EP0906287A1 - Substituted pyrazolyl-pyrazole derivatives and their use as herbicides - Google Patents

Substituted pyrazolyl-pyrazole derivatives and their use as herbicides

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Publication number
EP0906287A1
EP0906287A1 EP97924005A EP97924005A EP0906287A1 EP 0906287 A1 EP0906287 A1 EP 0906287A1 EP 97924005 A EP97924005 A EP 97924005A EP 97924005 A EP97924005 A EP 97924005A EP 0906287 A1 EP0906287 A1 EP 0906287A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
hydrogen
halogen
alkenyl
alkynyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97924005A
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German (de)
French (fr)
Inventor
Michael Ganzer
Helga Franke
Uwe Hartfiel
Jürgen Bohner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
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Hoechst Schering Agrevo GmbH
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Publication date
Application filed by Hoechst Schering Agrevo GmbH filed Critical Hoechst Schering Agrevo GmbH
Publication of EP0906287A1 publication Critical patent/EP0906287A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • C07D231/52—Oxygen atom in position 3 and nitrogen atom in position 5, or vice versa
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems

Definitions

  • the invention relates to new substituted pyrazolyl-pyrazoles, processes for their preparation and intermediates for their preparation and their use as agents with herbicidal activity.
  • No. 5,405,829 discloses pyrazolyl-pyrazoles with an unsubstituted amino group as herbicidally active compounds.
  • WO 94/08999 describes herbicidally active pyrazolyl-pyrazoles with, inter alia, a substituted amino group.
  • Substituted pyrazolyl-pyrazoles with herbicidal properties are also known from WO 96/09303.
  • the object of the present invention is to provide new substituted pyrazolyl-pyrazoles which do not have these disadvantages and which are superior in their biological properties to the compounds known hitherto.
  • R 2 C r C 4 alkyl, C r C 4 alkylthio, C r C 4 alkylsulfinyl, C r C 4 alkylsulfonyl, C r C 4 alkoxy, or C 1 -C 4 mono- or polysubstituted by halogen -Alkyl, C r C 4 -alkylthio, C r C 4 -alkylsulfonyl or C r C 4 -alkoxy,
  • R 1 and R 2 together form the group - (CH 2 ) m -,
  • R 3 is hydrogen or halogen
  • R 4 is hydrogen or C r C 4 alkyl
  • R 5 is hydrogen, nitro, cyano, -COOR 7 , the group
  • R 6 one of the groups
  • R 7 , R 8 and R 9 independently of one another are hydrogen or C 1 -C 4 -alkyl
  • R 8 and R 9 together with the adjacent nitrogen atom form a 5- or 6-membered saturated heterocyclic ring
  • R 10 is hydrogen, C r C 4 alkyl, mono- or polysubstituted by halogen, C r C 4 alkyl,
  • R 11 is C 5 -C 8 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, one or more times identically or differently by halogen, cyano, hydroxy or C r C 4 -alkoxy-substituted C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl or C 3 -C 6 -alkynyl, C 2 -C 8 -alkyl interrupted one or more times by oxygen, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C r C 4 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, C 1 -C 4 alkoxycarbonyl-C 1 - C 4 alkyl, which may optionally be substituted by halogen atoms, or
  • R 12 and R 13 independently of one another hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 3 -C 4 alkynyl or C r C 4 alkoxy, one or more times the same or different Halogen, cyano, carboxy, hydroxy, C 1 -C 4 alkoxy or C r C 4 alkoxycarbonyl substituted C r C 4 alkyl, C 2 -C 4 alkenyi or C 3 -C 4 alkynyl, A cyano,
  • R 14 and R 15 independently of one another hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, one or more times the same or different Halogen, cyano, hydroxy or C r C 4 alkoxy substituted C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, one or more times Oxygen interrupted C 2 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl or C 3 -C 8 alkynyl, C r C 4 alkoxycarbonyl- C 1 -C 4 alkyl, which may optionally be substituted by halogen, C 1 -C 4 -alkoxycarbonyl-C 2 -C 4 -alkenyl, which may optionally be substituted by
  • R 14 and R 15 together with the nitrogen atom form a saturated heterocyclic C 3 -C 6 ring which can be interrupted one or more times by oxygen or sulfur,
  • R 16 is hydrogen or C r C 4 alkyl
  • R 17 is hydrogen, C r C 4 alkyl or halogen C r C 4 alkyl
  • R 18 , R 19 , R 20 , R 21 , R 22 and R 24 independently of one another hydrogen, halogen, C r C 4 alkyl, C 2 -C 4 alkenyl or C 3 -C 4 alkynyl, carboxy or C r C 4 - alkoxycarbonyl, one or more identical or different halogen or cyano, nitro, hydroxy or C r C 4 alkoxy substituted C r C 4 alkyl, C 2 -C 4 alkenyl or C 3 -C 4 - Alkynyl,
  • R 23 and R 25 are hydrogen, halogen, C r C 4 alkyl, C 2 -C 4 alkenyl or C 3 -C 4 alkynyl, or
  • R 23 and R 25 together form a saturated or unsaturated three- to eight-membered ring, optionally containing one or more sulfur or oxygen atoms,
  • R 29 is hydrogen or halogen
  • R 31 is hydrogen, C r C 4 alkyl, C 5 -C 8 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 - Cg alkynyl, one or more times the same or different C 1 -C 6 alkyl substituted by halogen, cyano, hydroxy or C 1 -C 4 alkoxy, C 3 -C 6 - Cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, a C 2 -C 8 alkyl interrupted one or more times by oxygen, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloatkyl- C r C 4 alkyl, C 2 -C 8 alkenyl or C 3 -C 8 alkynyl, C r C 4 alkoxycarbonyl-C r C 4 alkyl, which may optionally be substituted by halogen, C 1 -C 4
  • R 32 is hydrogen, C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, one or more times the same or different by halogen, cyano, hydroxy or C r C 4 alkoxy substituted C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, a C 2 -C which is interrupted once or several times by oxygen 8- alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl or C 3 -C 8 alkynyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl, which may optionally be substituted by halogen can, C 1 -C 4 alkoxycarbonyl-C 2 -C 4 alkenyl, which may optionally be substituted by halogen
  • X is oxygen or sulfur and has a herbicidal action which is superior to that of the known compounds.
  • halogen includes fluorine, chlorine, bromine and iodine.
  • alkyl alkenyl and alkynyl
  • hydrocarbon radicals which can be branched or unbranched.
  • R 1 is methyl
  • R 2 difluoromethoxy, R 1 and R 2 together form the group - (CH 2 ) 4 -,
  • R 3 chlorine or bromine
  • R 4 is hydrogen
  • R 11 is C 5 -C 8 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, a C 2 -C 8 alkyl interrupted one or more times by oxygen, C 3 -C 8 cycloalkyl,
  • C 6 alkynyl one or more identical or different by halogen, Cyano, hydroxy or C r C 4 alkoxy substituted C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, with the proviso if R 12 and R 31 is hydrogen or R 12 is hydrogen and R 31 is C r C 4 alkyl, R 13 cannot be hydrogen,
  • X is oxygen and n is O and o is 1 or 2.
  • the compounds of general formula I according to the invention can be prepared by, for example
  • R 7 , R 8 and R 9 have the meaning given in the general formula I and X represents oxygen
  • R 26 , R 27 and R 28 independently of one another denote C r C 4 alkyl, implement or
  • R 6 is the group - (CH 2 ) 0 -A, where A is the cyano group and o is the one mentioned in the general formula I.
  • R 1 , R 2 , R 3 , R 4 and R 5 have the meaning given in the general formula I and B represents a leaving group, such as chlorine, bromine or methylsulfonyl, with an alkali metal salt of hydrocyanic acid, or
  • R 1 , R 2 , R 4 , R 5 and R 6 have the meaning given in the general formula I, with a suitable halogenating agent or
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 16 R 17 , and n have the meaning given in the general formula I and R, 3 J 0 U for C: r1 -CC 44 --alkyl stands with a compound of general formula IV or V
  • R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 and X have the meanings given in the general formula I, or
  • R 6 represents the group in which R 12 , R 13 and
  • R 31 have the meaning given in the general formula I and R 29 represents chlorine or bromine, a compound of the general formula le
  • R 6 represents the group in which R 11 , R 12 and
  • R 13 have the meaning given in the general formula I, a compound of the general formula Ig
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 11 , R 12 and R 13 have the meaning given in general formula I, and R 29 represents chlorine or bromine, reacted with a suitable base, or
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 12 , R 13 and R 29 have the meaning given in the general formula I and R 33 for hydroxy, chlorine, bromine or C r C 4 alkoxy stands with an alcohol of the general formula VII or an amine of the general formula VIII R »1 M 1-OH (VII) R 14 R 15 NH (VIII)
  • Process variant B) is advantageously carried out in such a way that the starting material of the general formula Ia is reacted with a salt of hydrocyanic acid in a suitable solvent at a temperature of 20 to 180 ° C.
  • Suitable solvents are, for example, ethers such as diethyl ether, tetrahydrofuran or 1,4-dioxane, amides such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, aromatic hydrocarbons such as benzene, toluene or xylene, or sulfoxides such as dimethyl sulfoxide. Lithium, sodium and potassium cyanide may be mentioned as suitable cyanides.
  • halogenation according to process variant C) can be carried out according to the known methods of halogenating heterocyclic aromatics, as described, for example, in Houben-Weyl, volume V / 4, page 233 ff (1960) or volume V / 3, page 511 ff (1962 ) with a halogenating agent in a suitable inert solvent.
  • halogenating agents that can be used are sulfuryl chloride, sodium hypochlorite, N-chlorosuccinimide, N-bromosuccinimide, chlorine or bromine.
  • the acetals or ketals can be according to process variant D) according to the in T.W. Greene "Protective Groups in Organic Synthesis", 1980, page 116 ff.
  • the compounds according to process variant E) can be prepared by the process specified in US Pat. No. 5,250,504.
  • the compounds according to process variant F) can be prepared by methods known per se for elimination, as described, for example, in J. March "Advanced Organic Chemistry” 2nd edition 1977, page 895 ff and the literature cited therein.
  • esterifications according to process stage G) are known per se and can be carried out by the customary methods, as described, for example, in Houben-Weyl, volume E5, page 659 ff (1985). The same applies to the amide formations, which are also described, for example, in Houben-Weyl, Volume E5, page 934 ff (1985).
  • solvents or diluents are used which are inert to the respective reactants.
