WO2013164245A1 - Composés régulateurs de croissance des plantes - Google Patents

Composés régulateurs de croissance des plantes Download PDF

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Publication number
WO2013164245A1
WO2013164245A1 PCT/EP2013/058607 EP2013058607W WO2013164245A1 WO 2013164245 A1 WO2013164245 A1 WO 2013164245A1 EP 2013058607 W EP2013058607 W EP 2013058607W WO 2013164245 A1 WO2013164245 A1 WO 2013164245A1
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Prior art keywords
cyano
alkyl
amine
halogen
hydrogen
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PCT/EP2013/058607
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English (en)
Inventor
Pierre Joseph Marcel Jung
Joerg LEIPNER
Mathilde Denise Lachia
Alain De Mesmaeker
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Syngenta Participations Ag
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Priority claimed from GBGB1207758.2A external-priority patent/GB201207758D0/en
Application filed by Syngenta Participations Ag filed Critical Syngenta Participations Ag
Publication of WO2013164245A1 publication Critical patent/WO2013164245A1/fr

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    • 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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • C07D403/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to novel non-steroidal brassinosteroid mimetic derivatives, to processes and intermediates for preparing them, to plant growth regulator compositions comprising them and to methods of using them for controlling the growth of plants and/or promoting the germination of seeds.
  • certain new non-steroidal brassinosteroid mimetic derivatives have properties that are useful for controlling the growth of plants and/or promoting the germination of seeds.
  • the new compounds of Formula (I) may result in improved plant growth properties, such as faster growth, faster germination, earlier germination, and / or reduced toxicity.
  • the compounds of Formula (I) may offer other advantages such as enhanced solubility, or be more advantageously formulated, provide more efficient delivery to the plant, provide improved uptake into the plant, or be more readily biodegradable.
  • each W is independently O or S
  • a 2 is C-Ri or nitrogen;
  • a 3 is C-X;
  • Ri is H, Ci-Cehaloalkyl, cyano, halogen, Ci-Cealkoxy, Ci-C 6 haloalkoxy, Ci-C 6 alkyl or Ci- Cealkyl substituted by one or more cyano, nitro, hydroxyl, amine;
  • X is halogen, Ci-C 6 haloalkyl, cyano, thiocyanate, nitro, Ci-C 6 alkoxy, Ci-Cehaloalkoxy, Ci- Cealkylthio, Ci-Cehaloalkylthio, Ci-Cealkylsulfinyl, Ci-Cehaloalkylsulfinyl, Ci-Cealkyl- sulfonyl, Ci-Cehaloalkylsulfonyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, amine, N- Ci-Cealkyl amine, N,N-di-Ci-C 6 alkyl amine, Ci-Cealkylcarbonyl, Ci-Cealkoxycarbonyl, Ci- C 6 haloalkoxycarbonyl, Ci-Cehaloalkylcarbonyl, Cs-Cscycloalkyl, formyl or mer
  • R 2 , R3, R 4 and R 5 are independently hydrogen, halogen, nitro, cyano, Ci-C 4 alkyl, Ci- C 4 haloalkyl, Ci-C 4 alkoxy, hydroxyl, -OC(0)R6, amine, N- Ci-C 3 alkyl amine or N,N-di-Ci- C 3 alkyl amine; and 5 is hydrogen, Ci-Cealkyl, Ci-Cealkoxy, or Ci-Cehaloalkyl; or salts or N-oxides thereof, and provided that the following compounds are excluded, wherein:
  • W is O
  • a 3 is C-X wherein X is amino
  • Ai and A 4 are C-Ri wherein Ri is H
  • a 2 is C-
  • Ri wherein Ri is H or methyl, and a) one of R 2 , R 3 , R 4 or R 5 is methyl, b) two of R 2 , R 3 , R 4 and R 5 are ethyl, c) one of R 2 , R 3 , R 4 or R5 is methyl and another is isopropyl or d) all of R 2 , R 3 , R 4 and R 5 are hydrogen;
  • W is O
  • a 3 is C-X wherein X is methyl or methylcarbonyl
  • Ai are C-Ri wherein Ri is H
  • R 2 , R 3 , R 4 and R 5 are hydrogen
  • W is O
  • a 3 is C-X wherein X is Br
  • Ai is C-Ri wherein Ri is H or Br
  • a 2 and A 4 are
  • W is O
  • a 3 is C-X wherein X is amino
  • Ai and A 4 are C-Ri wherein Ri is cyano
  • a 2 is
  • R 2 , R3, R4 and R 5 are hydrogen.
