH2CH2 H CF3 C0H O 0
A115 CH CH2 ACH H CF3 O 0
A116 CH CH2 H CF3 O 0 CCH A117 CH2CH2 ^CH H CF3 O 0
A148 CH2CH2 Ϊ>-CH8 H CF3 O 0
A149 CH2CH2 yCH2 H CF3 O 0
A151 CH2CH2 A -CH2 H CF3 O 0
Radical X2 X3 Ra4 Ra5 ^ p
A214 CH(OCH3)CH2 H CF3 O 0
A215 CH(OCH3)CH2 H CF;3 °
A220 CH(OCH3)CH2 H CF3 O 0
A221 CH(OCH3)CH2 H CF3 O 0
A222 CH(OCH3)CH2 /TA H CF3 O 0 N > _, N I CH3 A223 CH(OCH3)CH2 f^A" H CF3 O 0
A224 CH(OCH3)CH2 H CF3 O 0
Radical Ra4 Ra* Xi A225 CH(OCH3)CH2 H CF3 O 0
A228 CH(OCH3)CH2 H CF3 O 0
A229 CH(OCH3)CH2 H CF3 O 0
A230 CH(OCH3)CH2 H CF3 O 0
A231 CH(OCH3)CH2 H CF3 O 0
A232 CH(OCH3)CH2 H CF3 O 0
A233 CH(OCH3)CH2 H CF, O 0
A234 CH(OCH3)CH2 H CF3 O 0
A235 CH(OCH3)CH2 H CF3 O 0
Radical Ra4 Ra5 Xi
A239 CH(OCH3)CH2 H CF3 O 0
A240 CH(OCH3)CH2
A241 CH(OCH3)CH2 r CH, H CF3 O 0
CH, H CF3 O 0 o A242 CH(OCH3)CH2 CH, H CF3 O 0
A243 CH(OCH3)CH2 CH, H CF3 O 0 o A244 CH(OCH3)CH2 H CF3 O 0
A245 CH(OCH3)CH2 H CF3 O 0
A246 CH(OCH3)CH2 H CF3 O 0
A247 CH(OCH3)CH2 H CF3 O 0
A248 CH(OCH3)CH2 H CF3 O 0
A249 CH(OCH3)CH2 H CF3 O 0
Radical X2 X3 Ra4 Ra5 Xi p
A251 CH(OCH3)CH2 H CF3 O 0 A252 CH(OCH3)CH2 H CF3 O 0
A253 CH(OCH3)CH2 H CF3 O 0
A254 CH(OCH3)CH2 .CH2 H CF3 O
A255 CH(OCH3)CH2 H CF3 O 0
A259 CH(OCH3)CH2 H CF3 O 0
A260 CH(OCH3)CH2 H CF3 O 0
A261 CH(OCH3)CH2 H CF3 O 0
Radical χ2 χ3 Ra4 Ra5 Xi P A262 CH(OCH3)CH2 OH H CF3 O 0
A263 CH(OCH3)CH2 H CF3 O 0
A264 CH(OCH3)CH2 H CF3 O 0
A268 CH(OCH3)CH2 H CF3 O 0
A269 CH(OCH3)CH2 H CF3 O 0
A270 CH(OCH3)CH2 H CF3 O 0
A271 CH(OCH3)CH2 H CF3 O 0
A272 CH(OCH3)CH2 H CF3 O 0
A273 CH2CH(OCH3)CH2 CH3 H CF3 O 0 A274 CH2CH(OCH3)CH2 CH3CH2 H CF3 O 0 A275 CH2CH(OCH3)CH2 (CH3)2CH H CF3 O 0
Radical χ2 χ3 Ra4 Ra5 Xi P A276 CH2CH(OCH3)CH2 PhCH2 H CF3 O 0 A277 CH2CH(OCH3)CH2 CH3 H CF3 s 0 A278 CH2CH(OCH3)CH2 CH3 H CF3 SO 0 A279 CH2CH(OCH3)CH2 CH3 H CF3 SO2 0 A280 CH2CH(OCH3)CH2 CH3CH CH H CF3 O 0 A281 CH2CH(OCH3)CH2 CH3OCH2 H CF3 O 0 A282 CH2CH(OCH3)CH2 CH3CH OCH2 H CF3 O 0 A283 CH2CH(OCH3)CH2 CH3OCH2CH2 H CF3 O 0 A284 CH2CH(OCH3)CH2 CH3CH2OCH2CH2 H CF3 O 0 A285 CH2CH(OCH3)CH2 CH3OC(CH3)2CH2 H CF3 O 0 A286 CH2CH(OCH3)CH2 CH3OCH(CH3)CH2 H CF3 O 0 A287 CH2CH(OCH3)CH2 CH3OCH2CH(CH3) H CF3 O 0 A288 CH2CH(OCH3)CH2 CH3OCH2C(CH3)2 H CF3 O 0 A289 CH2CH(OCH3)CH2 CH3OCH(CH3) H CF3 O 0 A290 CH2CH(OCH3)CH2 CH3OC(CH3)2 H CF3 O 0 A291 CH2CH(OCH3)CH2 HC≡CCH2 H CF3 O 0 A292 CH2CH(OCH3)CH2 H2C=CHCH H CF3 O 0 A293 CH2CH(OCH3)CH2 CH3C≡CCH2 H CF3 O 0 A294 CH2CH(OCH3)CH2 [ H H CF3 O 0
A295 CH2CH(OCH3)CH2 Α H CF3 O 0
A296 CH2CH(OCH3)CH2 0o„ H CF3 O 0
A297 CH2CH(OCH3)CH2 CH H CF3 O 0 OA A298 CH2CH(OCH3)CH2 Co„ H CF3 O 0
A299 CH2CH(OCH3)CH2 CH H CF3 O
A300 CH2CH(OCH3)CH2 H CF3 O 0
Radical Ra4 Ra« Xi A301 CH2CH(OCH3)CH2 H CF3 O 0
A302 CH2CH(OCH3)CH2 H CF3 O 0 O^ H A303 CH2CH(OCH3)CH2 o H CF3 O 0 .CH A304 CH2CH(OCH3)CH2 /° H CF3 O 0 H , A OAHI A305 CH2CH(OCH3)CH2 H CF3 O 0
A306 CH2CH(OCH3)CH2 H CF3 O 0
A307 CH2CH(OCH3)CH2 f^ ^ H CF3 O 0 ^^OH A308 CH2CH(OCH3)CH2 H CF3 O 0
A309 CH2CH(OCH3)CH2 H CF3 O 0
A310 CH2CH(OCH3)CH2 H CF3 O 0
A311 CH2CH(OCH3)CH2 H CF3 O 0
A312 CH2CH(OCH3)CH2 H CF3 O 0
Radical X2 X3 Ra4 Ra5 X, p
A315 CH2CH(OCH3)CH2 H CF3 O 0
A316 CH2CH(OCH3)CH2 H Cp3 °
A317 CH2CH(OCH3)CH2 H Cp3 0
A318 CH2CH(OCH3)CH2 H CF; . 0
A319 CH2CH(OCH3)CH2 H CF3 Q
A320 CH2CH(OCH3)CH2 H Cp3 Q
A321 CH2CH(OCH3)CH2 H CF3 O 0
A322 CH2CH(OCH3)CH2 H CF3 O
A323 CH2CH(OCH3)CH2 H CF3 O 0
A324 CH2CH(OCH3)CH2 H CF3 O
Radical Ra4 Ra5 Xi A325 CH2CH(OCH3)CH2 H CF3 O
A326 CH2CH(OCH3)CH2 H CF, O
A327 CH2CH(OCH3)CH2 H CF3 O
A328 CH2CH(OCH3)CH2 H CF3 O 0
A329 CH2CH(OCH3)CH2 H CF3 O 0
A330 CH2CH(OCH3)CH2 t — CH2 H CF3 O 0
A331 CH2CH(OCH3)CH2 /^CH2 H CF3 O 0
A332 CH2CH(OCH3)CH2 CH, H CF3 O 0 O A333 CH2CH(OCH3)CH2 CH, H CF3 O 0
A334 CH2CH(OCH3)CH2 CH, H CF, O 0 O A335 CH2CH(OCH3)CH2 H CF, O 0
A336 CH2CH(OCH3)CH2 H CF3 O 0
A337 CH2CH(OCH3)CH2 H CF3 O 0
A338 CH2CH(OCH3)CH2 H CF3 O 0
Radical X2 X3 Ra4 Ra5 Xi p
A340 CH2CH(OCH3)CH2 H CF3 O
A341 CH2CH(OCH3)CH2 / 0"2 H CF3 O 0 OCH, A342 CH2CH(OCH3)CH2 H CF3 O 0
A343 CH2CH(OCH3)CH2 H CF3 O 0
A344 CH2CH(OCH3)CH2 H CF3 O
A345 CH2CH(OCH3)CH2 X»2 H CF3 O 0
A346 CH2CH(OCH3)CH2 H CF3 O 0
A347 CH2CH(OCH3)CH2 H CF3 O 0
A348 CH2CH(OCH3)CH2 H CF3 O
A349 CH2CH(OCH3)CH2 H CF3 O 0
A350 CH2CH(OCH3)CH2 H CF3 O 0
Radical X2 X3 Ra4 Ra5 X1 p
~ A351 CH2CH(OCH3)CH2 ^^ /CH 2 "p CFs" O (T
A352 CH2CH(OCH3)CH2 H CF3 O 0
A353 CH2CH(OCH3)CH2 H CF3 O
A354 CH2CH(OCH3)CH2 H CF3 O 0
A355 CH2CH(OCH3)CH2 H CF3 O 0
A356 CH2CH(OCH3)CH2 OCH3 H CF3 O 0 CΎCHZ A357 CH2CH(OCH3)CH2 H CF3 O 0
A358 CH2CH(OCH3)CH2 H CF3 O 0
A359 CH2CH(OCH3)CH2 /CH2 H CF3 O 0
A360 CH2CH(OCH3)CH2 H CF3 O 0
A361 CH2CH(OCH3)CH2 H CF3 O 0
A362 CH2CH(OCH3)CH2 H CF3 O 0
Radical X2 X3 Ra4 Ra5 X! p
~ A390 CH=CHCH2 ^ CH H CT^ O 0 o-l
A392 CH=CHCH2 ^\ H CF3 O 0 VCH A393 CH=CHCH2 ^\ H CF3 O 0 O^^.CH A394 CH=CHCH2 0^ H CF3 O 0 .CH
I CH, A404 • CH=CHCH2 H CF3 O
CH,
A421 CH=CHCH2 ° -CH2 H CF3 O 0
A422 CH=CHCH2 CH, H CF3 O 0
A423 CH=CHCH2 CH, H CF3 O 0 O
A425 CH=CHCH2 CH, H CF3 O o-
Radical X2 X3 Ra Ra5 X^ p A478 C≡CCH2 C ACCHH : H C O o"
A480 C≡CCH2 A^CH H CF3 O 0
A481 C≡CCH2 CH H CF3 O 0 V-f
A516 C≡CCH2 CH, H CF3 O 0 o
Radical Ra4 Ra5 Xi
A603 CH2 Ϊ>-CH2 H CF2CI O 0
A605 CH2 CH, H CF2CI O 0 O A606 CH2 AN-CH2 H CF2CI O 0
A658 CH2 9 o-~..CH H CHF2 O A1 A659 CH2 O CH H CHF2 O
A660 CH2 -CH H CHF2 O 0 OA A661 CH2 /^CH H CHF2 O 0
&
A748 CH2 ° CH H CF3 O
A749 CH2 H CF3 O CCH
A751 CH2 H CF3 O GCH A752 CH2 H CF3 O Cx
A785 CH2 CH, H CF3 O O A786 CH2 A ^CH2 H CF3 O
Radical Ra Ra5 Xi P
In the Table below, the ring linkage site for the substituent A in the case of rings is located at the carbon atom labelled "C", for example O ^ ; and in the case of open-chain structures, for
H3C- example, "(CH3)2C" denotes H,C
Radicals in which the substituent C-R2 is a ring, for example
(B16), are formed by combination of the substituent R2 with the substituent E in the meaning of R .