  • solvents or diluents are aliphatic, alicyclic and aromatic hydrocarbons, each of which may optionally be chlorinated, such as, for example, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, Methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichlorethylene and chlorobenzene, ethers such as, for example, diethyl ether, methyl ethyl ether, methyl t-butyl ether, diisopropyl ether, dibutyl ether, dioxane and tetrahydrofuran, ketones such as, for example, acetone, methyl ethyl ketone, methyl iso
  • the compounds according to the invention are worked up in the customary manner. Purification is carried out by crystallization or column chromatography.
  • the compounds according to the invention generally represent colorless or pale yellow colored crystalline or viscous substances, some of which are readily soluble in chlorinated hydrocarbons, such as methylene chloride or chloroform, ethers, such as diethyl ether or tetrahydrofuran, alcohols, such as methanol or Ethanol, ketones such as acetone or butanone, amides such as dimethylformamide or sulfoxides such as dimethyl sulfoxide.
  • chlorinated hydrocarbons such as methylene chloride or chloroform
  • ethers such as diethyl ether or tetrahydrofuran
  • alcohols such as methanol or Ethanol
  • ketones such as acetone or butanone
  • amides such as dimethylformamide or sulfoxides such as dimethyl sulfoxide.
  • the compounds according to the invention have a good herbicidal action on broad-leaved weeds and grasses.
  • a selective use is possible in different crops, for example in rapeseed, beets, soybeans, cotton, rice, corn, barley, wheat and other types of cereals.
  • Individual compounds are also suitable as selective herbicides in beets, cotton, soybeans, corn and cereals.
  • the compounds for weed control in permanent crops such as, for example, in forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and Hop plants are used.
  • the compounds of the invention can be used, for example, in the following
  • Plant genera are used:
  • Dicot weeds of the genera such as Sinapis, Lepidium, Galium, Stellaria,
  • Monocot weeds of the genera such as Avena, Alopecurus, Echinochloa, Setaria,
  • the application rates fluctuate between 0.001 and 5 kg / ha in the pre- and post-emergence.
  • the intensity and speed of action can be promoted, for example, by additives which increase the effectiveness, such as organic solvents, wetting agents and oils. Such additives may therefore allow the active ingredient dosage to be reduced.
  • the active compounds according to the invention or mixtures thereof are expediently in the form of preparations, such as powders, scattering agents, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and, if appropriate, adhesives, wetting agents, emulsifiers and / or dispersing aids applied.
  • Suitable liquid carriers are e.g. aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide, mineral oil fractions and vegetable oils.
  • Minerals such as bentonite, silica gel, talc, kaolin, attapulgite, limestone and vegetable products such as flour are suitable as solid carriers.
  • surface-active substances include calcium ligninsulfonate, polyethylene alkylphenyl ether, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates and substituted benzenesulfonic acids and their salts.
  • the proportion of the active ingredient (s) in the various preparations can vary within wide limits.
  • the agents contain about 10 to 90% by weight of active ingredient, about 90 to 10% by weight of liquid or solid carriers and optionally up to 20% by weight of surface-active substances.
  • the funds can be applied in a conventional manner, e.g. with water as a carrier in spray liquor quantities of about 100 to 1000 liters / ha.
  • Use of the agents in the so-called low-volume and ultra-low-volume process is just as possible as their application in the form of so-called microgranules.
  • preparations of these preparations can be carried out in a manner known per se, e.g. be carried out by grinding or mixing processes. If desired, preparations of the individual components can also be mixed shortly before their use, as is the case, for example, is carried out in practice in the so-called tank mix process.
  • the listed plant species were treated with the listed compounds at a rate of 0.03 kg of active ingredient / ha after emergence.
  • the compounds were sprayed evenly over the plants as an emulsion with 500 liters of water / ha.
  • the compounds according to the invention showed an excellent action against the weeds 2 weeks after the treatment, as can be seen from the table below.

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

Abstract

The invention concerns novel substituted pyrazolyl-pyrazoles of general formula (I) in which R<1>-R<6> have the meanings given in the description. The invention also concerns processes and intermediate products for their preparation and their use as herbicides.

Description

Beschreibung description
SUBSTITUIERTE PYRAZOLYL-PYRAZOLDERIVATE UND IHRE VERWENDUNG ALS HERBIZIDESUBSTITUTED PYRAZOLYL PYRAZOLE DERIVATIVES AND THEIR USE AS HERBICIDES
Die Erfindung betrifft neue substituierte Pyrazolyl-pyrazole, Verfahren zu ihrer Herstellung sowie Zwischenprodukte zu ihrer Herstellung und ihre Verwendung als Mittel mit herbizider Wirkung.The invention relates to new substituted pyrazolyl-pyrazoles, processes for their preparation and intermediates for their preparation and their use as agents with herbicidal activity.
Es ist bereits bekannt, daß Pyrazole herbizide Eigenschaften besitzen (WO 94/08999).It is already known that pyrazoles have herbicidal properties (WO 94/08999).
Aus US 5,405,829 sind Pyrazolyl-pyrazole mit einer unsubstituierten Aminogruppe als herbizid wirksame Verbindungen bekannt.No. 5,405,829 discloses pyrazolyl-pyrazoles with an unsubstituted amino group as herbicidally active compounds.
In WO 94/08999 sind herbizid wirksame Pyrazolyl-pyrazole unter anderem mit einer substituierten Aminogruppe beschrieben.WO 94/08999 describes herbicidally active pyrazolyl-pyrazoles with, inter alia, a substituted amino group.
Aus WO 96/09303 sind ebenfalls substituierte Pyrazolyl-pyrazole mit herbiziden Eigenschaften bekannt.Substituted pyrazolyl-pyrazoles with herbicidal properties are also known from WO 96/09303.
Häufig ist jedoch die Herbizidwirkung der bekannten Verbindungen nicht ausreichend, oder es treten bei entsprechender Herbizidwirkung Selektivitätsprobleme in landwirtschaftlichen Hauptkulturen auf.However, the herbicidal activity of the known compounds is frequently inadequate, or selectivity problems arise in main agricultural crops if the herbicidal activity is appropriate.
Aufgabe der vorliegenden Erfindung ist die Bereitstellung von neuen substituierten Pyrazolyl-pyrazolen, die diese Nachteile nicht aufweisen und die in ihren biologischen Eigenschaften den bisher bekannten Verbindungen überlegen sind.The object of the present invention is to provide new substituted pyrazolyl-pyrazoles which do not have these disadvantages and which are superior in their biological properties to the compounds known hitherto.
Es wurde nun gefunden, daß substituierte Pyrazolyl-pyrazole der allgemeinen Formel I Λ It has now been found that substituted pyrazolyl-pyrazoles of the general formula I Λ
in derin the
R1 CrC4-Alkyl,R 1 C r C 4 alkyl,
R2 CrC4-Alkyl, CrC4-Alkylthio, CrC4-Alkylsulfinyl, CrC4-Alkylsulfonyl, CrC4- Alkoxy, oder ein- oder mehrfach durch Halogen substituiertes C1-C4-Alkyl, CrC4-Alkylthio, CrC4-Alkylsulfonyl oder CrC4-Alkoxy,R 2 C r C 4 alkyl, C r C 4 alkylthio, C r C 4 alkylsulfinyl, C r C 4 alkylsulfonyl, C r C 4 alkoxy, or C 1 -C 4 mono- or polysubstituted by halogen -Alkyl, C r C 4 -alkylthio, C r C 4 -alkylsulfonyl or C r C 4 -alkoxy,
R1 und R2 gemeinsam die Gruppe -(CH2)m- bilden,R 1 and R 2 together form the group - (CH 2 ) m -,
R3 Wasserstoff oder Halogen,R 3 is hydrogen or halogen,
R4 Wasserstoff oder CrC4-Alkyl,R 4 is hydrogen or C r C 4 alkyl,
R5 Wasserstoff, Nitro, Cyano, -COOR7, die GruppeR 5 is hydrogen, nitro, cyano, -COOR 7 , the group
oder or
R6 eine der GruppenR 6 one of the groups
A A AA
R7, R8 und R9 unabhängig voneinander Wasserstoff oder C1-C4-Alkyl,R 7 , R 8 and R 9 independently of one another are hydrogen or C 1 -C 4 -alkyl,
R8 und R9 gemeinsam mit dem benachbarten Stickstoffatom einen 5- oder 6- gliedrigen gesättigten heterocyclischen Ring bilden,R 8 and R 9 together with the adjacent nitrogen atom form a 5- or 6-membered saturated heterocyclic ring,
R10 Wasserstoff, CrC4-Alkyl, ein- oder mehrfach durch Halogen substituiertes CrC4-Alkyl,R 10 is hydrogen, C r C 4 alkyl, mono- or polysubstituted by halogen, C r C 4 alkyl,
R11 C5-C8-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl, C3-C6-Alkinyl, ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Hydroxy oder CrC4-Alkoxy substituiertes C^Cg-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl oder C3-C6-Alkinyl, ein- oder mehrfach durch Sauerstoff unterbrochenes C2-C8-Alkyl, C3-C8-Cycloalkyl, C3-C8-Cycloalkyl-CrC4-alkyl, C3-C8-Alkenyl oder C3-C8-Alkinyl, C1-C4-Alkoxycarbonyl-C1-C4-alkyl, welches gegebenenfalls durch Halogenatome substituiert sein kann, oder C1-C4-Alkoxycarbonyl-C2-C4-alkenyl, welches gegebenenfalls durch Halogen substituiert ist, oder die Gruppe -(CH2)p-NR8R9 sein kann,R 11 is C 5 -C 8 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, one or more times identically or differently by halogen, cyano, hydroxy or C r C 4 -alkoxy-substituted C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl or C 3 -C 6 -alkynyl, C 2 -C 8 -alkyl interrupted one or more times by oxygen, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C r C 4 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, C 1 -C 4 alkoxycarbonyl-C 1 - C 4 alkyl, which may optionally be substituted by halogen atoms, or C 1 -C 4 alkoxycarbonyl-C 2 -C 4 alkenyl, which is optionally substituted by halogen, or the group - (CH 2 ) p -NR 8 R Can be 9
