WO2024068474A1 - Anilino-derivatives as plant growth promoters - Google Patents

Anilino-derivatives as plant growth promoters Download PDF

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Publication number
WO2024068474A1
WO2024068474A1 PCT/EP2023/076253 EP2023076253W WO2024068474A1 WO 2024068474 A1 WO2024068474 A1 WO 2024068474A1 EP 2023076253 W EP2023076253 W EP 2023076253W WO 2024068474 A1 WO2024068474 A1 WO 2024068474A1
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Prior art keywords
agents
fertilizer
plants
group
compound
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PCT/EP2023/076253
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French (fr)
Inventor
Nils Peters
Hans MOTTE
Dominique Audenaert
Tom Beeckman
Joris JOURQUIN
Wouter SMET
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Eurochem Antwerpen
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Publication of WO2024068474A1 publication Critical patent/WO2024068474A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/06—Nitrogen directly attached to an aromatic ring system
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/02—Amines; Quaternary ammonium compounds
    • A01N33/08—Amines; Quaternary ammonium compounds containing oxygen or sulfur
    • A01N33/10—Amines; Quaternary ammonium compounds containing oxygen or sulfur having at least one oxygen or sulfur atom directly attached to an aromatic ring system
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-nitrogen bonds, e.g. azides, diazo-amino compounds, diazonium compounds, hydrazine derivatives
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aldehyde or keto groups, or thio analogues thereof, directly attached to an aromatic ring system, e.g. acetophenone; Derivatives thereof, e.g. acetals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • 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
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P21/00—Plant growth regulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Definitions

  • the present invention relates to plant growth promoters, a method for promoting growth of a plant, a mixture for promoting growth of a plant, a fertilizer mixture, a process for its production and a method of fertilizing soils.
  • Fertilizer application should be site-specific to ensure optimum crop production with minimum environmental pollution.
  • Root hairs are important for nutrient and water uptake by plants. Induction of root hairs and root hair elongation results in an increased total root and root hair surface and as such in more uptake of nutrients, in particular phosphorous but also nitrogen, iron and other nutrients, and water and confers increased tolerance to nutrient starvation or drought stress or may improve plant growth and yield. Likewise, root hairs confer increased tolerance to salt stress and to osmotic stress. They are important in stress responses, not only by increasing the uptake surface, but also as biosensors. Root hairs are also important for anchorage and penetration in the soil. In this way, they allow better growth in high-strength (compact) soils.
  • Root hairs improve root-soil contact and they form the site of symbiotic interactions with soilliving microorganisms.
  • the later include arbuscular mycorrhiza and ectomycorrhiza. These fungi can make an extensive network in the soil to capture and translocate nutrients and water to the plants, but also assist foraging towards water or nutrients, signaling the direction in which the roots should grow.
  • Root hairs are also directly involved in the formation of root nodules in legume plants to establish a symbiosis with nitrogen fixing bacteria, and as such enhance nitrogen nutrition. Furthermore, root hairs prevent harmful micro-organisms from entering the plant. Root hair cells also secrete acids (e.g., malic and citric acid), which solubilize minerals in the soils to release nutrients.
  • acids e.g., malic and citric acid
  • these acids make phosphate available for the plant from phosphorous-containing resources in the soil such as rock phosphate or mineralized phosphate.
  • phosphorous-containing resources in the soil such as rock phosphate or mineralized phosphate.
  • an increased root hair number or surface generally improve plant fitness and growth efficiency.
  • the object underlying the present invention is to provide compounds as fertilizer additives that can act as plant growth promoters by increasing the total root hair surface of plants.
  • the compounds shall mitigate/alleviate nutrient starvation or drought stress of plants, and/or enhance the nutrient (fertilizer) use efficiency and/or improve the nutrient or water uptake of plants.
  • X heteroatom selected from the group consisting of nitrogen, oxygen and sulfur, preferably, X is nitrogen;
  • Rl; R2 independently hydrogen, C 1-20 -hydrocarbon residue, preferably a Cl-10, even more preferably a Cl-5 hydrocarbon residue, even more preferably a Cl-3 hydrocarbon residue, which can contain one to three halogen atoms and/or one to seven heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur, preferably, either Rl or R2 have a keto, an aldehyde, an amide and/or an amino group; and preferably characterized in that no oxygen double bond is present at the Cl atom of Rl and/or R2; even more preferably Rl is a C2 hydrocarbon with a carboxamide-group on C2 of Rl and R2 is hydrogen;
  • R3 independently hydrogen, halogen, heteroatom functional group, C ⁇ - hydrocarbon residue, C r5 hydrocarbon residue, even more preferably a C r3 hydrocarbon residue, which can contain one or two halogen atoms and/or one to three heteroatoms, selected from the group consisting of nitrogen, oxygen and sulfur, preferably oxygen, it also being possible for Rl and R3 to be covalently linked to form a 5- to 8-membered heterocyclic ring, which can contain 1 or 2 halogen atoms and/or one to three further heteroatoms in addition to the heteroatoms N already part of the heterocyclic ring, preferably R3 is a methoxy group n 0; 1; 2; 3; 4 or 5, preferably n is 0 or 1; as plant growth promoter.
  • compounds of the above general formula (I) can be successfully employed as plant growth promoters or root hair inducers or a combination thereof. They induce root hairs and root hair elongation and enhance the nutrient use efficiency and water uptake of plants. They mitigate/alleviate the nutrient starvation or drought stress of plants.
  • a preferred embodiment is the use of the compound of the general formula (I)
  • X heteroatom selected from the group consisting of nitrogen and oxygen, preferably, X is nitrogen;
  • Rl; R2 if X is nitrogen, Rl and R2 are independently hydrogen or a C r3 hydrocarbon residue, preferably a C 2 hydrocarbon residue, which can contain one to seven heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur, preferably, either Rl or R2 have a keto, an aldehyde, an amide and/or an amino group; and preferably characterized in that no oxygen double bond is p resent at th e Ci atom of Rl and/or R2; even more preferably Rl is a C2 hydrocarbon with a carboxamide-group on C2 of Rl and R2 is hydrogen;
  • Rl if X is oxygen, Rl is hydrogen or a C r3 hydrocarbon residue, preferably a C 2 hydrocarbon residue, which can contain one to seven heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur;
  • R3 independently hydrogen, halogen, heteroatom functional group, C ri2 - hydrocarbon residue, preferably a C r5 hydrocarbon residue, even more preferably a C r3 hydrocarbon residue, which can contain one or two halogen atoms and/or one to three heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur, preferably oxygen, it also being possible for R1 and R3 to be covalently linked to form a 5- to 8-membered heterocyclic ring, which can contain 1 or 2 halogen atoms and/or one to three further heteroatoms in addition to the heteroatoms N already part of the heterocyclic ring, preferably R3 is a hydrogen, a methyl-group or a methoxygroup; n 0; 1; 2; 3; 4 or 5, preferably n is 0 or 1; as plant growth promoter, wherein the plant grows promoter improves the root hair development, Phosphate use efficiency/uptake nutrient use efficiency of plants, nutrient
  • the compound of the formula (I) is one of the following compounds: Particularly preferred is the compound of the formula (II)
  • the compound of the formula (I) is not the following compound:
  • the compound of the formula (I) is not the following compound:
  • the pH range of the substrate or soil is from 4.5 to 7.5, preferably from 5 to 7, even more preferably from 5.5 to 6.5.
  • the use of the compounds of the formula (I) or of the formula (II) is preferably for improving root hair development, nutrient use efficiency of plants, nutrient uptake of plants, nutrient availability, water uptake of plants, nutrient and water foraging by plants, drought resistance, root penetration in the soil, anchorage in the soil, beneficial symbiotic interactions of plants, protection against harmful micro-organisms, plant growth or yield or for mitigating and/or reducing nutrient starvation, drought, salt, and/or osmotic stress of plants.
  • the object is furthermore achieved by a method for promoting growth of a plant, comprising adding to growing medium or soil in which the plant is grown, a compound as defined above.
  • the invention furthermore relates to a mixture containing at least one compound of general formula (I) as defined above, and at least one additional agrochemical agent, preferably selected from the group consisting of at least one inorganic and/or organic and/or organomineral fertilizer at least one nitrification inhibitor, preferably selected from the group consisting of 2-(3,4- dimethyl-pyrazol-l-yl)-succinic acid (DMPSA), 3,4-dimethylpyrazole (DMP), 3,4- dimethylpyrazolephosphate (DMPP), dicyandiamide (DCD), lH-l,2,4-triazole, 3- methylpyrazole (3-MP), 2-chloro-6-(trichloromethyl)-pyridine, 5-ethoxy-3- trich loromethy I - 1,2, 4-th iad iazol , 2 -a mino-4-ch I oro-6- methyl -pyrimidine, 2 -mercapto- benzothiazole
  • the invention furthermore relates to a fertilizer mixture, containing
  • the invention furthermore relates to a process for producing the fertilizer mixture as defined above by introducing the compound of the general formula (I) into the fertilizer, and/or applying the compound of the general formula (I) to the surface of the fertilizer.
  • the invention furthermore relates to a method of fertilizing soils exploited agriculturally or horticulturally including home and garden, wherein a fertilizer mixture containing compounds A and B
  • an effective amount preferably 10 to 10000 weight-ppm, more preferably 100 to 3000 weight-ppm, based on the fertilizer, of a compound of the general formula (I) as above, or compounds A and B separately, but within a period of 0 to 5 hours, preferably 0 to 1 hour, more preferably approximately at the same time, is applied onto or into the soils by any application technique.
  • R 1 and R 3 can be the same or different.
  • the compounds according to the present invention can be combined with a nitrification inhibitor and/or urease inhibitor.
  • the compound can also be used together or combined with or in admixture with an urease inhibitor, which is preferably selected from N-n-butylthiophosphoric triamide (NBTPT or NBPT) and/or N-n- propylthiophosphoric triamide (NPTPT or NPPT).
  • NBTPT N-n-butylthiophosphoric triamide
  • NPTPT N-n- propylthiophosphoric triamide
  • the compounds according to the present invention can as well be combined with a nitrification inhibitor and an urease inhibitor, specifically in case of fertilizers containing ammonium and urea and a source for phosphorus.
  • the weight ratio of compound of the present invention to nitrification inhibitor is preferably in the range of from 0.01 to 100 : 1, more preferably 0.1 to 10 : 1.
  • the weight ratio of compound of the present invention to urease inhibitor is preferably in the range of from 0.01 to 100 : 1, more preferably 0.1 to 10 : 1.
  • the weight ratio of nitrification inhibitor(s) to urease inhibitor is preferably in the range of from 0.1 to 10 : 1, more preferably 0.5 to 8 : 1, most preferably 1 to 6 : 1.
  • the compounds of the present invention can be combined with an inorganic and/or organic and/or organomineral fertilizer, specifically a fertilizer which contains a phosphorus source.
  • the present invention defines a mixture of the compounds of general formula (I) as defined above, with at least one customary agrochemical (auxiliary) agent. Therefore, the present invention defines a mixture of the compounds of general formula (I) as defined above, with
  • nitrification inhibitor preferably selected from the group consisting of 2-(3,4- dimethyl-pyrazol-l-yl)-succinic acid (DMPSA), 3,4-dimethylpyrazole (DMP), 3,4- dimethylpyrazolephosphate (DMPP), dicyandiamide (DCD), lH-l,2,4-triazole, 3- methylpyrazole (3-MP), 2-chloro-6-(trichloromethyl)-pyridine, 5-ethoxy-3- trichloromethyl-l,2,4-thiadiazol, 2 -a mi no-4-ch loro-6- methyl -pyrimidine, 2- mercaptobenzothiazole, 2-sulfanilamidothiazole, thiourea, sodium azide, potassium azide, 1- hydroxypyrazole, 2-methylpyrazole-l-carboxamide, 4-amino-l,2,4-triazole, 3-mercapto- 1,2,4-triazole, 2,4
  • DMP 3,
  • NBTPT N-n-butylthiophosphoric triamide
  • NPTPT N-n-propylthiophosphoric triamide
  • auxiliary agent preferably selected from the group consisting of aqueous and/or organic solvents, pH-adjusting agents, surfactants, wetting agents, spreading agents, adhesion promoters, carriers, fillers, viscosity-adjusting agents, emulsifiers, dispersants, sequestering agents, anti-settling agents, coalescing agents, rheology modifiers, defoaming agents, photo-protectors, anti-freeze agents, (additional or further) biostimulants, pesticides/plant protection products, biocides, (additional or further) plant growth regulators, safeners, penetrants, anticaking agents, mineral and/or vegetable oils and/or waxes, colorants and drift control agents, or mixtures thereof.
  • the compounds of the invention are preferably employed in combination with a fertilizer, more preferably a phosphorus source or an (ammonium) nitrogen-containing fertilizer, e.g. solid or liquid inorganic, organic and/or organomineral fertilizer, or manure.
  • a fertilizer more preferably a phosphorus source or an (ammonium) nitrogen-containing fertilizer, e.g. solid or liquid inorganic, organic and/or organomineral fertilizer, or manure.
  • the compound is for example employed on solid fertilizers, or is employed in liquid organic or inorganic or organomineral fertilizers or manure.
  • the compounds of general formula (I) are mostly known per se and can be synthesized according to standard techniques. They partly are commercially available compounds and can be obtained from ENAMINE Ltd., UkrOrgSynthesis Ltd., or Vitas-M Laboratory, Ltd. or from Merck Millipore, Burlington, MA, USA, or Merck KGaA.
  • the compounds of the invention are plant additives which can alleviate nutrient starvation or drought symptoms in plants and promote the growth of nutrient starvation or drought stressed plants. They may substantially improve the whole plant growth, especially in low nutrient or drought conditions.
  • the compound according to the present invention is useful for reducing the need for fertilizer for growing plants.
  • plant includes any monocot or dicot plant, such as a plant of the Fabaceae or Brassicaceae family, in particular Medicago sativa (Alfalfa).
  • said plant is grown under nutrient limiting conditions.
  • under nutrient limiting conditions means under low nutrient conditions, i.e., under a content of nutrients that is not optimal for the growth of the specific plant.
  • the mixture of the present invention provides a plant additive composition
  • a plant additive composition comprising: a compound of formula (I) as defined above and a formulation adjuvant, such as a carrier, a solvent or a surface-active agent.
  • plant additive composition is meant any kind of soil additive, soil amendment, fertilizer or soil conditioner, which can of course be used to modify a soil, but also in hydroponic cultures.
  • said plant additive composition is a composition for promoting plant growth and/or for alleviating nutrient starvation or drought symptoms.
  • the plant additive composition according to the present invention is typically not intended for use as a herbicide, in particular as a defoliant, a desiccant, an herbage killer, a germination inhibitor or a weed killer.
  • the plant additive composition can be a liquid or solid (typically granulated or powdered) composition, such as dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil flowables, aqueous dispersions, oil dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), or impregnated polymer films.
  • a liquid or solid (typically granulated or powdered) composition such as dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifi
  • the plant additive composition further comprises at least one primary nutrient selected from the group consisting of nitrogen and potassium, and/or at least one secondary nutrient selected from the group consisting of calcium, magnesium, sodium and sulfur, and/or at least one micronutrient selected from the group consisting of boron, cobalt, copper, iron, manganese, molybdenum and zinc.
  • said plant additive composition comprises a compound of formula (I) as defined above and at least one or the 2 primary nutrients as defined above.
  • said plant additive composition comprises a compound of formula (I) as defined above and at least one or the 2 primary nutrients and the 4 secondary nutrients as defined above.
  • said plant additive composition comprises a compound of formula (I) as defined above, nitrogen, potassium, calcium, magnesium, sodium, sulfur, boron, cobalt, copper, iron, manganese, molybdenum and zinc.
  • a liquid plant additive composition comprises a solvent such as a polar water-soluble solvent, a micelle or a surfactant.
  • the present invention provides a method for promoting the growth of a plant, comprising adding to the growing medium or soil on which said plant is grown, a compound of formula (I) as defined above, or a plant additive composition comprising a compound of formula (I) as defined above and a formulation adjuvant as defined above.
  • the method according to the present invention is not intended for promoting the growth of a plant by inhibiting the growth of another plant (e.g., a weed).
  • the growing medium includes liquid, semi-solid or solid medium suitable to support the growth of a plant.
  • it can be a mineral nutrient solution or an inert material such as heydite, clay pellets, perlite, vermiculite or rockwool.
  • the growing medium contains the nutrients required to support the growth of the plant.
  • the present invention provides the use of a compound of formula (I) as defined above for preparing a plant additive composition as defined above useful for promoting the growth of a plant.
  • One or more compounds of formula (I) can be employed as plant growth promoters in the fertilizer discussed below. Furthermore, it is possible to employ mixtures of one or more compounds of general formula (I). This is reflected by the expression formula (I).
  • the plant growth promoters of the present invention possess favorable toxicological properties, have a low vapor pressure, and are absorbed well in the soil. As a consequence, the plant growth promoter is neither emitted to the atmosphere by sublimation to any significant extent nor is easily leached by water. As a result, first of all, economic advantages arise, such as a high profitability in view of the longer-lasting effect of the plant growth promoters, and environmental advantages, such as a reduction in the burdening of air (climate gas-reducing) and of surface waters and ground water.
