EP4581022A1 - Herbicidal pyrazole compounds - Google Patents

Herbicidal pyrazole compounds

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Publication number
EP4581022A1
EP4581022A1 EP23762382.2A EP23762382A EP4581022A1 EP 4581022 A1 EP4581022 A1 EP 4581022A1 EP 23762382 A EP23762382 A EP 23762382A EP 4581022 A1 EP4581022 A1 EP 4581022A1
Authority
EP
European Patent Office
Prior art keywords
formula
group
c4alkyl
methyl
compound
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.)
Pending
Application number
EP23762382.2A
Other languages
German (de)
French (fr)
Inventor
Suzanna DALE
Philip Michael ELVES
James Alan Morris
Vikas SIKERVAR
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.)
Syngenta Crop Protection AG Switzerland
Original Assignee
Syngenta Crop Protection AG Switzerland
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Syngenta Crop Protection AG Switzerland filed Critical Syngenta Crop Protection AG Switzerland
Publication of EP4581022A1 publication Critical patent/EP4581022A1/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic 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
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to herbicidal compounds, to processes for their preparation, to herbicidal compositions which comprise the compounds, and to their use for controlling weeds, in particular in crops of useful plants, or for inhibiting plant growth.
  • Herbicidal pyrazole compounds are known, for example, from CN 105037342, WO2022/013293, W02022/101270 and WO2023/099354.
  • the present invention relates to alternative herbicidal pyrazole compounds.
  • A is CR 11 or N
  • Q is selected from the group consisting of hydrogen, Ci-Cs alkyl, C2-C8 alkenyl, C2-C8 alkynyl, Ci-Cs haloalkyl, C2-C8 haloalkenyl, C2-C8 haloalkynyl, Ci-C4alkoxy-Ci-C3alkyl-, Ci-C4haloalkoxy-Ci-C3alkyl-, Ci-C4alkoxy-Ci- Cshaloalkyl-, Ci-Cscyanoalkyl- (e.g -CH2CH2CN), C3-C6 cycloalkyl (optionally substituted by CN, fluoro or chloro), -S(O) p R 4 and -(CH2) n R 10 ;
  • R 1 is independently selected from the group consisting of halogen, -CN, C1- C2alkyl, Ci-C2haloalkyl, Cs-Cecycloalkyl, Ci-C2alkoxy- and Ci-C2haloalkoxy-;
  • R 3 is selected from the group consisting of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, -CN, NO2, C2-C4alkenyl, C2- C4alkynyl, -S(O) p Ci-C4alkyl, -S(O) p Ci-C4haloalkyl, -C(O)OCi-C4alkyl and - C(O)NR 8 R 9 ;
  • Ci-C4alkyl- and Ci-Cealkyl- includes, for example, methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl (/-Pr), n-butyl (n-Bu), isobutyl (/-Bu), sec-butyl and terf-butyl (t-Bu).
  • Ci-C2alkyl is methyl (Me, CH3) or ethyl (Et, C2H5).
  • Ci-Cshaloalkyl- includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2- fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 , 1 -difluoro-2,2,2-trichloroethyl, 2, 2,3,3- tetrafluoropropyl and 2,2,2-trichloroethyl, heptafluoro-n-propyl and perfluoro-n-hexyl.
  • Ci-C4haloalkyl- and Ci-C2haloalkyl include, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2- fluoroethyl, 2-chloroethyl, pentafluoroethyl, or 1 , 1 -difluoro-2,2,2-trichloroethyl.
  • Suitable SAAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • the mixing partners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012.
  • the compound of Formula (I) can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual.
  • the mixing ratio of the compound of Formula (I) to the mixing partner is preferably from 1 : 100 to 1000:1.
  • mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient” relates to the respective mixture of compound of Formula (I) with the mixing partner).
  • the compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners.
  • herbicide safeners include benoxacor, cloquintocet (including cloquintocet-mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen and oxabetrinil.
  • mixtures of a compound of Formula (I) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and/or metcamifen are particularly preferred.
  • the safeners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 16 th Edition (BCPC), 2012.
  • the reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02/34048.
  • the mixing ratio of compound of Formula (I) to safener is from 100: 1 to 1 :10, especially from 20: 1 to 1 : 1.
  • the present invention still further provides a method of controlling weeds at a locus said method comprising application to the locus of a weed controlling amount of a composition comprising a compound of Formula (I).
  • the present invention may further provide a method of selectively controlling weeds at a locus comprising crop plants and weeds, wherein the method comprises application to the locus of a weed controlling amount of a composition according to the present invention.
  • Controlling means killing, reducing or retarding growth or preventing or reducing germination. It is noted that the compounds of the present invention show a much-improved selectivity compared to know, structurally similar compounds. Generally the plants to be controlled are unwanted plants (weeds).
  • the rates of application of compounds of Formula I may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post- emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • the compounds of Formula I according to the invention are generally applied at a rate of from 10 to 2500 g/ha, especially from 25 to 1000 g/ha, more especially from 25 to 250 g/ha.
  • the application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.
  • Crop plants are to be understood as also including those crop plants which have been rendered tolerant to other herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, HPPD-, -PDS and ACCase-inhibitors) by conventional methods of breeding or by genetic engineering.
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO-, HPPD-, -PDS and ACCase-inhibitors
  • An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola).
  • crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.
  • the compounds of the present invention may also be used
  • Crop plants are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).
  • Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds).
  • the Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria.
  • Examples of toxins, or transgenic plants able to synthesise such toxins are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529.
  • transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®.
  • Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding (“stacked” transgenic events).
  • seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
  • Crop plants are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
  • output traits e.g. improved storage stability, higher nutritional value and improved flavour.
  • the compositions can be used to control unwanted plants (collectively, ‘weeds’).
  • weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.
  • Agrostis Alopecurus
  • Avena Brachiaria
  • Bromus Cenchrus
  • Cyperus Digitaria
  • Echinochloa Eleusine
  • Lolium Monochoria
  • compounds of formula I can be prepared by reacting compounds of formula II, with reagents of the formula III, wherein LGi is a halogen, preferably iodine, bromine or chlorine (or a pseudo-halogen leaving group, such as a (halo)alkyl or phenyl sulfonate ester, e.g. triflate), in the presence of a base, such as sodium hydride or an alkali earth metal hydride, carbonate (e.g.
  • sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide optionally in the presence of potassium iodide in an inert solvent such as tetrahydrofuran, dioxane, water, N,N- dimethylformamide DMF, N,N-dimethylacetamide, sulfolane or acetonitrile and the like, at temperatures between 0 and 120°C, by procedures well known to those skilled in the art.
  • compounds of formula I can be prepared by reacting compounds of formula II with compounds of formula lllaa under Mitsunobu reaction conditions.
  • Such reactions are well known to those skilled in the art and can be carried out in the presence of a suitable phosphine reagent such as triphenylphosphine or tributylphosphine and similar others and in the presence of an azodicarboxylate reagent such as diisopropyl azodicarboxylate or diethyl azodicarboxylate.
  • a suitable phosphine reagent such as triphenylphosphine or tributylphosphine and similar others
  • an azodicarboxylate reagent such as diisopropyl azodicarboxylate or diethyl azodicarboxylate.
  • the reaction is generally carried out in the presence of a solvent such as dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, toluene, and similar others and at temperature preferably in the range of -10 °C to the boiling point of solvent.
  • Compounds of formula II can be prepared by protecting group deprotection reaction from compounds of formula IV, wherein PG is a N-protecting group for example acetyl, trimethylsilylethoxymethyl (SEM), tert-butyloxycarbonyl, benzyl, p- methoxybenzyl (PMB) amongst others amino protecting groups.
  • PG is a N-protecting group for example acetyl, trimethylsilylethoxymethyl (SEM), tert-butyloxycarbonyl, benzyl, p- methoxybenzyl (PMB) amongst others amino protecting groups.
  • Such reactions are well known to those skilled in the art and can be carried out for example using base catalyzed such as using sodum hydroxide for the deprotection of acetyl group or acid catalyzed such as hydrochloric acid or 2,2,2-trifluoroacetic acid for the deprotection of trimethylsilylethoxymethyl (SEM), tert-butyloxycarbonyl or p-methoxybenzyl (PMB) group.
  • base catalyzed such as using sodum hydroxide for the deprotection of acetyl group
  • acid catalyzed such as hydrochloric acid or 2,2,2-trifluoroacetic acid for the deprotection of trimethylsilylethoxymethyl (SEM), tert-butyloxycarbonyl or p-methoxybenzyl (PMB) group.
