a mixture comprising a solid carrier containing a urease inhibitor and another solid carrier containing a nitrification inhibitor
By using a mixture of nitrification inhibitors and urease inhibitors, the problem of nitrogen loss caused by the rapid hydrolysis and nitrification of urea in the soil is solved, improving the utilization efficiency of urea fertilizer, enhancing plant health and crop yield, and reducing environmental pollution.
Patent Information
- Application Number
- CN202180009411.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Priority Date
- 2020-01-16
- Filing Date
- 2021-01-08
- Publication Date
- 2026-08-25
- Estimated Expiration
- 2041-01-08
AI Technical Summary
In existing technologies, urea rapidly hydrolyzes into ammonia and carbon dioxide in the soil, resulting in low nitrogen use efficiency, nitrogen loss and environmental pollution caused by ammonia emissions and nitrification processes. Furthermore, the stability and synergistic effect of urease inhibitors and nitrification inhibitors are insufficient.
By using a mixture containing nitrification inhibitors and urease inhibitors, and through the combination of solid carriers A and B, the synergistic effect of compounds I and II is optimized, thereby improving stability and nitrification inhibition, reducing ammonia and nitrous oxide emissions, and enhancing plant health and crop yield.
It improves the utilization efficiency of urea fertilizer, reduces ammonia and nitrous oxide emissions, enhances plant health and crop yield, improves the NH4-N/NO3-N ratio in the soil, extends the storage period of the compound, and reduces environmental pollution.
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Figure BDA0003745842070000091 
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Abstract
Description
[0001] This invention relates to a mixture comprising a nitrification inhibitor (compound I) and a urease inhibitor (compound II). Furthermore, this invention relates to the use of this combination comprising the nitrification inhibitor (compound I) and the urease inhibitor (compound II) in increasing the NH4-N / NO3-N ratio in soil (“NH4-N” is ammonium nitrogen, “NO3-N” is nitrate nitrogen), reducing nitrification, and enhancing plant health and / or providing better crop yield and / or better plant or crop quality and / or providing better stress tolerance and / or reducing ammonia and nitrous oxide emissions. Additionally, this invention relates to methods for enhancing plant health, including treating plants, soil, and / or sites with said mixture comprising the nitrification inhibitor (compound I) and the urease inhibitor (compound II).
[0002] Globally, the primary and ever-increasing amount of nitrogen used for fertilization is in the form of urea or urea-containing fertilizers. However, urea itself is a form of nitrogen that is absorbed in very small amounts (if any), being rapidly hydrolyzed by ureases, which are ubiquitous in the soil, to form ammonia and carbon dioxide. In some cases, gaseous ammonia is released into the atmosphere during this process and can no longer be used by plants in the soil, thus reducing fertilization efficiency.
[0003] It is known that nitrogen utilization when using urea-containing fertilizers can be improved by broadcasting the urea-containing fertilizers together with substances that can inhibit or reduce urease-induced cleavage (for a general review, see Kiss, S.). M. (2002) Improving Efficiency of Urea Fertilizers by Inhibition of Soil Urease Activity, ISBN 1-4020-0493-1, Kluwer Academic Publishers, Dordrecht, Netherlands. The most potent known urease inhibitors are, for example, N-alkylthiophosphoric triamine and N-alkylphosphoric triamine described in EP 0 119 487.
[0004] Alternatively, mixtures of N-alkylthiophosphoric triamines such as N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) can be used. These mixtures and their preparation are described, for example, in US 2010 / 218575 A1.
[0005] These urease inhibitors are described, for example, in U.S. Patent 4,530,714. For such compounds to function as urease inhibitors, they must first be converted to their corresponding oxoform. This oxoform then reacts with the urease, causing its inhibition.
[0006] It is preferable to apply the urease inhibitor together with urea onto or into the soil, as this ensures that the inhibitor comes into contact with the soil along with the fertilizer. The urease inhibitor can be incorporated into the urea prior to granulation or pelleting by, for example, dissolving it in a melt. Such methods are described, for example, in U.S. Patent 5,352,265. Another option is to apply the urease inhibitor, for example, in solution form to urea granules or pellets.
[0007] Appropriate application methods and suitable solvents are described, for example, in US 2010 / 218575 A1. Other suitable additives, such as amines selected from methyldiethanolamine, tetrahydroxypropylethylenediamine, trimethylaminoethylethanolamine, N,N,N′,N′-tetramethyl-1,6-hexanediamine, N,N′,N"-tris(dimethylaminopropyl)hexahydrotriazine and 2,2′-dimorpholinoethyl ether, are described in US 2011 / 0154874 A1.
[0008] The shelf life of this urease inhibitor is limited. Higher temperatures shorten the shelf life. For example, if urea is stored under tropical conditions, most of the urease inhibitor will typically decompose after about four weeks. If the urease inhibitor is introduced into the urea melt, decomposition is less severe. However, for the commercialization of urea stabilized with this urease inhibitor, it is generally crucial to apply the inhibitor to the urea and store the treated fertilizer until it is sown into the soil.
[0009] Nitrogen is an essential element for plant growth, health, and reproduction. Approximately 25% of the plant-available nitrogen in the soil (ammonium and nitrates) originates from organic nitrogen compounds such as humus, plant and animal remains, and the decomposition (mineralization) of organic fertilizers. About 5% is derived from rainfall. However, on a global scale, the largest portion (70%) is supplied to plants by inorganic nitrogen fertilizers. The main nitrogen fertilizers used include ammonium compounds or their derivatives, meaning that nearly 90% of the nitrogen fertilizer supplied worldwide is in the form of NH4. + Forms (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302) or based on neem extracts, including various compounds such as neem oil-coated fertilizers, neem-coated fertilizers, azadirachtin-coated fertilizers, and fertilizers containing neem cake from the neem tree (Azadirachta indica). This is especially true due to NH4. + Assimilation compared to other nitrogen sources such as NO3 - The fact that assimilation is more efficient in terms of energy.
[0010] Furthermore, because it is a cation, NH4 + It is electrostatically maintained by the negatively charged clay surface and the functional groups of soil organic matter. This bond is strong enough to limit NH4+ leaching into groundwater. +Loss. Conversely, negatively charged NO3... - It does not bind with the soil and is easily leachable from the root zone of plants. Furthermore, nitrate may be lost due to denitrification, which releases both nitrate and nitrite (NO2). - Microorganisms convert nitrogen into gaseous forms such as nitrous oxide (N2O) and molecular nitrogen (N2).
[0011] However, ammonium (NH4) + ) compounds are converted into nitrate (NO3) by soil microorganisms in a relatively short period of time during a process known as nitrification. - Nitrification is primarily carried out by two types of chemoaerotrophic bacteria—Nitrosomonas and Nitrobacter (AOB)—which are ubiquitous components of soil bacterial populations. The enzyme primarily responsible for nitrification is ammonia monooxygenase (AMO), which has also been found in ammonia-oxidizing archaea (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302).
[0012] This nitrification process typically leads to nitrogen loss and environmental pollution. Approximately 50% of applied nitrogen fertilizer is lost in the year it is applied due to various losses (see Nelson and Huber; Nitrification Inhibitors for Corn Production (2001), National Corn Handbook, Iowa State University).
[0013] As a countermeasure, the use of nitrification inhibitors has been proposed, which are mostly used in conjunction with fertilizers. Suitable nitrification inhibitors include biological nitrification inhibitors (BNIs), such as linoleic acid, alpha-linolenic acid, methyl coumarate, methyl ferulic acid, MHPP, hydroflavin, bradinolide, or sorgoleone (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302). Other suitable nitration inhibitors are synthetic chemical inhibitors, such as chlordime (Nitrapyrin), dicyandiamide (DCD), 3,4-dimethylpyrazole phosphate (DMPP), 4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (terrazole) or 2-sulfathiazole (ST) (Slangen and Kerkhoff, 1984, Fertilizer research, 5(1), 1-76).
[0014] EP 0 917 526 further mentions using polyacids to treat inorganic fertilizers containing nitrification inhibitors to improve the fixation of nitrification inhibitors in inorganic fertilizers. In addition, it can reduce the volatility of nitrification inhibitors.
[0015] However, many of these inhibitors work only slightly better or have undesirable side effects.
[0016] Given this situation, there is a continued need for compositions or mixtures that enhance plant health. Healthier plants are desirable because they lead, in particular, to better crop yields and / or better plant or crop quality. Healthier plants are also better resistant to biotic and abiotic stresses. Better stress tolerance, in turn, allows for lower pesticide dosages, which also helps avoid the development of tolerance to the corresponding pesticides.
[0017] One object of the present invention is to provide a composition or mixture containing a nitrification inhibitor and / or a urease inhibitor (compound II) that enhances plant health and / or provides better crop yield and / or better plant or crop quality and / or exhibits better stress tolerance and / or allows for reduced pesticide use and / or helps avoid the development of tolerance to the corresponding pesticide.
[0018] Another object of the present invention is to provide a composition or mixture containing a nitration inhibitor (compound I) and / or a urease inhibitor (compound II), each preferably acting synergistically:
[0019] (i) Improve the stability of compound I, and / or
[0020] (ii) To enhance the nitration inhibition effect of compound I, and / or
[0021] (iii) enhances the yield-increasing effect of compound I, and / or (iv) has a relatively long shelf life, especially before application to or coating nitrogen-containing fertilizers, and / or
[0022] (v) Reduce soil nitrous oxide emissions, and / or
[0023] (vi) Reduce ammonia emissions from the soil, and / or
[0024] (vii) Reduce nitrate leaching, and / or
[0025] (viii) It will not adversely affect the nitration inhibition effect and / or nitration inhibition activity of compound I, and / or
[0026] (ix) It can be easily and safely packaged, transported, and shipped, even in large quantities, and / or
[0027] (x) can be easily and safely treated and used for soil treatment, even in large quantities, and / or
[0028] (xi) Improve nutrient utilization efficiency, and / or
[0029] (xii) Improve the stability of compound II, and / or
[0030] (xiii) Improve plant growth (e.g., biomass, yield, root branching and length; compact growth in the case of ornamental plants), and / or
[0031] (xiv) It can have better-developed root systems, larger leaf area, greener leaves, stronger shoots, and / or
[0032] (xv) Improves plant defenses, and / or
[0033] (xvi) Improve plant health, and / or
[0034] (xvii) Improve plant quality, and / or
[0035] (xviii) Improve the storage of urease inhibitor (compound II) and / or prolong the utilization rate of urease inhibitor (compound II) in soil, and / or
[0036] (xix) Enhances the urease inhibitory effect of the urease inhibitor (compound II), and / or
[0037] (xx) Allows for a reduction in the dosage of urease inhibitor (compound II), and / or
[0038] (xxi) Improve seedling survival rates, such as those of transplanted seedlings, and / or
[0039] (xxii) To reduce or avoid adverse environmental or toxicological effects while still allowing for effective pest control, and / or
[0040] (xxiii) Able to have earlier seed germination and / or flowering, and / or
[0041] (xxiv) It is not toxicologically objectionable, and / or
[0042] (xxv) enables the simple handling and application of compounds I and II.
[0043] Objectives (xiii), (xiv), (xv), (xvi), (xvii) and (xxi) particularly relate to the following types of plants or seedlings, wherein such plants or seedlings are treated with the mixture or composition, or the mixture or composition of the present invention is applied to soil in which such plants or seedlings are placed.
[0044] The preferred objectives of the present invention are (i), (ii), (v), (vi), (vii), (xi), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii), (xix), (xx), (xxii), (xxiv), (xxv), the more preferred objectives of the present invention are (i), (ii), (v), (vi), (vii), (xii), (xiii), (xv), (xvi), (xix), (xx) and / or (xxii), the most preferred objectives of the present invention are (i), (ii), (v), (vii), (xvi), (xix) and / or (xxii), and the particularly preferred objectives of the present invention are (ii), (v), (vii), (xvi) and / or (xix).
[0045] The term "urease inhibitor" will also be referred to as "UI" below.
[0046] The term "in a synergistic manner" means that a composition or mixture containing a nitrification inhibitor (compound I) and a urease inhibitor (compound II) can satisfy one or more of objectives (i)-(xxiv) significantly better than either compound I or compound II alone, and preferably this better satisfaction of objectives compared to the individual compounds is demonstrated by calculations according to the Colby formula, see Colby, SR ("Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds, 15 (Pages 20-22, 1967).
[0047] This invention relates to a mixture comprising:
[0048] 1) A solid carrier A comprising at least one active compound I (nitration inhibitor) selected from the following:
[0049] a) 2-(3,4-dimethyl-1H-pyrazol-1-yl)succinic acid (hereinafter referred to as “DMPSA1”) and / or 2-(4,5-dimethyl-1H-pyrazol-1-yl)succinic acid (hereinafter referred to as “DMPSA2”; “DMPSA1” and / or “DMPSA2” are referred to as “DMPSA”) and / or their derivatives and / or their salts.
[0050] b) The glycolic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazole) Glycolate (hereinafter referred to as "DMPG") and / or its isomers and / or derivatives thereof,
[0051] c) Citrate addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazole) Citrate (hereinafter referred to as "DMPC") and / or its isomers and / or derivatives thereof,
[0052] d) Lactic addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazole) Lactate (hereinafter referred to as "DMPL") and / or its isomers and / or derivatives,
[0053] e) Mandelic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazole) Mandelates (hereinafter referred to as "DMPM") and / or their isomers and / or derivatives,
[0054] f) 1,2,4-triazole (hereinafter referred to as "TZ") and / or its derivatives and / or its salts,
[0055] g) 4-Chloro-3-methylpyrazole (hereinafter referred to as "ClMP") and / or its isomers and / or its derivatives and / or its salts,
[0056] h)N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)acetamide and / or its isomers and / or its derivatives and / or its salts,
[0057] i)N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)formamide and / or its isomers and / or its derivatives and / or its salts,
[0058] j)N-((3(5),4-dimethylpyrazol-1-yl)methyl)formamide and / or its isomers and / or its derivatives and / or its salts,
[0059] k)N-((4-chloro-3(5)-methylpyrazol-1-yl)methyl)formamide and / or its isomers and / or its derivatives and / or its salts,
[0060] l) A reaction adduct of dicyandiamide, urea, and formaldehyde, or a triazinone-formaldehyde-dicyandiamide adduct.
[0061] m)2-Cyano-1-((4-oxo-1,3,5-triazinan-1-yl)methyl)guanidine,
[0062] n)1-((2-cyanoguanidinyl)methyl)urea,
[0063] o)2-Cyano-1-((2-Cyanoguanidinyl)methyl)guanidine,
[0064] p)2-Chloro-6-trichloromethylpyridine (chloridium or N-serve),
[0065] q) Dicyandiamide (DCD, DIDIN),
[0066] r) 3,4-dimethylpyrazole phosphate and / or 4,5-dimethylpyrazole phosphate (DMPP, ENTEC) and / or their isomers and / or their derivatives,
[0067] s) 3,4-dimethylpyrazole and / or 4,5-dimethylpyrazole (DMP) and / or its isomers and / or its derivatives and / or its salts and / or its acid addition salts,
[0068] t) Ammonium thiosulfate (ATU),
[0069] u) Products containing neem and / or neem-based ingredients,
[0070] v) Linoleic acid,
[0071] w)α-Linolenic acid,
[0072] x) Methyl coumarate
[0073] y) Methyl ferulic acid,
[0074] methyl 3-(4-hydroxyphenyl)propionate (MHPP),
[0075] aa) hydroflavin,
[0076] bb) arm-shaped oxaliplatin,
[0077] cc) p-Benzoquinone,
[0078] dd)4-amino-1,2,4-triazole hydrochloride (ATC)
[0079] ee)1-Amino-2-thiourea (ASU),
[0080] 2-Amino-4-chloro-6-methylpyrimidine (AM),
[0081] 2-Mercaptobenzothiazole (MBT)
[0082] hh)5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (terrazole, etridiazole)
[0083] ii) 2-Sulfathiazole (ST),
[0084] 3-Methylpyrazole (3-MP),
[0085] kk)1,2,4-triazolium thiourea (TU),
[0086] ll) cyanamide,
[0087] mm) melamine,
[0088] nn) Zeolite powder,
[0089] oo) catechins,
[0090] pp) benzoquinone,
[0091] Sodium tetraborate (qq)
[0092] rr) allyl thiourea,
[0093] ss) chlorate, and
[0094] Zinc sulfate (tt); and
[0095] 2) Solid carrier B containing at least one active compound II (urease inhibitor) selected from P.1-P.61: p-benzoquinone (P.1), polyphenols (P.2), heterocyclic thiols (P.3), polyacrylamide and its derivatives (P.4), diacylhydroxamic acids (P.5), carbamophenols (P.6), aminophenols (P.7), brominated nitro compounds (P.8), thiourea (P.9), isohydroxamic esters (P.10), sodium chloride (P.11), sodium carbonate (P.12), urea phosphate (P.13), urea nitrate (P.14), ammonium thiosulfate (P.15), calcium chloride (P.16), fluoride salts (P.17), O-diaminophosphine oximes (P.15). 8), phosphonosulfonamides (P.19), diaminophosphates (P.20), polyphosphoryldiamines (P.21), cyclotriphosphonates (P.22), N-acylphosphoryltriamines (P.23), metal phosphoryl esters (P.24), diamidophosphothiophosphate S-aryl (alkyl) esters (P.25), N-n-butylthiophosphoryltriamine (NBPT) (P.26), N-n-propylthiophosphoryltriamine (NPPT) (P.27), mixtures containing N-n-butylthiophosphoryltriamine (NBPT) and N-n-propylthiophosphoryltriamine (NPPT) (P.28), mixtures containing N-n-butylthiophosphoryltriamine (NBPT) and N-n-propylthiophosphoryltriamine (NPP) A mixture of (T) wherein the total amount of active urease inhibitors contains NBPT in an amount of 50-90% by weight and NPPT in an amount of 10-50% by weight (P.29), phenyl diaminophosphate (PPD / PPDA) (P.30), 2-nitrophenylphosphotriamine (2-NPT) (P.31), 2,5-dimethyl-1,4-benzoquinone (P.32), hydroquinone (P.33), thymol (P.34), pyrocatechol (P.35), triacontyl palmitate (P.36), barbituric acid (P.37), thiobarbituric acid (P.38), triazoles (P.39), 3-substituted-4-amino-5-thio-1H,4H-1,2,4- Triazoles (P.40), α-hydroxyketones (P.41), α-diketones (P.42), hydroxyureas (P.43), triketoximes (P.44), boric acid or its salts or derivatives (P.45), sodium sulfate or other sulfates (P.46), sodium benzenesulfinate or other benzenesulfinates (P.47), sodium benzenesulfonate or other benzenesulfonates (P.48), sodium sulfite or other sulfites (P.49), iodoacetic acid (P.50), N-ethylmaleimide (P.51), p-hydroxymercuryl benzoate (P.52), p-chloromercuryl benzoate (P.53), dicumarol (P.54), 1,2,4-thiadiazole-5-thio compounds or their derivatives (P.55).
[0096] According to the general formula (Ia) for thiophosphoric triamine (P.56):
[0097] R 1 R 2 NP(X)(NH2)2 (Ia),
[0098] Where X is sulfur;
[0099] R 1 and R 2 Independently, they are H, substituted or unsubstituted 2-nitrophenyl, C1-C 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Heterocyclic aryl, C6-C 20 aryl or dialkylaminocarbonyl, wherein R 1 and R 2 Together with the nitrogen atoms that connect them, they define optional additional 5- or 6-membered saturated or unsaturated heterocyclic groups comprising one or two heteroatoms selected from nitrogen, oxygen, and sulfur;
[0100] According to the general formula (Ib) for phosphorylated triamine (P.57):
[0101] R 1 R 2 NP(Y)(NH2)2 (Ib),
[0102] Where Y is oxygen;
[0103] R 1 and R 2 Independently, they are H, substituted or unsubstituted 2-nitrophenyl, C1-C 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Heterocyclic aryl, C6-C 20 aryl or dialkylaminocarbonyl, wherein R 1 and R 2 Together with the nitrogen atom that connects them, they define optional additional 5- or 6-membered saturated or unsaturated heterocyclic groups comprising one or two heteroatoms selected from nitrogen, oxygen, and sulfur.
[0104] An adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde (P.58).
[0105] According to formula (Ic), the adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde (P.59):
[0106]
[0107] The adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde according to formula (Id) (P.60):
[0108]
[0109] According to formula (Ie), the adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde (P.61):
[0110]
[0111] The present invention also relates to a mixture comprising:
[0112] 1) A solid support A comprising at least one active compound I (nitration inhibitor), wherein the active compound I is 2-(3,4-dimethyl-1H-pyrazol-1-yl)succinic acid (hereinafter referred to as "DMPSA1") and / or 2-(4,5-dimethyl-1H-pyrazol-1-yl)succinic acid (hereinafter referred to as "DMPSA2") and / or its derivatives and / or its salts, and
[0113] 2) Solid carrier B containing at least one active compound II (urease inhibitor) selected from P.1-P.61: p-benzoquinone (P.1), polyphenols (P.2), heterocyclic thiols (P.3), polyacrylamide and its derivatives (P.4), diacylhydroxamic acids (P.5), carbamophenols (P.6), aminophenols (P.7), brominated nitro compounds (P.8), thiourea (P.9), isohydroxamic esters (P.10), sodium chloride (P.11), sodium carbonate (P.12), urea phosphate (P.13), urea nitrate (P.14), ammonium thiosulfate (P.15), calcium chloride (P.16), fluoride salts (P.17), O-diaminophosphine oximes (P.15). 8), phosphonosulfonamides (P.19), diaminophosphates (P.20), polyphosphoryldiamines (P.21), cyclotriphosphonates (P.22), N-acylphosphoryltriamines (P.23), metal phosphoryl esters (P.24), diamidophosphothiophosphate S-aryl (alkyl) esters (P.25), N-n-butylthiophosphoryltriamine (NBPT) (P.26), N-n-propylthiophosphoryltriamine (NPPT) (P.27), mixtures containing N-n-butylthiophosphoryltriamine (NBPT) and N-n-propylthiophosphoryltriamine (NPPT) (P.28), mixtures containing N-n-butylthiophosphoryltriamine (NBPT) and N-n-propylthiophosphoryltriamine (NPP) A mixture of (T) wherein the total amount of active urease inhibitors contains NBPT in an amount of 50-90% by weight and NPPT in an amount of 10-50% by weight (P.29), phenyl diaminophosphate (PPD / PPDA) (P.30), 2-nitrophenylphosphotriamine (2-NPT) (P.31), 2,5-dimethyl-1,4-benzoquinone (P.32), hydroquinone (P.33), thymol (P.34), pyrocatechol (P.35), triacontyl palmitate (P.36), barbituric acid (P.37), thiobarbituric acid (P.38), triazoles (P.39), 3-substituted-4-amino-5-thio-1H,4H-1,2,4- Triazoles (P.40), α-hydroxyketones (P.41), α-diketones (P.42), hydroxyureas (P.43), triketoximes (P.44), boric acid or its salts or derivatives (P.45), sodium sulfate or other sulfates (P.46), sodium benzenesulfinate or other benzenesulfinates (P.47), sodium benzenesulfonate or other benzenesulfonates (P.48), sodium sulfite or other sulfites (P.49), iodoacetic acid (P.50), N-ethylmaleimide (P.51), p-hydroxymercuryl benzoate (P.52), p-chloromercuryl benzoate (P.53), dicumarol (P.54), 1,2,4-thiadiazole-5-thio compounds or their derivatives (P.55).