  • the plant growth promoters can be applied to soils or substrates which are fertilized with an inorganic or organic or organomineral fertilizer. Typically, they are employed in a fertilizer mixture comprising such fertilizer and the compound of general formula (I). Typically, the compound of general formula (I) is employed in an amount of 10 to 10000 ppm by weight, more preferably 100 to 10000 ppm by weight, based on the fertilizer without water. The application amount is based on the dry fertilizer.
  • the plant growth promoters according to the present invention can be employed in substance, in solution, dispersion or emulsion. Therefore, the invention also relates to a solution, dispersion or emulsion containing the compound of general formula (I) of the present invention preferably in an amount of 0.1 to 50 wt%, more preferably 0.5 to 30 wt%, most preferably 1 to 20 wt%.
  • fertilizers are employed for forming a fertilizer mixture, containing compounds A and B
  • the water fraction in compound A and in the fertilizer mixture is often not more than 1.5 wt%, preferably not more than 1.0 wt%, more preferably not more than 0.5 wt%, most preferably not more than 0.3 wt%, and is therefore negligible in the balance of quantities.
  • Compounds A and B preferably make up at least 95 wt%, more preferably at least 98 wt% of the fertilizer mixture.
  • the nitrogen content of component A is often at least 12 wt%, preferably at least 20 wt%, more preferably at least 22 wt%.
  • the nitrogen content may be 25 to 29 wt%, particularly 26 to 28 wt%.
  • the nitrogen content can be divided between fast-acting nitrate nitrogen and slow-acting ammonium nitrogen.
  • the inorganic fertilizers preferably are ammonium- and/or urea-containing fertilizers, more preferably ammonium-containing fertilizers which can additionally contain urea.
  • Urea-containing fertilizers are further described in WO 2016/207210.
  • Fertilizers typically provide, in varying proportions: three main macronutrients:
  • K Potassium
  • micronutrients copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), zinc (Zn), boron (B). Of occasional significance are silicon (Si), cobalt (Co), and vanadium (V).
  • the fertilizers employed according to the present invention can be of natural or synthetic origin and are applied to soil or to plant tissues to supply one or more plant nutrients essential to the growth of plants.
  • the fertilizers employed according to the present invention should provide at least nitrogen as nutrient. Further nutrients are for example K and P.
  • Multinutrient f erti I izers/co m pl ex fertilizers provide two or more nutrients.
  • Inorganic fertilizers exclude carbon-containing materials except ureas.
  • Organic fertilizers are usually plant- or animal- derived matter.
  • Organomineral fertilizers (combination of inorganic and organic fertilizers) can be employed as well.
  • the main nitrogen-based straight fertilizer is ammonia or its solutions.
  • Ammonia nitrate is also widely used.
  • Urea is another popular source of nitrogen, having the advantage that it is solid and non-explosive.
  • a further nitrogen-based fertilizer is calcium ammonium nitrate.
  • the main straight phosphate fertilizers are the superphosphates.
  • "Single superphosphate” SSP consists of 14-18% P 2 O 5 , again in the form of Ca(H 2 PO 4 ) 2 , but also phosphogypsum (CaSO 4 • 2H 2 O).
  • Triple superphosphate typically consists of 44-48% of P 2 O 5 and no gypsum.
  • a mixture of single superphosphate and triple superphosphate is called double superphosphate. More than 90% of a typical superphosphate fertilizer is water-soluble.
  • Diammonium phosphate (DAP) quickly became the item of commerce as most widely used by the growers today, and it has the highest concentration of phosphate and nitrogen at 18 N- 46P 2 O 5 -0K 2 O
  • MAP Monoammonium phosphate
  • Granulated triple superphosphate is very similar to the superphosphate fertilizer that provides 46% P 2 O 5 , some calcium and sulfur to plants.
  • GTSP is formed by reaction of phosphate rock with phosphoric acid.
  • Superphosphoric acid is an acid used to make a concentrated or fluid fertilizer.
  • Phosphoric acid is used in granulation plants where ammonia is added to phosphoric acid to produce the ammoniated phosphate fertilizer
  • Phosphate fertilizers are obtained by extraction from phosphate rock, which contains two principal phosphorus-containing minerals, fluorapatite Ca 5 (PO 4 ) 3 F (CFA) and hydroxyapatite Ca 5 (PO 4 ) 3 OH. These minerals are converted into water-soluble phosphate salts by treatment with sulfuric (H 2 SO 4 ) or phosphoric acids (H 3 PO 4 ).
  • phosphate rock with up to a 20% phosphorus (P) content is dissolved with nitric acid (HNO 3 ) to produce a mixture of phosphoric acid (H 3 PO 4 ) and calcium nitrate (Ca(NO 3 ) 2 ).
  • HNO 3 nitric acid
  • Ca(NO 3 ) 2 calcium nitrate
  • This mixture can be combined with a potassium fertilizer to produce a compound fertilizer with the three macronutrients N, P and K in easily dissolved form.
  • the main potassium-based straight fertilizer is muriate of potash (MOP).
  • NP fertilizers Major two-component fertilizers provide both nitrogen and phosphorus to the plants. These are called NP fertilizers.
  • the main NP fertilizers are monoammonium phosphate (MAP) and diammonium phosphate (DAP).
  • the active ingredient in MAP is NH 4 H 2 PO 4 .
  • the active ingredient in DAP is (NH 4 ) 2 HPO 4 .
  • About 85% of MAP and DAP fertilizers are soluble in water.
  • NPK fertilizers are three-component fertilizers providing nitrogen, phosphorus and potassium. NPK fertilizers can be produced by mixing straight fertilizers as mentioned above in bulk or in each granule, as in Nitrophoska 9 . In some cases, chemical reactions can occur between the two or more components.
  • NPK fertilizers are at least three-component fertilizers providing nitrogen, phosphorus and potassium. NPK fertilizers can be produced by mixing straight fertilizers as mentioned above in bulk or in each granule, as in Nitrophoska 9 . In some cases, chemical reactions can occur between the two or more components.
  • monoammonium and diammonium phosphates which provide plants with both N and P, are produced by neutralizing phosphoric acid (from phosphate rock) and ammonia:
  • micronutrients may be present in the fertilizers.
  • the main micronutrients are molybdenum, zinc, boron and copper. These elements are typically provided as water-soluble salts.
  • Preferred fertilizers contain ammonium or urea.
  • Examples of preferred ammonium-containing fertilizers are NPK fertilizers, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate and ammonium phosphate.
  • Further preferred ingredients of the fertilizer compositions are for example trace elements, further minerals, standardizers, binders.
  • Organic fertilizers can describe those fertilizers with an organic or biologic origin, i.e. fertilizers derived from living or formerly living materials, like animals or plants or algae.
  • Fertilizers of an organic origin include animal wastes, plant wastes e.g. from food processing or agriculture, compost, and treated sewage sludge (biosolids).
  • Animal sources can be manures, but also products from the slaughter of animals, like blood meal, bone meal, feather meal, hides, hooves, and horns.
  • Fertilizers can include without limitation, ammonium sulfate, ammonium nitrate, ammonium sulfate nitrate, ammonium chloride, ammonium bisulfate, ammonium polysulfide, ammonium thiosulfate, aqueous ammonia, anhydrous ammonia, ammonium polyphosphate, aluminum sulfate, calcium nitrate, calcium ammonium nitrate, calcium sulfate, calcined magnesite, calcitic limestone, calcium oxide, hampene (chelated iron), dolomitic limestone, hydrate lime, calcium carbonate, diammonium phosphate, monoammonium phosphate, potassium nitrate, potassium bicarbonate, monopotassium phosphate, magnesium nitrate, magnesium sulfate, potassium sulfate, potassium chloride, sodium nitrates,
  • the micronutrient fertilizer material can comprise boric acid, a borate, a boron frit, copper sulfate, a copper frit, a copper chelate, a sodium tetraborate decahydrate, an iron sulfate, an iron oxide, iron ammonium sulfate, an iron frit, an iron chelate, a manganese sulfate, a manganese oxide, a manganese chelate, a manganese chloride, a manganese frit, a sodium molybdate, molybdic acid, a zinc sulfate, a zinc oxide, a zinc carbonate, a zinc frit, zinc phosphate, a zinc chelate or a combination thereof.
  • said fertilizer or fertilizer composition does not comprise insoluble selenium, selenium mineral, soluble selenium or salts thereof.
  • the treated (inorganic, organic or organomineral) fertilizers according to the invention are preferably present in powder form, prill form or in granule form.
  • formulations comprising the compound and agronomical adjuvants can be used for including the plant growth promoters in the fertilizer.
  • Agronomical adjuvants are, for example, solvents, dispersants, pH-adjusting agents, fillers, stability improvers, surfactants.
  • the plant growth promoters can be included in the fertilizer mixture by mixing it or the formulation containing it with a solid or liquid fertilizer or fertilizer formulation.
  • the fertilizer mixture is in solid form and the plant growth promoter is applied to the surface of the (inorganic, organic or organomineral) fertilizer.
  • the plant growth promoters or the formulation containing it can be introduced into the (inorganic, organic or organomineral) fertilizer and/or applied to the surface of the fertilizer.
  • Granules of fertilizers are impregnated or coated with the plant growth promoters, for example by being sprayed with a formulation like a solution or a dispersion of the plant growth promoters and subsequent drying.
  • the method is known, for example, from DE-A-41 28 828.
  • the sealing of the impregnated granules with, for example, a paraffin wax, which is an additional proposal in the latter document, is possible, but generally unnecessary.
  • Granulating assistants which can be employed for preparing solid fertilizer compositions can be lime, gypsum, silicon dioxide or kaolinite.
  • the plant growth promoters are customarily applied to the soil in amounts effective for the desired action.
  • Delivery of the plant growth promoters in liquid fertilizer formulations may be accomplished, for example, by fertigation with or without excess water as described in DE-C-102 30 593.
  • the fertilizer mixture can contain at least one nitrification inhibitor.
  • this at least one further nitrification inhibitor is inhibiting ammonia-oxidizing bacteria (AOB) and is preferably selected from the group consisting of 2-(3,4-dimethyl-pyrazol-l-yl)-succinic acid,
  • DMP 3,4-dimethylpyrazolephosphate
  • DCD dicyandiamide
  • lH-l,2,4-triazole 3-methylpyrazole (3-MP)
  • 2-chloro-6-(trichloromethyl)-pyridine 5-ethoxy- 3-tric h loro methyl -1,2, 4-th iadiazo I, 2 -a mi no-4-ch loro-6- methyl -pyrimidine, 2 -mercapto- benzothiazole, 2-sulfanilamidothiazole, thiourea, sodium azide, potassium azide, 1- hydroxypyrazole, 2-methylpyrazole-l-carboxamide, 4-amino-l,2,4-triazole, 3-mercapto-
  • the weight ratio of the compound of general formula (I) to the nitrification inhibitor is preferably 0.01 to 100 : 1, more preferably 0.1 to 10 : 1.
  • the fertilizer mixture can contain at least one urease inhibitor, which is preferably selected from N-n-butylthiophosphoric triamide (NBTPT) and/or N-n- propylthiophosphoric triamide (NPTPT).
  • NBTPT N-n-butylthiophosphoric triamide
  • NPTPTPT N-n- propylthiophosphoric triamide
  • a urease inhibitor is typically added when the fertilizer contains urea. Urea nitrogen is liberated as ammonium by the action of urease, and the ammonium can undergo nitrification. Therefore, it can be advantageous to combine a urease inhibitor with the nitrification inhibitor.
  • the weight ratio of plant growth promoter(s) to urease inhibitor is preferably in the range of from 0.01 to 100 : 1, more preferably 0.1 to 10 : 1.
  • Thiophosphoric triamides are known to be relatively easily converted to the corresponding phosphoric triamides and thiophosphoric diamides as well as other metabolites. Since, generally speaking, moisture cannot be entirely excluded, thiophosphoric triamide and the corresponding phosphoric triamide are frequently present in a mixture with one another. In this specification, therefore, the term “(thio)phosphoric triamide” identifies not only the pure thiophosphoric triamides and phosphoric triamides, respectively, but also mixtures thereof.
  • N-(n-butyl)thiophosphoric triamide and N-(n-)propylthiophosphoric triamide can be employed, as described in EP-A-1 820 788.
  • the fertilizer mixtures can contain other ingredients, like coatings, for example of inorganic or organic polyacids, which are described in US 6,139,596.
  • coatings of powders, prills and granules can be formed of inorganic material, such as sulfur- or mineral-based coatings, or with an organic polymer. Respective coatings are described in WO 2013/121384 on page 23, line 37 to page 24, line 16.
  • the agrochemical formulations comprising the compounds of formula (I) are used in "effective amounts". This means that they are used in a quantity which allows to obtain the desired effect which is a (synergistic) increase of the health or growth of a plant but which does not give rise to any phytotoxic symptom on the treated plant.
  • the agrochemical formulations comprising the compounds of formula (I) can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the agrochemical formulations comprising the compounds of formula (I) to the present invention.
  • the formulations are prepared in a known manner to the person skilled in the art.
  • the agrochemical formulations may also comprise auxiliaries which are customary in agrochemical formulations.
  • the auxiliaries used depend on the particular application form and active substance, respectively.
  • suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and inorganic thickeners, bactericides, antifreezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e.g. for seed treatment formulations).
  • Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.
  • Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g. ammonium sulfate, ammonium phosphate, ammoni
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, dibutylnaphthalenesulfonic acid and fatty acids, alkylsulfonates, alkyl-arylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxy-ethylene octylphenyl ether, ethoxy-ethylene octyl
  • methylcellulose methylcellulose
  • hydrophobically modified starches polyvinyl alcohols, polycarboxylates types, polyalkoxylates, polyvinylamines, polyvinylpyrrolidone and the copolymers therof.
  • thickeners i.e. compounds that impart a modified flowability to formulations, i.e. high viscosity under static conditions and low viscosity during agitation
  • polysaccharides and organic and inorganic clays such as Xanthan gum.
  • a biostimulant is any substance or microorganism, in the form in which it is applied to plants, seeds or the root environment with the intention to stimulate natural processes of plants benefiting nutrient use efficiency and/or tolerate to abiotic stress, regardless of its nutrient content, or any combination of such substances and/or microorganisms intended for this use.
  • a plant biostimulant is any microorganism or substance based on natural resources, in the form in which it is applied to plants, seeds or the soil and any other substrate with the intention to stimulate natural processes of plants to benefit their nutrient use efficiency and/or their tolerance to stress, regardless of its nutrients content, or any combination of such substances and/or microorganisms intended for this use.
  • a 'pesticide' is something that prevents, destroys, or controls a harmful organism ('pest') or dis-ease, or protects plants or plant products during production, storage and transport.
  • the term includes, amongst others: herbicides, fungicides, insecticides, acaricides, nematicides, molluscicides, rodenticides, growth regulators, repellents, rodenticides and biocides as well as plant protection products.
  • Plant protection products are 'pesticides' that protect crops or desirable or target plants. They are primarily used in the agricultural sector but also in forestry, horticulture, amenity areas and in home gardens. They contain at least one active substance and have one of the following functions: - protect plants or plant products against pests/diseases, before or after harvest;
  • They may also contain other components including safeners and synergists.
  • An active substance is any chemical, plant extract, pheromone or micro-organism (including viruses), that has action against 'pests' or on plants, parts of plants or plant products.
  • PGPs plant protection products
  • 'pesticide' is often used interchangeably with 'plant protection product', however, pesticide is a broader term that also covers non plant/crop uses, for example biocides.
  • Biocides like herbicides, bactericides, molluscicides, algicides, phytotoxicants, fungicides, and their mixtures can be added.
  • Bactericides may be added for preservation and stabilization of the formulation.
  • suitable bactericides are those based on dichlorophene and benzylalcohol hemi formal (Proxel® from ICI or Acticide 9 RS from Thor Chemie and Kathon 9 MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide 9 M BS from Thor Chemie).
  • suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • anti-foaming agents are silicone emulsions (such as e.g.
  • Suitable colorants are pigments of low water solubility and solvent-soluble, e.g. water- soluble, dyes.
  • adhesion promoters like tackifiers or binders, are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose 9 , Shin-Etsu, Japan).
  • Granules e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers.
  • solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite
  • the agrochemical formulations generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substances.
  • the compounds of the agrochemical formulations comprising the compounds of formula (I) are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to their NMR spectrum).
  • the compounds of the agrochemical formulations comprising the compounds of formula (I) can be used as such or in the form of their agricultural compositions, e.g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring.
  • the application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the compounds present in the agrochemical formulations comprising the compounds of formula (I).
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
  • concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil and such concentrates are suitable for dilution with water.
  • the active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1%, by weight of compounds of the agrochemical formulations comprising the compounds of formula (I).
  • the compounds of the agrochemical formulations comprising the compounds of formula (I) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.
  • UUV ultra-low-volume process
  • oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active compounds, if appropriate not until immediately prior to use (tank mix).
  • These agents can be admixed with the compounds of the agrochemical formulations comprising the compounds of formula (I) in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
  • compositions of this invention may also contain fertilizers (such as ammonium nitrate, urea, potash, and superphosphate), phytotoxicants and plant growth regulators (plant growth amendments) and safeners. These may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with the fertilizers.