  • SEM trimethylsilylethoxymethyl
  • PMB p-methoxybenzyl
  • Compounds of formula IV can be prepared from compounds of formula V, wherein R 12 is Ci-C4alkyl or phenyl via decarboxylation reaction.
  • the reaction can be carried out using base such as alkaline earth metal hydroxide or alkali metal hydroxide like sodium hydroxide or in the presence of acid such as aquous hydrochloric acid, sulfuric acid amongst others.
  • the reaction is generally carried out in the presence of a solvent such as water, ethanol, methanol, tetrahydrofuran or dioxane or combination of two or more solvent and at temperature in the range of room temperature to boiling point of solvent.
  • Compounds of formula V, wherein R 12 is Ci-C4alkyl or phenyl can be prepared by reacting compounds of formula VII, with reagents of the formula VI, wherein LG2 is a halogen, preferably iodine, bromine or chlorine (or a pseudo-halogen leaving group, such as a (halo)alkyl or phenyl sulfonate ester, e.g. triflate), in the presence of a base, such as sodium tert-butoxide, sodium hydride or an alkali earth metal hydride, carbonate (e.g.
  • a base such as sodium tert-butoxide, sodium hydride or an alkali earth metal hydride, carbonate (e.g.
  • potassium phosphate such as potassium phosphate optionally in the presence of potassium iodide in an inert solvent such as tetra hydrofuran, dioxane, water, N,N- dimethylformamide DMF, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane or acetonitrile and the like, at temperatures between 0 and 120°C, by procedures well known to those skilled in the art.
  • Compounds of formula VII can be prepared by the condensation reaction of compounds of formula VIII with compounds of formula XI (or its hydrochloric acid salt or trifluoroacetic acid salt), wherein PG is a N-protecting group for example acetyl, trimethylsilylethoxymethyl (SEM), tert-butyloxycarbonyl, benzyl, p-methoxybenzyl (PMB) amongst others amino protecting groups.
  • SEM trimethylsilylethoxymethyl
  • PMB p-methoxybenzyl
  • Compounds of formula VIII can be prepared by reacting compounds of formula IX, wherein R 11 is Ci-C4alkyl or phenyl with compounds of formula X in the presence of a base. Such reactions are known by the name of Claisen condensation reaction and well known to those skilled in the art. Reaction can be carried out using base such as lithium diisopropylamide, lithium tetramethylpiperidide, sodium ethoxide, sodium hydride amongst other bases in the presence of solvent such as tetrahydrofuran, ethanol, methanol and at temperature in the range of -80 °C to boiling point of solvent.
  • base such as lithium diisopropylamide, lithium tetramethylpiperidide, sodium ethoxide, sodium hydride amongst other bases in the presence of solvent such as tetrahydrofuran, ethanol, methanol and at temperature in the range of -80 °C to boiling point of solvent.
  • Step 2 Preparation of ethyl 2-[2-[(4-methoxyphenyl)methyl]-5- (trifluoromethyl)pyrazol-3-yl]acetate (I2)
  • Step 3 Preparation of ethyl 2-(5-chloropyrimidin-2-yl)-2-[2-[(4- methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]acetate (I3)
  • Step 1 Preparation of ethyl 6-chloro-6,6-difluoro-3,5-dioxo-hexanoate (I6)
  • reaction mixture was allowed to warm to room temperature over 30 minutes before being quenched with 1 M hydrochloric acid (200 mL) and extracted with ethyl acetate (2 x 80 mL). The combined organics were dried and concentrated to provide ethyl 6-chloro-6,6-difluoro-3,5-dioxo-hexanoate (I6) as an oil which was used directly in the next step.
  • reaction mixture was then cooled to room temperature before being diluted with 0.5 M hydrochloric acid (200 mL) and extracted with terf-butylmethyl ether (2 x 100 mL).
  • the combined organic extracts were concentrated and subjected to column chromatography on silica gel using 0-30% ethyl acetate in cyclohexane to give ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4-methoxyphenyl)methyl]pyrazol-3-yl]-2-(5- chloropyrimidin-2-yl)acetate I8 as a brown oil (6.53 g, 60%).
  • reaction mixture was cooled to room temperature before being diluted with ethyl acetate (100 mL) and neutralised with 2 M hydrochloric acid (100 mL).
  • the organic layer was then separated, and the aqueous layer extracted with ethyl acetate (100 mL).
  • the combined organic extracts were then concentrated and subjected to column chromatography on silica gel using 0-35% ethyl acetate in cyclohexane to give 5-chloro-2-[[5-[chloro(difluoro)methyl]-2-[(4- methoxyphenyl)methyl]pyrazol-3-yl]methyl]pyrimidine I9 as a beige oil (3.76 g).
  • Step 5 Preparation of 5-chloro-2-[[3-[chloro(difluoro)methyl]-1H-pyrazol-5- yl]methyl]pyrimidine (110)
  • Step 6 Preparation of 2-[[2-butyl-5-[chloro(difluoro)methyl]pyrazol-3- yl]methyl]-5-chloro-pyrimidine (1.020)
  • Diisopropyl azodicarboxylate (0.140 mL, 0.711 mmol) was then added dropwise, and the resulting mixture was allowed to warm to room temperature and stirred for 1 hour. The reaction was quenched by addition of methanol (20 mL), and the resulting mixture was concentrated and subjected to column chromatography on silica gel using 0-30% ethyl acetate in cyclohexane.
  • AMAPA Amaranthus palmeri
  • AMARE Amaranthus retoflexus
  • EHCG Echinochloa crus-galli
  • IPHE Ipomoea hederacea
  • SETFA Setaria faberi
  • the plants After cultivation for one day (pre-emergence) or after 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), the plants are sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone I water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). Compounds are applied at 250 g/ha unless otherwise stated. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) and watered twice daily.

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

Abstract

The present invention relates to compounds of Formula (I), or an agronomically acceptable salt of said compounds wherein A, Q, R1, R2, R3 and m are as defined herein. The invention further relates to herbicidal compositions which comprise a compound of Formula (I) and to the use of compounds of Formula (I) for controlling weeds, in particular in crops of useful plants.

Description

HERBICIDAL PYRAZOLE COMPOUNDS
The present invention relates to herbicidal compounds, to processes for their preparation, to herbicidal compositions which comprise the compounds, and to their use for controlling weeds, in particular in crops of useful plants, or for inhibiting plant growth.
Herbicidal pyrazole compounds are known, for example, from CN 105037342, WO2022/013293, W02022/101270 and WO2023/099354. The present invention relates to alternative herbicidal pyrazole compounds. Thus, according to the present invention there is provided a compound of Formula (I): or an agronomically acceptable salt thereof, wherein
A is CR11 or N;
Q is selected from the group consisting of hydrogen, Ci-Cs alkyl, C2-C8 alkenyl, C2-C8 alkynyl, Ci-Cs haloalkyl, C2-C8 haloalkenyl, C2-C8 haloalkynyl, Ci-C4alkoxy-Ci-C3alkyl-, Ci-C4haloalkoxy-Ci-C3alkyl-, Ci-C4alkoxy-Ci- Cshaloalkyl-, Ci-Cscyanoalkyl- (e.g -CH2CH2CN), C3-C6 cycloalkyl (optionally substituted by CN, fluoro or chloro), -S(O)pR4 and -(CH2)nR10;
R1 is independently selected from the group consisting of halogen, -CN, C1- C2alkyl, Ci-C2haloalkyl, Cs-Cecycloalkyl, Ci-C2alkoxy- and Ci-C2haloalkoxy-; R2 is selected from the group consisting of halogen, -CN, NO2, Ci-C4alkyl, C1- C4haloalkyl, Ci-C4alkoxy, -C(O)Ci-C4alkyl, -C(O)OCi-C4alkyl, Ci-C4haloalkoxy, -S(O)pCi-C4alkyl, -C(R6)=NOR7 and Cs-Cecycloalkyl;
R3 is selected from the group consisting of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, -CN, NO2, C2-C4alkenyl, C2- C4alkynyl, -S(O)pCi-C4alkyl, -S(O)pCi-C4haloalkyl, -C(O)OCi-C4alkyl and - C(O)NR8R9;
R4 is selected from the group consisting of Ci-C4alkyl, Ci-C4haloalkyl and C3- Cecycloalkyl;
R5 is selected from the group consisting of hydrogen, methyl, ethyl, -(CH2)- cyclopropyl, C2-C3 alkenyl, C2-C3 alkynyl and cyclopropyl;
R6 is selected from the group consisting of hydrogen, methyl and ethyl;
R7 is methyl or ethyl;
R8 is hydrogen or Ci-C4alkyl;
R9 is hydrogen or Ci-C4alkyl;
R10 is selected from the group consisting of -OH, -C(H)O, -C(O)R4, -S(O)PR4, -C(H)(OH)-CH2OH, -C(R6)=NOR5, -NR12R13, C3-C6 cycloalkyl (optionally substituted by CN, fluoro or hydroxy), a C3-C6 saturated heterocycle comprising one or more oxygen atoms (e.g tetrahydropyran and tetrahydrofuran), and a 5-membered heteroaryl (e.g pyrazolyl) which comprises from 1 to 3 heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, wherein said heteroaryl is optionally substituted by one or two substituents independently selected from the group consisting of halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C3- C4cycloalkyl, C1-C2 alkoxy and C1-C4 haloalkoxy;
R11 is selected from the group consisting of hydrogen, fluoro, chloro and CN; R12 and R13 are independently selected from the group consisting of Ci- C4alkyl, C3-C4cycloalkyl, Ci-C4alkyl-S(O)p-, C3-C4cycloalkyl-S(O)p-, Ci-C4alkyl- C(O)- and C3-C4cycloalkyl-C(O)-; m = 0, 1 or 2; n = 1 , 2 or 3; and p = 0, 1 or 2.
