BR112020016426B1 - USE OF AN N-FUNCTIONALIZED ALKOXY PYRAZOLE COMPOUND, NITRIFICATION REDUCING COMPOSITION, USE OF THE COMPOSITION, AGROCHEMICAL MIXTURE, METHOD FOR REDUCING NITRIFICATION AND METHOD FOR TREATING A FERTILIZER - Google Patents

Abstract

The present invention relates to the use of novel nitrification inhibitors of formula I, which are N-functionalized alkoxy pyrazole compounds. Furthermore, the invention relates to the use of compounds of formula I as nitrification inhibitors, i.e. to reduce nitrification, as well as agrochemical mixtures and compositions comprising the nitrification inhibitors of formula I.

Description

DESCRIPTION

[001] The present invention relates to novel nitrification inhibitors of formula I, which are N-functionalized alkoxy pyrazole compounds. Furthermore, the invention relates to the use of compounds of formula I as nitrification inhibitors, i.e. to reduce nitrification, as well as agrochemical mixtures and compositions comprising nitrification inhibitors of formula I. Also encompassed by the present invention are methods for reducing nitrification, said methods comprising treating plants, soil and/or sites where the plant is growing or is intended to grow, with said nitrification inhibitor and methods for treating a fertilizer or composition by applying said nitrification inhibitor.

[002] Nitrogen is an essential element for plant growth and reproduction. About 25% of the plant-available nitrogen in soils (ammonium and nitrate) originates from decomposition (mineralization) processes of organic nitrogen compounds such as humus, plant and animal residues, and organic fertilizers. Approximately 5% derives from rainfall. On a global basis, the largest proportion (70%), however, is supplied to the plant by inorganic nitrogen fertilizers. The nitrogen fertilizers used mainly comprise ammonium compounds or their derivatives, i.e. almost 90% of the nitrogen fertilizers applied worldwide are in the NH4+ form (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302). This is, inter alia, due to the fact that the assimilation of NH4+ is energetically more efficient than the assimilation of other nitrogen sources such as NO3-.

[003] Furthermore, being a cation, NH4+ is held electrostatically by negatively charged clay surfaces and functional groups of soil organic matter. This binding is strong enough to limit the loss of NH4+ by leaching into groundwater. On the other hand, NO3-, being negatively charged, does not bind to soil and is liable to be leached from the root zone of plants. In addition, nitrate can 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).

[004] However, ammonium compounds (NH4+) are converted by soil microorganisms into nitrates (NO3-) in a relatively short time in a process known as nitrification. Nitrification is carried out primarily by two groups of chemolithotrophic bacteria, ammonia-oxidizing bacteria (AOB) of the genera Nitrosomonas and Nitrobacter, which are ubiquitous components of soil bacterial populations. The enzyme, which is essentially responsible for nitrification, is ammonia monooxygenase (AMO), which has also been found in ammonia-oxidizing archaea (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302).

[005] The nitrification process often leads to nitrogen leaks and environmental pollution. As a result of the various losses, approximately 50% of 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).

[006] As a countermeasure, the use of nitrification inhibitors, especially in conjunction with fertilizers, has been suggested. Suitable nitrification inhibitors include biological nitrification inhibitors (BNIs) such as linoleic acid, alpha-linolenic acid, p-methyl coumarate, methyl ferulate, MHPP, Karanjin, brachylactone or p-benzoquinone sorgoleone (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302). Other suitable nitrification inhibitors are synthetic chemical inhibitors such as nitrapyrin, dicyandiamide (DCD), 3,4-dimethylpyrazole phosphate (DMPP), 4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole) or 2-sulfanilamidothiazole (ST) (Slangen and Kerkhoff 1984, Fertilizer research, 5(1), 176).

[007] However, many of these inhibitors work only suboptimally. Furthermore, the world population is expected to grow significantly in the next 20-30 years and therefore food production in sufficient quantity and quality is necessary. 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 gaseous emissions into the air have already reached critical levels in many places, causing water contamination and air pollution. However, fertilizer efficiency increases significantly and therefore less fertilizer can be applied, if nitrification inhibitors are used. Therefore, there is a clear need for new nitrification inhibitors as well as methods for using them.

[008] Sharma et al. (JP Sharma, HK Taneja, SS Tomar Pesticide Research Journal, 2006, 18(1), 7-11) discloses, among other things, 3-ethoxy-5-methylpyrazole as a nitrification inhibitor. However, this compound was found to have high volatility and is therefore disadvantageous for long-term applications.

[009] It was an object of the present invention to provide improved nitrification inhibitors.

[010] In particular, it was an object of the present invention to provide nitrification inhibitors which have a high activity as nitrification inhibitors, but at the same time have a reduced volatility and toxicity compared to the nitrification inhibitors described in the prior art.

[011] Furthermore, it was an object of the present invention to provide nitrification inhibitors, which can be prepared economically and which are environmentally safe.

[012] Surprisingly, it has been found that these objectives can be achieved using the nitrification inhibitors according to the present invention, which are N-functionalized alkoxy pyrazole compounds of formula I: or the salts, stereoisomers, tautomers or N-oxides thereof; wherein: - R1 is H, C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, CHRaC(=O)ORb, CHRaC(=O)NRbRc or phenyl, wherein said phenyl group is unsubstituted or substituted by one or more same or different Rx substituents; - R2 is halogen, C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, propargyl or phenyl, wherein said phenyl group is unsubstituted or substituted by one or more same or different Rx substituents; - RN is C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, propargyl or phenyl, wherein said groups are unsubstituted or substituted by one or more same or different Ry substituents; CHRaC(=O)ORb, CHRaC(=O)NRbRc, CH(C(=O)ORb)CH2(C(=O)ORb); C(=O)Rd, C(=O)ORb, C(=O)NRbRc, CHRaORb or CHRaNRe(C=O)Rf; and where: - Ra is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C8 cycloalkyl, phenyl or phenyl-C1-C2 alkyl; - Rb is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C8 cycloalkyl, phenyl or phenyl-C1-C2 alkyl; - Rc is H, C1-C4 alkyl, C1-C4 haloalkyl or phenyl; - Rd is H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, phenyl or phenyl-C1-C2 alkyl, wherein these groups are unsubstituted or substituted by a COOH group; - Re is H, C1-C4 alkyl, C3-C8 cycloalkyl or C6-C10 aryl; - Rf is H or C1-C4 alkyl; - Rx is halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; - Ry is halogen, CN, OH, NO2, COOH, NRbRc, NRb(C=O)Rf, C(=O)NRbRc, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylcarbonyl, C1-C4 alkylcarboxy, C1-C4 alkylthio, C1-C4 alkylsulfonyl and S(O)2NRbRc; and - n is 0, 1 or 2.

[013] The inventors have surprisingly found that by applying the compounds of formula I as defined above and hereinafter, the nitrification of ammonium to nitrate can be significantly reduced. Furthermore, the compounds of formula I surprisingly exhibit low toxicity and low volatility.

[014] Thus, according to one embodiment, the present invention relates to the use of an N-functionalized alkoxy pyrazole compound of formula I: or a salt, stereoisomer, tautomer or N-oxide thereof, as a nitrification inhibitor; wherein: - R1 is H, C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, CHRaC(=O)ORb, CHRaC(=O)NRbRc or phenyl, wherein said phenyl group is unsubstituted or substituted by one or more same or different Rx substituents; - R2 is halogen, C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, propargyl or phenyl, wherein said phenyl group is unsubstituted or substituted by one or more same or different Rx substituents; - RN is C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, propargyl or phenyl, wherein said groups are unsubstituted or substituted by one or more same or different Ry substituents; CHRaC(=O)ORb, CHRaC(=O)NRbRc, CH(C(=O)ORb)CH2(C(=O)ORb); C(=O)Rd, C(=O)ORb, C(=O)NRbRc, CHRaORb or CHRaNRe(C=O)Rf; and where: - Ra is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C8 cycloalkyl, phenyl or phenyl-C1-C2 alkyl; - Rb is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C8 cycloalkyl, phenyl or phenyl-C1-C2 alkyl; - Rc is H, C1-C4 alkyl, C1-C4 haloalkyl or phenyl; - Rd is H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, phenyl or phenyl-C1-C2 alkyl, wherein these groups are unsubstituted or substituted by a COOH group; - Re is H, C1-C4 alkyl, C3-C8 cycloalkyl or C6-C10 aryl; - Rf is H or C1-C4 alkyl; - Rx is halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; - Ry is halogen, CN, OH, NO2, COOH, NRbRc, NRb(C=O)Rf, C(=O)NRbRc, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylcarbonyl, C1-C4 alkylcarboxy, C1-C4 alkylthio, C1-C4 alkylsulfonyl and S(O)2NRbRc; and - n is 0, 1 or 2.

[015] In a preferred embodiment of said use, in said compound of formula I, R1 is C1-C6 alkyl, benzyl or allyl.

[016] In another preferred embodiment of said use, in said compound of formula I: - n is 0, i.e. R2 is absent; or - n is 1 and R2 is C1-C3 alkyl or phenyl.

[017] In another preferred embodiment of said use, in said compound of formula I, RN is C(=O)Rd, CHRaC(=O)ORb, CHRaC(=O)NRbRc, CH(C(=O)ORb)CH2(C(=O)ORb) or CHRaNRe(C=O)Rf.

[018] In another preferred embodiment of said use, in said compound of formula I: - Ra is H; - Rb is H or C1-C4 alkyl; - Rc is H or C1-C4 alkyl; - Rd is C1-C3 alkyl; - Re is H; and - Rf is H or CH3.

[019] In a further aspect, the present invention relates to a composition for use in reducing nitrification comprising at least one compound of formula I, as defined above, and at least one carrier.

[020] In a further aspect, the present invention relates to an agrochemical mixture comprising at least one fertilizer and at least one compound of formula I, as defined above; or at least one fertilizer and a composition, as mentioned above, for use in reducing nitrification.

[021] In a preferred embodiment, said compound of formula I, as defined above, is used in combination with a fertilizer to reduce nitrification. In another specific embodiment, said compound of formula I, as defined above, is used to reduce nitrification in combination with a fertilizer in the form of an agrochemical mixture, as mentioned above. In a further preferred embodiment, said reduction of nitrification, as mentioned above, occurs in or on a plant, in the root zone of a plant, in or on soil or soil substitutes and/or at the site where a plant is growing or is intended to grow.

[022] In another aspect, the present invention relates to a method for reducing nitrification, comprising treating a plant growing in soil or soil substitutes and/or the site or soil or soil substitutes where the plant is growing or is intended to grow, with at least one compound of formula I as defined above, or with an agrochemical composition as defined above. In a preferred embodiment of the method, the plant and/or the site or soil or soil substitutes where the plant is growing or is intended to grow is additionally supplied with a fertilizer. In a further preferred embodiment of the method, the application of the nitrification inhibitor, i.e. the compound of formula I, and said fertilizer is carried out simultaneously or with a time lag. In a particularly preferred embodiment, said time lag is an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks. In case of application with a time lag, the nitrification inhibitor can be applied first and then the fertilizer. In another preferred embodiment of the method, in a first step, the nitrification inhibitor as defined above is applied to seeds, to a plant and/or to the site where the plant is growing or is intended to grow, and in a second step, the fertilizer is applied to a plant and/or to the site where the plant is growing or is intended to grow, wherein the application of said nitrification inhibitor in the first step and the fertilizer in the second step is carried out with a time lag of at least 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 1 week, 2 weeks or 3 weeks. In other embodiments of application with a time lag, a fertilizer may be applied first and then the nitrification inhibitor as defined above may be applied. In another preferred embodiment of the method, in a first step, a fertilizer is applied to a plant and/or the site where the plant is growing or is intended to grow and, in a second step, the nitrification inhibitor as defined above is applied to seeds, to a plant and/or the site where the plant is growing or is intended to grow, wherein the application of said fertilizer in the first step and said nitrification inhibitor in the second step is carried out with a time lag of at least 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 1 week, 2 weeks or 3 weeks.

[023] In another aspect, the present invention relates to a method for treating a fertilizer, comprising applying a nitrification inhibitor as defined above; or to a method for treating a composition as defined above, comprising applying a nitrification inhibitor as defined above.

[024] In a preferred embodiment of the use, agrochemical mixture or method of the invention, said fertilizer is a solid or liquid inorganic fertilizer containing ammonium, such as NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; a solid or liquid organic fertilizer, such as liquid fertilizer, semi-liquid fertilizer, biogas fertilizer, stable fertilizer and straw fertilizer, worm humus, compost fertilizer, seaweed or guano; or a urea-containing fertilizer, such as urea, urea formaldehyde, anhydrous ammonium, urea-ammonium nitrate (UAN) solution, urea-sulfur, urea-based NPK fertilizers or urea-ammonium sulfate.

[025] In another preferred embodiment of the use or method of the invention, said plant is an agricultural plant, such as wheat, barley, oats, rye, soybean, corn, potato, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice or a vegetable such as spinach, lettuce, asparagus or cabbage; or sorghum; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or genetically modified form.

[026] Compounds of formula I can be prepared by standard organic chemistry procedures. Suitable methods for the preparation of 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.

[027] The OR1 group can be introduced by selecting suitable starting materials for the formation of the pyrazole ring.

[028] A general method for the synthesis of 3-alkoxypyrazoles comprises the reaction between hydrazine hydrochloride and various e-ketoesters as described by, for example: a) Sadrine Guillou, Frédéric J. Bonhomme, Yves L. Janin, Synthesis 2008, 3504-3508; or b) in WO 2010/015657 A2 and as shown below:

[029] RA and RB may be hydrogen or may have any of the meanings given above for R2.

[030] Mazaahir Kidwai, Arti Jain, Roona Poddar, Journal of Organometallic Chemistry, 696 (2011) 1939-1944, showed that N-substituted 3-alkoxypyrazoles are obtained directly if in the above reaction N-substituted hydrazine derivatives are used instead of hydrazine.

[031] Furthermore, the 3-alkoxy group can be introduced by alkylation of a suitable hydroxypyrazole derivative as described by, for example, a) D. Piomelli et al., Synthesis 2016, 2739-2756, or b) Sandrine Guillou, Yves L. Janin, Chem. Eur. J. 2010, 16, 4669 - 4677.

[032] Several methods for synthesizing pyrazoles having the alkoxy group at position 4 have been described by William F. Vernier, Laurent Gomez, Tetrahedron Letters 2017, 4587-4590.

[033] If RN is, for example, C1-C6 alkyl, the substituent RN can be introduced by reacting a compound of formula II with a compound of formula III, where LG represents a leaving group, according to the following scheme.

[034] For example, various RN-LG alkylating or acylating reagents can be used in analogy to the N-methylation of 3-methoxy-4-nitro-1H-pyrazole with methyl iodide, which affords 1-methyl-3-methoxy-4-nitro-1H-pyrazole as described in WO 2009/153589 A1 or in WO 2011/048082 A1.

[035] Introduction of a CH2OH group as RN can be accomplished by reacting pyrazole with formaldehyde, as described by Simona Lupsor, Mircea Iovu, and Florin Aonofriesei, Med. Chem. Res. 2012, 3035-3042.

[036] Similarly, a Michael addition can be performed with a maleic acid derivative forming the RN substituent.

[037] Methods for the preparation of pyrazole compounds, wherein RN is, for example, a formamide, are described in DE 10 2011 120 098 A1 and WO 2013/079197 A1.

[038] It should be understood that prior to the introduction of the RN substituent, different tautomers may be formed, resulting in the formation of a mixture of isomers after the introduction of the RN substituent. In certain preferred embodiments of the invention, such mixtures of isomers may be used as nitrification inhibitors.

[039] The R2 substituent can be introduced by standard reactions, including aromatic substitution reactions, or by selecting suitable starting materials for the formation of the pyrazole ring.

[040] Before describing in detail exemplary embodiments of the present invention, important definitions for understanding the present invention are given.

[041] As used in this specification and in the appended claims, the singular forms of “a” and “an” also include their respective plurals, unless the context clearly indicates otherwise. In the context of the present invention, the terms “about” and “approximately” denote a range of precision that one skilled in the art will understand to still ensure the technical effect of the feature in question. The term normally 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 as a preferred embodiment of the term “comprising”. If hereinafter a group is defined to comprise at least a certain number of embodiments, this is intended to also encompass a group that preferably consists only of these embodiments. Furthermore, the terms “first,” “second,” “third” or “(a),” “(b),” “(c),” “(d),” etc. and the like in the description and claims are used to distinguish between similar elements and not necessarily to describe a sequential or chronological order. It is to be understood that the terms so used are interchangeable in appropriate circumstances and that the embodiments of the invention described herein are capable of functioning in sequences other than those described or illustrated herein. In the case of the terms “first,” “second,” “third” or “(a),” “(b),” “(c),” “(d),” “i,” “ii,” etc., relating to the steps of a method or to the use or assay, there is no coherence of time or time interval between the steps, that is, the steps may be performed 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 patent application as set forth above or below. It should be understood that this invention is not limited to the particular methodology, protocols, reagents, etc. described herein, as these may vary. It should also 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 which will be limited only by the appended claims. Unless otherwise defined, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art.

[042] The term “nitrification inhibitor” should be understood in this context as a chemical substance that slows down or stops the nitrification process. Nitrification inhibitors, therefore, slow down the natural transformation of ammonium into nitrate, inhibiting the activity of bacteria such as Nitrosomonas spp. The term “nitrification”, as used herein, should be understood as the biological oxidation of ammonia (NH3) or ammonium (NH4+) with oxygen to nitrite (NO2-) followed by the oxidation of these nitrites to nitrates (NO3-) by microorganisms. In addition to nitrate (NO3-), nitrous oxide is also produced through nitrification. Nitrification is an important step in the nitrogen cycle in soil. Inhibition of nitrification can also reduce N2O losses. The term nitrification inhibitor is considered equivalent to the use of such a compound to inhibit nitrification.

[043] The term “compound(s) according to the invention” or “compounds of formula I” comprises the compound(s) as defined herein, as well as a stereoisomer, salt, tautomer or N-oxide thereof. The term “compound(s) of the present invention” should be understood as equivalent to the term “compound(s) according to the invention”, therefore also comprising a stereoisomer, salt, tautomer or N-oxide thereof.

[044] Depending on the substitution pattern, the compounds according to the invention may have one or more chirality centers, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the individual pure enantiomers and the pure diastereomers of the compounds according to the invention, and mixtures thereof and the use according to the invention of the pure enantiomers or pure diastereomers of the compounds according to the invention or mixtures thereof. Suitable compounds according to the invention also include all possible geometric stereoisomers (cis / trans isomers) and mixtures thereof. The cis / trans isomers may be present in relation to an alkene group, carbon-nitrogen double bond or amide group. The term “stereoisomers(s)” encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one chiral center in the molecule, as well as geometric isomers (cis/trans isomers). The present invention relates to all possible stereoisomers of the compounds of formula I, i.e. to individual enantiomers or diastereomers as well as to mixtures thereof.

[045] 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 relates to amorphous and crystalline compounds of formula I, mixtures of different crystalline states of the respective compound I, as well as to amorphous or crystalline salts thereof.

[046] The salts of the compounds of formula I are preferably agriculturally acceptable salts. They may be formed in a usual manner, for example 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 especially encompass 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. Useful acid addition salt anions are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and, preferably, phosphate and the anions of C1-C4 alkanoic acids, preferably formate, acetate, propionate and butyrate. They may preferably be formed by reacting a compound of formula I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

[047] The term “N-oxide” includes any compound of formula I in which a tertiary nitrogen atom, for example the nitrogen atom of pyridine, is oxidized to an N-oxide moiety.

[048] Tautomers of the compounds of formula I may be present if, for example, any of the substituents on the aromatic ring have tautomeric forms. Preferred tautomers include keto-enol tautomers.

[049] The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual members of the group. The sulfix Cn-Cm indicates in each case the possible number of carbon atoms in the group.

[050] The term “halogen” denotes, in each case, fluorine, bromine, chlorine or iodine, in particular, fluorine, chlorine or bromine.

[051] The term “alkyl” as used herein denotes in each case a straight or branched chain alkyl group normally having from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms. Preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl and 2,2-dimethylpropyl. Methyl, ethyl, n-propyl and isopropyl are particularly preferred.

[052] The term “haloalkyl” as used herein denotes in each case a straight or branched chain alkyl group generally having from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, especially 1 or 2 carbon atoms, in which the hydrogen atoms of this group are partially or fully replaced by halogen atoms. Preferred haloalkyl moieties are selected from C1-C4 haloalkyl, more preferably from C1-C3 haloalkyl or C1C2 haloalkyl, in particular from C1-C2 fluoroalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl and the like. Trifluoromethyl is particularly preferred according to the invention.

[053] The term “alkoxy” as used herein denotes in each case a straight or branched chain alkyl group which is attached via an oxygen group, generally having from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, especially 1 or 2 carbon atoms. Examples of alkoxy groups are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert-butyloxy and the like.

[054] The term “haloalkoxy”, as used in this document, denotes, in each case, a straight or branched chain alkoxy group generally having from 1 to 4 carbon atoms, preferably from 1 to 3 carbon atoms, especially 1 or 2 carbon atoms, in which the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms. Preferred haloalkoxy moieties include C1-C4 haloalkoxy, in particular C1-C2 fluoroalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoro-ethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and the like.

