CN111448177A

CN111448177A - Aqueous composition comprising 2- (dimethyl-1H-pyrazol-1-yl) succinic acid and ammonia

Info

Publication number: CN111448177A
Application number: CN201880079798.XA
Authority: CN
Inventors: D·赛林格
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2017-12-22
Filing date: 2018-12-12
Publication date: 2020-07-24
Also published as: WO2019121225A1; CL2020001705A1; BR112020010840A2; MX2020006670A; RU2020123422A3; RU2020123422A; AU2018387013A1; AR114041A1; EP3728166A1; AU2018387013B2

Abstract

The present invention relates to aqueous compositions comprising 2- (dimethyl-1H-pyrazol-1-yl) succinic acid and ammonia.

Description

Aqueous composition comprising 2- (dimethyl-1H-pyrazol-1-yl) succinic acid and ammonia

Nitrogen is an essential element for plant growth and reproduction. About 25% of the plant available nitrogen (ammonium and nitrate) in the soil originates from the decomposition processes (mineralization) of organic nitrogen compounds such as humus, plant and animal residues and organic fertilizers. Approximately 5% is derived from rainfall. However, on a global basis, the largest fraction (70%) is supplied to plants by inorganic nitrogen fertilizers. Without the use of nitrogen fertilizer, the earth will not be able to support its current population.

Soil microBiological conversion of organic nitrogen to ammonium (NH)₄ ⁺) Which is subsequently oxidized to Nitrate (NO) in a process known as nitration₃ ^-). Although very important for agriculture, nitrate is highly mobile in the soil and can be easily lost from the soil by leaching into groundwater. Nitrogen is further lost to gaseous form by microbial denitrification. Due to various losses, approximately 50% of the applied nitrogen is lost during the year of fertilizer addition (see Nelson and Huber; nitrification inhibitors for Corn production (2001), National Corn Handbook, Iowa State University).

Nitrification inhibitors such as pyrazole compounds may be used to reduce nitrification and thereby increase fertilization efficiency and reduce nitrogen content in groundwater and surface water and nitrogen oxide content in the atmosphere. A problem associated with the use of pyrazole compounds is their volatility, which leads to the loss of nitrification inhibitor during storage. To solve this problem, pyrazole derivatives having hydrophilic groups have been described in the prior art.

WO 96/24566 describes a process for the preparation of low-volatile pyrazole derivatives having hydrophilic groups, such as 2- (3-methyl-1H-pyrazol-1-yl) succinic acid, for use as nitrification inhibitors.

WO 2011/032904 and WO 2013/121384 describe 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid as nitrification inhibitor.

WO 2015/086823 relates in particular to formulations of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid, which is an aqueous solution comprising 20 to 40 wt.% of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid, wherein the solution has a pH value of more than 7.

However, the formulations of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid described in the prior art have disadvantages. In particular, alkaline pH values may be disadvantageous for alkali-sensitive fertilizers, such as ammonium-and/or urea-containing fertilizers, with which nitrification inhibitors may be applied in combination. Due to the alkaline pH, the ammonium is converted to ammonia, resulting in a loss of nitrogen in the soil. Furthermore, there is a need to provide formulations with higher active ingredient content to improve the transportation logistics. Furthermore, it is desirable to provide the formulation in the form of a solution without the addition of organic solvents.

It is therefore an object of the present invention to provide a formulation, preferably a solution of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid, which is compatible with alkali-sensitive fertilizers, such as ammonium-and/or urea-containing fertilizers.

It is a further object of the present invention to provide a formulation, preferably a solution of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid, which is advantageous for the transport logistics, i.e. by being able to use higher concentrations of 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid according to the invention, less water is contained in the formulation, so that the weight that has to be transported over long distances is reduced. Furthermore, the water input on the fertilizer, which may have a negative impact on the physico-chemical properties of the fertilizer, can be reduced by applying highly concentrated 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid.

It has surprisingly been found that one or both of the above objects can be achieved by an aqueous composition as described herein.

Thus, in one embodiment, the present invention relates to an aqueous composition comprising 2- (dimethyl-1H-pyrazol-1-yl) succinic acid and ammonia.

