WO2003076409A1 - Derives de 1-phenyl-3-phenylpyrazole utilises comme herbicides - Google Patents

Derives de 1-phenyl-3-phenylpyrazole utilises comme herbicides Download PDF

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WO2003076409A1
WO2003076409A1 PCT/EP2003/002646 EP0302646W WO03076409A1 WO 2003076409 A1 WO2003076409 A1 WO 2003076409A1 EP 0302646 W EP0302646 W EP 0302646W WO 03076409 A1 WO03076409 A1 WO 03076409A1
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halogen
ocf3
independently
alkyl
compound
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PCT/EP2003/002646
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English (en)
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Michel Muehlebach
Roman Fisera
Milan Karvas
Hermann Rempfler
Hans-Georg Brunner
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Syngenta Participations Ag
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Priority to AU2003218758A priority Critical patent/AU2003218758A1/en
Publication of WO2003076409A1 publication Critical patent/WO2003076409A1/fr

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    • 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
    • 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
    • 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
    • C07D231/16—Halogen atoms or nitro radicals

Definitions

  • the present invention relates to novel herbicidally active 1 ,3-diphenylpyrazoles, 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.
  • Substituted 1 ,5-diphenylpyrazoles are described, for example, in EP-A-268 554.
  • Substituted 1 ,3-diphenylpyrazoles are also known from Tetrahedron Lett. 2000, 41 , 4713-16. No reference is made to those compounds having biological activity, however.
  • the present invention accordingly relates to compounds of formula I
  • Ri and R 2 are each independently of the other C h alky!, C-*. 6 haloalkyl, C-*- 6 alkoxy, d- ⁇ halo- alkoxy, C-*- 6 alkylthio, d-ehaloalkylthio, C ⁇ .
  • R 9 , R 10 , Rn and R 12 are each independently of the others hydrogen, C ⁇ - 4 alkyl, C ⁇ . 4 - haloalkyl, C 3 . 6 cycloalkyl, C 2 . alkenyl, C 2 . 4 haloalkenyl, C 2 . 3 alkynyl, benzyl or phenyl, and R-* 0 may additionally be an alkali metal or alkaline earth metal, ammonium, a quaternary ammonium base or an amine, or
  • R ⁇ and R 12 together are C 2 . 5 alkylene, p is 0 or 1 ,
  • R 4 and R 6 are each independently of the other hydrogen, C ⁇ alkyl, d shaloalkyl or halogen, or
  • R 4 and R 6 together form a chemical bond
  • R 4 and R 6 together form a radical -CH 2 - or -CH 2 CH 2 -, which may be substituted by d ⁇ alkyl, d- 3 haloalkyl or by halogen, and
  • R 5 , R 7 and R 8 are each independently of the others hydrogen, d- 4 alkyl, d- 3 haloalkyl or halogen, and to enantiomers, and also to configurationally pure E or Z compounds as well as to
  • the alkyl groups appearing in the substituent definitions may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert- butyl.
  • the alkenyl radicals may be mono- or poly-unsaturated. Halogen is preferably fluorine, bromine or especially chlorine.
  • the radicals R 4 and R 6 may together form a chemical bond, so that a double bond is formed between the carbon atoms to which those radicals are bonded.
  • the present invention then includes both the configurationally pure E or Z compounds and E/Z mixtures.
  • radicals R 4 and R 6 together form a -CH 2 - or -CH 2 CH 2 - group, then together with the carbon atoms to which those radicals are bonded there is formed a three- or four-membered carbocyclic ring in the side chain which may be further substituted by C h alky!, d- 3 haloalkyl or by halogen.
  • Two adjacent R* ⁇ radicals or two adjacent R 2 radicals may together form a d- 3 alkylene chain and thus, together with the carbon atoms to which they are bonded, form a three- to five-membered carbocyclic ring.
  • Such rings may additionally contain one or two oxygen atoms, but two oxygen atoms cannot be adjacent to one another.
  • the resulting heterocyclic rings and also the said carbocyclic rings can be further substituted by halogen.