[0114] According to the general formula (Ia) for thiophosphoric triamine (P.56):
[0115] R 1 R 2 NP(X)(NH2)2 (Ia),
[0116] in
[0117] X is sulfur;
[0118] R 1 and R 2 Independently, they are H, substituted or unsubstituted 2-nitrophenyl, C1-C 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Heterocyclic aryl, C6-C 20 aryl or dialkylaminocarbonyl, wherein R 1 and R 2 Together with the nitrogen atoms that connect them, they define optional additional 5- or 6-membered saturated or unsaturated heterocyclic groups comprising one or two heteroatoms selected from nitrogen, oxygen, and sulfur;
[0119] According to the general formula (Ib) for phosphorylated triamine (P.57):
[0120] R 1 R 2 NP(Y)(NH2)2 (Ib),
[0121] in
[0122] Y stands for oxygen;
[0123] R 1 and R 2 Independently, they are H, substituted or unsubstituted 2-nitrophenyl, C1-C 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Heterocyclic aryl, C6-C 20 aryl or dialkylaminocarbonyl, wherein R 1 and R 2 Together with the nitrogen atom that connects them, they define optional additional 5- or 6-membered saturated or unsaturated heterocyclic groups comprising one or two heteroatoms selected from nitrogen, oxygen, and sulfur.
[0124] An adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde (P.58).
[0125] According to formula (Ic), the adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde (P.59):
[0126]
[0127] The adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde according to formula (Id) (P.60):
[0128]
[0129] According to formula (Ie), the adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde (P.61):
[0130]
[0131] The 1,2,4-thiadiazole-5-thio compound or its derivatives have been disclosed in WO05 / 007636A1.
[0132] Adducts of N-n-butylthiophosphoric triamine (NBPT), urea and formaldehyde, as well as adducts according to formulas (Ic), (Id) and (Ie), have been disclosed in WO 2017 / 019528.
[0133] The mixtures of the present invention also include kits containing a nitration inhibitor (compound I) and a urease inhibitor (compound II). The term "kit" here should be understood to mean a package comprising at least two separate parts, each of which can be independently removed from the package. Packages include boxes, appliances, reservoirs, containers, bags, or any packaging equipment. Packages whose separate parts are together only for a very short period in a single package are also considered kits. Kits can be used to administer the contents of the separate parts of the package in combination.
[0134] The present invention also relates to an agricultural chemical composition comprising an adjuvant and a mixture comprising at least one compound I and at least one compound II as active components.
[0135] The present invention also relates to the use of the mixtures or agrochemical compositions of the present invention in nitrification inhibition and / or enhancement of plant health and / or urease inhibition.
[0136] The present invention also relates to a method for improving the utilization efficiency of urea-containing fertilizers or inhibiting urease by using an effective amount of the mixture or agricultural chemical composition of the present invention.
[0137] The present invention also relates to a method for improving the efficacy of urea-containing fertilizers or inhibiting urease, comprising treating seeds, soil or plants with an effective amount of the mixture of the present invention or an agricultural chemical composition.
[0138] The present invention also relates to a method for enhancing plant health, comprising treating plants or plant propagation material or soil in which the plants are to grow with an effective amount of the mixture of the present invention or an agricultural chemical composition.
[0139] The present invention also relates to plant propagation materials comprising the mixtures or agrochemical compositions of the present invention at a rate of 0.1-10 kg of active substance per 100 kg of seeds.
[0140] In addition, a method for treating soil has been discovered, comprising applying the composition of the present invention to the soil in furrows and / or by fertilization and / or by broadcasting.
[0141] Furthermore, the use of the compositions of the present invention as additives or coating materials for nitrogen-containing fertilizers has been discovered.
[0142] The term "soil" should be understood as a natural body on the Earth's surface composed of living matter (e.g., microorganisms such as bacteria and fungi, animals and plants) and non-living matter (e.g., minerals and organic matter such as organic compounds of varying degrees of decomposition, liquids and gases), characterized by soil layers, which differ from the initial material due to various physical, chemical, biological, and anthropogenic processes. From an agricultural perspective, soil is primarily considered as the anchorage and main nutrient base for plants (the habitat for plant growth).
[0143] The term "fertilizer" should be understood as a compound applied to promote the growth of plants and fruits. Fertilizers are typically applied through the soil (for absorption by plant roots) or through foliar feeding (for absorption through leaves). The term "fertilizer" can be further subdivided into two main categories: a) organic fertilizers (composed of decaying plant / animal matter) and b) inorganic fertilizers (composed of chemicals and minerals). Organic fertilizers include manure, slurry, vermicompost, peat, seaweed, compost, sewage, and guano. Green manure crops are also commonly planted to add nutrients (especially nitrogen) to the soil. Manufactured organic fertilizers include, for example, compost, blood meal, bone meal, and seaweed extracts. Other examples are enzyme-digested proteins, fish meal, and feather meal. Decomposed crop residues from previous years are another source of fertility. In addition, natural minerals such as rock phosphates, potassium sulfates, and limestone are also considered inorganic fertilizers. Inorganic fertilizers are typically manufactured using chemical methods (such as the Haber-Bosch process), which also utilize natural sediments but chemically modify them (e.g., by concentrating superphosphate). Natural inorganic fertilizers include Chilean sodium nitrate, rock phosphates, and limestone.
[0144] "Manure" is organic matter used as organic fertilizer in agriculture. Depending on its structure, manure can be classified as liquid manure, semi-liquid manure, stable manure or soil manure, and grass manure. Depending on its source, manure can be classified as manure derived from animals or plants. Common forms of animal manure include feces, urine, farm slurry (liquid manure), or farmyard manure (FYM), which also contains a certain amount of plant material (usually straw), which may have been used as bedding for animals. Animals whose manure can be used as fertilizer include horses, cattle, pigs, sheep, chickens, turkeys, rabbits, and seabird guano from seabirds and bats. When used as fertilizer, the application rate of animal manure is highly dependent on its source (animal type). Plant manure can be derived from any kind of plant, and plants can be specifically cultivated for the purpose of fertilizing the soil (e.g., legumes), thereby improving soil structure and fertility. Furthermore, plant material used as manure can include rumen contents from slaughtered ruminants, hop residue (leftover from brewing beer), or seaweed.
[0145] "Pesticide" generally refers to chemical or biological agents (such as viruses, bacteria, antimicrobial agents, or disinfectants) that, through their effects, prevent, disable, kill, or otherwise thwart harmful substances. Targeted harmful substances can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microorganisms that damage property, cause trouble, spread disease, or act as disease vectors. The term "pesticide" also includes plant growth regulators that alter the expected growth, flowering, or reproductive rate of plants; defoliants that cause leaves or other foliage to fall from the plant, which generally promotes harvesting; desiccants that promote the drying of living tissues, such as unwanted above-ground parts of plants; plant activators that activate plant physiological functions to defend against certain harmful substances; safeners that reduce the undesirable herbicidal effects of pesticides on crops; and plant growth promoters that affect plant physiological functions, such as enhancing plant growth, biomass, yield, or any other quality parameter of the harvestable product of the crop.
[0146] The term "plant health" or "plant condition" as used in this article is intended to refer to the plant condition determined individually or in combination of several aspects. One indication of plant condition (indicator 1) is crop yield. "Crop" and "fruit" should be understood as any plant product that is further utilized after harvest, such as fruits, vegetables, nuts, grains, seeds, timber (e.g. in the case of afforestation plants), flowers (e.g. in the case of horticultural or ornamental plants), etc., which are anything of economic value produced by the plant. Another indication of plant condition (indicator 2) is plant vigor. Plant vigor is also manifested in several aspects, some of which are visual appearances, such as leaf color, fruit color and shape, the amount of dead basal leaves and / or leaf length, plant weight, plant height, internode length (lodging), number, robustness and productivity of tillers, ear length, root length, root robustness, nodule length, especially the length of root nodules, the timing of germination, emergence, flowering, grain maturation and / or senescence, protein content, sugar content, etc. Another sign of enhanced plant health (sign 3) is a reduction in biotic or abiotic stress factors. These three signs of plant health can be interdependent and mutually influential. For example, a reduction in biotic or abiotic stress may lead to better plant vigor, such as better and larger crops, and thus increased yield. Biotic stress, especially over longer periods, can have detrimental effects on plants. The term "biotic stress" as used in the context of this invention specifically refers to stress caused by living organisms. Therefore, plants affected by stress, their crops, and fruits experience a decline in quantity and quality. In terms of quality, proliferation and development are often severely affected, resulting in impacts on crops important for fruits or seeds. Growth may be slowed by stress; both structural polysaccharide synthesis and storage polysaccharide synthesis may be reduced or altered: these effects can lead to reduced biomass and changes in the nutritional value of the product. Abiotic stress includes drought, cold, increased UV, increased heat, or other changes in the plant environment that result in suboptimal growing conditions. The term "increased yield" as used herein refers to a measurably increased yield of the product of the corresponding plant relative to the same product produced under the same conditions but without the application of the compositions of this invention. According to the invention, it is preferred that the yield is increased by at least 2%, more preferably at least 4%, most preferably at least 7%, particularly preferably at least 10%, even more preferably at least 15%, most particularly preferably at least 20%, particularly more preferably at least 25%, particularly most preferably at least 30%, especially at least 35%, particularly more preferably at least 40%, particularly most preferably at least 45%, especially at least 50%, particularly preferably at least 55%, particularly more preferably at least 60%, particularly most preferably at least 65%, particularly at least 70%, for example at least 75%.According to the present invention, compared with the case where only compound I or compound II is used alone, the yield is preferably increased by at least 1%, more preferably at least 2%, most preferably at least 3%, particularly preferably at least 4%, even more preferably at least 5%, most particularly preferably at least 6%, particularly more preferably at least 7%, particularly most preferably at least 8%, especially at least 10%, particularly more preferably at least 12%, particularly most preferably at least 14%, particularly at least 16%, and especially preferably at least 18%. The yield increase may be due, for example, to a reduction in nitrification and a corresponding improvement in nitrogen nutrient uptake. As used herein, the term "improved plant vigor" refers to a measurable or significant increase or improvement in certain crop characteristics relative to the same factors in plants produced under the same conditions but without the application of the compositions of the present invention. Improved plant vigor can be characterized in particular by the following improved properties of the plant:
[0147] (a) Improved plant vitality,
[0148] (b) Improved plant quality and / or plant product quality, such as
[0149] (b) Increased protein content,
[0150] (c) Improved visual appearance,
[0151] (d) Delay aging,
[0152] (e) Enhanced root growth and / or a more developed root system (e.g., determined by root dry mass),
[0153] (f) Elevated nodules, especially root nodules,
[0154] (g) Longer spikelets,
[0155] (h) Larger leaves
[0156] (i) Fewer dead basal leaves,
[0157] (j) Increased chlorophyll content,
[0158] (k) Extended photosynthetic shelf life
[0159] (l) Improved nitrogen supply in plants
[0160] (m) Improved water use efficiency.
[0161] The improvement in plant vigor according to the invention specifically refers to the improvement of any one or more, or all of, the aforementioned plant characteristics. It further refers to the fact that, if not all of the aforementioned characteristics are improved, the unimproved characteristics do not deteriorate compared to plants not treated according to the invention, or at least do not deteriorate to the point that the negative effects outweigh the positive effects of the improving characteristics (i.e., there is always an overall positive effect that preferably leads to improved crop yield). Improved plant vigor may be due, for example, to a reduction in nitrification and, for example, regulation of plant growth.
[0162] Another typical problem in the field of pest control is the need to reduce the dosage rate of active ingredients to reduce or avoid adverse environmental or toxicological effects, while still allowing for effective pest control.
[0163] In view of effective tolerance management or effective plant growth regulation, the object of the present invention is to overcome the above-mentioned disadvantages and provide compositions (synergistic mixtures) that have improved plant growth regulation activity at the lowest possible application rate and with a reduced total amount of active compound applied, and especially have a broadened activity spectrum for certain indications.
[0164] This is particularly evident when the above mixtures are applied at rates in which individual components show no or negligible activity. The invention may also produce beneficial behavior during formulation or use, such as during grinding, sieving, emulsification, dissolving, or dispensing; improved storage and photostable stability; favorable residue formation; improved toxicological or ecotoxicological behavior; and improved plant performance, such as better growth, increased yield, better root development, larger leaf area, greener leaves, stronger shoots, fewer seeds required, lower phytotoxicity, loosening of plant defense systems, and good plant compatibility. Furthermore, even enhanced systemic action of pesticides as defined herein and / or persistence of herbicidal, fungicidal, insecticidal, acaricidal, nematicidal, and / or plant growth-regulating activities are anticipated.
[0165] Therefore, the object of the present invention is to provide a mixture that addresses the problems of reducing dosage rate and / or enhancing activity spectrum and / or improving tolerance management and / or promoting (enhancing) plant health and / or facilitating application on plants or in soil.
[0166] Therefore, we find that this objective is achieved through the mixtures and compositions defined herein.
[0167] Any reference to “compound I” refers to compound I itself or its agriculturally usable salt.
[0168] Any reference to “compound II” refers to compound II itself or its agriculturally usable salt.
[0169] Any reference to “compound III” refers to compound III itself or its agriculturally usable salt.
[0170] Agriculturally usable salts of active compounds I, II, and III particularly include salts of cations whose cations and anions do not adversely affect the nitration inhibition, urease inhibition, or pesticide action of the active compounds, or acid addition salts of those acids. Suitable cations are therefore especially alkali metal ions, preferably sodium and potassium ions; alkaline earth metal ions, preferably calcium, magnesium, and barium ions; transition metal ions, preferably manganese, copper, zinc, and iron ions; and, if desired, ammonium ions with 1-4 C1-C4 alkyl substituents and / or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, and others. The ions are sulfonium ions, preferably tri(C1-C4 alkyl)sulfonium, and sulfonium oxide ions, preferably tri(C1-C4 alkyl)sulfonium oxide. The anions of useful acid addition salts are mainly chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and anions of C1-C4 alkanic acids, preferably formate, acetate, propionate, and butyrate. They can be formed by reacting compound I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, or nitric acid.
[0171] The scope of this invention includes mixtures of (R)- and (S)- isomers of compound I and / or II and / or III having one or more chiral centers, as well as racemates. Due to the hindered rotation of asymmetricly substituted groups, hindered transisomers of active compound I and / or II and / or III may exist. They also form part of the subject matter of this invention.
[0172] The active compounds I and / or II and / or III of the present invention can exist in their N-oxide form. The term "N-oxide" includes any compound of the present invention having at least one tertiary nitrogen atom oxidized to an N-oxide structural moiety. The N-oxides of the compounds in the mixtures of the present invention can be prepared, in particular, by oxidizing the cyclic nitrogen atoms of the pyridine and / or pyrazole rings with a suitable oxidizing agent such as peroxycarboxylic acid or other peroxides. Those skilled in the art will know whether the compounds in the mixtures of the present invention, i.e., compounds I and / or II and / or III, can form N-oxides and at what position the N-oxides can form.
[0173] Compound II and / or mixtures or compositions of the present invention are suitable as urease inhibitors. They are suitable either directly or as appropriately formulated compositions (agrochemical compositions).
[0174] The mixtures or compositions of the present invention preferably have a urease inhibitory effect.
[0175] In one embodiment, the mixture or composition of the invention is applied or sprayed onto or in the soil, and preferably together with at least one fertilizer, a nitrogen fertilizer or a urea fertilizer, in furrows and / or applied to the soil by fertilization and / or broadcasting.
[0176] In another embodiment, the mixture or composition of the present invention is preferably applied to plants by foliar spraying. This can be done using conventional spraying techniques, for example, with water as a carrier, employing a spray volume of about 50-1000 l / ha (e.g., 300-400 l / ha). The mixture or composition can also be applied by low-volume or ultra-low-volume methods or in the form of microparticles. The mixture or composition of the present invention can be applied pre- or post-emergence, or together with crop seeds. Individual compounds and mixtures or compositions can also be applied by applying crop seeds pre-treated with the composition of the present invention. If active compounds I and II, and, if suitable, III, are not well tolerated by certain crops, an application technique (post-guided, final tillage procedure) can be used in which the mixture or composition of the present invention is sprayed using a spraying device to minimize contact with the leaves of sensitive crops, allowing the active compounds to reach the leaves of unwanted plants growing underneath or the bare soil surface.
[0177] The application of the mixtures or compositions of the present invention can be carried out before, during, and / or after unwanted plant emergence, preferably during and / or after.
[0178] In another embodiment, the mixtures or compositions of the present invention can be applied by treating seeds. Seed treatment essentially includes all procedures well known to those skilled in the art based on Compound II of the mixtures or compositions prepared therefrom (seed dressing, seed coating, seed dusting, seed soaking, seed coating, multi-layer seed coating, seed hulling, seed dripping, and seed granulation). The mixtures or compositions can then be applied diluted or undiluted.
[0179] The term "seed" includes all types of seeds, such as grains, seeds, fruits, tubers, seedlings, and similar forms. The preferred term used here describes grains and seeds. The seeds used may be from the aforementioned useful plants, but may also be from transgenic plants or plants obtained through conventional breeding methods.
[0180] Furthermore, it may be advantageous to apply the mixtures or compositions of the present invention, alone or in combination with other crop protectants, such as agents for controlling weeds, pests, or plant pathogenic fungi or bacteria. Also of interest is the miscibility with inorganic salt solutions used to treat nutrient and trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
[0181] As used herein, the term "metabolite" refers to any component, compound, substance, or byproduct (including, but not limited to, small molecule secondary metabolites, polyketides, fatty acid synthase products, non-ribosomal peptides, ribosomal peptides, proteins, and enzymes) produced by microorganisms (such as fungi and bacteria, especially the strains of this invention) that has any of the beneficial effects described herein, such as plant growth regulation activity or improvement of plant growth, plant water efficiency, plant health, plant appearance, or nitrification inhibition effects.
[0182] In this application, "weight%" means "percentage by weight".
[0183] Compound I (nitration inhibitor) can generally be included in the mixtures of the present invention in variable quantities. Preferably, the amount of Compound I, based on the total weight of the mixtures of the present invention, is no more than 95% by weight, more preferably no more than 90% by weight, most preferably no more than 85% by weight, even more preferably no more than 75% by weight, most particularly preferably no more than 65% by weight, particularly no more than 55% by weight, especially no more than 45% by weight, for example no more than 35% by weight, for example no more than 25% by weight, for example preferably no more than 15% by weight, for example more preferably no more than 5% by weight, for example most preferably no more than 2% by weight. Preferably, the amount of Compound I, based on the total weight of the mixtures of the present invention, is at least 0.001% by weight, more preferably at least 0.01% by weight, even more preferably at least 0.1% by weight, most preferably at least 1% by weight, even more preferably at least 4% by weight, most particularly preferably at least 9% by weight, especially at least 14% by weight, especially at least 19% by weight, for example at least 24% by weight.
[0184] The amount of preferred compound I, based on the total weight of solid carrier A, is no more than 95% by weight, more preferably no more than 90% by weight, most preferably no more than 85% by weight, even more preferably no more than 75% by weight, most particularly preferably no more than 65% by weight, particularly no more than 55% by weight, especially no more than 45% by weight, for example no more than 35% by weight, for example no more than 25% by weight, for example preferably no more than 15% by weight, for example more preferably no more than 5% by weight, for example most preferably no more than 2% by weight. The amount of preferred compound I, based on the total weight of the mixture of solid carrier A, is at least 0.001% by weight, more preferably at least 0.01% by weight, even more preferably at least 0.1% by weight, most preferably at least 1% by weight, even more preferably at least 4% by weight, most particularly preferably at least 9% by weight, especially at least 14% by weight, especially at least 19% by weight, for example at least 24% by weight.
[0185] Compound II (urease inhibitor) can generally be included in the mixture of the present invention in variable quantities. Preferably, the amount of Compound II, based on the total weight of solid carrier A, is no more than 95% by weight, more preferably no more than 90% by weight, most preferably no more than 85% by weight, even more preferably no more than 75% by weight, most particularly preferably no more than 65% by weight, particularly no more than 55% by weight, especially no more than 45% by weight, for example no more than 35% by weight, for example no more than 25% by weight, for example preferably no more than 15% by weight, for example more preferably no more than 5% by weight, for example most preferably no more than 2% by weight. Preferably, the amount of Compound II, based on the total weight of the mixture of solid carrier A, is at least 0.001% by weight, more preferably at least 0.01% by weight, even more preferably at least 0.1% by weight, most preferably at least 1% by weight, even more preferably at least 4% by weight, most particularly preferably at least 9% by weight, especially at least 14% by weight, especially at least 19% by weight, for example at least 24% by weight.
[0186] The amount of compound II, based on the total weight of solid carrier B, is preferably no more than 95% by weight, more preferably no more than 90% by weight, most preferably no more than 85% by weight, even more preferably no more than 75% by weight, most particularly preferably no more than 65% by weight, particularly no more than 55% by weight, especially no more than 45% by weight, for example no more than 35% by weight, for example no more than 25% by weight, for example preferably no more than 15% by weight, for example more preferably no more than 5% by weight, for example most preferably no more than 2% by weight. The amount of compound II, based on the total weight of the mixture of solid carrier B, is preferably at least 0.001% by weight, more preferably at least 0.01% by weight, even more preferably at least 0.1% by weight, most preferably at least 1% by weight, even more preferably at least 4% by weight, most particularly preferably at least 9% by weight, especially at least 14% by weight, especially at least 19% by weight, for example at least 24% by weight.
[0187] Particularly preferred are the mixtures of the present invention comprising nitration inhibitor, NBPT and NPPT, wherein NBPT is present in an amount of 1-99.99% by weight, more preferably 10-99.9% by weight, most preferably 20-99% by weight, particularly preferably 30-98% by weight, even more preferably 40-95% by weight, most preferably 50-90% by weight, especially 60-85% by weight, particularly preferably 72-80% by weight, for example 74-77% by weight, in each case based on the total weight of thiophosphoric triamines contained in the mixture of the present invention (i.e., NBPT and NPPT, if no other thiophosphoric triamines are present in the mixture).
[0188] In another preferred embodiment, compound II (UI) is selected from N-n-butylthiophosphoric triamine (NBPT) (P.26), N-n-propylthiophosphoric triamine (NPPT) (P.27), a mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) (P.28), a mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT), wherein NBPT is contained in an amount of 50-90% by weight and NPPT is contained in an amount of 10-50% by weight based on the total amount of active urease inhibitor (P.29), phenyl diaminophosphate (PPD / PPDA) (P.30), and 2-nitrophenylphosphoric triamine (2-NPT) (P.31).
[0189] In another preferred embodiment, compound II (UI) is p-benzoquinone.
[0190] In another preferred embodiment, compound II (UI) is a polyphenol.
[0191] In another preferred embodiment, compound II (UI) is a heterocyclic thiol.
[0192] In another preferred embodiment, compound II (UI) is polyacrylamide and its derivatives.
[0193] In another preferred embodiment, compound II (UI) is a diacylhydroxamic acid.
[0194] In another preferred embodiment, compound II (UI) is an aminocresol.
[0195] In another preferred embodiment, compound II (UI) is an aminophenol.
[0196] In another preferred embodiment, compound II (UI) is a brominated nitro compound.
[0197] In another preferred embodiment, compound II (UI) is thiourea.
[0198] In another preferred embodiment, compound II (UI) is an isohydroxamic ester.
[0199] In another preferred embodiment, compound II (UI) is sodium chloride.
[0200] In another preferred embodiment, compound II (UI) is sodium carbonate.
[0201] In another preferred embodiment, compound II (UI) is urea phosphate.
[0202] In another preferred embodiment, compound II (UI) is urea nitrate.
[0203] In another preferred embodiment, compound II (UI) is ammonium thiosulfate.
[0204] In another preferred embodiment, compound II (UI) is calcium chloride.
[0205] In another preferred embodiment, compound II (UI) is a fluoride salt.
[0206] In another preferred embodiment, compound II (UI) is an O-diaminophosphine oxime.
[0207] In another preferred embodiment, compound II (UI) is an oxyphosphonosulfonamide.
[0208] In another preferred embodiment, compound II (UI) is a diaminophosphate.
[0209] In another preferred embodiment, compound II (UI) is a polyphosphoramide.
[0210] In another preferred embodiment, compound II (UI) is a cyclotriphosphonate triene.
[0211] In another preferred embodiment, compound II (UI) is acylphosphoric triamine.
[0212] In another preferred embodiment, compound II (UI) is a metal phosphoryl ester.