  • the present invention also includes a method for regulating the growth of plants at a locus, wherein the method comprises applying to the locus a plant growth regulating amount of a compound of Formula (I)
  • each W is independently O or S
  • a 2 is C-Ri or nitrogen;
  • a 3 is C-X;
  • Ri is H, Ci-C 6 haloalkyl, cyano, halogen, Ci-Cealkoxy, Ci-C 6 haloalkoxy, Ci-Cealkyl or Ci- Cealkyl substituted by one or more cyano, nitro, hydroxyl, amine;
  • X is halogen, Ci-C 6 haloalkyl, cyano, thiocyanate, nitro, Ci-C 6 alkoxy, Ci-Cehaloalkoxy, Ci-
  • Re is hydrogen, Ci-Cealkyl, Ci-Cealkoxy, or Ci-Cehaloalkyl; or salts or N-oxides thereof,
  • the present invention further provides the use of a compound of Formula (I) as a plant growth regulator or a seed germination promoter.
  • the compounds of Formula (I) may exist in different geometric or optical isomers (diastereoisomers and enantiomers) or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds. The invention also covers all salts, N-oxides, and metalloidic complexes of the compounds of Formula (I).
  • Each alkyl moiety either alone or as part of a larger group is a straight or branched chain and is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, z ' so-propyl, n- butyl, sec-butyl, z ' so-butyl, tert-bvXy ⁇ or neo-pentyl.
  • the alkyl groups are preferably Ci to C 6 alkyl groups, more preferably C 1 -C 4 and most preferably C 1 -C 3 alkyl groups.
  • Each alkenyl moiety either alone or as part of a larger group is having at least one carbon-carbon double bond and is, for example, vinyl, allyl.
  • the alkenyl groups are preferably C 2 to C 6 alkenyl groups, more preferably C 2 -C 4 alkenyl groups.
  • Each alkynyl moiety either alone or as part of a larger group is having at least one carbon-carbon triple bond and is, for example, ethynyl, propargyl.
  • the alkynyl groups are preferably C 2 to Cealkynyl groups, more preferably C 2 -C 4 alkynyl groups.
  • alkynyl as used herein, unless otherwise indicated, includes alkyl moieties having at least one carbon- carbon triple bond wherein alkyl is as defined above.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkyl groups are alkyl groups which are substituted with one or more of the same or different halogen atoms and are, for example, -CF 3 , -CF 2 C1, -CH 2 CF 3 or -CH 2 CHF 2 .
  • Hydroxyalkyl groups are alkyl groups which are substituted with one or more hydroxyl group and are, for example, -CH 2 OH, -CH 2 CH 2 OH or -CH(OH)CH 3 .
  • aryl refers to a ring system which may be mono-, bi- or tricyclic. Examples of such rings include phenyl, naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred aryl group is phenyl.
  • alkenyl and alkynyl on their own or as part of another substituent, may be straight or branched chain and may preferably contain 2 to 6 carbon atoms, preferably 2 to 4, more preferably 2 to 3, and where appropriate, may be in either the (E)- or ( ⁇ -configuration. Examples include vinyl, allyl and propargyl.
  • cycloalkyl may be mono- or bi-cyclic, may be optionally substituted by one or more Ci-Cealkyl groups, and preferably contain 3 to 7 carbon atoms, more preferably 3 to 6 carbon atoms.
  • Examples of cycloalkyl include cyclopropyl,
  • heteroaryl refers to an aromatic ring system containing at least one heteroatom and consisting either of a single ring or of two or more fused rings.
  • single rings will contain up to three and bicyclic systems up to four heteroatoms which will preferably be chosen from nitrogen, oxygen and sulfur.
  • Examples of such groups include pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, furanyl, thiophenyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl and tetrazolyl.
  • a preferred heteroaryl group is pyridine.
  • heterocyclyl is defined to include heteroaryl and in addition their unsaturated or partially unsaturated analogues such as 4,5,6,7-tetrahydro-benzothiophenyl, 9H-fluorenyl, 3,4-dihydro-2H-benzo-l ,4-dioxepinyl, 2,3-dihydro-benzofuranyl, piperidinyl, 1 ,3-dioxolanyl, 1 ,3-dioxanyl, 4,5-dihydro-isoxazolyl, tetrahydrofuranyl and morpholinyl.