  • fertilizers such as ammonium nitrate, urea, potash, and superphosphate
  • phytotoxicants plant growth regulators
  • plant growth amendments plant growth amendments
  • safeners plant growth regulators
  • the weight ratio of the compounds generally depends from the properties of the compounds of the agrochemical formulations comprising the compounds of formula (I).
  • the compounds of the agrochemical formulations comprising the compounds of formula (I) can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used further as combination composition such as a kit of parts.
  • the user applies the composition according to the invention usually from a pre-dosage device, a knapsack sprayer, a spray tank or a spray plane.
  • the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquid or the agrochemical composition according to the invention is thus obtained.
  • 50 to 500 liters of the ready- to-use spray liquid are applied per hectare of agricultural useful area, preferably 50 to 400 liters.
  • the absolute amount of the active compounds, represented by formula (I), is used in a range between 1 mg/liter to 100 mg/liter, particularly in a range between 1 mg/l to 20 mg/l, particularly in a range between 1 mg/l to 25 mg/l, particularly in a range between 2 mg/l to 200 mg/l, particularly between 2 mg/l to 100 mg/l, particularly between 2 mg/l to 50 mg/l, particularly between 2 mg/l to 25 mg/l, particularly between 4 mg/l to 40 mg/l, particularly between 4 mg/l to 20 mg/l, particularly between 4 mg/l to 16 mg/l, particularly between 4 mg/l to 12 mg/l.
  • individual compounds of the agrochemical formulations comprising the compounds of formula (I) formulated as composition (or formulation) such as parts of a kit or parts of the inventive mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).
  • Agrochemical means any active substance that may be used in the agrochemical industry (including agriculture, horticulture, floriculture and home and garden uses, but also products intended for non-crop related uses such as public health/ pest control operator uses to control undesirable insects and rodents, household uses, such as household fungicides and insecticides and agents, for protecting plants or parts of plants, crops, bulbs, tubers, fruits (e.g. from harmful organisms, diseases or pests); for controlling, preferably promoting or increasing, the growth of plants; and/or for promoting the yield of plants, crops or the parts of plants that are harvested (e.g. its fruits, flowers, seeds etc.).
  • an “agrochemical composition” as used herein means a composition for agrochemical use, as herein defined, comprising at least one active substance of a compound of formula (I), optionally with one or more additives favoring optimal dispersion, atomization, deposition, leaf wetting, distribution, retention and/or uptake of agrochemicals.
  • additives are diluents, solvents, adjuvants, surfactants, wetting agents, spreading agents, oils, stickers, viscosity-adjusting agents (like thickeners, penetrants), pH- adjusting agents (like buffering agents, acidifiers), anti-settling agents, anti-freeze agents, photo-protectors, defoaming agents, biocides and/or drift control agents.
  • a “carrier”, as used herein, means any solid, semi-solid or liquid carrier in or on(to) which an active substance can be suitably incorporated, included, immobilized, adsorbed, absorbed, bound, encapsulated, embedded, attached, or comprised.
  • Non-limiting examples of such carriers include nanocapsules, microcapsules, nanospheres, microspheres, nanoparticles, microparticles, liposomes, vesicles, beads, a gel, weak ionic resin particles, liposomes, cochleate delivery vehicles, small granules, granulates, nano-tubes, bucky-balls, water droplets that are part of an water-in-oil emulsion, oil droplets that are part of an oil-in-water emulsion, organic materials such as cork, wood or other plant-derived materials (e.g.
  • inorganic materials such as talc, clay, microcrystalline cellulose, silica, alumina, silicates and zeolites, or even microbial cells (such as yeast cells) or suitable fractions or fragments thereof.
  • determining As used herein, the terms “determining”, “measuring”, “assessing”, “monitoring” and “assaying” are used interchangeably and include both quantitative and qualitative determinations.
  • the agrochemical composition is stable, both during storage and during utilization, meaning that the integrity of the agrochemical composition is maintained under storage and/or utilization conditions of the agrochemical composition, which may include elevated temperatures, freeze-thaw cycles, changes in pH or in ionic strength, UV-irradiation, presence of harmful chemicals and the like. More preferably, the compounds of formula (I), (II) as herein described remain stable in the agrochemical composition, meaning that the integrity and the activity of the compounds are maintained under storage and/or utilization conditions of the agrochemical composition, which may include elevated temperatures, freeze-thaw cycles, changes in pH or in ionic strength, UV-irradiation, presence of harmful chemicals and the like.
  • said compounds of formula (I), (II) remain stable in the agrochemical composition when the agrochemical composition is stored at ambient temperature for a period of two years or when the agrochemical composition is stored at 54° C for a period of two weeks.
  • the agrochemical composition of the present invention retains at least about 70% activity, more preferably at least about 70% to 80% activity, most preferably about 80% to 90% activity or more.
  • suitable carriers include, but are not limited to alginates, gums, starch, p-cyclodextrins, celluloses, polyurea, polyurethane, polyester, or clay.
  • the agrochemical composition may occur in any type of formulation, preferred formulations are powders, wettable powders, wettable granules, water dispersible granules, emulsions, emulsifiable concentrates, dusts, suspensions, suspension concentrates, suspoemulsions, capsule suspensions, aqueous dispersions, oil dispersions, aerosols, pastes, foams, slurries or flowable concentrates.
  • the invention provides the use of the agrochemical compositions of the invention for enhancing abiotic stress tolerance in plants.
  • the agrochemical composition according to the invention can be applied once to a crop, or it can be applied two or more times after each other with an interval between every two applications.
  • the agrochemical composition according to the invention can be applied alone or in mixture with other materials, preferably other agrochemical compositions, to the crop; alternatively, the agrochemical composition according to the invention can be applied separately to the crop with other materials, preferably other agrochemical compositions, applied at different times to the same crop.
  • the invention provides a method for the manufacture of (‘or the pro-duction of’ which is equivalent wording) an agrochemical composition according to the invention, comprising formulating a molecule of formula (I) as defined herein before, together with at least one customary agrochemical auxiliary agent.
  • Suitable manufacturing methods include, but are not limited to, high or low shear mixing, wet or dry milling, drip-casting, encapsulating, emulsifying, coating, encrusting, pilling, extrusion granulation, fluid bed granulation, co-extrusion, spray drying, spray chilling, atomization, addition or condensation polymerization, interfacial polymerization, in situ polymerization, coacervation, spray encapsulation, cooling melted dispersions, solvent evaporation, phase separation, solvent extraction, sol-gel polymerization, fluid bed coating, pan coating, melting, passive or active absorption or adsorption.
  • Customary agrochemical auxiliary agents are well-known in the art and preferably include, but are not limited to aqueous and/or organic solvents, pH-adjusting agents (like buffering agents, acidifiers), surfactants, wetting agents, spreading agents, adhesion promoters (like tackifiers, stickers), carriers, fillers, viscosity-adjusting agents (like thickeners), emulsifiers, dispersants, sequestering agents, anti-settling agents, coalescing agents, rheology modifiers, defoaming agents, photo-protectors, anti-freeze agents, additional or further biostimulants (including bacterial and/or fungal inoculants or microorganisms beside non-microbial materials), biocides (preferably selected from herbicides, bactericides, phytotoxicants, fungicides, pesticides/plant protection products and mixtures thereof), additional or further plant growth regulators, safeners, penetrants, anticaking agents, mineral and/or vegetable oils and/or waxes,
  • the additional auxiliary agent can refer to additional or further biostimulants and/or plant growth regulators which are different from the compounds in formula (I).
  • the insecticide can include an organophosphate, a carbamate, a pyrethroid, an acaricide, an alkyl phthalate, boric acid, a borate, a fluoride, sulfur, a haloaromatic substituted urea, a hydro-carbon ester, a biologically-based insecticide, or a combination thereof.
  • the herbicide used to remove unwanted plants, can comprise a chlorophenoxy compound, a nitrophenolic compound, a nitrocresolic compound, a dipyridyl compound, an acetamide, an aliphatic acide, an anilide, a benzamide, a benzoic acid, a benzoic acid derivative, anisic acid, an anisic acid derivative, a benzonitrile, benzothiadiazinone dioxide, a thiocarbamate, a carbamate, carbanilate, ch loro- py rid i ny I , a cyclohexenone derivative, a dinitroaminobenzene derivative, a fluorodinitrotoluidine compound, isoxazolidinone, nicotinic acide, isopropylamine, an isopropylamine derivative, oxadiazolinone, a phosphate, a phthalate, a picolinic acid compound, a triazine,
  • the fungicide can comprise a substituted benzene, a thiocarbamate, an ethylene bis dithiocarbamate, a thioph-thalidamide, a copper compound, an organomercury compound, an organotin compound, a cadmium compound, anilazine, benomyl, cyclohexamide, dodine, etridiazole, iprodione, metlax-yl, thiamimefon, triforine, or a combination thereof.
  • the fungal inoculant can comprise a fungal inoculant of the family Glomeraceae, a fungal inoculant of the family Claroidoglomeraceae, a fungal inoculant of the family Acaulosporaceae, a fungal inoculant of the family Sacculosprace-ae, a fungal inoculant of the family Entrophosporaceae, a fungal inoculant of the family Pacid-sproraceae, a fungal inoculant of the family Diversisporaceae, a fungal inoculant of the family Paraglomeraceae, a fungal inoculant of the family Archaeosporaceae, a fungal inoculant of the family Geosiphonaceae, a fungal inoculant of the family Ambisporacea, a fungal inoculant of the family Scutellosproaceae, a fungal inoculant of the family Dentiscultataceae
  • the bacterial inoculant can include a bacterial inoc-ulant of the genus Rhizobium, bacterial inoculant of the genus Bradyrhizobium, bacterial inocu-lant of the genus Mesorhizobium, bacterial inoculant of the genus Azorhizobium, bacterial inocu-lant of the genus Allorhizobium, bacterial inoculant of the genus Burkholderia, bacterial inoculant of the genus Sinorhizobium, bacterial inoculant of the genus Kluyvera, bacterial inoculant of the genus Azotobacter, bacterial inoculant of the genus Pseudomonas, bacterial inoculant of the genus Azospri/Hum, bacterial inoculant of the genus Bacillus, bacterial inoculant of the genus Streptomyces, bacterial inoculant of the genus Paen
  • the mixture can comprise additionally at least one microorganism selected from the list consisting of Bacillus subti/is strain 713, Bacillus amyloliquefaciens MBI 600, Bacillus pumillus QST2808, Pseudomonas f/uorescens, Bradyrhizobium japonicum, Trichoderma vireus, Pseudomonas putida, Trichoderma harzianum Rifai strain T22, Penicillium bi/aii, Mesorhizobium, Azospirillum, Azotobacter vinelandii and Clostridium pasteurianum, Glomus species.
  • Bacillus subti/is strain 713 Bacillus amyloliquefaciens MBI 600, Bacillus pumillus QST2808, Pseudomonas f/uorescens, Bradyrhizobium japonicum, Trichoderma vireus, Pseudomonas putida
  • the compounds of general formula (I) employed according to the present invention can be employed in combination with these auxiliaries.
  • the auxiliaries used depend on the particular application form and the active substance and preferably include solvents, solid carriers, dispersants or emulsifiers, such as solubilizers, protective colloids, surfactants and adhesion agents.
  • organic and inorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate, colorants and tackifiers or binders can be employed in combination with the nitrification inhibitors and in the fertilizer mixture. Suitable auxiliaries are discussed in WO 2013/121384 on pages 25 to 26.
  • oils, wetters, adjuvants, biostimulants, herbicides, bactericides, other fungicides and/or pesticides are for example discussed in WO 2013/121384 on pages 28/29.
  • the fertilizer mixtures are preferably in solid form, including powders, prills and granules. Furthermore, it is possible to deliver the nitrification inhibitor in the form of a formulation, solution or dispersion separately or simultaneously with a fertilizer.
  • the present invention also relates to a method of fertilizing soils exploited agriculturally or horticulturally, wherein a fertilizer mixture containing compounds A and B
  • the use of the plant growth promoters, according to the present invention, and of compositions containing them has the effect that there is an increase, in some cases considerably, in the yields and production of biomass of crop plants.
  • the plants to be treated or rooted in soil to be treated according to the invention are preferably selected from the group consisting of agricultural, silvicultural, ornamental and horticultural plants, each in its natural or genetically modified form.
  • non- transgenic agricultural plants are treated.
  • Preferred agricultural plants are field crops selected from the group consisting of potatoes, sugar beets, wheat, barley, rye, oat, sorghum, rice, maize, cotton, rapeseed, oilseed rape, canola, soybeans, peas, field beans, sunflowers, sugar cane; cucumbers, tomatoes, onions, leeks, lettuce, squashes; even more preferably the plant is selected from the group consisting of wheat, barley, oat, rye, soybean, maize, oilseed rape, cotton, sugar cane, rice and sorghum.
  • the plant to be treated is selected from the group consisting of tomato, potato, wheat, barley, oat, rye, soybean, maize, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice, sorghum, pasture grass and grazed land.
  • the plant to be treated is selected from the group consisting of tomato, potato, wheat, barley, oat, rye, soybean, maize, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice and sorghum.
  • the plants to be treated are selected from the group consisting of tomato, wheat, barley, oat, rye, maize, oilseed rape, canola, sugar cane, and rice.
  • the plant to be treated according to the method of the invention is an agricultural plant.
  • Agricultural plants are plants of which a part (e.g. seeds) or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibres (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds.
  • Preferred agricultural plants are for example cereals, e.g. wheat, rye, barley, triticale, oats, sorghum or rice, beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g.
  • Pasture grass and grassland are composed of grass or grass mixtures comprising for example Bluegrass (Poa spp.), Bentgrass (Agrostis spp.), Ryegrasses (Lolium spp.), Fescues (Festuca spp., hybrids, and cultivars), Zoysiagrass (Zoysia spp.), Bermudagrass (Cynodon spp.), St. Augustine grass, Bahiagrass (Paspalum), Centipedegrass (Eremachloa), Carpetgrass (Axonopus), Buffalograss and Grama grass.
  • Pastures may be also composed of mixtures comprising afore mentioned grasses, for example Ryegrass, and Trifolium species, for example Trifolium pratensis and Trifolium repens, Medicago species like Medicago sativa, Lotus species like Lotus corniculatus, and Melilotus species, for example Melilotus albus.
  • grasses for example Ryegrass
  • Trifolium species for example Trifolium pratensis and Trifolium repens
  • Medicago species like Medicago sativa Lotus species like Lotus corniculatus
  • Melilotus species for example Melilotus albus.
  • the plant to be treated according to the method of the invention is a horticultural plant.
  • the term "horticultural plants” are to be understood as plants which are commonly used in horticulture - e.g. the cultivation of ornamentals, herbs, vegetables and/or fruits.
  • ornamentals are turf, geranium, pelargonia, petunia, begonia and fuchsia.
  • vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas and lettuce and more preferably from tomatoes, onions, peas and lettuce.
  • fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots and blueberries. In horticulture, often a substrate replaces (part of) the soil.
  • the plant to be treated according to the method of the invention is an ornamental plant.
  • “Ornamental plants” are plants which are commonly used in gardening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia.
  • the plant to be treated according to the method of the invention is a silvicultural plant.
  • silvicultural plant is to be understood as trees, more specifically trees used in reforestation or industrial plantations.
  • Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening purposes.
  • silvicultural plants are conifers, like pines, in particular Pinus spec, fir and spruce, eucalyptus, tropical trees, like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec, poplar (cottonwood), in particular Populus spec, beech, in particular Fagus spec, birch, oil palm, and oak.
  • Plant growth promoters is to be understood as compounds of formula (I) that improve the nutrient or water acquisition and/or use of the plants treated therewith, and/or can lead to improved plant growth.
  • plants is to be understood as plants of economic importance and/or men-grown plants. They are preferably selected from agricultural, silvicultural, ornamental and horticultural plants, each in its natural or genetically modified form.
  • plant as used herein includes all parts of a plant, such as germinating seeds, emerging seedlings, herbaceous vegetation, as well as established woody plants, including all belowground portions (such as the roots) and aboveground portions.
  • soil is to be understood as a natural body comprised of living (e.g. microorganisms (such as bacteria and fungi), animals and plants) and non-living matter (e.g. minerals and organic matter (e.g. organic compounds in varying degrees of decomposition), liquid, and gases) that occurs on the land surface, and is characterized by soil horizons that are distinguishable from the initial material as a result of various physical, chemical, biological, and anthropogenic processes.
  • living e.g. microorganisms (such as bacteria and fungi), animals and plants) and non-living matter (e.g. minerals and organic matter (e.g. organic compounds in varying degrees of decomposition), liquid, and gases) that occurs on the land surface, and is characterized by soil horizons that are distinguishable from the initial material as a result of various physical, chemical, biological, and anthropogenic processes.
  • non-living matter e.g. minerals and organic matter (e.g. organic compounds in varying degrees of decomposition), liquid, and gases
  • Nitrification inhibitor is to be understood as any chemical substance which slows down or retards the nitrification process which is typically occurring in (fertilized) soil.
  • Nitrification inhibitors retard the natural transformation of ammonium into nitrate and target microorganisms and preferably ammonia-oxidizing bacteria (AOB), preferably by inhibiting the activity of the bacteria, such as Nitrosomonas spp. and/or Nitrosospira spp. They may additionally act on ammonia-oxidizing archaea (AOA).