The ammonia may be used in an amount to provide a composition having a pH of 7 or less. However, due to the presence of ammonia, 2- (dimethyl-1H-pyrazol-1-yl) succinic acid is at least partially present in the form of hydrogen succinate and/or succinate salt, which is advantageous for solubility. Thus, a high-concentration 2- (dimethyl-1H-pyrazol-1-yl) succinic acid solution can be obtained.

Even higher concentrations of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid can be obtained in solution if higher amounts of ammonia are used. Although the pH of these solutions is greater than 7, they are very advantageous because 2- (dimethyl-1H-pyrazol-1-yl) succinic acid concentrations of greater than 40% by weight can be obtained, which is advantageous for transport streams.

Preferred embodiments of the invention can be found in the claims and the description. It is to be understood that the features mentioned above and those yet to be explained below of the subject matter of the invention are preferred not only in the respective given combination, but also in other combinations without leaving the scope of the invention.

In connection with the above aspects of the invention, the following definitions are provided.

As used herein, the term "2- (dimethyl-1H-pyrazol-1-yl) succinic acid" (also abbreviated DMPSA) preferably refers to 2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid, 2- (4, 5-dimethyl-1H-pyrazol-1-yl) succinic acid, or a combination thereof. It will be appreciated that 2- (dimethyl-1H-pyrazol-1-yl) succinic acid may be present in deprotonated form in the compositions of the invention, thereby forming the corresponding hydrogen succinate (monoanion) or succinate (dianion). This applies in particular to the alkaline pH of the composition of the invention.

In the context of 2- (dimethyl-1H-pyrazol-1-yl) hydrogen succinate, the term "hydrogen succinate" means that one of the two acidic groups of the succinic acid group of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid is deprotonated.

In the context of 2- (dimethyl-1H-pyrazol-1-yl) succinate, the term "succinate" means that both acidic groups of the succinic acid group of 2- (dimethyl-1H-pyrazol-1-yl) succinate are deprotonated.

As used herein, the term "2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate" refers to 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, 2- (dimethyl-1H-pyrazol-1-yl) hydrogen succinate, 2- (dimethyl-1H-pyrazol-1-yl) succinate or a mixture thereof. Preferably, a mixture of acid, hydrogen succinate and succinate salt is present in the aqueous composition of the invention in chemical equilibrium.

Different isomers of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt are possible. As used herein, the term "isomer" describes a compound having the same chemical formula and molecular weight, but a different chemical structure. In the context of the present invention, 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt may preferably be present in the following forms:

2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt form;

-2- (4, 5-dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt form; or

-in the form of a mixture of isomers comprising

(i)2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt; and

(ii)2- (4, 5-dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt.

Preferably, 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present as a mixture of isomers as defined above. The possible isomers differ only in the position of the methyl group on the pyrazole radical.

As used herein, the term "aqueous composition" refers to a composition that includes water as a solvent. Preferably, the aqueous composition according to the present invention does not comprise a significant amount of any additional solvent. In particular, it is preferred that the composition comprises less than 30 wt%, preferably less than 25 wt%, more preferably less than 20 wt%, even more preferably less than 15 wt%, still more preferably less than 10 wt%, most preferably less than 5 wt% of additional solvent. It is particularly preferred that the composition comprises less than 3 wt%, more preferably less than 1 wt%, even more preferably less than 0.1 wt% of organic solvent. Most preferably, the composition is free of organic solvents. Furthermore, it is preferred that at least 70 wt.%, more preferably at least 80 wt.%, even more preferably at least 90 wt.%, most preferably at least 95 wt.%, particularly preferably at least 99 wt.%, particularly preferably at least 99.9 wt.% of the total amount of solvents in the aqueous composition is water.

As used herein, in the context of the aqueous composition according to the present invention, the term "solution" refers to an aqueous composition in which 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate salt and/or succinate salt is dissolved. In particular, at least 90 wt%, preferably at least 95 wt%, more preferably at least 99 wt%, most preferably at least 99.9 wt% of the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is dissolved. It is particularly preferred that the 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is completely dissolved.

Preferred embodiments regarding the aqueous composition of the present invention are described below.

As mentioned above, the present invention relates to aqueous compositions comprising 2- (dimethyl-1H-pyrazol-1-yl) succinic acid and ammonia.