together form a C2-C4alkylene chain which can be interrupted by oxygen and/or carbonyl and/or sulfur, with the proviso that the oxygen and sulfur atoms are separated by at least one methylene group;
Q in the formula A0-Q is Q2
Radical C-R2 A n Ri D
B1 CH2 CH2 0 H H B2 CH2 CH2 0 CH3 H B3 CH2 CH2 0 CH3 CH3 B4 (CH3)CH CH2 0 CH3 CH3 B5 (CH3)2C CH2 0 CH3 CH3 B6 CH CH 0 CH3 - B7 CH2 CH2 0 CH3 CH =CHCH2 B8 CH2 CH2 0 CH3 HC≡CCH2 B9 CH2 CH2 0 CH3 CH3S B10 CH2 CH2 0 CH3 CH3SO B11 CH2 CH2 0 CH3 CH3SO2 B12 CH2 CH2 0 CH3 CH3O B13 CH2 CH2 0 CH3 CH3OC(O) B14 CH2 CH2 0 CH3 CH3CH2OC(O) B15 CH2 (CH3)2C 0 H H
Radical C-R2 A n Ri D B16 o CH2 0 H H A B17 [ CH2 0 H H
B18 CH2 0 CH3 H
B19 CH2 0 CH3 CH3
B20 A CH2 0 H H
B21 CH2 0 CH3 H
B22 O CH2 0 CH, CH3
B23 (CH3)2C O 0 CH3 CH3 B24 CH2 O 0 CH3 CH3 B25 CH3N O 0 CH3 CH3
B27 CH3N CH2 0 CH3 CH3 B28 CH3N (CH3)CH 0 H H B29 CH3N (CH3)CH 0 CH3 H B30 NH (CH3)C 0 H - B31 NH CH 0 CH3 - B32 CH3N (CH3)C 0 H - B33 CH3N CH 0 CH3 - B34 O (CH3)2C 0 H - B35 O (CH3)2C 0 CH3 CH3 B36 O (CH3)2C 0 CH3 H B37 O (CH3)C 0 H - B38 O CH 0 CH3 - B39 (CH3)2C C=O 0 CH3 CH3 B40 (CH3)2C (OH)CH 0 CH3 CH3 B41 l C=O 0 CH3 CH3
Radical C-R2 A n R. D B42 l C=O 0 CH2 CH2
B44 (CH3)2C 0 CH3 CH3
or Q in the formula A0-Q is Q3
Radical R 34 R 35 R. 36
Radical R34 R35 36 C1 CH3 H OH C2 CH3 CH3 OH C3 H HC≡CCH2 OH C4 H CH3SO2 OH C5 H CH3 OH C6 H PhCH2 OH C7 CF3 CH3 OH C8 CH CH3 OH
C9 CH3OCH2CH2OCH2 CH3 OH C10 H CH3 CI C11 H CH3 NH2 C12 H CH3 CH3SO2NH C13 H CH3 CH3OCH2CH2S C14 H CH3 CH3OCH2CH2SO C15 H CH3 CH3OCH2CH2SO2 C16 H CH3 (CH3)2NC(O)NH C17 H CH3 PhC(O)O C18 H CH3 CH3OC(O)O C19 H CH3 CH3(CH2)7S C20 H CH3 CH3(CH2)7SO C21 H CH3 CH3(CH2)7SO2 C22 H CH3 (CH3)2NSO2NH C23 H CH3 PhS C24 H CH3 PhSO C25 H CH3 PhSO2
C28 H CH3 CH3SO2O C29 H CH3 p-Toly!SO2O
Radical R34 R35 R36
or Q in the formula A0-Q is Q4
Radical R49 R50 n
D1 [ H CH3 0
D3 [ H CH3 2
D4 [ H CF3 0
D5 £CH CF3 1
D6 ' | H CF3 2
D7 [ H Ph 0
D8 Ph 1 | H D9 [/ H Ph 2
D10 cH PhCH2 0
D11 [ H PhCH2 1
D12 [ H PhCH2 2
Table 3: Compounds of formula I. represented as compounds of the formula
Ao-Q
wherein Q is Q2 and Q2 is the radical B52:
B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52 B52
A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24 A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36 A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48 A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59 A60 A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72 A73 A74 A75 A76 A77 A78 A79 A80 A81 A82 A83 A84 A85 A86 A87 A88 A89 A90 A91 A92 A93 A94 A95 A96 A97 A98 A99 A100 A101 A102 A103 A104 A105 A106 A107 A108
A109 A110 A111 A112 A113 A114 A115 A116 A117 A118 A119 A120
A121 A122 A123 A124 A125 A126 A127 A128 A129 A130 A131 A132
A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144 A145 A146 A147 A148 A149 A150 A151 A152 A153 A154 A155 A156 A157 A158 A159 A160 A161 A162 A163 A164 A165 A166 A167 A168
A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180
A181 A182 A183 A184 A185 A 86 A187 A188 A189 A190 A191 A192
A193 A194 A195 A196 A197 A198 A199 A200 A201 A202 A203 A204
A205 A206 A207 A208 A209 A210 A211 A212 A213 A214 A215 A216
A217 A218 A219 A220 A221 A222 A223 A224 A225 A226 A227 A228
A229 A230 A231 A232 A233 A234 A235 A236 A237 A238 A239 A240
A241 A242 A243 A244 A245 A246 A247 A248 A249 A250 A251 A252
A253 A254 A255 A256 A257 A258 A259 A260 A261 A262 A263 A264
A265 A266 A267 A268 A269 A270 A271 A272 A273 A274 A275 A276
B52 £352 B52 B52 U2 BW B52 B52 B52 B52 B52 B52
^A277 A278 A279 A280 A281 A282 A283 A284 A285 A286 A287 A288
A289 A290 A291 A292 A293 A294 A295 A296 A297 A298 A299 A300 A301 A302 A303 A304 A305 A306 A307 A308 A309 A310 A311 A312
A313 A314 A315 A316 A317 A318 A319 A320 A321 A322 A323 A324 A325 A326 A327 A328 A329 A330 A331 A332 A333 A334 A335 A336
A337 A338 A339 A340 A341 A342 A343 A344 A345 A346 A347 A348 A349 A350 A351 A352 A353 A354 A355 A356 A357 A358 A359 A360 A361 A362 A363 A364 A365 A366 A367 A368 A369 A370 A371 A372 A373 A374 A375 A376 A377 A378 A379 A380 A381 A382 A383 A384 A385 A386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396 A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A408 A409 A410 A411 A412 A413 A414 A415 A416 A417 A418 A419 A420 A421 A422 A423 A424 A425 A426 A427 A428 A429 A430 A431 A432 A433 A434 A435 A436 A437 A438 A439 A440 A441 A442 A443 A444 A445 A446 A447 A448 A449 A450 A451 A452 A453 A454 A455 A456 A457 A458 A459 A460 A461 A462 A463 A464 A465 A466 A467 A468 A469 A470 A471 A472 A473 A474 A475 A476 A477 A478 A479 A480 A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492 A493 A494 A495 A496 A497 A498 A499 A500 A501 A502 A503 A504 A505 A506 A507 A508 A509 A510 A511 A512 A513 A514 A515 A516 A517 A518 A519 A520 A521 A522 A523 A524 A525 A526 A527 A528 A529 A530 A531 A532 A533 A534 A535 A536 A537 A538 A539 A540 A541 A542 A543 A544 A545 A546 A547 A548 A549 A550 A551 A552 A553 A554 A555 A556 A557 A558 A559 A560 A561 A562 A563 A564 A565 A566 A567 A568 A569 A570 A571 A572 A573 A574 A575 A576 A577 A578 A579 A580 A581 A582 A583 A584 A585 A586 A587 A588 A589 A590 A591 A592 A593 A594 A595 A596 A597 A598 A599 A600 A601 A602 A603 A604 A605 A606 A607 A608 A609 A610 A611 A612 A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 A623 A624 A625 A626 A627 A628 A629 A630 A631 A632 A633 A634 A635 A636 A637 A638 A639 A640 A641 A642 A643 A644 A645 A646 A647 A648 A649 A650 A651 A652 A653 A654 A655 A656 A657 A658 A659 A660 A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672
B52 ES52 §52 E352 EΪ52 J352 B52 §52 B52 B52 B52 B52
A673 A674 A675 A676 A677 A678 A679 A680 A681 A682 A683 A684
A685 A686 A687 A688 A689 A690 A691 A692 A693 A694 A695 A696
A697 A698 A699 A700 A701 A702 A703 A704 A705 A706 A707 A708
A709 A710 A711 A712 A713 A714 A715 A716 A717 A718 A719 A720
A721 A722 A723 A724 A725 A726 A727 A728 A729 A730 A731 A732
A733 A734 A735 A736 A737 A738 A739 A740 A741 A742 A743 A744
A745 A746 A747 A748 A749 A750 A751 A752 A753 A754 A755 A756
A757 A758 A759 A760 A761 A762 A763 A764 A765 A766 A767 A768
A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780
A781 A782 A783 A784 A785 A786 A787 A788 A789 A790 A791 A792
A793 A794 A795 A796 A797 A798 A799 A800 A801 A802 A803 A804
A805 A806 A807 A808 A809 A810 A811 A812 A813 A814 A815 A816
A817 A818 A819 A820 A821 A822 A823 A824 A825 A826 A827 A828
A829 A830 A831 A832
Table 4: Compounds of formula I, represented as compounds of the formula
Ao-Q
wherein Q is Q2 and Q2 is the radical B39:
B39 U9 B39 B39 B39 B39 B39 EΪ39 E339 B39 B39 B39
A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24 A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36 A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48 A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59 A60 A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72 A73 A74 A75 A76 A77 A78 A79 A80 A81 A82 A83 A84 A85 A86 A87 A88 A89 A90 A91 A92 A93 A94 A95 A96
B39 B39 B39 §39 B39 B39 B39 B39 B39 B39 §39 B39
" A97 A98 A99 A100 A101 A102 A103 A104 A105 A106 A107 A108 A109 A11O A111 A112 A113 A114 A115 A116 A117 A118 A119 A120 A121 A122 A123 A124 A125 A126 A127 A128 A129 A130 A131 A132 A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144 A145 A146 A147 A148 A149 A150 A151 A152 A153 A154 A155 A156 A157 A158 A159 A160, A161 A162 A163 A164 A165 A166 A167 A168 A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180 A181 A182 A183 A184 A185 A186 A187 A188 A189 A190 A191 A192 A193 A194 A195 A196 A197 A198 A199 A200 A201 A202 A203 A204 A205 A206 A207 A208 A209 A210 A211 A212 A213 A214 A215 A216 A217 A218 A219 A220 A221 A222 A223 A224 A225 A226 A227 A228 A229 A230 A231 A232 A233 A234 A235 A236 A237 A238 A239 A240 A241 A242 A243 A244 A245 A246 A247 A248 A249 A250 A251 A252 A253 A254 A255 A256 A257 A258 A259 A260 A261 A262 A263 A264 A265 A266 A267 A268 A269 A270 A271 A272 A273 A274 A275 A276 A277 A278 A279 A280 A281 A282 A283 A284 A285 A286 A287 A288 A289 A290 A291 A292 A293 A294 A295 A296 A297 A298 A299 A300 A301 A302 A303 A304 A305 A306 A307 A308 A309 A310 A311 A312 A313 A314 A315 A316 A317 A318 A319 A320 A321 A322 A323 A324 A325 A326 A327 A328 A329 A330 A331 A332 A333 A334 A335 A336 A337 A338 A339 A340 A341 A342 A343 A344 A345 A346 A347 A348 A349 A350 A351 A352 A353 A354 A355 A356 A357 A358 A359 A360 A361 A362 A363 A364 A365 A366 A367 A368 A369 A370 A371 A372 A373 A374 A375 A376 A377 A378 A379 A380 A381 A382 A383 A384 A385 A386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396 A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A408 A409 A410 A411 A412 A413 A414 A415 A416 A417 A418 A419 A420 A421 A422 A423 A424 A425 A426 A427 A428 A429 A430 A431 A432 A433 A434 A435 A436 A437 A438 A439 A440 A441 A442 A443 A444 A445 A446 A447 A448 A449 A450 A451 A452 A453 A454 A455 A456 A457 A458 A459 A460 A461 A462 A463 A464 A465 A466 A467 A468 A469 A470 A471 A472 A473 A474 A475 A476 A477 A478 A479 A480 A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492
B39 §39 §39 §39 §39 §39 §39 §39 §39 §39 §39 B39
A493 A494 A495 A496 A497 A498 A499 A500 A501 A502 A503 A504
A505 A506 A507 A508 A509 A510 A511 A512 A513 A514 A515 A516
A517 A518 A519 A520 A521 A522 A523 A524 A525 A526 A527 A528
A529 A530 A531 A532 A533 A534 A535 A536 A537 A538 A539 A540
A541 A542 A543 A544 A545 A546 A547 A548 A549 A550 A551 A552
A553 A554 A555 A556 A557 A558 A559 A560 A561 A562 A563 A564
A565 A566 A567 A568 A569 A570 A571 A572 A573 A574 A575 A576
A577 A578 A579 A580 A581 A582 A583 A584 A585 A586 A587 A588
A589 A590 A591 A592 A593 A594 A595 A596 A597 A598 A599 A600
A601 A602 A603 A604 A605 A606 A607 A608 A609 A610 A611 A612
A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 A623 A624
A625 A626 A627 A628 A629 A630 A631 A632 A633 A634 A635 A636
A637 A638 A639 A640 A641 A642 A643 A644 A645 A646 A647 A648
A649 A650 A651 A652 A653 A654 A655 A656 A657 A658 A659 A660
A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672 A673 A674 A675 A676 A677 A678 A679 A680 A681 A682 A683 A684 A685 A686 A687 A688 A689 A690 A691 A692 A693 A694 A695 A696
A697 A698 A699 A700 A701 A702 A703 A704 A705 A706 A707 A708
A709 A710 A71 1 A712 A713 A714 A715 A716 A717 A718 A719 A720
A721 A722 A723 A724 A725 A726 A727 A728 A729 A730 A731 A732
A733 A734 A735 A736 A737 A738 A739 A740 A741 A742 A743 A744
A745 A746 A747 A748 A749 A750 A751 A752 A753 A754 A755 A756
A757 A758 A759 A760 A761 A762 A763 A764 A765 A766 A767 A768
A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780
A781 A782 A783 A784 A785 A786 A787 A788 A789 A790 A791 A792
A793 A794 A795 A796 A797 A798 A799 A800 A801 A802 A803 A804
A805 A806 A807 A808 A809 A810 A811 A812 A813 A814 A815 A816
A817 A818 A819 A820 A821 A822 A823 A824 A825 A826 A827 A828
A829 A830 A831 A832
Table 5: Compounds of formula I. represented as compounds of the formula
wherein Q is Q2 and Q2 is the radical B3:
B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 B3 A8 A9 A10 A11 A12 A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24 A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36 A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48 A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59 A60 A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72 A73 A74 A75 A76 A77 A78 A79 A80 A81 A82 A83 A84 A85 A86 A87 A88 A89 A90 - A99 A100 A101 A102 A103 A104 A105 A106 A107 A108
A109 A110 A111 A112 A113 A114 A115 A116 A117 A118 A119 A120
A121 A122 A123 A124 A125 A126 A127 A128 A129 A130 A131 A132
A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144
A145 A146 A147 A148 A149 A150 A151 A152 A153 A154 A155 A156
A157 A158 A159 A160 A161 A162 A163 A164 A165 A166 A167 A168
A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180
A181 A182 A183 A184 A185 A186 A187 A188 A189 A190 A191 A192
A193 A194 A195 A196 A197 A198 A199 A200 A201 A202 A203 A204
A205 A206 A207 A208 A209 A210 A211 A212 A213 A214 A215 A216
A217 A218 A219 A220 A221 A222 A223 A224 A225 A226 A227 A228
A229 A230 A231 A232 A233 A234 A235 A236 A237 A238 A239 A240
A241 A242 A243 A244 A245 A246 A247 A248 A249 A250 A251 A252
A253 A254 A255 A256 A257 A258 A259 A260 A261 A262 A263 A264
A265 A266 A267 A268 A269 A270 A271 A272 A273 A274 A275 A276