  • Preferred values of W, A l s A 2 , A 3 , t, Ri, R 2 , R3, R4, R5 and X of the compound of formula I are, in any combination, as set out below:
  • W is O.
  • a 2 is C-Ri or nitrogen.
  • Ri is H, Ci-Cehaloalkyl, Ci-Cealkoxy, halogen, Ci-Cealkyl, or Ri is Ci-Cealkyl substituted by one or more halogen, hydroxyl or amine. More preferably Ri is H, methyl, methoxy or ethoxy; even more preferably Ri is H.
  • a 3 is C-X.
  • X is halogen, Ci-Cehaloalkyl, cyano, Ci-C 6 haloalkoxy, Ci-Cehaloalkylthio, Ci-Cehaloalkyl- sulfinyl, or Ci-Cehaloalkylsulfonyl; or X is heteroaryl optionally subtituted by one or more halogen, cyano, Ci-C 3 alkyl. More preferably X is halogen, Ci-Cehaloalkyl or cyano; even more preferably X is trifluoromethyl, cyano, bromo or chloro.
  • R 2 , R3, R4 and R 5 are independently hydrogen, halogen, cyano, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy; even more preferably R 2 , R3, R4 and R 5 are hydrogen.
  • W is O or S
  • A3 is C-X wherein X is cyano, C 1 -C 3 haloalkyl, bromo, chloro;
  • a 2 is C-Ri or nitrogen, wherein Ri is H or Ci-C 4 alkoxy;
  • A4 is C-Ri, wherein Ri is H or C 1 -C 4 alkyl
  • R 2 , R 3 , R4 and R 5 are hydrogen.
  • W is O
  • a 2 is C-Ri or nitrogen
  • Ri is H, methyl, methoxy or ethoxy
  • a 3 is C-X
  • X is halogen, Ci-C 6 haloalkyl, cyano, Ci-C 6 haloalkoxy, Ci-Cehaloalkylthio, Ci-Cehaloalkyl- sulfinyl, or Ci-Cehaloalkylsulfonyl; or X is heteroaryl optionally subtituted by one or more halogen, cyano, Ci-C 3 alkyl; and
  • R 2 , R 3 , R4 and R 5 are hydrogen.
  • X is halogen, Ci-Cehaloalkyl or cyano. In a further embodiment, X is trifluoromethyl, cyano, bromo or chloro. In one embodiment, X is not halogen when A 2 is C-Ri . In a further embodiment, X is trifluoromethyl or cyano.
  • Compounds of the present invention are particularly suitable for good uptake into the plant, through roots or shoots.
  • the pyrrolidine ring may be cleaved to form an alkyl chain terminating in a hydroxyl group as depicted in Formula (Ila),
  • pyrrolidine ring may be cleaved to form a equilibrium between compounds of Formula (Ila) and compounds of Formula (I).
  • Compounds of Formula (Ila) form may be biologically active.
  • a 3 is C-X wherein X is amino
  • Ai and A 4 are C-Ri wherein Ri is H
  • a 2 is C-Ri wherein Ri is H or methyl
  • a) one of R 2 , R 3 , R 4 or R 5 is methyl
  • two of R 2 , R 3 , R 4 and R 5 are ethyl
  • c) one of R 2 , R 3 , R 4 or R5 is methyl and another is isopropyl or d) all of R 2 , R3, R4 and R 5 are hydrogen.
  • a 3 is C-X wherein X is methyl or methylcarbonyl
  • Ai A 2 and A 4 are C- Ri wherein Ri is H
  • R 2 , R 3 , R 4 and R 5 are hydrogen.
  • W is O
  • a 3 is C-X wherein X is Br
  • Ai is C-Ri wherein Ri is H or Br
  • a 2 and A 4 are C-Ri wherein Ri is H
  • R 2 , R 3 , R 4 and R 5 are hydrogen.
  • W is O
  • a 3 is C-X wherein X is CI
  • Ai are C-Ri wherein Ri is H
  • a) two of R 2 , R 3 , R 4 and R 5 are methyl or b) all of R 2 , R 3 , R 4 and R 5 are hydrogen.