[055] The term "alkenyl" as used herein denotes in each case an at least individually unsaturated hydrocarbon radical, that is, a hydrocarbon radical having at least one carbon-carbon double bond, generally having 2 to 4 carbon atoms, preferably 2 or 3 carbon atoms, for example, vinyl, allyl (2-propen-1-yl), 1-propen-1-yl, 2-propen-2-yl, methallyl (2-methylprop-2-en-1-yl), 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl, 3-penten-1-yl, 4-penten-1-yl, 1-methylbut-2-en-1-yl, 2-ethylprop-2-en-1-yl and the like.

[056] The term "alkynyl" as used herein denotes in each case a hydrocarbon radical having at least one carbon-carbon triple bond and normally having 2 to 4, preferably 2 or 3 carbon atoms or 3 or 4 carbon atoms, for example, ethynyl, propargyl (2-propyn-1-yl, also known as prop-2-yn-1-yl), 1-propyn-1-yl (also known as prop-1-yn-1-yl), 1-methylprop-2-yn-1-yl, 2-butyn-1-yl, 3-butyn-1-yl, 1-pentyn-1-yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 1-methylbut-2-yn-1-yl, 1-ethylprop-2-yn-1-yl and the like. A preferred alkynyl group according to the invention is ethynyl.

[057] The term “phenylalkyl” as used herein denotes a phenyl group, which is bonded via an alkyl group, preferably a C1-C2 alkyl group, in particular a methyl (= phenylmethyl) group, to the remainder of the molecule. The most preferred phenylalkyl group is benzyl.

[058] The term “cycloalkyl”, as used herein and in the cycloalkyl portions of cycloalkoxy and cycloalkylthio, denotes, in each case, a monocyclic cycloaliphatic radical having usually from 3 to 10 or from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl and, preferably, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[059] The term “alkylcarbonyl” refers to an alkyl group, as defined above, that is bonded via the carbon atom of a carbonyl group (C=O) to the remainder of the molecule.

[060] The term “alkylcarboxy” as used herein refers to a straight or branched chain saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= C1-C4 alkylcarboxy), preferably 1 to 3 carbon atoms, which is bonded through the carboxyl group at any position in the alkyl group.

[061] The term “alkylthio” “(alkylsulfanyl: alkyl-S-)”, as used herein, refers to a straight or branched chain saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= C1-C4 alkylthio), more preferably 1 to 3 carbon atoms, which is bonded via a sulfur atom.

[062] The term “alkylsulfonyl” (alkyl-S(=O)2-), as used herein, refers to a straight or branched chain saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= C1-C4 alkylsulfonyl), preferably 1 to 3 carbon atoms, which is bonded through the sulfur atom of the sulfonyl group at any position in the alkyl group.

[063] As set out above, the present invention relates, in one aspect, to the use of an N-functionalized alkoxy pyrazole compound of formula I: or a salt, stereoisomer, tautomer or N-oxide thereof, as a nitrification inhibitor; wherein: - R1 is H, C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, CHRaC(=O)ORb, CHRaC(=O)NRbRc or phenyl, wherein said phenyl group is unsubstituted or substituted by one or more same or different Rx substituents; - R2 is halogen, C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, propargyl or phenyl, wherein said phenyl group is unsubstituted or substituted by one or more same or different Rx substituents; - RN is C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, propargyl or phenyl, wherein said groups are unsubstituted or substituted by one or more same or different Ry substituents; CHRaC(=O)ORb, CHRaC(=O)NRbRc, CH(C(=O)ORb)CH2(C(=O)ORb); C(=O)Rd, C(=O)ORb, C(=O)NRbRc, CHRaORb or CHRaNRe(C=O)Rf; and where: - Ra is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C8 cycloalkyl, phenyl or phenyl-C1-C2 alkyl; - Rb is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C8 cycloalkyl, phenyl or phenyl-C1-C2 alkyl; - Rc is H, C1-C4 alkyl, C1-C4 haloalkyl or phenyl; - Rd is H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, phenyl or phenyl-C1-C2 alkyl, wherein these groups are unsubstituted or substituted by a COOH group; - Re is H, C1-C4 alkyl, C3-C8 cycloalkyl or C6-C10 aryl; - Rf is H or C1-C4 alkyl; - Rx is halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; - Ry is halogen, CN, OH, NO2, COOH, NRbRc, NRb(C=O)Rf, C(=O)NRbRc, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylcarbonyl, C1-C4 alkylcarboxy, C1-C4 alkylthio, C1-C4 alkylsulfonyl and S(O)2NRbRc; and - n is 0, 1 or 2.

[064] It should be understood that if n is 2, two substituents R2 are present which are independently selected from the group of substituents defined above for R2.

[065] Preferred embodiments with respect to compounds of formula I, which are relevant to all aspects of the invention, are defined below.

[066] In one embodiment of the invention, the compound of formula I: is a compound of any of the following formulas I.1, I.2 or I.3.

[067] For compounds of formulae I.1, I.2 or I.3, it is preferred that n is 0 or 1, i.e. that R2 is absent or only one R2 is present.

[068] It should be understood that, depending on the synthesis of the compound of formula I, a mixture of, for example, a compound of formula I.1 and a compound of formula I.3 may also be present due to tautomerization prior to the step of introducing the N-substituent RN. Therefore, the compound of formula I may, in certain embodiments, also be present as a mixture of a compound of formula I.1 and a compound of formula I.3. Furthermore, mixtures of compounds of formula I.2 may be obtained, if at least one substituent R2 is present.

[069] Furthermore, it should be understood that, depending on the presence or absence of the substituent R2 and its position, different structures may be preferred with respect to compounds of formula I.

[070] Accordingly, the compound of formula I, in particular the compound of formula I.1, is, in a particularly preferred embodiment, a compound of any one of formulas I.1(i), I.1(ii) or I.1(iii) as illustrated below.

[071] In another particularly preferred embodiment, the compound of formula I, in particular the compound of formula I.2, is a compound of any one of formulas I.2(i), I.2(ii) or I.2(iii) as illustrated below.

[072] In another particularly preferred embodiment, the compound of formula I, in particular the compound of formula I.3, is a compound of any one of formulas I.3(i), I.3(ii) or I.3(iii) as illustrated below.

[073] In another preferred embodiment of the invention, in the compound of formula I, and preferably in the compounds of formulas I.1, I.2 or I.3, and in particular in the compounds of formulas I.1(i), I.1(ii), or I.1(iii), or in the compounds of formulas I.2(i), I.2(ii) or I.2(iii), or in the compounds of formulas I.3(i), I.3(ii) or I.3(iii), R1 is H, C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, CHRaC(=O)ORb, CHRaC(=O)NRbRc or phenyl, wherein said phenyl group is unsubstituted or substituted by one or more same or different substituents Rx; and R2, if present, is halogen, C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, propargyl or phenyl, wherein said phenyl group is unsubstituted or substituted by one or more same or different substituents Rx; wherein: - Ra, Rb, Rc and Rx are as defined above; - and especially preferably - R1 is C1-C6 alkyl, benzyl, allyl; and - R2, if present, is C1-C3 alkyl or phenyl.

[074] In relation to the above preferred embodiment, the meaning of RN corresponds to the meaning given above in relation to compounds of formula I.

[075] Thus, with respect to compounds of formulae I.1, I.2 or I.3, as defined above, it is particularly preferred that R2, if present, is C1-C3 alkyl or phenyl, and R1 is C1-C6 alkyl, benzyl, allyl.

[076] According to a preferred embodiment of the invention, the compound of formula I is a compound of formula I.1, wherein n is 0 or 1, and R2, if present, is C1-C3 alkyl or phenyl, and R1 is C1-C6 alkyl, benzyl, allyl.

[077] According to a preferred embodiment of the invention, the compound of formula I is a compound of formula I.2, wherein n is 0 or 1, and R2, if present, is C1-C3 alkyl or phenyl, and R1 is C1-C6 alkyl, benzyl, allyl.

[078] According to a preferred embodiment of the invention, the compound of formula I is a compound of formula I.3, wherein n is 0 or 1 and R2, if present, is C1-C3 alkyl or phenyl, and R1 is C1-C6 alkyl, benzyl, allyl.

[079] In relation to the above preferred embodiments, the meaning of RN corresponds to the meaning given above in relation to compounds of formula I.

[080] According to a particularly preferred embodiment, the compound of formula I is a compound of formula I.1(i), wherein R1 is C1-C6 alkyl, benzyl, allyl.

[081] According to a particularly preferred embodiment, the compound of formula I is a compound of formula I.1(ii), wherein R2 is C1-C3 alkyl or phenyl, and wherein R1 is C1-C6 alkyl, benzyl, allyl.

[082] According to a particularly preferred embodiment, the compound of formula I is a compound of formula I.1(iii), wherein R2 is C1-C3 alkyl or phenyl, and wherein R1 is C1-C6 alkyl, benzyl, allyl.

[083] According to a particularly preferred embodiment, the compound of formula I is a compound of formula I.2(i), wherein R1 is C1-C6 alkyl, benzyl, allyl.

[084] According to a particularly preferred embodiment, the compound of formula I is a compound of formula I.2(ii), wherein R2 is C1-C3 alkyl or phenyl, and wherein R1 is C1-C6 alkyl, benzyl, allyl.

[085] According to a particularly preferred embodiment, the compound of formula I is a compound of formula I.2(iii), wherein R2 is C1-C3 alkyl or phenyl, and wherein R1 is C1-C6 alkyl, benzyl, allyl.

[086] According to a particularly preferred embodiment, the compound of formula I is a compound of formula I.3(i), wherein R1 is C1-C6 alkyl, benzyl, allyl.

[087] According to a particularly preferred embodiment, the compound of formula I is a compound of formula I.3(ii), wherein R2 is C1-C3 alkyl or phenyl, and wherein R1 is C1-C6 alkyl, benzyl, allyl.

[088] According to a particularly preferred embodiment, the compound of formula I is a compound of formula I.3(iii), wherein R2 is C1-C3 alkyl or phenyl, and wherein R1 is C1-C6 alkyl, benzyl, allyl.

[089] In relation to the above particularly preferred embodiments, the meaning of RN corresponds to the meaning given above in relation to the compounds of formula I.

[090] In another embodiment of the invention, in the compound of formula I, and preferably in the compounds of formulas I.1, I.2 or I.3, and particularly in the compounds of formulas I.1(i), I.1(ii), or I.1(iii), or in the compounds of formulas I.2(i), I.2(ii) or I.2(iii), or in the compounds of formulas I.3(i), I.3(ii) or I.3(iii), RN is C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, propargyl or phenyl, wherein said groups are unsubstituted or substituted by one or more same or different Ry substituents; CHRaC(=O)ORb, CHRaC(=O)NRbRc, CH(C(=O)ORb)CH2(C(=O)ORb); C(=O)Rd, C(=O)ORb, C(=O)NRbRc, CHRaORb or CHRaNRe(C=O)Rf; where: - Ra is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C8 cycloalkyl, phenyl or phenyl-C1-C2 alkyl; - Rb is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C8 cycloalkyl, phenyl or phenyl-C1-C2 alkyl; - Rc is H, C1-C4 alkyl, C1-C4 haloalkyl or phenyl; - Rd is H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, phenyl or phenyl-C1-C2 alkyl, wherein these groups are unsubstituted or substituted by a COOH group; - Re is H, C1-C4 alkyl, C3-C8 cycloalkyl or C6-C10 aryl; - Rf is H or C1-C4 alkyl; - Ry is halogen, CN, OH, NO2, COOH, NRbRc, NRb(C=O)Rf, C(=O)NRbRc, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylcarbonyl, C1-C4 alkylcarboxy, C1-C4 alkylthio, C1-C4 alkylsulfonyl and S(O)2NRbRc; and, preferably, - RN is C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl, propargyl or phenyl, wherein said groups are unsubstituted or substituted by one or more identical or different Ry substituents; CHRaC(=O)ORb, CHRaC(=O)NRbRc, CH(C(=O)ORb)CH2(C(=O)ORb); C(=O)Rd, C(=O)ORb, C(=O)NRbRc, CHRaORb or CHRaNRe(C=O)Rf; where: - Ra is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C8 cycloalkyl, phenyl or phenyl-C1-C2 alkyl; - Rb is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C8 cycloalkyl, phenyl or phenyl-C1-C2 alkyl; - Rc is H, C1-C4 alkyl, C1-C4 haloalkyl or phenyl; - Rd is H or C1-C4 alkyl; - Re is H, or C1-C4 alkyl; - Rf is H or C1-C4 alkyl; - Ry is halogen, CN, OH, NO2, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy; and especially preferably, - RN is C(=O)Rd, CHRaC(=O)ORb, CHRaC(=O)NRbRc, CH(C(=O)ORb)CH2(C(=O)ORb) or CHRaNRe(C=O)Rf; where: - Ra is H; - Rb is H or C1-C4 alkyl; - Rc is H or C1-C4 alkyl; - Rd is C1-C3 alkyl; - Re is H; and - Rf is H or CH3.

[091] In a preferred embodiment of the invention, in the compound of formula I: - RN is C(=O)Rd, wherein, preferably, Rd is C1-C3 alkyl.

[092] Such compounds are referred to as compounds of formula IA:

[093] In another preferred embodiment of the invention, in the compound of formula I: - RN is CHRaC(=O)ORb, wherein, preferably, Ra is H, and Rb is H or C1-C4 alkyl.

[094] Such compounds are referred to as compounds of formula IB:

[095] In another preferred embodiment of the invention, in the compound of formula I: - RN is CHRaC(=O)NRbRc, wherein, preferably, Ra is H, and Rb is H or C1-C4 alkyl, and Rc is H or C1-C4 alkyl.

[096] Such compounds are referred to as compounds of formula IC:

[097] In another preferred embodiment of the invention, in the compound of formula I: - RN is CH(C(=O)ORb)CH2(C(=O)ORb), wherein, preferably, Rb is H or C1-C4 alkyl. In this context, the two Rb substituents may be identical or different from each other.

[098] Such compounds are referred to as compounds of formula ID:

[099] In another preferred embodiment of the invention, in the compound of formula I: - RN is CHRaNRe(C=O)Rf, wherein, preferably, Ra is H, and Re is H, and Rf is H or CH3.

[0100] Such compounds are referred to as compounds of formula IE:

[0101] It should be understood that the above preferences regarding R1 and R2 also apply to the above formulas I.A, I.B, I.C, I.D and I.E.

[0102] Thus, particularly preferred compounds for use according to the invention are compounds of formula I.1.A, I.1.B, I.1.C, I.1.D or I.1.E, which are represented below:

[0103] The meanings of R1 and R2 preferably correspond to the meanings given above in relation to the compounds of formula I, in particular the compounds of formula I.1. Furthermore, it is preferred that n is 0 or 1. If n is 1, each of the positions on the pyrazole ring may be held by R2 as indicated in relation to the compounds of formulae I.1(ii) or I.1(iii). Furthermore, the meanings of Ra, Rb, Rc, Rd, Re and Rf preferably correspond to the meanings given above in relation to the compounds of formulae I.A, I.B, I.C, I.D and I.E. It should be understood that if two Rb substituents are present, they may be identical or different from each other.

[0104] Furthermore, particularly preferred compounds for use according to the invention are compounds of formula I.2.A, I.2.B, I.2.C, I.2.D or I.2.E, which are represented below:

[0105] The meanings of R1 and R2 preferably correspond to the meanings given above in relation to the compounds of formula I, in particular the compounds of formula I.2. Furthermore, it is preferred that n is 0 or 1. If n is 1, each of the positions on the pyrazole ring may be held by R2 as indicated in relation to the compounds of formulae I.2(ii), or I.2(iii). Furthermore, the meanings of Ra, Rb, Rc, Rd, Re and Rf preferably correspond to the meanings given above in relation to the compounds of formulae I.A, I.B, I.C, I.D and I.E. It should be understood that if two Rb substituents are present, they may be identical or different from each other.

[0106] Furthermore, particularly preferred compounds for use according to the invention are compounds of formula I.3.A, I.3.B, I.3.C, I.3.D or I.3.E, which are represented below:

[0107]The meanings of R1 and R2 preferably correspond to the meanings given above in relation to the compounds of formula I, in particular the compounds of formula I.3. Furthermore, it is preferred that n is 0 or 1. If n is 1, each of the positions on the pyrazole ring may be held by R2 as indicated in relation to the compounds of formulae I.3(ii), or I.3(iii). Furthermore, the meanings of Ra, Rb, Rc, Rd, Re and Rf preferably correspond to the meanings given above in relation to the compounds of formulae I.A, I.B, I.C, I.D and I.E. It should be understood that if two Rb substituents are present, they may be identical or different from each other.

[0108]Thus, particularly preferred compounds of formula I, in particular compounds of formula I.1, I.2 or I.3, are compiled in the embodiments below. EMBODIMENT 1

[0109]Compounds of formula I.1(i), wherein RN is C(=O)Rd and corresponds, in each case, to a row of Table A(i). EMBODIMENT 2

[0110]Compounds of formula I.2(i), wherein RN is C(=O)Rd and corresponds, in each case, to a row of Table A(i). EMBODIMENT 3

[0111]Compounds of formula I.3(i), where RN is C(=O)Rd and corresponds, in each case, to a row of Table A(i): TABLE A(I)

[0112]The meaning of R1 in relation to embodiments 1 to 3 preferably corresponds to the meaning given above in relation to compounds of formula I, in particular compounds of formula I.1, I.2 or I.3. EMBODIMENT 4

[0113]Compounds of formula I.1(i), wherein RN is CHRaC(=O)ORb and corresponds, in each case, to a row of Table A(ii). EMBODIMENT 5

[0114]Compounds of formula I.2(i), wherein RN is CHRaC(=O)ORb and corresponds in each case to a row of Table A(ii). EMBODIMENT 6

[0115]Compounds of formula I.3(i), where RN is CHRaC(=O)ORb and corresponds, in each case, to a row of Table A(ii): TABLE A(II)

[0116] The meaning of R1 in relation to embodiments 4 to 6 preferably corresponds to the meaning given above in relation to compounds of formula I, in particular compounds of formula I.1, I.2 or I.3. EMBODIMENT 7

[0117] Compounds of formula I.1(i), wherein RN is CHRaC(=O)NRbRc and corresponds in each case to a row of Table A(iii). EMBODIMENT 8

[0118] Compounds of formula I.2(i), wherein RN is CHRaC(=O)NRbRc and corresponds in each case to a row of Table A(iii). EMBODIMENT 9

[0119] Compounds of formula I.3(i), where RN is CHRaC(=O)NRbRc and corresponds, in each case, to a row in Table A(iii):

[0120]

[0121] The meaning of R1 in relation to embodiments 7 to 9 preferably corresponds to the meaning given above in relation to compounds of formula I, in particular compounds of formula I.1, I.2 or I.3. EMBODIMENT 10

[0122] Compounds of formula I.1(i), wherein RN is CH(C(=O)ORb)CH2(C(=O)ORb) and corresponds, in each case, to a row of Table A(iv). EMBODIMENT 11

[0123] Compounds of formula I.2(i), wherein RN is CH(C(=O)ORb)CH2(C(=O)ORb) and corresponds, in each case, to a row of Table A(iv). EMBODIMENT 12

[0124] Compounds of formula I.3(i), where RN is CH(C(=O)ORb)CH2(C(=O)ORb) and corresponds, in each case, to a row of Table A(iv): TABLE A(IV)

[0125] The meaning of R1 in relation to embodiments 10 to 12 preferably corresponds to the meaning given above in relation to compounds of formula I, in particular compounds of formula I.1, I.2 or I.3. EMBODIMENT 13

[0126] Compounds of formula I.1(i), wherein RN is CHRaNRe(C=O)Rf and corresponds, in each case, to a row of Table A(v). EMBODIMENT 14

[0127] Compounds of formula I.2(i), wherein RN is CHRaNRe(C=O)Rf and corresponds, in each case, to a row of Table A(v). EMBODIMENT 15

[0128] Compounds of formula I.3(i), where RN is CHRaNRe(C=O)Rf and corresponds, in each case, to a row of Table A(v): TABLE A(V)

[0129] The meaning of R1 in relation to embodiments 13 to 15 preferably corresponds to the meaning given above in relation to compounds of formula I, in particular compounds of formula I.1, I.2 or I.3.