R12 und R13 unabhängig voneinander Wasserstoff, Halogen, C1-C4-Alkyl, C2-C4- Alkenyl, C3-C4-Alkinyl oder CrC4-Alkoxy, ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Carboxy, Hydroxy, C1-C4-Alkoxy oder CrC4-Alkoxycarbonyl substituiertes CrC4-Alkyl, C2-C4-Alkenyi oder C3-C4-Alkinyl, A Cyano, R 12 and R 13 independently of one another hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 3 -C 4 alkynyl or C r C 4 alkoxy, one or more times the same or different Halogen, cyano, carboxy, hydroxy, C 1 -C 4 alkoxy or C r C 4 alkoxycarbonyl substituted C r C 4 alkyl, C 2 -C 4 alkenyi or C 3 -C 4 alkynyl, A cyano,
R14 und R15 unabhängig voneinander Wasserstoff, C1-C6-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl oder C3-C6-Alkinyl, ein ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Hydroxy oder CrC4-Alkoxy substituiertes CrC6-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl oder C3-C6- Alkinyl, ein ein- oder mehrfach durch Sauerstoff unterbrochenes C2-C8-Alkyl, C3-C8-Cycloalkyl, C2-C8-Alkenyl oder C3-C8-Alkinyl, CrC4-Alkoxycarbonyl- C1-C4-alkyl, welches gegebenenfalls durch Halogen substituiert sein kann, C1-C4-Alkoxycarbonyl-C2-C4-alkenyl, welches gegebenenfalls durch Halogen substituiert sein kann, oder C1-C4-Alkoxycarbonyl,R 14 and R 15 independently of one another hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, one or more times the same or different Halogen, cyano, hydroxy or C r C 4 alkoxy substituted C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, one or more times Oxygen interrupted C 2 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl or C 3 -C 8 alkynyl, C r C 4 alkoxycarbonyl- C 1 -C 4 alkyl, which may optionally be substituted by halogen, C 1 -C 4 -alkoxycarbonyl-C 2 -C 4 -alkenyl, which may optionally be substituted by halogen, or C 1 -C 4 -alkoxycarbonyl,
R14 und R15 gemeinsam mit dem Stickstoffatom einen gesättigten heterocyclischen C3-C6-Ring bilden, der ein- oder mehrfach durch Sauerstoff oder Schwefel unterbrochen sein kann,R 14 and R 15 together with the nitrogen atom form a saturated heterocyclic C 3 -C 6 ring which can be interrupted one or more times by oxygen or sulfur,
R16 Wasserstoff oder CrC4-Alkyl,R 16 is hydrogen or C r C 4 alkyl,
R17 Wasserstoff, CrC4-Alkyl oder Halogen-CrC4-alkyl,R 17 is hydrogen, C r C 4 alkyl or halogen C r C 4 alkyl,
R18, R19, R20, R21, R22 und R24 unabhängig voneinander Wasserstoff, Halogen, CrC4-Alkyl, C2-C4-Alkenyl oder C3-C4-Alkinyl, Carboxy oder CrC4- Alkoxycarbonyl, ein ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Nitro, Hydroxy oder CrC4-Alkoxy substituiertes CrC4-Alkyl, C2-C4-Alkenyl oder C3-C4-Alkinyl,R 18 , R 19 , R 20 , R 21 , R 22 and R 24 independently of one another hydrogen, halogen, C r C 4 alkyl, C 2 -C 4 alkenyl or C 3 -C 4 alkynyl, carboxy or C r C 4 - alkoxycarbonyl, one or more identical or different halogen or cyano, nitro, hydroxy or C r C 4 alkoxy substituted C r C 4 alkyl, C 2 -C 4 alkenyl or C 3 -C 4 - Alkynyl,
R23 und R25 Wasserstoff, Halogen, CrC4-Alkyl, C2-C4-Alkenyl oder C3-C4-Alkinyl, oderR 23 and R 25 are hydrogen, halogen, C r C 4 alkyl, C 2 -C 4 alkenyl or C 3 -C 4 alkynyl, or
R23 und R25 gemeinsam einen gesättigten oder ungesättigten drei- bis achtgliedrigen Ring, gegebenenfalls ein oder mehrere Schwefel- oder Sauerstoffatome enthaltend, bilden,R 23 and R 25 together form a saturated or unsaturated three- to eight-membered ring, optionally containing one or more sulfur or oxygen atoms,
R29 Wasserstoff oder Halogen,R 29 is hydrogen or halogen,
R31 Wasserstoff, CrC4-Alkyl, C5-C8-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl, C3- Cg-Alkinyl, ein ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Hydroxy oder C1-C4-Alkoxy substituiertes C1-C6-Alkyl, C3-C6- Cycloalkyl, C2-C6-Alkenyl oder C3-C6-Alkinyl, ein ein- oder mehrfach durch Sauerstoff unterbrochenes C2-C8-Alkyl, C3-C8-Cycloalkyl, C3-C8-Cycloatkyl- CrC4-alkyl, C2-C8-Alkenyl oder C3-C8-Alkinyl, CrC4-Alkoxycarbonyl-CrC4- alkyl, welches gegebenenfalls durch Halogen substituiert sein kann, C1-C4-Alkoxycarbonyl-C2-C4-alkenyl, welches gegebenenfalls durch Halogen substituiert sein kann, oder die Gruppe -(CH2)p-NR8R9 , mit der Maßgabe falls R12 und R31 Wasserstoff oder R12 Wasserstoff und R31 CrC4-Alkyl sind, kann R13 nicht Wasserstoff oder Halogen sein,R 31 is hydrogen, C r C 4 alkyl, C 5 -C 8 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 - Cg alkynyl, one or more times the same or different C 1 -C 6 alkyl substituted by halogen, cyano, hydroxy or C 1 -C 4 alkoxy, C 3 -C 6 - Cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, a C 2 -C 8 alkyl interrupted one or more times by oxygen, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloatkyl- C r C 4 alkyl, C 2 -C 8 alkenyl or C 3 -C 8 alkynyl, C r C 4 alkoxycarbonyl-C r C 4 alkyl, which may optionally be substituted by halogen, C 1 -C 4 -Alkoxycarbonyl-C 2 -C 4 -alkenyl, which may optionally be substituted by halogen, or the group - (CH 2 ) p -NR 8 R 9 , with the proviso that if R 12 and R 31 are hydrogen or R 12 is hydrogen and R 31 C r C 4 alkyl, R 13 can not be hydrogen or halogen,
R32 Wasserstoff, CrC6-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl, C3-C6-Alkinyl, ein ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Hydroxy oder CrC4-Alkoxy substituiertes CrC6-Alkyl, C3-C6-Cycloalkyl, C2-C6- Alkenyl oder C3-C6-Alkinyl, ein ein- oder mehrfach durch Sauerstoff unterbrochenes C2-C8-Alkyl, C3-C8-Cycloalkyl, C2-C8-Alkenyl oder C3-C8- Alkinyl, C1-C4-Alkoxycarbonyl-C1-C4-alkyl, welches gegebenenfalls durch Halogen substituiert sein kann, C1-C4-Alkoxycarbonyl-C2-C4-alkenyl, welches gegebenenfalls durch Halogen substituiert sein kann, m 3 oder 4, n 0, 1 , 2 oder 3, o 1 , 2 oder 3, p 2, 3 oder 4 undR 32 is hydrogen, C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, one or more times the same or different by halogen, cyano, hydroxy or C r C 4 alkoxy substituted C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, a C 2 -C which is interrupted once or several times by oxygen 8- alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl or C 3 -C 8 alkynyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl, which may optionally be substituted by halogen can, C 1 -C 4 alkoxycarbonyl-C 2 -C 4 alkenyl, which may optionally be substituted by halogen, m 3 or 4, n 0, 1, 2 or 3, o 1, 2 or 3, p 2, 3 or 4 and
X Sauerstoff oder Schwefel bedeuten, eine den bekannten Verbindungen überlegene herbizide Wirkung besitzen.X is oxygen or sulfur and has a herbicidal action which is superior to that of the known compounds.
Die Bezeichnung Halogen umfaßt Fluor, Chlor, Brom und Jod.The term halogen includes fluorine, chlorine, bromine and iodine.
Die Bezeichnung "Alkyl" , "Alkenyl" und "Alkinyl" umfaßt Kohlenwasserstoffreste, die verzweigt oder unverzweigt sein können.The term "alkyl", "alkenyl" and "alkynyl" includes hydrocarbon radicals, which can be branched or unbranched.
Bevorzugt sind solche substituierte Pyrazolyl-pyrazole der allgemeinen Formel I, bei denenPreferred substituted pyrazolyl-pyrazoles of the general formula I are preferred in which
R1 Methyl,R 1 is methyl,
R2 Difluormethoxy, R1 und R2 gemeinsam die Gruppe -(CH2)4- bilden,R 2 difluoromethoxy, R 1 and R 2 together form the group - (CH 2 ) 4 -,
R3 Chlor oder Brom,R 3 chlorine or bromine,
R4 Wasserstoff,R 4 is hydrogen,
R5 Nitro oder Cyano,R 5 nitro or cyano,
R6 eine der Gruppen i x ? R 6 one of the groups i x?
R11 C5-C8-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl, C3-C6-Alkinyl, ein ein- oder mehrfach durch Sauerstoff unterbrochenes C2-C8-Alkyl, C3-C8-Cycloalkyl,R 11 is C 5 -C 8 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, a C 2 -C 8 alkyl interrupted one or more times by oxygen, C 3 -C 8 cycloalkyl,
C3-C8-Alkenyl oder C3-C8-Alkinyl, R12 Wasserstoff oder Methyl, R13 Wasserstoff oder Methyl, R16 Wasserstoff, R17 Wasserstoff, R18, R19, R20, R21, R22, R23, R24 und R24 unabhängig voneinander Wasserstoff,C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, R 12 hydrogen or methyl, R 13 hydrogen or methyl, R 16 hydrogen, R 17 hydrogen, R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 and R 24 independently of one another are hydrogen,
Halogen oder C1-C3-Alkyl, R23 und R25 gemeinsam einen gesättigten durch ein Sauerstoffatom unterbrochenen 3-atomigen Ring bilden, R29 Wasserstoff oder Halogen, R31 Wasserstoff, CrC4-Alkyl, C5-C8-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl, C3-Halogen or C 1 -C 3 alkyl, R 23 and R 25 together form a saturated 3-atom ring interrupted by an oxygen atom, R 29 is hydrogen or halogen, R 31 is hydrogen, C r C 4 alkyl, C 5 -C 8 -Alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 3 -
C6-Alkinyl, ein ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Hydroxy oder CrC4-Alkoxy substituiertes CrC6-Alkyl, C3-C6- Cycloalkyl, C2-C6-Alkenyl oder C3-C6-Alkinyl, mit der Maßgabe falls R12 und R31 Wasserstoff oder R12 Wasserstoff und R31 CrC4-Alkyl sind, kann R13 nicht Wasserstoff sein,C 6 alkynyl, one or more identical or different by halogen, Cyano, hydroxy or C r C 4 alkoxy substituted C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, with the proviso if R 12 and R 31 is hydrogen or R 12 is hydrogen and R 31 is C r C 4 alkyl, R 13 cannot be hydrogen,
X Sauerstoff bedeuten, und n O und o 1 oder 2 sind.X is oxygen and n is O and o is 1 or 2.
