WO2023203066A1 - Synergistic action as nitrification inhibitors of dcd oligomers with alkoxypyrazole and its oligomers - Google Patents

Synergistic action as nitrification inhibitors of dcd oligomers with alkoxypyrazole and its oligomers Download PDF

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Publication number
WO2023203066A1
WO2023203066A1 PCT/EP2023/060111 EP2023060111W WO2023203066A1 WO 2023203066 A1 WO2023203066 A1 WO 2023203066A1 EP 2023060111 W EP2023060111 W EP 2023060111W WO 2023203066 A1 WO2023203066 A1 WO 2023203066A1
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mixture
plant
fertilizer
methyl
reaction product
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PCT/EP2023/060111
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French (fr)
Inventor
Maarten Staal
Diana Westfalia MORAN PUENTE
Kailaskumar Borate
Ulrike Malang
Markus Schmid
Gregor Pasda
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5

Definitions

  • the present invention relates to a novel mixture of nitrification inhibitors comprising (i) an alkoxypyrazole compound of formula (I) or a salt, tautomer, or N-oxide thereof, and (ii) a nitrification inhibitor system comprising at least one reaction product A of (al) dicyandiamide (DCD), (bl) formaldehyde, optionally (cl) urea, and optionally (dl) an ammonia source; or at least one reaction product B of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, and optionally (c2) an organic acid or an inorganic acid, and optionally (d2) a primary, secondary or tertiary amine; in a weight ratio of from 100:1 to 1: 100.
  • the invention relates to the use of the mixture of the invention, methods of applying the mixture of the invention, and to agrochemical mixtures and compositions comprising the mixture of the invention
  • Nitrogen is an essential element for plant growth and reproduction. About 25% of the plant available nitrogen in soils (ammonium and nitrate) originate from decomposition processes (mineralization) of organic nitrogen compounds such as humus, plant and animal residues and organic fertilizers. Approximately 5% derive from rainfall. On a global basis, the biggest part (70%), however, is supplied to the plant by inorganic nitrogen fertilizers.
  • the mainly used nitrogen fertilizers comprise ammonium compounds or derivatives thereof, i.e. nearly 90% of the nitrogen fertilizers applied worldwide is in the NH 4 + form (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302). This is, inter alia, due to the fact that NH 4 + assimilation is energetically more efficient than assimilation of other nitrogen sources such as NO 3 _ .
  • NH 4 + is held electrostatically by the negatively charged clay surfaces and functional groups of soil organic matter. This binding is strong enough to limit NH 4 + -loss by leaching to groundwater.
  • NO 3 _ being negatively charged, does not bind to the soil and is liable to be leached out of the plants' root zone.
  • nitrate may be lost by denitrification which is the microbiological conversion of nitrate and nitrite (NO 2 _ ) to gaseous forms of nitrogen such as nitrous oxide (N 2 O) and molecular nitrogen (N 2 ).
  • ammonium (NH 4 + ) compounds are converted by soil microorganisms to nitrates (NO 3 _ ) in a relatively short time in a process known as nitrification.
  • the nitrification is carried out primarily by two groups of chemolithotrophic bacteria, ammonia-oxidizing bacteria (AOB) of the genus Nitrosomonas and Nitrobacter, which are ubiquitous component of soil bacteria populations.
  • AOB ammonia-oxidizing bacteria
  • the first enzyme, which is essentially responsible for nitrification is ammonia monooxygenase (AMO), which was also found in ammonia-oxidizing archaea (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302).
  • nitrification process typically leads to nitrogen leakage and environmental pollution. As a result of the various losses, approximately 50% of the applied nitrogen fertilizers are lost during the year following fertilizer addition (see Nelson and Huber; Nitrification inhibitors for corn production (2001), National Corn Handbook, Iowa State University). As countermeasure, the use of nitrification inhibitors, mostly together with fertilizers, was suggested.
  • Suitable nitrification inhibitors include biological nitrification inhibitors (BNIs) such as linoleic acid, linolenic acid, methyl cinnamate, 1,9-decanediol, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, MHPP, Karanjin, brachialacton or the p-benzoquinone sorgoleone (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302).
  • BNIs biological nitrification inhibitors
  • nitrification inhibitors are synthetic chemical inhibitors such as nitrapyrin, dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate (DMPP), 4-amino-l,2,4-triazole hydrochloride (ATC), l-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 5-ethoxy-3- trichloromethyl-l,2,4-thiodiazole (terrazole), or 2-sulfanilamidothiazole (ST) (S GmbH and Kerkhoff, 1984, Fertilizer research, 5(1), 1-76).
  • WO2019166561 describes alkoxypyrazoles as nitrification inhibitors.
  • US2016/0060184 Al describes nitrification inhibitor systems comprising dicyandiamide (DCD) adducts.
  • US2018/0170818 Al describes compositions and a method for making liquid fertilizer additives of biodegradable polymers and/or oligomers comprised of the reaction products of aldehyde(s) with cyano-containing nitrification inhibitors that have one or more aldehyde reactive groups.
  • US2022/0041520 Al relates to compositions and an method of making liquid fertilizer additives of biodegradable polmers and/or oligomers comprised of the reaction products of aldehyde(s) with cyano-containing nitrification inhibitors that have one or more aldehyde reactive groups selected from the group consisting of primary amines, secondary amines, amides, thiols, hydroxyls and phenols, wherein the cyano-group is conserved, utilizing a non-aqueous polar, aprotic organo liquid as the reaction medium.
  • nitrification inhibitors in particular to provide an improved activity regarding the reduction in am- moniacal nitrogen (NH 3 -N) oxidation rate and/or regarding the reduction of NO 3 _ production in soil or to keep the same activity, with lower amounts of nitrification inhibitors.
  • NH 3 -N am- moniacal nitrogen
  • NO 3 _ production in soil is decisive for the reduction of nitrate levels in the ground water, and because NO 3 is substrate for the formation of the greenhouse gas N 2 O in soil during denitrification (NO 3 -> N 2 Ot, N 2 t).
  • R 1 is CH 3 or CH 2 CH 3 ;
  • reaction product A at least one reaction product A of (al) dicyandiamide (DCD), (bl) formaldehyde, optionally (cl) urea, and optionally (dl) an ammonia source; or
  • reaction product B at least one reaction product B of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, and optionally (c2) an organic acid or an inorganic acid, and optionally (d2) a primary, secondary or tertiary amine; wherein components (i) and (ii) are present in a weight ratio of from 100:1 to 1:100.
  • DCD dicyandiamide
  • formaldehyde or paraformaldehyde optionally
  • c2 an organic acid or an inorganic acid
  • d2 a primary, secondary or tertiary amine
  • the inventors surprisingly found that by applying the mixture as defined above and hereinafter the nitrification of ammonium to nitrate can significantly be reduced or can be equally achieved with lower concentration of nitrification inhibitors.
  • a synergistic effect occurs regarding reduction of nitrification.
  • a surprisingly high reduction in ammoniacal nitrogen (NH 3 -N) oxidation rate and/or a surprisingly high reduction of NO 3 _ production can be observed.
  • a synergistic effect can be observed for the reduction of NO 3 _ production over a broad range of weight ratios of components (i) and (ii).
  • the inventors surprisingly found that the formulation of a mixture of nitrification inhibitors comprising dicyandiamide and alkoxypyrazoles can be improved when dicyandiamide was reacted in form of an inhibitor system comprising at least a reaction product A or at least one reaction product B.
  • the reaction product A comprises at least one adduct of formula (II) wherein
  • X 0 or are independently selected from the group consisting of wherein at least one of R 1 , R 2 , R 3 , and R 4 is different from
  • R 1 , R 2 , R 3 , and R 4 are wherein preferably the at least one adduct is selected from the group consisting of adducts of formulae (Ila), (lib), and (lie), and combinations thereof, and wherein particularly preferably the at least one adduct is selected from the group consisting of adducts of formula (Ila) and (lib), and combinations thereof.
  • reaction product B is a reaction product of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, (c2) methane sulfonic acid, and (d2) triethanolamine.
  • reaction product B is obtained utilizing a non-aqueous polar, aprotic organic liquid (NAPAOL), which is preferably dimethylsulfoxide.
  • NAPAOL non-aqueous polar, aprotic organic liquid
  • components (i) and (ii) are present in a weight ratio of from 50:1 to 1:50, preferably from 25:1 to 1:25 or from 10:1 to 1:10.
  • the present invention relates to a composition
  • a composition comprising the mixture of the invention and at least one carrier.
  • the present invention relates to an agrochemical mixture comprising (a) at least one fertilizer and (b) the mixture of the invention or the composition of the invention.
  • the present invention relates to the use of the mixture of the invention or the composition of the invention for reducing nitrification of a fertilizer, said reduction of nitrification preferably occurs in the root zone of a plant, in or on soil or soil substituents and/or at the locus where a plant is growing or is intended to grow.
  • the present invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus or soil or soil substituents where the plant is growing or is intended to grow with the mixture of a the invention or the composition of the invention, and optionally additionally with a fertilizer.
  • the application of the mixture of the invention or the composition of the invention and the fertilizer is carried out simultaneously or with a time lag, preferably an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.
  • the present invention relates to a method for treating a fertilizer or a fertilizer composition, comprising the application of a mixture of the invention or a composition of the invention to a fertilizer or fertilizer composition.
  • said fertilizer is an solid or liquid ammonium-containing inorganic fertilizer such as an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; an solid or liquid organic fertilizer such as liquid manure, semi-liquid manure, biogas manure, stable manure and straw manure, worm castings, compost, seaweed or guano, or an urea-containing fertilizer such as urea, formaldehyde urea, anhydrous ammonium, urea ammonium nitrate (UAN) solution, urea sulphur, urea based NPK-fertilizers, or urea ammonium sulfate.
  • NPK fertilizer ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate
  • the applied amount of the mixture is such that at least 0.1 % by weight of component (i) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer are applied, and at least 0.2 % by weight of component (ii) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer.
  • component (i) is applied in an amount of from 0.3 to 3 % by weight relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer, and component (ii) is applied in an amount of from 0.3 to 4 % by weight relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer.
  • said plant is an agricultural plant such as wheat, barley, oat, rye, soybean, corn, sorghum, potatoes, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice, oil palm, coffee, cacao, tea or a vegetable such as spinach, lettuce, asparagus, or cabbages; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or in a genetically modified form.
  • agricultural plant such as wheat, barley, oat, rye, soybean, corn, sorghum, potatoes, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice, oil palm, coffee, cacao, tea or a vegetable such as spinach, lettuce, asparagus, or cabbages; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or in a genetically modified form.
  • Compounds (i) of claim 1 can be prepared by standard processes of organic chemistry. Suitable methods for preparing pyrazole compounds in general are described in “Progress in Heterocyclic Chemistry”, Vol. 27, G.W. Gribble, J. A. Joule, Elsevier, 2015, Chapter 5.4.2.
  • a general method for the synthesis of 3-alkoxy-pyrazoles comprises the reaction between hydrazine hydrochloride and various p-ketoesters as described by, for example: a) Sadrine Guillou, Frederic J. Bon Subscribe, Yves L. Janin, Synthesis 2008, 3504-3508; or b) in WO 2010/015657 A2.
  • the 3-alkoxy group can be introduced by alkylating a suitable hy- droxypyrazole derivative as described e.g. by a) D. Piomelli and coworkers, Synthesis 2016, 2739-2756, or b) Sandrine Guillou, Yves L. Janin, Chem. Eur. J. 2010, 16, 4669 - 4677. Diverse methods to synthesize pyrazoles bearing the alkoxy group in the position 4 were described by William F. Vernier, Laurent Gomez, Tetrahedron Letters 2017 , 4587-4590. WO201916656 describes the compounds of formula (I) as nitrification inhibitors.
  • IH-pyrazoles especially those with different substituents in 3- and 5-position, may be present in the form of different annular tautomers, i.e. prototrophic tautomers, as described by a) Schaumann, Ernst, Methoden der Organischen Chemie, 1994, Houben-Weyl, E8b: Hetarene III and b) A. Giiven, N. Kani ⁇ kan, Journal of Molecular Structure (Theochem), 1999, 488, 125-134. It is to be understood that these annular tautomers of the compounds of formula I may be formed, as the hydrogen atom may migrate to the other nitrogen atom and vice versa.
  • the compounds of formula I may be present in the form of the different annular tautomers, or as a mixture thereof. Further, it is to be understood that the equilibrium between those tautomeric forms depends on the steric and electronic properties of the substituents present on the pyrazole ring of the compounds of formula I. Therefore, if pyrazolium ions of the compounds of formula I are formed, the different tautomers will typically result in two different isomers of the pyrazolium ion. In certain preferred embodiments of the invention, such isomer mixtures of pyrazolium ions of the compounds of formula I may be used.
  • a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only.
  • the terms “first”, “second”, “third” or “(a)”, “(b)”, “(c)”, “(d)” etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein.
  • first”, “second”, “third” or “(a)”, “(b)”, “(c)”, “(d)”, “i”, “ii” etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, i.e. the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below. It is to be understood that this invention is not limited to the particular methodology, protocols, reagents etc. described herein as these may vary.
  • Nitrification inhibitor is to be understood in this context as a chemical substance which slows down or stops the nitrification process. Nitrification inhibitors accordingly retard the natural transformation of ammonium into nitrate, by inhibiting the activity of bacteria such as Nitrosomonas spp.
  • the term "nitrification” as used herein is to be understood as the biological oxidation of ammonia (NH 3 ) or ammonium (NH 4 + ) with oxygen into nitrite (NO 2 _ ) followed by the oxidation of these nitrites into nitrates (NO 3 _ ) by microorganisms. Besides nitrate (NO 3 _ ) nitrous oxide is also produced through nitrification.
  • Nitrification is an important step in the nitrogen cycle in soil.
  • the inhibition of nitrification may thus also reduce N 2 O losses.
  • the term nitrification inhibitor is considered equivalent to the use of such a compound for inhibiting nitrification.
  • the term “nitrification inhibitor” is also used to describe the mixture of the invention.
  • compound of formula (I) comprises the compound(s) as defined herein as well as a salt, tautomer or N-oxide thereof.
  • the compounds of formula I may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention covers amorphous and crystalline compounds of formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formula I are preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality. Agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the mode of action of the compounds of formula I.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate.
  • They can preferably be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Preferred salts of the compounds of formula I are phosphate salts.
  • N-oxide includes any compound of formula I, wherein a tertiary nitrogen atom, e.g. the pyridine nitrogen atom, is oxidized to an N-oxide moiety.
  • Tautomers of the compounds of formula I may be present as described above.
  • tautomers may be present, as the hydrogen atom may migrate to the other nitrogen atom and vice versa.
  • the organic moieties mentioned in the above definition of the variable R 1 include CH 3 , i.e. methyl, and CH2CH3, i.e. ethyl.
  • the present invention relates in one aspect to a mixture comprising (i) an alkoxypyrazole compound of formula (I) or a salt, tautomer, or N-oxide thereof, wherein
  • R 1 is CH 3 or CH 2 CH 3 ;
  • reaction product A at least one reaction product A of (al) dicyandiamide (DCD), (bl) formaldehyde, optionally (cl) urea, and optionally (dl) an ammonia source; or
  • reaction product B at least one reaction product B of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, and optionally (c2) an organic acid or an inorganic acid, and optionally (d2) a primary, secondary or tertiary amine; wherein components (i) and (ii) are present in a weight ratio of from 100:1 to 1:100.
  • DCD dicyandiamide
  • formaldehyde or paraformaldehyde optionally
  • c2 an organic acid or an inorganic acid
  • d2 a primary, secondary or tertiary amine
  • R 1 is CH 3 .
  • R 1 is CH 2 CH 3 .
  • the alkoxypyrazole compound is present in the form of a salt, preferably in the form of a pyrazolium salt, such that the compound of formula (I) is present in cationic form.
  • Preferred anions are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbon- ate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate.
  • the alkoxypyrazole compound is present in the form of a phosphate salt.
  • reaction product A of (al) dicyandiamide (DCD), (bl) formaldehyde, and optionally (cl) urea, and optionally (dl) an ammonia source refers to a reaction product obtainable by reacting DCD, formaldehyde, urea, and an ammonia source.
  • the DCD (al) can be used as commercially available.
  • the formaldehyde (bl) can be used in many forms.
  • paraform solid, polymerized formaldehyde
  • formalin solutions aqueous solutions of formaldehyde, sometimes with methanol, in about 10 % by weight, about 20 % by weight, about 37 % by weight, about 44 % by weight, or about 50 % by weight, based on the weight of the formalin solution
  • the formaldehyde can be an aqueous solution having a concentration of formaldehyde ranging from about 10 % by weight to about 50 % by weight, based on a total weight of the aqueous solution.
  • Formaldehyde gas can also be used.
  • Formaldehyde substituted in part or in whole with substituted aldehydes such as acetaldehyde and/or propylaldehyde can be used as the source of formaldehyde.
  • substituted aldehydes such as acetaldehyde and/or propylaldehyde
  • One or more other aldehydes, such as glyoxal can be used in place of or in combination with formaldehyde. Any of these forms of formaldehyde sources can be used alone or in any combination to prepare the reaction product.
  • formaldehyde is an aqueous solution having a concentration of formaldehyde ranging from about 10 % by weight to about 50 % by weight, based on a total weight of the aqueous solution.
  • formaldehyde is an aqueous solution having a concentration of formaldehyde ranging from about 20 % by weight to about 50 % by weight, based on a total weight of the aqueous solution.
  • formaldehyde is an aqueous solution having a concentration of formaldehyde ranging from about 30 % by weight to about 50 % by weight, based on a total weight of the aqueous solution.
  • formaldehyde is an aqueous solution having a concentration of formaldehyde ranging from about 40 % by weight to about 50 % by weight, based on a total weight of the aqueous solution.
  • formaldehyde is an aqueous solution having a concentration of formaldehyde of about 50 % by weight, based on a total weight of the aqueous solution.
  • the urea (cl) can also be used in many forms.
  • the urea can be a solid in the form of pills, flakes, granules, and the like, and/or a solution, such as an aqueous solution.
  • the urea may be combined with another moiety, for example, formaldehyde and/or urea-formaldehyde adducts, often in aqueous solution.
  • at least a portion of the urea, if present, can be in the form of animal waste.
  • Any form of urea or urea in combination with formaldehyde can be used to make a urea-formaldehyde polymer. Both urea prill and combined urea-formaldehyde products can be used.
  • ammonia source refers to ammonia or any ammonium compound(s) that liberate ammonia when reacted with the formaldehyde and DCD.
  • Illustrative ammonia sources can include, but are not limited to, ammonium salts such as ammo- nium nitrate, aqueous ammonia or ammonium hydroxide, anhydrous ammonia, or combinations thereof.
  • Suitable aqueous ammonium solutions can have an ammonia concentration of about 28 % by weight, about 30 % by weight, about 32 % by weight, or about 35 % by weight, for example.
  • ammonia sources can include, but are not limited to, primary amines or substituted primary amines such as methyl amine, monomethanol amine, amino propanol, or any combination thereof. Difunctional amines such as ethylene diamine or any combination of organic amines provided that one primary amine group is available to form a triazone ring can be used.
  • Another source of ammonia can be in the form of animal waste such as urine and/or manure. Any of these ammonia sources can be used alone or in any combination to prepare the reaction product. And the ammonia source can be used in any form such a liquid, solid, and/or gas. In some embodiments, a specific ammonia source may be expressly excluded according to the present disclosure.
  • an ammonia source may expressly exclude the use of ammonium chloride.
  • Other ammonia sources may be excluded if such ammonia source has a pH in water of less than 7 and/or if such ammonia source provides an undesirable reduction in the pH of a reaction described herein for forming adducts.
  • Reactions carried out for production of adducts comprised in reaction product A can be carried out by reacting DCD with the further starting components under conditions that conserves the DCD.
  • adducts comprised in reaction product A are produced under basic or alkaline reaction conditions.
  • adducts can be formed by reacting DCD, a urea source, formaldehyde, and an ammonia source (preferably one that does not form an acid moiety during the reaction) under basic reaction conditions at a pH of greater than 7.
  • the basic reaction conditions can be at a pH ranging from a low of about 7 to a high about 11.
  • the basic reaction conditions can be at a pH ranging from a low of about 7.5 to a high about 10.5.
  • the basic reaction conditions can be at a pH ranging from a low of about 8 to a high about 10.
  • the basic reaction conditions can be at a pH ranging from a low of about 8.5 to a high about 9.5.
  • the basic reaction conditions can be at a pH ranging from a low of about 8.5 to a high about 9.
  • reaction product A produced under basic reaction conditions is prepared by combining, mixing, or otherwise contacting the reaction components to produce a reaction mixture having a pH greater than about 7.
  • a reaction mixture of formaldehyde, ammonia, DCD, and urea under the basic reaction conditions can have a pH ranging from a low of about 8 to a high of about 11.
  • a reaction mixture of formaldehyde, ammonia, DCD, and urea under the basic reaction conditions can have a pH ranging from a low of about 8.5 to a high of about 10.5.
  • a reaction mixture of formaldehyde, ammonia, DCD, and urea under the basic reaction conditions can have a pH ranging from a low of about 9 to a high of about 10.
  • a reaction mixture of formaldehyde, ammonia, DCD, and urea under the basic reaction conditions can have a pH ranging from a low of about 9 to a high of about 9.5.
  • the reaction mixture under the basic reaction conditions can also have a pH ranging from a low of about 8 to a high about 11, preferably, of about 8.5 to a high about 10.5, further preferably, of about 9 to a high about 10, and further preferably of about 9.5 to a high about 10.
  • Heat from the exothermic reaction can be allowed to heat the reaction mixture to a temperature ranging from a low of about 50° C to a high of about 100° C, preferably from a low of about 60° C to a high of about 90° C, further preferably from a low of about 60° C to a high of about 90° C, and further preferably from a low of about 65° C to a high of about 80° C, a time ranging from about 1 minute to about 3 hours.
  • the resulting reaction mixture can then be cooled to, for example, room temperature, to provide the reaction product A, which can include one or more adducts as described herein.
  • formaldehyde and a first portion of the ammonia source can be combined to form a first mixture.
  • the first mixture can be at least partially reacted, and the formaldehyde and ammonia may be present in the first mixture at a mole ratio of about 40:1 to about 5:1.
  • the first mixture can be at least partially reacted, and the formaldehyde and ammonia may be present in the first mixture at a mole ratio of about 35:1 to 10: 1.
  • the first mixture can be at least partially reacted, and the formaldehyde and ammonia may be present in the first mixture at a mole ratio of about 30:1 to 15: 1.
  • DCD can then be added to the first mixture or to the at least partially reacted first mixture to produce a second mixture.
  • the second mixture can be at least partially reacted, and DCD and formaldehyde can be present in the second mixture at a mole ratio of about 0.01:1 to about 2:1.
  • the second mixture can be at least partially reacted, and DCD and formaldehyde can be present in the second mixture at a mole ratio of about 0.05:1 to about 1:1.
  • the second mixture can be at least partially reacted, and DCD and formaldehyde can be present in the second mixture at a mole ratio of about 0.1:1 to about 0.5:1.
  • Urea can then be added to the second mixture or the at least partially reacted second mixture to produce a third mixture.
  • the third mixture can be at least partially reacted, and the urea and formaldehyde can be present in the third mixture at a mole ratio of about 0.1:1 to about 5:1.
  • the third mixture can be at least partially reacted, and the urea and formaldehyde can be present in the third mixture at a mole ratio of about 0.25:1 to about 2:1.
  • the third mixture can be at least partially reacted, and the urea and formaldehyde can be present in the third mixture at a mole ratio of about 0.5:1 to about 1:1.
  • a second portion of the ammonia source can be added to the third mixture to produce a fourth mixture.
  • the fourth mixture can be at least partially reacted to produce the reaction product A of formaldehyde, urea, ammonia, and DCD.
  • the temperature of the first mixture, second mixture, and third mixture can be maintained at a temperature ranging from about 25° C to about 70° C.
  • the temperature of the fourth mixture can range from about 60° C to about 90° C and can be held at the increased temperature for a period of time ranging from about 5 minutes to about 3 hours.
  • the mole ratio of formaldehyde:urea:DCD:ammonia in a reaction product according to some embodiments of this disclosure can be about 1:0.88:0.14:0.24.
  • Exothermic heat generated from the first mixture, second mixture, third mixture, fourth mixture, or any number of mixtures can be used, at least in part, as the heat source for heating any one or more of the reaction mixtures.
  • heat can be introduced to any one or more of the reaction mixtures to provide a heated reaction mixture via a heating coil or other heat exchanging device or system.
  • the temperature of the reaction mixtures can be maintained below a desired maximum temperature, e.g., 100° C., via a cooling coil or other heat exchanging device or system.
  • One or more bases or base compounds can be added before and/or during the reaction to any one or more of the reaction mixtures and/or the reaction product to maintain and/or adjust the pH thereof.
  • the reaction product A produced under basic reaction conditions can be maintained at a pH of about 8 to about 11 during the reaction and/or for the final reaction product A.
  • Illustrative base compounds suitable for adjusting the pH of the reaction product (A) can include, but are not limited to, ammonia, amines, e.g., primary, secondary, and tertiary amines and polyamines, sodium hydroxide (NaOH), potassium hydroxide (KOH), or any combination thereof.
  • An aqueous base solution can have any concentration.
  • an aqueous base solution of sodium hydroxide, potassium hydroxide, or a combination thereof having a concentration ranging from a low of about 5 % by weight to a high of about 75 % by weight, preferably from a low of about 10 % by weight to a high of about 50 % by weight and further preferably from a low of about 15 % by weight to a high of about 25 % by weight, can be introduced to one or more of the reaction mixtures and/or the reaction product A in order to adjust and/or maintain the pH between about 8 and about 11.
  • one or more pH buffering compounds which can buffer the pH of the reaction mixture(s) at a desired pH, can be added at the start of the reaction.
  • pH buffering compounds can include, but are not limited to, triethanolamine, sodium borate, potassium bicarbonate, sodium carbonate, potassium carbonate, or any combination thereof.
  • the one or more pH buffering compounds can be used in conjunction with one or more base compounds to adjust and/or maintain a desired pH of the reaction mixture(s).
  • the reaction product A produced under the basic reaction conditions can have a pH greater than 7.
  • the reaction product A of formaldehyde, the ammonia source, DCD, and urea produced under the basic reaction conditions can have a pH ranging from a low of about 8 to a high about 11, preferably from a low of about 8.5 to a high about 10.5, further preferably from a low of about 9 to a high about 10 and further preferably from a low of about 9 to a high about 9.5.
  • the reaction product A from the reaction of formaldehyde, urea, the ammonia source, and DCD can include from about 25 mol-% to about 65 mol-% formaldehyde, from about 10 mol- % to about 25 mol-% urea, from about 5 mol-% to about 25 mol-% ammonia, and from about 5 mol-%to about 25 mol-% DCD, based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • the formaldehyde is present in an amount ranging from a low of about 25 mol-% to a high of about 60 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • the formaldehyde is present in an amount ranging from a low of about 30 mol-% to a high of about 55 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • the formaldehyde is present in an amount ranging from a low of about 35 mol-% to a high of about 50 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • the urea is present in an amount ranging from a low of about 12 mol-% to a high of about 25 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • the urea is present in an amount ranging from a low of about 14 mol-% to a high of about 22 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • the urea is present in an amount ranging from a low of about 16 mol-% to a high of about 18 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • the ammonia is present in an amount ranging from a low of about 7 mol-% to a high of about 25 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • the ammonia is present in an amount ranging from a low of about 9 mol-% to a high of about 22 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • the ammonia is present in an amount ranging from a low of about 12 mol-% to a high of about 18 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • the DCD is present in an amount ranging from a low of about 7 mol-% to a high of about 25 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • the DCD is present in an amount ranging from a low of about 9 mol-% to a high of about 22 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • the DCD is present in an amount ranging from a low of about 12 mol-% to a high of about 18 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
  • reaction product A of formaldehyde, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 1:1 to about 8:1.
  • reaction product A of formaldehyde, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 2:1 to about 6:1. In another preferred embodiment, the reaction product A of formaldehyde, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 2.5:1 to about 5:1.
  • reaction product A of formaldehyde, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 3:1 to about 4:1.
  • reaction product A of formaldehyde, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 2:1 to about 4:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 1:1 to about 8:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 2:1 to about 6:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 3:1 to about 5:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 3.5:1 to about 4.5:1.
  • reaction product A of formaldehyde, the ammonia source, and DCD can have a molar ratio of formaldehyde to DCD ranging from about 1:1 to about 7:1.
  • reaction product A of formaldehyde, the ammonia source, and DCD can have a molar ratio of formaldehyde to DCD ranging from about 1.5:1 to about 6.5:1.
  • reaction product A of formaldehyde, the ammonia source, and DCD can have a molar ratio of formaldehyde to DCD ranging from about 2:1 to about 6:1.
  • reaction product A of formaldehyde, the ammonia source, and DCD can have a molar ratio of formaldehyde to DCD ranging from about 2.5:1 to about 5:1.
  • reaction product A of formaldehyde, the ammonia source, and DCD can have a molar ratio of formaldehyde to DCD ranging from about 2:1 to about 4:1.
  • reaction product A of formaldehyde, the ammonia source, and DCD can have a molar ratio of formaldehyde to DCD ranging from about 2.5:1 to about 3.5:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to DCD ranging from about 1:1 to about 8:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to DCD ranging from about 1:1 to about 7:1. In another preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to DCD ranging from about 2:1 to about 8:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to DCD ranging from about 3:1 to about 7.5:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to DCD ranging from about .5:1 to about 7:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to urea ranging from about 1:1 to about 4:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to urea ranging from about 1.1:1 to about 3.9:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to urea ranging from about 1:1 to about 2:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to urea ranging from about 1:1 to about 1.5:1.
  • reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to urea ranging from about 1:1 to about 1.3:1.
  • the reaction product A can be produced by reacting formaldehyde and DCD.
  • the reaction product A can be produced by reacting formaldehyde, DCD and an ammonia source.
  • product A can be produced by reacting formaldehyde, DCD and urea.
  • the reaction product A can be produced by reacting formaldehyde, an ammonia source, DCD, and urea.
  • the reaction is carried out in water. In a preferred embodiment, the reaction product is therefore obtained in the form of an aqueous solution.
  • the reaction product A may comprise various adducts.
  • the reaction product may comprise at least one adduct based on compounds (al) + (bl), at least one adduct based on compounds (al) + (bl) + (cl), at least one adduct based on compounds (al) + (bl) + (dl), and/or at least one adduct based on (al) + (bl) + (cl) + (dl).
  • reaction product A comprises adducts arising from the reaction (al), (bl), (cl) and (dl), which may be encompassed by the structure of formula (II) wherein
  • Reaction product A may comprise a plurality of different adducts.
  • reaction product A may include at least 1 adduct, at least 2 different adducts, at least 3 different adducts, at least 4 different adducts, at Ieast5 different adducts, at least 10 different adducts, at least 25 different adducts, at least 50 different adducts, or at least 100 different adducts.
  • the reaction product A comprises at least one adduct selected from adducts provided in Formula (Ila) [2-canyo-1-((4-oxo-1,3,5-triazinen-1-yl)methyl(guani- dine], Formula (lib) [1-((2-cyanoguanidino)methyl)urea] and Formula (lie) [2-cyano-1-((2- cyanoguanidino)methyl)guanidine].
  • the reaction product A can include one, two, or all three of the adducts shown in in Formulas (Ila) through (lie) in any combination.
  • the reaction product A comprises at least one adduct selected from the group consisting of adducts of formula (Ila) and (lib) and combinations thereof.
  • reaction product A further comprises at least one adduct comprising a polymeric backbone of formula (III) wherein z is an integer of 1 or greater, preferably 1 to 100.
  • a further, non-limiting example of an adduct may arise from the reaction of (al), (bl), (cl) and (dl) is shown in Formula (III*). As seen therein, the N-C-N — backbone is present in the adduct.
  • reaction product B of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, and optionally (c2) an organic acid, and optionally (d2) a primary secondary amine or tertiary amine refers to a reaction product obtainable by reacting DCD, formaldehyde or paraformaldehyde, an organic acid and a primary, secondary amine or tertiary amine.
  • the reaction product B can be produced by reacting formaldehyde and DCD. In another example, the reaction product B can be produced by reacting paraformaldehyde and DCD. In another example, reaction product B can be produced by reacting formaldehyde, DCD and an organic acid. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD and an organic acid. In another example, reaction product B can be produced by reacting formaldehyde, DCD and a primary amine. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD and a primary amine. In another example, reaction product B can be produced by reacting formaldehyde, DCD and a secondary amine.
  • reaction product B can be produced by reacting paraformaldehyde, DCD and a secondary amine. In another example, reaction product B can be produced by reacting formaldehyde, DCD and a tertiary amine. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD and a tertiary amine. In another example, reaction product B can be produced by reacting formaldehyde, DCD, an organic acid and a primary amine. In another example, reaction product B can be produced by reacting formaldehyde, DCD, an inorganic acid and a primary amine.
  • reaction product B can be produced by reacting paraformaldehyde, DCD, an organic acid and a primary amine.
  • reaction product B can be produced by reacting paraformaldehyde, DCD, an inorganic acid and a primary amine.
  • reaction product B can be produced by reacting formaldehyde, DCD, an organic acid and a secondary amine.
  • reaction product B can be produced by reacting formaldehyde, DCD, an inorganic acid and a secondary amine.
  • reaction product B can be produced by reacting paraformaldehyde, DCD, an organic acid and a secondary amine.
  • reaction product B can be produced by reacting paraformaldehyde, DCD, an inorganic acid and a secondary amine.
  • reaction product B can be produced by reacting formaldehyde, DCD, an organic acid and a tertiary amine.
  • reaction product B can be produced by reacting formaldehyde, DCD, an inorganic acid and a tertiary amine.
  • reaction product B can be produced by reacting paraformaldehyde, DCD, an organic acid and a tertiary amine.
  • reaction product B can be produced by reacting paraformaldehyde, DCD, an inorganic acid and a tertiary amine.
  • the DCD (a2), formaldehyde (b2) and paraformaldehyde (b2) can be used as commercially available.
  • organic acid or inorganic acid(c2) can be used.
  • organic acid can include, but are not limited to, methane sulfonic acid, paratoluene sulfonic acid and methane phosphonic acid.
  • inorganic acid can include, but are not limited to phosphoric acid, sulfonic acid, hydrochloric acid and nitric acid.
  • methane sulfonic acid as an organic acid is used.
  • phosphoric acid or sulfonic acid as an inorganic acid is used.
  • Any commercially available primary amine (d2) can be used.
  • Illustrative examples can include, but are not limited to, (Ci. 6 -alkyl)amines, diglycolamine and cyclohexylamine.
  • At least one primary amine selected from the group consisting of such as cyclohexylamine, diglycolamine and ethylamine or combinations thereof are used.
  • Any commercially available secondary amine (d2) can be used.
  • Illustrative examples include, but are not limited to, di(Ci. 6 -alkyl)olamines and di(Ci. 6 -alkyl)amines.
  • At least one secondary amine from the group consisting of diethanolamine, diethylamine, methylisopropylamine, diisopropanolamine, methylethanolamine, dicyclohexylamine and combinations thereof are used.
  • tertiary amine (d2) can be used.
  • Illustrative examples can include, but are not limited to tri(Ci. 6 -alkyl)olamines and tri(Ci. 6 -alkyl)amines.
  • trimethylamine is used.
  • triethanolamine is used.
  • reaction product B can be obtained by reacting a molar ratio of DCD to formaldehyde unit of 1:1 to 4:1.
  • reaction product B can be obtained by reacting a molar ratio of DCD to formaldehyde unit of 1:1 to 2:1.
  • reaction product B can be obtained by reacting a molar ratio of DCD to formaldehyde unit of 2:1 to 4:1.
  • reaction product B can be obtained by reacting paraformaldehyde and DCD in a weight ratio of about 1:7 to 1:15.
  • reaction product B can be obtained by reacting paraformaldehyde and DCD in a weight ratio of about 1:8: to 1:14.
  • reaction product B can be obtained by reacting paraformaldehyde and DCD in a weight ratio of about 1:9 to 1:13.
  • reaction product B can be obtained by reacting paraformaldehyde and DCD in a weight ratio of about 1:10 to 1:12.
  • reaction product B can be obtained by reacting paraformaldehyde and DCD in a weight ratio of about 1:10.5 to 1:1.1.5.
  • reaction product B can be obtained by reacting formaldehyde and DCD in a weight ratio of about 1:7 to 1:15.
  • reaction product B can be obtained by reacting formaldehyde and DCD in a weight ratio of about 1:8: to 1:14.
  • reaction product B can be obtained by reacting a primary amine and DCD in a weight ratio of about 1:30 to 1:44.
  • reaction product B can be obtained reacting a primary amine and DCD in a weight ratio of about 1:33 to 1:37.
  • reaction product B can be obtained by reacting a primary amine and DCD in a weight ratio of about 1:34 to 1:36.
  • reaction product B can be obtained by reacting a secondary amine and DCD in a weight ratio of about 1:30 to 1:44.
  • reaction product B can be obtained reacting a secondary amine and DCD in a weight ratio of about 1:33 to 1:37.
  • reaction product B can be obtained by reacting a secondary amine and DCD in a weight ratio of about 1:34 to 1:36.
  • reaction product B can be obtained by reacting a tertiary amine and DCD in a weight ratio of about 1:60 to 1:80.
  • reaction product B can be obtained reacting a tertiary amine and DCD in a weight ratio of about 1:65 to 1:75.
  • reaction product B can be obtained by reacting a tertiary amine and DCD in a weight ratio of about 1:68 to 1:70.
  • reaction product B is a reaction product of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, (c2) methane sulfonic acid, and (d2) triethanolamine.
  • the reaction product B is obtained by utilizing a nonaqueous polar, aprotic organic liquid (NAPAOL).
  • NAPAOL nonaqueous polar, aprotic organic liquid
  • NOSDAS non-aqueous organo solvent delivery system
  • an aprotic NOSDS comprising of one or more aprotic solvents from the group consisting of (1) dimethylsulfoxide and/or
  • R 5 S(O)xR 6 wherein R 5 and R 6 are each independently a Ci. 6 alkylene group, an aryl group, or Ci_ 3 alkylenearyl group or R 5 and R 6 with the sulfur to which they are attached form a 4 to 8 membered ring wherein R 5 and R 6 together are a Ci_ 6 alkylene group which optionally contains one or more atoms selected from the group consisting of 0, S, Se, Te, N, and P in the ring and x is 1 or 2;
  • one or more alkylene carbonates selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate
  • polyols capped with acetate or formate wherein the polyol portion selected from the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, butylene glycol, trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol and sorbitan, glucose, fructose, galactose and glycerin
  • one or more alkylene glycol alkyl ethers acetates selected from the group consisting of dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether acetate, and/or tripropylene glycol butyl ether acetate
  • an aprotic NOSDS comprising of one or more aprotic solvents from the group consisting of (1) dimethylsulfoxide and/or (2) dialkyl, diaryl, or arylalkyl sulfoxide(s) having the formula: R 5 S(O) X R 6 wherein R 5 and R 6 are each independently a Ci. 6 alkylene group, an aryl group, or C1.3 alkylenearyl group or R 5 and R 6 with the sulfur to which they are attached form a 4 to 8 membered ring wherein R 5 and R 6 together are a Ci. 6 alkylene group which optionally contains one or more atoms selected from the group consisting of 0, S, Se, Te, N, and P in the ring and x is 1 or 2; can serve as the reaction medium for obtaining the reaction product B.
  • reaction product B is obtained utilizing a non-aqueous polar, aprotic organic liquid (NAPAOL) is dimethylsulfoxide.
