WO2017198693A1 - A composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor - Google Patents

A composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor Download PDF

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WO2017198693A1
WO2017198693A1 PCT/EP2017/061807 EP2017061807W WO2017198693A1 WO 2017198693 A1 WO2017198693 A1 WO 2017198693A1 EP 2017061807 W EP2017061807 W EP 2017061807W WO 2017198693 A1 WO2017198693 A1 WO 2017198693A1
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alkyl
alkynyl
formula
halogen
unsubstituted
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PCT/EP2017/061807
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French (fr)
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Karl-Heinrich Schneider
Maik SCHLESINGER
Barbara Nave
Joachim Dickhaut
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment 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
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D9/00—Other inorganic fertilisers
    • C05D9/02—Other inorganic fertilisers containing trace elements
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Definitions

  • a composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor
  • the present invention relates to a composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor; a method for preparing the composition by contacting the
  • Nitrogen is an essential element for plant growth and reproduction. About 25% of the plant available nitrogen in soils (ammonium and nitrate) originate from decomposition processes (mineralization) of organic nitrogen compounds such as humus, plant and animal residues and organic fertilizers. Approximately 5% derive from rainfall. On a global basis, the biggest part (70%), however, is supplied to the plant by inorganic nitrogen fertilizers.
  • the mainly used nitrogen fertilizers comprise ammonium compounds or derivatives thereof, i.e.
  • nitrate may be lost by denitrification which is the microbiological conversion of nitrate and nitrite (NO2 " ) to gaseous forms of nitrogen such as nitrous oxide (N2O) and molecular nitrogen (N2).
  • ammonium (NH 4 + ) compounds are converted by soil microorganisms to nitrates (NO3 " ) in a relatively short time in a process known as nitrification.
  • the nitrification is carried out primarily by two groups of chemolithotrophic bacteria, ammonia-oxidizing bacteria (AOB) of the genus Nitrosomonas and Nitrobacter, which are ubiquitous component of soil bacteria populations.
  • AOB ammonia-oxidizing bacteria
  • Nitrobacter which are ubiquitous component of soil bacteria populations.
  • the enzyme, which is essentially responsible for nitrification is ammonia monooxygenase (AMO), which was also found in ammonia-oxidizing archaea.
  • nitrification process typically leads to nitrogen leakage and environmental pollution. As a result of the various losses, approximately 50% of the applied nitrogen fertilizers are lost during the year following fertilizer addition. As countermeasures the use of nitrification inhibitors, mostly together with fertilizers, was suggested. It is an ongoing challenge to futher improve nitrification inhibitors, their efficacy and their application.
  • Object of the present invention was to overcome the problems of the state of the art. The object was solved by a composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor.
  • the term "nitrification inhibitor" usually refers to a chemical substance which slows down or stops the nitrification process. Nitrification inhibitors accordingly retard the natural
  • nitrification as used herein may be understood as the biological oxidation of ammonia (NH3) or ammonium (NH 4 + ) with oxygen into nitrite (NO2 " ) followed by the oxidation of these nitrites into nitrates (NO3 " ) by microorganisms. Besides nitrate (NO3 " ) nitrous oxide is also produced though nitrification. Nitrification is an important step in the nitrogen cycle in soil. The inhibition of nitrification may thus also reduce N 2 0 losses.
  • nitrification inhibitors are the nitrification inhibitor of formula I (see below), linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro-6- (trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DI DI N), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4-amino-1 ,2,4-triazole hydrochloride (ATC), 1 -amido-2- thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5- ethoxy-3-trichloromethyl-1 ,2,4-thiodiazole
  • R 1 and R 2 are independently of each other selected from the group consisting of H, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl C1-C6- alkoxy, C2-C6-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 R e ;
  • C3-C8-cycloalkyl Cs-Cs-cycloalkenyl, heterocyclyl, aryl, hetaryl, C3-C8-cycloalkyl-Ci-C6- alkyl, C3-C8-cycloalkenyl-Ci-C6-alkyl, heterocyclyl-Ci-C6-alkyl, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents R a ;
  • A is phenyl, wherein said phenyl ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents R A ;
  • R A is selected from the group consisting of CN, halogen, N0 2 , OR b , NR c R d , C(Y)R b ,
  • C(Y)OR b C(Y)NR c R d , S(Y) m R b , S(Y) m OR , Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, wherein the C-atoms may in each case be unsubstituted or may carry 1 , 2 or 3 identical or different substituents R e ;
  • C3-C8-cycloalkyl Cs-Cs-cycloalkenyl, heterocyclyl, aryl, hetaryl, C3-C8-cycloalkyl-Ci-C6- alkyl, C3-C8-cycloalkenyl-Ci-C6-alkyl, heterocyclyl-Ci-C6-alkyl, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents R a ;
  • R a is selected from CN, halogen, NO2, CrC4-alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy; or two substituents R a on adjacent C-atoms may be a bridge selected from CH2CH2CH2CH2,
  • R b is selected from H, Ci-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, phenyl and benzyl;
  • R c and R d are independently of each other selected from the group consisting of H, C1-C4- alkyl, and Ci-C4-haloalkyl; or
  • R c and R d 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 independently of each other selected from halogen;
  • R e is selected from CN, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, and C1-C4- haloalkoxy;
  • Y is O or S
  • n 0, 1 or 2.
  • R a , R b , R c , R d , and R e are defined as follows:
  • R a is selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, or two substituents R a on adjacent C- atoms may be a OCH2CH2O bridge or a 0(CH2)0 bridge;
  • R b is selected from H, Ci-C6-alkyl, phenyl and benzyl;
  • R c and R d are independently of each other selected from the group consisting of H, Ci-C4-alkyl, and Ci-C4-haloalkyl;
  • R e is selected from halogen and Ci-C4-alkyl.
  • R 1 and R 2 are independently of each other selected from the group consisting of H, C2-C6-alkynyl, C2-C6-alkynyloxy, aryl-Ci- C6-alkyl, and hetaryl-Ci-C6-alkyl, wherein preferably at least one of R 1 and R 2 is H.
  • A is phenyl, wherein said phenyl ring is unsubstituted or carries 1 , 2, or 3 identical or different substituents R A .
  • R A is selected from the group consisting of halogen, NO2, NR c R d , Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1 or 2 identical or different substituents R a , wherein R a , R c and R d are as defined above.
  • R 1 is H and R 2 is selected from the group consisting of C2-C6-alkynyl, C2-C6-alkynyloxy, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-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.
  • R 1 is H and R 2 is selected from the group consisting of C2-C6-alkynyl, C2-C6-alkynyloxy, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-alkyl, and is most preferably hetaryl-Ci-C4-alkyl
  • R 2 -a represents a substituent selected from the group consisting of C2-C6-alkynyl, C2- C6-alkynyloxy, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-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.
  • both, R 1 and mpounds correspond to compounds of formula l.b.
  • A is phenyl, wherein said phenyl ring is unsubstituted or carries 1 , 2, or 3 identical or different substituents R A .
  • Such compounds correspond to compounds of formula 1.1 , wherein (R A ) n with n being 0, 1 , 2, or 3 indicates the above substitution possibilities for the compound.
  • n 1 or 2
  • I.1 2 Particular preferred are compounds, wherein n is 1 or 2, i.e. the following compounds 1.1 1 and I.1 2
  • the present invention relates to compounds of formula I, wherein R 1 is H, R 2 is R 2 -a, and A is phenyl, wherein said phenyl ring is unsubstituted or carries 1 , 2, or 3 identical or different substituents R A .
  • Such compounds are referred to compounds of formula 1.1. a, with compounds of formula 1.1 .a and compounds of formula l.1 2 .a being particularly preferred.
  • the present invention relates to compounds of formula I, wherein R 1 is H, R 2 is H, A is phenyl, wherein said phenyl ring is unsubstituted or carries 1 , 2, or 3 identical or different substituents R A .
  • Such compounds are referred to compounds of formula 1.1. b, with compounds of formula 1. . b and compounds of formula l.1 2 .b being particularly preferred.
  • R A is selected from the group consisting of halogen, N0 2 , NR c R d , Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkoxy, Ci-C 6 -alkylthio, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1 or 2 identical or different substituents R a , wherein R a , R c and R d are defined as follows: R a is selected from
  • the present invention relates in one embodiment to compounds of formula I, wherein R 1 and R 2 are independently of each other selected from the group consisting of H, C2-C6- alkynyl, C2-C6-alkynyloxy, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-alkyl, provided at least one of
  • R 1 and R 2 is H, and wherein
  • A is phenyl, wherein said phenyl ring is unsubstituted or carries 1 , 2, or 3 identical or different substituents R A , wherein
  • R A is selected from the group consisting of halogen, NO2, NR c R d , Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1 or 2 identical or different substituents R a , wherein R a , R c and R d are defined as follows:
  • R a is selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, or two substituents R a on adjacent C- atoms may be a OCH2CH2O bridge or a 0(CH2)0 bridge;
  • R c and R d are independently of each other selected from the group consisting of H, Ci-C4-alkyl, and Ci-C4-haloalkyl.
  • the nitrification inhibitor is the nitrification inhibitor of formula (II)
  • A is aryl or hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R A ;
  • R 1 and R 2 are independently of each other selected from H and Ci-C2-alkyl
  • R 3 is H, Ci-C4-haloalkyl, Ci-C4-hydroxyalkyl, ethynylhydroxymethyl, phenylhydroxymethyl, or aryl, wherein the aromatic ring may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R B ; and wherein
  • a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR 1 b , O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R'; and wherein R 1 b is H, C1-C4- alkyl, C 2 -C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl methyl, or OR9; or
  • B is aryl or hetaryl, wherein the aromatic ring of the ary or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R h ; or
  • a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R 1 b , O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from Ri; and wherein R 1 b is H, Ci-C 4 -alkyl, C 2 -C 4 -alkenyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - cycloalkylmethyl, or ORs; or
  • two substituents R A together represent a carbocyclic or heterocyclic ring, which is fused to A and may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R 1 c , O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R'; and wherein R 1 c is H, Ci-C 4 -alkyl, C2-C 4 -alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, C3-C6-heterocyclyl, C3-C6-heterocyclylmethyl or ORs; and wherein
  • Y 1 , Y 2 and Y 3 are independently of each other selected from O, S and N R 1 a , wherein R 1 a is in each case independently H, Ci-C 4 -alkyl, C 2 -C 4 -alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, ORs, SRs or N R m R n ;
  • R a and R b are independently of each other selected from
  • aryl or hetaryl wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R h ; or
  • a 3- to 10-membered, saturated or unsaturated heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R 1 b , O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R'; and wherein R 1 b is H, Ci-C 4 -alkyl, C 2 -C 4 -alkenyl, C3-C6-cycloalkyl, Cs-Ce-cycloalkylmethyl, or ORs;
  • a 3- to 10-membered saturated or unsaturated carbocycle or heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR 1b , O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R'; and wherein R 1b is H, C1-C4- alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl methyl, or OR9;
  • R f is Ci-C4-alkyl, Ci-C4-haloalkyl, NRiR k , OR', SR', aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R h ;
  • R9 is H or Ci-C 4 -alkyl
  • R 1d is H, Ci-C 4 -alkyl, C 2 -C 4 -alkenyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - cycloalkylmethyl, or ORs;
  • aryl, aryl-Ci-C2-alkyl, hetaryl, or hetaryl-Ci-C2-alkyl wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from halogen, CN, C1-C4- alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, C 2 -C 4 -alkynyloxy, OR9, and SRs; or
  • R j and R k are independently selected from H, OR9, SRs,
  • R' is H, Ci-C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, Ci-C 4 -haloalkyl,
  • R m and R n are independently selected from H and Ci-C 4 -alkyl.
  • A is phenyl or a 5- or 6-membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R A .
  • A is phenyl or a 6- membered hetaryl, in particular phenyl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R A .
  • A is phenyl.
  • Such compounds are typically solid at room temperature and are typically non-volatile and stable against hydrolysis.
  • R 1 and R 2 both represent hydrogen.
  • R 3 is hydrogen, Ci-C 4 -haloalkyl or ethinylhydroxymethyl, and preferably R 3 is hydrogen.
  • R A if present, is
  • Ci-C 4 -alkylene or C 2 -C 4 -alkenylene chain may in each case be unsubstituted or may be partially or fully substituted by CN or halogen;
  • a 3- to 14-membered saturated or unsaturated heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR 1b , O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R'; and wherein R 1b is H, Ci-C 4 -alkyl, C 2 -C 4 -alkenyl, C3-C6-cycloalkyl, C3- C6-cycloalkylmethyl, or ORs,
  • Y 1 , Y 2 and Y 3 are independently of each other selected from O, S and NR 1a , wherein R 1a is in each case independently H, CrC 4 -alkyl, OH, or NH 2 .
  • R a and R b are independently of each other selected from
  • R c is (i) H , Ci-C 4 -alkyl
  • R f is Ci-C 4 -alkyl
  • R h is halogen or Ci-C 4 -alkoxy
  • R' is (i) Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C 2 -C 4 -haloalkenyl; or
  • nitrification inhibitor of formula (II) are described in WO 2015/158853, which is incorporated herein by reference. d form the nitrification inhibitor is the nitrification inhibitor of formula (III)
  • R 1 and R 2 are independently selected from H and Ci-C2-alkyl
  • Ci-C4-haloalkyl or
  • R a is H, d-Cs-alkyl, Ci-C 8 -haloalkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl;
  • Cs-Cio-hetaryl or C6-Cio-aryl wherein the Cs-Cio-hetaryl or C6-Cio-aryl moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, OH, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, C2-C4- alkenyl, C2-C4-alkynyl, Cs-Ce-hetaryl and C6-aryl, wherein said Cs-Ce-hetaryl and C6-aryl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 substituents selected from halogen, CN, OH, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, C2-C4-alkenyl, and C2-C
  • R b is H, Ci-C 4 -alkyl, C 3 -C 8 -cycloalkyl, C 2 -C 4 -alkenyl, C 2 -C 8 -alkynyl, or C 6 -Cio-aryl;
  • R c and R d are independently of each other selected from the group consisting of H, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C 8 -cycloalkyl, C6-Cio-aryl, and Cs-Cio-hetaryl; or R c and R d together with the N-atom to which they are bonded form a 5- to 6-membered, saturated or unsaturated heterocycle, which may carry a further heteroatom being selected from O, S, and N as a ring member atom, of which S and/or N may optionally be oxidized, and wherein the heterocyclic ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 substituents, which are independently selected from halogen, CN, OH, NO2, Ci- C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, and Ci-C4-haloalkoxy;
  • V, W, X, Y, and Z are independently selected from N, CH and CRy,
  • R Y is selected from the group consisting of halogen, CN, NO2, OH, SH, NH2, Ci- C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-dialkylamino, and Ci-C4-haloalkyl;
  • n 0, 1 , or 2;
  • n 0, 1 , or 2;
  • p 0,1 , or 2.
  • p is 1 or 2. Accordingly, the following compounds I.p1 or compounds I.p2 are preferred according the invention.
  • R 1 and R 2 are H. In one preferred embodiment of said use, in said compound of formula I , R 1 and R 2 are H and p is 1 or 2.
  • Ci-C2-alkyl wherein the C6-Cio-aryl, Cs-Cio-hetaryl, Cs-Cio-carbocyclyl, and C5-C10- heterocyclyl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN , Ci-C4-alkyl, Ci-C4-alkoxy, and C1-C4- haloalkyl;
  • R a is H , Ci-C 4 -alkyl, or Ci-C 4 -haloalkyl
  • R c and R d are independently of each other selected from the group consisting of H , Ci-C4-alkyl, and Ci-C4-haloalkyl;
  • V, W, X, Y, and Z are independently selected from N , CH and CRy,
  • R Y is selected from the group consisting of halogen, CN , Ci-C4-alkyl, C1-C4- alkoxy, Ci-C4-alkylthio, Ci-C4-dialkylamino, and Ci-C4-haloalkyl.
  • R a is H , or Ci-C 4 -alkyl
  • R c and R d are independently of each other selected from the group consisting of H and Ci-C 4 - alkyl;
  • V, W, Y, and Z each represent CH
  • X represents CH or CRy
  • R Y is selected from the group consisting of halogen, CN , Ci-C 4 -alkyl, Ci-C 4 - alkoxy, Ci-C 4 -alkylthio, and Ci-C 4 -dialkylamino.
  • R a is H , or Ci-C 2 -alkyl
  • R c and R d are independently of each other selected from the group consisting of H and C1-C2- alkyl;
  • V, W, Y, and Z each represent CH
  • X represents CH or CRy
  • R Y is selected from the group consisting of halogen, CN , Ci-C2-alkyl, and C1-C2- alkoxy.
  • R 1 and R 2 are H ;
  • R a is H, or Ci-C 2 -alkyl
  • R c and R d are independently of each other selected from the group consisting of H and C1-C2- alkyl;
  • V, W, Y, and Z each represent CH, and X represents CH or CR y ,
  • R Y is selected from the group consisting of halogen, CN, Ci-C2-alkyl, and C1-C2- alkoxy;
  • n 0, 1 , or 2;
  • p 1 or 2.
  • p is 1 , R 1 and R 2 are H, and R 3 is option (i) as defined above. In one preferred embodiment, p is 1 , R 1 and R 2 are H , and R 3 is option (ii) as defined above. In one preferred embodiment, p is 1 , R 1 and R 2 are H , and R 3 is option (iii) as defined above. In one preferred embodiment, p is 2, R 1 and R 2 are H , and R 3 is option (i) as defined above. In one preferred embodiment, p is 2, R 1 and R 2 are H, and R 3 is option (ii) as defined above. In one preferred embodiment, p is 2, R 1 and R 2 are H, and R 3 is option (iii) as defined above. In one preferred embodiment, p is 2, R 1 and R 2 are H, and R 3 is option (iii) as defined above. In one preferred embodiment, p is 2, R 1 and R 2 are H, and R 3 is option (iii) as defined above.
  • nitrification inhibitor is the nitrification inhibitor of formula (IV)
  • R a is H , d-Cs-alkyl, d-d-alkenyl, d-d-alkynyl or d-Cio-aryl;
  • R b is H , Ci-d-alkyl, d-d-cycloalkyl, C 2 -d-alkenyl, C 2 -d-alkynyl, or d-Cio-aryl;
  • R c and R d are independently of each other selected from the group consisting of H , d-d-alkyl, and d-d-haloalkyl;
  • R 2 , R 3 and R 4 is C 2 -d-alkynyl.
  • said nitrification inhibitor is a compound of formula (IV)
  • R a is H, Ci-d-alkyl, C 2 -d-alkenyl, C 2 -d-alkynyl or d-Cio-aryl;
  • R b is H, Ci-d-alkyl, d-d-cycloalkyl, d-d-alkenyl, C 2 -d-alkynyl, or C 6 -Ci 0 -aryl; and wherein
  • R 2 , R 3 and R 4 are independently of each other selected from H, halogen, d-d-alkyl, d-d- cycloalkyl, C 2 -d-alkenyl, and C 2 -d-alkynyl;
  • R 2 , R 3 and R 4 is d-d-alkynyl.
  • R 1 is Ci-d- alkyl, preferably d-C 2 -alkyl. These compounds correspond to compounds of formula 1.1a, wherein R 1 -1 a represents d-d-alkyl, preferably d-C 2 -alkyl, e.g. CH3.
  • R 2 , R 3 and R 4 are independently of each other selected from H, Ci-C4-alkyl, and C2-C4-alkynyl, and preferably from H, Ci-C 2 -alkyl, and C 2 -C4-alkynyl, with the proviso that at least one of R 2 , R 3 , and R 4 is C 2 - C4-alkynyl.
  • R 2 -A, R 3 -A, and R 4 -A represent substituents selected from H, Ci-C4-alkyl, and C2-C4-alkynyl, and preferably from H, Ci-C2-alkyl, and C2-C4-alkynyl, with the proviso that at least one of R 2 -A, R 3 -A, and R 4 -A
  • R 1 is R 1 -1 a, and R 2 , R 3 and
  • R 4 correspond to R 2 -A, R 3 -A, and R 4 -A, with the proviso that at least one of R 2 -A, R 3 -A, and R 4 - A compounds correspond to compounds of formula l . l a.A.