Die erfindungsgemäßen Verbindungen der allgemeinen Formel I lassen sich herstellen, indem man beispielsweiseThe compounds of general formula I according to the invention can be prepared by, for example
A) eine Verbindung der allgemeinen Formel IIA) a compound of general formula II
x y • xy •
in der R1 , R2 und R3 die in der allgemeinen Formel I genannte Bedeutungen haben, mit einer Verbindung der allgemeinen Formel IIIin which R 1 , R 2 and R 3 have the meanings given in the general formula I, with a compound of the general formula III
in der R 5° für die Gruppe COOR 7' oder steht, wobei in which R 5 ° stands for the group COOR 7 'or, where
R7, R8 und R9 die in der allgemeinen Formel I genannte Bedeutung haben und X für Sauerstoff steht,R 7 , R 8 and R 9 have the meaning given in the general formula I and X represents oxygen,
und B für die Gruppe OR26 oder steht, wobei R26, R27 und R28 unabhängig voneinander CrC4-Alkyl bedeuten, umsetzt oderand B represents the group OR 26 or, where R 26 , R 27 and R 28 independently of one another denote C r C 4 alkyl, implement or
B) falls R6 für die Gruppe -(CH2)0-A steht, wobei A für die Cyanogruppe steht und o die in der allgemeinen Formel I genannteB) if R 6 is the group - (CH 2 ) 0 -A, where A is the cyano group and o is the one mentioned in the general formula I.
Bedeutung hat, eine Verbindung der allgemeinen Formel laHas meaning, a compound of the general formula la
H ι ( la ) H ι (la)
in der R1 , R2, R3, R4 und R5 die in der allgemeinen Formel I angegebene Bedeutung haben und B für eine Fluchtgruppe, wie Chlor, Brom oder Methylsulfonyl steht, mit einem Alkalisalz der Cyanwasserstoffsäure umsetzt, oderin which R 1 , R 2 , R 3 , R 4 and R 5 have the meaning given in the general formula I and B represents a leaving group, such as chlorine, bromine or methylsulfonyl, with an alkali metal salt of hydrocyanic acid, or
C) falls R3 für Halogen steht, eine Verbindung der allgemeinen Formel IbC) if R 3 is halogen, a compound of the general formula Ib
in der R1, R2, R4, R5 und R6 die in der allgemeinen Formel I angegebene Bedeutung haben, mit einem geeigneten Halogenierungsmitel umsetzt oderin which R 1 , R 2 , R 4 , R 5 and R 6 have the meaning given in the general formula I, with a suitable halogenating agent or
D) falls R6 für eine der Gruppen O 97/46536 PO7EP97/02690D) if R 6 for one of the groups O 97/46536 PO7EP97 / 02690
in denen R16, R17 R18, R19, R20, R21 R22, R23, R24, R25, n und X die in der allgemeinen Formel I angegebene Bedeutung haben, steht, eine Verbindung der allgemeinen Formel Ic oder Id,in which R 16 , R 17 R 18 , R 19 , R 20 , R 21 R 22 , R 23 , R 24 , R 25 , n and X have the meaning given in the general formula I, is a compound of the general formula Ic or Id,
in der R1, R2, R3, R4, R5, R16 R17, und n die in der allgemeinen Formel I angegebene Bedeutung haben und R ,3J0U für C :r1-CC44--Alkyl steht, mit einer Verbindung der allgemeinen Formel IV oder Vin which R 1 , R 2 , R 3 , R 4 , R 5 , R 16 R 17 , and n have the meaning given in the general formula I and R, 3 J 0 U for C: r1 -CC 44 --alkyl stands with a compound of general formula IV or V
AA
in denen R18, R19, R20, R21, R22, R23, R24, R25 und X die in der allgemeinen Formel I angegebene Bedeutunge haben, umsetzt, oder in which R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 and X have the meanings given in the general formula I, or
E) falls R6 für die Gruppe steht, in der R12, R13 und E) if R 6 represents the group in which R 12 , R 13 and
R31 die in der allgemeinen Formel I genannte Bedeutung haben und R29 für Chlor oder Brom steht, eine Verbindung der allgemeinen Formel leR 31 have the meaning given in the general formula I and R 29 represents chlorine or bromine, a compound of the general formula le
in der R1, R2, R3, R4 und R5 die in der allgemeinen Formel I angegebene Bedeutung haben zunächst durch Diazotierung zu einer Verbindung der allgemeinen Formel Ifin which R 1 , R 2 , R 3 , R 4 and R 5 have the meaning given in the general formula I, first by diazotization to give a compound of the general formula If
HH
in der R1, R2, R3, R4 und R5 die in der allgemeinen Formel I angegebene Bedeutung haben, mit einem Michael-Akzeptor der allgemeinen Formel VIin which R 1 , R 2 , R 3 , R 4 and R 5 have the meaning given in the general formula I, with a Michael acceptor of the general formula VI
in der R12, R13 und R31 die in der allgemeinen Formel I genannte Bedeutung haben, umsetzt, oder in which R 12 , R 13 and R 31 have the meaning given in general formula I, or
F) falls R6 für die Gruppe steht, in der R11, R12 und F) if R 6 represents the group in which R 11 , R 12 and
R13 die in der allgemeinen Formel I genannte Bedeutung haben, eine Verbindung der allgemeinen Formel IgR 13 have the meaning given in the general formula I, a compound of the general formula Ig
in der R1, R2, R3, R4, R5, R11, R12 und R13 die in der allgemeinen Formel I angegebene Bedeutung haben, und R29 für Chlor oder Brom steht, mit einer geeigneten Base umsetzt, oderin which R 1 , R 2 , R 3 , R 4 , R 5 , R 11 , R 12 and R 13 have the meaning given in general formula I, and R 29 represents chlorine or bromine, reacted with a suitable base, or
G) eine Verbindung der allgemeinen Formel Ih oder liG) a compound of the general formula Ih or li
in der R1, R2, R3, R4, R5, R12, R13 und R29 die in der allgemeinen Formel I angegebene Bedeutung haben und R33 für Hydroxy, Chlor, Brom oder CrC4-Alkoxy steht, mit einem Alkohol der allgemeinen Formel VII oder einem Amin der allgemeinen Formel VIII R »1M1-OH ( VII ) R 14R15NH ( VIII )in which R 1 , R 2 , R 3 , R 4 , R 5 , R 12 , R 13 and R 29 have the meaning given in the general formula I and R 33 for hydroxy, chlorine, bromine or C r C 4 alkoxy stands with an alcohol of the general formula VII or an amine of the general formula VIII R »1 M 1-OH (VII) R 14 R 15 NH (VIII)
in der R11, R14 und R15 die in der allgemeinen Formel I angegebene Bedeutung haben, umsetzt.in which R 11 , R 14 and R 15 have the meaning given in general formula I.
Die als Ausgangsmaterial verwendeten Verbindungen der allgemeinen Formel II gemäß Verfahrenvariante A sind bekannt. Ihre Herstellung ist in WO 94/08999 beschrieben.The compounds of general formula II used as starting material according to process variant A are known. Their manufacture is described in WO 94/08999.
Die erfindungsgemäßen Verbindungen der allgemeinen Formel I, in denen R5 für die Gruppe -COOR7 oder -CXNR8R9 steht (Verfahrensvariante A), lassen sich nach dem von Bisagni et al. in Tetrahedron 29, 435 (1973) beschriebenen Verfahren herstellen.The compounds of general formula I according to the invention in which R 5 represents the group -COOR 7 or -CXNR 8 R 9 (process variant A) can be prepared according to the method described by Bisagni et al. in Tetrahedron 29, 435 (1973).
Die Verfahrensvariante B) wird zweckmäßigerweise so ausgeführt, daß man das Ausgangsmaterial der allgemeinen Formel la in einem geeigneten Lösungsmittel bei einer Temperatur von 20 bis 180°C mit einem Salz der Cyanwasserstoffsäure umsetzt.Process variant B) is advantageously carried out in such a way that the starting material of the general formula Ia is reacted with a salt of hydrocyanic acid in a suitable solvent at a temperature of 20 to 180 ° C.
Als geeignete Lösungsmittel seien beispielsweise Ether, wie Diethylether, Tetrahydrofuran oder 1 ,4-Dioxan, Amide, wie Dimethylformamid, Dimethylacetamid oder N-Methylpyrrolidon, aromatische Kohlenwasserstoffe.wie Benzol, Toluol oder Xylol, oder Sulfoxide wie Dimethylsulfoxid genannt. Als geeignete Cyanide seien Lithium-, Natrium- und Kaliumcyanid genannt.Suitable solvents are, for example, ethers such as diethyl ether, tetrahydrofuran or 1,4-dioxane, amides such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, aromatic hydrocarbons such as benzene, toluene or xylene, or sulfoxides such as dimethyl sulfoxide. Lithium, sodium and potassium cyanide may be mentioned as suitable cyanides.
Die als Ausgangsmaterial verwendeten Verbindungen der allgemeinen Formel la sind bekannt. Ihre Herstellung ist in Wo 94/08999 beschrieben.The compounds of the general formula Ia used as starting material are known. Their manufacture is described in Wo 94/08999.
Die Halogenierung gemäß Verfahrensvariante C) läßt sich nach den an sich bekannten Verfahren der Halogenierung von heterocyclischen Aromaten, wie sie beispielsweise im Houben-Weyl, Band V/4, Seite 233 ff (1960) oder Band V/3, Seite 511 ff (1962) beschrieben sind, mit einem Halogenierungsmittel in einem geeigneten inerten Lösungsmittel durchführen. Als Halogenierungsmittel können z.B. Sulfurylchlorid, Natriumhypochlorit, N-Chlor- succinimid, N-Bromsuccinimid, Chlor oder Brom verwendet werden.The halogenation according to process variant C) can be carried out according to the known methods of halogenating heterocyclic aromatics, as described, for example, in Houben-Weyl, volume V / 4, page 233 ff (1960) or volume V / 3, page 511 ff (1962 ) with a halogenating agent in a suitable inert solvent. Examples of halogenating agents that can be used are sulfuryl chloride, sodium hypochlorite, N-chlorosuccinimide, N-bromosuccinimide, chlorine or bromine.
