NZ731389B2 - Benzylpropargylether as nitrification inhibitors - Google Patents

Benzylpropargylether as nitrification inhibitors Download PDF

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Publication number
NZ731389B2
NZ731389B2 NZ731389A NZ73138915A NZ731389B2 NZ 731389 B2 NZ731389 B2 NZ 731389B2 NZ 731389 A NZ731389 A NZ 731389A NZ 73138915 A NZ73138915 A NZ 73138915A NZ 731389 B2 NZ731389 B2 NZ 731389B2
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compound
plant
formula
fertilizer
nitrification
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NZ731389A
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NZ731389A (en
Inventor
Joachim Dickhaut
Barbara Nave
Gregor Pasda
Mihiret Tekeste Sisay
Wolfgang Weigelt
Alexander Wissemeier
Wolfram Zerulla
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Basf Se
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Priority claimed from PCT/EP2015/076554 external-priority patent/WO2016075289A1/en
Publication of NZ731389A publication Critical patent/NZ731389A/en
Publication of NZ731389B2 publication Critical patent/NZ731389B2/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01C—PLANTING; SOWING; FERTILISING
    • A01C1/00—Apparatus, or methods of use thereof, for testing or treating seed, roots, or the like, prior to sowing or planting
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D1/00—Fertilisers containing potassium
    • C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/34—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups bound to carbon atoms of six-membered aromatic rings and etherified hydroxy groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C07C205/38—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. nitrodiphenyl ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/42—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings and singly-bound oxygen atoms bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/17—Unsaturated ethers containing halogen
    • C07C43/174—Unsaturated ethers containing halogen containing six-membered aromatic rings
    • C07C43/176—Unsaturated ethers containing halogen containing six-membered aromatic rings having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/285—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings having unsaturation outside the six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
    • C07C65/28—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups having unsaturation outside the aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Abstract

The present invention relates to the use of compounds of formula (I) for reducing nitrification and to compositions comprising the compounds of formula (I) and to agricultural mixtures comprising at least one compound of formula (I) and at least one fertilizer. Furthermore, the present invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus or soil or soil substituents where the plant is growing or is intended to grow with a compound of formula (I) or a composition comprising a compound of formula (I)

Description

Benzylpropargylether as nitrification tors Description The t invention s to novel nitrification inhibitors of formula I. Moreover, the ion relates to the use of compounds of formula I as nitrification inhibitors, i.e. for reducing nitrification , as well as agrochemical mixtures and compositions comprising the nitrification inhibitors.
Further encompassed by the present invention are methods for reducing nitrification, said methods comprising the treatment of plants, soil and/or loci where the plant is g or is in­ tended to grow with said nitrification inhibitors and methods for treating a fertilizer or a composition by applying said nitrification inhibitor. en is an ial element for plant growth and reproduction. About 25% of the plant available nitrogen in soils (ammonium and nitrate) originate from decomposition processes (mineralization) of organic nitrogen compounds such as humus, plant and animal residues and organic fertilizers. Approximately 5% derive from rainfall. On a global basis, the biggest part (70%), however, is supplied to the plant by inorganic nitrogen fertilizers. The mainly used nitrogen fertilizers se ammonium nds or derivatives thereof, i.e. nearly 90% of the nitrogen fertilizers d worldwide is in the NhV form (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302). This is, inter alia, due to the fact that NhV assimilation is energetical­ ly more efficient than assimilation of other nitrogen sources such as NOa'.
Moreover, being a cation, NhV is held electrostatically by the negatively charged clay surfaces and functional groups of soil organic matter. This binding is strong enough to limit NhV-loss by leaching to groundwater. By contrast, NO3', being negatively charged, does not bind to the soil and is liable to be leached out of the plants' root zone. In on, nitrate may be lost by ification which is the microbiological conversion of nitrate and nitrite (NO2') to gaseous forms of nitrogen such as nitrous oxide (N2O) and lar nitrogen (N2).
However, ammonium (NH4+) compounds are converted by soil microorganisms to nitrates (NO3') in a relatively short time in a process known as nitrification. The nitrification is carried out ily by two groups of chemolithotrophic bacteria, a-oxidizing bacteria (AOB) of the genus Nitrosomonas and Nitrobacter, which are tous component of soil bacteria populations.
The enzyme, which is essentially responsible for nitrification is ammonia monooxygenase (AMO), which was also found in a-oxidizing archaea (Subbarao et al., 2012, Advances in Agronomy, 114, 249-302).
The nitrification s typically leads to nitrogen leakage and environmental pollution. As a result of the various losses, approximately 50% of the applied nitrogen fertilizers are lost during the year following fertilizer addition (see Nelson and Huber; Nitrification inhibitors for corn production (2001), National Corn Handbook, Iowa State University). 40 As countermeasures the use of nitrification inhibitors, mostly er with fertilizers, was suggested.
Suitable nitrification inhibitors include biological nitrification inhibitors (BNIs) such as linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, MHPP, Karanjin, brachialacton or the p-benzoquinone sorgoleone (Subbarao et al., 2012, Advances in Agrono- my, 114, 249-302). Further suitable ication tors are tic al inhibitors such as Nitrapyrin, dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate (DMPP), 4- amino-1,2,4-triazole hydrochloride (ATC), othiourea (ASU), 2-aminochloro methylpyrimidine (AM), 5-ethoxytrichloromethyl-1,2,4-thiodiazole (terrazole), or 2- sulfanilamidothiazole (ST) (Slangen and Kerkhoff, 1984, Fertilizer research, 5(1), 1-76).
Furthermore, pyrazole-based nitrification inhibitors have been described, e.g., in US 3,635,690, 031 B3.
However, many of these nitrification inhibitors have disadvantages, e.g. in terms of their environmental safety, and therefore need to be replaced.
Furthermore, the world population is expected to grow significantly in the next 20-30 years, and, therefore, food production in sufficient quantities and quality is necessary. In order to achieve this, the use of en fertilizers would have to double by 2050. For environmental reasons, this is not possible, since nitrate levels in drinking water, eutrophication of e water and gas emissions into the air have already reached critical levels in many places, causing water contamination and air pollution. However, izer efficiency increases significantly and less fertilizer may therefore be applied, if nitrification inhibitors are used. Therefore, there is a clear need for novel ication inhibitors, as well as for methods using them.
In particular, there is a need for nitrification tors with a high activity.
Furthermore, there is a need for nitrification inhibitors which are effective at low amounts, as low application rates typically result in economical and environmental advantages.
It was already ered more than 30 years ago that acetylene is a potent nitrification inhibitor. However, as acetylene is a gas, it has never gained any practical value as a nitrifi- cation inhibitor. G. W. McCarty et al. describe the inhibition of nitrification in soil by acetylenic compounds, such as phenylacetylene (Soil Sci. Soc. Am. J., vol. 50, 1986, pp. 1198- 1201). Phenylacetylene is also described as nitrification inhibitor in US 4,552,581 A. r, phenylacetylene does not satisfy the present needs e.g. in terms of a high activity at a low application rate.
It was therefore the object of the present invention to provide improved nitrification inhibitors in view of the prior art, or to at least provide the public with a useful choice.
The present ion addresses this need and relates to a novel nitrification inhibitor of formula I (I) or a isomer, salt, tautomer or N-oxide thereof, wherein 1 2 R and R are ndently of each other selected from the group consisting of H, C1- C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl C1-C6- 40 alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, wherein the s may in each case be unsubstituted or may carry 1, 2 or 3 identical or different substituents R ; C3-C8-cycloalkyl, C3-C8-cycloalkenyl, heterocyclyl, aryl, hetaryl, C3-C8-cycloalkyl-C1- C6-alkyl, C3-C8-cycloalkenyl-C1-C6-alkyl, heterocyclyl-C1-C6-alkyl, aryl-C1-C6-alkyl, and hetaryl-C1-C6-alkyl, phenoxy and benzyloxy, n the cyclic moieties may in each case be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different t- uents R ; A is phenyl, wherein said phenyl ring may be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents R ; wherein A b c d b R is selected from the group consisting of CN, halogen, NO2, OR , NR R , C(Y)R , b c d b b C(Y)OR , C(Y)NR R , S(Y)mR , S(Y)mOR , C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C1-C6-alkoxy, C1-C6- alkylthio, wherein the C-atoms may in each case be unsubstituted or may carry 1, 2 or 3 identical or different tuents R ; C3-C8-cycloalkyl, cycloalkenyl, heterocyclyl, aryl, hetaryl, C3-C8-cycloalkyl-C1- C6-alkyl, C3-C8-cycloalkenyl-C1-C6-alkyl, heterocyclyl-C1-C6-alkyl, aryl-C1-C6-alkyl, and hetaryl-C1-C6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may be tituted or may carry 1, 2, 3, 4, or 5 identical or different substituents R ; and wherein R is selected from CN, halogen, NO2, C1-C4-alkyl, C1-C4-haloalkyl and C1-C4-alkoxy; or two substituents R on adjacent C-atoms may be a bridge selected from CH 2CH 2CH 2CH 2, OCH 2CH 2CH 2, CH2OCH 2CH 2, OCH2CH 2O, OCH2OCH 2, CH2CH 2CH 2, CH2CH 2O, CH2OCH 2, O(CH 2)O, SCH2CH 2CH 2, CH2SCH 2CH 2, SCH2CH 2S, SCH2SCH 2, CH2CH 2S, CH2SCH 2, S(CH 2)S, and form together with the C atoms, to which the two R are bonded to, a 5- membered or 6-membered saturated carbocyclic or heteocyclic ring; R is selected from H, C1-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-haloalkyl, phenyl and benzyl; c d R and R are ndently of each other selected from the group consisting of H, C1- C4-alkyl, and C1-C4-haloalkyl; or c d R and R together with the N atom to which they are bonded form a 5- or 6-membered, saturated or unsaturated heterocycle, which may carry a r heteroatom being selected from O, S and N as a ring member atom and wherein the heterocycle may be unsubstituted or may carry 1, 2, 3, 4, or 5 substituents which are independently of each other selected from halogen; R is selected from CN, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4- haloalkoxy; Y is O or S; and m is 0, 1 or 2.
The inventors singly found that by applying the nd of formula I as defined herein the nitrification of ammonium to nitrate could significantly be reduced.
In a particular aspect, the t invention provides a nitrification ting mixture comprising 40 (i) at least one fertilizer selected from the group consisting of a solid or liquid ammoniumcontaining inorganic fertilizer; an ammonium-containing solid or liquid organic fertilizer selected from the group consisting of liquid manure, semi-liquid , biogas manure, sta- ble manure, straw manure, worm castings, t, seaweed or guano; and a ureacontaining fertilizer; and a; and (ii) at least one compound of formula (I) 45 [FOLLOWED BY PAGE 3a] ed from a compound of formula (1-8), or a compoundof formula (1-15): (1-8), (1-15). wherein the mixture inhibits nitrification of ammonium in a locus or soil or soil substituents where a plant is growing or is intended to grow.
In another particular aspect, the present invention provides a method for ng nitrifi- cation, comprising treating locus or soil or soil tuents where the plant is growing or is intended to grow with a compound of formula (I) selected from a nd of formula (1-8), or a compoundof formula (1-15): (1-8), (1-15) wherein: the plant and/or the locus or soil or soil substituents where the plant is growing or is intended to grow is additionally provided with a fertilizer; and the fertilizer is selected from the group consisting of a solid or liquid ammonium-containing inorganic fertilizer; a solid or liquid c fertilizer selected from the group consisting of liquid manure, semi-liquid , biogas manure, stable manure, straw manure, worm castings, t, seaweed or guano; and a urea-containing fertilizer.
Thus, in one aspect the present invention relates to the use of a nitrification inhibitor for reducing nitrification, wherein said nitrification inhibitor is a compound of a I as defined herein. a b c In a preferred embodiment of said use, in said compound of formula I, the radicals R , R , R , d e R , and R are defined as follows: R is selected from halogen, C1-C2-alkyl, alkoxy, or two tuents R on adjacent C-atoms may be a OCH2CH2O bridge or a O(CH2)O bridge; R is selected from H, C1-C6-alkyl, phenyl and benzyl; [FOLLOWED BY PAGE 4] Rc and Rdare independently of each other selected from the group consisting of H, Ci-C4-alkyl, and Ci-C4-haloalkyl; and Re is ed from halogen and Ci-C4-alkyl.
In another preferred embodiment of said use, in said compound of formula I, R1 and R2 are in- dependently of each other selected from the group consisting of H, C2-Cs-alkynyl, C2-C&- alkynyloxy, i-Ce-alkyl, and hetaryl-C-i-Ce-alkyl, n preferably at least one of R1 and R2 is H.
In yet another preferred embodiment of said use, in said compound of formula I, A is phenyl, n said phenyl ring is unsubstituted or carries 1,2, or 3 identical or different substituents RA.
In a particularly preferred embodiment of said use, in said compound of formula I, RA, if pre­ sent, is ed from the group consisting of halogen, NO2, NRcRd, C-i-Ce-alkyl, Ci-Ce-haloalkyl, C-i-Ce-alkoxy, C-i-Ce-alkylthio, phenoxy and benzyloxy, wherein the cyclic es may be unsubstituted or may carry 1 or 2 identical or different tuents Ra, wherein Ra, Rc and Rd are as defined above.
In a further , the present invention relates to the use of compound as defined above as a nitrification inhibitor. In a further aspect, the present invention relates to the use of a com­ pound as defined above as for reducing nitrification.
In a further aspect, the present invention relates to a composition for use in reducing nitrifica- tion, comprising at least one nitrification inhibitor as d above and at least one carrier.
In a further aspect, the present invention relates to an agrochemical composition for use in reducing nitrification, comprising at least one nitrification inhibitor as defined above and at least one carrier.
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 above; or at least one fertilizer and a composition as mentioned above for use in reducing nitrification.
In a preferred embodiment, said nd as defined above is used for reducing nitrification in ation with a fertilizer. In a further specific embodiment, said compound as defined above is used for reducing nitrification in combination with a fertilizer in the form of an agro- chemical mixture as mentioned above. In a r preferred embodiment, said ion of nitri­ on as mentioned above occurs in or on a plant, in the root zone of a plant, in or on soil or soil substituents and/or at the locus where a plant is growing or is intended to grow.
In another aspect, the present invention s to a method for reducing nitrification, compris­ ing treating a plant growing on soil or soil tuents and/or the locus or soil or soil substitu- ents where the plant is growing or is intended to grow with at least one compound as defined above, or with a ition as defined above, or with an agrochemical composition as defined above. In a preferred embodiment of the method, the plant and/or the locus or soil or soil substituents where the plant is growing or is intended to grow is additionally provided with a fertiliz­ er. In a further preferred ment of the method, the application of said nitrification inhibitor 40 and of said fertilizer is carried out simultaneously or with a time lag, wherein either said fertilizer or said nitrification inhibitor may be applied at first. In a particularly preferred embodiment, said time lag is an interval of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 1 week, 2 weeks or 3 weeks. In case of application with a time lag, a nitrification inhibitor as defined above may be applied first and then the fertilizer. In a further red embodiment of the method, in a first step a nitrification inhibitor as defined above is applied to seeds, to a plant and/or to the locus 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 locus where the plant is growing or is intended to grow, wherein the application of a 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 as defined above may be applied first and then a nitrification inhibitor as defined above may be applied. In a further preferred embodiment of the method, in a first step a fertilizer is applied to a plant and/or to the locus where the plant is growing or is intended to grow and in a second step a nitrification tor as defined above is applied to seeds, to a plant and/or to the locus where the plant is growing or is intended to grow, wherein the application of a said fetilizer in the first step and said nitrification inhibitor in the second step is carried out with a time lag of at least 1 day, 2days, 3 days, 4 days, 5, days, 6 days, 1 week, 2 weeks or 3 weeks.
In a further aspect, the present invention relates to a method for ng a fertilizer or a composition, comprising the application of a nitrification inhibitor as defined .
In a preferred embodiment of the use, agrochemical mixture or method of the ion, said fertilizer is an solid or liquid ammonium-containing inorganic fertilizer such as an NPK fertilizer, um nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; an solid or liquid organic fertilizer such as liquid manure , semi-liquid manure, stable , biogas manure and straw manure, worm castings, compost, seaweed or guano, or an ontaining fertilizer such as urea, formaldehyde urea, urea um nitrate (UAN) solution, urea sulphur, stabilized urea, urea based NPK-fertilizers, or urea ammonium sulfate .
In a further red embodiment of the use, agrochemical mixture or method of the invention , said plant is an agricultural plant such as wheat, , oat, rye, soybean, corn, potatoes, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice or a vegetable such as spinach, lettuce, asparagus, or cabbages; or sorghum; a silvicultural plant; an or- namental plant; or a ultural plant, each in its natural or in a genetically modified form.
In this specification where reference has been made to patent specifications, other external nts, or other sources of information, this is lly for the purpose of providing a context for discussing the features of the invention. Unless specifically stated ise, reference to such external documents is not to be construed as an admission that such documents, or such sources of information, in any jurisdiction, are prior art, or form part of the common general knowledge in the art. gh the present invention will be described with respect to particular embodiments, this description is not to be construed in a limiting sense. 40 In the description in this specification reference may be made to t matter which is not within the scope of the appended claims. That subject matter should be readily identifiable by a person skilled in the art and may assist in putting into practice the ion as defined in the appended claims.
[FOLLOWED BY PAGE 5a] Before describing in detail exemplary embodiments of the present invention, definitions ant for understanding the present invention are given.
As used in this specification and in the appended claims, the singular forms of "a" and "an" also include the respective plurals unless the t clearly dictates otherwise. In the context of the present invention, the terms " and "approximately" denote an interval of accuracy that a person skilled in the art will understand to still ensure the technical effect of the feature in on. The term typically indicates a ion from the indicated numerical value of ±20 %, preferably ±15 %, more preferably ±10 %, and even more pref- erably ±5 %. It is to be understood that the term "comprising" is not limiting. For the purposes of the present invention the term "consisting of" is considered to be a preferred embodiment of the term "comprising of". If hereinafter a group is defined to comprise at least a certain number of embodiments, this is [FOLLOWED BY PAGE 6] meant to also encompass a group which preferably consists of these embodiments only. Furthermore , the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of operation in other sequences than described or illustrated herein. In case the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or assay there is no time or time al coherence between the steps, i.e. the steps may be d out aneously or there may be time als of se- conds, minutes, hours, days, weeks, months or even years between such steps, unless other­ wise indicated in the application as set forth herein above or below. It is to be understood that this invention is not limited to the particular methodology, protocols, ts etc. bed herein as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention that will be limited only by the appended claims. Unless defined otherwise, all technical and ific terms used herein have the same meanings as commonly understood by one of ry skill in the art.
The term "nitrification inhibitor" is to be understood in this context as a chemical substance which slows down or stops the nitrification process. Nitrification inhibitors accordingly retard the l transformation of ammonium into nitrate, by inhibiting the activity of bacteria such as Nitrosomonas spp .The term "nitrification" as used herein is to be understood as the biological oxidation of ammonia (NHa) or ammonium (NhV) with oxygen into nitrite (NO2') followed by the oxidation of these nitrites into nitrates (NCV) by microorganisms. Besides nitrate (NO3') nitrous oxide is also produced though ication. Nitrification is an important step in the nitrogen cycle in soil. The inhibition of nitrification may thus also reduce N2O losses. The term nitrification inhibitor is considered equivalent to the use of such a compound for inhibiting nitrification.
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, preferably the compound(s) as defined herein as well as a stereoisomer, salt, or N-oxide thereof, more preferably the compound(s) as defined herein as well as a stereoisomer or salt thereof. The term "compound(s) of the present invention" is to be understood as equivalent to the term "compound(s) according to the invention", therefore also comprising a stereoisomer, salt, tautomer or N-oxide thereof. It is of course to be understood that ers can only be present, if a tuent is present at the nds of formula I, which covers tautomers such as keto-enol tautomers, imine-enamine tautomers, amide-imidic acid ers or the like. Otherwise , the term unds of formula I" does not encompass tautomers. Furthermore, it is to be understood that stereoisomers are only possible, if there is at least one centre of chirality in the le or if geometrical s (cis/trans isomers) can be formed.
The compounds of formula I may be amorphous or may exist in one or more different l- 40 line states (polymorphs) which may have ent macroscopic properties such as stability or show different biological properties such as activities. The present invention relates to ous and crystalline compounds of formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula I are ably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the nd of formula I has a basic onality. Agriculturally useful salts of the nds of formula I encompass especially the acid addition salts of those acids whose cati- ons and , respectively, have no adverse effect on the mode of action of the compounds of formula I. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate , carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4- alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by ng compounds of formula I with an acid of the corresponding anion, preferably of hydro­ c acid, romic acid, sulfuric acid, oric acid or nitric acid.
The term "N-oxide" includes any compound of formula I which has at least one tertiary nitrogen atom that is oxidized to an e moiety. Of course, N-oxides can only be formed, if a nitrogen atom is present within the compounds of formula I.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn- Cm indicates in each case the possible number of carbon atoms in the group.
The term "halogen" denotes in each case fluorine, bromine, ne or iodine, in particular fluorine , chlorine or bromine.
The term " as used herein and in the alkyl moieties of mino, alkylcarbonyl, alkylthio, ulfinyl, alkylsulfonyl and alkoxyalkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms. Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1- methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl , 1,2-dimethylpropyl, 1-methylpentyl, ylpentyl, 3-methylpentyl, 4-methylpentyl , 1,1-dimethylbutyl, 1,2-dimethylbutyl, methylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl , 3,3-dimethylbutyl, 1-ethyl butyl, 2-ethyl butyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1- ethylmethylpropyl, and 1-ethylmethylpropyl.