  • a 3 is C-X wherein X is I
  • Ai are C-Ri wherein Ri is H
  • a) two of R 2 , R 3 , R 4 and R 5 are methyl, or b) two of R 2 , R 3 , R 4 and R 5 are methyl and one of R 2 , R 3 , R 4 and R 5 is hydroxyl.
  • Table 1 below includes examples of compounds of Formula (I) wherein W is O, A l s A 2 , A 3i A4 and R 2 , R3, R4, R5 are as defined.
  • the compounds of Formula I according to the invention can be used as plant growth regulators or seed germination promoters by themselves, but they are generally formulated into plant growth regulation or seed germination promotion compositions using formulation adjuvants, such as carriers, solvents and surface-active agents (SFAs).
  • formulation adjuvants such as carriers, solvents and surface-active agents (SFAs).
  • the present invention further provides a plant growth regulator composition comprising a plant growth regulation compound as described hereinand an agriculturally acceptable formulation adjuvant or carrier.
  • the present invention further provides a seed germination promoter composition comprising a seed germination promoter compound as described hereinand an agriculturally acceptable formulation adjuvant or carrier.
  • the composition consists essentially of a compound of Formula I and an agriculturally acceptable formulation adjuvant or carrier.
  • the composition consists of a compound of Formula I and at least one agriculturally acceptable formulation adjuvant or carrier.
  • 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.
  • 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.
  • 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, many of which are known from the Manual on Development and Use of FAO Specifications for Plant Protection Products, 5th Edition, 1999.
  • Dustable powders may be prepared by mixing a compound of Formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders 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).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulphate
  • water-soluble organic solids such as a polysaccharide
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules 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 pre-formed 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.
  • a hard core material such as sands, silicates, mineral carbonates, sulphates or phosphates
  • 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).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • 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).
  • DC Dispersible Concentrates
  • a compound of Formula (I) may be prepared by dissolving a compound of Formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether.
  • organic solvent such as a ketone, alcohol or glycol ether.
  • surface active agent for example to improve water dilution or prevent crystallisation in a spray tank.
  • Emulsifiable concentrates 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).
  • 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
  • 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 SFAs, 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 may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of Formula (I) is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use 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.
  • SC Suspension concentrates
  • SCs 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.
  • 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 /? -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.
  • a suitable medium for example water or a water miscible liquid, such as n-propanol
  • Capsule suspensions (CS) may be prepared in a manner similar to the preparation of
  • 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 poly condensation 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).
  • additives include surface active agents (SFAs), spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), 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 SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs 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
  • alcohol ether sulphates for example sodium laureth-3-sulphate
  • ether carboxylates for
  • Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
  • Suitable SFAs 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); and lecithins.
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
  • hydrophilic colloids such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose
  • swelling clays such as bentonite or attapulgite.
  • the present invention also provides a method for promoting the germination of seeds, comprising applying to the seeds, or to a locus containing seeds, a seed germination promoting amount of a composition according to the present invention.
  • 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.
  • the composition may be applied in furrow or directly to a seed before or at the time of planting.
  • the compound of Formula (I) or composition of the present invention may be applied to a plant, part of the plant, plant organ, plant propagation material or a surrounding area thereof.
  • the invention relates to a method of treating a plant
  • the invention also relates to a plant propagation material treated with a compound of Formula (I) or a composition of the present invention.
  • the plant propagation material is a seed.
  • plant propagation material denotes all the generative parts of the plant, such as seeds, which can be used for the multiplication of the latter and vegetative plant materials such as cuttings and tubers.
  • seeds which can be used for the multiplication of the latter and vegetative plant materials such as cuttings and tubers.
  • vegetative plant materials such as cuttings and tubers.
  • Methods for applying active ingredients to plant propagation material, especially seeds are known in the art, and include dressing, coating, pelleting and soaking application methods of the propagation material.
  • the treatment can be applied to the seed at any time between harvest of the seed and sowing of the seed or during the sowing process.
  • the seed may also be primed either before or after the treatment.
  • the compound of Formula (I) may optionally be applied in combination with a controlled release coating or technology so that the compound is released over time.
  • composition of the present invention may be applied pre-emergence or post- emergence.
  • the composition may be applied pre or post-emergence, but preferably post-emergence of the crop.
  • the composition may be applied pre- emergence.
  • 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 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 0.001 to 2000 g/ha, especially from 0.01 to 400 g/ha.
  • the rate of application is generally between 0.0005 and 150g per 100kg of seed.