  • Benzyl and phenyl radicals may be in substituted form.
  • suitable substituents are halogen, d- alkyl, C ⁇ - 4 haloalkyl, d. alkoxy, C ⁇ alkyl- sulfonyl, -CN and -NO 2 .
  • Preferred alkali metal and alkaline earth metal atoms are sodium, potassium, calcium and magnesium.
  • Suitable quaternary ammonium bases are mono-, di-, tri- or tetra-alkylammonium and also corresponding hydroxyalkylammonium compounds, the alkyl radicals preferably containing from 1 to 6 carbon atoms. Accordingly, preferred amines have such alkyl and/or hydroxyalkyl substituents.
  • Enantiomers of the compounds of formula I can be formed by virtue of asymmetric centres which may be present in the molecule.
  • Preferred compounds of formula I are those wherein at least one of the substituents R , R 5) R 6 , R 7 and R 8 is halogen.
  • a further group of preferred compounds of formula I comprises those wherein R 4 and R 6 together form a chemical bond, special importance being attached to those compounds wherein R 8 is halogen, and especially to those wherein R 7 and R 8 are halogen.
  • R 4 and R 6 together form a chemical bond
  • m is 1
  • R occupies the meta-position of the phenyl ring
  • R 5 , R 7 and R 8 are as defined above.
  • R 4 and R 6 together form a chemical bond
  • m 2
  • the two R-* substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring
  • R 5 , R 7 and R 8 are each independently of the others hydrogen or halogen
  • p is 1 and R 3 is d- alkyl > C 2 -3alkynyl, halogen or -CN.
  • R and R 6 together form a chemical bond
  • n is 1
  • R 2 occupies the meta-position of the phenyl ring
  • R 5 , R 7 and R 8 are as defined above.
  • R 4 and R 6 together form a chemical bond
  • n is 2
  • the two R 2 substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring
  • R 5 , R 7 and R 8 are as defined above.
  • R 4 and R 6 together form a chemical bond
  • n is 1
  • R 2 occupies the meta- position of the phenyl ring
  • R 5 is each independently of the others hydrogen or halogen
  • p is 0.
  • R 4 and R 6 together form a chemical bond
  • n is 2
  • the two R 2 substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring
  • R 5 , R 7 and R 8 are each independently of the others hydrogen or halogen
  • p is O.
  • the sum of m + n is greater than or equal to 1.
  • the compounds of formula I can be prepared by means of processes known perse, for example those described in the following Schemes 1 to 4, for example by aiming to synthes- ise the 4- or 5-formylpyrazole intermediate, which can then be further modified en route to the end product (see Schemes 1 , 3 and 4), or instead taking the route by way of the appropriately substituted arylpentadienone intermediate (see Scheme 2).
  • Substituents R-* to R 12 in the Schemes are as defined above.
  • Compounds 6 are suitable as starting compounds for the synthesis of the compounds of formula I.
  • Compounds of formula I wherein the group (R 8 R 7 R 6 )C(R 5 R 4 )C- is to occupy the 5-position of the pyrazole ring are obtained by metallation of compounds 6 wherein Y is H or halogen using a customary metallating reagent, such as n-, sec- or tert- butyllithium or i-PrMgCI or (i-Pr) 2 Mg, optional transmetallation with a reagent such as e.g.
  • the metallated compounds 6 are reacted with, for example, B(OR') 3 , CISnR' 3 or CISiR' 3 and the new products 6_wherein Y is B(OR') 2 , SnR' 3 or SiR' 3 , R' being lower alkyl, are first isolated, optionally subjected to modification (for example hydrolysis of the boric acid ester to form the organoboric acid), and then, optionally in the presence of a Pd or Ni catalyst, reacted with a compound of the formula (R 8 R 7 R 6 )C(R 5 R )C-Q wherein Q is a halogen atom or a radical of the formula -0-SO 2 CF 3 .