[0130] With regard to the methods, uses, compositions and mixtures of the invention, and in particular with a view to their use, preference is given to the compounds of formula I compiled in the tables below. TABLE 1

[0131] Compounds of formula I.1(i) in which R2 is absent and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 2

[0132] Compounds of formula I.2(i) in which R2 is absent and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 3

[0133] Compounds of formula I.3(i) in which R2 is absent and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 4

[0134] Compounds of formula I.1(ii), wherein R2 is CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 5

[0135] Compounds of formula I.1(iii), wherein R2 is CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 6

[0136] Compounds of formula I.2(ii), wherein R2 is CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 7

[0137] Compounds of formula I.2(iii), wherein R2 is CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 8

[0138] Compounds of formula I.3(ii) in which R2 is CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 9

[0139] Compounds of formula I.3(iii) in which R2 is CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 10

[0140] Compounds of formula I.1(ii), wherein R2 is CH2CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 11

[0141] Compounds of formula I.1(iii), wherein R2 is CH2CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 12

[0142] Compounds of formula I.2(ii), wherein R2 is CH2CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 13

[0143] Compounds of formula I.2(iii), wherein R2 is CH2CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 14

[0144] Compounds of formula I.3(ii) in which R2 is CH2CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 15

[0145] Compounds of formula I.3(iii) in which R2 is CH2CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 16

[0146] Compounds of formula I.1(ii), wherein R2 is CH2CH2CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 17

[0147] Compounds of formula I.1(ii), wherein R2 is CH(CH3)2 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 18

[0148] Compounds of formula I.1(iii) in which R2 is CH2CH2CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 19

[0149] Compounds of formula I.1(iii), wherein R2 is CH(CH3)2 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 20

[0150] Compounds of formula I.2(ii), wherein R2 is CH2CH2CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 21

[0151] Compounds of formula I.2(ii), wherein R2 is CH(CH3)2 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 22

[0152] Compounds of formula I.2(iii), wherein R2 is CH2CH2CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 23

[0153] Compounds of formula I.2(iii), wherein R2 is CH(CH3)2 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 24

[0154] Compounds of formula I.3(ii) in which R2 is CH2CH2CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 25

[0155] Compounds of formula I.3(ii) in which R2 is CH(CH3)2 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 26

[0156] Compounds of formula I.3(iii) in which R2 is CH2CH2CH3 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 27

[0157] Compounds of formula I.3(iii) in which R2 is CH(CH3)2 and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 28

[0158] Compounds of formula I.1(ii), wherein R2 is phenyl and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 29

[0159] Compounds of formula I.1(iii) in which R2 is phenyl and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 30

[0160] Compounds of formula I.2(ii), wherein R2 is phenyl and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 31

[0161] Compounds of formula I.2(iii), wherein R2 is phenyl and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 32

[0162] Compounds of formula I.3(ii) in which R2 is phenyl and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE 33

[0163] Compounds of formula I.3(iii) in which R2 is phenyl and the combination of RN (C(=O)Rd) and R1 corresponds in each case to a row in Table B. TABLE B TABLE 34

[0164] Compounds of formula I.1(i) in which R2 is absent and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 35

[0165] Compounds of formula I.2(i) in which R2 is absent and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 36

[0166] Compounds of formula I.3(i) in which R2 is absent and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 37

[0167] Compounds of formula I.1(ii) in which R2 is CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 38

[0168] Compounds of formula I.1(iii) in which R2 is CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 39

[0169] Compounds of formula I.2(ii) in which R2 is CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 40

[0170] Compounds of formula I.2(iii) in which R2 is CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 41

[0171] Compounds of formula I.3(ii) in which R2 is CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 42

[0172] Compounds of formula I.3(iii) in which R2 is CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 43

[0173] Compounds of formula I.1(ii) in which R2 is CH2CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 44

[0174] Compounds of formula I.1(iii) in which R2 is CH2CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 45

[0175] Compounds of formula I.2(ii) in which R2 is CH2CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 46

[0176] Compounds of formula I.2(iii) in which R2 is CH2CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 47

[0177] Compounds of formula I.3(ii) in which R2 is CH2CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 48

[0178] Compounds of formula I.3(iii) in which R2 is CH2CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 49

[0179] Compounds of formula I.1(ii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 50

[0180] Compounds of formula I.1(ii), wherein R2 is CH(CH3)2 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 51

[0181] Compounds of formula I.1(iii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 52

[0182] Compounds of formula I.1(iii) wherein R2 is CH(CH3)2 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 53

[0183] Compounds of formula I.2(ii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 54

[0184] Compounds of formula I.2(ii), wherein R2 is CH(CH3)2 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 55

[0185] Compounds of formula I.2(iii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 56

[0186] Compounds of formula I.2(iii), wherein R2 is CH(CH3)2 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 57

[0187] Compounds of formula I.3(ii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 58

[0188] Compounds of formula I.3(ii) in which R2 is CH(CH3)2 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 59

[0189] Compounds of formula I.3(iii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 60

[0190] Compounds of formula I.3(iii) in which R2 is CH(CH3)2 and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 61

[0191] Compounds of formula I.1(ii) in which R2 is phenyl and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 62

[0192] Compounds of formula I.1(iii) in which R2 is phenyl and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 63

[0193] Compounds of formula I.2(ii), wherein R2 is phenyl and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 64

[0194] Compounds of formula I.2(iii), wherein R2 is phenyl and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 65

[0195] Compounds of formula I.3(ii) in which R2 is phenyl and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE 66

[0196] Compounds of formula I.3(iii), wherein R2 is phenyl and the combination of RN (CHRaC(=O)ORb) and R1 corresponds in each case to a row in Table C. TABLE C TABLE 67

[0197] Compounds of formula I.1(i) in which R2 is absent and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 68

[0198] Compounds of formula I.2(i) in which R2 is absent and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D.. TABLE 69

[0199] Compounds of formula I.3(i) in which R2 is absent and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 70

[0200] Compounds of formula I.1(ii), wherein R2 is CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 71

[0201] Compounds of formula I.1(iii) in which R2 is CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 72

[0202] Compounds of formula I.2(ii), wherein R2 is CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 73

[0203] Compounds of formula I.2(iii) in which R2 is CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 74

[0204] Compounds of formula I.3(ii) in which R2 is CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 75

[0205] Compounds of formula I.3(iii) in which R2 is CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 76

[0206] Compounds of formula I.1(ii) in which R2 is CH2CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 77

[0207] Compounds of formula I.1(iii) in which R2 is CH2CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 78

[0208] Compounds of formula I.2(ii), wherein R2 is CH2CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 79

[0209] Compounds of formula I.2(iii) in which R2 is CH2CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 80

[0210] Compounds of formula I.3(ii) in which R2 is CH2CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 81

[0211] Compounds of formula I.3(iii) in which R2 is CH2CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 82

[0212] Compounds of formula I.1(ii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 83

[0213] Compounds of formula I.1(ii) wherein R2 is CH(CH3)2 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 84

[0214] Compounds of formula I.1(iii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 85

[0215] Compounds of formula I.1(iii) wherein R2 is CH(CH3)2 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 86

[0216] Compounds of formula I.2(ii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 87

[0217] Compounds of formula I.2(ii), wherein R2 is CH(CH3)2 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 88

[0218] Compounds of formula I.2(iii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 89

[0219] Compounds of formula I.2(iii), wherein R2 is CH(CH3)2 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 90

[0220] Compounds of formula I.3(ii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 91

[0221] Compounds of formula I.3(ii) in which R2 is CH(CH3)2 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 92

[0222] Compounds of formula I.3(iii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 93

[0223] Compounds of formula I.3(iii) in which R2 is CH(CH3)2 and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 94

[0224] Compounds of formula I.1(ii) in which R2 is phenyl and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 95

[0225] Compounds of formula I.1(iii) in which R2 is phenyl and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 96

[0226] Compounds of formula I.2(ii) in which R2 is phenyl and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 97

[0227] Compounds of formula I.2(iii) in which R2 is phenyl and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 98

[0228] Compounds of formula I.3(ii) in which R2 is phenyl and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE 99

[0229] Compounds of formula I.3(iii), wherein R2 is phenyl and the combination of RN (CHRaC(=O)NRbRc) and R1 corresponds in each case to a row in Table D. TABLE D TABLE 100

[0230] Compounds of formula I.1(i) in which R2 is absent and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 101

[0231] Compounds of formula I.2(i) in which R2 is absent and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 102

[0232] Compounds of formula I.3(i) in which R2 is absent and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 103

[0233] Compounds of formula I.1(ii) in which R2 is CH3 and the combination of RN (CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 104

[0234] Compounds of formula I.1(iii) in which R2 is CH3 and the combination of RN (CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 105

[0235] Compounds of formula I.2(ii) in which R2 is CH3 and the combination of RN (CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 106

[0236] Compounds of formula I.2(iii) in which R2 is CH3 and the combination of RN (CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 107

[0237] Compounds of formula I.3(ii) in which R2 is CH3 and the combination of RN (CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 108

[0238] Compounds of formula I.3(iii) in which R2 is CH3 and the combination of RN (CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 109

[0239] Compounds of formula I.1(ii) in which R2 is CH2CH3 and the combination of RN (CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 110

[0240] Compounds of formula I.1(iii) wherein R2 is CH2CH3 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 111

[0241] Compounds of formula I.2(ii) in which R2 is CH2CH3 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 112

[0242] Compounds of formula I.2(iii) wherein R2 is CH2CH3 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 113

[0243] Compounds of formula I.3(ii) in which R2 is CH2CH3 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 114

[0244] Compounds of formula I.3(iii) in which R2 is CH2CH3 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 115

[0245] Compounds of formula I.1(ii) in which R2 is CH2CH2CH3 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 116

[0246] Compounds of formula I.1(ii) wherein R2 is CH(CH3)2 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 117

[0247] Compounds of formula I.1(iii) wherein R2 is CH2CH2CH3 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 118

[0248] Compounds of formula I.1(iii) wherein R2 is CH(CH3)2 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 119

[0249] Compounds of formula I.2(ii), wherein R2 is CH2CH2CH3 and the combination of RN (CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 120

[0250] Compounds of formula I.2(ii), wherein R2 is CH(CH3)2 and the combination of RN (CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 121

[0251] Compounds of formula I.2(iii) wherein R2 is CH2CH2CH3 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 122

[0252] Compounds of formula I.2(iii) wherein R2 is CH(CH3)2 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 123

[0253] Compounds of formula I.3(ii) in which R2 is CH2CH2CH3 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 124

[0254] Compounds of formula I.3(ii) wherein R2 is CH(CH3)2 and the combination of RN (CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 125

[0255] Compounds of formula I.3(iii) in which R2 is CH2CH2CH3 and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 126

[0256] Compounds of formula I.3(iii) in which R2 is CH(CH3)2 and the combination of RN (CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 127

[0257] Compounds of formula I.1(ii) in which R2 is phenyl and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 128

[0258] Compounds of formula I.1(iii) in which R2 is phenyl and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 129

[0259] Compounds of formula I.2(ii) in which R2 is phenyl and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 130

[0260] Compounds of formula I.2(iii) in which R2 is phenyl and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 131

[0261] Compounds of formula I.3(ii) in which R2 is phenyl and the combination of RN(CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE 132

[0262] Compounds of formula I.3(iii), wherein R2 is phenyl and the combination of RN (CH(C(=O)ORb)CH2(C(=O)ORb)) and R1 corresponds in each case to a row in Table E. TABLE E TABLE 133

[0263] Compounds of formula I.1(i) in which R2 is absent and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 134

[0264] Compounds of formula I.2(i) in which R2 is absent and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 135

[0265] Compounds of formula I.3(i) in which R2 is absent and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 136

[0266] Compounds of formula I.1(ii) in which R2 is CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 137

[0267] Compounds of formula I.1(iii) in which R2 is CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 138

[0268] Compounds of formula I.2(ii) in which R2 is CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 139

[0269] Compounds of formula I.2(iii) in which R2 is CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 140

[0270] Compounds of formula I.3(ii) in which R2 is CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 141

[0271] Compounds of formula I.3(iii) in which R2 is CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 142

[0272] Compounds of formula I.1(ii) in which R2 is CH2CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 143

[0273] Compounds of formula I.1(iii) in which R2 is CH2CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 144

[0274] Compounds of formula I.2(ii) in which R2 is CH2CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 145

[0275] Compounds of formula I.2(iii) in which R2 is CH2CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 146

[0276] Compounds of formula I.3(ii) in which R2 is CH2CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 147

[0277] Compounds of formula I.3(iii) in which R2 is CH2CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 148

[0278] Compounds of formula I.1(ii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 149

[0279] Compounds of formula I.1(ii) in which R2 is CH(CH3)2 and the combination of RN(CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 150 Compounds of formula I.1(iii) in which R2 is CH2CH2CH3 and the combination of RN(CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 151

[0280] Compounds of formula I.1(iii) in which R2 is CH(CH3)2 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 152

[0281] Compounds of formula I.2(ii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 153

[0282] Compounds of formula I.2(ii) wherein R2 is CH(CH3)2 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 154

[0283] Compounds of formula I.2(iii) wherein R2 is CH2CH2CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 155

[0284] Compounds of formula I.2(iii) wherein R2 is CH(CH3)2 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 156

[0285] Compounds of formula I.3(ii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 157

[0286] Compounds of formula I.3(ii) in which R2 is CH(CH3)2 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 158

[0287] Compounds of formula I.3(iii) in which R2 is CH2CH2CH3 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 159

[0288] Compounds of formula I.3(iii) in which R2 is CH(CH3)2 and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 160

[0289] Compounds of formula I.1(ii) in which R2 is phenyl and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 161

[0290] Compounds of formula I.1(iii) in which R2 is phenyl and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 162

[0291] Compounds of formula I.2(ii) in which R2 is phenyl and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 163

[0292] Compounds of formula I.2(iii) wherein R2 is phenyl and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 164

[0293] Compounds of formula I.3(ii) in which R2 is phenyl and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE 165

[0294] Compounds of formula I.3(iii) wherein R2 is phenyl and the combination of RN (CHRaNRe(C=O)Rf) and R1 corresponds in each case to a row in Table F. TABLE F

[0295] It has been found that the compounds as defined in the above tables are not only advantageous in terms of reducing nitrification, but also in view of the fact that they have advantageous properties, for example in terms of their low volatility and/or environmental safety. Furthermore, the compounds according to the present invention can be prepared economically.

[0296] It should be understood that combinations of the above compounds can also be used as nitrification inhibitors according to the present invention, in particular combinations of compounds, which are obtained as mixtures of isomers after the introduction of the N-substituent, as described above.

[0297] In relation to the methods, uses, compositions and mixtures of the invention, and in particular with a view to their use, the following preferred embodiments are additionally relevant.

[0298] In a central aspect, the present invention thus relates to the use of a compound of formula I, as defined herein, as a nitrification inhibitor, or to the use of a composition comprising said compound of formula I, as defined herein, for reducing nitrification. The compound of formula I or its derivatives or salts, as defined herein, in particular the compounds of formula I and/or their suitable salts or derivatives, as well as compositions comprising said compound of formula I or agrochemical mixtures comprising said compound of formula I, can be used to reduce nitrification.

[0299] The use may be based on the application of the nitrification inhibitor, agrochemical composition or mixture, as defined herein, to a plant growing in the soil and/or at the site where the plant is growing or is intended to grow, or the use may be based on the application of the nitrification inhibitor, agrochemical composition or mixture, as defined herein, to the soil where a plant is growing or is intended to grow or to soil substitutes. In specific embodiments, the nitrification inhibitor may be used to reduce nitrification in the absence of plants, for example as a preparatory activity for subsequent agricultural activity or to reduce nitrification in other technical areas that are not related to agriculture, for example for environmental purposes, water protection, energy production or the like. In specific embodiments, the nitrification inhibitor, or a composition comprising said nitrification inhibitor, according to the present invention, can be used for the reduction of nitrification in sewage water, slurry, manure or animal manure, for example, pig or cattle feces. For example, the nitrification inhibitor, or a composition comprising said nitrification inhibitor, according to the present invention, can be used for the reduction of nitrification in sewage plants, biogas plants, stables, liquid fertilizer tanks or containers, etc. Furthermore, the nitrification inhibitor, or a composition comprising said nitrification inhibitor, can be used in exhaust air systems, preferably in cowshed or stable exhaust air systems. Therefore, the present invention also relates to the use of compounds of formula I for treating exhaust air, preferably the exhaust air of stables and cowsheds. In other 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, for example in productive farming. Accordingly, the nitrification inhibitor or a composition comprising said nitrification inhibitor according to the present invention may be fed to an animal, for example a mammal, for example, together with suitable feed and thereby lead to a reduction of nitrification in the gastrointestinal tract of the animals, which in turn results in the reduction of emissions from the gastrointestinal tract. This activity, i.e. the feeding of the nitrification inhibitor or a composition comprising said nitrification inhibitor according to the present invention, may be repeated one to several times, for example every second, third, fourth, fifth, sixth, seventh day or every week, two weeks, three weeks or month, two months etc.

[0300] The use may further include the application of a nitrification inhibitor or its derivatives or salts, as defined herein above, in particular compounds of formula I and/or their suitable salts or derivatives, as well as compositions comprising said nitrification inhibitor or agrochemical mixtures comprising said nitrification inhibitor, as defined herein above, in environments, areas or zones where nitrification occurs or is assumed or expected to occur. Such environments, areas or zones may not comprise plants or soil. For example, the inhibitors may be used for inhibition of nitrification in laboratory environments, for example based on enzymatic reactions or the like. Use in greenhouses or similar indoor facilities is also envisaged.

[0301] The term “reduce nitrification” or “nitrification reduction” as used herein refers to a slowing down or stopping of nitrification processes, for example by slowing or eliminating the natural transformation of ammonium to nitrate. Such a reduction may be a complete or partial elimination of nitrification in the plant or location where the inhibitor or composition comprising said inhibitor is applied. For example, a partial elimination may result in a residual nitrification on or in the plant, or on or in the soil or soil substitutes where a plant grows or is intended to grow of about 90% to 1%, for example, 90%, 85%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10% or less than 10%, for example, 5% or less than 5% compared to a control situation in which the nitrification inhibitor is not used. In certain embodiments, a partial elimination may result in a residual nitrification on or in the plant, or on or in the soil or soil substitutes where a plant is grown or intended to be grown of below 1%, e.g., 0.5%, 0.1% or less compared to a control situation in which the nitrification inhibitor is not used.

[0302] The use of a nitrification inhibitor as defined herein above or a composition as defined herein to reduce nitrification may be a single use or may be a repeated use. As a single use, the nitrification inhibitor or corresponding compositions may be provided to their target sites, e.g., soil or site, or objects, e.g., plants, only once in a physiologically relevant time interval, e.g., once per year, or once every 2 to 5 years, or once during the life of a plant.

[0303] In other embodiments, the use may be repeated at least once per period of time, for example, the nitrification inhibitor, as defined herein above, or a composition, as defined herein, may be used to reduce nitrification at its target sites or objects twice 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 twice, or multiple times, i.e., that a repeat or multiple repeats of an application or treatment with a nitrification inhibitor may be anticipated. Such repeat may be 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or more frequent repeats of the use.

[0304] The nitrification inhibitor according to the present invention may be used in any suitable form. For example, it may be used as a coated or uncoated granule, in liquid or semi-liquid form, as a 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, fertilizers, additional water, coatings or any other ingredient.

[0305] The term “irrigation” as used herein refers to the watering of plants or the site or soil or soil substitutes 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.

[0306] In a further aspect, the invention relates to a composition for reducing nitrification comprising at least one nitrification inhibitor, wherein said nitrification inhibitor is a compound of formula I or a derivative, as defined herein above; and at least one carrier.

[0307] The term “composition for reducing nitrification”, as used herein, refers to a composition that is suitable, for example, comprises effective concentrations and amounts of ingredients, such as nitrification inhibitors, in particular compounds of formula I or derivatives, as defined herein, to reduce nitrification in any context or environment in which nitrification may occur. In one embodiment, nitrification may be reduced in or on or at the site of a plant. Typically, 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 plants and their environment, but may also include any other habitat of nitrifying bacteria or any location in which nitrification enzymatic activities may be found or may function in general, for example sewage facilities, biogas facilities, animal effluents from productive livestock, for example 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 tests known to the person skilled in the art. Such amounts and concentrations may be adjusted to the site, plant, soil, climatic conditions or any other suitable parameter that may influence nitrification processes.

[0308] A “vehicle”, as used herein, is a substance or composition that facilitates the delivery and/or release of the ingredients at the place or location of destination. The term includes, for example, agrochemical vehicles that facilitate the delivery and/or release of agrochemicals in their field of use, in particular on or into plants.

[0309] Examples of suitable carriers include solid carriers such as phytogels, or hydrogels, or mineral earths, for example, silicates, silica gel, talc, kaolins, limestone, lime, chalk, friable clay, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers such as, for example, a solid or liquid inorganic fertilizer containing ammonium, such as an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; a solid or liquid organic fertilizer, such as liquid fertilizer, semi-liquid fertilizer, stable fertilizer, biogas fertilizer and straw fertilizer, earthworm humus, compost fertilizer, seaweed or guano, or a fertilizer containing urea, such as urea, urea formaldehyde, anhydrous ammonium, urea-ammonium nitrate (UAN) solution, urea-sulfur, stabilized urea, urea- or urea-ammonium sulfate-based NPK fertilizers and products of vegetable origin, such as cereal flour, tree bark flour, wood flour and nutshell flour, cellulose powders and other solid carriers. Other suitable examples of carriers include fumed silica or precipitated silica, which can, for example, be used in solid formulations as a flow aid, anti-caking aid, grinding aid and as a vehicle for liquid active ingredients. Additional examples of suitable carriers are microparticles, e.g., microparticles that adhere to plant leaves and release their contents over a period of time. In specific embodiments, agrochemical carriers, such as composite gel microparticles that can be used to deliver plant protection actives, 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 adhesion agent on the surface, wherein the carrier granule adheres to the surface of plants, grasses and weeds, e.g., as disclosed in US 2007/0280981, can be used. In other specific embodiments, such carriers may include a specific, strongly binding molecule that ensures that the carrier adheres to the plant, seed and/or site where the plant is growing or intended to grow, until its contents are fully delivered. For example, the carrier may be or comprise cellulose binding domains (CBDs), which have been described as useful agents for binding molecular species to cellulose (see US 6,124,117); or direct fusions between a CBD and an enzyme; or a multifunctional fusion protein that may be used for delivery of encapsulated agents, wherein the multifunctional fusion proteins may consist of a first binding domain that is a carbohydrate binding domain and a second binding domain, wherein the first binding domain or the second binding domain may bind to a microparticle (see also WO 03/031477). Other suitable examples of carriers include bifunctional fusion proteins consisting of a CBD and an anti-RR6 antibody fragment that binds to a microparticle, which complex may be deposited on the ground or on cut grass (see also WO 03/031477). In another specific embodiment, the carrier may be active ingredient carrier granules that adhere, for example, to the surface of plants, grasses, weeds, seeds and/or the site where the plant is growing or intended to grow etc. using a moisture-active coating, for example including gum arabic, guar gum, karaya gum, gum tragacanth and locust bean gum. Upon application of the granule of the invention to a plant surface, water from precipitation, irrigation, dew, co-application with the granules from special application equipment or guttation water from the plant itself, may provide sufficient moisture for adhesion of the granule to the plant surface (see also US 2007/0280981).

