WO2004002947A1 - Phenoxypropenylphenyl derivatives and their use as herbicides - Google Patents
Phenoxypropenylphenyl derivatives and their use as herbicides Download PDFInfo
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- WO2004002947A1 WO2004002947A1 PCT/EP2003/006945 EP0306945W WO2004002947A1 WO 2004002947 A1 WO2004002947 A1 WO 2004002947A1 EP 0306945 W EP0306945 W EP 0306945W WO 2004002947 A1 WO2004002947 A1 WO 2004002947A1
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- 0 C*=CC(C)=C(C(OCCC1)=C1C=C*)O* Chemical compound C*=CC(C)=C(C(OCCC1)=C1C=C*)O* 0.000 description 5
- MUWMVXKCYWKCFV-UHFFFAOYSA-N CBc1cccc(CC#N)c1 Chemical compound CBc1cccc(CC#N)c1 MUWMVXKCYWKCFV-UHFFFAOYSA-N 0.000 description 1
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- C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
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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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
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- C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
- C07C205/38—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. nitrodiphenyl ethers
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- C07C217/80—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings
- C07C217/82—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring
- C07C217/84—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton having amino groups and etherified hydroxy groups bound to carbon atoms of non-condensed six-membered aromatic rings of the same non-condensed six-membered aromatic ring the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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- C07C225/02—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton
- C07C225/04—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated
- C07C225/08—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings
- C07C225/10—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated and containing rings with doubly-bound oxygen atoms bound to carbon atoms not being part of rings
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- C07C233/24—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring
- C07C233/25—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a six-membered aromatic ring having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
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- C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/44—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
- C07C235/46—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton with carbon atoms of carboxamide groups and singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring
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- C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
- C07C255/37—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by etherified hydroxy groups
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- C07C39/19—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring containing carbon-to-carbon double bonds but no carbon-to-carbon triple bonds
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- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
- C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
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- C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
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Abstract
Compounds of formula (I), wherein R01 is hydrogen, C1-C8alkyl, C3-C8alkenyl or C3-C8alkynyl; or R01 is phenyl or phenyl-C1-C6alkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, -CN, -NO2, C1-C8alkylthio, C1-C8alkylsulfinyl or C1-C8alkylsulfonyl; or R01 is C1-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, C1-C6alkylamino, di(C1-C6alkyl)amino or C1-C4alkoxy; n is 0, 1, 2, 3 or 4; each R1 independently is halogen, -CN, -SCN, -SF5, -NO2, -NH2, -C02R7, -CONR8R9, -C(S)NH2, -C(R10)=NOR11, -COR12, -OR13, -SR14, -SOR15, -SO2R16, -OSO2R17, C1-C8alkyl, C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl; or C1-C8alkyl, C2-C8alkenyl or C2-C8alkynyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -NO2, -NR18R19, -CO2R20, -CONR21R22, -COR23, -C(R24)=NOR25, -C(S)NR26R27, -C(C1-C4alkylthio)=NR28, -OR29, -SR30, -SOR31, -SO2R32 or C3-C6cycloalkyl; and/or each R1 independently is C3-C6cycloalkyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -NO2, -NR18R19, -CO2R20, -CONR21R22, -COR23, -C(R24)=NOR25, -C(S)NR26R27, -C(C1-C4alkylthio)=NR28, -SR30, -SOR31, -SO2R32 or C3C6cycloalkyl; and/or each R1 independently is phenyl, which in turn can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, -CN, -NO2, C1-C4alkylthio, C1-C4alkylsulfinyl or C1-C4alkylsulfonyl; and/or two adjacent R1 together form a C1-C7alkylene bridge, which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C1-C6alkyl or C1-C6alkoxy, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent R1 together form a C2-C7alkenylene bridge, which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C1-C6alkyl or C1-C6alkoxy, the total number of ring atoms being at least 5 and at most 9; R3 and R4 are each independently of the other hydrogen, halogen, -CN, C1-C4alkyl or C1-C4alkoxy; or R3 and R4 together are C2-C5alkylene; m is 1, 2, 3, 4 or 5; and R2, R7 to R32, X1 and X2 are as defined in claim 1, and the agrochemically acceptable salts, N-oxides and all stereoisomers and tautomers of the compounds of formula (I) are suitable for use as herbicides.
Description
PHENOXYPROPENYLPHENYL DERIVATIVES AND THEIR USE AS HERBICIDES
The present invention relates to novel, herbicidally active phenoxy-(E)-propenylphenyl derivatives, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.
4-Acylaminophenyl-3-phenylpropargyl and -3-phenylallyl ether derivatives having herbicidal activity are described, for example, in Japan Kokai Tokkyo Koho (1996), JP-A-08 157 435 (CAN 125:195200 AN 1996:531728 CAPLUS).
Novel phenoxy-(E)-propenylphenyl derivatives having herbicidal and growth-inhibiting properties have now been found.
The present invention accordingly relates to compounds of formula
Roi is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl; or
Roi is phenyl or phenyl-d-Cealkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C C4alkyl, C C halo- alkyl, Cι-C4alkoxy, -CN, -NO2, CrC8alkylthio, CrCβalkylsulfinyl or Cι-C8alkylsulfonyl; or
Roi is CrC8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by
-CN, CrC6alkylamino, di(C1-C6alkyl)amino or C C4alkoxy; n is O, 1 , 2, 3 or 4; each R, independently is halogen, -CN, -SCN, -SF5, -NO2l -NH2) -CO2R7, -CONR8R9,
-C(S)NH2> -C(R10)=NORn, -COR12, -OR13, -SR14, -SOR15, -SO2R16, -OSO2R17, C CBalkyl,
C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl; or CrC8alkyl, C2-C8alkenyl or C2-C8alkynyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -NO2,
-NR18R19> -CO2R20, -CONR21R22, -COR23, -C(R24)=NOR25l -C(S)NR26R27,
-C(CrC4alkylthio)=NR2s, -OR2g, -SR30, -SOR31, -SO2R32 or C3-C6cycloalkyl; and/or
each RT independently is C3-C6cycloalkyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -NO2, -NR18Rι9, -CO2R2o, -CONR2ιR22, -COR23, - C(R24)=NOR25, -C(S)NR26R27>
-SR30, -SOR31, -SO2R32 or C3- C6cycloalkyl; and/or each Ri independently is phenyl, which in turn can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C C alkyl, Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfinyl or d-C alkylsulfonyl; and/or two adjacent Ri together form a C C7alkylene bridge, which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta- substituted by halogen and/or mono-, di- or tri-substituted by CrC6alkyl or d-Cealkoxy, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent Ri together form a C2-C7alkenylene bridge, which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by O-C6alkyl or Cι-C6- alkoxy, the total number of ring atoms being at least 5 and at most 9; R3 and R4 are each independently of the other hydrogen, halogen, -CN, d-C4alkyl or Cι-C alkoxy; or
R3 and R4 together are C2-C5alkylene;
R7 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by C C4alkoxy or phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by CrC4alkyl, CrC4haloalkyl, Cι-C alkoxy, -CN, -NO2, CrC4alkylthio, C C4alkylsulfinyl or C C4alkylsulfonyl; R8 is hydrogen or d-C8alkyl;
R9 is hydrogen or C C8alkyl, or d-C8alkyl mono-, di- or tri-substituted by -COOH, CrC8alkoxycarbonyl or -CN, or
R9 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C C4alkyl, Cι-C4haloalkyl, C C4alkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or CrC4alkylsulfonyl; or R8 and R9 together are C2-C5alkylene; Rio is hydrogen, CrC4alkyl, Cι-C haloalkyl or C3-C6cycloalkyl;
Rn is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl; R12 is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; R13 is hydrogen, CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl; or
R13 is phenyl or phenyl-CrC6alkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C1-C4alkyl, C,-C4halo- alkyl, d-C4alkoxy, -CN, -NO2, d-C8alkylthio, CrC8alkylsulfinyl or d-dalkylsulfonyl, or R13 is Cι-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, d-C6alkylamino, di(Cι-C6alkyl)amino or C1-C4alkoxy;
R14 is hydrogen, C1-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN or CrC4alkoxy; R15, R16 and R17 are each independently of the others d-C8alkyl, C3-C8alkenyl or C3-C8- alkynyl, or C,-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or CrC4alkoxy; R18 is hydrogen or d-C8alkyl;
R19 is hydrogen, C1-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by CrC4alkyl, C1-C4haloalkyl, CrC4alkoxy, -CN, -NO2, C1-C4alky!thio, C,-C4- alkylsulfinyl or d-dalkylsulfonyl; or
R18 and R19 together are a C2-C5alkylene chain, which can be interrupted by an oxygen or a sulfur atom;
R20 is hydrogen, C,-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C,-C4alkyl, C1-C4haloalkyl, CrC4alkoxy, -CN, -NO2, C C4alkylthio, C C4- alkylsulfinyl or d-C4alkylsulfonyl; R21 is hydrogen or d-C8alkyl;
R22 is hydrogen or CrC8alkyl, or d-C8alkyl mono-, di- or tri-substituted by -COOH, CrC8- alkoxycarbonyl or -CN, or
R22 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, d-C4haloalkyl, CrC4alkoxy, -CN, -NO2, d-C4alkylthio, C1-C4alkylsulfinyl or d-C4alkylsulfonyl; or R21 and R22 together are C2-C5alkylene; R23 is hydrogen, C1-C4alkyl, d-Oihaloalkyl or C3-C6cycloalkyl; R24 is hydrogen, d-C4alkyl, d-dhaloalkyl or C3-C6cycloalkyl;
R25 is hydrogen, C,-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl; R26 is hydrogen or d-C8alkyl;
R27 is hydrogen or C1-C8alkyl, or d-C8alkyl mono-, di- or tri-substituted by -COOH, d-C8- alkoxycarbonyl or -CN, or
R27 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by CrC4alkyI, CrC4haloalkyl, d-C4alkoxy, -CN, -NO2, CrC4alkylthio, d-C4alkylsulfinyl or d-C4alkylsulfonyl; or R26 and R27 together are C2-C5alkylene; R28 is hydrogen or d-C8alkyl;
R29 and R30 are each independently of the other hydrogen, CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl, or -Cualkyl mono- to penta-substituted by halogen or mono-, di- or tri- substituted by -CN or C1-C4alkoxy;
R31 and R32 are each independently of the other CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or C,-C4alkoxy; m is 1 , 2, 3, 4 or 5; each R2 independently is halogen, -CN, -SCN, -OCN, -N3, -SF5, -NO2, -NR33R34, -CO2R35, -CONR36R37, -C(R38)=NOR39, -COR40, -OR41, -SR42, -SOR43, -SO.R^, -OSO2R45, -N([CO]pR46)COR47, -N(OR54)COR55, -N(R56)SO2R57, -N(SO2R58)SO2R59, -N=C(OR60)R61, -CR62(OR63)OR64, -OC(O)NR65R66, -SC(O)NR67R68, -OC(S)NR69R70 or -N-phthalimide; and/or R2 is a 5- to 7-membered heterocyclic ring system which can be aromatic or partially or fully saturated and which can contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for such a heterocyclic ring system in turn to be mono- to penta- substituted by halogen and/or mono-, di- or tri-substituted by C1-C4alkyl, C1-C4haloalkyl, hydroxy-d-C4alkyl, CrC4alkoxy, C,-C4haloalkoxy, d-dalkoxy-d-dalkyl, -CN, -NO2, d-dalkylthio, CrC6alkylsulfinyl or CrC6alkylsulfonyl; R33 is hydrogen or C C8alkyl; and
RM is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by CrC4alkyl, CrC4haloalkyl, d-C4alkoxy, -CN, -NO2, C1-C4alkylthio, C1-C4alkylsulfinyl or d-dalkylsulfonyl; or
R33 and R^ together are a C2-C5alkylene chain, which can be interrupted by an oxygen or a sulfur atom;
R35 is hydrogen, C C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by d-C4alkoxy or phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, d-C4haloalkyl, d-dalkoxy, -CN, -NO2, d-C4alkylthio, C1-C4alkylsulfinyl or CrC4alkylsulfonyl; R36 is hydrogen or CrC8alkyl;