  • the radical (R 8 R 7 R 6 )C(R 5 R 4 )C- may already be present in the compound (R 8 R 7 R 6 )C(R 5 R 4 )C-Q, or the substituents R 8 , R 7 , R 6 , R 5 or R 4 are introduced at a later stage by methods known perse.
  • compounds of formula I in which the group (R 8 R 7 R 6 )C(R 5 R 4 )C- is to occupy the 5-position of the pyrazole ring can also be obtained by reaction of compounds 6 wherein Y is halogen or a radical of the formula -O-SO 2 CF 3 (-OTf) (Heck reaction) or wherein Y is -N 2 + (Matsuda reaction), optionally in the presence of a Pd or Ni catalyst, with an olefin to form the compounds 7.
  • the compounds 6 wherein Y is H or halogen are converted by direct metallation or by means of a halogen-metal exchange, with, for example, n-butyl- lithium, into the corresponding organometal compounds, followed by quenching either with a CHO-donor, such as DMF, 1 -formylpiperidine, methyl formate or ethyl formate, or with a compound of the formula R 5 CO-L wherein L is a leaving group, such as halogen, -OMe or -OEt (Step 5).
  • a CHO-donor such as DMF, 1 -formylpiperidine, methyl formate or ethyl formate
  • L is a leaving group, such as halogen, -OMe or -OEt
  • the compounds 9 are obtained from 8 under conditions other than Wittig conditions by carrying out a reaction with (b) a compound of formula R 7 R 8 CXH wherein X is halogen in the presence of a base, for example KOH or DBU (1 ,8-diazabicyclo[5.4.0]undec-7-ene) (see V.K. Aggarwal et al., J. Org. Chem.
  • the intermediate carbinols of formula 6 wherein Y is (R 7 R 8 CX)-(R 5 )C(OH)- which are initially formed in this variant (b) are acylated in a one-pot process with the addition of, for example, acetic anhydride, and the acylated intermediate carbinols of formula 6 wherein Y is (R 7 R 8 CX)-(R 5 )C(OCOCH 3 )- are finally reduced to form the compounds 9, with dilution with e.g. acetic acid and addition of zinc, magnesium or sodium.
  • Dihalovinyl compounds 9 can accordingly be obtained, for example, by Pd- or Ni-catalysed reaction of trichloroethylene with a metallated form of the compounds 6, as described, for example, by G.
  • Compounds 6 wherein Y is trifluoromethanesulfon- ate (triflate) can also be obtained from compounds 3 (J. Fluorine Chem. 02, 135, 2000).
  • the compounds 3 are obtainable by customary condensation of the keto esters 1 with the arylhydrazines 2 (Step 1 a) in solvents such as acetic acid, methanol, ethanol or toluene, optionally in the presence of catalytic amounts of acid, e.g. HCI, H 2 SO , p-TsOH.
  • the compounds 6 can also be obtained by Sandmeyer reaction of the aminopyrazoles 5 (Step 3) either under the customary aqueous conditions (e.g. NaNO 2 , HCI, CuCI or NaNO 2 , AcOH/H 2 SO 4 , Cu 2 0, EtOH for reductive deamination) or under anhydrous conditions such as t-BuONO, Cul, CH 2 I -
  • Compounds 5 are obtained by condensation of cyanoketones 4 with arylhydrazines 2 (Step 1 b) in various solvents such as acetic acid, methanol, ethanol or toluene, optionally in the presence of catalytic amounts of acid, e.g. HCI, H 2 SO 4 , p-TsOH.
  • the starting compounds 1, 2 and 4 are either known or can be prepared by known methods.
  • Compounds of formula I can also be prepared from the starting compounds 4 (Scheme 2).
  • the aryldihalopentadienones 4 are condensed with appropriately substituted hydrazines 5 (Step 3) to form substituted ⁇ 2 -pyrazolines 6 (A.A. Dudinov et al., Chem. Heterocycl. Cmpd. (Engl. Transl.) 31, 1311 , 1995).