A277 A278 A279 A280 A281 A282 A283 A284 A285 A286 A287 A288
A289 A290 A291 A292 A293 A294 A295 A296 A297 A298 A299 A300
A301 A302 A303 A304 A305 A306 A307 A308 A309 A310 A311 A312
A313 A314 A315 A316 A317 A318 A319 A320 A321 A322 A323 A324
A325 A326 A327 A328 A329 A330 A331 A332 A333 A334 A335 A336
A337 A338 A339 A340 A341 A342 A343 A344 A345 A346 A347 A348
B3 §3 §3 §3 §3 §3 §3 §3 §3 §3 §3 B3
A349 A350 A351 A352 A353 A354 A355 A356 A357 A358 A359 A360
A361 A362 A363 A364 A365 A366 A367 A368 A369 A370 A371 A372
A373 A374 A375 A376 A377 A378 A379 A380 A381 A382 A383 A384
A385 A386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396
A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A408
A409 A410 A411 A412 A413 A414 A415 A416 A417 A418 A419 A420
A421 A422 A423 A424 A425 A426 A427 A428 A429 A430 A431 A432
A433 A434 A435 A436 A437 A438 A439 A440 A441 A442 A443 A444
A445 A446 A447 A448 A449 A450 A451 A452 A453 A454 A455 A456
A457 A458 A459 A460 A461 A462 A463 A464 A465 A466 A467 A468
A469 A470 A471 A472 A473 A474 A475 A476 A477 A478 A479 A480
A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492
A493 A494 A495 A496 A497 A498 A499 A500 A501 A502 A503 A504
A505 A506 A507 A508 A509 A510 A511 A512 A513 A514 A515 A516
A517 A518 A519 A520 A521 A522 A523 A524 A525 A526 A527 A528
A529 A530 A531 A532 A533 A534 A535 A536 A537 A538 A539 A540
A541 A542 A543 A544 A545 - - A554 A555 A556 A557 A558 A559 A560 A561 A562 A563 A564
A565 A566 A567 A568 A569 A570 A571 A572 A573 A574 A575 A576
A577 A578 A579 A580 A581 A582 A583 A584 A585 A586 A587 A588
A589 A590 A591 A592 A593 A594 A595 A596 A597 A598 A599 A600
A601 A602 A603 A604 A605 A606 A607 A608 A609 A610 A611 A612
A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 A623 A624
A625 A626 A627 A628 A629 A630 A631 A632 A633 A634 A635 A636 A644 A645 A646 A647 A648
A649 A650 A651 A652 A653 A654 A655 A656 A657 A658 A659 A660
A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672
A685 A686 A687 A688 A689 A690 A691 A692 A693 A694 A695 A696
A697 A698 A699 A700 A701 A702 A703 A704 A705 A706 A707 A708
A709 A710 A711 A712 A713 A714 A715 A716 A717 A718 A719 A720
A721 A722 A723 A724 A725 A726 - - - - - -
A733 A734 A735 A736 A737 A738 A739 A740 A741 A742 A743 A744
A745 A746 A747 A748 A749 A750 A751 A752 A753 A754 A755 A756
~B3 §3 §3 §3 §3 §3 §3 §3 §3 §3 §3 B3
"A757 A758 A759 A760 A761 A762 A763 A764 A765 A766 A767 A768 A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780 A781 A782 A783 A784 A785 A786 A787 A788 A789 A790 A791 A792 A793 A794 A795 A796 A797 A798 A799 A800 A801 A802 A803 A804 A805 A806 A807 A808 A809 A810 A811 A812 A813 A814 A815 A816 A817 A818 A819 A820 A821 A822 A823 A824 A825 A826 A827 A828 A829 A830 A831 A832 - - - - - - - -
Table 6: Compounds of formula I, represented as compounds of the formula
Ao-Q
wherein Q is Q3 and Q3 is the radical C5:
C5 C5 C5 C5 C5 C5 C5 C5 C5 C5 C5 C5
A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12 A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24 A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36 A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48 A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59 A60 A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72 A73 A74 A75 A76 A77 A78 A79 A80 A81 A82 A83 A84 A85 A86 A87 A88 A89 A90 A91 A92 A93 A94 A95 A96 A97 A98 A99 A100 A101 A102 A103 A104 A105 A106 A107 A108 A109 A110 A111 A112 A113 A114 A115 A116 A117 A118 A119 A120 A121 A122 A123 A124 A125 A126 A127 A128 A129 A130 A131 A132 A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144 A145 A146 A147 A148 A149 A150 A151 A152 A153 A154 A155 A156 A157 A158 A159 A160 A161 A162 A163 A164 A165 A166 A167 A168 A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180
_____ __ __ __ _ _ _ _ __ _ __ __
A181 A182 A183 A184 A185 A186 A187 A188 A189 A190 A191 A192 A193 A194 A195 A196 A197 A198 A199 A200 A201 A202 A203 A204 A205 A206 A207 A208 A209 A210 A211 A212 A213 A214 A215 A216 A217 A218 A219 A220 A221 A222 A223 A224 A225 A226 A227 A228 A229 A230 A231 A232 A233 A234 A235 A236 A237 A238 A239 A240 A241 A242 A243 A244 A245 A246 A247 A248 A249 A250 A251 A252 A253 A254 A255 A256 A257 A258 A259 A260 A261 A262 A263 A264 A265 A266 A267 A268 A269 A270 A271 A272 A273 A274 A275 A276 A277 A278 A279 A280 A281 A282 A283 A284 A285 A286 A287 A288 A289 A290 A291 A292 A293 A294 A295 A296 A297 A298 A299 A300 A301 A302 A303 A304 A305 A306 A307 A308 A309 A310 A311 A312 A313 A314 A315 A316 A317 A318 A319 A320 A321 A322 A323 A324 A325 A326 A327 A328 A329 A330 A331 A332 A333 A334 A335 A336 A337 A338 A339 A340 A341 A342 A343 A344 A345 A346 A347 A348 A349 A350 A351 A352 A353 A354 A355 A356 A357 A358 A359 A360 A361 A362 A363 A364 A365 A366 A367 A368 A369 A370 A371 A372 A373 A374 A375 A376 A377 A378 A379 A380 A381 A382 A383 A384 A385 A386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396 A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A408 A409 A410 A411 A412 A413 A414 A415 A416 A417 A418 A419 A420 A421 A422 A423 A424 A425 A426 A427 A428 A429 A430 A431 A432 A433 A434 A435 A436 A437 A438 A439 A440 A441 A442 A443 A444 A445 A446 A447 A448 A449 A450 A451 A452 A453 A454 A455 A456 A457 A458 A459 A460 A461 A462 A463 A464 A465 A466 A467 A468 A469 A470 A471 A472 A473 A474 A475 A476 A477 A478 A479 A480 A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492 A493 A494 A495 A496 A497 A498 A499 A500 A501 A502 A503 A504 A505 A506 A507 A508 A509 A510 A511 A512 A513 A514 A515 A516 A517 A518 A519 A520 A521 A522 A523 A524 A525 A526 A527 A528 A529 A530 A531 A532 A533 A534 A535 A536 A537 A538 A539 A540 A541 A542 A543 A544 A545 A546 A547 A548 A549 A550 A551 A552 A553 A554 A555 A556 A557 A558 A559 A560 A561 A562 A563 A564 A565 A566 A567 A568 A569 A570 A571 A572 A573 A574 A575 A576
~ C5 C5 C5 C5 C5 C5 C5 C5 C5 C5 C5 C5
~A577 A578 A579 A580 A581 A582 A583 A584 A585 A586 A587 A588 A589 A590 A591 A592 A593 A594 A595 A596 A597 A598 A599 A600 A601 A602 A603 A604 A605 A606 A607 A608 A609 A610 A611 A612 A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 A623 A624 A625 A626 A627 A628 A629 A630 A631 A632 A633 A634 A635 A636 A637 A638 A639 A640 A641 A642 A643 A644 A645 A646 A647 A648 A649 A650 A651 A652 A653 A654 A655 A656 A657 A658 A659 A660 A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672 A673 A674 A675 A676 A677 A678 A679 A680 A681 A682 A683 A684 A685 A686 A687 A688 A689 A690 A691 A692 A693 A694 A695 A696 A697 A698 A699 A700 A701 A702 A703 A704 A705 A706 A707 A708 A709 A710 A711 A712 A713 A714 A715 A716 A717 A718 A719 A720 A721 A722 A723 A724 A725 A726 A727 A728 A729 A730 A731 A732 A733 A734 A735 A736 A737 A738 A739 A740 A741 A742 A743 A744 A745 A746 A747 A748 A749 A750 A751 A752 A753 A754 A755 A756 A757 A758 A759 A760 A761 A762 A763 A764 A765 A766 A767 A768 A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780 A781 A782 A783 A784 A785 A786 A787 A788 A789 A790 A791 A792 A793 A794 A795 A796 A797 A798 A799 A800 A801 A802 A803 A804 A805 A806 A807 A808 A809 A810 A811 A812 A813 A814 A815 A816 A817 A818 A819 A820 A821 A822 A823 A824 A825 A826 A827 A828 A829 A830 A831 A832
Table 7: Compounds of formula I, represented as compounds of the formula
Ao-Q
wherein Q is Q3 and Q3 is the radical C2: C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2~
C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 A11 A12
A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24
A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36
A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48
A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59 A60
A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72
A73 A74 A75 . A76 A77 A78 A79 A80 A81 A82 A83 A84
A85 A86 A87 A88 A89 A90 A91 A92 A93 A94 A95 A96
A97 A98 A99 A100 A101 A102 A103 A104 A105 A106 A107 A108
A109 A110 A111 A112 A113 A114 A115 A116 A117 A118 A119 A120
A121 A122 A123 A124 A125 A126 A127 A128 A129 A130 A131 A132
A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144
A145 A146 A147 A148 A149 A150 A151 A152 A153 A154 A155 A156
A157 A158 A159 A160 A161 A162 A163 A164 A165 A166 A167 A168
A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180
A181 A182 A183 A184 A185 A186 A187 A188 A189 A190 A191 A192
A193 A194 A195 A196 A197 A198 A199 A200 A201 A202 A203 A204
A205 A206 A207 A208 A209 A210 A211 A212 A213 A214 A215 A216
A217 A218 A219 A220 A221 A222 A223 A224 A225 A226 A227 A228
A229 A230 A231 A232 A233 A234 A235 A236 A237 A238 A239 A240
A241 A242 A243 A244 A245 A246 A247 A248 A249 A250 A251 A252
A253 A254 A255 A256 A257 A258 A259 A260 A261 A262 A263 A264
A265 A266 A267 A268 A269 A270 A271 A272 A273 A274 A275 A276
A277 A278 A279 A280 A281 A282 A283 A284 A285 A286 A287 A288
A289 A290 A291 A292 A293 A294 A295 A296 A297 A298 A299 A300
A301 A302 A303 A304 A305 A306 A307 A308 A309 A310 A311 A312
A313 A314 A315 A316 A317 A318 A319 A320 A321 A322 A323 A324
A325 A326 A327 A328 A329 A330 A331 A332 A333 A334 A335 A336
A337 A338 A339 A340 A341 A342 A343 A344 A345 A346 A347 A348
A349 A350 A351 A352 A353 A354 A355 A356 A357 A358 A359 A360
A361 A362 A363 A364 A365 A366 A367 A368 A369 A370 A371 A372
A373 A374 A375 A376 A377 A378 A379 A380 A381 A382 A383 A384
A385 A386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396
C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2
A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A408
A409 A410 A411 A412 A413 A414 A415 A416 A417 A418 A419 A420
A421 A422 A423 A424 A425 A426 A427 A428 A429 A430 A431 A432
A433 A434 A435 A436 A437 A438 A439 A440 A441 A442 A443 A444
A445 A446 A447 A448 A449 A450 A451 A452 A453 A454 A455 A456
A457 A458 A459 A460 A461 A462 A463 A464 A465 A466 A467 A468
A469 A470 A471 A472 A473 A474 A475 A476 A477 A478 A479 A480
A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492
A493 A494 A495 A496 A497 A498 A499 A500 A501 A502 A503 A504
A505 A506 A507 A508 A509 A510 A511 A512 A513 A514 A515 A516
A517 A518 A519 A520 A521 A522 A523 A524 A525 A526 A527 A528
A529 A530 A531 A532 A533 A534 A535 A536 A537 A538 A539 A540
A541 A542 A543 A544 A545 A546 A547 A548 A549 A550 A551 A552
A553 A554 A555 A556 A557 A558 A559 A560 A561 A562 A563 A564
A565 A566 A567 A568 A569 A570 A571 A572 A573 A574 A575 A576
A577 A578 A579 A580 A581 A582 A583 A584 A585 A586 A587 A588
A589 A590 A591 A592 A593 A594 A595 A596 A597 A598 A599 A600
A601 A602 A603 A604 A605 A606 A607 A608 A609 A610 A611 A612
A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 A623 A624
A625 A626 A627 A628 A629 A630 A631 A632 A633 A634 A635 A636
A637 A638 A639 A640 A641 A642 A643 A644 A645 A646 A647 A648
A649 A650 A651 A652 A653 A654 A655 A656 A657 A658 A659 A660
A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672
A673 A674 A675 A676 A677 A678 A679 A680 A681 A682 A683 A684
A685 A686 A687 A688 A689 A690 A691 A692 A693 A694 A695 A696
A697 A698 A699 A700 A701 A702 A703 A704 A705 A706 A707 A708
A709 A710 A711 A712 A713 A714 A715 A716 A717 A718 A719 A720
A721 A722 A723 A724 A725 A726 A727 A728 A729 A730 A731 A732
A733 A734 A735 A736 A737 A738 A739 A740 A741 A742 A743 A744
A745 A746 A747 A748 A749 A750 A751 A752 A753 A754 A755 A756
A757 A758 A759 A760 A761 A762 A763 A764 A765 A766 A767 A768
A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780
A781 A782 A783 A784 A785 A786 A787 A788 A789 A790 A791 A792
~~C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 C2
~A793 A794 A795 A796 A797 A798 A799 A800 A801 A802 A803 A804 A805 A806 A807 A808 A809 A810 A811 A812 A813 A814 A815 A816 A817 A818 A819 A820 A821 A822 A823 A824 A825 A826 A827 A828 A829 A830 A831 A832 - -
Table 8: Compounds of formula I. represented as compounds of the formula
Ao-Q
wherein Q is Q3 and Q3 denotes the radicals D1, D2 or D3:
D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D3 D3 D3 D3 D3 D3 D3 D3 D3 D3 D3 D3