  • NAPAOL non-aqueous polar, aprotic organic liquid
  • reaction product B can be obtained by the following method: (a) dissolve the DCD (a2) in an aprotic solvent at temperatures in the range of about 30- 110° C, then cool to about 40-70° C and insure that pH is in the range of about 8-10, (b) slowly add the aldehyde (b2) and allow the exotherm to be controlled either through charge rate or removing the heat of reaction through a cooling median, (c) slowly heat the composition to about 70-90° C and hold for a period of time, (d) cool the composition to about 40- 70° C, and slowly charge enough of an acid catalyst to drop the pH to about 5-6.5 and let mix for an extended period of time to control the exotherm, (e) slowly heat the composition to about 90-115° C, f) after holding for a period of time, one can elect to place the batch under a vacuum to assist in removing water by-products, driving the reaction to more completion and removing any unreacted aldehyde (b2) and then cooling the batch.
  • DCD can be dispersed within dimethyl sulfoxide and then reacted with paraformaldehyde in a molar ratio of 3-4 moles of DCD to one reactive unit of paraformaldehyde.
  • the present invention relates in one aspect to a mixture comprising component (i) and component (ii).
  • Component (i) is the alkoxypyrazole compound, and component (ii) is the nitrification inhibitor system.
  • components (i) and (ii) are present in a weight ratio of from 50:1 to 1:50, preferably from 25:1 to 1:25.
  • components (i) and (ii) are present in a weight ratio of from 40:1 to 1:40.
  • components (i) and (ii) are present in a weight ratio of from 35:1 to 1:35.
  • components (i) and (ii) are present in a weight ratio of from 30:1 to 1:30.
  • components (i) and (ii) are present in a weight ratio of from 25:1 to 1:25.
  • components (i) and (ii) are present in a weight ratio of from 20:1 to 1:20.
  • components (i) and (ii) are present in a weight ratio of from 10:1 to 1:10, preferably from 5:1 to 1:5.
  • components (i) and (ii) are present in a weight ratio of from 8:1 to 1:8.
  • components (i) and (ii) are present in a weight ratio of from 5:1 to 1:5.
  • components (i) and (ii) are present in a weight ratio of from 4:1 to 1:4.
  • components (i) and (ii) are present in a weight ratio of from 3.5:1 to 1:3.5.
  • components (i) and (ii) are present in a weight ratio of from 3.2:1 to 1:3.2.
  • components (i) and (ii) are present in synergistically effective amounts, i.e. in relative amounts such that a synergistic effect regarding the inhibition of nitrification is achieved.
  • Synergism can be determined using Colby’s formula (Colby, S.R., Calculating synergistic and antagonistic responses of herbicide combinations, Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies.
  • E x + y - x • y/100
  • E expected efficacy, expressed in % of the untreated control, when using the mixture comprising the components (i) and (ii) at concentrations a and b
  • x efficacy, expressed in % of the untreated control, when using component (i) at the concentration a
  • y efficacy, expressed in % of the untreated control, when using component (ii) at the concentration b.
  • the mixture is applied in the following amounts.
  • the applied amount of the mixture is such that at least 0.1 % by weight of component (i) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer are applied, and at least 0.1 % by weight of component (ii) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer.
  • the applied amount of the mixture is such that at least 0.1 % by weight of component (i) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer are applied, and at least 0.2 % by weight of component (ii) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer.
  • the applied amount of the mixture is such that from 0.1 % to 3 % by weight of component (i) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer are applied, and from 0.1 % to 3 % by weight of component (ii) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer.
  • the applied amount of the mixture is such that from 0.1 % to 3 % by weight of component (i) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer are applied, and from 0.2 % to 3.13 % by weight of component (ii) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer.
  • the applied amount of the mixture is such that from 0.3 % to 3 % by weight of component (i) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer are applied, and from 0.3 % to 3 % by weight of component (ii) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer.
  • the applied amount of the mixture is such that from 0.1 % to 0.5 %, preferably from 0.1% to 0.3 % such as 0.1 % or 0.3 %, by weight of component (i) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer are applied, and from 0.1 % to 1 %, preferably from 0.15 % to 0.75 % such as 0.15 % or 0.75 %, by weight of component (ii) relative to the sum of NH 2 - and NH 4 -nitrogen content of the fertilizer.
  • inhibition of NO 3 -production was higher (cf.
  • Example 5 for example by at least 0.5 % or at least 1 % or at least 2 % or at least 3 % or at least 4 % or at least 5 % or at least 6 %, or at least 7 % or at least 8 % or at least 9 % or at least 10 % or at least 11 %.
  • the weight ratios of the applied components (i) and (ii) preferably correspond to the weight ratios defined above in connection with the mixtures of the invention.
  • components (i) and (ii) are provided in the mixtures of the invention in a weight ratio of from 50:1 to 1:50, preferably from 25:1 to 1:25.
  • components (i) and (ii) are provided in the mixtures of the invention in a weight ratio of from 10:1 to 1:10, preferably from 5:1 to 1:5.
  • the applied amounts of the mixture are then selected such that the above defined amounts of components (i) and (ii) are applied.
  • the use of the mixtures of the invention as a nitrification inhibitor may be based on the application of the mixture, the composition or the agrochemical mixture as defined herein to a plant growing on soil and/or the locus where the plant is growing or is intended to grow, or the use may be based on the application of the nitrification inhibitor, the composition or the agrochemical mixture as defined herein to soil where a plant is growing or is intended to grow or to soil substituents.
  • the nitrification inhibitor may be used for reducing nitrification in the absence of plants, e.g. as preparatory activity for subsequent agricultural activity, or for reducing nitrification in other technical areas, which are not related to agriculture, e.g.
  • the nitrification inhibitor, or a composition comprising said nitrification inhibitor according to the present invention may be used for the reduction of nitrification in sewage, slurry, manure or dung of animals, e.g. swine or bovine feces.
  • the nitrification inhibitor, or a composition comprising said nitrification inhibitor according to the present invention may be used for the reduction of nitrification in sewage plants, biogas plants, cowsheds, liquid manure tanks or containers etc.
  • the nitrification inhibitor, or a composition comprising said nitrification inhibitor may be used in exhaust air systems, preferably in exhaust air systems of stables or cowsheds.
  • the present invention therefore also relates to the use of the mixture of the invention for treating exhaust air, preferably the exhaust air of stables and cowsheds.
  • the nitrification inhibitor, or a composition comprising said nitrification inhibitor according to the present invention may be used for the reduction of nitrification in situ in animals, e.g. in productive livestock. Accordingly, the nitrification inhibitor, or a composition comprising said nitrification inhibitor according to the present invention may be fed to an animal, e.g.
  • nitrification inhibitor or a composition comprising said nitrification inhibitor according to the present invention may be repeated one to several times, e.g. each 2 nd , 3 rd , 4 th , 5 th , 6 th , 7 th day, or each week, 2 weeks, 3 weeks, or month, 2 months etc.
  • the use may further include the application of a nitrification inhibitor or compositions comprising said nitrification inhibitor, or agrochemical mixtures comprising said nitrification inhibitor as defined herein above to environments, areas or zones, where nitrification takes place or is assumed or expected to take place.
  • environments, areas or zones may not comprise plants or soil.
  • the nitrification inhibitor may be used for nitrification inhibition in laboratory environments, e.g. based on enzymatic reactions or the like. Also envisaged is the use in green houses or similar indoor facilities.
  • reducing nitrification or “reduction of nitrification” as used herein refers to a slowing down or stopping of nitrification processes, e.g. by retarding or eliminating the natural transformation of ammonium into nitrate. Such reduction may be a complete or partial elimination of nitrification at the plant or locus where the inhibitor or composition comprising said inhibitor is applied. For example, a partial elimination may result in a residual nitrifi- cation on or in the plant, or in or on the soil or soil substituents where a plant grows or is intended to grow of about 90% to 1%, e.g.
  • a partial elimination may result in a residual nitrification on or in the plant or in or on the soil or soil substituents where a plant grows or is intended to grow of below 1%, e.g. at 0.5%, 0.1% or less in comparison to a control situation where the nitrification inhibitor is not used.
  • nitrification inhibitor as defined herein above, or of a composition as defined herein for reducing nitrification may be a single use, or it may be a repeated use.
  • the nitrification inhibitor or corresponding compositions may be provided to their target sites, e.g. soil or loci, or objects, e.g. plants, only once in a physiologically relevant time interval, e.g. once a year, or once every 2 to 5 years, or once during the lifetime of a plant.
  • the use may be repeated at least once per time period, e.g. the nitrification inhibitor as defined herein above, or a composition as defined herein may be used for reducing nitrification at their target sites or objects two times within a time interval of days, weeks or months.
  • the term "at least once" as used in the context of a use of the nitrification inhibitor means that the inhibitor may be used two times, or several times, i.e. that a repetition or multiple repetitions of an application or treatment with a nitrification inhibitor may be envisaged. Such a repetition may be a 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or more frequent repetition of the use.
  • the nitrification inhibitor according to the present invention may be used in any suitable form.
  • it may be used as coated or uncoated granule, in liquid or semi-liquid form, as sprayable entity, or in irrigation approaches etc.
  • the nitrification inhibitor as defined herein may be applied or used as such, i.e. without formulations, fertilizer, additional water, coatings, or any further ingredient.
  • irrigation refers to the watering of plants or loci or soils or soil substituents where a plant grows or is intended to grow, wherein said watering includes the provision of the nitrification inhibitor according to the present invention together with water.
  • the invention relates to a composition for reducing nitrification comprising the mixture of the invention; and at least one carrier.
  • composition for reducing nitrification refers to a composition which is suitable, e.g. comprises effective concentrations and amounts of the components of the mixture of the invention for reducing nitrification in any context or environment in which nitrification may occur.
  • the nitrification may be reduced in or on or at the locus of a plant.
  • the nitrification may be reduced in the root zone of a plant.
  • the area in which such reduction of nitrification may occur is not limited to the plants and their environment, but may also include any other habitat of nitrifying bacteria or any site at which nitrifying enzymatic activities can be found or can function in a general manner, e.g.
  • nitrification inhibitors as defined herein may be determined according to suitable in vitro and in vivo testings known to the skilled person. These amounts and concentrations may be adjusted to the locus, plant, soil, climate conditions or any other suitable parameter which may have an influence on nitrification processes.
  • a "carrier” as used herein is a substance or composition which facilitates the delivery and/or release of the ingredients to the place or locus of destination. The term includes, for instance, agrochemical carriers which facilitate the delivery and/or release of agrochemicals in their field of use, in particular on or into plants.
  • suitable carriers include solid carriers such as phytogels, or hydrogels, or mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g.
  • an solid or liquid ammonium-containing inorganic fertilizer such as an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; an solid or liquid organic fertilizer such as liquid manure, semi-liquid manure, stable manure, biogas manure and straw manure, worm castings, compost, seaweed or guano, or an urea-containing fertilizer such as urea, formaldehyde urea, anhydrous ammonium, urea ammonium nitrate (UAN) solution, urea sulphur, stabilized urea, urea based NPK-fertilizers, or urea ammonium sulfate, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • an NPK fertilizer such as an NPK fertilizer, ammonium
  • suitable examples of carriers include fumed silica or precipitated silica, which may, for instance, be used in solid formulations as flow aid, anti-caking aid, milling aid and as carrier for liquid active ingredients.
  • suitable carriers are microparticles, for instance microparticles which stick to plant leaves and release their content over a certain period of time.
  • agrochemical carriers such as composite gel microparticles that can be used to deliver plant-protection active principles, e.g. as described in US 6,180,141; or compositions comprising at least one phytoactive compound and an encapsulating adjuvant, wherein the adjuvant comprises a fungal cell or a fragment thereof, e.g.
  • such carriers may include specific, strongly binding molecule which assure that the carrier sticks to the plant, the seed, and/or loci where the plant is growing or is intended to grow, till its content is completely delivered.
  • the carrier may be or comprise cellulose binding domains (CBDs) have been described as useful agents for attachment of molecular species to cellulose (see US 6,124,117); or direct fusions between a CBD and an enzyme; or a multifunctional fusion protein which may be used for delivery of encapsulated agents, wherein the multifunctional fusion proteins may consist of a first binding domain which is a carbohydrate binding domain and a second binding domain, wherein either the first binding domain or the second binding domain can bind to a microparticle (see also WO 03/031477).
  • CBDs cellulose binding domains
  • the carrier may be or comprise cellulose binding domains (CBDs) have been described as useful agents for attachment of molecular species to cellulose (see US 6,124,117); or direct fusions between a CBD and an enzyme; or a multifunctional fusion protein which may be used for delivery of encapsulated agents, wherein the multifunctional fusion proteins may consist of a first binding domain which is a carbohydrate binding domain and a second binding domain
  • carrier examples include bifunctional fusion proteins consisting of a CBD and an anti-RR6 antibody fragment binding to a microparticle, which complex may be deposited onto treads or cut grass (see also WO 03/031477).
  • the carrier may be active ingredient carrier granules that adhere to e.g. the surface of plants, grasses, weeds, seeds, and/or loci where the plant is growing or is intended to grow etc. using a moisture-active coating, for instance including gum arabic, guar gum, gum karaya, gum tragacanth and locust bean gum.
  • the carrier e.g. an agrochemical carrier
  • Polyaminoacids may be obtained according to any suitable process, e.g. by polymerization of single or multiple amino acids such as glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine and/or ornithine.
  • Polyaminoacids may be combined with a nitrification inhibitor according to the present invention and, in certain embodiments, also with further carriers as mentioned herein above, or other nitrification inhibitors as mentioned herein in any suitable ratio.
  • Polyaminoacids may be combined with a nitrification inhibitor according to the present invention in a ratio of 1 to 10 (polyaminoacids) vs. 0.5 to 2 (nitrification inhibitor according to the present invention).
  • the mixture of the invention or the composition of the invention comprising the mixture of the invention may further comprise additional ingredients, for example at least one pesticidal compound.
  • the mixture or composition may additionally comprise at least one herbicidal compound and/or at least one fungicidal compound and/or at least one insecticidal compound and/or at least one nematicide and/or at least one biopesticide and/or at least one biostimulant.
  • the mixture or composition may, in addition to the above indicated ingredients, further comprise one or more alternative or additional nitrification inhibitors.
  • alternative or additional nitrification inhibitors are linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro-6- (trichloromethyl)-pyridine (nitrapyrin or N-serve), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4-amino-l,2,4-triazole hydrochloride (ATC), l-amido-2-thiourea (ASU), 2-amino-4- chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3- trichloromethyl
  • the mixture or composition according to the present invention may further comprise 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve).
  • the mixture or composition according to the present invention may further comprise 5-ethoxy-3-trichloromethyl-l,2,4-thiodiazole (terrazole, etridiazole).
  • the mixture or composition according to the present invention may further comprise 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC).
  • DMPP 3,4-dimethyl pyrazole phosphate
  • the mixture or composition according to the present invention may further comprise 2-amino-4-chloro-6-methylpyrimidine (AM).
  • the mixture or composition according to the present invention may further comprise 2-mercapto-benzothiazole (MBT).
  • the mixture or composition according to the present invention may further comprise 2-sulfanilamidothiazole (ST).
  • ST 2-sulfanilamidothiazole
  • the mixture or composition according to the present invention may further comprise ammoniumthiosulfate (ATU).
  • ATU ammoniumthiosulfate
  • the mixture or composition according to the present invention may further comprise 3-methylpyrazol (3-MP).
  • the mixture or composition according to the present invention may further comprise 3,5-dimethylpyrazole (DMP).
  • DMP 3,5-dimethylpyrazole
  • the mixture or composition according to the present invention may further comprise 1 ,2,4-triazol .
  • the mixture or composition according to the present invention may further comprise thiourea (TU).
  • TU thiourea
  • the mixture or composition according to the present invention may further comprise linoleic acid.
  • the mixture or composition according to the present invention may further comprise alpha-linolenic acid.
  • the mixture or composition according to the present invention may further comprise methyl p-coumarate.
  • the mixture or composition according to the present invention may further comprise methyl 3-(4-hydroxyphenyl) propionate (MHPP).
  • MHPP methyl 3-(4-hydroxyphenyl) propionate
  • the mixture or composition according to the present invention may further comprise methyl ferulate.
  • the mixture or composition according to the present invention may further comprise Karanjin.
  • the mixture or composition according to the present invention may further comprise brachialacton.
  • the mixture or composition according to the present invention may further comprise p-benzoquinone sorgoleone.
  • the mixture or composition according to the present invention may further comprise 4-amino-l,2,4-triazole hydrochloride (ATC).
  • ATC 4-amino-l,2,4-triazole hydrochloride
  • the mixture or composition according to the present invention may further comprise l-amido-2-thiourea (ASU).
  • ASU l-amido-2-thiourea
  • the mixture or composition according to the present invention may further comprise N-((3(5)-methyl-lH-pyrazole-l-yl)methyl)acetamide.
  • the mixture or composition according to the present invention may further comprise N-((3(5)-methyl-lH-pyrazole-l-yl)methyl formamide.
  • the mixture or composition according to the present invention may further comprise N-(4-chloro-3(5)-methyl-pyrazole-l-ylmethyl)-formamide.
  • the mixture or composition according to the present invention may further comprise N-(3(5),4-dimethyl-pyrazole-l-ylmethyl)-formamide.
  • the mixture or composition according to the present invention may further comprise neem or products based on ingredients of neem. In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise cyanamide.
  • the mixture or composition according to the present invention may further comprise melamine.
  • the mixture or composition according to the present invention may further comprise zeolite powder.
  • the mixture or composition according to the present invention may further comprise batechol.
  • the mixture or composition according to the present invention may further comprise benzoquinone.
  • the mixture or composition according to the present invention may further comprise sodium terat borate.
  • the mixture or composition according to the present invention may further comprise zinc sulfate.
  • the mixture or composition according to the present invention may comprise a combination of the mixture of the invention and two entities selected from the group comprising: linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl feru- late, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzo- quinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4-amino-l,2,4-tria- zole hydrochloride (ATC), l-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3-
  • the mixture or composition according to the present invention may comprise a combination of the mixture of the invention and three, four or more entities selected from the group comprising: linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4-amino-l,2,4-triazole hydrochloride (ATC), l-amido-2-thiourea (ASU), 2-amino-4- chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3-
  • the mixture or composition may, in addition to the above indicated ingredients, further comprise one or more urease inhibitors.
  • urease inhibitors include N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain), N-(n-propyl) thiophosphoric acid triamide (NPPT), 2-nitrophenyl phosphoric triamide (2-NPT), further NXPTs known to the skilled person, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate, and mixtures of NBPT and NPPT (see e.g. US 8,075,659).
  • NBPT N-(n-butyl) thiophosphoric acid triamide
  • NPPT N-(n-propyl) thiophosphoric acid triamide
  • 2-NPT 2-nitrophenyl phosphoric triamide
  • PPD/PPDA phenylphosphorodiamidate
  • hydroquinone ammonium thiosulf
  • Such mixtures of NBPT and NPPT may comprise NBPT in amounts of from 40 to 95% wt.-% and preferably of 60 to 80% wt.-% based on the total amount of active substances.
  • Such mixtures are marketed as LIMUS, which is a composition comprising about 16.9 wt.-% NBPT and about 5.6 wt.-% NPPT and about 77.5 wt.-% of other ingredients including solvents and adjuvants.
  • the mixture or composition according to the present invention may further comprise N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain).
  • NBPT N-(n-butyl) thiophosphoric acid triamide
  • the mixture or composition according to the present invention may further comprise phenylphosphorodiamidate (PPD/PPDA).
  • the mixture or composition according to the present invention may further comprise N-(n-propyl) thiophosphoric acid triamide (NPPT).
  • NPPT N-(n-propyl) thiophosphoric acid triamide
  • the mixture or composition according to the present invention may further comprise 2-nitrophenyl phosphoric triamide (2-NPT).
  • the mixture or composition according to the present invention may further comprise hydroquinone.
  • the mixture or composition according to the present invention may further comprise ammonium thiosulfate.
  • the mixture or composition according to the present invention may further comprise neem.
  • the mixture or composition according to the present invention may further comprise cyanamide.
  • the mixture or composition according to the present invention may further comprise melamine.
  • the mixture or composition according to the present invention may further comprise a mixture of NBPT and NPPT such as LIMUS.
  • the mixture or composition according to the present invention may comprise a combination of the mixture of the invention and two or more entities selected from the group comprising: N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain), N-(n-propyl) thiophosphoric acid triamide (NPPT), 2-nitrophenyl phosphoric triamide (2-NPT), further NXPTs known to the skilled person, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate, and LIMUS.
  • NBPT N-(n-butyl) thiophosphoric acid triamide
  • NPPT N-(n-propyl) thiophosphoric acid triamide
  • 2-NPT 2-nitrophenyl phosphoric triamide
  • PPD/PPDA phenylphosphorodiamidate
  • hydroquinone ammonium thiosulfate
  • LIMUS LIMUS
  • the mixture or composition may, in addition to one, more or all of the above indicated ingredients, further comprise one or more plant growth regulators.
  • plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releasers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators, and further unclassified plant growth regulators.
  • Suitable examples of antiauxins to be used in a mixture or composition according to the present invention are clofibric acid or 2,3,5-tri-iodobenzoic acid.
  • auxins to be used in a mixture or composition according to the present invention are 4-CPA, 2,4-D, 2,4-DB, 2,4-DEP, dichlorprop, fenoprop, IAA (indole-3- acetic acid), IBA, naphthaleneacetamide, alpha-naphthaleneacetic acid, 1-naphthol, naphthoxyacetic acid, potassium naphthenate, sodium naphthenate or 2,4,5-T.
  • Suitable examples of defoliants to be used in a mixture or composition according to the present invention are calcium cyanamide, dimethipin, endothal, merphos, metoxuron, pentachlorophenol, thidiazuron, tributes, or tributyl phosphorotrithioate.
  • ethylene modulators to be used in a mixture or composition according to the present invention are aviglycine, 1-methylcyclopropene (1-MCP), Prohexadione (prohexadione calcium), or trinexapac (Trinexapac-ethyl).
  • Suitable examples of ethylene releasers to be used in a composition according to the present invention are ACC, et messagingl, ethephon, or glyoxime.
  • Suitable examples of gibberellins to be used in a mixture or composition according to the present invention are gibberelline or gibberellic acid.
  • Suitable examples of growth inhibitors to be used in a mixture or composition according to the present invention are abscisic acid, S-abscisic acid, ancymidol, butralin, carbaryl ,ch lor- phonium, chlorpropham, dikegulac, flumetralin, fluoridamid,fosamine, glyphosine, isopyrimol, jasmonic acid, maleic hydrazide, mepiquat (mepiquat chloride, mepiquat pentaborate), piproctanyl, prohydrojasmon, propham, or 2,3,5-tri-iodobenzoic acid.
  • Suitable examples of morphactins to be used in a mixture or composition according to the present invention are chlorfluren, chlorflurenol, dichlorflurenol, or flurenol
  • Suitable examples of growth retardants to be used in a mixture or composition according to the present invention are chlormequat (chlormequat chloride), daminozide, flurprimidol, mefluidide, paclobutrazol, tetcyclacis, uniconazole, metconazol.
  • Suitable examples of further unclassified plant growth regulators to be used in a mixture or composition according to the present invention are amidochlor, benzofluor, buminafos, carvone, choline chloride, ciobutide, clofencet, cloxyfonac, cyanamide, cyclanilide, cycloheximide, cyprosulfamide, epocholeone, ethychlozate, ethylene, fenridazon, fluprimidol, fluthi- acet, heptopargil, holosulf, inabenfide, karetazan, lead arsenate, methasulfocarb, pydanon, sintofen, diflufenzopyr or triapenthenol.
  • the mixture or composition according to the present invention may further comprise clofibric acid.
  • the mixture or composition according to the present invention may further comprise 2,3,5-tri-iodobenzoic acid.
  • the mixture or composition according to the present invention may further comprise 4-CPA.
  • the c mixture or omposition according to the present invention may further comprise 2,4-D.
  • the mixture or composition according to the present invention may further comprise 2,4-DB.
  • the mixture or composition according to the present invention may further comprise 2,4-DEP.
  • the mixture or composition according to the present invention may further comprise dichlorprop.
  • the mixture or composition according to the present invention may further comprise fenoprop.
  • the mixture or composition according to the present invention may further comprise IAA (indole-3-acetic acid).
  • mixture or composition according to the present invention may further comprise IBA.
  • the mixture or composition according to the present invention may further comprise naphthaleneacetamide.
  • the mixture or composition according to the present invention may further comprise alpha-naphthaleneacetic acid.
  • the mixture or composition according to the present invention may further comprise 1-naphthol.
  • the mixture or composition according to the present invention may further comprise naphthoxyacetic acid.
  • the mixture or composition according to the present invention may further comprise potassium naphthenate.
  • the mixture or composition according to the present invention may further comprise sodium naphthenate.
  • the mixture or composition according to the present invention may further comprise and 2,4,5-T.
  • the mixture or composition according to the present invention may further comprise 2iP.
  • the mixture or composition according to the present invention may further comprise 2,6-Dimethylpuridine (N -Oxid e-2 ,6- Lu Itid i ne) .
  • the mixture or composition according to the present invention may further comprise zeatin. In a further preferred embodiment, the mixture or composition according to the present invention may further comprise kinetin.
  • the mixture or composition according to the present invention may further comprise calcium cyanamide.
  • the mixture or composition according to the present invention may further comprise dimethipin.
  • the mixture or composition according to the present invention may further comprise endothal.
  • the mixture or composition according to the present invention may further comprise merphos.
  • the mixture or composition according to the present invention may further comprise metoxuron.
  • the mixture or composition according to the present invention may further comprise pentachlorophenol.
  • the mixture or composition according to the present invention may further comprise thidiazuron.
  • the mixture or composition according to the present invention may further comprise tribufos.
  • the mixture or composition according to the present invention may further comprise tributyl phosphorotrithioate.
  • the mixture or composition according to the present invention may further comprise aviglycine.
  • the mixture or composition according to the present invention may further comprise 1-methylcyclopropene.
  • a mixture or composition as defined herein in particular a mixture or composition further comprising a plant growth regulator as defined herein, may be used for the increase of plant health.
  • plant health as used herein is intended to mean a condition of the plant which is determined by several aspects alone or in combination with each other.
  • One indicator (indicator 1) for the condition of the plant is the crop yield.
  • “Crop” and “fruit” are to be understood as any plant product which is further utilized after harvesting, e.g. fruits in the proper sense, vegetables, nuts, grains, seeds, wood (e.g. in the case of silviculture plants), flowers (e.g. in the case of gardening plants, ornamentals) etc., that is anything of economic value that is produced by the plant.
  • Another indicator (indicator 2) for the condition of the plant is the plant vigor. The plant vigor becomes manifest in several aspects, too, some of which are visual appearance, e.g.
  • leaf color, fruit color and aspect amount of dead basal leaves and/or extent of leaf blades, plant weight, plant height, extent of plant verse (lodging), number, strong ness and productivity of tillers, panicles' length, extent of root system, strength of roots, extent of nodulation, in particular of rhizobial nodulation, point of time of germination, emergence, flowering, grain maturity and/or senescence, protein content, sugar content and the like.
  • Another indicator (indicator 3) for an increase of a plant's health is the reduction of biotic or abiotic stress factors.
  • the three above mentioned indicators for the health condition of a plant may be interdependent and may result from each other.
  • a reduction of biotic or abiotic stress may lead to a better plant vigor, e.g. to better and bigger crops, and thus to an increased yield.
  • Biotic stress especially over longer terms, can have harmful effects on plants.
  • the term "biotic stress” as used in the context of the present invention refers in particular to stress caused by living organisms.
  • the quantity and the quality of the stressed plants, their crops and fruits decrease.
  • reproductive development is usually severely affected with consequences on the crops which are important for fruits or seeds.
  • Growth may be slowed by the stresses; polysaccharide synthesis, both structural and storage, may be reduced or modified: these effects may lead to a decrease in biomass and to changes in the nutritional value of the product.
  • Abiotic stress includes drought, cold, increased UV, increased heat, or other changes in the environment of the plant, that leads to sub-optimal growth conditions.
  • the term "increased yield" of a plant as used herein means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the composition of the invention. According to the present invention, it is preferred that the yield be increased by at least 0,5 %, more preferred at least 1 %, even more preferred at least 2 %, still more preferred at least 4 %.
  • An increased yield may, for example, be due to a reduction of nitrification and a corresponding improvement of uptake of nitrogen nutrients.
  • improved plant vigor means that certain crop characteristics are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the composition of the present invention. Improved plant vigor can be characterized, among others, by following improved properties of a plant:
  • the improvement of the plant vigor according to the present invention particularly means that the improvement of anyone or several or all of the above mentioned plant characteristics are improved. It further means that if not all of the above characteristics are improved, those which are not improved are not worsened as compared to plants which were not treated according to the invention or are at least not worsened to such an extent that the negative effect exceeds the positive effect of the improved characteristic (i.e. there is always an overall positive effect which preferably results in an improved crop yield).
  • An improved plant vigor may, for example, be due to a reduction of nitrification and, e.g. a regulation of plant growth.
  • the mixture or composition may, in addition to the above indicated ingredients, further comprise one or more pesticides.
  • a pesticide is generally a chemical or biological agent (such as pesticidal active ingredient, compound, composition, virus, bacterium, antimicrobial or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests.
  • Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease.
  • pesticide includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
  • Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, microbial and biochemical pesticides:
  • Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classed as microbial pesticides, even though they are multi-cellular.
  • Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively non-toxic to mammals.
  • composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit comprising a) a composition comprising component 1) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.
  • pesticides I e. g. pesticida I ly-active substances and biopesticides
  • the compounds I in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them:
  • C14 demethylase inhibitors triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromu- conazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), dini- conazole-M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1.14), ip- conazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), pa- clobutrazole (B.1.20), penconazole (B.1.21), propiconazole
  • Deltal4-reductase inhibitors aldimorph (B.2.1), dodemorph (B.2.2), dodemorph-ac- etate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spiroxamine (B.2.8);
  • Nucleic acid synthesis inhibitors phenylamides or acyl amino acid fungicides benalaxyl (C.1.1), benalaxyl-M (C.1.2), ki- ralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7); other nucleic acid synthesis inhibitors: hymexazole (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrim- idin-4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-flu- oro-2-(4-chlorophenylmethoxy
  • D) Inhibitors of cell division and cytoskeleton tubulin inhibitors benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (DI.3), thiabendazole (D.1.4), thiophanate-methyl (D.1.5), 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5- phenyl-py rid azine (D.1.6), 3-ch loro-6- methyl -5- phenyl -4- (2, 4,6-trif I uoropheny I) py ridazine (D.1.7), /V-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]butanamide (D.1.8), /V-ethy I -2- [(3- ethynyl -8- methyl -6-quinolyl)oxy] -2- methylsulfanyl -acetamide (D.1.9), 2-
  • MAP / histidine kinase inhibitors fluoroimid (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fludioxonil (F.1.5); G protein inhibitors: quinoxyfen (F.2.1);
  • Phospholipid biosynthesis inhibitors edifenphos (G.1.1), iprobenfos (G.1.2), pyra- zophos (G.1.3), isoprothiolane (G.1.4); lipid peroxidation: dicloran (G.2.1), quintozene (G.2.2), tecnazene (G.2.3), tolclofos- methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7); phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7); compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1); inhibitors of oxysterol binding protein
  • Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity Ampelomyces quisqua/is, Aspergillus f/avus, Aureobasidium pullulans, Bacillus a/titudinis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. so/isa Isi, B. subti/is, B. subtilis iar. amyloliquefaciens, Candida oieophiia, C.
  • Ciavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonec- tria parasitica, Cryptococcus aibidus, Diiophosphora aiopecuri, Fusarium oxysporum, Cionostachys rosea catenulate (also named GHodadium catenulatum), Gliocladium ro- seum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicoia, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibaciius alvei, Paenibaciiius epiphyticus, P.
  • Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity harpin protein, Reynoutria sachaiinensis extract;
  • Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity Agrobacterium radiobacter, Bacillus cereus, B. firm us, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israeiensis, B. t. ssp. gaiieriae, B. t. ssp. kurstaki, B. t. ssp. tenebrio- nis, Beauveria bassiana, B.
  • Agrobacterium radiobacter Bacillus cereus, B. firm us, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israeiensis, B. t. ssp. gaiieriae, B. t. ssp. kurstaki, B. t
  • brongniartii Burkhoideria spp., Chromobacterium subtsugae, Cydia pomoneiia granulovirus (CpGV), Cryptophiebia ieucotreta granulovirus (CrleGV), Fiavobacterium spp., Heiicoverpa armigera nucleopolyhedrovirus (HearNPV), Heiicoverpa zea nucleopolyhedrovirus (HzNPV), Heiicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, isaria fumosorosea, LecaniciHium iongisporum, L.
  • HearNPV Heiicoverpa zea nucleopolyhedrovirus
  • HzSNPV Heiicoverpa zea single capsid nucleopolyhedrovirus
  • Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. ha/opraeferens, Bradyrhizobium spp., B. e/kanii, B. japonicum, B. liaoningense, B. lupini, De/ftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhi- zobium ieguminosarum bv. phaseoii, R. /. bv. trifoiii, R. /. bv. viciae, R. tropici, Sinorhizobium me! Hoti
  • M.l) Acetylcholine esterase (AChE) inhibitors M.1A carbamates, e.g. aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, me- thiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or M.1B organophosphates, e.g.
  • M.2A GABA-gated chloride channel antagonists M.2A cyclodiene organochlorine compounds, e.g. endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), e.g. ethiprole, fipronil, flufiprole, pyrafluprole, and pyriprole;
  • M.3A Sodium channel modulators from the class of M.3A pyrethroids, e.g. acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta- cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, al- pha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, e
  • Nicotinic acetylcholine receptor agonists M.4A neonicotinoids, e.g. acet- amiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds M.4A.1 4,5-Dihydro-N-nitro-l-(2-oxiranyl- methyl)-lH-imidazol-2-amine, M.4 A.2: (2 E-)-l-[(6-Ch Io ropy rid in -3-yl) methyl] -N'- nitro-2-pentylidenehydrazinecarboximidamide; or M4.A.3: l-[(6-Chloropyridin-3- y I) methyl] -7- methyl -8- nitro-5- pro poxy- 1,2, 3, 5, 6, 7-
  • Chloride channel activators from the class of avermectins and milbemycins e.g. abamectin, emamectin benzoate, ivermectin, lepimectin, or milbemectin;
  • Juvenile hormone mimics such as M.7A juvenile hormone analogues hydroprene, kinoprene, and methoprene; or M.7B fenoxycarb, or M.7C pyriproxyfen;
  • M.8A alkyl halides as methyl bromide and other alkyl halides, M.8B chloropicrin, M.8C sulfuryl fluoride, M.8D borax, or M.8E tartar emetic; M.9) Chordotonal organ TRPV channel modulators, e.g. M.9B pymetrozine; pyriflu- quinazon;
  • M.10 Mite growth inhibitors e.g. M.10A clofentezine, hexythiazox, and diflovidazin, or M.10B etoxazole;
  • Mite growth inhibitors e.g. M.10A clofentezine, hexythiazox, and diflovidazin, or M.10B etoxazole;
  • M.ll Microbial disruptors of insect midgut membranes, e.g. bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israeiensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, and Cry34/35Abl;
  • M.12 Inhibitors of mitochondrial ATP synthase, e.g. M.12A diafenthiuron, or M.12B organotin miticides such as azocyclotin, cyhexatin, or fenbutatin oxide, M.12C propar- gite, or M.12D tetradifon;
  • Nicotinic acetylcholine receptor (nAChR) channel blockers e.g. nereistoxin analogues bensultap, cartap hydrochloride, thiocyclam, or thiosultap sodium;
  • Inhibitors of the chitin biosynthesis type 0, such as benzoylureas e.g. bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, or triflumuron;
  • benzoylureas e.g. bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, or triflumuron;
  • Ecdyson receptor agonists such as diacylhydrazines, e.g. methoxyfenozide, te- bufenozide, halofenozide, fufenozide, or chromafenozide;
  • Octopamin receptor agonists e.g. amitraz
  • M.20 Mitochondrial complex III electron transport inhibitors, e.g. M.20A hydramethylnon, M.20B acequinocyl, M.20C fluacrypyrim; or M.20D bifenazate;
  • M.21 Mitochondrial complex I electron transport inhibitors, e.g. M.21A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21B rotenone;
  • M.22 Voltage-dependent sodium channel blockers, e.g. M.22A indoxacarb, M.22B meta- flumizone, or M.22B.1: 2-[2-(4-Cyanophenyl)-l-[3-(trifluoromethyl)phenyl]ethyl- idene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3- Ch loro-2- methyl phenyl) -2- [(4-chlorophenyl) [4- [methyl (methylsulf- onyl)a mi no] phenyl] methylene] -hydrazinecarboxamide;
  • Inhibitors of the of acetyl CoA carboxylase such as Tetronic and Tetramic acid derivatives, e.g. spirodiclofen, spiromesifen, or spirotetramat; M.23.1 spiropidion;
  • M.24 Mitochondrial complex IV electron transport inhibitors, e.g. M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide;
  • M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide
  • Mitochondrial complex II electron transport inhibitors such as beta-ketonitrile derivatives, e.g. cyenopyrafen or cyflumetofen; M.28) Ryanodine receptor-modulators from the class of diamides, e.g.
  • M.UN. insecticidal active compounds of unknown or uncertain mode of action e.g. afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, broflanilide, bromopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flomet- oquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, tioxazafen, M.UN.3: ll-(4-chloro-2,6- di methyl phenyl) -12- hydroxy- l,4-dioxa-9-azadispiro[4.2.4.2] -tetradec- 11 -en- 10- one,
  • M.UN.5 1 - [2-f I u oro-4- methyl -5- [(2, 2,2-trif I uoroethy I) sulfinyl] phenyl] -3 -(trifl uo- romethyl)-lH-l,2,4-triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582);
  • M.UN.8 fluazaindolizine
  • M.UN.9. a): 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl] -2 -methyl-N-(l-oxothietan-3-yl) benzamide
  • M.UN.10 5- [3- [2,6-dich loro-4- (3,3-dichloroa I lyl oxy) phenoxy] propoxy] -1H- pyrazole;
  • M.UN.ll.i 4-cyano-N-[2-cyano-5-[[2,6-dibromo-4-[l,2,2,3,3,3-hexafluoro-l-(trifluoro- methy I) propyl] phenyl] carbamoyl] phenyl] -2 -methyl -benzamide; M.UN.ll.j) 4-cy- ano-3-[(4-cyano-2-methyl-benzoyl)amino]-N -[2,6-dich loro-4- [1,2, 2, 3, 3, 3-hexa- f I uoro- 1 - (trifluoro methyl) propyl] phenyl] -2-f I uoro- benzamide; M.UN.ll.k) N-[5-[[2- ch Io ro-6-cya no-4- [1,2,2, 3,3,3 -hexafl uoro-1- (trifl uoro methyl
  • M. UN.14a 1 - [(6-Ch I oro-3 -py rid iny I) methyl] -1, 2,3,5, 6,7- hexa hydro-5 -methoxy-7- methyl-8-nitro-imidazo[l,2-a]pyridine; or M. UN.14b) l-[(6-Chloropyridin-3- yl)methyl]-7-methyl-8-nitro-l,2,3,5,6,7-hexahydroimidazo[l,2-a]pyridin-5-ol;
  • M. UN.16b l-(l,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4- ca r boxa m ide
  • M. UN.16c N,5-dimethyl-N-pyridazin-4-yl-l-(2,2,2-trifluoro-l-methyl- ethyl)pyrazole-4-carboxamide
  • M.UN.16d 1 -[1-(1 -cyanocyclo propyl) ethyl] -N -ethyl - 5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide
  • M.UN.16e N-ethyl-l-(2-flu- oro-l-methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;
  • M.UN.16f l-(l,2-dim ethyl propyl) -N,5-dimethyl-N-pyridazin-4-yl-pyrazo I e-4-car- boxamide;
  • M. UN.16g l-[l-(l-cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazin-4- yl-pyrazole-4-carboxamide;
  • M.UN.16h N-methy 1-1- (2-f I uoro-1- methyl -propyl] -5- methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;
  • M.UN.16i l-(4,4-difluorocyclo- hexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; or M.UN.16j) 1- (4,4-
  • M.UN.21 N-[4-Chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-l-methyl-3-(l,l,2,2,2- pe ntaf luoroethyl)-4-(trifluoromethy I) -IH-pyrazo I e-5 -carboxamide; M. UN.22a 2- (3- ethy I su Ifo ny I -2 - py ridy I ) -3 - methy I -6- (trif I uo rom et hy I) i m idazo [4,5- b] py rid i ne, or M.