  • R 1 -1 a represents Ci-
  • C 4 -alkyl, R 2 -alkynyl, R 3 -alkynyl, and R 4 -alkynyl represent a C2-C4-alkynyl group, and R 2 -A, R 3 -A, and R 4 -A, respectively, if present, represent a substituent selected from H, Ci-C 4 -alkyl, and C2-
  • R 1 is R 1 -1 b
  • R 2 , R 3 and R 4 correspond to R 2 -A, R 3 -A, and R 4 -A, with the proviso that at least one of R 2 -A, R 3 -A, and R 4 -A is C2-C4-alkynyl.
  • R 1 -1 b represents
  • R a is H, Ci-C 8 -alkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, or C 6 -Cio-aryl, and
  • R b is H, Ci-C4-alkyl, Cs-Cs-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C6-Cio-aryl; and wherein preferably R a is Ci-Cs-alkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, or C6-Cio-aryl, and R b is H, C1-C4- alkyl, Cs-Cs-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C6-Cio-aryl; and wherein particularly preferably R a is Ci-Cs-alkyl, or C6-Cio-aryl, and R b is H, Ci-C4-alkyl, Cs-Cs-cycloalkyl, or C6-C10- aryl. Furthermore, R 2 -alkynyl, R 3
  • R 2 -A, R 3 -A, and R 4 -A represent a substituent selected from H, C1-C4- alkyl
  • R 2 , R 3 and R 4 are C2-C4-alkynyl, preferabi C2-C3-alkynyl.
  • R 2 -A * , R 3 -A * and R 4 -A * represent substituents selected from H, Ci-Cs-alkyl, Cs-Cs-cycloalkyl, C2-Cs-alkenyl, C2-Cs-alkynyl and halogen, preferably from
  • Ci-C4-alkyl, and C 2 -C4-alkynyl and particularly preferably from H, Ci-C 2 -alkyl, and C 2 -C4- alkynyl, with the proviso that at least two of R 2 -A * , R 3 -A * , and R 4 -A * are C 2 -C4-alkyl, preferably
  • C2-C3-alkynyl e.g. ethynyl.
  • R 2 - alkynyl, R 3 -alkynyl, and R 4 -alkynyl represent a C2-C4-alkynyl group, preferably a C2-C3-alkynyl group, and R 2 -A * , R 3 -A * , and R 4 -A * , if present, represent C2-C4-alkynyl, preferably C2-C3- alkynyl, e.g. ethynyl.
  • R 1 is R 1 -1 a
  • R 2 , R 3 and R 4 correspond to R 2 -A*, R 3 -A*, and R 4 -A*, with the proviso that at least two of R 2 -A*, R 3 -A*, and
  • R 4 -A* are C2-C4-alkynyl, preferably C2-C3-alkynyl, e.g. ethynyl. These compounds correspond to compounds of formula l. l a.A*.
  • R 1 -1 a represents Ci-C4-alkyl
  • R 2 -alkynyl, R 3 -alkynyl, and R 4 -alkynyl represent a C2-C4- alkynyl group, preferably a C2-C3-alkynyl group, e.g. an ethynyl group
  • A* respectively, if present, represent a substituent selected from H, Ci-C4-alkyl, and C2-C4- alkynyl, and preferably from H, Ci-C2-alkyl, and C2-C4-alkynyl.
  • R 1 is R 1 -1 b
  • R 2 , R 3 and R 4 correspond to R 2 -A*, R 3 -A*, and R 4 -A*, with the proviso that at least two of R 2 -A*, R 3 -A*, and R 4 -A* are C2-C4-alkynyl, preferably C2-C3-alkynyl, e.g. ethynyl.
  • R 2 -alkynyl, R 3 -alkynyl, and R 4 -alkynyl represent a C2-C4- alkynyl group, preferably a C2-C3-alkynyl group, e.g. an ethynyl group, and R 2 -A*, R 3 -A*, and R 4 - A*, respectively, if present, represent a substituent selected from H, Ci-C4-alkyl, and C2-C4- alkynyl, and preferably from H, Ci-C2-alkyl, and C2-C4-alkynyl.
  • R a is H , Ci-Cs-alkyl, or C 6 -Cio-aryl
  • R b is H , Ci-C 4 -alkyl, C 3 -C 8 -cycloalkyl, or C 6 -Cio-aryl;
  • R 2 , R 3 and R 4 are independently of each other selected from H , Ci-Cs-alkyl, C3-C8 cycloalkyl, C2-Cs-alkynyl and halogen; with the proviso that at least one of R 2 , R 3 and R 4 is C2- Cs-alkynyl.
  • at least two of R 2 , R 3 and R 4 are C 2 -C 8 -alkynyl. More preferably, at least two of R 2 , R 3 and R 4 are C 2 -C 4 - alkynyl or C2-C3-alkynyl, in particular ethynyl, and the remaining substituent R 2 , R 3 , or R 4 is Ci- C 4 -alkyl or H .
  • R 1 is Ci-C 4 -alkyl or
  • the nitrification inhibitor is a compound of formula (IV)
  • R a is Ci-Cs-alkyl, or C 6 -Cio-aryl
  • R b is H , CrC 4 -alkyl, C 3 -C 8 -cycloalkyl, or C 6 -Ci 0 -aryl;
  • R 2 , R 3 and R 4 are independently of each other selected from H , Ci-Cs-alkyl, C3-C8- cycloalkyl, C2-Cs-alkynyl and halogen; with the proviso that at least one of R 2 , R 3 and R 4 is C2- Cs-alkynyl.
  • at least one of R 2 , R 3 and R 4 is C 2 -C 8 -alkynyl.
  • R 2 , R 3 and R 4 is C2-C4-alkynyl or C2-C3-alkynyl, in particular ethynyl, and the remaining substituents R 2 , R 3 , or R 4 are Ci-C4-alkyl or H.
  • at least two of R 2 , R 3 and R 4 are C2-Cs-alkynyl. More preferably, at least two of R 2 , R 3 and R 4 are C2-C4-alkynyl or C2- C3-alkynyl, in particular ethynyl, and the remaining substituents R 2 , R 3 , or R 4 are Ci-C4-alkyl or H.
  • the nitrification inhibitor is a compound of formula
  • R is CH 3 ;
  • R 2 , R 3 and R 4 are independently of each other selected from H, CH3 and ethynyl;
  • R 2 , R 3 and R 4 are ethynyl.
  • the nitrification inhibitor is the nitrification inhibitor of formula (V) or a stereoisomer, salt, tautomer or N-oxide thereof as a nitrification inhibitor,
  • R a is H, d-Cs-alkyl, C C 8 -haloalkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl;
  • Cs-Cio-hetaryl or C6-Cio-aryl wherein the Cs-Cio-hetaryl or C6-Cio-aryl moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, OH, Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkyl, C2-C 4 - alkenyl, C2-C 4 -alkynyl, Cs-C6-hetaryl and C6-aryl, wherein said Cs-C6-hetaryl and C6-aryl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 substituents selected from halogen, CN, OH, Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkyl, C2-C 4 -
  • R b is H, Ci-C 4 -alkyl, Cs-Cs-cycloalkyl, C2-C 4 -alkenyl, C2-Cs-alkynyl, or C6-Cio-aryl; and R c and R d are independently of each other selected from the group consisting of H, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Cs-cycloalkyl, C6-Cio-aryl, and Cs-Cio-hetaryl; or
  • R c and R d together with the N-atom to which they are bonded form a 5- to 6-membered
  • heterocyclic ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 substituents, which are independently selected from halogen, CN , OH , NO2, Ci- C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, and Ci-C4-haloalkoxy;
  • n O, 1 , or 2.
  • R 1 is a terminal C3-C4-alkynyl group, preferably propargyl.
  • R 1 -1 a represents a terminal C3-C4-alkynyl group, preferably propargyl.
  • the compound of formula (V) is a compound of formula 1.1 a, wherein R 1 -1 a is propargyl.
  • R 1 is a terminal C3-C4-allenyl group, preferably C3-allenyl.
  • R 1 -1 b represents a terminal C3-C4-allenyl group, preferably C3-allenyl.
  • the compound of formula (V) is a compound of compound of formula 1.1 b, wherein R 1 -1 b is Cs-allenyl.
  • R 2 , R 3 and R 4 are
  • R 3 -C represents a R 3 -substituent as defined above
  • R 2 -C and R 4 -C together represent a R 2 -R 4 -bridge as defined above.
  • R 1 is R 1 -1 a
  • R 2 , R 3 and R 4 correspond to R 2 -A, R 3 -A, and R 4 -A.
  • These compounds correspond to compounds of formula 1.1 a.A.
  • R 1 -1 a propargyl
  • Ci-C 8 -alkyl wherein the C-atoms may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN , and OR a ; C6-Cio-aryl, and Cs-C-io-hetaryl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN , OR a , Ci-C4-alkyl, Ci-C4-haloalkyl, and C2-C4-alkynyl; and particularly preferably
  • R 1 is R 1 -1 b
  • R 2 , R 3 and R 4 correspond to R 2 -A, R 3 -A, and R 4 -A.
  • These compounds correspond to compounds of formula 1.1 b.A.
  • unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN , OR a , CrC 4 -alkyl, CrC 4 -haloalkyl, and C2-C 4 -alkynyl; and particularly preferably selected from H, halogen, OR a , C( 0)OR a , and Ci-C 4 -alkyl, wherein R a is H, Ci-C 8 -alkyl, or Ci- Cs-haloalkyl.
  • R 1 is R 1 -1 a
  • R 2 , R 3 and R 4 correspond to R 2 -B, R 3 -B, and R 4 -B.
  • These compounds correspond to compounds of formula 1.1 a. B.
  • R 1 is R 1 -1 b
  • R 2 , R 3 and R 4 correspond to R 2 -B, R 3 -B, and R 4 -B. These compounds correspond to compounds of formula 1.1 b.B.
  • R 1 is R 1 -1 a
  • R 2 , R 3 and R 4 correspond to R 2 -C, R 3 -C, and R 4 -C.
  • These compounds correspond to compounds of formula l.l a.C.
  • R 1 -1 a propargyl
  • R 1 is R 1 -1 b, and R 2 ,
  • R 3 and R 4 correspond to R 2 -C, R 3 -C, and R 4 -C. These compounds correspond to compounds of formula 1.1 b.C.
  • said compound of formula (V) is a compound of formula l.l a.A as defined above or a compounds of formula 1.1 b. A as defined above.
  • nitrification inhibitor of formula (V) are described in WO 2016/124769, which is incorporated herein by reference.
  • the compounds of formula (I), (II), (III), (IV) or (V) may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention relates to amorphous and crystalline compounds of formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formula (I), (II), (III), (IV) or (V) are preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (I), (II), (III), (IV) or (V) has a basic functionality.
  • Agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the mode of action of the compounds of formula (I), (II), (III), (IV) or (V) .
  • 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 Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • the nitrification inhibitor has typically a molecular weight of up to 1000 g/mol, preferably up to 500 g/mol, and in particular up to 300 g/mol.
  • the nitrification inhibitor has typically a melting point below 50 °C, preferably below 35 °C, and in particular below 20 °C. Usually, the nitrification inhibitor is liquid at room temperature.
  • the nitrification inhibitor has typically a vapor pressure of at least 0.01 Pa at 20 °C, more preferably of at least 0.05 Pa at 20 °C, and in particular at least 0.1 Pa at 20 °C.
  • the nitrification inhibitor has a molecular weight up up to 1000 g/mol and a melting point below 50 °C, preferably a molecular weight up up to 500 g/mol and a melting point below 35 °C.
  • the composition may further comprise additional ingredients, for example at least one pesticidal compound, at least one additional nitrification inhibitors, at least one urease inhibitor, at least one plant growth regulators, or at least one fertilizer.
  • 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 and/or at least one biopesticide and/or at least one biostimulant.
  • the additional ingredient comprises a fertilizer.
  • the composition may, in addition to the above indicated ingredients, in particular in addition to the nitrification inhibitor of the compound of formula I, further comprise one or more additional nitrification inhibitors.
  • the composition may, in addition to the above indicated ingredients, in particular in addition to the nitrification inhibitor of the compound of formula I, further comprise one or more urease inhibitors.
  • urease inhibitors include N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain), N-(n-propyl) thiophosphoric acid triamide (NPPT), 2-nitrophenyl phosphoric triamide (2-NPT), further NXPTs known to the skilled person, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate, and LIMUS, i.e. a composition comprising about 16.9 wt.-% NBPT and about 5.6 wt.-% NPPT and about 77.5 wt.-% of other ingredients including solvents and adjuvants.
  • the composition may, in addition to one, more or all of the above indicated ingredients, in particular in addition to the nitrification inhibitor of the compound of formula I, further comprise one or more plant growth regulators.
  • plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releasers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators, and further unclassified plant growth regulators.
  • composition may, in addition to the above indicated ingredients, in particular in addition to the nitrification inhibitor of the compound of formula I, further comprise at least one fertilizer.
  • fertilizers is to be understood as chemical compounds applied to promote plant and fruit growth. Fertilizers are typically applied either through the soil (for uptake by plant roots), through soil substituents (also for uptake by plant roots), or by foliar feeding (for uptake through leaves). The term also includes mixtures of one or more different types of fertilizers as mentioned below.
  • fertilizers can be subdivided into several categories including: a) organic fertilizers (composed of decayed plant/animal matter), b) inorganic fertilizers (composed of chemicals and minerals) and c) urea-containing fertilizers.
  • Organic fertilizers include manure, e.g. liquid manure, semi-liquid manure, biogas manure, stable manure or straw manure, slurry, worm castings, peat, seaweed, compost, sewage, and guano. Green manure crops are also regularly grown to add nutrients (especially nitrogen) to the soil.
  • Manufactured organic fertilizers include compost, blood meal, bone meal and seaweed extracts. Further examples are enzyme digested proteins, fish meal, and feather meal. The decomposing crop residue from prior years is another source of fertility.
  • naturally occurring minerals such as mine rock phosphate, sulfate of potash and limestone are also considered inorganic fertilizers. Inorganic fertilizers are usually manufactured through chemical processes (such as the Haber process), also using naturally occurring deposits, while chemically altering them (e.g.
  • Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mine rock phosphate, limestone, and raw potash fertilizers.
  • the inorganic fertilizer may, in a specific embodiment, be a NPK fertilizer.
  • NPK fertilizers are inorganic fertilizers formulated in appropriate concentrations and combinations comprising the three main nutrients nitrogen (N), phosphorus (P) and potassium (K) as well as typically S, Mg, Ca and trace elements.
  • Urea-containing fertilizer may, in specific embodiments, be urea, formaldehyde urea, urea ammonium nitrate (UAN) solution, urea sulfur, stabilized urea, 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.
  • the fertilizer comprises an ammonium-containing inorganic fertilizer such as an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; an organic fertilizer such as liquid manure, semi- liquid manure, biogas manure, stable manure and straw manure, worm castings, compost, seaweed or guano; or an urea-containing fertilizer such as urea, formaldehyde urea, urea mmonium nitrate (UAN) solution, urea sulphur, stabilized urea, urea based NPK-fertilizers, or urea ammonium sulfate.
  • the fertilizer is an ammonium- containing fertilizer.
  • Fertilizers may be provided in any suitable form, e.g. as solid coated or uncoated granules, in liquid or semi-liquid form, as sprayable fertilizer, or via fertigation etc.
  • Coated fertilizers may be provided with a wide range of materials. Coatings may, for example, be applied to granular or prilled nitrogen (N) fertilizer or to multi-nutrient fertilizers. Typically, urea is used as base material for most coated fertilizers. Alternatively, ammonium or NPK fertilizers are used is base material for coated fertilizers. The present invention, however, also envisages the use of other base materials for coated fertilizers, any one of the fertilizer materials defined herein. In certain embodiments, elemental sulfur may be used as fertilizer coating. The coating may be performed by spraying molten S over solid urea granules, followed by an application of sealant wax to close fissures in the coating.
  • the S layer may be covered with a layer of organic polymers, preferably a thin layer of organic polymers.
  • coated fertilizers may be provided by reacting resin-based polymers on the surface of the fertilizer granule.
  • a further example of providing coated fertilizers includes the use of low permeability polyethylene polymers in combination with high
  • composition and/or thickness of the fertilizer coating may be adjusted to control, for example, the nutrient release rate for specific
  • the duration of nutrient release from specific fertilizers may vary, e.g. from several weeks to many months.
  • the presence of nitrification inhibitors in a mixture with coated fertilizers may accordingly be adapted. It is, in particular, envisaged that the nutrient release involves or is accompanied by the release of an nitrification inhibitor according to the present invention.
  • Coated fertilizers may be provided as controlled release fertilizers (CRFs).
  • these controlled release fertilizers are fully coated urea or N-P-K fertilizers, which are homogeneous and which typically show a pre-defined longevity of release.
  • the CRFs may be provided as blended controlled release fertilizer products which may contain coated, uncoated and/or slow release components.
  • these coated fertilizers may additionally comprise micronutrients.
  • these fertilizers may show a pre-defined longevity, e.g. in case of N-P-K fertilizers.
  • CRFs include patterned release fertilizers. These fertilizers typically show a pre-defined release patterns (e.g. hi/standard/lo) and a pre-defined longevity.
  • fully coated N-P-K, Mg and micronutrients may be delivered in a patterned release manner.
  • double coating approaches or coated fertilizers based on a programmed release may be delivered in a patterned release manner.
  • the fertilizer mixture may be provided as, or may comprise or contain a slow release fertilizer.
  • the fertilizer may, for example, be released over any suitable period of time, e.g. over a period of 1 to 5 months, preferably up to 3 months.
  • Typical examples of ingredients of slow release fertilizers are IBDU
  • isobutylidenediurea e.g. containing about 31-32 % nitrogen, of which 90% is water insoluble; or UF, i.e. an urea-formaldehyde product which contains about 38 % nitrogen of which about 70 % may be provided as water insoluble nitrogen; or CDU (crotonylidene diurea) containing about 32 % nitrogen; or MU (methylene urea) containing about 38 to 40% nitrogen, of which 25-60 % is typically cold water insoluble nitrogen; or MDU (methylene diurea) containing about 40% nitrogen, of which less than 25 % is cold water insoluble nitrogen; or MO (methylol urea) containing about 30% nitrogen, which may typically be used in solutions; or DMTU
  • TMTU tri methylene tetraurea
  • TMPU tri methylene pentaurea
  • UT urea triazone solution
  • fertigation refers to the application of fertilizers, optionally soil amendments, and optionally other water-soluble products together with water through an irrigation system to a plant or to the locus where a plant is growing or is intended to grow, or to a soil substituent as defined herein below.
  • liquid fertilizers or dissolved fertilizers may be provided via fertigation directly to a plant or a locus where a plant is growing or is intended to grow.
  • nitrification inhibitors according to the present invention, or in combination with additional nitrification inhibitors may be provided via fertigation to plants or to a locus where a plant is growing or is intended to grow.
  • Fertilizers and nitrification inhibitors according to the present invention may be provided together, e.g. dissolved in the same charge or load of material (typically water) to be irrigated.
  • fertilizers and nitrification inhibitors may be provided at different points in time.
  • the fertilizer may be fertigated first, followed by the nitrification inhibitor, or preferably, the nitrification inhibitor may be fertigated first, followed by the fertilizer.
  • the time intervals for these activities follow the herein above outlined time intervals for the application of fertilizers and nitrification inhibitors.
  • the present invention further relates to a method for reducing nitrification comprising treating a plant and/or the locus where the plant is growing or is intended to grow with the composition as defined herein.
  • plant is to be understood as a plant of economic importance and/or men-grown plant. In certain embodiments, the term may also be understood as plants which have no or no significant economic importance.
  • the plant is preferably selected from agricultural, silvicultural and horticultural (including ornamental) plants.
  • the term also relates to genetically modified plants.
  • plant as used herein further includes all parts of a plant such as germinating seeds, emerging seedlings, plant propagules, herbaceous vegetation as well as established woody plants including all belowground portions (such as the roots) and aboveground portions.
  • the plant is growing on soil.
