WO2019174974A1

WO2019174974A1 - Metal-organic-framework zif-8 as nitrification inhibitor

Info

Publication number: WO2019174974A1
Application number: PCT/EP2019/055474
Authority: WO
Inventors: Barbara Nave; Karl-Heinrich Schneider; Ullrich Mueller; Lukasz KARWACKI; Lena Arnold; Andrei-Nicolae PARVULESCU
Original assignee: Basf Se
Priority date: 2018-03-12
Filing date: 2019-03-06
Publication date: 2019-09-19

Abstract

The invention relates to a fertilizer composition comprising a) zeolitic imidazolate framework ZIF-8; and b) a fertilizer selected from liquid or solid ammonium-containing inorganic fertilizers, liquid or solid organic fertilizers, and urea-containing fertilizers. It also relates to a method for producing the fertilizer composition; the use of ZIF-8 as a nitrification inhibitor; and a method for reducing nitrification.

Description

Metal-Organic-Framework ZIF-8 as Nitrification Inhibitor

The invention relates to a fertilizer composition comprising the zeolitic imidazolate framework ZIF-8 and a fertilizer selected from liquid or solid ammonium-containing inorganic fertilizers, liquid or solid organic fertilizers, and urea-containing fertilizers. It also relates to a method for producing the fertilizer composition; the use of ZIF-8 as a nitrification inhibitor; a method for re- ducing nitrification; a method of fertilizing; plant propagation material, preferably seeds, corn- prising the fertilizer composition; a use of the fertilizer composition for fertilizing; a method for treating a fertilizer comprising the step of contacting ZIF-8 with the fertilizer; and a kit-of-parts comprising the fertilizer and ZIF-8. Combinations of embodiments with other embodiments are within the scope of the invention.

Fertilization technology is of growing impact due to the ever-increasing population of the world on the one hand side and the limited agriculturally available area on the other. Nearly 90% of the nitrogen fertilizers applied worldwide are in the NH4⁺-(ammonium)form (Subbarao et al., 2012, Advances in Agronomy, 1 14, 249-302). This is, inter alia, due to the fact that NH₄ ⁺- assimilation is energetically more effective than assimilation of other nitrogen sources, such as of NC>3 -containing fertilizers. Another advantage of NH₄ ⁺ as compared to NO3 is that it has a longer residence time in the soil. This effect is due to higher leaching of NO3 , and to the remov- al of NO3 by microbiological conversion to gaseous nitrogen-containing molecules, such as N2O and N₂. It is thus desirable to maintain the reduced NH₄ ⁺-form in the soil for as long as possible. However, NH₄ ⁺ is converted by soil microorganisms to NC>₃ in a relatively short time in a process known as nitrification. The nitrification is carried out primarily by chemolithographic bacteria, effecting an enzymatic transformation by virtue of ammonia monooxigenase. Nitrification typically leads to nitrogen leakage and environmental pollution. Approximately 50% of the applied ni- trogen fertilizers are lost during the year following fertilizer addition (Nelson et Huber, Nitrifica- tion inhibitors for corn production, 2001 , National Corn Handbook, Iowa State University). As a countermeasure against the loss by nitrification, nitrification inhibitors are commonly used. Typical drawbacks of common nitrification inhibitors are that they are expensive, degrade quick- ly in the soil and/or evaporate, and are toxic to humans or the environment. There is thus the need to find compounds that are capable to reduce nitrification. It is desirable that such corn- pounds be easy to prepare, non-toxic, stable, have a low evaporation or degradation rate, and are biodegradable. It is also desirable that such compounds are made of compounds that can be utilized by plants as micronutrients.

It was thus an object of the present invention to find compounds that can reduce nitrification, and which address the problems of common nitrification inhibitors as outlined above. It has been surprisingly found that the metal-organic-framework ZIF-8 is capable to reduce the nitrifi- cation of NH₃ and/or NH₄ ⁺, even if no additional nitrification inhibitor is present. ZIF-8 is non- toxic, biodegradable to micronutrients, easy and cheap to prepare, does not evaporate or de- grade too quickly, and is chemically and physically stable.

The invention thus relates to a fertilizer composition comprising

a) the zeolitic imidazolate framework ZIF-8; and

b) a fertilizer selected from liquid or solid ammonium-containing inorganic fertilizers, liquid or solid organic fertilizers, and urea-containing fertilizers. The fertilizer may either contain NH₄ ⁺-ions or NH₃, or may be able produce NH₄ ⁺ ions or NH₃ in the soil by decomposition, e.g. hydrolysis. 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 mat- ter), b) inorganic fertilizers (composed of chemicals and minerals) and c) urea-containing ferti- lizers.

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 de- composing crop residue from prior years is another source of fertility. In addition, naturally oc- curring minerals such as mine rock phosphate, sulfate of potash and limestone are also consid- ered 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. concen- trated 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 formulat- ed 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. Other inorganic fertilizers include ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate.

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 de- fined herein above may be added or additionally be present or be used at the same time or in connection with the urea-containing fertilizers. Urea-containing fertilizers are hydrolyzed by mi- croorganisms, thereby releasing ammonia that in turn forms ammonium-ions. Urea-containing fertilizers may thus be considered as a storage form of ammonium.

The fertilizer is selected from solid or liquid ammonium-containing inorganic fertilizers, such as an NPK fertilizers, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; solid or liquid organic fertilizers, such as liquid manure, semi-liquid manure, stable manure, biogas manure and straw manure, worm castings, compost, seaweed or guano, or an urea-containing fertilizer such as urea, formaldehyde urea, urea ammonium nitrate (UAN) solution, urea sulfur, stabilized urea, urea based NPK-fertilizers, urea ammonium sulfate, or a mixture thereof. Preferably, the fertilizer contains NH₄ ⁺-ions; more preferably the fertilizer is selected from solid or liquid ammonium-containing inorganic fertilizers. Fertilizers may be provided in any suitable form, e.g. as powders, solid coated or uncoated granules, in liquid or semi-liquid form, or as sprayable fertilizer. The fertilizer may be applied in the uses and methods of application via fertigation.

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 ferti- lizers are used is base material for coated fertilizers. The present invention, however, also en- visages 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 appli cation 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 con- trol, for example, the nutrient release rate for specific applications. The duration of nutrient re- lease 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 a nitrification inhibitor according to the present invention. Coated fertilizers may be provided as controlled release fertilizers (CRFs). In specific embodiments these controlled release fertilizers are fully coated urea or N-P-K fertilizers, which are homogeneous, and which typically show a pre-defined longevity of 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 micro- nutrients. In specific embodiments these fertilizers may show a pre-defined longevity, e.g. in case of N-P-K fertilizers. Additional envisaged examples of CRFs include patterned release fer- tilizers. 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 approach- es 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) contain- ing 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 wa- ter insoluble nitrogen; or TMTU (tri methylene tetraurea), which may be provided as component of UF products; or TMPU (tri methylene pentaurea), which may also be provided as component of UF products; or UT (urea triazone solution) which typically contains about 28 % nitrogen. The fertilizer mixture may also be long-term nitrogen-bearing fertiliser containing a mixture of acety- lene diurea and at least one other organic nitrogen-bearing fertiliser selected from methylene urea, isobutylidene diurea, crotonylidene diurea, substituted triazones, triuret or mixtures there- of.

The fertilizer composition may comprise the fertilizer at a concentration of from 1 to 99.9 wt%, preferably of from 10 to 99 wt%, more preferably of from 10 to 98 wt%, most preferably of from 20 to 80 wt% based on the total weight of the composition. The fertilizer composition may corn- prise at least 30 wt% of the fertilizer, preferably at least 50 wt%, more preferably at least 90 wt% of the fertilizer based on the total weigh of the fertilizer composition. The fertilizer composition may comprise up to 99.9 wt% of the fertilizer based on the total weight of the fertilizer composi- tion, preferably up to 98 wt%, more preferably up to 95 wt%, most preferably up to 90 wt%.