  • M. UN.23a 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2- ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide, or M. UN.23b) 4-[5-(3,5-di- chloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3- oxo-isoxazol id in -4-yl] -2 -methy I -benzamide;
  • the present invention furthermore relates to mixtures and compositions comprising at least one further active substance useful for plant protection, e. g. selected from the groups A) to N) (component 2), in particular one further herbicide selected from the group N).
  • at least one further active substance useful for plant protection e. g. selected from the groups A) to N) (component 2), in particular one further herbicide selected from the group N).
  • the order of application is not essential for working of the present invention.
  • the time between both applications may vary e. g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1.5 hours to 5 days, even more preferred from 2 hours to 1 day.
  • the pesticide I is applied as last treatment.
  • the solid material (dry matter) of the biopesticides (with the exception of oils such as Neem oil, Tagetes oil, etc.) are considered as active components (e. g. to be obtained after drying or evaporation of the extraction medium or the suspension medium in case of liquid formulations of the microbial pesticides).
  • the weight ratios and percentages used herein for a biological extract such as Quillay extract are based on the total weight of the dry content (solid material) of the respective extract(s).
  • the total weight ratios of compositions comprising at least one microbial pesticide in the form of viable microbial cells including dormant forms can be determined using the amount of CFU of the respective microorganism to calculate the total weight of the respective active component with the following equation that 1 x 10 10 CFU equals one gram of total weight of the respective active component.
  • Colony forming unit is measure of viable microbial cells, in particular fungal and bacterial cells.
  • CFU may also be understood as the number of (juvenile) individual nematodes in case of (entomopathogenic) nematode biopesticides, such as Steinernema feltiae.
  • the weight ratio of the components generally depends from the properties of the active components used, usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1, even more preferably in the range of from 1:4 to 4:1 and in particular in the range of from 1:2 to 2:1.
  • the weight ratio of the components usually is in the range of from 1000:1 to 1:1, often in the range of from 100: 1 to 1:1, regularly in the range of from 50:1 to 1:1, preferably in the range of from 20:1 to 1:1, more preferably in the range of from 10:1 to 1:1, even more preferably in the range of from 4:1 to 1:1 and in particular in the range of from 2:1 to 1:1.
  • the weight ratio of the components usually is in the range of from 1:1 to 1:1000, often in the range of from 1:1 to 1:100, regularly in the range of from 1:1 to 1:50, preferably in the range of from 1:1 to 1:20, more preferably in the range of from 1:1 to 1:10, even more preferably in the range of from 1:1 to 1:4 and in particular in the range of from 1:1 to 1:2.
  • the weight ratio of the components generally depends from the properties of the active components used, usually it is in the range of from 1:10,000 to 10,000:1, regularly in the range of from 1:100 to 10,000:1, preferably in the range of from 1:100 to 5,000:1, more preferably in the range of from 1:1 to 1,000:1, even more preferably in the range of from 1:1 to 500:1 and in particular in the range of from 10:1 to 300:1.
  • the weight ratio of the components usually is in the range of from 20,000:1 to 1:10, often in the range of from 10,000:1 to 1:1, regularly in the range of from 5,000:1 to 5:1, preferably in the range of from 5,000:1 to 10:1, more preferably in the range of from 2,000:1 to 30:1, even more preferably in the range of from 2,000:1 to 100:1 and in particular in the range of from 1,000:1 to 100:1.
  • the weight ratios of the components usually is in the range of from 1:20,000 to 10:1, often in the range of from 1:10,000 to 1:1, regularly in the range of from 1:5,000 to 1:5, preferably in the range of from 1:5,000 to 1:10, more preferably in the range of from 1:2,000 to 1:30, even more preferably in the range of from 1:2,000 to 1:100 and in particular in the range of from 1:1,000 to 1:100.
  • WO 05/123690 WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 10/139271, WO 11/028657, WO 12/168188, WO 07/006670, WO 11/77514; WO 13/047749, WO 10/069882, WO 13/047441, WO 03/16303, WO 09/90181, WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/24010, WO 13/047441, WO 13/162072, WO 13/092224,
  • WO 11/135833 ON 1907024, ON 1456054, ON 103387541, ON 1309897, WO 12/84812, ON 1907024, WO 09094442, WO 14/60177, WO 13/116251, WO 08/013622, WO 15/65922, WO 94/01546, EP 2865265, WO 07/129454, WO 12/165511, WO 11/081174, WO 13/47441).
  • Some compounds are identified by their CAS Registry Number which is separated by hyphens into three parts, the first consisting from two up to seven digits, the second consisting of two digits, and the third consisting of a single digit.
  • M.4 cycloxaprid is known from W02010/069266 and WO2011/069456.
  • M.4A.1 is known from CN 103814937; CN105367557, CN 105481839.
  • M.4A.2, guadipyr is known from WO 2013/003977, and M.4A.3 (approved as paichongding in China) is known from WO 2007/101369.
  • M.22B.1 is described in CN10171577 and M.22B.2 in CN102126994.
  • Spiropid- ion M.23.1 is known from WO 2014/191271.
  • M.28.1 and M.28.2 are known from W02007/101540.
  • M.28.3 is described in W02005/077934.
  • M.28.4 is described in W02007/043677.
  • M.28.5a) to M.28.5d) and M.28.5h) are described in WO 2007/006670, W02013/024009 and WO 2013/024010,
  • M.28.5i) is described in WO2011/085575,
  • M.28.6 can be found in WO2012/034472.
  • M.UN.3 is known from W02006/089633 and M.UN.4 from W02008/067911.
  • M.UN.5 is described in W02006/043635, and biological control agents on the basis of bacillus firmus are described in W02009/124707. Flupyrimin is described in WO2012/029672.
  • M.UN.8 is known from WO2013/055584.
  • M.UN.9.a) is described in W02013/050317.
  • M.UN.9.b) is described in WO2014/126208.
  • M.UN.10 is known from W02010/060379. Broflanilide and M.UN.ll.b) to M.UN.ll.h) are described in W02010/018714, and M.UN.lli) to M.UN.ll.p) in WO 2010/127926.
  • M.UN.12.c a) to M.UN.12.c) are known from W02010/006713
  • M.UN.12.d) and M.UN.12.e) are known from W02012/000896.
  • M. UN.14a) and M. UN.14b) are known from W02007/101369.
  • M. UN.16. a) to M.UN.16h) are described in W02010/034737, W02012/084670, and WO2012/143317, resp.
  • M.UN.16i) and M.UN.16j) are described in WO2015/055497.
  • M. UN.17a) to M.UN.17J) are described in W02015/038503.
  • M.UN.18 Tycloprazoflor is described in US2014/0213448.
  • M.UN.19 is described in W02014/036056.
  • M.UN.20 is known from W02014/090918.
  • M.UN.21 is known from EP2910126.
  • M. UN.22a and M. UN.22b are known from W02015/059039 and W02015/190316.
  • M. UN.23a and M. UN.23b are known from W02013/050302.
  • M. UN.24a) and M. UN.24b) are known from WO2012/126766.
  • Acynonapyr M.UN.25 is known from WO 2011/105506.
  • Benzpyrimoxan M.UN.26 is known from W02016/104516.
  • M.UN.27 is known from WO2016/174049.
  • M.UN.28 Oxazosulfyl is known from WO2017/104592.
  • M. UN.29a) to M.UN.29f) are known from W02009/102736 or W02013116053.
  • the biopesticides from group LI) and/or L2) may also have insecticidal, acaricidal, mollus- cidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity.
  • the biopesticides from group L3) and/or L4) may also have fungicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity.
  • the biopesticides from group L5) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
  • pumi/us INR-7 otherwise referred to as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by Erwinia tracheiphi/a (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumi/us KFP9F isolated from the rhizosphere of grasses in South Africa at least before 2008 (NRRL B-50754; WO 2014/029697; e. g. BAC-UP or FUSION-P from BASF Agricultural Specialities (Pty) Ltd., South Africa), B. pumi/us QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL B-30087; e.
  • B. simplex ABU 288 (NRRL B-50304; US 8,445,255), B. subti/is FB17 also called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC PTA- 11857; System. Appl. Microbiol. 27, 372-379, 2004; US 2010/0260735; WO 2011/109395); B. thuringiensis ssp. aizawai ABTS-1857 isolated from soil taken from a lawn in Ephraim, Wisconsin, U.S.A., in 1987 (also called ABG-6346; ATCC SD-1372; e. g.
  • tenebrionis NB-176-1 a mutant of strain NB-125, a wild type strain isolated in 1982 from a dead pupa of the beetle Tenebrio molitor (DSM 5480; EP 585 215 Bl; e. g. Novodor® from Valent BioSciences, Switzerland), Beauveria bassiana GHA (ATCC 74250; e. g. BotaniGard® 22WGP from Laverlam Int. Corp., USA), B. bassiana JW-1 (ATCC 74040; e. g. Naturalis® from CBC (Europe) S.r.L, Italy), B.
  • DSM 5480 Tenebrio molitor
  • EP 585 215 Bl e. g. Novodor® from Valent BioSciences, Switzerland
  • Beauveria bassiana GHA ATCC 74250; e. g. BotaniGard® 22WGP from Laverlam Int. Corp., USA
  • B. bassiana JW-1 AT
  • bassiana PPRI 5339 isolated from the larva of the tortoise beetle Conchy/octenia punctata (NRRL 50757; e. g. BroadBand® from BASF Agricultural Specialities (Pty) Ltd., South Africa), Bradyrhizobium e/kanii s ams SEMIA 5019 (also called 29W) isolated in Rio de Janeiro, Brazil and SEMIA 587 isolated in 1967 in the State of Rio Grande do Sul, from an area previously inoculated with a North American isolate, and used in commercial inoculants since 1968 (AppL Environ. Microbiol. 73(8), 2635, 2007; e. g. GELFIX 5 from BASF Agricultural Specialties Ltd., Brazil), B.
  • NRRL 50757 e. g. BroadBand® from BASF Agricultural Specialities (Pty) Ltd., South Africa
  • Bradyrhizobium e/kanii s ams SEMIA 5019 also called 29W
  • japonicum 532c isolated from Wisconsin field in U.S.A. (Nitragin 61A152; Can. J. Plant. Sci. 70, 661-666, 1990; e. g. in Rhizoflo®, Histick®, Hicoat® Super from BASF Agricultural Specialties Ltd., Canada), B. japonicum E-109 variant of strain USDA 138 (INTA E109, SEMIA 5085; Eur. J. Soil Biol. 45, 28-35, 2009; Biol. Fertil. Soils 47, 81-89, 2011); B. japonicum strains deposited at SEMIA known from AppL Environ. Microbiol.
  • SEMIA 5079 isolated from soil in Cerrados region, Brazil by Embrapa-Cerrados used in commercial inoculants since 1992 (CPAC 15; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum SEMIA 5080 obtained under lab condtions by Embrapa-Cerrados in Brazil and used in commercial inoculants since 1992, being a natural variant of SEMIA 586 (CB1809) originally isolated in U.S.A. (CPAC 7; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil); Burkhoideria sp.
  • CPAC 15 e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil
  • B. japonicum SEMIA 5080 obtained under lab condtions by Embrapa-Cerrados in Brazil and used in commercial inoculants since 1992, being a natural variant of
  • Heiicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (e. g. Gemstar® from Certis LLC, USA), Heiicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e. g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia), Heterorhabditis bacteriophora (e. g.
  • Met52® Novozymes Biologicals BioAg Group, Canada Metschnikowia fructicoia 277 isolated from grapes in the central part of Israel (US 6,994,849; NRRL Y-30752; e. g. formerly Shemer® from Agrogreen, Israel), Pae- ciiomyces Hacinus 25 ⁇ . isolated from infected nematode eggs in the Philippines (AGAL 89/030550; WC1991/02051; Crop Protection 27, 352-361, 2008; e. g. BioAct®from Bayer CropScience AG, Germany and MeloCon® from Certis, USA), Paenibaciiius a/ize/NAS6G6 isolated from the rhizosphere of grasses in South Africa at least before 2008
  • WO 2014/029697 NRRL B-50755; e.g. BAC-UP from BASF Agricultural Specialities (Pty) Ltd., South Africa
  • Jump Start® Provide® from Novozymes Biologicals BioAg Group, Canada
  • Reynoutria sachalinensis extract EP 0307510 Bl; e. g. Regalia® SC from Marrone BioInnovations, Davis, CA, USA or Milsana® from BioFa AG, Germany
  • Steinernema car- pocapsae e. g. Millenium® from BASF Agricultural Specialities Limited, UK
  • S. feitiae e. g.
  • the at least one pesticide II is selected from the groups LI) to L6):
  • Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity Aureobasidium pullulans bS ⁇ 14940 and DSM 14941 (Ll.l), Bacillus amy- loliquefaciens AP-188 (L.1.2), B. amyloliquefaciens ssp. plantarum D747 (L.1.3), B. amyloliquefaciens ssp. plantarum FZB24 (L.1.4), B. amyloliquefaciens ssp. plantarum FZB42 (L.1.5), B. amyloliquefaciens ssp.
  • subtiiis FB17 (L.1.15), Coniothyrium minitans CON/M/91-08 (L.1.16), Metschnikowia fructicoia NRRL Y-30752 (L.1.17), PeniciHium biiaiae ATCC 22348 (L.1.19), P. biiaiae ATCC 20851 (L.1.20), Peni- ciHium biiaiae ATCC 18309 (L.1.21), Streptomyces microfiavus NRRL B-50550 (L.1.22), T. harzianum f -22 (L.1.24);
  • Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity Bacillus firmus 1-1582 (L.3.1); B. thuringiensis ssp. aizawai ABTS- 1857 (L.3.2), B. t. ssp. kurstaki ABTS -351 (L.3.3), B. t. ssp. tenebrionis NB- 176-1 (L.3.5), Beauveria bassiana GHA (L.3.6), B. bassiana JW-1 (L.3.7), Burkhoideria sp.
  • A396 (L.3.9), Heiicov- erpa armigera nucleopolyhedrovirus (HearNPV) (L.3.10), Heiicoverpa zea nucleopolyhe- drovirus (HzNPV) ABA-NPV-U (L.3.11), Heiicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (L.3.12), Heterohabditis bacteriophora (L.3.13), Isaria fumosorosea Apopka-97 (L.3.14), Metarhizium anisopiiae iar. anisopiiae F52 (L.3.15), Paeciiomyces Pnl (L.3.17), Steinernema carpocapsae
  • the present invention relates to an agrochemical mixture comprising at least one fertilizer; and the mixture of the invention; or at least one fertilizer and the composition as mentioned above.
  • agrochemical mixture means a combination of at least two components, in the present case the mixture of compositions of the invention and the fertilizer.
  • the term is, however, not restricted to a physical mixture comprising the at least two components, but refers to any preparation form of at least one component and at least one further component, the use of which many be time- and/or locus-related.
  • the agrochemical mixtures may, for example, be formulated separately but applied in a temporal relationship, i.e. simultaneously or subsequently, the subsequent application having a time interval which allows a combined action of the compounds.
  • the individual components of the agrochemical mixtures according to the invention such as parts of a kit or parts of the binary mixture may be mixed by the user himself in a suitable mixing device.
  • further auxiliaries may be added, if appropriate.
  • fertilizers is to be understood as chemical compounds applied to promote plant and fruit growth. Fertilizers are typically applied either through the soil (for uptake by plant roots), through soil substituents (also for uptake by plant roots), or by foliar feeding (for uptake through leaves). The term also includes mixtures of one or more different types of fertilizers as mentioned below.
  • fertilizers can be subdivided into several categories including: a) organic fertilizers (composed of decayed plant/animal matter), b) inorganic fertilizers (composed of chemicals and minerals) and c) urea-containing fertilizers.
  • Organic fertilizers include manure, e.g. liquid manure, semi-liquid manure, biogas manure, stable manure or straw manure, slurry, worm castings, peat, seaweed, compost, sewage, and guano. Green manure crops are also regularly grown to add nutrients (especially nitrogen) to the soil.
  • Manufactured organic fertilizers include compost, blood meal, bone meal and seaweed extracts. Further examples are enzyme digested proteins, fish meal, and feather meal. The decomposing crop residue from prior years is another source of fertility.
  • naturally occurring minerals such as mine rock phosphate, sulfate of potash and limestone are also considered inorganic fertilizers.
  • Inorganic fertilizers are usually manufactured through chemical processes (such as the Haber process), also using naturally occurring deposits, while chemically altering them (e.g. concentrated triple superphosphate).
  • Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mine rock phosphate, limestone, and raw potash fertilizers.
  • the inorganic fertilizer may, in a specific embodiment, be a NPK fertilizer.
  • NPK fertilizers are inorganic fertilizers formulated in appropriate concentrations and combinations comprising the three main nutrients nitrogen (N), phosphorus (P) and potassium (K) as well as typically S, Mg, Ca, and trace elements.
  • Urea-containing fertilizer may, in specific embodiments, be urea, formaldehyde urea, anhydrous ammonium, urea ammonium nitrate (UAN) solution, urea sulfur, urea based NPK- fertilizers, or urea ammonium sulfate. Also envisaged is the use of urea as fertilizer. In case urea-containing fertilizers or urea are used or provided, it is particularly preferred that urease inhibitors as defined herein above may be added or additionally be present, or be used at the same time or in connection with the urea-containing fertilizers. Fertilizers may be provided in any suitable form, e.g. as solid coated or uncoated granules, in liquid or semi-liquid form, as sprayable fertilizer, or via fertigation etc.
  • Coated fertilizers may be provided with a wide range of materials. Coatings may, for example, be applied to granular or prilled nitrogen (N) fertilizer or to multi-nutrient fertilizers. Typically, urea is used as base material for most coated fertilizers. Alternatively, ammonium or NPK fertilizers are used as base material for coated fertilizers. The present invention, however, also envisages the use of other base materials for coated fertilizers, any one of the fertilizer materials defined herein.
  • elemental sulfur may be used as fertilizer coating. The coating may be performed by spraying molten S over urea granules, followed by an application of sealant wax to close fissures in the coating. In a further embodiment, the S layer may be covered with a layer of organic polymers, preferably a thin layer of organic polymers.
  • coated fertilizers may be provided by reacting resin-based polymers on the surface of the fertilizer granule.
  • a further example of providing coated fertilizers includes the use of low permeability polyethylene polymers in combination with high permeability coatings.
  • composition and/or thickness of the fertilizer coating may be adjusted to control, for example, the nutrient release rate for specific applications.
  • the duration of nutrient release from specific fertilizers may vary, e.g. from several weeks to many months.
  • the presence of nitrification inhibitors in a mixture with coated fertilizers may accordingly be adapted. It is, in particular, envisaged that the nutrient release involves or is accompanied by the release of the mixture of nitrification inhibitors according to the present invention.
  • Coated fertilizers may be provided as controlled release fertilizers (CRFs).
  • these controlled release fertilizers are fully coated urea or N-P-K fertilizers, which are homogeneous and which typically show a pre-defined longevity of release.
  • the CRFs may be provided as blended controlled release fertilizer products which may contain coated, uncoated and/or slow release components.
  • these coated fertilizers may additionally comprise micronutrients.
  • these fertilizers may show a pre-defined longevity, e.g. in case of N-P-K fertilizers.
  • envisaged examples of CRFs include patterned release fertilizers. These fertilizers typically show a pre-defined release patterns (e.g. hi/standard/lo) and a pre-defined longevity.
  • fully coated N-P-K, Mg and micronutrients may be delivered in a patterned release manner.
  • the fertilizer mixture may be provided as, or may comprise or contain a slow release fertilizer.
  • the fertilizer may, for example, be released over any suitable period of time, e.g. over a period of 1 to 5 months, preferably up to 3 months.
  • ingredients of slow release fertilizers are IBDU (isobutylidenediurea), e.g. containing about 31-32 % nitrogen, of which 90% is water insoluble; or UF, i.e.
  • an urea-formaldehyde product which contains about 38 % nitrogen of which about 70 % may be provided as water insoluble nitrogen; or CDU (crotonylidene diurea) containing about 32 % nitrogen; or MU (methylene urea) containing about 38 to 40% nitrogen, of which 25-60 % is typically cold water insoluble nitrogen; or MDU (methylene diurea) containing about 40% nitrogen, of which less than 25 % is cold water insoluble nitrogen; or MO (methylol urea) containing about 30% nitrogen, which may typically be used in solutions; or DMTU (diimethylene triurea) containing about 40% nitrogen, of which less than 25% is cold water insoluble nitrogen; or TMTU (tri methylene tetraurea), which may be provided as component of UF products; or TMPU (tri methylene pentaurea), which may also be provided as component of UF products; or UT (urea triazone solution) which typically contains about 28 % nitrogen.
  • CDU crot
  • the fertilizer mixture may also be long-term nitrogen-bearing fertiliser containing a mixture of acetylene diurea and at least one other organic nitrogen-bearing fertiliser selected from methylene urea, isobutylidene diurea, crotonylidene diurea, substituted triazones, triuret or mixtures thereof.
  • slow release fertilizers may be provided as coated fertilizers. They may also be combined with other fertilizers or fertilizer types.
  • the present invention further envisages fertilizer or fertilizer forms as defined herein above in combination with nitrification inhibitors as defined herein above and further in combination with urease inhibitors as defined herein above. Such combinations may be provided as coated or uncoated forms and/or as slow or fast release forms. Preferred are combinations with slow release fertilizers including a coating. In further embodiments, also different release schemes are envisaged, e.g. a slower or a faster release.
  • fertigation refers to the application of fertilizers, optionally soil amendments, and optionally other water-soluble products together with water through an irrigation system to a plant or to the locus where a plant is growing or is intended to grow, or to a soil substituent as defined herein below.
  • liquid fertilizers or dissolved fertilizers may be provided via fertigation directly to a plant or a locus where a plant is growing or is intended to grow.
  • nitrification inhibitors according to the present invention, or in combination with additional nitrification inhibitors may be provided via fertigation to plants or to a locus where a plant is growing or is intended to grow.
  • Fertilizers and nitrification inhibitors according to the present invention may be provided together, e.g. dissolved in the same charge or load of material (typically water) to be irrigated.
  • fertilizers and nitrification inhibitors may be provided at different points in time.
  • the fertilizer may be ferti- gated first, followed by the nitrification inhibitor, or preferably, the nitrification inhibitor may be fertigated first, followed by the fertilizer.
  • the time intervals for these activities follow the herein above outlined time intervals for the application of fertilizers and nitrification inhibitors.
  • the fertilizer is an ammonium-containing fertilizer.
  • the agrochemical mixture according to the present invention may comprise one fertilizer as defined herein above and the mixture or composition of the invention defined herein above.
  • the agrochemical mixture according to the present invention may comprise at least one or more than one fertilizer as defined herein above, e.g. 2, 3, 4, 5, 6, 6, 7, 8, 9, 10 or more different fertilizers (including inorganic, organic and urea-containing fertilizers) and the mixture of composition as defined herein above.
  • At least one is to be understood as 1, 2, 3 or more of the respective compound selected from the group consisting of fertilizers as defined herein above.
  • an agrochemical mixture may comprise further ingredients, compounds, active compounds or compositions or the like.
  • the agrochemical mixture may additionally comprise or composed with or on the basis of a carrier, e.g. an agrochemical carrier, preferably as defined herein.
  • the agrochemical mixture may further comprise at least one pesticidal compound.
  • the agrochemical mixture may additionally comprise at least one herbicidal compound and/or at least one fungicidal compound and/or at least one insecticidal compound.
  • the agrochemical mixture may, in addition to the above indicated ingredients, further comprise alternative or additional nitrification inhibitors such as linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, MHPP, Karanjin, brachialacton, p-benzoquinone sorgoleone, nitrapyrin, dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate (DMPP), 4-amino-l,2,4-triazole hydrochloride (ATC), l-amido-2- thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 5-ethoxy-3-trichloromethyl- 1 ,2,4-thiodiazole (terrazole), ammoniumthiosulfate (ATU), 3-methylpyrazol (3-MP), 3,5- dimethylpyrazole (DMP), 1,2,4-triazol and
  • the invention relates to a method for reducing nitrification, comprising treating a plant growing on soil and/or the locus where the plant is growing or is intended to grow with the mixture or composition as defined herein above.
  • plant is to be understood as a plant of economic importance and/or men- grown plant. In certain embodiments, the term may also be understood as plants which have no or no significant economic importance.
  • the plant is preferably selected from agricultural, silvicultural and horticultural (including ornamental) plants. The term also relates to genetically modified plants.
  • plant as used herein further includes all parts of a plant such as germinating seeds, emerging seedlings, plant propagules, herbaceous vegetation as well as established woody plants including all belowground portions (such as the roots) and aboveground portions.
  • the plant is growing on soil.
  • the plant may also grow differently, e.g. in synthetic laboratory environments or on soil substituents, or be supplemented with nutrients, water etc. by artificial or technical means.
  • the invention envisages a treatment of the zone or area where the nutrients, water etc. are provided to the plant.
  • the plant grows in green houses or similar indoor facilities.
  • locus is to be understood as any type of environment, soil, soil substituent, area or material where the plant is growing or intended to grow.
  • the term relates to soil or soil substituent on which a plant is growing.
  • the plant to be treated according to the method of the invention is an agricultural plant.
  • Agricultural plants are plants of which a part (e.g. seeds) or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibers (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds.
  • Preferred agricultural plants are for example cereals, e.g. wheat, rye, barley, triticale, oats, corn, sorghum or rice, beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g.
  • the plant to be treated according to the method of the invention is a horticultural plant.
  • the term "horticultural plants” are to be understood as plants which are commonly used in horticulture, e.g. the cultivation of ornamentals, vegetables and/or fruits.
  • ornamentals are turf, geranium, pelargonia, petunia, begonia and fuchsia.
  • vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas and lettuce and more preferably from tomatoes, onions, peas and lettuce.
  • fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots and blueberries.
  • the plant to be treated according to the method of the invention is an ornamental plant.
  • “Ornamental plants” are plants which are commonly used in gardening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia.
  • the plant to be treated according to the method of the invention is a silvicultural plant.
  • the term "silvicultural plant” is to be understood as trees, more specifically trees used in reforestation or industrial plantations.
  • Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening purposes.
  • silvicultural plants are conifers, like pines, in particular Pinus spec., fir and spruce, eucalyptus, tropical trees like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec., poplar (cottonwood), in particular Populus spec., beech, in particular Fagus spec., birch, oil palm, and oak.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant.
  • vegetative plant material such as cuttings and tubers (e.g. potatoes)
  • genetically modified plants is to be understood as plants, which genetic material has been modified by the use of recombinant DNA techniques in a way that under natural circumstances it cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as preny- lated, acetylated or farnesylated moieties or PEG moieties.
  • auxin herbicides such
  • herbicides e. bromoxynil or ioxynil herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors.
  • These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005, 269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci.
  • mutagenesis e.g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ 5 -endotoxins, e. g. CrylA(b), CrylA(c), CrylF, Cryl F(a2) , CryllA(b), CrylllA, Cryl IIB(bl) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VI Pl, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • VIP vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3- hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers of sodium
  • insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, e. g.
  • WO 02/015701 Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
  • These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.
  • WO 03/018810 MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bbl toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the CrylF toxin and PAT enzyme).
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • proteins are the so-called “pathogenesis-related proteins” (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytoph- thora infestans derived from the Mexican wild potato So/anum buibocastanum) or T4- lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amyivora) .
  • PR proteins pathogenesis-related proteins
  • plant disease resistance genes e. g. potato cultivars, which express resistance genes acting against Phytoph- thora infestans derived from the Mexican wild potato So/anum buibocastanum
  • T4- lysozym e.
  • plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • productivity e. g. bio mass production, grain yield, starch content, oil content or protein content
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada).
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany).
  • a modified amount of substances of content or new substances of content specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany).
  • soil substituent refers to a substrate which is able to allow the growth of a plant and does not comprise usual soil ingredients.
  • This substrate is typically an inorganic substrate which may have the function of an inert medium. It may, in certain embodiments, also comprise organic elements or portions.
  • Soil substituents may, for example, be used in hydroculture or hydroponic approaches, i.e. wherein plants are grown in soilless medium and/or aquatic based environments.
  • suitable soil substituents which may be used in the context of the present invention, are perlite, gravel, biochar, mineral wool, coconut husk, phyllosilicates, i.e.
  • sheet silicate minerals typically formed by parallel sheets of silicate tetrahedra with Si 2 O 5 or a 2:5 ratio, or clay aggregates, in particular expanded clay aggregates with a diameter of about 10 to 40 mm.
  • vermiculite i.e. a phyllosilicate with 2 tetrahedral sheets for every one octahedral sheet present.
  • soil substituents may, in specific embodiments, be combined with fertigation or irrigation as defined herein.
  • the treatment may be carried out during all suitable growth stages of a plant as defined herein.
  • the treatment may be carried out during the BBCH principle growth stages.
  • BBCH principal growth stage refers to the extended BBCH-scale which is a system for a uniform coding of phenologically similar growth stages of all mono- and dicotyledonous plant species in which the entire developmental cycle of the plants is subdivided into clearly recognizable and distinguishable longer-lasting developmental phases.
  • the BBCH-scale uses a decimal code system, which is divided into principal and secondary growth stages.
  • the abbreviation BBCH derives from the Federal Biological Research Centre for Agriculture and Forestry (Germany), the Bundessortenamt (Germany) and the chemical industry.
  • the invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with the mixture or composition as defined herein above at a growth stage (GS) between GS 00 and GS > BBCH 99 of the pant (e.g. when fertilizing in fall after harvesting apples) and preferably between GS 00 and GS 65 BBCH of the plant.
  • GS growth stage
  • the invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with a mixture or composition as defined herein above at a growth stage (GS) between GS 00 to GS 45, preferably between GS 00 and GS 40 BBCH of the plant.
  • GS growth stage
  • the invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with a mixture or composition as defined herein above at an early growth stage (GS), in particular a GS 00 to GS 05, or GS 00 to GS 10, or GS 00 to GS 15, or GS 00 to GS 20, or GS 00 to GS 25 or GS 00 to GS 33 BBCH of the plant.
  • GS early growth stage
  • the method for reducing nitrification comprises treating a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with a mixture or composition as defined herein above during growth stages including GS 00.
  • a mixture or composition as defined herein above is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at a growth stage between GS 00 and GS 55 BBCH, or of the plant.
  • a mixture or composition as defined herein above is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at the growth stage between GS 00 and GS 47 BBCH of the plant.
  • a mixture or composition is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow before and at sowing, before emergence, and until harvest (GS 00 to GS 89 BBCH), or at a growth stage (GS) between GS 00 and GS 65 BBCH of the plant.
  • the invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing with a mixture or composition as defined herein above, wherein the plant and/or the locus where plant is growing or is intended to grow is additionally provided with at least one fertilizer.
  • the fertilizer may be any suitable fertilizer, preferably a fertilizer as defined herein above. Also envisaged is the application of more than one fertilizer, e.g. 2, 3, 4, 5, 6, 7, 8, 9, 10 fertilizers, or of different fertilizer classes or categories.
  • the mixture or composition of the invention and at least one fertilizer is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at a growth stage between GS OOand GS 33 BBCH of the plant.
  • the mixture or composition of the invention and at least one fertilizer is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at a growth stage between GS 00 and GS 55 BBCH of the plant.
  • the mixture or composition of the invention and at least one fertilizer is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at sowing, before emergence, or at a growth stage (GS) between GS 00 and GS > BBCH 99 of the pant (e.g. when fertilizing in fall after harvesting apples) and preferably between GS 00 and 65 BBCH of the plant.
  • GS growth stage
  • time lag means that either the mixture or composition of the invention is applied before the fertilizer to the plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow; or the fertilizer is applied before the mixture or composition of the invention to the plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow.
  • time lag may be any suitable period of time which still allows to provide a nitrification inhibiting effect in the context of fertilizer usage.
  • the time lag may be a time period of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks, 11 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods.
  • the time lag is an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.
  • the time lag preferably refers to situations in which the mixture or composition of the invention is provided 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 11 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods before the application of a fertilizer as defined herein above.
  • the mixture or composition of the invention is applied between GS 00 to GS 33 BBCH of the plant, or between GS 00 and GS 65 BBCH of the plant, provided that the application of at least one fertilizer as defined herein above is carried out with a time lag of at least 1 day, e.g. a time lag of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, or more or any time period in between the mentioned time periods.
  • a time lag of at least 1 day e.g. a time lag of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, or more or any time
  • the mixture or composition of the invention which is applied between GS 00 to GS 33 BBCH of the plant, is provided 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks, 11 weeks, or 12 weeks before the application of a fertilizer as defined herein above.
  • At least one fertilizer as defined herein above is applied between GS 00 to GS 33 BBCH of the plant or between GS 00 and GS 65 BBCH of the plant, provided that the application of the mixture or composition of the invention is carried out with a time lag of at least 1 day, e.g. a time lag of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks or more or any time period in between the mentioned time periods.
  • a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow is treated at least once with the mixture or composition of the invention.
  • a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow is treated at least once with the mixture or composition of the invention, and at least once with a fertilizer as defined herein above.
  • the term "at least once" means that the application may be performed one time, or several times, i.e. that a repetition of the treatment with the mixture or composition of the invention and/or a fertilizer may be envisaged. Such a repetition may a 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or more frequent repetition of the treatment with a nitrification inhibitor and/or a fertilizer.
  • the repetition of treatment with the mixture or composition of the invention and a fertilizer may further be different. For example, while the fertilizer may be applied only once, the nitrification inhibitor may be applied 2 times, 3 times, 4 times etc.
  • the mixture or composition of the invention may be applied only once, the fertilizer may be applied 2 times, 3 times, 4 times etc. Further envisaged are all combination of numerical different numbers of repetitions for the application of the mixture or composition of the invention and a fertilizer as defined herein above.
  • Such a repeated treatment may further be combined with a time lag between the treatment of the mixture or composition of the invention and the fertilizer as described above.
  • the time interval between a first application and second or subsequent application of the mixture or composition of the invention and/or a fertilizer may be any suitable interval. This interval may range from a few seconds up to 3 months, e.g. from a few seconds up to 1 month, or from a few seconds up to 2 weeks. In further embodiments, the time interval may range from a few seconds up to 3 days or from 1 second up to 24 hours.
  • a method for reducing nitrification as described above is carried out by treating a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with at least one agrochemical mixture as defined herein above, or with a mixture or composition as defined herein above.
  • an agrochemical mixture comprising an ammonium- or urea-containing fertilizer and at least one nitrification inhibitor as defined herein above is applied before and at sowing, before emergence, and until GS > BBCH 99 of the pant (e.g. when fertilizing in fall after harvesting apples).
  • the agrochemical mixture is provided as kit of parts or as non-physical mixture, it may be applied with a time lag between the application of the nitrification inhibitor and the fertilizer or between the application of the nitrification inhibitor a secondary or further ingredient, e.g. a pesticidal compound as mentioned herein above.
  • plant propagules are preferably treated simultaneously (together or separately) or subsequently.
  • propagules or "plant propagules” is to be understood to denote any structure with the capacity to give rise to a new plant, e.g. a seed, a spore, or a part of the vegetative body capable of independent growth if detached from the parent.
  • the term “propagules” or “plant propagules” denotes for seed.
  • the application rates of the mixture or composition of the invention are between 0,01 g and 5 kg of active ingredient per hectare, preferably between 1 g and 1 kg of active ingredient per hectare, especially preferred between 50 g and 300 g of active ingredient per hectare depending on different parameters such as the specific active ingredient applied and the plant species treated.
  • amounts of from 0.001 g to 20 g per kg of seed, preferably from 0.01 g to 10 g per kg of seed, more preferably from 0.05 to 2 g per kg of seed of nitrification inhibitors may be generally required.
  • the compounds may be used in an effective and non-phyto- toxic amount. This means that they are used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotoxic symptoms on the treated plant or on the plant raised from the treated propagule or treated soil or soil substituents.
  • the application rates of fertilizers may be selected such that the amount of applied N is between 10 kg and 1000 kg per hectare, preferably between 50 kg and 700 kg per hectare.
  • mixture or composition of the invention can be present in different structural or chemical modifications whose biological activity may differ. They are likewise subject matter of the present invention.
  • nitrification inhibitor compounds according to the invention may be converted into customary types of compositions, e.g. agrochemical or agricultural compositions such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • agrochemical or agricultural compositions such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • composition type depends on the particular intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention.
  • composition types are suspensions (SC, 00, FS), emulsifiable concentrates (EC), emulsions (EW, EC, ES), microemulsions (ME), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, OP, OS) or granules (GR, FG, GG, MG), which can be watersoluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF).
  • SC, 00, FS, EC, WG, SG, WP, SP, SS, WS, GF are employed diluted.
  • Composition types such as OP, OS, GR, FG, GG and MG are usually used undiluted.
  • compositions are prepared in a known manner (see, for example, US 3,060,084, EP 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147- 48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hili, New York, 1963, S. 8-57 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701, US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J.
  • compositions or mixtures may also comprise auxiliaries which are customary, for example, in agrochemical compositions.
  • auxiliaries depend on the particular application form and active substance, respectively.
  • auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and inorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e.g. for seed treatment formulations).
  • Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as I ign in- sou Ifonic acid (Borresperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene-sulfonic acid (Nekal® types, BASF, GermanY),and fatty acids, alkylsulfonates, alkylarylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of aromatic sulfonic acids, such as I ign in- sou Ifonic acid (Borresperse®
  • methylcellulose g. methylcellulose
  • hydrophobically modified starches polyvinyl alcohols (Mowiol® types, Clariant, Switzerland), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvinylamines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers thereof.
  • suitable thickeners i.e. compounds that impart a modified flowability to compositions, i.e.
  • Xanthan gum Kelzan®, CP Kelco, U.S.A.
  • Rhodopol® 23 Rhodia, France
  • Veegum® R.T. Vanderbilt, U.S.A.
  • At- taclay® Engelhard Corp., NJ, USA
  • bactericides may be added for preservation and stabilization of the composition.
  • suitable bactericides are those based on dichlorophene and benzyl alcohol hemi formal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as al kyl isoth iazol i- nones and benzisothiazolinones (Acticide® MBS from Thor Chemie).
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • anti-foaming agents are silicone emulsions (such as e.g. Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.
  • Suitable colorants are pigments of low water solubility and water-soluble dyes, e.g. rho- damin B, C. I. pigment red 112, C. I. solvent red 1, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15: 1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • rho- damin B C. I. pigment red 112, C. I. solvent red 1, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15: 1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36
  • odorous substances may be present in the compositions as defined above.
  • Such odorous substances comprise citronel lyn itri I , citral, zertrahydrolinalool, tetrahydrogeraniol, geranonitril, beta-lonon R, rootanol, I inaly lacetat, morillol, and p-cre- sometylether.
  • tackifiers or binders examples are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan).
  • Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the components of the mixture of the invention and, if appropriate, further active substances, with at least one solid carrier.
  • Granules e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers.
  • suitable solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g. ammonium sulfate, ammoni
  • composition types are: i) Water-soluble concentrates (SL, LS) 10 parts by weight of a nitrification inhibitor are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves upon dilution with water. In this way, a composition having a content of 10% by weight of active substance is obtained. ii) Dispersible concentrates (DC) 20 parts by weight of a nitrification inhibitor are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, e.g. polyvinylpyrrolidone. Dilution with water gives a dispersion. The active substance content is 20% by weight.
  • a dispersant e.g. polyvinylpyrrolidone
  • Emulsifiable concentrates 15 parts by weight of a nitrification inhibitor are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The composition has an active substance content of 15% by weight.