_. __, . _ _ _ - A8 A9 A10 A11 A12 A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24 A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36 A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48 A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59 A60 A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72 A73 A74 A75 A76 A77 A78 A79 A80 A81 A82 A83 A84 A85 A86 A87 A88 A89 A90 - - - - - - - - A99 A100 A101 A102 A103 A104 A105 A106 A107 A108 A109 A110 A111 A112 A113 A114 A115 A116 A117 A118 A119 A120 A121 A122 A123 A124 A125 A126 A127 A128 A129 A130 A131 A132 A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144 A145 A146 A147 A148 A149 A150 A151 A152 A153 A154 A155 A156 A157 A158 A159 A160 A161 A162 A163 A164 A165 A166 A167 A168 A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180 A181 A182 A183 A184 A185 A186 A187 A188 A189 A190 A191 A192 A193 A194 A195 A196 A197 A198 A199 A200 A201 A202 A203 A204 A205 A206 A207 A208 A209 A210 A211 A212 A213 A214 A215 A216
D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D3 D3 D3 D3 D3 D3 D3 D3 D3 D3 D3 D3
A217 A218 A219 A220 A221 A222 A223 A224 A225 A226 A227 A228
A229 A230 A231 A232 A233 A234 A235 A236 A237 A238 A239 A240
A241 A242 A243 A244 A245 A246 A247 A248 A249 A250 A251 A252
A253 A254 A255 A256 A257 A258 A259 A260 A261 A262 A263 A264
A265 A266 A267 A268 A269 A270 A271 A272 A273 A274 A275 A276
A277 A278 A279 A280 A281 A282 A283 A284 A285 A286 A287 A288
A289 A290 A291 A292 A293 A294 A295 A296 A297 A298 A299 A300 A301 A302 A303 A304 A305 A306 A307 A308 A309 A310 A311 A312
A313 A314 A315 A316 A317 A318 A319 A320 A321 A322 A323 A324 A325 A326 A327 A328 A329 A330 A331 A332 A333 A334 A335 A336 A337 A338 A339 A340 A341 A342 A343 A344 A345 A346 A347 A348 A349 A350 A351 A352 A353 A354 A355 A356 A357 A358 A359 A360 A361 A362 A363 A364 A365 A366 A367 A368 A369 A370 A371 A372 A373 A374 A375 A376 A377 A378 A379 A380 A381 A382 A383 A384 A385 A386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396 A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A408 A409 A410 A411 A412 A413 A414 A415 A416 A417 A418 A419 A420 A421 A422 A423 A424 A425 A426 A427 A428 A429 A430 A431 A432 A433 A434 A435 A436 A437 A438 A439 A440 A441 A442 A443 A444 A445 A446 A447 A448 A449 A450 A451 A452 A453 A454 A455 A456 A457 A458 A459 A460 A461 A462 A463 A464 A465 A466 A467 A468 A469 A470 A471 A472 A473 A474 A475 A476 A477 A478 A479 A480 A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492 A493 A494 A495 A496 A497 A498 A499 A500 A501 A502 A503 A504 A505 A506 A507 A508 A509 A510 A511 A512 A513 A514 A515 A516 A517 A518 A519 A520 A521 A522 A523 A524 A525 A526 A527 A528 A529 A530 A531 A532 A533 A534 A535 A536 A537 A538 A539 A540 A541 A542 A543 A544 A545 - - - - - - - - A554 A555 A556 A557 A558 A559 A560 A561 A562 A563 A564 A565 A566 A567 A568 A569 A570 A571 A572 A573 A574 A575 A576 A577 A578 A579 A580 A581 A582 A583 A584 A585 A586 A587 A588
D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D1/D2/ D3 D3 D3 D3 D3 D3 D3 D3 D3 D3 D3 D3 A589 A590 A591 A592 A593 A594 A595 A596 A597 A598 A599 A600 A601 A602 A603 A604 A605 A606 A607 A608 A609 A610 A611 A612 A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 A623 A624 A625 A626 A627 A628 A629 A630 A631 A632 A633 A634 A635 A636 - - - - - - - A644 A645 A646 A647 A648 A649 A650 A651 A652 A653 A654 A655 A656 A657 A658 A659 A660 A661 A662 A663 A664 A665' A666 A667 A668 A669 A670 A671 A672 A685 A686 A687 A688 A689 A690 A691 A692 A693 A694 A695 A696 A697 A698 A699 A700 A701 A702 A703 A704 A705 A706 A707 A708 A709 A710 A711 A712 A713 A714 A715 A716 A717 A718 A719 A720 A721 A722 A723 A724 A725 A726 - - - - - - A733 A734 A735 A736 A737 A738 A739 A740 A741 A742 A743 A744 A745 A746 A747 A748 A749 A750 A751 A752 A753 A754 A755 A756 A757 A758 A759 A760 A761 A762 A763 A764 A765 A766 A767 A768 A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780 A781 A782 A783 A784 A785 A786 A787 A788 A789 A790 A791 A792 A793 A794 A795 A796 A797 A798 A799 A800 A801 A802 A803 A804 A805 A806 A807 A808 A809 A810 A811 A812 A813 A814 A815 A816 A817 A818 A819 A820 A821 A822 A823 A824 A825 A826 A827 A828 A829 A830 A831 A832 "* ~ " " " " " "
Table 9: Compounds of formula Ip:
wherein R-i, R2, R3, R4, X1 and p are as defined for the radical A, and n is 0, 1 or 2:
A A A A A A A A A A A A
_ _ _ _ _ _ _ A8 A9 A10 A11 A12 A13 A14 A15 A16 A17 A18 A19 A20 A21 A22 A23 A24 A25 A26 A27 A28 A29 A30 A31 A32 A33 A34 A35 A36 A37 A38 A39 A40 A41 A42 A43 A44 A45 A46 A47 A48 A49 A50 A51 A52 A53 A54 A55 A56 A57 A58 A59 A60 A61 A62 A63 A64 A65 A66 A67 A68 A69 A70 A71 A72 A73 A74 A75 A76 A77 A78 A79 A80 A81 A82 A83 A84 A85 A86 A87 A88 A89 A90 - - - - - - - - A99 A100 A101 A102 A103 A104 A105 A106 A107 A108 A109 A110 A111 A112 A113 A114 A115 A116 A117 A118 A119 A120 A121 A122 A123 A124 A125 A126 A127 A128 A129 A130 A131 A132 A133 A134 A135 A136 A137 A138 A139 A140 A141 A142 A143 A144 A145 A146 A147 A148 A149 A150 A151 A152 A153 A154 A155 A156 A157 A158 A159 A160 A161 A162 A163 A164 A165 A166 A167 A168
A169 A170 A171 A172 A173 A174 A175 A176 A177 A178 A179 A180
A181 A182 A183 A184 A185 A186 A187 A188 A189 A190 A191 A192
A193 A194 A195 A196 A197 A198 A199 A200 A201 A202 A203 A204
A205 A206 A207 A208 A209 A210 A211 A212 A213 A214 A215 A216
A217 A218 A219 A220 A221 A222 A223 A224 A225 A226 A227 A228
A229 A230 A231 A232 A233 A234 A235 A236 A237 A238 A239 A240
A241 A242 A243 A244 A245 A246 A247 A248 A249 A250 A251 A252
A253 A254 A255 A256 A257 A258 A259 A260 A261 A262 A263 A264
A265 A266 A267 A268 A269 A270 A271 A272 A273 A274 A275 A276
A277 A278 A279 A280 A281 A282 A283 A284 A285 A286 A287 A288
A289 A290 A291 A292 A293 A294 A295 A296 A297 A298 A299 A300
A301 A302 A303 A304 A305 A306 A307 A308 A309 A310 A311 A312
A313 A314 A315 A316 A317 A318 A319 A320 A321 A322 A323 A324
A325 A326 A327 A328 A329 A330 A331 A332 A333 A334 A335 A336
A337 A338 A339 A340 A341 A342 A343 A344 A345 A346 A347 A348
A349 A350 A351 A352 A353 A354 A355 A356 A357 A358 A359 A360
A361 A362 A363 A364 A365 A366 A367 A368 A369 A370 A371 A372
A373 A374 A375 A376 A377 A378 A379 A380 A381 A382 A383 A384
A385 A386 A387 A388 A389 A390 A391 A392 A393 A394 A395 A396
A397 A398 A399 A400 A401 A402 A403 A404 A405 A406 A407 A408
A409 A410 A411 A412 A413 A414 A415 A416 A417 A418 A419 A420
A421 A422 A423 A424 A425 A426 A427 A428 A429 A430 A431 A432
A433 A434 A435 A436 A437 A438 A439 A440 A441 A442 A443 A444
A445 A446 A447 A448 A449 A450 A451 A452 A453 A454 A455 A456
A457 A458 A459 A460 A461 A462 A463 A464 A465 A466 A467 A468
A469 A470 A471 A472 A473 A474 A475 A476 A477 A478 A479 A480
A481 A482 A483 A484 A485 A486 A487 A488 A489 A490 A491 A492
A493 A494 A495 A496 A497 A498 A499 A500 A501 A502 A503 A504
A505 A506 A507 A508 A509 A510 A511 A512 A513 A514 A515 A516
A517 A518 A519 A520 A521 A522 A523 A524 A525 A526 A527 A528
A529 A530 A531 A532 A533 A534 A535 A536 A537 A538 A539 A540
A541 A542 A543 A544 A545 A554 A555 A556 A557 A558 A559 A560 A561 A562 A563 A564
A565 A566 A567 A568 A569 A570 A571 A572 A573 A574 A575 A576
A577 A578 A579 A580 A581 A582 A583 A584 A585 A586 A587 A588
A589 A590 A591 A592 A593 A594 A595 A596 A597 A598 A599 A600
A601 A602 A603 A604 A605 A606 A607 A608 A609 A610 A611 A612
A613 A614 A615 A616 A617 A618 A619 A620 A621 A622 A623 A624
A625 A626 A627 A628 A629 A630 A631 A632 A633 A634 A635 A636 A644 A645 A646 A647 A648
A649 A650 A651 A652 A653 A654 A655 A656 A657 A658 A659 A660
A661 A662 A663 A664 A665 A666 A667 A668 A669 A670 A671 A672
A685 A686 A687 A688 A689 A690 A691 A692 A693 A694 A695 A696
A697 A698 A699 A700 A701 A702 A703 A704 A705 A706 A707 A708
A709 A710 A711 A712 A713 A714 A715 A716 A717 A718 A719 A720
A721 A722 A723 A724 A725 A726 - - - - - -
A733 A734 A735 A736 A737 A738 A739 A740 A741 A742 A743 A744
A745 A746 A747 A748 A749 A750 A751 A752 A753 A754 A755 A756
A757 A758 A759 A760 A761 A762 A763 A764 A765 A766 A767 A768
A769 A770 A771 A772 A773 A774 A775 A776 A777 A778 A779 A780
A781 A782 A783 A784 A785 A786 A787 A788 A789 A790 A791 A792
A793 A794 A795 A796 A797 A798 A799 A800 A801 A802 A803 A804
A805 A806 A807 A808 A809 A810 A811 A812 A813 A814 A815 A816
A817 A818 A819 A820 A821 A822 A823 A824 A825 A826 A827 A828
A829 A830 A831 A832 - - - - - - - -
Table 10: Compounds of formula I. represented as compounds of the formula
Ao-Q wherein A is A10:
A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10
B1 B2 . B4 B5 B6 B7 B8 B9 B10 B11 B12 B13 B14 B15 B16 B17 B18 B19 B20 B21 B22 B23 B24 B25 B26 B27 B28 B29 B30 B31 B32 B33 B34 B35 B36 B37 B38 - B40 B41 B42 B43 B44 B45 B46 B47 B48 B49 B50 B51 - B53 B54 B55 B56 B57 B58 B59 B60 B61 B62 B63 B64 B65 B66 B67 B68 B69 B70 B71 B72
A10 A10 A10 A10 A10 A/jo Ajjj AjO AΪO ATO AΪO A10 B73 B74 B75 B76 B77 B78 B79 B80 B8Ϊ B82 B83 B84 B85 B86 B87 B88 B89 B90 B91 B92 B93 B94 B96 B97 B98 B99 B100 B101 B102 B103 B104 B105 B106 B107 B108 B109 B110
Table 11 : Compounds of formula I, represented as compounds of the formula
Ao-Q
wherein A is A10:
A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10
C1 - C3 C4 - C6 C7 C8 C9 C10 C1 1 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27 - - - - - - - - -
Table 12: Compounds of formula I. represented as compounds of the formula
Ao-Q
wherein A is A10:
A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10 A10
D4 D5 D6 D7 D8 D9 D10 D11 D12
Table 13: Compounds of formula I, represented as compounds of the formula
Ao-Q
wherein A is A556:
A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556
B1 B2 B4 B5 B6 B.7 B8 B9 B10 B11 B12 B13 B14 B15 B16 B17 B18 B19 B20 B21 B22 B23 B24 B25 B26 B27 B28 B29 B30 B31 B32 B33 B34 B35 B36 B37 B38 - B40 B41 B42 B43 B44 B45 B46 B47 B48 B49 B50 B51 - B53 B54 B55 B56 B57 B58 B59 B60 B61 B62 B63 B64 B65 B66 B67 B68 B69 B70 B71 B72 B73 B74 B75 B76 B77 B78 B79 B80 B81 B82 B83 B84 B85 B86 B87 B88 B89 B90 B91 B92 B93 B94 B96 B97 B98 B99 B100 B101 B102 B103 B104 B105 B106 B107 B108 B109 B110 - - - - - - - - - -
Table 14: Compounds of formula I, represented as compounds of the formula
Ao-Q wherein A is A556:
A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556
C1 - C3 C4 - C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C27
Table 15: Compounds of formula I. represented as compounds of the formula
Ao-Q wherein A is A556:
A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556 A556
D4 D5 D6 D7 D8 D9 D10 D11 D12
Table 16: Compounds of formula I, represented as compounds of the formula
Ao-Q
wherein A is A646:
A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646
B1 B2 __, B4 B5 B6 B7 B8 B9 B10 B11 B12 B13 B14 B15 B16 B17 B18 B19 B20 B21 B22 B23 B24 B25 B26 B27 B28 B29 B30 B31 B32 B33 B34 B35 B36 B37 B38 - B40 B41 B42 B43 B44 B45 B46 B47 B48 B49 B50 B51 - B53 B54 B55 B56 B57 B58 B59 B60 B61 B62 B63 B64 B65 B66 B67 B68 B69 B70 B71 B72 B73 B74 B75 B76 B77 B78 B79 B80 B81 B82 B83 B84 B85 B86 B87 B88 B89 - B90 B91 B92 B93 B94 B96 B97 B98 B99 B100 B101 B102 B103 B104 B105 B106 B107 B108 B109 B110 - - - - - - - - - -
Table 17: Compounds of formula I, represented as compounds of the formula
Ao-Q
wherein A is A646:
A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646
C1 - C3 C4 - C6 C7 C8 C9 C10 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23 C24
A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646
~C2<5 C26 C27 - - - - - - - - -
Table 18: Compounds of formula I, represented as compounds of the formula
Ao-Q
wherein A is A646:
A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646 A646
D4 D5 D6 D7 D8 D9 D10 D11 D12
Compound No. 2.01 is known from The Pesticide Manual 12th ed., Entry No.: 467. Compound No. 2.02 (4-chloro-2-mesylphenyl-5-cyclopropyl-1 ,2-oxazol-4-yl ketone) is registered under Chemical Abstracts No. 141112-06-3. Compound No. 2.03 is known from The Pesticide Manual 12th ed., Entry No.: 710, and compound No. 2.04 is described under Entry No. 500. Compound No. 2.05 is known from The Pesticide Manual 12th ed., under Entry No.: 71 ; compound No. 2.06 under Entry No. 663; compound No. 2.07 under Entry No. 666; and compound No. 2.08 under Entry No. 70. Compounds Nos. 2.09 and 2.10 are described in WO 98/31681 , and mixtures of those compounds with herbicides are known from WO 99/65314. Compound No. 2.11 is described in Chemical Abstracts under the registration number CAS 192708-91-1.
Compound No. 2.12 is described in WO 98/42677 A1 and US 6,211 ,403 B1 and has the Chemical Abstracts registration number 128133-27-7. Compounds Nos. 2.13 and 2.14 and their preparation are known from WO/0015615. Compound No. 2.15 is described in EP-A-0 496 631 , and compound No. 2.16 is described in WO 03/092380. Compound No. 2.17 is known from WO 02/085118, and compound No. 2.18 from WO 00/021924.