In case the fertilizer is an ammonium-containing fertilizer, the composition may comprise the ammonium-containing fertilizer in a concentration of at least 80 wt%, preferably at least 90 wt%, more preferably at least 95 wt% based on the the total weight of the composition.

The composition comprises the zeolithic imidazolate framework ZIF-8 belonging to the class of metal-organic frameworks (MOF). MOFs are highly porous crystalline materials comprising metal ions or clusters coordinated by organic ligands, forming one-, two-, or three-dimensional structures. ZIF-8 is commercially available, e.g. under the tradename Basolite^® Z1200, and can be produced as described in Tanaka S. eta/., Chem. Let. 2012, vol. 41 , pp1337-1339, or Shi Q., Angew. Chem. Int. Ed., 2011 , vol. 50, pp 672-675, or WO2013/005160A1 (Examples, p.12- 15). ZIF-8 comprises Zn²⁺-ions, which are coordinated by methyl imidazole ligands. ZIF-8 is characterized by a pore size of approximately 11.6 A and a BET surface area of ca. 1600 m²/g (Tanaka S. et al., Chem. Let. 2012, vol. 41 , pp1337-1339). It has surprisingly been found that ZIF-8 is particularly useful for achieving the objects described above compared to other MOFs or zeolites with comparable characteristics, e.g. similar surface areas or pore sizes. ZIF-8 is solid at 25 °C and may be utilized in the composition, as well as the uses and methods of the invention in the form of a powder, or in the form of granules.

The fertilizer composition may comprise from 1 to 90 wt% of ZIF-8, preferably 1 to 60 wt%, more preferably 1 to 30 wt% based on the total weight of the fertilizer composition. The fertilizer composition usually comprises at least 10 wt% of ZIF-8, more preferably at least 20 wt% based on the total weight of the fertilizer composition. The fertilizer composition may contain up to 80 wt%, preferably up to 70 wt%, more preferably up to 40 wt% of ZIF-8, most preferably up to 10 wt% based on the total weight of the fertilizer composition.

The weight ratio of ZIF-8 to the fertilizer in the fertilizer composition is usually from 10:1 to 1 :100, preferably 1 :1 to 1 :10. The weight ratio of ZIF-8 to the fertilizer in the fertilizer composi- tion may be at up to 1 :2, preferably up to 1 :3, more preferably up to 1 :5. The weight ratio of ZIF- 8 to the fertilizer in the fertilizer composition may be at least 1 :50, preferably at least 1 :20.

The composition may further comprise additional ingredients, for example at least one pesti- cidal compound. For example, the composition may additionally comprise at least one active substance selected from the group of fungicides, insecticides, nematicides, herbicides, safen- ers, micronutrients, biopesticides and/or growth regulators. In one embodiment, the pesticide is an insecticide. In another embodiment, the pesticide is a fungicide. In yet another embodiment the pesticide is a herbicide. The skilled worker is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 16th Ed. (2013), The British Crop Protection Coun- cil, London. Suitable insecticides are insecticides from the class of the carbamates, organo- phosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spi- nosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin corn- pounds nereistoxin analogs, benzoylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymetrozin, flonicamid, clofentezin, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezine, cyromazine, amitraz, hydramethyl- non, acequinocyl, fluacrypyrim, rotenone, or their derivatives. Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydro- carbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothi- adiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic acid dia mides, chloronitriles cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2-amino)- pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic substances, isobenzo- furanones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazoli- dinediones, oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenyla- cetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyri- dines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyr- roloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thia- zolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, tri- phenyltin compounds, triazines, triazoles. Suitable herbicides are herbicides from the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cy- clohexanediones, dinitroanilines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxa- zoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxya- cetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrim- idinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonyla- minocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, tria zines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas.

Suitable plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene modu- lators, ethylene releasers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators, and further unclassified plant growth regulators.

Suitable micronutrients are compounds comprising boron, zinc, iron, copper, manganese, chlorine, and molybdenum.

Usually, the fertilizer composition does not comprise any other nitrification inhibitors, especially no compounds of formula (I), which are known from WO2016/075289,

or a stereoisomer, salt, tautomer or N-oxide thereof, wherein the variables have the following meaning:

R¹, R² independently H;

Ci-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, which groups are unsubstituted or substituted by one or more, same or different R^e; or

Cs-Cs-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, hetaryl-C C₆-alkyl, phenoxy, or benzyloxy, wherein the cyclic moieties are unsubstituted or substi- tuted by one or more, same or different R^a;

A phenyl, which is unsubstituted or substituted with one or more, same or different R^A;

R^A CN, halogen, N0₂, OR^b, NR^cR^d, C(Y)R^b, C(Y)OR^b, C(Y)NR^cR^d, S(Y)_mR^b, S(Y)_mOR^b;

Ci-C₆-alkyl, C₂-C₆-alkenyl, C₂-C₆-alkynyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, C₁-C₆- alkylthio, which groups are unsubstituted or substituted by one or more, same or dif- ferent R^e; or

Cs-Cs-cycloalkyl, Cs-Cs-cycloalkenyl, heterocyclyl, aryl, hetaryl, Cs-Cs-cycloalkyl-C-i- C₆-alkyl, Cs-Cs-cycloalkenyl-Ci-Ce-alkyl, heterocyclyl-Ci-C₆-alkyl, aryl-Ci-C₆-alkyl, hetaryl-Ci-C₆-alkyl, phenoxy, benzyloxy, wherein the cyclic moieties are unsubstitut- ed or substituted by one or more, same or different R^a;

R^a CN, halogen, NO₂, Ci-C₄-alkyl, Ci-C₄-haloalkyl, or Ci-C₄-alkoxy;

or two substituents R^a on adjacent C-atoms form a bridge 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 at- oms, to which the two R^a are bonded to, a 5-membered or 6-membered satu- rated carbocyclic or heteocyclic ring;

R^b H, Ci-C₆-alkyl, C₂-C₄-alkenyl, C₂-C₄-alkynyl, Ci-C₄-haloalkyl, phenyl or benzyl; R^c, R^d are independently of each other H, Ci-C₄-alkyl, or 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, wherein the heterocycle is unsubstituted or substituted with one or more, same or different halogen at- oms;

R^e CN, halogen, Ci-C₄-alkyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy, or Ci-C₄-haloalkoxy;

Y O or S; and

m 0, 1 or 2.

The variables of Compounds of formula (I) may have the following meanings:

R^a may be 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 may be H, Ci-C₆-alkyl, phenyl or benzyl. R^c and R^d may be independently H, Ci-C₄-alkyl, or Ci-C₄-haloalkyl.

R^e may be halogen, or Ci-C₄-alkyl.

R^A may be halogen, NO2, NR^cR^d, Ci-C₆-alkyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, Ci-C₆-alkylthio, phenoxy or benzyloxy, wherein the cyclic moieties may be unsubstituted or substituted with one or more, same or different R^a.

R¹ and R² may be independently H, C2-C6-alkynyl, C2-C6-alkynyloxy, aryl-Ci-C₆-alkyl, or hetar- yl-Ci-C₆-alkyl, wherein preferably at least one of R¹ and R² is H.

A may be phenyl, which is unsubstituted or substituted with 1 ,2, or 3, same or different R^A, preferably substituted with 1 or 2, same or different R^A.

In one embodiment, R¹ is H and R² is C2-C6-alkynyl, C2-C6-alkynyloxy, aryl-Ci-C₆-alkyl, or he- taryl-Ci-C₆-alkyl; preferably C2-C₄-alkynyl, C2-C₄-alkynyloxy, aryl-Ci-C₄-alkyl, or hetaryl-Ci-C₄- alkyl; most preferably hetaryl-Ci-C₄-alkyl; and in particular triazolylmethyl.

These compounds correspond to Compounds of formula (la).

If R² is triazolylmethyl, it is preferred that the triazole moiety is bonded to the methyl group via one of the nitrogen atoms. Furthermore, it is preferred that the triazole moiety is a 1 ,2,4-triazole moiety.