  • Emulsions (EW, EC, ES) 25 parts by weight of a nitrification inhibitor are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • the composition has an active substance content of 25% by weight.
  • Suspensions SC, 00, FS
  • 20 parts by weight of a nitrification inhibitor are comminuted with addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active substance suspension.
  • Dilution with water gives a stable suspension of the active substance.
  • the active substance content in the composition is 20% by weight.
  • Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of a nitrification inhibitor are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as water-dispersible or water-soluble granules by means of technical appliances (e.g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • the composition has an active substance content of 50% by weight.
  • Water-dispersible powders and water-soluble powders 75 parts by weight of a nitrification inhibitor are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dis- persion or solution of the active substance. The active substance content of the composition is 75% by weight.
  • Gel (GF) In an agitated ball mill, 20 parts by weight of a nitrification inhibitor are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine suspension of the active substance.
  • Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained.
  • Composition types to be applied undiluted ix
  • Oustable powders (OP, OS) 5 parts by weight of a nitrification inhibitor are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable composition having an active substance content of 5% by weight.
  • Granules (GR, FG, GG, MG) 0.5 parts by weight of a nitrification inhibitor is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spraydrying or the fluidized bed.
  • compositions e.g. agrochemical or agriculatural compositons
  • compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substance.
  • the active substances are employed in a purity offrom 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Water-soluble concentrates (LS), flowable concentrates (FS), powders for dry treatment (OS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES) emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted.
  • compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready- to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying or treating agrochemical or agricultural compounds or mixtures, or compositions as defined herein, respectively, on to plant propagation material, especially seeds, the plant and/or the locus where the plant is growing or intended to grow are known in the art, and include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • the compounds or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting.
  • a suspension-type (FS) composition may be used.
  • a FS composition may comprise 1-800 g/l of active substance, 1 200 g/l surfactant, o to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • the active substances can be used as such or in the form of their compositions, e.g.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • the substances can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
  • a wetter, tackifier, dispersant or emulsifier it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
  • the active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 90%, such as from 30 to 80%, e.g. from 35 to 45% or from 65 to 75% by weight of active substance.
  • the active substances may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.
  • UUV ultra-low-volume process
  • oils, wetters, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the active substances or the compositions comprising them, if appropriate not until immediately prior to use (tank mix).
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 : 100 to 100 : 1, preferably 1 : 10 to 10 : 1.
  • Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240®; alcohol alkoxylates such as Atplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON 30®; EO/PO block polymers, e.g. Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates such as Lutensol XP 80®; and dioctyl sulfosuccinate sodium such as Leophen RA®.
  • organic modified polysiloxanes such as Break Thru S 240®
  • alcohol alkoxylates such as Atplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON 30®
  • EO/PO block polymers e.g. Pluronic RPE 2035® and Genapol B®
  • alcohol ethoxylates such as Lutensol XP 80®
  • the invention in a further aspect relates to a method for treating a fertilizer or a composition.
  • This treatment includes the application of the mixture or composition of the invention to a fertilizer or a composition.
  • the treatment may accordingly result in the presence of the mixture or composition of the invention in a preparation of fertilizers or other compositions.
  • Such treatment may, for example, result in a homogenous distribution of nitrification inhibitors on or in fertilizer preparations.
  • Treatment processes are known to the skilled person and may include, for instance, dressing, coating, pelleting, dusting or soaking.
  • the treatment may be a coating of nitrification inhibitors with fertilizer preparations, or a coating of fertilizers with nitrification inhibitors.
  • the treatment may be based on the use of granulation methods as known to the skilled person, e.g. fluidized bed granulation.
  • the treatment may, in certain embodiments, be performed with a composition comprising the mixture as defined herein above, e.g. comprising besides the inhibitors a carrier or a pesticide or any other suitable additional compound as mentioned above.
  • the present invention relates to a method for treating seed or plant propagation material.
  • seed treatment refers to or involves steps towards the control of biotic stresses on or in seed and the improvement of shooting and development of plants from seeds.
  • biotic stresses such as fungal or insecticidal attack or which has difficulties obtaining sufficient suitable nitrogen-sources shows reduced germination and emergence leading to poorer plant or crop establishment and vigor, and consequently, to a reduced yield as compared to a plant propagation material which has been subjected to curative or preventive treatment against the relevant pest and which can grow without the damage caused by the biotic stress factor.
  • Methods for treating seed or plant propagation material according to the invention thus lead, among other advantages, to an enhanced plant health, a better protection against biotic stresses and an increased plant yield.
  • Seed treatment methods for applying or treating inventive mixtures and compositions thereof e.g. compositions or agrochemical compositions as defined herein above, and in particular combinations of nitrification inhibitors as defined herein above and secondary effectors such as pesticides, in particular fungicides, insecticides, nematicides and/or biopesticides and/or biostimulants, to plant propagation material, especially seeds, are known in the art, and include dressing, coating, film coating, pelleting and soaking application methods of the propagation material. Such methods are also applicable to the combinations or compositions according to the invention.
  • compositions comprising, besides a nitrification inhibitor according to the present invention, e.g. compositions as defined herein above, a fungicide and an insecticide, or a fungicide and a nematicide, or a fungicide and a biopesticide and/or biostimulant, or an insecticide and a nematicide, or an insecticide and a biopesticide and/or biostimulant, or a nematicide and a biopesticide and/or biostimulant, or a combination of a fungicide, insecticide and nematicide, or a combination of a fungicide, insecticide and biopesticide and/or biostimulant, or a combination of an insecticide, nematicide, and biopesticide etc.
  • a nitrification inhibitor e.g. compositions as defined herein above, a fungicide and an insecticide, or a fungicide and a nematicide, or a fungicide and a
  • the agricultural composition or combination comprising a nitrification inhibitor according to the present invention is applied or treated on to the plant propagation material by a method such that the germination is not negatively impacted.
  • a plant propagation material such as a seed
  • seed dressing is seed dressing, seed coating or seed pelleting and alike. It is preferred that the plant propagation material is a seed, seed piece (i.e. stalk) or seed bulb.
  • the present method can be applied to a seed in any physiological state, it is preferred that the seed be in a sufficiently durable state that it incurs no damage during the treatment process.
  • the seed would be a seed that had been harvested from the field; removed from the plant; and separated from any cob, stalk, outer husk, and surrounding pulp or other non-seed plant material.
  • the seed would preferably also be biologically stable to the extent that the treatment would cause no biological damage to the seed. It is believed that the treatment can be applied to the seed at any time between harvest of the seed and sowing of the seed or during the sowing process (seed directed applications).
  • the seed may also be primed either before or after the treatment.
  • Treatment could vary from a thin film (dressing) of the formulation containing the combination, for example, a mixture of active ingredient(s), on a plant propagation material, such as a seed, where the original size and/or shape are recognizable to an intermediary state (such as a coating) and then to a thicker film (such as pelleting with many layers of different materials (such as carriers, for example, clays; different formulations, such as of other active ingredients; polymers; and colorants) where the original shape and/or size of the seed is no longer recognizable.
  • An aspect of the present invention includes application of the composition, e.g. agricultural composition or combination comprising a nitrification inhibitor according to the present invention, onto the plant propagation material in a targeted fashion, including positioning the ingredients in the combination onto the entire plant propagation material or on only parts thereof, including on only a single side or a portion of a single side.
  • the composition e.g. agricultural composition or combination comprising a nitrification inhibitor according to the present invention
  • composition e.g. agricultural composition or combination comprising a nitrification inhibitor according to the present invention
  • Such techniques are known in the art, particularly in EP1124414, W007/67042, and W007/67044.
  • Application of the composition e.g.
  • agricultural composition, or combination comprising a nitrification inhibitor according to the present invention, onto plant propagation material also includes protecting the plant propagation material treated with the combination of the present invention by placing one or more pesticide- and nitrification inhibitor (Nl)-containing particles next to a pesticide- and Nl-treated seed, wherein the amount of pesticide is such that the pesticide-treated seed and the pesticidecontaining particles together contain an Effective Dose of the pesticide and the pesticide dose contained in the pesticide-treated seed is less than or equal to the Maximal Non-Phy- totoxic Dose of the pesticide.
  • Nl pesticide- and nitrification inhibitor
  • Controlled release coatings on the seeds wherein the ingredients of the combinations are incorporated into materials that release the ingredients over time.
  • controlled release seed treatment technologies are generally known in the art and include polymer films, waxes, or other seed coatings, wherein the ingredients may be incorporated into the controlled release material or applied between layers of materials, or both.
  • Seed can be treated by applying thereto the compounds present in the inventive mixtures in any desired sequence or simultaneously.
  • the seed treatment occurs to an unsown seed, and the term "unsown seed” is meant to include seed at any period between the harvest of the seed and the sowing of the seed in the ground for the purpose of germination and growth of the plant.
  • Treatment to an unsown seed is not meant to include those practices in which the active ingredient is applied to the soil or soil substituents but would include any application practice that would target the seed during the planting process.
  • the treatment occurs before sowing of the seed so that the sown seed has been pre-treated with the combination.
  • seed coating or seed pelleting are preferred in the treatment of the combinations according to the invention.
  • the ingredients in each combination are adhered on to the seed and therefore available for pest control.
  • the treated seeds can be stored, handled, sowed and tilled in the same manner as any other active ingredient treated seed.
  • Solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water- soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • Preferred examples of seed treatment formulation types or soil application for premix compositions are of WS, LS, ES, FS, WG or CS-type.
  • compositions in question give, after two-to-tenfold dilution, active components concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying or treating compositions or combinations comprising a nitrification inhibitor according to the present invention, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • mixtures or compositions according to the present invention are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • a pre-mix formulation for seed treatment application comprises 0.5 to 99.9 percent, especially 1 to 95 percent, of the desired ingredients, and 99.5 to 0.1 percent, especially 99 to 5 percent, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 percent, especially 0.5 to 40 percent, based on the pre-mix formulation.
  • a solid or liquid adjuvant including, for example, a solvent such as water
  • the auxiliaries can be a surfactant in an amount of 0 to 50 percent, especially 0.5 to 40 percent, based on the pre-mix formulation.
  • commercial products will preferably be formulated as concentrates (e.g., pre- mix composition (formulation), the end user will normally employ dilute formulations (e.g. tank mix composition).
  • the total amounts of active components applied are, depending on the kind of effect desired, from 0.001 to 10 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
  • the application rates may range from about 1 x 10 6 to 5 x 10 15 (or more) CFU/ha.
  • the spore concentration is about 1 x 10 7 to about 1 x 10 11 CFU/ha.
  • (ento- mopathogenic) nematodes as microbial pesticides (e.g.
  • the application rates preferably range inform about 1 x 10 5 to 1 x 10 12 (or more), more preferably from 1 x 10 8 to 1 x 10 11 , even more preferably from 5 x 10 8 to 1 x 10 10 individuals (e.g. in the form of eggs, juvenile or any other live stages, preferably in an infetive juvenile stage) per ha.
  • the amount of the mixture or composition of the invention is in the range from 0.01-10 kg, preferably from 0.1-1000 g, more preferably from 1-100 g per 100 kilogram of plant propagation material (preferably seeds).
  • the application rates with respect to plant propagation material preferably may range from about 1 x 10 6 to 1 x 10 12 (or more) CFU/seed.
  • the concentration is about 1 x 10 6 to about 1 x 10 11 CFU/seed.
  • the application rates with respect to plant propagation material may range from about 1 x 10 7 to 1 x 10 14 (or more) CFU per 100 kg of seed, preferably from 1 x 10 9 to about 1 x 10 11 CFU per 100 kg of seed.
  • Reaction product A was prepared according to the following procedure. In a reaction vessel, about 12.9 g of a 50% solution of formaldehyde was added at room temperature and the temperature was increased and maintained between 30 ° C and 50° C. A first portion of ammonium hydroxide (0.6 g) was then added to the reaction vessel and the temperature of the mixture was maintained below 60 ° C. About 2.6 g DCD was then added to the reaction vessel and the temperature of the mixture was adjusted to between 35 ° C and 50 ° C. About 13.78 g urea was then added to the reaction vessel. A second portion of ammonium hydroxide (250 g) was then added to the reaction vessel.
  • the temperature of the reaction mixture was allowed to exothermically increase about 90° C for less than 30 minutes and the temperature was reduced to 85° C and held for 120 minutes. After heating the reaction mixture to 85° C, distillation was started and carried out until 4.08 g of distillate was removed from the reaction mixture. 3.1 g of a 25 wt.-% solution of sodium hydroxide was added throughout the reaction and distilled as needed to adjust the pH. The pH of the reaction mixture was kept above 8.4 throughout the reaction. After distillation, the reaction mixture was cooled down to provide the reaction product A. The reaction product A had a final pH of 9.5.
  • Reaction product B was prepared according to the following procedure. 10.68 g of DMSO and 8.22 g of DCD were charged to a reaction flask, heated to 95° C, held until contents were clear and then cooled to 65° C. 0.737 g of paraformaldehyde were charged and the contents were then heated to 81° C over a 0.75 hour period and held 1.3 hr. until the solution became clear. The contents were cooled to 41.7° C and then 0.119 g of methane sulfonic acid/70% were added. The contents were mixed for 5 minutes and then the contents were slowly heated to 110° C over a 2.1 hr. period of time.
  • Reaction product A was prepared according to the following procedure. In a reaction vessel, 1290 g of a 50 wt.-% solution of formaldehyde was added at room temperature and the temperature was increased and maintained between 30 ° C and 50° C. A first portion of ammonium hydroxide (60 g) was then added to the reaction vessel and the temperature of the mixture was maintained below 60 ° C. 260 g of DCD were then added to the reaction vessel and the temperature of the mixture was adjusted to between 35 ° C and 50 ° C. 1378 g urea were then added to the reaction vessel. A second portion of ammonium hydroxide (250 g) was then added to the reaction vessel.
  • the temperature of the reaction mixture was allowed to exothermically increase about 90° C for less than 30 minutes and the temperature was reduced to 85° C and held for 120 minutes. After heating the reaction mixture to 85° C, distillation was started and carried out until 416.1 g of distillate was removed from the reaction mixture. A 25 wt.-% solution of sodium hydroxide was added throughout the reaction and distilled as needed to adjust the pH. The pH of the reaction mixture was kept above 8.4 throughout the reaction. After distillation, the reaction mixture was cooled down to provide the reaction product A. The reaction product A had a final pH of 9.12.
  • Reaction product B was prepared according to the following procedure. 106.82 g of DMSO and 82.26 g of DCD were charged to a reaction flask, heated to 95° C, held until contents were clear and then cooled to 65° C. 7.37 g of paraformaldehyde were charged and the contents were then heated to 81° C over a 0.75 hour period and held 1.3 hours until the solution became clear. The contents were cooled to 41.7° C and then 1.19 g of methane sulfonic acid (70%) were added. The contents were mixed for 5 minutes and then the contents were slowly heated to 110° C over a 2.1 hours, period of time.
  • Fertilizer Ammonium sulfate
  • Amount N 10 mg NH 4 -N/100 g soil
  • Soil soil Limburgerhof with pH(CaCI 2 ) 6.8; 73% sand, 23% silt, 4% clay, which is classified according to Food and Agriculture Organization of the United Nations (FAO) as a sandy loam
  • FEO Food and Agriculture Organization of the United Nations
  • Test solution containing the compounds of formula I or the comparative example in the appropriate concentration (0.3 or 1 % (w/w) of fertilized NH 4 - N), and 10 mg nitrogen in the form of ammonium sulfate-N (NH 4 -N) was added to the soil and everything was mixed well. Unfertilized controls received 1 ml pure water. Bottles were loosely capped to allow air exchange. The bottles were then incubated at 20 ° C for 14 days.
  • the inhibition (NI @ a specified concentration) is calculated as follows: inhibition in %

Abstract

The present invention relates to a novel mixture of nitrification inhibitors comprising (i) an alkoxypyrazole compound of formula (I) or a salt, tautomer, or N-oxide thereof, and (ii) a nitrification inhibitor system comprising (A) at least a reaction product A or (B) at least a reaction product B, in a weight ratio of from 100:1 to 1: 100. Moreover, the invention relates to the use of the mixture of the invention, methods of applying the mixture of the invention, and to agrochemical mixtures and compositions comprising the mixture of the invention.

Description

Synergistic action as nitrification inhibitors of DCD oligomers with alkoxypyrazole and its oligomers
FIELD OF THE INVENTION
The present invention relates to a novel mixture of nitrification inhibitors comprising (i) an alkoxypyrazole compound of formula (I) or a salt, tautomer, or N-oxide thereof, and (ii) a nitrification inhibitor system comprising at least one reaction product A of (al) dicyandiamide (DCD), (bl) formaldehyde, optionally (cl) urea, and optionally (dl) an ammonia source; or at least one reaction product B of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, and optionally (c2) an organic acid or an inorganic acid, and optionally (d2) a primary, secondary or tertiary amine; in a weight ratio of from 100:1 to 1: 100. Moreover, the invention relates to the use of the mixture of the invention, methods of applying the mixture of the invention, and to agrochemical mixtures and compositions comprising the mixture of the invention.
BACKGROUND OF THE INVENTION
Nitrogen is an essential element for plant growth and reproduction. About 25% of the plant available nitrogen in soils (ammonium and nitrate) originate from decomposition processes (mineralization) of organic nitrogen compounds such as humus, plant and animal residues and organic fertilizers. Approximately 5% derive from rainfall. On a global basis, the biggest part (70%), however, is supplied to the plant by inorganic nitrogen fertilizers. The mainly used nitrogen fertilizers comprise ammonium compounds or derivatives thereof, i.e. nearly 90% of the nitrogen fertilizers applied worldwide is in the NH4 + form (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302). This is, inter alia, due to the fact that NH4 + assimilation is energetically more efficient than assimilation of other nitrogen sources such as NO3 _.
Moreover, being a cation, NH4 + is held electrostatically by the negatively charged clay surfaces and functional groups of soil organic matter. This binding is strong enough to limit NH4 +-loss by leaching to groundwater. By contrast, NO3 _, being negatively charged, does not bind to the soil and is liable to be leached out of the plants' root zone. In addition, nitrate may be lost by denitrification which is the microbiological conversion of nitrate and nitrite (NO2 _) to gaseous forms of nitrogen such as nitrous oxide (N2O) and molecular nitrogen (N2).
However, ammonium (NH4 +) compounds are converted by soil microorganisms to nitrates (NO3 _) in a relatively short time in a process known as nitrification. The nitrification is carried out primarily by two groups of chemolithotrophic bacteria, ammonia-oxidizing bacteria (AOB) of the genus Nitrosomonas and Nitrobacter, which are ubiquitous component of soil bacteria populations. The first enzyme, which is essentially responsible for nitrification is ammonia monooxygenase (AMO), which was also found in ammonia-oxidizing archaea (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302).
The nitrification process typically leads to nitrogen leakage and environmental pollution. As a result of the various losses, approximately 50% of the applied nitrogen fertilizers are lost during the year following fertilizer addition (see Nelson and Huber; Nitrification inhibitors for corn production (2001), National Corn Handbook, Iowa State University). As countermeasure, the use of nitrification inhibitors, mostly together with fertilizers, was suggested. Suitable nitrification inhibitors include biological nitrification inhibitors (BNIs) such as linoleic acid, linolenic acid, methyl cinnamate, 1,9-decanediol, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, MHPP, Karanjin, brachialacton or the p-benzoquinone sorgoleone (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302). Further suitable nitrification inhibitors are synthetic chemical inhibitors such as nitrapyrin, dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate (DMPP), 4-amino-l,2,4-triazole hydrochloride (ATC), l-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 5-ethoxy-3- trichloromethyl-l,2,4-thiodiazole (terrazole), or 2-sulfanilamidothiazole (ST) (Slangen and Kerkhoff, 1984, Fertilizer research, 5(1), 1-76). WO2019166561 describes alkoxypyrazoles as nitrification inhibitors. US2016/0060184 Al describes nitrification inhibitor systems comprising dicyandiamide (DCD) adducts. US2018/0170818 Al describes compositions and a method for making liquid fertilizer additives of biodegradable polymers and/or oligomers comprised of the reaction products of aldehyde(s) with cyano-containing nitrification inhibitors that have one or more aldehyde reactive groups. US2022/0041520 Al relates to compositions and an method of making liquid fertilizer additives of biodegradable polmers and/or oligomers comprised of the reaction products of aldehyde(s) with cyano-containing nitrification inhibitors that have one or more aldehyde reactive groups selected from the group consisting of primary amines, secondary amines, amides, thiols, hydroxyls and phenols, wherein the cyano-group is conserved, utilizing a non-aqueous polar, aprotic organo liquid as the reaction medium.
However, many of these inhibitors only work sub-optimal. In addition, the world population is expected to grow significantly in the next 20-30 years, and, therefore, food production in sufficient quantities and quality is necessary. In order to achieve this, the use of nitrogen fertilizers would have to double by 2050. For environmental reasons, this is not possible, since nitrate levels in drinking water, eutrophication of surface water and gas emissions into the air have already reached critical levels in many places, causing water contamination and air pollution. However, fertilizer efficiency increases significantly and less fertilizer may therefore be applied, if more potent nitrification inhibitors are used.
Therefore, it was an object of the present invention to improve the performance of nitrification inhibitors, in particular to provide an improved activity regarding the reduction in am- moniacal nitrogen (NH3-N) oxidation rate and/or regarding the reduction of NO3 _ production in soil or to keep the same activity, with lower amounts of nitrification inhibitors. Of particular interest is the reduction of NO3 _ production in soil as this is decisive for the reduction of nitrate levels in the ground water, and because NO3 is substrate for the formation of the greenhouse gas N2O in soil during denitrification (NO3 -> N2Ot, N2t).
SUMMARY OF THE INVENTION
It has surprisingly been found that the above-mentioned object can be achieved by using a mixture comprising
(i) an alkoxypyrazole compound of formula (I)
Figure imgf000004_0001
or a salt, tautomer, or N-oxide thereof, wherein
R1 is CH3 or CH2CH3; and
(ii) a nitrification inhibitor system comprising
(A) at least one reaction product A of (al) dicyandiamide (DCD), (bl) formaldehyde, optionally (cl) urea, and optionally (dl) an ammonia source; or
(B) at least one reaction product B of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, and optionally (c2) an organic acid or an inorganic acid, and optionally (d2) a primary, secondary or tertiary amine; wherein components (i) and (ii) are present in a weight ratio of from 100:1 to 1:100.
The inventors surprisingly found that by applying the mixture as defined above and hereinafter the nitrification of ammonium to nitrate can significantly be reduced or can be equally achieved with lower concentration of nitrification inhibitors. In particular, it has been found that a synergistic effect occurs regarding reduction of nitrification. In particular, a surprisingly high reduction in ammoniacal nitrogen (NH3-N) oxidation rate and/or a surprisingly high reduction of NO3 _ production can be observed. In particular, a synergistic effect can be observed for the reduction of NO3 _ production over a broad range of weight ratios of components (i) and (ii).
Further, the inventors surprisingly found that the formulation of a mixture of nitrification inhibitors comprising dicyandiamide and alkoxypyrazoles can be improved when dicyandiamide was reacted in form of an inhibitor system comprising at least a reaction product A or at least one reaction product B.
In one preferred embodiment of the mixture, the reaction product A comprises at least one adduct of formula (II)
Figure imgf000004_0002
wherein
X is =0 or
Figure imgf000004_0003
are independently selected from the group consisting of
Figure imgf000005_0001
wherein at least one of R1, R2, R3, and R4 is different from
\H .
J and wherein, if X is =0, at least one of R1, R2, R3, and R4 is
Figure imgf000005_0002
wherein preferably the at least one adduct is selected from the group consisting of adducts of formulae (Ila), (lib), and (lie),
Figure imgf000005_0003
and combinations thereof, and wherein particularly preferably the at least one adduct is selected from the group consisting of adducts of formula (Ila) and (lib), and combinations thereof.
In a more preferred embodiment, the reaction product A further comprises at least one adduct comprising a polymeric backbone of formula (III)
Figure imgf000005_0004
wherein z is an integer of 1 or greater, preferably 1 to 100; at least one carbon in the backbone is substituted with the group
Figure imgf000005_0005
at least one carbon in the backbone is optionally substituted with the group =0; and each nitrogen in the backbone independently includes a substituent selected from the group consisting of
Figure imgf000006_0001
In a further preferred embodiment, the reaction product B is a reaction product of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, (c2) methane sulfonic acid, and (d2) triethanolamine.
In a more preferred embodiment, the reaction product B is obtained utilizing a non-aqueous polar, aprotic organic liquid (NAPAOL), which is preferably dimethylsulfoxide.
In a further preferred embodiment, components (i) and (ii) are present in a weight ratio of from 50:1 to 1:50, preferably from 25:1 to 1:25 or from 10:1 to 1:10.
In a further aspect, the present invention relates to a composition comprising the mixture of the invention and at least one carrier.
In a further aspect, the present invention relates to an agrochemical mixture comprising (a) at least one fertilizer and (b) the mixture of the invention or the composition of the invention.
In a further aspect, the present invention relates to the use of the mixture of the invention or the composition of the invention for reducing nitrification of a fertilizer, said reduction of nitrification preferably occurs in the root zone of a plant, in or on soil or soil substituents and/or at the locus where a plant is growing or is intended to grow.
In a further aspect, the present invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus or soil or soil substituents where the plant is growing or is intended to grow with the mixture of a the invention or the composition of the invention, and optionally additionally with a fertilizer.
In a preferred embodiment of said method, the application of the mixture of the invention or the composition of the invention and the fertilizer is carried out simultaneously or with a time lag, preferably an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.
In a further aspect, the present invention relates to a method for treating a fertilizer or a fertilizer composition, comprising the application of a mixture of the invention or a composition of the invention to a fertilizer or fertilizer composition.
In a preferred embodiment of the agrochemical mixture, the use, or the method as defined above, said fertilizer is an solid or liquid ammonium-containing inorganic fertilizer such as an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; an solid or liquid organic fertilizer such as liquid manure, semi-liquid manure, biogas manure, stable manure and straw manure, worm castings, compost, seaweed or guano, or an urea-containing fertilizer such as urea, formaldehyde urea, anhydrous ammonium, urea ammonium nitrate (UAN) solution, urea sulphur, urea based NPK-fertilizers, or urea ammonium sulfate.
In a further preferred embodiment of the use or the method as defined above, the applied amount of the mixture is such that at least 0.1 % by weight of component (i) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer are applied, and at least 0.2 % by weight of component (ii) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer. Preferably, component (i) is applied in an amount of from 0.3 to 3 % by weight relative to the sum of NH2- and NH4-nitrogen content of the fertilizer, and component (ii) is applied in an amount of from 0.3 to 4 % by weight relative to the sum of NH2- and NH4-nitrogen content of the fertilizer.
In a further preferred embodiment of the use or the method as defined above, said plant is an agricultural plant such as wheat, barley, oat, rye, soybean, corn, sorghum, potatoes, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice, oil palm, coffee, cacao, tea or a vegetable such as spinach, lettuce, asparagus, or cabbages; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or in a genetically modified form.
DETAILED DESCRIPTION
Compounds (i) of claim 1 can be prepared by standard processes of organic chemistry. Suitable methods for preparing pyrazole compounds in general are described in “Progress in Heterocyclic Chemistry”, Vol. 27, G.W. Gribble, J. A. Joule, Elsevier, 2015, Chapter 5.4.2. A general method for the synthesis of 3-alkoxy-pyrazoles comprises the reaction between hydrazine hydrochloride and various p-ketoesters as described by, for example: a) Sadrine Guillou, Frederic J. Bonhomme, Yves L. Janin, Synthesis 2008, 3504-3508; or b) in WO 2010/015657 A2. Further, the 3-alkoxy group can be introduced by alkylating a suitable hy- droxypyrazole derivative as described e.g. by a) D. Piomelli and coworkers, Synthesis 2016, 2739-2756, or b) Sandrine Guillou, Yves L. Janin, Chem. Eur. J. 2010, 16, 4669 - 4677. Diverse methods to synthesize pyrazoles bearing the alkoxy group in the position 4 were described by William F. Vernier, Laurent Gomez, Tetrahedron Letters 2017 , 4587-4590. WO201916656 describes the compounds of formula (I) as nitrification inhibitors.
It is to be understood that IH-pyrazoles, especially those with different substituents in 3- and 5-position, may be present in the form of different annular tautomers, i.e. prototrophic tautomers, as described by a) Schaumann, Ernst, Methoden der Organischen Chemie, 1994, Houben-Weyl, E8b: Hetarene III and b) A. Giiven, N. Kani§kan, Journal of Molecular Structure (Theochem), 1999, 488, 125-134. It is to be understood that these annular tautomers of the compounds of formula I may be formed, as the hydrogen atom may migrate to the other nitrogen atom and vice versa. Furthermore, it is to be understood that the compounds of formula I may be present in the form of the different annular tautomers, or as a mixture thereof. Further, it is to be understood that the equilibrium between those tautomeric forms depends on the steric and electronic properties of the substituents present on the pyrazole ring of the compounds of formula I. Therefore, if pyrazolium ions of the compounds of formula I are formed, the different tautomers will typically result in two different isomers of the pyrazolium ion. In certain preferred embodiments of the invention, such isomer mixtures of pyrazolium ions of the compounds of formula I may be used.
Before describing in detail exemplary embodiments of the present invention, definitions important for understanding the present invention are given.
As used in this specification and in the appended claims, the singular forms of "a" and "an" also include the respective plurals unless the context clearly dictates otherwise. In the context of the present invention, the terms "about" and "approximately" denote an interval of accuracy that a person skilled in the art will understand to still ensure the technical effect of the feature in question. The term typically indicates a deviation from the indicated numerical value of ± 20 %, preferably ± 15 %, more preferably ± 10 %, and even more preferably ± 5 %. It is to be understood that the term "comprising" is not limiting. For the purposes of the present invention the term "consisting of" is considered to be a preferred embodiment of the term "comprising of". If hereinafter a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only. Furthermore, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, i.e. the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below. It is to be understood that this invention is not limited to the particular methodology, protocols, reagents etc. described herein as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention that will be limited only by the appended claims. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art.
The term "nitrification inhibitor" is to be understood in this context as a chemical substance which slows down or stops the nitrification process. Nitrification inhibitors accordingly retard the natural transformation of ammonium into nitrate, by inhibiting the activity of bacteria such as Nitrosomonas spp. The term "nitrification" as used herein is to be understood as the biological oxidation of ammonia (NH3) or ammonium (NH4 +) with oxygen into nitrite (NO2 _) followed by the oxidation of these nitrites into nitrates (NO3 _) by microorganisms. Besides nitrate (NO3 _) nitrous oxide is also produced through nitrification. Nitrification is an important step in the nitrogen cycle in soil. The inhibition of nitrification may thus also reduce N2O losses. The term nitrification inhibitor is considered equivalent to the use of such a compound for inhibiting nitrification. In the context of the present invention relating to a mixture of components (i) and (ii) both being active as nitrification inhibitors, the term “nitrification inhibitor” is also used to describe the mixture of the invention.
The term "compound of formula (I)" comprises the compound(s) as defined herein as well as a salt, tautomer or N-oxide thereof.
The compounds of formula I may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention covers amorphous and crystalline compounds of formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula I are preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality. Agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the mode of action of the compounds of formula I. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can preferably be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid. Preferred salts of the compounds of formula I are phosphate salts.
The term "N-oxide" includes any compound of formula I, wherein a tertiary nitrogen atom, e.g. the pyridine nitrogen atom, is oxidized to an N-oxide moiety.
Tautomers of the compounds of formula I may be present as described above. For example, tautomers may be present, as the hydrogen atom may migrate to the other nitrogen atom and vice versa.
The organic moieties mentioned in the above definition of the variable R1 include CH3, i.e. methyl, and CH2CH3, i.e. ethyl.
As set out above, the present invention relates in one aspect to a mixture comprising (i) an alkoxypyrazole compound of formula (I)
Figure imgf000009_0001
or a salt, tautomer, or N-oxide thereof, wherein
R1 is CH3 or CH2CH3; and
(ii) a nitrification inhibitor system comprising
(A) at least one reaction product A of (al) dicyandiamide (DCD), (bl) formaldehyde, optionally (cl) urea, and optionally (dl) an ammonia source; or
(B) at least one reaction product B of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, and optionally (c2) an organic acid or an inorganic acid, and optionally (d2) a primary, secondary or tertiary amine; wherein components (i) and (ii) are present in a weight ratio of from 100:1 to 1:100.
In one embodiment of the mixture of the invention, in the alkoxypyrazole compound of formula (I), R1 is CH3.
In another embodiment of the mixture of the invention, in the alkoxypyrazole compound of formula (I), R1 is CH2CH3.
In can be preferred that the alkoxypyrazole compound is present in the form of a salt, preferably in the form of a pyrazolium salt, such that the compound of formula (I) is present in cationic form. Preferred anions are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbon- ate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.
In a preferred embodiment, the alkoxypyrazole compound is present in the form of a phosphate salt.
As used herein, the expression "reaction product A of (al) dicyandiamide (DCD), (bl) formaldehyde, and optionally (cl) urea, and optionally (dl) an ammonia source" refers to a reaction product obtainable by reacting DCD, formaldehyde, urea, and an ammonia source.
The DCD (al) can be used as commercially available.
The formaldehyde (bl) can be used in many forms. For example, paraform (solid, polymerized formaldehyde) and/or formalin solutions (aqueous solutions of formaldehyde, sometimes with methanol, in about 10 % by weight, about 20 % by weight, about 37 % by weight, about 44 % by weight, or about 50 % by weight, based on the weight of the formalin solution) are commonly used forms. For example, the formaldehyde can be an aqueous solution having a concentration of formaldehyde ranging from about 10 % by weight to about 50 % by weight, based on a total weight of the aqueous solution. Formaldehyde gas can also be used. Formaldehyde substituted in part or in whole with substituted aldehydes such as acetaldehyde and/or propylaldehyde can be used as the source of formaldehyde. One or more other aldehydes, such as glyoxal can be used in place of or in combination with formaldehyde. Any of these forms of formaldehyde sources can be used alone or in any combination to prepare the reaction product.
In a preferred embodiment, formaldehyde is an aqueous solution having a concentration of formaldehyde ranging from about 10 % by weight to about 50 % by weight, based on a total weight of the aqueous solution.
In another preferred embodiment, formaldehyde is an aqueous solution having a concentration of formaldehyde ranging from about 20 % by weight to about 50 % by weight, based on a total weight of the aqueous solution.
In another preferred embodiment, formaldehyde is an aqueous solution having a concentration of formaldehyde ranging from about 30 % by weight to about 50 % by weight, based on a total weight of the aqueous solution.
In another preferred embodiment, formaldehyde is an aqueous solution having a concentration of formaldehyde ranging from about 40 % by weight to about 50 % by weight, based on a total weight of the aqueous solution.
In another preferred embodiment, formaldehyde is an aqueous solution having a concentration of formaldehyde of about 50 % by weight, based on a total weight of the aqueous solution.
The urea (cl) can also be used in many forms. For example, the urea can be a solid in the form of pills, flakes, granules, and the like, and/or a solution, such as an aqueous solution. Further, the urea may be combined with another moiety, for example, formaldehyde and/or urea-formaldehyde adducts, often in aqueous solution. Further, at least a portion of the urea, if present, can be in the form of animal waste. Any form of urea or urea in combination with formaldehyde can be used to make a urea-formaldehyde polymer. Both urea prill and combined urea-formaldehyde products can be used.
As used herein, the term "ammonia source" (dl) refers to ammonia or any ammonium compound(s) that liberate ammonia when reacted with the formaldehyde and DCD. Illustrative ammonia sources can include, but are not limited to, ammonium salts such as ammo- nium nitrate, aqueous ammonia or ammonium hydroxide, anhydrous ammonia, or combinations thereof. Suitable aqueous ammonium solutions can have an ammonia concentration of about 28 % by weight, about 30 % by weight, about 32 % by weight, or about 35 % by weight, for example. Other suitable ammonia sources can include, but are not limited to, primary amines or substituted primary amines such as methyl amine, monomethanol amine, amino propanol, or any combination thereof. Difunctional amines such as ethylene diamine or any combination of organic amines provided that one primary amine group is available to form a triazone ring can be used. Another source of ammonia can be in the form of animal waste such as urine and/or manure. Any of these ammonia sources can be used alone or in any combination to prepare the reaction product. And the ammonia source can be used in any form such a liquid, solid, and/or gas. In some embodiments, a specific ammonia source may be expressly excluded according to the present disclosure. For example, an ammonia source may expressly exclude the use of ammonium chloride. Other ammonia sources may be excluded if such ammonia source has a pH in water of less than 7 and/or if such ammonia source provides an undesirable reduction in the pH of a reaction described herein for forming adducts.
Reactions carried out for production of adducts comprised in reaction product A can be carried out by reacting DCD with the further starting components under conditions that conserves the DCD.
In a preferred embodiment, adducts comprised in reaction product A are produced under basic or alkaline reaction conditions. For example, adducts can be formed by reacting DCD, a urea source, formaldehyde, and an ammonia source (preferably one that does not form an acid moiety during the reaction) under basic reaction conditions at a pH of greater than 7.
In a preferred embodiment, the basic reaction conditions can be at a pH ranging from a low of about 7 to a high about 11.
In another preferred embodiment, the basic reaction conditions can be at a pH ranging from a low of about 7.5 to a high about 10.5.
In another preferred embodiment, the basic reaction conditions can be at a pH ranging from a low of about 8 to a high about 10.
In another preferred embodiment, the basic reaction conditions can be at a pH ranging from a low of about 8.5 to a high about 9.5.
In another preferred embodiment, the basic reaction conditions can be at a pH ranging from a low of about 8.5 to a high about 9.
In a preferred embodiment, the reaction product A produced under basic reaction conditions is prepared by combining, mixing, or otherwise contacting the reaction components to produce a reaction mixture having a pH greater than about 7.
In a preferred embodiment, a reaction mixture of formaldehyde, ammonia, DCD, and urea under the basic reaction conditions can have a pH ranging from a low of about 8 to a high of about 11.
In another preferred embodiment, a reaction mixture of formaldehyde, ammonia, DCD, and urea under the basic reaction conditions can have a pH ranging from a low of about 8.5 to a high of about 10.5.
In another preferred embodiment, a reaction mixture of formaldehyde, ammonia, DCD, and urea under the basic reaction conditions can have a pH ranging from a low of about 9 to a high of about 10. In another preferred embodiment, a reaction mixture of formaldehyde, ammonia, DCD, and urea under the basic reaction conditions can have a pH ranging from a low of about 9 to a high of about 9.5. Similarly, the reaction mixture under the basic reaction conditions can also have a pH ranging from a low of about 8 to a high about 11, preferably, of about 8.5 to a high about 10.5, further preferably, of about 9 to a high about 10, and further preferably of about 9.5 to a high about 10.
Heat from the exothermic reaction can be allowed to heat the reaction mixture to a temperature ranging from a low of about 50° C to a high of about 100° C, preferably from a low of about 60° C to a high of about 90° C, further preferably from a low of about 60° C to a high of about 90° C, and further preferably from a low of about 65° C to a high of about 80° C, a time ranging from about 1 minute to about 3 hours.
The resulting reaction mixture can then be cooled to, for example, room temperature, to provide the reaction product A, which can include one or more adducts as described herein.
In another embodiment, formaldehyde and a first portion of the ammonia source can be combined to form a first mixture. In a preferred embodiment, the first mixture can be at least partially reacted, and the formaldehyde and ammonia may be present in the first mixture at a mole ratio of about 40:1 to about 5:1.
In another preferred embodiment, the first mixture can be at least partially reacted, and the formaldehyde and ammonia may be present in the first mixture at a mole ratio of about 35:1 to 10: 1.
In another preferred embodiment, the first mixture can be at least partially reacted, and the formaldehyde and ammonia may be present in the first mixture at a mole ratio of about 30:1 to 15: 1.