R37 is hydrogen or d-C8alkyl, or d-C8alkyl mono-, di- or tri-substituted by -COOH, d-C8alkoxycarbonyl or -CN, or
R37 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, CrC4haloalkyl, CrC4alkoxy, -CN, -NO2, C,-C4alkylthio, CrC4alkylsulfinyl or C.-C4alkylsulfonyl; or R36 and R37 together are C3-C5alkylene; R38 is hydrogen, C1-C4alkyl, C1-C4haloalkyl or C3-C6cycloalkyl;
R39 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, CrC4haloalkyl or C3-C6haloalkenyl; R40 is hydrogen, CrC4alkyl, C1-C4haloalkyl, C,-C8alkylthio, -C(O)-C(O)OCrC4alkyl or C3-C6cycloalkyl;
R41 is hydrogen, CrC8alkyl, C1-C8haloalkyl, C3-C8alkenyl, C3-C8alkynyl, C1-C6alkoxy-C1-C6- alkyl, d-dalkylcarbonyl, C,-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, CrC6alkoxy- d-C6alkoxycarbonyl, d-Cealkylthio-d-dalkyl, d-Cgalkylsulfinyl-d-Cgalkyl or CrC6alkyl- sulfonyl-d-C6alkyl; or
R41 is phenyl or phenyl-d-C6alkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, CrC4halo- alkyl, d-C4alkoxy, -CN, -NO2 or -S Ok -dalkyl, or
R41 is d-C8alkyl mono-, di- or tri-substituted by -COOH, d-Cβalkoxycarbonyl, d-C6alkyl- amino, d^ -dalkyOamino or -CN;
R42 is hydrogen, d-Cβalkyl, C3-C8alkenyl or C3-C8alkynyl, or C,-C8alkyl mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN or CrC4alkoxy; R43 and R44 are each independently of the other CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl, or C,-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or CrC4alkoxy;
R45 is d-C8alkyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri- substituted by -CN or C1-C4alkoxy, C3-C8alkenyl or C3-C8alkynyl, or R45 is phenyl, it being possible for the phenyl ring to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by CrC4alkyl, d-C4haloalkyl, C1-C4alkoxy, -CN, NO2, C.-C8alkylthio, d-dalkylsulfinyl or CrC8alkylsulfonyl; R46 is hydrogen, d-dalkyl, C3-C8alkenyl, C3-C8alkynyl or C,-C4haloalkyl; R47 is hydrogen, -Cealkyl, CrC4alkoxy, C3-C8alkenyl or C3-C8alkynyl, or C,-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, d-C4alkoxy, -d- alkoxycarbonyl, -NH2, C1-C4alkylamino, di(CrC4alkyl)amino, -NR48COR49, -NR50SO2R51 or -NR52CO2R53, or
R is phenyl or benzyl, each of which can in turn be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C C alkyl, d-C4haloalkyl, Cι-C4alkoxy, -CN, -NO , d-C4alkylthio, Cι-C4alkylsulfinyl or Cι-C alkylsulfonyl; p is 0 or 1 ;
R 8, R 9, R50, R51, R52 and R53 are each independently of the others hydrogen, Cι-C8alkyl, phenyl, benzyl or naphthyl, it being possible for the three last-mentioned aromatic radicals in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C8alkyl, C C4haloalkyl, Cι-C4alkoxy, Cι-C4alkylamino, di(Cι-C4alkyl)amino, -NH2, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or C C4alkylsulfonyl;
Rδ-j and R55 are each independently of the other hydrogen, C C8alkyl, or phenyl which in turn can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substijuted by Cι-C4- alkyl, CrC4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C8alkylthio, Cι-C8alkylsulfinyl or Cι-C8alkyl- sulfonyl;
R56 is hydrogen, Cι-C8alkyl, Cι-C4haloalkyl, d-C4alkoxy, C3-C8alkenyl, C3-C8alkynyl or benzyl, it being possible for benzyl in turn to be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by d-C alkyl, C C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, d-C8alkylthio, Cι-C8alkylsulfinyl or d-C8alkylsulfonyl;
R57 is d-C8alkyl, d-C4haloalkyl, phenyl, benzyl or naphthyl, it being possible for the latter three aromatic rings to be mono- to penta-substituted by halogen and/or mono-, di- or tri- substituted by Cι-C4alkyl, Cι-C4haloalkyl, C C alkoxy, d-C4alkylamino, di(d-C alkyl)amino, -NH2, -CN, -NO2, Cι-C4alkylthio, C1-C4alkylsulfinyl or C C4alkylsulfonyl; R58 and R59 are each independently of the other d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl, benzyl or naphthyl, it being possible for the latter three aromatic rings to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, Cι-C4halo- alkyl, C C4alkoxy, Cι-C alkylamino, di(C C4alkyl)amino, -NH2, -CN, -NO2, Cι-C4alkylthio, d-C4alkylsulfinyl or Cι-C4alkylsulfonyl;
R60 and R6ι are each independently of the other hydrogen or d-C6alkyl; R62> Re3 and R^ are each independently of the others hydrogen or Cι-C8alkyl, or R63 and R64 together form a C2-C5alkylene bridge;
Rθ5. Ree. β7. ββ, Rβ9 and R70 are each independently of the others hydrogen or d-C8alkyl, or
R65 and R66 together or R67 and R68 together or R69 and R70 together form a C2-C5alkylene bridge; and/or each R2 independently is d-C8alkyl, or d-C8alkyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -N3, -SCN, -NO2, -NR7ιR72, -CO2R73, -CONR74R75, -COR76( -C(R77)=NOR78, -C(S)NR79R8o, -C(C C4alkylthio)=NR81, -OH, -OR82, -SR83) -SOR^,
-SO2R85, -O(SO2)R86, -N(R87)CO2R88, -N(R89)COR90, -S+(R9ι)2, -N+(R92)3, -Si(R93)3 or C -C6cycloalkyl; and/or each R2 independently is d-C8alkyl substituted by a 5- to 7-membered heterocyclic ring system which can be aromatic or partially or fully saturated and which can contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for such a heterocyclic ring system in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C4alkyl, Cι-C4haloalkyl, hydroxy-C C4alkyl, C C4alkoxy, Cι-C4haloalkoxy, Cι-C4alkoxy-CrC4alkyl, -CN, -NO2, d-C6alkylthio, d-C6alkylsulfinyl or Cι-C6alkylsulfonyl; and/or each R2 independently is C2-C8alkenyl, or C2-C8alkenyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -NO2, -CO2R94, -CONR95R96, -COR97, -C(R98)=NOR99, -C(S)NR100Rιoι, -C(d-C4alkylthio)=NRι02, -ORι03) -Si(Rι04)3 or C3-C6cyclo- alkyl; and/or each R2 independently is C2-C8alkynyl, or C2-C8alkynyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -CO2R105, -CONRι06Rιo7, -COR108, -C(Ri09)=NOR110, -C(S)NRιι1R1i2, -C(d-C4alkylthio)=NR113, -OR114) -Si(Rn5)3 or C3-C6cyclo- alkyl; and/or each R2 independently is C3-C6cycloalkyl, or C3-C6cycloalkyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -CO2Rn6, -CONRT RH S, -CORn9, -C(Ri2o)=NOR12ι, -C(S)NRι22Ri23 or -C(Cι-C4alkylthio)=NRι24; and/or two adjacent R2 together form a Cι-C7alkylene bridge, which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta- substituted by halogen and/or mono-, di- or tri-substituted by d-C6alkyl or d-C6alkoxy, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent R2 together form a C2-C7alkenylene bridge, which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C6alkyl or d-C6- alkoxy, the total number of ring atoms being at least 5 and at most 9; R7ι is hydrogen or Cι-C8alkyl;
R72 is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C4alkyl, d-C4haloalkyl, C C4alkoxy, -CN, -NO2) C C4alkylthio, Cι-C4alkylsulfinyl or Cι-C4alkylsulfonyl; or
R71 and R72 together are a C2-C5alkylene chain, which can be interrupted by an oxygen or a sulfur atom;
R73 is hydrogen, C C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by Cι-C4alkoxy or phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, C C haloalkyl, d-C4alkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or d-C4alkylsulfonyl; R74 is hydrogen or d-C8alkyl;
R75 is hydrogen, d-C8alkyl or C3-C7cycloalkyl, or d-C8alkyl mono-, di- or tri-substituted by -COOH, d-C8alkoxycarbonyl, d-C6alkoxy or -CN; or
R75 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, d-C4haloalkyl, CrC4alkoxy, -CN, -NO2, d-C4alkylthio, C1-C4alkylsulfinyl or d-C4alkylsulfonyl; or
R74 and R75 together form a C2-C5alkylene chain, which can be interrupted by an oxygen or sulfur atom;
R76 is hydrogen, d-C4alkyl, d-C4haloalkyl or C3-C6cycloalkyl; R-π is hydrogen, Cι-C4alkyl, CrC4haloalkyl or C3-C6cycloalkyl;
R78 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl; and
R79 is hydrogen or d-C8alkyl;
R80 is hydrogen or Cι-C8alkyl, or d-C8alkyl mono-, di- or tri-substituted by -COOH, Cι-C8alkoxycarbonyl or -CN; or
Rβo is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, d-C4haloalkyl, C C4alkoxy, -CN, -NO2, CrC4alkylthio, C1-C4alkylsulfinyl or d-C alkylsulfonyl; or R79 and Rβo together are C2-C5alkylene; R81 is hydrogen or Cι-C8alkyl;
R82 is -Si(Cι-C6alkyl)3, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, or d-C8alkyl which is mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NH2, d- C6alkylamino, di(d-C6alkyl)amino or Cι-C4alkoxy;
R83 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, or Cι-C8alkyl which is mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NH2> d-Cβalkylamino, di(Cι-C6alkyl)amino or Cι-C alkoxy;
RfM, Res and Rβe are each independently of the others Cι-C8alkyl, C3-C8alkenyl or C3-C8- alkynyl, or C C8alkyl which is mono- to penta-substituted by halogen or mono-, di- or tri- substituted by -CN or Cι-C alkoxy;
R87 and R89 are each independently of the other hydrogen, d-C8alkyl or Cι-C8alkoxy;
R88 is C C8alkyl;
R90 is hydrogen or d-C8alkyl;
R91 is d-C4alkyl;
R92 and R93 are each independently of the other d-C6alkyl;
R94 is hydrogen, or C C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by Cι-C4alkoxy or phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C C alkyl, d-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, C C4alkylthio,
Cι-C4alkylsulfinyl or d-C4alkylsulfonyl;
R95 is hydrogen or C C8alkyl;
R96 is hydrogen or C C8alkyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -COOH, d-C8alkoxycarbonyl or -CN; or
R96 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by
Cι-C4alkyl, Cι-C4haloalkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, C C4alkylsulfinyl or
Cι-C4alkylsulfonyl; or
R95 and R96 together are C2-C5alkylene;
R97 and R98are each independently of the other hydrogen, Cι-C4alkyl, d-C4haloalkyl or
C3-C6cycloalkyl;
R99 is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or C3-C6haloalkenyl;
R100 is hydrogen or Cι-C8alkyl;
R101 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl mono-, di- or tri-substituted by -COOH,
Cι-C8alkoxycarbonyl or -CN; or
R101 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-dalkyl, d-C4haloalkyl, d-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, C C4alkylsulfinyl or d-C4alkylsulfonyl; or
R100 and R101 together are C2-C5alkylene;
R102 is hydrogen or Cι-C8alkyl;
R103 is hydrogen, C C8alkyl, -Si(Cι-C6alkyl)3, C3-C8alkenyl or C3-C8alkynyl;
Rιo4 is d-C6alkyl;
R105 is hydrogen, or C C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by Cι-C alkoxy or phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen and/or mono-,
di- or tri-substituted by C C4alkyl, C C4haloalkyl, d-C4alkoxy, -CN, -NO2, d-C4alkylthio,
C C alkylsulfinyl or Cι-C alkylsulfonyl;
R106 is hydrogen or Cι-C8alkyl;
Rι07 is hydrogen or d-C8alkyl, or Cι-C8alkyl mono-, di- or tri-substituted by -COOH,
C C8alkoxycarbonyl or -CN, or
R107 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, C C4haloalkyl, C C4alkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or
C C alkylsulfonyl; or
R106 and R107 together are C2-C5alkylene;
Rιos is hydrogen, d-C4alkyl, d-C4haloalkyl or C3-C6cycloalkyl;
Rι09 is hydrogen, d-C4alkyl, d-C4haloalkyl or C3-C6cycloalkyl;
R110 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl;
R,n is hydrogen or Cι-C8alkyl; $■
Rii2 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl mono-, di- or tri-substituted by -COOH, d-C8alkoxycarbonyl or -CN; or
R112 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, C C4haloalkyl, C C4alkoxy, -CN, -NO2, C C4alkylthio, Cι-C4alkylsulfinyl or
Cι-C4alkylsulfonyl; or
RJJ, and Rn2 together are C -C5alkylene;
R113 is hydrogen or Cι-C8alkyl;
R114 is hydrogen, d-C8alkyl, -Si(C1-C6alkyl)3, C3-C8alkenyl or C3-C8alkynyl;
R115 is d-C6alkyl;
Rue is hydrogen, or Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by Cι-C4alkoxy or phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C C4alkyl, d-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, C C4alkylthio, d-C alkylsulfinyl or Cι-C4alkylsulfonyl;
R117 is hydrogen or Cι-C8alkyl;
R118 is hydrogen or d-C8alkyl, or C C8alkyl mono-, di- or tri-substituted by -COOH,
C C8alkoxycarbonyl or -CN; or
R1 8 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, Cι-C4haloalkyl, d-C4alkoxy, -CN, -NO2, CrC4alkylthio, Cι-C4alkylsulfinyl or d-C4alkylsulfonyl; or
R117 and Rn8 together are C2-C5alkylene; R119 is hydrogen, Cι-C4alkyl, C C haloalkyl or C3-C6cycloalkyl; R120 is hydrogen, C C4alkyl, d-C haloalkyl or C3-C6cycloalkyl;
R121 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl; R122 is hydrogen or C C8alkyl;
R123 is hydrogen or C C8alkyl, or Cι-C8alkyl mono-, di- or tri-substituted by -COOH, Cι-C8alkoxycarbonyl or -CN; or