[0310] In another specific embodiment, the carrier, e.g. an agrochemical carrier, may be or comprise polyamino acids. The polyamino acids 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. The polyamino acids may be combined with a nitrification inhibitor according to the present invention and, in certain embodiments, also with other carriers as mentioned above, or other nitrification inhibitors as mentioned herein in any suitable proportion. For example, polyamino acids can be combined with a nitrification inhibitor according to the present invention in a ratio of 1 to 10 (polyamino acids) versus 0.5 to 2 (nitrification inhibitor according to the present invention).

[0311] The composition for reducing nitrification comprising at least one nitrification inhibitor as defined herein may further comprise additional ingredients, for example at least one pesticidal compound. For example, the composition may further 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.

[0312] In other embodiments, the composition may, in addition to the ingredients indicated above, in particular in addition to the nitrification inhibitor of the compound of formula I, further comprise one or more alternative or additional nitrification inhibitors. Examples of alternative or additional nitrification inhibitors envisaged are linoleic acid, alpha-linolenic acid, p-methyl coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl)propionate (MHPP), Karanjin, brachialactone, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethylpyrazole phosphate (DMPP, ENTEC), 4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (Terrazole, Etridiazole), 2-sulfanilamidothiazole (ST), ammonium thiosulfate (ATU), 3-methylpyrazole (3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-triazole thiourea (TU), N-(1H-pyrazolyl-methyl)acetamides such as N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)acetamide, and N-(1H-pyrazolylmethyl)form acids such as N-((3(5)-methyl-1H-pyrazol-1-yl)methylformamide, N-(4-chloro-3(5)-methyl-pyrazol-1-ylmethyl)-formamide, N-(3(5,4-dimethyl-pyrazol-1-ylmethyl)-formamide, neem, products based on neem ingredients, cyanamide, melamine, zeolite powder, catechol, benzoquinone, sodium tetraborate, sulfate act of zinc.

[0313] In a preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor compound of formula I and 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrine or N-serve).

[0314] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole, etridiazole).

[0315] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and dicyandiamide (DCD, DIDIN).

[0316] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 3,4-dimethylpyrazole phosphate (DMPP, ENTEC).

[0317] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2-amino-4-chloro-6-methylpyrimidine (AM).

[0318] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2-mercaptobenzothiazole (MBT).

[0319] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2-sulfanilamidothiazole (ST).

[0320] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and ammonium thiosulfate (ATU).

[0321] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 3-methylpyrazole (3-MP).

[0322] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 3,5-dimethylpyrazole (DMP).

[0323] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 1,2,4-triazole.

[0324] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and thiourea (TU).

[0325] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and linoleic acid.

[0326] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and alpha-linolenic acid.

[0327] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and methyl p-coumarate.

[0328] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor compound of formula I and methyl 3-(4-hydroxyphenyl)propionate (MHPP).

[0329] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and methyl ferulate.

[0330] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and Karanjin.

[0331] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and brachylactone.

[0332] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor compound of formula I and p-benzoquinone sorgoleone.

[0333] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 4-amino-1,2,4-triazole hydrochloride (ATC).

[0334] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor compound of formula I and 1-amido-2-thiourea (ASU).

[0335] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)acetamide.

[0336] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and N-((3(5)-methyl-1H-pyrazol-1-yl)methyl formamide.

[0337] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and N-(4-chloro-3(5)-methyl-pyrazol-1-ylmethyl)-formamide.

[0338] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and N-(3(5),4-dimethyl-pyrazol-1-ylmethyl)-formamide.

[0339] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor compound of formula I and neem or products based on neem ingredients.

[0340] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and cyanamide.

[0341] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and melamine.

[0342] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and zeolite powder.

[0343] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and batecol.

[0344] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and benzoquinone.

[0345] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and sodium tetraborate.

[0346] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and zinc sulfate.

[0347] In other embodiments, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and two entities selected from the group comprising: linoleic acid, alpha-linolenic acid, p-methyl coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl)propionate (MHPP), Karanjin, brachialactone, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethylpyrazole phosphate (DMPP, ENTEC), 4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT) (5)-methyl-1H-pyrazol-1-yl)methyl)acetamide, and N-(1H-pyrazolyl-methyl)formamides such as N-((3(5)-methyl-1H-pyrazol-1-yl)methylformamide, N-(4-chloro-3(5)-methyl-pyrazol-1-ylmethyl)-formamide, or N-(3(5,4-dimethyl-pyrazol-1-ylmethyl)-formamide, neem, base of neem ingredients, cyanamide, melamine, zeolite powder, catechol, benzoquinone, sodium tetraborate, zinc sulfate.

[0348] In yet another group of embodiments, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and three, four or more entities selected from the group comprising: linoleic acid, alpha-linolenic acid, p-methyl coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl)propionate (MHPP), Karanjin, brachialactone, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethylpyrazole phosphate (DMPP, ENTEC), 4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazol, etridiazole), 2-sulfanilamidothiazole (ST), ammonium thiosulfate (ATU), 3-methylpyrazole (3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-triazole and thiourea (TU), N-(1H-pyrazolyl-methyl)ace tamides such as N-((3(5)-methyl-1H-pyrazol-1-yl)methyl)acetamide, and N-(1H-pyrazolyl-methyl)formamides such as N-((3(5)-methyl-1H-pyrazol-1-yl)methylformamide, N-(4-chloro-3(5)-methyl-pyrazol-1-ylmethyl)-formamide, or N-(3(5,4-dimethyl-pyrazol-1-ylmethyl)-formamide, neem, products based on neem ingredients, cyanamide, melamine, zeolite powder, catechol, benzoquinone, sodium tetraborate, zinc sulfate.

[0349] In other embodiments, the composition may, in addition to the ingredients indicated above, in particular in addition to the nitrification inhibitor of the compound of formula I, 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), other NXPTs known to the person skilled in the art, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate and mixtures of NBPT and NPPT (see, for example, US 8,075,659). Such mixtures of NBPT and NPPT may comprise NBPT in amounts of from 40 to 95 wt. % and preferably from 60 to 80 wt. % based on the total amount of active ingredients. 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. % other ingredients including solvents and adjuvants.

[0350] In a preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and N-(n-butyl)thiophosphoric acid triamide (NBPT, Agrotain).

[0351] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and phenylphosphorodiamidate (PPD/PPDA).

[0352] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and N-(n-propyl) thiophosphoric acid triamide (NPPT).

[0353] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2-nitrophenyl phosphoric triamide (2-NPT).

[0354] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and hydroquinone.

[0355] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and ammonium thiosulfate.

[0356] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor compound of formula I and neem.

[0357] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and cyanamide.

[0358] In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and melamine.

[0359] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and a mixture of NBPT and NPPT, such as LIMUS.

[0360] In other embodiments, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I 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), other NXPTs known to the person skilled in the art, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate and LIMUS.

[0361] In other embodiments, the composition may, in addition to one, more or all of the above ingredients, in particular in addition to the nitrification inhibitor of the compound of formula I, further comprise one or more plant growth regulators. Examples of envisaged plant growth regulators are antauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releasers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators and other unclassified plant growth regulators.

[0362] Suitable examples of antauxins to be used in a composition according to the present invention are clofibric acid or 2,3,5-triiodobenzoic acid.

[0363] Suitable examples of auxins to be used in a composition according to the present invention are 4-CPA, 2,4-D, 2,4-DB, 2,4DEP, 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.

[0364] Suitable examples of cytokinins to be used in a composition according to the present invention are 2iP, 6-benzylaminopurine (6-BA) (= N-6-benzyladenine), 2,6-dimethylpuridine (N-oxide-2,6-Lultidine), 2,6-dimethylpyridine, kinetin or zeatin.

[0365] Suitable examples of defoliants to be used in a composition according to the present invention are calcium cyanamide, dimethipine, endothal, merfos, methoxuron, pentachlorophenol, thidiazuron, tribufos or tributyl phosphorotrithioate.

[0366] Suitable examples of ethylene modulators to be used in a composition according to the present invention are aviglycine, 1-methylcyclopropene (1-MCP), prohexadione (prohexadione calcium) or trinexapac (Trinexapac-ethyl).

[0367] Suitable examples of ethylene releasers to be used in a composition according to the present invention are ACC, etacelasil, ethephon or glyoxime.

[0368] Suitable examples of gibberellins to be used in a composition according to the present invention are gibberellin or gibberellic acid.

[0369] Suitable examples of growth inhibitors to be used in a composition according to the present invention are abscisic acid, S-abscisic acid, ancymidol, butralin, carbaryl, chlorophonium, chlorpropham, dikegulac, flumetraline, fluoridamid, fosamine, glyphosine, isopyrimidol, jasmonic acid, maleic hydrazide, mepiquat (mepiquat chloride, mepiquat pentaborate), piproctanil, prohydrojasmon, profam or 2,3,5-triiodobenzoic acid.

[0370] Suitable examples of morphactins to be used in a composition according to the present invention are chlorfluren, chlorflurenol, dichlorflurenol or flurenol.

[0371] Suitable examples of growth retardants to be used in a composition according to the present invention are chlormequat (chlormequat chloride), daminozide, flurprimidol, mefluidide, paclobutrazole, tetciclacis, uniconazole, metconazole.

[0372] Suitable examples of growth stimulants to be used in a composition according to the present invention are brassinolide, forchlorfenuron or himexazole.

[0373] Suitable examples of other unclassified plant growth regulators to be used in a composition according to the present invention are amidochlor, benzofluor, buminaphos, carvone, choline chloride, ciobutide, clofencet, cloxifonac, cyanamide, cyclanilide, cycloheximide, cyprosulfamide, epocoleone, eticlozate, ethylene, fenridazon, fluprimidol, fluthiacet, heptopargyl, holosulf, ina-benfide, karetazan, lead arsenate, metasulfocarb, pidanon, Sintofen, diflufenzopyr or triapentenol.

[0374] In a preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and at least one compound selected from the group comprising: abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine (= N-6 benzyladenine), brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, diflufenzopyr, dikegulac, dimetipin, 2,6-dimethylpyridine, ethefon, 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, paclobutrazol, prohexadione (prohexadione calcium), prohydrojasmon, thidiazuron, triapentenol, tributyl phosphorotrithioate, 2,3,5-triiodobenzoic acid, trinexapac-ethyl and uniconazole.

[0375] In a preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and clofibric acid.

[0376] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2,3,5-triiodobenzoic acid.

[0377] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 4-CPA.

[0378] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2,4-D.

[0379] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2,4-DB.

[0380] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2,4-DEP.

[0381] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and dichlorprop.

[0382] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor compound of formula I and fenoprop.

[0383] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and IAA (indole-3-acetic acid).

[0384] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and IBA.

[0385] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and naphthaleneacetamide.

[0386] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and alpha-naphthaleneacetic acid.

[0387] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 1-naphthol.

[0388] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and naphthoxyacetic acid.

[0389] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and potassium naphthenate.

[0390] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and sodium naphthenate.

[0391] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2,4,5-T.

[0392] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2iP.

[0393] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 6-benzylaminopurine (6-BA) (= N-6 benzyladenine).

[0394] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2,6-dimethylpuridine (N-oxide-2,6-lultidine).

[0395] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and zeatin.

[0396] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and kinetin.

[0397] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and calcium cyanamide.

[0398] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and dimethipine.

[0399] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and endothal.

[0400] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and merphos.

[0401] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and methoxuron.

[0402] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and pentachlorophenol.

[0403] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and thidiazuron.

[0404] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and tribufos.

[0405] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and tributyl phosphorotrithioate.

[0406] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and aviglycine.

[0407] In another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 1-methylcyclopropene.

[0408] A composition as defined herein, in particular a composition comprising a nitrification inhibitor as defined herein and a plant growth regulator as defined herein, can be used for increasing plant health.

[0409] The term “plant health” as used herein is intended to mean a condition of the plant which is determined by several aspects either singly or in combination with each other. One indicator (indicator 1) for the condition of the plant is the yield of the crop. “Crop” and “fruit” should be understood as any plant product which is still used after harvesting, for example, fruits in the proper sense, vegetables, nuts, grains, seeds, wood (e.g. in the case of forestry plants), flowers (e.g. in the case of gardening plants, ornamental plants) etc., i.e. something of economic value produced by the plant. Another indicator (indicator 2) for the condition of the plant is the vitality of the plant. Plant vitality is also manifested in several aspects, some of which are visual appearance, e.g. leaf color, fruit color and appearance, number of dead basal leaves and/or extent of leaf blades, plant weight, plant height, extent of the plant back (lodging), number, strength and productivity of shoots, length of panicles, extent of the root system, root strength, extent of nodulation, in particular rhizobial nodulation, time of germination, emergence, flowering, maturity and/or senescence of grains, protein content, sugar content and the like. Another indicator (indicator 3) for an increase in plant health is the reduction of biotic or abiotic stress factors. The three above-mentioned indicators for the health condition of a plant can be interdependent and can result from each other. For example, a reduction in biotic or abiotic stress can lead to improved plant vitality, e.g. to better and larger yields and thus to increased productivity. Biotic stress, especially in the long term, can have detrimental 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 quality of stressed plants, their yields and fruits decrease. As far as quality is concerned, reproductive development is usually severely affected, with consequences for crops that are important for fruits or seeds. Growth can be slowed down by stress; the synthesis of polysaccharides, both structural and storage, can be reduced or modified: these effects can lead to a decrease in biomass and changes in the nutritional value of the product. Abiotic stress includes drought, cold, increased UV radiation, increased heat or other changes in the plant's environment, which lead to suboptimal growing 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 is increased by at least 0.5%, more preferred by at least 1%, even more preferred by at least 2%, still more preferred by at least 4%. An increased yield may, for example, be due to a reduction in nitrification and a corresponding improvement in the uptake of nitrogenous nutrients. The term “improved plant vitality” as used herein means that certain characteristics of the crop 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. Enhanced plant vitality can be characterized by, among others, the following enhanced properties of a plant: (a) enhanced plant vitality, (b) enhanced quality of the plant and/or plant products, e.g., (c) higher protein content, (d) improved visual appearance, (e) delayed senescence, (e) increased root growth and/or a more developed root system (e.g., determined by root dry mass), (f) increased nodulation, in particular rhizobial nodulation, (g) longer panicles, (h) larger leaf blade, (i) fewer dead basal leaves, (j) increased chlorophyll content, (k) prolonged photosynthetically active period, and (l) improved nitrogen supply in the plant.

[0410] Improving plant vitality according to the present invention particularly means that the improvement of any one or more or all of the above-mentioned plant characteristics is improved. Furthermore, it means that if not all of the above characteristics are improved, those that are not improved are not worsened compared to plants that have not been treated according to the invention or at least are 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 that preferably results in a better crop yield). Improved plant vitality can for example be due to a reduction of nitrification and for example a regulation of plant growth.

[0411] In other embodiments, the composition may, in addition to the ingredients indicated above, in particular in addition to the nitrification inhibitor of the compound of formula I, further comprise one or more pesticides.

[0412] A pesticide is generally a chemical or biological agent (such as a pesticide active ingredient, compound, composition, virus, bacterium, antimicrobial, or disinfectant) that, through its effect, deters, incapacitates, kills, or discourages pests. Target pests may include insects, plant pathogens, weeds, molluscs, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisances, spread disease, or are vectors of disease. The term “pesticide” also includes plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to fall from a plant, usually to facilitate harvesting; desiccants that promote the drying of living tissue, such as unwanted plant tops; plant activators that activate plant physiology to defend against certain pests; phytotoxicity protectors that reduce the undesirable herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology, for example, to increase plant growth, biomass, yield or any other quality parameter of the harvestable products of a crop plant.

[0413] Biopesticides have been defined as a form of pesticides based on microorganisms (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 main 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 classified as microbial pesticides, despite being multicellular; and (2) Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively nontoxic to mammals.

[0414] According to one embodiment, the individual components of the composition according to the invention, such as parts of a kit or parts of a binary or ternary mixture, can be mixed by the user himself in a spray tank or any other type of container used for applications (e.g. seed treatment drums, seed pelletizing machines, knapsack sprayer) and other auxiliaries can be added, if appropriate.

[0415] Where live microorganisms such as microbial pesticides of groups L1), L3) and L5) are part of such a kit, care must be taken that the choice and quantities of the components (e.g. chemical pesticides) and other auxiliaries do not influence the viability of the microbial pesticides in the composition mixed by the user. In particular for bactericides and solvents, the compatibility with the respective microbial pesticide must be taken into account.

[0416] Accordingly, in one embodiment, 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 component and optionally an additional active component 3) as defined herein.