DCD can then be added to the first mixture or to the at least partially reacted first mixture to produce a second mixture. In a preferred embodiment, the second mixture can be at least partially reacted, and DCD and formaldehyde can be present in the second mixture at a mole ratio of about 0.01:1 to about 2:1.
In another preferred embodiment, the second mixture can be at least partially reacted, and DCD and formaldehyde can be present in the second mixture at a mole ratio of about 0.05:1 to about 1:1.
In another preferred embodiment, the second mixture can be at least partially reacted, and DCD and formaldehyde can be present in the second mixture at a mole ratio of about 0.1:1 to about 0.5:1.
Urea can then be added to the second mixture or the at least partially reacted second mixture to produce a third mixture. In a preferred embodiment, the third mixture can be at least partially reacted, and the urea and formaldehyde can be present in the third mixture at a mole ratio of about 0.1:1 to about 5:1.
In another preferred embodiment, the third mixture can be at least partially reacted, and the urea and formaldehyde can be present in the third mixture at a mole ratio of about 0.25:1 to about 2:1.
In another preferred embodiment, the third mixture can be at least partially reacted, and the urea and formaldehyde can be present in the third mixture at a mole ratio of about 0.5:1 to about 1:1.
A second portion of the ammonia source can be added to the third mixture to produce a fourth mixture. The fourth mixture can be at least partially reacted to produce the reaction product A of formaldehyde, urea, ammonia, and DCD. The temperature of the first mixture, second mixture, and third mixture can be maintained at a temperature ranging from about 25° C to about 70° C. The temperature of the fourth mixture can range from about 60° C to about 90° C and can be held at the increased temperature for a period of time ranging from about 5 minutes to about 3 hours. As a non-limiting example of a reaction product A, the mole ratio of formaldehyde:urea:DCD:ammonia in a reaction product according to some embodiments of this disclosure can be about 1:0.88:0.14:0.24.
Exothermic heat generated from the first mixture, second mixture, third mixture, fourth mixture, or any number of mixtures, can be used, at least in part, as the heat source for heating any one or more of the reaction mixtures. In another example, heat can be introduced to any one or more of the reaction mixtures to provide a heated reaction mixture via a heating coil or other heat exchanging device or system. The temperature of the reaction mixtures can be maintained below a desired maximum temperature, e.g., 100° C., via a cooling coil or other heat exchanging device or system.
One or more bases or base compounds can be added before and/or during the reaction to any one or more of the reaction mixtures and/or the reaction product to maintain and/or adjust the pH thereof. For example, the reaction product A produced under basic reaction conditions can be maintained at a pH of about 8 to about 11 during the reaction and/or for the final reaction product A. Illustrative base compounds suitable for adjusting the pH of the reaction product (A) can include, but are not limited to, ammonia, amines, e.g., primary, secondary, and tertiary amines and polyamines, sodium hydroxide (NaOH), potassium hydroxide (KOH), or any combination thereof. An aqueous base solution can have any concentration. For example, an aqueous base solution of sodium hydroxide, potassium hydroxide, or a combination thereof, having a concentration ranging from a low of about 5 % by weight to a high of about 75 % by weight, preferably from a low of about 10 % by weight to a high of about 50 % by weight and further preferably from a low of about 15 % by weight to a high of about 25 % by weight, can be introduced to one or more of the reaction mixtures and/or the reaction product A in order to adjust and/or maintain the pH between about 8 and about 11.
In another embodiment, one or more pH buffering compounds, which can buffer the pH of the reaction mixture(s) at a desired pH, can be added at the start of the reaction. Illustrative pH buffering compounds can include, but are not limited to, triethanolamine, sodium borate, potassium bicarbonate, sodium carbonate, potassium carbonate, or any combination thereof.
In another embodiment the one or more pH buffering compounds can be used in conjunction with one or more base compounds to adjust and/or maintain a desired pH of the reaction mixture(s).
The reaction product A produced under the basic reaction conditions can have a pH greater than 7. In one embodiment, the reaction product A of formaldehyde, the ammonia source, DCD, and urea produced under the basic reaction conditions can have a pH ranging from a low of about 8 to a high about 11, preferably from a low of about 8.5 to a high about 10.5, further preferably from a low of about 9 to a high about 10 and further preferably from a low of about 9 to a high about 9.5.
The reaction product A from the reaction of formaldehyde, urea, the ammonia source, and DCD can include from about 25 mol-% to about 65 mol-% formaldehyde, from about 10 mol- % to about 25 mol-% urea, from about 5 mol-% to about 25 mol-% ammonia, and from about 5 mol-%to about 25 mol-% DCD, based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In a preferred embodiment, the formaldehyde is present in an amount ranging from a low of about 25 mol-% to a high of about 60 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In another preferred embodiment, the formaldehyde is present in an amount ranging from a low of about 30 mol-% to a high of about 55 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In another preferred embodiment, the formaldehyde is present in an amount ranging from a low of about 35 mol-% to a high of about 50 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In a preferred embodiment, the urea is present in an amount ranging from a low of about 12 mol-% to a high of about 25 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In another preferred embodiment, the urea is present in an amount ranging from a low of about 14 mol-% to a high of about 22 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In another preferred embodiment, the urea is present in an amount ranging from a low of about 16 mol-% to a high of about 18 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In a preferred embodiment, the ammonia is present in an amount ranging from a low of about 7 mol-% to a high of about 25 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In another preferred embodiment, the ammonia is present in an amount ranging from a low of about 9 mol-% to a high of about 22 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In another preferred embodiment, the ammonia is present in an amount ranging from a low of about 12 mol-% to a high of about 18 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In a preferred embodiment, the DCD is present in an amount ranging from a low of about 7 mol-% to a high of about 25 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In another preferred embodiment, the DCD is present in an amount ranging from a low of about 9 mol-% to a high of about 22 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In another preferred embodiment, the DCD is present in an amount ranging from a low of about 12 mol-% to a high of about 18 mol-% based on the total weight of the formaldehyde, urea, ammonia, and DCD.
In a preferred embodiment, the reaction product A of formaldehyde, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 1:1 to about 8:1.
In another preferred embodiment, the reaction product A of formaldehyde, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 2:1 to about 6:1. In another preferred embodiment, the reaction product A of formaldehyde, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 2.5:1 to about 5:1.
In another preferred embodiment, the reaction product A of formaldehyde, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 3:1 to about 4:1.
In another preferred embodiment, the reaction product A of formaldehyde, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 2:1 to about 4:1.
In a preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 1:1 to about 8:1.
In another preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 2:1 to about 6:1.
In another preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 3:1 to about 5:1.
In another preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to ammonia ranging from about 3.5:1 to about 4.5:1.
In a preferred embodiment, the reaction product A of formaldehyde, the ammonia source, and DCD can have a molar ratio of formaldehyde to DCD ranging from about 1:1 to about 7:1.
In another preferred embodiment, the reaction product A of formaldehyde, the ammonia source, and DCD can have a molar ratio of formaldehyde to DCD ranging from about 1.5:1 to about 6.5:1.
In another preferred embodiment, the reaction product A of formaldehyde, the ammonia source, and DCD can have a molar ratio of formaldehyde to DCD ranging from about 2:1 to about 6:1.
In another preferred embodiment, the reaction product A of formaldehyde, the ammonia source, and DCD can have a molar ratio of formaldehyde to DCD ranging from about 2.5:1 to about 5:1.
In another preferred embodiment, the reaction product A of formaldehyde, the ammonia source, and DCD can have a molar ratio of formaldehyde to DCD ranging from about 2:1 to about 4:1.
In another preferred embodiment, the reaction product A of formaldehyde, the ammonia source, and DCD can have a molar ratio of formaldehyde to DCD ranging from about 2.5:1 to about 3.5:1.
In a preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to DCD ranging from about 1:1 to about 8:1.
In another preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to DCD ranging from about 1:1 to about 7:1. In another preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to DCD ranging from about 2:1 to about 8:1.
In another preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to DCD ranging from about 3:1 to about 7.5:1.
In another preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to DCD ranging from about .5:1 to about 7:1.
In a preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to urea ranging from about 1:1 to about 4:1.
In another preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to urea ranging from about 1.1:1 to about 3.9:1.
In another preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to urea ranging from about 1:1 to about 2:1.
In another preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to urea ranging from about 1:1 to about 1.5:1.
In another preferred embodiment, the reaction product A of formaldehyde, urea, the ammonia source, and DCD has a molar ratio of formaldehyde to urea ranging from about 1:1 to about 1.3:1.
The reaction product A can be produced by reacting formaldehyde and DCD. In another example, the reaction product A can be produced by reacting formaldehyde, DCD and an ammonia source. In yet another example, product A can be produced by reacting formaldehyde, DCD and urea. In still another example, the reaction product A can be produced by reacting formaldehyde, an ammonia source, DCD, and urea. Preferably, the reaction is carried out in water. In a preferred embodiment, the reaction product is therefore obtained in the form of an aqueous solution.
Depending on the amounts of the reactants and the reaction conditions, the reaction product A may comprise various adducts. In particular, the reaction product may comprise at least one adduct based on compounds (al) + (bl), at least one adduct based on compounds (al) + (bl) + (cl), at least one adduct based on compounds (al) + (bl) + (dl), and/or at least one adduct based on (al) + (bl) + (cl) + (dl).
In a preferred embodiment, the reaction product A comprises adducts arising from the reaction (al), (bl), (cl) and (dl), which may be encompassed by the structure of formula (II)
Figure imgf000016_0001
wherein
X is =0 or
Figure imgf000017_0001
are independently selected from the group consisting of
Figure imgf000017_0002
wherein at least one of R1, R2, R3, and R4 is different from =0, at least one of R1, R2, R3, and R4 is
Figure imgf000017_0003
Reaction product A may comprise a plurality of different adducts. For example, reaction product A may include at least 1 adduct, at least 2 different adducts, at least 3 different adducts, at least 4 different adducts, at Ieast5 different adducts, at least 10 different adducts, at least 25 different adducts, at least 50 different adducts, or at least 100 different adducts.
In a preferred embodiment, the reaction product A comprises at least one adduct selected from adducts provided in Formula (Ila) [2-canyo-1-((4-oxo-1,3,5-triazinen-1-yl)methyl(guani- dine], Formula (lib) [1-((2-cyanoguanidino)methyl)urea] and Formula (lie) [2-cyano-1-((2- cyanoguanidino)methyl)guanidine]. In some embodiments, the reaction product A can include one, two, or all three of the adducts shown in in Formulas (Ila) through (lie) in any combination.
Figure imgf000017_0004
In a preferred embodiment, the reaction product A comprises at least one adduct selected from the group consisting of adducts of formula (Ila) and (lib) and combinations thereof.
The adducts defined in Formula (Ila), Formula (lib) and Formula (lie) are non-limiting examples of reaction products as defined by the class of adducts in Formula (II). Adducts that may be formed according to the present disclosure may include any combination of groups encompassed by R1 to R4 in any number. In a preferred embodiment, reaction product A further comprises at least one adduct comprising a polymeric backbone of formula (III)
Figure imgf000018_0001
wherein z is an integer of 1 or greater, preferably 1 to 100.
Adducts having a backbone structure according to Formula (III) can be defined as following: at least one carbon in the backbone is substituted with the group
Figure imgf000018_0002
at least one carbon in the backbone is optionally substituted with the group =0; and each nitrogen in the backbone independently includes a substituent selected from the group consisting of:
Figure imgf000018_0003
A further, non-limiting example of an adduct may arise from the reaction of (al), (bl), (cl) and (dl) is shown in Formula (III*). As seen therein, the N-C-N — backbone is present in the adduct.
Figure imgf000018_0004
As used herein, the expression "reaction product B of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, and optionally (c2) an organic acid, and optionally (d2) a primary secondary amine or tertiary amine" refers to a reaction product obtainable by reacting DCD, formaldehyde or paraformaldehyde, an organic acid and a primary, secondary amine or tertiary amine.
The reaction product B can be produced by reacting formaldehyde and DCD. In another example, the reaction product B can be produced by reacting paraformaldehyde and DCD. In another example, reaction product B can be produced by reacting formaldehyde, DCD and an organic acid. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD and an organic acid. In another example, reaction product B can be produced by reacting formaldehyde, DCD and a primary amine. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD and a primary amine. In another example, reaction product B can be produced by reacting formaldehyde, DCD and a secondary amine. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD and a secondary amine. In another example, reaction product B can be produced by reacting formaldehyde, DCD and a tertiary amine. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD and a tertiary amine. In another example, reaction product B can be produced by reacting formaldehyde, DCD, an organic acid and a primary amine. In another example, reaction product B can be produced by reacting formaldehyde, DCD, an inorganic acid and a primary amine. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD, an organic acid and a primary amine. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD, an inorganic acid and a primary amine. In another example, reaction product B can be produced by reacting formaldehyde, DCD, an organic acid and a secondary amine. In another example, reaction product B can be produced by reacting formaldehyde, DCD, an inorganic acid and a secondary amine. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD, an organic acid and a secondary amine. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD, an inorganic acid and a secondary amine. In another example, reaction product B can be produced by reacting formaldehyde, DCD, an organic acid and a tertiary amine. In another example, reaction product B can be produced by reacting formaldehyde, DCD, an inorganic acid and a tertiary amine. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD, an organic acid and a tertiary amine. In another example, reaction product B can be produced by reacting paraformaldehyde, DCD, an inorganic acid and a tertiary amine.
The DCD (a2), formaldehyde (b2) and paraformaldehyde (b2) can be used as commercially available.
Any commercially available organic acid or inorganic acid(c2) can be used. Illustrative examples of the organic acid can include, but are not limited to, methane sulfonic acid, paratoluene sulfonic acid and methane phosphonic acid. Illustrative examples of the inorganic acid can include, but are not limited to phosphoric acid, sulfonic acid, hydrochloric acid and nitric acid.
In a preferred embodiment methane sulfonic acid as an organic acid is used.
In another preferred embodiment, phosphoric acid or sulfonic acid as an inorganic acid is used.
Any commercially available primary amine (d2) can be used. Illustrative examples can include, but are not limited to, (Ci.6-alkyl)amines, diglycolamine and cyclohexylamine.
In a preferred embodiment at least one primary amine selected from the group consisting of such as cyclohexylamine, diglycolamine and ethylamine or combinations thereof are used.
Any commercially available secondary amine (d2) can be used. Illustrative examples include, but are not limited to, di(Ci.6-alkyl)olamines and di(Ci.6-alkyl)amines.
In a preferred embodiment at least one secondary amine from the group consisting of diethanolamine, diethylamine, methylisopropylamine, diisopropanolamine, methylethanolamine, dicyclohexylamine and combinations thereof are used.
Any commercially available tertiary amine (d2) can be used. Illustrative examples can include, but are not limited to tri(Ci.6-alkyl)olamines and tri(Ci.6-alkyl)amines.
In a preferred embodiment trimethylamine is used. In another preferred embodiment triethanolamine is used.
In a preferred embodiment, reaction product B can be obtained by reacting a molar ratio of DCD to formaldehyde unit of 1:1 to 4:1.
In another preferred embodiment, reaction product B can be obtained by reacting a molar ratio of DCD to formaldehyde unit of 1:1 to 2:1.
In another preferred embodiment, reaction product B can be obtained by reacting a molar ratio of DCD to formaldehyde unit of 2:1 to 4:1.
In a preferred embodiment, reaction product B can be obtained by reacting paraformaldehyde and DCD in a weight ratio of about 1:7 to 1:15.
In another preferred embodiment, reaction product B can be obtained by reacting paraformaldehyde and DCD in a weight ratio of about 1:8: to 1:14.
In another preferred embodiment, reaction product B can be obtained by reacting paraformaldehyde and DCD in a weight ratio of about 1:9 to 1:13.
In another preferred embodiment, reaction product B can be obtained by reacting paraformaldehyde and DCD in a weight ratio of about 1:10 to 1:12.
In another preferred embodiment, reaction product B can be obtained by reacting paraformaldehyde and DCD in a weight ratio of about 1:10.5 to 1:1.1.5.
In a preferred embodiment, reaction product B can be obtained by reacting formaldehyde and DCD in a weight ratio of about 1:7 to 1:15.
In another preferred embodiment, reaction product B can be obtained by reacting formaldehyde and DCD in a weight ratio of about 1:8: to 1:14.
In another preferred embodiment, reaction product B can be obtained by reacting a primary amine and DCD in a weight ratio of about 1:30 to 1:44.
In another preferred embodiment, reaction product B can be obtained reacting a primary amine and DCD in a weight ratio of about 1:33 to 1:37.
In another preferred embodiment, reaction product B can be obtained by reacting a primary amine and DCD in a weight ratio of about 1:34 to 1:36.
In another preferred embodiment, reaction product B can be obtained by reacting a secondary amine and DCD in a weight ratio of about 1:30 to 1:44.
In another preferred embodiment, reaction product B can be obtained reacting a secondary amine and DCD in a weight ratio of about 1:33 to 1:37.
In another preferred embodiment, reaction product B can be obtained by reacting a secondary amine and DCD in a weight ratio of about 1:34 to 1:36.
In another preferred embodiment, reaction product B can be obtained by reacting a tertiary amine and DCD in a weight ratio of about 1:60 to 1:80.
In another preferred embodiment, reaction product B can be obtained reacting a tertiary amine and DCD in a weight ratio of about 1:65 to 1:75.
In another preferred embodiment, reaction product B can be obtained by reacting a tertiary amine and DCD in a weight ratio of about 1:68 to 1:70.
In a preferred embodiment, the reaction product B is a reaction product of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, (c2) methane sulfonic acid, and (d2) triethanolamine.
In another preferred embodiment, the reaction product B is obtained by utilizing a nonaqueous polar, aprotic organic liquid (NAPAOL). As used herein, the term "non-aqueous polar, aprotic organic liquid (NAPAOL)" refers to an aprotic NOSDAS (non-aqueous organo solvent delivery system) that is used specifically as the reaction medium.
In a preferred embodiment, an aprotic NOSDS comprising of one or more aprotic solvents from the group consisting of (1) dimethylsulfoxide and/or
(2) dialkyl, diaryl, or arylalkyl sulfoxide(s) having the formula:
R5S(O)xR6 wherein R5 and R6 are each independently a Ci.6 alkylene group, an aryl group, or Ci_3 alkylenearyl group or R5 and R6 with the sulfur to which they are attached form a 4 to 8 membered ring wherein R5 and R6 together are a Ci_6 alkylene group which optionally contains one or more atoms selected from the group consisting of 0, S, Se, Te, N, and P in the ring and x is 1 or 2;
(3) one or more alkylene carbonates selected from the group consisting of ethylene carbonate, propylene carbonate and butylene carbonate, (4) one or more polyols capped with acetate or formate wherein the polyol portion selected from the group consisting of ethylene glycol, 1,3 propylene glycol, 1,2 propylene glycol, butylene glycol, trimethylol propane, trimethylol ethane, pentaerythritol, sorbitol and sorbitan, glucose, fructose, galactose and glycerin, (5) one or more alkylene glycol alkyl ethers acetates selected from the group consisting of dipropylene glycol methyl ether acetate, tripropylene glycol methyl ether acetate, and/or tripropylene glycol butyl ether acetate and (6) isophorone (7) one or more diesters consisting of dimethylsuccinate, dimethyl adipate, diethyl glutarate, and dimethyl glutarate, (8) dimethylacet-amide, (9) dimethylformamide, (10) dimethyl-2-imidazolidi-none, (11) 1- Methyl-2-pyrrolidone, (12) hexamethylphos-phoramide, (13) 1,2-dimethyloxyethane, (14) 2- methoxyethyl ether, (15) cyclohexylpyrrolidone and (16) limonene, can serve as the reaction medium for obtaining the reaction product B.
In another preferred embodiment, an aprotic NOSDS comprising of one or more aprotic solvents from the group consisting of (1) dimethylsulfoxide and/or (2) dialkyl, diaryl, or arylalkyl sulfoxide(s) having the formula: R5S(O)XR6 wherein R5 and R6 are each independently a Ci.6 alkylene group, an aryl group, or C1.3 alkylenearyl group or R5 and R6 with the sulfur to which they are attached form a 4 to 8 membered ring wherein R5 and R6 together are a Ci.6 alkylene group which optionally contains one or more atoms selected from the group consisting of 0, S, Se, Te, N, and P in the ring and x is 1 or 2; can serve as the reaction medium for obtaining the reaction product B.
In another preferred embodiment, the reaction product B is obtained utilizing a non-aqueous polar, aprotic organic liquid (NAPAOL) is dimethylsulfoxide.
In a preferred embodiment, reaction product B can be obtained by the following method: (a) dissolve the DCD (a2) in an aprotic solvent at temperatures in the range of about 30- 110° C, then cool to about 40-70° C and insure that pH is in the range of about 8-10, (b) slowly add the aldehyde (b2) and allow the exotherm to be controlled either through charge rate or removing the heat of reaction through a cooling median, (c) slowly heat the composition to about 70-90° C and hold for a period of time, (d) cool the composition to about 40- 70° C, and slowly charge enough of an acid catalyst to drop the pH to about 5-6.5 and let mix for an extended period of time to control the exotherm, (e) slowly heat the composition to about 90-115° C, f) after holding for a period of time, one can elect to place the batch under a vacuum to assist in removing water by-products, driving the reaction to more completion and removing any unreacted aldehyde (b2) and then cooling the batch. In a variation, one can charge protic and aprotic solvents to improve flow properties and storage stability.
In a preferred embodiment, DCD can be dispersed within dimethyl sulfoxide and then reacted with paraformaldehyde in a molar ratio of 3-4 moles of DCD to one reactive unit of paraformaldehyde.
As set out above, the present invention relates in one aspect to a mixture comprising component (i) and component (ii).
Component (i) is the alkoxypyrazole compound, and component (ii) is the nitrification inhibitor system.
In a preferred embodiment, components (i) and (ii) are present in a weight ratio of from 50:1 to 1:50, preferably from 25:1 to 1:25.
In another preferred embodiment, components (i) and (ii) are present in a weight ratio of from 40:1 to 1:40.
In another preferred embodiment, components (i) and (ii) are present in a weight ratio of from 35:1 to 1:35.
In another preferred embodiment, components (i) and (ii) are present in a weight ratio of from 30:1 to 1:30.
In another preferred embodiment, components (i) and (ii) are present in a weight ratio of from 25:1 to 1:25.
In another preferred embodiment, components (i) and (ii) are present in a weight ratio of from 20:1 to 1:20.
It can be preferred that an excess of the nitrification inhibitor system is present.
In a preferred embodiment, components (i) and (ii) are present in a weight ratio of from 10:1 to 1:10, preferably from 5:1 to 1:5.
In another preferred embodiment, components (i) and (ii) are present in a weight ratio of from 8:1 to 1:8.
In another preferred embodiment, components (i) and (ii) are present in a weight ratio of from 5:1 to 1:5.
In another preferred embodiment, components (i) and (ii) are present in a weight ratio of from 4:1 to 1:4.
In another preferred embodiment, components (i) and (ii) are present in a weight ratio of from 3.5:1 to 1:3.5.
In another preferred embodiment, components (i) and (ii) are present in a weight ratio of from 3.2:1 to 1:3.2.
In general, it is preferred that components (i) and (ii) are present in synergistically effective amounts, i.e. in relative amounts such that a synergistic effect regarding the inhibition of nitrification is achieved. Synergism can be determined using Colby’s formula (Colby, S.R., Calculating synergistic and antagonistic responses of herbicide combinations, Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies.
Colby’s formula: E = x + y - x • y/100 E = expected efficacy, expressed in % of the untreated control, when using the mixture comprising the components (i) and (ii) at concentrations a and b; x = efficacy, expressed in % of the untreated control, when using component (i) at the concentration a; y = efficacy, expressed in % of the untreated control, when using component (ii) at the concentration b.
In connection with the methods and uses of the invention for reducing nitrification, it is preferred that the mixture is applied in the following amounts.
In one embodiment, the applied amount of the mixture is such that at least 0.1 % by weight of component (i) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer are applied, and at least 0.1 % by weight of component (ii) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer.
In another embodiment, the applied amount of the mixture is such that at least 0.1 % by weight of component (i) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer are applied, and at least 0.2 % by weight of component (ii) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer.
In one preferred embodiment, the applied amount of the mixture is such that from 0.1 % to 3 % by weight of component (i) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer are applied, and from 0.1 % to 3 % by weight of component (ii) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer.
In another preferred embodiment, the applied amount of the mixture is such that from 0.1 % to 3 % by weight of component (i) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer are applied, and from 0.2 % to 3.13 % by weight of component (ii) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer.
In a particularly preferred embodiment, the applied amount of the mixture is such that from 0.3 % to 3 % by weight of component (i) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer are applied, and from 0.3 % to 3 % by weight of component (ii) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer.
In another particularly preferred embodiment, the applied amount of the mixture is such that from 0.1 % to 0.5 %, preferably from 0.1% to 0.3 % such as 0.1 % or 0.3 %, by weight of component (i) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer are applied, and from 0.1 % to 1 %, preferably from 0.15 % to 0.75 % such as 0.15 % or 0.75 %, by weight of component (ii) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer. In such mixtures, inhibition of NO3-production was higher (cf. Example 5), for example by at least 0.5 % or at least 1 % or at least 2 % or at least 3 % or at least 4 % or at least 5 % or at least 6 %, or at least 7 % or at least 8 % or at least 9 % or at least 10 % or at least 11 %.
In connection with the above applied amounts of the components (i) and (ii) of the mixture, it is to be understood that the weight ratios of the applied components (i) and (ii) preferably correspond to the weight ratios defined above in connection with the mixtures of the invention. In certain preferred embodiment, components (i) and (ii) are provided in the mixtures of the invention in a weight ratio of from 50:1 to 1:50, preferably from 25:1 to 1:25. In other preferred embodiment, components (i) and (ii) are provided in the mixtures of the invention in a weight ratio of from 10:1 to 1:10, preferably from 5:1 to 1:5. The applied amounts of the mixture are then selected such that the above defined amounts of components (i) and (ii) are applied. In connection with the mixtures, compositions, uses and methods of the invention, the following preferred embodiments are additionally relevant. When it is referred to “nitrification inhibitor” hereinafter, this term refers to the mixture of the invention comprising components (i) and (ii) as defined above.
The use of the mixtures of the invention as a nitrification inhibitor may be based on the application of the mixture, the composition or the agrochemical mixture as defined herein to a plant growing on soil and/or the locus where the plant is growing or is intended to grow, or the use may be based on the application of the nitrification inhibitor, the composition or the agrochemical mixture as defined herein to soil where a plant is growing or is intended to grow or to soil substituents. In specific embodiments, the nitrification inhibitor may be used for reducing nitrification in the absence of plants, e.g. as preparatory activity for subsequent agricultural activity, or for reducing nitrification in other technical areas, which are not related to agriculture, e.g. for environmental, water protection, energy production or similar purposes. In specific embodiments, the nitrification inhibitor, or a composition comprising said nitrification inhibitor according to the present invention may be used for the reduction of nitrification in sewage, slurry, manure or dung of animals, e.g. swine or bovine feces. For example, the nitrification inhibitor, or a composition comprising said nitrification inhibitor according to the present invention may be used for the reduction of nitrification in sewage plants, biogas plants, cowsheds, liquid manure tanks or containers etc. Furthermore, the nitrification inhibitor, or a composition comprising said nitrification inhibitor may be used in exhaust air systems, preferably in exhaust air systems of stables or cowsheds. The present invention therefore also relates to the use of the mixture of the invention for treating exhaust air, preferably the exhaust air of stables and cowsheds. In further embodiments, the nitrification inhibitor, or a composition comprising said nitrification inhibitor according to the present invention may be used for the reduction of nitrification in situ in animals, e.g. in productive livestock. Accordingly, the nitrification inhibitor, or a composition comprising said nitrification inhibitor according to the present invention may be fed to an animal, e.g. a mammal, for instance together with suitable feed and thereby lead to a reduction of nitrification in the gastrointestinal tract of the animals, which in turn is resulting in reduction of emissions from the gastrointestinal tract. This activity, i.e. the feeding of nitrification inhibitor, or a composition comprising said nitrification inhibitor according to the present invention may be repeated one to several times, e.g. each 2nd, 3rd, 4th, 5th, 6th, 7th day, or each week, 2 weeks, 3 weeks, or month, 2 months etc.
The use may further include the application of a nitrification inhibitor or compositions comprising said nitrification inhibitor, or agrochemical mixtures comprising said nitrification inhibitor as defined herein above to environments, areas or zones, where nitrification takes place or is assumed or expected to take place. Such environments, areas or zones may not comprise plants or soil. For example, the nitrification inhibitor may be used for nitrification inhibition in laboratory environments, e.g. based on enzymatic reactions or the like. Also envisaged is the use in green houses or similar indoor facilities.
The term "reducing nitrification" or "reduction of nitrification" as used herein refers to a slowing down or stopping of nitrification processes, e.g. by retarding or eliminating the natural transformation of ammonium into nitrate. Such reduction may be a complete or partial elimination of nitrification at the plant or locus where the inhibitor or composition comprising said inhibitor is applied. For example, a partial elimination may result in a residual nitrifi- cation on or in the plant, or in or on the soil or soil substituents where a plant grows or is intended to grow of about 90% to 1%, e.g. 90%, 85%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10% or less than 10%, e.g. 5% or less than 5% in comparison to a control situation where the nitrification inhibitor is not used. In certain embodiments, a partial elimination may result in a residual nitrification on or in the plant or in or on the soil or soil substituents where a plant grows or is intended to grow of below 1%, e.g. at 0.5%, 0.1% or less in comparison to a control situation where the nitrification inhibitor is not used.
The use of a nitrification inhibitor as defined herein above, or of a composition as defined herein for reducing nitrification may be a single use, or it may be a repeated use. As single use, the nitrification inhibitor or corresponding compositions may be provided to their target sites, e.g. soil or loci, or objects, e.g. plants, only once in a physiologically relevant time interval, e.g. once a year, or once every 2 to 5 years, or once during the lifetime of a plant.
In other embodiments, the use may be repeated at least once per time period, e.g. the nitrification inhibitor as defined herein above, or a composition as defined herein may be used for reducing nitrification at their target sites or objects two times within a time interval of days, weeks or months. The term "at least once" as used in the context of a use of the nitrification inhibitor means that the inhibitor may be used two times, or several times, i.e. that a repetition or multiple repetitions of an application or treatment with a nitrification inhibitor may be envisaged. Such a repetition may be a 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or more frequent repetition of the use.
The nitrification inhibitor according to the present invention may be used in any suitable form. For example, it may be used as coated or uncoated granule, in liquid or semi-liquid form, as sprayable entity, or in irrigation approaches etc. In specific embodiments, the nitrification inhibitor as defined herein may be applied or used as such, i.e. without formulations, fertilizer, additional water, coatings, or any further ingredient.
The term "irrigation" as used herein refers to the watering of plants or loci or soils or soil substituents where a plant grows or is intended to grow, wherein said watering includes the provision of the nitrification inhibitor according to the present invention together with water.
In a further aspect the invention relates to a composition for reducing nitrification comprising the mixture of the invention; and at least one carrier.
The term " composition for reducing nitrification" as used herein refers to a composition which is suitable, e.g. comprises effective concentrations and amounts of the components of the mixture of the invention for reducing nitrification in any context or environment in which nitrification may occur. In one embodiment, the nitrification may be reduced in or on or at the locus of a plant. Typically, the nitrification may be reduced in the root zone of a plant. However, the area in which such reduction of nitrification may occur is not limited to the plants and their environment, but may also include any other habitat of nitrifying bacteria or any site at which nitrifying enzymatic activities can be found or can function in a general manner, e.g. sewage plants, biogas plants, animal effluents from productive livestock, e.g. cows, pigs etc.. "Effective amounts" or "effective concentrations" of nitrification inhibitors as defined herein may be determined according to suitable in vitro and in vivo testings known to the skilled person. These amounts and concentrations may be adjusted to the locus, plant, soil, climate conditions or any other suitable parameter which may have an influence on nitrification processes. A "carrier" as used herein is a substance or composition which facilitates the delivery and/or release of the ingredients to the place or locus of destination. The term includes, for instance, agrochemical carriers which facilitate the delivery and/or release of agrochemicals in their field of use, in particular on or into plants.
Examples of suitable carriers include solid carriers such as phytogels, or hydrogels, or mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g. an solid or liquid ammonium-containing inorganic fertilizer such as an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; an solid or liquid organic fertilizer such as liquid manure, semi-liquid manure, stable manure, biogas manure and straw manure, worm castings, compost, seaweed or guano, or an urea-containing fertilizer such as urea, formaldehyde urea, anhydrous ammonium, urea ammonium nitrate (UAN) solution, urea sulphur, stabilized urea, urea based NPK-fertilizers, or urea ammonium sulfate, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers. Further suitable examples of carriers include fumed silica or precipitated silica, which may, for instance, be used in solid formulations as flow aid, anti-caking aid, milling aid and as carrier for liquid active ingredients. Additional examples of suitable carriers are microparticles, for instance microparticles which stick to plant leaves and release their content over a certain period of time. In specific embodiments, agrochemical carriers such as composite gel microparticles that can be used to deliver plant-protection active principles, e.g. as described in US 6,180,141; or compositions comprising at least one phytoactive compound and an encapsulating adjuvant, wherein the adjuvant comprises a fungal cell or a fragment thereof, e.g. as described in WO 2005/102045; or carrier granules, coated with a lipophilic tackifier on the surface, wherein the carrier granule adheres to the surface of plants, grasses and weeds, e.g. as disclosed in US 2007/0280981 may be used. In further specific embodiments, such carriers may include specific, strongly binding molecule which assure that the carrier sticks to the plant, the seed, and/or loci where the plant is growing or is intended to grow, till its content is completely delivered. For instance, the carrier may be or comprise cellulose binding domains (CBDs) have been described as useful agents for attachment of molecular species to cellulose (see US 6,124,117); or direct fusions between a CBD and an enzyme; or a multifunctional fusion protein which may be used for delivery of encapsulated agents, wherein the multifunctional fusion proteins may consist of a first binding domain which is a carbohydrate binding domain and a second binding domain, wherein either the first binding domain or the second binding domain can bind to a microparticle (see also WO 03/031477). Further suitable examples of carriers include bifunctional fusion proteins consisting of a CBD and an anti-RR6 antibody fragment binding to a microparticle, which complex may be deposited onto treads or cut grass (see also WO 03/031477). In another specific embodiment the carrier may be active ingredient carrier granules that adhere to e.g. the surface of plants, grasses, weeds, seeds, and/or loci where the plant is growing or is intended to grow etc. using a moisture-active coating, for instance including gum arabic, guar gum, gum karaya, gum tragacanth and locust bean gum. Upon application of the inventive granule onto a plant surface, water from precipitation, irrigation, dew, co-application with the granules from spe- cial application equipment, or guttation water from the plant itself may provide sufficient moisture for adherence of the granule to the plant surface (see also US 2007/0280981).
In another specific embodiment the carrier, e.g. an agrochemical carrier, may be or comprise polyaminoacids. Polyaminoacids may be obtained according to any suitable process, e.g. by polymerization of single or multiple amino acids such as glycine, alanine, valine, leucine, isoleucine, phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine and/or ornithine. Polyaminoacids may be combined with a nitrification inhibitor according to the present invention and, in certain embodiments, also with further carriers as mentioned herein above, or other nitrification inhibitors as mentioned herein in any suitable ratio. For example, Polyaminoacids may be combined with a nitrification inhibitor according to the present invention in a ratio of 1 to 10 (polyaminoacids) vs. 0.5 to 2 (nitrification inhibitor according to the present invention).
The mixture of the invention or the composition of the invention comprising the mixture of the invention may further comprise additional ingredients, for example at least one pesticidal compound. For example, the mixture or composition may additionally comprise at least one herbicidal compound and/or at least one fungicidal compound and/or at least one insecticidal compound and/or at least one nematicide and/or at least one biopesticide and/or at least one biostimulant.
In further embodiments, the mixture or composition may, in addition to the above indicated ingredients, further comprise one or more alternative or additional nitrification inhibitors. Examples of envisaged alternative or additional nitrification inhibitors are linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro-6- (trichloromethyl)-pyridine (nitrapyrin or N-serve), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4-amino-l,2,4-triazole hydrochloride (ATC), l-amido-2-thiourea (ASU), 2-amino-4- chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3- trichloromethyl-l,2,4-thiodiazole (terrazole, etridiazole), 2-sulfanilamidothiazole (ST), ammoniumthiosulfate (ATU), 3-methylpyrazol (3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-tria- zol thiourea (TU), N-(lH-pyrazolyl-methyl)acetamides such as N-((3(5)-methyl-lH-pyra- zole-l-yl)methyl)acetamide, and N-(lH-pyrazolyl-methyl)formamides such as N-((3(5)- methyl-lH-pyrazole-l-yl) methyl formamide, N-(4-ch loro-3 (5) -methyl -pyrazole- 1-yl methyl) - formamide, N-(3(5),4-dimethyl-pyrazole-l-ylmethyl)-formamide, neem, products based on ingredients of neem, cyan amide, melamine, zeolite powder, catechol, benzoquinone, sodium terta board, zinc sulfate.
In a preferred embodiment, the mixture or composition according to the present invention may further comprise 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 5-ethoxy-3-trichloromethyl-l,2,4-thiodiazole (terrazole, etridiazole).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 2-amino-4-chloro-6-methylpyrimidine (AM). In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 2-mercapto-benzothiazole (MBT).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 2-sulfanilamidothiazole (ST).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise ammoniumthiosulfate (ATU).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 3-methylpyrazol (3-MP).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 3,5-dimethylpyrazole (DMP).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 1 ,2,4-triazol .
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise thiourea (TU).
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise linoleic acid.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise alpha-linolenic acid.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise methyl p-coumarate.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise methyl 3-(4-hydroxyphenyl) propionate (MHPP).
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise methyl ferulate.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise Karanjin.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise brachialacton.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise p-benzoquinone sorgoleone.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise 4-amino-l,2,4-triazole hydrochloride (ATC).
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise l-amido-2-thiourea (ASU).
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise N-((3(5)-methyl-lH-pyrazole-l-yl)methyl)acetamide.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise N-((3(5)-methyl-lH-pyrazole-l-yl)methyl formamide.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise N-(4-chloro-3(5)-methyl-pyrazole-l-ylmethyl)-formamide.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise N-(3(5),4-dimethyl-pyrazole-l-ylmethyl)-formamide.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise neem or products based on ingredients of neem. In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise cyanamide.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise melamine.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise zeolite powder.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise batechol.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise benzoquinone.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise sodium terat borate.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise zinc sulfate.
In further embodiments, the mixture or composition according to the present invention may comprise a combination of the mixture of the invention and two entities selected from the group comprising: linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl feru- late, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzo- quinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4-amino-l,2,4-tria- zole hydrochloride (ATC), l-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3-trichloromethyl-l,2,4-thiodiazole (ter- razole, etridiazole), 2-sulfanilamidothiazole (ST), ammoniumthiosulfate (ATU), 3- methylpyrazol (3-MP), 3,5-dimethylpyrazole (DMP), 1 ,2,4-triazol and thiourea (TU), N-(1H- pyrazolyl-methyl)acetamides such as N-((3(5)-methyl-lH-pyrazole-l-yl)methyl)acetamide, and N-(lH-pyrazolyl-methyl)formamides such as N-((3(5)-methyl-lH-pyrazole-l-yl)methyl formamide, N-(4-chloro-3(5)-methyl-pyrazole-l-ylmethyl)-formamide, or N-(3(5),4- dimethyl-pyrazole-l-ylmethyl)-formamide neem, products based on ingredients of neem, cyan amide, melamine, zeolite powder, catechol, benzoquinone, sodium terta board, zinc sulfate.