The term "haloalkyl" as used herein and in the haloalkyl moieties of haloalkylcarbonyl, haloalkoxycarbonyl, haloalkylthio, haloalkylsulfonyl, haloalkylsulfinyl, haloalkoxy and haloalkoxyalkyl, denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, ntly from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, n the hydrogen atoms of this group are partially or totally ed with halogen atoms. Preferred haloalkyl moieties are selected from Ci-C4-haloalkyl, more preferably from C1- Cs-haloalkyl or Ci-C2-haloalkyl, in particular from Ci-C2-fluoroalkyl such as fluoromethyl, romethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like.
The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl 40 group which is bonded via an oxygen atom and has usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, e.g. 1 or 2 carbon atoms.
Examples of an alkoxy group are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2- butyloxy, iso-butyloxy, tert.-butyloxy, and the like.
The term "alkoxyalkyl" as used herein refers to alkyl usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually sing 1 to 4, preferably 1 or 2 carbon atoms as defined above. Examples are CH2OCH3, 2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethyl.
The term thio "(alkylsulfanyl: alkyl-S-)" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylthio), more preferably 1 to 3 carbon atoms, which is attached via a sulfur atom.
The term "haloalkylthio" as used herein refers to an alkylthio group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
The term "alkenyl" as used herein denotes in each case a singly unsaturated hydrocarbon rad­ ical having usually 2 to 10, frequently 2 to 6, ably 2 to 4 carbon atoms, e.g. vinyl, allyl (2- propenyl), 1-propenyl, 2-propenyl, methallyl (2-methylpropenyl), 2-butenyl, 3- butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methylbutenyl, 2-ethylpropen- 1-yl and the like.
The term "alkenyloxy" as used herein denotes in each case an l group as defined above, which is bonded via an oxygen atom and has usually from 2 to 10, preferably from 2 to 6 or from 2 to 4 carbon atoms.
The term "alkynyl" as used herein denotes in each case a singly unsaturated hydrocarbon rad­ ical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. ethynyl, propargyl (2-propynyl), 1-propynyl, 1-methylpropynyl), 2-butynyl, 3-butynyl, 1- pentynyl, 3-pentynyl, 4-pentynyl, ylbutynyl, 1-ethylpropynyl and the like.
The term yloxy" as used herein denotes in each case an alkenyl group as defined above, which is bonded via an oxygen atom and has usually from 2 to 10, preferably from 2 to 6 or from 2 to 4 carbon atoms.
The term "cycloalkylalkyl" refers to a cycloalkyl group as defined above which is bonded via an alkyl group, such as a C-i-Ce-alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= cycloalkylmethyl), to the remainder of the molecule.
The term "cycloalkyl" as used herein and in the cycloalkyl moieties of cycloalkoxy and cycloalkylthio denotes in each case a monocyclic liphatic radical having usually from 3 to or from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The term "cycloalkenyl" as used herein and in the cycloalkenyl moieties of cycloalkenyloxy and cycloalkenylthio s in each case a monocyclic singly unsaturated non-aromatic radical having usually from 3 to 10, e.g. 3, or 4 or from 5 to 10 carbon atoms, preferably from 3- to 8 carbon atoms. Exemplary cycloalkenyl groups include cyclopropenyl, cycloheptenyl or cyclooctenyl. 40 The term alkenylalkyl" refers to a lkenyl group as defined above which is bonded via an alkyl group, such as a Ci-Ce-alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= cycloalkenylmethyl), to the remainder of the molecule.
The term "carbocycle" or cyclyl" includes in general a 3- to 12-membered, preferably a 3- to 8-membered or a 5- to 8-membered, more ably a 5- or 6-membered mono-cyclic, non-aromatic ring comprising 3 to 12, preferably 3 to 8 or 5 to 8, more preferably 5 or 6 carbon atoms. Preferably, the term "carbocycle" covers cycloalkyl and cycloalkenyl groups as defined above.
The term ocycle" or "heterocyclyl" includes in general 3- to 12-membered, preferably 3- to 8-membered or 5- to 8-membered, more preferably 5- or 6-membered, in particular 6-membered monocyclic heterocyclic non-aromatic radicals. The heterocyclic non-aromatic radicals usually comprise 1,2,3, 4, or 5, preferably 1,2 or 3 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO2. es of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, omatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, nyl-S-oxid (S-oxothietanyl), thietanyl- S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl , 1,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S- oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl, oxathiolanyl, piperidinyl, piperazinyl, l, dihydropyranyl, tetrahydropyranyl, 1,3-and 1,4-dioxanyl, thiopyranyl, S.oxoth10pyranyl, S-dioxothiopyranyl, othiopyranyl, S-oxodihydrothiopyranyl, S-dioxodihydrothiopyranyl, ydrothiopyranyl, S-oxotetrahydrothiopyranyl, S- dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl, S- dioxothiomorpholinyl, thiazinyl and the like. Examples for heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidinonyl, pyrrolidin-2,5-dionyl, imida- zolidinonyl, oxazolidinonyl, thiazolidinonyl and the like.
The term "aryl" includes mono-, bi- or tricyclic ic radicals having usually from 6 to 14, preferably 6, 10, or 14 carbon atoms. Exemplary aryl groups include phenyl, naphthyl and anthracenyl. Phenyl is preferred as aryl group.
The term "hetaryl" includes monocyclic 5- or 6-membered heteroaromatic radicals comprising as ring s 1,2, 3, or 4 heteroatoms selected from N, O and S. Examples of 5- or 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, or4-pyridyl, pyrimidinyl, i.e. 2-, 4-, or5- pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2- or 3-thienyl, furyl, i.e. 2- or 3-furyl, pyrrolyl, i.e. 2- or olyl, oxazolyl, i.e. 2-, 3-, or olyl, isoxazolyl, i.e. 3-, 4-, or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiazolyl, i.e. 3-, 4-, or 5-isothiazolyl, pyrazolyl, i.e. 1-, 3-, 4-, or 5-pyrazolyl, i.e. 1-, 2-, 4-, or 5-imidazolyl, oxadiazolyl, e.g. 2- or ,4]oxadiazolyl , 4- or 5-(1,2,3-oxadiazol)yl, 3- or 5-(1,2,4-oxadiazol)yl, 2- or 5-(1,3,4-thiadiazol)yl, thiadiazolyl , e.g. 2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1,2,3-thiadiazol)yl, 3- or 5-(1,2,4-thiadiazol)yl, triazolyl, e.g. 1H-, 2H- or 3H-1,2,3-triazolyl, 2H-triazolyl, 1H-, 2H-, or 4H-1,2,4-triazolyl and tetrazolyl, i.e. 1H- or 2H-tetrazolyl. The term "hetaryl" also es bicyclic 8 to 10-membered heteroaromatic radicals comprising as ring members 1,2 or 3 heteroatoms selected from N, O and S, wherein a 5- or 6-membered aromatic ring is fused to a phenyl ring or to a 5- or 6- ed aromatic radical. es of a 5- or 6-membered aromatic ring fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical include benzofuranyl, benzo- 40 thienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl, isochinolinyl, purinyl, 1,8-naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl or pyridoimidazolyl and the like. These fused l radicals may be bonded to the remainder of the molecule via any ring atom of 5- or 6-membered heteroaromatic ring or via a carbon atom of the fused phenyl moiety.
The terms "’’benzyloxy" and "phenoxy" refer to a benzyl and a phenyl group, respectively, which are bonded via an oxygen atom to the remainder of the molecule.
The terms "heterocyclylalkyl" and "hetarylalkyl" refer to heterocyclyl or l, respectively, as defined above which are bonded via a alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= heterocyclylmethyl or hetarylmethyl, respectively), to the remainder of the molecule.
The term "arylalkyl" refers to aryl as defined above, which is bonded via Ci-Ce-alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= arylmethyl or phenylmethyl), to the remainder of the molecule, examples including benzyl, 1-phenylethyl, 2-phenylethyl, etc.
The term "cyclic " can refer to any cyclic groups, which are present in the compounds of the present invention, and which are d above, e.g. cycloalkyl, cycloalkenyl, carbocycle, heterocycloalkyl, heterocycloalkenyl, heterocycle, aryl, hetaryl and the like.
As has been set out above, the present invention concerns in one aspect the use of a a com­ pound of formula I R1 R2 A'X’0'^%. (l) as a nitrification inhibitor for reducing nitrification wherein R1 and R2 are independently of each other selected from the group consisting of H, C-i-Cealkyl , C2-C6-alkenyl, C2-C6-alkynyl, C-i-Ce-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl C-i-Cealkoxy , alkenyloxy, C2-C6-alkynyloxy, wherein the C-atoms may in each case be unsubstituted or may carry 1,2 or 3 identical or different substituents Re; Cs-Cs-cycloalkyl, Ca-Cs-cycloalkenyl, heterocyclyl, aryl, hetaryl, Cs-Cs-cycloalkyl-Ci-Cealkyl , Cs-Cs-cycloalkenyl-C-i-Ce-alkyl, heterocyclyl-Ci-Cs-alkyl, aryl-C-i-Ce-alkyl, and hetaryl-C-i-Ce-alkyl, phenoxy and benzyloxy, n the cyclic moieties may in each case be unsubstituted or may carry 1,2,3, 4, or 5 cal or different substituents Ra; A is phenyl, wherein said phenyl ring may be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents RA; RA is selected from the group consisting of CN, halogen, NO2, ORb, NRcRd, C(Y)Rb, C(Y)ORb, C(Y)NRcRd, S(Y)mRb, S(Y)mORb, Ci-Ce-alkyl, alkenyl, C2-Cs-alkynyl, Ci-Ce-haloalkyl, C-i-Ce-alkoxy, C-i-Ce-alkylthio, wherein the s may in each case be tituted or may carry 1,2 or 3 identical or different substituents Re; Cs-Cs-cycloalkyl, cycloalkenyl, heterocyclyl, aryl, hetaryl, cycloalkyl-Ci-Cealkyl , Cs-Cs-cycloalkenyl-C-i-Ce-alkyl, heterocyclyl-Ci-Cs-alkyl, aryl-C-i-Ce-alkyl, and hetaryl-C-i-Ce-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may be 40 unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different tuents Ra; and wherein Ra is selected from CN, halogen, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy; or two substituents Ra on adjacent C-atoms may be a bridge ed from CH2CH2CH2CH2, OCH2CH2CH2, CH2OCH2CH2, OCH2CH2O, OCH2OCH2, CH2CH2CH2, CH2CH2O, CH2OCH2, 0(CH2)0, SCH2CH2CH2, CH2SCH2CH2, SCH2CH2S, SCH2SCH2, CH2CH2S, CH2SCH2, S(CH2)S, and form together with the C atoms, to which the two Ra are bonded to, a 5-membered or 6-membered saturated carbocyclic or heteocyclic ring; Rb is selected from H, Ci-Ce-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, phenyl and benzyl; Rc and Rd are independently of each other selected from the group consisting of H, C1-C4- alkyl, and Ci-C4-haloalkyl; or Rc and Rd together with the N atom to which they are bonded form a 5- or 6-membered, saturated or unsaturated heterocycle, which may carry a further heteroatom being selected from O, S and N as a ring member atom and wherein the heterocycle may be unsubstituted or may carry 1,2,3, 4, or 5 substituents which are ndently of each other selected from n; Re is selected from CN, halogen, alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, and C1-C4- haloalkoxy; Y is O or S; and m is 0, 1 or 2.
In one preferred embodiment of said compound of formula I as defined above, R1 is H and R2 is selected from the group consisting of C2-C6-alkynyl, C2-C6-alkynyloxy, aryl-C-i-Ce-alkyl, and hetaryl-Ci-Ce-alkyl, and is preferably selected from the group consisting of C2-C4-alkynyl, C2-C4- alkynyloxy, aryl-Ci-C4-alkyl, and hetaryl-Ci-C4-alkyl, and is most preferably hetaryl-Ci-C4-alkyl, in particular triazolylmethyl. These compounds correspond to compounds of formula I.a, wherein R2-a ents a substituent selected from the group consisting of C2-C6-alkynyl, C2-C6- alkynyloxy, aryl-Ci-Cs-alkyl, and hetaryl-C-i-Ce-alkyl, and is preferably selected from the group consisting of alkynyl, alkynyloxy, aryl-Ci-C4-alkyl, and hetaryl-Ci-C4-alkyl, and is more preferably selected from the group consisting of Ca-alkynyloxy and hetaryl-Ci-C4-alkyl, and is most preferably hetaryl-Ci-C4-alkyl, in ular lylmethyl. If R2-a is triazolylmethyl, it is preferred that the le moiety is bonded to the methyl group via one of the nitrogen at­ oms. Furthermore, it is preferred that the triazole moiety is a 1,2,4-triazole moiety.
H R2-a ^^o,) In another preferred embodiment of said nd of formula I as defined above, both, R1 and R2 are H. These compounds correspond to compounds of formula l.b. ^^d.b) In one embodiment of the compound of formula I, A is phenyl, wherein said phenyl ring is unsubstituted or s 1,2, or 3 identical or different substituents RA. Such compounds correspond to compounds of a 1.1, wherein (RA)n with n being 0, 1,2, or 3 indicates the above substitution possibilities for the compound.
R1 R2 (RA)n (1.1) Particular preferred are compounds, wherein n is 1 or 2, i.e. the following compounds 1.11 and R1 R2 R1 R2 (I.11) Ra (I.12) In connection with the compounds defined above, it is to be understood that the substituent(s) RA may be present at any carbon atom of the phenyl ring.
In a preferred ment, the present invention s to compounds of formula I, wherein R1 is H, R2 is R2-a, and A is phenyl, wherein said phenyl ring is tituted or carries 1,2, or 3 identical or different substituents RA. Such compounds are referred to compounds of formula 1.1.a, with nds of formula l.11.a and nds of formula l.12.a being particularly pre­ ferred.
Ra H R2-a H R2-a H R2-a (RA)n (l.1.a) (l.11.a) rA (I.12.a) In connection with the compounds defined above, it is to be understood that the substituent(s) RA may be present at any carbon atom of the phenyl ring.
In another preferred embodiment, the present ion relates to compounds of formula I, wherein R1 is H, R2 is H, A is , wherein said phenyl ring is unsubstituted or s 1,2, or 3 identical or different substituents RA. Such compounds are referred to compounds of formula l.1.b, with nds of formula l.11.b and compounds of formula l.12.b being particularly preferred.
Furthermore, it can be preferred that the phenyl ring is unsubstituted, i.e. that n in formu­ la 1.1.b isO.
In one preferred embodiment, the present ion therefore relates to compounds of formula I, wherein R1 is H, R2 is H, A is phenyl, wherein said phenyl ring is unsubstituted or carries 1, or 2 cal or different substituents RA.
Ra H H H H H H (RA)n (l.1.b) (l.11.b) ra (I.12.b) In connection with the compounds defined above, it is to be understood that the substituent(s) RA may be present at any carbon atom of the phenyl ring. In certain preferred embodiments of the invention, it is preferred that at least one substituent RA is present in para position with respect to the propargylether group.
For the compounds as defined above, i.e. I.a, l.b, 1.1, I.11,1.12, 1.1.a, l.11.a, l.12.a, l.1.b, l.11.b, l.12.b, it is particularly preferred that RA, if present, is selected from the group consisting of halo­ gen, NO2, NRcRd, C-i-Ce-alkyl, Ci-Ce-haloalkyl, Ci-Ce-alkoxy, Ci-Ce-alkylthio, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1 or 2 identical or different substituents Ra, wherein Ra, Rc and Rd are defined as follows: Ra is selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, or two substituents Ra on adjacent C- atoms may be a OCH2CH2O bridge or a 0(CH2)0 ; and Rc and Rd are independently of each other selected from the group consisting of H, C1-C4- alkyl, and Ci-C4-haloalkyl.
It is more preferred that RA is selected from the group consisting of halogen, NO2, C-i-Ce-alkyl, C-i-Ce-haloalkyl, Ci-Ce-alkoxy, and y, wherein the phenoxy group may be unsubstituted or may carry 1 or 2 identical or different substituents Ra, n Ra is selected from halogen.
It is more preferred that RA is selected from the group consisting of halogen, NO2, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C2-alkoxy, and phenoxy, wherein the y group may be unsubstituted or may carry 1 or 2 identical or different substituents Ra, n Ra is selected from halogen.
It is most preferred that RA is selected from the group consisting of fluorine, chlorine, bromine, NO2, CH3, CF3, methoxy, and phenoxy, wherein the phenoxy group may be unsubstituted or may carry 1 or 2 identical or different substituents Ra, wherein Ra is selected from fluorine, chlorine, or bromine.
In one particularly preferred embodiment of the compounds as defined above, in particular of the compounds of formula l.1.b, l.11.b, l.12.b as defined above, it is preferred that RA, if present, is selected from the group consisting of halogen, Ci-C4-alkyl, and Ci-C4-alkoxy.
In one especially preferred embodiment of the nds as d above, in particular of the compounds of a 1.1.b, l.11.b, l.12.b as d above, it is preferred that RA, if present, is selected from the group consisting of fluorine, chlorine, e, iodine, CH3, methoxy, ethoxy, and n-propoxy, n preferably at least one of these groups is present in para position with respect to the gylether group.
Thus, the present ion relates in one ment to compounds of a I, wherein R1 and R2 are ndently of each other selected from the group consisting of H, C2-C6- alkynyl, C2-C6-alkynyloxy, aryl-C-i-Ce-alkyl, and hetaryl-C-i-Ce-alkyl, provided at least one of R1 and R2 is H, and wherein A is phenyl, wherein said phenyl ring is unsubstituted or carries 1,2, or 3 identical or different substituents RA, wherein RA is selected from the group consisting of CN, halogen, NO2, C(Y)ORb, C(Y)NRcRd, NRcRd, C-i-Ce-alkyl, Ci-Ce-haloalkyl, C-i-Ce-alkoxy, C2-C6-alkynyloxy, C-i-Ce-alkylthio, phenoxy and benzyloxy, wherein the cyclic moieties may be tituted or may carry 1 or 2 identical or 40 different substituents Ra, n Ra, Rb, Rc and Rd are defined as follows: Ra is selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, or two substituents Ra on adjacent C- atoms may be a OCH2CH2O bridge or a 0(CH2)0 bridge; and Rb is H or Ci-C4-alkyl; Rc and Rd are independently of each other selected from the group consisting of H, C1-C4- alkyl, and Ci-C4-haloalkyl.
Thus, the present invention relates in one embodiment to compounds of formula I, n R1 and R2 are independently of each other selected from the group ting of H, C2-C6- alkynyl, C2-C6-alkynyloxy, aryl-C-i-Ce-alkyl, and hetaryl-C-i-Ce-alkyl, provided at least one of R1 and R2 is H, and wherein A is phenyl, wherein said phenyl ring is unsubstituted or carries 1,2, or 3 identical or different substituents RA, wherein RA is selected from the group consisting of halogen, NO2, NRcRd, Ci-Ce-alkyl, Ci-Cs-haloalkyl, C-i-Ce-alkoxy, Ci-Cs-alkylthio, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1 or 2 identical or different substituents Ra, n Ra, Rc and Rd are defined as follows: Ra is selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, or two tuents Ra on nt C- atoms may be a OCH2CH2O bridge or a 0 bridge; and Rc and Rd are independently of each other selected from the group consisting of H, C1-C4- alkyl, and Ci-C4-haloalkyl.
The above defined compounds of formula I are preferred in connection with the use as a ication inhibitor for reducing nitrification as defined herein.
In particular, the present invention relates in one preferred embodiment to the use of a com­ pound of formula 1.1.a, especially a compound of formula 1.11.a or l.12.a as defined above, as a nitrification inhibitor for ng nitrification, wherein RA is ed from the group consisting of halogen, NO2, C-i-Ce-alkyl, C-i-Ce-haloalkyl, Ci-Ce-alkoxy, and phenoxy, wherein the phenoxy group may be unsubstituted or may carry 1 or 2 identical or different substituents Ra, wherein Ra is selected from halogen.
In a more preferred ment, the present invention relates to the use of a compound of formula 1.1.a, ally a compound of formula l.11.a or l.12.a as defined above, as a nitrification inhibitor for reducing nitrification, wherein RA is selected from the group consisting of halogen, NO2, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C2-alkoxy, and phenoxy, n the y group may be unsubstituted or may carry 1 or 2 identical or ent substituents Ra, n Ra is selected from halogen.
In an even more preferred embodiment, the present invention relates to the use of a com­ pound of formula 1.1.a, ally a compound of formula l.11.a or l.12.a as defined above, as a nitrification inhibitor for reducing nitrification, wherein RA is selected from the group consisting of fluorine, chlorine, bromine, NO2, CH3, CF3, methoxy, and phenoxy, wherein the phenoxy group may be unsubstituted or may carry 1 or 2 identical or different substituents Ra, wherein 40 Ra is selected from fluorine, chlorine, or bromine.
It is to be understood that the above defined compounds of formula 1.1.a, in particular the compounds of a l.11.a or l.12.a, are not only preferred in connection with the use accord- ing to the present invention, but also in connection with the composition, the agrochemical mixture , and the s as defined herein.
Furthermore, the present invention s in another preferred embodiment to the use of a compound of formula M.b, especially a compound of formula l.11.b or l.12.b as defined above, as a nitrification inhibitor for reducing nitrification, wherein RA is selected from the group consisting of CN, halogen, NO2, C(Y)ORb, cRd, C-i-Ce-alkyl, Ci-Cs-alkoxy, alkynyloxy, and phenoxy, wherein the cyclic moiety may be unsubstituted or may carry 1 or 2 identical or ent substituents Ra, wherein Ra, Rb, Rc and Rd are defined as follows: Ra is selected from halogen, Ci-C2-alkyl, or alkoxy; and Rb is H, or Ci-C4-alkyl; Rc and Rd are independently of each other selected from the group consisting of H, or C1-C4- alkyl.