Ci-C4alkyl- and Ci-Cealkyl- includes, for example, methyl (Me, CH3), ethyl (Et, C2H5), n-propyl (n-Pr), isopropyl (/-Pr), n-butyl (n-Bu), isobutyl (/-Bu), sec-butyl and terf-butyl (t-Bu). Ci-C2alkyl is methyl (Me, CH3) or ethyl (Et, C2H5).
Halogen (or halo) includes, for example, fluorine, chlorine, bromine or iodine. The same correspondingly applies to halogen in the context of other definitions, such as haloalkyl.
Ci-Cshaloalkyl- includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2- fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 , 1 -difluoro-2,2,2-trichloroethyl, 2, 2,3,3- tetrafluoropropyl and 2,2,2-trichloroethyl, heptafluoro-n-propyl and perfluoro-n-hexyl. Ci-C4haloalkyl- and Ci-C2haloalkyl include, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2- fluoroethyl, 2-chloroethyl, pentafluoroethyl, or 1 , 1 -difluoro-2,2,2-trichloroethyl.
Ci-C4alkoxy and Ci-Csalkoxy includes, for example, methoxy and ethoxy.
Ci-Cshaloalkoxy- and Ci-Cshaloalkoxy- include, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2- fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy or 2,2,2-trichloroethoxy, preferably difluoromethoxy, 2-chloroethoxy or trifluoromethoxy.
C2-Csalkenyl- includes, for example, -CH=CH2 (vinyl) and -CH2-CH=CH2 (allyl).
C2-Csalkynyl- refers to a straight or branched hydrocarbon chain radical group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, having from two to four carbon atoms, and which is attached to the rest of the molecule by a single bond. Examples of C2-C4alkynyl include, but are not limited to, prop-1 -ynyl, propargyl (prop-2-ynyl), and but-1-ynyl.
Ci-C4alkyl-S- (alkylthio) includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.
Ci-C4alkyl-S(O)- (alkylsulfinyl) includes, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, secbutylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.
Ci-C4alkyl-S(O)2- (alkylsulfonyl) includes, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, secbutylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.
In one embodiment of the present invention, A is CR11 and R11 is selected from the group consisting of hydrogen, fluoro, chloro and CN, preferably fluoro or hydrogen.
In one embodiment of the present invention, A is N. In another embodiment of the present invention m is 1. Thus, in a preferred embodiment of the present invention there is provided a compound of Formula (la) wherein Q, R1, R2 and R3are as defined in claim 1 above.
In one embodiment of the present invention there is provided a compound of Formula (I) or Formula (la), wherein R1 is chloro. In one embodiment of the present invention there is provided a compound of Formula (I) or Formula (la), wherein R2 is halogen (e.g Cl or Br) or Ci-C4haloalkyl (e.g -CF3, -CHF2, -CF2CI).
In one embodiment of the present invention there is provided a compound of Formula (I) or Formula (la), wherein, R3 is hydrogen or halogen (e.g Cl).
In a preferred embodiment of the present invention there is provided a compound of Formula (I) or Formula (la), wherein Q is selected from the group consisting of hydrogen, Ci-Cs alkyl (e.g methyl, -CH2CH(CH3)2, n-butyl, n-pentyl), C2- C8 alkenyl (e.g -CH2CH2CH=CH2), Ci-C8 haloalkyl (e.g -CH2CH2CHF2, - CH2CH2CH2CHF2, -CH2CH2CF3, -CH2CH2CH2CF3), Ci-C4alkoxy-Ci-C3alkyl- (e.g - CH2OCH3, -CH2CH2OCH3), Ci-C4haloalkoxy-Ci-C3alkyl- (e.g -CH2OCH2CHF2, - CH2CH2OCH2CHF2), -S(O)PR4 (e.g -SO2CH2CH2CF3, -S-CH2CH2CF3) and -(CH2)nR10 (e.g -CH2CH2CH2OH, -CH2CH2C(H)(OH)CH2OH, -CH2CH2C(H)O)-OH, CH2CH2C(H)=N-OH, -CH2CH2C(H)=N-O-CH3 and -CH2CH2C(H)=N-O-CH2-cPr).
In one embodiment of the present invention there is provided a compound of Formula (I) or Formula (la), wherein Q is -(CH2)nR10, n is 1 , 2 or 3 and R10 is selected from the group consisting of -OH (e.g -CH2CH2CH2OH), -C(H)(OH)-CH2OH (e.g - CH2CH2C(H)(OH)CH2OH), -C(H)=NOR5 (e.g -CH2CH2C(H)=N-OH, -CH2CH2C(H)=N- O-CH3, -CH2CH2C(H)=N-O-CH2-cPr), and -NR12R13 (e.g -CH2CH2CH2N(CH3)SO2CH3.
In a preferred embodiment of the present invention, there is provided a compound of Formula (I) or Formula (la), wherein Q is Ci-Cs alkyl (e.g methyl, - CH2CH(CH3)2, n-butyl, n-pentyl).
In another preferred embodiment of the present invention, there is provided a compound of Formula (I) or Formula (la), wherein Q is Ci-Cs haloalkyl (e.g - CH2CH2CHF2, -CH2CH2CHF2, -CH2CH2CF3, -CH2CH2CH2CF3).
In another preferred embodiment of the present invention, there is provided a compound of Formula (I) or Formula (la), wherein Q is Ci-C4haloalkoxy-Ci-C3alkyl- e.g -CH2OCH2CHF2, -CH2CH2CH2OCH2CHF2).
The present invention further relates to a compound of Formula (I l-a): wherein R2 is CF2H or CF2CI.
Compounds of Formula (I) may contain asymmetric centres and may be present as a single enantiomer, pairs of enantiomers in any proportion or, where more than one asymmetric centre are present, contain diastereoisomers in all possible ratios. Typically one of the enantiomers has enhanced biological activity compared to the other possibilities.
The present invention also provides agronomically acceptable salts of compounds of Formula (I). Salts that the compounds of Formula (I) may form with amines, including primary, secondary and tertiary amines (for example ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition metals or quaternary ammonium bases are preferred.
The compounds of Formula (I) according to the invention can be used as herbicides by themselves, but they are generally formulated into herbicidal compositions using formulation adjuvants, such as carriers, solvents and surfaceactive agents (SAA). Thus, the present invention further provides a herbicidal composition comprising a herbicidal compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant. The composition can be in the form of concentrates which are diluted prior to use, although ready-to-use compositions can also be made. The final dilution is usually made with water, but can be made instead of, or in addition to, water, with, for example, liquid fertilisers, micronutrients, biological organisms, oil or solvents.
The herbicidal compositions generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, compounds of Formula I and from 1 to 99.9 % by weight of a formulation adjuvant which preferably includes from 0 to 25 % by weight of a surface-active substance. The compositions can be chosen from a number of formulation types. These include an emulsion concentrate (EC), a suspension concentrate (SC), a suspo- emulsion (SE), a capsule suspension (CS), a water dispersible granule (WG), an emulsifiable granule (EG), an emulsion, water in oil (EG), an emulsion, oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oil miscible flowable (OF), an oil miscible liquid (OL), a soluble concentrate (SL), an ultra-low volume suspension (Sil), an ultra-low volume liquid (UL), a technical concentrate (TK), a dispersible concentrate (DC), a soluble powder (SP), a wettable powder (WP) and a soluble granule (SG). The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of Formula (I).