In yet another group of embodiments, the mixture or composition according to the present invention may comprise a combination of the mixture of the invention and three, four or more entities selected from the group comprising: linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4-amino-l,2,4-triazole hydrochloride (ATC), l-amido-2-thiourea (ASU), 2-amino-4- chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3- trichloromethyl-l,2,4-thiodiazole (terrazole, etridiazole), 2-sulfanilamidothiazole (ST) ammoniumthiosulfate (ATU), 3-methylpyrazol (3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-tria- zol and thiourea (TU), N-(lH-pyrazolyl-methyl)acetamides such as N-((3(5)-methyl-lH- pyrazole-l-yl)methyl)acetamide, and N-(lH-pyrazolyl-methyl)formamides such as N-((3(5)- methyl-lH-pyrazole-l-yl) methyl formamide, N -(4-ch loro-3 (5) -methyl -pyrazole- 1-yl methyl) - formamide, or N-(3(5),4-dimethyl-pyrazole-l-ylmethyl)-formamide neem, products based on ingredients of neem, cyan amide, melamine, zeolite powder, catechol, benzoquinone, sodium terta board, zinc sulfate.
In further embodiments, the mixture or composition may, in addition to the above indicated ingredients, further comprise one or more urease inhibitors. Examples of envisaged urease inhibitors include N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain), N-(n-propyl) thiophosphoric acid triamide (NPPT), 2-nitrophenyl phosphoric triamide (2-NPT), further NXPTs known to the skilled person, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate, and mixtures of NBPT and NPPT (see e.g. US 8,075,659). Such mixtures of NBPT and NPPT may comprise NBPT in amounts of from 40 to 95% wt.-% and preferably of 60 to 80% wt.-% based on the total amount of active substances. Such mixtures are marketed as LIMUS, which is a composition comprising about 16.9 wt.-% NBPT and about 5.6 wt.-% NPPT and about 77.5 wt.-% of other ingredients including solvents and adjuvants.
In a preferred embodiment, the mixture or composition according to the present invention may further comprise N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise phenylphosphorodiamidate (PPD/PPDA).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise N-(n-propyl) thiophosphoric acid triamide (NPPT).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 2-nitrophenyl phosphoric triamide (2-NPT).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise hydroquinone.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise ammonium thiosulfate.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise neem.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise cyanamide.
In yet another preferred embodiment, the mixture or composition according to the present invention may further comprise melamine.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise a mixture of NBPT and NPPT such as LIMUS.
In further embodiments, the mixture or composition according to the present invention may comprise a combination of the mixture of the invention and two or more entities selected from the group comprising: N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain), N-(n-propyl) thiophosphoric acid triamide (NPPT), 2-nitrophenyl phosphoric triamide (2-NPT), further NXPTs known to the skilled person, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate, and LIMUS.
In further embodiments, the mixture or composition may, in addition to one, more or all of the above indicated ingredients, further comprise one or more plant growth regulators. Examples of envisaged plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releasers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators, and further unclassified plant growth regulators. Suitable examples of antiauxins to be used in a mixture or composition according to the present invention are clofibric acid or 2,3,5-tri-iodobenzoic acid.
Suitable examples of auxins to be used in a mixture or composition according to the present invention are 4-CPA, 2,4-D, 2,4-DB, 2,4-DEP, dichlorprop, fenoprop, IAA (indole-3- acetic acid), IBA, naphthaleneacetamide, alpha-naphthaleneacetic acid, 1-naphthol, naphthoxyacetic acid, potassium naphthenate, sodium naphthenate or 2,4,5-T.
Suitable examples of cytokinins to be used in a mixture or composition according to the present invention are 2iP, 6-Benzylaminopurine (6-BA) (= N-6 Benzyladenine), 2,6- Dimethylpuridine (N -Oxide-2,6- Lu Itid ine) , 2,6-Dimethyl pyridine, kinetin, or zeatin.
Suitable examples of defoliants to be used in a mixture or composition according to the present invention are calcium cyanamide, dimethipin, endothal, merphos, metoxuron, pentachlorophenol, thidiazuron, tributes, or tributyl phosphorotrithioate.
Suitable examples of ethylene modulators to be used in a mixture or composition according to the present invention are aviglycine, 1-methylcyclopropene (1-MCP), Prohexadione (prohexadione calcium), or trinexapac (Trinexapac-ethyl).
Suitable examples of ethylene releasers to be used in a composition according to the present invention are ACC, etacelasil, ethephon, or glyoxime.
Suitable examples of gibberellins to be used in a mixture or composition according to the present invention are gibberelline or gibberellic acid.
Suitable examples of growth inhibitors to be used in a mixture or composition according to the present invention are abscisic acid, S-abscisic acid, ancymidol, butralin, carbaryl ,ch lor- phonium, chlorpropham, dikegulac, flumetralin, fluoridamid,fosamine, glyphosine, isopyrimol, jasmonic acid, maleic hydrazide, mepiquat (mepiquat chloride, mepiquat pentaborate), piproctanyl, prohydrojasmon, propham, or 2,3,5-tri-iodobenzoic acid.
Suitable examples of morphactins to be used in a mixture or composition according to the present invention are chlorfluren, chlorflurenol, dichlorflurenol, or flurenol
Suitable examples of growth retardants to be used in a mixture or composition according to the present invention are chlormequat (chlormequat chloride), daminozide, flurprimidol, mefluidide, paclobutrazol, tetcyclacis, uniconazole, metconazol.
Suitable examples of growth stimulators to be used in a mixture or composition according to the present invention are brassinolide, forchlorfenuron, or hymexazol.
Suitable examples of further unclassified plant growth regulators to be used in a mixture or composition according to the present invention are amidochlor, benzofluor, buminafos, carvone, choline chloride, ciobutide, clofencet, cloxyfonac, cyanamide, cyclanilide, cycloheximide, cyprosulfamide, epocholeone, ethychlozate, ethylene, fenridazon, fluprimidol, fluthi- acet, heptopargil, holosulf, inabenfide, karetazan, lead arsenate, methasulfocarb, pydanon, sintofen, diflufenzopyr or triapenthenol.
In a preferred embodiment, the mixture or composition according to the present invention may comprise a combination of the mixture of the invention and at least one compound selected from the group comprising: abscisic acid, amidochlor, ancymidol, 6-benzylaminop- urine (= N-6 benzyladenine), brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, diflufenzopyr, dikegulac, dimethipin, 2,6- dimethylpyridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), 1-methylcyclopropene (1-MCP), naphthaleneacetic acid, N-6 benzyladenine, pa- clobutrazol, prohexadione (prohexadione calcium), prohydrojasmon, thidiazuron, tria- penthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid, trinexapac-ethyl, and uniconazole.
In a preferred embodiment, the mixture or composition according to the present invention may further comprise clofibric acid.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 2,3,5-tri-iodobenzoic acid.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 4-CPA.
In a further preferred embodiment, the c mixture or omposition according to the present invention may further comprise 2,4-D.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 2,4-DB.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 2,4-DEP.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise dichlorprop.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise fenoprop.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise IAA (indole-3-acetic acid).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise IBA.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise naphthaleneacetamide.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise alpha-naphthaleneacetic acid.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 1-naphthol.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise naphthoxyacetic acid.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise potassium naphthenate.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise sodium naphthenate.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise and 2,4,5-T.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 2iP.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 6-Benzylaminopurine (6-BA) (= N-6 Benzyladenine).
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 2,6-Dimethylpuridine (N -Oxid e-2 ,6- Lu Itid i ne) .
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise zeatin. In a further preferred embodiment, the mixture or composition according to the present invention may further comprise kinetin.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise calcium cyanamide.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise dimethipin.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise endothal.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise merphos.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise metoxuron.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise pentachlorophenol.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise thidiazuron.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise tribufos.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise tributyl phosphorotrithioate.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise aviglycine.
In a further preferred embodiment, the mixture or composition according to the present invention may further comprise 1-methylcyclopropene.
A mixture or composition as defined herein, in particular a mixture or composition further comprising a plant growth regulator as defined herein, may be used for the increase of plant health.
The term "plant health" as used herein is intended to mean a condition of the plant which is determined by several aspects alone or in combination with each other. One indicator (indicator 1) for the condition of the plant is the crop yield. "Crop" and "fruit" are to be understood as any plant product which is further utilized after harvesting, e.g. fruits in the proper sense, vegetables, nuts, grains, seeds, wood (e.g. in the case of silviculture plants), flowers (e.g. in the case of gardening plants, ornamentals) etc., that is anything of economic value that is produced by the plant. Another indicator (indicator 2) for the condition of the plant is the plant vigor. The plant vigor becomes manifest in several aspects, too, some of which are visual appearance, e.g. leaf color, fruit color and aspect, amount of dead basal leaves and/or extent of leaf blades, plant weight, plant height, extent of plant verse (lodging), number, strong ness and productivity of tillers, panicles' length, extent of root system, strength of roots, extent of nodulation, in particular of rhizobial nodulation, point of time of germination, emergence, flowering, grain maturity and/or senescence, protein content, sugar content and the like. Another indicator (indicator 3) for an increase of a plant's health is the reduction of biotic or abiotic stress factors. The three above mentioned indicators for the health condition of a plant may be interdependent and may result from each other. For example, a reduction of biotic or abiotic stress may lead to a better plant vigor, e.g. to better and bigger crops, and thus to an increased yield. Biotic stress, especially over longer terms, can have harmful effects on plants. The term "biotic stress" as used in the context of the present invention refers in particular to stress caused by living organisms. As a result, the quantity and the quality of the stressed plants, their crops and fruits decrease. As far as quality is concerned, reproductive development is usually severely affected with consequences on the crops which are important for fruits or seeds. Growth may be slowed by the stresses; polysaccharide synthesis, both structural and storage, may be reduced or modified: these effects may lead to a decrease in biomass and to changes in the nutritional value of the product. Abiotic stress includes drought, cold, increased UV, increased heat, or other changes in the environment of the plant, that leads to sub-optimal growth conditions. The term "increased yield" of a plant as used herein means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the composition of the invention. According to the present invention, it is preferred that the yield be increased by at least 0,5 %, more preferred at least 1 %, even more preferred at least 2 %, still more preferred at least 4 %. An increased yield may, for example, be due to a reduction of nitrification and a corresponding improvement of uptake of nitrogen nutrients. The term "improved plant vigor" as used herein means that certain crop characteristics are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the composition of the present invention. Improved plant vigor can be characterized, among others, by following improved properties of a plant:
(a) improved vitality of the plant,
(b) improved quality of the plant and/or of the plant products, e.g.
(b) enhanced protein content,
(c) improved visual appearance,
(d) delay of senescence,
(e) enhanced root growth and/or more developed root system (e.g. determined by the dry mass of the root),
(f) enhanced nodulation, in particular rhizobial nodulation,
(g) longer panicles,
(h) bigger leaf blade,
(i) less dead basal leaves,
(j) increased chlorophyll content
(k) prolonged photosynthetically active period
(l) improved nitrogen-supply within the plant
The improvement of the plant vigor according to the present invention particularly means that the improvement of anyone or several or all of the above mentioned plant characteristics are improved. It further means that if not all of the above characteristics are improved, those which are not improved are not worsened as compared to plants which were not treated according to the invention or are at least not worsened to such an extent that the negative effect exceeds the positive effect of the improved characteristic (i.e. there is always an overall positive effect which preferably results in an improved crop yield). An improved plant vigor may, for example, be due to a reduction of nitrification and, e.g. a regulation of plant growth. In further embodiments, the mixture or composition may, in addition to the above indicated ingredients, further comprise one or more pesticides.
A pesticide is generally a chemical or biological agent (such as pesticidal active ingredient, compound, composition, virus, bacterium, antimicrobial or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease. The term “pesticide” includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, microbial and biochemical pesticides:
1. Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classed as microbial pesticides, even though they are multi-cellular.
2. Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively non-toxic to mammals.
According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
When living microorganisms, such as microbial pesticides from groups LI), L3) and L5), form part of such kit, it must be taken care that choice and amounts of the components (e. g. chemical pesticides) and of the further auxiliaries should not influence the viability of the microbial pesticides in the composition mixed by the user. Especially for bactericides and solvents, compatibility with the respective microbial pesticide has to be taken into account.
Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit comprising a) a composition comprising component 1) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.
The following list of pesticides I (e. g. pesticida I ly-active substances and biopesticides), in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them:
A) Respiration inhibitors Inhibitors of complex III at Qo site: azoxystrobin (A.1.1), coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), man- destrobin (A.1.10), metominostrobin (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-l-methyl-allylideneaminooxymethyl)-phenyl)- 2-methoxyimino- /V-methyl-acetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb/ch loro- dincarb (A.1.20), famoxadone (A.1.21), fenamidone (A.1.21), methyl-/V-[2-[(l,4-dimethyl- 5 - ph e ny I -pyrazo I -3-yl) oxy I methyl] phenyl] - m eth oxy- carbarn ate (A.1.22), l-[2-[[l-(4- chloropheny I) pyrazol-3-yl]oxy methyl] -3- methyl -phenyl] -4- methyl -tetrazol -5-one (A.1.25), (2(2 £) -5- [l-(2,4-dichlorophenyl)pyrazol -3-yl] -oxy-2- methoxyi mi no- /V,3-di methyl -pent-3- enamide (A.1.34), (2]2 £) -5- [l-(4-chlorophenyl)pyrazol -3-yl] oxy-2- methoxyimino- /, 3- dimethyl-pent-3-enamide (A.1.35), pyriminostrobin (A.1.36), bifujunzhi (A.1.37), 2-(ortho- ((2,5-dimethylphenyl-oxymethylen)phenyl)-3-methoxy-acrylic acid methylester (A.1.38); inhibitors of complex III at Q, site: cyazofamid (A.2.1), amisulbrom (A.2.2), [(6S,7 /?,8/^ -8- benzyl -3- [(3- hydroxy-4- methoxy- py rid ine-2-carbony I) a mi no] -6- methyl -4,9- dioxo-l,5-dioxonan-7-yl] 2-methylpropanoate (A.2.3), fenpicoxamid (A.2.4); inhibitors of complex II: benodanil (A.3.1), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.11), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.15), penthiopyrad (A.3.16), pydiflumetofen (A.3.17), pyraziflumid (A.3.18), sedaxane (A.3.19), tecloftalam (A.3.20), thifluzamide (A.3.21), inpyrfluxam (A.3.22), pyrapropoyne (A.3.23), fluindapyr (A.3.28), methyl (£)-2-[2-[(5-cyano- 2- methyl -phenoxy) methyl] phenyl] -3- methoxy- prop-2-e noate (A.3.30), isoflucypram (A.3.31), 2- (difluoro methyl)- M(l,l,3-tri methyl -indan -4-yl) pyridine-3-carboxamide (A.3.32), 2 -(difluoro methyl)- /V- [(3 /)- 1,1, 3-tri methyl indan -4-yl] pyridine-3-carboxam ide (A.3.33), 2- (difluoromethyl)- M(3-ethyl-l, 1-di methyl -indan-4-y I) py rid ine-3 -carboxamide (A.3.34), 2- (di- fluoromethyl)- N- [(3 /? -3 -ethyl -1,1 -di methyl -indan-4-yl]pyridine-3-carboxam ide (A.3.35), 2- (difluoromethyl)- /V- (1,1 -di methyl -3- propyl -indan-4-yl)pyridine-3-carboxam ide (A.3.36), 2- (difluoromethyl)- N- [(3/^-1, 1-di methyl -3- propyl -indan -4-yl] py rid ine-3-carboxamide (A.3.37), 2- (difl u oro methyl) -M (3- iso butyl- 1,1 -di methyl -indan -4-yl) pyridine-3-carboxam ide (A.3.38), 2- (difluoro methyl)- N- [(3/^ -3-isobuty 1-1, 1-di methyl -indan-4-yl] pyridine-3-ca rbox- amide (A.3.39); other respiration inhibitors: diflumetorim (A.4.1); nitrophenyl derivates: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferim- zone (A.4.7); organometal compounds: fentin salts, e. g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.11); silthiofam (A.4.12);
B) Sterol biosynthesis inhibitors (SBI fungicides)
C14 demethylase inhibitors: triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromu- conazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), dini- conazole-M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1.14), ip- conazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), pa- clobutrazole (B.1.20), penconazole (B.1.21), propiconazole (B.1.22), prothioconazole (B.1.23), simeconazole (B.1.24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1.27), triadimenol (B.1.28), triticonazole (B.1.29), uniconazole (B.1.30), 2-(2,4-difluo- rophenyl)-l,l-difluoro-3-(tetrazol-l-yl)-l-[5-[4-(2,2,2-trifluoroethoxy)phenyl]- 2 - py ridy I] p ropa n -2 -ol (B.1.31), 2-(2,4-difluorophenyl)-l,l-difluoro-3-(tetrazol-l-yl)- 1- [5- [4- (trifluoromethoxy) phenyl] -2- pyridyl] propan-2-ol (B.1.32), ipfen trifluconazole (B.1.37), mefentrifluconazole (B.1.38), 2-(chloromethyl)-2-methyl-5-(p-tolylmethyl)- l-(l,2,4-triazol-l-ylmethyl)cyclopentanol (B.1.43); imidazoles: imazalil (B.1.44), pefurazoate (B.1.45), prochloraz (B.1.46), triflumizol (B.1.47); pyrimidines, pyridines, piperazines: fenari- mol (B.1.49), pyrifenox (B.1.50), triforine (B.1.51), [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-di- f I uoropheny I) isoxazol -4-yl] -(3- pyridyl) methanol (B.1.52);
Deltal4-reductase inhibitors: aldimorph (B.2.1), dodemorph (B.2.2), dodemorph-ac- etate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spiroxamine (B.2.8);
Inhibitors of 3-keto reductase: fenhexamid (B.3.1);
Other Sterol biosynthesis inhibitors: chlorphenomizole (B.4.1);
C) Nucleic acid synthesis inhibitors phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1), benalaxyl-M (C.1.2), ki- ralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7); other nucleic acid synthesis inhibitors: hymexazole (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrim- idin-4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-flu- oro-2-(4-chlorophenylmethoxy)pyrimidin-4 amine (C.2.8);
D) Inhibitors of cell division and cytoskeleton tubulin inhibitors: benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (DI.3), thiabendazole (D.1.4), thiophanate-methyl (D.1.5), 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5- phenyl-py rid azine (D.1.6), 3-ch loro-6- methyl -5- phenyl -4- (2, 4,6-trif I uoropheny I) py ridazine (D.1.7), /V-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]butanamide (D.1.8), /V-ethy I -2- [(3- ethynyl -8- methyl -6-quinolyl)oxy] -2- methylsulfanyl -acetamide (D.1.9), 2-[(3-ethynyl-8- methyl-6-quinolyl)oxy]-/V-(2-fluoroethyl)butanamide (D.1.10), 2-[(3-ethynyl-8-methyl-6- quinolyl)oxy]-/V-(2-fluoroethy I) -2-m ethoxy-acetamide (D.1.11), 2-[(3-ethynyl-8-methyl-6- quinolyl)oxy]- /V-propyl-butanamide (D.1.12), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2- methoxy- propyl -acetamide (D.1.13), 2- [(3-ethyny I -8- methyl -6-quinolyl) oxy] -2- methyl sulfa ny I- N- propyl -acetamide (D.1.14), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-/V-(2-fluo- roethy I) -2 -methyl sulf any I -acetamide (D.1.15), 4-(2-bromo-4-fluoro-phenyl)-/V-(2-chloro-6- fluoro- phenyl) -2,5-di methyl -pyrazol-3-amine (D.1.16); other cell division inhibitors: diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7);
E) Inhibitors of amino acid and protein synthesis methionine synthesis inhibitors: cyprodinil (E.1.1), mepanipyrim (E.1.2), pyrimethanil (E.1.3); protein synthesis inhibitors: blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hydrochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6);
F) Signal transduction inhibitors
MAP / histidine kinase inhibitors: fluoroimid (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fludioxonil (F.1.5); G protein inhibitors: quinoxyfen (F.2.1);
G) Lipid and membrane synthesis inhibitors
Phospholipid biosynthesis inhibitors: edifenphos (G.1.1), iprobenfos (G.1.2), pyra- zophos (G.1.3), isoprothiolane (G.1.4); lipid peroxidation: dicloran (G.2.1), quintozene (G.2.2), tecnazene (G.2.3), tolclofos- methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7); phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7); compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1); inhibitors of oxysterol binding protein: oxathiapiprolin (G.5.1), 2-{3-[2-(l-{[3,5-bis(di- f I uoro methyl- H- pyrazol- 1-yl] acetyl} pi peridi n-4-yl)-l, 3 -th i azo I -4-yl] -4,5-di hydro- 1,2-oxa- zol -5 -y I] ph e ny I methanesulfonate (G.5.2), 2-{3 - [2 - (1 -{[3 ,5- bis (d if I u oro methy I) - 1 H- py razol - 1-y I] acetyl] pi peridin -4-yl) 1,3-th iazol -4-yl] -4,5-di hyd ro- 1 ,2-oxazol -5-yl]-3-ch loropheny I methanesulfonate (G.5.3), 4- [1- [2- [3- (difluoromethyl) -5- methy I -pyrazol -1-y I] acetyl] -4- piperidyl]- /V-tetralin-l-yl-pyridine-2-carboxamide (G.5.4), 4- [1- [2- [3,5- bis (difluoromethyl) pyrazol -1-y I] acetyl] -4- piperidyl] -/V-tetra I in- 1-yl-pyridi ne-2-carboxam ide (G.5.5), 4- [1 - [2- [3- (d if I u o ro methy I) -5- (trif I uo ro methy I) py razo I - 1 -y I] acety I] -4- pi pe ridy I] - /V-tetra I i n - l-yl-pyridine-2-carboxamide (G.5.6), 4-[l-[2-[5-cyclopropyl-3-(difluoromethyl) pyrazol-l- yl] acetyl] -4- pi pe ridy I] -/V-tetra I in- 1-yl-pyridi ne-2-carboxam ide (G.5.7), 4- [1- [2 -[5- methyl -3- (trifluoromethyl) pyrazol -1-y I] acety I] -4- piperidyl] -/V-tetra I in-l-yl-pyridine-2-carboxam ide (G.5.8), 4- [1 - [2- [5- (d if I u o ro m ethyl) -3 - (trif I u oro methy I) py razo I - 1 -y I] acety I] -4- pi pe ridy I] - N- tetralin-l-yl-pyridine-2-carboxamide (G.5.9), 4- [1- [2- [3,5- bis(trif I uoromethyl) pyrazol - 1 - yl] acetyl] -4- piperidyl] -/V-tetra I in-l-yl-pyridine-2-carboxam ide (G.5.10), (4- [1 - [2- [5-cyclo- p ropy I -3 - (trif I u o ro methy I) py razo I - 1 -y I] acety I] -4- pi peridy I] - /V-tetra I i n - 1 -y I - py rid i ne-2-ca r- boxamide (G.5.11);
H) Inhibitors with Multi Site Action inorganic active substances: Bordeaux mixture (H.1.1), copper (H.1.2), copper acetate (H.1.3), copper hydroxide (H.1.4), copper oxychloride (H.1.5), basic copper sulfate (H.1.6), sulfur (H.1.7); thio- and dithiocarbamates: ferbam (H.2.1), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9); organochlorine compounds: anilazine (H.3.1), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.11); guanidines and others: guanidine (H.4.1), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-l/7,5/7-[l,4]di- thii no[2,3-c:5,6-c'] di pyrrole- 1 ,3,5,7 (2 H H) -tetraone (H.4.10);
I) Cell wall synthesis inhibitors inhibitors of glucan synthesis: validamycin (1.1.1), polyoxin B (1.1.2); melanin synthesis inhibitors: pyroquilon (1.2.1), tricyclazole (1.2.2), carpropamid (1.2.3), dicyclomet (1.2.4), fenoxanil (1.2.5);
J) Plant defence inducers acibenzolar-S-methyl (J.1.1), probenazole (J.1.2), isotianil (J.1.3), tiadinil (J.1.4), pro- hexadione-calcium (J.1.5); phosphonates: fosetyl (J.1.6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), calcium phosphonate (J.1.11), potassium phosphonate (J.1.12), potassium or sodium bicarbonate (J.1.9), 4-cyclopropyl-M(2,4-dimethoxy- phenyl)thiadiazole-5-carboxamide (J.1.10);
K) Unknown mode of action bronopol (K.1.1), chinomethionat (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclocymet (K.1.7), diclomezine (K.1.8), difenzoquat (K.1.9), difenzoquat-methylsulfate (K.1.10), diphenylamin (K.1.11), fenitropan (K.1.12), fenpyraza- mine (K.1.13), flumetover (K.1.14), flusulfamide (K.1.15), flutianil (K.1.16), harpin (K.1.17), methasulfocarb (K.1.18), nitrapyrin (K.1.19), nitrothal-isopropyl (K.1.20), tolprocarb (K.1.21), oxin-copper (K.1.22), proquinazid (K.1.23), tebufloquin (K.1.24), tecloftalam (K.1.25), triazoxide (K.1.26), /V '- (4- (4-chloro-3-trif I uoromethy I- phenoxy) -2,5-di methyl -phenyl)- Methyl - Mmethyl formamidine (K.1.27), /V'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl- phenyl)- ethyl- Mmethyl formamidine (K.1.28), /V- [4- [[3- [(4-chlorophenyl) methyl] -1,2,4- thiadiazol -5-yl] oxy] -2,5-di methyl -phenyl]- Methyl- N- methyl -formamidine (K.1.29), /V'-(5- b rom o-6- in dan -2 -y I oxy-2- methy 1-3 -pyridyl)- Methyl-Mmethyl-fo rm amidine (K.1.30), /V [5- b rom o-6- [1 -(3,5 -difluoro ph enyl)ethoxy]-2-m ethyl -3 -pyridyl]- Methyl- M methyl -fo rm amidine (K.1.31), N '-[5 -bro mo-6- (4- isop ropy I cyclo hexoxy) -2-methyl-3-py ridy I] - Methyl- M methyl - formamidine (K.1.32), N'- [5- bromo-2- methyl -6- (1- phenyl ethoxy) -3- pyridyl]- Methyl -M methy I -formamidine (K.1.33), /V'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl- propoxy)-phenyl)-Methyl-Mmethyl formamidine (K.1.34), /V'-(5-difluoromethyl-2-methyl-4- (3-trimethylsilanyl-propoxy)-phenyl)-Methyl-Mmethyl formamidine (K.1.35), 2-(4-chloro- phenyl)-M[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide (K.1.36),
3 - [5- (4-c h I o ro- p h eny I) -2,3 -d i m ethy I -isoxazol id i n -3 -y I] - py rid i n e (pyrisoxazole) (K.1.37), 3- [5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3 yl] -pyridine (K.1.38), 5-chloro-l-(4,6- dimethoxy-pyrimidin-2-yl)-2-methyl-lMbenzoimidazole (K.1.39), ethyl (2)-3-amino-2- cyano-3-phenyl-prop-2-enoate (K.1.40), picarbutrazox (K.1.41), pentyl M[6-[[(2)-[(l- methyltetrazol -5-yl) -phenyl -methylene] ami no] oxy methy I] -2- pyridyl] carbamate (K.1.42), but-3-ynyl M [6- [[(2) -[(1- methyltetrazol -5-yl) -phenyl -methylene] ami no] oxymethyl] -2- pyridyl] car ba mate (K.1.43), 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro- phenyl]propan-2-ol (K.1.44), 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phen- yl]propan-2-ol (K.1.45), quinofumelin (K.1.47), 9-fluoro-2,2-dimethyl-5-(3-quinolyl)- 3Ml,4-benzoxazepine (K.1.49), 2-(6-benzyl-2-pyridyl)quinazoline (K.1.50), 2- [6- (3-f I uoro-
4-methoxy-phenyl)-5-methyl-2-pyridyl]quinazoline (K.1.51), dichlobentiazox (K.1.52), N- (2,5 -d im et hyl-4-p he noxy-p he ny I) - Methyl-Mmethyl-fo rm amidine (K.1.53), py rife na mine (K.1.54).
L) Biopesticides
LI) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqua/is, Aspergillus f/avus, Aureobasidium pullulans, Bacillus a/titudinis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. so/isa Isi, B. subti/is, B. subtilis iar. amyloliquefaciens, Candida oieophiia, C. saitoana, Ciavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonec- tria parasitica, Cryptococcus aibidus, Diiophosphora aiopecuri, Fusarium oxysporum, Cionostachys rosea catenulate (also named GHodadium catenulatum), Gliocladium ro- seum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicoia, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibaciiius alvei, Paenibaciiius epiphyticus, P. poiymyxa, Pantoea vagans, PeniciHium biiaiae, Phiebiopsis gigantea, Pseudomonas sp., Pseudomonas chioraphis, Pseudozyma fioccuiosa, Pichia anomaia, Pythium oiigandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. iydicus, S. vio- iaceusniger, Taiaromyces fiavus, Trichoderma aspereiioides, T. aspereiium, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. po/ysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: harpin protein, Reynoutria sachaiinensis extract;
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firm us, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israeiensis, B. t. ssp. gaiieriae, B. t. ssp. kurstaki, B. t. ssp. tenebrio- nis, Beauveria bassiana, B. brongniartii, Burkhoideria spp., Chromobacterium subtsugae, Cydia pomoneiia granulovirus (CpGV), Cryptophiebia ieucotreta granulovirus (CrleGV), Fiavobacterium spp., Heiicoverpa armigera nucleopolyhedrovirus (HearNPV), Heiicoverpa zea nucleopolyhedrovirus (HzNPV), Heiicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, isaria fumosorosea, LecaniciHium iongisporum, L. muscarium, Metarhizium anisopiiae, M. anisopiiae ia r. anisopiiae, M. anisopiiae iar. acridum, Nomuraea riieyi, Paeciiomyces fumosoroseus, P. iiiacinus, Paenibaciiius popiiiiae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fiuorescens, Spodoptera Httoraiis nucleopolyhedrovirus (SpliNPV), Steinernema carpocap- sae, S. feitiae, S. kraussei, Streptomyces gaibus, S. microfiavus',
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (Z/2)-7,9-dodecadien-l-yl acetate, ethyl formate, (£)2)-2,4-ethyl decadienoate (pear ester), (2(2(£)-7,ll,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1-butanol, methyl eugenol, methyl jasmonate, (Ej2)-2,13-octadecadien-l-ol, (Z/2)-2,13-octadecadien-l-ol acetate, (£)2)-3,13-octadecadien-l-ol, (Z/)-l-octen-3-ol, pentatermanone, (Ej2(2)-3,8,ll-tetradeca- trienyl acetate, (2(£)-9,12-tetradecadien-l-yl acetate, (2)-7-tetradecen-2-one, (2)-9- tetradecen-l-yl acetate, (2)-ll-tetradecenal, (2)-ll-tetradecen-l-ol, extract of Chenopodium ambrosiodes, Neem oil, Quillay extract;
L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. ha/opraeferens, Bradyrhizobium spp., B. e/kanii, B. japonicum, B. liaoningense, B. lupini, De/ftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhi- zobium ieguminosarum bv. phaseoii, R. /. bv. trifoiii, R. /. bv. viciae, R. tropici, Sinorhizobium me! Hoti
M) Insecticides
M.l) Acetylcholine esterase (AChE) inhibitors: M.1A carbamates, e.g. aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, me- thiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or M.1B organophosphates, e.g. acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxy- fos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenami- phos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecar- bam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, and vamidothion;
M.2) GABA-gated chloride channel antagonists: M.2A cyclodiene organochlorine compounds, e.g. endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), e.g. ethiprole, fipronil, flufiprole, pyrafluprole, and pyriprole;
M.3) Sodium channel modulators from the class of M.3A pyrethroids, e.g. acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta- cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, al- pha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imi- prothrin, meperfluthrin,metofluthrin, momfluorothrin, epsilon-momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, sila- fluofen, tefluthrin, kappa-tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin, and transfluthrin; or M.3B sodium channel modulators such as DDT or methoxychlor;
M.4) Nicotinic acetylcholine receptor agonists (nAChR): M.4A neonicotinoids, e.g. acet- amiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds M.4A.1 4,5-Dihydro-N-nitro-l-(2-oxiranyl- methyl)-lH-imidazol-2-amine, M.4 A.2: (2 E-)-l-[(6-Ch Io ropy rid in -3-yl) methyl] -N'- nitro-2-pentylidenehydrazinecarboximidamide; or M4.A.3: l-[(6-Chloropyridin-3- y I) methyl] -7- methyl -8- nitro-5- pro poxy- 1,2, 3, 5, 6, 7- hexa hydroi mid azo [1,2 -a] pyridine; or M.4B nicotine; M.4C sulfoxaflor; M.4D flupyradifurone; M.4E triflumezo- pyrim;
M.5) Nicotinic acetylcholine receptor allosteric activators:spinosyns, e.g. spinosad or spinetoram;
M.6) Chloride channel activators from the class of avermectins and milbemycins, e.g. abamectin, emamectin benzoate, ivermectin, lepimectin, or milbemectin;
M.7) Juvenile hormone mimics, such as M.7A juvenile hormone analogues hydroprene, kinoprene, and methoprene; or M.7B fenoxycarb, or M.7C pyriproxyfen;
M.8) miscellaneous non-specific (multi-site) inhibitors, e.g. M.8A alkyl halides as methyl bromide and other alkyl halides, M.8B chloropicrin, M.8C sulfuryl fluoride, M.8D borax, or M.8E tartar emetic; M.9) Chordotonal organ TRPV channel modulators, e.g. M.9B pymetrozine; pyriflu- quinazon;
M.10 Mite growth inhibitors, e.g. M.10A clofentezine, hexythiazox, and diflovidazin, or M.10B etoxazole;
M.10) Mite growth inhibitors, e.g. M.10A clofentezine, hexythiazox, and diflovidazin, or M.10B etoxazole;
M.ll) Microbial disruptors of insect midgut membranes, e.g. bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israeiensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, and Cry34/35Abl;
M.12) Inhibitors of mitochondrial ATP synthase, e.g. M.12A diafenthiuron, or M.12B organotin miticides such as azocyclotin, cyhexatin, or fenbutatin oxide, M.12C propar- gite, or M.12D tetradifon;
M.13) Uncouplers of oxidative phosphorylation via disruption of the proton gradient, e.g. chlorfenapyr, DNOC, or sulflu ramid;
M.14) Nicotinic acetylcholine receptor (nAChR) channel blockers, e.g. nereistoxin analogues bensultap, cartap hydrochloride, thiocyclam, or thiosultap sodium;
M.15) Inhibitors of the chitin biosynthesis type 0, such as benzoylureas e.g. bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, or triflumuron;
M.16) Inhibitors of the chitin biosynthesis type 1, e.g. buprofezin;
M.17) Moulting disruptors, Dipteran, e.g. cyromazine;
M.18) Ecdyson receptor agonists such as diacylhydrazines, e.g. methoxyfenozide, te- bufenozide, halofenozide, fufenozide, or chromafenozide;
M.19) Octopamin receptor agonists, e.g. amitraz;
M.20) Mitochondrial complex III electron transport inhibitors, e.g. M.20A hydramethylnon, M.20B acequinocyl, M.20C fluacrypyrim; or M.20D bifenazate;
M.21) Mitochondrial complex I electron transport inhibitors, e.g. M.21A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21B rotenone;
M.22) Voltage-dependent sodium channel blockers, e.g. M.22A indoxacarb, M.22B meta- flumizone, or M.22B.1: 2-[2-(4-Cyanophenyl)-l-[3-(trifluoromethyl)phenyl]ethyl- idene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3- Ch loro-2- methyl phenyl) -2- [(4-chlorophenyl) [4- [methyl (methylsulf- onyl)a mi no] phenyl] methylene] -hydrazinecarboxamide;
M.23) Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid derivatives, e.g. spirodiclofen, spiromesifen, or spirotetramat; M.23.1 spiropidion;
M.24) Mitochondrial complex IV electron transport inhibitors, e.g. M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide;
M.25) Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives, e.g. cyenopyrafen or cyflumetofen; M.28) Ryanodine receptor-modulators from the class of diamides, e.g. flubendiamide, chlorantraniliprole, cyantraniliprole, tetraniliprole, M.28.1: (R)-3-Chlor-Nl-{2- methyl-4-[l,2,2,2 -tetrafluoro-l-(trifluoromethyl)ethyl]phenyl]-N2-(l-methyl-2- methylsulfonylethyl)phthalamid, M.28.2: (S)-3-Chloro-Nl-{2-methyl-4-[l,2,2,2-tet- raf I uoro-1- (trifl uoro methyl) ethyl] phenyl}- N2-(l- methyl -2- methylsulf- onylethyl)phthalamid, M.28.3: cyclaniliprole, or M.28.4: methyl-2-[3,5-dibromo-2- ({[3-bromo-l-(3-chlorpyridin-2-yl)-lH-pyrazol-5-yl]carbonyl}amino)benzoyl]-l,2- dimethylhydrazinecarboxylate; or M.28.5a) N-[4,6-dichloro-2-[(diethyl-lambda-4- su Ifany lid ene) car bam oy I] -phenyl] -2 -(3 -ch I oro-2 -pyridyl) -5- (trifluoromethyl) pyrazo I e-3 -carboxamide; M.28.5b) N-[4-ch loro-2- [(diethyl- la mbda-4- su Ifanylidene) carbamoyl] -6- methyl -phenyl] -2- (3-ch loro-2- pyridyl) -5- (trifluoromethyl) pyrazo I e-3 -carboxamide; M.28.5c) N-[4-ch loro-2- [(di-2- propyl -lam bda-4- su Ifanylidene) carbamoyl] -6- methyl -phenyl] -2- (3-ch loro-2- pyridyl) -5- (trifluoromethyl) pyrazo I e-3 -carboxamide; M.28.5d) N-[4,6-dich loro-2- [(di-2- propyl- la mbda- 4-su Ifanylidene) carbamoyl] -phenyl] -2- (3-ch loro-2- pyridyl) -5- (trifluoromethyl) pyrazo I e-3 -carboxamide; M.28.5h) N-[4,6-dibromo-2- [(diethyl- lam bda-4- su Ifany I id ene) carbamoyl] -phenyl] -2 -(3 -ch I oro-2 -pyridyl) -5- (trifluoromethyl) pyrazo I e-3 -carboxamide; M.28.5i) N-[2-(5-Amino-l,3,4-thiadiazol-2-yl)-4- chloro-6-methylphenyl]-3-bromo-l-(3-chloro-2-pyridinyl)-lH-pyrazole-5-carbox- amide; M.28.5j) 3-Chloro-l-(3-chloro-2-pyridinyl)-N-[2,4-dichloro-6-[[(l-cyano-l- methylethyl)amino]carbonyl] phenyl]-lH-pyrazole-5-carboxamide; M.28.5k) 3- Bromo-N-[2,4-dichloro-6-(methylcarbamoyl) phenyl]-l-(3,5-dichloro-2-pyridyl)-lH- py razo I e-5 -carboxamide; M.28.51) N - [4-Ch loro-2- [[(1,1 -di methyl ethyl) ami no] car- bony I] -6-m ethyl phenyl] -l-(3 -ch Io ro-2-pyridinyl)-3-(fluoromethoxy)-lH-pyrazo I e-5- carboxamide; or M.28.6: cyhalodiamide; or
M.29) Chordotonal organ Modulators - undefined target site, e.g. flonicamid;
M.UN. insecticidal active compounds of unknown or uncertain mode of action, e.g. afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, broflanilide, bromopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flomet- oquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, tioxazafen, M.UN.3: ll-(4-chloro-2,6- di methyl phenyl) -12- hydroxy- l,4-dioxa-9-azadispiro[4.2.4.2] -tetradec- 11 -en- 10- one,
M.UN.4: 3- (4’ -fl uoro-2,4-di methyl bi phenyl -3-yl) -4- hydroxy-8 -oxa -1 -azaspiro [4.5] dec-3 - en-2-one,
M.UN.5: 1 - [2-f I u oro-4- methyl -5- [(2, 2,2-trif I uoroethy I) sulfinyl] phenyl] -3 -(trifl uo- romethyl)-lH-l,2,4-triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582);
M.UN.6: flupyrimin;
M.UN.8: fluazaindolizine; M.UN.9. a): 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H- isoxazol-3-yl] -2 -methyl-N-(l-oxothietan-3-yl) benzamide; M.UN.9.b): fl uxa meta imide; M.UN.10: 5- [3- [2,6-dich loro-4- (3,3-dichloroa I lyl oxy) phenoxy] propoxy] -1H- pyrazole;
M.UN.ll.i) 4-cyano-N-[2-cyano-5-[[2,6-dibromo-4-[l,2,2,3,3,3-hexafluoro-l-(trifluoro- methy I) propyl] phenyl] carbamoyl] phenyl] -2 -methyl -benzamide; M.UN.ll.j) 4-cy- ano-3-[(4-cyano-2-methyl-benzoyl)amino]-N -[2,6-dich loro-4- [1,2, 2, 3, 3, 3-hexa- f I uoro- 1 - (trifluoro methyl) propyl] phenyl] -2-f I uoro- benzamide; M.UN.ll.k) N-[5-[[2- ch Io ro-6-cya no-4- [1,2,2, 3,3,3 -hexafl uoro-1- (trifl uoro methyl) propyl] phenyl] carbamoyl] -2 -cyano- phenyl] -4-cya no-2- methyl -benzamide; M. UN.11.1) N-[5-[[2- bromo-6-ch loro-4- [2,2,2 -trif I uoro-1- hydroxy- 1- (trifl uoro methyl) ethyl] phenyl] carbamoyl] -2 -cyano- phenyl] -4-cya no-2- methyl -benzamide; M.UN.ll.m) N-[5-[[2- bromo-6-chloro-4-[l,2,2,3,3,3-hexafluoro-l-(trifluoromethyl)propyl]phenyl]car- bamoy I] -2 -cyano- phenyl] -4-cya no-2- methyl -benzamide; M.UN.ll.n) 4-cya no- N- [2- cya no-5- [[2,6-dich I oro-4- [1,2, 2, 3, 3,3- hexafl uoro-1 -(trifluoromethyl) propyl] phenyl] carbamoyl] phenyl] -2 -methyl -benzamide; M.UN.ll.o) 4-cyano-N-[2-cy- ano-5- [[2,6-dich I oro-4- [1,2,2,2-tetraf I uoro-1- (trif I uorom ethyl) ethyl] phenyl] carbamoyl] phenyl] -2- methyl -benzamide; M.UN.ll.p) N-[5-[[2-bromo-6-chloro-4- [1,2, 2, 2 -tetrafl uoro-1 -(trif I uoro methyl) ethyl] phenyl] car bam oy I] -2-cya no- phenyl] -4- cyano-2-methyl-benzamide; or
M. UN.12. a) 2-(l,3-Dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine; M.UN.12.b) 2- [6- [2- (5- Fl u oro-3- py rid i ny I) -5 -th iazo ly I] -2- py rid i ny I] - py ri m id i n e; M.UN.12.c) 2-[6- [2-(3-Pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; M.UN.12.d) N-Methylsulfonyl- 6- [2- (3- py ridy I) th iazo I -5 -y I] py rid i n e-2 -ca r boxa m id e; M.UN.12.e) N-Methylsulfonyl- 6- [2- (3- py ridy I) th iazo I -5 -y I] py rid i n e-2 -ca r boxa m id e;
M. UN.14a) 1 - [(6-Ch I oro-3 -py rid iny I) methyl] -1, 2,3,5, 6,7- hexa hydro-5 -methoxy-7- methyl-8-nitro-imidazo[l,2-a]pyridine; or M. UN.14b) l-[(6-Chloropyridin-3- yl)methyl]-7-methyl-8-nitro-l,2,3,5,6,7-hexahydroimidazo[l,2-a]pyridin-5-ol;
M. UN.16a) l-isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; or
M. UN.16b) l-(l,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4- ca r boxa m ide; M. UN.16c) N,5-dimethyl-N-pyridazin-4-yl-l-(2,2,2-trifluoro-l-methyl- ethyl)pyrazole-4-carboxamide; M.UN.16d) 1 -[1-(1 -cyanocyclo propyl) ethyl] -N -ethyl - 5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.UN.16e) N-ethyl-l-(2-flu- oro-l-methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;
M.UN.16f) l-(l,2-dim ethyl propyl) -N,5-dimethyl-N-pyridazin-4-yl-pyrazo I e-4-car- boxamide; M. UN.16g) l-[l-(l-cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazin-4- yl-pyrazole-4-carboxamide; M.UN.16h) N-methy 1-1- (2-f I uoro-1- methyl -propyl] -5- methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.UN.16i) l-(4,4-difluorocyclo- hexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; or M.UN.16j) 1- (4,4-difluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide, M. UN.17a) N-(l -methyl ethyl) -2- (3- py rid iny I) -2 H-indazole-4-carboxam ide; M. UN.17b)
N -eye Io propyl -2- (3- py rid iny I) -2 H-indazole-4-carboxam ide; M. UN.17 c) N -cyclo- hexyl -2- (3- pyrid iny I) -2 H-indazole-4-carboxamide; M.UN.17d) 2-(3-pyridinyl)-N- (2,2,2-trifluoroethyl)-2H-indazole-4-carboxamide; M.UN.17e) 2 -(3 -pyrid iny I) -N- [(tetrahydro-2-furanyl) methyl]-2H-indazole-5-carboxamide; M.UN.17f) methyl 2- [[2- (3- pyrid inyl)-2H-indazol -5-yl] carbonyl] hydrazinecarboxylate; M. UN.17g) N- [(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide; M.UN.17h) N-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide;
M.UN.17i) 2 - (3 - py rid i ny I )-N-(2-pyrimidinylmethyl )-2H-indazole-5-carboxamide;
M.UN.17j) N-[(5-methyl-2-pyrazinyl) methyl]-2-(3-pyridinyl)-2H-indazole-5-carbox- amide, M.UN.18. tyclopyrazof lor;
M.UN.19 sarolaner, M.UN.20 lotilaner;
M.UN.21 N-[4-Chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-l-methyl-3-(l,l,2,2,2- pe ntaf luoroethyl)-4-(trifluoromethy I) -IH-pyrazo I e-5 -carboxamide; M. UN.22a 2- (3- ethy I su Ifo ny I -2 - py ridy I ) -3 - methy I -6- (trif I uo rom et hy I) i m idazo [4,5- b] py rid i ne, or M. UN.22b 2- [3 -ethyl sulfonyl -5- (trif I uoro methy I) -2- pyridyl] -3- methyl -6- (trifluoromethyl) i mid azo [4,5- b] pyridine;
M. UN.23a) 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2- ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide, or M. UN.23b) 4-[5-(3,5-di- chloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3- oxo-isoxazol id in -4-yl] -2 -methy I -benzamide;
M. UN.24a) N - [4-ch I oro-3- (eye Io propyl car ba moy I) phenyl] -2- methy I -5- (1,1, 2,2,2- penta - fluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide or M. UN.24b) N-[4-chloro-
3- [(1 -cyanocyclo propyl) carbamoyl] phenyl] -2- methyl -5- (1,1, 2, 2, 2- pentafl uoroethy I) -
4-(trifluoromethyl)pyrazole-3-carboxamide; M.UN.25 acynonapyr; M.UN.26 benzpy- rimoxan; M.UN.27 2-chloro-N-(l-cyanocyclopropyl)-5-[l-[2-methyl-5-(l,l,2,2,2- pentafluoroethyl)-4-(trifluoromethyl) pyrazol-3-yl] pyrazol-4-yl] benzamide; M.UN.28 Oxazosulfyl;
M. UN.29a) [(2S,3 R, 4R,5S,6S) -3,5 -di meth oxy-6- methy I -4- propoxy-tetra hydro pyran -2-yl] N - [4- [1- [4- (trif I uo rom ethoxy) phenyl] -1, 2, 4-triazol -3-yl] phenyl] carbamate;
M. UN.29 b) [(2S, 3 R, 4 R,5S,6S) -3, 4,5-tri meth oxy-6- methy I -tetra hyd ropy ran -2 -y I] N- [4- [1- [4- (trif I uoro meth oxy) phenyl] -1,2, 4-triazol -3-y I] phenyl] carbarn ate; M. UN.29c) [(2S,3 R,4 R,5S,6S) -3,5 -d im ethoxy-6- methy I -4- propoxy-tetra hyd ropy ran -2 -y I] N - [4- [1 - [4- (1,1, 2, 2, 2- pentafluoroethoxy) phenyl] -1,2, 4-triazol -3-y I] phenyl] car ba mate;
M.UN.29d) [(2S,3 R, 4 R,5S,6S) -3, 4,5-tri meth oxy-6- methy I -tetra hyd ropy ran -2 -y I] N- [4- [1- [4- (1,1, 2,2,2 -pentafluoroethoxy) phenyl] -1,2, 4-triazol -3-y I] phenyl] car ba mate; M.UN.29.e) (2Z) -3- (2- isop ropy I phenyl) -2 -[(E)- [4- [1- [4- (trif I uo rom ethoxy) phenyl] - l,2,4-triazol-3-yl]phenyl]methylenehydrazono]thiazolidin-4-one or M.UN.29f) (2Z)- 3- (2-isopropyl phenyl) -2- [(E)- [4- [1- [4- (1,1,2,2,2- pentafluoroethoxy) phenyl] -1,2, 4- triazol-3-yl] phenyl] methylenehydrazono]thiazolidin-4-one.