  • Plants in which the composition according to the invention can be used include crops such as cereals (for example wheat, barley, rye, oats); beet (for example sugar beet or fodder beet); fruits (for example pomes, stone fruits or soft fruits, such as apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries or blackberries); leguminous plants (for example beans, lentils, peas or soybeans); oil plants (for example rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts); cucumber plants (for example marrows, cucumbers or melons); fibre plants (for example cotton, flax, hemp or jute); citrus fruit (for example oranges, lemons, grapefruit or mandarins); vegetables (for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika); lauraceae (for example avocados, cinnamon or camphor); maize; rice; tobacco;
  • Crops are to be understood as also including those crops which have been modified by conventional methods of breeding or by genetic engineering.
  • the invention may be used in conjunction with crops that have been rendered tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-inhibitors).
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS-, PPO-, ACCase- and HPPD-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
  • Methods of rending crop plants tolerant to HPPD- inhibitors are known, for example from WO0246387; for example the crop plant is transgenic in respect of a polynucleotide comprising a DNA sequence which encodes an HPPD-inhibitor resistant HPPD enzyme derived from a bacterium, more particularly from Pseudomonas fluorescens or Shewanella colwelliana, or from a plant, more particularly, derived from a monocot plant or, yet more particularly, from a barley, maize, wheat, rice, Brachiaria, Chenchrus, Lolium, Festuca, Setaria, Eleusine, Sorghum or Avena species.
  • a polynucleotide comprising a DNA sequence which encodes an HPPD-inhibitor resistant HPPD enzyme derived from a bacterium, more particularly from Pseudomonas fluorescens or Shewanella colwelliana, or from a plant, more particularly, derived from a monocot plant or, yet more
  • Crops 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.
  • Crops 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.
  • Compounds of the present invention may be in the form of an ester or an acid, either of which may have plant growth regulating properties. As suggested in WO2009/109570, it is thought that the ester form of the compounds of Formula I may be hydro lysed in planta to the acid form. This may be a particular advantage where the esterified compounds are more readily taken up by the plant, for example through leaf tissue.
  • Compounds and compositions of the present invention may be applied in combination with other active ingredients or products for use in agriculture, including insecticides, fungicides, herbicides, plant growth regulators, crop enhancing compounds, nutrients and biologicals.
  • suitable mixing partners may be found in the Pesticide Manual, 15 th edition (published by the British Crop Protection Council). Such mixtures may be applied to a plant, plant propagation material or plant growing locus either simultaneously (for example as a pre-formulated mixture or a tank mix), or sequentially in a suitable timescale.
  • Co- application of pesticides with the present invention has the added benefit of minimising farmer time spent applying products to crops.
  • the compounds or composition of the present invention may be applied in combination with one or more other compounds having a crop enhancement effect.
  • Such compounds include micronutrients, saccharides, amino acids, flavonoids, quinines, and plant activators / growth stimulators.
  • such compounds include natural or synthetic hormones, auxins, brassinosteroids, gibberellins, abscisic acid, cytokinins, jasmonates, strigolactones, salicylic acid, ethylene, 1-methylcyclopropene, trinexapac-ethyl or derivatives thereof.
  • Such compounds also include pesticides that have a crop enhancement effect, for example strobilurins (including azoxystrobin, pyraclostrobin), and neonicotinoids (including thiamethoxam, and imidacloprid).
  • strobilurins including azoxystrobin, pyraclostrobin
  • neonicotinoids including thiamethoxam, and imidacloprid
  • the compounds of the invention may be made by the following methods. SCHEME 1
  • Compounds of Formula (I) may be prepared, in one step from a compound of Formula (IV) by reaction in the presence of compound of Formula (Ilia) by heating, optionally in the presence of an acid, such as acetic acid or a base, such as triethylamine.
  • an acid such as acetic acid or a base, such as triethylamine.
  • compounds of Formula (I) may be prepared, in one step from a compound of Formula (IV) by reaction in the presence of compound of Formula (V) by heating, optionally in the presence of an acid , such as acetic acid or a base, such as triethylamine.
  • an acid such as acetic acid or a base, such as triethylamine.