[0213] In another preferred embodiment, compound II (UI) is a diamidophosphothiophosphate S-aryl (alkyl) ester.
[0214] In another preferred embodiment, compound II (UI) is N-n-butylthiophosphoric triamine (NBPT).
[0215] In another preferred embodiment, compound II (UI) is N-n-propylthiophosphoric triamine (NPPT).
[0216] In another preferred embodiment, compound II (UI) is a mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT).
[0217] In another preferred embodiment, compound II (UI) is a mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT), wherein the total amount of active urease inhibitors contains NBPT in an amount of 50-90% by weight and NPPT in an amount of 10-50% by weight.
[0218] In another preferred embodiment, compound II (UI) is phenyl diaminophosphate (PPD / PPDA).
[0219] In another preferred embodiment, compound II (UI) is 2-nitrophenylphosphotriamine.
[0220] In another preferred embodiment, compound II (UI) is 2,5-dimethyl-1,4-benzoquinone.
[0221] In another preferred embodiment, compound II (UI) is hydroquinone.
[0222] In another preferred embodiment, compound II (UI) is thymol.
[0223] In another preferred embodiment, compound II (UI) is pyrocatechol.
[0224] In another preferred embodiment, compound II (UI) is triacontyl palmitate.
[0225] In another preferred embodiment, compound II (UI) is barbituric acid.
[0226] In another preferred embodiment, compound II (UI) is thiobarbituric acid.
[0227] In another preferred embodiment, compound II (UI) is a triazole.
[0228] In another preferred embodiment, compound II (UI) is a 3-substituted 4-amino-5-thio-1H,4H-1,2,4-triazole.
[0229] In another preferred embodiment, compound II (UI) is an α-hydroxy ketone.
[0230] In another preferred embodiment, compound II (UI) is an α-diketone.
[0231] In another preferred embodiment, compound II (UI) is a hydroxyurea.
[0232] In another preferred embodiment, compound II (UI) is a triketoxime.
[0233] In another preferred embodiment, compound II (UI) is boric acid or a salt or derivative thereof.
[0234] In another preferred embodiment, compound II (UI) is sodium sulfate or other sulfate.
[0235] In another preferred embodiment, compound II (UI) is sodium benzenesulfinate or other benzenesulfinate.
[0236] In another preferred embodiment, compound II (UI) is sodium benzenesulfonate or other benzenesulfonate.
[0237] In another preferred embodiment, compound II (UI) is sodium sulfite or other sulfite.
[0238] In another preferred embodiment, compound II (UI) is iodoacetic acid.
[0239] In another preferred embodiment, compound II (UI) is N-ethylmaleimide.
[0240] In another preferred embodiment, compound II (UI) is p-hydroxymercuric benzoate.
[0241] In another preferred embodiment, compound II (UI) is p-chloromercuryl benzoate.
[0242] In another preferred embodiment, compound II (UI) is dicoumarin.
[0243] In another preferred embodiment, compound II (UI) is a 1,2,4-thiadiazole-5-thio compound or a derivative thereof.
[0244] In another preferred embodiment, compound II (UI) is a thiophosphoric triamine according to general formula (Ia):
[0245] R 1 R 2 NP(X)(NH2)2 (Ia),
[0246] Where X is sulfur;
[0247] R 1 and R 2 Independently, they are H, substituted or unsubstituted 2-nitrophenyl, C1-C 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Heterocyclic aryl, C6-C 20 aryl or dialkylaminocarbonyl, wherein R 1 and R 2 Together with the nitrogen atoms that connect them, they define optional additional 5- or 6-membered saturated or unsaturated heterocyclic groups comprising one or two heteroatoms selected from nitrogen, oxygen, and sulfur;
[0248] In another preferred embodiment, compound II (UI) is a phosphoric acid triamine according to general formula (Ib):
[0249] R1 R 2 NP(Y)(NH2)2 (Ib),
[0250] Where Y is oxygen;
[0251] R 1 and R 2 Independently, they are H, substituted or unsubstituted 2-nitrophenyl, C1-C 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Heterocyclic aryl, C6-C 20 aryl or dialkylaminocarbonyl, wherein R 1 and R 2 Together with the nitrogen atom that connects them, they define optional additional 5 or 6-membered saturated or unsaturated heterocyclic groups comprising one or two heteroatoms selected from nitrogen, oxygen, and sulfur.
[0252] In another preferred embodiment, compound II (UI) is an adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde.
[0253] In another preferred embodiment, compound II (UI) is an adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde according to formula (Ic):
[0254]
[0255] In another preferred embodiment, compound II (UI) is an adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde according to formula (Id):
[0256]
[0257] In another preferred embodiment, compound II (UI) is an adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde according to formula (Ie):
[0258]
[0259] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is p-benzoquinone.
[0260] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a polyphenol.
[0261] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a heterocyclic thiol.
[0262] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is polyacrylamide and its derivatives.
[0263] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a diacylhydroxamic acid.
[0264] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is an aminocresol.
[0265] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is an aminophenol.
[0266] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a brominated nitro compound.
[0267] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is thiourea.
[0268] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is an isohydroxamic ester.
[0269] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or their salts and / or their derivatives, and compound II (UI) is sodium chloride.
[0270] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or their salts and / or their derivatives, and compound II (UI) is sodium carbonate.
[0271] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is urea phosphate.
[0272] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is urea nitrate.
[0273] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or their salts and / or their derivatives, and compound II (UI) is ammonium thiosulfate.
[0274] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or their salts and / or their derivatives and compound II (UI) is calcium chloride.
[0275] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or their salts and / or their derivatives, and compound II (UI) is a fluoride salt.
[0276] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is an O-diaminophosphine oxime.
[0277] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is an oxophosphonylsulfonamide.
[0278] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a diaminophosphate.
[0279] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a polyphosphoramide.
[0280] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a cyclotriphosphonate triene.
[0281] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is acylphosphoric triamine.
[0282] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a metal phosphoryl ester.
[0283] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a diamidophosphothiophosphate S-aryl (alkyl) ester.
[0284] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is N-n-butylthiophosphoric triamine (NBPT).
[0285] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is N-n-propylthiophosphoric triamine (NPPT).
[0286] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is a mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT).
[0287] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is a mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT), wherein NBPT is contained in an amount of 50-90% by weight and NPPT is contained in an amount of 10-50% by weight based on the total amount of active urease inhibitor.
[0288] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is phenyl diaminophosphate (PPD / PPDA).
[0289] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is 2-nitrophenylphosphotriamine.
[0290] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is 2,5-dimethyl-1,4-benzoquinone.
[0291] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is hydroquinone.
[0292] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is thymol.
[0293] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is pyrocatechol.
[0294] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or their salts and / or their derivatives, and compound II (UI) is triacontyl palmitate.
[0295] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is barbituric acid.
[0296] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is thiobarbituric acid.
[0297] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a triazole.
[0298] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a 3-substituted 4-amino-5-thio-1H,4H-1,2,4-triazole.
[0299] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is an α-hydroxy ketone.
[0300] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is an α-diketone.
[0301] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a hydroxyurea.
[0302] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is a triketoxime.
[0303] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is boric acid or its salts or derivatives.
[0304] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is sodium sulfate or other sulfates.
[0305] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is sodium benzenesulfinate or other benzenesulfinate salts.
[0306] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is sodium benzenesulfonate or other benzenesulfonate salts.
[0307] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is sodium sulfite or other sulfites.
[0308] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or their salts and / or their derivatives and compound II (UI) is iodoacetic acid.
[0309] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is N-ethylmaleimide.
[0310] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or their salts and / or their derivatives, and compound II (UI) is p-hydroxymercuric benzoate.
[0311] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is p-chloromercuryl benzoate.
[0312] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives and compound II (UI) is dicoumarin.
[0313] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is a 1,2,4-thiadiazole-5-thio compound or its derivatives.
[0314] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is a thiophosphoric triamine according to general formula (Ia):
[0315] R 1 R 2 NP(X)(NH2)2 (Ia),
[0316] Where X is sulfur;
[0317] R 1 and R 2 Independently, they are H, substituted or unsubstituted 2-nitrophenyl, C1-C 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Heterocyclic aryl, C6-C 20 aryl or dialkylaminocarbonyl, wherein R 1 and R 2 Together with the nitrogen atoms that connect them, they define optional additional 5- or 6-membered saturated or unsaturated heterocyclic groups comprising one or two heteroatoms selected from nitrogen, oxygen, and sulfur;
[0318] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is a phosphorylated triamine according to general formula (Ib):
[0319] R 1 R 2 NP(Y)(NH2)2 (Ib),
[0320] Where Y is oxygen;
[0321] R 1 and R 2 Independently, they are H, substituted or unsubstituted 2-nitrophenyl, C1-C 20 Alkyl, C3-C 20 cycloalkyl, C6-C 20 Heterocyclic aryl, C6-C 20 aryl or dialkylaminocarbonyl, wherein R 1 and R 2 Together with the nitrogen atom that connects them, they define optional additional 5 or 6-membered saturated or unsaturated heterocyclic groups comprising one or two heteroatoms selected from nitrogen, oxygen, and sulfur.
[0322] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or its derivatives, and compound II (UI) is an adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde.
[0323] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or derivatives thereof, and compound II (UI) is an adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde according to formula (Ic):
[0324]
[0325] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or derivatives thereof, and compound II (UI) is an adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde according to formula (Id):
[0326]
[0327] In another preferred embodiment, compound I is DMPSA1 and / or DMPSA2 and / or its salts and / or derivatives thereof, and compound II (UI) is an adduct of N-n-butylthiophosphoric triamine (NBPT), urea, and formaldehyde according to formula (Ie):
[0328]
[0329] Regarding compound I, DMPSA1 or DMPSA2 and their preparation, for example, it has been described in WO 2015 / 086823A2. DMPSA1 is described with formula I and DMPSA2 with formula II. DMPG, DMPC, DMPL and DMPM compounds and their preparation, for example, have been described in AU 2015 / 227487B1. N-((3(5)-methyl-1H-pyrazole-1-yl)methyl)acetamide compounds and their preparation, for example, have been described in DE 102013022031 B3. N-((3(5)-methyl-1H-pyrazole-1-yl)methyl)formamide, N-((4-chloro-3(5)-methylpyrazole-1-yl)methyl)formamide and N-((3(5),4-dimethylpyrazole-1-yl)methyl)formamide compounds and their preparation, for example, have been described in EP 2785697B1. The reactive adducts of dicyandiamide, urea, and formaldehyde, the triazinone-formaldehyde-dicyandiamide adduct, 2-cyano-1-((4-oxo-1,3,5-triazinyl-1-yl)methyl)guanidine, 1-((2-cyanoguanidinyl)methyl)urea, and 2-cyano-1-((2-cyanoguanidinyl)methyl)guanidine have been described in US 2016 / 0060184A1. 2-cyano-1-((4-oxo-1,3,5-triazinyl-1-yl)methyl)guanidine has the structure described in Formula III, 1-((2-cyanoguanidinyl)methyl)urea has the structure described in Formula IV, and 2-cyano-1-((2-cyanoguanidinyl)methyl)guanidine has the structure described in Formula V.
[0330]
[0331]
[0332] In a preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is 2-(3,4-dimethyl-1H-pyrazol-1-yl)succinic acid (DMPSA1) and / or 2-(4,5-dimethyl-1H-pyrazol-1-yl)succinic acid (DMPSA2) and / or its derivatives and / or its salts, more preferably DMPSA1 and / or DMPSA2, and most preferably DMPSA1.
[0333] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is a salt of DMPSA1 and / or DMPSA2, more preferably an alkali metal salt, alkaline earth metal salt or ammonium salt of DMPSA1 and / or DMPSA2, most preferably a potassium salt, sodium salt, magnesium salt or ammonium salt of DMPSA1 and / or DMPSA2, particularly preferably a potassium salt or ammonium salt of DMPSA1 and / or DMPSA2, especially a potassium salt of DMPSA1 and / or DMPSA2.
[0334] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is an alkali metal salt of DMPSA1 and / or DMPSA2.
[0335] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is an alkaline earth metal salt of DMPSA1 and / or DMPSA2.
[0336] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is an ammonium salt of DMPSA1 and / or DMPSA2.
[0337] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is a sodium salt of DMPSA1 and / or DMPSA2.
[0338] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is a magnesium salt of DMPSA1 and / or DMPSA2.
[0339] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0340] a) Solid carrier A containing DMPSA1 and / or DMPSA2 and / or their derivatives and / or their salts as compound I (nitration inhibitor), and
[0341] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 50-90% by weight of NBPT and 10-50% by weight of NPPT based on the total amount of active urease inhibitor (P.29) as solid carrier B of compound II (urease inhibitor).
[0342] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0343] a) Solid carrier A containing DMPSA1 and / or DMPSA2 and / or their derivatives and / or their salts as compound I (nitration inhibitor), and
[0344] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0345] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0346] a) Solid carrier A containing DMPSA1 and / or DMPSA2 and / or their derivatives and / or their salts as compound I (nitration inhibitor), and
[0347] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0348] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0349] a) An alkali metal salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0350] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 50-90% by weight of NBPT and 10-50% by weight of NPPT based on the total amount of active urease inhibitor (P.29) as solid carrier B of compound II (urease inhibitor).
[0351] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0352] a) An alkali metal salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0353] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0354] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0355] a) An alkali metal salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0356] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0357] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0358] a) A solid carrier A containing potassium salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0359] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 50-90% by weight of NBPT and 10-50% by weight of NPPT based on the total amount of active urease inhibitor (P.29) as solid carrier B of compound II (urease inhibitor).
[0360] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0361] a) A solid carrier A containing potassium salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0362] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0363] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0364] a) A solid carrier A containing potassium salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0365] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0366] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0367] a) An ammonium salt containing DMPSA1 and / or DMPSA2 as a solid support A for compound I (nitration inhibitor), and
[0368] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 50-90% by weight of NBPT and 10-50% by weight of NPPT based on the total amount of active urease inhibitor (P.29) as solid carrier B of compound II (urease inhibitor).
[0369] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0370] a) An ammonium salt containing DMPSA1 and / or DMPSA2 as a solid support A for compound I (nitration inhibitor), and
[0371] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0372] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0373] a) An ammonium salt containing DMPSA1 and / or DMPSA2 as a solid support A for compound I (nitration inhibitor), and
[0374] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0375] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0376] a) An alkaline earth metal salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0377] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 50-90% by weight of NBPT and 10-50% by weight of NPPT based on the total amount of active urease inhibitor (P.29) as solid carrier B of compound II (urease inhibitor).
[0378] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0379] a) An alkaline earth metal salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0380] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0381] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0382] a) An alkaline earth metal salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0383] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0384] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0385] a) A solid support A containing magnesium salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0386] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 50-90% by weight of NBPT and 10-50% by weight of NPPT based on the total amount of active urease inhibitor (P.29) as solid carrier B of compound II (urease inhibitor).
[0387] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0388] a) A solid support A containing magnesium salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0389] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0390] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0391] a) A solid support A containing magnesium salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0392] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0393] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one active compound I, wherein the active compound I is a salt of DMPSA1 and / or DMPSA2, more preferably an alkali metal salt, alkaline earth metal salt, or ammonium salt of DMPSA1 and / or DMPSA2, most preferably a potassium salt, sodium salt, magnesium salt, or ammonium salt of DMPSA1 and / or DMPSA2, particularly a potassium salt of DMPSA1 and / or DMPSA2, wherein compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, particularly more preferably 40:1-6.5:1, and particularly most preferably 25:1-6.5:1.
[0394] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is an alkali metal salt of DMPSA1 and / or DMPSA2, wherein compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0395] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one active compound I, wherein the active compound I is an alkaline earth metal salt of DMPSA1 and / or DMPSA2, wherein compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0396] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one active compound I, wherein the active compound I is an ammonium salt of DMPSA1 and / or DMPSA2, wherein compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0397] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one active compound I, wherein the active compound I is a sodium salt of DMPSA1 and / or DMPSA2, wherein compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0398] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is a magnesium salt of DMPSA1 and / or DMPSA2, wherein compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0399] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0400] a) Solid carrier A containing DMPSA1 and / or DMPSA2 and / or their derivatives and / or their salts as compound I (nitration inhibitor), and
[0401] b) Solid carrier B containing N-n-butylthiophosphoric triamine (NBPT) as compound II (urease inhibitor),
[0402] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0403] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0404] a) An ammonium and / or potassium salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0405] b) Solid carrier B containing N-n-butylthiophosphoric triamine (NBPT) as compound II (urease inhibitor),
[0406] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0407] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0408] a) DMPSA1 and / or DMPSA2 and / or their derivatives and / or their salts as compound I (nitration inhibitor), and
[0409] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) containing 50-90% by weight and 10-50% by weight of NPPT (P.29) is designated as compound II (urease inhibitor).
[0410] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0411] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0412] a) DMPSA1 and / or DMPSA2 and / or their derivatives and / or their salts as compound I (nitration inhibitor), and
[0413] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight and 15-35% by weight of NPPT as the total amount of active urease inhibitor, is designated as compound II (urease inhibitor).
[0414] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0415] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0416] a) DMPSA1 and / or DMPSA2 and / or their derivatives and / or their salts as compound I (nitration inhibitor), and
[0417] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT, wherein the total amount of active urease inhibitor is as compound II (urease inhibitor).
[0418] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0419] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0420] a) Alkali metal salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0421] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) containing 50-90% by weight and 10-50% by weight of NPPT (P.29) is designated as compound II (urease inhibitor).
[0422] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0423] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0424] a) An alkali metal salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0425] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0426] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0427] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0428] a) An alkali metal salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0429] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0430] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0431] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0432] a) A solid support A containing potassium salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0433] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 50-90% by weight of NBPT and 10-50% by weight of NPPT based on the total amount of active urease inhibitor (P.29) as solid carrier B of compound II (urease inhibitor).
[0434] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0435] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0436] a) A solid carrier A containing potassium salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0437] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0438] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0439] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0440] a) A solid carrier A containing potassium salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0441] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0442] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0443] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0444] a) An ammonium salt containing DMPSA1 and / or DMPSA2 as a solid support A for compound I (nitration inhibitor), and
[0445] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 50-90% by weight of NBPT and 10-50% by weight of NPPT based on the total amount of active urease inhibitor (P.29) as solid carrier B of compound II (urease inhibitor).
[0446] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0447] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0448] a) An ammonium salt containing DMPSA1 and / or DMPSA2 as a solid support A for compound I (nitration inhibitor), and
[0449] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0450] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0451] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0452] a) An ammonium salt containing DMPSA1 and / or DMPSA2 as a solid support A for compound I (nitration inhibitor), and
[0453] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0454] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0455] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one active compound I, wherein the active compound I is a salt of DMPSA1 and / or DMPSA2, more preferably an alkali metal salt, alkaline earth metal salt, or ammonium salt of DMPSA1 and / or DMPSA2, most preferably a potassium salt, sodium salt, magnesium salt, or ammonium salt of DMPSA1 and / or DMPSA2, particularly a potassium salt of DMPSA1 and / or DMPSA2, wherein compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0456] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is an alkali metal salt of DMPSA1 and / or DMPSA2, wherein compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0457] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one active compound I, wherein the active compound I is an alkaline earth metal salt of DMPSA1 and / or DMPSA2, wherein compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0458] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one active compound I, wherein the active compound I is an ammonium salt of DMPSA1 and / or DMPSA2, wherein compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0459] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one active compound I, wherein the active compound I is a sodium salt of DMPSA1 and / or DMPSA2, wherein compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0460] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is a magnesium salt of DMPSA1 and / or DMPSA2, wherein compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0461] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0462] a) Solid carrier A containing DMPSA1 and / or DMPSA2 and / or their derivatives and / or their salts as compound I (nitration inhibitor), and
[0463] b) Solid carrier B containing N-n-butylthiophosphoric triamine (NBPT) as compound II (urease inhibitor),
[0464] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0465] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0466] a) An ammonium and / or potassium salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0467] b) Solid carrier B containing N-n-butylthiophosphoric triamine (NBPT) as compound II (urease inhibitor),
[0468] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0469] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0470] a) Solid carrier A containing DMPSA1 and / or DMPSA2 and / or their derivatives and / or their salts as compound I (nitration inhibitor), and
[0471] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 50-90% by weight of NBPT and 10-50% by weight of NPPT based on the total amount of active urease inhibitor (P.29) as solid carrier B of compound II (urease inhibitor).
[0472] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0473] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0474] a) Solid carrier A containing DMPSA1 and / or DMPSA2 and / or their derivatives and / or their salts as compound I (nitration inhibitor), and
[0475] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0476] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0477] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0478] a) Solid carrier A containing DMPSA1 and / or DMPSA2 and / or their derivatives and / or their salts as compound I (nitration inhibitor), and
[0479] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0480] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0481] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0482] a) An alkali metal salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0483] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 50-90% by weight of NBPT and 10-50% by weight of NPPT based on the total amount of active urease inhibitor (P.29) as solid carrier B of compound II (urease inhibitor).
[0484] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0485] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0486] a) An alkali metal salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0487] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0488] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0489] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0490] a) An alkali metal salt containing DMPSA1 and / or DMPSA2 as a solid carrier A for compound I (nitration inhibitor), and
[0491] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0492] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0493] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0494] a) A solid carrier A containing potassium salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0495] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 50-90% by weight of NBPT and 10-50% by weight of NPPT based on the total amount of active urease inhibitor (P.29) as solid carrier B of compound II (urease inhibitor).
[0496] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0497] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0498] a) A solid carrier A containing potassium salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0499] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0500] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0501] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0502] a) A solid carrier A containing potassium salts of DMPSA1 and / or DMPSA2 as compound I (nitration inhibitor), and
[0503] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0504] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0505] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0506] a) An ammonium salt containing DMPSA1 and / or DMPSA2 as a solid support A for compound I (nitration inhibitor), and
[0507] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 50-90% by weight of NBPT and 10-50% by weight of NPPT based on the total amount of active urease inhibitor (P.29) as solid carrier B of compound II (urease inhibitor).
[0508] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0509] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0510] a) An ammonium salt containing DMPSA1 and / or DMPSA2 as a solid support A for compound I (nitration inhibitor), and
[0511] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 65-85% by weight of NBPT and 15-35% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0512] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0513] In another preferred embodiment, the mixture or composition of the present invention comprises:
[0514] a) An ammonium salt containing DMPSA1 and / or DMPSA2 as a solid support A for compound I (nitration inhibitor), and
[0515] b) A mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) comprising 72-78% by weight of NBPT and 22-28% by weight of NPPT as a solid carrier B for compound II (urease inhibitor).
[0516] Compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0517] In another preferred embodiment, the mixture or composition of the present invention comprises a solid carrier A containing DMPSA1 and / or DMPSA2 or a salt thereof as compound I (nitration inhibitor), wherein DMPSA1 is present in an amount of 50-99% by weight, more preferably 60-95% by weight, most preferably 70-90% by weight, particularly 75-86% by weight, especially preferably 78-82% by weight or 82-86% by weight, based on the total weight of all isomers of DMPSA.
[0518] In another preferred embodiment, the mixture or composition of the present invention comprises a solid carrier A containing DMPSA1 and / or DMPSA2 or a salt thereof as compound I (nitration inhibitor), wherein DMPSA2 is present in an amount of 1-50% by weight, more preferably 5-40% by weight, most preferably 10-30% by weight, particularly 14-25% by weight, especially preferably 18-22% by weight or 14-18% by weight, based on the total weight of all isomers of DMPSA.
[0519] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is an glycolic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazole) Glycolate (hereinafter referred to as "DMPG") and / or its isomers and / or derivatives thereof, with DMPG being the most preferred.
[0520] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is a citrate addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazole) Citrate (hereinafter referred to as "DMPC") and / or its isomers and / or derivatives thereof, with DMPC being the most preferred.
[0521] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is a lactate addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazole) Lactate (hereinafter referred to as "DMPL") and / or its isomers and / or derivatives thereof, with DMPL being the most preferred.