Soluble powders (SP) may be prepared by mixing a compound of Formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
Wettable powders (WP) may be prepared by mixing a compound of Formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).
Granules (GR) may be formed either by granulating a mixture of a compound of Formula (I) and one or more powdered solid diluents or carriers, or from preformed blank granules by absorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of Formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
Dispersible Concentrates (DC) may be prepared by dissolving a compound of Formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface-active agent (for example to improve water dilution or prevent crystallisation in a spray tank).
Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of Formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as Cs-Cio fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
Preparation of an EW involves obtaining a compound of Formula (I) either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SAAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SAAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of Formula (I) is present initially in either the water or the solvent/SAA blend. Suitable solvents for use in MEs include those hereinbefore described for use in in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water- soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil- in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of Formula (I). SCs may be prepared by ball or bead milling the solid compound of Formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of Formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
Aerosol formulations comprise a compound of Formula (I) and a suitable propellant (for example n-butane). A compound of Formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.
Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of Formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of Formula (I) and they may be used for seed treatment. A compound of Formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
The composition may include one or more additives to improve the biological performance of the composition, for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of Formula (I). Such additives include surface active agents (SAAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), modified plant oils such as methylated rape seed oil (MRSO), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of Formula (I). Wetting agents, dispersing agents and emulsifying agents may be SAAs of the cationic, anionic, amphoteric or non-ionic type.
Suitable SAAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
Suitable anionic SAAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di-/sopropyl- and tri-/sopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefine sulphonates, taurates, lignosulphonates and phosphates I sulphates of tristyrylphenols.
Suitable SAAs of the amphoteric type include betaines, propionates and glycinates.
Suitable SAAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); lecithins and sorbitans and esters thereof, alkyl polyglycosides and tristyrylphenols.
Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
The compounds of present invention can also be used in mixture with one or more additional herbicides and/or plant growth regulators. Examples of such additional herbicides or plant growth regulators include acetochlor, acifluorfen (including acifluorfen-sodium), aclonifen, ametryn, amicarbazone, aminopyralid, aminotriazole, atrazine, beflubutamid-M, benquitrione, bensulfuron (including bensulfuron-methyl), bentazone, bicyclopyrone, bilanafos, bipyrazone, bispyribac-sodium, bixlozone, bromacil, bromoxynil, butachlor, butafenacil, carfentrazone (including carfentrazone- ethyl), cloransulam (including cloransulam-methyl), chlorimuron (including chlorimuron-ethyl), chlorotoluron, chlorsulfuron, cinmethylin, clacyfos, clethodim, clodinafop (including clodinafop-propargyl), clomazone, clopyralid, cyclopyranil, cyclopyrimorate, cyclosulfamuron, cyhalofop (including cyhalofop-butyl), 2,4-D (including the choline salt and 2-ethylhexyl ester thereof), 2,4-DB, desmedipham, dicamba (including the aluminium, aminopropyl, bis-aminopropylmethyl, choline, dichloroprop, diglycolamine, dimethylamine, dimethylammonium, potassium and sodium salts thereof) diclosulam, diflufenican, diflufenzopyr, dimethachlor, dimethenamid-P, dioxopyritrione, diquat dibromide, diuron, epyrifenacil, ethalfluralin, ethofumesate, fenoxaprop (including fenoxaprop-P-ethyl), fenoxasulfone, fenpyrazone, fenquinotrione, fentrazamide, flazasulfuron, florasulam, florpyrauxifen (including florpyrauxifen-benzyl), fluazifop (including fluazifop-P-butyl), flucarbazone (including flucarbazone-sodium), flufenacet, flumetsulam, flumioxazin, fluometuron, fomesafen flupyrsulfuron (including flupyrsulfuron-methyl-sodium), fluroxypyr (including fluroxypyr-meptyl), fomesafen, foramsulfuron, glufosinate (including L-glufosinate and the ammonium salts of both), glyphosate (including the diammonium, isopropylammonium and potassium salts thereof), halauxifen (including halauxifen-methyl), haloxyfop (including haloxyfop-methyl), hexazinone, hydantocidin, imazamox (including R-imazamox), imazapic, imazapyr, imazethapyr, indaziflam, iodosulfuron (including iodosulfuron-methyl-sodium), iofensulfuron (including iofensulfuron-sodium), ioxynil, isoproturon, isoxaflutole, lancotrione, MCPA, MCPB, mecoprop-P, mesosulfuron (including mesosulfuron-methyl), mesotrione, metamitron, metazachlor, methiozolin, metolachlor, metosulam, metribuzin, metsulfuron, napropamide, nicosulfuron, norflurazon, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pendimethalin, penoxsulam, phenmedipham, picloram, pinoxaden, pretilachlor, primisulfuron-methyl, prometryne, propanil, propaquizafop, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen (including pyraflufen-ethyl), pyrasulfotole, pyridate, pyriftalid, pyrimisulfan, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quizalofop (including quizalofop- P-ethyl and quizalofop-P-tefuryl), rimisoxafen, rimsulfuron, saflufenacil, sethoxydim, simazine, S-metalochlor, sulfentrazone, sulfosulfuron, tebuthiuron, tefuryltrione, tembotrione, terbuthylazine, terbutryn, tetflupyrolimet, thiencarbazone, thifensulfuron, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, tribenuron (including tribenuron-methyl), triclopyr, trifloxysulfuron (including trifloxysulfuron-sodium), trifludimoxazin, trifluralin, triflusulfuron, tripyrasulfone, 3-(2- chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4-trifluoromethyl-3,6-dihydropyrimidin-1(2H)- yl)phenyl)-5-methyl-4,5-dihydroisoxazole-5-carboxylic acid ethyl ester, 4-hydroxy-1- methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1,5- dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 5-ethoxy-4-hydroxy-1- methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1-methyl-3-[4- (trifluoromethyl)-2-pyridyl]imidazolidin-2-one, 4-hydroxy-1,5-dimethyl-3-[1-methyl-5- (trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one, (4R)1-(5-tert-butylisoxazol-3-yl)-4- ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one, 4-amino-3-chloro-5-fluoro-6-(7-fluoro- 1 H-indol-6-yl)pyridine-2-carboxylic acid (including agrochemically acceptable esters thereof, for example, methyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1 H-indol-6- yl)pyridine-2-carboxylate, prop-2-ynyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1 H-indol- 6-yl)pyridine-2-carboxylate and cyanomethyl 4-amino-3-chloro-5-fluoro-6-(7-fluoro- 1 H-indol-6-yl)pyridine-2-carboxylate), 3-ethylsulfanyl-N-(1 ,3,4-oxadiazol-2-yl)-5- (trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-
(isopropylsulfanylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)- [1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(isopropylsulfonylmethyl)-N-(5-methyl- 1 ,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)-[1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, 3-(ethylsulfonylmethyl)-N-(5-methyl-1,3,4-oxadiazol-2-yl)-5-(trifluoromethyl)- [1,2,4]triazolo[4,3-a]pyridine-8-carboxamide, ethyl-2-[[3-[[3-chloro-5-fluoro-6-[3- methyl-2,6-dioxo-4-(trifluoromethyl)pyrimidin-1-yl]-2-pyridyl]oxy]acetate,6-chloro-4- (2,7-dimethyl-1-naphthyl)-5-hydroxy-2-methyl-pyridazin-3-one, tetrahydrofuran-2- ylmethyl (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoate, tetrahydrofuran-2-ylmethyl (2R)-2-[(4-amino-3,5-dichloro-6-fluoro-2- pyridyl)oxy]propanoate, tetrahydrofuran-2-ylmethyl 2-[(4-amino-3,5-dichloro-6-fluoro- 2-pyridyl)oxy]propanoate, 2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridyl)oxy]propanoic acid, 2-fluoro-N-(5-methyl-1 ,3,4-oxadiazol-2-yl)-3-[(R)-propylsulfinyl]-4-
(trifluoromethyl)benzamide, 2-fluoro-N-(5-methyl-1 ,3,4-oxadiazol-2-yl)-3- propylsulfinyl-4-(trifluoromethyl)benzamide, (2-fluorophenyl)methyl 6-amino-5-chloro- 2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylate and 6-amino-5- chloro-2-(4-chloro-2-fluoro-3-methoxy-phenyl)pyrimidine-4-carboxylic acid.