Furthermore, the present invention relates in another preferred embodiment to the use of a compound of formula M.b, especially a compound of formula l.11.b or l.12.b as defined above, as a nitrification inhibitor for reducing ication, wherein RA is selected from the group consisting of halogen, NO2, C-i-Ce-alkyl, C-i-Ce-haloalkyl, Ci-Ce-alkoxy, and phenoxy, wherein the y group may be unsubstituted or may carry 1 or 2 identical or different tuents Ra, wherein Ra is selected from halogen.
In a more preferred embodiment, the present ion relates to the use of a compound of formula M.b, especially a compound of formula l.11.b or l.12.b as defined above, as a ication tor for reducing nitrification, wherein RA is selected from the group consisting of halogen, NO2, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C2-alkoxy, and y, wherein the phenoxy group may be unsubstituted or may carry 1 or 2 identical or different substituents Ra, wherein Ra is selected from halogen.
In an even more preferred embodiment, the present invention relates to the use of a com- pound of formula M.b, especially a compound of formula 1.11.b or l.12.b as d above, as a nitrification inhibitor for reducing nitrification, wherein RA is selected from the group consisting of fluorine, chlorine, bromine, NO2, CH3, CF3, methoxy, and phenoxy, wherein the y group may be unsubstituted or may carry 1 or 2 identical or different substituents Ra, wherein Ra is selected from fluorine, chlorine, or bromine.
In one particularly preferred embodiment, the present invention relates to the use of a com­ pound of formula M.b, especially a compound of formula 1.11.b or l.12.b as defined above, as a nitrification inhibitor for ng nitrification, wherein RA, if present, is selected from the group consisting of halogen, Ci-C4-alkyl, and Ci- 40 oxy.
In one ularly preferred embodiment, the present invention relates to the use of a com­ pound of formula 1.1.b, especially a compound of formula 1.11.b or l.12.b as defined above, as a nitrification inhibitor for reducing nitrification, wherein RA, if present, is selected from the group consisting of fluorine, chlorine, bromine, iodine , CH3, methoxy, ethoxy, and n-propoxy, n preferably at least one of these groups is present in para position with respect to the gylether group.
It is to be understood that the above defined compounds of formula l.l.b, in particular the compounds of formula l.11.b or l.12.b, are not only preferred in connection with the use according to the present invention, but also in connection with the composition, the agrochemical mixture , and the methods as d herein.
In particular with a view to their use, preference is given to the compounds of a I com- piled in Table 1 below.
Table 1 No. Structure No. Structure 1-1 .0 1-8 1-2 Br 1-9 1-3 1-10 Cl Cl 1-4 1-11 Cl F .N /C^NH 'Cl O'- "O' 1-5 nQn; 1-12 Br 1-6 Cl Q o -o' 'o-N+ O' hnQn Q 1-13 F /p;N Cl nQni Q o 1-7 a ^Nt N—, O O Cl 1-14 No. Structure No. Structure 1-15 1-22 Cl ci Cl ____ ¦0'N* Cl Cl 1-18 Cl O' 1-25 1-19 O O. O.
Q O i—N N+ N,P> 'O' "O' N N 1-28 ltg7.Nv No. Structure No. Structure 1-30 1-32 I 1-31 O 1-33 O Q OH N In a central aspect the present invention thus relates to the use of a compound of formula I as defined herein as a ication inhibitor, or to the use of a composition comprising said compound of formula I as d herein for reducing nitrification. The compound of formula I or de- rivatives or salts thereof as defined herein, in particular the compounds of formula I and/or salts or suitable tives thereof, as well as compositions sing said compound of formula I, or agrochemical mixtures comprising said a compound of formula I may be used for reducing nitrification.
In a central aspect the present invention thus s to the use of a compound of formula I as defined herein, in particular any one of the compounds listed in Table 1 above, for reducing nitrification , or to the use of a composition comprising any one of the compounds listed in Table 1 and a carrier for ng nitrification. Furthermore, the present invention releates to an ltural mixture comprising any one of the compounds listed in Table 1 above and at least one fertilizer as defined herein. The compounds of a I or derivatives or salts thereof as defined herein, in ular compounds of formula I and/or salts thereof, as well as compositions comprising said compound of formula I, or agrochemical mixtures sing said compound of formula I may be used for reducing nitrification.
The compounds of Table 1 may be subdivided into compounds of formula 1.1 .a, i.e. com­ pounds 1-6, 1-7, 1-11, 1-12, 1-13, 1-17, 1-18, 1-20, 1-21, 1-22, and compounds of formula l.1.b, i.e. compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-8, 1-9, 1-10, 1-14, 1-15, 1-16, 1-19, 1-23, 1-24, 1-25, 1- 26,1-27,1-28,1-29,1-30,1-31,1-32,1-33.
In one embodiment of the invention, the compounds of formula I are compounds of formula l.l.a, which are selected from the group ting of compounds 1-6, 1-7, 1-11, 1-12, 1-13, 1- 17, 1-18, 1-20, 1-21, and 1-22, or which are structurally different from these compounds, but are characterized in that RA, if present, is selected from the group consisting of fluorine, chlorine, bromine, NO2, CH3, CF3, methoxy, and y, wherein the phenoxy group may be unsubstituted or may carry 1 or 2 identical or different substituents Ra, wherein Ra is selected from fluorine, chlorine, or bromine.
In one preferred embodiment of the invention, the compounds of formula I are nds of a l.l.a, which are selected from the group consisting of compounds 1-6, 1-7, 1-11, 1-12, 1-13, 1-17, 1-18, 1-20, 1-21, and1-22.
In another embodiment of the invention, the compounds of a I are compounds of a 1.1 .b, which are selected from the group consisting of compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-8, 1-9, 1-10, 1-14, 1-15 1-16, and 1-19, or which are structurally different from these compounds, but are terized in that RA, if present, is selected from the group ting of fluorine, chlorine, bromine, NO2, CH3, CF3, methoxy, and phenoxy, wherein the phenoxy group may be unsubstituted or may carry 1 or 2 identical or different substituents Ra, wherein Ra is selected from fluorine, chlorine, or bromine.
In yet another embodiment of the invention, the compounds of formula I are compounds of formula l.1.b, which are selected from the group consisting of compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-8, 1-9, 1-10, 1-14, 1-15 1-16, 1-19, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-32, and 1-33, or which are structurally ent from these compounds, but are characterized in that RA, if present, is ed from the group ting of n, Ci-C4-alkyl, and Ci-C4-alkoxy, and ably from fluorine, chlorine, bromine, iodine, CH3, methoxy, ethoxy, and n-propoxy.
In a preferred embodiment of the invention, the compounds of formula I are compounds of formula 1.1 .b, which are selected from the group consisting of compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-8, 1-9, 1-10, 1-14, 1-15, 1-16, 1-19, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-32, and 1-33. In a particularly preferred preferred embodiment of the invention, the compounds of formula I are compounds of formula 1.1 .b, which are selected from the group consisting of compounds 1-2, 1-5, 1-8, 1-14, 1-15, 1-21, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1- 32, and 1-33, preferably from the group consisting of compounds 1-8, 1-14, 1-15, 1-25, 1-26, 1- 27, 1-28, 1-29, and 1-32.
In one embodiment of the above mentioned aspects of the invention, in particular the use ac­ cording to the invention, the compound of formula I is the compound 1-1 as defined in Table 1 above.
In another embodiment, the compound of formula I is the compound 1-2 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-3 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-4 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-5 as defined above.
In yet another embodiment, the nd of formula I is the compound 1-6 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-7 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-8 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-9 as defined above.
In yet another embodiment, the compound of formula I is the nd 1-10 as defined above.
In yet r embodiment, the compound of a I is the compound 1-11 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-12 as d above. 40 In yet another embodiment, the nd of formula I is the compound 1-13 as defined above.
In yet another embodiment, the compound of formula I is the nd 1-14 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-15 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-16 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-17 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-18 as d above.
In yet another embodiment, the compound of formula I is the compound 1-19 as defined above.
In yet another embodiment, the nd of formula I is the compound 1-20 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-21 as defined above.
In yet r embodiment, the compound of formula I is the compound 1-22 as defined above.
In yet another ment, the compound of formula I is the compound 1-23 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-24 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-25 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-26 as defined above.
In yet another embodiment, the compound of a I is the compound 1-27 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-28 as d above.
In yet another embodiment, the compound of formula I is the compound 1-29 as defined above.
In yet another ment, the compound of formula I is the compound 1-30 as defined above.
In yet another embodiment, the compound of a I is the compound 1-31 as defined above.
In yet another embodiment, the compound of formula I is the compound 1-32 as defined above.
In yet r ment, the compound of formula I is the compound 1-33 as defined above. 40 It has been found that the above listed compounds of formula I have advantageous ties in terms of a high activity in particular at low concentrations. Furthermore, the compounds may exhibit a high stability in terms of ysis and thus a reduced toxicity.
The use according to the invention may be based on the ation of the nitrification inhibitor, the composition or the agrochemical mixture as defined herein to a plant growing on soil and/or the locus where the plant is growing or is intended to grow, or the use may be based on the application of the nitrification inhibitor, the composition or the agrochemical mixture as defined herein to soil where a plant is growing or is intended to grow or to soil substituents. In ic embodiments, the nitrification tor may be used for reducing nitrification in the absence of plants, e.g. as preparatory activity for subsequent agricultural activity, or for reducing nitrification in other technical areas, which are not related to agriculture, e.g. for environmental, water pro­ tection, energy production or similar purposes. In specific embodiments, the nitrification inhibi- tor, or a composition comprising said nitrification inhibitor according to the present invention may be used for the reduction of nitrification in sewage, slurry, manure or dung of animals, e.g. swine or bovine feces. For example, the nitrification inhibitor, or a composition comprising said ication inhibitor according to the present invention may be used for the reduction of nitrification in sewage , biogas plants, cowsheds, liquid manure tanks or containers etc. In further embodiments, the nitrification inhibitor, or a composition comprising said nitrification tor according to the present invention may be used for the reduction of nitrification in situ in animals , e.g. in productive livestock. Accordingly, the nitrification inhibitor, ora ition comprising said nitrification tor according to the present ion may be fed to an animal, e.g. a mammal, for instance together with suitable feed and thereby lead to a reduction of nitrifica- tion in the gastrointestinal tract of the animals, which in turn is resulting in reduction of emissions from the gastrointestinal tract. This activity, i.e. the feeding of nitrification inhibitor, or a composition comprising said nitrification inhibitor ing to the present invention may be repeated one to several times, e.g. each 2nd, 3rd, 4th, 5th, 6th, 7th day, or each week, 2 weeks, 3 weeks, or month, 2 months etc.
The use may further include the application of a ication inhibitor or derivatives or salts thereof as defined herein above, in particular compounds of formula I and/or salts or suitable derivatives thereof, as well as compositions comprising said nitrification inhibitor, or agrochemi­ cal mixtures comprising said nitrification inhibitor as defined herein above to environments, areas or zones, where nitrification takes place or is assumed or expected to take place. Such envi- ronments, areas or zones may not comprise plants or soil. For example, the inhibitors may be used for nitrification inhibition in laboratory nments, e.g. based on enzymatic ons or the like. Also envisaged is the use in green houses or r indoor facilities.
The term "reducing nitrification" or "reduction of nitrification" as used herein refers to a slowing down or stopping of nitrification processes, e.g. by retarding or eliminating the natural transfor- mation of ammonium into nitrate. Such ion may be a complete or partial elimination of nitrification at the plant or locus where the inhibitor or composition comprising said inhibitor is applied. For example, a partial elimination may result in a al nitrification on or in the plant, or in or on the soil or soil substituents where a plant grows or is intended to grow of about 90% to 1%, e.g. 90%, 85%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10% or less than 10%, e.g. 5% 40 or less than 5% in comparison to a control situation where the nitrification inhibitor is not used.
In certain embodiments, a l ation may result in a residual nitrification on or in the plant or in or on the soil or soil substituents where a plant grows or is intended to grow of below 1 %, e.g. at 0.5%, 0.1 % or less in comparison to a control situation where the ication inhibi­ tor is not used.
The use of a nitrification inhibitor as defined herein above, or of a composition as defined here­ in for reducing nitrification may be a single use, or it may be a repeated use. As single use, the nitrification inhibitor or corresponding compositions may be ed to their target sites, e.g. soil or loci, or objects, e.g. plants, only once in a physiologically relevant time interval, e.g. once a year, or once every 2 to 5 years, or once during the lifetime of a plant.
In other embodiments, the use may be repeated at least once per time period, e.g. the nitrifica­ tion tor as defined herein above, or a composition as d herein may be used for re- ducing nitrification at their target sites or objects two times within a time interval of days, weeks or . The term "at least once" as used in the context of a use of the nitrification inhibitor means that the inhibitor may be used two times, or several times, i.e. that a repetition or multiple repetitions of an ation or treatment with a nitrification inhibitor may be envisaged. Such a repetition may be a 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or more frequent repetition of the use.
The nitrification tor according to the present invention may be used in any suitable form.
For example, it may be used as coated or uncoated granule, in liquid or semi-liquid form, as sprayable entity, or in irrigation approaches etc. In specific embodiments, the nitrification inhibitor as defined herein may be applied or used as such, i.e. without formulations, fertilizer, addi- tional water, coatings, or any further ingredient.
The term "irrigation" as used herein refers to the watering of plants or loci or soils or soil substituents where a plant grows or is intended to grow, wherein said watering includes the provision of the nitrification inhibitor according to the present ion together with water.
In a further aspect the invention s to a composition for reducing nitrification sing 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.
The term " composition for reducing nitrification" as used herein refers to a ition which is suitable, e.g. comprises effective concentrations and amounts of ingredients such as nitrifica­ tion inhibitors, in particular nds of formula I or derivatives as defined herein, for reducing nitrification in any context or environment in which nitrification may occur. In one embodiment, the nitrification may be reduced in or on or at the locus of a plant. Typically, the ication may be reduced in the root zone of a plant. However, the area in which such reduction of nitrification may occur is not limited to the plants and their environment, but may also include any other habitat of nitrifying bacteria or any site at which ying enzymatic activities can be found or can function in a general manner, e.g. sewage plants, biogas , animal effluents from productive livestock, e.g. cows, pigs etc.. "Effective amounts" or tive concentrations" of nitrification inhibitors as defined herein may be ined according to suitable in vitro and in vivo testings known to the skilled person. These amounts and concentrations may be adjusted to the locus, plant, soil, climate conditions or any other suitable parameter which may have an influ- 40 ence on nitrification processes.
A "carrier" as used herein is a nce or composition which facilitates the delivery and/or release of the ingredients to the place or locus of destination. The term includes, for instance, emical carriers which facilitate the ry and/or release of agrochemicals in their field of use, in particular on or into plants.
Examples of suitable carriers include solid carriers such as phytogels, or hydrogels, or mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g., a solid or liquid ammonium-containing nic fertilizer such as an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium ate; an solid or liquid organic fertilizer such as liquid manure, semi-liquid manure, stable manure, biogas manure and straw manure, worm castings, compost, seaweed or guano, or an ontaining fertilizer such as urea, formalde­ hyde urea, urea ammonium nitrate (UAN) on, urea sulphur, stabilized urea, urea based NPK-fertilizers, or urea ammonium sulfate, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose s and other solid carriers.
Further le examples of carriers include fumed silica or precipitated silica, which may, for instance, be used in solid formulations as flow aid, anti-caking aid, milling aid and as carrier for liquid active ingredients. Additional examples of suitable carriers are microparticles, for instance microparticles which stick to plant leaves and e their content over a certain period of time.
In specific embodiments, agrochemical carriers such as composite gel microparticles that can be used to deliver plant-protection active principles, e.g. as described in US 6,180,141; or com- ons comprising at least one phytoactive compound and an encapsulating adjuvant, where­ in the adjuvant comprises a fungal cell or a nt f, e.g. as described in WO 2005/102045; or carrier granules, coated with a lipophilic tackifier on the surface, wherein the carrier granule adheres to the surface of plants, grasses and weeds, e.g. as disclosed in US 2007/0280981 may be used. In further specific ments, such carriers may include specif- ic, strongly binding molecule which assure that the r sticks to the plant, the soil, or the locus where the plant is growing till its content is completely delivered. For instance, the carrier may be or se cellulose binding domains (CBDs) have been described as useful agents for attachment of lar species to cellulose (see US 6,124,117); or direct fusions between a CBD and an enzyme; or a multifunctional fusion protein which may be used for delivery of encapsulated agents, wherein the multifunctional fusion proteins may consist of a first g domain which is a carbohydrate binding domain and a second binding domain, wherein either the first binding domain or the second binding domain can bind to a microparticle (see also WO 03/031477). Further suitable es of carriers include bifunctional fusion proteins consisting of a CBD and an anti-RR6 dy fragment binding to a microparticle, which x may be deposited onto treads or cut grass (see also WO 03/031477). In another specific embodiment the carrier may be active ingredient carrier es that adhere to the surface of plants, grasses and weeds or the soil, or the locus where the plant is growing etc. using a moisture-active coating, for instance including gum arabic, guar gum, gum karaya, gum tragacanth and locust bean gum. Upon application of the inventive granule onto a plant surface, water from precipita- 40 tion, irrigation, dew, co-application with the es from special application equipment, or guttation water from the plant itself may provide sufficient moisture for adherence of the granule to the plant surface (see also US 2007/0280981).
In another ic ment the carrier, e.g. an agrochemical carrier, may be or comprise polyaminoacids. Polyaminoacids may be obtained according to any suitable process, e.g. by polymerization of single or le amino acids such as glycine, alanine, valine, e, isoleucine , phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, nine, asparagine, glu- tamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine and/or ornithine.
Polyaminoacids may be combined with a nitrification inhibitor according to the present invention and, in certain embodiments, also with further carriers as mentioned herein above, or other nitri­ fication tors as mentioned herein in any suitable ratio. For example, Polyaminoacids may be combined with a nitrification inhibitor according to the present invention in a ratio of 1 to 10 (polyaminoacids) vs. 0.5 to 2 (nitrification inhibitor according to the present invention).
The composition for reducing nitrification comprising at least one nitrification tor as defined herein may further comprise additional ingredients, for example at least one pesticidal compound. For example, the composition may additionally comprise at least one herbicidal compound and/or at least one fungicidal compound and/or at least one insecticidal compound and/or at least one nematicide.
In further embodiments, the composition may, in addition to the above indicated ingredients, in particular in on to the ication inhibitor of the nd of formula I, further comprise one or more alternative or additional nitrification inhibitors. Examples of envisaged alternative or additional nitrification tors are linoleic acid, linolenic acid, methyl p-coumarate, methyl te, methyl 3-(4-hydroxyphenyl) nate (MHPP), Karanjin, brachialacton, pbenzoquinone sorgoleone, 2-chloro(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), methyl pyrazole phosphate (DMPP, ENTEC), 4-amino-1,2,4- triazole hydrochloride (ATC), 1-amidothiourea (ASU), 2-aminochloromethylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxytrichloromethyl-1,2,4-thiodiazole (terrazole, etridiazole), 2-sulfanilamidothiazole (ST), umthiosulfate (ATU), 3-methylpyrazol (3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-triazol thiourea (TU), N-(1 H-pyrazolyl-methyl)acetamides such as N-((3(5)-methyl-1 H-pyrazoleyl)methyl)acetamide, and N-(1 H-pyrazolyl- methyl)formamides such as N-((3(5)-methyl-1 H-pyrazoleyl)methyl formamide, N-(4-chloro- 3(5)-methyl-pyrazole-1 hyl)-formamide, N-(3(5),4-dimethyl-pyrazole-1 -ylmethyl)- formamide, neem, products based on ingredients of neem, cyan amide, melamine, zeolite pow­ der, catechol, benzoquinone, sodium terta board, zinc sulfate.
In a preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of a I and 2-chloro (trichloromethyl)-pyridine (nitrapyrin or N-serve).
In a further preferred ment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 5-ethoxy 40 trichloromethyl-1,2,4-thiodiazole (terrazole, etridiazole).
In a further preferred embodiment, the composition according to the t invention may se a combination of the nitrification inhibitor of the compound of formula I and dicyandiamide (DCD, DIDIN).
In a further 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- dimethyl pyrazole phosphate (DMPP, ENTEC).
In a further 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 chloromethylpyrimidine (AM).
In a further preferred embodiment, the ition according to the present invention may comprise a combination of the ication inhibitor of the compound of formula I and 2- to-benzothiazole (MBT).
In a further preferred embodiment, the ition according to the t invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2- sulfanilamidothiazole (ST).
In a further preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and ammoniumthiosulfate (ATU).
In a further preferred embodiment, the ition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 3- methylpyrazol (3-MP).
In a further red embodiment, the composition according to the present invention may comprise a combination of the ication tor of the compound of formula I and 3,5- dimethylpyrazole (DMP).
In a further 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- triazol.
In a further preferred embodiment, the composition according to the present ion may se a ation of the nitrification inhibitor of the compound of formula I and thiourea (TU).
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of a I and linoleic acid.
In yet another preferred ment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and alphalinolenic acid.
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of a I and methyl pcoumarate.
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of a I and methyl 3- (4-hydroxyphenyl) propionate (MHPP). 40 In yet r preferred ment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and methyl ferulate.