N) Herbicides herbicides from the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N- phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, or ureas.
The present invention furthermore relates to mixtures and compositions comprising at least one further active substance useful for plant protection, e. g. selected from the groups A) to N) (component 2), in particular one further herbicide selected from the group N).
By applying components (i) and (ii) of the mixture of the invention together with at least one active substance from groups A) to N) a synergistic plant health effect can be obtained, i.e. more than simple addition of the individual effects is obtained (synergistic mixtures).
This can be obtained by applying components (i) and (ii) of the mixture and at least one further active substance simultaneously, either jointly (e. g. as tank-mix) or separately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention.
When applying components (i) and (ii) of the mixture and a pesticide I sequentially the time between both applications may vary e. g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1.5 hours to 5 days, even more preferred from 2 hours to 1 day. In case of a mixture comprising a pesticide II selected from group L), it is preferred that the pesticide I is applied as last treatment.
According to the invention, the solid material (dry matter) of the biopesticides (with the exception of oils such as Neem oil, Tagetes oil, etc.) are considered as active components (e. g. to be obtained after drying or evaporation of the extraction medium or the suspension medium in case of liquid formulations of the microbial pesticides).
In accordance with the present invention, the weight ratios and percentages used herein for a biological extract such as Quillay extract are based on the total weight of the dry content (solid material) of the respective extract(s).
The total weight ratios of compositions comprising at least one microbial pesticide in the form of viable microbial cells including dormant forms, can be determined using the amount of CFU of the respective microorganism to calculate the total weight of the respective active component with the following equation that 1 x 1010 CFU equals one gram of total weight of the respective active component. Colony forming unit is measure of viable microbial cells, in particular fungal and bacterial cells. In addition, here “CFU” may also be understood as the number of (juvenile) individual nematodes in case of (entomopathogenic) nematode biopesticides, such as Steinernema feltiae.
In the binary mixtures and compositions according to the invention the weight ratio of the components generally depends from the properties of the active components used, usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1, even more preferably in the range of from 1:4 to 4:1 and in particular in the range of from 1:2 to 2:1.
According to further embodiments, the weight ratio of the components usually is in the range of from 1000:1 to 1:1, often in the range of from 100: 1 to 1:1, regularly in the range of from 50:1 to 1:1, preferably in the range of from 20:1 to 1:1, more preferably in the range of from 10:1 to 1:1, even more preferably in the range of from 4:1 to 1:1 and in particular in the range of from 2:1 to 1:1.
According to further embodiments, the weight ratio of the components usually is in the range of from 1:1 to 1:1000, often in the range of from 1:1 to 1:100, regularly in the range of from 1:1 to 1:50, preferably in the range of from 1:1 to 1:20, more preferably in the range of from 1:1 to 1:10, even more preferably in the range of from 1:1 to 1:4 and in particular in the range of from 1:1 to 1:2.
According to further embodiments, the weight ratio of the components generally depends from the properties of the active components used, usually it is in the range of from 1:10,000 to 10,000:1, regularly in the range of from 1:100 to 10,000:1, preferably in the range of from 1:100 to 5,000:1, more preferably in the range of from 1:1 to 1,000:1, even more preferably in the range of from 1:1 to 500:1 and in particular in the range of from 10:1 to 300:1.
According to further embodiments, the weight ratio of the components usually is in the range of from 20,000:1 to 1:10, often in the range of from 10,000:1 to 1:1, regularly in the range of from 5,000:1 to 5:1, preferably in the range of from 5,000:1 to 10:1, more preferably in the range of from 2,000:1 to 30:1, even more preferably in the range of from 2,000:1 to 100:1 and in particular in the range of from 1,000:1 to 100:1.
According to further embodiments, the weight ratios of the components usually is in the range of from 1:20,000 to 10:1, often in the range of from 1:10,000 to 1:1, regularly in the range of from 1:5,000 to 1:5, preferably in the range of from 1:5,000 to 1:10, more preferably in the range of from 1:2,000 to 1:30, even more preferably in the range of from 1:2,000 to 1:100 and in particular in the range of from 1:1,000 to 1:100.
These ratios are also suitable for inventive mixtures applied by seed treatment.
The active substances listed under groups A) to K), their preparation and their activity e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by IUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO 02/22583; WO 02/40431;
WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388;
WO 03/66609; WO 03/74491; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689;
WO 05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 10/139271, WO 11/028657, WO 12/168188, WO 07/006670, WO 11/77514; WO 13/047749, WO 10/069882, WO 13/047441, WO 03/16303, WO 09/90181, WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/24010, WO 13/047441, WO 13/162072, WO 13/092224,
WO 11/135833, ON 1907024, ON 1456054, ON 103387541, ON 1309897, WO 12/84812, ON 1907024, WO 09094442, WO 14/60177, WO 13/116251, WO 08/013622, WO 15/65922, WO 94/01546, EP 2865265, WO 07/129454, WO 12/165511, WO 11/081174, WO 13/47441). Some compounds are identified by their CAS Registry Number which is separated by hyphens into three parts, the first consisting from two up to seven digits, the second consisting of two digits, and the third consisting of a single digit.
The commercially available compounds of the group M listed above may be found in The Pesticide Manual, 17th Edition, C. MacBean, British Crop Protection Council (2015) among other publications. The online Pesticide Manual is updated regularly and is accessible through http://bcpcdata.com/ pesticide-manual.html.
Another online data base for pesticides providing the ISO common names is http://www.alanwood.net/ pesticides.
The M.4 cycloxaprid is known from W02010/069266 and WO2011/069456. M.4A.1 is known from CN 103814937; CN105367557, CN 105481839. M.4A.2, guadipyr, is known from WO 2013/003977, and M.4A.3 (approved as paichongding in China) is known from WO 2007/101369. M.22B.1 is described in CN10171577 and M.22B.2 in CN102126994. Spiropid- ion M.23.1 is known from WO 2014/191271. M.28.1 and M.28.2 are known from W02007/101540. M.28.3 is described in W02005/077934. M.28.4 is described in W02007/043677. M.28.5a) to M.28.5d) and M.28.5h) are described in WO 2007/006670, W02013/024009 and WO 2013/024010, M.28.5i) is described in WO2011/085575, M.28.5j) in WO2008/134969, M.28.5k) in US2011/046186 and M.28.51) in W02012/034403. M.28.6 can be found in WO2012/034472. M.UN.3 is known from W02006/089633 and M.UN.4 from W02008/067911. M.UN.5 is described in W02006/043635, and biological control agents on the basis of bacillus firmus are described in W02009/124707. Flupyrimin is described in WO2012/029672. M.UN.8 is known from WO2013/055584. M.UN.9.a) is described in W02013/050317. M.UN.9.b) is described in WO2014/126208. M.UN.10 is known from W02010/060379. Broflanilide and M.UN.ll.b) to M.UN.ll.h) are described in W02010/018714, and M.UN.lli) to M.UN.ll.p) in WO 2010/127926. M. UN.12. a) to M.UN.12.c) are known from W02010/006713, M.UN.12.d) and M.UN.12.e) are known from W02012/000896. M. UN.14a) and M. UN.14b) are known from W02007/101369. M. UN.16. a) to M.UN.16h) are described in W02010/034737, W02012/084670, and WO2012/143317, resp., and M.UN.16i) and M.UN.16j) are described in WO2015/055497. M. UN.17a) to M.UN.17J) are described in W02015/038503. M.UN.18 Tycloprazoflor is described in US2014/0213448. M.UN.19 is described in W02014/036056. M.UN.20 is known from W02014/090918. M.UN.21 is known from EP2910126. M. UN.22a and M. UN.22b are known from W02015/059039 and W02015/190316. M. UN.23a and M. UN.23b are known from W02013/050302. M. UN.24a) and M. UN.24b) are known from WO2012/126766. Acynonapyr M.UN.25 is known from WO 2011/105506. Benzpyrimoxan M.UN.26 is known from W02016/104516. M.UN.27 is known from WO2016/174049. M.UN.28 Oxazosulfyl is known from WO2017/104592. M. UN.29a) to M.UN.29f) are known from W02009/102736 or W02013116053.
The biopesticides from group LI) and/or L2) may also have insecticidal, acaricidal, mollus- cidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L3) and/or L4) may also have fungicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L5) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
Many of these biopesticides have been deposited under deposition numbers mentioned herein (the prefices such as ATCC or DSM refer to the acronym of the respective culture collection, for details see e. g. here: http://www. wfcc.info/ccinfo/collection/by acronym/), are referred to in literature, registered and/or are commercially available: mixtures of Aure- obasidium pullulans bS \ 14940 and DSM 14941 isolated in 1989 in Konstanz, Germany (e. g. blastospores in BlossomProtect® from bio-ferm GmbH, Austria), Azospirillum brasilense Sp245 originally isolated in wheat reagion of South Brazil (Passo Fundo) at least prior to 1980 (BR 11005; e. g. GELFIX® Gramineas from BASF Agricultural Specialties Ltd., Brazil), A. brasilense strains Ab-V5 and Ab-V6 (e. g. in AzoMax from Novozymes BioAg Produtos papra Agriculture Ltda., Quattro Barras, Brazil or Simbiose-Maiz® from Simbiose-Agro, Brazil; Plant Soil 331, 413-425, 2010), Bacillus amyloliquefaciens strain AP-188 (NRRL B- 50615 and B-50331; US 8,445,255); B. amyloliquefaciens spp. plantarum V l 47 isolated from air in Kikugawa-shi, Japan (US 20130236522 Al; FERM BP-8234; e. g. Double Nickel™ 55 WDG from Certis LLC, USA), B. amyloliquefaciens spp. plantarum FZB24 isolated from soil in Brandenburg, Germany (also called SB3615; DSM 96-2; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. Taegro® from Novozyme Biologicals, Inc., USA), B. amyloliquefaciens ssp. plantarum FZB42 isolated from soil in Brandenburg, Germany (DSM 23117; J. Plant Dis. Prot. 105, 181-197, 1998; e. g. RhizoVital® 42 from AbiTEP GmbH, Germany), B. amyloliquefaciens ssp. plantarum MBI600 isolated from faba bean in Sutton Bonington, Nottinghamshire, U.K. at least before 1988 (also called 1430; NRRL B-50595; US 2012/0149571 Al; e. g. Integral® from BASF Corp., USA), B. amyloliquefaciens spp. plantarum QST-713 isolated from peach orchard in 1995 in California, U.S.A. (NRRL B-21661; e. g. Serenade® MAX from Bayer Crop Science LP, USA), B. amyloliquefaciens spp. plantarum TJ1000 isolated in 1992 in South Dakoda, U.S.A, (also called 1BE; ATCC BAA-390; CA 2471555 Al; e. g. Quick- Roots™ from TJ Technologies, Watertown, SD, USA), B. firmusC C 1-1582, a variant of parental strain EIP-N1 (CNCM 1-1556) isolated from soil of central plain area of Israel (WO 2009/126473, US 6,406,690; e. g. Votivo® from Bayer CropScience LP, USA), B. pumi/us GHA 180 isolated from apple tree rhizosphere in Mexico (IDAC 260707-01; e. g. PRO-MIX® BX from Premier Horticulture, Quebec, Canada), B. pumi/us INR-7 otherwise referred to as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by Erwinia tracheiphi/a (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumi/us KFP9F isolated from the rhizosphere of grasses in South Africa at least before 2008 (NRRL B-50754; WO 2014/029697; e. g. BAC-UP or FUSION-P from BASF Agricultural Specialities (Pty) Ltd., South Africa), B. pumi/us QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL B-30087; e. g. Sonata® or Ballad® Plus from Bayer Crop Science LP, USA), B. simplex ABU 288 (NRRL B-50304; US 8,445,255), B. subti/is FB17 also called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC PTA- 11857; System. Appl. Microbiol. 27, 372-379, 2004; US 2010/0260735; WO 2011/109395); B. thuringiensis ssp. aizawai ABTS-1857 isolated from soil taken from a lawn in Ephraim, Wisconsin, U.S.A., in 1987 (also called ABG-6346; ATCC SD-1372; e. g. XenTari® from BioFa AG, Munsingen, Germany), B. t. ssp. kurstaki ABTS -351 identical to HD-1 isolated in 1967 from diseased Pink Bollworm black larvae in Brownsville, Texas, U.S.A. (ATCC SD-1275; e. g. Dipel® DF from Valent BioSciences, IL, USA), B. t. ssp. kurstakiS A isolated from E. sac- charina larval cadavers (NRRL B-50753; e. g. Beta Pro® from BASF Agricultural Specialities (Pty) Ltd., South Africa), B. t. ssp. tenebrionis NB-176-1, a mutant of strain NB-125, a wild type strain isolated in 1982 from a dead pupa of the beetle Tenebrio molitor (DSM 5480; EP 585 215 Bl; e. g. Novodor® from Valent BioSciences, Switzerland), Beauveria bassiana GHA (ATCC 74250; e. g. BotaniGard® 22WGP from Laverlam Int. Corp., USA), B. bassiana JW-1 (ATCC 74040; e. g. Naturalis® from CBC (Europe) S.r.L, Italy), B. bassiana PPRI 5339 isolated from the larva of the tortoise beetle Conchy/octenia punctata (NRRL 50757; e. g. BroadBand® from BASF Agricultural Specialities (Pty) Ltd., South Africa), Bradyrhizobium e/kanii s ams SEMIA 5019 (also called 29W) isolated in Rio de Janeiro, Brazil and SEMIA 587 isolated in 1967 in the State of Rio Grande do Sul, from an area previously inoculated with a North American isolate, and used in commercial inoculants since 1968 (AppL Environ. Microbiol. 73(8), 2635, 2007; e. g. GELFIX 5 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum 532c isolated from Wisconsin field in U.S.A. (Nitragin 61A152; Can. J. Plant. Sci. 70, 661-666, 1990; e. g. in Rhizoflo®, Histick®, Hicoat® Super from BASF Agricultural Specialties Ltd., Canada), B. japonicum E-109 variant of strain USDA 138 (INTA E109, SEMIA 5085; Eur. J. Soil Biol. 45, 28-35, 2009; Biol. Fertil. Soils 47, 81-89, 2011); B. japonicum strains deposited at SEMIA known from AppL Environ. Microbiol. 73(8), 2635, 2007: SEMIA 5079 isolated from soil in Cerrados region, Brazil by Embrapa-Cerrados used in commercial inoculants since 1992 (CPAC 15; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum SEMIA 5080 obtained under lab condtions by Embrapa-Cerrados in Brazil and used in commercial inoculants since 1992, being a natural variant of SEMIA 586 (CB1809) originally isolated in U.S.A. (CPAC 7; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil); Burkhoideria sp. A396 isolated from soil in Nikko, Japan, in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio Innovations, Inc., USA), Coniothyrium minitans CON/M/91-08 isolated from oilseed rape (WO 1996/021358; DSM 9660; e. g. Contans® WG, Intercept® WG from Bayer CropScience AG, Germany), harpin (alpha-beta) protein (Science 257, 85-88, 1992; e. g. Messenger™ or HARP-N-Tek from Plant Health Care pic, U.K.), Heiicoverpa armigera nucleopolyhedrovirus (HearNPV) (J. Invertebrate Pathol. 107, 112-126, 2011; e. g. Helicovex® from Adermatt Biocontrol, Switzerland; Diplomata® from Koppert, Brazil; Vivus® Max from AgBiTech Pty Ltd., Queensland, Australia), Heiicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (e. g. Gemstar® from Certis LLC, USA), Heiicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e. g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia), Heterorhabditis bacteriophora (e. g. Nemasys® G from BASF Agricultural Specialities Limited, UK), isaria fumosorosea Apopka-97 isolated from mealy bug on gynura in Apopka, Florida, U.S.A. (ATCC 20874; Biocontrol Science TechnoL 22(7), 747-761, 2012; e. g. PFR-97™ or PreFeRal® from Certis LLC, USA), Metarhizium anisopiiae a . anisopiiae F52 also called 275 or V275 isolated from codling moth in Austria (DSM 3884, ATCC 90448; e. g. Met52® Novozymes Biologicals BioAg Group, Canada), Metschnikowia fructicoia 277 isolated from grapes in the central part of Israel (US 6,994,849; NRRL Y-30752; e. g. formerly Shemer® from Agrogreen, Israel), Pae- ciiomyces Hacinus 25\. isolated from infected nematode eggs in the Philippines (AGAL 89/030550; WC1991/02051; Crop Protection 27, 352-361, 2008; e. g. BioAct®from Bayer CropScience AG, Germany and MeloCon® from Certis, USA), Paenibaciiius a/ize/NAS6G6 isolated from the rhizosphere of grasses in South Africa at least before 2008
(WO 2014/029697; NRRL B-50755; e.g. BAC-UP from BASF Agricultural Specialities (Pty) Ltd., South Africa), Paenibaciiius strains isolated from soil samples from a variety of European locations including Germany: P. epiphyticus Lul7015 (WO 2016/020371; DSM 26971), P. poiymyxa ssp. plantarum Lu 16774 (WO 2016/020371; DSM 26969), P. p. ssp. plantarum strain Lul7007 (WO 2016/020371; DSM 26970); Pasteuria nishizawae Pnl isolated from a soybean field in the mid-2000s in Illinois, U.S.A. (ATCC SD-5833; Federal Register 76(22), 5808, February 2, 2011; e.g. Clariva™ PN from Syngenta Crop Protection, LLC, USA), PeniciHium bi/aiae (also called P. bilaii) strains ATCC 18309 (= ATCC 74319), ATCC 20851 and/or ATCC 22348 (= ATCC 74318) originally isolated from soil in Alberta, Canada (Fertilizer Res. 39, 97-103, 1994; Can. J. Plant Sci. 78(1), 91-102, 1998; US 5,026,417, WO 1995/017806; e. g. Jump Start®, Provide® from Novozymes Biologicals BioAg Group, Canada), Reynoutria sachalinensis extract (EP 0307510 Bl; e. g. Regalia® SC from Marrone BioInnovations, Davis, CA, USA or Milsana® from BioFa AG, Germany), Steinernema car- pocapsae (e. g. Millenium® from BASF Agricultural Specialities Limited, UK), S. feitiae (e. g. Nemashield® from BioWorks, Inc., USA; Nemasys® from BASF Agricultural Specialities Limited, UK), Streptomyces microf/avus RM B-50550 (WO 2014/124369; Bayer CropScience, Germany), Trichoderma aspereiioides JM41R isolated in South Africa (NRRL 50759; also referred to as T. fertile e. g. Trichoplus® from BASF Agricultural Specialities (Pty) Ltd., South Africa), T. harzianum f -22 also called KRL-AG2 (ATCC 20847; BioControl 57, 687-696, 2012; e. g. Plantshield® from BioWorks Inc., USA or SabrEx™ from Advanced Biological Marketing Inc., Van Wert, OH, USA).
According to one embodiment of the inventive mixtures and compositions, the at least one pesticide II is selected from the groups LI) to L6):
LI) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Aureobasidium pullulans bS \ 14940 and DSM 14941 (Ll.l), Bacillus amy- loliquefaciens AP-188 (L.1.2), B. amyloliquefaciens ssp. plantarum D747 (L.1.3), B. amyloliquefaciens ssp. plantarum FZB24 (L.1.4), B. amyloliquefaciens ssp. plantarum FZB42 (L.1.5), B. amyloliquefaciens ssp. plantarum MBI600 (L.1.6), B. amyloliquefaciens ssp. plantarum QST-713 (L.1.7), B. amyloliquefaciens ssp. plantarum TJ1000 (L.1.8), B. pumiius GB3f (L.1.9), B. pumiius GS\I 180 (L.1.10), B. pumiius INR-7 (L.1.11), B. pumiius QST 2808 (L.1.13), B. simplex ABU 288 (L.1.14), B. subtiiis FB17 (L.1.15), Coniothyrium minitans CON/M/91-08 (L.1.16), Metschnikowia fructicoia NRRL Y-30752 (L.1.17), PeniciHium biiaiae ATCC 22348 (L.1.19), P. biiaiae ATCC 20851 (L.1.20), Peni- ciHium biiaiae ATCC 18309 (L.1.21), Streptomyces microfiavus NRRL B-50550 (L.1.22), T. harzianum f -22 (L.1.24);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: harpin protein (L.2.1), Reynoutria sachalinensis extract (L.2.2);
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Bacillus firmus 1-1582 (L.3.1); B. thuringiensis ssp. aizawai ABTS- 1857 (L.3.2), B. t. ssp. kurstaki ABTS -351 (L.3.3), B. t. ssp. tenebrionis NB- 176-1 (L.3.5), Beauveria bassiana GHA (L.3.6), B. bassiana JW-1 (L.3.7), Burkhoideria sp. A396 (L.3.9), Heiicov- erpa armigera nucleopolyhedrovirus (HearNPV) (L.3.10), Heiicoverpa zea nucleopolyhe- drovirus (HzNPV) ABA-NPV-U (L.3.11), Heiicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (L.3.12), Heterohabditis bacteriophora (L.3.13), Isaria fumosorosea Apopka-97 (L.3.14), Metarhizium anisopiiae iar. anisopiiae F52 (L.3.15), Paeciiomyces Pnl (L.3.17), Steinernema carpocapsae
Figure imgf000051_0001
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: cis-jasmone (L.4.1), methyl jasmonate (L.4.2), Quillay extract (L.4.3);
L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. In a further aspect the present invention relates to an agrochemical mixture comprising at least one fertilizer; and the mixture of the invention; or at least one fertilizer and the composition as mentioned above.
In the terms of the present invention "agrochemical mixture" means a combination of at least two components, in the present case the mixture of compositions of the invention and the fertilizer. The term is, however, not restricted to a physical mixture comprising the at least two components, but refers to any preparation form of at least one component and at least one further component, the use of which many be time- and/or locus-related.
The agrochemical mixtures may, for example, be formulated separately but applied in a temporal relationship, i.e. simultaneously or subsequently, the subsequent application having a time interval which allows a combined action of the compounds.
Furthermore, the individual components of the agrochemical mixtures according to the invention such as parts of a kit or parts of the binary mixture may be mixed by the user himself in a suitable mixing device. In specific embodiments further auxiliaries may be added, if appropriate.
The term "fertilizers" is to be understood as chemical compounds applied to promote plant and fruit growth. Fertilizers are typically applied either through the soil (for uptake by plant roots), through soil substituents (also for uptake by plant roots), or by foliar feeding (for uptake through leaves). The term also includes mixtures of one or more different types of fertilizers as mentioned below.
The term "fertilizers" can be subdivided into several categories including: a) organic fertilizers (composed of decayed plant/animal matter), b) inorganic fertilizers (composed of chemicals and minerals) and c) urea-containing fertilizers.
Organic fertilizers include manure, e.g. liquid manure, semi-liquid manure, biogas manure, stable manure or straw manure, slurry, worm castings, peat, seaweed, compost, sewage, and guano. Green manure crops are also regularly grown to add nutrients (especially nitrogen) to the soil. Manufactured organic fertilizers include compost, blood meal, bone meal and seaweed extracts. Further examples are enzyme digested proteins, fish meal, and feather meal. The decomposing crop residue from prior years is another source of fertility. In addition, naturally occurring minerals such as mine rock phosphate, sulfate of potash and limestone are also considered inorganic fertilizers.
Inorganic fertilizers are usually manufactured through chemical processes (such as the Haber process), also using naturally occurring deposits, while chemically altering them (e.g. concentrated triple superphosphate). Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mine rock phosphate, limestone, and raw potash fertilizers.
The inorganic fertilizer may, in a specific embodiment, be a NPK fertilizer. "NPK fertilizers" are inorganic fertilizers formulated in appropriate concentrations and combinations comprising the three main nutrients nitrogen (N), phosphorus (P) and potassium (K) as well as typically S, Mg, Ca, and trace elements.
Urea-containing fertilizer may, in specific embodiments, be urea, formaldehyde urea, anhydrous ammonium, urea ammonium nitrate (UAN) solution, urea sulfur, urea based NPK- fertilizers, or urea ammonium sulfate. Also envisaged is the use of urea as fertilizer. In case urea-containing fertilizers or urea are used or provided, it is particularly preferred that urease inhibitors as defined herein above may be added or additionally be present, or be used at the same time or in connection with the urea-containing fertilizers. Fertilizers may be provided in any suitable form, e.g. as solid coated or uncoated granules, in liquid or semi-liquid form, as sprayable fertilizer, or via fertigation etc.
Coated fertilizers may be provided with a wide range of materials. Coatings may, for example, be applied to granular or prilled nitrogen (N) fertilizer or to multi-nutrient fertilizers. Typically, urea is used as base material for most coated fertilizers. Alternatively, ammonium or NPK fertilizers are used as base material for coated fertilizers. The present invention, however, also envisages the use of other base materials for coated fertilizers, any one of the fertilizer materials defined herein. In certain embodiments, elemental sulfur may be used as fertilizer coating. The coating may be performed by spraying molten S over urea granules, followed by an application of sealant wax to close fissures in the coating. In a further embodiment, the S layer may be covered with a layer of organic polymers, preferably a thin layer of organic polymers.
Further envisaged coated fertilizers may be provided by reacting resin-based polymers on the surface of the fertilizer granule. A further example of providing coated fertilizers includes the use of low permeability polyethylene polymers in combination with high permeability coatings.
In specific embodiments the composition and/or thickness of the fertilizer coating may be adjusted to control, for example, the nutrient release rate for specific applications. The duration of nutrient release from specific fertilizers may vary, e.g. from several weeks to many months. The presence of nitrification inhibitors in a mixture with coated fertilizers may accordingly be adapted. It is, in particular, envisaged that the nutrient release involves or is accompanied by the release of the mixture of nitrification inhibitors according to the present invention.
Coated fertilizers may be provided as controlled release fertilizers (CRFs). In specific embodiments these controlled release fertilizers are fully coated urea or N-P-K fertilizers, which are homogeneous and which typically show a pre-defined longevity of release. In further embodiments, the CRFs may be provided as blended controlled release fertilizer products which may contain coated, uncoated and/or slow release components. In certain embodiments, these coated fertilizers may additionally comprise micronutrients. In specific embodiments these fertilizers may show a pre-defined longevity, e.g. in case of N-P-K fertilizers.
Additionally, envisaged examples of CRFs include patterned release fertilizers. These fertilizers typically show a pre-defined release patterns (e.g. hi/standard/lo) and a pre-defined longevity. In exemplary embodiments fully coated N-P-K, Mg and micronutrients may be delivered in a patterned release manner.
Also envisaged are double coating approaches or coated fertilizers based on a programmed release.
In further embodiments the fertilizer mixture may be provided as, or may comprise or contain a slow release fertilizer. The fertilizer may, for example, be released over any suitable period of time, e.g. over a period of 1 to 5 months, preferably up to 3 months. Typical examples of ingredients of slow release fertilizers are IBDU (isobutylidenediurea), e.g. containing about 31-32 % nitrogen, of which 90% is water insoluble; or UF, i.e. an urea-formaldehyde product which contains about 38 % nitrogen of which about 70 % may be provided as water insoluble nitrogen; or CDU (crotonylidene diurea) containing about 32 % nitrogen; or MU (methylene urea) containing about 38 to 40% nitrogen, of which 25-60 % is typically cold water insoluble nitrogen; or MDU (methylene diurea) containing about 40% nitrogen, of which less than 25 % is cold water insoluble nitrogen; or MO (methylol urea) containing about 30% nitrogen, which may typically be used in solutions; or DMTU (diimethylene triurea) containing about 40% nitrogen, of which less than 25% is cold water insoluble nitrogen; or TMTU (tri methylene tetraurea), which may be provided as component of UF products; or TMPU (tri methylene pentaurea), which may also be provided as component of UF products; or UT (urea triazone solution) which typically contains about 28 % nitrogen. The fertilizer mixture may also be long-term nitrogen-bearing fertiliser containing a mixture of acetylene diurea and at least one other organic nitrogen-bearing fertiliser selected from methylene urea, isobutylidene diurea, crotonylidene diurea, substituted triazones, triuret or mixtures thereof.
Any of the above mentioned fertilizers or fertilizer forms may suitably be combined. For instance, slow release fertilizers may be provided as coated fertilizers. They may also be combined with other fertilizers or fertilizer types. The same applies to the presence of the mixture of nitrification inhibitors according to the present invention, which may be adapted to the form and chemical nature of the fertilizer and accordingly be provided such that its release accompanies the release of the fertilizer, e.g. is released at the same time or with the same frequency. The present invention further envisages fertilizer or fertilizer forms as defined herein above in combination with nitrification inhibitors as defined herein above and further in combination with urease inhibitors as defined herein above. Such combinations may be provided as coated or uncoated forms and/or as slow or fast release forms. Preferred are combinations with slow release fertilizers including a coating. In further embodiments, also different release schemes are envisaged, e.g. a slower or a faster release.
The term "fertigation" as used herein refers to the application of fertilizers, optionally soil amendments, and optionally other water-soluble products together with water through an irrigation system to a plant or to the locus where a plant is growing or is intended to grow, or to a soil substituent as defined herein below. For example, liquid fertilizers or dissolved fertilizers may be provided via fertigation directly to a plant or a locus where a plant is growing or is intended to grow. Likewise, nitrification inhibitors according to the present invention, or in combination with additional nitrification inhibitors, may be provided via fertigation to plants or to a locus where a plant is growing or is intended to grow. Fertilizers and nitrification inhibitors according to the present invention, or in combination with additional nitrification inhibitors, may be provided together, e.g. dissolved in the same charge or load of material (typically water) to be irrigated. In further embodiments, fertilizers and nitrification inhibitors may be provided at different points in time. For example, the fertilizer may be ferti- gated first, followed by the nitrification inhibitor, or preferably, the nitrification inhibitor may be fertigated first, followed by the fertilizer. The time intervals for these activities follow the herein above outlined time intervals for the application of fertilizers and nitrification inhibitors. Also envisaged is a repeated fertigation of fertilizers and nitrification inhibitors according to the present invention, either together or intermittently, e.g. every 2 hours, 6 hours, 12 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days or more.
In particularly preferred embodiments, the fertilizer is an ammonium-containing fertilizer.
The agrochemical mixture according to the present invention may comprise one fertilizer as defined herein above and the mixture or composition of the invention defined herein above. In further embodiments, the agrochemical mixture according to the present invention may comprise at least one or more than one fertilizer as defined herein above, e.g. 2, 3, 4, 5, 6, 6, 7, 8, 9, 10 or more different fertilizers (including inorganic, organic and urea-containing fertilizers) and the mixture of composition as defined herein above.
The term "at least one" is to be understood as 1, 2, 3 or more of the respective compound selected from the group consisting of fertilizers as defined herein above.
In addition to at least one fertilizer and at least one nitrification inhibitor as defined herein above, an agrochemical mixture may comprise further ingredients, compounds, active compounds or compositions or the like. For example, the agrochemical mixture may additionally comprise or composed with or on the basis of a carrier, e.g. an agrochemical carrier, preferably as defined herein. In further embodiments, the agrochemical mixture may further comprise at least one pesticidal compound. For example, the agrochemical mixture may additionally comprise at least one herbicidal compound and/or at least one fungicidal compound and/or at least one insecticidal compound.