For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled
release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is additionally possible to apply a coating (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time.
The compounds of formula I can be used as herbicides in unmodified form, that is to say as obtained in the synthesis, but they 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, suspensions, mixtures of a suspension and an emulsion (suspoemulsions), wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are selected in accordance with the intended objectives and the prevailing circumstances.
The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
Depending upon the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485. In addition, the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon'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-III, Chemical Publishing Co., New York, 1980-81 , are also suitable for the preparation of the herbicidal compositions according to the invention.
The active ingredient can also be contained in very fine microcapsules consisting of a polymer. Microcapsules contain the active ingredients in a porous carrier. This enables the active ingredient to be released into the surroundings in controlled amounts. Microcapsules usually have a diameter of from 0.1 to 500 microns. They contain active ingredient in an amount of about from 25 to 95 % by weight of the capsule weight. The active ingredients can be present in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution. The encapsulating membranes comprise, for example, natural and synthetic gums, cellulose, styrene-butadiene copolymers, polyacrylo- nitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers known to the person skilled in the art. Alternatively it is possible for very fine microcapsules to be formed wherein the active ingredient is present in the form of finely divided particles in a solid matrix of a base substance, but in that case the microcapsule is not encapsulated.
The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters thereof or mixtures of such oils and oil derivatives.
The amount of oil additive in the composition according to the invention is generally from 0.01 to 2 %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared.
Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® obtainable from Rhόne-Poulenc Canada Inc., alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. A preferred additive contains as active components essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers.
Especially preferred oil additives comprise alkyl esters of higher fatty acids (C8-C22), especially the methyl derivatives of C12-C18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid. Those esters are known as methyl laurate (CAS-111-82-0),
methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Henkel subsidiary Cognis GMBH, DE).
The application and action of the oil additives can be improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485.
Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C12-C22 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available, preferred surfactants are the Genapol types (Clariant AG, Muttenz, Switzerland). Also preferred for use as surface-active substances are silicone surfactants, especially polyalkyl-oxide- modified heptamethyltrisiloxanes, such as are commercially available as e.g. Silwet L-77®, and also perfluorinated surfactants. The concentration of surface-active substances in relation to the total additive is generally from 1 to 30 % by weight.
Examples of oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, CA) and Actipron® (BP Oil UK Limited, GB).
The addition of an organic solvent to the oil additive/surfactant mixture can also bring about a further enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation) types. The concentration of such solvents can be from 10 to 80 % by weight of the total weight.
Such oil additives, which are also described, for example, in US-A-4 834 908, are suitable for the composition according to the invention. A commercially available oil additive is known by the name MERGE®, is obtainable from the BASF Corporation and is essentially described, for example, in US-A-4 834 908 in col. 5, as Example COC-1. A further oil additive that is suitable according to the invention is SCORE® (Novartis Crop Protection Canada.)
ln addition to the oil additives listed above, in order to enhance the action of the compositions according to the invention it is also possible for formulations of alkyl pyrrolidones, such as are commercially available e.g. as Agrimax®, to be added to the spray mixture. Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly-1 -p-menthene, such as are commercially available as e.g. Bond®, Courier® or Emerald®, can also be used to enhance action. Solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, can also be added as action-enhancing agent to the spray mixture.
The herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of 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 will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
The HPPD inhibitors, especially the compounds of formula I, are generally applied to the plant or to the locus thereof at rates of application of from 0.001 to 2 kg/ha, especially from 0.005 to 1 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent upon the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
The HPPD inhibitors according to the invention are distinguished by herbicidal and growth- inhibiting properties and/or by properties improving on the existing pest- and/or fungus- resistance of the useful plants, allowing them to be used in pest-resistant and/or fungus- resistant transgenic crops of useful plants, especially in cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops (for example citrus fruit, coffee, bananas), rape, maize and rice. Preference is given to the use of the HPPD inhibitors according to the invention in pest-resistant transgenic crops of maize and cotton, especially in maize.
ln the context of the present invention, pest-resistant and/or fungus-resistant transgenic useful plants include expressly those useful plants which, in addition to pest-resistance and/or fungus-resistance, additionally possess herbicide tolerance. Of the group of herbicide-tolerant useful plants, according to the invention preference is given to those having tolerance to glyphosate, glufosinate ammonium, ALS (acetolactate synthase) inhibitors, e.g. sulfonylureas, for example primisulfuron, prosulfuron and trifloxysulfuron, or bromoxynil, such as Bt11 maize or Herculex I® maize.
In the context of the present invention, pest-resistant transgenic crop plants are to be understood as being those which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus'.
Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CryΙIIB(bl ) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
In the context of the present invention there are to be understood by δ-endotoxins, for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c, or vegetative insecticidal proteins (VIP), for example VIP1 , VIP2, VIP3 or VIP3A, expressly also
hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ). An example for a truncated toxin is a truncated CrylA(b), which is expressed in the Bt11 maize from Syngenta Seed SAS, as described below. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylllA055, a cathepsin-D- recognition sequence is inserted into a CrylllA toxin (see WO 03/018810).
Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
The following harmful insects from different taxonomic groups are especially common in maize crops: Ostrinia nubilalis, European corn borer Agrotis ipsilon, black cutworm Helicoverpa zea, corn earworm Spodoptera frugiperda, fall armyworm Diatraea grandiosella, southwestern corn borer Elasmopalpus lignosellus, lesser cornstalk borer Diatraea saccharalis, sugarcane borer Diabrotica virgifera virgifera, western corn rootworm Diabrotica longicornis barberi, northern corn rootworm
Diabrotica undecimpunctata howardi, southern corn rootworm Melanotus spp., wireworms Cyclocephala borealis, northern masked chafer (white grub) Cyclocephala immaculata, southern masked chafer (white grub) Popillia japonica, Japanese beetle Chaetocnema pulicaria, corn flea beetle Sphenophorus maidis, maize billbug Rhopalosiphum maidis, corn leaf aphid Anuraphis maidiradicis, corn root aphid Blissus leucopterus leucopterus, chinch bug Melanoplus femurrubrum, redlegged grasshopper Melanoplus sanguinipes, migratory grasshopper Hylemya platura, seedcorn maggot Agromyza parvicornis, corn blotch leafminer Anaphothrips obscurus, grass thrips Solenopsis milesta, thief ant Tetranychus urticae, twospotted spider mite
Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl ) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin); Bollgard I® (cotton variety that expresses a CrylA(c) toxin); Bollgard II® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT® (cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a CrylllA toxin); Nature- Gard® and Protecta®.
Further examples of such transgenic crops are:
1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR 96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated CrylA(b) toxin. Bt1 1 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer {Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a CrylA(b) toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium.
3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified CrylllA toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a CrylllB(bl) toxin and has resistance to certain Coleoptera insects.
5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02.
6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON
810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacte um sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
Transgenic crops of insect-resistant plants are also described in BATS (Zentrum fur Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) Report 2003, (http://bats.ch).
In the context of the present invention, fungus-resistant transgenic crop plants are to be understood as being those which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353 191. The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A- 0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
The method according to the invention is suitable especially in transgenic insect-resistant useful plant crops.
The method according to the invention is suitable very especially in transgenic useful plant crops that contain a coding sequence which codes for a δ-endotoxin or a vegetative insecticidal protein (VIP) toxin.
The method according to the invention is very especially suitable in transgenic useful plant crops that contain a coding sequence which codes for a toxin selected from the group CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ), Cry9c, VIP1 , VIP2, VIP3 and VIP3A.
The method according to the invention is especially suitable in Bt11 maize and Bt176 maize from Syngenta Crop Protection AG; in YieldGard®, YieldGard Plus® and YieldGard Rootworm® from the Monsanto Company; in Starlink® from Bayer AG and in Herculex I®; more especially in Bt11 maize.
The method according to the invention is very especially suitable in transgenic useful plant crops that contain a coding sequence which codes for a toxin selected from the group CrylA(b), CrylllA and VIP3A.
The method according to the invention is more especially suitable in transgenic useful plant crops that express a CrylllA toxin modified by insertion of a non-naturally present protease recognition sequence, such as, for example, CrylllA055. Toxins of that kind are described specifically in WO 03/018810, which is incorporated by this reference in the present application. The use of the method according to the invention in transgenic useful plant crops that express CrylllA055 is very especially preferred.