In yet another preferred embodiment, the composition according to the t invention may comprise a combination of the nitrification inhibitor of the compound of formula I and Karanjin.
In yet another preferred embodiment, the composition ing to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and brachialacton.
In yet another red embodiment, the composition according to the present ion may comprise a combination of the nitrification inhibitor of the compound of formula I and pbenzoquinone sorgoleone.
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).
In yet another preferred embodiment, the composition according to the t invention may comprise a ation of the nitrification inhibitor of the compound of formula I and 1-amidolthiourea (ASU).
In yet r 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-1 H-pyrazole-1 -yl)methyl)acetamide.
In yet another preferred embodiment, the composition according to the present invention may se a ation of the nitrification inhibitor of the compound of formula I and N-((3(5)- methyl-1 H-pyrazole-1 thyl formamide.
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the ication inhibitor of the compound of a I and N-(4- chloro-3(5)-methyl-pyrazoleylmethyl)-formamide.
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the ication inhibitor of the compound of formula I and N-(3(5),4- dimethyl-pyrazoleylmethyl)-formamide.
In yet r preferred embodiment, the composition according to the present invention may se a combination of the nitrification inhibitor of the compound of formula I and neem or ts based on ingredients of neem.
In yet another red embodiment, the composition ing to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and cyanamide.
In yet another preferred ment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and melamine.
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.
In yet another preferred embodiment, the composition according to the t invention may se a combination of the ication inhibitor of the compound of formula I and batechol. 40 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.
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 terat borate.
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of the ication tor of the compound of formula I and zinc sul­ fate.
In further embodiments, the composition ing 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, methyl p-coumarate, methyl ferulate, methyl ydroxyphenyl) propionate (MHPP), in, brachialacton, p- uinone sorgoleone, 2-chloro(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP, , 4-amino-1,2,4- triazole hloride (ATC), 1-amidothiourea (ASU), 2-aminochloromethylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxytrichloromethyl-1,2,4-thiodiazole (terrazole, etridiazole), 2-sulfanilamidothiazole (ST), ammoniumthiosulfate (AID), 3-methylpyrazol (3-MP), 3,5-dimethylpyrazole (DMP), 1,2,4-triazol and thiourea (TU), N-(1 H-pyrazolyl-methyl)acetamides such as N-((3(5)-methyl-1 zoleyl)methyl)acetamide, and N-(1 H-pyrazolylmethyl )formamides such as N-((3(5)-methyl-1H-pyrazoleyl)methyl formamide, N-(4-chloro- 3(5)-methyl-pyrazoleylmethyl)-formamide, or ),4-dimethyl-pyrazoleylmethyl)- formamide neem, products based on ingredients of neem, cyan amide, melamine, zeolite powder , catechol, benzoquinone, sodium terta board, zinc sulfate.
In yet another group of embodiments, the composition according to the present ion may comprise a combination of the nitrification inhibitor of the compound of a I and three, four or more entities selected from the group comprising: linoleic acid, alpha-linolenic acid, methyl p- coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4- amino-1,2,4-triazole hydrochloride (ATC), 1-amidothiourea (ASU), 2-aminochloro methylpyrimidine (AM), apto-benzothiazole (MBT), 5-ethoxytrichloromethyl-1,2,4- thiodiazole (terrazole, etridiazole), 2-sulfanilamidothiazole (ST) ammoniumthiosulfate (ATU), 3- methylpyrazol (3-MP), methylpyrazole (DMP), 1,2,4-triazol and thiourea (TU), N-(1H- pyrazolyl-methyl)acetamides such as N-((3(5)-methyl-1 H-pyrazoleyl)methyl)acetamide, and N-(1 H-pyrazolyl-methyl)formamides such as N-((3(5)-methyl-1 H-pyrazoleyl)methyl formamide, N-(4-chloro-3(5)-methyl-pyrazoleylmethyl)-formamide, or N-(3(5),4-dimethyl- pyrazoleylmethyl)-formamide neem, products based on ients of neem, cyan amide, melamine, zeolite powder, catechol, uinone, sodium terta board, zinc sulfate.
In further embodiments, the composition may, in addition to the above indicated ingredients, in particular in on to the nitrification inhibitor of the compound of formula I, further comprise one or more urease inhibitors. es of envisaged urease inhibitors include N-(n-butyl) 40 thiophosphoric acid triamide (NBPT, Agrotain), N-(n-propyl) thiophosphoric acid triamide (NPPT), 2-nitrophenyl phosphoric de (2-NPT), further NXPTs known to the skilled person, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate, and mixtures of NBPT and NPPT (see e.g. US 8,075,659). Such mixtures of NBPT and NPPT may comprise NBPT in amounts of from 40 to 95% wt.-% and preferably of 60 to 80% wt.-% based on the total amount of active substances. Such mixtures are ed as HMDS, which is a composition sing about 16.9 wt.-% NBPT and about 5.6 wt.-% NPPT and about 77.5 wt.-% of other ingredients including solvents and adjuvants.
In a preferred embodiment, the composition according to the present invention may se a combination of the nitrification inhibitor of the compound of formula I and N-(n-butyl) thiophosphoric acid de (NBPT, in).
In a further 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).
In a further preferred embodiment, the composition according to the t ion may comprise a combination of the nitrification inhibitor of the compound of formula I and N-(npropyl ) thiophosphoric acid triamide (NPPT).
In a further preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification tor of the compound of formula I and 2- nitrophenyl phosphoric triamide ).
In a further 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.
In a further preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification tor of the compound of formula I and ammonium thiosulfate.
In yet another preferred embodiment, the composition according to the present ion may se a combination of the nitrification inhibitor of the compound of formula I and neem.
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.
In yet another preferred embodiment, the composition according to the t invention may comprise a combination of the nitrification inhibitor of the compound of formula I and melamine.
In a further preferred embodiment, the composition ing 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.
In further embodiments, the composition according to the t invention may comprise a combination of the nitrification inhibitor of the compound of a 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), further NXPTs known to the skilled person, phenylphosphorodiamidate (PPD/PPDA), hydroqui- none, ammonium thiosulfate, and LIMUS. 40 In further embodiments, the composition may, in on to one, more or all of the above indi­ cated ingredients, in particular in addition to the nitrification inhibitor of the compound of formula I, further se one or more plant growth tors. es of envisaged plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releas- ers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators, and fur­ ther unclassified plant growth regulators.
Suitable examples of antiauxins to be used in a ition according to the present invention are clofibric acid or 2,3,5-tri-iodobenzoic acid. le examples of auxins to be used in a composition ing to the present invention are 4-CPA, 2,4-D, 2,4-DB, 2,4-DEP, dichlorprop, fenoprop, IAA (indoleacetic acid), I BA, naphthaleneacetamide, naphthaleneacetic acid, thol, oxyacetic acid, potassium naphthenate, sodium naphthenate or2,4,5-T.
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, orzeatin. le examples of defoliants to be used in a composition according to the present invention are m cyanamide, dimethipin, endothal, merphos, metoxuron , pentachlorophenol, thidiazuron, tribufos, or tributyl orotrithioate.
Suitable examples of ethylene modulators to be used in a ition ing to the present invention are cine, 1-methylcyclopropene (1-MCP) adione (prohexadione calcium), ortrinexapac (Trinexapac-ethyl).
Suitable examples of ethylene releasers to be used in a composition according to the present ion are ACC, etacelasil, on, or glyoxime.
Suitable examples of gibberellins to be used in a composition according to the present invention are gibberelline or gibberellic acid.
Suitable examples of growth inhibitors to be used in a composition according to the present invention are abscisic acid, S-abscisic acid, dol, butralin, carbaryl ,chlorphonium, chlorpropham, dikegulac, flumetralin, fluoridamid,fosamine, glyphosine, isopyrimol, jasmonic acid, maleic hydrazide, mepiquat (mepiquat chloride, mepiquat pentaborate), piproctanyl, prohydrojasmon, propham, or 2,3,5-tri-iodobenzoic acid.
Suitable examples of morphactins to be used in a composition according to the t invention are chlorfluren, chlorflurenol, rflurenol, orflurenol Suitable examples of growth retardants to be used in a composition according to the present invention are chlormequat (chlormequat chloride), zide, flurprimidol, mefluidide, paclobutrazol, tetcyclacis, azole, metconazol.
Suitable examples of growth stimulators to be used in a ition according to the present invention are brassinolide, forchlorfenuron, or hymexazol.
Suitable examples of further unclassified plant growth regulators to be used in a composition according to the present invention are amidochlor, benzofluor, buminafos, carvone, choline de, ciobutide, clofencet, cloxyfonac, cyanamide, cyclanilide, cycloheximide, cyprosulfamide, epocholeone, ethychlozate, ethylene, fenridazon, fluprimidol, fluthiacet, heptopargil, holosulf, inabenfide, karetazan, lead arsenate, methasulfocarb, pydanon, sintofen, diflufenzopyr or triapenthenol 40 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 com­ pound selected from the group comprising: abscisic acid, amidochlor, ancymidol, 6- benzylaminopurine (= N-6 benzyladenine), brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, ilide, daminozide, diflufenzopyr, dikegulac, dimethipin, 2,6- dimethylpyridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indoleacetic acid, maleic hydrazide, mefluidide, at (mepiquat chloride), 1- methylcyclopropene (1-MCP), naphthaleneacetic acid, N-6 benzyladenine, paclobutrazol, prohexadione (prohexadione calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid, apac-ethyl, and uniconazole.
In a red 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.
In a further 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-tri- iodobenzoic acid.
In a further preferred embodiment, the composition according to the present invention may comprise a ation of the nitrification inhibitor of the nd of a I and 4-CPA.
In a further preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification tor of the compound of formula I and 2,4-D.
In a further preferred embodiment, the composition according to the present ion may comprise a combination of the nitrification inhibitor of the compound of formula I and 2,4-DB.
In a further preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification tor of the compound of a I and 2,4-DEP.
In a r 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.
In a further preferred ment, the composition according to the present ion may comprise a combination of the nitrification inhibitor of the compound of formula I and fenoprop.
In a further preferred embodiment, the composition according to the present ion may comprise a combination of the nitrification inhibitor of the compound of formula I and IAA (indoleacetic acid).
In a further red embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and I BA.
In a further preferred embodiment, the ition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and naphthaleneacetamide.
In a further preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification tor of the compound of formula I and alpha- naphthaleneacetic acid.
In a further red embodiment, the composition according to the present invention may comprise a combination of the ication inhibitor of the compound of formula I and 1-naphthol.
In a r preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 40 naphthoxyacetic acid.
In a further preferred embodiment, the composition ing to the present invention may se a combination of the nitrification inhibitor of the nd of formula I and potassium naphthenate.
In a r preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification tor of the nd of formula I and sodium naphthenate.
In a further preferred embodiment, the composition according to the t invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2,4,5-T.
In a further preferred embodiment, the composition according to the t invention may comprise a combination of the nitrification inhibitor of the compound of formula I and 2iP.
In a further preferred embodiment, the composition according to the present invention may se a combination of the nitrification inhibitor of the compound of formula I and 6- Benzylaminopurine (6-BA) (= N-6 Benzyladenine).
In a further 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 de-2,6-Lultidine).
In a further 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.
In a r preferred embodiment, the composition according to the present ion may comprise a combination of the nitrification inhibitor of the compound of a I and kinetin.
In a r preferred embodiment, the composition according to the present invention may se a combination of the nitrification tor of the compound of formula I and calcium cyanamide.
In a further preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of a I and ipin.
In a further preferred ment, the ition according to the t invention may se a combination of the nitrification inhibitor of the compound of formula I and endothal.
In a further 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.
In a further preferred embodiment, the composition according to the present invention may comprise a combination of the ication inhibitor of the nd of formula I and metoxuron.
In a further 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.
In a further 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.
In a further red embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and tribufos.
In a further preferred ment, the composition ing to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and tributyl phosphorotrithioate. 40 In a further 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.
In a further red embodiment, the composition ing to the present invention may comprise a combination of the nitrification tor of the compound of formula I and 1- methylcyclopropene. ( A composition as defined herein, in particular a ition comprising a nitrification tor as d herein and a plant growth tor as defined herein, may be used for the se of plant health.
The term "plant health" as used herein is intended to mean a condition of the plant which is determined by several s alone or in combination with each other. One indicator (indicator 1) for the condition of the plant is the crop yield. "Crop" and "fruit" are to be understood as any plant product which is further utilized after harvesting, e.g. fruits in the proper sense, vegetables , nuts, grains, seeds, wood (e.g. in the case of silviculture plants), flowers (e.g. in the case of gardening plants, ornamentals) etc., that is anything of economic value that is produced by the plant. Another indicator (indicator 2) for the condition of the plant is the plant vigor. The plant vigor becomes manifest in several aspects, too, some of which are visual appearance, e.g. leaf color, fruit color and aspect, amount of dead basal leaves and/or extent of leaf , plant weight, plant height, extent of plant verse (lodging), number, strong ness and productivity of tillers, panicles' , extent of root system, strongness of roots, extent of nodulation, in par­ ticular of rhizobial nodulation, point of time of germination, emergence, flowering, grain maturity and/or senescence, protein content, sugar content and the like. Another indicator (indicator 3) for an increase of a plant's health is the reduction of biotic or abiotic stress factors. The three above mentioned indicators for the health condition of a plant may be interdependent and may result from each other. For e, a ion of biotic or abiotic stress may lead to a better plant vigor, e.g. to better and bigger crops, and thus to an increased yield. Biotic stress, especially over longer terms, can have l 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 ty and the quality of the stressed plants, their crops and fruits decrease. As far as quality is concerned, reproductive development is usually severely affected with conse­ quences on the crops which are important for fruits or seeds. Growth may be slowed by the stresses; polysaccharide sis, both structural and storage, may be reduced or modified: these effects may lead to a decrease in biomass and to changes in the nutritional value of the product. Abiotic stress includes drought, cold, increased UV, increased heat, or other changes in the environment of the plant, that leads to sub-optimal growth conditions. The term "increased yield" of a plant as used herein means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the composition of the invention. Accord­ ing to the present invention, it is preferred that the yield be increased by at least 0,5 %, more red at least 1 %, even more preferred at least 2 %, still more preferred at least 4 %. An 40 increased yield may, for example, be due to a reduction of ication and a corresponding improvement of uptake of nitrogen nutrients. The term "improved plant vigor" as used herein means that certain crop characteristics are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same ions, but without the application of the ition of the present invention. Improved plant vigor can be characterized , among others, by ing improved properties of a plant: (a) improved vitality of the plant, (b) improved quality of the plant and/or of the plant products, e.g. (b) enhanced n content, (c) ed visual ance, (d) delay of senescence, (e) enhanced root growth and/or more developed root system (e.g. determined by the dry mass of the root), (f) enhanced nodulation, in particular rhizobial nodulation, (g) longer panicles, (h) bigger leaf blade, (i) less dead basal leaves, (j) increased chlorophyll t (k) prolonged photosynthetically active period (l) improved nitrogen-supply within the plant The improvement of the plant vigor according to the present invention particularly means that the ement of anyone or several or all of the above mentioned plant characteristics are improved. It further means that if not all of the above characteristics are improved, those which are not improved are not worsened as compared to plants which were not treated according to the invention or are at least not worsened to such an extent that the negative effect exceeds the positive effect of the improved characteristic (i.e. there is always an overall positive effect which preferably results in an improved crop yield). An improved plant vigor may, for example, be due to a ion of nitrification and , e.g. a regulation of plant growth.
In further embodiments, the composition may, in addition to the above indicated ingredients, in particular in addition to the nitrification inhibitor of the compound of a I, further comprise one or more pesticides.
A pesticide is an agent that through its effect deters, incapacitates, kills or otherwise discour­ ages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals , fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are s for disease. The term "pesticide" includes also plant growth regulators that alter the ed growth, flowering, or reproduction rate of ; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop ; and plant growth ers that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a 40 crop plant.
According to one ment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack r) and further auxiliaries may be added, if appropriate.
Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit comprising a) a composition comprising component 1) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.