[0522] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is a mandelic acid addition salt of 3,4-dimethylpyrazole (3,4-dimethylpyrazole) Mandelate (hereinafter referred to as "DMPM") and / or its isomers and / or derivatives thereof, with DMPM being the most preferred.
[0523] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is 1,2,4-triazole (hereinafter referred to as "TZ") and / or its derivatives and / or its salts, most preferably TZ.
[0524] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is 4-chloro-3-methylpyrazole (hereinafter referred to as "ClMP") and / or its isomers and / or its derivatives and / or its salts, most preferably ClMP.
[0525] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)acetamide and / or its isomers and / or its derivatives and / or its salts, most preferably N-((3-methyl-1H-pyrazol-1-yl)methyl)acetamide and / or N-((5-methyl-1H-pyrazol-1-yl)methyl)acetamide.
[0526] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)formamide and / or its isomers and / or its derivatives and / or its salts, most preferably N-((3-methyl-1H-pyrazol-1-yl)methyl)formamide and / or N-((5-methyl-1H-pyrazol-1-yl)methyl)formamide.
[0527] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is N-((3(5),4-dimethylpyrazol-1-yl)methyl)formamide and / or its isomers and / or its derivatives and / or its salts, most preferably N-((3,4-dimethyl-1H-pyrazol-1-yl)methyl)formamide and / or N-((4,5-dimethyl-1H-pyrazol-1-yl)methyl)formamide.
[0528] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is N-((4-chloro-3(5)-methylpyrazol-1-yl)methyl)formamide and / or its isomers and / or its derivatives and / or its salts, most preferably N-((4-chloro-3-methylpyrazol-1-yl)methyl)formamide and / or N-((4-chloro-5-methylpyrazol-1-yl)methyl)formamide.
[0529] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one active compound I, wherein the active compound I is a reaction adduct of dicyandiamide, urea and formaldehyde, preferably a reaction adduct of dicyandiamide, urea and formaldehyde as described in US 2016 / 0060184 A1.
[0530] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one active compound I, wherein the active compound I is a triazinone-formaldehyde-dicyandiamide adduct, preferably as described in US 2016 / 0060184A1.
[0531] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is 2-cyano-1-((4-oxo-1,3,5-triazin-1-yl)methyl)guanidine.
[0532] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one active compound I, wherein the active compound I is 1-((2-cyanoguanidinyl)methyl)urea.
[0533] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing a compound I, wherein the compound I is 2-cyano-1-((2-cyanoguanidinyl)methyl)guanidine.
[0534] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing a compound I, wherein the compound I is 2-chloro-6-trichloromethylpyridine (chlorodimethylpyridine or N-serve).
[0535] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is dicyandiamide (DCD, DIDIN).
[0536] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one compound I, wherein the compound I is 3,4-dimethylpyrazole phosphate and / or 4,5-dimethylpyrazole phosphate (DMPP, ENTEC) and / or its isomers and / or derivatives thereof.
[0537] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one compound I, wherein the compound I is 3,4-dimethylpyrazole and / or 4,5-dimethylpyrazole (DMP) and / or its isomers and / or its derivatives and / or its salts and / or its acid addition salts.
[0538] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is dicyandiamide (DCD, DIDIN).
[0539] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is ammonium thiosulfate (ATU).
[0540] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is neem.
[0541] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is linoleic acid.
[0542] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is α-linolenic acid.
[0543] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is methyl p-coumarate.
[0544] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is methyl ferulic acid.
[0545] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is methyl 3-(4-hydroxyphenyl)propionate (MHPP).
[0546] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is a styrax lactone.
[0547] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is sorgoleone.
[0548] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one compound I, wherein the compound I is 4-amino-1,2,4-triazole hydrochloride (ATC).
[0549] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is 1-amido-2-thiourea (ASU).
[0550] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one compound I, wherein the compound I is 2-amino-4-chloro-6-methylpyrimidine (AM).
[0551] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one compound I, wherein the compound I is 2-mercaptobenzothiazole (MBT).
[0552] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (terrazole, etridiazole).
[0553] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is 2-sulfathiazole (ST).
[0554] In another preferred embodiment, the present invention relates to a mixture comprising a solid support A containing at least one compound I, wherein the compound I is 3-methylpyrazole (3-MP).
[0555] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is 1,2,4-triazolethiourea (TU).
[0556] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is cyanamide.
[0557] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is melamine.
[0558] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is zeolite powder.
[0559] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is catechol.
[0560] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is benzoquinone.
[0561] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is sodium tetraborate.
[0562] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is allyl thiourea.
[0563] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is a chlorate.
[0564] In another preferred embodiment, the present invention relates to a mixture comprising a solid carrier A containing at least one compound I, wherein the compound I is zinc sulfate.
[0565] Particularly preferred is compound I, which is selected from a mixture of compounds IA-I.AX: IA: 2-(3,4-dimethyl-1H-pyrazol-1-yl)succinic acid (DMPSA1) and / or 2-(4,5-dimethyl-1H-pyrazol-1-yl)succinic acid (DMPSA2),
[0566] IB: Salt of DMPSA1 and / or DMPSA2
[0567] IC: Potassium salt of DMPSA1 and / or DMPSA2
[0568] ID: Ammonium salts of DMPSA1 and / or DMPSA2
[0569] IE: Sodium salts of DMPSA1 and / or DMPSA2
[0570] IF: 3,4-Dimethylpyrazole Diethyl glycolate (DMPG),
[0571] IG: 3,4-Dimethylpyrazole Citrate (DMPC),
[0572] IH: 3,4-Dimethylpyrazole Lactate (DMPL),
[0573] IJ: 3,4-Dimethylpyrazole Lactate (DMPM),
[0574] IK: 1,2,4-triazole (TZ),
[0575] IL: 4-Chloro-3-methylpyrazole (ClMP)
[0576] IM: N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)acetamide,
[0577] IN: N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)formamide,
[0578] IO: N-((3(5),4-dimethylpyrazol-1-yl)methyl)formamide,
[0579] IP: N-((4-chloro-3(5)-methylpyrazol-1-yl)methyl)formamide,
[0580] IQ: A reaction adduct of dicyandiamide, urea, and formaldehyde, or a triazinone-formaldehyde-dicyandiamide adduct.
[0581] IR: 2-cyano-1-((4-oxo-1,3,5-triazin-1-yl)methyl)guanidine,
[0582] IS: 1-((2-cyanoguanidinyl)methyl)urea,
[0583] IT: 2-Cyano-1-((2-Cyanoguanidinyl)methyl)guanidine,
[0584] IU: 2-Chloro-6-(trichloromethyl)pyridine (chloridium or N-serve),
[0585] IV: Dicyandiamide (DCD, DIDIN)
[0586] IW: 3,4-Dimethylpyrazole phosphate and / or 4,5-Dimethylpyrazole phosphate (DMPP, ENTEC) and / or their isomers and / or their derivatives.
[0587] IX: 3,4-Dimethylpyrazole and / or 4,5-dimethylpyrazole (DMP) and / or its isomers and / or its derivatives and / or its salts and / or its acid addition salts.
[0588] IY: Ammonium thiosulfate (ATU)
[0589] IZ: Neem,
[0590] I.AA: Linoleic acid,
[0591] I.AB: Alpha-linolenic acid,
[0592] I.AC: Methyl coumarate,
[0593] I.AD: Methyl ferulic acid,
[0594] I.AE: Methyl 3-(4-hydroxyphenyl)propionate (MHPP),
[0595] I.AF: Brassyl lactone,
[0596] I.AG: p-Benzoquinone,
[0597] I.AH: 4-Amino-1,2,4-triazole hydrochloride (ATC),
[0598] I.AI: 1-Amino-2-thiourea (ASU),
[0599] I.AJ: 2-Amino-4-chloro-6-methylpyrimidine (AM),
[0600] I.AK: 2-Mercaptobenzothiazole (MBT),
[0601] I.AL: 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole (chlorpyrifos, tebuconazole),
[0602] I.AM: 2-Sulfathiazole (ST),
[0603] I.AN: 3-Methylpyrazole (3-MP),
[0604] I.AO: 1,2,4-Triazolium thiourea (TU),
[0605] I.AP: Cyanamine,
[0606] I.AQ: Melamine
[0607] I.AR: Zeolite powder,
[0608] I.AS: Catechol,
[0609] I.AT: Benzoquinone,
[0610] I.AU: Sodium tetraborate,
[0611] I.AV: Allyl thiourea,
[0612] I.AW: Chlorate, or
[0613] I.AX: Zinc sulfate.
[0614] In one aspect of the invention, compound I is selected from the following compounds: IA, IB, IC, ID, IE, IL, IM, IN, IO, IP, IQ, IR, IS, IT, IU, IV, IW, IX, IY, IZ, I.AA, I.AB, I.AC, I.AD, I.AE, I.AF, I.AG, I.AH, I.AI, I.AJ, I.AK, I.AL, I.AM, I.AN, I.AO, I.AP, I.AQ, I.AR, I.AS, I.AT, I.AU, I.AV, I.AW, or I.AX, more preferably selected from the following compounds: IA, IB, IC, ID, IE, IL, IM, IN, IO, IP, IQ, IR, IS, IT, IU, IV, IW, IX, IY, I.AX, and most preferably selected from the following compounds: IA, IB, IC, ID, IE, IL, IM, IN, IO, IP, IQ, IR, IS.
[0615] Compound II (UI) may also have fungicidal, insecticidal, acaricidal, molluscicidal, pheromone-like, nematicidal, plant stress-reducing, plant growth-regulating, plant growth-promoting, and / or yield-enhancing activities.
[0616] Furthermore, the present invention relates to an agricultural chemical composition comprising at least one compound I and at least one compound II (UI) as described above, and, if necessary, at least one suitable adjuvant.
[0617] The mixtures and compositions of the present invention may also be used together with other pesticides, such as herbicides, insecticides, growth regulators, fungicides, or fertilizers, as a premix or, if appropriate, added (bucket mix) immediately before use.
[0618] In one embodiment, the mixture of the present invention comprises a solid carrier A containing at least one active compound I (nitrification inhibitor) or an agriculturally usable salt thereof, an active compound II, and an active compound III selected from herbicides, insecticides, fungicides, growth regulators, biopesticides, urease inhibitors, nitrification inhibitors, and denitrification inhibitors.
[0619] Combining a composition containing at least one compound I and at least one compound II with other urease inhibitors often leads to improved nitrification inhibition and / or improved plant health and / or improved urease inhibition. Furthermore, synergistic effects are observed in many cases.
[0620] The mixtures and compositions of the present invention are suitable as nitrification inhibitors, plant yield improvers or plant health improvers.
[0621] The term "plant propagation material" should be understood to refer to all propagating parts of a plant, such as seeds, as well as asexual plant material that can be used to propagate plants, such as cuttings and tubers (e.g., potatoes). This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, buds, and other plant parts, including seedlings and seedlings transplanted from soil after germination or emergence. These seedlings may also be protected prior to transplanting by full or partial treatment via soaking or watering.
[0622] Preferably, the treatment of plant propagation materials by the mixtures and compositions of the present invention is used to improve the efficiency of urea-containing fertilizers or to inhibit urease.
[0623] The term "cultivated plants" should be understood to include plants that have been modified through breeding, mutagenesis, or genetic engineering, including but not limited to agricultural biotechnology products that are marketed or developed (see [link to relevant documentation]). http: / / cera-gmc.org / (See the GM Crop Database). Genetically modified plants are plants whose genetic material is modified using recombinant DNA technology in a way that is not easily obtained through hybridization, mutation, or natural recombination under natural conditions. Typically, one or more genes are integrated into the genetic material of a genetically modified plant to improve certain plant properties. This type of gene modification also includes, but is not limited to, targeted post-translational modifications of proteins, oligopeptides, or polypeptides, such as through glycosylation or polymer additions like isoprenelation, acetylation, or farnesylation of structural moieties or PEGylation.
[0624] Plants conditioned through breeding, mutagenesis, or genetic engineering become tolerant to specific classes of herbicides, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonylureas (e.g., see US 6,222,100, WO 01 / 82685, WO 00 / 26390, WO97 / 41218, WO 98 / 02526, WO 98 / 02527, WO 04 / 106529, WO 05 / 20673, WO 03 / 14357, WO 03 / 13225, WO 03 / 14356, WO 04 / 16073) or imidazolinone ... 00 / 26390, WO 00 / 26390, WO 00 / 26390, WO 00 / 26390, WO 00 / 26390, WO 00 / 26390, WO 00 / 26390 WO 01 / 82685, WO 00 / 026390, WO 97 / 41218, WO 98 / 002526, WO 98 / 02527, WO 04 / 106529, WO 05 / 20673, WO 03 / 014357, WO 03 / 13225, WO 03 / 14356, WO 04 / 16073); enolpyruvylshikimate 3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (e.g., see WO 92 / 00377); glutamine synthase (GS) inhibitors, such as glufosinate (e.g., see EP-A 242 236, EP-A 242 246) or oxynil herbicide (e.g., see US 5,559,024). Several cultivated plants have been made tolerant to herbicides through conventional breeding methods (mutation), such as tolerance to imidazolinones like imazapyridine. Summer-sown rapeseed (Canola, BASF SE, Germany). Genetic engineering methods have been used to confer tolerance to herbicides such as glyphosate and glufosinate on cultivated plants like soybeans, cotton, corn, sugar beets, and rapeseed. Some of these can be marketed under trademarks. (Glyphosate-tolerant, Monsanto, USA) and (Glufosinate-tolerant, Bayer CropScience, Germany) Commercially available.
[0625] Furthermore, this also includes plants from which one or more insecticidal proteins can be synthesized using recombinant DNA technology, particularly those from Bacillus bacteria, especially Bacillus thuringiensis, such as δ-endotoxins, e.g., CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1), or Cry9c; asexual insecticidal proteins (VIPs), e.g., VIP1, VIP2, VIP3, or VIP3A; insecticidal proteins from nematode-inhabiting bacteria, e.g., Photorhabdus or Xenorhabdus; animal-produced toxins such as scorpion venom, spider venom, wasp venom, or other insect-specific neurotoxins; and fungal toxins, e.g., Streptomycetes. Toxins; phytohemagglutinins, such as pea or barley lectins; lectins; protease inhibitors, such as trypsin inhibitors, serine protease inhibitors, potato tuber-specific protein (patatin), cysteine protease inhibitors, or papain inhibitors; ribosome-inactivating proteins (RIPs), such as ricin, corn-RIP, absinthecin, loofah seed protein, saponins, or bryodin; steroid metabolic enzymes, such as 3-hydroxysteroid oxidase, ecdysone-IDP glycosyltransferase, cholesterol oxidase, ecdysone inhibitors, or HMG-CoA reductase; ion channel blockers, such as sodium or calcium channel blockers; juvenile hormone esterases; helicokinin receptors; Synthesizers, bibenzyl synthases, chitosanases, or glucanases. In the context of this invention, these insecticidal proteins or toxins are also specifically understood to include protoxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by novel combinations of different protein domains (see, for example, WO 02 / 015701). Other examples of such toxins or genetically modified plants capable of synthesizing these toxins are disclosed, for example, in EP-A 374753, WO 93 / 007278, WO 95 / 34656, EP-A 427 529, EP-A 451 878, WO 03 / 18810, and WO 03 / 52073. Methods for producing such genetically modified plants are generally known to those skilled in the art and are described, for example, in the aforementioned publications. These insecticidal proteins contained in genetically modified plants confer tolerance to all taxonomically classified arthropod pests, particularly beetles (Coeloptera), dipterans (Diptera), moths (Lepidoptera), and nematodes (Nematoda). Genetically modified plants capable of synthesizing one or more insecticidal proteins are described, for example, in the aforementioned publications; some of these are commercially available, such as... (Corn varieties that produce the toxin Cry1Ab) Plus (corn varieties that produce the toxins Cry1Ab and Cry3Bb1), (Corn varieties that produce the toxin Cry9c) RW (a maize variety that produces the toxins Cry34Ab1 and Cry35Ab1 and the enzyme phosphinic acid-N-acetyltransferase [PAT]); 33B (a cotton variety that produces the toxin Cry1Ac), I (cotton varieties that produce the toxin Cry1Ac), II (cotton varieties that produce toxins Cry1Ac and Cry2Ab2); (Cotton varieties that produce VIP toxin); (Potato varieties that produce the toxin Cry3A); Bt11 (e.g.) CB) and Bt176 of Syngenta Seeds SAS (a maize variety that produces the toxin Cry1Ab and PAT enzyme), MIR604 of Syngenta Seeds SAS (a maize variety that produces a modified version of the toxin Cry3A, see WO03 / 018810), MON 863 of Monsanto Europe SA (a maize variety that produces the toxin Cry3Bb1), IPC 531 of Monsanto Europe SA (a cotton variety that produces a modified version of the toxin Cry1Ac), and 1507 of Pioneer Overseas Corporation (a maize variety that produces the toxin Cry1F and PAT enzyme).
[0626] Furthermore, this includes plants capable of synthesizing one or more proteins that enhance resistance or tolerance to bacterial, viral, or fungal pathogens using recombinant DNA technology. Examples of such proteins are so-called "pathogenesis-associated proteins" (PR proteins, see, for example, EP-A 392 225), plant disease resistance genes (e.g., potato varieties expressing resistance genes against the pathogenic fungus *Phytophthora infestans* from the Mexican wild potato *Solanum bulbocastanum*), or T4 lysozyme (e.g., potato varieties capable of synthesizing these proteins with enhanced resistance to bacteria such as *Erwinia amylvora*). Methods for producing these genetically modified plants are generally known to those skilled in the art and are described, for example, in the aforementioned publications.
[0627] In addition, it includes plants that can synthesize one or more proteins to increase yield (e.g., biomass production, grain yield, starch content, oil content, or protein content) through the use of recombinant DNA technology, and that are tolerant to drought, salt, or other growth-limiting environmental factors or to pests and pathogens such as fungi, bacteria, and viruses.
[0628] Furthermore, this also includes plants that, through the use of recombinant DNA technology, contain altered or novel amounts of substances to particularly improve human or animal nutrition, such as oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e.g., oilseed crops). Rapeseed (DOW Agro Sciences, Canada).
[0629] In addition, this includes plants that contain altered or new amounts of substances through the use of recombinant DNA technology to particularly improve the production of raw materials, such as potatoes that produce increased amounts of amylopectin (e.g. Potatoes (BASF SE, Germany).
[0630] Plant propagation material may be preventively treated with the mixtures and compositions of the present invention during or before planting or transplanting.
[0631] The present invention particularly relates to a method for protecting plant propagation material from pests, wherein the plant propagation material is treated with an effective amount of the mixture of the present invention.
[0632] Depending on the application method, the mixtures or compositions of the present invention can be additionally used on many other crops to increase yield, improve productivity (e.g., biomass production, grain yield, starch content, oil content, or protein content), improve plant health, or improve or regulate plant growth. Examples of suitable crops include: onion (Allium cepa), pineapple (Ananascomosus), peanut (Arachis hypogaea), asparagus (Asparagus officinalis), oat (Avenasativa), beet (Beta vulgaris spec.altissima), beet (Beta vulgaris spec.rapa), rapeseed (Brassica napus var. napus), rutabaga (Brassica napus var. napobrassica), and rutabaga var.Silvestris, kale (Brassica oleracea), black mustard (Brassicanigra), large-leaf tea (Camellia sinensis), safflower (Carthamus tinctorius), American pecan (Caryaillinoinensis), lemon (Citrus limon), sweet orange (Citrus sinensis), small-fruited coffee (Coffea arbica) (medium-fruited coffee (Coffea canephora), large-fruited coffee (Coffea liberica)), cucumber (Cucumissativus), bermudagrass (Cynodon dactylon), carrot (Daucus carota), oil palm (Elaeisguineensis), European strawberry (Fragaria vesca), soybean (Glycine max), upland cotton (Gossypium hirsutum) (tree cotton (Gossypium arboreum), herb cotton (Gossypium herbaceum), kapok (Gossypium vitifoolium)), sunflower (Helianthus) (List of genera and species follows)Pistachios (Pistacia vera), peas (Pisum sativum), sweet cherries (Prunus avium), ornamental peaches (Prunus persica), pears (Pyrus communis), apricots (Prunus armeniaca), sour cherries (Prunus cerasus), almonds (Prunus dulcis), and plums (Prunus domestica), blackcurrants (Ribes sylvestre), castor beans (Ricinus communis), sugarcane (Saccharum officinarum), rye (Secale cereale), white mustard (Sinapis alba), potatoes (Solanum tuberosum), bicolor millet (Sorghum vulgare), cacao (Theobroma cacao), red clover (Trifolium pratense), common wheat (Triticum aestivum), triticale, durum wheat (Triticum durum), broad beans (Vicia) faba, grapes (Vitisvinifera), and corn (Zea mays).
[0633] Preferred crops include peanut (Arachis hypogaea), sugar beet (Beta vulgarisspec.altissima), European rapeseed (Brassica napus var.napus), kale (Brassica oleracea), lemon (Citrus limon), sweet orange (Citrus sinensis), small-fruited coffee (Coffea arabica) (medium-fruited coffee (Coffea canephora), large-fruited coffee (Coffea liberica)), bermudagrass (Cynodon dactylon), soybean (Glycine max), upland cotton (Gossypium hirsutum) (tree cotton (Gossypium arboreum), herb cotton (Gossypium herbaceum), kapok (Gossypium vitifolium)), sunflower (Helianthus annuus), barley (Hordeum vulgare), walnut (Juglans regia), lentil (Lensculinaris), flax (Linum usitatissimum), and tomato (Lycopersicon). The genera include *Lycopersicum*, *Malus spec.*, *Medicago sativa*, *Nicotiana tabacum* (yellow-flowered tobacco (N. rustica)), *Olea europaea*, *Oryza sativa*, *Phaseolus lunatus*, *Phaseolus vulgaris*, *Pistacia vera*, *Pisum sativum*, *Prunus dulcis*, *Saccharum officinarum*, *Secale cereale*, *Solanum tuberosum*, *Sorghum bicolor* (sorghum (S. vulgare)), *Triticale*, *Triticum aestivum*, *Triticum durum*, *Viciafaba*, *Vitis vinifera*, and *Zea mays*.
[0634] The preferred crops are cereal crops, corn, soybeans, rice, oilseed rape, cotton, potatoes, peanuts, or perennial crops.
[0635] The mixtures or compositions of the present invention can also be used in crops that have been modified by mutagenesis or genetic engineering to provide new traits to the plants or to modify existing traits.
[0636] The term “crop” as used in this article also includes plants (agricultural crops) that have been modified by mutagenesis or genetic engineering to provide new traits or modify existing traits.
[0637] Mutagenesis includes random mutagenesis techniques using X-rays or mutagenic chemicals, but there are also targeted mutagenesis techniques to induce mutations at specific locations in the plant genome. Targeted mutagenesis techniques typically use oligonucleotides or proteins such as CRISPR / Cas, zinc finger nucleases, TALENs, or a wide range of nucleases to achieve a targeted effect.
[0638] Genetic engineering typically uses recombinant DNA techniques, which are not easily obtained naturally through hybridization, mutagenesis, or natural recombination, to produce modifications in the plant genome. One or more genes are usually integrated into the plant genome to add or improve traits. These integrated genes are also known in the art as transgenes, and plants containing such transgenes are called transgenic plants. This plant conversion method usually produces several conversion events, which differ in the genomic location where the transgene has been integrated. Plants containing a specific transgene at a specific genomic location are often described as containing a specific "event," which is referred to by the event name. Traits that have been introduced into plants or modified include, in particular, herbicide tolerance, insect resistance, increased yield, and tolerance to abiotic conditions such as drought.
[0639] Increased yields are achieved by using the transgenic athb17 present in maize event MON87403 to increase ear biomass or by using the transgenic bbx32 present in soybean event MON87712 to increase photosynthesis.
[0640] Crops containing modified oil content have been produced using transgenic genes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A, and fatb1-A. Soybean events containing at least one of these genes are: 260-05, MON87705, and MON87769.