  • That reaction can be carried out in various solvents such as acetic acid, methanol, ethanol or toluene, optionally in the presence of catalytic amounts of acid, e.g.
  • the oxidation to form the corresponding dihalovinylpyrazoles 7 can be carried out under various conditions, e.g. by the use of air, DDQ (J.A. Katzenellenbogen et al., Org. Letters 2, 2833, 2000), chloranil, MnO 2 , KMnO 4 or Phl(OAc) 2 in various solvents such as DMSO, benzene, toluene, xylene, water, acetone or methylene chloride.
  • DDQ J.A. Katzenellenbogen et al., Org. Letters 2, 2833, 2000
  • chloranil MnO 2 , KMnO 4 or Phl(OAc) 2
  • solvents such as DMSO, benzene, toluene, xylene, water, acetone or methylene chloride.
  • the starting compounds 4 are obtainable by aldol condensation of compounds 2 with various aryl alkyl ketones 3 (Step 2) (YN. Maeskii et al., Chem. Heterocycl. Cmpd (Engl. Transl.) 6, 1081 , 1970).
  • Compounds 2 can be obtained by free radical R 8 R 7 CX 2 -addition to vinyl ethers, (Step 1). They are described e.g. in Houben-Weyl, Vol. V/3, p. 973, 1962. It is possible to use free radical starters, for example dibenzoyl peroxide, AIB ⁇ , sodium dithionite (W.-Y. Huang et al., J. Fluorine Chem.
  • the compounds of formula I can also be prepared from compounds 4 (Scheme 3).
  • the compounds 4 are converted into the compounds 5 (Step 3) under conditions as described in Step 6 of Scheme 1.
  • the compounds of formula I can also be prepared from the pyrazolones 6.
  • the preparation of those compounds is illustrated in Scheme 1.
  • the compounds 6 are formylated (Step 5, see DE 2438779) and the aldehyde compounds 7 so obtained are converted into the products 8 under the conditions described for Step 6 in Scheme 1.
  • the compounds of formula I can also be prepared from the compounds 10.
  • the compounds 10 are converted into the compounds 4 (Step 8) under conditions as described in Step 5 of Scheme 1.
  • the compounds 10 are converted into the compounds 5 (Step 9) under conditions as described in Step 7 of Scheme 1.
  • compounds of formula I having a radical (R 8 R 7 R 6 )C(R 5 R )C- in the 4- postion of the pyrazole ring compounds H are obtained from 10 (Step 10) under conditions as described in Step 4 of Scheme 1.
  • the radical (R 8 R 7 R 6 )C(R 5 R 4 )C- may already be present in the starting compound 10, or the substituents R 8 , R 7 , R 6l R5 or R are introduced at a later stage by methods known per se.
  • the compounds 10 can be obtained from the 1 ,3-diphenylpyrazoles 9 by halogenation of the 4-pyrazole position (Step 7) under conditions as described, for example, in Can. J. Chem. 1986, 64, 2211-19.
  • the starting compounds 9 are either known or can be prepared by known methods.
  • the compounds of formula I can also be prepared from compounds 4 by 1 ,3-dipolar cyclo- addition of diphenylnitrile imine, prepared in situ, to alkenes and alkynes to form 1 ,3-di- phenyl- ⁇ 2 -pyrazolines and 1 ,3-diphenylpyrazoles (R. Huisgen et al., Chem. Ber. 776, 3438, 1983; ibid., Tetrahedron 77, 3, 1962) (Scheme 4).
  • the preferred compounds of formula I having a dihalovinyl substituent in the 5-position of the pyrazole ring can be obtained by reaction of the compounds 4 with a base, preferably triethylamine, in the presence of either an alkyne, e.g. propargylaldehyde acetal, or an alkene, e.g. acrolein or acrolein acetal (Step 3).
  • the compounds 5 are then obtainable by hydrolysis or oxidation (under the conditions described in Step 4 of Scheme 2).
  • the compounds 5 can be converted (Step 4) into the products 6 under the conditions described in Step 6 of Scheme 1.