  • Compounds of Formula (I) may be prepared from a compound of Formula (Ila) by reaction in the presence of a coupling reagent, such as Diimidazolyl ketone, DCC (N,N'-dicyclohexyl- carbodiimide), EDCI (l-Ethyl-3-(3-dimethylaminopropyl)carbodiimide monohydrochloride) or BOP-C1 (bis(2-oxo-3-oxazolidinyl)phosphonic chloride), optionally in the presence of a base, such as pyridine, triethylamine, 4-(dimethylamino)pyridine or diisopropylethylamine, and optionally in the presence of a nucleophilic catalyst, such as hydroxybenzotriazole.
  • a coupling reagent such as Diimidazolyl ketone, DCC (N,N'-dicyclohexyl- carbodiimide), EDCI (l-E
  • compounds of Formula (I) may be prepared from a compound of Formula (Ila) by reaction in the presence of anhydride or acid chloride derivatives such as acetic anhydride or phenyl optionally in presence of a base such as sodium acetate.
  • anhydride or acid chloride derivatives such as acetic anhydride or phenyl optionally in presence of a base such as sodium acetate.
  • compounds of Formula (I) may be prepared from a compound of Formula (Ila) via acid halides of Formula (lib) within X is a leaving group such as chloride by reaction of compound (Ila) under standard conditions, such as treatment with thionyl chloride or oxalyl chloride.
  • the reaction may be carried out under basic conditions (for example in the presence of pyridine, triethylamine, 4-(dimethylamino)pyridine or diisopropylethylamine), optionally in the presence of a nucleophilic catalyst.
  • the reaction may be conducted in a biphasic system comprising an organic solvent, preferably ethyl acetate, and an aqueous solvent, preferably a solution of sodium bicarbonate.
  • Compounds of Formula (Ila) may be made by treatment of compounds of Formula (II), wherein R is alkyl substituted or not such methyl, by hydrolysis under standard conditions, such as treatment with an alkali hydroxide, such as sodium hydroxide or potassium
  • hydroxide in a solvent, such as ethanol or tetrahydroiuran, in the presence of water.
  • a solvent such as ethanol or tetrahydroiuran
  • Another alternative is the treatment of the ester of Formula (II) with an acid, such as trifluoroacetic acid, in a solvent, such as dichloromethane, followed by addition of water.
  • the reaction is carried out preferably at a temperature of from -20 °C to +100 °C, more preferably from 20 °C to 80 °C, in particular at 50 °C.
  • Compounds of formula (Ila) may be made by treatment of compounds of formula (IV) by treatment with a anhydride derivatives of formula (V), such as succinyl anhydride, in a solvent, such as tetrahydroiuran.
  • a reaction is carried out preferably at a temperature of from -20°C to +120°C, more preferably from 20°C to 120°C.
  • compounds of Formula (I) may be prepared from a compound of Formula (II), when R is alkyl substituted or not such methyl by heating in presence of a acid or a base, such as hydrogen chloride or caesium carbonate and, optionally in the presence of a nucleophilic catalyst such as potassium iodide.
  • a acid or a base such as hydrogen chloride or caesium carbonate
  • a nucleophilic catalyst such as potassium iodide.
  • Compounds of Formula (II) may be prepared from a compound of Formula (IV) via acylation by reaction of a compounds of Formula (III) within Z is halogen such as chlorine and R is alkyl substituted or not such as methyl. Such reactions are usually carried out in the presence of a base, and optionally in the presence of a nucleophilic catalyst. Alternatively, it is possible to conduct the reaction in a biphasic system comprising an organic solvent, preferably ethyl acetate, and an aqueous solvent, preferably a solution of sodium hydrogen carbonate.
  • Compounds of Formula (lie) wherein W is O may be prepared from a compound of Formula (II) wherein W are oxygen, by treatment with a thio-transfer reagent, such as Lawesson's reagent or phosphorus pentasulfide.
  • a thio-transfer reagent such as Lawesson's reagent or phosphorus pentasulfide.
  • Capillary 3.00 kV, Cone: 30.00 V, Extractor: 2.00 V, Source Temperature: 100°C,
  • Step 1 Method A: methyl 4-oxo-4-[[5-(cyano)-2-pyridyl]amino]butanoate II.1
  • the 6-amino-3-pyridinecarbonitrile (Commercialy available, 0.470 g, 1.0 eq.) was dissolved in tetrahydroiuran (10 mL) then N,N-dimethylaniline (0.5 mL, 1.0 eq.) and methyl-4-chloro- 4-oxo-butanoate (0.54 mL, 1.1 eq.) were successively added. The mixture was reflux for 12 h. The reaction was stopped and the solution was partitioned between ethyl acetate and water. The aqueous layer was separated and extracted with ethyl acetate (2x). The combined organic layer were dried on magnesium sulfate and concentrated under vacuum.