  • AOB ammonia-oxidizing bacteria
  • the nitrification inhibitor is most often combined with a fertilizer, preferably an (ammonium) nitrogen-containing fertilizer, e.g. solid or liquid inorganic, organic and/or organomineral fertilizer, or manure.
  • Nitrification is to be understood as the biological oxidation of ammonia (NH 3 ) or ammonium ( N H 4 + ) with oxygen into nitrite (NO 2 ) followed by the oxidation of these nitrites into nitrates (NOf) by microorganisms. Besides nitrate (NOf) nitrous oxide is also produced though nitrification. Nitrification is an important step in the nitrogen cycle in soil.
  • fertilizers are to be understood as (chemical) compounds applied to promote plant and fruit growth. Fertilizers are typically applied either through the soil (for uptake by plant roots) or by foliar feeding (for uptake through leaves).
  • the term “fertilizers” can be subdivided into two major categories: a) organic fertilizers (composed of decayed plant/animal matter) and b) inorganic fertilizers (composed of chemicals and minerals).
  • Organic fertilizers include slurry, worm castings, peat, seaweed, sewage, and guano.
  • Manufactured organic fertilizers include compost, blood meal, bone meal and seaweed extracts. Further examples are enzymatically digested proteins, fish meal, and feather meal.
  • inorganic fertilizers are usually manufactured through chemical processes (such as the Haber-Bosch process), also using naturally occurring deposits, while chemically altering them (e.g. concentrated triple superphosphate).
  • Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mine rock phosphate, and limestone.
  • organomineral fertilizers can be mentioned, as a combination of inorganic and organic fertilizers.
  • fertilizer is defined as synthetic fertilizers comprising urea, excluding any naturally occurring fertilizers comprising urea (for instance manure as an example for a naturally occurring fertilizer comprising urea).
  • Examples of fertilizer comprising urea are urea ammonium nitrate (UAN), isobutylidene diurea (IBDU), crotonylidene diurea (CDU) and urea formaldehyde (UF).
  • UAN urea ammonium nitrate
  • IBDU isobutylidene diurea
  • CDU crotonylidene diurea
  • UF formaldehyde
  • Urea is usually made as granulated material or prills.
  • Urea fertilizer can be produced by dropping the liquid urea from a prill tower while drying the product.
  • Urea can also be obtained as a liquid formulation, which may be used for foliar application, e.g. on potatoes, wheat, vegetables and soybeans as well as liquid application to the field. It is commonly mixed with ammonium nitrate to form UAN with 28% N.
  • locus plant habitat
  • soil any type of environment, soil, area or material where the plant is growing or intended to grow.
  • Especially preferred according to the invention is soil.
  • Figure 1 shows representative images of the effect of tested compounds on root hair induction and elongation. Scale bar is 0.5 mm.
  • Figure 2 shows representative images of the effect of comparative examples 1 to 3 as compared to the control on root hair induction and elongation. Scale bar is 0.5 mm.
  • Figure 3 shows representative images of the effect of examples 2 and 11 and comparative examples 4 and 5 as compared to the control- Scale bar is 0.5 mm.
  • Arabidopsis tha/iana Columbia-0 seedlings were grown on a modified Murashige and Skoog medium (modMS - 1.25 mM KH 2 PO 4 , 20 mM N H 4 NO 3 , 0.1 mM H3BO3, 3 mM CaCI 2 , 0.1 M CoCI 2 *6H 2 O, 0.1 M CuSO 4 *5H 2 O, 0.1 mM Na 2 EDTA*2H 2 O, 0.1 mM FeSO 4 *7H 2 O, 1.5 mM MgSO 4 *7H 2 O, 0.1 mM MnSO 4 *H 2 O, 1 M Na 2 MoO 4 *4H 2 O, 5 M KI, 19 mM KNO 3 , 0.03 mM ZnSO 4 *7H 2 O, 0.1 g/L myo-inositol, 0.5% of sucrose and 0.5 g/L MES (pH 5,7)).
  • modified Murashige and Skoog medium modified Murashige and Sk
  • Arabidopsis seeds were stratified for 2 days at 4 0 C before germination. Seedlings were germinated in climate-controlled growth chambers at 22 0 C under continuous light (100 p mol m ’ s '). Unless stated otherwise, tested compounds were dissolved in DMSO and had a final concentration of 10 pM (0.1 % DMSO). For correct comparison, the compound solvent DMSO (final concentration 0.1%) was also added to the no compound controls.
  • roots were imaged using a stereomicroscope or a VHX-6000. The number and length of the root hairs was determined at 4 to 6 mm above the root meristem. Root hair length was measured using the ImageJ software.
  • a low phosphate modMS was used, containing 1 p M KH2PO4.
  • the modMS contained 50 mM NaCI or 100 mM sorbitol.
  • rosette area measurements Arabidopsis seedlings were grown for 15 (phosphate starvation experiment) or 20 days (osmotic stress assay) on horizontal plates.
  • For primary root length measurements Arabidopsis seedlings were grown for 12 days on vertical plates. In both cases, germination and growth occurred as described above and plates were scanned using a flatbed scanner (EPSON Expression 11000XL), after which the rosette area or primary root length was measured using ImageJ software.
  • a carboxamide group at position 2 of the hydrocarbon group substituted on the heteroatom e.g. example 11 ( an ) - Table
  • Table 1 Anilino-derivatives and structural variants with a positive effect on root hair length and/or root hair number as shown by the average total root hair length per mm root. Compounds were dissolved in DMSO (final concentration 0.1 %) and the effect of the compounds was compared to a no compound control that contained only the solvent (DMSO 0.1 %).
  • the root hair promoting compounds are expected to have a growth promoting effect, in particular in conditions where those important resources are limited.
  • two Arabidopsis growth experiments in phosphate starvation conditions were performed, using a low phosphate medium. Different concentrations of example 2 and 11 were tested.
  • the primary root length was assessed, which is a trait known to be severely and negatively affected by phosphate starvation stress.
  • the rosette area of the plants were measured to assess the effect on growth.
  • example 2 and example 11 have positive effect on the root and rosette growth (Table 2).
  • Table 2 Anilino-derivatives with a positive effect on root hair length and/or root hair number show a positive growth effect in phosphate starvation conditions.
  • example 2 To verify the positive effect on water uptake, an osmotic stress experiment with example 2 was conducted. The osmolytes NaCI or sorbitol were used that limit water availability. As shown in Table 3, example 2 has a positive effect on the growth of Arabidopsis plants.
  • Table 3 The anilin o-containing example 2 that has a positive effect on root hair length and/or root hair number show a positive growth effect in water limiting conditions.

Abstract

The use of a compound of the general formula (I) as growth promoter.

Description

Anilino-derivatives as plant growth promoters
Description
The present invention relates to plant growth promoters, a method for promoting growth of a plant, a mixture for promoting growth of a plant, a fertilizer mixture, a process for its production and a method of fertilizing soils.
The use of nitrogen and phosphorus in the form of fertilizers are necessitated by cropping to fulfil in the food demand of a growing population. Fertilizer application should be site-specific to ensure optimum crop production with minimum environmental pollution.
Root hairs are important for nutrient and water uptake by plants. Induction of root hairs and root hair elongation results in an increased total root and root hair surface and as such in more uptake of nutrients, in particular phosphorous but also nitrogen, iron and other nutrients, and water and confers increased tolerance to nutrient starvation or drought stress or may improve plant growth and yield. Likewise, root hairs confer increased tolerance to salt stress and to osmotic stress. They are important in stress responses, not only by increasing the uptake surface, but also as biosensors. Root hairs are also important for anchorage and penetration in the soil. In this way, they allow better growth in high-strength (compact) soils. Root hairs improve root-soil contact and they form the site of symbiotic interactions with soilliving microorganisms. The later include arbuscular mycorrhiza and ectomycorrhiza. These fungi can make an extensive network in the soil to capture and translocate nutrients and water to the plants, but also assist foraging towards water or nutrients, signaling the direction in which the roots should grow. Root hairs are also directly involved in the formation of root nodules in legume plants to establish a symbiosis with nitrogen fixing bacteria, and as such enhance nitrogen nutrition. Furthermore, root hairs prevent harmful micro-organisms from entering the plant. Root hair cells also secrete acids (e.g., malic and citric acid), which solubilize minerals in the soils to release nutrients. For example, these acids make phosphate available for the plant from phosphorous-containing resources in the soil such as rock phosphate or mineralized phosphate. As a result, an increased root hair number or surface generally improve plant fitness and growth efficiency. These roles and benefits are shown or discussed in numerous peer-reviewed articles, including Vissenberg et al., 2020, J Exp Bot., 71 (8) :2412 -2427 ; Wang et al., 2020, Plant Physiol., 184(1) : 176- 193; Zou et al, 2019, Pak. J. Bot., 51(2); Kwasniewski et al., 2016, J Exp Bot., 67 (4) : 1079-94; Haling et al., 2013, J Exp Bot., 64(12) :3711-3721; Wang et al, 2008, J Plant Res., 121:87-96; Grierson and Schiefelbein, 2002, Arabidopsis Book., l:e0060.
The object underlying the present invention is to provide compounds as fertilizer additives that can act as plant growth promoters by increasing the total root hair surface of plants. Preferably, the compounds shall mitigate/alleviate nutrient starvation or drought stress of plants, and/or enhance the nutrient (fertilizer) use efficiency and/or improve the nutrient or water uptake of plants.
The objects are achieved by the use of a compound of the general formula (I)
Figure imgf000003_0001
with the following definitions:
X heteroatom, selected from the group consisting of nitrogen, oxygen and sulfur, preferably, X is nitrogen;
Rl; R2 independently hydrogen, C1-20-hydrocarbon residue, preferably a Cl-10, even more preferably a Cl-5 hydrocarbon residue, even more preferably a Cl-3 hydrocarbon residue, which can contain one to three halogen atoms and/or one to seven heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur, preferably, either Rl or R2 have a keto, an aldehyde, an amide and/or an amino group; and preferably characterized in that no oxygen double bond is present at the Cl atom of Rl and/or R2; even more preferably Rl is a C2 hydrocarbon with a carboxamide-group on C2 of Rl and R2 is hydrogen;
R3 independently hydrogen, halogen, heteroatom functional group, C^^- hydrocarbon residue, Cr5 hydrocarbon residue, even more preferably a Cr3 hydrocarbon residue, which can contain one or two halogen atoms and/or one to three heteroatoms, selected from the group consisting of nitrogen, oxygen and sulfur, preferably oxygen, it also being possible for Rl and R3 to be covalently linked to form a 5- to 8-membered heterocyclic ring, which can contain 1 or 2 halogen atoms and/or one to three further heteroatoms in addition to the heteroatoms N already part of the heterocyclic ring, preferably R3 is a methoxy group n 0; 1; 2; 3; 4 or 5, preferably n is 0 or 1; as plant growth promoter. According to the present invention, it has been found that compounds of the above general formula (I) can be successfully employed as plant growth promoters or root hair inducers or a combination thereof. They induce root hairs and root hair elongation and enhance the nutrient use efficiency and water uptake of plants. They mitigate/alleviate the nutrient starvation or drought stress of plants.
A preferred embodiment is the use of the compound of the general formula (I)
Figure imgf000004_0001
With the following definitions:
X heteroatom, selected from the group consisting of nitrogen and oxygen, preferably, X is nitrogen;
Rl; R2 if X is nitrogen, Rl and R2 are independently hydrogen or a Cr3 hydrocarbon residue, preferably a C2 hydrocarbon residue, which can contain one to seven heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur, preferably, either Rl or R2 have a keto, an aldehyde, an amide and/or an amino group; and preferably characterized in that no oxygen double bond is p resent at th e Ci atom of Rl and/or R2; even more preferably Rl is a C2 hydrocarbon with a carboxamide-group on C2 of Rl and R2 is hydrogen;
Rl if X is oxygen, Rl is hydrogen or a Cr3 hydrocarbon residue, preferably a C2 hydrocarbon residue, which can contain one to seven heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur;
R3 independently hydrogen, halogen, heteroatom functional group, Cri2- hydrocarbon residue, preferably a Cr5 hydrocarbon residue, even more preferably a Cr3 hydrocarbon residue, which can contain one or two halogen atoms and/or one to three heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur, preferably oxygen, it also being possible for R1 and R3 to be covalently linked to form a 5- to 8-membered heterocyclic ring, which can contain 1 or 2 halogen atoms and/or one to three further heteroatoms in addition to the heteroatoms N already part of the heterocyclic ring, preferably R3 is a hydrogen, a methyl-group or a methoxygroup; n 0; 1; 2; 3; 4 or 5, preferably n is 0 or 1; as plant growth promoter, wherein the plant grows promoter improves the root hair development, Phosphate use efficiency/uptake nutrient use efficiency of plants, nutrient uptake of plants, nutrient availability, water uptake of plants, nutrient and water foraging by plants, drought resistance, root penetration in the soil, anchorage in the soil, beneficial symbiotic interactions of plants, protection against harmful micro-organisms, and/or plant growth or yield; and/or for mitigating and/or reducing nutrient starvation, drought, salt, and/or osmotic stress of plants.
In a preferred embodiment, the compound of the formula (I) is one of the following compounds:
Figure imgf000005_0001
Figure imgf000006_0001
Particularly preferred is the compound of the formula (II)
Figure imgf000007_0001
(H)
In another embodiment, the compound of the formula (I) is not the following compound:
Figure imgf000007_0002
In another embodiment, the compound of the formula (I) is not the following compound:
Figure imgf000007_0003
In a preferred embodiment or the present use, the pH range of the substrate or soil is from 4.5 to 7.5, preferably from 5 to 7, even more preferably from 5.5 to 6.5.
The use of the compounds of the formula (I) or of the formula (II) is preferably for improving root hair development, nutrient use efficiency of plants, nutrient uptake of plants, nutrient availability, water uptake of plants, nutrient and water foraging by plants, drought resistance, root penetration in the soil, anchorage in the soil, beneficial symbiotic interactions of plants, protection against harmful micro-organisms, plant growth or yield or for mitigating and/or reducing nutrient starvation, drought, salt, and/or osmotic stress of plants.
The object is furthermore achieved by a method for promoting growth of a plant, comprising adding to growing medium or soil in which the plant is grown, a compound as defined above.
The invention furthermore relates to a mixture containing at least one compound of general formula (I) as defined above, and at least one additional agrochemical agent, preferably selected from the group consisting of at least one inorganic and/or organic and/or organomineral fertilizer at least one nitrification inhibitor, preferably selected from the group consisting of 2-(3,4- dimethyl-pyrazol-l-yl)-succinic acid (DMPSA), 3,4-dimethylpyrazole (DMP), 3,4- dimethylpyrazolephosphate (DMPP), dicyandiamide (DCD), lH-l,2,4-triazole, 3- methylpyrazole (3-MP), 2-chloro-6-(trichloromethyl)-pyridine, 5-ethoxy-3- trich loromethy I - 1,2, 4-th iad iazol , 2 -a mino-4-ch I oro-6- methyl -pyrimidine, 2 -mercapto- benzothiazole, 2-sulfanilamidothiazole, thiourea, sodium azide, potassium azide, 1- hydroxypyrazole, 2-methylpyrazole-l-carboxamide, 4-amino-l,2,4-triazole, 3-mercapto- 1,2,4-triazole, 2,4-diamino-6-trichloromethyl-5-triazine, carbon bisulfide, ammonium thiosulfate, sodium trithiocarbonate, 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl carbamate and N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-alanine methyl ester, at least one urease inhibitor, preferably selected from N-n-butylthiophosphoric triamide (NBTPT or NBPT) and/or N-n-propylthiophosphoric triamide (NPTPT or NPPT), at least one customary agrochemical auxiliary agent, preferably selected from the group consisting of aqueous and/or organic solvents, pH-adjusting agents, surfactants, wetting agents, spreading agents, adhesion promoters, carriers, fillers, viscosity-adjusting agents, emulsifiers, dispersants, sequestering agents, anti-settling agents, coalescing agents, rheology modifiers, defoaming agents, photo-protectors, anti-freeze agents, (additional or further) biostimulants, pesticides/plant protection products, biocides, (additional or further) plant growth regulators, safeners, penetrants, anticaking agents, mineral and/or vegetable oils and/or waxes, colorants and drift control agents, and mixtures thereof.
The invention furthermore relates to a fertilizer mixture, containing
A. an inorganic and/or organic and/or organomineral fertilizer and
B. 10 to 10000 weight-ppm, based on the fertilizer, of a compound of the general formula
(I) as defined above.
The invention furthermore relates to a process for producing the fertilizer mixture as defined above by introducing the compound of the general formula (I) into the fertilizer, and/or applying the compound of the general formula (I) to the surface of the fertilizer. The invention furthermore relates to a method of fertilizing soils exploited agriculturally or horticulturally including home and garden, wherein a fertilizer mixture containing compounds A and B
A. an inorganic and/or organic and/or organomineral fertilizer and
B. an effective amount, preferably 10 to 10000 weight-ppm, more preferably 100 to 3000 weight-ppm, based on the fertilizer, of a compound of the general formula (I) as above, or compounds A and B separately, but within a period of 0 to 5 hours, preferably 0 to 1 hour, more preferably approximately at the same time, is applied onto or into the soils by any application technique.
The term “independently” defines that the meaning for each residue can be selected independent of the meaning for another member or binding position of the mentioned residues. For example, R1 and R3 can be the same or different.