The weeds to be controlled may be both monocotyledonous and dicotyledenous weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The compositions according to the invention may additionally also comprise growth regulators, for example trinexapac (744), chlormequat chloride (129), clofencet (148),
cyclanilide (170), ethephon (281 ), flurprimidol (355), gibberellic acid (379), inabenfide (421), maleic hydrazide (449), mefluidide (463), mepiquat chloride (465), paclobutrazol (548), prohexadione-calcium (595), uniconazole (746) or thidiazuron (703). The composition according to the invention may also comprise fungicides, for example azoxystrobin (43), epoxiconazole (48), benomyl (60), bromuconazole (89), bitertanol (77), carbendazim (107), cyproconazole (189), cyprodinil (190), diclomezine (220), difenoconazole (228), diniconazole (247), epoxiconazole (48), ethirimol (284), etridiazole (294), fenarimol (300), fenbuconazole (302), fenpiclonil (311), fenpropidin (313), fenpropimorph (314), ferimzone (321), fludioxonil (334), fluquinconazole (349), flutolanil (360), flutriafol (361), imazalil (410), ipconazole (426), iprodione (428), isoprothiolane (432), kasugamycin (438), kresoxim-methyl (439), spiroxamine (441 ), mepronil (466), myclobutanil (505), nuarimol (528), pefurazoate (554), pencycuron (556), phthalide (576), probenazole (590), prochloraz (591), propiconazole (607), pyrazophos (619), pyroquilon (633), quinoxyfen (638), quintozene (639), tebuconazole (678), tetraconazole (695), thiabendazole (701 ), thifluzamide (705), triadimefon (720), triadimenol (721 ), tricyclazole (734), tridemorph (736), triflumizole (738), triforine (742), triticonazole (745) or vinclozolin (751). The number in parenthesis after each active ingredient refers to the respective entry number for that active ingredient in The Pesticide Manual, eleventh ed., British Crop Protection Council, 1997.
Biological Examples
Example B1 : Post-emergence herbicidal action
Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastic pots. When the test plants have reached the 2- to 3-leaf stage, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying in an optimum concentration (500 litres of water/ha). The test plants are then grown on in a greenhouse under optimum conditions. After a test duration of 2 to 3 weeks, the test is evaluated in accordance with a scale of eleven ratings (10 = total damage, 0 = no action). Ratings of from 7 to 10 (especially from 8 to 10) indicate good to very good herbicidal action. In this test the test compounds exhibit a good herbicidal action while largely protecting the useful plant.
It has been found, surprisingly, that specific safeners are suitable for mixing with the composition according to the invention. The present invention therefore relates also to a method
of controlling undesirable plant growth in pest-resistant and/or fungus-resistant transgenic useful plant crops, which process comprises applying to the plants or to the locus thereof a herbicidally effective amount of at least one herbicide selected from the class of HPPD inhibitors together with an amount, effective for herbicide antagonism, of at least one safener.
The present invention relates also to a herbicidal and plant-growth-inhibiting composition for controlling undesirable plant growth in pest-resistant and/or fungus-resistant transgenic useful plant crops, which comprises a herbicidally effective amount of at least one herbicide selected from the class of HPPD inhibitors together with an amount, effective for herbicide antagonism, of at least one safener, on an inert carrier.
The composition according to the invention is suitable especially for controlling undesirable plant growth in transgenic pest-resistant useful plant crops.
In the context of the present invention, compounds especially suitable as safeners are: a compound selected from the compound formula 3.1
and the compound of formula 3.5
and the compound of formula 3.6
and of formula 3.10
and of formula 3.15
H3C and of formula 3.17
and of formula 3.18
and of formula 3.19
The compounds of formulae 3.1 to 3.19 are known and are described, for example, in The Pesticide Manual, eleventh ed., British Crop Protection Council, 1997 under entry numbers 61 (formula 3.1 , benoxacor), 304 (formula 3.2, fenclorim), 154 (formula 3.3, cloquintocet), 462 (formula 3.4, mefenpyr-diethyl), 377 (formula 3.5, furilazole), 363 (formula 3.8, fluxo- fenim), 213 (formula 3.9, dichlormid) and 350 (formula 3.10, flurazole). The compound of formula 3.11 is known by the name MON 4660 (Monsanto) and is described e.g. in EP-A-0 436 483.
The compound of formula 3.6 (AC 304415) is described, for example, in EP-A-0 613 618, and the compound of formula 3.7 in DE-A-2 948 535. The compound of formula 3.12 (isoxadifen, 4,5-dihydro-5,5-diphenyl-1 ,2-oxazole-3-carboxylic acid) is described under Chemical Abstracts No. 209866-92-2 and in DE-A-4 331 448, and the compound of formula 3.13 is described in DE-A-3 525 205. The compound of formula 3.14 is known e.g. from US-A-5,215,570, and the compound of formula 3.15 from EP-A-0 929 543. The compound of formula 3.16 is described in WO 99/00020. In addition to the compound of formula 3.16, the other 3-(5-tetrazolylcarbonyl)-2-quinolones described in WO 99/00020, especially the compounds specifically disclosed in Tables 1 and 2 on pages 21 to 29, are also suitable for the protection of crop plants from the phytotoxic action of the compound of formula I. The compound of formula 3.17 is described e.g. in US-A-6,162,762.
Crop plants that can be protected by the safeners of formulae 3.1 to 3.19 against the harmful action of the above-mentioned herbicides include the transgenic useful plant crops mentioned above.
Areas under cultivation will be understood as including land already under cultivation with the crop plants or where seed material of the crop plants has been sown as well as land intended for the cropping with those crop plants.
Depending upon the intended use, a safener of formula 3.1 to 3.19 can be used for pretreating the seed material of the crop plant (dressing the seed or seedlings) or it can be incorporated into the soil before or after sowing. It can, however, also be applied alone or together with the herbicide after emergence of the plants. Treatment of the plants or the seed material with the safener can therefore take place in principle independently of the time of application of the herbicide. Treatment of the plant may, however, be carried out also by simultaneous application of herbicide and safener (e.g. in the form of a tank mixture). The rate of application of safener relative to herbicide is largely dependent upon the mode of application. Where a field treatment is carried out either by using a tank mixture with a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of herbicide to safener will usually be from 100:1 to 1 :10, preferably from 20:1 to 1 :1. In field treatment it is usual to apply from 0.001 to 1.0 kg safener/ha, preferably from 0.001 to 0.25 kg safener/ha.
The compositions according to the invention are suitable for all methods of application commonly used in agriculture, including pre-emergence application, post-emergence application and seed dressing.
For seed dressing, generally from 0.001 to 10 g of safener/kg of seed, especially from 0.05 to 2 g of safener/kg of seed, are applied. If the safener is applied in liquid form, with seed soaking, shortly before sowing, it is advantageous to use safener solutions containing the active ingredient in a concentration of from 1 to 10 000 ppm, especially from 100 to 1000 ppm.
For application, the safeners of formulae 3.1 to 3.19 or combinations of such safeners with the HPPD inhibitors are advantageously processed together with the adjuvants customary in formulation technology into formulations, for example into emulsifible concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations have already been described above in connection with herbicides.
Various methods and techniques come into consideration for the use of safeners, for example the following:
i) Seed dressing a) Dressing the seeds with a wettable powder formulation of a compound of formula 3.1 to 3.19 by shaking in a vessel until the formulation is evenly distributed over the surface of the seeds (dry dressing). In this method about from 1 to 500 g of compound of formula 3.1 to 3.19 (from 4 g to 2 kg of wettable powder) are used per 100 kg of seed material. b) Dressing the seeds with an emulsifiable concentrate of the compound of formula 3.1 to 3.19 in accordance with method a) (wet dressing). c) Dressing by immersing the seed material in a liquor containing from 100 to 1000 ppm of the compound of formula 3.1 to 3.19 for 1 to 72 hours and optionally subsequently drying the seeds (immersion dressing).
Dressing the seed material or treating the germinated seedling are naturally the preferred methods of application, because the treatment with the active ingredient is directed entirely
at the target crop. It is customary to use from 1 to 1000 g of antidote, especially from 5 to 250 g of antidote, per 100 kg of seed material, but depending upon the method used, which also allows the addition of other active ingredients or micronutrients, it is possible to use concentrations above and below the limits indicated (repeat dressing).
ii) Application in the form of a tank mixture
A liquid formulation of a mixture of antidote and HPPD inhibitor (in a respective quantity ratio of from 10:1 to 1 :100) is used, the rate of application of HPPD inhibitor being from 0.005 to
5.0 kg per hectare. Such tank mixtures are applied before or after sowing. iii) Application to the seed furrow
The compound of formula 3.1 or 3.2 is introduced into the open, sown seed furrow in the form of an emulsifiable concentrate, wettable powder or granules. When the seed furrow has been covered over, the herbicide is applied by the pre-emergence method in customary manner. iv) Controlled release of active ingredient
A solution of the compound of formula 3.1 to 3.19 is applied to granular mineral carriers or polymerised granules (urea/formaldehyde) and dried. If desired, a coating can be applied
(coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time.
Preferred formulations have especially the following compositions (% = percent by weight):
Emulsifiable concentrates: active ingredient mixture: 1 to 90 %, preferably 5 to 20 % surface-active agent: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
Dusts: active ingredient mixture: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient mixture: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 %
surface-active agent: 1 to 40 %, preferably 2 to 30 %
Wettable powders: active ingredient mixture: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
Granules: active ingredient mixture: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
Biological Example: Safening action .
The test plants are raised to the 2- to 4-leaf stage in plastics containers under greenhouse conditions. At that stage, the HPPD inhibitors alone and mixtures of those herbicides with the compounds to be tested as safeners are applied to the test plants. Application is effected in the form of an aqueous suspension of the test compounds, prepared from a 25 % wettable powder (Example F3, b) according to WO 97/34485) or a suspension concentrate as in Example F8, using 200-500 I of water/ha. 3 weeks after application, the phytotoxic action of the herbicides on the crop plants, e.g. cereals, is evaluated in accordance with a percentage scale. 100 % indicates that the test plant has died, 0 % indicates no phytotoxic action. The mixtures according to the invention exhibit a good action in this test.
Claims
1. A method of controlling undesirable plant growth in pest-resistant and/or fungus-resistant transgenic useful plant crops, which process comprises applying at least one herbicide selected from the class of HPPD inhibitors in a herbicidally effective amount to the transgenic useful plant crops or to the locus thereof.
2. A method according to claim 1 , wherein the herbicide corresponds to a compound of formula I
,O l- (» Q wherein Q is an organic substituent which is so chosen that the compound of formula I has a pK value of from 1 to 5;
T is T!