  • the plant may also grow differently, e.g. in synthetic laboratory environments or on soil substituents, or be supplemented with nutrients, water etc. by artificial or technical means.
  • the invention envisages a treatment of the zone or area where the nutrients, water etc. are provided to the plant. Also envisaged is that the plant grows in green houses or similar indoor facilities.
  • locus is to be understood as any type of environment, soil, soil substituent, area or material where the plant is growing or intended to grow.
  • the locus relates to soil or soil substituent on which a plant is growing.
  • soil substituent refers to a substrate which is able to allow the growth of a plant and does not comprise usual soil ingredients. This substrate is typically an anorganic substrate which may have the function of an inert medium. It may, in certain embodiments, also comprise organic elements or portions. Soil substituents may, for example, be used in hydroculture or hydroponic approaches, i.e. wherein plants are grown in soilless medium and/or aquatic based environments.
  • soil substituents which may be used in the context of the present invention, are perlite, gravel, biochar, mineral wool, coconut husk, phyllosilicates, i.e. sheet silicate minerals, typically formed by parallel sheets of silicate tetrahedra with S12O5 or a 2:5 ratio, or clay aggregates, in particular expanded clay aggregates with a diameter of about 10 to 40 mm. Particularly preferred is the employment of vermiculite, i.e. a phyllosilicate with 2 tetrahedral sheets for every one octahedral sheet present.
  • the use of soil substituents may, in specific embodiments, be combined with fertigation or irrigation as defined herein.
  • the plant to be treated according to the method of the invention is an agricultural plant.
  • Agricultural plants are plants of which a part (e.g. seeds) or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibres (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds.
  • Preferred agricultural plants are for example cereals, e.g. wheat, rye, barley, triticale, oats, corn, sorghum or rice, beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g.
  • “horticultural plants” are to be understood as plants which are commonly used in horticulture, e.g. the cultivation of ornamentals, vegetables and/or fruits.
  • ornamentals are turf, geranium, pelargonia, petunia, begonia and fuchsia.
  • vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas and lettuce and more preferably from tomatoes, onions, peas and lettuce.
  • fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots and blueberries.
  • the plant to be treated according to the method of the invention is an ornamental plants.
  • “Ornamental plants” are plants which are commonly used in gardening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia.
  • the plant to be treated according to the method of the invention is a silvicultural plants.
  • the term "silvicultural plant” is to be understood as trees, more specifically trees used in reforestation or industrial plantations.
  • Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening purposes.
  • silvicultural plants are conifers, like pines, in particular Pinus spec, fir and spruce, eucalyptus, tropical trees like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec, poplar (cottonwood), in particular Populus spec, beech, in particular Fagus spec, birch, oil palm, and oak.
  • genetically modified plants is to be understood as plants, which genetic material has been modified by the use of recombinant DNA techniques in a way that under natural circumstances it cannot readily be obtained by cross breeding, mutations or natural
  • genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • the treatment may be carried out during all suitable growth stages of a plant as defined herein.
  • the treatment may be carried out during the BBCH principle growth stages.
  • the term "BBCH principal growth stage” refers to the extended BBCH- scale which is a system for a uniform coding of phenologically similar growth stages of all mono- and dicotyledonous plant species in which the entire developmental cycle of the plants is subdivided into clearly recognizable and distinguishable longer-lasting developmental phases.
  • the invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing with at least one nitrification inhibitor as defined herein above, e.g.
  • a nitrification inhibitor being a compound of formula I, or a derivative thereof at a growth stage (GS) between GS 00 and GS 99 BBCH of the plant, or between GS 00 to GS 33 BBCH of the plant, or between GS 00 and GS 55 BBCH, or between GS 00 and GS 47 BBCH, or between 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 of the plant.
  • GS growth stage
  • the invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing with at least one nitrification inhibitor as defined herein above, e.g. 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 envisaged is the application of more than one fertilizer, e.g. 2, 3, 4, 5, 6, 7, 8, 9, 10 fertilizers, or of different fertilizer classes or categories.
  • At least one nitrification inhibitor as defined herein above e.g. a nitrification inhibitor being a compound of formula I, or a 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, or between GS 00 and GS 55, or between GS 00 and GS 65 BBCH.
  • the application of said nitrification inhibitor and of said fertilizer as defined herein above is carried out simultaneously or with a time lag.
  • time lag 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 substituents and/or the locus where the plant is growing or is intended to grow.
  • Such time lag may be any suitable period of time which still allows to provide a nitrification inhibiting effect in the context of fertilizer usage.
  • 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, 1 1 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 1 1 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods.
  • the time lag is an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.
  • the time lag preferably refers to situations in which the 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, 1 1 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 1 1 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods before the application of a fertilizer as defined herein above.
  • 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, e.g. with a nitrification inhibitor being a compound of formula I, or a derivative thereof.
  • 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, e.g. 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 time interval between a first application and second or subsequent application of a nitrification 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
  • the time interval may range from a few seconds up to 3 days or from 1 second up to 24 hours.
  • the application rates of nitrification inhibitors are between 0,01 g and 5 kg of active ingredient per hectare, preferably between 1 g and 1 kg of active ingredient per hectare, especially preferred between 50 g and 300 g of active ingredient per hectare depending on different parameters such as the specific active ingredient applied and the plant species treated.
  • amounts of from 0.001 g to 20 g per kg of seed, preferably from 0.01 g to 10 g per kg of seed, more preferably from 0.05 to 2 g per kg of seed of nitrification inhibitors may be generally required.
  • the application rates of fertilizers may be between 10 kg and 1000 kg per hectare, preferably between 50 kg and 700 kg per hectare, in certain cases between 50 kg and 400 kg per hectare.
  • the nitrification inhibitor compounds according to the invention, their N-oxides and/or salts etc. may be converted into customary types of compositions, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g.
  • CS, ZC pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF).
  • WP wettable powders or dusts
  • pressings e.g. BR, TB, DT
  • granules e.g. WG, SG, GR, FG, GG, MG
  • gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF).
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin,
  • Suitable solid carriers or fillers are mineral earths, e.g.
  • silicates silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch;
  • fertilizers e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas
  • products of vegetable origin e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants e.g. in red, blue, or green
  • Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers. Examples for composition types are:
  • Water-soluble concentrates (SL, LS) 10 parts by weight of a nitrification inhibitor such as a compound of formula I according to the invention are dissolved in 90 parts by weight of water or in a water-soluble solvent.
  • 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.
  • DC Dispersible concentrates
  • compound 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.
  • Emulsifiable concentrates 15 parts by weight of a nitrification inhibitor such as a compound of formula I according to the invention are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion.
  • the composition has an active substance content of 15% by weight.
  • Emulsions 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 of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • the composition has an active substance content of 25% by weight.
  • Suspensions SC, 00, FS
  • 20 parts by weight of a nitrification inhibitor such as a compound of formula I according to the invention are comminuted with addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active substance suspension.
  • Dilution with water gives a stable suspension of the active substance.
  • the active substance content in the composition is 20% by weight.
  • Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of a nitrification inhibitor such as a compound of formula I according to the invention are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as water-dispersible or water-soluble granules by means of technical appliances (e.g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • the composition has an active substance content of 50% by weight.
  • Water-dispersible powders and water-soluble powders 75 parts by weight of a nitrification inhibitor such as a compound of formula 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.
  • composition types to be applied undiluted ix Oustable powders (OP, OS) 5 parts by weight of a nitrification inhibitor such as a compound 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.
  • Granules GR, FG, GG, MG 0.5 parts by weight of a nitrification inhibitor such as a
  • compound of formula I according to the invention is ground finely and associated with 99.5 parts by weight of carriers.
  • Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5-2% by weight.
  • ULV solutions 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 10% by weight.
  • compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of nitrification inhibitor.
  • the nitrification inhibitor are employed in a purity offrom 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • the compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • the present invention relates to a method for treating seed or plant propagation material.
  • seed treatment refers to or involves steps towards the control of biotic stresses on or in seed and the improvement of shooting and development of plants from seeds. Seed treatment methods for applying or treating inventive mixtures and compositions thereof, e.g.
  • compositions comprising, besides a nitrification inhibitor according to the present invention, e.g.
  • compositions as defined herein above a fungicide and an insecticide, or a fungicide and a nematicide, or a fungicide and a biopesticide and/or biostimulant, or an instecticide and a nematicide, or an insecticide and a biopesticide and/or biostimulant, or a nematicide and a biopesticide and/or biostimulant, or a combination of a fungicide, insecticide and nematicide, or a combination of a fungicide, insecticide and biopesticide and/or biostimulant, or a combination of an insecticide, nematicide, and biopesticide etc.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g.
  • potatoes which can be used for the multiplication of the plant.
  • This includes seeds, grains, roots, fruits, tubers, bulbs, rhizomes, cuttings, spores, offshoots, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil, meristem tissues, single and multiple plant cells and any other plant tissue from which a complete plant can be obtained.
  • the compositon according to the present invention is applied or treated on to the plant propagation material by a method such that the germination is not negatively impacted.
  • a plant propagation material such as a seed
  • seed dressing is seed dressing, seed coating or seed pelleting and alike. It is preferred that the plant propagation material is a seed, seed piece (i.e. stalk) or seed bulb.
  • Solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • Preferred examples of seed treatment formulation types or soil application for pre-mix compositions are of WS, LS, ES, FS, WG or CS-type.
  • compositions in question give, after two-to-tenfold dilution, active components
  • compositions or combinations comprising a nitrification inhibitor according to the present invention e.g. as defined herein above on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • compositions or combinations comprising a nitrification inhibitor according to the present invention are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • a pre-mix formulation for seed treatment application comprises 0.5 to 99.9 percent, especially 1 to 95 percent, of the desired ingredients, and 99.5 to 0.1 percent, especially 99 to 5 percent, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 percent, especially 0.5 to 40 percent, based on the pre-mix formulation.
  • a solid or liquid adjuvant including, for example, a solvent such as water
  • the auxiliaries can be a surfactant in an amount of 0 to 50 percent, especially 0.5 to 40 percent, based on the pre-mix formulation.
  • commercial products will preferably be formulated as concentrates (e.g., pre- mix composition (formulation), the end user will normally employ dilute formulations (e.g. tank mix composition).
  • compositions or combinations comprising a nitrification inhibitor according to the present invention e.g. as defined herein above (based on total weight of active components) is in the range from 0.01-10 kg, preferably from 0.1 -1000 g, more preferably from 1 -100 g per 100 kilogram of plant propagation material (preferably seeds).
  • compositions as defined herein, respectively, on to plant propagation material, especially seeds are known in the art, and include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • the composition is applied on to the plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting.
  • a suspension-type (FS) composition may be used.
  • a FS composition may comprise 1-800 g/l of active substance, 1 200 g/l surfactant, 0 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 mesoporous silicon dioxide particles may have a pore size in the range from 1 to 25 nm, preferably from 1 .5 to 15 nm, and in particular from 2 to 10 nm.
  • the pore size may be determined by Barrett-Joyner-Halenda (BJH) analysis.
  • BJH Barrett-Joyner-Halenda
  • the mesoporous silicon dioxide particles may have have a pore volume in the range from 1 to 25 cm 3 /g, preferably from 2 to 15 cm 3 /g, and in particular from 3 to 10 cm 3 /g.
  • the mesoporous silicon dioxide particles may have a pore volume in the range from 0.5 to 10 cm 3 /g, preferably from 0.5 to 5 cm 3 /g, and in particular from 0.8 to 2 cm 3 /g.
  • the pore volume may be determined by Barrett-Joyner-Halenda (BJH) analysis.
  • the mesoporous silicon dioxide particles may have an average particle size in the range from 1 to 100 ⁇ , preferably from 5 to 70 ⁇ , in particular from 10 to 50 ⁇ . In another form the mesoporous silicon dioxide particles may have an average particle size in the range from 0.1 to 100 ⁇ , preferably from 1 to 70 ⁇ , in particular from 10 to 50 ⁇ . The average particle size may be determined by laser diffraction.
  • the mesoporous silicon dioxide particles may have a surface area in the range from 500 to 1350 m 2 /g, preferably from 700 to 1 150 m 2 /g. The surface area may be determined by BET analysis.
  • the mesoporous silicon dioxide particles are mesostructured with a hexagonal symmetry, such as hexagonally close packed cylindrical pore channels belonging to the p6mm space group.
  • Typical examples of mesoporous silicon dioxide particles with a hexagonal symmetry are MCM-41 , FSM-16, SBA-3 and SBA-15.
  • the mesoporous silicon dioxide particles are preferably MSM-41 and SBA-15, wherein SBA-15 type is particularly preferred.
  • SBA-15 The preparation of SBA-15 in known from US 6,592,764 B1 .
  • the free hydroxy groups of the silicon dioxide surface may form chemical bonds with other functional groups in such chemically modified mesoporous silicon dioxide particles.
  • chemically modified mesoporous silicon dioxide particles have a different chemical structure compared to mesoporous silicon dioxide particles, which can be analyzed by 1 H-NMR or infrared spectroscopy.
  • the term “mesoporous silicon dioxide particles” may be also understood as “mesoporous silicon dioxide particles free of chemical modifications” or “mesoporous silicon dioxide particles with pristine surfaces", respectively.
  • the chemically modified mesoporous silicon dioxide particles may offer some disadvantages compared to mesoporous silicon dioxide particles, depending on intended application: In case, the interaction of the loaded material with the silica material is enhanced by chemical modification, the release would be much slower, the degree of loading would probably be lower, and additional chemical modification steps are indisputably required.
  • the mesoporous silicon dioxide particles are obtainable by contacting a surfactant (e.g. an amphiphilic block copolymer), a water glass solution or suitable silicon alkoxides, such as tetraethylorthosilicate and tetramethylorthosilicate, and an acidifying agent.
  • a surfactant e.g. an amphiphilic block copolymer
  • suitable silicon alkoxides such as tetraethylorthosilicate and tetramethylorthosilicate
  • an acidifying agent e.g. an amphiphilic block copolymer
  • the preparation of the mesoporous silicon dioxide particles is free of any chemical modification steps, such chemical reactions of the hydroxy groups of the silicon dioxide.
  • the weight ratio of the mesoporous silicon dioxide particles to the nitrification inhibitor may be in the range from 99:1 to 10:90, preferably 95:5 to 15:85, and in particular from 90:10 to 20:
  • the weight ratio of the mesoporous silicon dioxide particles to the nitrification inhibitor may be in the range from 50:50 to 10:90, preferably 40:60 to 10:90, and in particular from 30:70 to 15:85.
  • the loading of the mesoporous silicon dioxide particles with the nitrification inhibitor may be at least 2 g, preferably at least 5 g, more preferably at least 7 g, and in particular at least 8 g of the nitrification inhibitor per gram of the mesoporous silicon dioxide particles (e.g. of the SBA-15 type).
  • the mesoporous silicon dioxide particles e.g. of the SBA-15 type
  • the nitrification inhibitor e.g. the compound of formula I
  • the nitrification inhibitor has a molecular weight up up to 1000 g/mol.
  • the mesoporous silicon dioxide particles e.g. of the SBA-15 type
  • the nitrification inhibitor e.g. the compound of formula I
  • the nitrification inhibitor has a molecular weight up up to 1000 g/mol.
  • the mesoporous silicon dioxide particles e.g. of the SBA-15 type
  • the nitrification inhibitor e.g. the compound of formula I
  • the nitrification inhibitor has a molecular weight up up to 500 g/mol.
  • the mesoporous silicon dioxide particles e.g. of the SBA-15 type
  • the nitrification inhibitor e.g. the compound of formula I
  • the nitrification inhibitor has a molecular weight up up to 1000 g/mol.
  • the mesoporous silicon dioxide particles e.g. of the SBA-15 type
  • the nitrification inhibitor e.g. the compound of formula I
  • the nitrification inhibitor has a molecular weight up up to 1000 g/mol.
  • the mesoporous silicon dioxide particles have a pore size in the range from 2 to 10 nm and a surface area in the range from 700 to 1350 m 2 /g, and the nitrification inhibitor (e.g. the compound of formula I) has a molecular weight up up to 500 g/mol.
  • the invention further relates to a method for preparing the composition according to the invention by contacting the mesoporous silicon dioxide particles and the nitrification inhibitor. The contacting may be done in a temperature range from 0 to 100 °C, preferably from 5 to 40 °C, and in particular from 10 to 30 °C.
  • the mesoporous silicon dioxide particles and the nitrification inhibitor may be present in a weight ratio of the
  • mesoporous silicon dioxide particles to the nitrification inhibitor in the range from 99:1 to 10:90, preferably 95:5 to 15:85, and in particular from 90:10 to 20:80.
  • the contacting may be done by stirring or shaking the components.
  • the present invention offers various advantages: The loss of the nitrification inhibitor by evaporation after treating a plant and/or the locus where the plant is growing or intended to grow is reduced. The amount of nitrification inhibitor which is released to the plant and/or the locus where the plant is growing or intended to grow can be controlled. The loading of the composition with nitrification inhibitor can be controlled easily and thus adapted to the plant or soil. The maximum release of nitrification inhibitor can be controlled and thus adapted to the plant or soil.
  • the application rate of the nitrification inhibitor can be reduced because there is less loss by evaporation of the nitrification inhibitor once it was applied to the locus. There would be no need to a costly additional chemical modification step of the mesoporous silicon dioxide particles.
  • Example 1 Prepartion of mesoporous silica
  • a dry powder of mesoporous silicon dioxide particles was prepared according to literature from an aqueous solution of either sodium silicate, potassium silicate or tetraethoxysilan and
  • Pluronic® P123 (amphiphilic block copolymer of EO/PO/EO structure, average molecular weight 5750 g/mol, 30 wt% EO), which was acidified and dried to yield SBA-15 type.
  • the surface area of the mesoporous silicon dioxide particles was 728 m2/g as determined by BET analysis.
  • the pore size of the mesoporous silicon dioxide particles was 6.9 nm as determined by Barrett-Joyner-Halenda (BJH) analysis.
  • the pore volume of the mesoporous silicon dioxide particles was 0.966 cm3/g as determined by Barrett-Joyner-Halenda (BJH) analysis.
  • the average particle size of the mesoporous silicon dioxide particles was 10 to 50 ⁇ as determined by laser diffraction.
  • Example 2 Loading of mesoporous silica with nitrification inhibitor
  • the powder (2.0 g) was mixed with 6.5 g of the liquid nitrification inhibitor 1-chloro-4-((prop-2- yn-1 -yloxy)methyl)benzene (formula I-26 as shown in Table 1 ) at room temperature for 30 min to yield a paste.

Abstract

A composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor The present invention relates to a composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor; a method for preparing the composition by contacting the mesoporous silicon dioxide particles and the nitrification inhibitor; and a method for reducing nitrification comprising treating a plant and/or the locus where the plant is growing or is intended to grow with the composition.

Description

A composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor
The present invention relates to a composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor; a method for preparing the composition by contacting the
mesoporous silicon dioxide particles and the nitrification inhibitor; and a method for reducing nitrification comprising treating a plant and/or the locus where the plant is growing or is intended to grow with the composition. The present invention comprises combinations of preferred features with other preferred features. Nitrogen is an essential element for plant growth and reproduction. About 25% of the plant available nitrogen in soils (ammonium and nitrate) originate from decomposition processes (mineralization) of organic nitrogen compounds such as humus, plant and animal residues and organic fertilizers. Approximately 5% derive from rainfall. On a global basis, the biggest part (70%), however, is supplied to the plant by inorganic nitrogen fertilizers. The mainly used nitrogen fertilizers comprise ammonium compounds or derivatives thereof, i.e. nearly 90% of the nitrogen fertilizers applied worldwide is in the NH4 + form. This is, inter alia, due to the fact that NH4+ assimilation is energetically more efficient than assimilation of other nitrogen sources such as N03-. Moreover, being a cation, NH4 + is held electrostatically by the negatively charged clay surfaces and functional groups of soil organic matter. This binding is strong enough to limit NH4 +-loss by leaching to groundwater. By contrast, NO3", being negatively charged, does not bind to the soil and is liable to be leached out of the plants' root zone. In addition, nitrate may be lost by denitrification which is the microbiological conversion of nitrate and nitrite (NO2") to gaseous forms of nitrogen such as nitrous oxide (N2O) and molecular nitrogen (N2). However, ammonium (NH4 +) compounds are converted by soil microorganisms to nitrates (NO3") in a relatively short time in a process known as nitrification. The nitrification is carried out primarily by two groups of chemolithotrophic bacteria, ammonia-oxidizing bacteria (AOB) of the genus Nitrosomonas and Nitrobacter, which are ubiquitous component of soil bacteria populations. The enzyme, which is essentially responsible for nitrification is ammonia monooxygenase (AMO), which was also found in ammonia-oxidizing archaea.