In another preferred embodiment, both R¹ and R² are H. These compounds correspond to Compounds of formula (lb).

In another embodiment, A is phenyl, which is unsubstituted or substituted with one or more, same or different R^A. Such compounds correspond to Compounds of formula (lc), wherein n is 0, 1 , 2, 3, 4, or 5. Usually, the variable n is 1 or 2.

In connection with the compounds defined above, it is to be understood that the substituent(s) R^A may be present at any carbon atom of the phenyl ring.

In one embodiment, the present invention relates to Compounds of formula (I), wherein R¹ is H, A is phenyl, which is unsubstituted or substituted with one or more, same or different R^A, and wherein R² is C2-C6-alkynyl, C2-C6-alkynyloxy, aryl-Ci-C₆-alkyl, or hetaryl-Ci-C₆-alkyl, preferably C2-C₄-alkynyl, C2-C₄-alkynyloxy, aryl-Ci-C₄-alkyl, or hetaryl-Ci-C₄-alkyl, more preferably C3- alkynyloxy or hetaryl-Ci-C₄-alkyl, most preferably hetaryl-Ci-C₄-alkyl, in particular triazolylme- thyl.

In another embodiment, the present invention relates to Compounds of formula (I), wherein R¹ is H, R² is H, A is phenyl, which is unsubstituted or substituted with one or more, same or differ- ent R^A. Such compounds are Compounds of formula (Id).

In one embodiment, n in Compounds of formula (Id) is 0. In another embodiment, n in Corn- pounds of formula (Id) is 1. In another embodiment, n in Compounds of formula (Id) is 2. Typi- cally, R^A in formula (Id) is Cl in para position, and n is 1.

In connection with the compounds defined above, it is to be understood that the substituent(s) R^A may be present at any carbon atom of the phenyl ring. In certain preferred embodiments of the invention, it is preferred that at least one substituent R^A is present in para position with re- spect to the propargylether group.

In one embodiment, R^A is halogen, NO₂, NR^cR^d, Ci-C₆-alkyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, C₁- C₆-alkylthio, phenoxy, or benzyloxy, wherein the cyclic moieties are unsubstituted or substituted with one or more, same or different R^a; wherein

R^a is halogen, Ci-C₂-alkyl, Ci-C₂-alkoxy, or two substituents R^a on adjacent C-atoms are a OCH₂CH₂O bridge or a 0(CH₂)0 bridge; and

R^c and R^d are independently of each other H, Ci-C₄-alkyl, or Ci-C₄-haloalkyl.

In another embodiment, R^A is halogen, NO₂, Ci-C₆-alkyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, or phe- noxy, wherein the phenoxy group is unsubstituted or substituted with one or more, same or dif- ferent halogen atoms.

In another embodiment, R^A is halogen, NO₂, Ci-C₂-alkyl, Ci-C₂-haloalkyl, Ci-C₂-alkoxy, or phenoxy, wherein the phenoxy group may be unsubstituted or substituted with one or more, same or different halogen atoms.

In another embodiment, R^A is F, Cl, Br, NO₂, CH₃, CF₃, methoxy, or phenoxy, wherein the phenoxy group is unsubstituted or substituted with one or more, same or different halogen at- oms selected from F, Cl, and Br.

In another embodiment, in particular in case of Compounds of formula (Id) as defined above, R^A is halogen, Ci-C₄-alkyl, and Ci-C₄-alkoxy. In another embodiment, in particular in case of Compounds of formula (Id) as defined above, R^A is F, Cl, Br, I, CH₃, methoxy, ethoxy, and n- propoxy, wherein preferably at least one of these groups is present in para position with respect to the propargylether group.

In one embodiment, the variables of Compounds of formula (I) are defined as follows:

R¹, R² independently H; or

C₂-C₆-alkynyl, C₂-C₆-alkynyloxy, aryl-Ci-C₆-alkyl, or hetaryl-Ci-C₆-alkyl, provided at least one of R¹ and R² is H;

R^A CN, halogen, N0₂, C(Y)OR^b, C(Y)NR^cR^d, NR^cR^d, Ci-C₆-alkyl, Ci-C₆-haloalkyl, Ci-C₆- alkoxy, C₂-C₆-alkynyloxy, Ci-C₆-alkylthio; or

phenoxy, benzyloxy, wherein the cyclic moieties are unsubstituted or substituted with one or more, same or different R^a; R^a halogen, Ci-C₂-alkyl, Ci-C₂-alkoxy, or two substituents R^a on adjacent C- atoms are a OCH₂CH₂O bridge, or a 0(CH₂)0 bridge;

R^b H or Ci-C₄-alkyl;

R^c, R^d are independently H, Ci-C₄-alkyl, or Ci-C₄-haloalkyl.

In another embodiment, the variables of Compounds of formula (I) are defined as follows:

R¹, R² independently H; or

C₂-C₆-alkynyl, C₂-C₆-alkynyloxy, aryl-Ci-C6-alkyl, or hetaryl-Ci-C6-alkyl, provided at least one of R¹ and R² is H;

R^A halogen, NO₂, NR^cR^d, Ci-C₆-alkyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, Ci-C₆-alkylthio; or phenoxy, benzyloxy, wherein the cyclic moieties are unsubstituted or substituted with one or more, same or different R^a;

R^a halogen, Ci-C₂-alkyl, Ci-C₂-alkoxy, or two substituents R^a on adjacent C- atoms are a OCH₂CH₂O bridge, or a 0(CH₂)0 bridge;

R^c, R^d are independently H, Ci-C₄-alkyl, or Ci-C₄-haloalkyl.

R¹ H;

R² C₂-C₆-alkynyl, C₂-C₆-alkynyloxy, aryl-Ci-C₆-alkyl, or hetaryl-Ci-C₆-alkyl; preferably C₂-C₄- alkynyl, C₂-C₄-alkynyloxy, aryl-Ci-C₄-alkyl, or hetaryl-Ci-C₄-alkyl; more preferably C₃- alkynyloxy or hetaryl-Ci-C₄-alkyl; most preferably hetaryl-Ci-C₄-alkyl; in particular triazol- ylmethyl;

R^A halogen, NO₂, Ci-C₆-alkyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy; or

phenoxy, which is unsubstituted or substituted with one or more, same or different halogen atoms.

R¹ H;

R^A F, Cl, Br, NO₂, CH₃, CF₃, CH₃O, phenoxy, which is unsubstituted or substituted by one or more, same or different halogen atoms selected from F, Cl, and Br.

In one embodiment, the variables of Compounds of formula (Id) are defined as follows:

R^A CN, halogen, N0₂, C(Y)OR^b, C(Y)NR^cR^d, Ci-C₆-alkyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, C₂- C₆-alkynyloxy, or phenoxy, which is unsubstituted or substituted with one or more, same or different R^a;

R^a halogen, Ci-C₂-alkyl, or Ci-C₂-alkoxy;

R^b H, or Ci-C₄-alkyl;

R^c, R^d are independently H, or Ci-C₄-alkyl. In another embodiment, the Compounds of formula (I) relate to Compounds of formula (Id) and R^A is halogen, NO2, Ci-C₆-alkyl, Ci-C₆-haloalkyl, Ci-C₆-alkoxy, or phenoxy, which is unsubsti- tuted or substituted with one or more, same or different halogen atoms.

In another embodiment, the Compounds of formula (I) relate to Compounds of formula (Id) and R^A is halogen, NO2, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C2-alkoxy, or phenoxy, which is unsubsti- tuted or substituted with one or more, same or different halogen atoms.

In another embodiment, the Compounds of formula (I) relate to Compounds of formula (Id) and R^A is F, Cl, Br, NO2, CH₃, CF₃, CH₃O, or phenoxy, which is unsubstituted or substituted with one or more, same or different halogen atoms selected from F, Cl, and Br.

In another embodiment, the Compounds of formula (I) relate to Compounds of formula (Id) and R^A is F, Cl, Br, NO2, CH₃, CF₃, CH₃O, CH₃CH2O, or CH₃CH2CH2O, wherein preferably at least one of these groups is present in para position with respect to the propargylether group.