[0417] The following list of pesticides I (e.g. pesticidal and biopesticidal active substances), in conjunction with which compounds I may be used, is intended to illustrate possible combinations, but is not limitative: A) Respiration Inhibitors: - Complex III inhibitors at the Qo site: azoxystrobin (A.1.1), coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), phenaminstrobin (A.1.6), phenoxystrobin/fluphenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), mandestrobin (A.1.10), metominostrobin (A.1.11), orisastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyramethostrobin (A.1.15), pyroxystrobin (A.1.16), trifloxystrobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-methyl-acetamide (A.1.18), piribencarb (A.1.19 ), triclopiricarb/ chlorodincarb (A.1.20), famoxadone (A.1.21), fenamidone (A.1.21), methyl-N-[2-[(1,4-dimethyl-5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate (A.1.22), 1-[2-[[1-(4-chloro-phenyl)pyrazol-3-yl]oxy-methyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one (A.1.25), (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.34), (Z, 2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,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 methyl ester (A.1.38); - Complex III inhibitors at the Qi site: cyazofamide (A.2.1), amisulbrom (A.2.2), [(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonan-7-yl]2-methylpropanoate (A.2.3), fenpicoxamide (A.2. 4); - Complex II inhibitors: benodanil (A.3.1), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxine (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furamethpyr (A.3.10), isofetamide ( A.3.11) tifluzamide (A.3.21), inpirfluxam (A.3.22), pyrapropoin (A.3.23), fluindapyr (A.3.28), methyl (E)-2-[2-[(5-cyano-2-methyl-phenoxy)methyl]phenyl]-3-methoxy-prop-2-enoate (A.3.30), isoflucipram (A.3.31), 2-(difluoromethyl)- N-(1,1,3-trimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.32), 2-(difluoromethyl)-N-[(3R)-1,1,3-trimethylindan-4-yl]pyridine-3-carboxamide (A.3.33), 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3- carboxamide (A.3.34) -[(3R)-1,1-dimethyl-3-propyl-indan-4-yl]-pyridine-3-carboxamide (A.3.37), 2-(difluoromethyl)-N-(3-isobutyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.38), 2-(difluoromethyl)-N-[(3R)- 3-isobutyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (A.3.39); - Other respiration inhibitors: diflumetorin (A.4.1); nitrophenyl derivatives: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptildinocap (A.4.6), ferimzone (A.4.7); organometallic 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), bromuconazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-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), ipconazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazol (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), (B.1.29) (tetrazol-1-yl) -1[5-[4- (trifluoromethoxy) phenyl] -2- pyridyl] propan-2-ol (B.1.32), ipfentrifluconazole (B.1.37), mefentrifluconazole (B.1.38), 2- (chloromethyl) -2-methyl-5- (p-tolylmethyl) -1- (1,2,4-triazol-1-ylmethyl) cyclopentanol (B .1.43); imidazoles: imazalil (B.1.44), pefurazoate (B.1.45), prochloraz (B.1.46), triflumizole (B.1.47); pyrimidines, pyridines, piperazines: fenarimol (B.1.49), pyrifenox (B.1.50), triforine (B.1.51), [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1.52); - Delta-14-reductase inhibitors: aldimorph (B.2.1), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spiroxamine (B.2.8); - 3-keto reductase inhibitors: fenhexamide (B.3.1); - Other sterol biosynthesis inhibitors: chlorfenomizole (B.4.1); C) Nucleic acid synthesis inhibitors: - Phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1), benalaxyl-M (C.1.2), kiralaxyl (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), octilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-fluoro-2-(4-chlorophenylmethoxy)pyrimidine-4-amine (C.2.8); D) Cell division and cytoskeleton inhibitors: Tubulin inhibitors: benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (D.1.3), thiabendazole (D.1.4), thiophanate-methyl (D.1.5), 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine (D.1.6), -6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine (D.1.7), N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]butanamide (D.1.8), N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)butanamide (D.1.10), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-methoxy-acetamide quinolyl)oxy]-2-methylsulfanyl-N-propyl-quinolyl (D.1.14), )oxy]-N-(2-fluoroethyl)-2-methylsulfanyl-acetamide (D.1.15), 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-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) Amino acid and protein synthesis inhibitors: - 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), oxytetracycline (E.2.6); F) Signal transduction inhibitors: - MAP/histidine kinase inhibitors: fluoroimide (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fludioxonil (F.1.5); - Protein G inhibitors: quinoxyfen (F.2.1); G) Lipid and membrane synthesis inhibitors: - Phospholipid biosynthesis inhibitors: edifenphos (G.1.1), iprobenphos (G.1.2), pyrazophos (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), cloroneb (G.2.6), etridiazole (G.2.7); - Phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1), flumorph (G.3.2), mandipropamide (G.3.3), pirimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7); - Compounds that affect cell membrane permeability and fatty acids: propamocarb (G.4.1); - Oxysterol binding protein inhibitors: oxathiapiprolin (G.5.1), 2-{3-[2-(1-{[3,5-bis(difluoromethyl-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate (G.5.2), 3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate (G.5.3) 4-[1-[2-[3- (difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.4), 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.5), -[1-[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.6), 4-[1-[2-[5-cyclopropyl-3-(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N- carboxamide (G.5.7) 1-yl-pyridine-2-carboxamide (G.5.9), 4-[1-[2-[3,5-bis(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.10), (4-[1-[2-[5-cyclopropyl- 3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (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), dichlorophene (H. 3, 7), hexachlorobenzene (H.3.8), pentachlorphenol (H.3.9) and its salts, phthalide (H.3. 10), tolylfluanide (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(albesylate) (H.4.8), dithianone (H.4.9), 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6- c’]dipyrrole-1,3,5,7(2H,6H)-tetraone (H.4.10); I) cell wall synthesis inhibitors: - Glucan synthesis inhibitors: validamycin (I.1.1), polyoxin B (I.1.2); - Melanin synthesis inhibitors: pyroquilone (I.2.1), tricyclazole (I.2.2), carpropamide (I.2.3), dicyclometh (I.2.4), fenoxanil (I.2.5); J) Plant defense inducers: - Acibenzolar-S-methyl (J.1.1), probenazole (J.1.2), isotianil (J.1.3), thiadinil (J.1.4), prohexadione-calcium (J.1.5); phosphonates: fosetyl (J.1.6), fosetyl-aluminium (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-N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide (J.1.10); K) Unknown mode of action: - Bronopol (K.1.1), chinomethionate (K.1.2), ciflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclocimet (K.1.7), diclomezine (K.1.8), diphenzoquat (K.1.9), diphenzoquat-methylsulfate (K.1 .10), diphenylamine (K.1.11), fenitropan (K.1.12), fenpyrazamine (K.1.13), flumetover (K.1.14), flusulfamide (K.1.15), flutianil (K.1.16), harpin (K.1.17), metasulfocarb (K.1.18), nitrapyrin (K.1.19), nitrotal-isopropyl (K.1.20) methyl formamidine (K.1.27), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.28), N'-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4- thiadiazol-5-yl]oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine (K.1.29), N'-(5-bromo-6-indan-2-yloxy-2-methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine (K.1.30), N'-[5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methyl -3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.31), N'-[5-bromo-6-(4-isopropylcyclohexoxy)-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.32), N'-[5-bromo-2-methyl-6-(1-phenylethoxy)-3-pyridyl]-N-ethyl-N-methylformamid ina (K.1.33) yl)- N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide (K.1.36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole) (K.1.37), 3-[5-(4-methylphenyl)-2,3- dimethyl-isoxazolidin-3-yl]-pyridine (K.1.38), ethyl 5-chloro-1-(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1H-benzoimidazole (K.1.39), picarbutrazox (K.1.41), Pentyl 6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.42), but-3-ynyl-N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]-amino]oxymethyl]-2-pyridyl]carbamate (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]phenyl]propan-2-ol (K.1.45), quinofumelin (K.1.47), 9-fluoro-2,2-dimethyl- (3-quinolyl)-3H-1,4-benzoxazepine (K.1.49), 2-(6-benzyl-2-pyridyl) quinazoline (K.1.50), 2-[6-(3-fluoro-4-methoxy-phenyl)-5-methyl-2-pyridyl]quinazoline (K.1.51), diclobentiazox (K.1.52), N’-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine (K.1.53). pyriphenamine (K.1.54); I) Biopesticides: II) Microbial pesticides with fungicidal, bactericidal, virucidal and/or activating activity of plant defense activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. tilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryptococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenulate (also called Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. enzymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibacillus alvei, Paenibacillus epiphyticus, P. polymyxa, Pantoea vagans, Penicillium bilaiae, Pseu domonas sp., Pseudomonas chloraphis, Pseudozyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, Zucchini yellow mosaic virus (avirulent lineage); L2) Biochemical pesticides with fungicidal, bactericidal, virucidal and/or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract; L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bassiana, B. brongniartii, Burkholderia spp., Chromobacterium subtsugae, Cydia pomonella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV), Flavobacterium spp., Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucleopolyhedrovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, Metarhizium anisopliae, M. anisopliae var. anisopliae, M. anisopliae var. acridum, Nomuraea rileyi, Paecilomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus (SpliNPV), Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomyces galbus, S. microflavus; L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (E,Z)-7,9-di- dodecadien-1-yl ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,11,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1-butanol, methyl eugenol, cis- jasmone, methyl jasmonate, (E,Z)-2,13-octadecadien-1-ol, (E,Z)-2,13-octadecadiel-1-ol acetate, (E,Z)-3,13-octadecadien-1-ol, (R)-1-octen-3-ol, pentatermanone, (E,Z,Z)-3,8,11-tetradecatrienyl acetate, (Z,E)-9,12-tetradecadien-1-yl, (Z)-7-tetradecen-2-one, (Z)-9-tetradecen-1-yl acetate, (Z)-11-tetradecenal, (Z)-11-tetradecen-1-ol, Chenopodium ambrosiodes extract, Neem oil, Quillay extract; L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoter and/or yield promoting activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhizobium leguminosarum bv. phaseoli, R. l. bv. trifolii, R. l. bv. viciae, R. tropici, and Sinorhizobium meliloti; M) Insecticides: M.1) Acetylcholine esterase (AChE) inhibitors: M.1A carbamates, e.g., aldicarb, alanicarb, bendiocarb, benfuracarb, butocarboxime, butoxycarboxim, carbaryl, carbofuran, carbosulfan, etiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, tiofanox, trimetacarb, XMC, xylylcarb and triazamate; or M.1B organophosphates, e.g. acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chloridexyphos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinifos, disulfoton, EPN, ethion, ethoprophos, famfur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imiciaphos, isofenphos, isopropyl-O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, metidathion, mevinphos, monocrotophos, naled, omethatoate, oxydemeton-methyl, parathion, parathion-methyl, phentoate, phorate, fosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetanphos, prothiofos, pyraclofos, pyridafenthion, quinalphos, sulfotep, tebupyrimphos, temephos, terbufos, tetrachlorvinphos, thiometone, triazophos, trichlorfon and vamidothion; M.2) GABA-dependent chloride channel antagonists: M.2A organochlorine cyclodiene compounds, e.g. endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), e.g. ethiprole, fipronil, flufiprole, pyrafluprole and pyriprole; M.3) Sodium channel modulators of the M.3A class pyrethroids, e.g., acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin, metofluthrin, momfluorothrin, epsilon-momfluorothrin, permethrin, fenothrin, pralethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa-tefluthrin, tetramethylfuthrin, tetramethrin, tralomethrin, and transfluthrin, or M.3B sodium channel modulators such as DDT or methoxychlor; M.4) Nicotinic acetylcholine receptor (nAChR) agonists: M.4A neonicotinoids, for example acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds M.4A.1 4,5-dihydro-N-nitro-1-(2-oxiranylmethyl)-1H-imidazol-2-amine, M.4A.2: (2E)-1-[(6-chloropyridin-3-yl)methyl]-N'-nitro-2-pentylidenehydrazine carboxymidamide; or M4.A.3: 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5-propoxy-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridine; or M.4B nicotine; M.4C sulfoxaflor; M.4D flupyradifurone; M.4E triflumezopyrim; M.5) Nicotinic acetylcholine receptor allosteric activators: spinosyns, e.g. spinosad or spinetoram; M.6) Chloride channel activators of the avermectin and milbemycin class, e.g. abamectin, emamectin benzoate, ivermectin, lepimectin, or milbemectin; M.7) Juvenile hormone mimics, such as M.7A juvenile hormone analogues such as hydroprene, quinoprene, and methoprene; or M.7B fenoxycarb or M.7C pyriproxyfen; M.8) Miscellaneous nonspecific (multi-site) inhibitors, e.g. M.8A alkyl halides such 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; pyrifluquinazone; M.10) Mite growth inhibitors, e.g., M.10A clofentezine, hexythiazox, and diflovidazin, or M.10B etoxazole; M.11) Microbial disruptors of insect midgut membranes, e.g., Bacillus thuringiensis or Bacillus sphaericus and the insecticidal proteins they produce, such as Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp. kurstaki, and Bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1; 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 propargite or M.12D tetradifon; M.13) Uncouplers of oxidative phosphorylation by disruption of the proton gradient, e.g. chlorfenapyr, DNOC or sulfluramid; M.14) Nicotinic acetylcholine receptor (nAChR) channel blockers, e.g. nereistoxin analogues like bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium; M.15) Chitin biosynthesis type 0 inhibitors, such as benzoylureas, e.g. bistrifluron, chlorfluazuron, diflubenzuron, flucicloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron or triflumuron; M.16) Chitin biosynthesis type 1 inhibitors, e.g. buprofezin; M.17) Molting disruptors, Dipteran, e.g. cyromazine; M.18) Ecdysone receptor agonists, such as diacylhydrazines, e.g. methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide; M.19) Octopamine 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, e.g. fenazaquine, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21B rotenone; M.22) Voltage-gated sodium channel blockers, for example M.22A indoxacarb, or M.22B metaflumizone, or M.22B.1: 2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3-chloro-2-methylphenyl)-2-[(4-chlorophenyl)-[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide; M.23) Acetyl-CoA carboxylase inhibitors such as tetronic and tetramic acid derivatives, for example spirodiclofen, spiromesifen or spirotetramat; M.23.1 spiropidion; M.24) Inhibitors of mitochondrial complex IV electron transport, e.g. M.24A phosphine such as aluminium phosphide, calcium phosphide, zinc phosphide or phosphine, or M.24B cyanide; M.25) Inhibitors of mitochondrial complex II electron transport, such as beta-ketonitrile derivatives, e.g. cyenopyrafen or cyflumetofen; M.28) Ryanodine receptor modulators of the diamide class, e.g., flubendiamide, chlorantraniliprole, cyantraniliprole, tetraniliprole, M.28.1: (R)-3-chloro-N1-{2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamide, M.28.2: (S)-3-chloro-N1-{2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamide, M.28.3: cyclaniliprole, or M.28.4: methyl-2-[3,5-dibromo- 2-({[3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)benzoyl]-1,2-dimethylhydrazinecarboxylate, or M.28.5a) N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanilidene)-carbamoyl]-phenyl]-2-(3-chloro-2-pyrid yl)-5-(trifluoromethyl)pyrazol-3-carboxamide; M.28.5b) N-[4-chloro-2-[(diethyl-lambda-4-sulfanilidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazol-3-carboxamide; M.28.5c) N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanilidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazol-3-carboxamide; M.28.5d) N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanilidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazol-3-carboxamide; M.28.5h) N-[4,6-dibromo-2-[(diethyl-lambda-4-sulfanilidene)-carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazol-3-carboxamide; M.28.5i) N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methyl-phenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazol-5-carboxamide; M.28.5j) 3-chloro-1-(3-chloro-2-pyridinyl)-N-[2,4-dichloro-6-[[(1-cyano-1-methylethyl)amino]carbonyl]phenyl]-1H-pyrazol-5-carboxamide; M.28.5k) 3-bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-1-(3,5-dichloro-2-pyridyl)-1H-pyrazol-5-carboxamide; M.28.5l) N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methyl-phenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1H-pyrazol-5-carboxamide; or M.28.6: cyhalodiamide; or M.29) Chordotonal organ modulators - undefined target site, for example, flonicamid; M.UN. Insecticidal active compounds of unknown or uncertain mode of action, e.g., afidopiropen, afoxolaner, azadiractin, amidoflumet, benzoximate, broflanilide, bromopropylate, quinomethionate, cryolite, dichloromezothiaz, dicofol, flufenerim, flomethoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, methoxadaiazone, piperonyl butoxide, piflubumide, pyridalyl, thioxazafen, M.UN.3: 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-11-en-10-one, M.UN.4: 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1- azaspiro[4.5]dec-3-en-2-one, M.UN.5: 1-[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl] phenyl]-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine, or active with Bacillus firmus base (Votivo, I-1582); M.UN.6: flupirimin; M.UN.8: fluazaindolizine; M.UN.9.a): 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1-oxothietan-3-yl)benzamide; M.UN. 9.b): fluxametamide; M.UN.10: 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1H-pyrazole; M.UN.11.i) 4-cyano-N-[2-cyano-5-[[2,6-dibromo-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)-propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.UN.11.j) 4-cyano-3-[(4-cyano-2-methyl-benzoyl)amino]-N-[2,6-dichloro-4-[1,2,2,3, 3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide; M.UN.11.k) N-[5-[[2-chloro-6-cyano-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; M.UN.11.l) N-[5-[[2-bromo-6-chloro-4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; M.UN.11.m) N-[5-[[2-bromo-6-chloro-4-[1,2,2, 3,3,3-hexafluoro-1-(trifluoromethyl)-propyl]phenyl] carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; M.UN.11.n) 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)-propyl] phenyl] carbamoyl] phenyl]-2-methyl-benzamide; M.UN.11.o) 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.UN.11.p) N-[5-[[2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; or M.UN.12.a) 2-(1,3-dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine; M.UN.12.b) 2-[6-[2-(5-fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine, M.UN.12.c) 2-[6-[2-(3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; M.UN.12.d) N-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; M.UN.12.e) N-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; M.UN.14a) 1-[(6-chloro-3-pyridinyl)methyl]-1,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro-imidazo[1,2-a]pyridine; or M.UN.14b) 1-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-5-ol; M.UN.16a) 1-isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazol-4-carboxamide; or M.UN.16b) 1-(1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide; M.UN.16c) N,5-dimethyl-N-pyridazin-4-yl-1-(2,2,2-trifluoro-1-methyl-ethyl)pyrazol-4-carboxamide; M.UN.16d) 1-[1-(1-cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide; M.UN.16e) N-ethyl-1-(2-fluoro-1-methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide; M.UN.16f) 1-(1,2-dimethyl-propyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazol-4-carboxamide; M.UN.16g) 1 [1-(1-cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazin-4-yl-pyrazol-4-carboxamide; M.UN.16h) N-methyl -1-(2-fluoro-1-methyl-propyl]-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide; M.UN.16i) 1-(4,4-difluorocyclohexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazol-4-carboxamide; or M.UN.16j) 1-(4,4-difluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazol-4-carboxamide; M.UN.17a) N-(1-methylethyl)-2-(3-pyridinyl)-2H-indazol-4-carboxamide; M.UN.17b) N-cyclopropyl-2-(3-pyridinyl)-2H-indazol-4-carboxamide; M.UN.17c) N-cyclohexyl-2-(3-pyridinyl)-2H-indazol-4-carboxamide; M.UN.17d) 2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H-indazol-4-carboxamide; M.UN.17e) 2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H-indazol-5-carboxamide; M.UN.17f) methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate; M.UN.17g) N-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazol-5-carboxamide; M.UN.17h) N-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide; M.UN.17i) 2-(3-pyridinyl)-N-(2-pyrimidinylmethyl)-2H-indazol-5-carboxamide; M.UN.17j) N-[(5-methyl-2-pyrazinyl)methyl]-2-(3-pyridinyl)-2H-indazol-5-carboxamide; M.UN.18. cyclopyrazoflor; M.UN.19 sarolaner; M.UN.20 lotilaner; M.UN.21 N-[4-chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1-methyl-3-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazol-5-carboxamide; M.UN.22a 2-(3-ethylsulfonyl-2-pyridyl)-3-methyl-6-(trifluoromethyl)imidazo[4,5-b] pyridine, or M.UN.22b 2-[3-ethylsulfonyl-5-(trifluoromethyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[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-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl) -4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide; M.UN.24a) N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3-carboxamide or M.UN.24b) N-[4-chloro-3-[(1-cyanocyclopropyl) carbamoyl]phenyl]-2-methyl-5-(1,1,2, 2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3-carboxamide; M.UN.25 acinonapyr; M.UN.26 benzpyrimoxane; M.UN.27 2-chloro-N-(1-cyanocyclopropyl)-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]benzamide; M.UN.28 oxazosulfyl; M.UN.29a) [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl] N-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl] phenyl] carbamate; M.UN.29b) [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl] N-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl] carbamate; M.UN.29c) [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl] N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl] carbamate; M.UN.29d) [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl] N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl] carbamate; M.UN.29.e) (2Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylenehydrazono]thiazolidin-4-one or M.UN.29f) (2Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[1 -[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylenehydrazono]thiazolidin-4-one; and N) Herbicides: - herbicides of the classes of 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, phosphoramidates, phosphorodithioates, phthalates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolecarboxamides, triazolopyrimidines, triketones, uracils or ureas.

[0418] The present invention also relates to agrochemical compositions comprising a mixture of at least one compound of formula I, that is to say a nitrification inhibitor of the present invention (compound I or component I) and at least one additional active substance useful for plant protection, for example selected from groups A) to N) (component 2), in particular an additional herbicide selected from group N).

[0419] By applying compounds I together with at least one active substance from groups A) to N) a synergistic phytosanitary effect can be obtained, i.e. more than a simple addition of the individual effects is obtained (synergistic mixtures).

[0420] This can be achieved by applying compounds I and at least one additional active substance simultaneously, either together (e.g. as a tank mix) or separately, or in succession, whereby 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 quantity at the time of application of the additional active substance(s). The order of application is not essential for the work of the present invention.

[0421] When applying compound I and a pesticide I sequentially, the time between the two applications may vary, for example, between 2 hours to 7 days. A wider variation ranging from 0.25 hours to 30 days is also possible, preferably from 0.5 hours to 14 days, particularly from 1 hour to 7 days or from 1.5 hours to 5 days, and even more preferred from 2 hours to 1 day. In the case of a mixture comprising a pesticide II selected from group L), it is preferred that pesticide I is applied as the last treatment.

[0422] According to the invention, the solid material (dry matter) of the biopesticides (with the exception of oils such as Neem oil, Tagetes oil, etc.) is considered as the active component (for example, to be obtained after drying or evaporation of the extraction medium or suspension medium in the case of liquid formulations of the microbial pesticides).

[0423] 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).

[0424] The total weight ratios of compositions comprising at least one microbial pesticide in the form of viable microbial cells including inactive forms, can be determined by 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 is equal to one gram of total weight of the respective active component. Colony forming unit is the measure of viable microbial cells, in particular fungal and bacterial cells. Furthermore, here “CFU” can also be understood as the number of individual (juvenile) nematodes in the case of nematode (entomopathogenic) biopesticides, such as Steinernema feltiae.

[0425] In the binary mixtures and compositions according to the invention, the weight ratio of component 1) and component 2) generally depends on the properties of the active components used, is generally in the range of 1:100 to 100:1, regularly in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1, even more preferably in the range of 1:4 to 4:1 and in particular in the range of 1:2 to 2:1.

[0426] According to other embodiments of the binary mixtures and compositions, the weight ratio of component 1) and component 2) is typically in the range of 1000:1 to 1:1, often in the range of 100:1 to 1:1, regularly in the range of 50:1 to 1:1, preferably in the range of 20:1 to 1:1, more preferably in the range of 10:1 to 1:1, even more preferably in the range of 4:1 to 1:1 and in particular in the range of 2:1 to 1:1.

[0427] According to other embodiments of the binary mixtures and compositions, the weight ratio of component 1) and component 2) is typically in the range of 1:1 to 1:1000, often in the range of 1:1 to 1:100, regularly in the range of 1:1 to 1:50, preferably in the range of 1:1 to 1:20, more preferably in the range of 1:1 to 1:10, even more preferably in the range of 1:1 to 1:4 and in particular in the range of 1:1 to 1:2.

[0428] According to other embodiments of the mixtures and compositions, the weight ratio of component 1) and component 2) generally depends on the properties of the active components used, is generally in the range of 1:10,000 to 10,000:1, regularly in the range of 1:100 to 10,000:1, preferably in the range of 1:100 to 5,000:1, more preferably in the range of 1:1 to 1,000:1, even more preferably in the range of 1:1 to 500:1 and in particular in the range of 10:1 to 300:1.

[0429] According to other embodiments of the mixtures and compositions, the weight ratio of component 1) and component 2) is generally in the range of 20,000:1 to 1:10, generally in the range of 10,000:1 to 1:1, regularly in the range of 5,000:1 to 5:1, preferably in the range of 5,000:1 to 10:1, more preferably in the range of 2,000:1 to 30:1, even more preferably in the range of 2,000:1 to 100:1 and in particular in the range of 1,000:1 to 100:1.

[0430] According to other embodiments of the mixtures and compositions, the weight ratio of component 1) and component 2) is generally in the range of 1:20,000 to 10:1, generally in the range of 1:10,000 to 1:1, regularly in the range of 1:5,000 to 1:5, preferably in the range of 1:5,000 to 1:10, more preferably in the range of 1:2,000 to 1:30, even more preferably in the range of 1:2,000 to 1:100 and in particular in the range of 1:1,000 to 1:100.

[0431] In ternary mixtures, i.e. compositions according to the invention comprising component 1) and component 2) and a compound III (component 3), the weight ratio of component 1) and component 2) depends on the properties of the active substances used, is generally in the range of 1:100 to 100:1, regularly in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1 and in particular in the range of 1:4 to 4:1, and the weight ratio of component 1) and component 3) is generally in the range of 1:100 to 100:1, regularly in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1 and in particular in the range 1:4 to 4:1.

[0432] Any other active components are, if desired, added in a ratio of 20:1 to 1:20 to component 1).

[0433] These ratios are also suitable for the inventive mixtures applied by seed treatment.