The nitrification process typically leads to nitrogen leakage and environmental pollution. As a result of the various losses, approximately 50% of the applied nitrogen fertilizers are lost during the year following fertilizer addition. As countermeasures the use of nitrification inhibitors, mostly together with fertilizers, was suggested. It is an ongoing challenge to futher improve nitrification inhibitors, their efficacy and their application. Object of the present invention was to overcome the problems of the state of the art. The object was solved by a composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor. The term "nitrification inhibitor" usually refers to a chemical substance which slows down or stops the nitrification process. Nitrification inhibitors accordingly retard the natural
transformation of ammonium into nitrate, by inhibiting the activity of bacteria such as
Nitrosomonas spp.
The term "nitrification" as used herein may be understood as the biological oxidation of ammonia (NH3) or ammonium (NH4 +) with oxygen into nitrite (NO2") followed by the oxidation of these nitrites into nitrates (NO3") by microorganisms. Besides nitrate (NO3") nitrous oxide is also produced though nitrification. Nitrification is an important step in the nitrogen cycle in soil. The inhibition of nitrification may thus also reduce N20 losses.
Examples of nitrification inhibitors are the nitrification inhibitor of formula I (see below), linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro-6- (trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DI DI N), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4-amino-1 ,2,4-triazole hydrochloride (ATC), 1 -amido-2- thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5- ethoxy-3-trichloromethyl-1 ,2,4-thiodiazole (terrazole, etridiazole), 2-sulfanilamidothiazole (ST), ammoniumthiosulfate (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-pyrazole-1 - yl)methyl)acetamide), and N-(1 H-pyrazolyl-methyl)formamides (such as N-((3(5)-methyl-1 H- pyrazole-1 -yl)methyl formamide, N-(4-chloro-3(5)-methyl-pyrazole-1 -ylmethyl)-formamide, or N- (3(5),4-dimethyl-pyrazole-1 -ylmethyl)-formamide). The nitrification inhibitor is preferably the nitrification inhibitor of formula I
or a stereoisomer, salt, tautomer or N-oxide thereof,
wherein
R1 and R2 are independently of each other selected from the group consisting of H, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl C1-C6- alkoxy, C2-C6-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;
C3-C8-cycloalkyl, Cs-Cs-cycloalkenyl, heterocyclyl, aryl, hetaryl, C3-C8-cycloalkyl-Ci-C6- alkyl, C3-C8-cycloalkenyl-Ci-C6-alkyl, heterocyclyl-Ci-C6-alkyl, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical 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;
wherein
RA is selected from the group consisting of CN, halogen, N02, ORb, NRcRd, C(Y)Rb,
C(Y)ORb, C(Y)NRcRd, S(Y)mRb, S(Y)mOR , Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, wherein the C-atoms may in each case be unsubstituted or may carry 1 , 2 or 3 identical or different substituents Re;
C3-C8-cycloalkyl, Cs-Cs-cycloalkenyl, heterocyclyl, aryl, hetaryl, C3-C8-cycloalkyl-Ci-C6- alkyl, C3-C8-cycloalkenyl-Ci-C6-alkyl, heterocyclyl-Ci-C6-alkyl, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents Ra;
and wherein
Ra is selected from CN, halogen, NO2, CrC4-alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy; or two substituents Ra on adjacent C-atoms may be a bridge selected 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-C6-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 independently of each other selected from halogen;
Re is selected from CN, halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, and C1-C4- haloalkoxy;
Y is O or S; and
m is 0, 1 or 2.
In a preferred embodiment, in said compound of formula I , the radicals Ra, Rb, Rc, Rd, and Re 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;
Rb is selected from H, Ci-C6-alkyl, phenyl and benzyl;
Rc and Rd are independently of each other selected from the group consisting of H, Ci-C4-alkyl, and Ci-C4-haloalkyl; and
Re is selected from halogen and Ci-C4-alkyl.
In another preferred embodiment, in said compound of formula I , R1 and R2 are independently of each other selected from the group consisting of H, C2-C6-alkynyl, C2-C6-alkynyloxy, aryl-Ci- C6-alkyl, and hetaryl-Ci-C6-alkyl, wherein preferably at least one of R1 and R2 is H. In yet another preferred embodiment, in said compound of formula I, A is phenyl, wherein said phenyl ring is unsubstituted or carries 1 , 2, or 3 identical or different substituents RA.
In a particularly preferred embodiment, in said compound of formula I, RA, if present, is selected from the group consisting of halogen, NO2, NRcRd, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-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 as defined above. 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-Ci-C6-alkyl, and hetaryl-Ci-C6-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 represents a substituent selected from the group consisting of C2-C6-alkynyl, C2- C6-alkynyloxy, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-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.
Figure imgf000005_0001
In another preferred embodiment of said compound of formula I as defined above, both, R1 and mpounds correspond to compounds of formula l.b.
Figure imgf000005_0002
In one embodiment of the compound of formula I, A is phenyl, wherein said phenyl ring is unsubstituted or carries 1 , 2, or 3 identical or different substituents RA. Such compounds correspond to compounds of formula 1.1 , wherein (RA)n with n being 0, 1 , 2, or 3 indicates the above substitution possibilities for the compound.
Figure imgf000005_0003
Particular preferred are compounds, wherein n is 1 or 2, i.e. the following compounds 1.11 and I.12
Figure imgf000005_0004
In a preferred embodiment, the present invention relates to compounds of formula I, wherein R1 is H, R2 is R2-a, and A is phenyl, wherein said phenyl ring is unsubstituted or carries 1 , 2, or 3 identical or different substituents RA. Such compounds are referred to compounds of formula 1.1. a, with compounds of formula 1.1 .a and compounds of formula l.12.a being particularly preferred.
Figure imgf000006_0001
In another preferred embodiment, the present invention 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 , 2, or 3 identical or different substituents RA. Such compounds are referred to compounds of formula 1.1. b, with compounds of formula 1. . b and compounds of formula l.12.b being particularly preferred.
Figure imgf000006_0002
(1.1 .b) (1.1 .b) (1.12.b) For the compounds as defined above, i.e. I. a, l.b, 1.1 , I.11, I.12, 1.1. a, 1.11.a, l.12.a, 1.1 .b, l.11.b, l.12.b, it is particularly preferred that RA, if present, is selected from the group consisting of halogen, N02, NRcRd, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-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 bridge; and Rc and Rd are independently of each other selected from the group consisting of H, Ci-C4-alkyl, and Ci-C4-haloalkyl.
Thus, the present invention relates in one embodiment to compounds of formula I, wherein R1 and R2 are independently of each other selected from the group consisting of H, C2-C6- alkynyl, C2-C6-alkynyloxy, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-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-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-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 bridge; and
Rc and Rd are independently of each other selected from the group consisting of H, Ci-C4-alkyl, and Ci-C4-haloalkyl.
In particular with a view to their use, preference is given to the compounds of formula I compiled in Table 1 below.
Figure imgf000007_0001
Figure imgf000008_0001
In another preferred form the nitrification inhibitor is the nitrification inhibitor of formula (II)
Figure imgf000009_0001
or a stereoisomer, salt, tautomer or N-oxide thereof,
wherein
A is aryl or hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RA;
R1 and R2 are independently of each other selected from H and Ci-C2-alkyl; and
R3 is H, Ci-C4-haloalkyl, Ci-C4-hydroxyalkyl, ethynylhydroxymethyl, phenylhydroxymethyl, or aryl, wherein the aromatic ring may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RB; and wherein
RA is
(i) halogen, CN, NRaRb, ORc, SRC, C(=Y1)RC, C(=Y1)ORc, C(=Y1)SRC, C(=Y1)NRaRb, Y2C(=Y1)RC, Y2C(=Y1)ORc, Y2C(=Y1)SRC, Y2C(=Y1)NRaRb, Y3Y2C(=Y1)RC,
Figure imgf000009_0002
C(=N-N RaRb)R9, S(=0)2Rf,
NR9S(=0)2Rf, S(=0)2Y2C(=Y )Rc, S(=0)2Y2C(=Y )ORc, S(=0)2Y2C(=Y )SRc,
S(=0)2Y2C(=Y )NRaRb, N02, NON-CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C C4- haloalkyl, Ci-C4-cyanoalkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, C2-C4-alkynyl-Ci-C2- hydroxyalkyl, C2-C4-alkynyloxy;
Figure imgf000009_0003
Figure imgf000009_0004
Ci-C4-alkylene-Y2- C(=Y1)RC, C2-C4-alkenylene-Y2-C(=Y1)Rc, C C4-alkylene-NRaRb, C2-C4-alkenylene- NRaR , Ci-C4-alkylene-ORc, C2-C4-alkenylene-ORc, Ci-C4-alkylene-SRc, C2-C4- alkenylene-SRc, wherein the Ci-C4-alkylene or C2-C4-alkenylene chain may in each case be unsubstituted or may be partially or fully substituted by OR9, CN, halogen or phenyl; (iii) aryl, aryl-Ci-C2-alkyl, hetaryl or hetaryl-Ci-C2-alkyl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh;
(iv) a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1 b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R'; and wherein R1 b is H, C1-C4- alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl methyl, or OR9; or
(v) L-B, wherein
L is -CH2-, -CH=CH-, -C≡C-, -C(=0)- or -CH=, and
B is aryl or hetaryl, wherein the aromatic ring of the ary or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R1 b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from Ri; and wherein R1 b is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, or ORs; or
(vi) two substituents RA together represent a carbocyclic or heterocyclic ring, which is fused to A and may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R1 c, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R'; and wherein R1 c is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, C3-C6-heterocyclyl, C3-C6-heterocyclylmethyl or ORs; and wherein
RB is NH-C(=0)-(CrC4-alkyl), NH-C(=0)-(C2-C4-alkenyl), NH-C(=0)-(CrC2-alkoxy-Ci-C2- alkyl), NH-C(=0)-(C3-C6-cycloalkyl), NH-S(=0)2-(Ci-C4-alkyl), or N02;
and wherein
Y1 , Y2 and Y3 are independently of each other selected from O, S and N R1 a, wherein R1 a is in each case independently H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, ORs, SRs or N RmRn;
Ra and Rb are independently of each other selected from
(i) H, N RjRk, OR', SR', Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, C(=Y )R', C(=Y )OR', C(=Y )SR', C(=Y )N RiRk, C(=Y )C(=Y2)R', S(=0)2Rf;
(ii) aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
Ra and Rb together with the nitrogen atom to which they are bound form
(iii) a hetaryl group which may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
(iv) a 3- to 10-membered, saturated or unsaturated heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R1 b, O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R'; and wherein R1 b is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, Cs-Ce-cycloalkylmethyl, or ORs;
Rc is
(i) H, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C(=0)OR', C(=0)SR', C(=0)N RiRk;
(ii) Ci-C4-alkylene-C(=0) R', Ci-C4-alkylene-C(=0)OR', wherein the Ci-C4-alkylene chain may in each case be unsubstituted or may be partially or fully substituted by ORs, CN, halogen, or phenyl; (iii) aryl, aryl-Ci-C2-alkyl, hetaryl, or hetaryl-Ci-C2-alkyl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
(iv) a 3- to 10-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R'; and wherein R1b is H, C1-C4- alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl methyl, or OR9;
Rd and Re are independently selected from C C4-alkyl, Ci-C4-haloalkyl, NRiRk, OR1, SR1, CN, C(=Y1)R', C(=Y1)OR', C(=Y1)SR', or C(=Y1)NRiRk;
Rf is Ci-C4-alkyl, Ci-C4-haloalkyl, NRiRk, OR', SR', aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh;
R9 is H or Ci-C4-alkyl;
Rh is halogen, CN, N02, NRiRk, OR', SR', Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4- haloalkyl, d-C4-alkoxy, C2-C4-alkynyloxy, C(=Y )R', C(=Y )OR', C(=Y )SR', C(=Y )NRiRk, aryl, aryloxy, hetaryl and hetaryloxy;
Ri is
(i) halogen, CN, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, C2-C4- haloalkenyl;
(ii) =NR1d, wherein R1d is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, or ORs;
(iii) =0, =S, NRjRk, OR', SR', C(=Y1)R', C(=Y1)OR', C(=Y1)SR', C(=Y1)NRRk;
(iv) aryl, aryl-Ci-C2-alkyl, hetaryl, or hetaryl-Ci-C2-alkyl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from halogen, CN, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, OR9, and SRs; or
(v) C3-C6-cycloalkyl, or 3- to 6-membered heterocyclyl, wherein the cycloalkyl ring or the heterocyclyl ring may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from halogen, CN, C1-C4- alkyl, ORs, and SR9;
Rj and Rk are independently selected from H, OR9, SRs,
Figure imgf000011_0001
C(=Y1)NRmRn, CrC4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C C4-haloalkyl, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, ORs, and SR9;
R' is H, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl,
Figure imgf000011_0002
C(=Y1)SR9, C(=Y1)NRmRn, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, ORs, and SRs; and
Rm and Rn are independently selected from H and Ci-C4-alkyl. In a preferred embodiment in said compound of formula (II), A is phenyl or a 5- or 6-membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RA. In a more preferred embodiment of said use, in said compound of formula (II), A is phenyl or a 6- membered hetaryl, in particular phenyl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RA. In a most preferred embodiment, A is phenyl. Such compounds are typically solid at room temperature and are typically non-volatile and stable against hydrolysis. In another preferred embodiment of said compound of formula (II), R1 and R2 both represent hydrogen. In yet another preferred embodiment of said compound of formula (II), R3 is hydrogen, Ci-C4-haloalkyl or ethinylhydroxymethyl, and preferably R3 is hydrogen.
In still another preferred embodiment of said compound of formula I, RA, if present, is
(i) halogen, CN, NRaRb, ORc, C(=Y1)RC, C(=Y1)ORc, C(=Y1)SRC, C(=Y1)NRaRb, Y2C(=Y1)RC,
Figure imgf000012_0001
S(=0)2Rf, N02, Ci-C6-alkyl, C2-C6- Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyl-Ci-C2-hydroxyalkyl, C2-C4-alkynyloxy;
(ii) C2-C4-alkenylene-C(=Y1)Rc, C2-C4-alkenylene-Y2-C(=Y1)Rc, wherein the Ci-C4-alkylene or C2-C4-alkenylene chain may in each case be unsubstituted or may be partially or fully substituted by CN or halogen;
(iii) aryl, wherein the aromatic ring of the aryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from
Rh; or
(iv) a 3- to 14-membered saturated or unsaturated heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R'; and wherein R1b is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3- C6-cycloalkylmethyl, or ORs,
wherein preferably Y1, Y2 and Y3 are independently of each other selected from O, S and NR1a, wherein R1a is in each case independently H, CrC4-alkyl, OH, or NH2.
Ra and Rb are independently of each other selected from
(i) H, NH2, Ci-C4-alkyl, Ci-C4-hydroxyalkyl, C(=0)H, C(=S)H, C(=N-H)H, C(=N-(Ci- C4)alkyl))H, C(=N-OH)H, C(=N-NH2)H, or
Ra and Rb together with the nitrogen atom to which they are bound form
(iv) a 3- to 10-membered, saturated or unsaturated heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-haloalkenyl, and =0; and wherein R1 b is H , Ci-C4-alkyl, or OH ;
Rc is (i) H , Ci-C4-alkyl; or
(iv) a 3- to 10-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R1 b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from CrC4-alkyl, CrC4-haloalkyl, C2-C4- haloalkenyl, and =0; and wherein R1 b is preferably H , Ci-C4-alkyl, or OH ;
Rd and Re are independently selected from N H2 and C(=0)OH ;
Rf is Ci-C4-alkyl;
Rh is halogen or Ci-C4-alkoxy;
and
R' is (i) Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-haloalkenyl; or
(iii) =0.
In a particularly preferred embodiment of compound of formula (I I), R1 and R2 both represent hydrogen, R3 is hydrogen, and A is phenyl, wherein the aromatic ring is substituted by 1 , 2, or 3 substituent(s) RA, wherein the substituent(s) RA are independently of each other selected from halogen, CN , N H2, C(=0)N RaRb, N HC(=0)N RaRb, N HC(=S)N RaRb, N HC(=0) H , Ci-C4-alkoxy, C2-C4-alkynyl-Ci-C2-hydroxyalkyl, and C2-C4-alkynyloxy, wherein Ra and Rb are in each case independently of each other selected from H , Ci-C2-alkyl, N H2, Ci-C2-hydroxyalkyl, or wherein Ra and Rb may together with the nitrogen atom to which they are bonded form a morpholine ring.
The nitrification inhibitor of formula (II) are described in WO 2015/158853, which is incorporated herein by reference. d form the nitrification inhibitor is the nitrification inhibitor of formula (III)
Figure imgf000013_0001
or a stereoisomer, salt, tautomer or N-oxide thereof,
wherein
R1 and R2 are independently selected from H and Ci-C2-alkyl;
and wherein
R3 is
(i) C(=0)Ra, C(=0)ORa, C(=0)N RcRd, C(=N-OH)Ra, C(=N-OH)N RcRd, C(=N-Rb)Ra, C(=N-Rb)N RcRd, C(=N-R*)Ra, or C(=N-R*)N RcRd; or (ii) d-Ce-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C3-C8-cycloalkenyl, or C2-C8-alkynyl, wherein the C-atoms of these groups may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, ORa, NO2, NRcRd, NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, S(0)nRa, and S(0)nNRcRd; or (iii) C6-Ci4-aryl, Cs-Cu-hetaryl, C6-Ci4-aryl-Ci-C2-alkyl, or C5-Ci4-hetaryl-Ci-C2-alkyl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, Rx, ORa, SRa, NRcRd, NRb(C=0)Ra, NRb(C=0)NRcRd, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, S(0)nRa,
S(0)nNRcRd, CrC4-alkyl, C C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C C4-alkylen- ORa, CrC4-alkylen-NRcRd, C6-Ci0-aryl, C6-Cio-aryl-Ci-C2-alkyl, C5-Ci0-hetaryl, C5-C10- hetaryl-Ci-C2-alkyl, Cs-Cio-carbocyclyl, C5-Cio-carbocyclyl-Ci-C2-alkyl, C5-C10- heterocyclyl, and C5-Cio-heterocyclyl-Ci-C2-alkyl, wherein the C6-Cio-aryl, Cs-Cio-hetaryl, Cs-Cio-carbocyclyl, and Cs-Cio-heterocyclyl moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, N02, OH, SH, NH2, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-dialkylamino, and
Ci-C4-haloalkyl; or
(iv) C5-Ci4-carbocyclyl, C5-Ci4-carbocyclyl-Ci-C2-alkyl, Cs-Cu-heterocyclyl, or C5-C14- heterocyclyl-Ci-C2-alkyl, wherein the heterocyclyl rings may carry 1 , 2, 3, 4, or 5 heteroatoms being selected from O, S, and N, of which S and/or N may optionally be oxidized, and wherein the carbocyclic or heterocyclic rings may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, =S, halogen, CN, Rx, ORa, SRa, N02, NRcRd, NRb(C=0)Ra, NRb(C=0)NRcRd, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, S(0)nRa, S(0)nNRcRd, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-alkylen-ORa, Ci-C4-alkylen-NRcRd, C6-Cio-aryl, C6- Cio-aryl-Ci-C2-alkyl, Cs-Cio-hetaryl, C5-Cio-hetaryl-Ci-C2-alkyl, Cs-Cio-carbocyclyl, C5-
Cio-carbocyclyl-Ci-C2-alkyl, Cs-Cio-heterocyclyl, and C5-Cio-heterocyclyl-Ci-C2-alkyl, wherein the C6-Cio-aryl, Cs-Cio-hetaryl, Cs-Cio-carbocyclyl, and Cs-Cio-heterocyclyl moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, NO2, OH, SH, NH2, Ci-C4-alkyl, C1-C4- alkoxy, Ci-C4-alkylthio, Ci-C4-dialkylamino, and Ci-C4-haloalkyl; or
and wherein
Ra is H, d-Cs-alkyl, Ci-C8-haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl;
Cs-Cio-hetaryl or C6-Cio-aryl, wherein the Cs-Cio-hetaryl or C6-Cio-aryl moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, OH, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, C2-C4- alkenyl, C2-C4-alkynyl, Cs-Ce-hetaryl and C6-aryl, wherein said Cs-Ce-hetaryl and C6-aryl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 substituents selected from halogen, CN, OH, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, C2-C4-alkenyl, and C2-C4- alkynyl;
Rb is H, Ci-C4-alkyl, C3-C8-cycloalkyl, C2-C4-alkenyl, C2-C8-alkynyl, or C6-Cio-aryl; and
Rc and Rd are independently of each other selected from the group consisting of H, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C8-cycloalkyl, C6-Cio-aryl, and Cs-Cio-hetaryl; or Rc and Rd together with the N-atom to which they are bonded form a 5- to 6-membered, saturated or unsaturated heterocycle, which may carry a further heteroatom being selected from O, S, and N as a ring member atom, of which S and/or N may optionally be oxidized, and wherein the heterocyclic ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 substituents, which are independently selected from halogen, CN, OH, NO2, Ci- C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, and Ci-C4-haloalkoxy;
and wherein
Rx is
Figure imgf000015_0001
wherein § marks the connection to the atom to which Rx is bonded; and
wherein V, W, X, Y, and Z are independently selected from N, CH and CRy,
wherein RY is selected from the group consisting of halogen, CN, NO2, OH, SH, NH2, Ci- C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-dialkylamino, and Ci-C4-haloalkyl;
and wherein
m is 0, 1 , or 2;
n is 0, 1 , or 2; and
p is 0,1 , or 2.