[0641] Tolerance to abiotic conditions, especially drought tolerance, was improved through the use of the transgenic cspB included in the maize event MON87460 and through the use of the soybean event IND- The included transgenic Hahb-4 is produced.
[0642] Traits are typically combined by combining genes during conversion events or by combining different events during the breeding process. Preferred combinations of traits include herbicide tolerance to different classes of herbicides, insect tolerance to different insect species, especially to Lepidoptera and Coleoptera, herbicide tolerance with resistance to one or more types of insects, herbicide tolerance with increased yield, and combinations of herbicide tolerance and tolerance to abiotic conditions.
[0643] Plants containing individual or stacked traits, as well as the genes and events that provide these traits, are known in the art. For example, detailed information about mutagenic or integrated genes and the corresponding events can be obtained from organizations such as the International Service for the Acquisition of Agri-biotech Applications (ISAAA). http: / / www.isaaa.org / gmapprovaldatabase ) and “Center for Environmental Risk Assessment (CERA)” ( http: / / cera-gmc.org / GMCropDatabase The website and patent applications such as EP 3028573 and WO2017 / 011288 are available.
[0644] Using the compositions of this invention on crops may result in effects specific to crops containing certain genes or events. These effects may involve changes in growth behavior or tolerance to biotic or abiotic stressors. Such effects may in particular include increased yield, increased resistance or tolerance to insect, nematode, fungal, bacterial, mycoplasma, viral or viroid pathogens, as well as early vigor, early or delayed maturity, cold or heat tolerance, and changes in amino acid or fatty acid profiles or contents.
[0645] In a similarly preferred embodiment, the present invention relates to a method for improving the urease inhibition effect (hereinafter referred to as "UI effect"), wherein seeds, plants or soil are treated with an effective amount of the mixture of the present invention in UI amount.
[0646] The term "UI effective amount" refers to the amount of the mixture of the present invention sufficient to achieve the UI effect as defined below. Further illustrative information regarding the amount to be used, the method of application, and suitable proportions is given below. However, those skilled in the art will fully recognize that this amount can vary widely and depends on various factors such as climate, target species, location, application method, soil type, the cultivated plant or material being treated, and climatic conditions.
[0647] According to the present invention, the UI effect is improved by at least 2%, more preferably at least 4%, most preferably at least 7%, particularly preferably at least 10%, even more preferably at least 15%, most particularly preferably at least 20%, particularly more preferably at least 25%, particularly most preferably at least 30%, especially at least 35%, particularly more preferably at least 40%, particularly most preferably at least 45%, especially at least 50%, particularly preferably at least 55%, particularly more preferably at least 60%, particularly most preferably at least 65%, particularly at least 70%, for example at least 75%. The improvement in UI effect can typically be, for example, 5-10%, more preferably 10-20%, and most preferably 20-30%.
[0648] The UI effect can be measured according to the following study on ammonia volatilization loss: The method used to measure NH3 volatilization loss of urea in the laboratory is described by Fenn & Kissel (1973) (in Ammonia volatilization from surface applications of ammonium compounds on calcareous soils: I. General theory. Soil Sci. Am. Proc. 37, 855-859) and Terman (1979) (in Volatilization losses of nitrogen as ammonia from surface-applied fertilizers, organic amendments and crop residues. Advances in Agronomy 31, 189-223). In short, after surface application of 0.25 g of nitrogen in different formulations of urea, air was passed through a gas exchange container over 200 g of soil (loamy sand, pH (CaCl2) 6.8) from Limburgerhof—with a water content of approximately 55% of its water-holding capacity—for up to 21 days. To wash NH3 from air exiting the container at a rate of approximately 4 L / min, it was bubbled through 200 mL of 0.15 N H2SO4 solution. NH3-N in the solution was quantified to NH4-N in regular intervals using an automated analyzer.
[0649] In another preferred embodiment, the present invention relates to a method for improving nitrification inhibition, wherein seeds, plants or soil are treated with an effective amount of the mixture of the present invention containing NI.
[0650] The term "NI effective amount" refers to the amount of the mixture of the present invention sufficient to achieve the nitrification inhibition effect as defined below. Further illustrative information regarding the amount to be used, the method of application, and suitable proportions is given below. However, those skilled in the art will fully recognize that this amount can vary widely and depends on various factors such as climate, target species, location, application method, soil type, the cultivated plant or material being treated, and climatic conditions.
[0651] According to the present invention, the nitration inhibition effect is increased by at least 2%, more preferably at least 4%, most preferably at least 7%, particularly preferably at least 10%, more particularly preferably at least 15%, most particularly preferably at least 20%, particularly more preferably at least 25%, particularly most preferably at least 30%, especially at least 35%, particularly more preferably at least 40%, particularly most preferably at least 45%, particularly at least 50%, especially preferably at least 55%, especially more preferably at least 60%, especially most preferably at least 65%, especially at least 70%, for example at least 75%. The increase in nitration inhibition effect can typically be, for example, 5-10%, more preferably 10-20%, and most preferably 20-30%. The nitration inhibition effect can be measured according to the following examples:
[0652] Fill 100g of soil (incubated at 20°C for 2 weeks to activate microbial biomass) into a 500ml plastic bottle (e.g., soil sampled from the field) and moisten to 50% of its water capacity. Fertilizer is then applied to the corresponding product containing the composition and mixture of the present invention at an appropriate concentration.
[0653] Ensure the treated fertilizer particles are evenly distributed in the soil. The amount of fertilizer applied corresponds to 10 mg of reduced nitrogen per bottle.
[0654] Loosely cover each bottle to allow air exchange. Then incubate each bottle at 20°C for 28 days.
[0655] For analysis, 300 ml of 1% K₂SO₄ solution was added to a bottle containing soil and shaken at 150 rpm for 2 hours in a horizontal shaker. The entire solution was then filtered through a Macherey-Nagel MN 807 filter. 1 / 4. Analyze the ammonium content of the filtrate using an automated analyzer (Merck, AA11) at 550 nm. Calculate:
[0656]
[0657] In another preferred embodiment, the present invention relates to a method for improving plant health, wherein plants are treated with a plant-health-effective amount of the mixture of the present invention.
[0658] The term "plant health effective amount" refers to the amount of the mixture of the present invention sufficient to achieve the plant health effects defined below. Further illustrative information regarding the amount to be used, the method of application, and suitable proportions is given below. However, those skilled in the art will fully recognize that this amount can vary widely and depends on various factors, such as the cultivated plant or material being treated and climatic conditions.
[0659] Healthier plants are desirable because they lead, in particular, to better yields and / or better plant or crop quality, specifically better quality of harvested plant parts. Healthier plants are also better resistant to biotic and / or abiotic stresses. High tolerance to biotic stresses, in turn, allows those skilled in the art to reduce pesticide application rates and thus slow the development of tolerance to the corresponding pesticides.
[0660] It must be emphasized that the above-mentioned effects of the mixture of the present invention, namely enhanced plant health, exist even when the plant is not under biological stress and especially when the plant is not under pest stress.
[0661] For example, in terms of seed treatment and soil application, plants clearly suffering from fungal or insect infestations show reduced germination and emergence compared to plant propagation material that has been treated or prevented for the relevant pests and can grow without damage caused by biological stress factors, resulting in poorer plant or crop rooting and vigor, and thus reduced yield.
[0662] However, the method of the present invention leads to enhanced plant health even in the absence of any biological stress. This means that the positive effects of the mixture of the present invention cannot be explained solely by the nitrification inhibition or urease inhibition activities of compounds I and II, but are based on other active characteristics. Therefore, the application of the mixture of the present invention can also be carried out in the absence of pest stress.
[0663] In another preferred embodiment, the present invention relates to a method for improving the health of plants grown from said plant propagation material, wherein the plant propagation material is treated with an effective amount of the mixture of the present invention.
[0664] The plant health indicators listed below, selected from yield, plant vigor, quality, and plant tolerance to abiotic and / or biotic stresses, should be understood as each individually or preferably in combination as a preferred embodiment of the invention.
[0665] According to the present invention, "increased yield" of a plant refers to a measurable increase in the product yield of the corresponding plant compared to the same product yield of a plant produced under the same conditions but without the application of the mixture of the present invention.
[0666] For seed treatments, such as inoculation and / or foliar application, yield increases can be characterized in particular by the following improved plant properties: increased plant weight; and / or increased plant height; and / or increased biomass, such as higher total fresh weight (FW) or dry weight (DW); and / or increased number of flowers per plant; and / or higher grain and / or fruit yield; and / or more tillers or lateral branches (branches); and / or larger leaves; and / or increased shoot growth; and / or increased protein content; and / or increased oil content; and / or increased starch content; and / or increased pigment content; and / or increased chlorophyll content (chlorophyll content is positively correlated with the photosynthetic rate of the plant and therefore higher chlorophyll content leads to higher plant yield) and / or improved plant quality; and / or better nitrogen uptake (N uptake).
[0667] "Grain" and "fruit" should be understood as any plant product that is further utilized after harvest, such as fruit, vegetables, nuts, grains, seeds, timber (e.g. in the case of afforestation plants), flowers (e.g. in the case of garden plants, ornamental plants), and anything else of economic value produced by plants in the proper sense.
[0668] According to the invention, the yield is increased by at least 2%, more preferably at least 4%, most preferably at least 7%, particularly preferably at least 10%, even more preferably at least 15%, most preferably at least 20%, particularly more preferably at least 25%, particularly most preferably at least 30%, especially at least 35%, particularly more preferably at least 40%, particularly most preferably at least 45%, especially at least 50%, particularly preferably at least 55%, particularly more preferably at least 60%, particularly most preferably at least 65%, particularly at least 70%, for example at least 75%.
[0669] According to the invention, the yield—if measured in the absence of pest stress—is increased by at least 2%, more preferably at least 4%, most preferably at least 7%, particularly preferably at least 10%, even more preferably at least 15%, most preferably at least 20%, particularly more preferably at least 25%, particularly preferably at least 30%, especially at least 35%, particularly more preferably at least 40%, particularly most preferably at least 45%, particularly at least 50%, especially preferably at least 55%, especially more preferably at least 60%, especially most preferably at least 65%, especially at least 70%, for example at least 75%.
[0670] Another indicator of plant condition is plant vitality. Plant vitality is reflected in several aspects, such as general visual appearance.
[0671] For foliar application, improved plant vigor can be characterized in particular by the following improved plant properties: improved plant vitality; and / or improved plant growth; and / or improved plant development; and / or improved visual appearance; and / or improved plant uprightness (fewer plant nodes / lodging and / or larger leaves; and / or larger size; and / or increased plant height; and / or increased tiller number; and / or increased lateral branch number; and / or increased number of flowers per plant; and / or increased shoot growth; and / or enhanced photosynthetic activity (e.g., based on increased stomatal conductance and / or increased CO2 assimilation rate)); and / or earlier flowering; and / or Or earlier fruiting; and / or earlier grain maturity; and / or fewer nonproductive tillers; and / or fewer dead basal leaves; and / or less supply (such as fertilizer or water) required; and / or greener leaves; and / or full maturity under a shortened plant growth period; and / or easier harvesting; and / or faster and more uniform maturity; and / or longer shelf life; and / or longer ears; and / or delayed senescence; and / or stronger and / or more productive tillers; and / or better component extractability; and / or improved seed quality (for sowing in the next seed production season); and / or reduced ethylene production and / or inhibited plant absorption of it.
[0672] Another indicator of plant condition is the “quality” of the plant and / or its products. According to the invention, quality improvement refers to a measurable or significant increase or improvement in certain plant characteristics, such as the content or composition of certain components, compared to plants produced under the same conditions but without the application of the mixtures of the invention. Quality improvement can be characterized in particular by the following improved properties of the plant or its products: increased nutrient content; and / or increased protein content; and / or increased oil content; and / or increased starch content; and / or increased fatty acid content; and / or increased metabolite content; and / or increased carotenoid content; and / or increased sugar content; and / or increased amounts of essential amino acids; and / or improved nutrient composition; and / or improved protein composition; and / or improved fatty acid composition; and / or improved metabolite composition; and / or improved carotenoid composition; and / or improved sugar composition; and / or improved amino acid composition; and / or improved or optimal fruit color; and / or improved leaf color; and / or higher storage capacity; and / or better processability of the harvested product.
[0673] Another indicator of plant condition is the plant's tolerance or resistance to biotic and / or abiotic stressors. Biotic and abiotic stresses, especially over longer periods, can have detrimental effects on plants.
[0674] Biological stress is caused by living organisms, while abiotic stress is caused by extreme environments, for example. According to the present invention, “enhanced tolerance or resistance to biological and / or abiotic stress factors” means (1.) that certain adverse effects caused by biological and / or abiotic stresses are reduced by a measurable or significant amount compared to plants exposed to the same conditions but not treated with the mixture of the present invention, and (2.) that the adverse effects are reduced not by the direct action of the mixture of the present invention on the stress factor, for example, by its fungicidal or insecticidal effect of directly killing microorganisms or pests, but by stimulating the plant’s own defensive response to said stress factor.
[0675] Adverse factors caused by biological stresses such as pathogens and pests are widely known and are caused by living organisms such as competing plants (e.g., weeds), microorganisms (e.g., plant pathogenic fungi and / or bacteria) and / or viruses.
[0676] Adverse effects caused by abiotic stress are also well known and can often be observed as reduced plant vigor (see above), such as smaller yields and / or less vigor. Examples of these two effects can be, in particular, scorched leaves, fewer flowers, premature maturity, delayed crop maturity, and reduced nutritional value.
[0677] Abiotic stresses can be caused by, for example, extreme temperatures such as heat or cold (thermal stress / cold stress); and / or large temperature variations; and / or seasonal temperature anomalies; and / or drought (drought stress); and / or extreme humidity; and / or high salinity (salt stress); and / or radiation (e.g., increased UV radiation due to ozone layer depletion); and / or increased ozone concentration (ozone stress); and / or organic pollution (e.g., phytotoxic amounts of pesticides); and / or inorganic pollution (e.g., heavy metal contaminants).
[0678] As a result of biotic and / or abiotic stress factors, the quantity and quality of plants affected by stress decrease. In terms of quality (as defined above), proliferation and development are usually severely affected, resulting in impacts on crops important for fruits or seeds. Protein synthesis, accumulation, and storage are largely affected by temperature; growth is slowed by almost all types of stress; and the synthesis of structural polysaccharides and storage polysaccharides are reduced or altered: these effects lead to reduced biomass (yield) and changes in the nutritional value of products.
[0679] As noted above, the aforementioned indicators of plant health can be interdependent and mutually consequential. For example, increased tolerance to biotic and / or abiotic stresses may lead to better plant vigor, such as better and larger crops, and thus increased yields. Conversely, a more developed root system may lead to increased tolerance to biotic and / or abiotic stresses. However, these interdependencies and interactions are neither fully known nor fully understood, and therefore the distinct indicators are described separately.
[0680] In one embodiment, the mixture of the present invention achieves increased yield of plants or their products. In another embodiment, the mixture of the present invention achieves enhanced vigor of plants or their products. In yet another embodiment, the mixture of the present invention achieves improved quality of plants or their products. In still another embodiment, the mixture of the present invention achieves enhanced tolerance and / or resistance to biotic stresses of plants or their products. In yet another embodiment, the mixture of the present invention achieves enhanced tolerance and / or resistance to abiotic stresses of plants or their products.
[0681] The present invention also relates to agricultural chemical compositions comprising an adjuvant and at least one compound I and at least one compound II, or a cell-free extract of compound II or at least one metabolite of it having a NI effect or a UI effect and / or a mutant of compound II having a NI effect or a UI effect and producing at least one metabolite as defined herein, or a metabolite or extract of a mutant of the present invention.
[0682] Agricultural chemical compositions contain an effective amount of NI or a plant health-effective amount of compound I. This amount can vary over a wide range and depends on various factors such as weather, target species, location, application method, soil type, the cultivated plant or material being treated, and climatic conditions.
[0683] The agricultural chemical composition contains an effective or plant-health-effective amount of compound II, or a cell-free extract thereof, or at least one metabolite of compound II having urease-inhibiting activity, and / or a mutant of compound II having urease-inhibiting activity and producing at least one metabolite as defined herein, or a urease-inhibiting metabolite or extract of such mutant. This amount can vary widely and depends on various factors such as the species of fungus or pest to be controlled, the cultivated plant or material being treated, and climatic conditions.
[0684] According to one embodiment, the user can mix the components of the composition of the present invention themselves in a spray can or any other type of container used for application (e.g., seed treatment drum, seed granulator, backpack sprayer), such as portions of a kit or portions of a binary or ternary mixture, and may add other adjuvants if appropriate. When live microorganisms form part of the kit, care must be taken that the selection and amount of other portions of the kit (e.g., chemical pesticides) and other adjuvants should not affect the viability of the microbial pesticide in the user-mixed composition. In particular, the compatibility of the corresponding microbial pesticide must be considered with respect to fungicides and solvents.
[0685] Therefore, one embodiment of the present invention is a kit for preparing useful pesticide compositions, the kit comprising a) a composition comprising compound I as defined herein and at least one adjuvant; and b) a composition comprising compound II as defined herein and at least one adjuvant; and optionally c) a composition comprising at least one adjuvant and optionally another active component III as defined herein.
[0686] The compounds, mixtures, or compositions of this invention can be converted into types commonly used in agrochemical compositions, such as solutions, emulsions, suspensions, powders, pastes, granules, molded products, capsules, and mixtures thereof. Examples of composition types are suspensions (SC, OD, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES, ME), capsules (e.g., CS, ZC), pastes, tablets, wettable powders or granules (WP, SP, WS, DP, DS), molded products (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticides (e.g., LN), and gel formulations for treating plant propagation materials such as seeds (e.g., GF). These and other composition types are defined in “Catalogue of pesticide formulation types and international coding system,” Technical Monograph, Vol. 2, 6th edition, May 2008, CropLife International.
[0687] The compositions are prepared in a known manner as described in Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, AgrowReports DS243, T&F Informa, London, 2005.
[0688] Suitable additives include solvents, liquid carriers, solid fillers, surfactants, dispersants, emulsifiers, wetting agents, auxiliary agents, solvents, penetration enhancers, protective colloids, adhesives, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, defoamers, colorants, viscous agents, and binders.
[0689] Suitable solvents and liquid carriers are water and organic solvents, such as medium to high boiling point mineral oil fractions, such as kerosene and diesel; oils of vegetable or animal origin; aliphatic, cyclic, and aromatic hydrocarbons, such as toluene, paraffin, tetrahydronaphthalene, and alkylated naphthalene; alcohols, such as ethanol, propanol, butanol, benzyl alcohol, and cyclohexanol; diols; DMSO; ketones, such as cyclohexanone; esters, such as lactates, carbonates, fatty acid esters, and γ-butyrolactone; fatty acids; phosphonates; amines; amides, such as N-methylpyrrolidone and fatty acid dimethylamide; and mixtures thereof.
[0690] Suitable solid fillers are mineral soils, such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, and magnesium oxide; polysaccharides, such as cellulose and starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and urea; and plant-derived products, such as cereal flour, bark flour, wood flour, and nut shell flour, as well as mixtures thereof.
[0691] Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic, and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. These surfactants can be used as emulsifiers, dispersants, solvents, wetting agents, penetration enhancers, protective colloids, or auxiliaries. Examples of surfactants are listed in McCutcheon's, Volume 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
[0692] Suitable anionic surfactants are alkali metal, alkaline earth metal, or ammonium salts of sulfonic acids, sulfuric acids, phosphoric acids, and carboxylic acids, as well as mixtures thereof. Examples of sulfonates are alkyl aryl sulfonates, diphenyl sulfonates, α-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates, or sulfosuccinamides. Examples of sulfates are sulfates of fatty acids and oils, sulfates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, or sulfates of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates and carboxylated alcohols or alkylphenol ethoxylates.
[0693] Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, glycosyl surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids, or fatty acid esters that have been alkoxylated by 1-50 equivalents. Ethylene oxide and / or propylene oxide can be used for alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucosamides or fatty acid chain alkanolamides. Examples of esters are fatty acid esters, glycerides, or monoglycerides. Examples of glycosyl surfactants are sorbitol, ethoxylated sorbitol, sucrose and glucose esters, or alkyl polyglucosides. Examples of polymeric surfactants are homopolymers or copolymers of vinylpyrrolidone, vinyl alcohol, or vinyl acetate.
[0694] Suitable cationic surfactants are quaternary surfactants, such as quaternary ammonium compounds having one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkyl betaines and imidazolines. Suitable block polymers are AB or ABA type block polymers containing blocks of polyethylene oxide and polypropylene oxide, or ABC type block polymers containing blocks of alkanols, polyethylene oxide, and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali metal salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamine or polyvinylamine.
[0695] Suitable adjuvants are compounds that possess negligible pesticide activity or even no pesticide activity themselves, but which improve the biological properties of compound I against the target analyte. Examples are surfactants, mineral or vegetable oils, and other adjuvants. Other examples are listed in Knowles, Adjuvants and Additives, Agrow Reports DS256, T&F Informa UK, 2006, Chapter 5.
[0696] Suitable thickeners are polysaccharides (such as xanthan gum and carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
[0697] Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones. Suitable antifreeze agents are ethylene glycol, propylene glycol, urea, and glycerin. Suitable defoamers are polysiloxanes, long-chain alcohols, and fatty acid salts. Suitable colorants (e.g., red, blue, or green) are low-water-soluble pigments and water-soluble dyes. Examples are inorganic colorants (e.g., iron oxide, titanium dioxide, ferric hexacyanate) and organic colorants (e.g., alizarin colorants, azo colorants, and phthalocyanine colorants). Suitable tackifiers or adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, polyacrylates, biowaxes or synthetic waxes, and cellulose ethers.
[0698] When live microorganisms form part of the composition, such compositions can be prepared by conventional means to contain at least one adjuvant (inert component) in addition to the active ingredient (see, for example, HDBurges: Formulation of Microbial Biopesticides, Springer, 1998). Suitable conventional types of such compositions are suspensions, powders, pastes, granules, molded products, capsules, and mixtures thereof. Examples of composition types are suspensions (SC, OD, FS), capsules (e.g., CS, ZC), pastes, tablets, wettable powders or granules (WP, SP, WS, DP, DS), molded products (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticides (e.g., LN), and gel formulations for treating plant propagation materials such as seeds (e.g., GF). It must be considered here that the choice of formulation type or adjuvant should not affect the viability of the microorganisms during the storage of the composition and when it is finally applied to soil, plants, or plant propagation materials. Suitable formulations are mentioned, for example, in WO2008 / 002371, US 6,955,912, and US 5,422,107.
[0699] Examples of suitable adjuvants are those mentioned earlier in this document, where care must be taken to ensure that the selection and amount of such adjuvants do not affect the activity of the microbial pesticide in the composition. Especially for fungicides and solvents, compatibility with the corresponding microorganisms of the microbial pesticide must be considered. Furthermore, compositions containing microbial pesticides may further contain stabilizers or nutrients and UV protectants. Suitable stabilizers or nutrients include, for example, α-tocopherol, trehalose, glutamate, potassium sorbate, and various sugars such as glucose, sucrose, lactose, and maltodextrin (HDBurges: Formulation of Microbial Biopesticides, Springer, 1998). Suitable UV protectants include, for example, inorganic compounds such as titanium dioxide, zinc oxide, and iron oxide pigments, or organic compounds such as benzophenones, benzotriazoles, and phenyltriazines. In addition to the adjuvants mentioned herein for compositions containing Compound I, the composition may contain 0.1-80% stabilizers or nutrients and 0.1-10% UV protectants.
[0700] Examples of composition types and their preparation are as follows:
[0701] i) Water-soluble concentrates (SL, LS)
[0702] Dissolve 10-60 wt% of Compound I and 5-15 wt% of wetting agent (e.g., alcohol alkoxylate) in water and / or a water-soluble solvent (e.g., alcohol) added to 100 wt%. The active substance dissolves upon dilution with water.