Die Acetale bzw. Ketale lassen sich nach der Verfahrensvariante D) gemäß den in T.W. Greene "Protective Groups in Organic Synthesis", 1980, Seite 116 ff beschriebenen Methoden herstellen.The acetals or ketals can be according to process variant D) according to the in T.W. Greene "Protective Groups in Organic Synthesis", 1980, page 116 ff.
Die als Ausgangsmaterial verwendeten Verbindungen der allgemeinen Formel Ic und Id sind bekannt. Ihre Herstellung ist in WO 94/08999 beschrieben.The compounds of general formula Ic and Id used as starting material are known. Their manufacture is described in WO 94/08999.
Die Verbindungen gemäß Verfahrensvariante E) können nach dem im US Patent 5,250,504 angegebenen Verfahren hergestellt werden.The compounds according to process variant E) can be prepared by the process specified in US Pat. No. 5,250,504.
Die als Ausgangsmaterial verwendeten Verbindungen der allgemeinen Formel le sind bekannt. Ihre Herstellung ist in WO 94/08999 beschrieben.The compounds of the general formula Ie used as starting material are known. Their manufacture is described in WO 94/08999.
Die Verbindungen gemäß Verfahrensvariante F) können nach an sich bekannten Verfahren zur Eliminierung, wie sie beispielsweise in J. March "Advanced Organic Chemistry" 2nd edition 1977, Seite 895 ff und dort zitierte Literatur beschrieben sind, hergestellt werden.The compounds according to process variant F) can be prepared by methods known per se for elimination, as described, for example, in J. March "Advanced Organic Chemistry" 2nd edition 1977, page 895 ff and the literature cited therein.
Die Veresterungen gemäß Verfahrensstufe G) sind an sich bekannt und können nach den üblichen Methoden, wie sie beispielsweise im Houben-Weyl, Band E5, Seite 659 ff (1985) beschrieben sind, durchgeführt werden. Gleiches gilt für die Amidbildungen, die ebenfalls beispielsweise im Houben-Weyl, Band E5, Seite 934 ff (1985) beschrieben sind.The esterifications according to process stage G) are known per se and can be carried out by the customary methods, as described, for example, in Houben-Weyl, volume E5, page 659 ff (1985). The same applies to the amide formations, which are also described, for example, in Houben-Weyl, Volume E5, page 934 ff (1985).
Die einzelnen Verfahrensstufen können mit oder ohne Lösungsmittel durchgeführt werden, wobei im Bedarfsfall solche Lösungs- bzw. Verdünnungsmittel zum Einsatz kommen.die gegenüber den jeweiligen Reaktanden inert sind. Beispiele für solche Lösungsmittel bzw. Verdünnungsmittel sind aliphatische, alicyclische und aromatische Kohlenwasserstoffe, die jeweils gegebenenfalls chloriert sein können, wie zum Beispiel Hexan, Cyclohexan, Petrolether, Ligroin, Benzol, Toluol, Xylol, Methylenchlorid, Chloroform, Kohlenstofftetrachlorid, Ethylenchlorid, Trichlorethylen und Chlorbenzol, Ether, wie zum Beispiel Diethylether, Methylethylether, Methyl-t- butylether, Diisopropylether, Dibutylether, Dioxan und Tetrahydrofuran, Ketone, wie zum Beispiel Aceton, Methylethykβton, Methyl isopropylketon und Methylisobutylketon, Nitrile, wie zum Beispiel Acetonitril und Propionitril, Alkohole, wie zum Beispiel Methanol, Ethanol, Isopropanol, Butanol, tert.-Butanol, tert - Amylalkohol und Ethylenglycol, Ester, wie zum Beispiel Ethylacetat und Amylacetat, Säureamide, wie zum Beispiel Dimethylformamid und Dimethylacetamid, Sulfoxide, wie zum Beispiel Dimethylsulfoxid, und Sulfone, wie zum Beispiel Sulfolan, Basen, wie zum Beispiel Pyridin und Triethylamin, Carbonsäuren, wie zum Beispiel Essigsäure und Mineralsäuren, wie zum Beispiel Schwefelsäure und Salzsäure.The individual process steps can be carried out with or without solvent, and if necessary, solvents or diluents are used which are inert to the respective reactants. Examples of such solvents or diluents are aliphatic, alicyclic and aromatic hydrocarbons, each of which may optionally be chlorinated, such as, for example, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, Methylene chloride, chloroform, carbon tetrachloride, ethylene chloride, trichlorethylene and chlorobenzene, ethers such as, for example, diethyl ether, methyl ethyl ether, methyl t-butyl ether, diisopropyl ether, dibutyl ether, dioxane and tetrahydrofuran, ketones such as, for example, acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone and methyl isobutyl ketone and methyl , such as, for example, acetonitrile and propionitrile, alcohols, such as, for example, methanol, ethanol, isopropanol, butanol, tert-butanol, tert-amyl alcohol and ethylene glycol, esters, such as, for example, ethyl acetate and amyl acetate, acid amides, such as, for example, dimethylformamide and dimethylacetamide, Sulfoxides such as dimethyl sulfoxide and sulfones such as sulfolane, bases such as pyridine and triethylamine, carboxylic acids such as acetic acid and mineral acids such as sulfuric acid and hydrochloric acid.
Die Aufarbeitung der erfindungsgemäßen Verbindungen erfolgt in der üblichen Art und Weise. Eine Aufreinigung erfolgt durch Kristallisation oder Säulenchromatographie.The compounds according to the invention are worked up in the customary manner. Purification is carried out by crystallization or column chromatography.
Die erfindungsgemäßen Verbindungen steilen in der Regel farblose oder schwach gelb gefärbte kristalline oder zähflüssige Substanzen dar, die zum Teil gut löslich in chlorierten Kohlenwasserstoffen, wie zum Beispiel Methylenchlorid oder Chloroform, Ethern, wie zum Beispiel Diethylether oder Tetrahydrofuran, Alkoholen, wie zum Beispiel Methanol oder Ethanol, Ketonen, wie zum Beispiel Aceton oder Butanon, Amiden, wie zum Beispiel Dimethylformamid, oder auch Sulfoxiden, wie zum Beispiel Dimethylsulfoxid, sind.The compounds according to the invention generally represent colorless or pale yellow colored crystalline or viscous substances, some of which are readily soluble in chlorinated hydrocarbons, such as methylene chloride or chloroform, ethers, such as diethyl ether or tetrahydrofuran, alcohols, such as methanol or Ethanol, ketones such as acetone or butanone, amides such as dimethylformamide or sulfoxides such as dimethyl sulfoxide.
Die erfindungsgemäßen Verbindungen zeigen eine gute herbizide Wirkung bei breitblättrigen Unkräutern und Gräsern. Ein selektiver Einsatz ist in verschiedenen Kulturen möglich, z.B. in Raps, Rüben, Sojabohnen, Baumwolle, Reis, mais, Gerste, Weizen und anderen Getreidearten. Einzelne Verbindungen sind auch als Selektivherbizide in Rüben, Baumwolle, Soja, Mais und Getreide geeignet. Ebenso können die Verbindungen zur Unkrautbekämpfung in Dauerkulturen, wie z.B. in Forst-, Ziergehölz-, Obst-, Wein-, Citrus-, Nuß-, Bananen, Kaffee-, Tee-, Gummi-, ölpalm-, Kakao-, Beerenfrucht- und Hopfenanlagen eingesetzt werden. Die erfindungsgemaßen Verbindungen können z.B. bei den folgendenThe compounds according to the invention have a good herbicidal action on broad-leaved weeds and grasses. A selective use is possible in different crops, for example in rapeseed, beets, soybeans, cotton, rice, corn, barley, wheat and other types of cereals. Individual compounds are also suitable as selective herbicides in beets, cotton, soybeans, corn and cereals. Likewise, the compounds for weed control in permanent crops, such as, for example, in forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and Hop plants are used. The compounds of the invention can be used, for example, in the following
Pflanzengattungen verwendet werden:Plant genera are used:
Dikotyle Unkräuter der Gattungen wie Sinapis, Lepidium, Galium, Stellaria,Dicot weeds of the genera such as Sinapis, Lepidium, Galium, Stellaria,
Matricaria, Anthemis, Galinsoga, Chβnopodium, Brassica, Urtica, Senecio,Matricaria, Anthemis, Galinsoga, Chβnopodium, Brassica, Urtica, Senecio,
Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbaniia,Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbaniia,
Ambrosia, Cirsium, Sonchus, Soianum, Lamium, Veronica, Abuliton, Datura, Viola,Ambrosia, Cirsium, Sonchus, Soianum, Lamium, Veronica, Abuliton, Datura, Viola,
Galeopsis, Papaver, Centaurea und Chrysanthemum;Galeopsis, papaver, centaurea and chrysanthemum;
Monokotyle Unkräuter der Gattungen wie Avena, Alopecurus, Echinochloa, Setaria,Monocot weeds of the genera such as Avena, Alopecurus, Echinochloa, Setaria,
Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Elymus,Panicum, Digitaria, Poa, Eleusine, Brachiaria, Lolium, Bromus, Cyperus, Elymus,
Sagittaria, Monochoria, Fimbristylis, Eleocharis, Ischaemum und Apera.Sagittaria, Monochoria, Fimbristylis, Eleocharis, Ischaemum and Apera.
Die Aufwandmengen schwanken je nach Anwendungsart im Vor- und Nachauflauf zwischen 0,001 bis 5 kg/ha.Depending on the type of application, the application rates fluctuate between 0.001 and 5 kg / ha in the pre- and post-emergence.
Eine Förderung der Wirkintensität und der Wirkungsgeschwindigkeit kann zum Beispiel durch wirkungssteigernde Zusätze, wie organische Lösungsmittel, Netzmittel und öle, erzielt werden. Solche Zusätze lassen daher gegebenenfalls eine Verringerung der Wirkstoffdosierung zu.The intensity and speed of action can be promoted, for example, by additives which increase the effectiveness, such as organic solvents, wetting agents and oils. Such additives may therefore allow the active ingredient dosage to be reduced.