D is hydrogen or R3;
E is hydrogen or R4; or
D and E together are C2-C3alkylene which can be mono- or poly-substituted by R6;
A is d-C2alkylene which can be mono- or poly-substituted by R5; or A may additionally be carbonyl, oxygen or -N-R7- when D and E are other than C2-C3alkylene;
Rι> 2, R3. R . R5 and R6 are each independently of the others hydrogen, Cι-C alkyl, phenyl,
CrC4alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl or d-C alkoxycarbonyl; or R2 and R4 together form a C2-C4alkylene chain which can be interrupted by oxygen and/or carbonyl and/or sulfur, with the proviso that the oxygen and sulfur atoms are separated by at least one methylene group;
R7 is Cι-C alkyl, alkoxycarbonyl or CrC alkylcarbonyl; o3B is hydroxy, O"M+, wherein M+ is an alkali metal cation or ammonium cation, halogen, Cι-C12alkylsulfonyloxy, amino, C C4alkylthio, C C12alkylsulfinyl, Cι-C12alkylsulfonyl, CrCehaloalkylthio, C C^haloalkylsulfinyl, d-C^haloalkylsulfonyl, d-Cealkoxy-d-Cealkylthio, CrC6alkoxy-CrC6alkylsulfinyl, d-Cealkoxy-d-Cealkylsulfonyl, C3-C12alkenylthio, C3-C12- alkenylsulfinyl, C3-Cι2alkenylsulfonyl, C3-C-|2alkynylthio, C3-C12alkynylsulfinyl, C3-C12alkynyl- sulfonyl, d-C- alkoxycarbonyl-C|-C-4alkylthio, d-C4alkoxycarbonyI-CrC-4alkylsulfinyl, Crdalkoxycarbonyl-Crdalkylsulfonyl, (d-C4alkoxy)2P(O)O, C C4alkyl-(Cι-C4alkoxy)- P(O)O, H(Cι-C4alkoxy)P(O)O, Rre/R∞βN, R039R04oNNH, R04ι R0 2NC(O)O-, R0 3Ro4 NC(O)NH-, d-Cι8alkylcarbonyloxy, C2-Cι8alkenylcarbonyloxy, C2-C18alkynyl- carbonyloxy, C3-C6cycloalkylcarbonyloxy, d-Cι2alkoxycarbonyloxy, C C^alkylthiocarbonyl- oxy or d-C12alkylthiocarbamoyl, wherein the alkyl, alkenyl and alkynyl groups can be substituted by halogen, d-C6alkoxy, d-C6alkylthio, C C6alkylsulfinyl, CrCealkylsulfonyl or by cyano; or
R036 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy, benzoyloxy or benzoyl-CrC6alkoxy, wherein the phenyl groups can in turn be substituted one or more times by halogen, nitro, cyano, d-C4alkyl, d-C4haloalkyl, d-C4- alkoxy and/or d-C4haloalkoxy, or R036 is a group Het0 -thio, Het08-sulfinyl, Het09-sulfonyl, Het0ι0-(CO)O or Het0ιrN(R04 ); wherein
Het07, Het08, Het09, Het010 and Het0n are each independently of the others a five- to ten- membered monocyclic or annellated bicyclic ring system which may be aromatic or partially saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, and each ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system itself can be substituted by d-C6alkyl, d-C6- haloalkyl, d-C6alkoxy, d-C6haloalkoxy, d-C6alkylthio, CrC6alkylsulfinyl, CrC6alkylsulfonyl, di(d-C4alkyl)aminosulfonyl, di(d-C-4alkyl)amino, halogen, cyano, nitro or by phenyl, and the substituents on the nitrogen atom in the heterocyclic ring are other than halogen; o37, Ro3s. o39, Ro o, R04ι . Ro42, Ro43, Ro^ and R047 are each independently of the others hydrogen or C C6alkyl; or
R037 and R038 together or R039 and R04o together or R04ι and R042 together or R043 and R044 together are pyrrolidino, piperidino, morpholino or thiomorpholino, which can be mono- or poly-substituted by methyl groups; or T is T2
R3 is hydrogen, d-C alkyl, CrC haloalkyl, C3-C6cycloalkyl, C2-C4alkenyl, C2-C4alkynyl or benzyl, it being possible for the phenyl group to be substituted one or more times by d-C6alkyl, d-C6haloalkyl, CrC6alkoxy, CrC6haloalkoxy, halogen, cyano, hydroxy and/or nitro;
R35 is hydrogen, d-C4alkyl, CrC haloalkyl, C3-C6cycloalkyl, C3-C4alkenyl, C3-C4alkynyl or benzyl, it being possible for the phenyl group to be substituted one or more times by d-C6alkyl, d-C6haloalkyl, CrC6alkoxy, CrC6haloalkoxy, halogen, cyano, hydroxy and/or nitro;
R36 is hydroxy, O"M+, wherein M+ is an alkali metal cation or ammonium cation, halogen, d-C12alkylsulfonyloxy, amino, C C4alkylthio, C C12alkylsulfinyl, CrCealkylsulfonyl, CrCehaloalkylthio, d-d2haloalkylsulfinyl, C C12haloalkylsulfonyl, CrC6alkoxy-CrC6alkylthio, CrC6alkoxy-CrC6alkylsulfinyl, CrC6alkoxy-CrC6alkylsulfonyl, C3-d2alkenylthio, C3-C12- alkenylsulfinyl, C3-C12alkenylsulfonyl, C3-Cι2alkynylthio, C3-Cι2alkynylsulfinyl, C3-d2alkynyl- sulfonyl, CrC4alkoxycarbonyl-d-C4alkylthio, d-C4alkoxycarbonyl-CrC4alkylsulfinyl, CrC4alkoxycarbonyl-CrC4alkylsulfonyl, (C C4alkoxy)2P(O)O, CrC4alkyl-(C C4alkoxy)- P(O)O, H(C C4alkoxy)P(O)O, R37R38N, R39R40NNH, R41R42NC(O)O-, R43R44NC(O)NH-, CrC18alkylcarbonyloxy, C2-C18alkenylcarbonyloxy, C2-C18alkynylcarbonyloxy, C3-C6- cycloalkylcarbonyloxy, CrC12alkoxycarbonyloxy, d-d2alkylthiocarbonyloxy or C C12- alkylthiocarbamoyl, wherein the alkyl, alkenyl and alkynyl groups can be substituted by halogen, C C6alkoxy, d-C6alkylthio, CrC6alkylsulfinyl, d-C6alkylsulfonyl or by cyano; or R36 is phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonylamino, phenyl- sulfonyloxy, benzoyloxy or benzoyl-d-C6alkoxy, it being possible for the phenyl groups in turn to be substituted one or more times by halogen, nitro, cyano, C C4alkyl, d-C4haloalkyl, C C4alkoxy and/or d-C4haloalkoxy, or R36 is a group Het7-thio, Het8-sulfinyl, Hetg-sulfonyl, Het10-(CO)O or Het N(R 7); wherein Het7, Het8, Het9, Het10 and Het-n are each independently of the others a five- to ten- membered monocyclic or annellated bicyclic ring system which may be aromatic or partially saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, and each ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system itself can be substituted by d-C6alkyl, d-C6- haloalkyl, d-C6alkoxy, CrC6haloalkoxy, d-C6alkylthio, CrC6alkylsulfinyl, CrCealkylsulfonyl, di(CrC4alkyl)aminosulfonyl, di(d-C4alkyl)amino, halogen, cyano, nitro or by phenyl, and the substituents on the nitrogen atom in the heterocyclic ring are other than halogen; R37, 38, R39, R4o. R41, R42, R43, R44 and R47 are each independently of the others hydrogen or d-C6alkyl; or
R37 and R38 together or R39 and R40 together or R41 and R 2 together or R^ and R^ together are pyrrolidino, piperidino, morpholino or thiomorpholino, which can be mono- or poly- substituted by methyl groups; or T is T3
wherein
R4g is d-C alkyl, d-C4haloalkyl, C3-C6cycloalkyl or halo-substituted C3-C6cycloalkyl;
Z01 is a chemical bond, S, SO or SO2;
R50 is hydrogen or CrC3alkylene which can be substituted by the following substituents: halogen, hydroxy, CrC6alkoxy, C2-C6alkenyl, C2-C6alkynyl, C3-C6cycloalkyl, CrC6alkoxy- d-C6alkoxy, CrC6alkoxy-CrC6alkoxy-CrC6alkoxy, (3-oxetanyl)-oxy, CrC6alkyl-substituted
(3-oxetanyl)-oxy, benzylthio, benzylsulfinyl, benzylsulfonyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, it being possible for the phenyl- and benzyl-containing groups in turn to be substituted by one or more CrC6alkyl, d-C6haloalkyl, d-C6alkoxy,
CrC6haloalkoxy, halogen, cyano, hydroxy and/or nitro groups; or R50 is phenyl, it being possible for the phenyl-containing group in turn to be substituted by one or more d-C6alkyl, C C6haloalkyl, CrC6alkoxy, CrC6haloalkoxy, halogen, cyano, hydroxy and/or nitro groups, or R50 is C3-C6cycloalkyl, d-C6alkoxy- or d-C6alkyl-substituted C3-C6cycloalkyl, 3-oxetanyl or C C6alkyl-substituted 3-oxetanyl; or T is T4 
wherein
R0 5 is CrC6alkyI, d-C6haloalkyl, C3-C6cycloalkyl or halo-substituted C3-C6cycloalkyl; or an agronomically acceptable salt, isomer or enantiomer thereof.
3. A method according to claim 2, wherein the herbicide corresponds to a compound of formula Iz
D is hydrogen or R3;
E is hydrogen or R4; or
D and E together are C2-C3alkylene which can be mono- or poly-substituted by R6;
A is d-C2alkylene which can be mono- or poly-substituted by R5; or A may additionally be carbonyl, oxygen or -N-R7- when D and E are other than C2-C3alkylene;
Ri. R2, R3, R4, R5 and R6 are each independently of the others hydrogen, C C alkyl, phenyl, d-C4alkoxy, halogen, hydroxy, cyano, hydroxycarbonyl or d-C4alkoxycarbonyl; and
R7 is d-C4alkyl, alkoxycarbonyl or d-C alkylcarbonyl, or an agronomically acceptable salt, isomer or enantiomer thereof.
4. A method according to claim 2, wherein Q is Q^ 
wherein
AT is methine, C(Ra-,) or N(O)p; p is 0 or 1 ;
Rai is hydrogen, Crdalkyl, hydroxy, CrC6alkoxy, CrC6haloalkoxy, C3-C6alkenyloxy, C3-C6haloalkenyloxy, C3-C6alkynyloxy, CrC alkylcarbonyloxy, CrC alkylsulfonyloxy, tosyloxy, d-daikylthio, d-C4alkylsulfinyl, C C4alkylsulfonyl, CrC4alkylamino, di-C C4alkyl- amino, d-C4alkoxycarbonyl, C C4haloalkyl, formyl, cyano, halogen, phenyl or phenoxy; it being possible for phenyl in turn to be substituted by d-C3alkyl, C C3haloalkyl, d-C3alkoxy, CrC3haloalkoxy, halogen, cyano or by nitro; or Raj is a three- to ten-membered monocyclic ring system or, together with Ra2 or Ra5, annellated mono- or bi-cyclic ring system which may be interrupted by oxygen, sulfur, SO, SO2, NRa6, carbonyl and/or by =NORa7, the ring system, unless it is annellated, being bonded to the carbon atom of the substituent A^ directly or by way of a d-C4alkylene, -CH=CH-, -C≡C-, -CH2O-, -CH2N(C C4alkyl)-, -CH2S-, -CH2SO- or -CH2SO2- group, and the ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system can itself be mono-, di- or tri-substituted by d-C6alkyl, C C6- haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C C6alkoxy, d-Cehaloaikoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, CrC6alkylthio, C C6haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, CrC4alkoxy-CrC2alkylthio, CrC4alkylca'rbonyl-CrC2alkylthio, CrC4alkoxycarbonyl-C C2alkylthio, cyano-CrC alkylthio, CrC6alkylsulfinyl, d-C6haloalkylsulfinyl, CrC6alkylsulfonyl, CrC6haloalkylsulfonyl, amino- sulfonyl, CrC2alkylaminosulfonyl, di(C1-C2alkyl)aminosulfonyl, di(C C4alkyl)amino, halogen, cyano, nitro, phenyl and/or benzylthio, it being possible for phenyl and benzylthio in turn to be substituted on the phenyl ring by C C3alkyl, d-C3haloalkyl, CrC3alkoxy, d-C3- haloalkoxy, halogen, cyano or by nitro, and substituents on the nitrogen atom in the heterocyclic ring are other than halogen; or Raj is the group -X5-X7 or the group -X6-X5-X7; wherein X6 is a CrC6alkylene, C3-C6alkenylene or C3-C6alkynylene chain which can be mono- or poly-substituted by halogen and/or by X8, the unsaturated bonds of the chain not being bonded directly to the substituent X5;
X8 is hydroxy, d-C6alkoxy, C3-C6cycloalkyloxy, CrC6alkoxy-C C6alkoxy, CrC6alkoxy-CrC6- alkoxy-d-C6alkoxy or CrC2alkylsulfonyloxy;
X5 is oxygen, -O(CO)-, -(CO)O-, -O(CO)O-, -N(d-C4alkyl)-O-, -O-N(d-C4alkyl)-, thio, sulfinyl, sulfonyl, -SO2N(C C4alkyl)-, -N(d-C4alkoxy)SO2-, -N(d-C4alkyl)SO2-, -N(CrC2alkoxy-d-C2alkyl)SO2- or -N(C C4alkyl)-;
Ra6 is hydrogen, d-C4alkyl, d-C4alkylthio-CrC4carbonyl, CrC alkylsulfinyl-CrC4carbonyl, d-C4alkylsulfonyl-CrC4carbonyl, d-dalkoxycarbonyl, d-C alkylcarbonyl, phenylcarbonyl or phenyl, it being possible for the phenyl groups in turn to be substituted by d-C4alkyl, d-C4haloalkyl, d-C alkoxy, d-C haloalkoxy, d-C4alkylcarbonyl, d-C4alkoxycarbonyl, d-C4alkylamino, di-d-C4alkylamino, C C alkyl-S-, d-C4alkyl-SO-, d-C4alkyl-SO2, d-C4alkyl-S(O)2O, d-C4haloalkyl-S-, d-C4haloalkyl-SO, CrC4haloalkyl-SO2, C C4halo- alkyl-S(O)2O, CrC4alkyl-S(O)2NH, d-C4alkyl-S(O)2N(Cι-C4alkyl), halogen, nitro or by cyano; Ra7 is CrC4alkyl;