[0703] ii) Dispersible concentrate (DC)
[0704] Dissolve 5-25 wt% of Compound I and 1-10 wt% of a dispersant (e.g., polyvinylpyrrolidone) in an organic solvent (e.g., cyclohexanone) added to a concentration of 100 wt%. Dilute with water to obtain the dispersion. iii) Emulsifiable concentrate (EC)
[0705] Dissolve 15-70 wt% of Compound I and 5-10 wt% of emulsifier (e.g., calcium dodecylbenzenesulfonate and castor oil ethoxylate) in a water-insoluble organic solvent (e.g., an aromatic hydrocarbon) added to 100 wt%. Dilute with water to obtain an emulsion.
[0706] iv) Emulsions (EW, EO, ES)
[0707] 5-40 wt% of Compound I and 1-10 wt% of emulsifier (e.g., calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% of a water-insoluble organic solvent (e.g., an aromatic hydrocarbon). The mixture is then introduced into 100 wt% water using an emulsifier to form a homogeneous emulsion. The emulsion is diluted with water to obtain a final emulsion.
[0708] v) Suspension (SC, OD, FS)
[0709] In a stirred ball mill, 20-60 wt% of Compound I is subjected to underwater milling with the addition of 2-10 wt% dispersant and wetting agent (e.g., sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt% thickener (e.g., xanthan gum), and up to 100 wt% water to obtain a finely ground active substance suspension. The suspension is then diluted with water to obtain a stable active substance suspension. For FS type compositions, up to 40 wt% binder (e.g., polyvinyl alcohol) is added.
[0710] vi) Water-dispersible particles and water-soluble particles (WG, SG)
[0711] Compound I (50-80 wt%) is finely ground with up to 100 wt% dispersant and wetting agent (e.g., sodium lignin sulfonate and alcohol ethoxylate) and prepared into water-dispersible or water-soluble particles using industrial equipment (e.g., extruder, spray tower, fluidized bed). Diluting with water yields a stable dispersion or solution of the active substance.
[0712] vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
[0713] 50-80 wt% of Compound I was milled in a rotor-stator mill with the addition of 1-5 wt% dispersant (e.g., sodium lignosulfonate), 1-3 wt% wetting agent (e.g., alcohol ethoxylate), and up to 100 wt% solid support (e.g., silica gel). The mixture was diluted with water to obtain a stable dispersion or solution of the active substance.
[0714] viii) Gel (GW, GF)
[0715] In a stirred ball mill, 3-10 wt% of a dispersant (e.g., sodium lignin sulfonate), 1-5 wt% of a thickener (e.g., carboxymethyl cellulose), and 5-25 wt% of compound I were added and submerged in water to 100 wt% to obtain a fine suspension of the active substance. The suspension was then diluted with water to obtain a stable suspension of the active substance.
[0716] ix) Microemulsion (ME)
[0717] Add 5-20 wt% of Compound I to 5-30 wt% of an organic solvent blend (e.g., fatty acid dimethylamide and cyclohexanone), 10-25 wt% of a surfactant blend (e.g., alcohol ethoxylate and arylphenol ethoxylate), and 100 wt% of water. Stir the mixture for 1 hour to spontaneously generate a thermodynamically stable microemulsion.
[0718] x) Microcapsules (CS)
[0719] An oil phase comprising 5-50 wt% Compound I, 0-40 wt% water-insoluble organic solvent (e.g., aromatic hydrocarbons), and 2-15 wt% acrylic monomers (e.g., methyl methacrylate, methacrylic acid, and di- or triacrylates) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). Free radical polymerization initiated by a free radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% Compound I of the present invention, 0-40 wt% water-insoluble organic solvent (e.g., aromatic hydrocarbons), and isocyanate monomers (e.g., diphenylmethane-4,4'-diisocyanate) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). The addition of a polyamine (e.g., hexamethylenediamine) results in the formation of polyurea microcapsules. The monomer amount is 1-10 wt%. wt% refers to the entire CS composition.
[0720] xi) Sprinkleable powder (DP, DS)
[0721] 1-10% by weight of compound I is finely ground and thoroughly mixed with a solid support (e.g., finely crushed kaolin) added up to 100% by weight.
[0722] xii) Particles (GR, FG)
[0723] 0.5-30 wt% of Compound I is finely ground and combined with up to 100 wt% of a solid support (e.g., silicate). Granulation is achieved by extrusion, spray drying, or fluidized bed.
[0724] xiii) Ultra-low volume liquids (UL)
[0725] Dissolve 1-50% by weight of compound I in an organic solvent (e.g., an aromatic hydrocarbon) added up to 100% by weight.
[0726] Composition types i)-xiii) may optionally contain other adjuvants, such as 0.1-1 wt% bactericide, 5-15 wt% antifreeze, 0.1-1 wt% defoamer and 0.1-1 wt% colorant.
[0727] Composition types i)-vii) may optionally contain other adjuvants, such as 0.1-1 wt% bactericide, 5-15 wt% antifreeze, 0.1-1 wt% defoamer, 0.1-80% stabilizer or nutrient, 0.1-10% UV protectant and 0.1-1 wt% colorant.
[0728] Composition types i)-xi) may optionally contain other adjuvants, such as 0.1-1% by weight of bactericide, 5-15% by weight of antifreeze, 0.1-1% by weight of defoamer and 0.1-1% by weight of colorant.
[0729] Agricultural chemical compositions are typically characterized by containing an effective amount of the active ingredient as defined above. They typically contain 0.01-95% by weight, preferably 0.1-90% by weight, and especially 0.5-75% by weight of the active component, particularly the active substance.
[0730] For treating plant propagation material, especially seeds, seed treatment solutions (LS), suspension emulsions (SE), flowable concentrates (FS), dry treatment powders (DS), slurry treatment water-dispersible powders (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are commonly used.
[0731] Preferred examples of seed treatment formulations or premixed compositions for soil application are WS, LS, ES, FS, WG, or CS types.
[0732] The composition, after being diluted 2-10 times, provides an active ingredient concentration of 0.01-60% by weight, preferably 0.1-40% by weight, in ready-to-use formulations. Application can be carried out before or during sowing. Methods of applying or treating compound I and compound II, and their combinations, to plant propagating material, especially seeds, include seed dressing, coating, granulation, powdering, and soaking, as well as application within furrows of the propagating material. Preferably, compound I and compound II, or their combinations, are applied to the plant propagating material separately by methods that do not induce germination, such as seed dressing, granulation, coating, and powdering.
[0733] Premixed formulations for seed treatment applications typically contain 0.5-99.9%, particularly 1-95%, of the desired ingredient and 99.5-0.1%, particularly 99-5%, of solid or liquid adjuvants (e.g., including solvents such as water), wherein the adjuvants may be surfactants in amounts of 0-50%, particularly 0.5-40%, based on the premixed formulation. Although commercially available products are preferably formulated as concentrates (e.g., premixed compositions (formulations)), end users typically use diluted formulations (e.g., tank-mixed compositions).
[0734] Seed treatment methods for applying or treating plant propagating materials, particularly seeds, with the mixtures and compositions of the present invention are known in the art and include methods such as seed dressing, coating, granulation, and soaking of the propagating material. Such methods can also be used in the combinations of the present invention. In a preferred embodiment, the mixtures of the present invention are applied or treated with plant propagating materials in a manner that does not adversely affect germination. Therefore, examples of suitable methods for applying (or treating) plant propagating materials such as seeds are seed dressing, seed coating, or seed granulation, etc.
[0735] Preferred plant propagation materials are seeds, cuttings (i.e. stems), or bulbs.
[0736] Although the method of the present invention is believed to be applicable to seeds in any physiological state, it is preferred that the seeds be in a state sufficiently durable to avoid damage during the treatment. The seeds are typically field-harvested seeds; seeds extracted from the plant; and seeds separated from any rachis, stem, husk, and surrounding pulp or other non-seed plant material. The seeds are preferably also biologically stable to the extent that the treatment will not cause biological damage to them. The treatment is believed to be applied to the seeds at any time between seed harvesting and sowing, or during sowing (for seed-directed application). The seeds may also be coated with a coloring layer before or after the treatment.
[0737] In the process of treating propagation material, it is desirable for the components to be uniformly distributed in the mixture of the present invention and to adhere to the seeds. The treatment can proceed from a thin film (seed coating) containing the formulation, such as a mixture of active ingredients, on plant propagation material such as seeds—where the original size and / or shape is distinguishable—to an intermediate state (such as coating) and then to a thicker film (such as granulation with many layers of different materials (such as carriers, such as clay; different formulations, such as different formulations of other active ingredients; polymers; and colorants))—where the original shape and / or size can no longer be distinguished by change.
[0738] One aspect of the invention includes applying the mixture of the invention to plant propagation material in a targeted manner, which includes distributing the components of the mixture throughout the plant propagation material or only on a portion thereof, including distribution on only one side or a portion of one side. Those skilled in the art will understand these methods of application from the specifications provided in EP 954213B1 and WO 06 / 112700.
[0739] The mixture of the present invention can also be used in the form of "pills" or "granules" or a suitable substrate, and the treated pellets or substrate are placed or sown close to the plant propagation material. Such techniques are known in the art, particularly in EP 1124414, WO07 / 67042, and WO 07 / 67044. The application of the combination described herein to plant propagation material also includes protecting the plant propagation material treated with the combination of the present invention by placing one or more pesticide-containing granules close to the pesticide-treated seeds, wherein the amount of pesticide is such that the pesticide-treated seeds and the pesticide-containing granules together contain an effective dose of pesticide, and the pesticide dose contained in the pesticide-treated seeds is less than or equal to the maximum non-phytotoxic dose of the pesticide. Such techniques are known in the art, particularly in WO 2005 / 120226.
[0740] Applying these combinations to seeds also includes controlled-release coatings on seeds, wherein the components of these combinations are incorporated into materials that release these components over time. Examples of controlled-release seed treatment technologies are generally known in the art and include polymer films, waxes, or other seed coatings, wherein these components may be incorporated into controlled-release materials or applied between material layers, or both.
[0741] Seeds can be treated in any desired order or simultaneously by applying compounds present in the mixtures of the present invention to them.
[0742] Seed treatment is performed on unsown seeds, and the term "unsown" is intended to include seeds at any stage between seed harvesting and sowing in the soil to germinate and grow into plants.
[0743] Treatment of unsown seeds does not intend to include practices in which the active ingredients are applied to the soil, but does include any application practices in the planting process that target the seeds.
[0744] Preferably, this treatment is performed before seed sowing, so that the sown seeds have already been pretreated with the combination. Seed coating or seed granulation is particularly preferred in the treatment of the combinations of the present invention. As a result of this treatment, the components of each combination adhere to the seeds and can therefore be used for pest control.
[0745] The treated seeds can be stored, disposed of, sown, and cultivated in the same way as seeds treated with any other active ingredient.
[0746] The present invention relates in particular to a method for protecting plant propagation material from pests and / or improving the health of plants grown from said plant propagation material, wherein soil in which the plant propagation material is sown is treated with an effective amount of the mixture of the present invention.
[0747] The present invention particularly relates to a method for protecting plant propagation material from pests, wherein soil in which plant propagation material is sown is treated with an effective amount of the mixture of the present invention.
[0748] The present invention particularly relates to a method for protecting plant propagation material from harmful fungi, wherein soil in which plant propagation material is sown is treated with an effective amount of the mixture of the present invention.
[0749] The present invention relates in particular to a method for protecting plant propagation material from animal pests (insects, mites or nematodes), wherein soil in which plant propagation material is sown is treated with an effective amount of the mixture of the present invention.
[0750] In one implementation, the treatment is performed as a foliar application.
[0751] In another implementation, the treatment is carried out as a soil application.
[0752] In one implementation, the treatment is performed as a seed treatment.
[0753] When used for plant protection, the total amount of active ingredient applied depends on the desired effect and ranges from 0.001 to 10 kg / ha, preferably 0.005 to 2 kg / ha, more preferably 0.05 to 0.9 kg / ha, and especially 0.1 to 0.75 kg / ha.
[0754] When used in plant protection through seed treatment, the amount of the mixture of the present invention (based on the total weight of the active components) is 0.01-10 kg, preferably 0.1-1000 g, more preferably 1-100 g / 100 kg of plant propagation material (preferably seeds).
[0755] When used to protect materials or store products, the amount of active ingredient applied depends on the type of area to be treated and the desired effect. Commonly used application rates for material protection include, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of treated material.
[0756] Various types of oils, wetting agents, adjuvants, fertilizers or micronutrients, and other pesticides (e.g., herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides) can be added as premixes to mixtures or compositions containing them, or, if appropriate, added (in a barrel mix) immediately before use. These agents can be mixed with the mixtures or compositions of the present invention at a weight ratio of 1:100-100:1, preferably 1:10-10:1.
[0757] According to one embodiment, the polyether polymethylsiloxane copolymer can be added to the mixture or composition of the present invention, preferably at a weight ratio of 1:100-100:1, more preferably 1:10-10:1, and especially 1:5-5:1, based on the total weight of compound I and compound II.
[0758] According to another embodiment, mineral oil or vegetable oil may be added to the mixture or composition of the present invention, preferably in a weight ratio of 1:100-100:1, more preferably 1:10-10:1, and especially 1:5-5:1, based on the total weight of compound I and compound II.
[0759] Users typically use the mixtures or compositions of this invention in pre-dosing devices, backpack sprayers, spray cans, spray aircraft, or irrigation systems. The agrochemical composition is usually formulated with water, buffers, and / or other adjuvants to the desired application concentration to obtain a ready-to-use spray or the agrochemical composition of this invention. 20-2000 liters, preferably 50-400 liters, of ready-to-use spray are typically applied per hectare of agricultural land.
[0760] In one embodiment, at least one compound I and at least one compound II are applied simultaneously, i.e., as a mixture or separately, or sequentially, to soil, plants, or plant propagules.
[0761] Furthermore, we found that, compared with the application of each component alone, simultaneous, i.e., combined or separate, application of solid carrier A containing at least one active compound I and solid carrier B containing at least one active compound II, or sequential application of solid carrier A containing at least one active compound I and solid carrier B containing at least one active compound II, synergistically improved the efficacy of pest control, plant health improvement, or nitrification inhibition.
[0762] In one embodiment, compound I and compound II are present in synergistically effective amounts.
[0763] When at least one compound I and at least one compound II are administered sequentially, the time between the two administrations can vary, for example, from 2 hours to 7 days. 0.25 hours to 30 days, preferably 0.5 hours to 14 days, particularly 1 hour to 7 days or 1.5 hours to 5 days, and even more preferably a wider range within the range of 2 hours to 1 day, are also possible.
[0764] In mixtures and compositions, the proportions of compounds are advantageously selected to produce synergistic effects.
[0765] The term “synergistic effect” should be understood, in particular, as defined by the Colby formula (Colby, SR, “Calculating the synergistic and antagonistic responses of herbicide combinations”, Weeds, 15, pp. 20-22, 1967).
[0766] The term "synergistic effect" should also be understood as the effect defined by the Tammes method (Tammes, PML, "Isoboles, a graphic representation of synergism in pesticides", Netherl. J. Plant Pathol. 70, 1964).
[0767] According to the present invention, the weight ratios and percentages used for biological extracts are based on the total weight of the dry content (solid material) of the respective extracts.
[0768] For mixtures of the present invention comprising compound I (nitration inhibitor) and compound II (UI), the weight ratio of compound I to compound II generally depends on the performance of the active substances used, and is typically 1:1000-1000:1, often 1:500-500:1, preferably 1:250-250:1, more preferably 1:100-100:1, most preferably 1:70-70:1, particularly preferably 1:50-50:1, and particularly more preferably 1: 30-30:1, particularly preferred 1:20-20:1, especially 1:15-15:1, especially preferred 1:10-10:1, especially more preferred 1:8-8:1, especially preferred 1:6.5-6.5:1, especially 1:5-5:1, particularly preferred 1:4-4:1, particularly more preferred 1:3-3:1, particularly preferred 2.5:1-1:2.5, especially 1:2-2:1, for example 1:1.5-1.5:1. For the mixtures of the present invention, the weight ratio of compound I to compound II generally depends on the properties of the active substances used, and it is generally no greater than 1000:1, often no greater than 250:1, preferably no greater than 100:1, more preferably no greater than 50:1, most preferably no greater than 30:1, particularly preferably no greater than 15:1, particularly more preferably no greater than 8:1, particularly most preferably no greater than 4:1, especially no greater than 2:1, particularly preferably no greater than 1:1, particularly more preferably no greater than 1:2, particularly most preferably no greater than 1:4, especially no greater than 1:8, particularly preferably no greater than 1:15, particularly more preferably no greater than 1:30, particularly most preferably no greater than 1:50, particularly no greater than 1:100, for example preferably no greater than 1:250, for example no greater than 1:1000. For the mixtures of the present invention, the weight ratio of compound I to compound II generally depends on the properties of the active substances used, and is generally at least 1000:1, often at least 250:1, preferably at least 100:1, more preferably at least 50:1, most preferably at least 30:1, particularly preferably at least 15:1, particularly more preferably at least 8:1, particularly most preferably at least 4:1, especially at least 2:1, particularly preferably at least 1:1, particularly more preferably at least 1:2, particularly most preferably at least 1:4, especially at least 1:8, especially preferably at least 1:15, especially more preferably at least 1:30, especially most preferably at least 1:50, especially at least 1:100, for example preferably at least 1:250, for example at least 1:1000.
[0769] In another preferred embodiment, compound I and compound II are present in a weight ratio of 250:1-1:250, preferably 100:1-1:100, more preferably 50:1-1:50, more preferably 30:1-1:30, most preferably 15:1-1:15, particularly 8:1-1:8, especially preferably 4:1-1:4, especially more preferably 2:1-1:2, and especially most preferably 1.5:1-1:1.5.
[0770] In another preferred embodiment, compound I and compound II are present in a weight ratio of 250:1-1:250, preferably 100:1-1:100, more preferably 50:1-1:50, more preferably 30:1-1:30, most preferably 15:1-1:15, particularly 8:1-1:8, especially preferably 4:1-1:4, especially more preferably 2:1-1:2, and especially most preferably 1.5:1-1:1.5, wherein the total weight of compound II is based on the amount of solid material (dry matter) of compound II.
[0771] In another preferred embodiment, compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-6.5:1, more preferably 1000:1-6.5:1, even more preferably 300:1-6.5:1, most preferably 100:1-6.5:1, particularly 75:1-6.5:1, especially preferably 55:1-6.5:1, especially more preferably 40:1-6.5:1, and especially most preferably 25:1-6.5:1.
[0772] In another preferred embodiment, compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-13:1, more preferably 1000:1-13:1, even more preferably 300:1-13:1, most preferably 100:1-13:1, particularly 75:1-13:1, especially preferably 55:1-13:1, especially more preferably 40:1-13:1, and especially most preferably 25:1-13:1.
[0773] In another preferred embodiment, compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-19:1, more preferably 1000:1-19:1, even more preferably 300:1-19:1, most preferably 100:1-19:1, particularly 75:1-19:1, especially preferably 55:1-19:1, especially more preferably 40:1-19:1, and especially most preferably 25:1-19:1.
[0774] In another preferred embodiment, compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-30:1, more preferably 1000:1-30:1, even more preferably 300:1-30:1, most preferably 100:1-30:1, particularly 75:1-30:1, especially preferably 55:1-30:1, and even more preferably 40:1-30:1.
[0775] In another preferred embodiment, compound I and compound II are present in a weight ratio of 10000:1-1:100, preferably 5000:1-45:1, more preferably 1000:1-45:1, even more preferably 300:1-45:1, most preferably 100:1-45:1, particularly 75:1-45:1, and especially preferably 55:1-45:1.
[0776] In another preferred embodiment, compound I and compound II are present in a weight ratio of 150:1-6.5:1, preferably 100:1-19:1, more preferably 75:1-25:1, even more preferably 70:1-30:1, most preferably 65:1-35:1, particularly 60:1-40:1, especially preferably 55:1-45:1, and even more preferably 53:1-47:1.
[0777] In another preferred embodiment, compound I and compound II are present in a weight ratio of 200:1-6.5:1, preferably 120:1-13:1, more preferably 75:1-19:1, even more preferably 60:1-19:1, most preferably 50:1-22:1, particularly 45:1-25:1, especially preferably 40:1-30:1, and especially more preferably 38:1-32:1.
[0778] In another preferred embodiment, compound I and compound II are present in a weight ratio of 150:1-1:1, preferably 70:1-6.5:1, more preferably 45:1-8:1, even more preferably 40:1-10:1, most preferably 35:1-13:1, particularly 30:1-15:1, especially preferably 25:1-17:1, and especially more preferably 23:1-19:1.
[0779] In another preferred embodiment, compound I and compound II are present in a weight ratio of 60:1 to 1:100, preferably 60:1 to 1:10, more preferably 60:1 to 1:1, even more preferably 60:1 to 3:1, most preferably 60:1 to 6.5:1, particularly 60:1 to 13:1, especially preferably 60:1 to 19:1, especially more preferably 60:1 to 25:1, especially most preferably 60:1 to 30:1, for example preferably 60:1 to 35:1, for example more preferably 60:1 to 40:1, for example 60:1 to 45:1.
[0780] In another preferred embodiment, compound I and compound II are present in a weight ratio of 45:1-1:100, preferably 45:1-1:10, more preferably 45:1-1:1, even more preferably 45:1-3:1, most preferably 45:1-6.5:1, particularly 45:1-13:1, especially preferably 45:1-19:1, especially more preferably 45:1-25:1, especially most preferably 45:1-30:1, for example 45:1-35:1. In another preferred embodiment, compound I and compound II are present in a weight ratio of 30:1-1:100, preferably 30:1-1:10, more preferably 30:1-1:1, even more preferably 30:1-3:1, most preferably 30:1-6.5:1, especially 30:1-13:1, particularly preferably 30:1-19:1, especially more preferably 30:1-25:1.
[0781] According to other embodiments of the binary mixture and composition, the weight ratio of compound I to compound II is generally in the range of 1000:1 to 1:1, often 100:1 to 1:1, frequently 50:1 to 1:1, preferably 20:1 to 1:1, more preferably 10:1 to 1:1, even more preferably 4:1 to 1:1, especially in the range of 2:1 to 1:1.
[0782] According to other embodiments of the binary mixture and composition, the weight ratio of compound I to compound II is generally in the range of 1:1 to 1:1000, often 1:1 to 1:100, frequently 1:1 to 1:50, preferably 1:1 to 1:20, more preferably 1:1 to 1:10, even more preferably 1:1 to 1:4, especially in the range of 1:1 to 1:2.
[0783] According to other embodiments of the mixture and composition, the weight ratio of compound I and compound II generally depends on the properties of the active component used, and it is generally in the range of 1:10,000-10,000:1, often 1:100-10,000:1, preferably 1:100-5,000:1, more preferably 1:1-1,000:1, even more preferably 1:1-500:1, especially in the range of 10:1-300:1.
[0784] According to other embodiments of the mixture and composition, the weight ratio of compound I to compound II is generally in the range of 20,000:1 to 1:10, often 10,000:1 to 1:1, frequently 5,000:1 to 5:1, preferably 5,000:1 to 10:1, more preferably 2,000:1 to 30:1, even more preferably 2,000:1 to 100:1, and especially in the range of 1,000:1 to 100:1.
[0785] According to other embodiments of the mixture and composition, the weight ratio of compound I to compound II is generally in the range of 1:20,000-10:1, often 1:10,000-1:1, frequently 1:5,000-1:5, preferably 1:5,000-1:10, more preferably 1:2,000-1:30, even more preferably 1:2,000-1:100, and especially in the range of 1:1,000-1:100.
[0786] In the ternary mixture, i.e., the composition of the present invention comprising compound I, compound II and compound III, the weight ratio of compound I to compound II depends on the properties of the active substances used, and is generally in the range of 1:100-100:1, often 1:50-50:1, preferably 1:20-20:1, more preferably 1:10-10:1, especially in the range of 1:4-4:1, and the weight ratio of compound I to compound III is generally in the range of 1:100-100:1, often 1:50-50:1, preferably 1:20-20:1, more preferably 1:10-10:1, especially in the range of 1:4-4:1.