Zweckmäßig werden die erfindungsgemäßen Wirkstoffe oder deren Mischungen in Form von Zubereitungen, wie Pulvern, Streumitteln, Granulaten, Lösungen, Emulsionen oder Suspensionen, unter Zusatz von flüssigen und/oder festen Trägerstoffen bzw. Verdünnungsmitteln und gegegenenfalls Haft-, Netz-, Emuigier- und/oder Dispergierhilfsmitteln angewandt.The active compounds according to the invention or mixtures thereof are expediently in the form of preparations, such as powders, scattering agents, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and, if appropriate, adhesives, wetting agents, emulsifiers and / or dispersing aids applied.
Geeignete flüssige Trägerstoffe sind z.B. aliphatische und aromatische Kohlenwasserstoffe, wie Benzol, Toluol, Xylol, Cyclohexanon, Isophoron, Dimethylsulfoxid, Dimethylformamid, weiterhin Mineralölfraktionen und Pflanzenöle.Suitable liquid carriers are e.g. aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide, mineral oil fractions and vegetable oils.
Als feste Trägerstoffe eignen sich Mineralien, wi z.B. Bentonit, Silicagel, Talkum, Kaolin, Attapulgit, Kalkstein und pflanzliche Produkte, wie z.B. Mehle. An oberflächenaktiven Stoffen sind zu nennen z.B. Calciumligninsulfonat, Polyethylenalkylphenylether, Naphthalinsulfonsäuren und deren Salze, Phenolsulfonsäuren und deren Salze, Formaldehydkondensate, Fettalkoholsulfate sowie substituierte Benzolsulfonsäuren und deren Salze.Minerals such as bentonite, silica gel, talc, kaolin, attapulgite, limestone and vegetable products such as flour are suitable as solid carriers. Examples of surface-active substances include calcium ligninsulfonate, polyethylene alkylphenyl ether, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates and substituted benzenesulfonic acids and their salts.
Der Anteil des bzw. der Wirkstoffe(s) in den verschiedenen Zubereitungen kann in weiten Grenzen variieren. Beispielsweise enthalten die Mittel etwa 10 bis 90 Gew.-% Wirkstoff, etwa 90 bis 10 Gew.-% flüssige oder feste Trägerstoffe sowie gegebenenfalls bis zu 20 Gew.-% oberflächenaktive Stoffe.The proportion of the active ingredient (s) in the various preparations can vary within wide limits. For example, the agents contain about 10 to 90% by weight of active ingredient, about 90 to 10% by weight of liquid or solid carriers and optionally up to 20% by weight of surface-active substances.
Die Ausbringung der Mittel kann in üblicher Weise erfolgen, z.B. mit Wasser als Träger in Spritzbrühmengen von etwa 100 bis 1000 Liter/ha. Eine Anwendung der Mittel im sogenannten Low-Volume und Ultra-Low-Volume-Verfahren ist ebenso möglich wie ihre Applikation in Form von sogenannten Mikrogranulaten.The funds can be applied in a conventional manner, e.g. with water as a carrier in spray liquor quantities of about 100 to 1000 liters / ha. Use of the agents in the so-called low-volume and ultra-low-volume process is just as possible as their application in the form of so-called microgranules.
Die Herstellung dieser Zubereitungen kann in an sich bekannter Art und Weise, z.B. durch Mahl- oder Mischverfahren, durchgeführt werden. Gewünschtenfalls können Zubereitungen der Einzelkomponenten auch erst kurz vor ihrer Verwendung gemischt werden, wie es z.B. im sogenannten Tankmixverfahren in der Praxis durchgeführt wird.The preparation of these preparations can be carried out in a manner known per se, e.g. be carried out by grinding or mixing processes. If desired, preparations of the individual components can also be mixed shortly before their use, as is the case, for example, is carried out in practice in the so-called tank mix process.
Die nachfolgenden Beispiele beschreiben die Herstellung der erfindungsgemäßen Verbindungen. The following examples describe the preparation of the compounds according to the invention.
Beispiel 1 (Verfahren D)Example 1 (Method D)
1 -(4-Brom-5-difluormethoxy-1 -methyl-3-pyrazolyl)-5-(4,7-dihydro-1 ,3-dioxepin-2-yl)- 1 H-pyrazol-4-carbonitril1 - (4-Bromo-5-difluoromethoxy-1-methyl-3-pyrazolyl) -5- (4,7-dihydro-1, 3-dioxepin-2-yl) - 1 H-pyrazole-4-carbonitrile
3,0 g (7,1 mmol) 1-(4-Brom-5-difluormethoxy-1-methyl-3-pyrazolyl)-5-(1 ,1- diethoxyethyl)-1 H-pyrazol-4-carbonitril werden in 50 ml Toluol gelöst und anschließend 6,3 g (71 mmol) cis-2,3-Buten-1,4-diol und eine katalytische Menge p- Toluolsulf onsäure zugegeben. Man kocht eine halbe Stunde am Wasserabscheider, wäscht die abgekühlte Lösung mit Natriumchlorid-Lösung, trocknet mit Magnesiumsulfat und engt ein. Der Rückstand wird mittels Säulenchromatographie gereinigt.3.0 g (7.1 mmol) of 1- (4-bromo-5-difluoromethoxy-1-methyl-3-pyrazolyl) -5- (1, 1-diethoxyethyl) -1 H-pyrazole-4-carbonitrile are added in 50 ml of toluene dissolved and then 6.3 g (71 mmol) of cis-2,3-butene-1,4-diol and a catalytic amount of p-toluenesulfonic acid added. The mixture is boiled for half an hour on a water separator, the cooled solution is washed with sodium chloride solution, dried with magnesium sulfate and concentrated. The residue is purified by column chromatography.
Ausbeute: 2,5 g A 83 % der Theorie Fp.: 90-91 °CYield: 2.5 g of A 83% of theory. Mp .: 90-91 ° C.
Beispiel 2 (Verfahren E)Example 2 (Method E)
1-(4-Chlor-5-difluormethoxy-1-methyl-3-pyrazolyl)-4-cyano-5-pyrazolyl-3-(2-chlor-2- methy I -prop ionsäuremethy lester1- (4-Chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl) -4-cyano-5-pyrazolyl-3- (2-chloro-2-methyl I-propionic acid methyl ester
Man legt 1 ,5 g (13 mmol) tert.-Butylnitrit, 15 ml Methacrylsäuremethylester und 1,0 g Kupfer-ll-chlorid in 15 ml Acetonitril vor und gibt in 3 Portionen 2,55 g (10 mmol) 5- Amino-1 -(4-chlor-5-dif luormethoxy-1 -methyl-3-pyrazolyl)-4-pyrazolcarbonitril zu. Es wird 2 Stunden bei Raumtemperatur gerührt, auf 50 ml 2-normale Salzsäure gegeben und dreimal mit Dichlormethan extrahiert, über Magnesiumsulfat getrocknet und eingeengt. Die Aufreinigung erfolgt mittels Säulenchromatographie mit Hexan/Essigestergemischen. Ausbeute: 1 ,65 g & 46 % der Theorie Fp.: 65βC Beispiel 3 (Verfahren F)1.5 g (13 mmol) of tert-butyl nitrite, 15 ml of methyl methacrylate and 1.0 g of copper-II-chloride in 15 ml of acetonitrile are initially introduced, and 2.55 g (10 mmol) of 5-amino- 1 - (4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl) -4-pyrazole carbonitrile. The mixture is stirred at room temperature for 2 hours, added to 50 ml of 2N hydrochloric acid and extracted three times with dichloromethane, dried over magnesium sulfate and concentrated. The purification is carried out by means of column chromatography with hexane / ethyl acetate mixtures. Yield: 1.65 g & 46% of theory Mp .: 65 β C Example 3 (Method F)
1-(4-Chlor-5-difluormethoxy-1-methyl-3-pyrazolylH-cyano-5-pyrazolyl-3-(2-methyl)- prop-2-ensäuremethylester1- (4-Chloro-5-difluoromethoxy-1-methyl-3-pyrazolylH-cyano-5-pyrazolyl-3- (2-methyl) prop-2-enoic acid methyl ester
Man legt 73 mg (2,45 mmol) Natriumhydrid (80 %ig) in 20 ml absolutem Dimethylformamid vor und gibt 1,0 g (2,45 mmol) 1-(4-Chlor-5-difluormethoxy-1- methyl-3-pyrazolyl)-4-cyano-5-pyrazolyl-3-(2-chlor-2-methyl)- propionsäuremethylester hinzu. Es wird 2 Stunden bei 60°C gerührt, das Lösungsmittel abgezogen und der Rückstand mittels Säulenchromatographie mit Hexan/Essigestergemisch gereinigt. Ausbeute: 0,56 g * 61 % der Theorie Fp.: 88°C73 mg (2.45 mmol) of sodium hydride (80%) in 20 ml of absolute dimethylformamide are introduced and 1.0 g (2.45 mmol) of 1- (4-chloro-5-difluoromethoxy-1-methyl-3) are added -pyrazolyl) -4-cyano-5-pyrazolyl-3- (2-chloro-2-methyl) - methyl propionate. The mixture is stirred at 60 ° C. for 2 hours, the solvent is stripped off and the residue is purified by means of column chromatography with a hexane / ethyl acetate mixture. Yield: 0.56 g * 61% of theory, mp: 88 ° C.