Particularly preferred Compounds of formula (I) are compiled in Table A below Table A.

The compounds of Table A may be subdivided into Compounds of formula (la), i.e. corn- pounds 1-6, 1-7, 1-11, 1-12, 1-13, 1-17, 1-18, 1-20, 1-21, 1-22, and Compounds of formula (lb),

1.e. compounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-8, 1-9, 1-10, 1-14, 1-15, 1-16, 1-19, 1-23, 1-24, 1-25, 1- 26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-32, 1-33.

In one embodiment of the invention, the Compounds of formula (I) are Compounds of formula (la), which are selected from compounds 1-6, 1-7, 1-11, 1-12, 1-13, 1-17, 1-18, 1-20, 1-21, and 1-22, or which are structurally different from these compounds, but are characterized in that R^A, if present, is selected from the group consisting of F, Cl, Br, NO2, CH₃, CF₃, methoxy, and phe- noxy, wherein the phenoxy group is unsubstituted or substituted with 1 or 2, same or different halogen atoms selected from F, Cl, and Br.

In one embodiment, the Compounds of formula (I) are compounds 1-6, 1-7, 1-11, 1-12, 1-13, 1-17, 1-18, 1-20, 1-21, or 1-22. In another embodiment, the Compounds of formula (I) are corn- pounds 1-1, 1-2, 1-3, 1-4, 1-5, 1-8, 1-9, 1-10, 1-14, 1-151-16, or 1-19, or which are structurally different from these compounds, but are characterized in that R^A, if present, is selected from F, Cl, Br, NO2, CH₃, CF₃, CH₃O, and phenoxy, wherein the phenoxy group is unsubstituted or sub- stituted with 1 or 2, same or different halogen atoms selected from F, Cl, and Br.

In another embodiment of the invention, the Compounds of formula (I) are compounds 1-1, 1-

2, 1-3, 1-4, 1-5, 1-8, 1-9, 1-10, 1-14, 1-151-16, 1-19, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1- 30, 1-31, 1-32, or 1-33, or which are structurally different from these compounds, but are char- acterized in that R^A, if present, is selected from halogen, Ci-C₄-alkyl, and Ci-C4-alkoxy, and preferably from F, Cl, Br, I, CH₃, CH₃0, CH3CH2O, and CH₃CH₂CH₂0.

In a preferred embodiment of the invention, Compounds of formula (I) are compounds 1-1, 1- 2, 1-3, 1-4, 1-5, 1-8, 1-9, 1-10, 1-14, 1-15, 1-16, 1-19, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-32, or 1-33. In another embodiment, Compounds of formula (I) are compounds 1- 2, 1-5, 1-8, 1-14, 1-15, 1-21, 1-23, 1-24, 1-25, 1-26, 1-27, 1-28, 1-29, 1-30, 1-31, 1-32, or 1-33, preferably compounds 1-8, 1-14, 1-15, 1-25, 1-26, 1-27, 1-28, 1-29, or 1-32.

In one embodiment Compound of formula (I) is the compound of formula 1-1 as defined in Ta ble A above. In one embodiment Compound of formula (I) is the compound of formula 1-2 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of for- mula 1-3 as defined in Table A above. In one embodiment Compound of formula (I) is the corn- pound of formula 1-4 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-5 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-6 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-7 as defined in Table A above.

In one embodiment Compound of formula (I) is the compound of formula 1-8 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-9 as de- fined in Table A above. In one embodiment Compound of formula (I) is the compound of formu- la 1-10 as defined in Table A above. In one embodiment Compound of formula (I) is the corn- pound of formula 1-11 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-12 as defined in Table A above. In one embodiment Corn- pound of formula (I) is the compound of formula 1-13 as defined in Table A above. In one em- bodiment Compound of formula (I) is the compound of formula 1-14 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-15 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-16 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-17 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-18 as defined in Table A above. In one embodiment Compound of for- mula (I) is the compound of formula 1-19 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-20 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-21 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-22 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-23 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-24 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-25 as defined in Table A above. In one embodiment Compound of for- mula (I) is the compound of formula 1-26 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-27 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-28 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-29 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-30 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-31 as defined in Table A above. In one embodiment Compound of formula (I) is the compound of formula 1-32 as defined in Table A above. In one embodiment Compound of for- mula (I) is the compound of formula 1-33 as defined in Table A above.

The term“Compounds of formula (I)”,“Compounds of formula (la)”,“Compounds of formula (lb)”,“Compounds of formula (lc)”, or“Compounds of formula (Id)” comprises the compound(s) as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof, preferably the compound(s) as defined herein as well as a stereoisomer, salt, or N-oxide thereof, more prefer- ably the compound(s) as defined herein as well as a stereoisomer or salt thereof.

It is of course to be understood that tautomers can only be present, if a substituent is present at the respective compounds, which covers tautomers such as keto-enol tautomers, imine- enamine tautomers, amide-imidic acid tautomers or the like. Furthermore, it is to be understood that stereoisomers are only possible, if there is at least one centre of chirality in the molecule or if geometrical isomers (cis/trans isomers) can be formed.

Compounds of formula (I) may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention relates to compositions comprising amorphous and crystalline Compounds of formula (I), mixtures of different crystalline states of the respective compound of formula (I), as well as amorphous or crystalline salts thereof. Usually, Compounds of formula (I) utilized for the composition, the uses and methods of application, and the methods of production, are usually liquids. In case they are solids, they are usually applied in the form of a solution in water or an organic solvent, e.g. CH₃OH.

Salts of Compounds of formula (I) are preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in ques- tion if Compounds of formula (I) have a basic functionality. Agriculturally useful salts of Corn- pounds 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 Compounds of formu- la (I). Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensul- fate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, car- bonate, 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 term "N-oxide" includes Compounds of formula (I) which have at least one tertiary nitro- gen atom that is oxidized to an N-oxide moiety. Of course, N-oxides can only be formed, if a nitrogen atom is present within Compounds of formula (I).