The following list of pesticides I (e. g. pesticidally-active substances), in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them: A) Respiration inhibitors - Inhibitors of complex III at Q0 site (e. g. strobilurins): azoxystrobin (A.1.1), coumethoxy- strobin (A.1.2), coumoxystrobin ), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl ), mandestrobin (A.1.10), metominostrobin (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyraclostrobin 4), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)methylallylideneaminooxymethyl )-phenyl)methoxyimino-N-methyl-acetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb/chlorodincarb (A.1.20), famoxadone (A.1.21), done (A.1.21), methyl-A/-[2-[(1,4-dimethylphenyl-pyrazolyl)oxylmethyl]phenyl]-N- methoxy-carbamate (A.1.22), hloro[[1-(4-chlorophenyl)-1 zolyl]oxymethyl]- phenyl]methyl-tetrazolone (A. 1.23), 1-[3-bromo[[1-(4-chlorophenyl)pyrazolyl]oxymethyl ]phenyl]methyl-tetrazoIone (A.1.24), 1-[2-[[1-(4-chlorophenyl)pyrazolyl]oxy- methyl]methyl-phenyl]methyl-tetrazolone (A. 1.25), 1 -[2-[[1 -(4-chlorophenyl)pyrazol- 3- yl]oxymethyl]fluoro-phenyl]methyl-tetrazolone (A.1.26), 1 1 -(2,4-dichloropheny !)pyrazolyl]oxymethyl]fluoro-phenyl]methyl-tetrazolone (A.1.27), 1- [2-[[4-(4-chlorophenyl)thiazolyl]oxymethyl]methyi-phenyl]methyl-tetrazolone (A.1.28), 1-[3-chloro[[4-(p-tolyl)thiazolyl]oxymethyl]phenyl]methyl-tetrazolone (A.1.29), 1-[3-cyclopropyl[[2-methyl(1-methylpyrazolyl)phenoxy]methyl]phenyl]- 4- methyl-tetrazolone (A. 1.30), 1 -[3-(difluoromethoxy)[[2-methyl(1 -methylpyrazol- 3- yl)phenoxy]methyl]phenyl]methyl-tetrazolone (A.1.31), 1 -methyl[3-methyl- 2- thyl(1-methylpyrazolyl)phenoxy]methyl]phenyl]tetrazolone 2), 1-me- thyl[3-methyl[[1-[3-(trifluoromethyl)phenyl]-ethylideneamino]oxymethyl]phenyl]tetrazol- 5- one (A.1.33), (Z,2£)[1-(2,4-dichlorophenyl)pyrazolyl]-oxymethoxyimino-A/,3- dimethyl-pentenamide 4), (Z,2£)[1-(4-chlorophenyl)pyrazolyl]oxy methoxyimino-/V,3-dimethyl-pentenamide (A. 1.35), (Z,2£)[1-(4-chlorofluorophenyl olyl]oxymethoxyimino-A/,3-dimethyl-pentenamide (A.1.36), inhibitors of complex III at Qi site: cyazofamid (A.2.1), amisulbrom (A.2.2), [(3S,6S,7R,8R) 40 benzyl[(3-acetoxymethoxy-pyridinecarbonyl)amino]methyl-4,9-dioxo-1,5-dioxonanyl ] 2-methylpropanoate (A.2.3), [(3S,6S,7R,8R)benzyl[[3-(acetoxymethoxy)- 4- methoxy-pyridinecarbonyl]amino]methyl-4,9-dioxo-1,5-dioxonanyl] 2-methylpropanoate ), [(3S,6S,7R,8R)benzyl[(3-isobutoxycarbonyloxymeth- oxy-pyridinecarbonyl)amino]methyl-4,9-dioxo-1,5-dioxonanyl] 2-methylpropanoate (A.2.5), [(3S,6S,7R,8R)benzyl[[3-(1,3-benzodioxolylmethoxy)methoxy-pyridine- 2- carbonyl]amino]methyl-4,9-dioxo-1,5-dioxonanyl] 2-methylpropanoate (A.2.6); (3S,6S,7R,8R)[[(3-hydroxymethoxypyridinyl)carbonyl]amino]methyl-4,9-dioxo- 8-(phenylmethyl)-1,5-dioxonanyl ylpropanoate (A.2.7), (3S,6S,7R,8R)benzyl- 3- [3-[(isobutyryloxy)methoxy]methoxypicolinamido]methyl-4,9-dioxo-1,5-dioxonanyl isobutyrate (A.2.8); - inhibitors of complex II (e. g. carboxamides): benodanil (A.3.1), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.11), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin 4), penflufen (A.3.14), opyrad (A.3.15), sedaxane (A.3.16), talam (A.3.17), thifluzamide (A.3.18), N-(4'- trifluoromethylthiobiphenylyl)difluoromethylmethyl-1 H-pyrazolecarboxamide 9), N-(2-(1,3,3-trimethyl-butyl)-phenyl)-1,3-dimethylfluoro-1 H-pyrazole- 4- carboxamide (A.3.20), 3-(difluoromethyl)methyl-N-(1,1,3-trimethylindanyl)pyrazole carboxamide (A.3.21), 3-(trifluoromethyl)methyl-N-(1,1,3-trimethylindanyl)pyrazole carboxamide 2), 1,3-dimethyl-N-(1,1,3-trimethylindanyl)pyrazolecarboxamide (A.3.23), 3-(trifluoromethyl)-1,5-dimethyl-N-(1 J^-trimethylindan^-y^pyrazole^- carboxamide (A.3.24), trimethyl-N-(1,1,3-trimethylindanyl)pyrazolecarboxamide (A.3.25), N-(7-fluoro-1,1,3-trimethyl-indanyl)-1,3-dimethyl-pyrazolecarboxamide (A.3.26), N-[2-(2,4-dichlorophenyl)methoxy-1 -methyl-ethyl](difluoromethyl)-1 -methylpyrazolecarboxamide (A.3.27); - other respiration inhibitors (e. g. complex I, uncouplers): diflumetorim (A.4.1), (5,8-difluoroquinazolinyl )-{2-[2-fluoro(4-trifluoromethylpyridinyloxy)-phenyl]-ethyl}-amine (A.4.2); nitrophenyl derivates: binapacryl (A.4.3), ton (AAA), dinocap (A.4.5), nam ); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.11); and ofam (A.4.12); B) Sterol biosynthesis inhibitors (SBI fungicides) - C14 ylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1.1), anol (B.1.2), bromuconazole (B.1.3), cyproconazole (B.1 A), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole-M (B.1.7), epoxiconazole ), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole 4), zole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole (B.1.20), penconazole (B.1.21), propiconazole (B.1.22), prothioconazole (B.1.23), simeconazole (B.1.24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1.27), triadimenol (B.1.28), triticonazole (B.1.29), uniconazole (B.1.30), 1-[rel-(2S;3R)(2-chlorophenyl)(2,4-difluorophenyl)- oxiranylmethyl]thiocyanato-1 H-[1,2,4]triazolo 1), -(2S;3R)(2-chlorophenyl)difluorophenyl)-oxiranylmethyl]-2H-[1,2,4]triazolethiol (B.1.32), 2-[2-chloro(4- chlorophenoxy)phenyl]-1 -(1,2,4-triazol-1 -yl)pentanol (B.1.33), 1 -[4-(4-chlorophenoxy) (trifluoromethyl)phenyl]-1 -cyclopropyl(1,2,4-triazol-1 -yl)ethanol (B. 1.34), 2-[4-(4-chlorophenoxy )(trifluoromethyl)phenyl](1,2,4-triazolyl)butanol (B.1.35), 2-[2-chloro(4- chlorophenoxy)phenyl](1,2,4-triazolyl)butanol (B.1.36), 2-[4-(4-chlorophenoxy) (trifluoromethyl)phenyl]methyl(1,2,4-triazolyl)butanol (B.1.37), 2-[4-(4- chlorophenoxy)(trifluoromethyl)phenyl](1,2,4-triazolyl)propanol (B.1.38), 2-[2- chloro(4-chlorophenoxy)phenyl]methyl(1,2,4-triazolyl)butanol (B.1.39), 4- chlorophenoxy)(trifluoromethyl)phenyl](1,2,4-triazolyl)pentanol (B.1.40), 4- fluorophenoxy)(trifluoromethyl)phenyl](1,2,4-triazolyl)propanol (B.1.41), 2-[2- chloro(4-chlorophenoxy)phenyl]-1 -(1,2,4-triazol-1 -yl)pentynol (B. 1.51); imidazoles: imazalil (B.1.42), pefurazoate (B.1.43), oraz (B.1.44), triflumizol (B.1.45); pyrimidines, pyridines and piperazines: fenarimol (B.1.46), nuarimol 7), pyrifenox 8), triforine (B.1.49), [3-(4-chlorofluoro-phenyl)(2,4-difluorophenyl)isoxazolyl]-(3- pyridyl)methanol (B.1.50); - Deltal4-reductase tors: aldimorph (B.2.1), rph (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); - Inhibitors of 3-keto reductase: fenhexamid (B.3.1); C) Nucleic acid synthesis inhibitors - phenylamides or acyl amino acid ides: benalaxyl (C.1.1), benalaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1.4), xyl-M (mefenoxam, C.1.5), ofurace (C.1.6), oxadixyl (C.1.7); - : hymexazole (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5- fluorocytosine (C.2.5), 5-fluoro(p-tolylmethoxy)pyrimidinamine (C.2.6), ro(4- fluorophenylmethoxy)pyrimidinamine (C.2.7); D) Inhibitors of cell division and eleton - tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl (D1.1), carbendazim (D1.2), fuberidazole (D1.3), thiabendazole (D1.4), thiophanate-methyl (D1.5); triazolopyrimidines: 5-chloro(4-methylpiperidinyl)(2,4,6-trifluorophenyl)-[1,2,4]triazolo [1,5-a]pyrimidine (D1.6); - other cell division inhibitors: diethofencarb (D2.1), ethaboxam (D2.2), uron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriofenone (D2.7); E) Inhibitors of amino acid and protein synthesis - methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil (E.1.1), mepanipyrim ), pyrimethanil (E.1.3); - protein synthesis inhibitors: blasticidin-S (E.2.1), kasugamycin ), kasugamycin hydrochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6), polyoxine (E.2.7), validamycin A (E.2.8); F) Signal transduction inhibitors - MAP / histidine kinase inhibitors: fluoroimid (F.1.1), iprodione ), procymidone (F.1.3), vinclozolin (F.1.4), fenpiclonil (F.1.5), fludioxonil ); - G protein tors: quinoxyfen (F.2.1); 40 G) Lipid and ne synthesis inhibitors - Phospholipid biosynthesis inhibitors: edifenphos (G.1.1), iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1.4); - lipid peroxidation: dicloran (G.2.1), quintozene ), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7); - phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1), flumorph (G.3.2), ropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7) and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-butyl) carbamic acid-(4- fluorophenyl) ester (G.3.8); - compounds affecting cell ne permeability and fatty acides: propamocarb (G.4.1); - fatty acid amide ase inhibitors: oxathiapiprolin (G.5.1), 2-{3-[2-(1-{[3,5-bis(difluoromethyl-1 zol-1 -yl]acetyl}piperidinyl)-1,3-thiazolyl]-4,5-dihydro-1,2-oxazol yl}phenyl esulfonate (G.5.2), 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1 H-pyrazol yl]acetyl}piperidinyl) 1,3-thiazolyl]-4,5-dihydro-1,2-oxazolyl}chlorophenyl methanesulfonate (G.5.3); H) tors with Multi Site Action - inorganic active substances: Bordeaux mixture (H.1.1), copper acetate (H.1.2), copper hydroxide (H.1.3), copper oride (H.1.4), basic copper sulfate (H.1.5), sulfur (H.1.6); - thio- and dithiocarbamates: ferbam (H.2.1), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram ), propineb (H.2.6), thiram (H.2.7), zineb ), ziram (H.2.9); - organochlorine compounds (e. g. imides, sulfamides, nitriles): anilazine (H.3.1), chlorothalonil (H.3.2), captafol ), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, ide (H.3.10), tolylfluanid (H.3.11), N-(4-chloronitro-phenyl)-N-ethylmethylbenzenesulfonamide (H.3.12); - ines and others: guanidine ), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), tadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), non (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 - inhibitors of glucan synthesis: validamycin (1.1.1), polyoxin B (1.1.2); - melanin synthesis inhibitors: pyroquilon (1.2.1), tricyclazole (I.2.2), pamid (1.2.3), dicyclomet (1.2.4), nil (1.2.5); J) Plant defence inducers - acibenzolar-S-methyl (J.1.1), probenazole (J.1.2), isotianil (J.1.3), tiadinil (J.1.4), prohexadione-calcium (J.1.5); phosphonates: fosetyl (J.1.6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), potassium or sodium bicarbonate (J.1.9); K) Unknown mode of action bronopol (K.1.1), chinomethionat (K.1.2), cyflufenamid (K.1.3), cymoxanil ), dazomet (K.1.5), debacarb (K.1.6), diclomezine (K.1.7), difenzoquat (K.1.8), difenzoquatmethylsulfate (K.1.9), diphenylamin (K.1.10), fenpyrazamine (K.1.11), flumetover (K.1.12), flusulfamide (K.1.13), flutianil (K.1.14), methasulfocarb (K.1.15), nitrapyrin (K.1.16), nitrothalisopropyl (K.1.18), oxathiapiprolin (K.1.19), tolprocarb 0), oxin-copper (K.1.21), 40 proquinazid (K.1.22), tebufloquin (K.1.23), tecloftalam (K.1.24), triazoxide (K.1.25), 2-butoxy- 6-iodopropylchromenone (K.1.26), 2-[3,5-bis(difluoromethyl)-1 H-pyrazolyl][4-(4- {5-[2-(propynyloxy)phenyl]-4,5-dihydro-1,2-oxazolyl}-1,3-thiazolyl)piperidin yl]ethanone (K.1.27), 2-[3,5-bis(difluoromethyl)-1 H-pyrazolyl][4-(4-{5-[2-fluoro(prop- 2-yn-1 -yloxy)phenyl]-4,5-dihydro-1,2-oxazolyl}-1,3-thiazolyl)piperidin-1 -yl]ethanone (K.1.28), 2-[3,5-bis(difluoromethyl)-1 H-pyrazolyl][4-(4-{5-[2-chloro(propynyloxy l]-4,5-dihydro-1,2-oxazolyl}-1,3-thiazolyl)piperidinyl]ethanone (K.1.29), N- (cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)phenyl acetamide (K.1.30), N'-(4-(4-chlorotrifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl- N-methyl formamidine (K.1.31), N'-(4-(4-fluorotrifluoromethyl-phenoxy)-2,5-dimethylphenyl )-N-ethyl-N-methyl idine (K.1.32), N'-(2-methyltrifluoromethyl(3-trimethylsilanyl-propoxy )-phenyl)-N-ethyl-N-methyl formamidine (K.1.33), N'-(5-difluoromethyl- 2-methyl(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), methoxy-acetic acid 6-tert-butylfluoro-2,3-dimethyl-quinolinyl ester 5), 3-[5-(4- methylphenyl)-2,3-dimethyl-isoxazolidinyl]-pyridine (K.1.36), 3-[5-(4-chloro-phenyl)-2,3- yl-isoxazolidinyl]-pyridine (pyrisoxazole) (K.1.37), N-(6-methoxy-pyridinyl) cyclopropanecarboxylic acid amide (K.1.38), 5-chloro(4,6-dimethoxy-pyrimidinyl) methyl-1 H-benzoimidazole (K.1.39), 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)- olyl]propynyloxy-acetamide, ethyl (Z)aminocyanophenyl-prop enoate (K.1.40), picarbutrazox (K.1.41), pentyl N-[6-[[(Z)-[(1-methyltetrazolyl)-phenylmethylene ]amino]oxymethyl]pyridyl]carbamate (K.1.42), 2-[2-[(7,8-difluoromethyl quinolyl)oxy]fluoro-phenyl]propanol (K.1.43), 2-[2-fluoro[(8-fluoromethyl yl)oxy]phen-yl]propanol 4), 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroiso- quinolinyl)quinoline (K.1.45), 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolinyl)quinoline (K.1.46), 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolinyl)quinoline (K.1.47), 9-fluoro-2,2-dimethyl(3-quinolyl)-3H-1,4-benzoxazepine 8); M) Insecticides M.1) Acetylcholine esterase (AChE) inhibitors from the class of: M.1A carbamates, for ex­ ample aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, encarb, fenobucarb, formetanate, furathiocarb , isoprocarb, methiocarb, yl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of M.1B phosphates, for example acephate, hiphos, azinphos-ethyl, az- inphosmethyl, fos, thoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, hos, demeton-S-methyl, diazinon, dichlorvos/ DDVR, dicrotophos, dimethoate, dimethylvinphos, disulfoton, ERN, ethion, ethoprophos , famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos , isofenphos, isopropyl O- (methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos , propetamphos, ofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos , temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon 40 and vamidothion; M.2) GABA-gated chloride channel antagonists such as: M.2A iene organochlorine compounds, as for example endosulfan or chlordane; or M.2B es (phenylpyrazoles ), as for example ethiprole, fipronil, flufiprole, pyrafluprole and pyriprole; M.3) Sodium channel tors from the class of M.3A pyrethroids, for example acrinathrin , rin, d-cis-trans allethrin, s rin, hrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin , lambda-cyhalothrin, gamma-cyhalothrin, ethrin, 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, permethrin, phenothrin, thrin, profluthrin, pyrethrin (pyrethrum), hrin, uofen, tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin and transfluthrin; or M.3B sodium channel modulators such as DDT or methoxychlor; M.4) Nicotinic acetylcholine receptor agonists (nAChR) from the class of M.4A neonicotinoids , for example acetamiprid, clothianidin, cycloxaprid, furan, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds M.4A.2: (2E-)[(6- Chloropyridinyl)methyl]-N'-nitropentylidenehydrazinecarboximidamide; or M4.A.3: 1-[(6-Chloropyridinyl)methyl]methylnitropropoxy-1,2,3,5,6,7- hexahydroimidazo[1,2-a]pyridine; or from the class M.4B nicotine; M.5) nic acetylcholine receptor allosteric activators from the class of spinosyns, for example spinosad or oram; M.6) Chloride l activators from the class of avermectins and ycins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin; M.7) Juvenile hormone mimics, such as M.7A juvenile hormone analogues as hydroprene, kinoprene and methoprene; or others as M.7B carb or M.7C pyriproxyfen; M.8) miscellaneous non-specific (multi-site) inhibitors, for example M.8A alkyl halides as methyl bromide and other alkyl halides, or M.8B chloropicrin, or M.8C sulfuryl fluoride, or M.8D borax, or M.8E tartar emetic; M.9) Selective homopteran feeding blockers, for example M.9B ozine, or M.9C flonicamid M.10) Mite growth inhibitors, for example M.10A clofentezine, hexythiazox and diflovidazin, or M.10B ole; M.11) ial disrupters of insect midgut membranes, for example bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai , bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebri- onis, or the Bt crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCrySA, CrySAb, Cry3Bb and Cry34/35Ab1; M.12) Inhibitors of mitochondrial ATP synthase, for example M.12A diafenthiuron, or M.12B organotin miticides such as azocyclotin, cyhexatin or fenbutatin oxide, or M.12C propargite, or M.12D tetradifon; 40 M.13) Uncouplers of oxidative phosphorylation via tion of the proton gradient, for example enapyr, DNOC or sulfluramid; M.14) Nicotinic acetylcholine receptor (nAChR) channel blockers, for example nereistoxin analogues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium; M.15) Inhibitors of the chitin biosynthesis type 0, such as benzoylureas as for example fluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron or triflumuron; M.16) Inhibitors of the chitin biosynthesis type 1, as for e buprofezin; M.17) ng disrupters, Dipteran, as for example cyromazine; M.18) Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfenozide, nozide, halofenozide, fufenozide or chromafenozide; M.19) Octopamin receptor agonists, as for example amitraz; M.20) Mitochondrial complex III electron transport inhibitors, for example M.20A e- thylnon, or M.20B acequinocyl, or M.20C fluacrypyrim; M.21) Mitochondrial complex I electron transport inhibitors, for example M.21A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad ortolfenpyrad, or M.21B rotenone; M.22) Voltage-dependent sodium l rs, for example M.22A indoxacarb, or M.22B metaflumizone, or M.22B.1: 2-[2-(4-Cyanophenyl)[3- (trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]- hydrazinecarboxamide or 2: N-(3-Chloromethylphenyl)[(4- chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]- hydrazinecarboxamide; M.23) Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid derivatives , for example spirodiclofen, spiromesifen or spirotetramat; M.24) Mitochondrial complex IV on transport inhibitors, for example M.24A phosphine such as aluminium phosphide, m phosphide, phosphine or zinc phosphide, or M.24B cyanide; M.25) Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives , for example yrafen or cyflumetofen; M.28) Ryanodine receptor-modulators from the class of diamides, as for example flubendiamide , ntraniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), tetraniliprole, or the phthalamide compounds M.28.1: (R)Chlor-N1-{2-methyl[1,2,2,2- tetrafluor-1 -(trifluormethyl)ethyl]phenyl}-N2-(1 -methyl methylsulfonylethyl)phthalamid and M.28.2: (S)Chlor-N1-{2-methyl[1,2,2,2- tetrafluor-1 -(trifluormethyl)ethyl]phenyl}-N2-(1 -methyl methylsulfonylethyl)phthalamid, or the compound M.28.3: 3-bromo-N-{2-bromo chloro[(1 -cyclopropylethyl)carbamoyl]phenyl}-1 -(3-chlorpyridinyl)-1 H-pyrazole carboxamide sed ISO name: cyclaniliprole), or the compound : methyl- 2-[3,5-dibromo({[3-bromo(3-chlorpyridinyl)-1H-pyrazolyl]carbonyl}- amino)benzoyl]-1,2-dimethylhydrazinecarboxylate; ora compound selected from a) to M.28.5d) and M.28.5h) to M.28.5I): M.28.5a) N-[4,6-dichloro[(diethyllambdasulfanylidene )carbamoyl]-phenyl](3-chloropyridyl) 40 (trifluoromethyl)pyrazolecarboxamide; M.28.5b) N-[4-chloro[(diethyl-lambda sulfanylidene)carbamoyl]methyl-phenyl](3-chloropyridyl) (trifluoromethyl)pyrazolecarboxamide; M.28.5c) N-[4-chloro[(dipropyl-lambda- 4-sulfanylidene)carbamoyl]methyl-phenyl](3-chloropyridyl) (trifluoromethyl)pyrazolecarboxamide; M.28.5d) N-[4,6-dichloro[(dipropyllambdasulfanylidene )carbamoyl]-phenyl](3-chloropyridyl)(trifluoromethyl )pyrazolecarboxamide; M.28.5h) N-[4,6-dibromo[(diethyl-lambda sulfanylidene)carbamoyl]-phenyl](3-chloropyridyl)(trifluoromethyl)pyrazole carboxamide; i) N-[2-(5-Amino-1,3,4-thiadiazolyl)chloromethylphenyl]- 3-bromo(3-chloropyridinyl)-1 H-pyrazolecarboxamide; M.28.5j) 3-Chloro(3- chloropyridinyl)-N-[2,4-dichloro[[(1-cyanomethylethyl)amino]carbonyl]phenyl]- 1 H-pyrazolecarboxamide; k) o-N-[2,4-dichloro (methylcarbamoyl)phenyl](3,5-dichloropyridyl)-1 H-pyrazolecarboxamide; M.28.5I) N-[4-Chloro[[(1,1 -dimethylethyl)amino]carbonyl]methylphenyl]-1 -(3- chloropyridinyl)(fluoromethoxy)-1 H-pyrazolecarboxamide; or a compound selected from M.28.6: N-(2-cyanopropanyl)-N-(2,4-dimethylphenyl)iodobenzene- 1.2- dicarboxamide; or M.28.7: 3-Chloro-N-(2-cyanopropanyl)-N-(2,4- dimethylphenyl)-benzene-1,2-dicarboxamide; M.29) insecticidal active compounds of unknown or uncertain mode of action, as for example afidopyropen, aner, azadirachtin, amidoflumet, benzoximate, bifenazate, broflanilide, bromopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, afon, fluopyram, flupyradifurone, fluralaner , metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, pyrifluquinazon, sul- foxaflor, tioxazafen, triflumezopyrim, or the compounds; M.29.3: 11-(4-chloro-2,6-dimethylphenyl)hydroxy-1,4-dioxaazadispiro[4.2.4.2]- tetradecenone, or the compound M.29.4: 3-(4’-fluoro-2,4-dimethylbiphenyl yl)hydroxyoxaazaspiro[4.5]decenone, or the nd : 1-[2- methyl[(2,2,2-trifluoroethyl)sulfinyl]phenyl](trifluoromethyl)-1 H-1,2,4- triazoleamine, or actives on basis of bacillus firmus (Votivo, 1-1582); or a compound selected from the group of M.29.6, wherein the compound is ed from M.29.6a) to M.29.6k): M.29.6a) N-[1-[(6-chloropyridyl)methyl] pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6b) (E/Z)-N-[1 -[(6-chlorofluoro pyridyl)methyl]pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6c) (E/Z)-2,2,2- trifluoro-N-[1 -[(6-fluoropyridyl)methyl]pyridylidene]acetamide; d) N- [1-[(6-bromopyridyl)methyl]pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6e) (E/Z)-N-[1-[1-(6-chloropyridyl)ethyl]pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6f) (E/Z)-N-[1-[(6-chloropyridyl)methyl]pyridylidene]-2,2-difluoroacetamide ; M.29.6g) (E/Z)chloro-N-[1 -[(6-chloropyridyl)methyl]pyridylidene]- 2.2- difluoro-acetamide; M.29.6h) (E/Z)-N-[1-[(2-chloropyrimidinyl)methyl] pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6i) (E/Z)-N-[1-[(6-chloro pyridyl)methyl]pyridylidene]-2,2,3,3,3-pentafluoro-propanamide.); M.29.6j) N-[1 -[(6- chloropyridyl)methyl]pyridylidene]-2,2,2-trifluoro-thioacetamide; or M.29.6k) N- [1-[(6-chloropyridyl)methyl]pyridylidene]-2,2,2-trifluoro-N'-isopropyl-acetamidine; 40 or the compounds M.29.8: 8-chloro-N-[2-chloromethoxyphenyl)sulfonyl] oromethyl)-imidazo[1,2-a]pyridinecarboxamide; or the compounds M.29.9.a): 