Beispiel 4 (Verfahren G)Example 4 (Method G)
(E)-3-[1-(4-Chlor-5-difluormethoxy-1-methyl-3-pyrazolyl)-4-cyano-5-pyrazolyl]- acrylsäure-(2,2-dimethoxyethyl)-ester(E) -3- [1- (4-Chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl) -4-cyano-5-pyrazolyl] acrylic acid (2,2-dimethoxyethyl) ester
Man legt 1 g (2,76 mmol) 1-(4-Chlor-5-difluormethoxy-1-methyl-3-pyrazolyl)-4- cyano-5-pyrazolyl-3-propionsäurechlorid in 20 ml Dichlormethan vor und gibt bei Raumtemperatur 0,28 g (2,76 mmol) Triethylamin und 0,29 g (2,76 mmol) Glykolaldehyddimethylacetal hinzu. Es wird 2 Stunden bei Raumtemperatur gerührt, das Lösungsmittel abgezogen und der Rückstand mittels Säulenchromatographie mit Hexan/Essigestergemischen gereinigt. Ausbeute: 0,80 g * 67 % der Theorie Fp.: 92βC1 g (2.76 mmol) of 1- (4-chloro-5-difluoromethoxy-1-methyl-3-pyrazolyl) -4-cyano-5-pyrazolyl-3-propionic acid chloride in 20 ml of dichloromethane are added and the mixture is added at room temperature 0.28 g (2.76 mmol) of triethylamine and 0.29 g (2.76 mmol) of glycol aldehyde dimethyl acetal were added. The mixture is stirred at room temperature for 2 hours, the solvent is stripped off and the residue is purified by column chromatography with hexane / ethyl acetate mixtures. Yield: 0.80 g * 67% of theory Mp .: 92 β C
Analog werden die nachfolgenden erfindungsgemäßen Verbindungen der Formel I hergestellt, wobei R4 gleich Wasserstoff ist und ein "t" über einer Doppelbindung die trans-Konfiguration dieser Doppelbindung bedeutet. TabelleThe following compounds of the formula I according to the invention are prepared analogously, where R 4 is hydrogen and a “t” over a double bond means the trans configuration of this double bond. table
Die nachfolgenden Anwendungsbeispiele erläutern die Erfindung:The following application examples explain the invention:
Anwendungsbeispiele:Examples of use:
Es bedeuter 1It means 1
ALOMY Alopecurus myosuroidesALOMY Alopecurus myosuroides
AGRRE Elymus repensAGRRE Elymus repens
AVEFA Avena fatuaAVEFA Avena fatua
SETVI Setaria viridisSETVI Setaria viridis
PANSS Panicum sp.PANSS Panicum sp.
SORHA Sorghum halepenseSORHA Sorghum halepense
ECHCG Echinochloa crus-galliECHCG Echinochloa crus-galli
DIGSA Digitaria sanguinalisDIGSA Digitaria sanguinalis
POAAN Poa annuaPOAAN Poa annua
LOLMU Lolium multiflorumLOLMU Lolium multiflorum
ABUTH Abutilon theophrastiABUTH Abutilon theophrasti
GALAP Galium aparineGALAP Galium aparine
PHBPU Pharbitis purpureumPHBPU Pharbitis purpureum
MATCH Matricaria chamomilla POLPE Polygonum sp.MATCH Matricaria chamomilla POLPE Polygonum sp.
VERPE Veronica persicaVERPE Veronica persica
CHEAL Chenopodium albumCHEAL Chenopodium album
AMARE Amaranthus retroflexusAMARE Amaranthus retroflexus
STEME Stellaria mediaSTEME Stellaria media
0 = keine Schädigung0 = no damage
1 = 1 - 24 % Schädigung1 = 1 - 24% damage
2 = 25 - 74 % Schädigung2 = 25 - 74% damage
3 = 75 - 89 % Schädigung3 = 75 - 89% damage
4 = 90 - 100 % Schädigung4 = 90 - 100% damage
Im Gewächshaus wurden die aufgeführten Pflanzenspezies nach dem Auflaufen mit den aufgeführten Verbindungen in einer Aufwandmenge von 0,03 kg Wirkstoff/ha behandelt. Die Verbindungen wurden zu diesem Zweck als Emulsion mit 500 Litern Wasser/ha gleichmäßig über die Pflanzen versprüht. Hier zeigten 2 Wochen nach der Behandlung die erfindungsgemäßen Verbindungen eine ausgezeichnete Wirkung gegen das Unkraut, wie aus nachfolgender Tabelle zu ersehen ist.In the greenhouse, the listed plant species were treated with the listed compounds at a rate of 0.03 kg of active ingredient / ha after emergence. For this purpose, the compounds were sprayed evenly over the plants as an emulsion with 500 liters of water / ha. Here, the compounds according to the invention showed an excellent action against the weeds 2 weeks after the treatment, as can be seen from the table below.

Claims

Patentansprüche claims
1. Substituierte Pyrazolyl-pyrazole der allgemeinen Formel I1. Substituted pyrazolyl-pyrazoles of the general formula I
in derin the
R1 CrC4-Alkyl,R 1 C r C 4 alkyl,
R2 CrC4-Alkyi, CrC4-Alkylthio, C1-C4-Alkylsulfinyl, CrC4-Alkylsulfonyl, CrC4-R 2 C r C 4 alkyl, C r C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C r C 4 alkylsulfonyl, C r C 4 -
Alkoxy, oder ein- oder mehrfach durch Halogen substituiertes C1-C4-Alkyl,Alkoxy, or C 1 -C 4 alkyl which is mono- or polysubstituted by halogen,
CrC4-Alkylthio, CrC4-Alkylsulfonyl oder CrC4-Alkoxy, R1 und R2 gemeinsam die Gruppe -(CH2)m- bilden, R3 Wasserstoff oder Halogen, R4 Wasserstoff oder C1-C4-Alkyl, R5 Wasserstoff, Nitro, Cyano, -COOR7, die GruppeC r C 4 alkylthio, C r C 4 alkylsulfonyl or C r C 4 alkoxy, R 1 and R 2 together form the group - (CH 2 ) m -, R 3 is hydrogen or halogen, R 4 is hydrogen or C 1 -C 4 alkyl, R 5 hydrogen, nitro, cyano, -COOR 7 , the group
R° eine der GruppenR ° one of the groups
Λ Λ
R7, R8 und R9 unabhängig voneinander Wasserstoff oder CrC4-Alkyl,R 7 , R 8 and R 9 independently of one another are hydrogen or C r C 4 alkyl,
R8 und R9 gemeinsam mit dem benachbarten Stickstoffatom einen 5- oder 6- gliedrigen gesättigten heterocyclischen Ring bilden,R 8 and R 9 together with the adjacent nitrogen atom form a 5- or 6-membered saturated heterocyclic ring,
R10 Wasserstoff, Cj-C^-Alkyl, ein- oder mehrfach durch Halogen substituiertes CrC4-Alkyl,R 10 is hydrogen, C j -C ^ alkyl, mono- or polysubstituted by halogen, C r C 4 alkyl,
R11 C5-C8-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl, C3-C6-Alkinyl, ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Hydroxy oder C^C^AIkoxy substituiertes C1-C6-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl oder C3-C6-Alkinyl, ein- oder mehrfach durch Sauerstoff unterbrochenes C2-C8-Alkyl, C3-C8-Cycloalkyl, C3-C8-Cycloalkyl-CrC4-alkyl, C3-C8-Alkenyl oder C3-C8-Alkinyl, C1-C4-Alkoxycarbonyl-C1-C4-alkyl, welches gegebenenfalls durch Halogenatome substituiert sein kann, oder C1-C4-Alkoxycarbonyl-C2-C4-alkenyl, welches gegebenenfalls durch Halogen substituiert ist, oder die Gruppe -(CH2)p-NR8R9 sein kann,R 11 is C 5 -C 8 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, one or more times identically or differently by halogen, cyano, hydroxy or C ^ C 1 -C 6 substituted C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, C 2 -C 8 alkyl interrupted one or more times by oxygen , C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-C r C 4 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl, which can optionally be substituted by halogen atoms, or C 1 -C 4 alkoxycarbonyl-C 2 -C 4 alkenyl, which is optionally substituted by halogen, or the group - (CH 2 ) p -NR 8 R 9 can be
R12 und R13 unabhängig voneinander Wasserstoff, Halogen, C1-C4-Alkyl, C2-C4- Alkenyl, C3-C4-Alkinyl oder C^C^AIkoxy, ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Carboxy, Hydroxy, C1-C4-Alkoxy oder CrC4-Alkoxycarbonyl substituiertes CrC4-Alkyl, C2-C4-Alkenyl oder C3-C4-Alkinyl, 14R 12 and R 13 independently of one another are hydrogen, halogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 3 -C 4 -alkynyl or C 1 -C 4 -alkoxy, one or more times identically or differently by halogen , Cyano, carboxy, hydroxy, C 1 -C 4 alkoxy or C r C 4 alkoxycarbonyl substituted C r C 4 alkyl, C 2 -C 4 alkenyl or C 3 -C 4 alkynyl, 14
A Cyano, oder A cyano, or
R14 und R15 unabhängig voneinander Wasserstoff, C1-C6-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl oder C3-C6-Alkinyl, ein ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Hydroxy oder CrC4-Alkoxy substituiertes CrC6-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl oder C3-C6- Alkinyl, ein ein- oder mehrfach durch Sauerstoff unterbrochenes C2-C8-Alkyl, C3-C8-Cycloalkyl, C2-C8-Alkenyl oder C3-C8-Alkinyl, CrC4-Alkoxycarbonyl- CrC4-alkyl, welches gegebenenfalls durch Halogen substituiert sein kann, C1-C4-Alkoxycarbonyl-C2-C4-alkenyl, welches gegebenenfalls durch Halogen substituiert sein kann, oder Cj-C^AIkoxycarbonyl,R 14 and R 15 independently of one another hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, one or more times the same or different Halogen, cyano, hydroxy or C r C 4 alkoxy substituted C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, one or more times Oxygen interrupted C 2 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl or C 3 -C 8 alkynyl, C r C 4 alkoxycarbonyl C r C 4 alkyl, which optionally may be substituted by halogen, C 1 -C 4 alkoxycarbonyl-C 2 -C 4 alkenyl, which may be optionally substituted by halogen, or C j ^ -C alkoxycarbonyl,
R14 und R15 gemeinsam mit dem Stickstoffatom einen gesättigten heterocyclischen C3-C6-Ring bilden, der ein- oder mehrfach durch Sauerstoff oder Schwefel unterbrochen sein kann,R 14 and R 15 together with the nitrogen atom form a saturated heterocyclic C 3 -C 6 ring which can be interrupted one or more times by oxygen or sulfur,
R16 Wasserstoff oder CrC4-Alkyl,R 16 is hydrogen or C r C 4 alkyl,