The mixing partners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, Sixteenth Edition, British Crop Protection Council, 2012.
The compound of Formula (I) can also be used in mixtures with other agrochemicals such as fungicides, nematicides or insecticides, examples of which are given in The Pesticide Manual. The mixing ratio of the compound of Formula (I) to the mixing partner is preferably from 1 : 100 to 1000:1.
The mixtures can advantageously be used in the above-mentioned formulations (in which case "active ingredient" relates to the respective mixture of compound of Formula (I) with the mixing partner).
The compounds or mixtures of the present invention can also be used in combination with one or more herbicide safeners. Examples of such safeners include benoxacor, cloquintocet (including cloquintocet-mexyl), cyprosulfamide, dichlormid, fenchlorazole (including fenchlorazole-ethyl), fenclorim, fluxofenim, furilazole, isoxadifen (including isoxadifen-ethyl), mefenpyr (including mefenpyr-diethyl), metcamifen and oxabetrinil.
Particularly preferred are mixtures of a compound of Formula (I) with cyprosulfamide, isoxadifen-ethyl, cloquintocet-mexyl and/or metcamifen.
The safeners of the compound of Formula (I) may also be in the form of esters or salts, as mentioned e.g. in The Pesticide Manual, 16th Edition (BCPC), 2012. The reference to cloquintocet-mexyl also applies to a lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulfonium or phosphonium salt thereof as disclosed in WO 02/34048.
Preferably the mixing ratio of compound of Formula (I) to safener is from 100: 1 to 1 :10, especially from 20: 1 to 1 : 1.
The present invention still further provides a method of controlling weeds at a locus said method comprising application to the locus of a weed controlling amount of a composition comprising a compound of Formula (I). Moreover, the present invention may further provide a method of selectively controlling weeds at a locus comprising crop plants and weeds, wherein the method comprises application to the locus of a weed controlling amount of a composition according to the present invention. ‘Controlling’ means killing, reducing or retarding growth or preventing or reducing germination. It is noted that the compounds of the present invention show a much-improved selectivity compared to know, structurally similar compounds. Generally the plants to be controlled are unwanted plants (weeds). ‘Locus’ means the area in which the plants are growing or will grow. The application may be applied to the locus pre-emergence and/or postemergence of the crop plant. Some crop plants may be inherently tolerant to herbicidal effects of compounds of Formula (I). Preferred crop plants include maize, wheat, barley and rice.
The rates of application of compounds of Formula I may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post- emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed(s) to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop. The compounds of Formula I according to the invention are generally applied at a rate of from 10 to 2500 g/ha, especially from 25 to 1000 g/ha, more especially from 25 to 250 g/ha.
The application is generally made by spraying the composition, typically by tractor mounted sprayer for large areas, but other methods such as dusting (for powders), drip or drench can also be used.
Crop plants are to be understood as also including those crop plants which have been rendered tolerant to other herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, HPPD-, -PDS and ACCase-inhibitors) by conventional methods of breeding or by genetic engineering. An example of a crop that has been rendered tolerant to imidazolinones, e.g. imazamox, by conventional methods of breeding is Clearfield® summer rape (canola). Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include e.g. glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®. The compounds of the present invention may also be used in conjunction with plants disclosed in W02020/236790.
Crop plants are also to be understood as being those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-451 878, EP-A-374 753, WO 93/07278, WO 95/34656, WO 03/052073 and EP-A-427 529. Examples of transgenic plants comprising one or more genes that code for an insecticidal resistance and express one or more toxins are KnockOut® (maize), Yield Gard® (maize), NuCOTIN33B® (cotton), Bollgard® (cotton), NewLeaf® (potatoes), NatureGard® and Protexcta®. Plant crops or seed material thereof can be both resistant to herbicides and, at the same time, resistant to insect feeding (“stacked” transgenic events). For example, seed can have the ability to express an insecticidal Cry3 protein while at the same time being tolerant to glyphosate.
Crop plants are also to be understood to include those which are obtained by conventional methods of breeding or genetic engineering and contain so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).
The compositions can be used to control unwanted plants (collectively, ‘weeds’). The weeds to be controlled may be both monocotyledonous species, for example Agrostis, Alopecurus, Avena, Brachiaria, Bromus, Cenchrus, Cyperus, Digitaria, Echinochloa, Eleusine, Lolium, Monochoria, Rottboellia, Sagittaria, Scirpus, Setaria and Sorghum, and dicotyledonous species, for example Abutilon, Amaranthus, Ambrosia, Chenopodium, Chrysanthemum, Conyza, Galium, Ipomoea, Nasturtium, Sida, Sinapis, Solanum, Stellaria, Veronica, Viola and Xanthium.
In a further aspect of the present invention there is provided the use of a compound of Formula (I) as defined herein as a herbicide.
Processes for preparation of compounds of Formula (I)
Processes for preparation of compounds, e.g. a compound of formula (I) (which optionally can be an agrochemically acceptable salt thereof), are now described, and form further aspects of the present invention.
Scheme 1 :
In scheme 1 compounds of formula I can be prepared by reacting compounds of formula II, with reagents of the formula III, wherein LGi is a halogen, preferably iodine, bromine or chlorine (or a pseudo-halogen leaving group, such as a (halo)alkyl or phenyl sulfonate ester, e.g. triflate), in the presence of a base, such as sodium hydride or an alkali earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, optionally in the presence of potassium iodide in an inert solvent such as tetrahydrofuran, dioxane, water, N,N- dimethylformamide DMF, N,N-dimethylacetamide, sulfolane or acetonitrile and the like, at temperatures between 0 and 120°C, by procedures well known to those skilled in the art. Alternatively compounds of formula I can be prepared by reacting compounds of formula II with compounds of formula lllaa under Mitsunobu reaction conditions. Such reactions are well known to those skilled in the art and can be carried out in the presence of a suitable phosphine reagent such as triphenylphosphine or tributylphosphine and similar others and in the presence of an azodicarboxylate reagent such as diisopropyl azodicarboxylate or diethyl azodicarboxylate. The reaction is generally carried out in the presence of a solvent such as dichloromethane, tetrahydrofuran, 2-methyltetrahydrofuran, toluene, and similar others and at temperature preferably in the range of -10 °C to the boiling point of solvent.
Compounds of formula II can be prepared by protecting group deprotection reaction from compounds of formula IV, wherein PG is a N-protecting group for example acetyl, trimethylsilylethoxymethyl (SEM), tert-butyloxycarbonyl, benzyl, p- methoxybenzyl (PMB) amongst others amino protecting groups. Such reactions are well known to those skilled in the art and can be carried out for example using base catalyzed such as using sodum hydroxide for the deprotection of acetyl group or acid catalyzed such as hydrochloric acid or 2,2,2-trifluoroacetic acid for the deprotection of trimethylsilylethoxymethyl (SEM), tert-butyloxycarbonyl or p-methoxybenzyl (PMB) group.
Compounds of formula IV can be prepared from compounds of formula V, wherein R12 is Ci-C4alkyl or phenyl via decarboxylation reaction. The reaction can be carried out using base such as alkaline earth metal hydroxide or alkali metal hydroxide like sodium hydroxide or in the presence of acid such as aquous hydrochloric acid, sulfuric acid amongst others. The reaction is generally carried out in the presence of a solvent such as water, ethanol, methanol, tetrahydrofuran or dioxane or combination of two or more solvent and at temperature in the range of room temperature to boiling point of solvent.
Compounds of formula V, wherein R12 is Ci-C4alkyl or phenyl can be prepared by reacting compounds of formula VII, with reagents of the formula VI, wherein LG2 is a halogen, preferably iodine, bromine or chlorine (or a pseudo-halogen leaving group, such as a (halo)alkyl or phenyl sulfonate ester, e.g. triflate), in the presence of a base, such as sodium tert-butoxide, sodium hydride or an alkali earth metal hydride, carbonate (e.g. sodium carbonate, potassium carbonate or cesium carbonate) or hydroxide, or phosphate such as potassium phosphate optionally in the presence of potassium iodide in an inert solvent such as tetra hydrofuran, dioxane, water, N,N- dimethylformamide DMF, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane or acetonitrile and the like, at temperatures between 0 and 120°C, by procedures well known to those skilled in the art.