  • the compounds 4 are obtainable by known methods from the hydrazides 3 (Step 2). Those compounds are known per se or can be prepared by customary methods.
  • R-i and R 2 are each independently of the other d. 6 alkyl, d-ehaloalkyl, d- 6 alkoxy, d-ehalo- alkoxy, d- 6 alkylthio, d- 6 haloalkylthio, d- 6 alkylsulfinyl, C ⁇ . 6 haloalkylsulfinyl, d- 6 alkylsulfonyl, d-ehaloalkylsulfonyl, C ⁇ - 8 alkylcarbonyl, d.
  • haloalkylcarbonyl, halogen, -CN, -NO 2 or -SF 5 , or two adjacent R-* substituents or two adjacent R 2 substituents are, independently of one another, d- 3 alkylene, d- 3 alkylene containing 1 or 2 oxygen atoms, there being no oxygen- oxygen bond, C ⁇ - 3 haloalkylene or d.
  • 3 haloalkylene containing 1 or 2 oxygen atoms, there being no oxygen-oxygen bond, m and n are each independently of the other 0, 1 , 2 or 3,
  • R 3 is d- 4 alkyl, C ⁇ . 4 haloalkyl, C ⁇ - 4 alkoxy, C*
  • R 9 , R 10 , R- 11 and R 12 are each independently of the others hydrogen, d- 4 alkyl, d. - haloalkyl, C 3 - 6 cycloalkyl, C 2 - 4 alkenyl, C 2 .
  • R 10 may additionally be an alkali metal or alkaline earth metal, a quaternary ammonium base or an amine, or R- 11 and R- 12 together are C 2 - 5 alkylene, p is 0, 1 , 2 or 3, preferably 0 or 1 ,
  • R 4 and R 6 are each independently of the other hydrogen, d- 4 alkyl, d- 3 haloalkyl or halogen, or
  • R 4 and R 6 together form a chemical bond
  • R 4 and R 6 together form a radical -CH 2 - or -CH 2 CH 2 -, which may be substituted by d- alkyl,
  • R 5 , R 7 and R 8 are each independently of the others hydrogen, C ⁇ - 4 alkyl, C ⁇ . 3 haloalkyl or halogen, at least one of those substituents being other than hydrogen, the compounds of formulae
  • the reactions to form compounds of formula I are advantageously performed in aprotic, inert organic solvents.
  • 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, nitriles, such as aceto- nitrile and propionitrile, amides, such as N,N-dimethylformamide, diethylformamide and N- methylpyrrolidinone.
  • the reaction temperatures are preferably from -78°C to +120°C.
  • the reactions generally proceed slightly exothermically and can generally be carried out at room temperature.
  • the reaction mixture may, if appropriate, be heated for a short time to a temperature up to its boiling point.
  • the reaction times may likewise be shortened by the addition of a few drops of base as reaction catalyst.
  • Suitable bases are especially tertiary amines, such as trimethyl- amine, triethylamine, quinuclidine, 1 ,4-diazabicyclo[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.
  • hydrides e.g. sodium or calcium hydride
  • hydroxides such as sodium or potassium hydroxide
  • carbonates such as sodium or potassium carbonate
  • 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.
  • the compounds of formula I may 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.
  • 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.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers.
  • formulation adjuvants for example solvents or solid carriers.
  • Surface-active compounds surfactants
  • solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO97/34485.
  • surfactants conventionally employed in formulation technology which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., “Tensid-Taschenbuch", Carl Hanser Verlag, Kunststoff/Vienna 1981 , and M. 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.
  • a surfactant especially from 0.1 to 25 % by weight
  • compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • stabilisers for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • 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.
  • 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 may 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.
  • 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.