The compounds according to the present invention can be combined with a nitrification inhibitor and/or urease inhibitor.
Furthermore, specifically if the fertilizer contains urea, the compound can also be used together or combined with or in admixture with an urease inhibitor, which is preferably selected from N-n-butylthiophosphoric triamide (NBTPT or NBPT) and/or N-n- propylthiophosphoric triamide (NPTPT or NPPT).
The compounds according to the present invention can as well be combined with a nitrification inhibitor and an urease inhibitor, specifically in case of fertilizers containing ammonium and urea and a source for phosphorus.
If the compound of the present invention is combined with a nitrification inhibitor, the weight ratio of compound of the present invention to nitrification inhibitor is preferably in the range of from 0.01 to 100 : 1, more preferably 0.1 to 10 : 1.
If the compound according to the present invention is combined with a urease inhibitor, the weight ratio of compound of the present invention to urease inhibitor is preferably in the range of from 0.01 to 100 : 1, more preferably 0.1 to 10 : 1.
If the nitrification inhibitor is combined with N-n-butylthiophosphoric triamide (NBTPT) and/or N-n-propylthiophosphoric triamide (NPTPT), the weight ratio of nitrification inhibitor(s) to urease inhibitor is preferably in the range of from 0.1 to 10 : 1, more preferably 0.5 to 8 : 1, most preferably 1 to 6 : 1.
Furthermore, the compounds of the present invention can be combined with an inorganic and/or organic and/or organomineral fertilizer, specifically a fertilizer which contains a phosphorus source.
Furthermore, it is possible to combine the compounds of the present invention with at least one customary agrochemical (auxiliary) agent. Therefore, the present invention defines a mixture of the compounds of general formula (I) as defined above, with
- at least one fertilizer, or
- at least one nitrification inhibitor, preferably selected from the group consisting of 2-(3,4- dimethyl-pyrazol-l-yl)-succinic acid (DMPSA), 3,4-dimethylpyrazole (DMP), 3,4- dimethylpyrazolephosphate (DMPP), dicyandiamide (DCD), lH-l,2,4-triazole, 3- methylpyrazole (3-MP), 2-chloro-6-(trichloromethyl)-pyridine, 5-ethoxy-3- trichloromethyl-l,2,4-thiadiazol, 2 -a mi no-4-ch loro-6- methyl -pyrimidine, 2- mercaptobenzothiazole, 2-sulfanilamidothiazole, thiourea, sodium azide, potassium azide, 1- hydroxypyrazole, 2-methylpyrazole-l-carboxamide, 4-amino-l,2,4-triazole, 3-mercapto- 1,2,4-triazole, 2,4-diamino-6-trichloromethyl-5-triazine, carbon bisulfide, ammonium thiosulfate, sodium trithiocarbonate, 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl carbamate and N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-alanine methyl ester, or
- at least one urease inhibitor, preferably selected from N-n-butylthiophosphoric triamide (NBTPT) and/or N-n-propylthiophosphoric triamide (NPTPT), or
- at least one customary agrochemical auxiliary agent, preferably selected from the group consisting of aqueous and/or organic solvents, pH-adjusting agents, surfactants, wetting agents, spreading agents, adhesion promoters, carriers, fillers, viscosity-adjusting agents, emulsifiers, dispersants, sequestering agents, anti-settling agents, coalescing agents, rheology modifiers, defoaming agents, photo-protectors, anti-freeze agents, (additional or further) biostimulants, pesticides/plant protection products, biocides, (additional or further) plant growth regulators, safeners, penetrants, anticaking agents, mineral and/or vegetable oils and/or waxes, colorants and drift control agents, or mixtures thereof.
The term “additional or further” describes biostimulants and/or plant growth regulators that are different from the compounds of general formula (I).
The compounds of the invention are preferably employed in combination with a fertilizer, more preferably a phosphorus source or an (ammonium) nitrogen-containing fertilizer, e.g. solid or liquid inorganic, organic and/or organomineral fertilizer, or manure. The compound is for example employed on solid fertilizers, or is employed in liquid organic or inorganic or organomineral fertilizers or manure.
The compounds of general formula (I) are mostly known per se and can be synthesized according to standard techniques. They partly are commercially available compounds and can be obtained from ENAMINE Ltd., UkrOrgSynthesis Ltd., or Vitas-M Laboratory, Ltd. or from Merck Millipore, Burlington, MA, USA, or Merck KGaA.
The compounds of the invention are plant additives which can alleviate nutrient starvation or drought symptoms in plants and promote the growth of nutrient starvation or drought stressed plants. They may substantially improve the whole plant growth, especially in low nutrient or drought conditions.
Advantageously, the compound according to the present invention is useful for reducing the need for fertilizer for growing plants.
The term “plant” includes any monocot or dicot plant, such as a plant of the Fabaceae or Brassicaceae family, in particular Medicago sativa (Alfalfa).
In another embodiment, said plant is grown under nutrient limiting conditions. As used herein, the term “under nutrient limiting conditions” means under low nutrient conditions, i.e., under a content of nutrients that is not optimal for the growth of the specific plant.
The mixture of the present invention provides a plant additive composition comprising: a compound of formula (I) as defined above and a formulation adjuvant, such as a carrier, a solvent or a surface-active agent.
By “plant additive composition” is meant any kind of soil additive, soil amendment, fertilizer or soil conditioner, which can of course be used to modify a soil, but also in hydroponic cultures.
More particularly, said plant additive composition is a composition for promoting plant growth and/or for alleviating nutrient starvation or drought symptoms.
The plant additive composition according to the present invention is typically not intended for use as a herbicide, in particular as a defoliant, a desiccant, an herbage killer, a germination inhibitor or a weed killer.
The plant additive composition can be a liquid or solid (typically granulated or powdered) composition, such as dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil flowables, aqueous dispersions, oil dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as carrier), or impregnated polymer films.
In a particular embodiment, the plant additive composition further comprises at least one primary nutrient selected from the group consisting of nitrogen and potassium, and/or at least one secondary nutrient selected from the group consisting of calcium, magnesium, sodium and sulfur, and/or at least one micronutrient selected from the group consisting of boron, cobalt, copper, iron, manganese, molybdenum and zinc.
Advantageously, said plant additive composition comprises a compound of formula (I) as defined above and at least one or the 2 primary nutrients as defined above. Advantageously, said plant additive composition comprises a compound of formula (I) as defined above and at least one or the 2 primary nutrients and the 4 secondary nutrients as defined above.
Advantageously, said plant additive composition comprises a compound of formula (I) as defined above, nitrogen, potassium, calcium, magnesium, sodium, sulfur, boron, cobalt, copper, iron, manganese, molybdenum and zinc.
Advantageously, a liquid plant additive composition comprises a solvent such as a polar water-soluble solvent, a micelle or a surfactant.
The present invention provides a method for promoting the growth of a plant, comprising adding to the growing medium or soil on which said plant is grown, a compound of formula (I) as defined above, or a plant additive composition comprising a compound of formula (I) as defined above and a formulation adjuvant as defined above.
The method according to the present invention is not intended for promoting the growth of a plant by inhibiting the growth of another plant (e.g., a weed).
The growing medium includes liquid, semi-solid or solid medium suitable to support the growth of a plant. By way of example, it can be a mineral nutrient solution or an inert material such as heydite, clay pellets, perlite, vermiculite or rockwool. Advantageously, the growing medium contains the nutrients required to support the growth of the plant.
The present invention provides the use of a compound of formula (I) as defined above for preparing a plant additive composition as defined above useful for promoting the growth of a plant.
One or more compounds of formula (I) can be employed as plant growth promoters in the fertilizer discussed below. Furthermore, it is possible to employ mixtures of one or more compounds of general formula (I). This is reflected by the expression formula (I).
It is expected that the plant growth promoters of the present invention possess favorable toxicological properties, have a low vapor pressure, and are absorbed well in the soil. As a consequence, the plant growth promoter is neither emitted to the atmosphere by sublimation to any significant extent nor is easily leached by water. As a result, first of all, economic advantages arise, such as a high profitability in view of the longer-lasting effect of the plant growth promoters, and environmental advantages, such as a reduction in the burdening of air (climate gas-reducing) and of surface waters and ground water.
The plant growth promoters can be applied to soils or substrates which are fertilized with an inorganic or organic or organomineral fertilizer. Typically, they are employed in a fertilizer mixture comprising such fertilizer and the compound of general formula (I). Typically, the compound of general formula (I) is employed in an amount of 10 to 10000 ppm by weight, more preferably 100 to 10000 ppm by weight, based on the fertilizer without water. The application amount is based on the dry fertilizer.
The plant growth promoters according to the present invention can be employed in substance, in solution, dispersion or emulsion. Therefore, the invention also relates to a solution, dispersion or emulsion containing the compound of general formula (I) of the present invention preferably in an amount of 0.1 to 50 wt%, more preferably 0.5 to 30 wt%, most preferably 1 to 20 wt%.
Preferably, according to the present invention, fertilizers are employed for forming a fertilizer mixture, containing compounds A and B
A. an inorganic and/or organic and/or organomineral fertilizer and
B. 10 to 10000 weight-ppm, more preferably 100 to 10000 weight-ppm, based on the fertilizer, of the compound of general formula (I) as defined above.
The water fraction in compound A and in the fertilizer mixture is often not more than 1.5 wt%, preferably not more than 1.0 wt%, more preferably not more than 0.5 wt%, most preferably not more than 0.3 wt%, and is therefore negligible in the balance of quantities. Compounds A and B preferably make up at least 95 wt%, more preferably at least 98 wt% of the fertilizer mixture.
The nitrogen content of component A (without water), is often at least 12 wt%, preferably at least 20 wt%, more preferably at least 22 wt%. For example, the nitrogen content may be 25 to 29 wt%, particularly 26 to 28 wt%. The nitrogen content can be divided between fast-acting nitrate nitrogen and slow-acting ammonium nitrogen.
The inorganic fertilizers preferably are ammonium- and/or urea-containing fertilizers, more preferably ammonium-containing fertilizers which can additionally contain urea.
Urea-containing fertilizers are further described in WO 2016/207210.
Fertilizers typically provide, in varying proportions: three main macronutrients:
- Nitrogen (N): leaf growth
- Phosphorus (P): Development of roots, flowers, seeds, fruit;
- Potassium (K): Strong stem growth, movement of water in plants, promotion of flowering and fruiting; three secondary macronutrients: calcium (Ca), magnesium (Mg), and sulfur (S);
- micronutrients: copper (Cu), iron (Fe), manganese (Mn), molybdenum (Mo), zinc (Zn), boron (B). Of occasional significance are silicon (Si), cobalt (Co), and vanadium (V).
The fertilizers employed according to the present invention can be of natural or synthetic origin and are applied to soil or to plant tissues to supply one or more plant nutrients essential to the growth of plants. The fertilizers employed according to the present invention should provide at least nitrogen as nutrient. Further nutrients are for example K and P. Multinutrient f erti I izers/co m pl ex fertilizers provide two or more nutrients. Inorganic fertilizers exclude carbon-containing materials except ureas. Organic fertilizers are usually plant- or animal- derived matter.
Organomineral fertilizers (combination of inorganic and organic fertilizers) can be employed as well.
The main nitrogen-based straight fertilizer is ammonia or its solutions. Ammonia nitrate is also widely used. Urea is another popular source of nitrogen, having the advantage that it is solid and non-explosive. A further nitrogen-based fertilizer is calcium ammonium nitrate.
The main straight phosphate fertilizers are the superphosphates. "Single superphosphate" (SSP) consists of 14-18% P2O5, again in the form of Ca(H2PO4)2, but also phosphogypsum (CaSO4 • 2H2O). Triple superphosphate (TSP) typically consists of 44-48% of P2O5 and no gypsum. A mixture of single superphosphate and triple superphosphate is called double superphosphate. More than 90% of a typical superphosphate fertilizer is water-soluble.
Diammonium phosphate (DAP) quickly became the item of commerce as most widely used by the growers today, and it has the highest concentration of phosphate and nitrogen at 18 N- 46P2O5-0K2O
Monoammonium phosphate (MAP) is essentially the same as DAP, but it has a lower concentration of nitrogen at 11 N - 52 P2O5 -0 K2O. It is completely water soluble and has granular material; it mixes well and frequently serves as an ingredient in bulk-blended fertilizers.
Granulated triple superphosphate (GTSP) is very similar to the superphosphate fertilizer that provides 46% P2O5, some calcium and sulfur to plants. GTSP is formed by reaction of phosphate rock with phosphoric acid.
Superphosphoric acid is an acid used to make a concentrated or fluid fertilizer.
Phosphoric acid is used in granulation plants where ammonia is added to phosphoric acid to produce the ammoniated phosphate fertilizer
Phosphate fertilizers are obtained by extraction from phosphate rock, which contains two principal phosphorus-containing minerals, fluorapatite Ca5(PO4)3F (CFA) and hydroxyapatite Ca5(PO4)3OH. These minerals are converted into water-soluble phosphate salts by treatment with sulfuric (H2SO4) or phosphoric acids (H3PO4).
In the nitrophosphate process or Odda process, phosphate rock with up to a 20% phosphorus (P) content is dissolved with nitric acid (HNO3) to produce a mixture of phosphoric acid (H3PO4) and calcium nitrate (Ca(NO3)2). This mixture can be combined with a potassium fertilizer to produce a compound fertilizer with the three macronutrients N, P and K in easily dissolved form. The main potassium-based straight fertilizer is muriate of potash (MOP).
Binary (NP, PK) fertilizers can be employed as well:
Major two-component fertilizers provide both nitrogen and phosphorus to the plants. These are called NP fertilizers. The main NP fertilizers are monoammonium phosphate (MAP) and diammonium phosphate (DAP). The active ingredient in MAP is NH4H2PO4. The active ingredient in DAP is (NH4)2HPO4. About 85% of MAP and DAP fertilizers are soluble in water. NPK fertilizers are three-component fertilizers providing nitrogen, phosphorus and potassium. NPK fertilizers can be produced by mixing straight fertilizers as mentioned above in bulk or in each granule, as in Nitrophoska9. In some cases, chemical reactions can occur between the two or more components.
NPK fertilizers are at least three-component fertilizers providing nitrogen, phosphorus and potassium. NPK fertilizers can be produced by mixing straight fertilizers as mentioned above in bulk or in each granule, as in Nitrophoska9. In some cases, chemical reactions can occur between the two or more components.
For example, monoammonium and diammonium phosphates, which provide plants with both N and P, are produced by neutralizing phosphoric acid (from phosphate rock) and ammonia:
NH3 + H3PO4 (NH4)H2PO4
2 NH3 + H3PO4 (NH4)2HPO4
Besides the main constituents, like N, P and K, micronutrients (trace elements) may be present in the fertilizers. The main micronutrients are molybdenum, zinc, boron and copper. These elements are typically provided as water-soluble salts.
Preferred fertilizers contain ammonium or urea. Examples of preferred ammonium-containing fertilizers are NPK fertilizers, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate and ammonium phosphate.
Further preferred ingredients of the fertilizer compositions are for example trace elements, further minerals, standardizers, binders.
Organic fertilizers can describe those fertilizers with an organic or biologic origin, i.e. fertilizers derived from living or formerly living materials, like animals or plants or algae. Fertilizers of an organic origin include animal wastes, plant wastes e.g. from food processing or agriculture, compost, and treated sewage sludge (biosolids). Animal sources can be manures, but also products from the slaughter of animals, like blood meal, bone meal, feather meal, hides, hooves, and horns.
Soil amendments, like peat or coir, bark and sawdust can also be included. Fertilizers can include without limitation, ammonium sulfate, ammonium nitrate, ammonium sulfate nitrate, ammonium chloride, ammonium bisulfate, ammonium polysulfide, ammonium thiosulfate, aqueous ammonia, anhydrous ammonia, ammonium polyphosphate, aluminum sulfate, calcium nitrate, calcium ammonium nitrate, calcium sulfate, calcined magnesite, calcitic limestone, calcium oxide, hampene (chelated iron), dolomitic limestone, hydrate lime, calcium carbonate, diammonium phosphate, monoammonium phosphate, potassium nitrate, potassium bicarbonate, monopotassium phosphate, magnesium nitrate, magnesium sulfate, potassium sulfate, potassium chloride, sodium nitrates, magnesian limestone, magnesia, disodium dihydromolybdate, cobalt chloride hexahydrate, nickel chloride hexahydrate, indole butyric acid, L-tryptophan, urea, urea-formaldehydes, urea ammonium nitrate, sulfur-coated urea, polymer-coated urea, isobutylidene diurea, K2SO4-2MgSO4, kainite, sylvinite, kieserite, Epsom salts, elemental sulfur, marl, ground oyster shells, fish meal, oil cakes, fish manure, blood meal, rock phosphate, super phosphates, slag, bone meal, wood ash, biochar, algae, algae extract, struvite, manure, bat guano, peat moss, compost, green sand, cottonseed meal, feather meal, crab meal, fish emulsion or a combination thereof. The micronutrient fertilizer material can comprise boric acid, a borate, a boron frit, copper sulfate, a copper frit, a copper chelate, a sodium tetraborate decahydrate, an iron sulfate, an iron oxide, iron ammonium sulfate, an iron frit, an iron chelate, a manganese sulfate, a manganese oxide, a manganese chelate, a manganese chloride, a manganese frit, a sodium molybdate, molybdic acid, a zinc sulfate, a zinc oxide, a zinc carbonate, a zinc frit, zinc phosphate, a zinc chelate or a combination thereof. In a particular embodiment, said fertilizer or fertilizer composition does not comprise insoluble selenium, selenium mineral, soluble selenium or salts thereof.