[0434] The active substances listed in groups A) to K), their preparation and their activity, e.g. against harmful fungi, are known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by the 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 13/16207 2, WO 13/092224, WO 11/135833, CN 1907024, CN 1456054, CN 103387541, CN 1309897, WO 12/84812, CN 1907024, WO 09094442, WO 14/60177, 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 of two to seven digits, the second consisting of two digits and the third consisting of a single digit.

[0435] Commercially available group M compounds listed above can be found in The Pesticide Manual, 17th Edition, C. MacBean, British Crop Protection Board (2015), among other publications. The online Pesticide Manual is updated regularly and can be accessed at http://bcpcdata.com/pesticide-manual.html.

[0436] Another online pesticide database that provides ISO common names is http://www.alanwood.net/pesticides.

[0437] M.4 cycloxaprid is known from WO 2010/069266 and WO 2011/069456. M.4A.1 is known from CN 103814937; CN 105367557, CN 105481839. M.4A.2, guadipir, 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 CN 10171577 and M.22B.2 in CN 102126994. Spiropidion M.23.1 is known from WO 2014/191271. M.28.1 and M.28.2 are known from WO 2007/101540. M.28.3 is described in WO 2005/077934. M.28.4 is described in WO 2007/043677. M.28.5a) to M.28.5d) and M.28.5h) are described in WO 2007/006670, WO 2013/024009 and WO 2013/024010, M.28.5i) is described in WO 2011/085575, M.28.5j) in WO 2008/134969, M.28.5k) in US 2011/046186 and M.28.5l) in WO 2012/034403. M.28.6 can be found in WO 2012/034472. M.UN.3 is known from WO 2006/089633 and M.UN.4 from WO 2008/067911. M.UN.5 is described in WO 2006/043635, and biological control agents based on Bacillus firmus are described in WO 2009/124707. Flupirimin is described in WO 2012/029672. M.UN.8 is known from WO 2013/055584. M.UN.9.a) is described in WO 2013/050317. M.UN.9.b) is described in WO 2014/126208. M.UN.10 is known from WO 2010/060379. Broflanilide and M.UN.11.b) to M.UN.11.h) are described in WO 2010/018714 and M.UN.11i) to M.UN.11.p) in WO 2010/127926. M.UN.12.a) to M.UN.12.c) are known from WO 2010/006713, M.UN.12.d) and M.UN.12.e) are known from WO 2012/000896. M.UN.14a) and M.UN.14b) are known from WO 2007/101369. M.UN.16.a) to M.UN.16h) are described in WO 2010/034737, WO 2012/084670 and WO 2012/143317, respectively, and M.UN.16i) and M.UN.16j) are described in WO 2015/055497. M.UN.17a) to M.UN.17.j) are described in WO 2015/038503. M.UN.18 ticloprazoflor is described in US 2014/0213448. M.UN.19 is described in WO 2014/036056. M.UN.20 is known from WO 2014/090918. M.UN.21 is known from EP 2910126. M.UN.22a and M.UN.22b are known from WO 2015/059039 and WO 2015/190316. M.UN.23a and M.UN.23b are known from WO 2013/050302. M.UN.24a) and M.UN.24b) are known from WO 2012/126766. Acinonapyr M.UN.25 is known from WO 2011/105506. Benzpyrimoxan M.UN.26 is known from WO 2016/104516. M.UN.27 is known from WO 2016/174049. M.UN.28 oxazosulfyl is known from WO 2017/104592. M.UN.29a) to M.UN.29f) are known from WO 2009/102736 or WO 2013116053.

[0438] Biopesticides of group L1) and/or L2) may also have insecticidal, acaricidal, molluscidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoter and/or yield enhancing activity. Biopesticides of group L3) and/or L4) may also have fungicidal, bactericidal, virucidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoter and/or yield enhancing activity. Biopesticides of group L5) may also have fungicidal, bactericidal, virucidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.

[0439] Many of these biopesticides have been deposited under the deposit number mentioned here (the prefixes such as ATCC or DSM refer to the acronym of the respective culture collection, for more details see e.g. here: http://www.wfcc.info/ccinfo/collection/by acronym/), are referred to in the literature, registered and/or are commercially available: mixtures of Aureobasidium pullulans DSM 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 the wheat region of Southern Brazil (Passo Fundo) at least before 1980 (BR11005, e.g. GELFIX® Gramineae from BASF Agricultural Specialties Ltd., Brazil), strains of A. brasilense Ab-V5 and Ab-V6 (e.g., in AzoMax from Novozymes BioAg Produtos para Agricultura Ltda. Quattro Barras, Brazil or Simbiose-Maíz® 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 D747 isolated from air in Kikugawa-shi, Japan (US 20130236522 A1; 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 broad bean kernel in Sutton Bonington, Nottinghamshire, UK at least before 1988 (also called 1430; NRRL B-50595; US 2012/0149571 A1; e.g. Integral® from BASF Corp., USA), B. amyloliquefaciens spp. plantarum QST-713 isolated from peach orchard in 1995 in California, USA (NRRL B-21661; e.g. Serenade® MAX from Bayer Crop Science LP, USA), B. amyloliquefaciens spp. plantarum TJ1000 isolated in 1992 in South Dakota, USA (also called 1BE; ATCC BAA-390; CA 2471555 A1; e.g. QuickRoots™ from TJ Technologies, Watertown, SD, USA), B. firmus CNCM I-1582, a variant of the parental line EIP-N1 (CNCM I-1556) isolated from soil of the central flat area of Israel (WO 2009/126473, US 6,406,690; e.g. Votivo® from Bayer CropScience LP, USA), B. pumilus GHA 180 isolated from apple rhizosphere in Mexico (IDAC 260707-01; e.g. PRO-Mix® BX from Premier Horticulture, Quebec, Canada), B. pumilus INR-7 also referred to as BU-F22 and BU-F33 isolated by at least before 1993 from cucumber infested with Erwinia tracheiphila (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumilus 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 Specialties (Pty) Ltd., South Africa), B. pumilus 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. subtilis 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 collected from a peat bog in Ephraim, Wisconsin, USA, in 1987 (also called ABG-6346; ATCC SD-1372; e.g. from XenTari® Biofa AG, Munich, Germany), B. t. ssp. kurstaki ABTS-351 identical to HD-1 isolated in 1967 from diseased pink bogworm larvae in Brownsville, Texas, USA (ATCC SD-1275; e.g. Dipel® DF from Valent BioSciences, IL, USA), B. t. ssp. kurstaki SB4 isolated from larval cadavers of E. saccharina (NRRL B-50753; e.g. Beta Pro® from BASF Agricultural Specialties (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 B1; 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 Conchyloctenia punctata (NRRL 50757; e.g. BroadBand® from BASF Agricultural Specialties (Pty) Ltd., South Africa), strains of Bradyrhizobium elkanii SEMIA 5019 (also called 29W) isolated in Rio de Janeiro, Brazil and SEMIA 587 isolated in 1967 in Rio Grande do Sul State, 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., GELFIX5 from BASF Agricultural Specialities Ltd., Brazil), B. japonicum 532c isolated from Wisconsin field in the USA (Nitragin 61A152; Can. J. Plant. Sci. 70, 661-666, 1990; for example, in Rhizoflo®, Histick®, Hicoat® Super from BASF Agricultural Specialties Ltd., Canada), B. japonicum E-109 variant of USDA line 138 (INTA E109, SEMIA 5085; Eur. J. Soil Biol. 45, 28–35, 2009; Biol. Fertil. Soils 47, 81–89, 2011); B. japonicum lines deposited at SEMIA, known from Appl. Environ. Microbiol. 73 (8), 2635, 2007: SEMIA 5079 isolated from soil in the Cerrados region, Brazil by Embrapa-Cerrados used in commercial inoculants since 1992 (CPAC 15; e.g., GELFIX5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum SEMIA 5080 obtained under laboratory conditions by Embrapa-Cerrados in Brazil and used in commercial inoculants since 1992, being a natural variant of SEMIA 586 (CB1809) originally isolated in the USA (CPAC 7; e.g. GELFIX5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil); Burkholderia 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 plc, UK), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (J. Invertebrate Pathol. 107, 112–126, 2011; e.g. Helicovex® from Andermatt Biocontrol, Switzerland; Diplomata® from Koppert, Brazil; Vivus® Max from AgBiTech Pty Ltd., Queensland, Australia), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV) (e.g., Gemstar® from Certis LLC, USA), Helicoverpa zea nucleopolyhedrovirus ABA-NPV-U (e.g., Heligen® from AgBiTech Pty Ltd., Queensland, Australia), Heterorhabditis bacteriophora (e.g., Nemasys® G from BASF Agricultural Specialties Limited, UK), Isaria fumosorosea Apopka-97 isolated from mealybug on gynura in Apopka, Florida, USA (ATCC 20874; Biocontrol Science Technol. 22 (7), 747–761, 2012; e.g. PFR-97™ or PreFeRal® from Certis LLC, USA), Metarhiziun anisopliae var. anisopliae F52 also called 275 or V275 isolated from the apple moth in Austria (DSM 3884, ATCC 90448; e.g. Met52® Novozymes Biologicals BioAg Group, Canada), Metschnikowia fructicola 277 isolated from grapes in central Israel (US 6,994,849; NRRL Y-30752; e.g. formerly Shemer® from Agrogreen, Israel), Paecilomyces ilacinus 251 isolated from infected nematode eggs in the Philippines (AGAL 89/030550; WO 1991/02051; Crop Protection 27, 352–361, 2008; e.g. BioAct® from Bayer CropScience AG, Germany and MeloCon® from Certis, USA), Paenibacillus alvei NAS6G6 isolated from rhizosphere of grasses in South Africa at least before 2008 (WO 2014/029697; NRRL B-50755; e.g. BAC-UP from BASF Agricultural Specialties (Pty) Ltd., South Africa), Paenibacillus strains isolated from soil samples from a variety of European locations including Germany: P. epiphyticus Lu17015 (WO 2016/020371; DSM 26971), P. polymyxa ssp. plantarum Lu16774 (WO 2016/020371; DSM 26969), P. p. ssp. plantarum strain Lu17007 (WO 2016/020371; DSM 26970); Pasteuria nishizawae Pn1 isolated from a soybean field in the mid-2000s in Illinois, USA (ATCC SD-5833; Federal Register 76(22), 5808, February 2, 2011; e.g. Clariva™ PN from Syngenta Crop Protection, LLC, USA), Penicillium bilaiae (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 0307510B1; e.g. from Regalia® SC Marrone Bioinovations, Davis, CA, USA or Milsana® from BioFa AG, Germany), Steinernema carpocapsae (e.g. Millenium® from BASF Agricultural Specialties Limited, UK), S. feltiae (e.g. Nemashield® from BioWorks, Inc., USA; Nemasys® from BASF Agricultural Specialities Limited, UK), Streptomyces microflavus NRRL B-50550 (WO 2014/124369; Bayer CropScience, Germany), Trichoderma asperelloides JM41Risolada in South Africa (NRRL 50759; also referred to as T. fertile; e.g. from Trichoplus® by BASF Agricultural Specialties (Pty) Ltd., South Africa), T. harzianum T-22 also called KRL-AG2 (ATCC 20847; BioControl 57, 687-696, 2012; e.g. Plantshield® by BioWorks Inc., USA or SabrEx™ by Advanced Biological Marketing Inc., Van Wert, OH, USA).

[0440] According to an embodiment of the inventive mixtures, the at least one pesticide II is selected from groups L1) to L6): L1) Microbial pesticides with fungicidal, bactericidal, virucidal and/or plant defense activating activity: Aureobasidium pullulans DSM 14940 and DSM 14941 (L1.1), Bacillus amyloliquefaciens 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. pumilus GB34 (L.1.9), B. pumilus GHA 180 (L.1.10), B. pumilus INR-7 (L.1.11), B. pumilus QST 2808 (L.1.13), B. simplex ABU 288 (L.1.14), B. subtilis FB17 (L.1.15), thyrium minitans CON/M/91-08 (L.1.16), Metschnikowia fructicola NRRL Y 30752 (L.1.17), Penicillium bilaiae ATCC 22348 (L.1.19), P. bilaiae ATCC 20851 (L.1.20), Penicillium bilaiae ATCC 18309 (L.1.21), Streptomyces microflavus NRRL B-50550 (L.1.22), T. harzianum T-22 (L.1.24); L2) Biochemical pesticides with fungicidal, bactericidal, virucidal and/or plant defense activating activity: harpin protein (L.2.1), Reynoutria sachalinensis extract (L.2.2); L3) Microbial pesticides with insecticidal, acaricidal, molluscicidal and/or nematicidal activity: Bacillus firmus I 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), Burkholderia sp. A396 (L.3.9), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (L.3.10), Helicoverpa zea nucleopolyhedrovirus (HzNPV) ABA-NPV-U (L.3.11) .13), Isaria fumosorosea Apopka-97 (L.3.14), Metarhizium anisopliae var. anisopliae F52 (L.3.15), Paecilomyces lilacinus 251 (L.3.16), Pasteuria nishizawae Pn1 (L.3.17), Steinernema carpocapsae (L.3.18), S. feltiae (L.3.19); L4) Biochemical pesticides with insecticidal, acaricidal, molluscicidal, pheromone and/or nematicidal activity: cis-jasmone (L.4.1), methyl jasmonate (L.4.2), Quillay extract (L.4.3); and L5) Microbial pesticides with plant stress reducing, plant growth regulating, plant growth promoting and/or yield enhancing activity.

[0441] In a further aspect, the present invention relates to an agrochemical mixture comprising at least one fertilizer; and at least one nitrification inhibitor as defined herein above; or at least one fertilizer and a composition as mentioned above.

[0442] In terms of the present invention, “agrochemical mixture” means a combination of at least two compounds. The term, however, is not restricted to a physical mixture comprising at least two compounds, but refers to any form of preparation of at least one compound and at least one other compound, the use of which may be time and/or place related.

[0443] Agrochemical mixtures can, for example, be formulated separately but applied in a temporal relationship, that is, simultaneously or subsequently, the subsequent application having a time interval that allows a combined action of the compounds.

[0444] Furthermore, the individual compounds of the agrochemical mixtures according to the invention, as parts of a kit or parts of the binary mixture, can be mixed by the user himself in a suitable mixing device. In specific embodiments, further auxiliaries can be added if appropriate.

[0445] The term “fertilizers” should be understood as chemical compounds applied to promote the growth of plants and fruits. Fertilizers are typically applied through the soil (for uptake by plant roots), through soil replacers (also for uptake by plant roots) or by foliar feeding (for uptake by leaves). The term also includes mixtures of one or more different types of fertilizers, as mentioned below.

[0446] The term “fertilizers” can be subdivided into several categories, including: a) organic fertilizers (composed of decomposed plant/animal matter), b) inorganic fertilizers (composed of chemicals and minerals) and c) fertilizers containing urea.

[0447] Organic fertilizers include manure, for example, liquid fertilizer, semi-liquid fertilizer, biogas fertilizer, stable manure or straw manure, slurry, earthworm humus, peat, seaweed, compost manure, sewage water and guano. Green manure crops are also grown regularly to add nutrients (especially nitrogen) to the soil. Manufactured organic fertilizers include compound manures, blood meal, bone meal and seaweed extracts. Other examples are enzyme-digested proteins, fish meal and feather meal. Decomposing crop residue from previous years is another source of fertility. In addition, naturally occurring minerals such as mine rock phosphate, sulphate of potash and limestone are also considered inorganic fertilizers.

[0448] Inorganic fertilizers are generally 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.

[0449] The inorganic fertilizer may, in a specific embodiment, be an NPK fertilizer. “NPK fertilizers” are inorganic fertilizers formulated in appropriate concentrations and combinations, comprising the three major nutrients nitrogen (N), phosphorus (P), and potassium (K), as well as, typically, S, Mg, Ca, and trace elements.

[0450] The urea-containing fertilizer may in specific embodiments be urea solution, urea formaldehyde, anhydrous ammonium, urea ammonium nitrate (UAN), urea-sulfur, urea-based NPK fertilizers or urea-ammonium sulfate. It is also envisaged to use urea as a fertilizer. In the event that urea or urea-containing fertilizers are used or provided, it is particularly preferred that urease inhibitors as defined above may be added or additionally present, or are used at the same time or in connection with the urea-containing fertilizers.

[0451] Fertilizers may be supplied in any suitable form, for example as coated or uncoated solid granules, in liquid or semi-liquid form, as a sprayable fertilizer, or via fertigation etc.

[0452] Coated fertilizers can be provided with a wide range of materials. Coatings can, for example, be applied to granular or prilled nitrogen (N) fertilizers or to multi-nutrient fertilizers. Typically, urea is used as the base material for most coated fertilizers. Alternatively, ammonium or NPK fertilizers are used as the base material for coated fertilizers. The present invention, however, also provides for the use of other base materials for coated fertilizers, any of the fertilizer materials defined herein. In certain embodiments, elemental sulfur can be used as a fertilizer coating. The coating can be carried out by spraying molten S onto urea granules, followed by an application of sealant wax to close cracks in the coating. In a further embodiment, the S layer can be covered with a layer of organic polymers, preferably a thin layer of organic polymers.

[0453] Other envisaged coated fertilizers may be provided by reacting resin-based polymers on the surface of the fertilizer granule. Another example of providing coated fertilizers includes the use of low permeability polyethylene polymers in combination with high permeability coatings.

[0454] In specific embodiments, the composition and/or thickness of the fertilizer coating may be adjusted to control, for example, the rate of nutrient release for specific applications. The duration of nutrient release from specific fertilizers may vary, for example, 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 a nitrification inhibitor in accordance with the present invention.

[0455] 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 exhibit a predefined release longevity. In other embodiments, CRFs may be provided as controlled release blended 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 exhibit a predefined longevity, for example in the case of N-P-K fertilizers.

[0456] Additionally, envisaged examples of CRFs include standardized release fertilizers. These fertilizers typically feature pre-defined release patterns (e.g., high/standard/low) and a pre-defined longevity. In exemplary embodiments, the fully coated N-P-K, Mg, and micronutrients may be delivered in a standardized release manner.

[0457] Double coating approaches or coated fertilizers based on a programmed release are also envisaged.

[0458] In other 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, for example over a period of 1 to 5 months, preferably up to 3 months. Typical examples of slow-release fertilizer ingredients are IBDU (isobutylidene diurea), for example, containing about 31-32% nitrogen, of which 90% is water insoluble; or UF, i.e., a urea-formaldehyde product containing about 38% nitrogen, of which about 70% may be provided as water-insoluble nitrogen; or CDU (crotonylidene diurea) containing about 32% nitrogen; or MU (methylene urea) containing about 38-40% nitrogen, of which 25-60% is typically cold water insoluble nitrogen; or MDU (methylene diurea) containing about 40% nitrogen, of which less than 25% is cold-water insoluble nitrogen; or MO (methylol urea) containing about 30% nitrogen, which can typically be used in solutions; or DMTU (di-methylene triurea) containing about 40% nitrogen, of which less than 25% is cold-water insoluble nitrogen; or TMTU (tri-methylene tetraurea), which can be supplied as a component of UF products; or TMPU (tri-methylene pentaurea), which can also be supplied as a component of UF products; or UT (triazone urea solution) which typically contains about 28% nitrogen. The fertilizer mixture may also be a long-term nitrogen-containing fertilizer containing a mixture of acetylene diurea and at least one other organic nitrogen-containing fertilizer selected from methylene urea, isobutylidene diurea, crotonylidene diurea, substituted triazones, triuret or mixtures thereof.

[0459] Any of the above-mentioned fertilizers or fertilizer forms can be suitably combined. For example, slow-release fertilizers can be provided as coated fertilizers. They can also be combined with other fertilizers or fertilizer types. The same applies to the presence of a nitrification inhibitor according to the present invention, which can be adapted to the form and chemical nature of the fertilizer and consequently be provided in such a way that its release accompanies the release of the fertilizer, for example it is released at the same time or with the same frequency. The present invention further contemplates fertilizer or fertilizer forms as defined herein above in combination with nitrification inhibitors as defined herein above and additionally in combination with urease inhibitors as defined above. Such combinations can be provided as coated or uncoated forms and/or as slow or fast release forms. Combinations with slow-release fertilizers including a coating are preferred. In other embodiments, different release schemes are also envisaged, for example a slower or faster release.

[0460] The term “fertigation” as used herein refers to the application of fertilizers, optionally soil improvers, and optionally other water-soluble products together with water via an irrigation system, to a plant or to the site where a plant is growing or intended to grow, or to a soil replacer as defined herein below. For example, liquid fertilizers or dissolved fertilizers may be provided via fertigation directly to a plant or a site where a plant is growing or 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 site where a plant is growing or intended to grow. The fertilizers and nitrification inhibitors according to the present invention, or in combination with additional nitrification inhibitors, may be provided together, for example, dissolved in the same charge or load of material (typically water) to be irrigated. In other embodiments, the fertilizers and nitrification inhibitors may be provided at different points in time. For example, the fertilizer may be fertigated 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 time intervals outlined above for the application of fertilizers and nitrification inhibitors. Also contemplated is repeated fertigation of fertilizers and nitrification inhibitors according to the present invention, either together or intermittently, for example, every 2 hours, 6 hours, 12 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days or more.

[0461] In particularly preferred embodiments, the fertilizer is an ammonium-containing fertilizer.

[0462] The agrochemical mixture according to the present invention may comprise a fertilizer as defined herein above and a nitrification inhibitor of formula I as defined herein above. In other embodiments, the agrochemical mixture according to the present invention may comprise at least one or more than one fertilizer as defined herein above, for example 2, 3, 4, 5, 6, 6, 7, 8, 9, 10 or more different fertilizers (including inorganic, organic and urea-containing fertilizers) and at least one nitrification inhibitor of formula I as defined above, preferably a nitrification inhibitor of formula I selected from Table 1.