Compounds of formula VII can be prepared by the condensation reaction of compounds of formula VIII with compounds of formula XI (or its hydrochloric acid salt or trifluoroacetic acid salt), wherein PG is a N-protecting group for example acetyl, trimethylsilylethoxymethyl (SEM), tert-butyloxycarbonyl, benzyl, p-methoxybenzyl (PMB) amongst others amino protecting groups. Such reactions are well known in the literature and can be carried out optionally in the presence of an acid catalyst such as acetic acid.
Compounds of formula VIII can be prepared by reacting compounds of formula IX, wherein R11 is Ci-C4alkyl or phenyl with compounds of formula X in the presence of a base. Such reactions are known by the name of Claisen condensation reaction and well known to those skilled in the art. Reaction can be carried out using base such as lithium diisopropylamide, lithium tetramethylpiperidide, sodium ethoxide, sodium hydride amongst other bases in the presence of solvent such as tetrahydrofuran, ethanol, methanol and at temperature in the range of -80 °C to boiling point of solvent.
The following non-limiting examples provide specific synthesis methods for representative compounds of the present invention, as referred to in the Table below.
Example 1 : Preparation of 5-chloro-2-[[2-(4,4-difluorobutyl)-5-
(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine (1.005)
(1.005) Step 1 : Preparation of ethyl 6,6,6-trifluoro-3,5-dioxo-hexanoate (11)
To an ice-cooled solution of diisopropylamine (22 mL, 157 mmol) in THF (110 mL) in a 250 mL round bottomed flask was added n-butyllithium (2.5 M in hexanes, 65 mL, 160 mmol) over approximately 30 minutes. The mixture was stirred for 30 minutes, treated dropwise with ethyl acetoacetate (6.8 mL, 54 mmol) and was stirred for a further 45 minutes at 0°C. The reaction mixture was then cooled to -78°C, treated dropwise with ethyl trifluoroacetate (8.3 mL, 70 mmol) and stirred for 3 hours. The mixture was quenched with hydrochloric acid, diluted with water and extracted with ethyl acetate. The combined organics were dried and concentrated to provide ethyl 6,6,6-trifluoro-3,5-dioxo-hexanoate 11 as an oil which was used as such in the next step.
Step 2: Preparation of ethyl 2-[2-[(4-methoxyphenyl)methyl]-5- (trifluoromethyl)pyrazol-3-yl]acetate (I2)
To a solution of the ethyl 6,6,6-trifluoro-3,5-dioxo-hexanoate 11 (prepared in step 1) in acetic acid (90 mL) in a 100 mL flask was added (4-methoxybenzyl)hydrazine hydrochloride (10.56 g, 54.29 mmol) and the resulting mixture was allowed to stir for 1.5 hours at room temperature. The mixture was diluted with tert-butylmethyl ether and washed with water and brine. The organics were concentrated and subjected to column chromatography on silica gel using 0-30% ethyl acetate in cyclohexane to give ethyl 2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]acetate I2 as a yellow oil (11.97 g, 59% yield). 1H NMR (400 MHz, CDCh) 5 = 7.10 - 7.04 (m, 2H), 6.88 - 6.83 (m, 2H), 6.50 (s, 1H), 5.35 (s, 2H), 4.12 (q, 2H), 3.79 (s, 3H), 3.54 (s, 2H), 1.24 (t, 3H)
Step 3: Preparation of ethyl 2-(5-chloropyrimidin-2-yl)-2-[2-[(4- methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]acetate (I3)
To a solution of ethyl 2-[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3- yl]acetate 12 (4.22 g, 11.71 mmol) in dimethyl sulfoxide (40 mL) in a 250 mL flask was added 2,5-dichloropyrimidine (3.71 g, 24.9 mmol) and potassium phosphate tribasic (7.86 g, 36.3 mmol) and the reaction mixture was stirred at 60°C for 3.5 hours. The mixture was allowed to stand at room temperature overnight and then was stirred at 60°C for an additional hour. The mixture was cooled to room temperature, diluted with water and extracted with tert-butylmethyl ether. The combined organics were concentrated and subjected to column chromatography on silica gel using 0- 40% ethyl acetate in cyclohexane to give ethyl 2-(5-chloropyrimidin-2-yl)-2-[2-[(4- methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3-yl]acetate I3 as a yellow oil (5.19 g, 73% yield). 1H NMR (400 MHz, CDC ) 6 = 8.55 (s, 2H), 6.98 - 6.92 (m, 2H), 6.79 - 6.74 (m, 2H), 6.69 (s, 1 H), 5.45 - 5.31 (m, 3H), 4.20 - 4.11 (m, 2H), 3.77 (s, 3H), 1.21
- 1.16 (m, 3H)
Step 4: Preparation of 5-chloro-2-[[2-[(4-methoxyphenyl)methyl]-5- (trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine (I4)
To a solution of ethyl 2-(5-chloropyrimidin-2-yl)-2-[2-[(4-methoxyphenyl)methyl]-5- (trifluoromethyl)pyrazol-3-yl]acetate I3 (5.19 g, 8.56 mmol) in methanol (40 mL) in a 250 mL flask was added 2 M aqueous sodium hydroxide (40 mL) and the reaction mixture was stirred at 60°C for 1.5 hours. The mixture was cooled to room temperature and concentrated to half volume. The residues were then acidified with hydrochloric acid and extracted with ethyl acetate. The combined organics were dried and concentrated to give 5-chloro-2-[[2-[(4-methoxyphenyl)methyl]-5- (trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine I4 as an orange oil (3.92 g, quantitative yield). 1 H NMR (400 MHz, CDCh) 6 = 8.55 (s, 2H), 7.05 - 6.95 (m, 2H), 6.84 - 6.75 (m, 2H), 6.47 (s, 1 H), 5.40 (s, 2H), 4.22 (s, 2H), 3.78 (s, 3H)
Step 5: Preparation of 5-chloro-2-[[3-(trifluoromethyl)-1H-pyrazol-5- yl]methyl]pyrimidine (I5)
A solution of 5-chloro-2-[[2-[(4-methoxyphenyl)methyl]-5-(trifluoromethyl)pyrazol-3- yl]methyl]pyrimidine 14 (3.92 g, 8.56 mmol) in 2,2,2-trifluoroacetic acid (14 mL) in a 100 mL flask was stirred at 90°C for one hour. The mixture was cooled to room temperature, slowly transferred into an aqueous sodium bicarbonate solution and then extracted with ethyl acetate. The combined organics were concentrated and subjected to column chromatography on silica gel using 0-60% ethyl acetate in cyclohexane to give 5-chloro-2-[[3-(trifluoromethyl)-1 H-pyrazol-5-yl]methyl]pyrimidine I5 as an off-white solid (2.365 g, 98% yield). 1 H NMR (400 MHz, CDCh) 6 = 8.70 (s, 2H), 6.49 (s, 1 H), 4.41 (s, 2H)
Step 6: Preparation of 5-chloro-2-[[2-(4,4-difluorobutyl)-5-
(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine (1.005)
To a 25 mL flask was added 5-chloro-2-[[3-(trifluoromethyl)-1 H-pyrazol-5- yl]methyl]pyrimidine I5 (98 mg, 0.336 mmol) and potassium carbonate (129 mg, 0.933 mmol). The mixture was treated with a solution of 4-bromo-1,1 -difluorobutane (90 mg, 0.520 mmol) in acetonitrile (1.5 mL) and was stirred at 70 °C and stirred for 1.5 hours. On completion, the mixture was allowed to cool before being diluted with water and extracted with ethyl acetate. The combined organics were concentrated and subjected prep-HPLC chromatography to give 5-chloro-2-[[2-(4,4-difluorobutyl)- 5-(trifluoromethyl)pyrazol-3-yl]methyl]pyrimidine 1.005 as a colourless oil (27 mg, 22% yield). 1H NMR (400 MHz, CDCI3) 5 = 8.65 (s, 2H), 6.43 (s, 1 H), 5.83 (tt, 1H), 4.32 (s, 2H), 4.26 (t, 2H), 2.10 - 1.96 (m, 2H), 1.94 - 1.78 (m, 2H).