  • 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 may be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon,
  • Example P1 Preparation of 4-(2,2-dichlorovinyl)-1 -(2,4-difluorophenyl)-3-(3-trifluoro- methylphenyl)-1 H-pyrazole (3)
  • Step 1 Preparation of ⁇ /-(2,4-dif luorophenyl)- ⁇ / '-[1 -(3-trifluoromethylphenyl)-ethylidene]- hydrazine (1 )
  • Step 2 Preparation of 1 -(2,4-dif luorophenyl)-3-(3-trif luoromethylphenyl)-1 H-pyrazole-4- carbaldehyde (2)
  • reaction mixture is discharged into ice/water and adjusted to a pH value of 7 with concentrated NaOH; the resulting suspension is briefly cooled, then filtered and washed with water. The precipitate is dried. 11.3 g (95% of theory) of the aldehyde (2) are obtained in the form of a solid having a melting point of 55-57°C.
  • Step 3 Preparation of 4-(2,2-dichlorovinyl)-1-(2,4-difluorophenyl)-3-(3-trifluoromethyl- phenyl)-1 H-pyrazole (3)
  • Step 1 Preparation of 3-(4-chlorophenyl)-1 -(3-trif luoromethylphenyl)-1 H-pyrazole-4- carbaldehyde (4)
  • Step 2 Preparation of 3-(4-chlorophenyl)-4-(2,2-dichlorovinyl)-1-(3-trifluoromethylphenyl)- 1 H-pyrazole (5)
  • the cooled reaction mixture is clarified by filtration and the filtrate is concentrated by evaporation.
  • the residue is purified by means of preparative HPLC on silica gel (gradient ethyl acetate/hexane from 9% to 100%) and the product is crystallised from hexane with the addition of a small amount of ethyl acetate. 780 mg (16% of theory) of the dichlorovinyl- pyrazole (5) are obtained in the form of a solid having a melting point of 94-96°C.
  • Example P3 Preparation of 1 -(3-chlorophenyl)-5-(2,2-dichlorovinyl)-3-(4-trifluoromethyl- phenyl)-1 H-pyrazole (8)
  • Step 1 Preparation of ethyl-(1 ,3,3,3-tetrachloropropyl) ether (6)
  • Step 2 Preparation of 5,5-dichloro-1 -(4-trif luoromethylphenyl)-penta-2,4-dien-1 -one (7)
  • Step 3 Preparation of 1 -(3-chlorophenyl)-5-(2,2-dichlorovinyl)-3-(4-trifluoromethyl- phenyl)-1 H-pyrazole (8)
  • Example P4 Preparation of 3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1 -(3-trifluoromethyl- phenyl)-4.5-dihydro-1 H-pyrazole (10) and 3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1-(3- trifluoromethylphenyl)-1 H-pyrazole (11)
  • Step 1 Preparation of 5,5-dichloro-1 -(4-chlorophenyl)-penta-2,4-dien-1 -one (9)
  • Step 2 Preparation of 3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1 -(3-trif luoromethylphenyl)- 4,5-dihydro-1 H-pyrazole (10) and 3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1-(3-tri- fluoromethylphenyl)-1 H-pyrazole (11 )
  • Example P6 Preparation of 3-(4-chlorophenyl)-5-(2.2-dibromovinyl)-1 -(3-trif luoromethyl- phenvD-1 H-pyrazole (16) and 5-(2,2-difluorovinyl)-3-(4-fluorophenyl)-1-(3-trifluoromethyl- phenyl)-1 H-pyrazole (17)
  • Step 1 Preparation of 5-(4-chlorophenyl)-2-(3-trifluoromethylphenyl)-2,4-dihydro-pyrazol- 3-one (13)
  • the reaction mixture is completely concentrated, the residue is taken up in saturated Na 2 CO 3 solution and the aqueous phase is extracted with ethyl acetate. The organic phase is dried over sodium sulfate, filtered and concentrated by evaporation.
  • the product is partially crystallised from ethyl acetate/hexane 1 :1 (5.7 g).
  • the mother liquor is purified by column chromatography on silica gel using hexane/ethyl acetate 4:1 (2.45 g). In total, 8.15 g (45% of theory) of the pyrazolone (13) are obtained in the form of a solid having a melting point of 173-174°C.