The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix C_n- C_m indicates in each case the possible number of carbon atoms in the group. The term "halo- gen" denotes in each case fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), in particular fluo- rine, chlorine or bromine. The term "alkyl" as used herein and in the alkyl moieties of alkylamino, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms. Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso- butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 , 1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2- dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 ,1 ,2- trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl, and 1-ethyl-2-methylpropyl. The term "haloalkyl" as used herein and in the haloalkyl moieties of haloalkylcarbonyl, haloal- koxycarbonyl, haloalkylthio, haloalkylsulfonyl, haloalkylsulfinyl, haloalkoxy and haloalkoxyalkyl, denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 car- bon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are selected from Ci-C4-haloalkyl, more preferably from Ci-C3-haloalkyl or Ci-C2-haloalkyl, in particular from Ci-C2-fluoroalkyl such as fluoromethyl, difluoromethyl, trifluo- romethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like. The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group which is bonded via an oxygen atom and has usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, e.g. 1 or 2 carbon atoms. Examples of an alkoxy group are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2- butyloxy, iso-butyloxy, tert.-butyloxy, and the like. The term "alkoxyalkyl" as used herein refers to alkyl usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 4, preferably 1 or 2 carbon atoms as defined above. Examples are CH2OCH3, CH2-OC2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethyl. The term "alkylthio "(alkylsulfanyl: alkyl-S-)" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylthio), more preferably 1 to 3 carbon atoms, which is attached via a sulfur atom. The term "haloalkylthio" as used herein refers to an alkylthio group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. The term "alkenyl" as used herein denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. vinyl, allyl (2- propen-1-yl), 1 -propen-1 -yl, 2-propen-2-yl, methallyl (2-methyl prop-2-en-1-yl), 2-buten-1-yl, 3- buten-1-yl, 2-penten-1-yl, 3-penten-1-yl, 4-penten-1-yl, 1-methylbut-2-en-1-yl, 2-ethylprop-2-en- 1 -yl and the like. The term“alkenyloxy” as used herein denotes in each case an alkenyl group as defined above, which is bonded via an oxygen atom and has usually from 2 to 10, preferably from 2 to 6 or from 2 to 4 carbon atoms. The term "alkynyl" as used herein denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. ethynyl, propargyl (2-propyn-1-yl), 1-propyn-1-yl, 1-methylprop-2-yn-1- yl), 2-butyn-1-yl, 3-butyn-1-yl, 1-pentyn-1-yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 1-methylbut-2-yn-1-yl, 1-ethylprop-2-yn-1-yl and the like. The term "alkynyloxy" as used herein denotes in each case an alkenyl group as defined above, which is bonded via an oxygen atom and has usually from 2 to 10, preferably from 2 to 6 or from 2 to 4 carbon atoms. The term "cycloalkylalkyl" refers to a cycloalkyl group as defined above which is bonded via an alkyl group, such as a Ci-C₆-alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= cycloalkylmethyl), to the remainder of the molecule. The term "cycloalkyl" as used herein and in the cycloalkyl moieties of cycloal- koxy and cycloalkylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 or from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclo- hexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "cycloalkenyl" as used herein and in the cycloalkenyl moieties of cy- cloalkenyloxy and cycloalkenylthio denotes in each case a monocyclic singly unsaturated non- aromatic radical having usually from 3 to 10, e.g. 3, or 4 or from 5 to 10 carbon atoms, prefera- bly from 3- to 8 carbon atoms. Exemplary cycloalkenyl groups include cyclopropenyl, cyclohep- tenyl or cyclooctenyl. The term "cycloalkenylalkyl" refers to a cycloalkenyl group as defined above which is bonded via an alkyl group, such as a Ci-C₆-alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= cycloalkenylmethyl), to the remainder of the molecule. The term “carbocycle” or“carbocyclyl” includes in general a 3- to 12-membered, preferably a 3- to 8- membered or a 5- to 8-membered, more preferably a 5- or 6-membered mono-cyclic, non- aromatic ring comprising 3 to 12, preferably 3 to 8 or 5 to 8, more preferably 5 or 6 carbon at- oms. Preferably, the term“carbocycle” covers cycloalkyl and cycloalkenyl groups as defined above. The term“heterocycle” or "heterocyclyl" includes in general 3- to 12-membered, prefera- bly 3- to 8-membered or 5- to 8-membered, more preferably 5- or 6-membered, in particular 6- membered monocyclic heterocyclic non-aromatic radicals. The heterocyclic non-aromatic radi cals usually comprise 1 , 2, 3, 4, or 5, preferably 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO2. Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S-oxothietanyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihy- drofuranyl, 1 ,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S- oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl, oxathiolanyl, piper- idinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1 ,3- and 1 ,4-dioxanyl, thiopyranyl, S.oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxodihydrothiopyranyl, S- dioxodihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetrahydrothiopyranyl, S- dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl, S- dioxothiomorpholinyl, thiazinyl and the like. Examples for heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazoli- din-2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl and the like. The term“aryl” includes mono-, bi- or tricyclic aromatic radicals having usually from 6 to 14, preferably 6, 10, or 14 carbon atoms. Exemplary aryl groups include phenyl, naphthyl and anthracenyl. Phenyl is preferred as aryl group. The term "hetaryl" includes monocyclic 5- or 6-membered heteroaromatic radicals corn- prising as ring members 1 , 2, 3, or 4 heteroatoms selected from N, O and S. Examples of 5- or 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, or 4-pyridyl, pyrimidinyl, i.e.

2-, 4-, or 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2- or 3-thienyl, furyl, i.e. 2-or 3-furyl, pyrrolyl, i.e. 2- or 3-pyrrolyl, oxazolyl, i.e. 2-, 3-, or 5-oxazolyl, isoxazolyl, i.e. 3-, 4-, or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiazolyl, i.e. 3-, 4-, or

5-isothiazolyl, pyrazolyl, i.e. 1-, 3-, 4-, or 5-pyrazolyl, i.e. 1-, 2-, 4-, or 5-imidazolyl, oxadiazolyl, e.g. 2- or 5-[1 ,3,4]oxadiazolyl, 4- or 5-(1 ,2,3-oxadiazol)yl, 3- or 5-(1 ,2,4-oxadiazol)yl, 2- or 5-(1 ,3,4-thiadiazol)yl, thiadiazolyl, e.g. 2- or 5-(1 ,3,4-thiadiazol)yl, 4- or 5-(1 ,2,3-thiadiazol)yl, 3- or 5-(1 ,2,4-thiadiazol)yl, triazolyl, e.g. 1 H-, 2H- or 3H-1 ,2,3-triazol-4-yl, 2 H-triazol-3-yl , 1 H-, 2H-, or 4H-1 ,2,4-triazolyl and tetrazolyl, i.e. 1 H- or 2H-tetrazolyl. The term "hetaryl" also includes bicyclic 8 to 10-membered heteroaromatic radicals comprising as ring members 1 , 2 or 3 het- eroatoms selected from N, O and S, wherein a 5- or 6-membered heteroaromatic ring is fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical. Examples of a 5- or 6- membered heteroaromatic ring fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl, isochinolinyl, purinyl, 1 ,8- naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl or pyridoimidazolyl and the like. These fused hetar- yl radicals may be bonded to the remainder of the molecule via any ring atom of 5- or 6- membered heteroaromatic ring or via a carbon atom of the fused phenyl moiety. The terms “’’benzyloxy” and“phenoxy” refer to a benzyl and a phenyl group, respectively, which are bond- ed via an oxygen atom to the remainder of the molecule. The terms "heterocyclylalkyl" and "he- tarylalkyl" refer to heterocyclyl or hetaryl, respectively, as defined above which are bonded via a Ci-C₆-alkyl group or a Ci-C₄-alkyl group, in particular a methyl group (= heterocyclylmethyl or hetaryl methyl, respectively), to the remainder of the molecule. The term“arylalkyl” refers to aryl as defined above, which is bonded via Ci-C₆-alkyl group or a Ci-C₄-alkyl group, in particular a methyl group (= arylmethyl or phenylmethyl), to the remainder of the molecule, examples includ- ing benzyl, 1-phenylethyl, 2-phenylethyl, etc. The term“cyclic moiety” can refer to any cyclic groups, which are present in the compounds of the present invention, and which are defined above, e.g. cycloalkyl, cycloalkenyl, carbocycle, heterocycloalkyl, heterocycloalkenyl, heterocy- cle, aryl, hetaryl and the like.

In another embodiment, the fertilizer composition comprises an additional nitrification inhibitor. In another embodiment, the fertilizer composition comprises an additional nitrification inhibitor, but no Compound of formula (I). In another embodiment, the fertilizer composition comprises a Compound of formula (I).

Examples of envisaged additional nitrification inhibitors are linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 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, N-(3(5),4-dimethyl-pyrazole-1 -ylmethyl)- formamide, neem, products based on ingredients of neem, cyan amide, melamine, zeolite pow- der, catechol, benzoquinone, sodium terta board, zinc sulfate, and Compounds of formula (I), as defined above.