[0463] In another group of embodiments, the agrochemical mixture according to the present invention may comprise at least one or more than one nitrification inhibitor of formula I as defined herein above, preferably more than one nitrification inhibitor of formula I selected from Table 1, for example 2, 3, 4, 5, 6, 6, 7, 8, 9, 10 or more different nitrification inhibitors as defined herein above or as provided in Table 1 and at least one fertilizer as defined herein above.

[0464] The term “at least one” should be understood as 1, 2, 3 or more of the respective compound selected from the group consisting of fertilizers, as defined herein above (also referred to as compound A), and nitrification inhibitors of formula I, as defined herein above (also referred to as compound B).

[0465] In addition to at least one fertilizer and at least one nitrification inhibitor, as defined herein above, an agrochemical mixture may comprise additional ingredients, compounds, active compounds or compositions or the like. For example, the agrochemical mixture may additionally comprise or be composed of or based on a carrier, e.g., an agrochemical carrier, preferably as defined herein. In other embodiments, the agrochemical mixture may further comprise at least one pesticide compound. For example, the agrochemical mixture may additionally comprise at least one herbicide compound and/or at least one fungicide compound and/or at least one insecticide compound.

[0466] In other embodiments, the agrochemical mixture may, in addition to the ingredients indicated above, in particular in addition to the nitrification inhibitor of the compound of formula I and the fertilizer, further comprise alternative or additional nitrification inhibitors, such as linoleic acid, alpha-linolenic acid, p-methyl coumarate, methyl ferulate, MHPP, Karanjin, brachialactone, p-benzoquinone sorgoleone, nitrapyrin, dicyandiamide (DCD), 3,4-dimethylpyrazole phosphate (DMPP), 4-amino-1,2,4-triazole hydrochloride (ATC), 1-amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 5-ethoxy-3-trichloromethyl-1,2,4-thiodiazole (terrazole), ammonium thiosulfate (ATU), 3-methylpyrazole (3-MP) -pyrazol-1-yl)methylformamide, N-(4-chloro-3(5)-methyl-pyrazol-1-ylmethyl)-formamide, or N-(3(5,4-dimethyl-pyrazol-1-ylmethyl)-formamide.

[0467] Furthermore, the invention relates to a method for reducing nitrification, comprising treating a plant growing in the soil and/or the place where the plant is growing or is intended to grow with at least one nitrification inhibitor, as defined above, that is, with a nitrification inhibitor being a compound of formula I, or a derivative thereof, or a composition comprising said nitrification inhibitor.

[0468] The term “plant” should be understood as a plant of economic importance and/or a plant cultivated by man. In certain embodiments, the term may also be understood as plants that have no economic importance or do not have significant economic importance. The plant is preferably selected from agricultural, forestry and horticultural (including ornamental) plants. The term also refers to genetically modified plants.

[0469] 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 below-ground portions (such as roots) and above-ground portions.

[0470] Within the context of the method for reducing nitrification, it is assumed that the plant is growing in soil. In specific embodiments, the plant may also be grown in a different manner, for example in synthetic laboratory environments or in soil substitutes, or supplemented with nutrients, water etc. by artificial or technical means. In such scenarios, the invention envisages a treatment of the zone or area where nutrients, water etc. are supplied to the plant. It is also envisaged that the plant will be grown in greenhouses or similar indoor facilities.

[0471] The term “site” should be understood as any type of environment, soil, soil substitute, area or material where the plant is growing or is intended to grow. Preferably, the term refers to the soil or soil substitute in which a plant is growing.

[0472] 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 are harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fiber (e.g. cotton, flax), fuels (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; beets, e.g. sugar beets or fodder beets; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or currants; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rapeseed, oilseed rape, canola, linseed, mustard, olive, sunflower, coconut, cocoa beans, castor oil plants, oil palm, peanuts or soybeans; squashes, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, squash or paprika; lauraceae plants, such as avocados, cinnamon or camphor; energy plants and raw materials, such as corn, soybeans, rapeseed, canola, sugar cane or oil palm; tobacco; nuts; coffee; tea; bananas; vines (table grapes and vines for grape juice); hops; peat; natural rubber plants.

[0473] In another embodiment, the plant to be treated according to the method of the invention is a horticultural plant. The term “horticultural plants” should be understood as plants that are normally used in horticulture, for example the cultivation of ornamental plants, vegetables and/or fruits. Examples of ornamental plants are turf, geranium, pelargonia, petunia, begonia and fuchsia. Examples of vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas and lettuce and, more preferably, tomatoes, onions, peas and lettuce. Examples of fruits are apples, pears, cherries, strawberries, citrus fruits, peaches, apricots and blueberries.

[0474] In another embodiment, the plant to be treated according to the method of the invention is an ornamental plant. “Ornamental plants” are plants that are commonly used in gardening, for example in parks, gardens and balconies. Examples are: turf, geranium, pelargonia, petunia, begonia and fuchsia.

[0475] 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 the commercial production of forest products such as timber, pulp, paper, rubber, Christmas trees or young trees for gardening purposes. Examples of silvicultural plants are conifers such as pines, in particular Pinus spec., fir and spruce, eucalyptus, tropical trees such as teak, rubber, oil palm, willow (Salix), in particular Salix spec., poplar, in particular Populus spec., beech, in particular Fagus spec., birch, oil palm and oak.

[0476] The term “plant propagation material” should be understood as denoting all 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, branches, shoots, corms and other parts of plants, including seedlings and young plants, which will be transplanted after germination or after emergence from the soil, meristem, single and multiple plant cells and any other plant tissue from which a complete plant can be obtained.

[0477] The term “genetically modified plants” should be understood as plants, the genetic material of which has been modified by the use of recombinant DNA techniques in a manner that, under natural circumstances, cannot easily be obtained by crossing, 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, for example by glycosylation or polymer additions, such as prenylated, acetylated or farnesylated moieties or PEG moieties.

[0478] Plants that have been modified by breeding, mutagenesis, or genetic engineering, for example, have been made tolerant to applications of specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4-D; bleaching herbicides such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvyl shikimate 3-phosphate synthase (EPSP) 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 herbicides (i.e., bromoxynil or ioxynil) as a result of conventional breeding methods or genetic engineering. In addition, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to glyphosate and glufosinate or to glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are, for example, 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 cited therein. Several crop plants have been rendered herbicide tolerant by conventional breeding methods (mutagenesis), e.g. Clearfield® summer oilseed 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 make crop plants such as soybeans, cotton, corn, sugar beets and oilseed rape tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate tolerant, Monsanto, USA), Cultivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate tolerant, Bayer CropScience, Germany).

[0479] Furthermore, plants which are also covered by the use of recombinant DNA techniques capable of synthesizing one or more insecticidal proteins, especially those known from the Bacillus genus of bacteria, particularly from Bacillus thuringiensis, such as δ-endotoxins, e.g., CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b), CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins (VIPs), e.g., VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins from nematode-colonizing bacteria, e.g., Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnoid toxins, wasp toxins or other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins; plant lecithins, such as pea or barley lecithins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome inactivating proteins (RIP), such as ricin, corn-RIP, abrin, lufin, saporin or bryodin; enzymes of steroid metabolism, such as 3-hydroxysteroid oxidase, ecdysteroid ID-glycosyltransferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA reductase; ion channel blockers, such as sodium or calcium channel blockers; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention, these insecticidal proteins or toxins are to be expressly understood also as pretoxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a novel combination of protein domains (see, for example, WO 02/015701). Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 and WO 03/52073.

[0480] Methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the above-mentioned publications. These insecticidal proteins contained in the genetically modified plants confer on the plants, which produce these proteins, tolerance to harmful pests of all taxonomic groups of arthropods, especially to beetles (Coeloptera), two-winged insects (Diptera) and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable of synthesizing one or more insecticidal proteins are, for example, described in the publications mentioned above, and some of which are commercially available, such as YieldGard® (maize cultivars producing the Cry1Ab toxin), YieldGard® Plus (maize cultivars producing the Cry1Ab and Cry3Bb1 toxins), StarLink® (maize cultivars producing the Cry9c toxin), Herculex® RW (maize cultivars producing Cry34Ab1, Cry35Ab1 and the enzyme phosphinothricin-N-acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the Cry1Ac toxin), Bollgard® I (cotton cultivars producing the Cry1Ac toxin), Bollgard® II (cotton cultivars producing the Cry1Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars that produce a VIP toxin); NewLeaf® (potato cultivars that produce the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (e.g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (maize cultivars producing the Cry1Ab toxin and the PAT enzyme), MIR604 from Syngenta Seeds SAS, France (maize cultivars producing a modified version of the Cry3A toxin, see WO 03/018810), MON 863 from Monsanto Europe SA, Belgium (maize cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the Cry1Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium (maize cultivars producing the Cry1F toxin and the PAT enzyme).

[0481] Furthermore, plants are also covered by the use of recombinant DNA techniques capable of synthesizing one or more proteins to increase the resistance or tolerance of these plants to bacterial, viral or fungal pathogens. Examples of such proteins are so-called “pathogenesis-related proteins” (PR proteins, see e.g. EP-A 392 225), plant disease resistance genes (e.g. potato cultivars expressing resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanum) or T4-lysozyme (e.g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). 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.

[0482] In addition, plants are also covered by the use of recombinant DNA techniques capable of synthesizing one or more proteins to increase productivity (e.g., biomass production, grain yield, starch content, oil content, or protein content), tolerance to drought, salinity, or other growth-limiting environmental factors, or tolerance to fungal, bacterial, or viral pests and pathogens of these plants.

[0483] In addition, plants containing, by the use of recombinant DNA techniques, a modified amount of content substances or new content substances specifically to improve human or animal nutrition are also covered, for example oil crops producing health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e.g. Nexera® rapeseed, Dow Agro Sciences, Canada).

[0484] Furthermore, plants are also covered which contain, by the use of recombinant DNA techniques, a modified amount of content substances or new content substances, specifically to improve the production of raw material, for example potatoes which produce higher amounts of amylopectin (e.g. Amflora® potato, BASF SE, Germany).

[0485] The term “soil substitute” as used herein refers to a substrate that is capable of allowing the growth of a plant and does not comprise usual soil ingredients. This substrate is typically an inorganic substrate that may have the function of an inert medium. It may, in certain embodiments, also comprise organic elements or moieties. Soil substitutes may, for example, be used in hydrocultural or hydroponic approaches, i.e. where plants are grown in soilless media and/or aquatic environments. Examples of suitable soil substitutes that may be used in the context of the present invention are perlite, gravel, biochar, mineral wool, coconut shell, phyllosilicates, i.e. sheet silicate minerals typically formed by parallel sheets of silicate tetrahedra with Si2O5 or a ratio of 2:5, or clay aggregates, in particular expanded clay aggregates with a diameter of about 10 to 40 mm. Particularly preferred is the use of vermiculite, that is, a phyllosilicate with 2 tetrahedral sheets for each octahedral sheet present.

[0486] The use of soil replacers may, in specific embodiments, be combined with fertigation or irrigation as defined herein.

[0487] In specific embodiments, the treatment may be performed during all suitable growth stages of a plant as defined herein. For example, the treatment may be performed during the BBCH main growth stages.

[0488] The term “main growth stage BBCH” 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 development cycle of plants is subdivided into clearly recognizable and distinguishable longer lasting development phases. The BBCH scale uses a decimal code system, which is divided into main 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.

[0489] In one embodiment, the invention relates to a method for reducing nitrification comprising treating a plant growing in soil or soil substitutes and/or the site where the plant is growing or intended to grow, with at least one nitrification inhibitor as defined above, i.e. with a nitrification inhibitor being a compound of formula I, or a derivative thereof in a growth phase (GS) between GS 00 and GS > BBCH 99 of the plant (e.g. when fertilizing in the fall after harvesting apples) and preferably between GS 00 and GS 65 BBCH of the plant.

[0490] In one embodiment, the invention relates to a method for reducing nitrification comprising treating a plant growing in soil or soil substitutes and/or the site where the plant is growing or intended to grow with at least one nitrification inhibitor as defined above, i.e. with a nitrification inhibitor being a compound of formula I or a derivative thereof at a growth stage (GS) between GS 00 to GS 45, preferably between GS 00 and GS 40 BBCH of the plant.

[0491] In a preferred embodiment, the invention relates to a method for reducing nitrification comprising treating a plant growing in soil or soil substituents and/or the site where the plant is growing or intended to grow with at least one nitrification inhibitor as defined above, i.e. with a nitrification inhibitor being a compound of formula I, or a derivative thereof 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 in soil or soil substitutes and/or the site where the plant is growing or intended to grow, with at least one nitrification inhibitor as defined above during the growth stages, including GS 00.

[0492] In another specific embodiment of the invention, at least one nitrification inhibitor as defined above, i.e. a nitrification inhibitor being a compound of formula I or a derivative thereof, is applied to a plant growing in soil or soil substitutes and/or to the site where the plant is growing or is intended to grow at a growth stage between GS 00 and GS 55 BBCH, or to the plant.

[0493] In a further embodiment of the invention, at least one nitrification inhibitor as defined above, i.e. a nitrification inhibitor being a compound of formula I or a derivative thereof, is applied to a plant growing in soil or soil substitutes and/or to the site where the plant is growing or is intended to grow at the growth stage between GS 00 and GS 47 BBCH of the plant.

[0494] In one embodiment of the invention, at least one nitrification inhibitor as defined above, i.e. a nitrification inhibitor being a compound of formula I or a derivative thereof, is applied to a plant growing in soil or soil substitutes and/or to the site 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.

[0495] In a preferred embodiment, the invention relates to a method for reducing nitrification comprising treating a plant growing in soil or soil substitutes and/or the site where the plant is growing, with at least one nitrification inhibitor as defined above, i.e. with a nitrification inhibitor being a compound of formula I, or a derivative thereof, wherein the plant and/or the site where the 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 above. It is also envisaged to apply more than one fertilizer, for example 2, 3, 4, 5, 6, 7, 8, 9, 10 fertilizers, or from different classes or categories of fertilizers.

[0496] In specific embodiments of the invention, at least one nitrification inhibitor as defined above, i.e. a nitrification inhibitor being a compound of formula I or a derivative thereof and at least one fertilizer, are applied to a plant growing in soil or soil substitutes and/or to the site where the plant is growing or is intended to grow, at a growth stage between GS 00 and GS 33 BBCH of the plant.

[0497] In specific embodiments of the invention, at least one nitrification inhibitor as defined above, i.e. a nitrification inhibitor being a compound of formula I or a derivative thereof and at least one fertilizer, are applied to a plant growing in soil or soil substitutes and/or to the site where the plant is growing or is intended to grow, at a growth stage between GS 00 and GS 55 BBCH of the plant.

[0498] In other specific embodiments of the invention, at least one nitrification inhibitor as defined above, i.e. a nitrification inhibitor being a compound of formula I or a derivative thereof and at least one fertilizer, are applied to a plant growing in soil or soil substitutes and/or to the site 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 plant (e.g. when fertilizing in autumn after apple harvest) and preferably between GS 00 and 65 BBCH of the plant.

[0499] According to a preferred embodiment of the present invention, the application of said nitrification inhibitor and said fertilizer, as defined above, is carried out simultaneously or with a time lag. The term “time lag” as used herein means that the nitrification inhibitor is applied before the fertilizer to the plant growing in the soil or to the soil substitutes and/or to the site where the plant is growing or intended to grow; or the fertilizer is applied before the nitrification inhibitor to the plant growing in the soil or to the soil substitutes and/or to the site where the plant is growing or intended to grow. Such a time lag may be any suitable period of time that still allows for providing a nitrification inhibitory effect in the context of fertilizer use. 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 a time interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks. Time lag preferably refers to situations where the nitrification inhibitor, as defined above, is supplied 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 period of time between the mentioned time periods prior to the application of a fertilizer, as defined above.

[0500] In another specific embodiment of the invention, at least one nitrification inhibitor as defined above, that is, a nitrification inhibitor being a compound of formula I, or a derivative thereof, 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 above is carried out with a time lag of at least 1 day, for example, 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 period of time between the mentioned time periods. It is preferred that nitrification inhibitors, which are applied between GS 00 to GS 33 BBCH of the plant, be supplied 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 prior to the application of a fertilizer as defined above.

[0501] 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 at least one nitrification inhibitor as defined herein above, that is to say of a nitrification inhibitor being a compound of formula I, or a derivative thereof, is carried out with a time lag of at least 1 day, for example 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 period of time between the mentioned time periods.

[0502] According to a specific embodiment of the present invention, a plant growing in soil or soil substitutes and/or the site where the plant is growing or is intended to grow is treated at least once with a nitrification inhibitor as defined above, i.e. with a nitrification inhibitor being a compound of formula I or a derivative thereof. In a further specific embodiment of the present invention, a plant growing in soil or soil substitutes and/or the site where the plant is growing or is intended to grow is treated at least once with a nitrification inhibitor as defined above, i.e. with a nitrification inhibitor being a compound of formula I or a derivative thereof, and at least once with a fertilizer as defined above.

[0503] The term “at least once” means that the application can be carried out once, or several times, that is, that a repetition of the treatment with a nitrification inhibitor and/or a fertilizer can be envisaged. Such repetition can be a frequent repetition of 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or more of the treatment with a nitrification inhibitor and/or a fertilizer. The repetition of the treatment with a nitrification inhibitor and a fertilizer can also be different. For example, while the fertilizer can be applied only once, the nitrification inhibitor can be applied 2 times, 3 times, 4 times etc. Alternatively, while the nitrification inhibitor can be applied only once, the fertilizer can be applied 2 times, 3 times, 4 times etc. Furthermore, all combinations of different numerical numbers of repetitions for the application of a nitrification inhibitor and a fertilizer as defined above are envisaged.

[0504] This repeated treatment can also be combined with a time lag between the treatment with the nitrification inhibitor and the fertilizer, as described above.

[0505] The time interval between a first application and the second or subsequent application of the nitrification inhibitor and/or a fertilizer may be any suitable interval. This interval may range from a few seconds to 3 months, for example, from a few seconds to 1 month, or from a few seconds to 2 weeks. In other embodiments, the time interval may range from a few seconds to 3 days or from 1 second to 24 hours.

[0506] In other specific embodiments, a method for reducing nitrification as described above is carried out by treating a plant growing in soil or soil substitutes and/or the site where the plant is growing or intended to grow, with at least one agrochemical mixture as defined herein above, or with a composition for reducing nitrification, as defined herein above.

[0507] In another embodiment of the invention, an agrochemical mixture comprising an ammonium- or urea-containing fertilizer and at least one nitrification inhibitor as defined above is applied before and during sowing, before emergence, and up to GS > BBCH 99 of the plant (e.g. when fertilizing in the fall after apple harvest). If the agrochemical mixture is supplied as a kit of parts or as a non-physical mixture, it can be applied with a time lag between the application of the nitrification inhibitor and the fertilizer or between the application of the nitrification inhibitor and a secondary or additional ingredient, for example a pesticidal compound as mentioned above.

[0508] In another embodiment, the plant propagules are preferably treated simultaneously (together or separately) or subsequently.

[0509] The term “propagules” or “plant propagules” should be understood as denoting any structure with the capacity to originate a new plant, for example, a seed, a spore or a part of the vegetative body capable of growing independently if separated from the parent. In a preferred embodiment, the term “propagules” or “plant propagules” means seed.

[0510] 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 nitrification inhibitors, i.e. of the compound of formula I, 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 seed treatment, amounts of 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 generally be required.

[0511] As expected, if nitrification inhibitors and fertilizers (or other ingredients) are used, or if mixtures thereof, the compounds can be used in an effective and non-phytotoxic amount. This means that they are used in an amount that allows the desired effect to be obtained, but which does not give rise to any phytotoxic symptoms in the treated plant or in the plant originating from the treated propagule or from the treated soil or soil replacers. For use according to the invention, fertilizer application rates can be selected such that the amount of N applied is between 10 kg and 1000 kg per hectare, preferably between 50 kg and 700 kg per hectare.

[0512] The nitrification inhibitor compounds according to the invention, for example compound I as defined herein above or a derivative thereof as defined herein above, may be present in different structural or chemical modifications whose biological activity may differ. They are also the subject of the present invention.

[0513] The nitrification inhibitor compounds according to the invention, their N-oxides and/or salts etc. can be converted into usual types of compositions, for example agrochemical or agricultural compositions such as solutions, emulsions, suspensions, powders, dusts, pastes and granules.

[0514] The type of composition depends on the specific intended purpose; in each case, a fine and uniform distribution of the compound according to the invention must be ensured. Examples of composition types are suspensions (SC, 00, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), microemulsions (ME), pastes, tablets, wettable powders or dusts (WP, SP, SS, WS, OP, OS) or granules (GR, FG, GG, MG), which can be water-soluble or wettable, as well as gel formulations for the treatment of plant propagation material such as seeds (GF). Typically, composition types (e.g. SC, 00, FS, EC, WG, SG, WP, SP, SS, WS, GF) are used diluted. Composition types such as OP, OS, GR, FG, GG and MG are generally used undiluted.

[0515] 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, December 4, 1967, 14748, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 et seq. 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, 1963, pp. 8-57 et seq.). 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 also include auxiliaries that are customary, for example, in agrochemical compositions. The auxiliaries used depend on the specific form of application and the active substance, respectively.