The treated (inorganic, organic or organomineral) fertilizers according to the invention are preferably present in powder form, prill form or in granule form.
Besides the compound of the general formula (I), formulations comprising the compound and agronomical adjuvants can be used for including the plant growth promoters in the fertilizer. Agronomical adjuvants are, for example, solvents, dispersants, pH-adjusting agents, fillers, stability improvers, surfactants.
The plant growth promoters can be included in the fertilizer mixture by mixing it or the formulation containing it with a solid or liquid fertilizer or fertilizer formulation. Preferably, the fertilizer mixture is in solid form and the plant growth promoter is applied to the surface of the (inorganic, organic or organomineral) fertilizer.
In a process for producing the fertilizer mixture of the present invention, the plant growth promoters or the formulation containing it can be introduced into the (inorganic, organic or organomineral) fertilizer and/or applied to the surface of the fertilizer.
Granules of fertilizers are impregnated or coated with the plant growth promoters, for example by being sprayed with a formulation like a solution or a dispersion of the plant growth promoters and subsequent drying. The method is known, for example, from DE-A-41 28 828. The sealing of the impregnated granules with, for example, a paraffin wax, which is an additional proposal in the latter document, is possible, but generally unnecessary. Granulating assistants which can be employed for preparing solid fertilizer compositions can be lime, gypsum, silicon dioxide or kaolinite.
An alternative is the addition of the nitrification inhibitor during the actual production of the fertilizer or in the slurry, for example.
As a rule, the plant growth promoters are customarily applied to the soil in amounts effective for the desired action.
Delivery of the plant growth promoters in liquid fertilizer formulations may be accomplished, for example, by fertigation with or without excess water as described in DE-C-102 30 593.
The fertilizer mixture can contain at least one nitrification inhibitor. Preferably, this at least one further nitrification inhibitor is inhibiting ammonia-oxidizing bacteria (AOB) and is preferably selected from the group consisting of 2-(3,4-dimethyl-pyrazol-l-yl)-succinic acid,
3.4-dimethylpyrazole (DMP), 3,4-dimethylpyrazolephosphate (DMPP), dicyandiamide (DCD), lH-l,2,4-triazole, 3-methylpyrazole (3-MP), 2-chloro-6-(trichloromethyl)-pyridine, 5-ethoxy- 3-tric h loro methyl -1,2, 4-th iadiazo I, 2 -a mi no-4-ch loro-6- methyl -pyrimidine, 2 -mercapto- benzothiazole, 2-sulfanilamidothiazole, thiourea, sodium azide, potassium azide, 1- hydroxypyrazole, 2-methylpyrazole-l-carboxamide, 4-amino-l,2,4-triazole, 3-mercapto-
1.2.4-triazole, 2,4-diamino-6-trichloromethyl-5-triazine, carbon bisulfide, ammonium thiosulfate, sodium tri-thiocarbonate, 2,3-dihydro-2,2-dimethyl-7-benzofuranol methyl carbamate and N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-alanine methyl ester. Also nitrification inhibitors inhibiting ammonia-oxidizing archaea (AOA) can be employed together with the compound of general formula (I).
When the nitrification inhibitor is employed, the weight ratio of the compound of general formula (I) to the nitrification inhibitor is preferably 0.01 to 100 : 1, more preferably 0.1 to 10 : 1.
Furthermore, the fertilizer mixture can contain at least one urease inhibitor, which is preferably selected from N-n-butylthiophosphoric triamide (NBTPT) and/or N-n- propylthiophosphoric triamide (NPTPT). A urease inhibitor is typically added when the fertilizer contains urea. Urea nitrogen is liberated as ammonium by the action of urease, and the ammonium can undergo nitrification. Therefore, it can be advantageous to combine a urease inhibitor with the nitrification inhibitor.
If the compound of general formula (I) of the present invention is combined with N-n- butylthiophosphoric triamide (NBTPT) and/or N-n-propylthiophosphoric triamide (NPTPT), the weight ratio of plant growth promoter(s) to urease inhibitor is preferably in the range of from 0.01 to 100 : 1, more preferably 0.1 to 10 : 1.
Thiophosphoric triamides are known to be relatively easily converted to the corresponding phosphoric triamides and thiophosphoric diamides as well as other metabolites. Since, generally speaking, moisture cannot be entirely excluded, thiophosphoric triamide and the corresponding phosphoric triamide are frequently present in a mixture with one another. In this specification, therefore, the term “(thio)phosphoric triamide” identifies not only the pure thiophosphoric triamides and phosphoric triamides, respectively, but also mixtures thereof.
According to the present invention, also mixtures of N-(n-butyl)thiophosphoric triamide and N-(n-)propylthiophosphoric triamide can be employed, as described in EP-A-1 820 788.
The fertilizer mixtures can contain other ingredients, like coatings, for example of inorganic or organic polyacids, which are described in US 6,139,596.
Furthermore, coatings of powders, prills and granules can be formed of inorganic material, such as sulfur- or mineral-based coatings, or with an organic polymer. Respective coatings are described in WO 2013/121384 on page 23, line 37 to page 24, line 16.
As stated above, the agrochemical formulations comprising the compounds of formula (I) are used in "effective amounts". This means that they are used in a quantity which allows to obtain the desired effect which is a (synergistic) increase of the health or growth of a plant but which does not give rise to any phytotoxic symptom on the treated plant.
For use according to the present invention, the agrochemical formulations comprising the compounds of formula (I) can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the agrochemical formulations comprising the compounds of formula (I) to the present invention. The formulations are prepared in a known manner to the person skilled in the art.
The agrochemical formulations may also comprise auxiliaries which are customary in agrochemical formulations. The auxiliaries used depend on the particular application form and active substance, respectively. Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and inorganic thickeners, bactericides, antifreezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e.g. for seed treatment formulations).
Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as cyclohexanone and gamma-butyrolactone, fatty acid dimethylamides, fatty acids and fatty acid esters and strongly polar solvents, e.g. amines such as N-methylpyrrolidone.
Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
Suitable surfactants (adjuvants, wetters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, dibutylnaphthalenesulfonic acid and fatty acids, alkylsulfonates, alkyl-arylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearyl-phenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquid and proteins, denatured proteins, polysaccharides (e.g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols, polycarboxylates types, polyalkoxylates, polyvinylamines, polyvinylpyrrolidone and the copolymers therof. Examples for thickeners (i.e. compounds that impart a modified flowability to formulations, i.e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and inorganic clays such as Xanthan gum.
A biostimulant is any substance or microorganism, in the form in which it is applied to plants, seeds or the root environment with the intention to stimulate natural processes of plants benefiting nutrient use efficiency and/or tolerate to abiotic stress, regardless of its nutrient content, or any combination of such substances and/or microorganisms intended for this use.
A plant biostimulant is any microorganism or substance based on natural resources, in the form in which it is applied to plants, seeds or the soil and any other substrate with the intention to stimulate natural processes of plants to benefit their nutrient use efficiency and/or their tolerance to stress, regardless of its nutrients content, or any combination of such substances and/or microorganisms intended for this use.
A 'pesticide' is something that prevents, destroys, or controls a harmful organism ('pest') or dis-ease, or protects plants or plant products during production, storage and transport.
The term includes, amongst others: herbicides, fungicides, insecticides, acaricides, nematicides, molluscicides, rodenticides, growth regulators, repellents, rodenticides and biocides as well as plant protection products.
Plant protection products (PPP) are 'pesticides' that protect crops or desirable or target plants. They are primarily used in the agricultural sector but also in forestry, horticulture, amenity areas and in home gardens. They contain at least one active substance and have one of the following functions: - protect plants or plant products against pests/diseases, before or after harvest;
- influence the life processes of plants (such as substances influencing their growth, excluding nutrients);
- preserve plant products;
- destroy or prevent growth of undesired plants or parts of plants.
They may also contain other components including safeners and synergists.
An active substance is any chemical, plant extract, pheromone or micro-organism (including viruses), that has action against 'pests' or on plants, parts of plants or plant products.
The most common use of pesticides is in the form of plant protection products (PPPs).
The term 'pesticide' is often used interchangeably with 'plant protection product', however, pesticide is a broader term that also covers non plant/crop uses, for example biocides.
Biocides, like herbicides, bactericides, molluscicides, algicides, phytotoxicants, fungicides, and their mixtures can be added.
Bactericides may be added for preservation and stabilization of the formulation. Examples for suitable bactericides are those based on dichlorophene and benzylalcohol hemi formal (Proxel® from ICI or Acticide9 RS from Thor Chemie and Kathon9 MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide9 M BS from Thor Chemie). Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Examples for anti-foaming agents are silicone emulsions (such as e.g. Silikon9 SRE, Wacker, Germany or Rhodorsil9, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and agrochemical formulations comprising the compounds of formula (I) thereof.
Suitable colorants are pigments of low water solubility and solvent-soluble, e.g. water- soluble, dyes.
Examples for adhesion promoters, like tackifiers or binders, are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose9, Shin-Etsu, Japan).
Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
Anticaking agents like oils and/or waxes can be added. The agrochemical formulations generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substances. The compounds of the agrochemical formulations comprising the compounds of formula (I) are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to their NMR spectrum).
The compounds of the agrochemical formulations comprising the compounds of formula (I) can be used as such or in the form of their agricultural compositions, e.g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring. The application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the compounds present in the agrochemical formulations comprising the compounds of formula (I).
Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1%, by weight of compounds of the agrochemical formulations comprising the compounds of formula (I).
The compounds of the agrochemical formulations comprising the compounds of formula (I) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.
Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active compounds, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compounds of the agrochemical formulations comprising the compounds of formula (I) in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
Compositions of this invention may also contain fertilizers (such as ammonium nitrate, urea, potash, and superphosphate), phytotoxicants and plant growth regulators (plant growth amendments) and safeners. These may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with the fertilizers. In the agrochemical formulations comprising the compounds of formula (I), the weight ratio of the compounds generally depends from the properties of the compounds of the agrochemical formulations comprising the compounds of formula (I).
The compounds of the agrochemical formulations comprising the compounds of formula (I) can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used further as combination composition such as a kit of parts.
The user applies the composition according to the invention usually from a pre-dosage device, a knapsack sprayer, a spray tank or a spray plane. Here, the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquid or the agrochemical composition according to the invention is thus obtained. Usually, 50 to 500 liters of the ready- to-use spray liquid are applied per hectare of agricultural useful area, preferably 50 to 400 liters.
In a particular embodiment the absolute amount of the active compounds, represented by formula (I), is used in a range between 1 mg/liter to 100 mg/liter, particularly in a range between 1 mg/l to 20 mg/l, particularly in a range between 1 mg/l to 25 mg/l, particularly in a range between 2 mg/l to 200 mg/l, particularly between 2 mg/l to 100 mg/l, particularly between 2 mg/l to 50 mg/l, particularly between 2 mg/l to 25 mg/l, particularly between 4 mg/l to 40 mg/l, particularly between 4 mg/l to 20 mg/l, particularly between 4 mg/l to 16 mg/l, particularly between 4 mg/l to 12 mg/l.
According to one embodiment, individual compounds of the agrochemical formulations comprising the compounds of formula (I) formulated as composition (or formulation) such as parts of a kit or parts of the inventive mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).
“Agrochemical”, as used herein, means any active substance that may be used in the agrochemical industry (including agriculture, horticulture, floriculture and home and garden uses, but also products intended for non-crop related uses such as public health/ pest control operator uses to control undesirable insects and rodents, household uses, such as household fungicides and insecticides and agents, for protecting plants or parts of plants, crops, bulbs, tubers, fruits (e.g. from harmful organisms, diseases or pests); for controlling, preferably promoting or increasing, the growth of plants; and/or for promoting the yield of plants, crops or the parts of plants that are harvested (e.g. its fruits, flowers, seeds etc.).
An “agrochemical composition” as used herein means a composition for agrochemical use, as herein defined, comprising at least one active substance of a compound of formula (I), optionally with one or more additives favoring optimal dispersion, atomization, deposition, leaf wetting, distribution, retention and/or uptake of agrochemicals. As a non-limiting example such additives are diluents, solvents, adjuvants, surfactants, wetting agents, spreading agents, oils, stickers, viscosity-adjusting agents (like thickeners, penetrants), pH- adjusting agents (like buffering agents, acidifiers), anti-settling agents, anti-freeze agents, photo-protectors, defoaming agents, biocides and/or drift control agents.
A “carrier”, as used herein, means any solid, semi-solid or liquid carrier in or on(to) which an active substance can be suitably incorporated, included, immobilized, adsorbed, absorbed, bound, encapsulated, embedded, attached, or comprised. Non-limiting examples of such carriers include nanocapsules, microcapsules, nanospheres, microspheres, nanoparticles, microparticles, liposomes, vesicles, beads, a gel, weak ionic resin particles, liposomes, cochleate delivery vehicles, small granules, granulates, nano-tubes, bucky-balls, water droplets that are part of an water-in-oil emulsion, oil droplets that are part of an oil-in-water emulsion, organic materials such as cork, wood or other plant-derived materials (e.g. in the form of seed shells, wood chips, pulp, spheres, beads, sheets or any other suitable form), paper or cardboard, inorganic materials such as talc, clay, microcrystalline cellulose, silica, alumina, silicates and zeolites, or even microbial cells (such as yeast cells) or suitable fractions or fragments thereof.
The terms "effective amount", "effective dose" and "effective amount", as used herein, mean the amount needed to achieve the desired result or results. More exemplary information about amounts, ways of application and suitable ratios to be used is given below. The skilled artisan is well aware of the fact that such an amount can vary in a broad range and is dependent on various factors such as the treated cultivated plant as well as the climatic and soil conditions.
As used herein, the terms “determining”, "measuring”, "assessing”, “monitoring” and “assaying” are used interchangeably and include both quantitative and qualitative determinations.
It is understood that the agrochemical composition is stable, both during storage and during utilization, meaning that the integrity of the agrochemical composition is maintained under storage and/or utilization conditions of the agrochemical composition, which may include elevated temperatures, freeze-thaw cycles, changes in pH or in ionic strength, UV-irradiation, presence of harmful chemicals and the like. More preferably, the compounds of formula (I), (II) as herein described remain stable in the agrochemical composition, meaning that the integrity and the activity of the compounds are maintained under storage and/or utilization conditions of the agrochemical composition, which may include elevated temperatures, freeze-thaw cycles, changes in pH or in ionic strength, UV-irradiation, presence of harmful chemicals and the like. Most preferably, said compounds of formula (I), (II) remain stable in the agrochemical composition when the agrochemical composition is stored at ambient temperature for a period of two years or when the agrochemical composition is stored at 54° C for a period of two weeks. Preferably, the agrochemical composition of the present invention retains at least about 70% activity, more preferably at least about 70% to 80% activity, most preferably about 80% to 90% activity or more. Examples of suitable carriers include, but are not limited to alginates, gums, starch, p-cyclodextrins, celluloses, polyurea, polyurethane, polyester, or clay. The agrochemical composition may occur in any type of formulation, preferred formulations are powders, wettable powders, wettable granules, water dispersible granules, emulsions, emulsifiable concentrates, dusts, suspensions, suspension concentrates, suspoemulsions, capsule suspensions, aqueous dispersions, oil dispersions, aerosols, pastes, foams, slurries or flowable concentrates.
In yet another embodiment the invention provides the use of the agrochemical compositions of the invention for enhancing abiotic stress tolerance in plants.
The agrochemical composition according to the invention can be applied once to a crop, or it can be applied two or more times after each other with an interval between every two applications. The agrochemical composition according to the invention can be applied alone or in mixture with other materials, preferably other agrochemical compositions, to the crop; alternatively, the agrochemical composition according to the invention can be applied separately to the crop with other materials, preferably other agrochemical compositions, applied at different times to the same crop.
In yet another embodiment the invention provides a method for the manufacture of (‘or the pro-duction of’ which is equivalent wording) an agrochemical composition according to the invention, comprising formulating a molecule of formula (I) as defined herein before, together with at least one customary agrochemical auxiliary agent. Suitable manufacturing methods are known in the art and include, but are not limited to, high or low shear mixing, wet or dry milling, drip-casting, encapsulating, emulsifying, coating, encrusting, pilling, extrusion granulation, fluid bed granulation, co-extrusion, spray drying, spray chilling, atomization, addition or condensation polymerization, interfacial polymerization, in situ polymerization, coacervation, spray encapsulation, cooling melted dispersions, solvent evaporation, phase separation, solvent extraction, sol-gel polymerization, fluid bed coating, pan coating, melting, passive or active absorption or adsorption.
Customary agrochemical auxiliary agents are well-known in the art and preferably include, but are not limited to aqueous and/or organic solvents, pH-adjusting agents (like buffering agents, acidifiers), surfactants, wetting agents, spreading agents, adhesion promoters (like tackifiers, stickers), carriers, fillers, viscosity-adjusting agents (like thickeners), emulsifiers, dispersants, sequestering agents, anti-settling agents, coalescing agents, rheology modifiers, defoaming agents, photo-protectors, anti-freeze agents, additional or further biostimulants (including bacterial and/or fungal inoculants or microorganisms beside non-microbial materials), biocides (preferably selected from herbicides, bactericides, phytotoxicants, fungicides, pesticides/plant protection products and mixtures thereof), additional or further plant growth regulators, safeners, penetrants, anticaking agents, mineral and/or vegetable oils and/or waxes, colorants and drift control agents or any suitable combination thereof.