R123 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, Cι-C4haloalkyl, C C4alkoxy, -CN, -NO2, d-C4alkylthio, C1-C4alkylsulfinyl or Cι-C alkylsulfonyl; or
R122 and Rι23 together are C2-C5alkylene; and Rι24 is hydrogen or d-C8alkyl;
X1 and X2 are each independently of the other hydrogen, or d-C8alkyl, C2-C8alkenyl or C2-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, d-C4alkoxy, -OH, -OC(O)CH3, -OC(O)C6H5, -OCH2C6H5 or -OCH2CH--CH2; or
X1 and X2 are each independently of the other halogen, -CN, -NO2, -COOR125, -CHO, -COR126, -CH(OH)R127, -CH(ORi28)Ri29, acetoxy, Cι-C8alkoxy, C C8haloalkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, Cι-C8alkylthio, d-C8haloalkylthio, C3-C8alkenylthio, C3-C8alkynylthio, d-C8alkylsulfinyl, d-C8haloalkylsulfinyl, C3-C8alkenylsulfinyl, C3- C8alkynylsulfinyl, d-C8alkylsulfonyl, d-C8haloalkylsulfonyl, C3-C8alkenylsulfonyl, C3- C8alkynylsulfonyl, benzoyloxy, benzyloxy, benzylthio, phenoxy, phenylthio, phenylsulfinyl, benzylsulfinyl, phenylsulfonyl, benzylsulfonyl or phenyl, it being possible for the last- mentioned 10 aromatic rings in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, d-C alkoxy, d-C4alkyl or d-C4haloalkyl, or Xi and X2 are each independently of the other -C(O)N(Rι30)Rι3ι;
R125 is hydrogen, or Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or Cι-C4alkoxy, or is benzyl, which in turn can be mono- to penta-substituted by halogen and/or mono-, di- or tri- substituted by -CN, d-C4alkyl, C C haloalkyl or Cι-C4alkoxy; R126. R127 and Rι2g are each independently of the others Cι-C8alkyl, C2-C8alkenyl or C2-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or C C4alkoxy;
R128 is C C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which can be mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN or Cι-C4alkoxy, or is benzyl,
which in turn can be mono- to penta-substituted by halogen and/or mono-, di- or tri- substituted by -CN, d-C4alkyl, Cι-C4haloalkyl or d-C4alkoxy;
Rι30 and Rι31 are each independently of the other hydrogen, or C C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or Cι-C4alkoxy, or is phenyl, which in turn can be mono- to penta- substituted by halogen and/or mono-, di- or tri-substituted by -CN, Cι-C4alkyl, C -C4haloalkyl or d-C alkoxy; or
R130 and Rι31 together with the nitrogen atom to which they are bonded form a three- to eight-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring, and to the agrochemically acceptable salts, N-oxides and all stereoisomers and tautomers of the compounds of formula I.
In the nomenclature used for the present herbidically active phenoxy-(E)-propenylphenyl derivatives, the "-(E)-" is intended to refer explicitly to the trans double-bond isomers in accordance with the geometry of the propenyloxy bridging members shown below:
(X1 = H)
(X2 = H)
The trans-geometry shown above is intended to apply irrespective of the choice of double- bond substituents Xi and X2 within the scope of the given definition. For example, there are also included those isomeric compounds of formula I wherein the substituents Xi and X are different from one another and X, and/or X2 are other than hydrogen, and are termed cis double-bond isomers in accordance with the Cahn-lngold-Prelog system. The Cahn-lngold-
Prelog system weights two groups of different substituents at sp2-hybridised carbon atoms, e.g. X, and -O-C(R3)R4- , and X2 and phenyl in accordance with a defined, predetermined set of sequence rules (cf. Angew. Chem. Int. Ed. Engl. 5, 385-415 (1966)).
Thus in certain cases wherein X, is, for example, -NO2 and X2 is hydrogen, or X, is hydrogen and X2 is, for example, -COOR125, cis double-bond isomers can also be included within the scope of the present compounds of formula I designated "-(E)-".
In brief, those cis double-bond isomers which, by virtue of the choice of X, and/or X2 within the scope of the given definition and in accordance with the Cahn-lngold-Prelog system, have the two highest weighted substituents arranged on the same side of the double bond are likewise be included herein.
Two examples illustrate this sitt jation:
(see also Jerry March in "Advanced Organic Chemistry, Reactions, Mechanisms, and Structure", second edition, 1977, Mc Graw-Hill Book Company, pages 113-117).
When n is 0, all the free valencies on the phenoxy ring of the compounds of formula I are occupied by hydrogen. When m is 1 , 2, 3, 4 or 5, the 5 potential valencies on the phenylalkene ring of the compounds of formula I are occupied independently of one another once, twice, three times, four times or five times by the substituents indicated under R2. Accordingly in the phenylalkene ring at least one valency is occupied by a substituent defined under R2.
Examples of substituents that are formed when R5 and R6 together or R18 and R19 together or R36 and R37 together or R74 and R75 together are a C2-C5alkylene chain which can be interrupted by an oxygen or a sulfur atom are piperidine, morpholine, thiomorpholine and pyrrolidine.
Examples of heterocyclic ring systems which can be aromatic or partially or fully saturated in the definition of R2 are:
The alkyl groups appearing in the definitions of substituents can be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, and also the isomers of pentyl, hexyl, heptyl and octyl.
Alkenyl and alkynyl groups can likewise be straight-chain or branched, this applying also to the alkyl, alkenyl and alkynyl moiety of hydroxyalkyl, cyanoalkyl, alkylcarbonyl, alkyl- carbonylalkyl, alkoxycarbonyl, alkenyloxyalkyl, alkynyloxyalkyl, alkylthioalkyl, alkoxyalkyl, alkylamino, dialkylamino, phenylalkyl and e.g. the groups -C(R10)=NOR11 and -CR62(OR63)OR64.
Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine.
Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, penta- fluoroethyl, 1 ,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl;
preferably trichloromethyl, difluorochloromethyl, difluoromethyl, t fluoromethyl and dichloro- fluoromethyl.
As haloalkenyl there come into consideration, for example, alkenyl groups mono- or poly- substituted by halogen, halogen being in particular bromine, iodine and especially fluorine and chlorine, for example 2- and 3-fluoropropenyl, 2- and 3-chloropropenyl, 2- and 3-bromo- propenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluoro-but-2-en-1-yl and 4,4,4-trichloro-but-2-en-1-yl. Of the alkenyl radicals mono- to penta-substituted by halogen special preference is given to those having a chain length of 3 or 4 carbon atoms. The alkenyl groups can be substituted by halogen at saturated or unsaturated carbon atoms.
As haloalkynyl there come into consideration, for example, alkynyl groups mono- to penta- substituted by halogen, halogen being bromine, iodine and especially fluorine and chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn-1-yl. Of the alkynyl radicals mono- to penta-substituted by halogen special preference is given to those having a chain length of from 3 to 5 carbon atoms.
Alkylcarbonyl is especially acetyl and propionyl.
Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1 -yl and cyanopropyl.
Hydroxyalkyl is, for example, 2-hydroxyethyl, 3-hydroxypropyl and 2,3-dihydroxypropyl.
Alkoxy groups have preferably a chain length of from 1 to 6, especially from 1 to 4, carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy, and also the pentyloxy and hexyloxy isomers; preferably methoxy and ethoxy.
Alkoxy, alkenyl, alkynyl, alkoxyalkyl, alkylthio, alkylthioalkyl, alkylsulfonyl, alkylsulfonylalkyl, alkylsulfinyl, alkylsulfinylalkyl, alkoxycarbonyl, alkenylthio, alkenylsulfonyl, alkenylsulfinyl, alkynylsulfonyl, alkynylthio and alkynylsulfinyl groups are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups can be mono- or poly-unsaturated. Alkenyl is to be understood as being, for example, vinyl, allyl, methallyl, 1-methylvinyl or but-2-en-1-yl. Alkynyl is, for example, ethynyl, propargyl, but-2-yn-1-yl, 2-methylbutyn-2-yl or but-3-yn-2-yl.
Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy or 2,2,2- trichloroethoxy.
Alkylthio groups have preferably a chain length of from 1 to 4 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butyl- thio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methyl- sulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec- butylsulfinyl or tert-butylsulfinyl; preferably methylsulfinyl or ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
Haloalkylsulfonyl is, for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoro- methylsulfonyl, chloromethylsulfonyl, trichloromethylsulfonyl, 2-fluoroethylsulfonyl, 2,2,2- trifluoroethylsulfonyl or 2,2,2-trichloroethylsulfonyl.
Alkoxyalkyl groups have preferably from 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
Alkylamino is, for example, methylamino, ethylamino and the propyl- and butyl-amino isomers.
Dialkylamino is, for example, dimethylamino, diethylamino and the dipropyl- and dibutyl- amino isomers.
Cycloalkyl radicals that come into consideration as substituents are, for example, cyclo- propyl, cyclobutyl, cyclopentyl and cyclohexyl.
Corresponding meanings can also be assigned to the substituents in combined definitions, for example alkoxyalkoxycarbonyl, alkoxycarbonylalkyl, alkenyloxycarbonyl, R13O-, alkyl- sulfinylalkyl, -C(R24)=NOR25, -C(CrC4alkylthio)=NR28, -N=C(OR60)R61, -CR^ORe-JOR^ and -N([CO]pR46)COR47.
Substituents wherein two adjacent R, together form a C1-C7alkylene bridge which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which
can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by CrC6alkyl or d-C6alkoxy, the total number of ring atoms being at least 5 and at most 9, and/or two adjacent R, together form a C2-C7alkenylene bridge which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C1-C6alkyl or C C6- alkoxy, the total number of ring atoms being at least 5 and at most 9, have, for example, the following structures:
Substituents wherein two adjacent R2 together form a d-C7alkylene bridge which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C6- alkyl or d-dalkoxy, the total number of ring atoms being at least 5 and at most 9, and/or two adjacent R2 together form a C2-C7alkenylene bridge which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C6alkyl or CrC6- alkoxy, the total number of ring atoms being at least 5 and at most 9, have, for example, the following structures:
The invention relates also to the salts which the compounds of formula I are able to form especially with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Suitable salt-formers are described, for example, in WO 98/41089.
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,-C18alkylamines, C1-C4hydroxyalkylamines 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, octa- decylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyl- octylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propyl- amine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-
diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-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, morph- oline, piperidine, pyrrolidine, indoline, quinuclidine 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.
Preferred quaternary ammonium bases suitable for salt formation correspond e.g. to the formula [N(RaRbRcRd)]OH wherein Ra, Rt>, Rc and Rd are each independently of the others d-C alkyl. Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
Preferred compounds of formula I are those wherein R82 is -Si(Cι-C6alkyl)3, C3-C8alkenyl, C3- C8alkynyl, or C C8alkyl which is mono- to penta-substituted by halogen or mono-, di- or tri- substituted by -CN, -NH2, d-C6alkylamino, di(d-C6alkyl)amino or Cι-C alkoxy;
Also preferred compounds of formula I are those wherein R2 is a 5- to 7-membered heterocyclic ring system which can be aromatic or partially or fully saturated and which can contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for such a heterocyclic ring system in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, C1-C4haloalkyl, hydroxy-d-C4alkyl, Ci- C4alkoxy, Cι-C4alkoxy-C C4alkyl, -CN, -NO2, d-C6alkylthio, C C6alkylsulfinyl or Cι-C6alkylsulfonyl; and/or each R2 independently is d-C8alkyl substituted by a 5- to 7-membered heterocyclic ring system which can be aromatic or partially or fully saturated and which can contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for such a heterocyclic ring system in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C C4alkyl. d-C4haloalkyl, hydroxy-Cι-C alkyl, d-C alkoxy, d-C4alkoxy-d-C4alkyl, -CN, -NO2, d-C6alkylthio, C C6alkylsulfinyl or C C6alkylsulfonyl.