  • Step 2 Preparation of 5-bromo-3-(4-chlorophenyl)-1 -(3-trif luoromethylphenyl)-1 H-pyrazole (14)
  • the reaction mixture is slowly discharged into ice/water, the organic phase is separated off and the aqueous phase is extracted with ethyl acetate; the combined organic phases are washed with water, then dried over sodium sulfate, filtered and concentrated by evaporation.
  • the residue is purified by means of preparative HPLC on silica gel (gradient ethyl acetate/hexane from 9% to 100%). 1.09 g (54% of theory) of the bromo-pyrazole (14) are obtained in the form of a viscous oil.
  • Step 4 Preparation of 3-(4-chlorophenyl)-5-(2,2-dibromovinyl)-1 -(3-trif luoromethylphenyl)- 1 H-pyrazole (16)
  • triphenylphosphine 950 mg are added in portions to a solution, cooled to -20°C, of 210 mg of aldehyde (15) (Example P6, Step 3) and 600 mg of carbon tetrabromide in 10 ml of methylene chloride.
  • the reaction mixture is stirred at from -20°C to -30°C for one hour.
  • Saturated sodium chloride solution is added to the reaction mixture; the organic phase is separated off and the aqueous phase is extracted with methylene chloride.
  • the combined organic phases are dried over sodium sulfate, filtered and concentrated by evaporation.
  • Step 5 Preparation of 5-(2,2-difluorovinyl)-3-(4-fluorophenyl)-1 -(3-trifluoromethylphenyl)- 1 H-pyrazole (17)
  • Step 1 Preparation of 5-(4-chlorophenyl)-2-(3-trifluoromethylphenyl)-2H-pyrazol-3-yl- amine (18)
  • reaction mixture is completely concentrated and the residue is caused to crystallise by azeotropic treatment with toluene (4x 20 ml) and diethyl ether (3x 20ml).
  • 14.0 g (97% of theory) of the aminopyrazole (18) are obtained in the form of a solid having a melting point of 128-130°C, which is used in the next reaction without further purification.
  • Step 3 Preparation of 3-(4-chlorophenyl)-1 -(3-trif luoromethylphenyl)-5-vinyl-1 H-pyrazole (20)
  • reaction mixture is completely concentrated and the residue is purified by column chromatography on silica gel using hexane/ethyl acetate 9:1. 110 mg (78% of theory) of the vinyl-pyrazole (20) are obtained in the form of a solid having a melting point of 97-99°C.

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Abstract

L'invention concerne des composés représentés par la formule I, dans laquelle les substituants sont définis selon la revendication 1. Ces composés peuvent être utilisés comme herbicides.
PCT/EP2003/002646 2002-03-14 2003-03-13 Derives de 1-phenyl-3-phenylpyrazole utilises comme herbicides WO2003076409A1 (fr)

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JPWO2007010731A1 (ja) * 2005-07-15 2009-01-29 Jsr株式会社 含窒素芳香族化合物およびその製造方法、重合体およびプロトン伝導膜
US7714014B2 (en) 2005-12-09 2010-05-11 The Regents Of The University Of California Targeting GLI proteins in human cancer by small molecules
US8188083B2 (en) 2007-06-28 2012-05-29 Abbott Laboratories Triazolopyridazines
WO2013039990A1 (fr) 2011-09-13 2013-03-21 Monsanto Technology Llc Procédés et compositions de lutte contre les mauvaises herbes
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US10968449B2 (en) 2015-01-22 2021-04-06 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10988764B2 (en) 2014-06-23 2021-04-27 Monsanto Technology Llc Compositions and methods for regulating gene expression via RNA interference
US11091770B2 (en) 2014-04-01 2021-08-17 Monsanto Technology Llc Compositions and methods for controlling insect pests