4-[5-(3,5-dichlorophenyl)(trifluoromethyl)-4H- isoxazolyl]methyl-N-(1-oxothietanyl)benzamide; or M.29.9.b): 4-[5-(3,5- Dichlorophenyl)trifluoromethyl-4,5-dihydroisoxazolyl]-N-[(methoxyimino)methyl]- 2-methylbenzamide; or M.29.10: 5-[3-[2,6-dichloro(3,3-dichloroallyloxy)phenoxy]propoxy]-1 zole; or a compound selected from the group of M.29.11, wherein the compound is se­ lected from M.29.11b) to M.29.11p): 1.b) 3-(benzoylmethylamino)-N-[2-bromo- 4- ,3,3,3-hexafluoro(trifluoromethyl)propyl](trifluoromethyl)phenyl]fluoro- benzamide; M.29.11.c) 3-(benzoylmethylamino)fluoro-N-[2-iodo[1,2,2,2- tetrafluoro(trifluoromethyl)ethyl](trifluoromethyl)phenyl]-benzamide; M.29.11 .d) N-[3-[[[2-iodo[1,2,2,2-tetrafluoro(trifluoromethyl)ethyl] (trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; M.29.11 .e) N-[3- [[[2-bromo[1,2,2,2-tetrafluoro(trifluoromethyl)ethyl] uoromethyl)phenyl]amino]carbonyl]fluorophenyl]fluoro-N-methyl-benzamide; M.29.11 .f) 4-fluoro-N-[2-fluoro[[[2-iodo[1,2,2,2-tetrafluoro(trifluoromethyl)- ethyl](trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; M.29.11 .g) 3-fluoro-N-[2-fluoro[[[2-iodo[1,2,2,2-tetrafluoro(trifluoromethyl)- ethyl](trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; M.29.11.h) 2-chloro-N-[3-[[[2-iodo[1,2,2,2-tetrafluoro(trifluoromethyl)ethyl] (trifluoromethyl)phenyl]amino]carbonyl]phenyl]- 3-pyridinecarboxamide; M.29.11.1) 4- cyano-N-[2-cyano[[2,6-dibromo[1,2,2,3,3,3-hexafluoro(trifluoromethyl)- propyl]phenyl]carbamoyl]phenyl]methyl-benzamide; 1 .j) 4-cyano[(4- cyanomethyl-benzoyl)amino]-N-[2,6-dichloro[1,2,2,3,3,3-hexafluoro (trifluoromethyl)propyl]phenyl]fluoro-benzamide; M.29.11 .k) N-[5-[[2-chloro cyano[1,2,2,3,3,3-hexafluoro(trifluoromethyl)propyl]phenyl]carbamoyl]cyanophenyl ]cyanomethyl-benzamide; 1.1) N-[5-[[2-bromochloro[2,2,2- trifluorohydroxy(trifluoromethyl)ethyl]phenyl]carbamoyl]cyano-phenyl] cyanomethyl-benzamide; M.29.11 .m) N-[5-[[2-bromochloro[1,2,2,3,3,3- hexafluoro(trifluoromethyl)propyl]phenyl]carbamoyl]cyano-phenyl]cyano methyl-benzamide; M.29.11 .n) 4-cyano-N-[2-cyano[[2,6-dichloro[1,2,2,3,3,3- hexafluoro(trifluoromethyl)propyl]phenyl]carbamoyl]phenyl]methyl-benzamide; M.29.11 .o) 4-cyano-N-[2-cyano[[2,6-dichloro[1,2,2,2-tetrafluoro uoromethyl)ethyl]phenyl]carbamoyl]phenyl]methyl-benzamide; M.29.11 .p) N-[5- [[2-bromochloro[1,2,2,2-tetrafluoro(trifluoromethyl)ethyl]phenyl]carbamoyl] cyano-phenyl]cyanomethyl-benzamide; or a nd selected from the group of M.29.12, wherein the compound is se­ lected from M.29.12a) to M.29.12m): M.29.12.a) 2-(1,3-Dioxanyl)[2-(3-pyridinyl)- - thiazolyl]-pyridine; M.29.12.b) 2-[6-[2-(5-Fluoropyridinyl)thiazolyl]pyridinyl]- pyrimidine; M.29.12.c) 2-[6-[2-(3-Pyridinyl)thiazolyl]pyridinyl]-pyrimidine; M.29.12.d) N-Methylsulfonyl[2-(3-pyridyl)thiazolyl]pyridinecarboxamide; M.29.12.e) N-Methylsulfonyl[2-(3-pyridyl)thiazolyl]pyridinecarboxamide; 40 M.29.12.f) N-Ethyl-N-[4-methyl(3-pyridyl)thiazolyl]methylthio-propanamide; M.29.12.g) N-Methyl-N-[4-methyl(3-pyridyl)thiazolyl]methylthio-propanamide; M.29.12.h) N,2-Dimethyl-N-[4-methyl(3-pyridyl)thiazolyl]methylthiopropanamide ; M.29.12.i) N-Ethylmethyl-N-[4-methyl(3-pyridyl)thiazolyl] methylthio-propanamide; M.29.12.j) N-[4-Chloro(3-pyridyl)thiazolyl]-N-ethyl methylthio-propanamide; M.29.12.k) N-[4-Chloro(3-pyridyl)thiazolyl]- N,2-dimethylmethylthio-propanamide; M.29.12.1) N-[4-Chloro(3-pyridyl)thiazol yl]-N-methylmethylthio-propanamide; M.29.12.m) N-[4-Chloro(3-pyridyl)thiazol- 5-yl]-N-ethylmethylthio-propanamide; or the compounds M.29.14a) 1-[(6-Chloropyridinyl)methyl]-1 ^SAGy-hexahydro- S-methoxy-Z-methyl-S-nitro-imidazon ,2-a]pyridine; or M.29.14b) 1-[(6-Chloropyridin- 3- hyl]methylnitro-1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridinol; or the compounds M.29.16a) 1-isopropyl-N,5-dimethyl-N-pyridazinyl-pyrazole carboxamide; or M.29.16b) 1-(1,2-dimethylpropyl)-N-ethylmethyl-N-pyridazinylpyrazolecarboxamide ; M.29.16c) N,5-dimethyl-N-pyridazinyl(2,2,2-trifluoro methyl-ethyl)pyrazolecarboxamide; M.29.16d) 1-cyanocyclopropyl)ethyl]-N- ethylmethyl-N-pyridazinyl-pyrazolecarboxamide; M.29.16e) N-ethyl-1 -(2- fluoromethyl-propyl)methyl-N-pyridazinyl-pyrazolecarboxamide; M.29.16f) -dimethylpropyl)-N,5-dimethyl-N-pyridazinyl-pyrazolecarboxamide; M.29.16g) 1-[1-(1-cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazinyl-pyrazole carboxamide; M.29.16h) N-methyl(2-fluoromethyl-propyl]methyl-N-pyridazin- 4- yl-pyrazolecarboxamide; M.29.16i) 1-(4,4-difluorocyclohexyl)-N-ethylmethyl-N- pyridazinyl-pyrazolecarboxamide; or M.29.16j) 1-(4,4-difluorocyclohexyl)-N,5- dimethyl-N-pyridazinyl-pyrazolecarboxamide; N) Herbicides ides from the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, hiadiazinones, bipyridylium, carbamates, chloroacetamides, carboxylic acids, cyclohexanediones, dinitroanilines, ophenol, diphenyl ether, glycines, olinones, oles, isoxazolidinones, nitriles, N- phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, pyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, olinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, or ureas.
The present invention furthermore s to agrochemical compositions comprising a mix­ ture of at least one compound of formula I, i.e. a nitrification inhibitor of the present invention (compound I or component I) and at least one further active substance useful for plant protection , e. g. ed from the groups A) to N) (component 2), in particular one r fungicide, e. g. one or more fungicide from the groups A) to K), as described above, and if desired one suitable solvent or solid carrier. Those mixtures are of particular interest, since many of them at 40 the same application rate show higher efficiencies against harmful fungi. Furthermore, combat­ ing harmful fungi with a mixture of compounds I and at least one fungicide from groups A) to K), as described above, is more efficient than combating those fungi with individual compounds I or individual fungicides from groups A) to K).
By applying compounds I together with at least one active substance from groups A) to N) a synergistic plant health effect can be obtained, i.e. more than simple addition of the individual effects is obtained (synergistic mixtures).
This can be obtained by applying the compounds I and at least one further active substance simultaneously, either y (e. g. as tank-mix) or separately, or in succession, wherein the time interval n the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of ation of the further active substance(s). The order of ation is not essential for g of the present invention.
When applying compound I and a pesticide I sequentially the time between both applications may vary e. g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1.5 hours to 5 days, even more preferred from 2 hours to 1 day. In case of a mixture comprising a pesticide II ed from group L), it is preferred that the pesticide I is applied as last treat- ment.
In the binary mixtures and compositions according to the invention the weight ratio of the component 1) and the component 2) generally s from the properties of the active components used, usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1, even more preferably in the range of from 1:4 to 4:1 and in particular in the range of from 1:2 to 2:1.
According to r embodiments of the binary mixtures and compositions, the weight ratio of the component 1) and the ent2) usually is in the range of from 1000:1 to 1:1, often in the range of from 100: 1 to 1:1, regularly in the range of from 50:1 to 1:1, preferably in the range of from 20:1 to 1:1, more preferably in the range of from 10:1 to 1:1, even more preferably in the range of from 4:1 to 1:1 and in particular in the range of from 2:1 to 1:1.
According to a further embodiments of the binary mixtures and compositions, the weight ratio of the component 1) and the component 2) usually is in the range of from 1:1 to 1:1000, often in the range of from 1:1 to 1:100, regularly in the range of from 1:1 to 1:50, ably in the range of from 1:1 to 1:20, more preferably in the range of from 1:1 to 1:10, even more preferably in the range of from 1:1 to 1:4 and in particular in the range of from 1:1 to 1:2.
According to further embodiments of the mixtures and compositions, the weight ratio of the component 1) and the component 2) generally depends from the properties of the active components used, usually it is in the range of from 1:10,000 to :1, regularly in the range of from 1:100 to 10,000:1, preferably in the range of from 1:100 to 5,000:1, more preferably in the range of from 1:1 to 1,000:1, even more preferably in the range of from 1:1 to 500:1 and in par­ ticular in the range of from 10:1 to 300:1.
According to further embodiments of the mixtures and compositions, the weight ratio of the component 1) and the component 2) y is in the range of from 20,000:1 to 1:10, often in the 40 range of from 10,000:1 to 1:1, regularly in the range of from 5,000:1 to 5:1, preferably in the range of from 5,000:1 to 10:1, more preferably in the range of from 2,000:1 to 30:1, even more ably in the range of from 2,000:1 to 100:1 and in particular in the range of from 1,000:1 to 100:1.
According to further embodiments of the mixtures and compositions, the weight ratio of the ent 1) and the component 2) usually is in the range of from 1:20,000 to 10:1, often in the range of from 1:10,000 to 1:1, regularly in the range of from 1:5,000 to 1:5, ably in the range of from 0 to 1:10, more preferably in the range of from 1:2,000 to 1:30, even more preferably in the range of from 0 to 1:100 and in particular in the range of from 1:1,000 to 1:100.
In the ternary mixtures, i.e. compositions according to the invention comprising the compo­ nent 1) and component 2) and a compound III (component 3), the weight ratio of component 1) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular in the range of from 1:4 to 4:1, and the weight ratio of component 1) and component 3) usually it is in the range of from 1:100 to 100:1, regularly in the range of from 1:50 to 50:1, preferably in the range of from 1:20 to 20:1, more preferably in the range of from 1:10 to 10:1 and in particular in the range of from 1:4 to 4:1.
Any further active ents are, if desired, added in a ratio of from 20:1 to 1:20 to the component 1).
These ratios are also suitable for inventive mixtures applied by seed treatment.
The active substances referred to as component 2, their preparation and their ty e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by IUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031; EP-A226 917; EP-A243 970; EP-A256 503; EP-A428 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 657, WO2012/168188, WO 2007/006670, WO 81, WO 13/007767, WO 862, WO 13/127704, WO 009, WO 13/024010 and WO 13/047441, WO 13/162072, WO 13/092224, WO 11/135833).
The commercially available compounds of the group M listed above may be found in The Pesticide Manual, 16th Edition, C. MacBean, British Crop Protection Council (2013) among other publications. The online Pesticide Manual is updated regularly and is accessible through 40 http://bcpcdata.com/pesticide-manual.html. Another online data base for pesticides providing the ISO common names is /www.alanwood.net/pesticides. The M.4 otinoid aprid is known from WO2010/069266 and WO2011/069456, the neonicotinoid M.4A.2, sometimes also to be named as yr, is known from WO2013/003977, and the neonicotinoid M.4A.3 (approved as paichongding in China) is known from W02007/101369.
The metaflumizone analogue M.22B.1 is described in CN10171577 and the analogue M.22B.2 in CN102126994. The phthalamides M.28.1 and M.28.2 are both known from W02007/101540.
The anthranilamide M.28.3 is described in W02005/077934. The hydrazide compound M.28.4 is described in W02007/043677. The anthranilamides M.28.5a) to M.28.5d) and M.28.5h) are described in M.28.5i) is described in WO2011/085575, J) in W02008/134969, M.28.5k) in US2011/046186 and M.28.5I) in /034403. The diamide nds M.28.6 and M.28.7 can be found in CN102613183. The etal-substituted cyclic ketoenol derivative M.29.3 is known from W02006/089633 and the biphenyl-substituted yclic ketoenol derivative M.29.4 from W02008/067911. The triazoylphenylsulfide M.29.5 is described in W02006/043635, and biological control agents on the basis of bacillus firmus are described in W02009/124707. The compounds M.29.6a) to M.29.6i) listed under M.29.6 are described in WO2012/029672, and M.29.6j) and M.29.6k) in WO2013/129688. The nematicide M.29.8 is known from WO2013/055584. The isoxazoline M.29.9.a) is described in WO2013/050317. The isoxazoline M.29.9.b) is described in WO2014/126208. The lyl-type analogue M.29.10 is known from WO2010/060379. The carboxamides broflanilide and M.29.11 .b) to M.29.11 .h) are described in /018714, and the carboxamides M.29.11i) to M.29.11.p) in WO2010/127926. The pyridylthiazoles M.29.12.a) to 2.c) are known from WO2010/006713, 2.d) and 2.e) are known from W02012/000896, and M.29.12.f) to M.29.12.m) from WO2010/129497. The compounds M.29.14a) and M.29.14b) are known from W02007/101369. The pyrazoles M.29.16.a) to M.29.16h) are described in WO2010/034737, /084670, and WO2012/143317, respectively, and the pyrazoles M.29.16i) and M.29.16j) are described in US 61/891437.
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 as defined herein above; or at least one fertilizer and a composition as mentioned above.
In the terms of the t invention "agrochemical mixture" means a combination of at least two compounds. The term is, however, not restricted to a physical mixture comprising at least two compounds, but refers to any preparation form of at least one compound and at least one further compound, the use of which many be time- and/or locus-related.
The emical mixtures may, for example, be formulated separately but applied in a tem­ poral relationship, i.e. simultaneously or subsequently, the subsequent application having a time interval which allows a combined action of the compounds.
Furthermore, the individual compounds of the agrochemical mixtures according to the invention such as parts of a kit or parts of the binary mixture may be mixed by the user himself in a suitable mixing . In specific ments further aries may be added, if appropriate. 40 The term "fertilizers" is to be understood as chemical compounds applied to promote plant and fruit growth. izers are typically applied either through the soil (for uptake by plant roots), through soil substituents (also for uptake by plant roots), or by foliar feeding (for uptake through leaves). The term also includes mixtures of one or more different types of fertilizers as mentioned below.
The term "fertilizers" can be subdivided into several categories including: a) organic fertilizers (composed of d plant/animal matter), b) inorganic fertilizers (composed of chemicals and minerals) and c) urea-containing fertilizers.
Organic fertilizers include manure, e.g. liquid , semi-liquid manure, biogas manure, stable manure or straw manure, slurry, worm castings, peat, seaweed, compost, sewage, and guano. Green manure crops are also regularly grown to add nutrients (especially nitrogen) to the soil. Manufactured organic fertilizers include compost, blood meal, bone meal and d extracts. Further examples are enzyme digested proteins, fish meal, and feather meal. The de­ composing crop residue from prior years is another source of fertility. In addition, naturally occurring minerals such as mine rock phosphate, sulfate of potash and limestone are also considered inorganic fertilizers. nic fertilizers are y manufactured h chemical processes (such as the Haber process), also using naturally occurring deposits, while chemically altering them (e.g. concen­ trated triple superphosphate). Naturally occurring inorganic fertilizers include n sodium nitrate, mine rock ate, limestone, and raw potash fertilizers.
The nic fertilizer may, in a specific embodiment, be a NPK fertilizer. "NPK fertilizers" are inorganic fertilizers formulated in appropriate concentrations and combinations comprising the three main nutrients nitrogen (N), phosphorus (P) and potassium (K) as well as typically S, Mg, Ca, and trace elements.
Urea-containing izer may, in ic embodiments, be urea, formaldehyde urea, anhydrous ammonium, urea ammonium nitrate (UAN) on, urea sulfur, urea based NPK- fertilizers, or urea ammonium sulfate. Also envisaged is the use of urea as fertilizer. In case urea-containing fertilizers or urea are used or provided, it is particularly preferred that urease inhibitors as defined herein above may be added or additionally be present, or be used at the same time or in connection with the urea-containing fertilizers.
Fertilizers may be provided in any suitable form, e.g. as solid coated or ed granules, in liquid or semi-liquid form, as sprayable fertilizer, or via fertigation etc.
Coated fertilizers may be ed with a wide range of materials. Coatings may, for example, be applied to ar or prilled nitrogen (N) fertilizer or to multi-nutrient fertilizers. Typically, urea is used as base al for most coated fertilizers. Alternatively, ammonium or NPK fertilizers are used as base material for coated fertilizers. The present invention, however, also envisages the use of other base materials for coated fertilizers, any one of the izer materials d herein. In certain embodiments, elemental sulfur may be used as fertilizer coating. The coating may be performed by spraying molten S over urea granules, followed by an application of sealant wax to close fissures in the coating. In a further embodiment, the S layer may be covered with a layer of organic polymers, preferably a thin layer of c polymers.
Further envisaged coated fertilizers may be provided by reacting resin-based polymers on the 40 surface of the fertilizer granule. A further example of ing coated izers includes the use of low permeability polyethylene polymers in combination with high permeability coatings.
In specific embodiments the ition and/or thickness of the fertilizer coating may be ad­ justed to control, for e, the nutrient release rate for specific applications. The duration of nutrient release from specific fertilizers may vary, e.g. from several weeks to many months. The presence of nitrification inhibitors in a mixture with coated fertilizers may ingly be adapted. It is, in particular, envisaged that the nutrient release involves or is accompanied by the e of a nitrification inhibitor according to the present invention.
Coated fertilizers may be provided as controlled release fertilizers (CRFs). In specific embodiments these controlled release fertilizers are fully coated urea or N-P-K fertilizers, which are homogeneous and which typically show a pre-defined longevity of e. In r embodiments , the CRFs may be provided as blended controlled release izer products which may contain coated, ed and/or slow release components. In certain embodiments, these coated fertilizers may additionally comprise micronutrients. In specific embodiments these izers may show a pre-defined longevity, e.g. in case of N-P-K fertilizers.
Additionally ged es of CRFs include patterned release fertilizers. These fertilizers typically show a pre-defined release patterns (e.g. hi/standard/lo) and a fined longevity. In exemplary embodiments fully coated N-P-K, Mg and micronutrients may be red in a pat­ terned release manner.
Also envisaged are double coating ches or coated fertilizers based on a mmed In further embodiments the fertilizer mixture may be provided as, or may comprise or contain a slow release fertilizer. The fertilizer may, for example, be released over any le period of time, e.g. over a period of 1 to 5 , preferably up to 3 months. Typical examples of ingredients of slow release fertilizers are IBDU (isobutylidenediurea), e.g. containing about 31-32 % nitrogen, of which 90% is water insoluble; or UF, i.e. an urea-formaldehyde product which contains about 38 % nitrogen of which about 70 % may be ed as water insoluble nitrogen; or CDU (crotonylidene diurea) containing about 32 % nitrogen; or MU lene urea) containing about 38 to 40% nitrogen, of which 25-60 % is typically cold water insoluble nitrogen; or MDU (methylene diurea) containing about 40% nitrogen, of which less than 25 % is cold water insoluble nitrogen; or MO (methylol urea) containing about 30% nitrogen, which may typically be used in solutions; or DMTU (diimethylene triurea) containing about 40% nitrogen, of which less than % is cold water insoluble nitrogen; orTMTU (tri methylene tetraurea), which may be provided as ent of UF products; or TMPU (tri methylene pentaurea), which may also be provided as component of UF products; or UT (urea triazone solution) which typically contains about 28 % nitrogen. The fertilizer mixture may also be long-term nitrogen-bearing fertilizer containing a mixture of acetylene diurea and at least one other organic nitrogen-bearing fertilizer selected from methylene urea, isobutylidene , crotonylidene diurea, substituted triazones, triuret or mixtures thereof.
Any of the above mentioned fertilizers or fertilizer forms may suitably be combined. For instance , slow release fertilizers may be provided as coated izers. They may 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 may be adapted to the form and chemical 40 nature of the fertilizer and accordingly be provided such that its release accompanies the release of the fertilizer, e.g. is released at the same time or with the same frequency. The present ion further envisages fertilizer or fertilizer forms as defined herein above in combination with nitrification inhibitors as defined herein above and further in combination with urease inhibi- tors as defined herein above. Such combinations may be provided as coated or uncoated forms and/or as slow or fast release forms. Preferred are combinations with slow release fertilizers including a coating. In r embodiments, also different release schemes are envisaged, e.g. a slower or a faster release.