In one preferred embodiment of said compound of formula (III), p is 1 or 2. Accordingly, the following compounds I.p1 or compounds I.p2 are preferred according the invention.
Figure imgf000015_0002
In one preferred embodiment of said compound of formula (III), R1 and R2 are H. In one preferred embodiment of said use, in said compound of formula I , R1 and R2 are H and p is 1 or 2.
In another preferred embodiment of said use, in said compound of formula (III),
R3 is
(i) C(=0)Ra, C(=N-OH)Ra, or C(=N-R*)NRcRd; or
(ii) Ci-Cs-alkyl, Cs-Cs-cycloalkyl, C2-Cs-alkenyl, or C2-Cs-alkynyl, wherein the C-atoms of these groups may in each case be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, or CN; or
(iii) C6-Ci4-aryl, Cs-Cu-hetaryl, C6-Ci4-aryl-Ci-C2-alkyl, or C5-Ci4-hetaryl-Ci-C2-alkyl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN, Rx, ORa, SRa, N02, NRcRd, C1-C4- alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C6-Cio-aryl, C6-Cio-aryl-Ci-C2-alkyl, C5-Cio-hetaryl, C5-Cio-hetaryl-Ci-C2-alkyl, Cs-Cio-carbocyclyl, C5-Cio-carbocyclyl-Ci-C2- alkyl, Cs-Cio-heterocyclyl, and C5-Cio-heterocyclyl-Ci-C2-alkyl, wherein the C6-Cio-aryl, C5-Cio-hetaryl, Cs-Cio-carbocyclyl, and Cs-Cio-heterocyclyl moieties may in each case be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN , Ci-C4-alkyl, Ci-C4-alkoxy, and Ci-C4-haloalkyl; or
(iv) C5-Ci4-carbocyclyl, C5-Ci4-carbocyclyl-Ci-C2-alkyl, Cs-Cu-heterocyclyl, or C5-C14- heterocyclyl-Ci-C2-alkyl, wherein the heterocyclyl rings may carry 1 , 2, or 3 heteroatoms being selected from O, S, and N , of which S and/or N may optionally be oxidized, and wherein the carbocyclic or heterocyclic rings may in each case be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from =0, =S, halogen, CN , Rx, ORa, SRa, N02, N RcRd, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, C6-Cio- aryl, C6-Cio-aryl-Ci-C2-alkyl, Cs-Cio-hetaryl, C5-Cio-hetaryl-Ci-C2-alkyl, C5-C10- carbocyclyl, C5-Cio-carbocyclyl-Ci-C2-alkyl, Cs-Cio-heterocyclyl, and Cs-Cio-heterocyclyl-
Ci-C2-alkyl, wherein the C6-Cio-aryl, Cs-Cio-hetaryl, Cs-Cio-carbocyclyl, and C5-C10- heterocyclyl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN , Ci-C4-alkyl, Ci-C4-alkoxy, and C1-C4- haloalkyl;
wherein
Ra is H , Ci-C4-alkyl, or Ci-C4-haloalkyl; and
Rc and Rd are independently of each other selected from the group consisting of H , Ci-C4-alkyl, and Ci-C4-haloalkyl;
and wherein
Rx is
Figure imgf000016_0001
wherein § marks the connection to the atom to which Rx is bonded; and
wherein V, W, X, Y, and Z are independently selected from N , CH and CRy,
wherein RY is selected from the group consisting of halogen, CN , Ci-C4-alkyl, C1-C4- alkoxy, Ci-C4-alkylthio, Ci-C4-dialkylamino, and Ci-C4-haloalkyl.
In a further preferred embodiment of said use, in said compound of formula (III),
R3 is
(i) C(=N-OH)Ra, or C(=N-R*)N RcRd; or
(ii) C2-C4-alkynyl; or
(iii) C6-Cio-aryl, Cs-Cio-hetaryl, C6-Cio-aryl-Ci-C2-alkyl, or C5-Cio-hetaryl-Ci-C2-alkyl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN , Rx, ORa, SRa, N RcRd, Ci-C4-alkyl, Ci-C4-haloalkyl, C6-aryl, and Cs-Ce-hetaryl, wherein the C6-aryl and Cs-C6-hetaryl moieties may in each case be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN , Ci-C4-alkyl, Ci-C4-alkoxy, and Ci-C4-haloalkyl; or
(iv) Cs-Cio-heterocyclyl, wherein the heterocyclyl ring may carry 1 , 2, or 3 heteroatoms being selected from O, S, and N , of which S and/or N may optionally be oxidized, and wherein the heterocyclic ring may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from =0, halogen, CN , Rx, 0Ra, SRa, N RcRd, CrC4-alkyl, d-C4- haloalkyl, C6-aryl, and Cs-Ce-hetaryl, wherein the C6-aryl and Cs-Ce-hetaryl moieties may in each case be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN , Ci-C4-alkyl, Ci-C4-alkoxy, and Ci-C4-haloalkyl; or wherein
Ra is H , or Ci-C4-alkyl;
Rc and Rd are independently of each other selected from the group consisting of H and Ci-C4- alkyl;
and wherein
Rx is
Figure imgf000017_0001
wherein § marks the connection to the atom to which Rx is bonded; and
wherein V, W, Y, and Z each represent CH , and X represents CH or CRy,
wherein RY is selected from the group consisting of halogen, CN , Ci-C4-alkyl, Ci-C4- alkoxy, Ci-C4-alkylthio, and Ci-C4-dialkylamino.
In a more preferred embodiment of said compound of formula (III),
R3 is
(i) C(=N-OH)Ra, or C(=N-Rx)N RcRd; or
(ii) Cs-alkynyl; or
(iii) C6-aryl or Cs-Cio-hetaryl;
wherein
Ra is H , or Ci-C2-alkyl;
Rc and Rd are independently of each other selected from the group consisting of H and C1-C2- alkyl;
and wherein
Rx is
Figure imgf000017_0002
wherein § marks the connection to the atom to which Rx is bonded; and
wherein V, W, Y, and Z each represent CH , and X represents CH or CRy,
wherein RY is selected from the group consisting of halogen, CN , Ci-C2-alkyl, and C1-C2- alkoxy.
Thus, it is preferred for the compounds of formula (III) that
R1 and R2 are H ;
R3 is
(i) C(=N-OH)Ra, or C(=N-Rx)N RcRd; or
(ii) C3-alkynyl; or (iii) C6-aryl or Cs-Cio-hetaryl;
wherein
Ra is H, or Ci-C2-alkyl;
Rc and Rd are independently of each other selected from the group consisting of H and C1-C2- alkyl;
and wherein
Rx is
Figure imgf000018_0001
wherein § marks the connection to the atom to which Rx is bonded; and
wherein V, W, Y, and Z each represent CH, and X represents CH or CRy,
wherein RY is selected from the group consisting of halogen, CN, Ci-C2-alkyl, and C1-C2- alkoxy;
m is 0, 1 , or 2; and
p is 1 or 2.
In one preferred embodiment, p is 1 , R1 and R2 are H, and R3 is option (i) as defined above. In one preferred embodiment, p is 1 , R1 and R2 are H , and R3 is option (ii) as defined above. In one preferred embodiment, p is 1 , R1 and R2 are H , and R3 is option (iii) as defined above. In one preferred embodiment, p is 2, R1 and R2 are H , and R3 is option (i) as defined above. In one preferred embodiment, p is 2, R1 and R2 are H, and R3 is option (ii) as defined above. In one preferred embodiment, p is 2, R1 and R2 are H, and R3 is option (iii) as defined above.
The nitrification inhibitor of formula (II I) are described in WO 2016/180859, which is
incorporated herein by reference.
In another preferred form the nitrification inhibitor is the nitrification inhibitor of formula (IV)
Figure imgf000018_0002
or a stereoisomer, salt, tautomer or N-oxide thereof,
wherein
R1 is H, CH2NRbC(=0)Ra, CH2OC(=0)Ra, CH2ORa,
d-Ce-alkyl, or Cs-Cs-cycloalkyl, wherein the C-atoms may in each case be unsubstituted or may carry 1 , 2 or 3 identical or different substituents selected from halogen, CN, OH, N02, COOH, NRcRd, NRb(C=0)Ra, C(=0)NRcRd, Ci-C4-alkoxy, Ci-C4-alkylcarbonyl, Ci- C4-alkylcarboxy, Ci-C4-alkylthio, Ci-C4-alkylsulfonyl, and S(0)2NRcRd;
and wherein
R2, R3 and R4 are independently of each other selected from H, halogen, CN, OH, NO2 NRcRd, NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, S(0)2Ra, S(0)2NRcRd, d-Ce-alkyl, d-d-alkoxy, Ci-d-alkylthio, d-d-cycloalkyl, C2-C8-alkenyl, C2-C6-alkynyl, wherein the C-atoms may in each case be unsubstituted or may carry 1 , 2 or 3 identical or different substituents selected from halogen, CN , OH , N02, COOH , N RcRd,
N Rb(C=0) Ra, C(=0) N RcRd, Ci-C4-alkoxy, Ci-C4-alkylcarbonyl, Ci-C4-alkylcarboxy, Ci- d-alkylthio, Ci-d-alkylsulfonyl, and S(0)2N RcRd;
and wherein
Ra is H , d-Cs-alkyl, d-d-alkenyl, d-d-alkynyl or d-Cio-aryl;
Rb is H , Ci-d-alkyl, d-d-cycloalkyl, C2-d-alkenyl, C2-d-alkynyl, or d-Cio-aryl; and
Rc and Rd are independently of each other selected from the group consisting of H , d-d-alkyl, and d-d-haloalkyl;
with the proviso that at least one of R2, R3 and R4 is C2-d-alkynyl.
In a preferred embodiment, said nitrification inhibitor is a compound of formula (IV)
Figure imgf000019_0001
or a stereoisomer, salt, tautomer or N-oxide thereof,
wherein
R1 is H, d-Cs-alkyl, CH2NRbC(=0)Ra, CH2OC(=0)Ra, or CH2ORa;
wherein
Ra is H, Ci-d-alkyl, C2-d-alkenyl, C2-d-alkynyl or d-Cio-aryl; and
Rb is H, Ci-d-alkyl, d-d-cycloalkyl, d-d-alkenyl, C2-d-alkynyl, or C6-Ci0-aryl; and wherein
R2, R3 and R4 are independently of each other selected from H, halogen, d-d-alkyl, d-d- cycloalkyl, C2-d-alkenyl, and C2-d-alkynyl;
with the proviso that at least one of R2, R3 and R4 is d-d-alkynyl.
In one preferred embodiment of said compound of formula (IV) as defined above, R1 is Ci-d- alkyl, preferably d-C2-alkyl. These compounds correspond to compounds of formula 1.1a, wherein R1-1 a represents d-d-alkyl, preferably d-C2-alkyl, e.g. CH3.
Figure imgf000019_0002
In another preferred embodiment of said compound of formula (IV) as defined above, R1 is CH2NR C(=0)Ra, wherein Ra is H , d-d-alkyl, d-d-alkenyl, C2-d-alkynyl, or d-do-aryl, and Rb is H , d-d-alkyl, d-d-cycloalkyl, d-d-alkenyl, C2-d-alkynyl, or d-do-aryl; and wherein preferably Ra is d-d-alkyl, d-d-alkenyl, d-d-alkynyl, or d-do-aryl, and Rb is H , Ci-d- alkyl, d-d-cycloalkyl, C2-d-alkenyl, C2-d-alkynyl, or d-Cio-aryl; and wherein particularly preferably Ra is Ci-C8-alkyl, or d-Cio-aryl, and Rb is H , Ci-d-alkyl, Cs-Cs-cycloalkyl, or d-Cio- aryl. These compounds correspond to compounds of formula 1.1 b, wherein R1-1 b represents CH2NRbC(=0)Ra, wherein Ra and Rb are as defined above.
Figure imgf000020_0001
In a preferred embodiment of said compound of formula (IV) as defined above, R2, R3 and R4 are independently of each other selected from H, Ci-C4-alkyl, and C2-C4-alkynyl, and preferably from H, Ci-C2-alkyl, and C2-C4-alkynyl, with the proviso that at least one of R2, R3, and R4 is C2- C4-alkynyl. These compounds correspond to compounds of formula I .A, wherein R2-A, R3-A, and R4-A represent substituents selected from H, Ci-C4-alkyl, and C2-C4-alkynyl, and preferably from H, Ci-C2-alkyl, and C2-C4-alkynyl, with the proviso that at least one of R2-A, R3-A, and R4-A
Figure imgf000020_0002
The specific compounds with one of R2-A, R3-A, and R4-A being C2-C4-alkynyl are referred to as compounds of formula I.A(R2-A=alkynyl), formula I .A(R3-A=alkynyl), and formula I .A(R4- A=alkynyl), respectively, wherein R2-alkynyl, R3-alkynyl, and R4-alkynyl represent a C2-C4- alkynyl group, and R2-A, R3-A, and R4-A, respectively, if present, represent a substituent selected from H, Ci-C4-alkyl, and C2-C4-alkynyl, and preferably from H, Ci-C2-alkyl, and C2-C4- alkynyl.
Figure imgf000020_0003
I.A(R2-A=alkynyl) I .A(R3-A=alkynyl) I.A(R -A=alkynyl)
In a more preferred embodiment of said compound of formula (IV), R1 is R1-1 a, and R2, R3 and
R4 correspond to R2-A, R3-A, and R4-A, with the proviso that at least one of R2-A, R3-A, and R4- A compounds correspond to compounds of formula l . l a.A.
Figure imgf000020_0004
Exemplary compounds include compounds of formula l .1 a.A(R2-A=alkynyl), formula l .1 a.A(R3-
A=alkynyl), and formula l .1 a.A(R4-A=alkynyl). In these generic formulae, R1-1 a represents Ci-
C4-alkyl, R2-alkynyl, R3-alkynyl, and R4-alkynyl represent a C2-C4-alkynyl group, and R2-A, R3-A, and R4-A, respectively, if present, represent a substituent selected from H, Ci-C4-alkyl, and C2-
Figure imgf000020_0005
l.1 a.A(R2-A=alkynyl) l .1 a.A(R3-A=alkynyl) l .1 a.A(R -A=alkynyl) In another more preferred embodiment of said compound of formula (IV), R1 is R1-1 b, and R2, R3 and R4 correspond to R2-A, R3-A, and R4-A, with the proviso that at least one of R2-A, R3-A, and R4-A is C2-C4-alkynyl. These compounds correspond to compounds of formula
Figure imgf000021_0001
Exemplary compounds include compounds of formula l.1 b.A(R2-A=alkynyl), formula l.1 b.A(R3-
A=alkynyl), and formula l.1 b.A(R4-A=alkynyl). In these generic formulae, R1-1 b represents
CH2NRbC(=0)Ra, wherein Ra is H, Ci-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, or C6-Cio-aryl, and
Rb is H, Ci-C4-alkyl, Cs-Cs-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C6-Cio-aryl; and wherein preferably Ra is Ci-Cs-alkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, or C6-Cio-aryl, and Rb is H, C1-C4- alkyl, Cs-Cs-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C6-Cio-aryl; and wherein particularly preferably Ra is Ci-Cs-alkyl, or C6-Cio-aryl, and Rb is H, Ci-C4-alkyl, Cs-Cs-cycloalkyl, or C6-C10- aryl. Furthermore, R2-alkynyl, R3-alkynyl, and R4-alkynyl represent a C2-C4-alkynyl group, and
R2-A, R3-A, and R4-A, respectively, if present, represent a substituent selected from H, C1-C4- alkyl,
Figure imgf000021_0002
l.1 b.A(R2-A=alkynyl) l.1 b.A(R3-A=alkynyl) l.1 b.A(R -A=alkynyl)
In another preferred embodiment of said compound of formula (IV) as defined above, at least two of R2, R3 and R4 are C2-C4-alkynyl, preferabi C2-C3-alkynyl. These compounds correspond to compounds of formula I.A*, wherein R2-A*, R3-A* and R4-A* represent substituents selected from H, Ci-Cs-alkyl, Cs-Cs-cycloalkyl, C2-Cs-alkenyl, C2-Cs-alkynyl and halogen, preferably from
H, Ci-C4-alkyl, and C2-C4-alkynyl, and particularly preferably from H, Ci-C2-alkyl, and C2-C4- alkynyl, with the proviso that at least two of R2-A*, R3-A*, and R4-A* are C2-C4-alkyl, preferably
C2-C3-alkynyl, e.g. ethynyl.
Figure imgf000021_0003
The specific compounds with two of R2-A*, R3-A*, and R4-A* being C2-C4-alkynyl, preferably C2-C3-alkynyl, are referred to as compounds of formula I.A(R2-A*+R3-A*=alkynyl), formula
I. A(R3-A*+R4-A*=alkynyl), and formula I.A(R2-A*+R4-A*=alkynyl), respectively, wherein R2- alkynyl, R3-alkynyl, and R4-alkynyl represent a C2-C4-alkynyl group, preferably a C2-C3-alkynyl group, and R2-A*, R3-A*, and R4-A*, if present, represent C2-C4-alkynyl, preferably C2-C3- alkynyl, e.g. ethynyl.
Figure imgf000021_0004
I.A(R2-A*+R3-A*=alkynyl) I .A(R3-A*+R -A*=alkynyl) I .A(R2-A*+R -A*=alkynyl) Compounds of formula I .A(R2-A*+R3-A*=alkynyl) are particularly preferred according to the present invention.
In a more preferred embodiment of said compound of formula (IV), R1 is R1-1 a, and R2, R3 and R4 correspond to R2-A*, R3-A*, and R4-A*, with the proviso that at least two of R2-A*, R3-A*, and
R4-A* are C2-C4-alkynyl, preferably C2-C3-alkynyl, e.g. ethynyl. These compounds correspond to compounds of formula l. l a.A*.
Figure imgf000022_0001
Exemplary compounds include compounds of formula l .1 a.A*(R2-A*+R3-A*= alkynyl), formula l.1 a.A*(R3-A*+R4-A*= alkynyl), and formula l .1 a.A*(R2-A*+R4-A*= alkynyl). In these generic formulae, R1-1 a represents Ci-C4-alkyl, R2-alkynyl, R3-alkynyl, and R4-alkynyl represent a C2-C4- alkynyl group, preferably a C2-C3-alkynyl group, e.g. an ethynyl group, and R2-A*, R3-A*, and R4-
A*, respectively, if present, represent a substituent selected from H, Ci-C4-alkyl, and C2-C4- alkynyl, and preferably from H, Ci-C2-alkyl, and C2-C4-alkynyl.