Suitable nitrification inhibitors also include

a) 2-(3,4-dimethyl-1 H-pyrazol-1-yl)succinic acid (referred to as“DMPSA1” in the following) and/or 2-(4,5-dimethyl-1 H-pyrazol-1-yl)succinic acid (referred to as“DMPSA2” in the follow- ing), and/or a derivative thereof, and/or a salt thereof;

b) glycolic acid addition salt of 3,4-dimethyl pyrazole (3,4-dimethyl pyrazolium glycolate, re- ferred to as“DMPG” in the following), and/or an isomer thereof, and/or a derivative thereof; c) citric acid addition salt of 3,4-dimethyl pyrazole (3,4-dimethyl pyrazolium citrate, referred to as“DMPC” in the following), and/or an isomer thereof, and/or a derivative thereof;

d) lactic acid addition salt of 3,4-dimethyl pyrazole (3,4-dimethyl pyrazolium lactate, referred to as“DMPL” in the following), and/or an isomer thereof, and/or a derivative thereof;

e) mandelic acid addition salt of 3,4-dimethyl pyrazole (3,4-dimethyl pyrazolium mandelate, referred to as“DMPM” in the following), and/or an isomer thereof, and/or a derivative there- of;

f) 1 ,2,4-triazole (referred to as„TZ“ in the following), and/or a derivative thereof, and/or a salt thereof;

g) 4-Chloro-3-methylpyrazole (referred to as„CIMP” in the following), and/or an isomer there- of, and/or a derivative thereof, and/or a salt thereof; h) a reaction adduct of dicyandiamide, urea and formaldehyde, or a triazonyl-formaldehyde- dicyandiamide adduct;

i) 2-cyano-1 -((4-oxo-1 ,3,5-triazinan-1 -yl)methyl)guanidine,

j) 1 -((2-cyanoguanidino)methyl)urea;

k) 2-cyano-1 -((2-cyanoguanidino)methyl)guanidine;

L) 3,4-dimethyl pyrazole phosphate;

m) allylthiourea, and

n) chlorate salts.

The weight ratio of the additional nitrification inhibitor to ZIF-8 in the fertilizer composition is usually 10:1 to 1 :100, preferably 2:1 to 1 :50, more preferably 1 :3 to 1 :50, and in particular 1 :3 to 1 :10. The weight ratio of the additional nitrification inhibitor to ZIF-8 may be at least 1 :30, pref- erably at least 1 :20. The weight ratio of the additional nitrification inhibitor to ZIF-8 may be up to 5:1 , preferably up to 1 :3, more preferably up to 1 :4.

The fertilizer composition may comprise from 1 to 90 wt% of the additional nitrification inhibitor, preferably 1 to 60 wt%, more preferably 1 to 30 wt% with regard to the total weight of the ferti- lizer composition. The fertilizer composition usually comprises at least 0.5 wt% of the additional nitrification inhibitor, more preferably at least 1 wt%, most preferably at least 2 wt%, especially preferably at least 10 wt%, and particularly preferably at least 20 wt% with regard to the total weight of the fertilizer composition. The fertilizer composition may contain up to 80 wt%, prefer- ably up to 70 wt%, more preferably up to 40 wt%, most preferably up to 10 wt% of the additional nitrification inhibitor with regard to the total weight of the fertilizer composition.

The fertilizer composition may 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, ammoni- um thiosulfate, and mixtures of NBPT and NPPT (see e.g. US 8,075,659). Such mixtures of NBPT and NPPT may comprise NBPT in amounts of from 40 to 95% wt.-% and preferably of 60 to 80% wt.-% based on the total amount of active substances. Such mixtures are marketed as LIMUS, which is a composition comprising about 16.9 wt.-% NBPT and about 5.6 wt.-% NPPT and about 77.5 wt.-% of other ingredients including solvents and adjuvants.

The compositions may comprise auxiliaries. Suitable auxiliaries are solvents, carriers (e.g. liq uid carriers, and solid carriers) or fillers, surfactants, dispersants, emulsifiers, wetters, adju- vants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, hu- mectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders. Suitable solvents and liquid carri- ers 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 hydro- carbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclo- hexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mix- tures 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; polysaccharides, 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. Suita- ble surfactants are surface-active compounds, such as anionic, cationic, nonionic and ampho- teric 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 con- densed 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 sur- factants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based sur- factants, 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 vi- nylacetate. 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 poly- mers 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 polypro- pylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl- amines or polyethyleneamines. Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound of formula (I) on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Re- ports DS256, T&F Informa UK, 2006, chapter 5. Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone deriva- tives 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 polyvinylpyrrolidons, polyvi- nylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

The fertilizer composition can be converted into customary types of agrochemical composi- tions, e. g. solutions, suspensions, dusts, powders, pastes, granules, pressings, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), 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), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further corn- positions types are defined in the“Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6^th Ed. May 2008, CropLife International.

Preferably, the fertilizer composition is in the form of a suspension, dust, powder, paste, gran- ule, pressing, or mixtures thereof. Preferably, the fertilizer composition is in the form of a pow- der or a granule.

Examples for composition types and their preparation are:

i) Water-soluble concentrates (SL, LS)

10-60 wt% of the fertilizer composition and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) ad 100 wt%. The active substance dissolves upon dilution with water.

ii) Dispersible concentrates (DC)

5-25 wt% of the fertilizer composition and 1 -10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in organic solvent (e.g. cyclohexanone) ad 100 wt%. Dilution with water gives a dis persion.

iii) Suspensions (SC, OD, FS)

In an agitated ball mill, 20-60 wt% of the fertilizer composition is comminuted with addition of 2- 10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1 - 2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a suspension. Dilution with water gives a stable suspension of the fertilizer composition. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added.

iv) Water-dispersible granules and water-soluble granules (WG, SG)

50-80 wt% of the fertilizer composition is ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt%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 fertilizer composition.

v) Water-dispersible powders and water-soluble powders (WP, SP, WS)

50-80 wt% of the fertilizer composition is ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and solid carrier (e.g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the fertilizer composition.

vi) Gel (GW, GF)

In an agitated ball mill, 5-25 wt% of the fertilizer composition comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. carboxymethylcellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable gel of the fertilizer composition.

vii) Dustable powders (DP, DS)

1 -10 wt% of the fertilizer composition is ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt%.

viii) Granules (GR, FG)

0.5-30 wt% of the fertilizer composition is ground finely and associated with solid carrier (e.g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or the fluidized bed.

The compositions types i) to viii) may optionally comprise further auxiliaries, such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1 -1 wt% anti-foaming agents, and 0,1 -1 wt% col- ora nts.

Solutions for seed treamtent (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble pow- ders (SS), and gels (GF) are usually employed for the purposes of treatment of plant propaga- tion materials, particularly seeds. The compositions in question give, after two-to-tenfold dilu- tion, 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 sow ing. Methods for applying the fertilizer composition on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, the fertilizer composition is applied on to the plant propa- gation material by a method such that germination is not induced, e.g. by seed dressing, pellet ing, coating and dusting.

The invention also relates to a process for producing the fertilizer composition. The composi- tions are prepared in a known manner, such as described by Mollet and Grubemann, Formula- tion technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. For the production of the composition, the fertilizer is usually contacted with ZIF-8. To this end, the fertilizer, or a solu- tion comprising fertilizer may be contacted with ZIF-8, wherein ZIF-8 is typically in the form of a powder, or in the form of granules. The fertilizer is also typically in the form of a powder or a granule.

In case a solution of the fertilizer is applied, the solvent is typically removed after the contact- ing with ZIF-8 by elevated temperatures or reduced pressure. This may result in a physico- chemical state in which the fertilizer is adsorbed on ZIF-8. In case ZIF-8 is in form of a powder, the powder may subsequently be granulated.

The fertilizer composition may also be obtained by mixing powders or granules of the fertilizer, with granules or powders containing ZIF-8, by grinding a composition comprising the fertilizer and ZIF-8, and/or by co-granulation of the fertilizer with ZIF-8. Suitable co-granulation techniques are known to the skilled person. Typically, the co- granulation process is a wet granulation process, in which a spray liquid - typically containing water, ethanol, or isopropanol - is sprayed on the powder to be granulated. In one embodiment, the powder to be granulated comprises both the fertilizer and ZIF-8. In another embodiment, the fertilizer and ZIF-8 are only mixed during the co-granulation process step, i.e. that one compo- nent is initially charged to the granulation device, and the other component is gradually added to the device during the co-granulation process, e.g. by addition to the spray liquid.

In case of a wet granulation process, a spray liquid may be sprayed on the powder before or during granulation, and may contain a binder, such as polyvinyl pyrrolidone. Typical co- granulation processes include fluidized bed granulation and spouted bed granulation. The spray liquid is typically removed after or during co-granulation by evaporation at elevated tempera- tures.