Example 2: Preparation of 2-[[2-butyl-5-[chloro(difluoro)methyl]pyrazol-3- yl]methyl]-5-chloro-pyrimidine (1.020)
(1.020)
Step 1 : Preparation of ethyl 6-chloro-6,6-difluoro-3,5-dioxo-hexanoate (I6)
An ice-cooled solution of THF (80 mL) and lithium diisopropylamide solution (2.0 M in THF/heptane/ethylbenzene, 70 mL, 140 mmol) was treated dropwise with ethyl acetoacetate (5.10 mL, 40.3 mmol) and the resulting mixture was allowed to stir for 30 minutes at 0 °C. The reaction mixture was then cooled to -78°C, treated dropwise with ethyl chlorodifluoroacetate (6.60 mL, 52.1 mmol) and stirred for an additional 3.5 hours. The reaction mixture was allowed to warm to room temperature over 30 minutes before being quenched with 1 M hydrochloric acid (200 mL) and extracted with ethyl acetate (2 x 80 mL). The combined organics were dried and concentrated to provide ethyl 6-chloro-6,6-difluoro-3,5-dioxo-hexanoate (I6) as an oil which was used directly in the next step.
Step 2: Preparation of ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4- methoxyphenyl)methyl]pyrazol-3-yl]acetate (I7)
To a solution of ethyl 6-chloro-6,6-difluoro-3,5-dioxo-hexanoate (16) (prepared in step 1 , example 2) in acetic acid (40 mL) in a 100 mL flask was added (4- methoxybenzyl)hydrazine hydrochloride (7.05 g, 36.3 mmol) and the resulting mixture was allowed to stir at room temperature for 15 hours. The reaction mixture was concentrated and subjected to column chromatography on silica gel using 0- 30% ethyl acetate in cyclohexane to give ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4- methoxyphenyl)methyl]pyrazol-3-yl]acetate I7 as a brown oil (7.87 g, 48% yield). "' H NMR (400 MHz, chloroform) 5 = 7.10 - 7.04 (m, 2H), 6.89 - 6.82 (m, 2H), 6.50 (s, 1 H), 5.35 (s, 2H), 4.12 (q, 2H), 3.79 (s, 3H), 3.53 (s, 2H), 1.24 (t, 3H)
Step 3: Preparation of ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4- methoxyphenyl)methyl]pyrazol-3-yl]-2-(5-chloropyrimidin-2-yl)acetate (I8)
To a solution of ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4- methoxyphenyl)methyl]pyrazol-3-yl]acetate I7 (7.87 g, 21.9 mmol) in dimethyl sulfoxide (55 mL) in a 250 mL round bottomed flask was added 2,5- dichloropyrimidine (9.85 g, 66.1 mmol) and potassium phosphate tribasic (19.4 g, 89.5 mmol). The reaction mixture was warmed to 70 °C and was stirred for 3.5 hours. The reaction mixture was then cooled to room temperature before being diluted with 0.5 M hydrochloric acid (200 mL) and extracted with terf-butylmethyl ether (2 x 100 mL). The combined organic extracts were concentrated and subjected to column chromatography on silica gel using 0-30% ethyl acetate in cyclohexane to give ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4-methoxyphenyl)methyl]pyrazol-3-yl]-2-(5- chloropyrimidin-2-yl)acetate I8 as a brown oil (6.53 g, 60%). "' H NMR (400 MHz, chloroform) 5 = 8.55 (s, 2H), 6.99 - 6.92 (m, 2H), 6.79 - 6.75 (m, 2H), 6.68 (s, 1H), 5.45 - 5.33 (m, 3H), 4.20 - 4.09 (m, 2H), 3.77 (s, 3H), 1.19 (t, 3H).
Step 4: Preparation of 5-chloro-2-[[5-[chloro(difluoro)methyl]-2-[(4- methoxyphenyl)methyl]pyrazol-3-yl]methyl]pyrimidine (I9)
A solution of ethyl 2-[5-[chloro(difluoro)methyl]-2-[(4-methoxyphenyl)methyl]pyrazol- 3-yl]-2-(5-chloropyrimidin-2-yl)acetate I8 (6.52 g, 13.8 mmol) in methanol (70 mL) in a 250 mL round bottomed flask was treated with 2 M aqueous sodium hydroxide solution (70 mL, 140 mmol). The resulting mixture was warmed to 60°C and was allowed to stir for 2 hours. The reaction mixture was cooled to room temperature before being diluted with ethyl acetate (100 mL) and neutralised with 2 M hydrochloric acid (100 mL). The organic layer was then separated, and the aqueous layer extracted with ethyl acetate (100 mL). The combined organic extracts were then concentrated and subjected to column chromatography on silica gel using 0-35% ethyl acetate in cyclohexane to give 5-chloro-2-[[5-[chloro(difluoro)methyl]-2-[(4- methoxyphenyl)methyl]pyrazol-3-yl]methyl]pyrimidine I9 as a beige oil (3.76 g). "' H NMR (400 MHz, chloroform) 5 = 8.55 (s, 2H), 7.00 (d, 2H), 6.79 (d, 2H), 6.46 (s, 1 H), 5.40 (s, 2H), 4.21 (s, 2H), 3.78 (s, 3H).
Step 5: Preparation of 5-chloro-2-[[3-[chloro(difluoro)methyl]-1H-pyrazol-5- yl]methyl]pyrimidine (110)
A solution of 5-chloro-2-[[5-[chloro(difluoro)methyl]-2-[(4- methoxyphenyl)methyl]pyrazol-3-yl]methyl]pyrimidine I9 (3.756 g, 9.408 mmol) in 2,2,2-trifluoroacetic acid (15 mL) in a 100 mL round bottomed flask was warmed to 70°C and was allowed to stir for 3 hours. The reaction mixture was allowed to cool to room temperature before being added to water (200 mL), causing a precipitate to form. The mixture was filtered, and the aqueous filtrate was adjusted to pH>8 by addition solid potassium bicarbonate. The mixture was then extracted with ethyl acetate (2 x 100 mL) and the combined organics were then concentrated before being subjected to column chromatography on silica gel using 40-70% ethyl acetate in cyclohexane to give 5-chloro-2-[[3-[chloro(difluoro)methyl]-1 H-pyrazol-5- yl]methyl]pyrimidine 110 as an off-white solid (1.211 g). NMR (400 MHz, chloroform) 5 = 11.55 (br s, 1 H), 8.70 (s, 2H), 6.49 (s, 1 H), 4.40 (s, 2H)
Step 6: Preparation of 2-[[2-butyl-5-[chloro(difluoro)methyl]pyrazol-3- yl]methyl]-5-chloro-pyrimidine (1.020)
To a 25 mL flask was added 5-chloro-2-[[3-[chloro(difluoro)methyl]-1 H-pyrazol-5- yl]methyl]pyrimidine 110 (106 mg, 0.380 mmol) and triphenylphosphine (200 mg, 0.763 mmol). The vessel was evacuated and backfilled with nitrogen gas three times, before 2-methyltetrahydrofuran (2.50 mL) and 1-butanol (0.070 mL, 0.76 mmol) were added and the resulting solution was stirred and cooled to 0 °C. Diisopropyl azodicarboxylate (0.140 mL, 0.711 mmol) was then added dropwise, and the resulting mixture was allowed to warm to room temperature and stirred for 1 hour. The reaction was quenched by addition of methanol (20 mL), and the resulting mixture was concentrated and subjected to column chromatography on silica gel using 0-30% ethyl acetate in cyclohexane. The product rich fractions were concentrated and subjected to reverse-phase column chromatography on C-18 silica gel using 60-100% acetonitrile in water, both with 0.1% formic acid to give 2-[[2-butyl- 5-[chloro(difluoro)methyl]pyrazol-3-yl]methyl]-5-chloro-pyrimidine 1.020 as a colourless oil (21.1 mg). 1 H NMR (400 MHz, chloroform) 5 = 8.66 (s, 2H), 6.37 (s, 1 H), 4.31 (s, 2H), 4.17 (t, 2H), 1.83 - 1.75 (m, 2H), 1.39 - 1.29 (m, 2H), 0.93 (t, 3H).
Table 1. Compounds of the present invention
Biological Examples
Seeds of a variety of test species are sown in standard soil in pots Amaranthus palmeri (AMAPA), Amaranthus retoflexus (AMARE), Echinochloa crus-galli (ECHCG), Ipomoea hederacea (IPOHE), Setaria faberi (SETFA). After cultivation for one day (pre-emergence) or after 8 days cultivation (post-emergence) under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity), the plants are sprayed with an aqueous spray solution derived from the formulation of the technical active ingredient in acetone I water (50:50) solution containing 0.5% Tween 20 (polyoxyethelyene sorbitan monolaurate, CAS RN 9005-64-5). Compounds are applied at 250 g/ha unless otherwise stated. The test plants are then grown in a glasshouse under controlled conditions in a glasshouse (at 24/16°C, day/night; 14 hours light; 65 % humidity) and watered twice daily. After 13 days for pre and postemergence, the test is evaluated for the percentage damage caused to the plant. The biological activities are shown in the following table on a five-point scale (5 = 81- 100%; 4 = 61-80%; 3=41-60%; 2=21-40%; 1=0-20%).