In a preferred embodiment, 2- (dimethyl-1H-pyrazol-1-yl) succinic acid is at least partially present in the form of hydrogen succinate and/or succinate salt.

In another preferred embodiment, the ammonia is at least partially present in the form of ammonium cations.

Thus, it will be understood that 2- (dimethyl-1H-pyrazol-1-yl) succinic acid and ammonia are present in the composition of the invention in an acid-base equilibrium. In particular, to some extent, one or two protons of the succinic acid moiety of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid can be transferred to one or two equivalents of ammonia, forming hydrogen succinate or succinate anion, and one ammonium cation per hydrogen succinate anion, and two ammonium cations per succinate anion.

The invention therefore also relates to aqueous compositions comprising hydrogen 2- (dimethyl-1H-pyrazol-1-yl) succinate and/or 2- (dimethyl-1H-pyrazol-1-yl) succinate and an ammonium cation. In other words, the present invention relates to aqueous compositions comprising ammonium hydrogen 2- (dimethyl-1H-pyrazol-1-yl) succinate and/or diammonium 2- (dimethyl-1H-pyrazol-1-yl) succinate. In a preferred embodiment, the aqueous composition additionally contains 2- (dimethyl-1H-pyrazol-1-yl) succinic acid and ammonia due to the acid-base equilibrium in the composition. Furthermore, if the composition is obtained by using an excess of ammonia compared to the acidic group of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, an additional amount of ammonia may be present.

In view of the above, it may be preferred that the aqueous composition of the present invention comprises 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt and ammonia and/or ammonium cation. These components are preferably present in an acid-base equilibrium.

With regard to the above-described aqueous composition of the present invention, it is preferable that 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present in a dissolved form.

In a preferred embodiment, the aqueous composition of the present invention is a solution. In particular, it is preferred to dissolve at least 90 wt%, preferably at least 95 wt%, more preferably 99 wt%, most preferably 99.9 wt% of the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate. It is particularly preferred that the 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is completely dissolved.

The solubility of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt may depend on the ratio of the two isomeric forms present in the aqueous composition.

In one embodiment, 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, its hydrogen succinate salt and/or succinate salt is present in the following form:

-2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt.

In another embodiment, 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt thereof is present in the form of:

-2- (4, 5-dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt.

-in the form of a mixture of isomers comprising

Preferably 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt thereof is present as the above isomeric mixture. The solubility of the mixture of isomers may be higher than that of the individual isomers.

As the isomer mixture, preferred is

(ii)2- (4, 5-dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present in a molar ratio of 5:95 to 95:5, preferably 50:50 to 95:5, more preferably 70:30 to 90: 10.

The aqueous composition of the present invention can be obtained by mixing 2- (dimethyl-1H-pyrazol-1-yl) succinic acid and ammonia in water.

In a preferred embodiment, the composition is obtained by using ammonia in an amount such that the molar ratio of ammonia to 2- (dimethyl-1H-pyrazol-1-yl) succinic acid is from 1:1 to 10:1, preferably from 2:1 to 6: 1. The pH of the aqueous composition can be varied by varying the amount of ammonia relative to 2- (dimethyl-1H-pyrazol-1-yl) succinic acid. Further details regarding this and regarding the amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid in the aqueous composition are provided below.

In another embodiment, the present invention relates to a method of preparing an aqueous composition for inhibiting nitrification, comprising the steps of:

-mixing 2- (dimethyl-1H-pyrazol-1-yl) succinic acid and ammonia in water.

In a preferred embodiment, 2- (dimethyl-1H-pyrazol-1-yl) succinic acid is suspended in water, followed by the addition of ammonia.

In another preferred embodiment, 2- (dimethyl-1H-pyrazol-1-yl) succinic acid is added to an aqueous ammonia solution.

Suitable molar ratios of ammonia to 2- (dimethyl-1H-pyrazol-1-yl) succinic acid are from 1:1 to 10:1, preferably from 2:1 to 6: 1. Further details regarding this and regarding the amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid in the aqueous composition are provided below.

In another embodiment, the present invention relates to an aqueous composition obtainable by the process as defined above.

With regard to the aqueous compositions of the invention and with regard to the process of the invention, the following preferences are relevant in respect of the amounts of ammonia and/or ammonium and 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt.