Ra2 is hydrogen, CrC6alkyl, CrC6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, vinyl substituted by d-C2alkoxycarbonyl or by phenyl, C2-C6alkynyl, C2-C6haloalkynyl, ethynyl substituted by trimethylsilyl, hydroxy, d-C2alkoxy, d-C2alkoxycarbonyl or by phenyl, C3-C6allenyl, C3-C6- cycloalkyl, halo-substituted C3-C6cycloalkyl, CrC6alkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, CrC6haloalkoxy, C3-C6haloalkenyloxy, cyano-d-C4alkoxy, Cι-C4alkoxy-CrC alkoxy, Cj-C4- alkylthio-d-C4alkoxy, CrC4alkylsulfinyl-d-C-4alkoxy, d-C4alkylsulfonyl-CrC4alkoxy, d-C4- alkoxycarbonyl-CrC alkoxy, Cι-C6alkylthio, CrC6alkylsulfinyl, CrC6alkylsulfonyl, CrCehaloalkylthio, CrCehaloalkylsulfinyl, Crdshaloalkylsulfonyl, CrC4alkoxycarbonyl-CrC4alkylthio, CrC4alkoxycarbonyl-CrC4alkylsulfinyl, CrC4alkoxycarbonyl-d-C4alkylsulfonyl, benzyl-S-, benzyl-SO-, benzyl-SO2-, CrC6alkylamino, di-C2-C6alkylamino, d-C6alkylaminosulfonyl, di(CrC6alkylamino)sulfonyl, benzyloxy, benzyl, phenyl, phenoxy, phenylthio, phenylsulfinyl or phenylsulfonyl, it being possible for the phenyl-containing groups in turn to be substituted by d-C3alkyl, d-C3haloalkyl, C C3alkoxy, C C3haloalkoxy, halogen, cyano or by nitro, or Ra2 is OS-C C4alkyl, OSO-d-C4alkyl, OSO2-CrC4alkyl, OS-d-C4haloalkyl, OSO-C C4- haloalkyl, OSO2-d-C4haloalkyl, N(C C4alkyl)-S-CrC4alkyl, N(C C4alkyl)-SO-CrC4alkyl, N(C1-C alkyl)-SO2-Cι-C4alkyl, cyano, carbamoyl, d-C4alkoxycarbonyl, formyl, halogen, rhodano, amino, hydroxy-d-C4alkyl, CrC4alkoxy-C C4alkyl, d-C4alkyl-S-d-C4alkyl, CrC4alkyl-SO-C C4alkyl, d-C4alkyl-SO2-CrC4alkyl, cyano-Cι-C4alkyl, d-C6alkyl- carbonyloxy-CrC4alkyl, CrC4alkoxycarbonyl-CrC4alkyl, d-C4alkoxycarbonyloxy-CrC4alkyl, CrC4rhodano-CrC4alkyl, benzoyloxy-d-C alkyl, C2-C6oxiranyl, CrC4alkylamino-d-C4alkyl, di(CrC4alkyl)amino-CrC4alkyl, CrC12alkylthiocarbonyl-CrC4alkyl or formyl-CrC4alkyl, or Ra2 is a five- to ten-membered monocyclic or annellated bicyclic ring system which may be aromatic or partially saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system being bonded to the pyridine ring by way of a d-C4alkylene, -CH=CH-, -C≡C-, -CH2O-, -CH2N(CrC4alkyl)-, -CH2SO- or -CH2SO2- group, and each ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system itself can be mono-, di- or tri-substituted by CrC6alkyl, CrCehaloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, CrC6alkoxy, CrC6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, CrC6alkylthio, CrCehaloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5- acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C4cyanoalkylthio, CrC6alkylsulfinyl, d-C6- haloalkylsulfinyl, CrC6alkylsulfonyl, CrC6haloalkylsulfonyl, aminosulfonyl, Cι-C2alkylamino- sulfonyl, di(d-C2alkyl)anninosulfonyl, di(CrC4alkyl)amino, halogen, cyano, nitro, phenyl and/or by benzylthio, it being possible for phenyl and benzylthio in turn to be substituted on the phenyl ring by d-C3alkyl, d-C3haloalkyl, d-C3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro, and substituents on the nitrogen atom in the heterocyclic ring are other than halogen; or Ra2 is the group -Xι-X3 or the group -X2-Xj-X3; wherein
X2 is a CrC6alkylene, C3-C6alkenylene or C3-C6alkynylene chain which can be mono- or poly-substituted by halogen or by X4, the unsaturated bonds of the chain not being bonded directly to the substituent X^
X is hydroxy, CrC6alkoxy, C3-C6cycloalkyloxy, CrC6alkoxy-CrC6alkoxy, CrC6alkoxy-CrC6- alkoxy-CrC6alkoxy or CrC2alkylsulfonyloxy;
XT is oxygen, -O(CO)-, -(CO)O-, -O(CO)O-, -N(d-C4alkyl)-O-, -O-N(C C4alkyl)-, thio, sulfinyl, sulfonyl, -SO2N(d-C4alkyl)-, -N(CrC4alkyl)SO2-, -N(CrC2alkoxy-d-C2alkyl)SO2- or -N(d-C4alkyl)-;
X3 and X7 are each independently of the other a d-C8alkyl, C3-C6alkenyl or C3-C6alkynyl group which is mono- or poly-substituted by the following substituents: halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, d-C6alkoxy, CrC6alkoxycarbonyl, C2-C6- alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, halo-substituted C3-C6cycloalkyl, C3-C6alkenyloxy, C3-C6aIkynyloxy, CrC6haloalkoxy, C3-C6haloalkenyloxy, cyano-CrC6alkoxy, CrC6alkoxy-Cι-Cealkoxy, CrC6alkoxy-CrC6alkoxy-CrC6alkoxy, CrC6- alkylthio-d-Cealkoxy, CrC6alkylsulfinyl-CrC6alkoxy, CrCealkylsulfonyl-CrC6alkoxy, d-C6- alkoxycarbonyl-CrC6alkoxy, CrC6alkoxycarbonyl, d-C6alkylcarbonyl, CrC6alkylthio, CrC6alkylsulfinyl, CrCealkylsulfonyl, CrCehaloalkylthio, d-C-ehaloalkylsulfinyl, d-C6halo- alkylsulfonyl, oxiranyl, which can in turn be substituted by Cι-C6alkyl, (3-oxetanyl)-oxy, which can in turn be substituted by d-C6alkyl, benzylthio, benzylsulfinyl, benzylsulfonyl, CrC6alkyl- amino, di(d-C6alkyl)amino, C C4alkyl-S(O)2O, CrC4alkyl-N(CrC4alkyl)SO2-, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl and/or phenylsulfonyl; it being possible for the phenyl- or benzyl-containing groups in turn to be substituted by one or more CrC6alkyl, CrCehaloalkyl, CrC6alkoxy, d-C6haloalkoxy, halogen, cyano, hydroxy and/or nitro groups, or
X3 and X7 are each independently of the other phenyl which can be substituted one or more times by d-C6alkyl, CrCehaloalkyl, d-dsalkoxy, CrC6haloalkoxy, halogen, cyano, hydroxy and/or nitro; or
X3 and X7 are each independently of the other C3-C6cycloalkyl, CrC6alkoxy- or d-C6alkyl- substituted C3-C6cycloalkyl, 3-oxetanyl or CrC6alkyl-substituted 3-oxetanyl; or X3 and X7 are each independently of the other a five- to ten-membered monocyclic or annellated bicyclic ring system which may be aromatic or saturated or partially saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system being bonded to the substituent ^ or X5 directly or by way of a d-C alkylene, C2-C4alkenyl-C C4alkylene, C2-C4alkynyl-d-C4alkylene, -N(d-C4alkyl)-CrC4alkylene, -SO- d-C4alkylene or -SO2-d-C4alkylene group, and each ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system can itself be mono-, di- or tri-substituted by d-C6alkyl, CrC6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, d-C6alkoxy, hydroxy, CrC6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, CrC6alkylthio, d-Cehaloalkylthio, C3-C6alkenylthio, C3-C6halo- alkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkylthio, C3-C5acetylalkylthio, C3-C6alkoxycarbonyl- alkylthio, C2-C4cyanoalkylthio, d-C6alkylsulfinyl, CrC6haloalkylsulfinyl, CrCealkylsulfonyl, CrC6haloalkylsulfonyl, aminosulfonyl, CrC2alkylaminosulfonyl, di(CrC2alkyl)aminosulfonyl, di(CrC4alkyl)amino, halogen, cyano, nitro, phenyl and/or by benzylthio, it being possible for phenyl and benzylthio in turn to be substituted on the phenyl ring by d-C3alkyl, d-C3halo- alkyl, d-C3alkoxy, d-C3ha!oalkoxy, halogen, cyano or by nitro, and the substituents on the nitrogen atom in the heterocyclic ring are other than halogen;
Ra3 is hydrogen, d-C6alkyl, CrCehaloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, CrC6alkoxy, Cj-Cehaloalkoxy, d-C6alkylthio, d-C6alkyl- sulfinyl, CrCealkylsulfonyl, d-Cehaloalkylthio, CrCehaloalkylsulfinyl, CrCehaloalkylsulfonyl, CrC6alkylamino, di-C2-C6alkylamino, CrC6alkylaminosulfonyl, di-C2-C6alkylaminosulfonyl, phenyl, phenylthio, phenylsulfinyl, phenylsulfonyl or phenoxy, it being possible for phenyl in turn to be substituted by d-C3alkyl, CrC3haloalkyl, C C3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro, or Ra3 is -N(CrC4alkyl)-S-C C4alkyl, -N(d-C4alkyl)-SO-CrC4alkyl, -N(CrC4alkyl)-SO2-CrC4alkyl, cyano, halogen, amino, d-C4alkoxy-CrC4alkyl, Cι-C4alkyl-S- CrC4alkyl, d-C4alkyl-SO-d-C4alkyl or d-C4alkyl-SO2-CrC4alkyl; Ra is hydrogen, d-C6alkyl, hydroxy, d-C6alkoxy, d-C6haloalkoxy, C3-C6alkenyloxy, C3-C6haloalkenyloxy, C3-C6alkynyloxy, d-C4alkylcarbonyloxy, d-C4alkylsulfonyloxy, tosyloxy, d-C4alkylthio, Cι-C4alkylsulfinyl, Cι-C4alkylsulfonyl, d-C alkylamino, di-d- C alkylamino, d-C4alkoxycarbonyl, CrC4haloalkyl, formyl, cyano, halogen, phenyl or phenoxy, it being possible for phenyl in turn to be substituted by d-C3alkyl, d-C3haloalkyl, Cι-C3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro; or Ra4 is a five- to ten-membered monocyclic ring system or, with Ra3, annellated bicyclic ring system which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, the ring system, unless it is annellated, being bonded to the ring containing the substituent A directly or by way of a C C4alkylene, -CH=CH-, -C≡C-, -CH2O-, -CH2N(d-C4alkyl)-, -CH2S-, -CH2SO- or -CH2SO2- group, and the ring system may contain not more than two oxygen atoms and not more than two sulfur atoms, and the ring system can itself be mono-, di- or tri-substituted by CrC6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, CrC6alkoxy, d-C6haloalkoxy, C3-C6alk- enyloxy, C3-C6alkynyloxy, d-C6alkylthio, d-Cehaloalkylthio, C3-C6alkenylthio, C3-C6halo- alkenylthio, C3-C6alkynylthio, d-C4alkoxy-CrC2alkylthio, d-C alkylcarbonyl-CrC2alkylthio, CrC4alkoxycarbonyl-d-C2alkylthio, cyano-d-C alkylthio, d-C6alkylsulfinyl, CrCehaloalkylsulfinyl, d-C6alkylsulfonyl, CrCehaloalkylsulfonyl, aminosulfonyl, CrC2alkylamino- sulfonyl, di(C1-C2alkyl)aminosulfonyl, di(Cι-C4alkyl)amino, halogen, cyano, nitro, phenyl and/or by benzylthio, it being possible for phenyl and benzylthio in turn to be substituted on the phenyl ring by d-C3alkyl, d-C3haloalkyl, d-C3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro, and substituents on the nitrogen atom in the heterocyclic ring are other than halogen;
Ra5 is hydrogen, CrC6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, CrC6alkoxy, CrC6haloalkoxy, CrC6alkylthio, d-C6alkyl- sulfinyl, CrC6alkylsulfonyl, d-Cehaloalkylthio, CrCehaloalkylsulfinyl, CrCehaloalkylsulfonyl, Cι-C6alkylamino, di-C2-C6alkylamino, CrC6alkylaminosulfonyl, di-C2-C6alkylaminosulfonyl, phenyl, phenylthio, phenylsulfinyl, phenylsulfonyl or phenoxy, it being possible for phenyl in turn to be substituted by d-C3alkyl, CrC3haloalkyl, d-C3alkoxy, d-C3haloalkoxy, halogen, cyano or by nitro, or Ra5 is -N(d-C4alkyl)-S-CrC alkyl, -N(CrC4alkyl)-SO-CrC4alkyl, -N(d-C4alkyl)-SO2-CrC4alkyl, cyano, halogen, amino, C C4alkoxy-CrC alkyl, d-C4alkyl-S- C C4alkyl, C C4alkyl-SO-CrC4alkyl or CrC4alkyl-SO2-C C4alkyl, or an agronomically acceptable salt/N-oxide/isomer/enantiomer of such a compound.
5. A method according to claim 1 , wherein the herbicide is applied together with at least one safener.
6. A method according to claim 1 , wherein the transgenic useful plant crop is a maize crop that contains a coding sequence which codes for a toxin selected from the group CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl), Cryθc, VIP1 , VIP2, VIP3 and VIP3A.
7. A method according to claim 1 , wherein the transgenic useful plant crop is a Bt11 crop, Bt176 crop, YieldGard® crop, YieldGard Plus® crop, YieldGard Rootworm® crop, Starlink® crop or Herculex I® crop.
8. A method according to claim 1 , wherein the transgenic useful plant crop is a maize crop that expresses CrylllA055.
9. A herbicidal and plant-growth-inhibiting composition for controlling undesirable plant growth in pest-resistant and/or fungus-resistant transgenic useful plant crops, which comprises a herbicidally effective amount of at least one herbicide selected from the class of HPPD inhibitors, on an inert carrier.
10. A composition according to claim 9 for controlling undesirable plant growth in Bt11 crops, Bt176 crops, YieldGard® crops, YieldGard Plus® crops, YieldGard Rootworm® crops, Starlink® crops or Herculex I® crops.
11. A composition according to claim 9 which comprises a safener.
12. Use of at least one herbicide selected from the class of HPPD inhibitors for controlling undesirable plant growth in pest-resistant and/or fungus-resistant transgenic useful plant crops.
13. Use according to claim 12 for controlling undesirable plant growth in Bt11 crops, Bt176 crops, YieldGard® crops, YieldGard Plus® crops, YieldGard Rootworm® crops, Starlink® crops or Herculex I® crops.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9187762B2 (en) | 2010-08-13 | 2015-11-17 | Pioneer Hi-Bred International, Inc. | Compositions and methods comprising sequences having hydroxyphenylpyruvate dioxygenase (HPPD) activity |
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