If the compounds in formula (I) are considered as biostimulants and/or plant growth regulators, the additional auxiliary agent can refer to additional or further biostimulants and/or plant growth regulators which are different from the compounds in formula (I). The insecticide can include an organophosphate, a carbamate, a pyrethroid, an acaricide, an alkyl phthalate, boric acid, a borate, a fluoride, sulfur, a haloaromatic substituted urea, a hydro-carbon ester, a biologically-based insecticide, or a combination thereof. The herbicide, used to remove unwanted plants, can comprise a chlorophenoxy compound, a nitrophenolic compound, a nitrocresolic compound, a dipyridyl compound, an acetamide, an aliphatic acide, an anilide, a benzamide, a benzoic acid, a benzoic acid derivative, anisic acid, an anisic acid derivative, a benzonitrile, benzothiadiazinone dioxide, a thiocarbamate, a carbamate, carbanilate, ch loro- py rid i ny I , a cyclohexenone derivative, a dinitroaminobenzene derivative, a fluorodinitrotoluidine compound, isoxazolidinone, nicotinic acide, isopropylamine, an isopropylamine derivative, oxadiazolinone, a phosphate, a phthalate, a picolinic acid compound, a triazine, a triazole, a ura-cil, a urea derivative, endothall, sodium chlorate, or a combination thereof. The fungicide can comprise a substituted benzene, a thiocarbamate, an ethylene bis dithiocarbamate, a thioph-thalidamide, a copper compound, an organomercury compound, an organotin compound, a cadmium compound, anilazine, benomyl, cyclohexamide, dodine, etridiazole, iprodione, metlax-yl, thiamimefon, triforine, or a combination thereof. The fungal inoculant can comprise a fungal inoculant of the family Glomeraceae, a fungal inoculant of the family Claroidoglomeraceae, a fungal inoculant of the family Acaulosporaceae, a fungal inoculant of the family Sacculosprace-ae, a fungal inoculant of the family Entrophosporaceae, a fungal inoculant of the family Pacid-sproraceae, a fungal inoculant of the family Diversisporaceae, a fungal inoculant of the family Paraglomeraceae, a fungal inoculant of the family Archaeosporaceae, a fungal inoculant of the family Geosiphonaceae, a fungal inoculant of the family Ambisporacea, a fungal inoculant of the family Scutellosproaceae, a fungal inoculant of the family Dentiscultataceae, a fungal inoculant of the family Racocetraceae, a fungal inoculant of the phylum Basidiomycota, a fungal inoculant of the phylum Ascomycota, a fungal inoculant of the phylum Zygomycota, a fungal inoculant of the genus Glomus or a combination thereof. The bacterial inoculant can include a bacterial inoc-ulant of the genus Rhizobium, bacterial inoculant of the genus Bradyrhizobium, bacterial inocu-lant of the genus Mesorhizobium, bacterial inoculant of the genus Azorhizobium, bacterial inocu-lant of the genus Allorhizobium, bacterial inoculant of the genus Burkholderia, bacterial inoculant of the genus Sinorhizobium, bacterial inoculant of the genus Kluyvera, bacterial inoculant of the genus Azotobacter, bacterial inoculant of the genus Pseudomonas, bacterial inoculant of the genus Azospri/Hum, bacterial inoculant of the genus Bacillus, bacterial inoculant of the genus Streptomyces, bacterial inoculant of the genus PaenibaciHus, bacterial inoculant of the genus Paracoccus, bacterial inoculant of the genus Enterobacter, bacterial inoculant of the genus Alcaligenes, bacterial inoculant of the genus Mycobacterium, bacterial inoculant of the genus Trichoderma, bacterial inoculant of the genus G/ioc/adium, bacterial inoculant of the genus Klebsiella, or a combination thereof.
Also, the mixture can comprise additionally at least one microorganism selected from the list consisting of Bacillus subti/is strain 713, Bacillus amyloliquefaciens MBI 600, Bacillus pumillus QST2808, Pseudomonas f/uorescens, Bradyrhizobium japonicum, Trichoderma vireus, Pseudomonas putida, Trichoderma harzianum Rifai strain T22, Penicillium bi/aii, Mesorhizobium, Azospirillum, Azotobacter vinelandii and Clostridium pasteurianum, Glomus species. The compounds of general formula (I) employed according to the present invention can be employed in combination with these auxiliaries. The auxiliaries used depend on the particular application form and the active substance and preferably include solvents, solid carriers, dispersants or emulsifiers, such as solubilizers, protective colloids, surfactants and adhesion agents. Furthermore, organic and inorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate, colorants and tackifiers or binders can be employed in combination with the nitrification inhibitors and in the fertilizer mixture. Suitable auxiliaries are discussed in WO 2013/121384 on pages 25 to 26.
Further possible preferred ingredients are oils, wetters, adjuvants, biostimulants, herbicides, bactericides, other fungicides and/or pesticides. They are for example discussed in WO 2013/121384 on pages 28/29.
The fertilizer mixtures are preferably in solid form, including powders, prills and granules. Furthermore, it is possible to deliver the nitrification inhibitor in the form of a formulation, solution or dispersion separately or simultaneously with a fertilizer.
For respective applications, reference can be made to US 6,139,596 and WO 2013/121384 as well as WO 2015/086823 and WO 2016/207210.
The present invention also relates to a method of fertilizing soils exploited agriculturally or horticulturally, wherein a fertilizer mixture containing compounds A and B
A. an inorganic and/or organic and/or organomineral fertilizer and
B. 10 to 10000 weight-ppm, based on the inorganic fertilizer, of a compound of general formula (I) as defined above, or compounds A and B separately, but within a period of 0 to 5 hours, preferably 0 to 1 hour, more preferably approximately at the same time, is applied to the soils.
In parallel with the improvement of the utilization of phosphorus and possibly nitrogen in the phosphorus and possibly ammonium- or urea-containing mineral, organic and organomineral fertilizers, the use of the plant growth promoters, according to the present invention, and of compositions containing them has the effect that there is an increase, in some cases considerably, in the yields and production of biomass of crop plants.
The plants to be treated or rooted in soil to be treated according to the invention are preferably selected from the group consisting of agricultural, silvicultural, ornamental and horticultural plants, each in its natural or genetically modified form. Preferably, non- transgenic agricultural plants are treated.
Preferred agricultural plants are field crops selected from the group consisting of potatoes, sugar beets, wheat, barley, rye, oat, sorghum, rice, maize, cotton, rapeseed, oilseed rape, canola, soybeans, peas, field beans, sunflowers, sugar cane; cucumbers, tomatoes, onions, leeks, lettuce, squashes; even more preferably the plant is selected from the group consisting of wheat, barley, oat, rye, soybean, maize, oilseed rape, cotton, sugar cane, rice and sorghum. In a preferred embodiment of the invention, the plant to be treated is selected from the group consisting of tomato, potato, wheat, barley, oat, rye, soybean, maize, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice, sorghum, pasture grass and grazed land.
In another preferred embodiment of the invention, the plant to be treated is selected from the group consisting of tomato, potato, wheat, barley, oat, rye, soybean, maize, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice and sorghum.
In an especially preferred embodiment of the invention, the plants to be treated are selected from the group consisting of tomato, wheat, barley, oat, rye, maize, oilseed rape, canola, sugar cane, and rice.
In one embodiment, the plant to be treated according to the method of the invention is an agricultural plant. "Agricultural plants" are plants of which a part (e.g. seeds) or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibres (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds. Preferred agricultural plants are for example cereals, e.g. wheat, rye, barley, triticale, oats, sorghum or rice, beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rapeseed, oilseed rape, canola, linseed, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as maize, soybean, rapeseed, canola, sugar cane or oil palm; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants.
Pasture grass and grassland are composed of grass or grass mixtures comprising for example Bluegrass (Poa spp.), Bentgrass (Agrostis spp.), Ryegrasses (Lolium spp.), Fescues (Festuca spp., hybrids, and cultivars), Zoysiagrass (Zoysia spp.), Bermudagrass (Cynodon spp.), St. Augustine grass, Bahiagrass (Paspalum), Centipedegrass (Eremachloa), Carpetgrass (Axonopus), Buffalograss and Grama grass. Pastures may be also composed of mixtures comprising afore mentioned grasses, for example Ryegrass, and Trifolium species, for example Trifolium pratensis and Trifolium repens, Medicago species like Medicago sativa, Lotus species like Lotus corniculatus, and Melilotus species, for example Melilotus albus.
In one embodiment, the plant to be treated according to the method of the invention is a horticultural plant. The term "horticultural plants" are to be understood as plants which are commonly used in horticulture - e.g. the cultivation of ornamentals, herbs, vegetables and/or fruits. Examples for ornamentals are turf, geranium, pelargonia, petunia, begonia and fuchsia. Examples for vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas and lettuce and more preferably from tomatoes, onions, peas and lettuce. Examples for fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots and blueberries. In horticulture, often a substrate replaces (part of) the soil.
In one embodiment, the plant to be treated according to the method of the invention is an ornamental plant. “Ornamental plants" are plants which are commonly used in gardening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia.
In one embodiment, the plant to be treated according to the method of the invention is a silvicultural plant. The term "silvicultural plant" is to be understood as trees, more specifically trees used in reforestation or industrial plantations. Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening purposes. Examples for silvicultural plants are conifers, like pines, in particular Pinus spec, fir and spruce, eucalyptus, tropical trees, like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec, poplar (cottonwood), in particular Populus spec, beech, in particular Fagus spec, birch, oil palm, and oak.
The following definitions apply:
The term “Plant growth promoters” is to be understood as compounds of formula (I) that improve the nutrient or water acquisition and/or use of the plants treated therewith, and/or can lead to improved plant growth.
The term "plants" is to be understood as plants of economic importance and/or men-grown plants. They are preferably selected from agricultural, silvicultural, ornamental and horticultural plants, each in its natural or genetically modified form. The term "plant" as used herein includes all parts of a plant, such as germinating seeds, emerging seedlings, herbaceous vegetation, as well as established woody plants, including all belowground portions (such as the roots) and aboveground portions.
The term "soil" is to be understood as a natural body comprised of living (e.g. microorganisms (such as bacteria and fungi), animals and plants) and non-living matter (e.g. minerals and organic matter (e.g. organic compounds in varying degrees of decomposition), liquid, and gases) that occurs on the land surface, and is characterized by soil horizons that are distinguishable from the initial material as a result of various physical, chemical, biological, and anthropogenic processes.
The term "nitrification inhibitor" is to be understood as any chemical substance which slows down or retards the nitrification process which is typically occurring in (fertilized) soil. Nitrification inhibitors retard the natural transformation of ammonium into nitrate and target microorganisms and preferably ammonia-oxidizing bacteria (AOB), preferably by inhibiting the activity of the bacteria, such as Nitrosomonas spp. and/or Nitrosospira spp. They may additionally act on ammonia-oxidizing archaea (AOA). The nitrification inhibitor is most often combined with a fertilizer, preferably an (ammonium) nitrogen-containing fertilizer, e.g. solid or liquid inorganic, organic and/or organomineral fertilizer, or manure.
The term "nitrification" is to be understood as the biological oxidation of ammonia (NH3) or ammonium ( N H 4 +) with oxygen into nitrite (NO2 ) followed by the oxidation of these nitrites into nitrates (NOf) by microorganisms. Besides nitrate (NOf) nitrous oxide is also produced though nitrification. Nitrification is an important step in the nitrogen cycle in soil.
The term "fertilizers" is to be understood as (chemical) compounds applied to promote plant and fruit growth. Fertilizers are typically applied either through the soil (for uptake by plant roots) or by foliar feeding (for uptake through leaves). The term "fertilizers" can be subdivided into two major categories: a) organic fertilizers (composed of decayed plant/animal matter) and b) inorganic fertilizers (composed of chemicals and minerals). Organic fertilizers include slurry, worm castings, peat, seaweed, sewage, and guano. Manufactured organic fertilizers include compost, blood meal, bone meal and seaweed extracts. Further examples are enzymatically digested proteins, fish meal, and feather meal. The decomposing crop residue from prior years and manure are another source of fertility. In addition, naturally occurring minerals, such as mine rock phosphate, sulfate of potash and limestone, are also considered as belonging to inorganic fertilizers. Inorganic fertilizers are usually manufactured through chemical processes (such as the Haber-Bosch process), also using naturally occurring deposits, while chemically altering them (e.g. concentrated triple superphosphate). Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mine rock phosphate, and limestone. As a third category organomineral fertilizers can be mentioned, as a combination of inorganic and organic fertilizers.
The term "fertilizer comprising urea" (urea fertilizer) is defined as synthetic fertilizers comprising urea, excluding any naturally occurring fertilizers comprising urea (for instance manure as an example for a naturally occurring fertilizer comprising urea). Examples of fertilizer comprising urea are urea ammonium nitrate (UAN), isobutylidene diurea (IBDU), crotonylidene diurea (CDU) and urea formaldehyde (UF). Urea is usually made as granulated material or prills. Urea fertilizer can be produced by dropping the liquid urea from a prill tower while drying the product. Urea can also be obtained as a liquid formulation, which may be used for foliar application, e.g. on potatoes, wheat, vegetables and soybeans as well as liquid application to the field. It is commonly mixed with ammonium nitrate to form UAN with 28% N.
The term "locus" (plant habitat) is to be understood as any type of environment, soil, area or material where the plant is growing or intended to grow. Especially preferred according to the invention is soil.
The invention is further illustrated by the following examples which show that the compounds of formula (I) are strong root hair inducers. Brief description of the drawings
Figure 1 shows representative images of the effect of tested compounds on root hair induction and elongation. Scale bar is 0.5 mm.
Figure 2 shows representative images of the effect of comparative examples 1 to 3 as compared to the control on root hair induction and elongation. Scale bar is 0.5 mm.
Figure 3 shows representative images of the effect of examples 2 and 11 and comparative examples 4 and 5 as compared to the control- Scale bar is 0.5 mm.
Examples
We report on a group of substances that induce root hairs and root hair elongation. These substances were found by testing and screening a variety of small molecules for their root hair inducing capacity.
I. Materials and methods
For root hair measurements, Arabidopsis tha/iana Columbia-0 seedlings were grown on a modified Murashige and Skoog medium (modMS - 1.25 mM KH2PO4, 20 mM N H4NO3, 0.1 mM H3BO3, 3 mM CaCI2, 0.1 M CoCI2*6H2O, 0.1 M CuSO4*5H2O, 0.1 mM Na2EDTA*2H2O, 0.1 mM FeSO4*7H2O, 1.5 mM MgSO4*7H2O, 0.1 mM MnSO4*H2O, 1 M Na2MoO4*4H2O, 5 M KI, 19 mM KNO3, 0.03 mM ZnSO4*7H2O, 0.1 g/L myo-inositol, 0.5% of sucrose and 0.5 g/L MES (pH 5,7)). Arabidopsis seeds were stratified for 2 days at 4 0 C before germination. Seedlings were germinated in climate-controlled growth chambers at 22 0 C under continuous light (100 p mol m ’ s '). Unless stated otherwise, tested compounds were dissolved in DMSO and had a final concentration of 10 pM (0.1 % DMSO). For correct comparison, the compound solvent DMSO (final concentration 0.1%) was also added to the no compound controls.
After 10 days of growth on vertical plate, roots were imaged using a stereomicroscope or a VHX-6000. The number and length of the root hairs was determined at 4 to 6 mm above the root meristem. Root hair length was measured using the ImageJ software.
For growth assays in phosphate starvation conditions, a low phosphate modMS was used, containing 1 p M KH2PO4. For osmotic stress assays, the modMS contained 50 mM NaCI or 100 mM sorbitol.
For rosette area measurements, Arabidopsis seedlings were grown for 15 (phosphate starvation experiment) or 20 days (osmotic stress assay) on horizontal plates. For primary root length measurements, Arabidopsis seedlings were grown for 12 days on vertical plates. In both cases, germination and growth occurred as described above and plates were scanned using a flatbed scanner (EPSON Expression 11000XL), after which the rosette area or primary root length was measured using ImageJ software.
II. Results 1. Anilino-derivatives induce root hairs
To identify new substances that induce root hairs, the root hair-inducing effect of a set of small molecules was assessed. It was observed that a group of anilino-based molecules or variants showed a positive effect on root hair number and/or length (Table 1/Figure 1). Multiple substitutions on the benzene ring enhance the effect (compare for example example 8 (
Figure imgf000031_0001
Table 1/Figurel), while the presence of an alkyl- or other hydrocarbon group on the heteroatom enhances the effect as well (compare for example example 15 (
Figure imgf000031_0002
) - Table
1/Figurel). A carboxamide group at position 2 of the hydrocarbon group substituted on the heteroatom (e.g. example 11 (
Figure imgf000031_0003
an ) - Table
1/Figure 1) extremely amplifies this effect. A ring-closure by two substitutions on the benzene ring (e.g. example 25 (
Figure imgf000031_0004
) - Table 1/Figure 1) also has a positive effect. Finally, we also observed that the nitrogen of the anilino might be replaced by another heteroatom (e.g. example
Figure imgf000031_0005
) - Table 1).