Figure imgf000022_0002
-alkynyl l .1 a.A*(R2-A*+R3-A*= alkynyl) l.1 a.A*(R3-A*+R -A*= alkynyl) l.1 a.A*(R2-A*+R -A*= alkynyl) In another more preferred embodiment of said compound of formula I , R1 is R1-1 b, and R2, R3 and R4 correspond to R2-A*, R3-A*, and R4-A*, with the proviso that at least two of R2-A*, R3-A*, and R4-A* are C2-C4-alkynyl, preferably C2-C3-alkynyl, e.g. ethynyl. These compounds correspond to compounds of formula 1.1 b.A*.
Figure imgf000022_0003
Exemplary compounds include compounds of formula l .1 b.A(R2-A*+R3-A*= alkynyl), formula l.1 b.A(R3-A*+R4-A*= alkynyl), and formula l .1 b.A(R2-A*+R4-A*= alkynyl). In these generic formulae, R1-1 b represents CH2NRbC(=0)Ra, wherein Ra is H , Ci-C8-alkyl, C2-C8-alkenyl, C2-C8- alkynyl, or C6-Cio-aryl; and Rb is H, Ci-C4-alkyl, Cs-Cs-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C6-Cio-aryl; and wherein preferably Ra is Ci-Cs-alkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, or C6-C10- aryl; and Rb is H, Ci-C4-alkyl, Cs-Cs-cycloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, or C6-Cio-aryl; and wherein particularly preferably Ra is Ci-Cs-alkyl, or C6-Cio-aryl; and Rb is H, Ci-C4-alkyl, Cs-Cs- cycloalkyl, or C6-Cio-aryl. Furthermore, R2-alkynyl, R3-alkynyl, and R4-alkynyl represent a C2-C4- alkynyl group, preferably a C2-C3-alkynyl group, e.g. an ethynyl group, and R2-A*, R3-A*, and R4- A*, respectively, if present, represent a substituent selected from H, Ci-C4-alkyl, and C2-C4- alkynyl, and preferably from H, Ci-C2-alkyl, and C2-C4-alkynyl.
Figure imgf000023_0001
-alkynyl l.1 b.A*(R2-A*+R3-A*= alkynyl) l.1 b.A*(R3-A*+R4-A*= alkynyl) l.1 b.A*(R2-A*+R4-A*= alkynyl)
Figure imgf000023_0002
or a stereoisomer, salt, tautomer or N-oxide thereof,
wherein
R is H , Ci-Cs-alkyl, or CH2N RbC(=0)Ra;
wherein
Ra is H , Ci-Cs-alkyl, or C6-Cio-aryl; and
Rb is H , Ci-C4-alkyl, C3-C8-cycloalkyl, or C6-Cio-aryl;
and wherein R2, R3 and R4 are independently of each other selected from H , Ci-Cs-alkyl, C3-C8 cycloalkyl, C2-Cs-alkynyl and halogen; with the proviso that at least one of R2, R3 and R4 is C2- Cs-alkynyl.
In one preferred embodiment of formula (IV), R1 is Ci-C4-alkyl or CH2NRbC(=0) Ra with Ra being H or Ci-C4-alkyl and Rb being H or CH3. In another preferred embodiment of formula IV, at least two of R2, R3 and R4 are C2-C8-alkynyl. More preferably, at least two of R2, R3 and R4 are C2-C4- alkynyl or C2-C3-alkynyl, in particular ethynyl, and the remaining substituent R2, R3, or R4 is Ci- C4-alkyl or H . In a particularly preferred embodiment of formula IV, R1 is Ci-C4-alkyl or
CH2N RbC(=0)Ra with Ra being H or Ci-C4-alkyl and Rb being H or CH3; and at least two of R2, R3 and R4 are C2-C4-alkynyl or C2-C3-alkynyl, in particular ethynyl; and the remaining substituent R2, R3, or R4 is C C4-alkyl or H .
In another preferred embodiment the nitrification inhibitor is a compound of formula (IV")
Figure imgf000023_0003
or a stereoisomer, salt, tautomer or N-oxide thereof,
wherein
R1 is H , d-Ce-alkyl, or CH2N R C(=0)Ra;
wherein
Ra is Ci-Cs-alkyl, or C6-Cio-aryl; and
Rb is H , CrC4-alkyl, C3-C8-cycloalkyl, or C6-Ci0-aryl;
and wherein R2, R3 and R4 are independently of each other selected from H , Ci-Cs-alkyl, C3-C8- cycloalkyl, C2-Cs-alkynyl and halogen; with the proviso that at least one of R2, R3 and R4 is C2- Cs-alkynyl. In one preferred embodiment of formula IV", R1 is Ci-C4-alkyl or CH2N R C(=0) Ra with Ra being Ci-C4-alkyl and Rb being H or CH3. In another preferred embodiment of formula IV", at least one of R2, R3 and R4 is C2-C8-alkynyl. More preferably, at least one of R2, R3 and R4 is C2-C4-alkynyl or C2-C3-alkynyl, in particular ethynyl, and the remaining substituents R2, R3, or R4 are Ci-C4-alkyl or H. In another preferred embodiment of formula IV", at least two of R2, R3 and R4 are C2-Cs-alkynyl. More preferably, at least two of R2, R3 and R4 are C2-C4-alkynyl or C2- C3-alkynyl, in particular ethynyl, and the remaining substituents R2, R3, or R4 are Ci-C4-alkyl or H. In a particularly preferred embodiment of formula IV", R1 is Ci-C4-alkyl or CH2NRbC(=0)Ra with Ra being Ci-C4-alkyl and Rb being H or CH3; and at least one of R2, R3 and R4 is C2-C4- alkynyl or C2-C3-alkynyl, in particular ethynyl; and the remaining substituents R2, R3, or R4 are Ci-C4-alkyl or H. In another particularly preferred embodiment of formula IV", R1 is Ci-C4-alkyl or CH2NRbC(=0)Ra with Ra being Ci-C4-alkyl and Rb being H or CH3; and at least two of R2, R3 and R4 are C2-C4-alkynyl or C2-C3-alkynyl, in particular ethynyl; and the remaining substituent R2, R3, or R4 is Ci-C4-alkyl or H. In another particularly preferred embodiment the nitrification inhibitor is a compound of formula
Figure imgf000024_0001
or a stereoisomer, salt, tautomer or N-oxide thereof,
wherein
R is CH3;
R2, R3 and R4 are independently of each other selected from H, CH3 and ethynyl;
with the proviso that at least two of R2, R3 and R4 are ethynyl.
The nitrification inhibitor of formula (IV), (IV), (IV") and (IV") are described in WO 2016/097318, which is incorporated herein by reference.
In another preferred form the nitrification inhibitor is the nitrification inhibitor of formula (V)
Figure imgf000024_0002
or a stereoisomer, salt, tautomer or N-oxide thereof as a nitrification inhibitor,
wherein
R1 is C3-C6-alkynyl, with the proviso that if R1 is C3-alkynyl, it is propargyl, or C3-C6-allenyl, wherein the C-atoms of these groups may in each case be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN, ORa, NO2, NRcRd, NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, S(0)mRa, and S(0)mNRcRd;
and wherein R2, R3 and R4 are independently of each other selected from H, halogen, CN, ORa, NO2, NRcRd, NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, S(0)mRa, S(0)mNRcRd;
Ci-Cs-alkyl, Cs-Cs-cycloalkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, wherein the C-atoms of these groups may in each case be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN, ORa, N02, NRcRd, NRb(C=0)Ra, C(=0)Ra,
C(=0)ORa, C(=0)NRcRd, S(0)mRa, and S(0)mNRcRd;
C6-Cio-aryl, and Cs-Cio-hetaryl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, ORa, CrC4-alkyl, d-C4-haloalkyl, C2-C4-alkenyl, and C2-C4-alkynyl;
or R3 and R4 together form a bridge, which forms together with the atoms to which R3 and R4 are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10-membered carbocyclic or heterocyclic ring, wherein the heterocyclic ring may carry 1 , 2, or 3 heteroatoms being selected from O, S, and N, of which S and/or N may optionally be oxidized, and wherein the carbocyclic or heterocyclic ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN,
ORa, N02, NRcRd, NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, 0(C=0)NRcRd, Ci- C4-alkyl, Ci-C4-haloalkyl, C6-Cio-aryl, Cs-Cio-hetaryl, Cs-Cio-carbocyclyl, and C5-C10- heterocyclyl, wherein the C6-Cio-aryl, Cs-Cio-hetaryl, Cs-Cio-carbocyclyl, and C5-C10- heterocyclyl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN, Ci-C4-alkyl, and Ci-C4-haloalkyl; or R2 and R4 together form a bridge, which forms together with the atoms to which R2 and R4 are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10-membered carbocyclic or heterocyclic ring, wherein the heterocyclic ring may carry 1 , 2, or 3 heteroatoms being selected from O, S, and N, of which S and/or N may optionally be oxidized, and wherein the carbocyclic or heterocyclic ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN, ORa, N02, NRcRd, NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, 0(C=0)NRcRd, Ci- C4-alkyl, Ci-C4-haloalkyl, C6-Cio-aryl, Cs-Cio-hetaryl, Cs-Cio-carbocyclyl, and C5-C10- heterocyclyl, wherein the C6-Cio-aryl, Cs-Cio-hetaryl, Cs-Cio-carbocyclyl, and C5-C10- heterocyclyl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN, Ci-C4-alkyl, and Ci-C4-haloalkyl; and wherein
Ra is H, d-Cs-alkyl, C C8-haloalkyl, C2-C8-alkenyl, C2-C8-alkynyl;
Cs-Cio-hetaryl or C6-Cio-aryl, wherein the Cs-Cio-hetaryl or C6-Cio-aryl moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, OH, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, C2-C4- alkenyl, C2-C4-alkynyl, Cs-C6-hetaryl and C6-aryl, wherein said Cs-C6-hetaryl and C6-aryl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 substituents selected from halogen, CN, OH, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, C2-C4-alkenyl, and C2-C4- alkynyl;
Rb is H, Ci-C4-alkyl, Cs-Cs-cycloalkyl, C2-C4-alkenyl, C2-Cs-alkynyl, or C6-Cio-aryl; and Rc and Rd are independently of each other selected from the group consisting of H, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Cs-cycloalkyl, C6-Cio-aryl, and Cs-Cio-hetaryl; or
Rc and Rd together with the N-atom to which they are bonded form a 5- to 6-membered,
saturated or unsaturated heterocycle, which may carry a further heteroatom being selected from O, S, and N as a ring member atom, of which S and/or N may optionally be oxidized, and wherein the heterocyclic ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 substituents, which are independently selected from halogen, CN , OH , NO2, Ci- C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, and Ci-C4-haloalkoxy;
and wherein
m is O, 1 , or 2.
In one preferred embodiment the compound of formula (V) as defined above, R1 is a terminal C3-C4-alkynyl group, preferably propargyl. These compounds correspond to compounds of formula 1.1 a, wherein R1-1 a represents a terminal C3-C4-alkynyl group, preferably propargyl.
Figure imgf000026_0001
Preferably, the compound of formula (V) is a compound of formula 1.1 a, wherein R1-1 a is propargyl.
(1.1 a with R -1 a=propargyl)
In one preferred embodiment of said use, in the compound of formula (V) as defined above, R1 is a terminal C3-C4-allenyl group, preferably C3-allenyl. These compounds correspond to compounds of formula 1.1 b, wherein R1-1 b represents a terminal C3-C4-allenyl group, preferably C3-allenyl.
Figure imgf000026_0003
Preferably, the compound of formula (V) is a compound of compound of formula 1.1 b, wherein R1-1 b is Cs-allenyl.
Figure imgf000026_0004
(1.1 b with R -1 b=C3-allenyl)
In one preferred embodiment of said use, in the compound of formula (V) as defined above, R2, R3 and R4 are independently of each other selected from H , halogen, CN , ORa, NO2, N RcRd, NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)N RcRd, S(0)mRa, S(0)mNRcRd; Ci-C8-alkyl, C3-C8- cycloalkyi, C2-Cs-alkenyl, C2-Cs-alkynyl, wherein the C-atoms of these groups may in each case be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN, ORa, NO2, NRcRd, NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, S(0)mRa, and
S(0)mNRcRd; C6-Cio-aryl, and Cs-Cio-hetaryl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, ORa, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, and C2-C4-alkynyl; wherein Ra, Rb, Rc, and Rd are as defined above.
In a more preferred embodiment of said compound of formula (V), R2, R3 and R4 are
independently of each other selected from H, halogen, ORa, C(=0)ORa, and Ci-C4-alkyl, wherein Ra is H, Ci-Ce-alkyI, or Ci-Ce-haloalkyl. These compounds correspond to compounds of formula I . A, wherein R2-A, R3-A, and R4-A represent the R2, R3, and R4 substituents as defined above.
Figure imgf000027_0001
In one preferred embodiment of said use, in the compound of formula (V), R2 is selected from H, halogen, CN, ORa, N02, NRcRd, NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, S(0)mRa, S(0)mNRcRd; Ci-Ce-alkyI, C3-C8-cycloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, wherein the C-atoms of these groups may in each case be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN, ORa, N02, NRcRd, NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, S(0)mRa, and S(0)mNRcRd; C6-Cio-aryl, and Cs-Cio-hetaryl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, ORa, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, and C2-C4-alkynyl; and R3 and R4 together form a bridge, which forms together with the atoms to which R3 and R4 are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10- membered carbocyclic or heterocyclic ring, wherein the heterocyclic ring may carry 1 , 2, or 3 heteroatoms being selected from O, S, and N, of which S and/or N may optionally be oxidized, and wherein the carbocyclic or heterocyclic ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN, ORa, NO2, NRcRd,
NR (C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, 0(C=0)NRcRd, Ci-C4-alkyl, Ci-C4-haloalkyl, C6-Cio-aryl, Cs-Cio-hetaryl, Cs-Cio-carbocyclyl, and Cs-Cio-heterocyclyl, wherein the C6-Cio-aryl, Cs-Cio-hetaryl, Cs-Cio-carbocyclyl, and Cs-Cio-heterocyclyl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN, Ci- C4-alkyl, and Ci-C4-haloalkyl, wherein Ra, Rb, Rc, and Rd are as defined above. In a more preferred embodiment, R2 is selected from H, halogen, ORa, C(=0)ORa, and Ci-C4-alkyl; and R3 and R4 together form a bridge, which forms together with the atoms to which R3 and R4 are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10-membered carbocyclic ring, wherein the carbocyclic ring may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from =0, halogen, CN, and ORa, wherein Ra is H, C-i-Cs-alkyl, or C-i-Cs- haloalkyl. These compounds correspond to compounds of formula I .B, wherein R2-B represents a R2-substituent as defined above, and R3-B and R4-B together represent a R3-R4-bridge as defined above.
Figure imgf000028_0001
In one preferred embodiment of said use, in the compound of formula (V), R3 is selected from H, halogen, CN, ORa, N02, NRcRd, NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, S(0)mRa, S(0)mNRcRd; Ci-Cs-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C2-C8-alkynyl, wherein the C-atoms of these groups may in each case be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN, ORa, N02, NRcRd, NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, S(0)mRa, and S(0)mNRcRd; C6-Cio-aryl, and Cs-Cio-hetaryl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, ORa, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, and C2-C4-alkynyl; and R2 and R4 together form a bridge, which forms together with the atoms to which R2 and R4 are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10- membered carbocyclic or heterocyclic ring, wherein the heterocyclic ring may carry 1 , 2, or 3 heteroatoms being selected from O, S, and N, of which S and/or N may optionally be oxidized, and wherein the carbocyclic or heterocyclic ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN, ORa, N02, NRcRd,
NRb(C=0)Ra, C(=0)Ra, C(=0)ORa, C(=0)NRcRd, 0(C=0)NRcRd, C C4-alkyl, C C4-haloalkyl, C6-Cio-aryl, Cs-Cio-hetaryl, Cs-Cio-carbocyclyl, and Cs-Cio-heterocyclyl, wherein the C6-Cio-aryl, Cs-Cio-hetaryl, Cs-Cio-carbocyclyl, and Cs-Cio-heterocyclyl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN, Ci- C4-alkyl, and Ci-C4-haloalkyl, wherein Ra, Rb, Rc, and Rd are as defined above. In a more preferred embodiment, R3 is selected from H, halogen, ORa, C(=0)ORa, and Ci-C4-alkyl; and R2 and R4 together form a bridge, which forms together with the atoms to which R2 and R4 are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10-membered carbocyclic ring, wherein the carbocyclic ring may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from =0, halogen, CN, and ORa, wherein Ra is H, Ci-Cs-alkyl, or d-Cs- haloalkyl. These compounds correspond to compounds of formula I.C, wherein R3-C represents a R3-substituent as defined above, and R2-C and R4-C together represent a R2-R4-bridge as defined above.
Figure imgf000028_0002
(I.C)
In one particularly preferred embodiment of said compound of formula (V), R1 is R1-1 a, and R2, R3 and R4 correspond to R2-A, R3-A, and R4-A. These compounds correspond to compounds of formula 1.1 a.A.
Preferred compounds include compounds of formula M a.A with R1-1 a=propargyl. In the compounds of formula M a.A, preferably in the compounds of formula M a.A with
R1-1 a=propargyl, R2-A, R3-A< and R4-A are most preferably independently selected from H , halogen, CN , ORa, C(=0)Ra, C(=0)ORa, C(=0) N RcRd; Ci-C8-alkyl, wherein the C-atoms may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN , and ORa; C6-Cio-aryl, and Cs-C-io-hetaryl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN , ORa, Ci-C4-alkyl, Ci-C4-haloalkyl, and C2-C4-alkynyl; and particularly preferably selected from H , halogen, ORa, C(=0)ORa, and Ci-C4-alkyl, wherein Ra is H , Ci-C8-alkyl, or Ci- Cs-haloalkyl.
In one particularly preferred embodiment of said compound of formula (V), R1 is R1-1 b, and R2, R3 and R4 correspond to R2-A, R3-A, and R4-A. These compounds correspond to compounds of formula 1.1 b.A.
Figure imgf000029_0002
Preferred compounds include compounds of formula 1.1 b.A with R1-1 b=C3-allenyl. In the compounds of formula 1.1 b.A, preferably in the compounds of formula 1.1 b.A with R1-1 b=C3- allenyl, R2-A, R3-A and R4-A are most preferably independently selected from H, halogen, CN , ORa, C(=0)Ra, C(=0)ORa, C(=0) N RcRd; Ci-C8-alkyl, wherein the C-atoms may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN , and ORa; C6-Cio-aryl, and Cs-C-io-hetaryl, wherein the aromatic moieties may in each case be
unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN , ORa, CrC4-alkyl, CrC4-haloalkyl, and C2-C4-alkynyl; and particularly preferably selected from H, halogen, ORa, C(=0)ORa, and Ci-C4-alkyl, wherein Ra is H, Ci-C8-alkyl, or Ci- Cs-haloalkyl.
In one particularly preferred embodiment of said compound of formula (V), R1 is R1-1 a, and R2, R3 and R4 correspond to R2-B, R3-B, and R4-B. These compounds correspond to compounds of formula 1.1 a. B.