TABLE B1 Post-emergence Test
T A B L E B2 Pre-emergence Test
NT = Not tested.

Claims

1. A compound of Formula (I): or an agronomically acceptable salt thereof, wherein
A is CR11 or N;
Q is selected from the group consisting of hydrogen, Ci-Cs alkyl, C2-C8 alkenyl, C2-C8 alkynyl, Ci-Cs haloalkyl, C2-C8 haloalkenyl, C2-C8 haloalkynyl, Ci-C4alkoxy-Ci-C3alkyl-, Ci-C4haloalkoxy-Ci-C3alkyl-, Ci-C4alkoxy-Ci- Cshaloalkyl-, Ci-Cscyanoalkyl-, C3-C6 cycloalkyl (optionally substituted by CN, fluoro or chloro), -S(O)pR4 and -(CH2)nR10;
R1 is independently selected from the group consisting of halogen, -CN, C1- C2alkyl, Ci-C2haloalkyl, Cs-Cecycloalkyl, Ci-C2alkoxy- and Ci-C2haloalkoxy-;
R2 is selected from the group consisting of halogen, -CN, NO2, Ci-C4alkyl, C1- C4haloalkyl, Ci-C4alkoxy, -C(O)Ci-C4alkyl, -C(O)OCi-C4alkyl, Ci-C4haloalkoxy, -S(O)pCi-C4alkyl, -C(R6)=NOR7 and Cs-Cecycloalkyl;
R3 is selected from the group consisting of hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, -CN, NO2, C2-C4alkenyl, C2- C4alkynyl, -S(O)pCi-C4alkyl, -S(O)pCi-C4haloalkyl, -C(O)OCi-C4alkyl and - C(O)NR8R9;
R4 is selected from the group consisting of Ci-C4alkyl, Ci-C4haloalkyl and C3- Cecycloalkyl; R5 is selected from the group consisting of hydrogen, methyl, ethyl, -(CH2)- cyclopropyl, C2-C3 alkenyl, C2-C3 alkynyl and cyclopropyl;
R6 is selected from the group consisting of hydrogen, methyl and ethyl;
R7 is methyl or ethyl;
R8 is hydrogen or Ci-C4alkyl;
R9 is hydrogen or Ci-C4alkyl;
R10 is selected from the group consisting of -OH, -C(H)O, -C(O)R4, -S(O)PR4, -C(H)(OH)-CH2OH, -C(R6)=NOR5, -NR12R13 C3-C6 cycloalkyl (optionally substituted by CN, fluoro or hydroxy), a C3-C6 saturated heterocycle comprising one or more oxygen atoms, and a 5-membered heteroaryl which comprises from 1 to 3 heteroatoms each independently selected from the group consisting of oxygen, nitrogen and sulphur, wherein said heteroaryl is optionally substituted by one or two substituents independently selected from the group consisting of halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl, C3- C4cycloalkyl, C1-C2 alkoxy and C1-C4 haloalkoxy;
R11 is selected from the group consisting of hydrogen, fluoro, chloro and CN;
R12 and R13 are independently selected from the group consisting of C1- C4alkyl, C3-C4cycloalkyl, Ci-C4alkyl-S(O)p-, C3-C4cycloalkyl-S(O)p-, Ci-C4alkyl- C(O)- and C3-C4cycloalkyl-C(O)-; m = 0, 1 or 2; n = 1 , 2 or 3; and p = 0, 1 or 2.
2. A compound of Formula (I) according to claim 1 , which is of Formula (la) wherein Q, R1, R2 and R3 are as defined in claim 1 above.
3. A compound according to any one of the previous claims, wherein R1 is chloro.
4. A compound according to any one of the previous claims, wherein R2 is halogen or Ci-C4haloalkyl.
5. A compound according to any one of the previous claims, wherein R3 is hydrogen or halogen.
6. A compound according to any one of the previous claims, wherein Q is selected from the group consisting of hydrogen, Ci-Cs alkyl, C2-C8 alkenyl, Ci- Cs haloalkyl, Ci-C4alkoxy-Ci-C3alkyl-, Ci-C4haloalkoxy-Ci-C3alkyl-, -S(O)PR4 and -(CH2)nR10.
7. A compound according to claim 6, wherein Q is -(CH2)nR10, n is 1 , 2 or 3 and R10 is selected from the group consisting of -OH, -C(H)(OH)-CH2OH and - C(H)=NOR5.
8. A compound according to claim 6, wherein Q is Ci-Cs alkyl.
9. A compound according to claim 6, wherein Q is Ci-Cs haloalkyl.
10. A compound according to claim 6, wherein Q is Ci-C4haloalkoxy-Ci-C3alkyl-.
11. A herbicidal composition comprising a compound according to any one of the previous claims and an agriculturally acceptable formulation adjuvant. A herbicidal composition according to claim 11 , further comprising at least one additional pesticide. A herbicidal composition according to claim 12, wherein the additional pesticide is a herbicide or herbicide safener. A method of controlling weeds at a locus comprising application to the locus of a weed controlling amount of a composition according to any one of claims 11 to 13. A compound of Formula (I l-a): wherein R2 is CF2H or CF2CI. Use of a compound of Formula (I) as defined in claim 1 as a herbicide.
EP23762382.2A 2022-09-01 2023-08-25 Herbicidal pyrazole compounds Pending EP4581022A1 (en)

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WO2025209544A1 (en) * 2024-04-02 2025-10-09 青岛清原化合物有限公司 Pyrazole pyrimidine compound and preparation method therefor, herbicidal composition, and use
CN121085895A (en) * 2024-06-03 2025-12-09 青岛清原化合物有限公司 Substituted pyrazole compound, preparation method thereof, weeding composition and application

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR8600161A (en) 1985-01-18 1986-09-23 Plant Genetic Systems Nv CHEMICAL GENE, HYBRID, INTERMEDIATE PLASMIDIO VECTORS, PROCESS TO CONTROL INSECTS IN AGRICULTURE OR HORTICULTURE, INSECTICIDE COMPOSITION, PROCESS TO TRANSFORM PLANT CELLS TO EXPRESS A PLANTINIDE TOXIN, PRODUCED BY CULTURES, UNITED BY BACILLA
EP0374753A3 (en) 1988-12-19 1991-05-29 American Cyanamid Company Insecticidal toxines, genes coding therefor, antibodies binding them, transgenic plant cells and plants expressing these toxines
EP0427529B1 (en) 1989-11-07 1995-04-19 Pioneer Hi-Bred International, Inc. Larvicidal lectins and plant insect resistance based thereon
UA48104C2 (en) 1991-10-04 2002-08-15 Новартіс Аг Dna fragment including sequence that codes an insecticide protein with optimization for corn, dna fragment providing directed preferable for the stem core expression of the structural gene of the plant related to it, dna fragment providing specific for the pollen expression of related to it structural gene in the plant, recombinant dna molecule, method for obtaining a coding sequence of the insecticide protein optimized for corn, method of corn plants protection at least against one pest insect
US5530195A (en) 1994-06-10 1996-06-25 Ciba-Geigy Corporation Bacillus thuringiensis gene encoding a toxin active against insects
AR031027A1 (en) 2000-10-23 2003-09-03 Syngenta Participations Ag AGROCHEMICAL COMPOSITIONS
AR037856A1 (en) 2001-12-17 2004-12-09 Syngenta Participations Ag CORN EVENT
WO2013126283A1 (en) * 2012-02-20 2013-08-29 E. I. Du Pont De Nemours And Company Fungicidal pyrazoles
CN105037342B (en) 2015-08-07 2018-10-09 华中农业大学 Pyrazole ether compounds with activity of weeding and its application
AR118951A1 (en) 2019-05-20 2021-11-10 Syngenta Crop Protection Ag COMPOSITIONS AND METHODS FOR WEED CONTROL
GB202011068D0 (en) 2020-07-17 2020-09-02 Syngenta Crop Protection Ag Improvements in or relating to organic compounds
GB202017990D0 (en) 2020-11-16 2020-12-30 Syngenta Crop Protection Ag Improvements in or relating to organic compounds
GB202117474D0 (en) 2021-12-03 2022-01-19 Syngenta Crop Protection Ag Improvements in or relating to organic compounds

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