Preference is also given to compounds of formula I wherein n = 0, or each R, independently is halogen, -CN, -NO2, -C(R10)=NORn, -OR13, -SO2R16, -OSO2R17, d-C8alkyl or C≥-Cβ.
alkenyl, and/or Cι-C8alkyl mono-, di- or tri-substituted by halogen or -CN; Rι0 is hydrogen or Cι-C4alkyl; and Rn is Cι-C8alkyl, wherein Ri3, Ri6 and R17 are as defined for formula I.
Preference is likewise given to compounds of formula I wherein R0ι is hydrogen, Cι-C8alkyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN. Of those compounds, special preference is given to those wherein R0ι is Cι-C4alkyl, or d-C4alkyl mono-, di- or tri-substituted by halogen or mono-substituted by -CN.
Preference is also given to those compounds of formula I wherein m = 0, or each R2 independently is halogen, -CN, -SCN, -OCN, -N3, -CONR36R37, -C(R38)=NOR39, -COR^, -OR4i, -OSO2R45, -N([CO]pR46)COR47, -N(R56)SO2R57, -N(SO2R58)SO2R59, -N=C(OR6o)R6ι or Cι-C8alkyl, and/or d-C8alkyl mono-, di- or tri-substituted by halogen, -CN, -N3, -SCN, -CONR74R75, -COR76, -C(R77)=NOR78, -C(S)NR79R80, -OR82, -SOR^, -SO2R85 or -N(R89)COR90, wherein R36 to R4i, R^ to R47, R∞ to R61, R74 to R80) R82, Rs4, R85, eg. R90 and the suffix p are as defined for formula I.
Important compounds of formula I are those wherein n = 0, or each R^ independently is halogen, -CN, -NO2, -C(Rι0)=NOR11, -OR13, -SO2Rι6, -OSO2R,7, Cι-C8alkyl or C2-C8alkenyl, and/or d-C8alkyl mono-, di- or tri-substituted by halogen or -CN; m = 0, or each R2 independently is halogen, -CN, -SCN, -OCN, -N3, -CONR36R37, -C(R3s)=NOR39, -COR-io, -OR41, -OSO2R45, -N([CO]pR46)COR47, -N(R56)SO2R57, -N(SO2R58)SO2R59) -N=C(OR60)R6ι or Cι-C8alkyl, and/or Cι-C8alkyl mono-, di- or tri-substituted by halogen, -CN, -N3, -SCN, -CONR74R75, -COR76) -C(R77)=NOR78l -C(S)NR79R80, -OR82, -SORβ-,, -SO2R85 or -N(R89)COR90; R10 is hydrogen or Cι-C4alkyl; and Rn is d-C8alkyl, wherein Rι3, Rι6, R17, R36 to R4t, R45 to R47, R56 to R6ι, R74 to Rβo, R82, Rw, Res, R89) R9o and the suffix p are as defined for formula I.
Also important are compounds of formula I wherein R0ι is hydrogen, C C8alkyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN; m = 0, or each R2 independently is halogen, -CN, -SCN, -OCN, -N3) -CONR36R37,
-OR41, -OSO2R45, -N([CO]pR46)COR47, -(R56)SO2R57, -N(SO2R58)SO2R59, -N=C(OR6o)R6ι or CrC8alkyl, and/or Cι-C8alkyl mono-, di- or tri-substituted by halogen, -CN, -N3, -SCN, -CONR74R75l -COR76>
-OR82, -SOR84, -SO2R85 or -N(R89)COR90, wherein R36 to R4ι, R^ to R47, Rse to R6i, R74 to R80, R82, Re-,, R85, R89, R∞ and the suffix p are as defined for formula I.
The compounds of formula I can be prepared analogously to known compounds, for example by reacting a compound of formula II
Those processes for the preparation of compounds of formula I are illustrated in Reaction Scheme 1.
Reaction scheme 1
For L = leaving group e.g. halogen, mesylate, tosylate or triflate:
Route A): base e.g. K2CO3,
R, 02 solvent e.g. THF, or
OR 01 phase transfer conditions
(R.)n oH For L = acyloxy: (F ) Route B): transition metal cat. e.g.
R3 R4 X. m Pd(OAc)2/C6H5CN, solvent e.g. THF
For L = OH:
Route C): Mitsunobu reaction
According to Reaction Scheme 1 , Route A), the compounds of formula I can be obtained, for example, by alkylation of the phenol of formula II with a compound of formula III under typical alkylation conditions in the presence of a base in an inert organic solvent either with cooling of the reaction mixture to temperatures < 15°C, at room temperature (15-25°C) or with heating to the reflux temperature of the solvent used.
Suitable bases are, for example, carbonates, e.g. potassium carbonate or sodium hydrogen carbonate, alkali metal or alkaline earth metal hydroxides, for example sodium or potassium hydroxide, alcoholates, for example sodium methanolate or sodium tert-butanolate, amines, for example triethylamine, pyridine or Hϋnig's base.
Solvents that come into consideration include ethers, for example tetrahydrofuran (THF), dioxane or dimethoxyethane, ketones, for example acetone or methyl ethyl ketone, nitriles, for example acetonithle, amides, for example N,N-dimethylformamide (DMF) or dimethyl- acetamide, sulfoxides, for example dimethyl sulfoxide (DMSO), or 1-methyl-2-pyrrolidone, and also aromatic hydrocarbons, for example toluene or xylenes, and halogenated hydrocarbons, for example 1 ,2-dichloroethane. Alcohols, for example ethanol or tert-butanol, are preferably used together with the corresponding alkali metal alcoholates.
Suitable leaving groups for Route A) in Reaction Scheme 1 are, for example, halogen, e.g. chlorine, bromine or iodine, and also -OS(O)2CH3, -OS(O)2C6H5, -OS(O)2-C6H4-4-CH3 or
-OS(O)2CF3.
Such base-catalysed alkylations are described, for example, in Synthesis 2001 , 1959;
Organic Letters 2001(3), 1649; J. Org. Chem. 2000(65), 3085; ibid. 1993(58), 2068;
Anticancer Research 1999(19), 3757; Bioorganic & Medicinal Chemistry Letters 1999(9),
3439; Chem. Communic. 1998, 1639; and Tetrahedron Lett. 1997(38), 7337.
The alkylation under phase transfer catalytic conditions in accordance with Route A) in Reaction Scheme 1 is described, for example, in Tetrahedron Lett. 2000(41), 6893; and EP-A-0 636 367, the base being used in solid form or in aqueous phase together with an inert, lipophilic solvent, e.g. aromatic or halogenated hydrocarbons, for example toluene, benzene or dichloromethane, and a phase transfer catalyst. Examples of phase transfer catalysts are tetrabutylammonium salts, for example tetrabutylammonium chloride, bromide, hydroxide or tetrafluoroborate or tetrabutylammonium hydrogen sulfate.
For L as an acyloxy group in a compound of formula III, for example -OC(O)CH3, -OC(O)C6H5 or -OC(O)OC2H5, the alkylation reaction can be carried out in accordance with Reaction Scheme 1 , Route B), using transition metal catalysts, e.g. palladium(ll) acetate / phenylcyanide (Pd(OAc)2/C6H5CN), 1 ,5-diphenyl-1 ,4-pentadien-3-one palladium / triphenylphosphine (Pd(dba)2/P(C6H5)3) or tetrakis(triphenylphosphine)palladium (Pd[(P(C6H5)3]4), preferably in an ether, for example tetrahydrofuran (THF), as solvent. Such alkylation reactions are described, for example, in Topics in Catalysis 2000(13), 311 ; Synthetic Communic. 2000(30), 3955; J. Am. Chem. Soc. 2000(122), 3534; and Synlett 1998, 741.
A further method by which the compounds of formula I can be prepared is carried out with the aid of the Mitsunobu reaction analogously to that described in J. Chem. Soc, Perkin Trans I 2000, 4265; WO 00/63153; Chem. Communic. 2000, 475; or Chem. Lett. 1986, 2097. That synthesis route is shown in diagrammatic form as Route C) in Reaction Scheme 1.
Accordingly, the mixture consisting of the phenol of formula II, allyl alcohol of formula III wherein L is a OH function, and triphenylphosphine in an inert solvent is reacted with an aza- dicarboxylic acid derivative either with cooling (temperature < 15°C), at room temperature (15-25°C) or with heating up to the reflux temperature of the solvent used. Suitable inert solvents are e.g. aromatic hydrocarbons, for example toluene or the xylene isomers, ethers,
for example THF, dioxane or 1 ,2-dimethoxyethane; suitable azadicarboxylic acid derivatives are e.g. azadicarboxylic acid dimethyl ester, diethyl ester or diisopropyl ester.
The allyl alcohols of formula III wherein L is a OH function or a derivative thereof that are used can be prepared according to standard methods in a manner analogous to that described e.g. in Angew. Chem., Int. Ed. 2001(40), 1439; Tetrahedron Lett. 2000(41), 6893; ibid. 1996(37), 2507; J. Org. Chem. 1996(61), 7139; or J. Org. Chem. 1994(59), 4143. Such coupling reactions have become known e.g. as Stille, Suzuki or Hiyama coupling. Reaction Scheme 2 shows such a coupling reaction in diagrammatic form.
IV: M= e.g. -Sn(CH3)3, -B(OH)2, V: Y= Br, I, -OS(O)2CF3
-B(OCH3)2 or -Si(C6H5)3
III: L= -O-Z, wherein Z= C6H5C(O)-, CH3OCH2- -Si(CH3)2tert-butyl or is
-o
In the above Reaction Scheme, R2, R3, R4, m, X, and X2 in the compounds of formulae IV and V are as defined for formula I and Z in the compound of formula IV is an oxygen- protecting group, e.g. benzoyl, methoxymethyl (MOM), tetrahydropyranyl or tert-butyl- dimethylsilyl (TBDMS, -Si(CH3)2-tert-butyl), which can readily be introduced and removed again by customary standard methods.
M in the compound of formula IV is a trivalent Sn or Si radical or a divalent B radical, for example -Sn(CH3)3, -Sn(n-butyl)3, -Sn(C6H5)3, -Si(CH2CH3)3, -Si(C6H5)3, -Si(CH3)CI2,
-Si(CH3)2(tert-C4H9), -SiH2(C6H5), -Si(C6H5)2(CH3), -Si(C6H5)(CH3)2, -B(OH)2, -BCI2, -B(OCH3)2,
BBN (9-borabicyclo[3.3.1]nonane), -B(C6H11)2 or -B[CH(CH3)CH(CH3)2]2 Y in the compound of formula V is, for example, bromine, iodine or -OS(O)2CF3. The coupling reaction according to Reaction Scheme 2 is preferably effected in an inert organic solvent, for example an ether, e.g. THF or dioxane, an amide, for example N,N-dimethyl- formamide (DMF), N,N-dimethylacetamide or N-methylpyrrolidone (NMP), or an aromatic hydrocarbon, for example toluene or benzene, at room temperature or with heating. Suitable catalysts are, for example, palladium/C charged with As(C6H5)3, palladium(ll) chloride diacetonitrile complex (PdCI2(CH3CN)2), tetrakis(triphenylphosphine)palladium (Pd[P(C6H5)3]4), palladium bis(triphenylphosphine) dichloride (PdCI2[P(C6H5)3]2), 1 ,5- diphenyl-1 ,4-pentadien-3-one palladium complex/P(C6H5)3, [Pd2(dba)3]»CHCI3»P(2- furyiyCul, it generally being possible to use copper iodide as co-catalyst. In certain cases it is also possible to use lithium salts, for example lithium chloride (LiCI). Suitable bases for such a coupling reaction are, for example, tripotassium phosphate (K3PO4) or alcoholates, for example sodium ethanolate or potassium tert-butanolate.