The invention also relates to the use of ZIF-8 as a nitrification inhibitor. The term "nitrification inhibitor" is to be understood in the context of this specification as a chemical substance which slows down or stops the nitrification process. Nitrification inhibitors accordingly retard the natu- ral transformation of ammonium into nitrate, by inhibiting the activity of bacteria such as Nitro- somonas spp .The term "nitrification" as used herein is to be understood as the biological oxida- tion of ammonia (NH₃) or ammonium (NH₄ ⁺) with oxygen into nitrite (NO₂ ) followed by the oxida- tion 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 N2O losses. The term nitrification inhibitor is considered equivalent to the use of such a compound for inhibiting nitrification. Typically, ZIF-8 reduces the nitrification of at least 20% at 15 °C over a period of 3 weeks, preferably at least 40%, more preferably at least 60% as compared to a fertilizer composition that does not contain ZIF-8 or any other nitrification inhibitor.

Another object is a method for reducing nitrification, comprising treating plant propagation ma- terial, a plant growing on soil or soil substituents and/or the locus or soil or soil substituents where the plant is growing or is intended to grow with ZIF-8 or the fertilizer composition. Another object is a method of fertilizing comprising treating plant propagation material, a plant growing on soil or soil substituents, and/or the locus or soil or soil substituents, where the plant is grow- ing or is intended to grow with the fertilizer composition. Another object is the use of the fertilizer composition for fertilizing plant propagation material, a plant growing on soil or soil substituents and/or the locus or soil or soil substituents where the plant is growing or is intended to grow.

The term "reducing nitrification" or "reduction of nitrification" as used herein refers to a slowing down or stopping of nitrification processes, e.g. by retarding or eliminating the natural transfor- mation of ammonium into nitrate. Such reduction may be a complete or partial elimination of nitrification at the plant or locus where composition is applied. For example, a partial elimination may result in a residual nitrification on or in the plant, or in or on the soil or soil substituents where a plant grows or is intended to grow of 90% to 1 %, e.g. 90%, 85%, 80%, 70%, 60%,

50%, 40%, 30%, 20%, 10% or less than 10%, e.g. 5% or less than 5% in comparison to a con- trol situation in which the composition is not used. In certain embodiments, a partial elimination may result in a residual nitrification on or in the plant or in or on the soil or soil substituents where a plant grows or is intended to grow of below 1 %, e.g. at 0.5%, 0.1 % or less in compari- son to a control situation where the nitrification inhibitor is not used.

In one embodiment of the methods of application, the plant is an agricultural plant and/or the propagation material relates to propagation material of such agricultural plants, wherein the ag- ricultural plant is selected from wheat, barley, oat, rye, soybean, corn, potatoes, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice or a vegetable such as spinach, lettuce, asparagus, or cabbages; or sorghum; a silvicultural plant; an ornamental plant; and a horticul tural plant, each in its natural or in a genetically modified form.

In one embodiment, the plant to be treated according to the method of the invention is an agri cultural plant. "Agricultural plants" are plants of which a part (e.g. seeds) or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibers (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds. Preferred agricultural plants are for example cereals, e.g. wheat, rye, barley, tritica- le, oats, corn, sorghum or rice, beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspber- ries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil 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 squash- es, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as or- anges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cab- bages, 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. Ex- amples for ornamentals are turf, geranium, pelargonia, petunia, begonia and fuchsia. Examples for vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas and lettuce and more preferably from tomatoes, onions, peas and lettuce. Examples for fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots and blueberries.

In a further embodiment, the plant to be treated according to the method of the invention is an ornamental plant. Ornamental plants" are plants which are commonly used in gardening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia.

In another embodiment of the present invention, the plant to be treated according to the meth- od of the invention is a silvicultural plant. The term "silvicultural plant" is to be understood as trees, more specifically trees used in reforestation or industrial plantations. Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening purposes. Examples for silvicultural plants are conifers, like pines, in particular Pinus spec., fir and spruce, eucalyptus, tropical trees like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec., poplar (cottonwood), in particular Populus spec., beech, in particular Fagus spec., birch, oil palm, and oak.

Suitable methods of treatment include inter alia soil treatment, seed treatment, in furrow appli cation, and foliar application. Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection. Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pellet ing. In furrow applications typically include the steps of making a furrow in cultivated land, seed- ing the furrow with seeds, applying the pesticidally active compound to the furrow, and closing the furrow.

The treatment according to the methods of application and uses according to the invention may also be carried out by fertigation. The term "fertigation" as used herein refers to the appli cation of fertilizers - in this case of the fertilizer composition, 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, the fertilizer composition, optionally 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. The fertilizer composition, and optionally the additional nitrification inhibitors according to the present invention may be provided together, e.g. dissolved in the same charge or load of mate- rial (typically water) to be irrigated. In further embodiments, the fertilizer composition, optionally the additional nitrification inhibitors may be provided at different points in time. For example, the ZIF-8 may be fertigated first, followed by the fertilizer and optionally the additional nitrification inhibitors, or preferably, the fertilizer and optionally the additional nitrification inhibitors may be fertigated first, followed by ZIF-8. Also envisaged is a repeated fertigation of the fertilizer corn- position and optionally 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 term "plant propagation material" refers to 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, roots, fruits, tubers, bulbs, rhi- zomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.

The term“seed” embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like, and means in a preferred embodiment true seeds.

The term "soil substituent" as used herein refers to a substrate which is capable to allow the growth of a plant and does not comprise usual soil ingredients. This substrate is typically an inorganic substrate which may have the function of an inert medium. It may, in certain embodi- ments, 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 tetrahe- dra 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 term“where the plant is intended to grow” refers to a place, which is chosen by an applicant, such as a farmer, for growing a desired plant, such as a crop plant.

For the methods of application, the application rates of the fertilizer composition may be be- tween 10 kg and 1000 kg per hectare, preferably between 50 kg and 700 kg per hectare, in cer- tain cases between 50 kg and 400 kg per hectare.

The term“treatment of seeds” comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in- furrow application methods. Preferably, the seed treatment application of the fertilizer composi- tion is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.

The invention also relates to plant propagation material comprising the fertilizer composition.

In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of the fertilizer composition of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material are generally required.

Preferred plant propagation materials are seeds coated with or containing the composition.

The term "coated with and/or containing" generally signifies that the fertilizer composition is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredients may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.

Suitable seed is for example seed of cereals, root crops, oil crops, vegetables, spices, orna- mentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, ba- nanas, rice, oilseed rape, turnip rape, sugar beet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucum- bers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.

In addition, the fertilizer composition may also be used for the treatment of seeds from plants, which have been modified by mutagenesis or genetic engineering, and which e.g. tolerate the action of herbicides or fungicides or insecticides.

Conventional seed treatment formulations include for example powders for dry treatment DS, water dispersible powders for slurry treatment WS, and water-soluble powders SS. These for- mulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter. Preferably, the formulations are applied such that germination is not included.

In the treatment of seed, the application rates of the fertilizer composition are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more prefera- bly from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.

The invention therefore also relates to seed comprising the fertilizer composition. The amount of the fertilizer composition will in general vary from 0.1 g to 10 kg per 100 kg of seed, prefera- bly from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.

In the uses and methods of application according to the invention, the application of ZIF-8 and the fertilizer may be carried out simultaneously or with a time lag, wherein either said fertilizer or ZIF-8 may be applied first. Preferably, said time lag is an interval of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 1 week, 2 weeks or 3 weeks. In case of application with a time lag, ZIF-8 may be applied first and then the fertilizer. In another embodiment, in a first step ZIF-8 is ap- plied to plant propagation material, to a plant and/or to the locus where the plant is growing or is intended to grow and in a second step the fertilizer is applied to the plant propagation material, the plant and/or to the locus where the plant is growing or is intended to grow, wherein the ap- plication of ZIF-8 in the first step and the fertilizer in the second step is carried out with a time lag of at least 1 day, 2 days, 3 days, 4 days, 5, days, 6 days, 1 week, 2 weeks or 3 weeks.