[0516] Examples of suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (as additional solubilizers, protective colloids, surfactants and adhesion agents), organic and inorganic thickeners, bactericides, anti-freeze agents, anti-foaming agents, if appropriate, colorants and adhesion or binding agents (e.g. for seed treatment formulations). Suitable solvents are water, organic solvents such as medium to high boiling point mineral oil fractions such as kerosene or diesel oil, in addition coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as cyclohexanone and gamma-butyrolactone, fatty acid dimethylamides, fatty acids and fatty acid esters and strongly polar solvents, e.g. amines such as N-methylpyrrolidone.

[0517] Suitable surfactants (adjuvants, wetting agents, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids such as ligninsulfonic acid (types Borresperse®, Borregard, Norway), phenolsulfonic acid, naphthalenesulfonic acid (types Morwet®, Akzo Nobel, USA), dibutylnaphthalenesulfonic acid (types Nekal®, BASF, Germany) and fatty acids, alkylsulfonates, alkylarylsulfonates, alkylsulfates, lauryl ether sulfates, fatty alcohol sulfates and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, in addition condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene ether octylphenyl, ethoxylated isooctylphenol, octylphenol, nonylphenol, polyglycol alkylphenyl ethers, polyglycol tributylphenyl ether, polyglycol tristearylphenyl ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, polyglycol lauryl alcohol acetal, sorbitol esters, lignin-sulfite and protein waste liquors, denatured proteins, polysaccharides (e.g. methyl cellulose), hydrophobically modified starches, polyvinyl alcohols (types Mowiol®, Clariant, Switzerland), polycarboxylates (types Sokolan®, BASF, Germany), polyalkoxylates, polyvinylamines (types Lupasol®, BASF, Germany), polyvinylpyrrolidone and copolymers thereof. Examples of suitable thickeners (i.e. compounds that impart a modified fluidity to compositions, i.e. high viscosity under static conditions and low viscosity during stirring) are organic and inorganic polysaccharides and clays such as xanthan gum (Kelzan®, CP Kelco, USA), Rhodopol® 23 (Rhodia, France), Veegum® (RT Vanderbilt, USA) or Attaclay® (Engelhard Corp., NJ, USA).

[0518] In specific embodiments, bactericides may be added for preservation and stabilization of the composition. Examples of suitable bactericides are those based on dichlorophene and benzyl alcohol hemiformal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide® MBS from Thor Chemie).

[0519] Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerine. Examples of antifoaming agents are silicone emulsions (such as, for example, Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long-chain alcohols, fatty acids, fatty acid salts, fluoro-organic compounds and mixtures thereof.

[0520] Suitable dyes are pigments with low water solubility and water-soluble paints, for example, rhodamine B, C.I. pigment red 112 and 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.

[0521] In addition, odoriferous substances may be present in the compositions, as defined above. Such odoriferous substances include citronelinitril, citral, zertrahydrolinalool, tetrahydrogeraniol, geranonitril, beta-lonone R, rootanol, linalylacetate, morilol and p-cresomethyl ether.

[0522] Examples of tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan).

[0523] Powders, spreading materials and dusts can be prepared by concomitantly mixing or grinding the compound of formula I and, if appropriate, other active substances, with at least one solid carrier. Granules, for example 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 gel, silicates, talc, kaolin, attaclay, limestone, lime, chalk, friable clay, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin, such as cereal flour, tree bark flour, wood flour and nutshell flour, cellulose powders or other solid carriers.

[0524] Examples of composition types are: i) Water-soluble concentrates (SL, LS): 10 parts by weight of a nitrification inhibitor, such as a compound of formula I according to the invention, are dissolved in 90 parts by weight of water or in a water-soluble solvent. Alternatively, wetting agents or other auxiliaries are added. The active substance dissolves after dilution with water. In this way, a composition with a content of 10% by weight of active substance is obtained; ii) Dispersible concentrates (DC): 20 parts by weight of a nitrification inhibitor, such as a compound of formula I according to the invention, are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water provides a dispersion. The active substance content is 20% by weight; iii) Emulsifiable concentrates (EC): 15 parts by weight of a nitrification inhibitor, such as a compound of formula I, according to the invention, are dissolved in 75 parts by weight of xylene with the 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, EO, ES): 25 parts by weight of a nitrification inhibitor, such as a compound of formula I, according to the invention, are dissolved in 35 parts by weight of xylene with the 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 transformed 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 a stirred ball mill, 20 parts by weight of a nitrification inhibitor, such as a compound of formula I according to the invention, are ground with the 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 suspension of the active substance. 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, such as a compound of formula I according to the invention, are finely ground with the addition of 50 parts by weight of dispersants and wetting agents and prepared as water-dispersible or water-soluble granules by means of technical apparatus (e.g. extrusion, spray tower, fluidized bed). Dilution in water provides 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, such as a compound of formula I according to the invention, are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water provides a stable dispersion or solution of the active substance. The active substance content of the composition is 75% by weight; viii) Gel (GF): In a stirred ball mill, 20 parts by weight of a nitrification inhibitor, such as a compound of formula I according to the invention, are ground with the addition of 10 parts by weight of dispersants, 1 part by weight of a wetting gelling agent and 70 parts by weight of water or an organic solvent to provide a fine suspension of the active substance. Dilution with water provides a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained; 2. Types of composition to be applied undiluted: ix) Sprayable powders (OP, OS): 5 parts by weight of a nitrification inhibitor, such as a compound of formula I according to the invention, are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This provides a sprayable 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, such as a compound of formula I according to the invention, are finely ground and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray drying or fluidized bed. This provides 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; and xi) ULV solutions (UL): 10 parts by weight of a nitrification inhibitor, such as a compound of formula I according to the invention, are dissolved in 90 parts by weight of an organic solvent, for example xylene. This provides a composition to be applied undiluted, having an active substance content of 10% by weight.

[0525] The compositions, for example agrochemical or agricultural compositions, generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, more preferably between 0.5 and 90%, by weight of active substance. The active substances are used with a purity of 90% to 100%, preferably of 95% to 100% (according to the NMR spectrum).

[0526] Water-soluble concentrates (LS), fluid concentrates (FS), dry treatment powders (OS), water-dispersible powders for sludge treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are generally employed for the purpose of treating plant propagation materials, particularly seeds.

[0527] These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted.

[0528] The compositions in question give, after dilution two to ten times, active substance concentrations of 0.01 to 60% by weight, preferably 0.1 to 40% by weight, in the ready-to-use preparations. The application can be carried out before or during sowing.

[0529] Methods for applying or treating agrochemical or agricultural compounds or mixtures, or compositions as defined herein, respectively, to plant propagation material, especially seeds, on the plant and/or at the site where the plant is growing or intended to grow are known in the art, and include methods of applying the propagation material by covering, coating, pelleting, dusting, dipping and in-furrowing. In a preferred embodiment, the compounds or compositions thereof, respectively, are applied to the plant propagation material by a method such that germination is not induced, for example, by covering, pelleting, coating and dusting seeds

[0530] In a preferred embodiment, a suspension type composition (FS) may be used. Typically, a FS composition may comprise 1-800 g/I of active substance, 1-200 g/I of surfactant, 0-200 g/I of antifreeze agent, 0-400 g/I of binder, 0-200 g/I of a pigment and up to 1 liter of solvent, preferably water.

[0531] The active substances can be used as such or in the form of their compositions, for example in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, sprayable products, spreading materials or granules, by means of spraying, atomizing, dusting, spreading, brushing, dipping or pouring.

[0532] The application forms depend entirely on the intended purposes; the aim is 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.

[0533] To prepare oil emulsions, pastes or dispersions, the substances, as such, or dissolved in an oil or solvent, can be homogenized in water by means of a wetting agent, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetting agent, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and these concentrates are suitable for dilution in water.

[0534] The concentrations of active substance in the ready-to-use preparations can vary within relatively wide ranges. In general, they are from 0.0001 to 90%, such as from 30 to 80%, for example from 35 to 45% or from 65 to 75% by weight of active substance. The active substances can also be successfully used in the ultra-low volume (ULV) process, whereby compositions comprising more than 95% by weight of active substance can be used, or even the active substance can be used without additives.

[0535] Various types of oils, wetting agents, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the active substances or to the compositions comprising them, if appropriate not until immediately before use (tank mixing). These agents may be mixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

[0536] Adjuvants that may 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, for example Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates such as Lutensol XP 80®; and sodium dioctyl sulfosuccinate such as Leophen RA®.

[0537] In a further aspect, the invention relates to a method for treating a fertilizer or a composition. This treatment includes the application of a nitrification inhibitor which is a compound of formula I, as defined herein above, to a fertilizer or a composition. The treatment may consequently result in the presence of said nitrification inhibitor in a fertilizer preparation or other compositions. This treatment may, for example, result in a homogeneous distribution of nitrification inhibitors on or in fertilizer preparations. Treatment processes are known to the person skilled in the art and may include, for example, covering, coating, pelletizing, dusting or dipping. 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 is known to the person skilled in the art, for example, fluidized bed granulation. The treatment may, in certain embodiments, be carried out with a composition comprising the nitrification inhibitor as defined herein above, for example comprising, in addition to the inhibitor, a carrier or a pesticide or any other suitable additional compound as mentioned above.

[0538] In another specific embodiment, the present invention relates to a method for the treatment of seeds or plant propagation material. The term “seed treatment” as used herein refers to or involves steps for the control of biotic stresses on or in seeds and the improvement of the emergence and development of plants from seeds. For seed treatment it is evident that a plant suffering from biotic stress, such as fungal or insecticidal attack, or which has difficulties in obtaining sufficient adequate nitrogen sources, exhibits reduced germination and emergence leading to poorer plant establishment and vitality or crops and consequently to a reduced yield compared to a plant propagation material which has been subjected to curative or preventive treatment against the relevant pest, and which is allowed to grow without the damage caused by the biotic stress factor. The methods for the treatment of seeds or plant propagation material according to the invention thus lead, among other advantages, to improved plant health, better protection against biotic stresses and a higher plant yield.

[0539] Seed treatment methods for applying or treating inventive mixtures and compositions thereof, for example agrochemical compositions or 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 methods of applying the propagation material by covering, coating, film coating, pelleting and dipping. Such methods are also applicable to the combinations or compositions according to the invention.

[0540] In other embodiments, the seed treatment is carried out with compositions comprising, in addition to a nitrification inhibitor according to the present invention, for example 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.

[0541] 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 to plant propagation material by a method such that germination is not negatively impacted. Accordingly, examples of suitable methods for applying (or treating) a plant propagation material, such as a seed, are seed dressing, seed coating or seed pelleting and the like. It is preferred that the plant propagation material is a seed, a seed piece (i.e. peduncle) or a seed bulb.

[0542] While it is believed that the present method may be applied to a seed in any physiological state, it is preferable that the seed be in a sufficiently durable state that it will not incur damage during the treatment process. Typically, the seed would be a seed that has 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, in that the treatment would not cause biological damage to the seed. It is believed that the treatment may be applied to the seed at any time between harvesting the seed and sowing the seed or during the sowing process (directed seed applications). The seed may also be prepared before or after treatment.

[0543] Uniform distribution of the ingredients in compositions or mixtures as defined herein and their adherence to the seeds is desired during the treatment of propagation material. The treatment may range from a thin film (coating) of the formulation containing the combination, e.g. 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 intermediate state (such as a coating) and then to a thicker film (such as pelleting) with many layers of different materials (such as carriers, e.g. 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.

[0544] One aspect of the present invention includes applying the composition, e.g. agricultural composition or combination comprising a nitrification inhibitor according to the present invention, e.g. as defined herein above, to plant propagation material in a targeted manner, including positioning the ingredients in the combination over the entire plant propagation material or only on parts thereof, including on only a single side or a part of a single side. One skilled in the art will understand these application methods from the description provided in EP 954213 B1 and WO 06/112700.

[0545] The composition, e.g. agricultural composition or combination comprising a nitrification inhibitor according to the present invention, e.g. as defined herein above, may also be used in the form of a “capsule” or “granule” or a suitable substrate and by placing or sowing the treated capsule or substrate next to a plant propagation material. Such techniques are known in the art, particularly in EP 1124414, WO 07/67042 and WO 07/67044. The application of the composition, e.g. agricultural composition, or combination comprising a nitrification inhibitor according to the present invention, e.g. as defined above, to plant propagation material also includes protecting the plant propagation material treated with the combination of the present invention by placing one or more particles containing nitrification inhibitors (NI) and pesticide in proximity to a seed treated with pesticide and NI, wherein the amount of pesticide is such that the pesticide-treated seed and the pesticide-containing particles together contain an Effective Dose of the pesticide, and the dose of pesticide contained in the pesticide-treated seed is less than or equal to the Maximum Non-Phytotoxic Dose of the pesticide. Such techniques are known in the art, particularly in WO 2005/120226.

[0546] Application of the combinations to seed also includes controlled-release coatings on 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 polymeric 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.

[0547] Seeds can be treated by applying to them the compounds present in the mixtures of the invention in any desired sequence or simultaneously.

[0548] Seed treatment occurs to an unsown seed, and the term “unsown seed” is intended to include seed at any period between the harvesting of the seed and the sowing of the seed in the soil for the purpose of germination and plant growth.

[0549] Treatment to an unsown seed is not intended to include practices in which the active ingredient is applied to the soil or soil replacers, but includes any application practice that targets the seed during the planting process.

[0550] Preferably, the treatment takes place prior to sowing the seed so that the sown seed has been pretreated 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 to the seed and thus available for pest control.

[0551] Treated seeds can be stored, handled, sown and tilled in the same way as any other seed treated with an active ingredient.

[0552] Seed treatment solutions (LS), suspoemulsions (SE), flowable concentrates (FS), dry treatment powders (DS), water dispersible powders for slurry treatment (WS), water soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are generally employed for the purpose of treating plant propagation materials, primarily seeds. Preferred examples of seed treatment or soil application formulation types for premix compositions are of the WS, LS, ES, FS, WG or CS type.

[0553] The compositions in question provide, after dilution two to ten times, concentrations of active components of 0.01 to 60% by weight, preferably of 0.1 to 40%, in the ready-to-use preparations. The 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, for example as defined herein above, to plant propagation material, especially seeds, include methods of applying the propagation material by covering, coating, pelleting, dusting, dipping and in-furrow application. Preferably, compositions or combinations comprising a nitrification inhibitor according to the present invention, for example as defined herein above, are applied to the plant propagation material by a method such that germination is not induced, for example by covering, pelleting, coating and dusting of seeds.

[0554] Typically, a premix 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), wherein the adjuvants may be a surfactant in an amount of 0 to 50 percent, especially 0.5 to 40 percent, based on the premix formulation. While commercial products will preferably be formulated as concentrates (e.g., premix composition (formulation)), the end user will typically employ diluted formulations (e.g., tank mix composition).

[0555] When used for plant protection, the total amounts of active components applied are, depending on the type 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. Application rates may vary from about 1 x 106 to 5 x 1015 (or more) CFU/ha. Preferably, the spore concentration is from about 1 x 107 to about 1 x 1011 CFU/ha. In the case of (entomopathogenic) nematodes as microbial pesticides (e.g. Steinernema feltiae), application rates preferably range from 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 living stage, preferably in an effective juvenile stage) per ha.

[0556] When employed in plant protection by seed treatment, the amount of compositions or combinations comprising a nitrification inhibitor according to the present invention, for example as defined herein above (based on the total weight of the active components) is in the range of 0.01 to 10 kg, preferably 0.1 to 1000 g, more preferably 1 to 100 g per 100 kg of plant propagation material (preferably seeds). Application rates relative to the plant propagation material may preferably range from about 1 x 106 to 1 x 1012 (or more) CFU/seed. Preferably, the concentration is from about 1 x 106 to about 1 x 1011 CFU/seed. Alternatively, application rates in relation 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.

[0557] The present invention is further illustrated by the following examples.

EXAMPLES EXAMPLE 1

[0558] The compounds of the invention were tested as follows in terms of the inhibition of nitrification: - 100 g of soil are filled into 500 ml plastic jars (e.g. soil sampled from the field) and moistened to 50% of the water holding capacity. The soil is incubated at 20 °C for two weeks to activate the microbial biomass. 1 ml of the test solution, containing the compound at the appropriate concentration (usually 0.3 or 1% nitrogen N), or DMSO and 10 mg of nitrogen in the form of ammonium sulfate-N is added to the soil and everything is mixed well. The jars are capped, but loosely, to allow air exchange. The jars are then incubated at 20 °C for 0 and 14 days.

[0559] For analysis, 300 ml of a 1% K2SO4 solution is added to the flask containing the soil and shaken for 2 hours on a horizontal shaker at 150 rpm. Then, the entire solution is filtered through a filter (Macherey-Nagel Filter MN 807%). The ammonium and nitrate content is then analyzed in the filtrate on an automatic analyzer at 550 nm (Merck, AA11).

[0560] Inhibition (NI at a specified concentration) is calculated as follows:

[0561] The following compounds of general formula I.1(i) were tested: * In each case, the best NI value obtained is given (only compounds with values > 20).

[0562] In addition, the following compounds of general formula I.3(i) were tested: * In each case, the best NI value obtained is given (only compounds with values > 20).

[0563] In addition, the following compounds of general formula I.3(ii) were tested: * In each case, the best NI value obtained is given (only compounds with values > 20).

Claims (14)

1. USE OF AN N-FUNCTIONALIZED ALKOXY PYRAZOLE COMPOUND of formula I: or a salt, stereoisomer, tautomer or N-oxide thereof, wherein: - R1 is C1-C6 alkyl, benzyl, or allyl; - R2 is halogen, C1-C6 alkyl, C3-C6 cycloalkyl, benzyl, allyl or phenyl, wherein said phenyl group is unsubstituted or substituted by one or more same or different Rx substituents; - RN is CHRaC(=O)ORb, CHRaC(=O)NRbRc, CH(C(=O)ORb)CH2(C(=O)ORb); C(=O)Rd or CHRaNRe(C=O)Rf; and wherein: - Ra is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C8 cycloalkyl, phenyl or phenyl-C1-C2 alkyl; - Rb is H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C8 cycloalkyl, phenyl or phenyl-C1-C2 alkyl; - Rc is H, C1-C4 alkyl, C1-C4 haloalkyl or phenyl; - Rd is H, C1-C8 alkyl, C2-C8 alkenyl, C2-C8 alkynyl, phenyl or phenyl-C1-C2 alkyl, wherein these groups are unsubstituted or substituted by a COOH group; - Re is H, C1-C4 alkyl, C3-C8 cycloalkyl or C6-C10 aryl; - Rf is H or C1-C4 alkyl; - Rx is halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy; and - n is 0, 1 or 2, characterized by being a nitrification inhibitor. 2. USE, according to claim 1, characterized in that: n is 0, that is, R2 is absent; or n is 1 and R2 is C1-C3 alkyl or phenyl. 3. USE according to any one of claims 1 to 2, characterized in that: Ra is H; Rb is H or C1-C4 alkyl; Rc is H or C1-C4 alkyl; Rd is C1-C3 alkyl; Re is H; and Rf is H or CH3. 4. NITRIFICATION REDUCING COMPOSITION, characterized by comprising at least one compound of formula I, as defined in any one of claims 1 to 3, and at least one vehicle. 5. USE OF THE COMPOSITION, as defined in claim 4, characterized by being as a nitrification inhibitor. 6. AGROCHEMICAL MIXTURE, characterized by comprising: (i) at least one fertilizer; and (ii) at least one compound of formula I, as defined in any one of claims 1 to 3, or the composition, as defined in claim 4. 7. USE according to any one of claims 1 to 3 or 5, characterized in that said compound of formula I is used in combination with a fertilizer, optionally in the form of the agrochemical mixture as defined in claim 6. 8. USE according to any one of claims 1 to 3 or 5 or 7, characterized in that said nitrification reduction occurs in or on a plant, in the root zone of a plant, in or on soil or soil substitutes and/or at the site where a plant is growing or is intended to grow. 9. A method for reducing nitrification, comprising treating a plant growing in soil or soil substitutes and/or the site or soil or soil substitutes where the plant is growing or intended to grow, with at least one compound of formula I as defined in any one of claims 1 to 3, or a composition as defined in claim 4. 10. The method of claim 9, wherein the plant and/or the site or soil or soil substitutes where the plant is growing or is intended to grow is additionally supplied with a fertilizer. 11. METHOD according to any one of claims 9 to 10, characterized in that the application of said compound of formula I and said fertilizer is carried out simultaneously or with a time delay, preferably an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks. 12. METHOD FOR TREATING A FERTILIZER or a composition, characterized by comprising the application of a compound of formula I, as defined in any one of claims 1 to 3. 13. AGROCHEMICAL MIXTURE, according to claim 6, use, according to any one of claims 5 or 7 to 8, or method, according to any one of claims 10 to 12, characterized in that said fertilizer is a solid or liquid inorganic fertilizer containing ammonium, such as an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; a solid or liquid organic fertilizer, such as liquid fertilizer, semi-liquid fertilizer, biogas fertilizer, stable fertilizer and straw fertilizer, worm humus, compost fertilizer, seaweed or guano; or a fertilizer containing urea, such as urea, urea formaldehyde, anhydrous ammonium, urea-ammonium nitrate (UAN) solution, urea-sulfur, urea-based NPK fertilizers, or urea-ammonium sulfate. 14. USE according to any one of claims 8 or 13, or method according to any one of claims 9 to 11 or 13, characterized in that said plant is an agricultural plant, such as wheat, barley, oats, rye, soybean, corn, potato, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice, or a vegetable such as spinach, lettuce, asparagus or cabbage; or sorghum; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or genetically modified form.