The compounds of formula IV
Reaction Scheme 3 shows by way of illustration three synthesis routes for the preparation of compounds of formula IV
Reaction Scheme 3
Route D):
X: Z=H or protecting group IV: M= -Si(CH3)CI2; e.g. -Si(CH3)2-tert-C4H9; X,=H X2= e.g. H, alkyl, haloalkyl, cyanoalkyl, alkoxyalkyl
Route E):
X2=H xι_H
Route F):
X: Z=H or protecting group IV: M= -B(OCH3)2 or e.g. -Si(CH3)3; -B(OH)2;
X2= e.g. H, alkyl, haloalkyl, X1=H alkoxyalkyl
According to Reaction Scheme 3, Route D), a compound of formula X wherein R3 and R4 are as defined for formula I, X2 is hydrogen, C,-C8alkyl, or CrC8alkyl substituted by halogen, -CN or CrC4alkoxy, and Z is hydrogen or an O-protecting group, e.g. -Si(CH3)2-tert-butyl, -Si(C2H5)3, benzoyl, benzyl, allyl or methoxymethyl (MOM), is reacted e.g. with methyl- dichlorosilane in an inert solvent, for example toluene, xylene, dichloromethane, 1 ,2-dichloroethane, THF, dioxane or acetone either with cooling, at room temperature or with heating in the presence of a catalyst, e.g. Rh(cod)2BF4/2.P(C6H5)3, Pt(CH2=CH2)2(PCy3) or
H2PtCI6»6H2O, to form the desired target compound of formula IV wherein M is -Si(CH3)CI2, and X, is hydrogen.
According to Route E) in Reaction Scheme 3, a compound of formula X wherein R3, R4, X2 and Z are as defined can also be reacted with a trialkyltin hydride (=hydrostannylation), e.g. H-Sn(C4H9)3, in an inert solvent as indicated above under Route D) to form the desired target compound of formula IV wherein M is -Sn(C4H9)3 and X, is hydrogen. Finally, according to Route F) in Reaction Scheme 3, a compound of formula X wherein R3, R4, X2 and Z are as defined can be reacted by means of hydroborination with a borane derivative, e.g. H-B(OCH3)2, 9-BBN-H (9-borabicyclo[3.3.1]nonane), Mes2B-H (dimesityl- borane), Sia2B-H (disiamylborane), Chx2B-H (dicyclohexylborane), pinacolborane or catecholborane, to form the desired alkylene boron compound of formula IV wherein M is e.g. -B(OCH3)2 or -B(OH)2 and X, is hydrogen. That reaction can be carried out without a solvent or in an inert solvent as indicated above, at room temperature or with heating, without or in the presence of a catalyst. A suitable catalyst is, for example, BH3»Et2NC6H5.
The allyl alcohols of formula III wherein R2, m, X, and X2 are as defined for formula I and R3 and R4 are hydrogen can also be readily obtained by means of reduction of the corresponding cinnamic acid derivatives of formula VI wherein R2, m, X, and X2 are as defined and R is hydrogen, d-C4alkyl, allyl, unsubstituted or substituted benzyl, -Si(CH3)3, -Si(iso-C3H7)3 or -Si(CH3)2-tert-butyl, in a manner analogous to that described e.g. in Org. Lett. 2001 (3), 739; ibid. 2000(2), 3521; J. Org. Chem. 2000(65), 7690; Tetr. Asymm. 2000(11), 2801; or Helv. Chim. Acta 2000(83), 972. Reaction Scheme 4 shows such a reductive preparation method in diagrammatic form.
Reaction Scheme 4
VI R3, R4 = hydrogen
halogenation acylation sulfonylation
L= CI, Br, I, tosylate, mesylate III: L= acyloxy e.g. -OC(O)CH3 or -OC(0)OC2H5
Suitable reducing agents are, for example, hydrides, e.g. lithium aluminium hydride or diisobutylaluminium hydride, in inert organic solvents, such as ethers, e.g. diethyl ether, THF or dioxane, aromatic or halogenated hydrocarbons, for example toluene or dichloromethane.
The halogenation of an alcohol of formula III can be carried out analogously to known standard halogenations. For example, bromination can be carried out with carbon tetra- bromide in the presence of triphenylphosphine (Synthesis 1998, 1015-1018) in methylene chloride. Chlo nation is carried out with mineral acids, for example with concentrated hydrochloric acid (J. Org. Chem. 1955(20), 95) or with para-toluenesulfonic acid chloride (tosyl chloride, p-TsCI) in the presence of an amine, for example triethylamine, in a solvent, for example methylene chloride (Tetrahedron Lett. 1984(25), 2295). Sulfonylation of an alcohol of formula III is likewise a standard reaction in organic chemistry and can be carried out, for example, with a sulfonic acid chloride, for example mesyl
chloride, methanesulfonic anhydride or para-toluenesulfonic acid chloride (p-TsCI) in the presence of a tertiary amine, for example triethylamine, or an aromatic amine, for example py dine, in a solvent, for example a chlorinated hydrocarbon, for example carbon tetra- chloride or methylene chloride, or an amine, for example pyridine. Such reactions are generally known and are described, for example, in J. Org. Chem. 1997(62), 8987; J. Het. Chem. 1995(32), 875-882; and Tetrahedron Lett. 1997(38), 8671-8674.
The acylation of an alcohol of formula ill can be carried out analogously to known standard acylations, for example with the corresponding acyl halides or anhydrides.
A large number of customary standard methods are known for the preparation of the substituted cinnamic acid derivatives of formula VI that are used. Some of those methods are shown in diagrammatic form by way of example in Reaction Scheme 5.
Reaction Scheme 5 introduction and conversion of functional groups according to standard processes e.g. electrophilic/nucleophilic aromatic substitution, oxidation, reduction etc.
Via VI
Heck reaction Wittig reaction (C6H5)3P=C-COOR IX
VII V: Y= Br, I, -OS(O)2CF3 VIII
For example, starting from compounds of formulae V and VII wherein R is hydrogen, C1-C4alkyl, allyl; benzyl unsubstituted or substituted on the aromatic ring; -Si(CH3)3, -Si(iso-
C3H7) or -Si(CH3)2-tert-butyl, and Y is bromine, iodine or -OS(O)2CF3, the Heck reaction is suitable as a method of synthesising compounds of formula VI.
Starting from the benzaldehyde of formula VIII, the Wittig reaction with the so-called Wittig reagent of formula IX is a further suitable method for synthesising compounds of formula VI, there generally being obtained (E)/(Z) isomeric mixtures of the cinnamic acid derivatives of formula VI which can be separated into the pure (E) and (Z) isomers by known methods, e.g. by means of silica gel column chromatography, fractional crystallisation or distillation.
In such a method the substituents R2, m, X, and X2 in the starting compounds of formulae V,
VII, VIII and IX are to be so selected within the scope of the meanings given for formula I that the substitution pattern or the reactivity of the starting compounds is compatible with the reaction to be carried out.
Finally, the functionalised cinnamic acid derivatives of formula VI can be obtained from the known cinnamic acid derivatives of formula Via, some of which are commercially available, for example by introduction and conversion of functional groups e.g. by means of electro- philic and/or nucleophilic aromatic substitution, substitution, oxidation and reduction. All those methods of synthesis are standard in organic chemistry and are described, for example, in M.B. Smith, J. March in "March's Advanced Organic Chemistry", John Wiley, New York, 2001; R.C. Larock in "Comprehensive Organic Transformations", VCH, New York, Weinheim 1989; B.M. Trost & I. Fleming, Editors, "Comprehensive Organic Synthesis", Pergamon Press, Oxford 1991 , Volumes 1-9; and B.S. Furniss et al. "Vogel's Textbook of Practical Organic Chemistry", Longman Scientific & Technical, 1989, Harlow.
For all four Reaction Schemes 1, 2, 4 and 5 it is generally the case that the various substituents R, and R2 in compounds of formulae II, III, V, VI and VIII are either already present at the outset or can be introduced in succession only at a later stage of the reaction sequence e.g. by nucleophilic or electrophilic aromatic substitution and by suitable conversion of functional groups.
The following comments apply to the individual reaction steps in Reaction Schemes 1 to 5: The reactions to form compounds of formula I are advantageously performed in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetra- chloromethane and chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane, nitrites, such as aceto- nitrile and propionitrile, and amides, such as N,N-dimethylformamide, diethylformamide and
N-methylpyrrolidinone. The reaction temperatures are preferably from -20°C to +120°C. The reactions generally proceed slightly exothermically and can generally be carried out at room temperature. In order to shorten the reaction time or to initiate the reaction, brief heating, up to the boiling point of the reaction mixture, can be carried out. The reaction times can likewise be shortened by the addition of a few drops of base as reaction catalyst. Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diaza- bicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene and 1,5-diazabicyclo[5.4.0]undec-7- ene, but it is also possible to use inorganic bases, such as hydrides, e.g. sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or hydrogen carbonates, such as potassium or sodium hydrogen carbonate.
The compounds of formula I can be isolated in customary manner by concentration and/or evaporation of the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
Most of the starting compounds of formula II used in Reaction Scheme 1 for the preparation of compounds of formula I are known or they can be prepared analogously to known processes.
The starting compounds of formulae IV, V, VII, VIII, IX and X used in Reaction Schemes 2, 3 and 5 are likewise known, some of them are commercially available or they can be prepared analogously to known processes.
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 also possible to apply a coating (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time.
The compounds of formula I can be used as herbicides in their 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, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions,
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 chosen 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) can 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-Taschen- buch", 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 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 can 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 compounds of formula I are generally applied to plants or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on 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 can vary within wide limits as a function of those parameters.
The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control. The term "crops" is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic techniques. The weeds to be controlled can be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Panicum, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Euphorbia, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The following Examples further illustrate but do not limit the invention.
Preparation Examples
Example P1 : Preparation of 3-ιr2-(cvanomethyl)phenvπ-2-propenoic acid tert-butyl ester
NMR it is a mixture of 4 parts of the desired target compound and 1 part of the bromide used.
Η-NMR (TMS, CDCI3): 1.54 ppm (s, 9H); 3.77 ppm (s, 2H); 6.40 ppm (d, 1H); 7.27-
7.50 ppm (m, 4H); 7.56 ppm (d, 1H).
Example P2: Preparation of 3-r2-(cyanomethyl)phenvn-2-propenoic acid
3.02 g of the crude product described in Example P1 are introduced into 40 ml of a 1/1 mixture of dichloromethane (CH2CI2) and trifluoroacetic acid and stirred at 20°C for
2.5 hours. The mixture is then poured into 300 ml of ice-water, and the organic solvent is removed in vacuo. The aqueous phase is stirred, the precipitate is filtered off, washed with water and dried at 50°C in vacuo. 2.30 g of the desired title compound are obtained in the form of a beige solid.
1H-NMR (TMS, DMSO-D6): 4.60 ppm (s, 2H); 6.53 ppm (d, 1 H); 7.39-7.70 ppm (m, 5H);
12.47 ppm (broad signal, 1H).
Example P3: Preparation of 3-(3-hvdroxy-1-phenyl-1-(E)-propenyl)-benzeneacetonitrile
2.30 g of the acid from Example P2 are suspended in 20 ml of dry tetrahydrofuran (THF). With stirring, 6.50 ml of triethyl borate are added and then, at 20°C, 1.35 ml of borane dimethyl sulfide complex are slowly added dropwise using a syringe. The temperature is maintained at below 22°C by cooling with a water bath. After subsequently stirring for three hours, thin-layer analysis of a sample (silica gel; eluant: hexane/ethyl acetate 1/1) shows that the starting compound is no longer present. With stirring, 6.50 ml of methanol are slowly added dropwise. After subsequently being stirred for 15 minutes, the mixture is poured into ice-water and extracted with ether; the ether phase is dried over sodium sulfate, filtered, and completely concentrated by evaporation in vacuo. The crude product is purified by means of column chromatography over silica gel (eluant: hexane/ethyl acetate 1/1). The desired title compound is obtained in the form of a colourless resin in a yield of 0.63 g.
1H-NMR (TMS, CDCI3): 1.50 ppm (broad signal, 1H); 3.75 ppm (s, 2H); 4.36 ppm (d, 2H); 6.36-6.45 ppm (m, 1 H); 6.60 and 6.65 ppm (m, 1 H); 7.17-7.37 ppm (m, 4 H).
Example P4: Preparation of r3-r(E)-3-(4-fluoro-2-methoxy-phenoxy)-propenvπ-phenyl1- acetonitrile
OCH. CH2-C≡N OCH3 CH2-C≡N
P- -OH + H°\ ,CH- — F- θ ,CH,
^^ CH 2-CH \-^ ^ ^ (Comp. No. 1.072)
0.52 g of 4-fluoro-2-methoxy-phenol is dissolved in 20 ml of dry THF, and then 0.63 g of the alcohol prepared in Example P3 and 1.03 g of triphenylphosphine are added. Then, with stirring, 0.63 ml of azadicarboxylic acid ethyl ester is slowly added dropwise using a syringe and the mixture is then stirred overnight at 20°C. The next day, the mixture is partitioned between 1 M hydrochloric acid and diethyl ether. After extraction by shaking and separation of the phases, the organic phase is dried over sodium sulfate, filtered, and completely concentrated in vacuo. The resulting crude product is purified by means of column chromatography over silica gel (eluant: hexane/ethyl acetate 3/1). 0.67 g of the target compound is obtained in the form of a yellow oil. Rf value 0.27 (silica gel 60F254; eluant: hexane/ethyl acetate 3/1).