[0787] If necessary, any other active compound may be added to compound I in a ratio of 20:1 to 1:20.
[0788] These proportions are also suitable for the mixtures of the present invention applied via seed treatment.
[0789] In other specific embodiments, the mixtures or compositions or packages of the present invention may additionally contain fertilizer. When the mixture or package containing compound I (nitrification inhibitor) and compound II (UI) is used with fertilizer, or when the mixture is provided in combination with fertilizer, the mixture may be provided or used as an agricultural chemical mixture.
[0790] For the purposes of this invention, "agricultural chemical mixture" refers to a combination of at least three or more compounds. However, the term is not limited to a physical mixture containing three or more compounds, but refers to any formulation of said compounds whose use may be related to time and / or place.
[0791] Agricultural chemical mixtures can be prepared separately, but applied in a time-dependent manner, i.e., simultaneously or sequentially, with the time intervals between sequential applications allowing for the combined action of the compounds.
[0792] Furthermore, users can mix the various compounds of the agricultural chemical mixture of the present invention themselves in a suitable mixing device, such as the portions of a package or the portions of the mixture. In specific embodiments, other adjuvants may be added if appropriate.
[0793] The term "fertilizer" should be understood as a compound applied to promote the growth of plants and fruits. Fertilizers are typically applied through the soil (to be absorbed by plant roots), through soil substitutes (also to be absorbed by plant roots), or through foliar feeding (to be absorbed through the leaves). The term also includes mixtures of one or more different types of fertilizers as described below.
[0794] The term "fertilizer" can be further divided into several categories, including: a) organic fertilizers (composed of plant / animal matter), b) inorganic fertilizers (composed of chemicals and minerals) and c) urea-containing fertilizers.
[0795] Organic fertilizers include manure such as liquid fertilizer, semi-liquid fertilizer, biogas slurry, stable manure or straw manure, slurry, liquid manure, sewer sludge, vermicompost, peat, seaweed, compost, sewage, and guano. Green manure crops (fertilizer crops) are also commonly planted to add nutrients (especially nitrogen) to the soil. Manufactured organic fertilizers include, for example, compost, blood meal, bone meal, and seaweed extracts. Other examples are enzyme-digested protein, fish meal, and feather meal. Decomposed crop residues from previous years are another source of fertility.
[0796] Inorganic fertilizers are typically manufactured using chemical methods (such as the Haber-Bosch process), which also utilize natural sediments but chemically modify them (e.g., by concentrating superphosphate). Natural inorganic fertilizers include sodium nitrate, rock phosphates, limestone, potassium sulfate, potassium chloride, and potassium chloride.
[0797] Typical solid fertilizers are in crystalline, granular, or pellet form. Typical nitrogen-containing inorganic fertilizers include ammonium nitrate, calcium ammonium nitrate, ammonium sulfate, ammonium thionitrate, calcium nitrate, diammonium hydrogen phosphate, monoammonium phosphate, ammonium thiosulfate, and calcium cyanamide.
[0798] Inorganic fertilizers can be categorized as NPK fertilizers. "NPK fertilizers" are inorganic fertilizers formulated at appropriate concentrations, containing the three main nutrients nitrogen (N), phosphorus (P), and potassium (K), and usually also sulfur (S), magnesium (Mg), calcium (Ca), and trace elements. "NK fertilizers" contain two main nutrients, nitrogen (N) and potassium (K), and usually also sulfur (S), magnesium (Mg), calcium (Ca), and trace elements. "NP fertilizers" contain two main nutrients, nitrogen (N) and phosphorus (P), and usually also sulfur (S), magnesium (Mg), calcium (Ca), and trace elements.
[0799] In specific implementations, the urea-containing fertilizer may be formaldehyde urea, UAN, urea sulfur, stabilized urea, urea-based NPK fertilizer, or urea ammonium sulfate. It also includes the use of urea as a fertilizer. When using or providing urea-containing fertilizers or urea, it is particularly preferred that urease inhibitors as defined above may be added, or they may be present additionally, or used simultaneously or in combination with urea-containing fertilizers.
[0800] Fertilizers can be provided in any suitable form, such as as coated or uncoated granules, in liquid or semi-liquid form, as sprayable fertilizers, or via drip irrigation.
[0801] A wide range of materials can be provided for coated fertilizers. For example, coating can be applied to granular or particulate nitrogen (N) fertilizers or multinutrient fertilizers. Urea is typically used as the base material for most coated fertilizers. However, the invention also includes other base materials for coated fertilizers—any fertilizer as defined herein. In some embodiments, elemental sulfur can be used as the fertilizer coating. This coating can be carried out by spraying molten sulfur onto urea granules and then applying a sealing wax to seal any cracks in the coating. In another embodiment, the sulfur layer can be covered with an organic polymer layer, preferably a thin layer of organic polymer. In yet another embodiment, the coated fertilizer is preferably a physical mixture of coated and uncoated fertilizers.
[0802] Other coated fertilizers included can be provided by reacting a resin-based polymer on the surface of the fertilizer particles. Another example of providing coated fertilizers includes the use of a low-permeability polyethylene polymer in combination with a high-permeability coating.
[0803] In specific embodiments, the composition and / or thickness of the fertilizer coating can be adjusted to control the nutrient release rate, for example, for a specific application. The duration of nutrient release from a specific fertilizer can vary, for example, from several weeks to several months. Therefore, nitrification inhibitors and compound II (UI) can be adapted to be present in mixtures with the coated fertilizer. Particularly feasible is that nutrient release involves or accompanies the release of the nitrification inhibitors and compound II (UI) of the present invention.
[0804] Coated fertilizers can be provided as controlled-release fertilizers (CRFs). In specific embodiments, these controlled-release fertilizers are fully coated NPK fertilizers that are homogeneous and typically exhibit a predetermined long-term release. In other embodiments, CRFs can be provided as blended controlled-release fertilizer products that may contain coated, uncoated, and / or slow-release components. In some embodiments, these coated fertilizers may additionally contain micronutrients. In specific embodiments, these fertilizers can exhibit a predetermined long-term release, such as in the case of NPK fertilizers.
[0805] Additional feasible examples of CRF include combination-release fertilizers. These fertilizers typically exhibit a predetermined release combination (e.g., high / standard / low) and a predetermined long-term duration. In an exemplary embodiment, fully encapsulated NPK, Mg, and micronutrients can be delivered in a combination-release manner.
[0806] Another feasible approach is a double-coating method or a coated fertilizer based on programmed release.
[0807] In other embodiments, the fertilizer mixture may be provided as a slow-release fertilizer or may contain or contain slow-release fertilizer. The fertilizer may be released, for example, over any suitable time period, such as 1-5 months, preferably up to 3 months. Typical examples of slow-release fertilizer components are IBDU (isobutylene diurea), for example containing about 31-32% nitrogen, of which 90% is water-insoluble; or UF, i.e., a urea-formaldehyde product containing about 38% nitrogen, of which about 70% can be provided as water-insoluble nitrogen; or CDU (carbaryl diurea) containing about 32% nitrogen; or MU (methylene urea) containing about 38-40% nitrogen, of which 25-60% is typically cold water-insoluble nitrogen; or MDU (methylene diurea) containing about 40% nitrogen. The fertilizer mixture may contain less than 25% nitrogen that is insoluble in cold water; or MO (hydroxymethylurea) containing about 30% nitrogen, which is generally available in solution; or DMTU (dimethylenetriurea) containing about 40% nitrogen, of which less than 25% is insoluble in cold water; or TMTU (trimethylenetetraurea), which may be provided as a component of UF products; or TMPU (trimethylenepentaurea), which may also be provided as a component of UF products; or UT (urea triazine ketone solution), which generally contains about 28% nitrogen. The fertilizer mixture may also be a long-term nitrogen fertilizer containing acetylenide and at least one other organic nitrogen fertilizer selected from methyleneurea, isobutylene diurea, crotonyl diurea, substituted triazine ketones, 1,3-dicarbamoylurea (triuret), or mixtures thereof.
[0808] Any of the fertilizers or fertilizer forms described above can be suitably combined. For example, slow-release fertilizers can be provided as coated fertilizers. They can also be combined with other fertilizers or fertilizer types. This also applies to the presence of the nitrification inhibitor or compound II (UI) of the present invention, which can be adapted to the form and chemical properties of the fertilizer and thus can be provided such that its release accompanies the release of the fertilizer, for example, at the same time or at the same frequency. Furthermore, the present invention includes fertilizers or fertilizer forms as defined above in combination with nitrification inhibitors and compound II (UI) as defined above, and further in combination with urease inhibitors as defined above. Such combinations can be provided in coated or uncoated form and / or in slow-release or fast-release form. Combinations with coated slow-release fertilizers are preferred. In other embodiments, different release schemes are also used, such as slower or faster releases.
[0809] As used herein, the term "drip irrigation fertilization" refers to the application of fertilizer, optional soil conditioner, and optional other water-soluble products, along with water, through an irrigation system to plants or sites where plants are growing or intended to grow, or soil substitutes as defined below. For example, liquid fertilizer or dissolved fertilizer may be provided directly to plants or sites where plants are growing or intended to grow via drip irrigation fertilization. Similarly, the nitrification inhibitors of the present invention, or in combination with additional nitrification inhibitors, may be provided to plants or sites where plants are growing or intended to grow via drip irrigation fertilization. The fertilizers and nitrification inhibitors of the present invention, or in combination with additional nitrification inhibitors, may be provided together, for example, dissolved in the same feed or package of the irrigated material (typically water). In other embodiments, the fertilizers and nitrification inhibitors may be provided at different times. For example, the fertilizer may be drip-dried first, followed by the mixture or composition of the present invention, or preferably, the mixture or composition of the present invention may be drip-dried first, followed by the fertilizer. The time intervals for these activities follow the time intervals described above for the application of fertilizers and nitrification inhibitors, for example, from 0.25 hours to 30 days, preferably from 0.5 hours to 14 days, particularly from 1 hour to 7 days or 1.5 hours to 5 days, and even more preferably from 2 hours to 1 day. It is also feasible to repeatedly drip-apply the fertilizers of the present invention and mixtures or compositions thereof, either together or intermittently, for example every 2 hours, 6 hours, 12 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days or longer.
[0810] In a further preferred embodiment, the fertilizer may be applied first to the soil or plants, followed by the mixture or composition of the present invention, or preferably, the mixture or composition of the present invention may be applied first to the soil or plants, followed by the fertilizer. The time intervals between these activities follow the time intervals described above for the application of fertilizer and nitrification inhibitor, for example, from 0.25 hours to 30 days, preferably from 0.5 hours to 14 days, particularly from 1 hour to 7 days or 1.5 hours to 5 days, and even more preferably from 2 hours to 1 day. It is also feasible to repeatedly apply the fertilizer and the mixture or composition of the present invention, either together or intermittently, for example every 2 hours, 6 hours, 12 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days, or longer.
[0811] In a particularly preferred embodiment, the fertilizer is an ammonium-containing fertilizer.
[0812] The term “at least one” should be understood as 1, 2, 3 or more compounds selected from fertilizers as defined above and nitrification inhibitors (also referred to as compound I) and urease inhibitors (also referred to as compound II) as defined above.
[0813] In a preferred embodiment of the present invention, the solid carrier A is fertilizer.
[0814] In another preferred embodiment of the present invention, the solid carrier A is a fertilizer selected from ammonium nitrate, calcium ammonium nitrate, ammonium sulfate, ammonium thionitrate, calcium nitrate, diammonium hydrogen phosphate, monoammonium phosphate, ammonium thiosulfate, calcium cyanamide, NPK fertilizer, NK fertilizer, NP fertilizer, urea and urea sulfate.
[0815] In another preferred embodiment of the present invention, the solid carrier A is a fertilizer selected from ammonium nitrate, calcium ammonium nitrate, ammonium sulfate, ammonium thionitrate, calcium nitrate, diammonium hydrogen phosphate, monoammonium phosphate, ammonium thiosulfate, calcium cyanamide, NPK fertilizer, NK fertilizer, and NP fertilizer.
[0816] In another preferred embodiment of the invention, the solid carrier B is fertilizer.
[0817] In another preferred embodiment of the present invention, the solid carrier B is a fertilizer selected from ammonium nitrate, calcium ammonium nitrate, ammonium sulfate, ammonium thionitrate, calcium nitrate, diammonium hydrogen phosphate, monoammonium phosphate, ammonium thiosulfate, calcium cyanamide, NPK fertilizer, NK fertilizer, NP fertilizer, urea, and urea sulfate.
[0818] In another preferred embodiment of the invention, the solid carrier B is urea or urea sulfate.
[0819] In another preferred embodiment of the present invention, solid carrier A and solid carrier B are fertilizers.
[0820] In another preferred embodiment of the present invention, solid carrier A and solid carrier B are fertilizers selected from ammonium nitrate, calcium ammonium nitrate, ammonium sulfate, ammonium thionitrate, calcium nitrate, diammonium hydrogen phosphate, monoammonium phosphate, ammonium thiosulfate, calcium cyanamide, NPK fertilizer, NK fertilizer, NP fertilizer, urea and urea sulfate.
[0821] In another preferred embodiment of the present invention, solid carrier A is urea and solid carrier B is urea.
[0822] In another preferred embodiment of the invention, solid carrier A is ammonium sulfate or ammonium thionitrate and solid carrier B is urea.
[0823] In another preferred embodiment of the invention
[0824] - Solid carrier A is ammonium sulfate and / or ammonium thionitrate, and
[0825] Compound I is 3,4-dimethylpyrazole phosphate and / or 4,5-dimethylpyrazole phosphate (DMPP, ENTEC), and
[0826] -Solid carrier B is urea, and
[0827] - Compound II is selected from N-n-butylthiophosphoric triamine (NBPT) (P.26), N-n-propylthiophosphoric triamine (NPPT) (P.27), a mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) (P.28), a mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT), wherein NBPT is contained in an amount of 50-90% by weight and NPPT is contained in an amount of 10-50% by weight based on the total amount of active urease inhibitor (P.29), phenyl diaminophosphate (PPD / PPDA) (P.30), and 2-nitrophenylphosphoric triamine (2-NPT) (P.31).
[0828] In another preferred embodiment of the invention
[0829] - Solid carrier A is ammonium sulfate and / or ammonium thionitrate, and
[0830] Compound I is 3,4-dimethylpyrazole phosphate and / or 4,5-dimethylpyrazole phosphate (DMPP, ENTEC), and
[0831] -Solid carrier B is urea, and
[0832] - Compound II is a mixture containing N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) (P.28).
[0833] In another preferred embodiment of the invention
[0834] - Solid carrier A is ammonium sulfate and / or ammonium thionitrate, and
[0835] Compound I is 3,4-dimethylpyrazole phosphate and / or 4,5-dimethylpyrazole phosphate (DMPP, ENTEC), and
[0836] -Solid carrier B is urea, and
[0837] - Compound II is N-n-butylthiophosphoric triamine (NBPT) (P.26).
[0838] In another preferred embodiment of the invention
[0839] - Solid carrier A is ammonium sulfate and / or ammonium thionitrate and / or calcium ammonium nitrate, and
[0840] - Compound I is a potassium, sodium, or ammonium salt of DMPSA1 and / or DMPSA2, and
[0841] -Solid carrier B is urea, and
[0842] - Compound II is selected from N-n-butylthiophosphoric triamine (NBPT) (P.26), N-n-propylthiophosphoric triamine (NPPT) (P.27), a mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) (P.28), a mixture comprising N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT), wherein NBPT is contained in an amount of 50-90% by weight and NPPT is contained in an amount of 10-50% by weight based on the total amount of active urease inhibitor (P.29), phenyl diaminophosphate (PPD / PPDA) (P.30), and 2-nitrophenylphosphoric triamine (2-NPT) (P.31).
[0843] In another preferred embodiment of the invention
[0844] - Solid carrier A is ammonium sulfate and / or ammonium thionitrate and / or calcium ammonium nitrate, and
[0845] - Compound I is a potassium, sodium, or ammonium salt of DMPSA1 and / or DMPSA2, and
[0846] -Solid carrier B is urea, and
[0847] - Compound II is a mixture containing N-n-butylthiophosphoric triamine (NBPT) and N-n-propylthiophosphoric triamine (NPPT) (P.28).
[0848] In another preferred embodiment of the invention
[0849] - Solid carrier A is ammonium sulfate and / or ammonium thionitrate and / or calcium ammonium nitrate, and
[0850] - Compound I is a potassium, sodium, or ammonium salt of DMPSA1 and / or DMPSA2, and
[0851] -Solid carrier B is urea, and
[0852] - Compound II is N-n-butylthiophosphoric triamine (NBPT) (P.26).
[0853] According to another embodiment, the solid carrier A may also be mineral soil, such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; plant-derived products, such as grain flour, bark flour, wood flour, nut shell flour, and mixtures thereof.
[0854] According to another embodiment, the solid carrier B may also be mineral soil, such as silicates, silica gel, talc, kaolin, limestone, lime, chalk, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; plant-derived products, such as grain flour, bark flour, wood flour, nut shell flour, and mixtures thereof.
[0855] In a specific implementation, the treatment can be performed during all suitable growth stages of the plant as defined herein. For example, the treatment can be performed during the BBCH main growth stage.
[0856] The term "BBCH Major Growth Stage" refers to the extended BBCH standard, a system for uniformly encoding phenological growth stages in all monocotyledonous and dicotyledonous plant varieties, where the entire developmental cycle of a plant is subdivided into longer, clearly identifiable and distinguishable developmental stages. The BBCH standard uses a decimal coding system, which is divided into major and minor growth stages. The abbreviation BBCH is derived from the Federal Biological Research Centre for Agriculture and Forestry (Germany), the Bundessortenamt (Germany), and the chemical industry.
[0857] In one embodiment, the present invention relates to a method for reducing nitrification, comprising treating plants growing on soil or soil substitutes and / or sites where plants grow or are intended to grow with the mixture or composition of the present invention during the growth stage (GS) of plants between GS 00-GS>BBCH 99, preferably between GS 00-GS 65BBCH (e.g., when fertilizing after harvesting apples in the fall).
[0858] In one embodiment, the present invention relates to a method for reducing nitrification, comprising treating plants growing on soil or soil substitutes and / or sites where plants are growing or intended to grow at a growth stage (GS) between GS 00 and GS 45, preferably between GS 00 and GS 40BBCH, with a mixture or composition of the present invention (hereinafter referred to as mixture (Q)).
[0859] In a preferred embodiment, the present invention relates to a method for reducing nitrification, comprising treating plants growing on soil or soil substitutes and / or sites where plants are growing or intended to grow with mixtures or compositions of the present invention during the early growth stages (GS), particularly GS 00-GS 05, or GS 00-GS 10, or GS 00-GS 15, or GS 00-GS 20, or GS 00-GS 25 or GS 00-GS 33BBCH. In a particularly preferred embodiment, the method for reducing nitrification comprises treating plants growing on soil or soil substitutes and / or sites where plants are growing or intended to grow with mixtures or compositions of the present invention during the growth stages, including GS 00.
[0860] In another specific embodiment of the invention, the mixture or composition of the invention is applied to plants growing on soil or soil substitutes and / or to sites where the plants are growing or intended to grow, during the growth stage of the plants between GS 00 and GS 55BBCH.
[0861] In another embodiment of the invention, the mixture or composition of the invention is applied to the plant growing on soil or a soil substitute and / or the site where the plant is growing or intended to grow during the growth stage of the plant between GS 00 and GS 47BBCH.
[0862] In one embodiment of the invention, the mixture or composition of the invention is applied to plants growing on soil or soil substitutes and / or the site where the plants grow or are intended to grow, before and at sowing, before emergence and until harvest (GS00-GS 89BBCH), or during the growth stage (GS) of the plants between GS 00-GS 65BBCH.
[0863] Test Details
[0864] Incubation experiment:
[0865] The same amount of nitrogen and the same amount of AI (active ingredient) were applied in all treatments. In the cases of the two tested nitrification inhibitors DMPP and DMPSA, it was 1% NI (nitrification inhibitor) relative to the sum of NH2-N and NH4-N of the corresponding carrier fertilizer, and 0.04% relative to urea in the cases of the two UI (urease inhibitors) NBPT and Limus. In the cases where only a portion of the fertilizer was treated with NI or UI, the concentration of the corresponding AI was higher, and thus the total amount of NI was the same as in the control treatment.
[0866] Measurement of nitrification inhibition effect:
[0867] Fill 100g of soil (incubated at 20°C for 2 weeks to activate microbial biomass) into a 500ml plastic bottle (e.g., soil sampled from the field) and moisten to 50% of its water capacity. Fertilizer is then applied to the corresponding product containing the composition and mixture of the present invention at an appropriate concentration.
[0868] Ensure the treated fertilizer particles are evenly distributed in the soil. The amount of fertilizer applied corresponds to 10 mg of reduced nitrogen per bottle.
[0869] Loosely cover each bottle to allow air exchange. Then incubate each bottle at 20°C for 28 days.
[0870] For analysis, 300 ml of 1% K₂SO₄ solution was added to a bottle containing soil and shaken at 150 rpm for 2 hours in a horizontal shaker. The entire solution was then filtered through a Macherey-Nagel MN 807 filter. 1 / 4. Analyze the ammonium content of the filtrate using an automated analyzer (Merck, AA11) at 550 nm. Calculate:
[0871]
[0872] Volatilization test:
[0873] As a measure of urea stabilization effect, the loss of volatile NH3 from urea applied to the soil surface was used to detect the urea stabilization effect.
[0874] Fill a 500mL laboratory bottle with 176g of air-dried soil, then fill it with deionized water to 50% of its water capacity and incubate it at room temperature (about 21°C) for 24 hours.
[0875] Distribute urea granules evenly onto the soil in each bottle. Treat each granule with 5 μL of the corresponding product containing the composition and mixture of the present invention at an appropriate concentration. The amount of nitrogen applied is 80 mg per bottle.
[0876] NH3-free air is constantly blown through the bottle at a rate of approximately 4 L / min to bubble through the washer solution, which is periodically replaced and the NH4 is analyzed by an automated analyzer. + .
[0877] The activity of the urease inhibitor has been demonstrated if the cumulative NH3 loss in the treated solution is significantly lower than that in the untreated control (urea only)—which cannot be attributed to the pH effect in the solution.
[0878] result:
[0879] 1. Fertilizer = Urea
[0880] 1.1 Combinations of DMPP with NBPT and Limus (NBPT+NPPT) respectively
[0881] A. Reduce NH3 emissions from urea using NBPT and Limus respectively (UI effect)
[0882] Test parameters: %NH3-N of N applied (cumulative, DAT = number of days after treatment)
[0883] deal with DAT 3 DAT 7 DAT 10 DAT 14 urea 4.2 26.5 32.8 37.0 <![CDATA[Urea + DMPP + NBPT 1 > 3.1 22.1 34.1 41.0 <![CDATA[Urea + DMPP and Urea + NBPT 2 > 0.6 3.3 6.1 10.7
[0884] 1 DMPP and NBPT are on the same urea granules
[0885] 2 A physical mixture of urea granules treated only with DMPP and urea granules treated only with NBPT (bulk mixed fertilizer).
[0886] The total DMPP and total NBPT amounts are the same as those of urea + DMPP + NBPT.
[0887] • High NH3-N loss in control-treated urea
[0888] NBPT did not reduce NH3-N loss because NBPT was destroyed by DMPP.
[0889] • Applying NBPT only to urea granules and mixing it with DMPP-treated urea granules significantly reduces the loss of NH3-N from urea.
[0890] Test parameters: %NH3-N of N applied (cumulative, DAT = number of days after treatment)
[0891] deal with DAT 3 DAT 7 DAT 10 DAT 14 urea 4.2 26.5 32.8 37.0 <![CDATA[Urea + DMPP + Limus 1 > 3.7 21.9 33.1 37.9 <![CDATA[Urea + DMPP and Urea + Limus 2 > 0.6 2.7 6.0 10.6
[0892] 1 DMPP and Limus on the same urea granules
[0893] 2 A physical mixture of urea granules treated only with DMPP and urea granules treated only with Limus (bulk compound fertilizer).