Figure imgf000029_0003
Preferred compounds include compounds of formula M a.B with R1-1 a=propargyl. In the compounds of formula M a.B, preferably in the compounds of formula M a.B with R1-1 a=propargyl, R2-B is most preferably selected from H , halogen, CN , ORa, C(=0) Ra, C(=0)ORa, C(=0)N RcRd; d-Cs-alkyl, wherein the C-atoms may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN , and ORa; C6-Cio-aryl, and C5-Cio-hetaryl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN , ORa, C1-C4- alkyl, Ci-C4-haloalkyl, and C2-C4-alkynyl; and R3-B and R4-B most preferably together form a bridge, which forms together with the atoms to which R3-B and R4-B are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10-membered carbocyclic ring, wherein the carbocyclic ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN , ORa, 0(C=0)N RcRd, C5-Cio-hetaryl, and C5-C10- heterocyclyl, wherein the Cs-C-io-hetaryl, and Cs-C-io-heterocyclyl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN , and Ci-C4-haloalkyl; and particularly preferably R2-B is selected from H, halogen, ORa,
C(=0)ORa, and Ci-C4-alkyl; and R3-B and R4-B together form a bridge, which forms together with the atoms to which R3-B and R4-B are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10-membered carbocyclic ring, wherein the carbocyclic ring may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from =0, halogen, CN , and 0Ra; wherein Ra is H, Ci-C8-alkyl, or CrC8-haloalkyl. In one particularly preferred embodiment of said compound of formula (V), R1 is R1-1 b, and R2, R3 and R4 correspond to R2-B, R3-B, and R4-B. These compounds correspond to compounds of formula 1.1 b.B.
Figure imgf000030_0001
Preferred compounds include compounds of formula 1.1 b.B with R1-1 b=C3-allenyl. In the compounds of formula 1.1 b.B, preferably in the compounds of formula 1.1 b.B with R1-1 b=C3- allenyl, R2-B is most preferably selected from H, halogen, CN , ORa, C(=0)Ra, C(=0)ORa, C(=0)N RcRd; d-Ce-alkyl, wherein the C-atoms may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN , and ORa; C6-Cio-aryl, and C5-C10- hetaryl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN , ORa, Ci-C4-alkyl, C1-C4- haloalkyl, and C2-C4-alkynyl; and R3-B and R4-B most preferably together form a bridge, which forms together with the atoms to which R3-B and R4-B are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10-membered carbocyclic ring, wherein the carbocyclic ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN , ORa, 0(C=0) N RcRd, C5-Cio-hetaryl, and C5-Cio-heterocyclyl, wherein the C5-C10- hetaryl, and Cs-Cio-heterocyclyl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN , and Ci-C4-haloalkyl; and particularly preferably R2-B is selected from H, halogen, 0Ra, C(=0)ORa, and Ci-C4-alkyl; and R3-B and R4-B together form a bridge, which forms together with the atoms to which R3-B and R4-B are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10-membered carbocyclic ring, wherein the carbocyclic ring may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from =0, halogen, CN , and ORa; wherein Ra is H , Ci- Cs-alkyl, or Ci-Cs-haloalkyl.
In one particularly preferred embodiment of said compound of formula (V), R1 is R1-1 a, and R2, R3 and R4 correspond to R2-C, R3-C, and R4-C. These compounds correspond to compounds of formula l.l a.C.
Figure imgf000031_0001
(l.l a.C)
Preferred compounds include compounds of formula l.l a.C with R1-1 a=propargyl. In the compounds of formula l.l a.C, preferably in the compounds of formula l.l a.C with
R1-1 a=propargyl, R3-C is most preferably selected from H, halogen, CN , ORa, C(=0)Ra, C(=0)ORa, C(=0)N RcRd; Ci-Cs-alkyl, wherein the C-atoms may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN , and ORa; C6-Cio-aryl, and Cs-C-io-hetaryl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN , ORa, C1-C4- alkyl, Ci-C4-haloalkyl, and C2-C4-alkynyl; and R2-C and R4-C most preferably together form a bridge, which forms together with the atoms to which R2-C and R4-C are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10-membered carbocyclic ring, wherein the carbocyclic ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN , ORa, 0(C=0)N RcRd, C5-Cio-hetaryl, and C5-C10- heterocyclyl, wherein the Cs-C-io-hetaryl, and Cs-C-io-heterocyclyl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN , and Ci-C4-haloalkyl; and particularly preferably R3-C is selected from H, halogen, ORa,
C(=0)ORa, and Ci-C4-alkyl; and R2-C and R4-C together form a bridge, which forms together with the atoms to which R2-C and R4-C are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10-membered carbocyclic ring, wherein the carbocyclic ring may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from =0, halogen, CN , and ORa; wherein Ra is H, Ci-C8-alkyl, or Ci-C8-haloalkyl.
In one particularly preferred embodiment of said compound of formula (V), R1 is R1-1 b, and R2,
R3 and R4 correspond to R2-C, R3-C, and R4-C. These compounds correspond to compounds of formula 1.1 b.C.
Figure imgf000031_0002
(M b.C) Preferred compounds include compounds of formula 1.1 b.C with R1-1 b=C3-allenyl. In the compounds of formula 1.1 b.C, preferably in the compounds of formula 1.1 b.C with R1-1 b=C3- allenyl, R3-C is most preferably selected from H, halogen, CN , ORa, C(=0) Ra, C(=0)ORa, C(=0)N RcRd; Ci-Ce-alkyl, wherein the C-atoms may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from halogen, CN , and ORa; C6-Cio-aryl, and C5-C10- hetaryl, wherein the aromatic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from halogen, CN , ORa, Ci-C4-alkyl, C1-C4- haloalkyl, and C2-C4-alkynyl; and R2-C and R4-C most preferably together form a bridge, which forms together with the atoms to which R2-C and R4-C are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10-membered carbocyclic ring, wherein the carbocyclic ring may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN , ORa, 0(C=0) N RcRd, C5-Cio-hetaryl, and C5-Cio-heterocyclyl, wherein the C5-C10- hetaryl, and Cs-Cio-heterocyclyl moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from =0, halogen, CN , and Ci-C4-haloalkyl; and particularly preferably R3-C is selected from H, halogen, ORa, C(=0)ORa, and Ci-C4-alkyl; and R2-C and R4-C together form a bridge, which forms together with the atoms to which R2-C and R4-C are bonded an annulated partly or fully unsaturated, or aromatic 5 to 10-membered carbocyclic ring, wherein the carbocyclic ring may be unsubstituted or may carry 1 , 2, or 3 identical or different substituents selected from =0, halogen, CN , and 0Ra; wherein Ra is H, Ci- Ce-alkyl, or d-Ce-haloalkyl.
In one particularly preferred embodiment of said compound of formula (V) is a compound of formula l.l a.A as defined above or a compounds of formula 1.1 b. A as defined above.
The nitrification inhibitor of formula (V) are described in WO 2016/124769, which is incorporated herein by reference.
The compounds of formula (I), (II), (III), (IV) or (V) may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention relates to amorphous and crystalline compounds of formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula (I), (II), (III), (IV) or (V) are preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (I), (II), (III), (IV) or (V) has a basic functionality. Agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the mode of action of the compounds of formula (I), (II), (III), (IV) or (V) .
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 Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The nitrification inhibitor has typically a molecular weight of up to 1000 g/mol, preferably up to 500 g/mol, and in particular up to 300 g/mol.
The nitrification inhibitor has typically a melting point below 50 °C, preferably below 35 °C, and in particular below 20 °C. Usually, the nitrification inhibitor is liquid at room temperature. The nitrification inhibitor has typically a vapor pressure of at least 0.01 Pa at 20 °C, more preferably of at least 0.05 Pa at 20 °C, and in particular at least 0.1 Pa at 20 °C.
In a preferred form the nitrification inhibitor has a molecular weight up up to 1000 g/mol and a melting point below 50 °C, preferably a molecular weight up up to 500 g/mol and a melting point below 35 °C.
The composition may further comprise additional ingredients, for example at least one pesticidal compound, at least one additional nitrification inhibitors, at least one urease inhibitor, at least one plant growth regulators, or at least one fertilizer. 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 and/or at least one biopesticide and/or at least one biostimulant. Preferably, the additional ingredient comprises a fertilizer. 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 formula I, further comprise one or more additional nitrification inhibitors.
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 formula I, further comprise one or more urease inhibitors. Examples of envisaged urease inhibitors include N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain), N-(n-propyl) thiophosphoric acid triamide (NPPT), 2-nitrophenyl phosphoric triamide (2-NPT), further NXPTs known to the skilled person, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate, and LIMUS, i.e. a composition comprising about 16.9 wt.-% NBPT and about 5.6 wt.-% NPPT and about 77.5 wt.-% of other ingredients including solvents and adjuvants.
In further embodiments, the composition may, in addition to one, more or all of the above indicated ingredients, in particular in addition to the nitrification inhibitor of the compound of formula I, further comprise one or more plant growth regulators. Examples of envisaged plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releasers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators, and further unclassified plant growth regulators.
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 formula I, further comprise at least one fertilizer.
The term "fertilizers" is to be understood as chemical compounds applied to promote plant and fruit growth. Fertilizers are typically applied either through the soil (for uptake by plant roots), through soil substituents (also for uptake by plant roots), or by foliar feeding (for uptake through leaves). The term also includes mixtures of one or more different types of fertilizers as mentioned below. The term "fertilizers" can be subdivided into several categories including: a) organic fertilizers (composed of decayed plant/animal matter), b) inorganic fertilizers (composed of chemicals and minerals) and c) urea-containing fertilizers.
Organic fertilizers include manure, e.g. liquid manure, semi-liquid manure, biogas manure, stable manure or straw manure, slurry, worm castings, peat, seaweed, compost, sewage, and guano. Green manure crops are also regularly grown to add nutrients (especially nitrogen) to the soil. Manufactured organic fertilizers include compost, blood meal, bone meal and seaweed extracts. Further examples are enzyme digested proteins, fish meal, and feather meal. The decomposing crop residue from prior years is another source of fertility. In addition, naturally occurring minerals such as mine rock phosphate, sulfate of potash and limestone are also considered inorganic fertilizers. Inorganic fertilizers are usually manufactured through chemical processes (such as the Haber process), also using naturally occurring deposits, while chemically altering them (e.g.
concentrated triple superphosphate). Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mine rock phosphate, limestone, and raw potash fertilizers. The inorganic fertilizer may, in a specific embodiment, be a NPK fertilizer. "NPK fertilizers" are inorganic fertilizers formulated in appropriate concentrations and combinations comprising the three main nutrients nitrogen (N), phosphorus (P) and potassium (K) as well as typically S, Mg, Ca and trace elements.
Urea-containing fertilizer may, in specific embodiments, be urea, formaldehyde urea, urea ammonium nitrate (UAN) solution, urea sulfur, stabilized urea, 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.
In a preferred form the fertilizer comprises an ammonium-containing inorganic fertilizer such as an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; an organic fertilizer such as liquid manure, semi- liquid manure, biogas manure, stable manure and straw manure, worm castings, compost, seaweed or guano; or an urea-containing fertilizer such as urea, formaldehyde urea, urea mmonium nitrate (UAN) solution, urea sulphur, stabilized urea, urea based NPK-fertilizers, or urea ammonium sulfate. In particularly preferred embodiments, the fertilizer is an ammonium- containing fertilizer.
Fertilizers may be provided in any suitable form, e.g. as solid coated or uncoated granules, in liquid or semi-liquid form, as sprayable fertilizer, or via fertigation etc.
Coated fertilizers may be provided with a wide range of materials. Coatings may, for example, be applied to granular or prilled nitrogen (N) fertilizer or to multi-nutrient fertilizers. Typically, urea is used as base material for most coated fertilizers. Alternatively, ammonium or NPK fertilizers are used is base material for coated fertilizers. The present invention, however, also envisages the use of other base materials for coated fertilizers, any one of the fertilizer materials defined herein. In certain embodiments, elemental sulfur may be used as fertilizer coating. The coating may be performed by spraying molten S over solid urea granules, followed by an application of sealant wax to close fissures in the coating. In a further embodiment, the S layer may be covered with a layer of organic polymers, preferably a thin layer of organic polymers. Further envisaged coated fertilizers may be provided by reacting resin-based polymers on the surface of the fertilizer granule. A further example of providing coated fertilizers includes the use of low permeability polyethylene polymers in combination with high
permeability coatings. In specific embodiments the composition and/or thickness of the fertilizer coating may be adjusted to control, for example, the nutrient release rate for specific
applications. The duration of nutrient release from specific fertilizers may vary, e.g. from several weeks to many months. The presence of nitrification inhibitors in a mixture with coated fertilizers may accordingly be adapted. It is, in particular, envisaged that the nutrient release involves or is accompanied by the release of an 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 release. In further embodiments, the CRFs may be provided as blended controlled release fertilizer products which may contain coated, uncoated and/or slow release components. In certain embodiments, these coated fertilizers may additionally comprise micronutrients. In specific embodiments these fertilizers may show a pre-defined longevity, e.g. in case of N-P-K fertilizers. Additionally envisaged examples of CRFs include patterned release fertilizers. These fertilizers typically show a pre-defined release patterns (e.g. hi/standard/lo) and a pre-defined longevity. In exemplary embodiments fully coated N-P-K, Mg and micronutrients may be delivered in a patterned release manner. Also envisaged are double coating approaches or coated fertilizers based on a programmed release. In further embodiments the fertilizer mixture may be provided as, or may comprise or contain a slow release fertilizer. The fertilizer may, for example, be released over any suitable period of time, e.g. over a period of 1 to 5 months, preferably up to 3 months. Typical examples of ingredients of slow release fertilizers are IBDU
(isobutylidenediurea), e.g. containing about 31-32 % nitrogen, of which 90% is water insoluble; or UF, i.e. an urea-formaldehyde product which contains about 38 % nitrogen of which about 70 % may be provided as water insoluble nitrogen; or CDU (crotonylidene diurea) containing about 32 % nitrogen; or MU (methylene urea) containing about 38 to 40% nitrogen, of which 25-60 % is typically cold water insoluble nitrogen; or MDU (methylene diurea) containing about 40% nitrogen, of which less than 25 % is cold water insoluble nitrogen; or MO (methylol urea) containing about 30% nitrogen, which may typically be used in solutions; or DMTU
(diimethylene triurea) containing about 40% nitrogen, of which less than 25% is cold water insoluble nitrogen; or TMTU (tri methylene tetraurea), which may be provided as component of UF products; or TMPU (tri methylene pentaurea), which may also be provided as component of UF products; or UT (urea triazone solution) which typically contains about 28 % nitrogen.
The term "fertigation" as used herein refers to the application of fertilizers, optionally soil amendments, and optionally other water-soluble products together with water through an irrigation system to a plant or to the locus where a plant is growing or is intended to grow, or to a soil substituent as defined herein below. For example, liquid fertilizers or dissolved fertilizers may be provided via fertigation directly to a plant or a locus where a plant is growing or is intended to grow. Likewise, nitrification inhibitors according to the present invention, or in combination with additional nitrification inhibitors, may be provided via fertigation to plants or to a locus where a plant is growing or is intended to grow. Fertilizers and nitrification inhibitors according to the present invention, or in combination with additional nitrification inhibitors, may be provided together, e.g. dissolved in the same charge or load of material (typically water) to be irrigated. In further embodiments, fertilizers and nitrification inhibitors may be provided at different points in time. For example, the fertilizer may be fertigated first, followed by the nitrification inhibitor, or preferably, the nitrification inhibitor may be fertigated first, followed by the fertilizer. The time intervals for these activities follow the herein above outlined time intervals for the application of fertilizers and nitrification inhibitors. Also envisaged is a repeated fertigation of fertilizers and nitrification inhibitors according to the present invention, either together or intermittently, e.g. every 2 hours, 6 hours, 12 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days or more.
The present invention further relates to a method for reducing nitrification comprising treating a plant and/or the locus where the plant is growing or is intended to grow with the composition as defined herein.
The term "plant" is to be understood as a plant of economic importance and/or men-grown plant. In certain embodiments, the term may also be understood as plants which have no or no significant economic importance. The plant is preferably selected from agricultural, silvicultural and horticultural (including ornamental) plants. The term also relates to genetically modified plants. The term "plant" as used herein further includes all parts of a plant such as germinating seeds, emerging seedlings, plant propagules, herbaceous vegetation as well as established woody plants including all belowground portions (such as the roots) and aboveground portions.
Within the context of the method for reducing nitrification it is assumed that the plant is growing on soil. In specific embodiments, the plant may also grow differently, e.g. in synthetic laboratory environments or on soil substituents, or be supplemented with nutrients, water etc. by artificial or technical means. In such scenarios, the invention envisages a treatment of the zone or area where the nutrients, water etc. are provided to the plant. Also envisaged is that the plant grows in green houses or similar indoor facilities.
The term "locus" is to be understood as any type of environment, soil, soil substituent, area or material where the plant is growing or intended to grow. Preferably, the locus relates to soil or soil substituent on which a plant is growing. 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 embodiments, also comprise organic elements or portions. Soil substituents may, for example, be used in hydroculture or hydroponic approaches, i.e. wherein plants are grown in soilless medium and/or aquatic based environments. Examples of suitable soil substituents, which may be used in the context of the present invention, are perlite, gravel, biochar, mineral wool, coconut husk, phyllosilicates, i.e. sheet silicate minerals, typically formed by parallel sheets of silicate tetrahedra with S12O5 or a 2:5 ratio, or clay aggregates, in particular expanded clay aggregates with a diameter of about 10 to 40 mm. Particularly preferred is the employment of vermiculite, i.e. a phyllosilicate with 2 tetrahedral sheets for every one octahedral sheet present. The use of soil substituents may, in specific embodiments, be combined with fertigation or irrigation as defined herein.
In one embodiment, the plant to be treated according to the method of the invention is an agricultural plant. "Agricultural plants" are plants of which a part (e.g. seeds) or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibres (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds. Preferred agricultural plants are for example cereals, e.g. wheat, rye, barley, triticale, oats, corn, sorghum or rice, beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, oil-seed rape, canola, linseed, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, canola, sugar cane or oil palm; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants. In a further embodiment, the plant to be treated according to the method of the invention is a horticultural plant. The term
"horticultural plants" are to be understood as plants which are commonly used in horticulture, e.g. the cultivation of ornamentals, vegetables and/or fruits. Examples for ornamentals are turf, geranium, pelargonia, petunia, begonia and fuchsia. Examples for vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas and lettuce and more preferably from tomatoes, onions, peas and lettuce. Examples for fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots and blueberries.
In a further embodiment, the plant to be treated according to the method of the invention is an ornamental plants. "Ornamental plants" are plants which are commonly used in gardening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia. In another embodiment of the present invention, the plant to be treated according to the method of the invention is a silvicultural plants. The term "silvicultural plant" is to be understood as trees, more specifically trees used in reforestation or industrial plantations.
Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening purposes.
Examples for silvicultural plants are conifers, like pines, in particular Pinus spec, fir and spruce, eucalyptus, tropical trees like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec, poplar (cottonwood), in particular Populus spec, beech, in particular Fagus spec, birch, oil palm, and oak.
The term "genetically modified plants" is to be understood as plants, which genetic material has been modified by the use of recombinant DNA techniques in a way that under natural circumstances it cannot readily be obtained by cross breeding, mutations or natural
recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
In specific embodiments, the treatment may be carried out during all suitable growth stages of a plant as defined herein. For example, the treatment may be carried out during the BBCH principle growth stages. The term "BBCH principal growth stage" refers to the extended BBCH- scale which is a system for a uniform coding of phenologically similar growth stages of all mono- and dicotyledonous plant species in which the entire developmental cycle of the plants is subdivided into clearly recognizable and distinguishable longer-lasting developmental phases. In one embodiment the invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing with at least one nitrification inhibitor as defined herein above, e.g. with a nitrification inhibitor being a compound of formula I, or a derivative thereof at a growth stage (GS) between GS 00 and GS 99 BBCH of the plant, or between GS 00 to GS 33 BBCH of the plant, or between GS 00 and GS 55 BBCH, or between GS 00 and GS 47 BBCH, or between 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 of the plant.
In a preferred embodiment the invention relates to a method for reducing nitrification comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing with at least one nitrification inhibitor as defined herein above, e.g. 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 envisaged is the application of more than one fertilizer, e.g. 2, 3, 4, 5, 6, 7, 8, 9, 10 fertilizers, or of different fertilizer classes or categories. In specific embodiments of the invention, at least one nitrification inhibitor as defined herein above, e.g. a nitrification inhibitor being a compound of formula I, or a 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, or between GS 00 and GS 55, or between GS 00 and GS 65 BBCH. According to a preferred embodiment of the present invention the application of said nitrification inhibitor and of said fertilizer as defined herein above is carried out simultaneously or with a time lag. The term "time lag" as used herein means that either the 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 substituents and/or the locus where the plant is growing or is intended to grow. Such time lag may be any suitable period of time which still allows to provide a nitrification inhibiting effect in the context of fertilizer usage. For example, the time lag may be a time period of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 1 1 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 1 1 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods.