R17 Wasserstoff, CrC4-Alkyl oder Halogen-CrC4-alkyl,R 17 is hydrogen, C r C 4 alkyl or halogen C r C 4 alkyl,
R18, R19, R20, R21, R22 und R24 unabhängig voneinander Wasserstoff, Halogen, CrC4-Alkyl, C2-C4-Alkenyl oder C3-C4-Alkinyl, Carboxy oder CrC4- Alkoxycarbonyl, ein ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Nitro, Hydroxy oder Cj-C^AIkoxy substituiertes CrC4-Alkyl, C2-C4-Alkenyl oder C3-C4-Alkinyl,R 18 , R 19 , R 20 , R 21 , R 22 and R 24 independently of one another hydrogen, halogen, C r C 4 alkyl, C 2 -C 4 alkenyl or C 3 -C 4 alkynyl, carboxy or C r C 4 - alkoxycarbonyl, a mono- or polysubstituted by identical or different halogen, cyano, nitro, hydroxy, or C j ^ -C alkoxy-substituted C r C 4 alkyl, C 2 -C 4 alkenyl or C 3 -C 4 - Alkynyl,
R23 und R25 Wasserstoff, Halogen, CrC4-Alkyl, C2-C4-Alkenyl oder C3-C4-Alkinyl, oderR 23 and R 25 are hydrogen, halogen, C r C 4 alkyl, C 2 -C 4 alkenyl or C 3 -C 4 alkynyl, or
R23 und R25 gemeinsam einen gesättigten oder ungesättigten drei- bis achtgliedrigen Ring, gegebenenfalls ein oder mehrere Schwefel- oder Sauerstoffatome enthaltend, bilden,R 23 and R 25 together form a saturated or unsaturated three- to eight-membered ring, optionally containing one or more sulfur or oxygen atoms,
R29 Wasserstoff oder Halogen,R 29 is hydrogen or halogen,
R31 Wasserstoff, CrC4-Alkyl, C5-C8-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl, C3- C6-Alkinyl, ein ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Hydroxy oder C1-C4-Alkoxy substituiertes C^Cρ-Alkyl, C3-C6- Cycloalkyl, C2-C6-Alkenyl oder C3-C6-Alkinyl, ein ein- oder mehrfach durch Sauerstoff unterbrochenes C2-C8-Alkyl, C3-C8-Cycloalkyl, C3-C8-Cycloalkyl- CrC4-alkyl, C2-C8-Alkenyl oder C3-C8-Alkinyl, CrC4-Alkoxycarbonyl-CrC4- alkyl, welches gegebenenfalls durch Halogen substituiert sein kann, C1-C4-Alkoxycarbonyl-C2-C4-alkenyl, welches gegebenenfalls durch Halogen substituiert sein kann, oder die Gruppe -(CH2)p-NR8R9 , mit der Maßgabe falls R12 und R31 Wasserstoff oder R12 Wasserstoff und R31 CrC4-Alkyl sind, kann R13 nicht Wasserstoff oder Halogen sein,R 31 is hydrogen, C r C 4 alkyl, C 5 -C 8 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 - C 6 alkynyl, one or more times the same or C 1 -C 4 -alkyl, C 3 -C 6 - substituted differently by halogen, cyano, hydroxy or C 1 -C 4 alkoxy Cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, a C 2 -C 8 alkyl interrupted one or more times by oxygen, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl- C r C 4 alkyl, C 2 -C 8 alkenyl or C 3 -C 8 alkynyl, C r C 4 alkoxycarbonyl-C r C 4 alkyl, which may optionally be substituted by halogen, C 1 -C 4 -Alkoxycarbonyl-C 2 -C 4 -alkenyl, which may optionally be substituted by halogen, or the group - (CH 2 ) p -NR 8 R 9 , with the proviso that if R 12 and R 31 are hydrogen or R 12 is hydrogen and R 31 C r C 4 alkyl, R 13 can not be hydrogen or halogen,
R32 Wasserstoff, CrC6-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl, C3-C6-Alkinyl, ein ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Hydroxy oder CrC4-Alkoxy substituiertes C1-C6-Alkyl, C3-C6-Cycloalkyl, C2-C6- Alkenyl oder C3-C6-Alkinyl, ein ein- oder mehrfach durch Sauerstoff unterbrochenes C2-C8-Alkyl, C3-C8-Cycloalkyl, C2-C8-Alkenyl oder C3-C8- Alkinyl, C1-C4-Alkoxycarbonyl-C1-C4-alkyl, welches gegebenenfalls durch Halogen substituiert sein kann, C1-C4-Alkoxycarbonyl-C2-C4-alkenyl, welches gegebenenfalls durch Halogen substituiert sein kann, m 3 oder 4, n 0, 1 , 2 oder 3, o 1, 2 oder 3, p 2, 3 oder 4 undR 32 is hydrogen, C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, one or more times the same or different by halogen, cyano, hydroxy or C r C 4 alkoxy substituted C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, a C 2 - which is interrupted once or several times by oxygen C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl or C 3 -C 8 alkynyl, C 1 -C 4 alkoxycarbonyl-C 1 -C 4 alkyl, which is optionally substituted by halogen can be C 1 -C 4 alkoxycarbonyl-C 2 -C 4 alkenyl, which may optionally be substituted by halogen, m 3 or 4, n 0, 1, 2 or 3, o 1, 2 or 3, p 2 , 3 or 4 and
X Sauerstoff oder Schwefel bedeuten.X is oxygen or sulfur.
2. Substituierte Pyrazolyl-pyrazole der allgemeinen Formel I, in der2. Substituted pyrazolyl-pyrazoles of the general formula I in which
R1 Methyl,R 1 is methyl,
R2 Difluormethoxy,R 2 difluoromethoxy,
R1 und R2 gemeinsam die Gruppe -(CH2)4- bilden,R 1 and R 2 together form the group - (CH 2 ) 4 -,
R3 Chlor oder Brom,R 3 chlorine or bromine,
R4 Wasserstoff,R 4 is hydrogen,
R5 Nitro oder Cyano, R6 eine der GruppenR 5 nitro or cyano, R 6 one of the groups
R11 C5-C8-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkenyl, C3-C6-Alkinyl, ein ein- oder mehrfach durch Sauerstoff unterbrochenes C2-C8-Alkyl, C3-C8-Cycloalkyl, C3-C8-Alkenyl oder C3-C8-Alkinyl,R 11 is C 5 -C 8 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 3 -C 6 alkynyl, a C 2 -C 8 alkyl interrupted one or more times by oxygen, C 3 -C 8 cycloalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl,
R12 Wasserstoff oder Methyl,R 12 is hydrogen or methyl,
R13 Wasserstoff oder Methyl,R 13 is hydrogen or methyl,
R16 Wasserstoff,R 16 is hydrogen,
R17 Wasserstoff,R 17 is hydrogen,
R18, R19, R20, R21, R22 R23, R24 und R25 unabhängig voneinander Wasserstoff, Halogen oder C^C-j-Alkyl,R 18, R 19, R 20, R 21, R 22 R 23, R 24 and R 25 are independently hydrogen, halogen or C ^ C- j alkyl,
R23 und R25 gemeinsam einen gesättigten durch ein Sauerstoffatom unterbrochenen 3-atomigen Ring bilden,R 23 and R 25 together form a saturated 3-atom ring interrupted by an oxygen atom,
R29 Wasserstoff oder Halogen,R 29 is hydrogen or halogen,
R31 Wasserstoff, CrC4-Alkyl, C5-C8-Alkyl, C3-C6-Cycloalkyl, C2-C6-Alkθnyl, C3- C6-Alkinyl, ein ein- oder mehrfach gleich oder verschieden durch Halogen, Cyano, Hydroxy oder CrC4-Alkoxy substituiertes CrC6-Alkyl, C3-C6- Cycloalkyl, C2-C6-Alkenyl oder C3-C6-Alkinyl, mit der Maßgabe falls R12 und R31 Wasserstoff oder R12 Wasserstoff und R31 CrC4-Alkyl sind, kann R13 nicht Wasserstoff sein, X Sauerstoff bedeuten, und n O und o 1 oder 2 sind.R 31 is hydrogen, C r C 4 alkyl, C 5 -C 8 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkynyl, C 3 - C 6 alkynyl, one or more times the same or differently substituted by halogen, cyano, hydroxy or C r C 4 alkoxy, C r C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl or C 3 -C 6 alkynyl, with the proviso if R 12 and R 31 are hydrogen or R 12 is hydrogen and R 31 is C r C 4 alkyl, R 13 cannot be hydrogen, X is oxygen and n is O and o is 1 or 2.
3. Mittel mit herbizider Wirkung, gekennzeichnet durch einen Gehalt an mindestens einer Verbindung gemäß den Ansprüchen 1 oder 2.3. Agents with herbicidal activity, characterized by a content of at least one compound according to claims 1 or 2.
4. Mittel mit herbizider Wirkung gemäß Anspruch 3, in Mischung mit Träger¬ und/oder Hilfsstoffen.4. Agents with herbicidal activity according to claim 3, in a mixture with vehicles and / or auxiliaries.
5. Verwendung von Verbindungen gemäß den Ansprüchen 1 oder 2 zur Bekämpfung monokotyler und dikotyler Unkrautarten in landwirtschaftlichen Hauptkulturen. 5. Use of compounds according to claims 1 or 2 for combating monocotyledonous and dicotyledonous weed species in main agricultural crops.
EP97924005A 1996-06-06 1997-05-26 Substituted pyrazolyl-pyrazole derivatives and their use as herbicides Withdrawn EP0906287A1 (en)

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PCT/EP1997/002690 WO1997046536A1 (en) 1996-06-06 1997-05-26 Substituted pyrazolyl-pyrazole derivatives and their use as herbicides

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AU2003265394A1 (en) * 2002-08-14 2004-03-03 Ppd Discovery, Inc. Prenylation inhibitors containing dimethyl-cyclobutane and methods of their synthesis and use
WO2004016592A1 (en) * 2002-08-14 2004-02-26 Ppd Discovery, Inc. Prenylation inhibitors and methods of their synthesis and use
US6649638B1 (en) * 2002-08-14 2003-11-18 Ppd Discovery, Inc. Prenylation inhibitors and methods of their synthesis and use
JP2010502788A (en) * 2006-09-01 2010-01-28 ザ ルブリゾル コーポレイション Lubricating composition
US20110009463A1 (en) * 2007-10-17 2011-01-13 Yuri Karl Petersson Geranylgeranyl transferase inhibitors and methods of making and using the same
AR103468A1 (en) * 2015-01-23 2017-05-10 Kyoyu Agri Co Ltd DERIVED FROM SUBSTITUTED PIRAZOLILPIRAZOL AND ITS EMPLOYMENT AS A HERBICIDE
AR103467A1 (en) * 2015-01-23 2017-05-10 Kyoyu Agri Co Ltd DERIVED FROM SUBSTITUTED PIRAZOLILPIRAZOL AND ITS EMPLOYMENT AS A HERBICIDE
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TW201630908A (en) * 2015-01-23 2016-09-01 協友股份有限公司 Substituted pyrazolylpyrazole derivative and use of same as herbicide
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