  • methyl 4-[(5-bromo-2-pyridyl)amino]-3,3-dimethyl-4-oxo-butanoate 11.5 was synthesised starting from 5-bromo-2-aminopyridine (commercially available) and 2,2-dimethylbutanedioic acid 1 -methyl ester (commercially available) by generating the acid chloride using oxalyl chloride and one drop of N,N- dimethylformamide in dichloromethane: LC-MS (Method D): RT 0.91, 315 (M- H + ).
  • Step 1 Method B: methyl 4-[[4,5-bis(trifluoromethyl)-2-pyridyl]amino]-4-oxo-butanoate hydrate (13)
  • Methyl succinamate (1.29 g, 9.6177 mmol) , carbonic acid dicesium (2.61141 g, 8.0147 mmol) , 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (0.213 g, 0.3607 mmol) , and Pd2(dba)3 (0.22695 g, 0.2404 mmol) were added to a solution of 2-chloro-4,5- bis(trifluoromethyl)pyridine (Commercialy available, 2 g, 8.0147 mmol) in 1,4-dioxane (8.015 mL). The mixture obtained was purged with azote and the reaction was heated at 100°c for 12h.
  • Step 2 Method A: 4-oxo-4-[[5-(cyano)-2-pyridyl] amino] butanoic acid 12.1
  • the 6-amino-3-pyridinecarbonitrile (commercially available, 1 g, 8.40 mmol) was dissolved in tetrahydrofuran (20 mL) then succinic anhydride (1.04g, 10.5 mmol) was added, the mixture was stirred at 100 °C for 12 h. The reaction was stopped and the solution was washed with a saturated solution of sodium carbonate. The organic layer was concentrated under vacuum. The residue was purified by flash chromatography eluting with methanol-ethyl acetate (5/95) to give 4-[(5-cyano-2-pyridyl)amino]-4-oxo-butanoic acid A2 (0.325 g, 18%).
  • Lithium hydroxide (0.308 g, 12.86 mmol) was added at ambient temperature to a solution of: methyl 4-oxo-4-[[5-(cyano)-2-pyridyl] amino] butanoate II.1 (3 g, 12.86 mmol) in a mixture of tetrahydrofurann (100 ml) and water (20 mL).
  • the reaction mixture was stirred at room temperature for 4 h.
  • the reaction is not finished 0.5 eq of LiOH was added the reaction was stirred at room temperature for 4 h.
  • the reaction was stopped by dilution with a mixture of water and ethyl acetate. After separation, the aqueous phase was acidified by addition of aqueous hydrochloric acid (concentrated) and the precipited was filtered to give the desired compound 12.1 (35.4%).
  • Step 3 l-[5-(cyano)-2-pyridyl] pyrrolidine-2, 5-dione Al
  • Butanoic acid 4-[(5-bromo-2-pyridinyl)amino]-4-oxo- (other names: Abrasin, Bikinin: commercially available, 0.5g, 3 mmol) was dissolved in xylene (10 mL) then succinic anhydride (0.4 g, 4 mmol) was added, the mixture was stirred at 140 °C for 5 h with a dean- stark. After cooling down the dean- stark was removed and acetyl chloride (0.5 g, 0.4 mL, 6 mmol) was added to the mixture. Then, the mixture was stirred at 140 °C for 3 h. The residue was dissolved with ethyl acetate and washed with a saturated solution of sodium
  • 6-(2,5-dioxopyrrolidin-l-yl)-2,4-dimethyl-pyridine-3-carbonitrile A12 from 6- amino-2,4-dimethyl-pyridine-3-carbonitrile (commercially available): 1H NMR (400 MHz, CDCI3) ⁇ 7.26 (s, 1H), 7.09 (s, 1H), 2.94 (s, 4H), 2.78 (s, 3H), 2.60 (s,
  • Methyl 4-[(5-bromopyrazin-2-yl)amino]-4-oxo-butanoate (11.3, 200 mg, 0.694 mmol) was dissolved in N,N-dimethylformamide (4.5 mL) in a microwave vial and 2- (tributylstannyl)thiophene (1.2 equiv., 0.83 mmol, 0.2785 ml) and tetrakis (triphenylphosphine) palladium(O) (0.069 mmol) were added.