In further embodiments, the agrochemical mixture may, in addition to the above indicated ingredients, further comprise alternative or additional nitrification inhibitors such as linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, MHPP, Karanjin, brachialacton, p-benzoquinone sorgoleone, nitrapyrin, dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate (DMPP), 4-amino-l,2,4-triazole hydrochloride (ATC), l-amido-2- thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 5-ethoxy-3-trichloromethyl- 1 ,2,4-thiodiazole (terrazole), ammoniumthiosulfate (ATU), 3-methylpyrazol (3-MP), 3,5- dimethylpyrazole (DMP), 1,2,4-triazol and thiourea (TU) and/or sulfathiazole (ST), N-(1H- pyrazolyl-methyl)acetamides such as N-((3(5)-methyl-lH-pyrazole-l-yl)methyl)acetamide, and/or N-(lH-pyrazolyl-methyl)formamides such as N-((3(5)-methyl-lH-pyrazole-l- yl)methyl formamide, N-(4-chloro-3(5)-methyl-pyrazole-l-ylmethyl)-formamide, or N- (3(5),4-dimethyl-pyrazole-l-ylmethyl)-formamide.
Furthermore, the invention relates to a method for reducing nitrification, comprising treating a plant growing on soil and/or the locus where the plant is growing or is intended to grow with the mixture or composition as defined herein above.
The term "plant" is to be understood as a plant of economic importance and/or men- grown plant. In certain embodiments, the term may also be understood as plants which have no or no significant economic importance. The plant is preferably selected from agricultural, silvicultural and horticultural (including ornamental) plants. The term also relates to genetically modified plants.
The term "plant" as used herein further includes all parts of a plant such as germinating seeds, emerging seedlings, plant propagules, herbaceous vegetation as well as established woody plants including all belowground portions (such as the roots) and aboveground portions.
Within the context of the method for reducing nitrification it is assumed that the plant is growing on soil. In specific embodiments, the plant may also grow differently, e.g. in synthetic laboratory environments or on soil substituents, or be supplemented with nutrients, water etc. by artificial or technical means. In such scenarios, the invention envisages a treatment of the zone or area where the nutrients, water etc. are provided to the plant. Also envisaged is that the plant grows in green houses or similar indoor facilities. The term "locus" is to be understood as any type of environment, soil, soil substituent, area or material where the plant is growing or intended to grow. Preferably, the term relates to soil or soil substituent on which a plant is growing.
In one embodiment, the plant to be treated according to the method of the invention is an agricultural plant. "Agricultural plants" are plants of which a part (e.g. seeds) or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibers (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds. Preferred agricultural plants are for example cereals, e.g. wheat, rye, barley, triticale, oats, corn, sorghum or rice, beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, oil-seed rape, canola, linseed, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, canola, sugar cane or oil palm; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants.
In a further embodiment, the plant to be treated according to the method of the invention is a horticultural plant. The term "horticultural plants" are to be understood as plants which are commonly used in horticulture, e.g. the cultivation of ornamentals, vegetables and/or fruits. Examples for ornamentals are turf, geranium, pelargonia, petunia, begonia and fuchsia. Examples for vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas and lettuce and more preferably from tomatoes, onions, peas and lettuce. Examples for fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots and blueberries.
In a further embodiment, the plant to be treated according to the method of the invention is an ornamental plant. "Ornamental plants" are plants which are commonly used in gardening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia.
In another embodiment of the present invention, the plant to be treated according to the method of the invention is a silvicultural plant. The term "silvicultural plant" is to be understood as trees, more specifically trees used in reforestation or industrial plantations. Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening purposes. Examples for silvicultural plants are conifers, like pines, in particular Pinus spec., fir and spruce, eucalyptus, tropical trees like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec., poplar (cottonwood), in particular Populus spec., beech, in particular Fagus spec., birch, oil palm, and oak.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, grains, roots, fruits, tubers, bulbs, rhizomes, cuttings, spores, offshoots, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil, meristem tissues, single and multiple plant cells and any other plant tissue from which a complete plant can be obtained.
The term "genetically modified plants" is to be understood as plants, which genetic material has been modified by the use of recombinant DNA techniques in a way that under natural circumstances it cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as preny- lated, acetylated or farnesylated moieties or PEG moieties.
Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4-D; bleacher herbicides such as hydroxylphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvylshikimate-3- phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005, 269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1185; and references quoted therein. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.), Cultivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate-tolerant, Bayer CropScience, Germany).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as <5 -endotoxins, e. g. CrylA(b), CrylA(c), CrylF, Cryl F(a2) , CryllA(b), CrylllA, Cryl IIB(bl) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VI Pl, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenorhabdus s pp. ; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3- hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (heli- cokinin receptors); stilbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g.
WO 02/015701). Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the CrylAb toxin), YieldGard® Plus (corn cultivars producing CrylAb and Cry3Bbl toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Abl, Cry35Abl and the enzyme phosphinothricin-N-acetyltransferase [PAT]); Nu- COTN® 33B (cotton cultivars producing the CrylAc toxin), Bollgard® I (cotton cultivars producing the CrylAc toxin), Bollgard® II (cotton cultivars producing CrylAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Btll (e. g. Agrisure® CB) and Btl76 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bbl toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the CrylF toxin and PAT enzyme).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called “pathogenesis-related proteins” (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytoph- thora infestans derived from the Mexican wild potato So/anum buibocastanum) or T4- lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amyivora) . The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada).
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany).
The term "soil substituent" as used herein refers to a substrate which is able to allow the growth of a plant and does not comprise usual soil ingredients. This substrate is typically an inorganic substrate which may have the function of an inert medium. It may, in certain embodiments, also comprise organic elements or portions. Soil substituents may, for example, be used in hydroculture or hydroponic approaches, i.e. wherein plants are grown in soilless medium and/or aquatic based environments. Examples of suitable soil substituents, which may be used in the context of the present invention, are perlite, gravel, biochar, mineral wool, coconut husk, phyllosilicates, i.e. sheet silicate minerals, typically formed by parallel sheets of silicate tetrahedra with Si2O5 or a 2:5 ratio, or clay aggregates, in particular expanded clay aggregates with a diameter of about 10 to 40 mm. Particularly preferred is the employment of vermiculite, i.e. a phyllosilicate with 2 tetrahedral sheets for every one octahedral sheet present.
The use of soil substituents may, in specific embodiments, be combined with fertigation or irrigation as defined herein.
In specific embodiments, the treatment may be carried out during all suitable growth stages of a plant as defined herein. For example, the treatment may be carried out during the BBCH principle growth stages.
The term "BBCH principal growth stage" refers to the extended BBCH-scale which is a system for a uniform coding of phenologically similar growth stages of all mono- and dicotyledonous plant species in which the entire developmental cycle of the plants is subdivided into clearly recognizable and distinguishable longer-lasting developmental phases. The BBCH-scale uses a decimal code system, which is divided into principal and secondary growth stages. The abbreviation BBCH derives from the Federal Biological Research Centre for Agriculture and Forestry (Germany), the Bundessortenamt (Germany) and the chemical industry.
In one embodiment the invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with the mixture or composition as defined herein above at a growth stage (GS) between GS 00 and GS > BBCH 99 of the pant (e.g. when fertilizing in fall after harvesting apples) and preferably between GS 00 and GS 65 BBCH of the plant. In one embodiment the invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with a mixture or composition as defined herein above at a growth stage (GS) between GS 00 to GS 45, preferably between GS 00 and GS 40 BBCH of the plant.
In a preferred embodiment the invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with a mixture or composition as defined herein above at an early growth stage (GS), in particular a GS 00 to GS 05, or GS 00 to GS 10, or GS 00 to GS 15, or GS 00 to GS 20, or GS 00 to GS 25 or GS 00 to GS 33 BBCH of the plant. In particularly preferred embodiments, the method for reducing nitrification comprises treating a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with a mixture or composition as defined herein above during growth stages including GS 00.
In a further, specific embodiment of the invention, a mixture or composition as defined herein above is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at a growth stage between GS 00 and GS 55 BBCH, or of the plant.
In a further embodiment of the invention, a mixture or composition as defined herein above is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at the growth stage between GS 00 and GS 47 BBCH of the plant.
In one embodiment of the invention, a mixture or composition is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow before and at sowing, before emergence, and until harvest (GS 00 to GS 89 BBCH), or at a growth stage (GS) between GS 00 and GS 65 BBCH of the plant.
In a preferred embodiment the invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing with a mixture or composition as defined herein above, wherein the plant and/or the locus where plant is growing or is intended to grow is additionally provided with at least one fertilizer. The fertilizer may be any suitable fertilizer, preferably a fertilizer as defined herein above. Also envisaged is the application of more than one fertilizer, e.g. 2, 3, 4, 5, 6, 7, 8, 9, 10 fertilizers, or of different fertilizer classes or categories.
In specific embodiments of the invention, the mixture or composition of the invention and at least one fertilizer is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at a growth stage between GS OOand GS 33 BBCH of the plant.
In specific embodiments of the invention, the mixture or composition of the invention and at least one fertilizer is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at a growth stage between GS 00 and GS 55 BBCH of the plant.
In further specific embodiments of the invention, the mixture or composition of the invention and at least one fertilizer is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at sowing, before emergence, or at a growth stage (GS) between GS 00 and GS > BBCH 99 of the pant (e.g. when fertilizing in fall after harvesting apples) and preferably between GS 00 and 65 BBCH of the plant.
According to a preferred embodiment of the present invention the application of the mixture or composition of the invention and of said fertilizer as defined herein above is carried out simultaneously or with a time lag. The term "time lag" as used herein means that either the mixture or composition of the invention is applied before the fertilizer to the plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow; or the fertilizer is applied before the mixture or composition of the invention to the plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow. Such time lag may be any suitable period of time which still allows to provide a nitrification inhibiting effect in the context of fertilizer usage. For example, the time lag may be a time period of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks, 11 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods. Preferably, the time lag is an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks. The time lag preferably refers to situations in which the mixture or composition of the invention is provided 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 11 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods before the application of a fertilizer as defined herein above.
In another specific embodiment of the invention the mixture or composition of the invention is applied between GS 00 to GS 33 BBCH of the plant, or between GS 00 and GS 65 BBCH of the plant, provided that the application of at least one fertilizer as defined herein above is carried out with a time lag of at least 1 day, e.g. a time lag of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, or more or any time period in between the mentioned time periods. It is preferred that the mixture or composition of the invention, which is applied between GS 00 to GS 33 BBCH of the plant, is provided 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks, 11 weeks, or 12 weeks before the application of a fertilizer as defined herein above.
In another specific embodiment of the invention, at least one fertilizer as defined herein above is applied between GS 00 to GS 33 BBCH of the plant or between GS 00 and GS 65 BBCH of the plant, provided that the application of the mixture or composition of the invention is carried out with a time lag of at least 1 day, e.g. a time lag of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks or more or any time period in between the mentioned time periods.
According to a specific embodiment of the present invention a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow is treated at least once with the mixture or composition of the invention. In a further specific embodiment of the present invention a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow is treated at least once with the mixture or composition of the invention, and at least once with a fertilizer as defined herein above.
The term "at least once" means that the application may be performed one time, or several times, i.e. that a repetition of the treatment with the mixture or composition of the invention and/or a fertilizer may be envisaged. Such a repetition may a 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or more frequent repetition of the treatment with a nitrification inhibitor and/or a fertilizer. The repetition of treatment with the mixture or composition of the invention and a fertilizer may further be different. For example, while the fertilizer may be applied only once, the nitrification inhibitor may be applied 2 times, 3 times, 4 times etc. Alternatively, while the mixture or composition of the invention may be applied only once, the fertilizer may be applied 2 times, 3 times, 4 times etc. Further envisaged are all combination of numerical different numbers of repetitions for the application of the mixture or composition of the invention and a fertilizer as defined herein above.
Such a repeated treatment may further be combined with a time lag between the treatment of the mixture or composition of the invention and the fertilizer as described above.
The time interval between a first application and second or subsequent application of the mixture or composition of the invention and/or a fertilizer may be any suitable interval. This interval may range from a few seconds up to 3 months, e.g. from a few seconds up to 1 month, or from a few seconds up to 2 weeks. In further embodiments, the time interval may range from a few seconds up to 3 days or from 1 second up to 24 hours.
In further specific embodiments, a method for reducing nitrification as described above is carried out by treating a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with at least one agrochemical mixture as defined herein above, or with a mixture or composition as defined herein above.
In another embodiment of the invention, an agrochemical mixture comprising an ammonium- or urea-containing fertilizer and at least one nitrification inhibitor as defined herein above is applied before and at sowing, before emergence, and until GS > BBCH 99 of the pant (e.g. when fertilizing in fall after harvesting apples). In case the agrochemical mixture is provided as kit of parts or as non-physical mixture, it may be applied with a time lag between the application of the nitrification inhibitor and the fertilizer or between the application of the nitrification inhibitor a secondary or further ingredient, e.g. a pesticidal compound as mentioned herein above.
In a further embodiment, plant propagules are preferably treated simultaneously (together or separately) or subsequently.
The term "propagules" or "plant propagules" is to be understood to denote any structure with the capacity to give rise to a new plant, e.g. a seed, a spore, or a part of the vegetative body capable of independent growth if detached from the parent. In a preferred embodiment, the term "propagules" or "plant propagules" denotes for seed.
For a method as described above, or for a use according to the invention, in particular for seed treatment and in furrow application, the application rates of the mixture or composition of the invention are between 0,01 g and 5 kg of active ingredient per hectare, preferably between 1 g and 1 kg of active ingredient per hectare, especially preferred between 50 g and 300 g of active ingredient per hectare depending on different parameters such as the specific active ingredient applied and the plant species treated. In the treatment of seed, amounts of from 0.001 g to 20 g per kg of seed, preferably from 0.01 g to 10 g per kg of seed, more preferably from 0.05 to 2 g per kg of seed of nitrification inhibitors may be generally required.
As a matter of course, if nitrification inhibitors and fertilizers (or other ingredients), or if mixtures thereof are employed, the compounds may be used in an effective and non-phyto- toxic amount. This means that they are used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotoxic symptoms on the treated plant or on the plant raised from the treated propagule or treated soil or soil substituents. For the use according to the invention, the application rates of fertilizers may be selected such that the amount of applied N is between 10 kg and 1000 kg per hectare, preferably between 50 kg and 700 kg per hectare.
The mixture or composition of the invention can be present in different structural or chemical modifications whose biological activity may differ. They are likewise subject matter of the present invention.
The nitrification inhibitor compounds according to the invention, their N-oxides and/or salts etc. may be converted into customary types of compositions, e.g. agrochemical or agricultural compositions such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
The composition type depends on the particular intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention. Examples for composition types are suspensions (SC, 00, FS), emulsifiable concentrates (EC), emulsions (EW, EC, ES), microemulsions (ME), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, OP, OS) or granules (GR, FG, GG, MG), which can be watersoluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF). Usually the composition types (e.g. SC, 00, FS, EC, WG, SG, WP, SP, SS, WS, GF) are employed diluted. Composition types such as OP, OS, GR, FG, GG and MG are usually used undiluted.
The compositions are prepared in a known manner (see, for example, US 3,060,084, EP 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147- 48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hili, New York, 1963, S. 8-57 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701, US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, New York, 1961), Hance et al.: Weed Control Handbook (8th Ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation technology (Wiley VCH Verlag, Weinheim, 2001). Compositions or mixtures may also comprise auxiliaries which are customary, for example, in agrochemical compositions. The auxiliaries used depend on the particular application form and active substance, respectively.
Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and inorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e.g. for seed treatment formulations). Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as cyclohex- anone and gamma-butyrolactone, fatty acid dimethylamides, fatty acids and fatty acid esters and strongly polar solvents, e.g. amines such as N-methylpyrrolidone.
Suitable surfactants (adjuvants, wetters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as I ign in- sou Ifonic acid (Borresperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene-sulfonic acid (Nekal® types, BASF, GermanY),and fatty acids, alkylsulfonates, alkylarylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and proteins, denatured proteins, polysaccharides (e. g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols (Mowiol® types, Clariant, Switzerland), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvinylamines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers thereof. Examples of suitable thickeners (i.e. compounds that impart a modified flowability to compositions, i.e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan®, CP Kelco, U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt, U.S.A.) or At- taclay® (Engelhard Corp., NJ, USA).
In specific embodiments, bactericides may be added for preservation and stabilization of the composition. Examples for suitable bactericides are those based on dichlorophene and benzyl alcohol hemi formal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as al kyl isoth iazol i- nones and benzisothiazolinones (Acticide® MBS from Thor Chemie).
Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Examples for anti-foaming agents are silicone emulsions (such as e.g. Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.
Suitable colorants are pigments of low water solubility and water-soluble dyes, e.g. rho- damin B, C. I. pigment red 112, C. I. solvent red 1, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15: 1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Furthermore, odorous substances may be present in the compositions as defined above. Such odorous substances comprise citronel lyn itri I , citral, zertrahydrolinalool, tetrahydrogeraniol, geranonitril, beta-lonon R, rootanol, I inaly lacetat, morillol, and p-cre- sometylether.
Examples for tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan). Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the components of the mixture of the invention and, if appropriate, further active substances, with at least one solid carrier. Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers. Examples of such suitable solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
Examples for composition types are: i) Water-soluble concentrates (SL, LS) 10 parts by weight of a nitrification inhibitor are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves upon dilution with water. In this way, a composition having a content of 10% by weight of active substance is obtained. ii) Dispersible concentrates (DC) 20 parts by weight of a nitrification inhibitor are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, e.g. polyvinylpyrrolidone. Dilution with water gives a dispersion. The active substance content is 20% by weight. iii) Emulsifiable concentrates (EC) 15 parts by weight of a nitrification inhibitor are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The composition has an active substance content of 15% by weight. iv) Emulsions (EW, EC, ES) 25 parts by weight of a nitrification inhibitor are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The composition has an active substance content of 25% by weight. v) Suspensions (SC, 00, FS) In an agitated ball mill, 20 parts by weight of a nitrification inhibitor are comminuted with addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. The active substance content in the composition is 20% by weight. vi) Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of a nitrification inhibitor are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as water-dispersible or water-soluble granules by means of technical appliances (e.g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. The composition has an active substance content of 50% by weight. vii) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of a nitrification inhibitor are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dis- persion or solution of the active substance. The active substance content of the composition is 75% by weight. viii) Gel (GF) In an agitated ball mill, 20 parts by weight of a nitrification inhibitor are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained. 2. Composition types to be applied undiluted ix) Oustable powders (OP, OS) 5 parts by weight of a nitrification inhibitor are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable composition having an active substance content of 5% by weight. x) Granules (GR, FG, GG, MG) 0.5 parts by weight of a nitrification inhibitor is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spraydrying or the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5-10% by weight, preferably an active substance content of 0.5-2% by weight. xi) ULV solutions (UL) 10 parts by weight of a nitrification inhibitor are dissolved in 90 parts by weight of an organic solvent, e.g. xylene. This gives a composition to be applied undiluted having an active substance content of 10% by weight.
The compositions, e.g. agrochemical or agriculatural compositons, generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substance. The active substances are employed in a purity offrom 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Water-soluble concentrates (LS), flowable concentrates (FS), powders for dry treatment (OS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES) emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted.
The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready- to-use preparations. Application can be carried out before or during sowing.
Methods for applying or treating agrochemical or agricultural compounds or mixtures, or compositions as defined herein, respectively, on to plant propagation material, especially seeds, the plant and/or the locus where the plant is growing or intended to grow are known in the art, and include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. In a preferred embodiment, the compounds or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting.
In a preferred embodiment, a suspension-type (FS) composition may be used. Typically, a FS composition may comprise 1-800 g/l of active substance, 1 200 g/l surfactant, o to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water. The active substances can be used as such or in the form of their compositions, e.g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring.
The application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active substances according to the invention. Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 90%, such as from 30 to 80%, e.g. from 35 to 45% or from 65 to 75% by weight of active substance. The active substances may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.
Various types of oils, wetters, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the active substances or the compositions comprising them, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 : 100 to 100 : 1, preferably 1 : 10 to 10 : 1.
Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240®; alcohol alkoxylates such as Atplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON 30®; EO/PO block polymers, e.g. Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates such as Lutensol XP 80®; and dioctyl sulfosuccinate sodium such as Leophen RA®.
In a further aspect the invention relates to a method for treating a fertilizer or a composition. This treatment includes the application of the mixture or composition of the invention to a fertilizer or a composition. The treatment may accordingly result in the presence of the mixture or composition of the invention in a preparation of fertilizers or other compositions. Such treatment may, for example, result in a homogenous distribution of nitrification inhibitors on or in fertilizer preparations. Treatment processes are known to the skilled person and may include, for instance, dressing, coating, pelleting, dusting or soaking. In a specific embodiment, the treatment may be a coating of nitrification inhibitors with fertilizer preparations, or a coating of fertilizers with nitrification inhibitors. The treatment may be based on the use of granulation methods as known to the skilled person, e.g. fluidized bed granulation. The treatment may, in certain embodiments, be performed with a composition comprising the mixture as defined herein above, e.g. comprising besides the inhibitors a carrier or a pesticide or any other suitable additional compound as mentioned above.
In a further specific embodiment, the present invention relates to a method for treating seed or plant propagation material. The term "seed treatment" as used herein refers to or involves steps towards the control of biotic stresses on or in seed and the improvement of shooting and development of plants from seeds. For seed treatment it is evident that a plant suffering from biotic stresses such as fungal or insecticidal attack or which has difficulties obtaining sufficient suitable nitrogen-sources shows reduced germination and emergence leading to poorer plant or crop establishment and vigor, and consequently, to a reduced yield as compared to a plant propagation material which has been subjected to curative or preventive treatment against the relevant pest and which can grow without the damage caused by the biotic stress factor. Methods for treating seed or plant propagation material according to the invention thus lead, among other advantages, to an enhanced plant health, a better protection against biotic stresses and an increased plant yield.
Seed treatment methods for applying or treating inventive mixtures and compositions thereof, e.g. compositions or agrochemical compositions as defined herein above, and in particular combinations of nitrification inhibitors as defined herein above and secondary effectors such as pesticides, in particular fungicides, insecticides, nematicides and/or biopesticides and/or biostimulants, to plant propagation material, especially seeds, are known in the art, and include dressing, coating, film coating, pelleting and soaking application methods of the propagation material. Such methods are also applicable to the combinations or compositions according to the invention.
In further embodiments, the treatment of seeds is performed with compositions comprising, besides a nitrification inhibitor according to the present invention, e.g. compositions as defined herein above, a fungicide and an insecticide, or a fungicide and a nematicide, or a fungicide and a biopesticide and/or biostimulant, or an insecticide and a nematicide, or an insecticide and a biopesticide and/or biostimulant, or a nematicide and a biopesticide and/or biostimulant, or a combination of a fungicide, insecticide and nematicide, or a combination of a fungicide, insecticide and biopesticide and/or biostimulant, or a combination of an insecticide, nematicide, and biopesticide etc.
In a preferred embodiment, the agricultural composition or combination comprising a nitrification inhibitor according to the present invention, e.g. as defined herein above, is applied or treated on to the plant propagation material by a method such that the germination is not negatively impacted. Accordingly, examples of suitable methods for applying (or treating) a plant propagation material, such as a seed, is seed dressing, seed coating or seed pelleting and alike. It is preferred that the plant propagation material is a seed, seed piece (i.e. stalk) or seed bulb.
Although it is believed that the present method can be applied to a seed in any physiological state, it is preferred that the seed be in a sufficiently durable state that it incurs no damage during the treatment process. Typically, the seed would be a seed that had been harvested from the field; removed from the plant; and separated from any cob, stalk, outer husk, and surrounding pulp or other non-seed plant material. The seed would preferably also be biologically stable to the extent that the treatment would cause no biological damage to the seed. It is believed that the treatment can be applied to the seed at any time between harvest of the seed and sowing of the seed or during the sowing process (seed directed applications). The seed may also be primed either before or after the treatment.
Even distribution of the ingredients in compositions or mixtures as defined herein and adherence thereof to the seeds is desired during propagation material treatment. Treatment could vary from a thin film (dressing) of the formulation containing the combination, for example, a mixture of active ingredient(s), on a plant propagation material, such as a seed, where the original size and/or shape are recognizable to an intermediary state (such as a coating) and then to a thicker film (such as pelleting with many layers of different materials (such as carriers, for example, clays; different formulations, such as of other active ingredients; polymers; and colorants) where the original shape and/or size of the seed is no longer recognizable.
An aspect of the present invention includes application of the composition, e.g. agricultural composition or combination comprising a nitrification inhibitor according to the present invention, onto the plant propagation material in a targeted fashion, including positioning the ingredients in the combination onto the entire plant propagation material or on only parts thereof, including on only a single side or a portion of a single side. One of ordinary skill in the art would understand these application methods from the description provided in EP954213B1 and W006/112700.
The composition, e.g. agricultural composition or combination comprising a nitrification inhibitor according to the present invention, can also be used in form of a "pill" or “pellet” or a suitable substrate and placing, or sowing, the treated pill, or substrate, next to a plant propagation material. Such techniques are known in the art, particularly in EP1124414, W007/67042, and W007/67044. Application of the composition, e.g. agricultural composition, or combination comprising a nitrification inhibitor according to the present invention, onto plant propagation material also includes protecting the plant propagation material treated with the combination of the present invention by placing one or more pesticide- and nitrification inhibitor (Nl)-containing particles next to a pesticide- and Nl-treated seed, wherein the amount of pesticide is such that the pesticide-treated seed and the pesticidecontaining particles together contain an Effective Dose of the pesticide and the pesticide dose contained in the pesticide-treated seed is less than or equal to the Maximal Non-Phy- totoxic Dose of the pesticide. Such techniques are known in the art, particularly in W02005/120226.
Application of the combinations onto the seed also includes controlled release coatings on the seeds, wherein the ingredients of the combinations are incorporated into materials that release the ingredients 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 the ingredients may be incorporated into the controlled release material or applied between layers of materials, or both.
Seed can be treated by applying thereto the compounds present in the inventive mixtures in any desired sequence or simultaneously.
The seed treatment occurs to an unsown seed, and the term "unsown seed" is meant to include seed at any period between the harvest of the seed and the sowing of the seed in the ground for the purpose of germination and growth of the plant.
Treatment to an unsown seed is not meant to include those practices in which the active ingredient is applied to the soil or soil substituents but would include any application practice that would target the seed during the planting process.
Preferably, the treatment occurs before sowing of the seed so that the sown seed has been pre-treated with the combination. In particular, seed coating or seed pelleting are preferred in the treatment of the combinations according to the invention. As a result of the treatment, the ingredients in each combination are adhered on to the seed and therefore available for pest control. The treated seeds can be stored, handled, sowed and tilled in the same manner as any other active ingredient treated seed.
Solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water- soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. Preferred examples of seed treatment formulation types or soil application for premix compositions are of WS, LS, ES, FS, WG or CS-type.
The compositions in question give, after two-to-tenfold dilution, active components concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating compositions or combinations comprising a nitrification inhibitor according to the present invention, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, mixtures or compositions according to the present invention are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
Typically, a pre-mix formulation for seed treatment application comprises 0.5 to 99.9 percent, especially 1 to 95 percent, of the desired ingredients, and 99.5 to 0.1 percent, especially 99 to 5 percent, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 percent, especially 0.5 to 40 percent, based on the pre-mix formulation. Whereas commercial products will preferably be formulated as concentrates (e.g., pre- mix composition (formulation), the end user will normally employ dilute formulations (e.g. tank mix composition).
When employed in plant protection, the total amounts of active components applied are, depending on the kind of effect desired, from 0.001 to 10 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha. The application rates may range from about 1 x 106 to 5 x 1015 (or more) CFU/ha. Preferably, the spore concentration is about 1 x 107 to about 1 x 1011 CFU/ha. In the case of (ento- mopathogenic) nematodes as microbial pesticides (e.g. Steinernema feltiae), the application rates preferably range inform about 1 x 105 to 1 x 1012 (or more), more preferably from 1 x 108 to 1 x 1011, even more preferably from 5 x 108 to 1 x 1010 individuals (e.g. in the form of eggs, juvenile or any other live stages, preferably in an infetive juvenile stage) per ha.
When employed in plant protection by seed treatment, the amount of the mixture or composition of the invention (based on total weight of active components) is in the range from 0.01-10 kg, preferably from 0.1-1000 g, more preferably from 1-100 g per 100 kilogram of plant propagation material (preferably seeds). The application rates with respect to plant propagation material preferably may range from about 1 x 106 to 1 x 1012 (or more) CFU/seed. Preferably, the concentration is about 1 x 106 to about 1 x 1011 CFU/seed. Alternatively, the application rates with respect to plant propagation material may range from about 1 x 107 to 1 x 1014 (or more) CFU per 100 kg of seed, preferably from 1 x 109 to about 1 x 1011 CFU per 100 kg of seed.
The present invention is further illustrated by the following examples.
Examples Example 1: Preparation of reaction product A
Reaction product A was prepared according to the following procedure. In a reaction vessel, about 12.9 g of a 50% solution of formaldehyde was added at room temperature and the temperature was increased and maintained between 30 ° C and 50° C. A first portion of ammonium hydroxide (0.6 g) was then added to the reaction vessel and the temperature of the mixture was maintained below 60 ° C. About 2.6 g DCD was then added to the reaction vessel and the temperature of the mixture was adjusted to between 35 ° C and 50 ° C. About 13.78 g urea was then added to the reaction vessel. A second portion of ammonium hydroxide (250 g) was then added to the reaction vessel. The temperature of the reaction mixture was allowed to exothermically increase about 90° C for less than 30 minutes and the temperature was reduced to 85° C and held for 120 minutes. After heating the reaction mixture to 85° C, distillation was started and carried out until 4.08 g of distillate was removed from the reaction mixture. 3.1 g of a 25 wt.-% solution of sodium hydroxide was added throughout the reaction and distilled as needed to adjust the pH. The pH of the reaction mixture was kept above 8.4 throughout the reaction. After distillation, the reaction mixture was cooled down to provide the reaction product A. The reaction product A had a final pH of 9.5.
Example 2: Preparation of reaction product B
Reaction product B was prepared according to the following procedure. 10.68 g of DMSO and 8.22 g of DCD were charged to a reaction flask, heated to 95° C, held until contents were clear and then cooled to 65° C. 0.737 g of paraformaldehyde were charged and the contents were then heated to 81° C over a 0.75 hour period and held 1.3 hr. until the solution became clear. The contents were cooled to 41.7° C and then 0.119 g of methane sulfonic acid/70% were added. The contents were mixed for 5 minutes and then the contents were slowly heated to 110° C over a 2.1 hr. period of time. At 110° C, a vacuum of 54-65 mm Hg was applied to the reaction flask for 0.8 hr., the vacuum was broken by nitrogen, 0.237 g of triethanolamine/99% were charged and then the contents were cooled to <45° C and packaged. The yield was 18.9 g and the calculated amount of DCD was 43.5%
Table 1: Characterization.
Figure imgf000071_0001
Example 3: Preparation of reaction product A
Reaction product A was prepared according to the following procedure. In a reaction vessel, 1290 g of a 50 wt.-% solution of formaldehyde was added at room temperature and the temperature was increased and maintained between 30 ° C and 50° C. A first portion of ammonium hydroxide (60 g) was then added to the reaction vessel and the temperature of the mixture was maintained below 60 ° C. 260 g of DCD were then added to the reaction vessel and the temperature of the mixture was adjusted to between 35 ° C and 50 ° C. 1378 g urea were then added to the reaction vessel. A second portion of ammonium hydroxide (250 g) was then added to the reaction vessel. The temperature of the reaction mixture was allowed to exothermically increase about 90° C for less than 30 minutes and the temperature was reduced to 85° C and held for 120 minutes. After heating the reaction mixture to 85° C, distillation was started and carried out until 416.1 g of distillate was removed from the reaction mixture. A 25 wt.-% solution of sodium hydroxide was added throughout the reaction and distilled as needed to adjust the pH. The pH of the reaction mixture was kept above 8.4 throughout the reaction. After distillation, the reaction mixture was cooled down to provide the reaction product A. The reaction product A had a final pH of 9.12.
Table 2
Figure imgf000072_0001
Table 3
Figure imgf000072_0002
Example 4: Preparation of reaction product B
Reaction product B was prepared according to the following procedure. 106.82 g of DMSO and 82.26 g of DCD were charged to a reaction flask, heated to 95° C, held until contents were clear and then cooled to 65° C. 7.37 g of paraformaldehyde were charged and the contents were then heated to 81° C over a 0.75 hour period and held 1.3 hours until the solution became clear. The contents were cooled to 41.7° C and then 1.19 g of methane sulfonic acid (70%) were added. The contents were mixed for 5 minutes and then the contents were slowly heated to 110° C over a 2.1 hours, period of time. At 110° C, a vacuum of 54- 65 mm Hg was applied to the reaction flask for 0.8 hours, the vacuum was broken by nitrogen, 2.37 g of triethanolamine (99%) were charged and then the contents were cooled to <45° C and packaged. The yield was 189.08 g and the calculated amount of DCD was 43.5%.
Table 4
Figure imgf000073_0001
Table 5
Figure imgf000073_0002
Example 5: Incubation trials with oligomeric DCD and alkoxypyrazoles
Amount soil: 50 g
Fertilizer: Ammonium sulfate
Amount N: 10 mg NH4-N/100 g soil
Number of replicates: 4
Method:
100 g Soil (soil Limburgerhof with pH(CaCI2) 6.8; 73% sand, 23% silt, 4% clay, which is classified according to Food and Agriculture Organization of the United Nations (FAO) as a sandy loam) was filled into 500 ml plastic bottles and was moistened to 50% water holding capacity. The soil was incubated at 20 ° C for two weeks prior to the experiments to acti- vate the microbial biomass. 1 ml Test solution, containing the compounds of formula I or the comparative example in the appropriate concentration (0.3 or 1 % (w/w) of fertilized NH4- N), and 10 mg nitrogen in the form of ammonium sulfate-N (NH4-N) was added to the soil and everything was mixed well. Unfertilized controls received 1 ml pure water. Bottles were loosely capped to allow air exchange. The bottles were then incubated at 20 ° C for 14 days.
For analysis, 300 ml of a 1% K2SO4-solution was added to the bottle containing the soil and was shaken for 2 hours in a horizontal shaker at 150 rpm. Then the whole solution was filtered through a filter (Macherey-Nagel Filter MN 807 %). Ammonium and nitrate content was then analyzed in the filtrate using an autoanalyzer at 550 nm (Merck, AA11). Ammonium was quantified via an indophenol blue dye at 660 nm.
The inhibition (NI @ a specified concentration) is calculated as follows: inhibition in %
Figure imgf000074_0001
Inhibition of N03-production after 28 days:
Table 6: Measured.
Figure imgf000074_0002
Table 7: Calculated by Colby.
Figure imgf000074_0003
Figure imgf000075_0001
Table 8: Difference between measurement and calculation.
Figure imgf000075_0002
Based on the differences between measured and calculated values for the inhibition of N03 production (Table 8), the tested Alkoxypyrazole has a synergistic effect when combined with oligomers of DCD.

Claims

Claims
1. A mixture comprising
(i) an alkoxypyrazole compound of formula (I)
Figure imgf000076_0001
or a salt, tautomer, or N-oxide thereof, wherein
R1 is CH3 or CH2CH3; and
(ii) a nitrification inhibitor system comprising at least one reaction product A or B of (al, a2) dicyandiamide (DCD) and (bl, b2) formaldehyde or paraformaldehyde, and, optionally,
(i) (cl) urea and/or (dl) an ammonia source to yield reaction product A; or
(ii) (c2) an organic acid or an inorganic acid and/or (d2) a primary, secondary or tertiary amine to yield reaction product B; wherein components (i) and (ii) are present in a weight ratio of from 100:1 to 1:100.
2. The mixture according to claim 1, wherein the reaction product A comprises at least one adduct of formula (II)
Figure imgf000076_0002
wherein X is =0 or
Figure imgf000076_0003
are independently selected from the group consisting of
Figure imgf000076_0004
wherein at least one of R1, R2, R3, and R4 is different from and wherein, if X is =0, at least one of R1, R2, R3, and R4 is
Figure imgf000077_0001
wherein preferably the at least one adduct is selected from the group consisting of adducts of formulae (Ila), (lib), and (lie),
Figure imgf000077_0002
and combinations thereof, and wherein particularly preferably the at least one adduct is selected from the group consisting of adducts of formula (Ila) and (lib), and combinations thereof.
3. The mixture according to any one of claims 1 or 2, wherein the reaction product A further comprises at least one adduct comprising a polymeric backbone of formula (III)
Figure imgf000077_0003
wherein z is an integer of 1 or greater, preferably 1 to 100; at least one carbon in the backbone is substituted with the group
Figure imgf000077_0004
at least one carbon in the backbone is optionally substituted with the group =0; and each nitrogen in the backbone independently includes a substituent selected from the group consisting of
Figure imgf000077_0005
4. The mixture according to claim 1, wherein the reaction product B is a reaction product of (a2) dicyandiamide (DCD), (b2) formaldehyde or paraformaldehyde, (c2) methane sulfonic acid, and (d2) triethanolamine.
5. The mixture according to claim 1 or 4, wherein the reaction product B is obtained utilizing a non-aqueous polar, aprotic organic liquid (NAPAOL), which is preferably dimethylsulfoxide.
6. The mixture according to any one of claims 1 to 5, wherein components (i) and (ii) are present in a weight ratio of from 50:1 to 1:50, preferably from 25:1 to 1:25 or from 10:1 to 1:10.
7. A composition comprising the mixture of any one of claims 1 to 6 and at least one carrier.
8. An agrochemical mixture comprising (a) at least one fertilizer and (b) the mixture of any one of claims 1 to 6 or the composition of claim 7.
9. Use of the mixture of any one of claims 1 to 6 or the composition of claim 7 for reducing nitrification of a fertilizer, wherein said reduction of nitrification preferably occurs in the root zone of a plant, in or on soil or soil substituents and/or at the locus where a plant is growing or is intended to grow.
10. A method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus or soil or soil substituents where the plant is growing or is intended to grow with the mixture of any one of claims 1 to 6 or the composition of claim 7, and optionally additionally with a fertilizer.
11. The method of claim 10, wherein the application of the mixture of any one of claims 1 to 6 or the composition of claim 7 and the fertilizer is carried out simultaneously or with a time lag, preferably an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.
12. A method for treating a fertilizer or a fertilizer composition, comprising the application of a mixture of any one of claims 1 to 6 or a composition of claim 7 to a fertilizer or fertilizer composition.
13. The agrochemical mixture of claim 8, the use of claim 9, or the method of any one of claims 10 to 12, wherein said fertilizer is an solid or liquid ammonium-containing inorganic ferti-lizer such as an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; an solid or liquid organic fertilizer such as liquid manure, semi-liquid manure, biogas manure, stable manure and straw manure, worm castings, compost, seaweed or guano, or an urea-containing fertilizer such as urea, formaldehyde urea, anhydrous ammonia, urea ammonium nitrate (UAN) solution, urea sulphur, urea based NPK-fertilizers, or urea ammonium sulfate.
14. The use of any one of claims 9 or 13 or the method of any one of claims 10, 11 or 13, wherein the applied amount of the mixture is such that at least 0.1 % by weight of component (i) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer are applied, and at least 0.2 % by weight of component (ii) relative to the sum of NH2- and NH4-nitrogen content of the fertilizer.
15. The use of claim 9 or 14 or the method of any one of claims 10, 11 or 14, wherein said plant is an agricultural plant such as wheat, barley, oat, rye, soybean, corn, sorghum, potatoes, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice, oil palm, coffee, cacao, tea or a vegetable such as spinach, lettuce, asparagus, or cabbages; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or in a genetically modified form.
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