[0894] The total DMPP and total Limus amounts are the same as those for urea + DMPP + Limus.
[0895] • High NH3-N loss in control-treated urea
[0896] • Limus did not reduce NH3-N loss because Limus was destroyed by DMPP.
[0897] • Applying Limus only to urea granules and mixing it with DMPP-treated urea granules significantly reduces the loss of NH3-N from urea.
[0898] B. Inhibition of nitrification via DMPP (NI effect)
[0899] Test parameters: % NH4-N recovery of applied N (DAT = days after treatment)
[0900]
[0901]
[0902] 1 DMPP and NBPT are on the same urea granules
[0903] 2 A physical mixture of urea granules treated only with DMPP and urea granules treated only with NBPT (bulk mixed fertilizer).
[0904] The total DMPP and total NBPT amounts are the same as those of urea + DMPP + NBPT.
[0905] • In the control treatment of urea, there was no NH4-N recovery due to the lack of nitrification inhibitors.
[0906] • High NH4-N recovery in the treatment of "urea + DMPP + NBPT"
[0907] • 28 days after treatment, the NH4-N recovery in the treatment of "a physical mixture of urea particles treated with DMPP only and urea particles treated with NBPT only" was the same as that in the control treatment "DMPP and NBPT on the same urea particles".
[0908] Test parameters: % NH4-N recovery of applied N (DAT = days after treatment)
[0909] deal with DAT 28 urea 0 <![CDATA[Urea + DMPP + Limus 1 > 53.6 <![CDATA[Urea + DMPP and Urea + Limus 2 > 54.1
[0910] 1 DMPP and Limus on the same urea granules
[0911] 2 A physical mixture of urea granules treated only with DMPP and urea granules treated only with Limus (bulk compound fertilizer).
[0912] The total DMPP and total Limus amounts are the same as those for urea + DMPP + Limus.
[0913] • In the control treatment of urea, there was no NH4-N recovery due to the lack of nitrification inhibitors.
[0914] • High NH4-N recovery in the treatment of "urea + DMPP + Limus"
[0915] • 28 days after treatment, NH4-N recovery in the treatment of “physical mixture of urea granules treated with DMPP only and urea granules treated with Limus only” was the same as in the control treatment “DMPP and Limus on the same urea granules”.
[0916] Overall Summary:
[0917] • The nitration inhibitor DMPP cannot be combined with the urease inhibitors NBPT and Limus on the same urea particles because DMPP disrupts the urea granules.
[0918] • The alternatives to the combination of DMPP with the urease inhibitors NBPT and Limus are physical mixtures (bulk fertilizer mixes) consisting of a portion of urea granules treated with DMPP alone and a portion of urea granules treated with NMPT and Limus alone.
[0919] • NBPT and Limus showed significantly better UI performance in bulk fertilizers with DMPP compared to their combination on the same urea granules.
[0920] • The NI effect of DMPP in bulk fertilizer blends containing NBPT and Limus is the same as that in the same urea granules.
[0921] 1.2DMPSA combined with NBPT and Limus (NBPT+NPPT) respectively
[0922] A. Reduce NH3 emissions from urea using NBPT and Limus respectively (UI effect)
[0923] Test parameters: %NH3-N of N applied (cumulative, DAT = number of days after treatment)
[0924] deal with DAT 3 DAT 7 DAT 10 DAT 14 urea 4.2 26.5 32.8 37.0 <![CDATA[Urea + DMPSA + NBPT 1 > 0.4 2.0 3.7 8.0 <![CDATA[Urea + DMPSA and Urea + NBPT 2 > 0.6 3.1 5.5 10.4
[0925] 1 DMPSA and NBPT are on the same urea granules
[0926] 2 A physical mixture of urea granules treated only with DMPSA and urea granules treated only with NBPT (bulk compound fertilizer).
[0927] The total DMPSA and total NBPT amounts are the same as those for urea + DMPSA + NBPT.
[0928] • High NH3-N loss in control-treated urea
[0929] • Applying NBPT only to urea granules, or mixing it with DMPSA-treated urea granules, significantly reduces NH3-N loss from urea.
[0930] There was no difference in UI performance between processing "DMPSA and NBPT on the same urea granules" and processing "a physical mixture (bulk fertilizer) of urea granules, some treated with DMPSA and some treated with NBPT".
[0931] Test parameters: %NH3-N of N applied (cumulative, DAT = number of days after treatment)
[0932] deal with DAT 3 DAT 7 DAT 10 DAT 14 urea 4.2 26.5 32.8 37.0 <![CDATA[Urea + DMPSA + Limus 1 > 0.4 1.8 4.1 7.8 <![CDATA[Urea + DMPSA and Urea + Limus 2 > 0.5 3.4 6.8 11.9
[0933] 1 DMPSA and Limus are on the same urea granules
[0934] 2 A physical mixture of urea granules treated only with DMPSA and urea granules treated only with Limus (bulk compound fertilizer).
[0935] The total DMPSA and total Limus amounts were the same as those for urea + DMPSA + Limus.
[0936] • High NH3-N loss in control-treated urea
[0937] • Applying Limus only to urea granules, or mixing it with DMPSA-treated urea granules, significantly reduces NH3-N loss from urea.
[0938] There is no difference in UI effect between processing "DMPSA and Limus on the same urea granules" and processing "a physical mixture of urea granules treated only with DMPSA and urea granules treated only with Limus (bulk compound fertilizer)".
[0939] B. Inhibition of nitrification via DMPSA (NI effect)
[0940] Test parameters: % NH4-N recovery of applied N (DAT = days after treatment)
[0941] deal with DAT 28 urea 0 <![CDATA[Urea + DMPSA + NBPT 1 > 48.9 <![CDATA[Urea + DMPSA and Urea + NBPT 2 > 18.9
[0942] 1 DMPSA and NBPT are on the same urea granules
[0943] 2 A physical mixture of urea granules treated only with DMPSA and urea granules treated only with NBPT (bulk compound fertilizer).
[0944] The total DMPSA and total NBPT amounts are the same as those for urea + DMPSA + NBPT.
[0945] • In the control treatment of urea, there was no NH4-N recovery due to the lack of nitrification inhibitors.
[0946] • High NH4-N recovery in the treatment of "urea + DMPSA + NBPT"
[0947] • Significantly higher NH4-N recovery in DAT 28 compared to untreated control urea in treating a physical mixture of urea granules treated only with DMPSA and urea granules treated only with NBPT.
[0948] Test parameters: % NH4-N recovery of applied N (DAT = days after treatment)
[0949] deal with DAT 28 urea 0 <![CDATA[Urea + DMPSA + Limus 1 > 50.9 <![CDATA[Urea + DMPSA and Urea + Limus 2 > 18.7
[0950] 1 DMPSA and Limus are on the same urea granules
[0951] 2 A physical mixture of urea granules treated only with DMPSA and urea granules treated only with Limus (bulk compound fertilizer).
[0952] The total DMPSA and total Limus amounts were the same as those for urea + DMPSA + Limus.
[0953] • In the control treatment of urea, there was no NH4-N recovery due to the lack of nitrification inhibitors.
[0954] • High NH4-N recovery in the treatment of "urea + DMPSA + Limus"
[0955] • Significantly higher NH4-N recovery in DAT 28 compared to untreated control urea in treating a physical mixture of urea particles treated only with DMPSA and urea particles treated only with Limus.
[0956] Overall summary of Experiment 1:
[0957] • An alternative to the combination of DMPSA with the urease inhibitors NBPT and Limus on the same urea granules is a physical mixture (bulk compound fertilizer) consisting of a portion of urea granules treated with DMPSA alone and a portion of urea granules treated with NBPT and Limus alone.
[0958] • The UI effects of NBPT and Limus in bulk fertilizer blends with DMPSA were more or less the same as those in the same urea granules.
[0959] • Compared to untreated urea, DMPSA still maintains NI effect in bulk fertilizer blends containing NBPT and Limus, respectively.
[0960] 2. Fertilizer = Piammon 33S as an example of a sulfur-containing fertilizer
[0961] To produce Piammon in a fertilizer plant, 50% urea and 50% ammonium sulfate (AS) are used. Piammon granules contain nitrogen and sulfur.
[0962] The same nitrogen and sulfur composition can be obtained from a physical mixture (bulk compound fertilizer) of a portion of urea and a portion of ammonium sulfate (AS). In this mixture, the granules contain only N (in the case of urea granules) and contain both N and S (in the case of AS granules).
[0963] 2.1 Combinations of DMPP with NBPT and Limus (NBPT+NPPT) respectively
[0964] A. Reduce Piammon NH3 emissions using NBPT and Limus respectively (UI effect)
[0965] Test parameters: %NH3-N of N applied (cumulative, DAT = number of days after treatment)
[0966] deal with DAT 3 DAT 7 DAT 10 DAT 14 Piammon 1.8 11.7 20.2 22.2 <![CDATA[AS and urea 1 > 2.6 13.5 21.5 23.3 <![CDATA[Piammon+DMPP+NBPT 2 ]]> 1.5 7.3 15.7 20.4 <![CDATA[AS + DMPP and urea + NBPT 3 > 0.7 2.1 4.7 9.6
[0967] 1 A physical mixture of AS and urea. Total N and S amounts are the same as Piammon's.
[0968] 2 DMPP and NBPT on the same particle
[0969] 3 A physical mixture of ammonium sulfate granules treated only with DMPP and urea granules treated only with NBPT (bulk compound fertilizer).
[0970] The total DMPP and total NBPT amounts are the same as those of Piammon+DMPP+NBPT.
[0971] • High NH3-N loss in control treatments Piammon and physical mixtures of AS and urea.
[0972] • NBPT hardly reduces NH3-N loss because NBPT is destroyed by DMPP.
[0973] • Applying NBPT only to urea particles and mixing it with DMPP-treated AS particles significantly reduces the loss of NH3-N from urea.
[0974] Test parameters: %NH3-N of N applied (cumulative, DAT = number of days after treatment)
[0975] deal with DAT 3 DAT 7 DAT 10 DAT 14 Piammon 1.8 11.7 20.2 22.2 <![CDATA[AS and urea 1 > 2.6 13.5 21.5 23.3 <![CDATA[Piammon+DMPP+Limus 2 ]]> 1.6 10.3 19.2 23.8 <![CDATA[AS+DMPP and urea+Limus 3 > 0.7 2.2 4.5 7.4
[0976] 1 A physical mixture of AS and urea. Total N and S amounts are the same as Piammon's.
[0977] 2 DMPP and Limus on the same particle
[0978] 3 A physical mixture of ammonium sulfate granules treated only with DMPP and urea granules treated only with Limus (bulk compound fertilizer).
[0979] The total DMPP and total Limus amounts are the same as those of Piammon+DMPP+Limus.
[0980] High NH3-N loss in control treatments of Piammon and physical mixtures of AS and urea
[0981] • Limus hardly reduces NH3-N loss because Limus is destroyed by DMPP.
[0982] • If Limus is applied only to urea particles and mixed with DMPP-treated AS particles, the loss of NH3-N from urea is significantly reduced.
[0983] B. Inhibition of nitrification via DMPP (NI effect)
[0984] Test parameters: % NH4-N recovery of applied N (DAT = days after treatment)
[0985] deal with DAT 28 Piammon 1.0 <![CDATA[AS and urea 1 > 0.3 <![CDATA[Piammon+DMPP+NBPT 2 ]]> 37.9 <![CDATA[AS + DMPP and urea + NBPT 3 > 36.0
[0986] 1 A physical mixture of AS and urea. Total N and S amounts are the same as Piammon's.
[0987] 2 DMPP and NBPT are on the same particles.
[0988] 3 A physical mixture of ammonium sulfate granules treated only with DMPP and urea granules treated only with NBPT (bulk compound fertilizer).
[0989] The total DMPP and total NBPT amounts are the same as those of Piammon+DMPP+NBPT.
[0990] • Due to the lack of nitrification inhibitors, NH4-N recovery was very low in the control treatments Piammon and AS+ urea.
[0991] High NH4-N recovery in two treatments with nitrification inhibitors
[0992] There was no difference in NH4-N recovery between DMPP and NBPT on the same particles (“Piammon+DMPP+NBPT”) and DMPP and NBPT on different particles (DMPP on AS and NBPT on urea).
[0993] Test parameters: % NH4-N recovery of applied N (DAT = days after treatment)
[0994] deal with DAT 28 Piammon 1.0 <![CDATA[AS and urea 1 > 0.3 <![CDATA[Piammon+DMPP+Limus 2 ]]> 28.7 <![CDATA[AS+DMPP and urea+Limus 3 > 29.6
[0995] 1 A physical mixture of AS and urea. Total N and S amounts are the same as Piammon's.
[0996] 2 DMPP and Limus on the same particle
[0997] 3 A physical mixture of ammonium sulfate granules treated only with DMPP and urea granules treated only with Limus (bulk compound fertilizer).
[0998] The total DMPP and total NBPT amounts are the same as those of Piammon+DMPP+Limus.
[0999] • Due to the lack of nitrification inhibitors, NH4-N recovery was very low in the control treatments Piammon and AS+ urea.
[1000] High NH4-N recovery in two treatments with nitrification inhibitors
[1001] There was no difference in NH4-N recovery between DMPP and Limus on the same particles (“Piammon+DMPP+Limus”) and DMPP and Limus on different particles (DMPP on AS and Limus on urea).
[1002] Overall Summary:
[1003] • The nitration inhibitor DMPP cannot be combined with the urease inhibitors NBPT and Limus on the same Piammon particle because DMPP disrupts the UI.
[1004] • An alternative to the combination of DMPP with the urease inhibitors NBPT and Limus is a physical mixture of AS granules treated with DMPP alone and urea granules treated with NBPT and Limus alone (bulk compound fertilizer).
[1005] • NBPT and Limus showed significantly better UI performance in bulk fertilizer blends with DMPP compared to their combination on the same Piammnon granules.
[1006] • The NI effect of DMPP in bulk fertilizer blends containing NBPT and Limus was the same as that in the same Piammnon granules.
[1007] 2.2 Combining DMPSA with NBPT and Limus (NBPT+NPPT) respectively. A. Reducing NH3 emissions from Piammon through NBPT and Limus respectively (UI effect).
[1008] Test parameters: %NH3-N of N applied (cumulative, DAT = number of days after treatment)
[1009] deal with DAT 3 DAT 7 DAT 10 DAT 14 Piammon 1.8 11.7 20.2 22.2 <![CDATA[AS and urea 1 > 2.6 13.5 21.5 23.3 <![CDATA[Piammon+DMPSA+NBPT 2 ]]> 0.8 2.4 4.8 9.4 <![CDATA[AS+DMPSA and urea+NBPT 3 > 0.9 2.5 4.9 8.4
[1010] 1 A physical mixture of AS and urea. Total N and S amounts are the same as Piammon's.
[1011] 2 DMPSA and NBPT on the same particle
[1012] 3 A physical mixture of ammonium sulfate granules treated only with DMPSA and urea granules treated only with NBPT (bulk compound fertilizer).
[1013] The total DMPSA and total NBPT amounts are the same as those of Piammon+DMPSA+NBPT.
[1014] High NH3-N loss in control treatments of Piammon and physical mixtures of AS and urea
[1015] • Applying NBPT only to Piammon particles and mixing it with DMPSA-treated AS particles significantly reduces NH3-N loss from urea.
[1016] There was no difference in UI performance between processing "DMPSA and NBPT on the same granules" and processing "a physical mixture of AS granules treated only with DMPSA and urea granules treated only with NBPT (bulk compound fertilizer)".
[1017] Test parameters: %NH3-N of N applied (cumulative, DAT = number of days after treatment)
[1018] deal with DAT 3 DAT 7 DAT 10 DAT 14 Piammon 1.8 11.7 20.2 22.2 <![CDATA[AS and urea 1 > 2.6 13.5 21.5 23.3 <![CDATA[Piammon+DMPSA+Limus 2 ]]> 0.7 2.3 4.5 8.7 <![CDATA[AS+DMPSA and urea+Limus 3 > 0.6 2.0 4.1 7.1
[1019] 1 A physical mixture of AS and urea. Total N and S amounts are the same as Piammon's.
[1020] 2 DMPSA and Limus on the same particles
[1021] 3 A physical mixture of ammonium sulfate granules treated only with DMPSA and urea granules treated only with Limus (bulk compound fertilizer).
[1022] The total DMPSA and total NBPT amounts are the same as those of Piammon+DMPSA+Limus.
[1023] High NH3-N loss in control treatments of Piammon and physical mixtures of AS and urea
[1024] • Applying Limus only to Piammon particles and mixing it with DMPSA-treated AS particles significantly reduces NH3-N loss from urea.
[1025] There was no difference in UI performance between processing "DMPSA and Limus on the same granules" and processing "a physical mixture (bulk fertilizer blend) of AS granules treated only with DMPSA and urea granules treated only with Limus".
[1026] B. Inhibition of nitrification via DMPSA (NI effect)
[1027] Test parameters: % NH4-N recovery of applied N (DAT = days after treatment)
[1028] deal with DAT 28 Piammon 1.0 <![CDATA[AS and urea 1 > 0.3 <![CDATA[Piammon+DMPSA+NBPT 2 ]]> 30.5 <![CDATA[AS+DMPSA and urea+NBPT 3 > 11.4
[1029] 1 A physical mixture of AS and urea. Total N and S amounts are the same as Piammon's.
[1030] 2 DMPSA and NBPT on the same particle
[1031] 3 A physical mixture of ammonium sulfate granules treated only with DMPSA and urea granules treated only with NBPT (bulk compound fertilizer).
[1032] The total DMPSA and total NBPT amounts are the same as those of Piammon+DMPSA+NBPT.
[1033] • Due to the lack of nitrification inhibitors, NH4-N recovery was very low in the control treatments Piammon and AS+ urea.
[1034] High NH4-N recovery in two treatments with nitrification inhibitors
[1035] Significant NH4-N recovery of DMPSA and NBPT on different particles (DMPSA on AS and NBPT on urea) at lower levels compared to “Piammon” but compared to “Piammon+DMPSA+NBPT”.
[1036] Test parameters: % NH4-N recovery of applied N (DAT = days after treatment)
[1037] deal with DAT 28 Piammon 1.0 <![CDATA[AS and urea 1 > 0.3 <![CDATA[Piammon+DMPSA+Limus 2 ]]> 28.4 <![CDATA[AS+DMPSA and urea+Limus 3 > 12.7
[1038] 1 A physical mixture of AS and urea. Total N and S amounts are the same as Piammon's.
[1039] 2 DMPSA and Limus on the same particles
[1040] 3 A physical mixture of ammonium sulfate granules treated only with DMPSA and urea granules treated only with Limus (bulk compound fertilizer).
[1041] The total DMPSA and total NBPT amounts are the same as those of Piammon+DMPSA+Limus.
[1042] • Due to the lack of nitrification inhibitors, NH4-N recovery was very low in the control treatments Piammon and AS+ urea.
[1043] High NH4-N recovery in two treatments with nitrification inhibitors
[1044] Significant NH4-N recovery of DMPSA and Limus on different particles (DMPSA on AS and Limus on urea) at lower levels compared to “Piammon” but compared to “Piammon+DMPSA+Limus”.
[1045] Overall Summary:
[1046] • The alternative to Piammon, which is treated with DMPSA and urease inhibitors NBPT and Limus respectively, is a physical mixture of AS granules treated with DMPSA alone and urea granules treated with NBPT and Limus respectively (bulk compound fertilizer).
[1047] Regarding the UI effects of NBPT and Limus respectively, there is no difference between the combination of NI and UI on the same particle and the physical mixture of DMPSA on AS particles and UI on urea particles.
[1048] • DMPSA still showed significant NI effect in bulk fertilizers containing NBPT and Limus, but at a lower level compared to the control with a combination of NI and UI on the same particles.
Claims
1. A physical mixture comprising: 1) Solid carrier A, wherein solid carrier A contains at least one active compound I as a nitration inhibitor, but does not contain a urease inhibitor, wherein compound I is selected from: r) 3,4-dimethylpyrazole phosphate and / or 4,5-dimethylpyrazole phosphate, as well as 2) Solid carrier B, wherein solid carrier B contains at least one active compound II as a urease inhibitor, but does not contain a nitration inhibitor, wherein compound II is selected from: N-n-butylthiophosphoric triamine and mixtures comprising N-n-butylthiophosphoric triamine and N-n-propylthiophosphoric triamine (NPPT), Solid carrier A and solid carrier B are fertilizers, each selected from ammonium nitrate, calcium ammonium nitrate, ammonium sulfate, ammonium thionitrate, calcium nitrate, ammonium thiosulfate, calcium cyanamide, NPK fertilizer, NK fertilizer, NP fertilizer, urea, and urea sulfate.
2. The physical mixture according to claim 1, wherein solid carrier A and solid carrier B are fertilizers, each selected from diammonium hydrogen phosphate and monoammonium phosphate.
3. The physical mixture according to claim 1, wherein compound II is a mixture comprising N-n-butylthiophosphoric triamine and N-n-propylthiophosphoric triamine.
4. The physical mixture of claim 2, wherein compound II is a mixture comprising N-n-butylthiophosphoric triamine and N-n-propylthiophosphoric triamine.
5. The physical mixture according to any one of claims 1-4, wherein compound I and compound II are present in a weight ratio of 100:1 to 6.5:
1.
6. The physical mixture according to any one of claims 1-4, wherein compound I and compound II are present in a weight ratio of 100:1 to 19:
1.
7. The physical mixture according to any one of claims 1-4, wherein the mixture is obtained by a method comprising the following steps: (a1) Treat solid support A with compound I; (b1) Treat solid support B with compound II before, after, or simultaneously with step (a1). (c1) The solid carrier A to be treated in step (a1) is blended with the solid carrier B to be treated in step (b1).
8. The physical mixture of claim 5, wherein the mixture is obtained by a method comprising the following steps: (a1) Treat solid support A with compound I; (b1) Treat solid support B with compound II before, after, or simultaneously with step (a1). (c1) The solid carrier A to be treated in step (a1) is blended with the solid carrier B to be treated in step (b1).
9. The physical mixture of claim 6, wherein the mixture is obtained by a method comprising the following steps: (a1) Treat solid support A with compound I; (b1) Treat solid support B with compound II before, after, or simultaneously with step (a1). (c1) The solid carrier A to be treated in step (a1) is blended with the solid carrier B to be treated in step (b1).
10. A physical mixture according to any one of claims 1 and 3-4, wherein the mixture is obtained by a method comprising the following steps: (a1) Treat solid support A with compound I; (b1) Treat solid support B with compound II before, after, or simultaneously with step (a1). (c1) Blend the solid carrier A to be treated in step (a1) with the solid carrier B to be treated in step (b1). Solid carrier A is urea and solid carrier B is urea.
11. The physical mixture according to any one of claims 1 and 3-4, wherein solid carrier A and solid carrier B are urea.
12. An agricultural chemical composition comprising an adjuvant and a physical mixture according to any one of claims 1-11.
13. A method for improving fertilizer use efficiency or enhancing plant health, comprising treating plants or plant propagation material or soil in which plants are to grow with an effective amount of a physical mixture as defined in any one of claims 1-11 or an agricultural chemical composition as defined in claim 12.
14. A method for inhibiting urease, comprising treating a plant or plant propagation material or soil in which the plant is to grow with an effective amount of a physical mixture as defined in any one of claims 1-11 or an agricultural chemical composition as defined in claim 12.
15. Use of a physical mixture as defined in any one of claims 1-11 or an agricultural chemical composition as defined in claim 12 in improving fertilizer use efficiency or enhancing plant health.
16. Use of a physical mixture as defined in any one of claims 1-11 or an agricultural chemical composition as defined in claim 12 in nitrification inhibition or urease inhibition.
Citation Information
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