The term "fertigation" as used herein refers to the application of fertilizers, optionally soil ents, and optionally other water-soluble products together with water h an irrigation system to a plant or to the locus where a plant is growing or is intended to grow, or to a soil substituent as defined herein below. For example, liquid izers or dissolved fertilizers may be provided via fertigation directly to a plant or a locus where a plant is growing or is intended to grow. se, nitrification inhibitors according to the present invention, or in combination with additional nitrification inhibitors, may be provided via fertigation to plants or to a locus where a plant is growing or is intended to grow. Fertilizers and nitrification inhibitors according to the present invention, or in combination with additional nitrification tors, may be provided together , e.g. dissolved in the same charge or load of material (typically water) to be irrigated. In further embodiments, fertilizers and nitrification inhibitors may be provided at different points in time. For example, the fertilizer may be fertigated first, ed by the nitrification inhibitor, or ably, the nitrification inhibitor may be fertigated first, followed by the fertilizer. The time intervals for these activities follow the herein above outlined time als for the application of fertilizers and nitrification inhibitors. Also envisaged is a ed fertigation of fertilizers and ication inhibitors according to the present invention, either together or intermittently, e.g. every 2 hours, 6 hours, 12 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days or more.
In particularly preferred embodiments, the fertilizer is an ammonium-containing fertilizer.
The agrochemical mixture according to the present invention may comprise one fertilizer as defined herein above and one nitrification inhibitor of formula I as defined herein above. In fur­ ther ments, the agrochemical mixture according to the present invention may comprise at least one or more than one fertilizer as defined herein above, e.g. 2, 3, 4, 5, 6, 6, 7, 8,9,10 or more different fertilizers (including inorganic, organic and ontaining fertilizers) and at least one nitrification inhibitor of a I as defined herein above, preferably one ication inhibitor of formula I selected from Table 1.
In another group of embodiments the agrochemical e according to the t 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, e.g. 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.
The term "at least one" is to be understood as 1,2, 3 or more of the respective compound ed from the group consisting of izers as defined herein above (also designated as compound A), and nitrification inhibitors of formula I as defined herein above (also designated as compound B). 40 In addition to at least one fertilizer and at least one nitrification inhibitor as defined herein above, an agrochemical mixture may comprise further ingredients, nds, active compounds or compositions or the like. For example, the agrochemical mixture may additionally comprise or composed with or on the basis of a carrier, e.g. an agrochemical carrier, preferably as defined herein. In further embodiments, the agrochemical mixture may further comprise at least one pesticidal nd. For example, the agrochemical mixture may additionally comprise at least one herbicidal compound and/or at least one fungicidal compound and/or at least one insecticidal compound.
In further embodiments, the agrochemical e may, in addition to the above indicated in­ gredients, in ular in addition to the nitrification inhibitor of the compound of formula I and the fertilizer, further comprise alternative or additional ication inhibitors such as linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, MHPP, Karanjin, brachialacton, quinone sorgoleone, nitrapyrin, dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate , 4-amino-1,2,4-triazole hydrochloride (ATC), 1-amidothiourea (ASU), 2-amino chloromethylpyrimidine (AM), 5-ethoxytrichloromethyl-1,2,4-thiodiazole (terrazole), ammoniumthiosulfate (ATU), 3-methylpyrazol (3-MP), methylpyrazole (DMP), 1,2,4-triazol and thiourea (TU) and/or sulfathiazole (ST), N-(1 H-pyrazolyl-methyl)acetamides such as N- ((3(5)-methyl-1 H-pyrazoleyl)methyl)acetamide, and/or N-(1 H-pyrazolyl-methyl)formamides such as N-((3(5)-methyl-1 zoleyl)methyl formamide, hloro-3(5)-methyl-pyrazole- 1-ylmethyl)-formamide, or N-(3(5),4-dimethyl-pyrazoleylmethyl)-formamide.
Furthermore, the ion relates to a method for reducing nitrification, comprising treating a plant growing on soil and/or the locus where the plant is growing or is intended to grow with at least one nitrification inhibitor as defined herein above, i.e. with an nitrification inhibitor being a compound of formula I, ora derivative thereof, ora ition comprising said nitrification inhibitor.
The term "plant" is to be understood as a plant of economic ance and/or men-grown plant. In certain embodiments, the term may also be understood as plants which have no or no icant economic importance. The plant is preferably selected from agricultural, silvicultural and horticultural (including ornamental) plants. The term also relates to cally ed plants.
The term "plant" as used herein further includes all parts of a plant such as germinating seeds, emerging seedlings, plant propagules, herbaceous vegetation as well as established woody plants including all belowground portions (such as the roots) and aboveground portions.
Within the context of the method for reducing nitrification it is assumed that the plant is grow­ ing on soil. In specific embodiments, the plant may also grow differently, e.g. in synthetic labora­ tory environments or on soil substituents, or be supplemented with nutrients, water etc. by artifi­ cial or technical means. In such ios, the invention envisages a treatment of the zone or area where the nutrients, water etc. are provided to the plant. Also envisaged is that the plant grows in green houses or similar indoor facilities.
The term "locus" is to be understood as any type of environment, soil, soil substituent, area or al where the plant is growing or intended to grow. Preferably, the term relates to soil or soil substituent on which a plant is growing. 40 In one embodiment, the plant to be d according to the method of the invention is an agri­ al plant. "Agricultural plants" are plants of which a part (e.g. seeds) or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibers (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds. Preferred agricultural plants are for example s, e.g. wheat, rye, barley, tritica- le, oats, corn, sorghum or rice, beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspber­ ries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil , such as rape, oil-seed rape, canola, linseed, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squash­ es, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as or­ anges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages , carrots, onions, tomatoes, potatoes, cucurbits or paprika; eous plants, such as avocados, cinnamon or camphor; energy and raw material , such as corn, soybean, rape, canola, sugar cane or oil palm; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants.
In a r embodiment, the plant to be treated according to the method of the invention is a horticultural plant. The term "horticultural plants" are to be tood as plants which are commonly used in horticulture, e.g. the cultivation of ornamentals, vegetables and/or . Ex­ amples for ornamentals are turf, geranium, pelargonia, petunia, begonia and a. Examples for vegetables are potatoes, es, peppers, cucurbits, cucumbers, melons, watermelons, , onions, carrots, cabbage, beans, peas and lettuce and more preferably from tomatoes, onions, peas and lettuce. Examples for fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots and blueberries.
In a further embodiment, the plant to be treated according to the method of the invention is an ornamental plant. "Ornamental plants" are plants which are commonly used in gardening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia.
In another embodiment of the present invention, the plant to be treated according to the meth­ od of the invention is a silvicultural plant. The term cultural plant" is to be understood as trees, more specifically trees used in station or industrial plantations. Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening es. Examples for silvicultural plants are conifers, like pines, in particular Pinus spec., fir and spruce, eucalyptus, tropical trees like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec., poplar nwood), in particular Populus spec., beech, in particular Fagus spec., birch, oil palm, and oak.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. pota- toes), which can be used for the lication of the plant. This includes seeds, grains, roots, fruits, tubers, bulbs, es, cuttings, spores, offshoots, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after ation or after emergence from soil, meristem tissues, single and multiple plant cells and any other plant tissue from which a complete plant can be obtained. 40 The term "genetically modified plants" is to be tood as plants, which genetic material has been ed by the use of recombinant DNA ques in a way that under natural cir­ cumstances it cannot y be obtained by cross breeding, mutations or natural recombination.
Typically, one or more genes have been integrated into the genetic material of a genetical- ly modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin ides such as dicamba or2,4-D; bleacher herbicides such as hydroxylphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvylshikimatephosphate synthase ) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as inate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic ering. rmore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as ance to both sate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD tors, auxin herbicides, or ACCase inhibitors. These herbicide ance technologies are e. g. described in Pest Managem. Sci. 61, 2005, 246; 61, 2005, 258; 61,2005, 277; 61, 2005, 269; 61,2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1185; and refer­ ences quoted n. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of ng (mutagenesis), e. g. ield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tol­ erant to herbicides such as glyphosate and glufosinate, some of which are commercially ble under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.), Cultivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate-tolerant, Bayer CropScience, Germany). rmore, plants are also covered that are by the use of recombinant DMA techniques ca­ pable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as 5-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c; tive insecticidal ns (VIP), e. g. VIP1, VIP2, VIPS or VIP3A; insecticidal proteins of bacteria colonizing des , e. g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other -specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant s, such as pea or barley lectins; agglutinins ; nase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, 40 ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone tors or A- reductase; ion channel blockers, such as blockers of sodium or m channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present ion these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or ise modified proteins. Hybrid proteins are characterized by a new combination of pro­ tein domains, (see, e. g. WO 02/015701). Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal ns contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda ). cally modified plants e to synthesize one or more insecticidal proteins are, e. g., described in the publications ned above, and some of which are commercially availa­ ble such as ard® (corn cultivars producing the CrylAb toxin), YieldGard® Plus (corn cultivars producing CrylAb and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c tox­ in), Herculex® RW (corn cultivars producing Cry34Ab1, Cry35Ab1 and the enzyme phosphinothricin-N-acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the Cry1 Ac , Bollgard® I (cotton cultivars ing the CrylAc toxin), Bollgard® II (cotton cul­ tivars producing CrylAc and Cry2Ab2 toxins); VIPCOT® (cotton ars producing a VIP-toxin); Newleaf® (potato ars producing the Cry3A toxin); a®, NatureGard®, KnockOut®, rd®, Protecta®, Bt11 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, , (corn cultivars producing the CrylAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f.
WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from r as Corporation, Belgium (corn cultivars producing the Cry1F toxin and PAT enzyme).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogene­ sis-related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express ance genes acting against Phytophthora infestans de­ rived from the Mexican wild potato m bulbocastanum) orT4-lysozym (e. g. potato ars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. rmore, plants are also covered that are by the use of inant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or n content), tolerance to drought, salinity or other 40 growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of nces of content or new substances of content, specifically to im- prove human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada).
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to im­ prove raw al production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SB, Germany).
The term "soil substituent" as used herein refers to a substrate which is able to allow the growth of a plant and does not comprise usual soil ingredients. This substrate is typically an anorganic substrate which may have the function of an inert medium. It may, in certain embod­ iments, also comprise organic elements or portions. Soil substituents may, for example, be used in hydroculture or hydroponic approaches, i.e. wherein plants are grown in soilless medium and/or aquatic based environments. Examples of suitable soil substituents, which may be used in the context of the present invention, are perlite, gravel, biochar, l wool, coconut husk, phyllosilicates, i.e. sheet silicate minerals, typically formed by parallel sheets of silicate tetrahedra with SbOs or a 2:5 ratio, or clay aggregates, in particular ed clay aggregates with a diameter of about 10 to 40 mm. Particularly preferred is the employment of vermiculite, i.e. a phyllosilicate with 2 tetrahedral sheets for every one octahedral sheet present.
The use of soil substituents may, in specific embodiments, be ed with fertigation or irri- gation as defined herein.
In specific embodiments, the treatment may be carried out during all suitable growth stages of a plant as defined herein. For example, the treatment may be carried out during the BBCH prin­ ciple growth stages.
The term "BBCFI principal growth stage" refers to the extended BBCH-scale which is a system for a uniform coding of phenologically similar growth stages of all mono- and dicotyledonous plant species in which the entire developmental cycle of the plants is subdivided into clearly recognizable and guishable -lasting developmental . The BBCH-scale uses a decimal code , which is divided into principal and secondary growth stages. The abbre­ viation BBCH derives from the l Biological Research Centre for Agriculture and ry ny), the Bundessortenamt (Germany) and the al ry.
In one embodiment the invention relates to a method for reducing nitrification comprising treat­ ing a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with at least one nitrification inhibitor as defined herein above, i.e. with a nitrifi­ cation inhibitor being a compound of formula I, or a derivative thereof at a growth stage (GS) between GS 00 and GS > BBCH 99 of the pant (e.g. when fertilizing in fall after harvesting apples ) and preferably between GS 00 and GS 65 BBCH of the plant.
In one embodiment the invention relates to a method for ng nitrification comprising treat­ ing a plant growing on soil or soil tuents and/or the locus where the plant is growing or is 40 intended to grow with at least one nitrification inhibitor as defined herein above, i.e. with a ication inhibitor being a compound of formula I, or a derivative f at a growth stage (GS) between GS 00 to GS 45, preferably between GS 00 and GS 40 BBCH of the plant.
In a preferred embodiment the ion relates to a method for reducing nitrification compris­ ing treating a plant growing on soil or soil substituents and/or the locus where the plant is g or is intended to grow with at least one nitrification inhibitor as defined herein above, i.e. with a nitrification inhibitor being a compound of a 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 red embodiments , the method for reducing nitrification comprises treating a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with at least one nitrification inhibitor as defined herein above during growth stages including GS 00.
In a further, specific embodiment of the invention, at least one nitrification inhibitor as defined herein above, i.e. a nitrification tor being a compound of formula I, or a derivative thereof is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at a growth stage n GS 00 and GS 55 BBCH, or of the plant.
In a further ment of the invention, at least one nitrification inhibitor as defined herein above, i.e. a ication inhibitor being a compound of formula I, or a derivative thereof is ap­ plied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at the growth stage n GS 00 and GS 47 BBCH of the plant.
In one embodiment of the invention, at least one nitrification inhibitor as defined herein above, i.e. a nitrification inhibitor being a compound of formula I, or a tive thereof is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow before and at sowing, before nce, and until harvest (GS 00 to GS 89 BBCH), or at a growth stage (GS) between GS 00 and GS 65 BBCH of the plant.
In a red embodiment the invention relates to a method for reducing nitrification compris­ ing treating a plant growing on soil or soil substituents and/or the locus where the plant is growing with at least one ication tor as defined herein above, i.e. with a nitrification inhibitor being a compound of formula I, or a derivative thereof wherein the plant and/or the locus where plant is growing or is intended to grow is additionally provided with at least one fertilizer. The fertilizer may be any suitable fertilizer, preferably a fertilizer as defined herein above. Also en­ visaged is the application of more than one fertilizer, e.g. 2, 3, 4, 5, 6, 7, 8, 9, 10 fertilizers, or of different izer classes or categories.
In specific embodiments of the invention, at least one nitrification inhibitor as defined herein above, i.e. a nitrification inhibitor being a compound of formula I, ora derivative thereof and at least one fertilizer is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at a growth stage between GS OOand GS 33 BBCH of the plant.
In specific embodiments of the invention, at least one nitrification inhibitor as defined herein above, i.e. a nitrification inhibitor being a nd of formula I, or a derivative thereof and at least one fertilizer is applied to a plant g on soil or soil substituents and/or the locus 40 where the plant is growing or is intended to grow at a growth stage between GS 00 and GS 55 BBCH of the plant.
In further specific embodiments of the invention, at least one nitrification inhibitor as defined herein above, i.e. a nitrification inhibitor being a compound of formula I, or a derivative thereof and at least one fertilizer is d to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is ed to grow at sowing, before emergence, or at a growth stage (GS) between GS 00 and GS > BBCH 99 of the pant (e.g. when fertilizing in fall after harvesting apples) and preferably between GS 00 and 65 BBCH of the plant.
According to a preferred embodiment of the present invention the application of said nitrification inhibitor and of said izer as defined herein above is carried out simultaneously or with a time lag. The term "time lag" as used herein means that either the nitrification inhibitor is applied before the fertilizer to the plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow; or the fertilizer is applied before the nitrification inhibitor to the plant growing on soil or soil tuents and/or the locus where the plant is growing or is intended to grow. Such time lag may be any suitable period of time which still allows to provide a nitrification inhibiting effect in the context of fertilizer usage. For example, the time lag may be a time period of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 11 weeks, 12 weeks, 4 months, 5 , 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in n the mentioned time periods. ably , the time lag is an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks. The time lag preferably refers to situations in which the nitrification inhibitor as defined above is provided 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 11 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods before the application of a izer as defined herein above.
In another specific embodiment of the invention at least one nitrification inhibitor as defined herein above, i.e. a nitrification inhibitor being a nd 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 herein above is carried out with a time lag of at least 1 day, e.g. a time lag of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, or more or any time period in between the mentioned time periods. It is preferred that the nitrification inhibitors, which is applied between GS 00 to GS 33 BBCH of the plant, is provided 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 11 weeks, or 12 weeks before the application of a fertilizer as defined herein above.
In r specific embodiment of the ion, at least one fertilizer as d herein above is d 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 40 above, i.e. of a nitrification inhibitor being a compound of formula I, ora derivative thereof, is carried out with a time lag of at least 1 day, e.g. a time lag of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks or more or any time period in between the mentioned time periods.
According to a specific embodiment of the present invention a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow is treated at least once with a nitrification inhibitor as defined herein 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 on soil or soil substituents and/or the locus where the plant is g or is intended to grow is treated at least once with a nitrification inhibitor as defined herein 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 herein above.
The term "at least once" means that the application may be performed one time, or several times, i.e. that a repetition of the treatment with a nitrification inhibitor and/or a izer may be envisaged. Such a repetition may a 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or more nt repetition of the treatment with a nitrification inhibitor and/or a fertilizer. The repetition of treatment with a ication inhibitor and a fertilizer may further be different. For example, while the fertilizer may be applied only once, the ication inhibitor may be applied 2 times, 3 times, 4 times etc. Alternatively, while the nitrification inhibitor may be applied only once, the fertilizer may be d 2 times, 3 times, 4 times etc. Further ged are all combination of cal ent numbers of tions for the application of a ication inhibitor and a fertilizer as defined herein above.
Such a repeated treatment may further be combined with a time lag between the treatment of the nitrification tor and the fertilizer as described above.
The time interval between a first application and second or subsequent application of a nitrifi- cation inhibitor and/or a fertilizer may be any suitable interval. This interval may range from a few seconds up to 3 months, e.g. from a few seconds up to 1 month, or from a few seconds up to 2 weeks. In further embodiments, the time interval may range from a few seconds up to 3 days or from 1 second up to 24 hours.
In further specific embodiments, a method for reducing nitrification as bed above is car­ ried out by ng a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with at least one agrochemical mixture as defined herein above, or with a composition for reducing nitrification as defined herein above.
In another ment of the invention, an agrochemical mixture comprising an ammonium- or ontaining fertilizer and at least one nitrification inhibitor as defined herein above is ap­ plied before and at sowing, before emergence, and until GS > BBCH 99 of the pant (e.g. when fertilizing in fall after harvesting apples In case the agrochemical mixture is provided as kit of parts or as non-physical mixture, it may be applied with a time lag between the application of the nitrification inhibitor and the fertilizer or between the application of the nitrification inhibitor a 40 secondary or further ingredient, e.g. a pesticidal nd as mentioned herein above.
In a further embodiment plant propagules are preferably treated simultaneously (together or separately) or subsequently.
The term "propagules" or "plant propagules" is to be tood to denote any structure with the capacity to give rise to a new plant, e.g. a seed, a spore, or a part of the vegetative body capable of independent growth if ed from the parent. In a preferred embodiment, the term "propagules" or "plant propagules" denotes for seed.
For a method as described above, or for a use according to the invention, in particular for seed treatment and in furrow application, the application rates of 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 n 50 g and 300 g of active ingredient per hectare depending on different parameters such as the specific active ingredient applied and the plant species treated. In the treatment of seed, amounts of from 0.001 g to 20 g per kg of seed, preferably from 0.01 g to 10 g per kg of seed, more preferably from 0.05 to 2 g per kg of seed of nitrification inhibitors may be generally required.
As a matter of course, if nitrification inhibitors and fertilizers (or other ingredients), or if mix­ tures f are employed, the compounds may be used in an effective and ytotoxic amount. This means that they are used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotoxic symptoms on the treated plant or on the plant raised from the treated propagule or treated soil or soil substituents. For the use according to the invention, the application rates of fertilizers may be selected such that the amount of applied N is between 10 kg and 1000 kg per hectare, preferably between 50 kg and 700 kg per hectare.
The nitrification inhibitor nds according to the ion, e.g. compound I as defined herein above, or derivative thereof as d herein above can be present in different ural or chemical modifications whose biological ty may differ. They are likewise t matter of the present invention.
The nitrification inhibitor compounds according to the invention, their N-oxides and/or salts etc. may be converted into customary types of compositions, e.g. agrochemical or agricultural compositions such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
The composition type depends on the ular intended purpose; in each case, it should en­ sure a fine and uniform distribution of the nd according to the invention. Examples for composition types are suspensions (SC, 00, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), microemulsions (ME), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, OP, OS) or granules (GR, FG, GG, MG), which can be watersoluble or wettable, as well as gel formulations for the ent of plant propagation materials such as seeds (GF). Usually the composition types (e.g. SC, 00, FS, EC, WG, SG, WP, SP, SS, WS, GF) are employed diluted.
Composition types such as OP, OS, GR, FG, GG and MG are usually used undiluted.
The compositions are prepared in a known manner (see, for example, US 3,060,084, EP 707 445 (for liquid concentrates), Browning: meration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hili, New York, 1963, S. 8-57 40 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US ,232,701, US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed l as a Science (J. Wiley & Sons, New York, 1961), Hance et al.: Weed Control Handbook (8th Ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and ann, A.: Formulation technology (Wiley VCH Verlag, Weinheim, 2001). Compositions or mixtures may also comprise auxiliaries which are customary, for example, in agrochemical compositions. The auxiliaries used depend on the particular application form and active substance, respectively. es for suitable auxiliaries are ts, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti-foaming , if appropriate colorants and tackifiers or binders (e.g. for seed treatment formulations). Suitable solvents are water , organic solvents such as l oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, l, propanol, butanol and cyclohexanol, s, 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.
Suitable surfactants (adjuvants, wetters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid sperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene-sulfonic acid (Nekal® types, BASF, GermanY),and fatty acids, alkylsulfonates, alkylarylsulfonates, alkyl sulfates, laurylether sul- fates, fatty alcohol sulfates, and sulfated hexa-, hepta- and canolates, sulfated fatty l glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, y-ethylene octylphenyl ether, ethoxylated ylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl ycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol , lignin-sulfite waste liquors and proteins, denatured proteins, polysaccharides (e. g. methylcellulose), hydrophobically modified es, nyl alcohols l® types, Clariant, Switzerland), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvinylamines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers thereof. Examples of suitable thickeners (i.e. compounds that impart a modified flowability to itions, i.e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan®, CP Kelco, U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt, ) or Attaclay® (Engelhard Corp., NJ, USA).