  • Argon was bubbling through the mixture for ca. 5 min and the vial was heated under microwave irradiations for 10 min at 150 °C.
  • Bioassays Two bioassays were developed in order to assay the activity of the compounds of the present invention.
  • the activity of the compound was quantified in beans based on its effect on the elongation of the petiole of the second leaf.
  • the compound's effect on the root growth of wheat was determined.
  • Example Bl Bean assay
  • French beans Phaseolus vulgaris of the variety Fulvio were sown in 0.5 L pots in a sandy loam without additional fertilizer. Plants grew under greenhouse conditions at 22/18 °C (day/night) and 80% relative humility; light was supplemented above 25 kLux.
  • Plants were treated with test compounds eleven days after sowing, when the second internode was 2-5 mm long. Before application, the compounds were each dissolved in dimethyl sulfoxide and diluted in a mixture of ethanol and water (1 : 1 ratio by volume). Five micro litres of the test compound was pipetted to the wound created after abscising the bract leaf from the base of the second internode. Fourteen days after application, the length of the petiole of the second leaf (measured from the base of the petiole to the base of the first leaflet) was determined in order to quantify the activity of the compounds.
  • test compounds were dissolved in small volumes of dimethyl sulfoxide and diluted to the appropriate concentration with water.
  • Wheat (Triticum aestivum) seeds of the variety Arina were sown in mini-pouches (10.5 x 9.0 cm) containing 5 mL of the appropriate compound solution.
  • the mini pouches were stored at 17°C for three days to enable the seeds to germinate. Plants were then stored at 5°C. Twelve days after sowing/application, plants were removed from the mini-pouches and scanned. The effect of the compounds was quantified by determining plant (root and shoot) area and curliness of the roots (curliness is an indicator of brassinosteroid-type activity).

Abstract

La présente invention porte sur de nouveaux dérivés non stéroïdiens mimétiques de brassinostéroïdes, sur des procédés et intermédiaires permettant de les préparer, sur des compositions de régulateur de croissance des plantes les comprenant et sur leurs procédés d'utilisation pour réguler la croissance de plantes et/ou favoriser la germination de graines.
PCT/EP2013/058607 2012-05-02 2013-04-25 Composés régulateurs de croissance des plantes WO2013164245A1 (fr)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
WO2014131735A1 (fr) * 2013-02-28 2014-09-04 Syngenta Participations Ag Utilisation de composés chimiques en tant qu'herbicides

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US4072499A (en) * 1976-12-22 1978-02-07 Monsanto Company Use of pyridyl phthalimides as plant growth regulants
US4124375A (en) * 1977-10-12 1978-11-07 Monsanto Company Substituted phthalimides for regulating the growth of plants
EP0579835A1 (fr) * 1991-11-12 1994-01-26 Nippon Soda Co., Ltd. Materiau de conversion de la longueur d'onde de la lumiere, a usage dans l'agriculture
WO2008049729A1 (fr) * 2006-10-12 2008-05-02 Vib Vzw Mimétique de brassinostéroïde non-stéroïdien
WO2009109570A1 (fr) * 2008-03-03 2009-09-11 Gmi - Gregor-Mendel-Institut Für Molekulare Pflanzenbiologie Gmbh Inhibiteurs pour la signalisation des brassinostéroïdes

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
US4072499A (en) * 1976-12-22 1978-02-07 Monsanto Company Use of pyridyl phthalimides as plant growth regulants
US4124375A (en) * 1977-10-12 1978-11-07 Monsanto Company Substituted phthalimides for regulating the growth of plants
EP0579835A1 (fr) * 1991-11-12 1994-01-26 Nippon Soda Co., Ltd. Materiau de conversion de la longueur d'onde de la lumiere, a usage dans l'agriculture
WO2008049729A1 (fr) * 2006-10-12 2008-05-02 Vib Vzw Mimétique de brassinostéroïde non-stéroïdien
WO2009109570A1 (fr) * 2008-03-03 2009-09-11 Gmi - Gregor-Mendel-Institut Für Molekulare Pflanzenbiologie Gmbh Inhibiteurs pour la signalisation des brassinostéroïdes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014131735A1 (fr) * 2013-02-28 2014-09-04 Syngenta Participations Ag Utilisation de composés chimiques en tant qu'herbicides

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