In other embodiments of application with a time lag, a fertilizer may be applied first and then ZIF-8 may be applied. In a further preferred embodiment of the method, in a first step a fertilizer is applied to a plant and/or to the locus where the plant is growing or is intended to grow and in a second step ZIF-8 is applied to plant propagation material, to a plant and/or to the locus where the plant is growing or is intended to grow, wherein the application of a the fertilizer in the first step and the composition in the second step is carried out with a time lag of at least 1 day, 2days, 3 days, 4 days, 5, days, 6 days, 1 week, 2 weeks or 3 weeks.

The methods of application and uses of the fertilizer composition may be a single application or use, or it may be a repeated application or use. As single application or use, the fertilizer composition may be provided to their target sites, e.g. soil or loci, or objects, e.g. plants, only once in a physiologically relevant time interval, e.g. once a year, or once every 2 to 5 years, or once during the lifetime of a plant.

In other embodiments, the application or use may be repeated at least once per time period, e.g. the composition may be used for reducing nitrification at their target sites or objects two times within a time interval of days, weeks or months. The term "at least once" as used in the context of a use of the composition means that the composition may be used two times, or sev- eral times, i.e. that a repetition or multiple repetitions of an application or treatment with the composition may be envisaged. Such a repetition may be a 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or more frequent repetition of the use.

In one embodiment, the methods of application include the treatment of the plant propagation material, the plant and/or the locus or soil or soil substituents where the plant is growing or is intended to grow, with an additional compound selected from a fertilizer, nitrification inhibitor, urease inhibitor, plant growth regulator, micronutrient and pesticide.

The application of the fertilizer composition and the additional compound may be carried out simultaneously or with a time lag, wherein either said additional compound or the fertilizer corn- position may be applied first. Preferably, said time lag is an interval of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 1 week, 2 weeks or 3 weeks. In case of application with a time lag, the fertilizer composition may be applied first and then the additional compound. In another embod- iment, in a first step the fertilizer composition is applied to plant propagation material, to a plant and/or to the locus where the plant is growing or is intended to grow and in a second step the additional compound is applied to the plant propagation material, the plant and/or to the locus where the plant is growing or is intended to grow, wherein the application of the fertilizer corn- position in the first step and the additional compound in the second step is carried out with a time lag of at least 1 day, 2 days, 3 days, 4 days, 5, days, 6 days, 1 week, 2 weeks or 3 weeks.

In other embodiments of application with a time lag, the additional compound may be applied first and then the fertilizer composition may be applied. In a further preferred embodiment of the method, in a first step the additional compound is applied to a plant and/or to the locus where the plant is growing or is intended to grow and in a second step the fertilizer composition is ap- plied to plant propagation material, to a plant and/or to the locus where the plant is growing or is intended to grow, wherein the application of a the additional compound in the first step and the fertilizer composition in the second step is carried out with a time lag of at least 1 day, 2days, 3 days, 4 days, 5, days, 6 days, 1 week, 2 weeks or 3 weeks.

The invention also relates to a method for treating a fertilizer, comprising contacting the ferti- lizer with ZIF-8. The contacting may be achieved by mixing, co-grinding, co-granulating, co- precipitation, adsorption and other techniques familiar to the skilled person and as described above.

The invention also relates to a kit-of-parts comprising a fertilizer and ZIF-8 as individual com- ponents of the fertilizer composition or partially premixed components, e.g. components corn- prising the fertilizer and ZIF-8 and/or mixing partners {e.g. further nitrification inhibitors, urease inhibitors, pesticides, plant growth regulators, micronutrients, auxiliaries etc.) as defined above, which may be mixed by the user himself, e.g. in a spray tank, and further auxiliaries may be added, if appropriate.

Advantages of the invention are that ZIF-8 is biodegradable and does not require a desiccation step prior to application. ZIF-8 is cheap, stable, is and non-toxic. Compared to other nitrification inhibitors, ZIF-8 does not evaporate or degrade too quickly. It is easy to handle and safe for the applicant. The following examples illustrate the invention.

Examples:

ZIF-8 was purchased as Basolite® Z1200 from SigmaAldrich.

Nitrification Inhibitor A: 1-chloro-4-(prop-2-ynoxymethyl) benzene (compound 1-15 of Table A) Preparation Example 1 : Nitrification Inhibitor A on ZIF -8

ZIF-8 powder (10 g) was placed in a porcelain dish. The ZIF-8 powder was in the activated stage with virtually nothing adsorbed in the pores of the material. Nitrification Inhibitor A A (3 g, below 2% impurities) was slowly added at 20 to 25 °C to the manually agitated ZIF-8 powder over a period of 15 minutes to result in Sample A containing 23 wt% of Nitrification Inhibitor A based on the total weight of Sample A.

Working Example 1 : Nitrogen retention in field trials

An area of sandy soil, previously untreated with fertilizer or other agricultural products near the field station Limburgerhof, was treated as follows. Drainage pipes of 20 cm in length and 12cm diameter were inserted 10 cm deep into the soil. A treatment as indicated in a line of Table 1 was added on top of the soil under which a pipe was buried. At the beginning of the experiment and after three weeks, the pipes were dug out of the soil with its content, the content emptied into a bag and frozen on site. The soil was then analyzed for NFU-nitrogen content in the labora- tory according to the following method: Samples were defrosted for 24 h, then sieved through a 5-6 mm mesh sieve. 200 g of the thus homogenized samples were put into 1 L plastic bottles and 600 ml. of a K2SO4 solution (1 % (w/w) K2SO4 in water) were added. The samples were then shaken for 2 h end over end. The solution was filtered to remove the soil and 50 ml. of the fil- trate retained for analysis in a Continuous Flow Analyzer for NFU-nitrogen content. The results were summarized in Table 1.

Table 1 : Field trial results

Claims

1 ) Fertilizer composition comprising

a) the zeolitic imidazolate framework ZIF-8; and

b) a fertilizer selected from liquid or solid ammonium-containing inorganic fertilizers, liquid or solid organic fertilizers, and urea-containing fertilizers.

2) The composition of claim 1 , wherein the weight ratio of ZIF-8 to the fertilizer is from 10:1 to 1 :100.

3) The composition of claim 1 or 2, wherein the composition comprises ZIF-8 in a concentra- tion of from 1 to 30 wt% based on the total weight of the composition.

4) The composition according to any of claims 1 to 3, wherein the composition comprises the fertilizer in a concentration of from 1 to 99.9 wt% based on the total weight of the composi- tion.

5) The composition according to any of claims 1 to 4, wherein the composition is in the form of a powder or granule.

6) The composition according to any of claims 1 to 5, wherein the fertilizer is NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sul- fate or ammonium phosphate, liquid manure, semi-liquid manure, biogas manure, stable manure and straw manure, worm castings, compost, seaweed or guano, urea, formalde- hyde urea, urea ammonium nitrate solution, urea sulphur, stabilized urea, urea based NPK-fertilizers, or urea ammonium sulfate.

7) The composition according to any of claims 1 to 6, wherein the fertilizer is an ammonium- containing inorganic fertilizer.

8) The composition according to any of claims 1 to 7, comprising an additional nitrification inhibitor.

9) The composition according to any of claims 1 to 8, comprising a urease inhibitor.

10) The composition according to any of claims 1 to 9, comprising a pesticidal compound.

1 1 ) A method for producing the fertilizer composition as defined in any of claims 1 to 10, wherein ZIF-8 is contacted with a fertilizer as defined in any of claims 1 to 7.

12) The method of claim 1 1 , wherein ZIF-8 is in the form of a powder or granule.

13) The method of claim 1 1 or 12, wherein the fertilizer is in the form of a solution. 14) The use of ZIF-8 as a nitrification inhibitor.

15) A method for reducing nitrification, comprising the step of treating plant propagation mate- rial, a plant growing on soil or soil substituents and/or the locus or soil or soil substituents where the plant is growing or is intended to grow with ZIF-8, or the fertilizer composition as defined in any of claims 1 to 10.