CN114560811A (zh) * 2022-03-11 2022-05-31 中国药科大学 1,3,5-三取代-吡唑-4羧酸衍生物及其制备方法和应用
WO2023202545A1 (fr) * 2022-04-22 2023-10-26 西北农林科技大学 Utilisation d'un composé de diphényl pyrazole en tant que synergiste désherbant
US11807857B2 (en) 2014-06-25 2023-11-07 Monsanto Technology Llc Methods and compositions for delivering nucleic acids to plant cells and regulating gene expression

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1377247A (en) * 1971-04-19 1974-12-11 Ciba Geigy Ag Pyrazoline compounds as optical brighteners
US4746354A (en) * 1985-03-16 1988-05-24 Bayer Aktiengesellschaft 4-nitro-1-phenylpyrazoles, composition containing them, and method of using them to combat unwanted vegetation
DE3817298A1 (de) * 1987-05-22 1988-12-01 Squibb & Sons Inc Phosphorhaltige hmg-coa-reduktase-inhibitoren, verfahren zu ihrer herstellung, ihre verwendung und neue zwischenprodukte
WO1993025535A1 (fr) * 1992-06-11 1993-12-23 Rhone Poulenc Agriculture Ltd. Pyrazole-(thio)-carboxamides herbicides
WO1998005649A1 (fr) * 1996-08-01 1998-02-12 Basf Aktiengesellschaft 3-phenylpyrazoles substitues
WO1998024767A1 (fr) * 1996-12-05 1998-06-11 Pfizer Limited Pyrazoles antiparasitaires

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1377247A (en) * 1971-04-19 1974-12-11 Ciba Geigy Ag Pyrazoline compounds as optical brighteners
US4746354A (en) * 1985-03-16 1988-05-24 Bayer Aktiengesellschaft 4-nitro-1-phenylpyrazoles, composition containing them, and method of using them to combat unwanted vegetation
DE3817298A1 (de) * 1987-05-22 1988-12-01 Squibb & Sons Inc Phosphorhaltige hmg-coa-reduktase-inhibitoren, verfahren zu ihrer herstellung, ihre verwendung und neue zwischenprodukte
WO1993025535A1 (fr) * 1992-06-11 1993-12-23 Rhone Poulenc Agriculture Ltd. Pyrazole-(thio)-carboxamides herbicides
WO1998005649A1 (fr) * 1996-08-01 1998-02-12 Basf Aktiengesellschaft 3-phenylpyrazoles substitues
WO1998024767A1 (fr) * 1996-12-05 1998-06-11 Pfizer Limited Pyrazoles antiparasitaires

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
BULLETIN DE LA SOCIETE CHIMIQUE DE FRANCE (1980), (5-6, PT. 2), 309-15 *
CHEM. BER., vol. 116, no. 10, 1983, pages 3438 - 3460 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; PASHKEVICH, K. I. ET AL: "Fluoroalkyl -containing mono- and bispyrazoles", XP002244093, retrieved from STN Database accession no. 94:192214 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; PEGLION, JEAN LOUIS ET AL: "Synthesis of perfluoroalkylpyrazoles: identification by fluorine -19 NMR and comparison with hydrocarbon homologs", XP002244094, retrieved from STN Database accession no. 94:3961 *
DATABASE CROSSFIRE BEILSTEIN [online] Beilstein Institut zur Förderung der Chemischen Wissenschaften, Frankfurt am Main, DE; XP002244095, Database accession no. 959930(BRN) *
DATABASE CROSSFIRE BEILSTEIN [online] Beilstein Institut zur Förderung der Chemischen Wissenschaften, Frankfurt am Main, DE; XP002244096, Database accession no. 923263(BRN) *
J. ORG. CHEM. USSR, vol. 2, 1966, pages 191 - 195 *
PEGLION, JEAN LOUIS ET AL: "Comparative reactivities of perfluoroalkylpyrazoles and their hydrocarbon analogs. I. Bromination and nitration", BULLETIN DE LA SOCIETE CHIMIQUE DE FRANCE (1982), (3-4, PT. 2), 89-94, XP002049311 *
ZHURNAL VSESOYUZNOGO KHIMICHESKOGO OBSHCHESTVA IM. D. I. MENDELEEVA (1981), 26(1), 105-7 *

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