Example P5: Preparation of 3-[3-(4-fluoro-2-methoxy-phenoxy)-1-(E)-propenvn-chloro-
2.40 g of 4-fluoro-2-methoxy-phenol are introduced into dry THF and then 3.11 g of 3-(3- hydroxy-1-phenyl-1-(E)-propenyl-chlorobenzene and 4.76 g of triphenylphosphine are added. With stirring, at 20°C, 2.88 ml of azadicarboxylic acid diethyl ester are added dropwise and the mixture is then stirred overnight. The reaction mixture is then partitioned between diethyl ether and 1 M hydrochloric acid solution. After extraction by shaking and separation of the phases, the organic phase is dried over sodium sulfate, filtered, and completely concentrated in vacuo, yielding 1.54 g of a resin which is purified by column chromatography twice over silica gel (eluants: hexane/ethyl acetate 15/1 and toluene/hexane 3/1). 0.59 g of the desired target compound is obtained in a purity of 90%. Rf value 0.55 (silica gel 60F254; eluant: toluene/hexane 3/1).
Example P6: Preparation of r2-r(E)-3-(4-fluoro-2-methoxy-phenoxy)-propenyll-phenyl1- acetonitrile
, N N
/0CH> C _ 0CH3 C (Comp. No. 1.187)
0.23 g of the allyl alcohol described in Example P9, 0.17 g of 4-fluoro-2-methoxy-phenol and 0.33 g of triphenylphosphine are introduced into 5 ml of absolute THF. With stirring, 0.20 ml of azadicarboxylic acid diethyl ester is slowly added and the mixture is stirred overnight at 20°C. The reaction mixture is then partitioned between diethyl ether and 1 M hydrochloric acid. After extraction by shaking and separation of the phases, the organic phase is washed with brine, dried over sodium sulfate, filtered, and completely concentrated by evaporation in vacuo. The crude product is purified by means of column chromatography over silica gel (eluant: at first hexane, then hexane/ethyl acetate 8/1), yielding 0.10 g of the desired title compound in the form of a brown-yellow resin.
1H-NMR (TMS, CDCI3): 3.71 ppm (s, 2 H); 3.88 ppm (s, 3 H); 4.76 ppm (d x d, 2 H); 6.32- 6.37 ppm (m, 1 H); 6.55-6.69 ppm (m, 2 H); 6.81-6.91 ppm (m, 2 H); 7.29-7.50 ppm (m, 4 H).
Example P7: Preparation of r4-r(E)-3-(4-fluoro-2-methoxy-phenoxy)-propenvH-phenvH- acetonitrile
0.23 g of 4-(3-hydroxy-1-phenyl-1-(E)-propenyl)-benzeneacetonitrile, 0.20 g of 4-fluoro-2- methoxy-phenol and 0.39 g of triphenylphosphine are introduced into 5.0 ml of absolute THF. With stirring, at 20°C, 0.24 ml of azadicarboxylic acid diethyl ester is slowly added dropwise and the mixture is stirred overnight at 20°C. The mixture is then partitioned between diethyl ether and 1M hydrochloric acid. After extraction by shaking and separation of the phases, the organic phase is washed with brine, dried over sodium sulfate, filtered, and completely concentrated by evaporation in vacuo. The crude product is purified by means of column chromatography over silica gel (eluant (gradient)): at first hexane, then hexane/ethyl acetate 8/1), yielding 0.22 g of the desired target compound in the form of a pale yellow solid.
1H-NMR (TMS, CDCI3): 3.74 ppm (s, 2 H); 3.87 ppm (s, 3 H); 4.72 ppm (d x d, 2 H); 6.40- 6.72 ppm (m, 4 H); 6.84-6.89 ppm (m, 1 H); 7.26-7.42 ppm (m, 4 H).
Example P8: Preparation of r2-r(E)-3-(tetrahvdro-2H-pyran-2-yloxy)-propenyπ-phenyl]- acetonitrile
5.53 g of tetrahydro-2-(2-propynyloxy)-2H-pyran are introduced into a round-bottomed flask under an argon atmosphere. Then 8.67 ml of 4,4,5,5-tetramethyl-1 ,3,2-dioxaborolane are added and the mixture is stirred at an oil bath temperature of 100°C for 4 hours. The oil bath temperature is then adjusted to 130°C and stirring is continued for 24 hours, followed by cooling to 20°C. The resulting intermediate can be used directly for the next step. 4.0 g of the intermediate obtained above are dissolved in benzene and then, with stirring, 3.62 g of 2-iodo-benzeneacetonitrile are added. With stirring, 13.9 ml of a 21% sodium ethanolate solution in ethanol are added dropwise, vigorous evolution of gas being observed initially. The reaction mixture is degassed with the aid of argon gas passed through the mixture and then 0.26 g of tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) is added. Stirring is then continued for W hours with heating to reflux temperature. After being cooled to 20°C the mixture is partitioned between diethyl ether and cold 2M aqueous sodium hydroxide solution. After extraction by shaking and separation of the phases, the organic phase is washed with brine, dried over sodium sulfate, filtered, and completely concentrated by evaporation in vacuo. The resulting crude product is purified by means of column chromatography over silica gel (eluant: hexane/ethyl acetate 4/1), yielding 0.61 g of the desired title compound in the form of a yellow-brown oil. Rf value 0.31 (silica gel 60F254; eluant: hexane/ethyl acetate 3/1).
Example P9: Preparation of 2-(3-hvdroxy-1-phenyl-1-(E)-propenyl)-benzeneacetonitrile
In a manner analogous to that described in Examples P1 to P9 or in accordance with the methods as described in Reaction Schemes 1 to 5 and in the references indicated, it is also possible to obtain the preferred compounds listed in the following Tables. The temperatures given in the column headed "Phys. data" indicate the melting point (m.p.) of the compounds in question.
Table 1: Compounds of formula la
Example B1 : Herbicidal action prior to emergence of the plants (pre-emerqence action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. Immediately after sowing, 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 emulsiflable 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 in a greenhouse under optimum conditions. After a test duration of 4 weeks, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Test plants: Panicum, Digitaria, Euphorbia, Amaranthus
Table B1 : Concentration 1000 g active ingredient/ha
The same results are obtained when the compounds of formula I are formulated in accordance with the other Examples analogously to WO 97/34485.
Example B2: Post-emergence herbicidal action
Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. When the test plants are at 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 emulsiflable 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 nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Test plants: Panicum (Pani), Scirpus, Euphorbia (Euph), Abutilon (Abut), Amaranthus (Amar), Stellaria, Veronica
The same results are obtained when the compounds of formula I are formulated in accordance with the other Examples analogously to WO 97/34485.
Claims
1. A compound of formula
Roi is hydrogen, CrCsalkyl, C3-C8alkenyl or C3-C8alkynyl; or
Roi is phenyl or phenyl-CrC6alkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C C alkyl, d-C4halo- alkyl, C C4alkoxy, -CN, -NO2, Cι-C8alkylthio, C C8alkylsulfinyl or CrC8alkylsulfonyl; or Roi is Cι-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, CrC6alkylamino, di(Cι-C6alkyl)amino or C C4alkoxy; n is O, 1 , 2, 3 or 4; each Ri independently is halogen, -CN, -SCN, -SF5, -NO2, -NH2, -CO2R7, -CONR8R9, -C(S)NH2, -C(Rιo)=NORn, -COR12, -ORι3, -SRι4, -SOR15, -SO2R16, -OSO2Rι7, Cι-C8alkyl, C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl; or Cι-C8alkyl, C2-C8alkenyl or C2-Cealkynyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -NO2, -NRi8Rig, -CO2R20, -CONR2ιR22, -COR23, -C(R24)=NOR25, -C(S)NR26R27, -C(C C4alkylthio)=NR28, -OR29, -SR30, -SOR3ι, -SO2R32 or C3-C6cycloalkyl; and/or each Ri independently is C3-C6cycloalkyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -NO2, -NR18Rι9, -CO2R20, -CONR21R22, -COR23, - C(R24)=NOR25, -C(S)NR26R27) -C(C C4alkylthio)=NR28, -SR30) -SOR3ι, -SO2R32 or C3- C6cycloalkyl; and/or each Ri independently is phenyl, which in turn can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C alkyl, C C haloalkyl, CrC4alkoxy, -CN, -NO2, Cι-C alkylthio, Cι-C alkylsulfinyl or Cι-C4alkylsulfonyl; and/or two adjacent Rt together form a Cι-C7alkylene bridge, which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta- substituted by halogen and/or mono-, di- or tri-substituted by d-C6alkyl or CrC6alkoxy, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent RT together form a C2-C7alkenylene bridge, which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by CrC6alkyl or d-C6- alkoxy, the total number of ring atoms being at least 5 and at most 9; R3 and R4 are each independently of the other hydrogen, halogen, -CN, d-C alkyl or C C4alkoxy; or
R3 and R4 together are C2-C5alkylene;
R7 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by Cι-C4alkoxy or pherjyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by CrC alkyl, Cι-C haloalkyl, CrC4alkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or d-C4alkylsulfonyl; R8 is hydrogen or C -C8alkyl;
R9 is hydrogen or Cι-C8alkyl, or CrC8alkyl mono-, di- or tri-substituted by -COOH, CrC8alkoxycarbonyl or -CN, or
R9 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C4alkyl, C C4haloalkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, d-C4alkylsulfinyl or Cι-C4alkylsulfonyl; or R8 and R9 together are C2-C5alkylene; R o is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
Rn is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl; Rι2 is hydrogen, Cι-C4alkyl, C C4haloalkyl or C3-C6cycloalkyl; R13 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl; or
R13 is phenyl or phenyl-Cι-C6alkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C alkyl, d-C4halo- alkyl, Cι-C alkoxy, -CN, -NO2, CrC8alkylthio, C C8alkylsulfinyl or Cι-C8alkylsulfonyl, or Rι3 is Cι-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, Cι-C6alkylamino, di(C C6alkyl)amino or Cι-C4alkoxy;
Rι4 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN or Cι-C alkoxy; R15, Ri6 and Ri7 are each independently of the others Cι-C8alkyl, C3-C8alkenyl or C3-C8- alkynyl, or CrC8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or d-C alkoxy; Rι8 is hydrogen or Cι-C8alkyl;
R19 is hydrogen, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C4alkyl, C C4haloalkyl, d-C4alkoxy, -CN, -NO2, Cι-C alkylthio, C C4- alkylsulfinyl or Cι-C alkylsulfonyl; or
Rι8 and R19 together are a C2-C5alkylene chain, which can be interrupted by an oxygen or a sulfur atom;
R20 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C4alkyl, C C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, CrC4- alkylsulfinyl or Cι-C4alkylsulfonyl; R2ι is hydrogen or Cι-C8alkyl;
R22 is hydrogen or Cι-C8alkyl, or C C8alkyl mono-, di- or tri-substituted by -COOH, C C8- alkoxycarbonyl or -CN, or
R22 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, Cι-C4haloalkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, C C4alkylsulfinyl or Cι-C4alkylsulfonyl; or R2ι and R22 together are C2-C5alkylene; R23 is hydrogen, d-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; R24 is hydrogen, Cι-C alkyl, C C4haloalkyl or C3-C6cycloalkyl;
R25 is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or C3-C6haloalkenyl; R26 is hydrogen or Cι-C8alkyl;
R27 is hydrogen or C -C8alkyl, or Cι-C8alkyl mono-, di- or tri-substituted by -COOH, d-C8- alkoxycarbonyl or -CN, or
R27 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or C C4alkylsulfonyl; or R26 and R27 together are C2-C5alkylene; R28 is hydrogen or Cι-C8alkyl;