Preferably, the time lag is an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks. The time lag preferably refers to situations in which the 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, 1 1 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 1 1 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods before the application of a fertilizer as defined herein above. 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, e.g. 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 growing or is intended to grow is treated at least once with a nitrification inhibitor as defined herein above, e.g. 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 time interval between a first application and second or subsequent application of a nitrification 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.
For a method as described above, or for a use according to the invention, the application rates of nitrification inhibitors, e.g. of the compound of formula I are between 0,01 g and 5 kg of active ingredient per hectare, preferably between 1 g and 1 kg of active ingredient per hectare, especially preferred between 50 g and 300 g of active ingredient per hectare depending on different parameters such as the specific active ingredient applied and the plant species treated. In 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.
For the method according to the invention, the application rates of fertilizers may be between 10 kg and 1000 kg per hectare, preferably between 50 kg and 700 kg per hectare, in certain cases between 50 kg and 400 kg per hectare. The nitrification inhibitor compounds according to the invention, their N-oxides and/or salts etc. may be converted into customary types of compositions, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF).
Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin,
tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof. Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch;
fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.). Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates. Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or
vinylacetate. Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and
benzisothiazolinones. Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers. Examples for composition types are:
i) Water-soluble concentrates (SL, LS) 10 parts by weight of a nitrification inhibitor such as a compound of formula I according to the invention are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves upon dilution with water. In this way, a composition having a content of 10% by weight of active substance is obtained.
ii) Dispersible concentrates (DC) 20 parts by weight of a nitrification inhibitor such as a
compound 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.
iii) Emulsifiable concentrates (EC) 15 parts by weight of a nitrification inhibitor such as a compound of formula I according to the invention are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The composition has an active substance content of 15% by weight.
iv) Emulsions (EW, EO, ES) 25 parts by weight of a nitrification inhibitor such as a compound of formula I according to the invention are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The composition has an active substance content of 25% by weight.
v) Suspensions (SC, 00, FS) In an agitated ball mill, 20 parts by weight of a nitrification inhibitor such as a compound of formula I according to the invention are comminuted with addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. The active substance content in the composition is 20% by weight. vi) Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of a nitrification inhibitor such as a compound of formula I according to the invention are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as water-dispersible or water-soluble granules by means of technical appliances (e.g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. The composition has an active substance content of 50% by weight.
vii) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of a nitrification inhibitor such as a compound of formula 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 dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained. 2. Composition types to be applied undiluted ix) Oustable powders (OP, OS) 5 parts by weight of a nitrification inhibitor such as a compound 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
compound of formula I according to the invention is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5-2% by weight.
xi) ULV solutions (UL) 10 parts by weight of a nitrification inhibitor such as a compound of formula I according to the invention are dissolved in 90 parts by weight of an organic solvent, e.g. xylene. This gives a composition to be applied undiluted having an active substance content of 10% by weight.
The compositions, generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of nitrification inhibitor. The nitrification inhibitor are employed in a purity offrom 90% to 100%, preferably from 95% to 100% (according to NMR spectrum). The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing.
In a further specific embodiment, the present invention relates to a method for treating seed or plant propagation material. The term "seed treatment" as used herein refers to or involves steps towards the control of biotic stresses on or in seed and the improvement of shooting and development of plants from seeds. Seed treatment methods for applying or treating inventive mixtures and compositions thereof, e.g. compositons as defined herein above, and in particular combinations of nitirificaiton inhibitors as defined herein above and secondary effectors such as pesticides, in particular fungicides, insecticides, nematicides and/or biopesticides and/or biostimulants, to plant propagation material, especially seeds, are known in the art, and include dressing, coating, filmcoating, pelleting and soaking application methods of the propagation material. Such methods are also applicable to the combinations or compositions according to the invention. In further embodiments, the treatment of seeds is performed with compositions comprising, besides a nitrification inhibitor according to the present invention, e.g. compositions as defined herein above, a fungicide and an insecticide, or a fungicide and a nematicide, or a fungicide and a biopesticide and/or biostimulant, or an instecticide and a nematicide, or an insecticide and a biopesticide and/or biostimulant, or a nematicide and a biopesticide and/or biostimulant, or a combination of a fungicide, insecticide and nematicide, or a combination of a fungicide, insecticide and biopesticide and/or biostimulant, or a combination of an insecticide, nematicide, and biopesticide etc.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g.
potatoes), which can be used for the multiplication of the plant. This includes seeds, grains, roots, fruits, tubers, bulbs, rhizomes, cuttings, spores, offshoots, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil, meristem tissues, single and multiple plant cells and any other plant tissue from which a complete plant can be obtained.
In a preferred embodiment, the compositon according to the present invention is applied or treated on to the plant propagation material by a method such that the germination is not negatively impacted. Accordingly, examples of suitable methods for applying (or treating) a plant propagation material, such as a seed, is seed dressing, seed coating or seed pelleting and alike. It is preferred that the plant propagation material is a seed, seed piece (i.e. stalk) or seed bulb.
Solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
Preferred examples of seed treatment formulation types or soil application for pre-mix compositions are of WS, LS, ES, FS, WG or CS-type.
The compositions in question give, after two-to-tenfold dilution, active components
concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating compositions or combinations comprising a nitrification inhibitor according to the present invention, e.g. as defined herein above on to plant propagation 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 present invention, e.g. as defined herein above are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
Typically, a pre-mix formulation for seed treatment application comprises 0.5 to 99.9 percent, especially 1 to 95 percent, of the desired ingredients, and 99.5 to 0.1 percent, especially 99 to 5 percent, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 percent, especially 0.5 to 40 percent, based on the pre-mix formulation. Whereas commercial products will preferably be formulated as concentrates (e.g., pre- mix composition (formulation), the end user will normally employ dilute formulations (e.g. tank mix composition).
When employed in plant protection by seed treatment, the amount of compositions or combinations comprising a nitrification inhibitor according to the present invention, e.g. as defined herein above (based on total weight of active components) is in the range from 0.01-10 kg, preferably from 0.1 -1000 g, more preferably from 1 -100 g per 100 kilogram of plant propagation material (preferably seeds).
Methods for applying the compositions as defined herein, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. In a preferred embodiment, the composition is applied on to the plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting. In a preferred embodiment, a suspension-type (FS) composition may be used. Typically, a FS composition may comprise 1-800 g/l of active substance, 1 200 g/l surfactant, 0 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.
Mesoporous silicon dioxide particles and their preparation are known and they are commercially available.
The mesoporous silicon dioxide particles may have a pore size in the range from 1 to 25 nm, preferably from 1 .5 to 15 nm, and in particular from 2 to 10 nm. The pore size may be determined by Barrett-Joyner-Halenda (BJH) analysis. The mesoporous silicon dioxide particles may have have a pore volume in the range from 1 to 25 cm3/g, preferably from 2 to 15 cm3/g, and in particular from 3 to 10 cm3/g. In another form the mesoporous silicon dioxide particles may have a pore volume in the range from 0.5 to 10 cm3/g, preferably from 0.5 to 5 cm3/g, and in particular from 0.8 to 2 cm3/g. The pore volume may be determined by Barrett-Joyner-Halenda (BJH) analysis.
The mesoporous silicon dioxide particles may have an average particle size in the range from 1 to 100 μηη, preferably from 5 to 70 μηη, in particular from 10 to 50 μηη. In another form the mesoporous silicon dioxide particles may have an average particle size in the range from 0.1 to 100 μηη, preferably from 1 to 70 μηη, in particular from 10 to 50 μηη. The average particle size may be determined by laser diffraction. The mesoporous silicon dioxide particles may have a surface area in the range from 500 to 1350 m2/g, preferably from 700 to 1 150 m2/g. The surface area may be determined by BET analysis.
Preferably, the mesoporous silicon dioxide particles are mesostructured with a hexagonal symmetry, such as hexagonally close packed cylindrical pore channels belonging to the p6mm space group. Typical examples of mesoporous silicon dioxide particles with a hexagonal symmetry are MCM-41 , FSM-16, SBA-3 and SBA-15.
The mesoporous silicon dioxide particles are preferably MSM-41 and SBA-15, wherein SBA-15 type is particularly preferred. The preparation of SBA-15 in known from US 6,592,764 B1 .
Beside mesoporous silicon dioxide particles there are chemically modified mesoporous silicon dioxide particles known in the art. For example the free hydroxy groups of the silicon dioxide surface may form chemical bonds with other functional groups in such chemically modified mesoporous silicon dioxide particles. Thus, chemically modified mesoporous silicon dioxide particles have a different chemical structure compared to mesoporous silicon dioxide particles, which can be analyzed by 1 H-NMR or infrared spectroscopy. The term "mesoporous silicon dioxide particles" may be also understood as "mesoporous silicon dioxide particles free of chemical modifications" or "mesoporous silicon dioxide particles with pristine surfaces", respectively.
The chemically modified mesoporous silicon dioxide particles may offer some disadvantages compared to mesoporous silicon dioxide particles, depending on intended application: In case, the interaction of the loaded material with the silica material is enhanced by chemical modification, the release would be much slower, the degree of loading would probably be lower, and additional chemical modification steps are indisputably required.
Typically, the mesoporous silicon dioxide particles are obtainable by contacting a surfactant (e.g. an amphiphilic block copolymer), a water glass solution or suitable silicon alkoxides, such as tetraethylorthosilicate and tetramethylorthosilicate, and an acidifying agent. Usually, the preparation of the mesoporous silicon dioxide particles is free of any chemical modification steps, such chemical reactions of the hydroxy groups of the silicon dioxide. The weight ratio of the mesoporous silicon dioxide particles to the nitrification inhibitor may be in the range from 99:1 to 10:90, preferably 95:5 to 15:85, and in particular from 90:10 to 20:80.
In another form the weight ratio of the mesoporous silicon dioxide particles to the nitrification inhibitor may be in the range from 50:50 to 10:90, preferably 40:60 to 10:90, and in particular from 30:70 to 15:85.
The loading of the mesoporous silicon dioxide particles with the nitrification inhibitor may be at least 2 g, preferably at least 5 g, more preferably at least 7 g, and in particular at least 8 g of the nitrification inhibitor per gram of the mesoporous silicon dioxide particles (e.g. of the SBA-15 type).
In one preferred form the mesoporous silicon dioxide particles (e.g. of the SBA-15 type) have a pore size in the range from 1 to 25 nm and a surface area in the range from 500 to 1350 m2/g, and the nitrification inhibitor (e.g. the compound of formula I) has a molecular weight up up to 1000 g/mol.
In another preferred form the mesoporous silicon dioxide particles (e.g. of the SBA-15 type) have a pore size in the range from 1 .5 to 15 nm and a surface area in the range from 700 to 1350 m2/g, and the nitrification inhibitor (e.g. the compound of formula I) has a molecular weight up up to 1000 g/mol.
In another preferred form the mesoporous silicon dioxide particles (e.g. of the SBA-15 type) have a pore size in the range from 1 .5 to 15 nm and a surface area in the range from 700 to 1350 m2/g, and the nitrification inhibitor (e.g. the compound of formula I) has a molecular weight up up to 500 g/mol.
In another preferred form the mesoporous silicon dioxide particles (e.g. of the SBA-15 type) have a pore size in the range from 2 to 10 nm and a surface area in the range from 700 to 1350 m2/g, and the nitrification inhibitor (e.g. the compound of formula I) has a molecular weight up up to 1000 g/mol.
In another preferred form the mesoporous silicon dioxide particles (e.g. of the SBA-15 type) have a pore size in the range from 2 to 10 nm and a surface area in the range from 500 to 1350 m2/g, and the nitrification inhibitor (e.g. the compound of formula I) has a molecular weight up up to 1000 g/mol.
In another preferred form the mesoporous silicon dioxide particles have a pore size in the range from 2 to 10 nm and a surface area in the range from 700 to 1350 m2/g, and the nitrification inhibitor (e.g. the compound of formula I) has a molecular weight up up to 500 g/mol. The invention further relates to a method for preparing the composition according to the invention by contacting the mesoporous silicon dioxide particles and the nitrification inhibitor. The contacting may be done in a temperature range from 0 to 100 °C, preferably from 5 to 40 °C, and in particular from 10 to 30 °C. For preparing the composition the mesoporous silicon dioxide particles and the nitrification inhibitor may be present in a weight ratio of the
mesoporous silicon dioxide particles to the nitrification inhibitor in the range from 99:1 to 10:90, preferably 95:5 to 15:85, and in particular from 90:10 to 20:80. The contacting may be done by stirring or shaking the components. The present invention offers various advantages: The loss of the nitrification inhibitor by evaporation after treating a plant and/or the locus where the plant is growing or intended to grow is reduced. The amount of nitrification inhibitor which is released to the plant and/or the locus where the plant is growing or intended to grow can be controlled. The loading of the composition with nitrification inhibitor can be controlled easily and thus adapted to the plant or soil. The maximum release of nitrification inhibitor can be controlled and thus adapted to the plant or soil. The application rate of the nitrification inhibitor can be reduced because there is less loss by evaporation of the nitrification inhibitor once it was applied to the locus. There would be no need to a costly additional chemical modification step of the mesoporous silicon dioxide particles.
The following example is provided for illustrative purposes. Example 1 : Prepartion of mesoporous silica
A dry powder of mesoporous silicon dioxide particles was prepared according to literature from an aqueous solution of either sodium silicate, potassium silicate or tetraethoxysilan and
Pluronic® P123 (amphiphilic block copolymer of EO/PO/EO structure, average molecular weight 5750 g/mol, 30 wt% EO), which was acidified and dried to yield SBA-15 type.
The surface area of the mesoporous silicon dioxide particles was 728 m2/g as determined by BET analysis. The pore size of the mesoporous silicon dioxide particles was 6.9 nm as determined by Barrett-Joyner-Halenda (BJH) analysis. The pore volume of the mesoporous silicon dioxide particles was 0.966 cm3/g as determined by Barrett-Joyner-Halenda (BJH) analysis. The average particle size of the mesoporous silicon dioxide particles was 10 to 50 μηη as determined by laser diffraction.
Example 2: Loading of mesoporous silica with nitrification inhibitor
The powder (2.0 g) was mixed with 6.5 g of the liquid nitrification inhibitor 1-chloro-4-((prop-2- yn-1 -yloxy)methyl)benzene (formula I-26 as shown in Table 1 ) at room temperature for 30 min to yield a paste.
Workup A): The powder was filtered and washed with 10 ml of water, and dried at room temperature for 18 hours. The loading of the meoporous silicon dioxide particles was 28.5 wt% as determined by TGA. Workup B): As alternative, the powder was filtered and dried at room temperature for 18 h. The loading of the meoporous silicon dioxide particles was 68.5 wt% as determined by TGA.
Example 3: Release profile
The release profile of a sample from Example 2 from Workup B was determined at 21 °C. The sample was weighted out and the resulting weight loss is summarized in Table 2:
Table 2:
Days Weight loss [%]
Start 0
1 12
2 25
3 37
4 45
7 53

Claims

160377
WO 2017/198693 PCT/EP2017/061807
49
Claims
A composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor. 2. The composition according to claim 1 wherein the mesoporous silicon dioxide particles have an average particle size in the range from 0.1 to 100 μηη, preferably from 10 to 70 μηη.
The composition according to claim 1 or 2 wherein the mesoporous silicon dioxide particles have a pore size in the range from 1 to 25 nm, preferably from 2 to 10 nm.
The composition according to any of claims 1 to 3 wherein the mesoporous silicon dioxide particles have a surface area in the range from 500 to 1350 m2/g, preferably from 700 to 1 150 m2/g. 5. The composition according to any of claims 1 to 4 wherein the mesoporous silicon dioxide particles are of the SBA-15 type.
The composition according to any of claims 1 to 5 wherein the weight ratio of the mesoporous silicon dioxide particles to the nitrification inhibitor is in the range from 90:10 to 20:80.
7. The composition according to any of claims 1 to 6 further comprising a fertilizer. 8. The composition according to claim 7 wherein said fertilizer is an solid or liquid ammonium- containing inorganic fertilizer such as an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; an solid or liquid organic fertilizer such as liquid manure, semi-liquid manure, biogas manure, stable manure and straw manure, worm castings, compost, seaweed or guano, or an urea-containing fertilizer such as urea, formaldehyde urea, urea mmonium nitrate (UAN) solution, urea sulphur, stabilized urea, urea based NPK-fertilizers, or urea ammonium
The composition according to any of claims 1 to 8 wherein the nitrification inhibitor is a compound of formula I
Figure imgf000050_0001
or a stereoisomer, salt, tautomer or N-oxide thereof,
wherein
R1 and R2are independently of each other selected from the group consisting of H, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ci-C4-alkoxy-CrC4-alkyl C1-C6- alkoxy, C2-C6-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; 160377
WO 2017/198693 PCT/EP2017/061807
50
C3-C8-cycloalkyl, Cs-Cs-cycloalkenyl, heterocyclyl, aryl, hetaryl, Cs-Ce-cycloalkyl-d- C6-alkyl, C3-C8-cycloalkenyl-Ci-C6-alkyl, heterocyclyl-CrC6-alkyl, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may in each case be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical 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;
wherein
RA is selected from the group consisting of CN , halogen, NO2, ORb, N RcRd, C(Y)Rb, C(Y)ORb, C(Y)N RcRd, S(Y)mRb, S(Y)mOR ,
Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ci-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 substituents Re;
C3-C8-cycloalkyl, Cs-Cs-cycloalkenyl, heterocyclyl, aryl, hetaryl, C3-Cs-cycloalkyl-Ci- C6-alkyl, C3-C8-cycloalkenyl-Ci-C6-alkyl, heterocyclyl-Ci-C6-alkyl, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1 , 2, 3, 4, or 5 identical or different substituents 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 selected 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-C6-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 independently of each other selected from halogen;
Re is selected from CN , halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, and C1-C4- haloalkoxy;
Y is O or S; and
m is 0, 1 or 2.
10. The composition according to any of claims 1 to 9 wherein the radicals Ra, Rb, Rc, Rd, and Re 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;
Rb is selected from H, Ci-C6-alkyl, phenyl and benzyl;
Rc and Rd are independently of each other selected from the group consisting of H, Ci-C4- alkyl, and Ci-C4-haloalkyl; and
Re is selected from halogen and Ci-C4-alkyl.
The composition according to any of claims 1 to 10 wherein in said compound of formula I, R1 and R2are independently of each other selected from the group consisting of H, C2-C6- alkynyl, C2-C6-alkynyloxy, aryl-Ci-C6-alkyl, and hetaryl-Ci-C6-alkyl,
wherein preferably at least one of R1 and R2 is H.
The composition according to any of claims 1 to 1 1 wherein in said compound of formula I, A is phenyl, wherein said phenyl ring is unsubstituted or carries 1 , 2, or 3 identical or different substituents RA.
The composition according to any of claims 1 to 12 wherein in said compound of formula I, if present,
RA is selected from the group consisting of halogen, NO2, NRcRd, Ci-C6-alkyl, C1-C6- haloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1 or 2 identical or different substituents Ra wherein Ra and Rc and Rd are as defined in claim 9 or 10.
14. The composition according to any of claims 1 to 13 wherein the nitrification inhibitor has a molecular weight up up to 1000 g/mol and a melting point below 50 °C, preferably a molecular weight up up to 500 g/mol and a melting point below 35 °C.
15. A method for preparing the composition as defined in any of claims 1 to 14 by contacting the mesoporous silicon dioxide particles and the nitrification inhibitor.
16. A method for reducing nitrification comprising treating a plant and/or the locus where the plant is growing or is intended to grow with the composition as defined in any of claims 1 to 14. 17. The method of claim 15, wherein the plant and/or the locus where the plant is growing or is intended to grow is additionally provided with a fertilizer.
PCT/EP2017/061807 2016-05-17 2017-05-17 A composition comprising mesoporous silicon dioxide particles and a nitrification inhibitor WO2017198693A1 (en)

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