In specific ments, bactericides may be added for preservation and stabilization of the composition. Examples for suitable bactericides are those based on dichlorophene and benzyl alcohol hemi formal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide® MBS from Thor Chemie). 40 Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Examples for oaming agents are silicone emulsions (such as e.g. Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, organic compounds and mixtures thereof.
Suitable colorants are pigments of low water lity and water-soluble dyes, e.g. in B, C. I. pigment red 112, C. I. solvent red 1, pigment blue 15:4, pigment blue 15:3, pigment blue :2, pigment blue 15: 1, pigment blue 80, t yellow 1, t yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, t red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Furthermore odorous substances may be present in the compositions as defined above. Such odorous substances comprise citronellynitril, citral, zertrahydrolinalool, tetrahydrogeraniol, geranonitril, beta-lonon R, rootanol, lacetat, morillol, and p-cresometylether.
Examples for iers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan).
Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding compound of formula I and, if appropriate, further active substances, with at least one solid carrier. Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers. Examples of such suitable solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, te, aceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, izers, such as, e.g. ammonium sulfate, arm- monium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
Examples for composition types are: i) Water-soluble concentrates (SL, IS) 10 parts by weight of a nitrification inhibitor such as a nd of formula I according to the invention are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves upon dilution with water. In this way, a composition having a content of 10% by weight of active substance is obtained. ii) sible concentrates (DC) 20 parts by weight of a nitrification inhibitor such as a com­ pound of formula I according to the invention are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, e.g. polyvinylpyrrolidone.
Dilution with water gives a dispersion. The active substance content is 20% by weight. ill) Emulsifiable concentrates (EC) 15 parts by weight of a nitrification inhibitor such as a com­ pound of formula I according to the ion are dissolved in 75 parts by weight of xylene with addition of calcium lbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The ition 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 addition 40 of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. on with water gives an on.
The composition has an active nce content of 25% by weight. v) Suspensions (SC, 00, FS) In an agitated ball mill, 20 parts by weight of a nitrification inhibi­ tor such as a compound of formula I according to the invention are comminuted with addition of parts by weight of dispersants and wetting agents and 70 parts by weight of water or an or­ ganic solvent to give a fine active substance suspension. Dilution with water gives a stable sus- pension 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 ication inhibitor such as a compound of a I according to the invention are ground fine­ ly with on of 50 parts by weight of dispersants and wetting agents and prepared as water- dispersible or water-soluble granules by means of technical appliances (e.g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
The composition has an active substance content of 50% by weight. vii) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of a nitrification tor such as a compound of a I according to the invention are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
The active substance content of the composition is 75% by weight. viii) Gel (GF) In an agitated ball mill, 20 parts by weight of a nitrification inhibitor such as a compound of formula I according to the invention are comminuted with addition of 10 parts by weight of sants, 1 part by weight of a gelling agent s and 70 parts by weight of wa­ ter or of an organic solvent to give a fine suspension of the active nce. Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained. 2. Composition types to be applied undiluted ix) Oustable powders (OP, OS) 5 parts by weight of a nitrification inhibitor such as a com- pound of formula I according to the invention are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable composition having an active substance content of 5% by weight. x) Granules (GR, FG, GG, MG) 0.5 parts by weight of a nitrification inhibitor such as a nd of a I according to the ion is ground finely and associated with 99.5 parts by weight of carriers. Current s are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5-10% by weight, preferably an active substance content of 0.5-2% by weight. xi) ULV ons (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, e.g. xylene. This gives a composition to be applied undiluted having an active substance content of % by .
The compositions, e.g. agrochemical or agriculatural compositons, generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substance. The active substances are employed in a purity offrom 90% to 40 100%, preferably from 95% to 100% (according to NMR spectrum).
Water-soluble concentrates (LS), le concentrates (FS), powders for dry treatment (OS), dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES) emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted.
The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during .
Methods for applying or treating agrochemical or agricultural nds or mixtures, or com­ positions as defined herein, respectively, on to plant propagation material, especially seeds, the plant and/or the locus where the plant is growing or intended to grow are known in the art, and include dressing, g, pelleting, dusting, soaking and in-furrow application methods of the propagation material. In a preferred embodiment, the compounds or the itions thereof, respectively, are d on to the plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting.
In a preferred embodiment, a suspension-type (FS) composition may be used. Typically, a FS composition may comprise 1-800 g/l of active nce, 1 200 g/l surfactant, o to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
The active substances can be used as such or in the form of their compositions, e.g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions , pastes, dustable ts, materials for spreading, or granules, by means of spraying, ing, dusting, spreading, brushing, immersing or pouring.
The application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active substances according to the invention. s application forms can be prepared from on concentrates, pastes or wettable powders (sprayable s, oil dispersions) by adding water.
To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifi­ er. Alternatively, it is possible to prepare concentrates composed of active substance, , tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for on with water.
The active substance concentrations in the ready-to-use preparations can be varied within rel­ atively wide ranges. In general, they are from 0.0001 to 90%, such as from 30 to 80%, e.g. from to 45% or from 65 to 75% by weight of active substance. The active substances may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives. 40 Various types of oils, s, adjuvants, herbicides, bactericides, other ides and/or pesticides may be added to the active substances or the compositions comprising them, if appropriate not until ately prior to use (tank mix). These agents can be admixed with the com- positions according to the invention in a weight ratio of 1 : 100 to 100 : 1, preferably 1 : 10 to 10 Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240®; alcohol alkoxylates such as Atplus 245®, Atplus MBA 1303®, Plurafac IF 300® and Lutensol ON 30®; EO/PO block polymers, e.g. ic RPE 2035® and Genapol B®; al­ cohol ethoxylates such as Lutensol XP 80®; and dioctyl sulfosuccinate sodium such as Leophen RA®.
In a r 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 accordingly result in the presence of said nitrification inhibitor in a preparation of fertilizers or other compositions.
Such treatment may, for example, result in a homogenous distribution of nitrification inhibitors on or in fertilizer ations. Treatment ses are known to the skilled person and may include, for instance, dressing, coating, pelleting, dusting or g. In a specific embodiment, the treatment may be a coating of ication inhibitors with fertilizer preparations, or a coating of izers with nitrification inhibitors. The treatment may be based on the use of granulation methods as known to the skilled person, e.g. fluidized bed ation. The treatment may, in certain embodiments, be med with a composition comprising the nitrification inhibitor as defined herein above, e.g. comprising besides the inhibitor a carrier or a ide or any other suitable additional compound as mentioned above.
In a further specific embodiment, the present invention relates to a method for treating seed or plant propagation material. The term "seed treatment" as used herein refers to or es steps towards the control of biotic stresses on or in seed and the improvement of shooting and development of plants from seeds. For seed treatment it is evident that a plant suffering from biotic es such as fungal or insecticidal attack or which has difficulties obtaining sufficient le nitrogen-sources shows reduced germination and emergence leading to poorer plant or crop establishment and vigor, and consequently, to a reduced yield as compared to a plant propaga­ tion material which has been subjected to ve or preventive treatment against the relevant pest and which can grow without the damage caused by the biotic stress . Methods for treating seed or plant propagation material according to the ion thus lead, among other advantages, to an enhanced plant health, a better protection against biotic stresses and an increased plant yield.
Seed treatment methods for applying or treating ive mixtures and compositions thereof, e.g. compositions or agrochemical compositions as defined herein above, and in particular combinations of ication inhibitors as defined herein above and secondary effectors such as pesticides, in particular fungicides, insecticides, and/or nematicides, to plant propagation mate­ rial, ally seeds, are known in the art, and include dressing, coating, ating, pelleting 40 and soaking application methods of the propagation material. Such methods are also applicable to the combinations or compositions according to the invention.
In further embodiments, the treatment of seeds is performed with compositions sing, besides a nitrification inhibitor according to the present invention, e.g. compositions as defined herein above, a fungicide and an insecticide, or a fungicide and a nematicide, or an insecticide and a nematicide, or a combination of a ide, insecticide and nematicide, etc.
In a preferred embodiment, the agricultural ition or combination comprising a nitrifica­ tion inhibitor according to the present invention, e.g. as defined herein above, is applied or treated on to the plant propagation material by a method such that the ation is not nega­ tively ed. Accordingly, examples of suitable methods for ng (or treating) a plant propagation material, such as a seed, is seed dressing, seed coating or seed pelleting and alike. It is red that the plant propagation material is a seed, seed piece (i.e. stalk) or seed bulb.
Although it is believed that the present method can be applied to a seed in any physiological state, it is preferred that the seed be in a sufficiently durable state that it incurs no damage during the treatment process. Typically, the seed would be a seed that had been harvested from the field; d from the plant; and separated from any cob, stalk, outer husk, and surround­ ing pulp or other non-seed plant material. The seed would preferably also be ically stable to the extent that the treatment would cause no biological damage to the seed. It is believed that the treatment can be applied to the seed at any time between harvest of the seed and sowing of the seed or during the sowing process (seed directed applications). The seed may also be primed either before or after the treatment.
Even distribution of the ingredients in compositions or mixtures as defined herein and adher- ence f to the seeds is desired during ation material treatment. Treatment could vary from a thin film (dressing) of the formulation containing the combination, for example, a mixture of active ingredient(s), on a plant propagation material, such as a seed, where the origi­ nal size and/or shape are recognizable to an intermediary state (such as a coating) and then to a thicker film (such as pelleting with many layers of different materials (such as carriers, for ex- ample, clays; different formulations, such as of other active ingredients; rs; and colorants ) where the original shape and/or size of the seed is no longer recognizable.
An aspect of the present invention includes application of the composition, e.g. agricultural composition or combination sing a nitrification inhibitor according to the present invention , e.g. as defined herein above, onto the plant propagation material in a targeted fashion, ing positioning the ingredients in the combination onto the entire plant propagation material or on only parts thereof, including on only a single side or a portion of a single side. One of ordinary skill in the art would understand these ation methods from the description provid­ ed in EP954213B1 and WO06/112700.
The composition, e.g. agricultural composition or combination comprising a nitrification - tor according to the present invention, e.g. as d herein above, can also be used in form of a "pill" or "pellet" or a le substrate and placing, or , the treated pill, or substrate, next to a plant propagation material. Such techniques are known in the art, particularly in EP1124414, W007/67042, and W007/67044. Application of the composition, e.g. agricultural composition, or combination comprising a nitrification inhibitor according to the present inven- 40 tion, e.g. as defined herein above, onto plant propagation material also includes protecting the plant propagation material treated with the ation of the present invention by placing one or more ide- and nitrification inhibitor (Nl)-containing particles next to a pesticide- and Nltreated seed, wherein the amount of pesticide is such that the pesticide-treated seed and the pesticide- containing particles er contain an ive Dose of the ide and the ide dose contained in the pesticide-treated seed is less than or equal to the Maximal Non- Phytotoxic Dose of the pesticide. Such techniques are known in the art, particularly in W02005/120226.
Application of the combinations onto the seed also includes lled release coatings on the seeds, wherein the ingredients of the combinations are incorporated into materials that release the ingredients over time. Examples of controlled release seed treatment logies are generally known in the art and include polymer films, waxes, or other seed coatings, wherein the ingredients may be orated into the controlled release material or applied between layers of materials, or both.
Seed can be treated by applying thereto the compound s present in the inventive mixtures in any desired sequence or simultaneously.
The seed treatment occurs to an unsown seed, and the term "unsown seed" is meant to include seed at any period between the harvest of the seed and the sowing of the seed in the ground for the purpose of germination and growth of the plant.
Treatment to an unsown seed is not meant to include those practices in which the active ingredient is applied to the soil or soil substituents but would include any application practice that would target the seed during the planting process.
Preferably, the treatment occurs before sowing of the seed so that the sown seed has been pre-treated with the combination. In particular, seed coating or seed ing are preferred in the treatment of the combinations according to the invention. As a result of the treatment, the ingredients in each combination are adhered on to the seed and therefore available for pest control.
The treated seeds can be stored, handled, sowed and tilled in the same manner as any other active ingredient treated seed.
Solutions for seed treatment (IS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible s for slurry treatment (WS), water-soluble pow­ ders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant ation materials, particularly seeds. Preferred ex­ amples of seed ent formulation types or soil application for pre-mix compositions are of WS, LS, ES, FS, WG or CS-type.
The compositions in on give, after two-to-tenfold dilution, active components concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations.
Application can be carried out before or during sowing. Methods for applying or treating itions or combinations comprising a nitrification inhibitor according to the present invention , e.g. as defined herein above on to plant ation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, compositions or combinations comprising a nitrification inhibitor according to the t invention, e.g. as defined herein above are applied on to the plant propa­ 40 gation material by a method such that germination is not induced, e. g. by seed dressing, pellet­ ing, coating and dusting.
Typically, a pre-mix ation for seed ent 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 e, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 percent, especially 0.5 to 40 percent, based on the pre-mix formulation. Whereas commercial products will preferably be formulated as concentrates (e.g., pre- mix composition (formulation), the end user will normally employ dilute formulations (e.g. tank mix composition).
When ed in plant protection, the total amounts of active components applied are, depending on the kind of effect desired, from 0.001 to 10 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha. The application rates may range from about 1 x 106 to 5 x 1015 (or more) CFU/ha. Preferably, the spore concentration is about 1 x 107 to about 1 x 1011 CFU/ha. In the case of (entomopathogenic) nematodes as microbial pesticides (e.g. Steinernema feltiae), the application rates ably range inform about 1 x 105 to 1 x 1012 (or more), more preferably from 1 x 108 to 1 x 1011, even more preferably from 5 x 108 to 1 x 1010 individuals (e.g. in the form of eggs, juvenile or any other live , preferably in an infetive juvenile stage) per ha.
When employed in plant protection by seed treatment, the amount of itions or combinations comprising a nitrification inhibitor according to the t invention, e.g. as defined herein above (based on total weight of active ents) is in the range from 0 kg, preferably from 0.1-1000 g, more preferably from 1-100 g per 100 kilogram of plant propagation material (preferably seeds). The application rates with respect to plant propagation material preferably may range from about 1 x 106 to 1 x 1012 (or more) CFU/seed. Preferably, the concentration is about 1 x 106 to about 1 x 1011 CFU/seed. Alternatively, the application rates with respect to plant propagation material may range from about 1 x 107 to 1 x 1014 (or more) CFU per 100 kg of seed, preferably from 1 x 109 to about 1 x 1011 CFU per 100 kg of seed.
The following example is provided for illustrative purposes. It is thus understood that the example is not to be construed as limiting. The skilled person in the art will clearly be able to envisage further modifications of the principles laid out herein.
EXAMPLES Example 1: The compounds of the invention have been tested as follows in terms of the inhibition of nitrification Soil was sampled fresh from a field (e.g. Limburgerhof), dried and sieved through a 500 pm sieve. Approximately 200 mg of soil were placed into each well of a 48 well plate. Compounds, or DMSO alone, were added at a concentration of 10 ppm, dissolved in 1% DMSO. 6 pmol um sulfate was added per well as well as 4.8 mg NaCIOs. uently, the samples were incubated at room temperature for up to 72 hrs. After the in­ 40 cubation period 64 mg KCI were added and mixed. 25 pi of the atant were placed into a fresh plate and 260 pi of a color reaction solution (from Merck Nr 1.11799.0100) were added.
Measurements were taken with a Tecan plate Reader at 540 nm wavelength.
The results of the measurements (with a dose of 10 ppm) were that all compounds 1-1 to 1-22 as shown in Table 1 above, supra trated an inhibition of £ 10 % ed to a control (DMSO only). Futhermore, the compounds 1-23 to 1-33 as shown in Table 1 above (with a dose of 5±1 ppm), supra trated an inhibition of s 15 % compared to a control (DMSO only).
Inhibition is calculated as x = % activity compared to control, and converted to 100-x to give the value of inhibition, rather than activity.
Example 1.1: The results for the compounds tested with a dose of 10 ppm are provided in the following Ta­ ble 1.1. In each case, the best inhibition value (IN) obtained for a compound is provided.
Table 1.1 No. Compound IN No. Compound IN 1-1 .0. 15 1-8 .0. 57 1-2 Br 48 1-9 20 1-3 11 1-10 Cl Cl 14 1-4 15 1-11 Cl 12 Q o 1-5 F- 27 .Nt /^NH Cl -o" "O' 1-6 Cl 10 1-12 Br 15 Q o Q -crN+ Cl vo- 1-7 11 (Qj)N—. 1-13 F 10 Q o Q II "O O’ No. Compound IN No. Compound IN 1-14 Cl 56 1-19 O 15 1-15 Cl 58 1-20 10 O. O. 1-16 11 M O. Q •Cl N 1-17 10 1-21 20 0 0^ Q .Nt Cl Cl u0.Nx O' 1-18 Cl 10 1-22 Cl 11 o o: Q 'Cl nQn NIP> Comparative Example 1.2: For comparative purposes phenylacetylene was tested under the same conditions as outlined above with a dose of 10 ppm. The following tion value was obtained.
Table 1.2 Comp. Ex.1.2 Structure IN Phenylacetylene 7 Example 1.3: The results for the compounds tested with a dose of 5±1 ppm are provided in the ing Table 1.3. In each case, the best inhibition value (IN) obtained for a compound is provided.
Table 1.3 No. Compound IN No. Compound IN 1-23 18 1-29 37 1-24 .0. 18 1-30 N 25 1-25 87 Q 1-31 18 1-26 69 OH 1-32 I 53 1-27 59 O' 1-33 O 24 1-28 88

Claims (13)

Claims
1. A nitrification inhibiting mixture comprising: (i) at least one fertilizer selected from the group consisting of a solid or liquid ammonium- 5 containing inorganic fertilizer; an ammonium-containing solid or liquid organic fertilizer selected from the group consisting of liquid manure, semi-liquid manure, biogas manure, stable manure, straw manure, worm gs, compost, seaweed or guano; and a ntaining izer; and (ii) at least one compound of formula (I) selected from a compound of a (1-8), or a compound of formula (1-15): 15 (1-8), (1-15) wherein the mixture ts nitrification of ammonium in a locus or soil or soil substituents 20 where a plant is growing or is intended to grow.
2. A method for reducing nitrification, comprising treating locus or soil or soil substituents where the plant is growing or is ed to grow with a compound of formula (I) selected from a compound of a (1-8), or a compound of formula (1-15): (1-8), 30 (1-15) wherein: the plant and/or the locus or soil or soil substituents where the plant is growing or is intended to grow is additionally provided with a fertilizer; and the fertilizer is selected from the group consisting of a solid or liquid ammonium-containing 35 inorganic fertilizer; a solid or liquid organic fertilizer selected from the group consisting of liquid manure, semi-liquid manure, biogas manure, stable , straw manure, worm castings, compost, seaweed or guano; and a urea-containing fertilizer.
3. The method of claim 2, comprising applying the compound of formula (I) and the fertilizer simultaneously or with a time lag.
4. The method of claim 2 or 3, wherein said plant is an agricultural plant selected from 5 the group consisting of wheat, barley, oat, rye, n, corn, potatoes, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, and rice; a vegetable plant selected from the group consisting of spinach, lettuce, asparagus, cabbages, and sorghum; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or in a genetically modified form.
5. The method of any one of claims 2 to 4, wherein the nd of formula (I) is applied as a composition comprising the compound of formula (I) and a carrier.
6. The method of any one of claims 2 to 4, wherein the compound of formula (I) is ap- 15 plied as a composition comprising (i) at least one fertilizer; and (ii) at least one nd of formula (I).
7. The method of claim 3, comprising applying the compound of formula (I) and the fertilizer with a time lag selected from the group consisting of 1 day, 2 days, 3 days, 1 week, 2 20 weeks and 3 weeks.
8. The nitrification inhibiting mixture of claim 1, wherein said fertilizer is a solid or liquid ammonium-containing inorganic fertilizer ed from the group consisting of an NPK fertilizer , ammonium nitrate, m ammonium nitrate, ammonium sulfate nitrate, ammonium 25 sulfate or ammonium phosphate.
9. The nitrification inhibiting mixture of claim 1, wherein said fertilizer is a ureacontaining fertilizer ed from the group consisting of urea, formaldehyde urea, urea ammonium e (UAN) solution, urea sulphur, ized urea, urea based NPK-fertilizers, 30 or urea ammonium sulfate.
10. The method of claim 2, wherein said izer is a solid or liquid ammoniumcontaining inorganic izer selected from the group consisting of an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate 35 or um phosphate.
11. The method of claim 2, wherein said fertilizer is a urea-containing fertilizer selected from the group consisting of urea, formaldehyde urea, urea ammonium nitrate (UAN) on , urea r, ized urea, urea based NPK-fertilizers, or urea ammonium sulfate.
12. The nitrification inhibiting mixture of claim 1, substantially as herein described with reference to any one of the examples thereof.
13. The method of claim 2, substantially as herein described with reference to any one of 45 the examples thereof.
NZ731389A 2015-11-13 Benzylpropargylether as nitrification inhibitors NZ731389B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP14193313 2014-11-14
EP14200097 2014-12-23
EP15170534 2015-06-03
PCT/EP2015/076554 WO2016075289A1 (en) 2014-11-14 2015-11-13 Benzylpropargylether as nitrification inhibitors

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NZ731389B2 true NZ731389B2 (en) 2023-11-28

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