R29 and R30 are each independently of the other hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri- substituted by -CN or d-C alkoxy;
R3ι and R32 are each independently of the other Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or d-C4alkoxy; m is 1 , 2, 3, 4 or 5; each R2 independently is halogen, -CN, -SCN, -OCN, -N3, -SF5, -NO2, -NR^R^, -CO2R35, -CONR36R37, -C(R38)=NOR39, -COR40, -OR41, -SR42, -SOR43, -SO2R44, -OSO2R45, -N([CO]pR46)COR47, -N(OR54)COR55, -N(R56)SO2R57, -N(SO2R58)SO2R59, -N=C(OR60)R6ι, -CR62(OR63)OR64, -OC(O)NR65R66, -SC(O)NR67R68, -OC(S)NR69R70 or -N-phthalimide; and/or R2 is a 5- to 7-membered heterocyclic ring system which can be aromatic or partially or fully saturated and which can contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for such a heterocyclic ring system in turn to be mono- to penta- substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, Cι-C4haloalkyl, hydroxy-d-C4alkyl, d-C4alkoxy, d-C4haloalkoxy, Cι-C4alkoxy-C C4alkyl, -CN, -NO2, Cι-C6alkylthio, d-C6alkylsulfinyl or Cι-C6alkylsulfonyl; R33 is hydrogen or Cι-C8alkyl; and
R34 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C4alkyl, C C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, C C4alkylthio, C C4- alkylsulfinyl or C C4alkylsulfonyl; or
R33 and R34 together are a C2-C5alkylene chain, which can be interrupted by an oxygen or a sulfur atom;
R35 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or C -C8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by Cι-C4alkoxy or phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C alkyl, C C4haloalkyl, C C alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfinyl or Cι-C4alkylsulfonyl; R36 is hydrogen or C C8alkyl;
R37 is hydrogen or d-C8alkyl, or C -C8alkyl mono-, di- or tri-substituted by -COOH, Cι-C8alkoxycarbonyl or -CN, or
R37 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C4alkyl, C C4haloalkyl, CrC4alkoxy, -CN, -NO2, C C4alkylthio, C1-C4alky!sulfinyl or d-C4alkylsulfonyl; or R36 and R37 together are C3-C5alkylene; R38 is hydrogen, d-C4alkyl, Cι-C haloalkyl or C3-C6cycloalkyl;
R39 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl; R40 is hydrogen, C C4alkyl, Cι-C4haloalkyl, C C8alkylthio, -C(O)-C(O)OCι-C4alkyl or C3-C6cycloalkyl;
R4ι is hydrogen, d-C8alkyl, Cι-C8haloalkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C6alkoxy-Cι-C6- alkyl, Cι-C8alkylcarbonyl, Cι-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, d-C6alkoxy- d-C6alkoxycarbonyl, d-C6alkylthio-Cι-C6alkyl, Cι-C6alkylsulfinyl-Cι-C6alkyl or d-C6alkyl- sulfonyl-C C6alkyl; or
R ι is phenyl or phenyl-d-C6alkyl, it being possible for the phenyl rings in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, C C4halo- alkyl, C C4alkoxy, -CN, -NO2 or -S(O)2C C8alkyl, or
R ι is Cι-C8alkyl mono-, di- or tri-substituted by -COOH, Cι-C8alkoxycarbonyl, C C6alkyl- amino, di(d-C6alkyl)amino or -CN;
R42 is hydrogen, d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN or C C4alkoxy; R^ and R44 are each independently of the other C C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or Cι-C4alkoxy;
R 5 is d-C8alkyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri- substituted by -CN or Cι-C4alkoxy, C3-C8alkenyl or C3-C8alkynyl, or R45 is phenyl, it being possible for the phenyl ring to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by CrC4alkyl, d-C4haloalkyl, d-C4alkoxy, -CN, NO2, Cι-C8alkylthio, Ci -C8alky Isulf inyl or d-C8alkylsulfonyl; R46 is hydrogen, C C8alkyl, C3-C8alkenyl, C3-C8alkynyl or Cι-C4haloalkyl; R47 is hydrogen, d-C8alkyl, CrC alkoxy, C3-C8alkenyl or C3-C8alkynyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, d-C alkoxy, d-C8- alkoxycarbonyl, -NH2, CrC4alkylamino, di(CrC alkyl)amino, -NR48COR49, -NR50SO2R5ι or -NR52CO2R53, or
R47 is phenyl or benzyl, each of which can in turn be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C4alkyl, C C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C alkylsulfinyl or Cι-C alkylsulfonyl; p is O or 1 ;
R 8, R49. Rδo, R51, R52 and R53 are each independently of the others hydrogen, d-C8alkyl, phenyl, benzyl or naphthyl, it being possible for the three last-mentioned aromatic radicals in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C8alkyl, C C4haloalkyl, C C4alkoxy, C C4alkylamino, di(C C4alkyl)amino, -NH2, -CN, -NO2, CrC4alkylthio, Cι-C4alkylsulfinyl or C C4alkylsulfonyl;
Rij-, and R55 are each independently of the other hydrogen, d-C8alkyl, or phenyl which in turn can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by CrC4- alkyl, C C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, d-C8alkylthio, d-C8alkylsulfinyl or Cι-C8alkyl- sulfonyl; R56 is hydrogen, CrC8alkyl, d-C4haloalkyl, d-C4alkoxy, C3-C8alkenyl, C3-C8alkynyl or benzyl, it being possible for benzyl in turn to be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by Cι-C alkyl, Cι-C4haloalkyl, Cι-C alkoxy, -CN, -NO2, d-C8alkylthio, C C8alkylsulfinyl or d-C8alkylsulfonyl;
R57 is Cι-C8alkyl, d-C haloalkyl, phenyl, benzyl or naphthyl, it being possible for the latter three aromatic rings to be mono- to penta-substituted by halogen and/or mono-, di- or tri- substituted by d-C alkyl, C C haloalkyl, d-C4alkoxy, Cι-C4alkylamino, di(Cι-C4alkyl)amino, -NH2, -CN, -NO2, d-C4alkylthio, C C4alkylsulfinyl or C C4alkylsulfonyl; R58 and R59 are each independently of the other Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl, benzyl or naphthyl, it being possible for the latter three aromatic rings to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C4alkyl, C C4halo- alkyl, C C4alkoxy, Cι-C4alkylamino, di(Cι-C4alkyl)amino, -NH2, -CN, -NO2, C,-C4alkylthio, C C4alkylsulfinyl or C C alkylsulfonyl;
R60 and R6ι are each independently of the other hydrogen or d-C6alkyl; R62. Rβ3 and R64 are each independently of the others hydrogen or Cι-C8alkyl, or R63 and RM together form a C2-C5alkylene bridge;
Res. R66. R67. Rββ, Rβ9 and R70 are each independently of the others hydrogen or Cι-C8alkyl, or
R65 and R66 together or R67 and R68 together or R69 and R70 together form a C2-C5alkylene bridge; and/or each R2 independently is Cι-C8alkyl, or Cι-C8alkyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -N3, -SCN, -NO2, -NR7ιR72, -CO2R73, -CONR74R75, -COR76, -C(R77)=NOR78> -C(S)NR79R80, -C(Cι-C4alkylthio)=NR8ι, -OH, -OR82, -SR83, -SOR84, -SO2R85> -O(SO2)R86, -N(R87)CO2R88, -N(R89)COR90, -S+(R9ι)2, -N+(R92)3, -Si(R93)3 or C3-C6cycloalkyl; and/or each R2 independently is d-C8alkyl substituted by a 5- to 7-membered heterocyclic ring system which can be aromatic or partially or fully saturated and which can contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for such a heterocyclic ring system in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C alkyl, d-C haloalkyl, hydroxy-Cι-C alkyl, d-C alkoxy, Cι-C4haloalkoxy, C C4alkoxy-Cι-C4alkyl, -CN, -NO2, d-C6alkylthio, d-C6alkylsulfinyl or Cι-C6alkylsulfonyl; and/or each R2 independently is C2-C8alkenyl, or C2-C8alkenyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -NO2, -CO2R9 , -CONR95Rg6, -COR97, -C(R98)=NOR99, -C(S)NRιooRιoι, -C(d-C4alkylthio)=NRιo2, -ORι03, -Si(Rι0 )3 or C3-C6cyclo- alkyl; and/or each R2 independently is C2-C8alkynyl, or C2-C8alkynyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -CO2Rιo5, -CONRι06Rιo7, -CORι08, 
-ORn4, -Si(Rn5)3 or C3-C6cyclo- alkyl; and/or each R2 independently is C3-C6cycloalkyl, or C3-C6cycloalkyl mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, -CO2Rn6, -CONRnTrRnβ, -CORn9, -C(R120)=NORι2ι, -C(S)NR122Rι23 or -C(C C4alkylthio)=NRι24; and/or two adjacent R2 together form a Cι-C7alkylene bridge, which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta- substituted by halogen and/or mono-, di- or tri-substituted by d-C6alkyl or d-C6alkoxy, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent R2 together form a C2-C7alkenylene bridge, which can be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which can be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C6alkyl or d-C6- alkoxy, the total number of ring atoms being at least 5 and at most 9; R7ι is hydrogen or Cι-C8alkyl;
R72 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C C4alkyl, Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, d-C4alkylsulfinyl or Cι-C4alkylsulfonyl; or
R7ι and R72 together are a C2-C5alkylene chain, which can be interrupted by an oxygen or a sulfur atom;
R73 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or CrC8alkyl, C3-C8alkenyl or C3-C8alkynyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by Cι-C4alkoxy or phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C4alkyl, Cι-C haloalkyl, Cι-C4alkoxy, -CN, -NO2, C C4alkylthio, Cι-C4alkylsulfinyl or C C4alkylsulfonyl; R74 is hydrogen or d-C8alkyl;
R75 is hydrogen, d-C8alkyl or C3-C7cycloalkyl, or d-C8alkyl mono-, di- or tri-substituted by -COOH, Cι-C8alkoxycarbonyl, d-C6alkoxy or -CN; or
R75 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by C,-C4alkyl, C C4haloalkyl, d-C4alkoxy, -CN, -NO2, C C alkylthio, C C4alkylsulfinyl or Cι-C alkylsulfonyl; or
R74 and R75 together form a C2-C5alkylene chain, which can be interrupted by an oxygen or sulfur atom; R76 is hydrogen, d-C4alkyl, C C4haloalkyl or C3-C6cycloalkyl; R77 is hydrogen, C -C4alkyl, C C4haloalkyl or C3-C6cycloalkyl;
R78 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl; and
R79 is hydrogen or C C8alkyl;
Rao is hydrogen or d-C8alkyl, or d-C8alkyl mono-, di- or tri-substituted by -COOH, d-C8alkoxycarbonyl or -CN; or
Rβo is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, C,-C4alkylthio, d-C4alkylsulfinyl or d-C4alkylsulfonyl; or R79 and Rβo together are C2-C5alkylene; R8ι is hydrogen or d-C8alkyl;
R82 is -Si(Cι-C6alkyl)3, CrC8alkyl, C3-C8alkenyl, C3-C8alkynyl, or C C8alkyl which is mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NH2, d-Cealkylamino, di(Cι-C6alkyl)amino or d-C alkoxy;
Rrø is hydrogen, C C8alkyl, C -C8alkenyl, C3-C8alkynyl, or Cι-C8alkyl which is mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, -NH2, Cι-C6alkylamino, di(Cι-C6alkyl)amino or Cι-C4alkoxy;
Rw, Res and R86 are each independently of the others Cι-C8alkyl, C3-C8alkenyl or C3-C8- alkynyl, or d-C8alkyl which is mono- to penta-substituted by halogen or mono-, di- or tri- substituted by -CN or Cι-C alkoxy;
R87 and R89 are each independently of the other hydrogen, d-C8alkyl or CrC8alkoxy; Rββ is Cι-C8alkyl; Rg0 is hydrogen or Cι-C8alkyl; R91 is Cι-C4alkyl;
R92 and R93 are each independently of the other d-C6alkyl;
R94 is hydrogen, or d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by C C4alkoxy or phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, C,-C4alkylthio, CrC alkylsulfinyl or d-C4alkylsulfonyl; R95 is hydrogen or C C8alkyl;
R96 is hydrogen or d-C8alkyl, or Cι-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -COOH, d-C8alkoxycarbonyl or -CN; or R96 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-C4alkyl, Cι-C4haloalkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, C C4alkylsulfinyl or
CrC4alkylsulfonyl; or
R95 and R96 together are C2-C5alkylene;
R97 and R98are each independently of the other hydrogen, Cι-C4alkyl, Cι-C haloalkyl or
C3-C6cycloalkyl;
R99 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl;