Table 1: Anilino-derivatives and structural variants with a positive effect on root hair length and/or root hair number as shown by the average total root hair length per mm root. Compounds were dissolved in DMSO (final concentration 0.1 %) and the effect of the compounds was compared to a no compound control that contained only the solvent (DMSO 0.1 %).
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
As root hairs are known to increase nutrient and water uptake, the root hair promoting compounds are expected to have a growth promoting effect, in particular in conditions where those important resources are limited. To verify the positive effect on nutrient uptake, two Arabidopsis growth experiments in phosphate starvation conditions were performed, using a low phosphate medium. Different concentrations of example 2 and 11 were tested. In experiment 1, the primary root length was assessed, which is a trait known to be severely and negatively affected by phosphate starvation stress. In experiment 2, the rosette area of the plants were measured to assess the effect on growth. In both experiments, example 2 and example 11 have positive effect on the root and rosette growth (Table 2).
Table 2: Anilino-derivatives with a positive effect on root hair length and/or root hair number show a positive growth effect in phosphate starvation conditions.
Figure imgf000036_0002
Figure imgf000037_0001
To verify the positive effect on water uptake, an osmotic stress experiment with example 2 was conducted. The osmolytes NaCI or sorbitol were used that limit water availability. As shown in Table 3, example 2 has a positive effect on the growth of Arabidopsis plants.
Table 3: The anilin o-containing example 2 that has a positive effect on root hair length and/or root hair number show a positive growth effect in water limiting conditions.
Figure imgf000037_0002
We furthermore tested structural variants that have a keton (amide) group adjacent to the aniline N, including molecules that were previously described as plant growth inhibiting herbicides. In contrast to the tested examples, these molecules have no positive effect on root hair length and/or root hair number (Table 4/Figure 2, Figure 3). Counterexample 4 showed, in contrast to the claimed examples, a high phytotoxicity (see insets in Figure 3). Altogether, this shows that the action of previously claimed plant growth regulating molecules differ from the actions of the molecules in claims 1-3.
Table 4: Counterexamples: anilino-derivates with a keton (amide) group adjacent to the aniline N have no positive effect on root hair length and/or root hair number. NA = not analyzed.
Figure imgf000038_0001

Claims

Claims
1. The use of a compound of the general formula (I)
Figure imgf000039_0001
With the following definitions:
X heteroatom, selected from the group consisting of nitrogen and oxygen, preferably, X is nitrogen;
Rl; R2 if X is nitrogen, Rl and R2 are independently hydrogen or a Cr3 hydrocarbon residue, preferably a C2 hydrocarbon residue, which can contain one to seven heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur, preferably, either Rl or R2 have a keto, an aldehyde, an amide and/or an amino group; and preferably characterized in that no oxygen double bond is p resent at th e Ci atom of Rl and/or R2; even more preferably Rl is a C2 hydrocarbon with a carboxamide-group on C2 of Rl and R2 is hydrogen;
Rl if X is oxygen, Rl is hydrogen or a Cr3 hydrocarbon residue, preferably a C2 hydrocarbon residue, which can contain one to seven heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur;
R3 independently hydrogen, halogen, heteroatom functional group, Cri2- hydrocarbon residue, preferably a Cr5 hydrocarbon residue, even more preferably a Cr3 hydrocarbon residue, which can contain one or two halogen atoms and/or one to three heteroatoms, selected from the group consisting of nitrogen, oxygen and sulphur, preferably oxygen, it also being possible for Rl and R3 to be covalently linked to form a 5- to 8-membered heterocyclic ring, which can contain 1 or 2 halogen atoms and/or one to three further heteroatoms in addition to the heteroatoms N already part of the heterocyclic ring, preferably R3 is a hydrogen, a methyl-group or a methoxygroup; n 0; 1; 2; 3; 4 or 5, preferably n is 0 or 1; as plant growth promoter, wherein the plant grows promoter improves the root hair development, Phosphate use efficiency/uptake nutrient use efficiency of plants, nutrient uptake of plants, - nutrient availability, water uptake of plants, nutrient and water foraging by plants, drought resistance, root penetration in the soil, - anchorage in the soil, beneficial symbiotic interactions of plants, protection against harmful micro-organisms, and/or plant growth or yield; and/or for mitigating and/or reducing nutrient starvation, drought, salt, and/or osmotic stress of plants. The use according to claim 1, wherein the compound of the formula (I) is selected from one the following compounds:
Figure imgf000040_0001
Figure imgf000041_0001
The use according any one of the preceding claims, wherein the compound of the formula (I) is a compound of the formula (II):
Figure imgf000041_0002
(ID
4. The use of any of the preceding claims wherein the pH range of the substrate or soil is from 4.5 to 7.5, preferably from 5 to 7, even more preferably from 5.5 to 6.5;
5. A mixture containing at least one compound of general formula (I) as defined any one of the preceding claims, and at least one additional agrochemical agent, preferably selected from the group consisting of at least one inorganic and/or organic and/or organomineral fertilizer, at least one nitrification inhibitor, preferably selected from the group consisting of
2-(3,4-dimethyl-pyrazol-l-yl)-succinic acid (DMPSA), 3,4-dimethylpyrazole (DMP),
3.4-dimethylpyrazolephosphate (DMPP), dicyandiamide (DCD), 1 H - 1,2,4-triazole,
3-methylpyrazole (3-MP), 2-chloro-6-(trichloromethyl)-pyridine, 5-ethoxy-3- trich loromethy I - 1,2, 4-th iad iazol , 2 -a mino-4-c hl oro-6- methyl -pyrimidine, 2- mercapto-benzothiazole, 2-sulfanilamidothiazole, thiourea, sodium azide, potassium azide, 1-hydroxypyrazole, 2-methylpyrazole-l-carboxamide, 4-amino-
1.2.4-triazole, 3- mercapto- 1,2,4-triazole, 2,4-diamino-6-trich loromethy I -5-triazine, carbon bisulfide, ammonium thiosulfate, sodium trithiocarbonate, 2,3-dihydro-2,2- dimethyl-7-benzofuranol methyl carbamate and N-(2,6-dimethylphenyl)-N- (methoxyacetyl)-alanine methyl ester, at least one urease inhibitor, preferably selected from N-n-butylthiophosphoric triamide (NBPT) and/or N-n-propylthiophosphoric triamide (NPPT), at least one customary agrochemical auxiliary agent, preferably selected from the group consisting of aqueous and/or organic solvents, pH-adjusting agents, surfactants, wetting agents, spreading agents, adhesion promoters, carriers, fillers, viscosity-adjusting agents, emulsifiers, dispersants, sequestering agents, antisettling agents, coalescing agents, rheology modifiers, defoaming agents, photoprotectors, anti-freeze agents, biostimulants, pesticides, biocides, plant growth regulators, safeners, penetrants, anticaking agents, mineral and/or vegetable oils and/or waxes, colorants and drift control agents, and mixtures thereof.
6. A fertilizer mixture, containing
A. an inorganic and/or organic and/or organomineral fertilizer and
B. effective amount, preferably 10 to 10000 weight-ppm, based on the fertilizer, of a compound of the general formula (I) as defined in any one of claims 1 to 3.
7. The fertilizer mixture as claimed in claim 5, wherein the fertilizer mixture is in solid form and the compound of the general formula (I) is incorporated into the fertilizer or is applied to the surface of the, preferably inorganic, fertilizer.
8. The fertilizer mixture as claimed in one of claims 5 or 6, wherein the fertilizer mixture contains at least one additional agrochemical agent, preferably selected from the group consisting of
- at least one nitrification inhibitor, preferably selected from the group consisting of 2-
(3,4-dimethyl-pyrazol-l-yl)-succinic acid (DMPSA), 3,4-dimethylpyrazole (DMP), 3,4-dimethylpyrazolephosphate (DMPP), dicyandiamide (DCD), lH-l,2,4-triazole, 3- methylpyrazole (3-MP), 2-chloro-6-(trichloromethyl)-pyridine, 5-ethoxy-3- trich loro methyl - 1 ,2,4-thiadiazol , 2-amino-4-ch loro-6- methyl -pyrimidine, 2- mercapto-benzothiazole, 2-sulfanilamidothiazole, thiourea, sodium azide, potassium azide, 1-hydroxypyrazole, 2-methylpyrazole-l-carboxamide, 4-amino-l,2,4-triazole, 3- mercapto- 1,2, 4-triazo I e, 2,4-diamino-6-trichloromethyl-5-triazine, carbon bisulfide, ammonium thiosulfate, sodium trithiocarbonate, 2,3-dihydro-2,2-dimethyl- 7-benzofuranol methyl carbamate and N-(2,6-dimethylphenyl)-N-(methoxyacetyl)- alanine methyl ester,
- at least one urease inhibitor, preferably selected from N-n-butylthiophosphoric triamide (NBPT) and/or N-n-propylthiophosphoric triamide (NPPT),
- at least one customary agrochemical auxiliary agent, preferably selected from the group consisting of aqueous and/or organic solvents, pH-adjusting agents, surfactants, wetting agents, spreading agents, adhesion promoters, carriers, fillers, viscosity-adjusting agents, emulsifiers, dispersants, sequestering agents, antisettling agents, coalescing agents, rheology modifiers, defoaming agents, photoprotectors, anti-freeze agents, biostimulants, pesticides/plant production products, biocides, plant growth regulators, safeners, penetrants, anticaking agents, mineral and/or vegetable oils and/or waxes, colorants and drift control agents, and mixtures thereof.
9. A process for producing the fertilizer mixture as claimed in one of claims 5 to 7 by introducing the compound of the general formula (I) into the fertilizer, and/or applying the compound of the general formula (I) to the surface of the fertilizer.
10. A method of fertilizing soils exploited agriculturally or horticulturally, wherein a fertilizer mixture containing compounds A and B
A. an inorganic and/or organic and/or organomineral fertilizer and
B. 10 to 10000 weight-ppm, based on the fertilizer, of a compound of the general formula (I) as defined in one claims 1 to 3, or compounds A and B separately, but within a period of 0 to 5 hours, preferably 0 to 1 hour, more preferably approximately at the same time, is applied to the soils.
PCT/EP2023/076253 2022-09-27 2023-09-22 Anilino-derivatives as plant growth promoters WO2024068474A1 (en)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1178871A (en) * 1966-01-07 1970-01-21 Basf Ag Substituted N-Phenyl Carbamates and Herbicides containing them
US4283221A (en) * 1972-02-07 1981-08-11 Ciba-Geigy Corporation Plant growth regulating agent
EP0124154A2 (en) * 1983-04-22 1984-11-07 Shell Internationale Researchmaatschappij B.V. Aniline compositions, their preparation, compositions containing them, and method of combating fungus and/or combating or regulating plant growth
DE4128828A1 (en) 1991-08-30 1993-03-04 Basf Ag AMMONIUM OR UREA-CONTAINED DISPENSERS AND METHOD FOR THEIR PRODUCTION
US6139596A (en) 1996-08-06 2000-10-31 Basf Aktiengesellschaft Nitrification inhibitors and the use of polyacids to treat mineral fertilizers containing a nitrification inhibitor
DE10230593C1 (en) 2002-07-06 2003-08-07 Compo Gmbh & Co Kg Fertilizing agricultural or horticultural substrates, especially for growth of fruit or vegetable crops, by applying water containing nitrogen fertilizer and nitrification inhibitor in the absence of excess water
EP1820788A1 (en) 2006-02-16 2007-08-22 BASF Aktiengesellschaft Preparations with improved urease-inhibiting properties and those preparations containing urea based fertilizers.
WO2013121384A2 (en) 2012-02-16 2013-08-22 Basf Se Mixtures for reducing nitrous oxide and/or ammonia emission from soils
WO2015086823A2 (en) 2013-12-13 2015-06-18 Eurochem Agro Gmbh Fertilizer mixture containing nitrification inhibitor
WO2016207210A1 (en) 2015-06-22 2016-12-29 Eurochem Agro Gmbh Mixture for treating fertilisers containing urea

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1178871A (en) * 1966-01-07 1970-01-21 Basf Ag Substituted N-Phenyl Carbamates and Herbicides containing them
US4283221A (en) * 1972-02-07 1981-08-11 Ciba-Geigy Corporation Plant growth regulating agent
EP0124154A2 (en) * 1983-04-22 1984-11-07 Shell Internationale Researchmaatschappij B.V. Aniline compositions, their preparation, compositions containing them, and method of combating fungus and/or combating or regulating plant growth
DE4128828A1 (en) 1991-08-30 1993-03-04 Basf Ag AMMONIUM OR UREA-CONTAINED DISPENSERS AND METHOD FOR THEIR PRODUCTION
US6139596A (en) 1996-08-06 2000-10-31 Basf Aktiengesellschaft Nitrification inhibitors and the use of polyacids to treat mineral fertilizers containing a nitrification inhibitor
DE10230593C1 (en) 2002-07-06 2003-08-07 Compo Gmbh & Co Kg Fertilizing agricultural or horticultural substrates, especially for growth of fruit or vegetable crops, by applying water containing nitrogen fertilizer and nitrification inhibitor in the absence of excess water
EP1820788A1 (en) 2006-02-16 2007-08-22 BASF Aktiengesellschaft Preparations with improved urease-inhibiting properties and those preparations containing urea based fertilizers.
WO2013121384A2 (en) 2012-02-16 2013-08-22 Basf Se Mixtures for reducing nitrous oxide and/or ammonia emission from soils
WO2015086823A2 (en) 2013-12-13 2015-06-18 Eurochem Agro Gmbh Fertilizer mixture containing nitrification inhibitor
WO2016207210A1 (en) 2015-06-22 2016-12-29 Eurochem Agro Gmbh Mixture for treating fertilisers containing urea

Non-Patent Citations (14)

* Cited by examiner, † Cited by third party
Title
GRIERSONSCHIEFELBEIN: "Arabidopsis Book.", vol. 1, 2002, pages: e0060
HALING ET AL., J EXP BOT., vol. 64, no. 12, 2013, pages 3711 - 3721
HALL RANDAL C. ET AL: "Synthesis of Dinitroaniline as Plant Growth Regulators and for Identification of Amines", J. AGRIC. FOOD CHEM., vol. 20, no. 3, 1 May 1972 (1972-05-01), pages 546 - 552, XP093040352, DOI: 10.1021/jf60181a010 *
KWASNIEWSKI ET AL., J EXP BOT., vol. 67, no. 4, 2016, pages 1079 - 94
LAO S-H ET AL: "3,4-Dichloroaniline is detoxified and exported via different pathways in Arabidopsis and soybean", PHYTOCHEMISTRY, ELSEVIER, AMSTERDAM , NL, vol. 63, no. 6, 1 July 2003 (2003-07-01), pages 653 - 661, XP004433860, ISSN: 0031-9422, DOI: 10.1016/S0031-9422(03)00289-9 *
LI AIXIA ET AL: "Action of Salicylic Acid on Plant Growth", FRONTIERS IN PLANT SCIENCE, vol. 13, 27 April 2022 (2022-04-27), XP093040325, DOI: 10.3389/fpls.2022.878076 *
SKINNER J J: "Effect of Vanillin as a Soil Constituent", vol. 18, no. 12, 19 April 1915 (1915-04-19), pages 321 - 330, XP093040236, Retrieved from the Internet <URL:https://www.jstor.org/stable/pdf/43477431.pdf?refreqid=excelsior:9ba9d7cd4dfd2715763627cb62df4781&ab_segments=&origin=&initiator=&acceptTC=1> *
TAO NAN ET AL: "Effects of aniline on growth, oxidative and DNA damage of rice (Oryza sativa L.) seedlings", ENVIRONMENTAL TECHNOLOGY & INNOVATION, vol. 28, 29 April 2022 (2022-04-29), pages 102583, XP093039940, ISSN: 2352-1864, DOI: 10.1016/j.eti.2022.102583 *
TAO NAN ET AL: "Genotoxicity and growth inhibition effects of aniline on wheat", CHEMOSPHERE, PERGAMON PRESS, OXFORD, GB, vol. 169, 24 November 2016 (2016-11-24), pages 467 - 473, XP029853045, ISSN: 0045-6535, DOI: 10.1016/J.CHEMOSPHERE.2016.11.063 *
VISSENBERG ET AL., J EXP BOT., vol. 71, no. 8, 2020, pages 2412 - 2427
WANG ET AL., J PLANT RES., vol. 121, 2008, pages 87 - 96
WANG ET AL., PLANT PHYSIOL., vol. 184, no. 1, 2020, pages 176 - 193
ZHANG X-H ET AL: "Phytotoxicity of dimethyl sulfoxide (DMSO) to rice seedlings", INTERNATIONAL JOURNAL OF ENVIRONMENTAL SCIENCE AND TECHNOLOGY, CENTER FOR ENVIRONMENT AND ENERGY RESEARCH AND STUDIES (C E E R S), IR, vol. 13, no. 2, 14 October 2015 (2015-10-14), pages 607 - 614, XP035971581, ISSN: 1735-1472, [retrieved on 20151014], DOI: 10.1007/S13762-015-0899-6 *
ZOU ET AL., PAK. J. BOT., vol. 51, no. 2, 2019

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