R100 is hydrogen or d-C8alkyl;
R101 is hydrogen or d-C8alkyl, or Cι-C8alkyl mono-, di- or tri-substituted by -COOH,
Cι-C8alkoxycarbonyl or -CN; or
R101 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by d-dalkyl, C C4haloalkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, C C4alkylsulfinyl or d-dalkylsulfonyl; or
Ri00 and R101 together are C2-C5alkylene;
Rι02 is hydrogen or Cι-C8alkyl;
R103 is hydrogen, C C8alkyl, -Si(Cι-C6alkyl)3, C3-C8alkenyl or C3-C8alkynyl;
Rιo is Cι-C6alkyl;
R105 is hydrogen, or d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by Cι-C4alkoxy or phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by CrC4alkyl, C C4haloalkyl, C C4alkoxy, -CN, -NO2, CrC4alkylthio,
C C4alkylsulfinyl or Cι-C alkylsulfonyl;
R106 is hydrogen or C C8alkyl;
Rι0 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl mono-, di- or tri-substituted by -COOH,
Cι-C8alkoxycarbonyl or -CN, or
Ri07 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by
C,-C4alkyl, d-C4haloalkyl, d-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, C C4alkylsulfinyl or d-C4alkylsulfonyl; or
R106 and Rι07 together are C2-C5alkylene;
Ri08 is hydrogen, Cι-C4alkyl, d-C haloalkyl or C3-C6cycloalkyl;
R109 is hydrogen, d-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R110 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C haloalkyl or C3-C6haloalkenyl;
R111 is hydrogen or Cι-C8alkyl; Ri12 is hydrogen or d-C8alkyl, or d-C8alkyl mono-, di- or tri-substituted by -COOH,
Cι-C8alkoxycarbonyl or -CN; or
Rιι2 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by
Cι-C alkyl, C C4haloalkyl, C C4alkoxy, -CN, -NO2, C C4alkylthio, C C4alkylsulfinyl or
Cι-C4alkylsulfonyl; or
Rm and R1 2 together are C2-C5alkylene;
R113 is hydrogen or Cι-C8alkyl;
Rn4 is hydrogen, d-C8alkyl, -Si(Cι-C6alkyl)3, C3-C8alkenyl or C3-C8alkynyl;
R115 is Cι-C6alkyl;
Rii6 is hydrogen, or d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by Cι-C4alkoxy or phenyl, it being possible for phenyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C alkyl, Cι-C4haloalkyl, d-C4alkoxy, -CN, -NO2, C C4alkylthio,
Cι-C4alkylsulfinyl or d-C4alkylsulfonyl;
Rι 7 is hydrogen or Cι-C8alkyl;
Rue is hydrogen or CrC8alkyl, or Cι-C8alkyl mono-, di- or tri-substituted by -COOH,
Cι-C8alkoxycarbonyl or -CN; or
Rue is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by
Cι-C alkyl, C C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, C C4alkylthio, d-C4alkylsulfinyl or d-C4alkylsulfonyl; or
Rn7 and Rn8 together are C2-C5alkylene;
Rug is hydrogen, C C4alkyl, d-C4haloalkyl or C3-C6cycloalkyl;
Rι20 is hydrogen, d-C4alkyl, C C4haloalkyl or C3-C6cycloalkyl;
R12ι is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or C3-C6haloalkenyl;
R122 is hydrogen or d-C8alkyl;
Rι23 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl mono-, di- or tri-substituted by -COOH, d-C8alkoxycarbonyl or -CN; or
R123 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, it being possible for phenyl and benzyl in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by
C C4alkyl, Cι-C4haloalkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfinyl or
C C4alkylsulfonyl; or
Rι22 and Rι23 together are C2-C5alkylene; and
Ri2 is hydrogen or Cι-C8alkyl; Xi and X2 are each independently of the other hydrogen, or Cι-C8alkyl, C2-C8alkenyl or C2-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN, C C4alkoxy, -OH, -OC(O)CH3, -OC(O)C6H5, -OCH2C6H5 or -OCH2CH=CH2; or
Xi and X2 are each independently of the other halogen, -CN, -NO2, -COORι25, -CHO, -CORi26, -CH(OH)Rι27, -CH(ORι28)Ri29, acetoxy, CrC8alkoxy, Cι-C8haloalkoxy, C3-C8alkenyloxy, C3-C8alkynyloxy, Cι-C8alkylthio, d-C8haloalkylthio, C3-C8alkenylthio, C3-C8alkynylthio, CrC8alkylsulfinyl, Cι-C8haloalkylsulfinyl, C3-C8alkenylsulfinyl, C3- C8alkynylsulfinyl, Cι-C8alkylsulfonyl, C C8haloalkylsulfonyl, C3-C8alkenylsulfonyl, C3- C8alkynylsulfonyl, benzoyloxy, benzyloxy, benzylthio, phenoxy, phenylthio, phenylsulfinyl, benzylsulfinyl, phenylsulfonyl, benzylsulfonyl or phenyl, it being possible for the last- mentioned 10 aromatic rings in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by -CN, CrC alkoxy, Cι-C4alkyl or Cι-C4haloalkyl, or X and X2 are each independently of the other -C(O)N(Rι30)Rι3ι;
R125 is hydrogen, or d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or Cι-C4alkoxy, or is benzyl, which in turn can be mono- to penta-substituted by halogen and/or mono-, di- or tri- substituted by -CN, Cι-C4alkyl, C C4haloalkyl or C C4alkoxy;
Ri26. R127 and Rι29 are each independently of the others Cι-C8alkyl, C2-C8alkenyl or C2-C8- alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri- substituted by -CN or Cι-C alkoxy;
Rι28 is d-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which can be mono- to penta- substituted by halogen or mono-, di- or tri-substituted by -CN or Cι-C4alkoxy, or is benzyl, which in turn can be mono- to penta-substituted by halogen and/or mono-, di- or tri- substituted by -CN, Cι-C4alkyl, d-C4haloalkyl or Cι-C4alkoxy;
R130 and R13ι are each independently of the other hydrogen, or Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, each of which can be mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN or d-C4alkoxy, or is phenyl, which in turn can be mono- to penta- substituted by halogen and/or mono-, di- or tri-substituted by -CN, C C4alkyl, Cι-C4haloalkyl or Cι-C4alkoxy; or
Rι30 and Ri3ι together with the nitrogen atom to which they are bonded form a three- to eight-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring, or an agrochemically acceptable salt, N-oxide or any stereoisomer or tautomer of such a compound of formula I.
2. A compound according to claim 1 , wherein R82 is -Si(d-C6alkyl)3, C3-C8alkenyl, C3- C8alkynyl, or d-C8alkyl which is mono- to penta-substituted by halogen or mono-, di- or tri- substituted by -CN, -NH2, d-C6alkylamino, di(d-C6alkyl)amino or C C4alkoxy.
3. A compound according to claim 1 , wherein R2 is a 5- to 7-membered heterocyclic ring system which can be aromatic or partially or fully saturated and which can contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for such a heterocyclic ring system in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C4alkyl, d-C haloalkyl, hydroxy-d-C alkyl, Cι-C4alkoxy, Cι-C4- alkoxy-d-dalkyl, -CN, -NO2, C C6alkylthio, Cι-C6alkylsulfinyl or d-C6alkylsulfonyl; and/or each R2 independently is C C8alkyl substituted by a 5- to 7-membered heterocyclic ring system which can be aromatic or partially or fully saturated and which can contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, it being possible for such a heterocyclic ring system in turn to be mono- to penta-substituted by halogen and/or mono-, di- or tri-substituted by Cι-C4alkyl, Cι-C4haloalkyl, hydroxy-Cι-C4alkyl, d-C4alkoxy, Cι-C4- alkoxy-Cι-C4alkyl, -CN, -NO2, C,-C6alkylthio, Cι-C6alkylsulfinyl or d-C6alkylsulfonyl.
4. A compound according to claim 3, wherein n = 0, or each R independently is halogen, -CN, -NO2, -C(Rιo)=NORn, -OR13, -SO2R16> -OSO2Rι7, d-C8alkyl or C2-C8alkenyl, and/or Cι-C8alkyl mono-, di- or tri-substituted by halogen or -CN; Rι0 is hydrogen or Cι-C4alkyl; and Rn is d-C8alkyl, wherein Rι3, Rι6 and Rι7 are as defined in claim 1.
5. A compound according to claim 3, wherein R0ι is hydrogen, Cι-C8alkyl, or C -C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN.
6. A compound according to claim 5, worin R0ι is Cι-C4alkyl, or Cι-C alkyl mono-, di- or tri- substituted by halogen or mono-substituted by -CN.
7. A compound according to claim 1 , wherein m = 0, or each R2 independently is halogen, -CN, -SCN, -OCN, -N3> -CONRasR^, -C(R38)--NOR39, -COR40> -OR41 l -OSO^, -N([CO]pR 5)COR47, -N(R56)SO2R5 , -N(SO2R58)SO2R59, -N=C(OR6o)R6ι or Cι-C8alkyl, and/or d-C8alkyl mono-, di- or tri-substituted by halogen, -CN, -N3, -SCN, -CONR74R75, -COR76) -C(R77)=NOR78, -C(S)NR79R80, -OR82, -SOR^, -SO2R85 or -N(R8g)COR90, wherein R∞ to R4ι, R^ to R47, Rδe to R6ι, R7 to R80, R82, M, R8S, Reg, R90 and the suffix p are as defined in claim 1.
8. A compound according to claim 1 , wherein n = 0, or each R independently is halogen, -CN, -NO2, -C(Rιo)=NOR,ι, -ORι3, -SO2Rι6, -OSO2Rι7l C C8alkyl or C2-C8alkenyl, and/or Cι-C8alkyl mono-, di- or tri-substituted by halogen or -CN; m = 0, or each R2 independently is halogen, -CN, -SCN, -OCN, -N3, -CONR36R37, -C(R38)=NOR39, -COR^, -OR41, -OSO^, -N([CO]pR46)COR47, -N(R56)SO2R57, -N(SO2R58)SO2R5g, 
or Cι-C8alkyl, and/or C C8alkyl mono-, di- or tri-substituted by halogen, -CN, -N3, -SCN, -CONR74R75, -COR76, -C(R77)=NOR78, -C(S)NR79R80, -OR82, -SOR8 , -SO2R85 or -N(R89)COR9o; Rio is hydrogen or C C4alkyl; and Rn is Cι-C8alkyl, wherein Rι3, Rι6, Rι7, R∞ to R4ι, R45 to R47, R^ to R6ι, R74 to Rβo, R82, Rs-i. Res, Rsg, R90 and the suffix p are as defined in claim 1.
9. A compound according to claim 1 , wherein R01 is hydrogen, d-C8alkyl, or d-C8alkyl mono- to penta-substituted by halogen or mono-, di- or tri-substituted by -CN; m = 0, or each R2 independently is halogen, -CN, -SCN, -OCN, -N3, -CONR36R37> -C(R38)=NOR39, -COR^, -OR41 ) -OSO2R45, -N([CO]pR46)COR47, -(R56)SO2R57> -N(SO2R5β)SO2R59, -N=C(OR6o)R6ι or C -C8alkyl, and/or d-C8alkyl mono-, di- or tri-substituted by halogen, -CN, -N3, -SCN, -CONR74R75, -COR76, -C(R77)=NOR78, -C(S)NR79R8o, -OR82, -SOR84( -SO2Rβ5 or -N(R89)COR90, wherein to R41, R^ to R47) R∞ to R61, R74 to Rso, R82, R^, Rss, R89, R∞ and the suffix p are as defined in claim 1.
10. A process for the preparation of a compound of formula I according to claim 1 , which comprises reacting a compound of formula II
a) with a compound of formula III
c) with a compound of formula III
11. A herbicidal and plant-growth-inhibiting composition which comprises a herbicidally effective amount of a compound of formula I on an inert carrier.
12. A method of controlling undesired plant growth, which comprises applying a herbicidally effective amount of a compound of formula I, or of a composition comprising such a compound, to the plants or to the locus thereof.
13. A method of inhibiting plant growth, which comprises applying a herbicidally effective amount of a compound of formula I, or of a composition comprising such a compound, to the plants or to the locus thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2003249909A AU2003249909A1 (en) | 2002-07-01 | 2003-06-30 | Phenoxypropenylphenyl derivatives and their use as herbicides |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH11592002 | 2002-07-01 | ||
| CH1159/02 | 2002-07-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004002947A1 true WO2004002947A1 (en) | 2004-01-08 |
Family
ID=29783985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP2003/006945 WO2004002947A1 (en) | 2002-07-01 | 2003-06-30 | Phenoxypropenylphenyl derivatives and their use as herbicides |
Country Status (3)
| Country | Link |
|---|---|
| AR (1) | AR041182A1 (en) |
| AU (1) | AU2003249909A1 (en) |
| WO (1) | WO2004002947A1 (en) |
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| Publication number | Publication date |
|---|---|
| AR041182A1 (en) | 2005-05-04 |
| AU2003249909A1 (en) | 2004-01-19 |
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