For improving the transport stream, it is generally preferred that the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present in the composition in an amount corresponding to at least 10 wt. -%, preferably at least 20 wt. -%, based on the total weight of the composition, of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid.

In a preferred embodiment, the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present in the composition in an amount corresponding to 10 to 70% by weight, preferably 20 to 60% by weight, of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, based on the total weight of the composition.

Depending on the pH of the composition, various concentrations of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate salt, and/or succinate salt may be achieved to provide compatibility with base-sensitive fertilizers and/or to further improve transportation streams.

In one embodiment, the composition has a pH of 7 or less, preferably 4 to 6.9, in water.

In this respect, it is preferred that the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present in the composition in an amount corresponding to 10-40 wt. -%, preferably 20-35 wt. -%, based on the total weight of the composition, of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid.

Preferably, the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present in the composition in an amount corresponding to 15-30 wt. -%, preferably 15-20 or 20-25 wt. -%, of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid based on the total weight of the composition.

In the following preferred embodiments, the term "2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate" is referred to as "DMPSA and/or a derivative thereof", and "2- (dimethyl-1H-pyrazol-1-yl) succinic acid" is referred to as "DMPSA". All of these preferred embodiments are optionally also preferably combined with the above pH of the composition of 7 or less, preferably 4 to 6.9.

In a preferred embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 10 to 15 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 15 to 20 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 16 to 21 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 17 to 22 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 18 to 23 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 19 to 24 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 20 to 25 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 21 to 26 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 22 to 27 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 23 to 28 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 24 to 29 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 25 to 30 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 26 to 31 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 27 to 32 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 28 to 33 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 29 to 34 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 30 to 35 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 31 to 36 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 32 to 37 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 33 to 38 weight percent DMPSA based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 34 to 39 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 35 to 40 wt.% DMPSA, based on the total weight of the composition.

As mentioned above, these DMPSA concentrations are preferably achieved at a pH of the composition of 7 or less, preferably in the range of 4-6.9. More preferably, the pH is from 4.5 to 6.5, especially from 4.8 to 6.2. The pH may be adjusted by the amount of ammonia in the composition, as explained further below.

In a particularly preferred embodiment, compositions having the parameters of Table A are preferred according to the invention.

TABLE A

Total amount of DMPSA and/or derivatives thereof, calculated as weight% of DMPSA based on the total weight of the composition

pH measured in Water, i.e. aqueous compositions

With respect to the above-described embodiments involving compositions having acidic pH values and/or certain DMPSA concentrations, it is further preferred that the compositions are obtained by using ammonia in an amount such that the molar ratio of ammonia to 2- (dimethyl-1H-pyrazol-1-yl) succinic acid is from 1:1 to 2.5:1, preferably from 1.8:1 to 2.5: 1. In particular, such a ratio preferably establishes an acidic pH value as defined above. It is to be understood that this ratio relates to the components before any acid-base reaction occurs. Thus, after the chemical equilibrium in the composition is established, the molar ratio relates to the total amount of ammonia and ammonium relative to the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, 2- (dimethyl-1H-pyrazol-1-yl) hydrogen succinate and 2- (dimethyl-1H-pyrazol-1-yl) succinate.

Thus, in a preferred embodiment, the molar ratio of (a) ammonia and ammonium to (b)2- (dimethyl-1H-pyrazol-1-yl) succinic acid, 2- (dimethyl-1H-pyrazol-1-yl) hydrogen succinate and 2- (dimethyl-1H-pyrazol-1-yl) succinate is from 1:1 to 2.5:1, preferably from 1.8:1 to 2.5: 1.

Thus, in a particularly preferred embodiment, compositions having the parameters of table B are preferred according to the invention.

TABLE B

In another embodiment of the invention, the composition has a pH in water of greater than 7, preferably from 8 to 12.

In this respect, it is preferred that the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present in the composition in an amount corresponding to more than 40 to 70 wt. -%, preferably more than 40 to 60 wt. -%, of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid based on the total weight of the composition.

Preferably, the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present in the composition in an amount corresponding to more than 40 to 58 wt. -%, preferably more than 40 to 50 wt. -% or 50-58 wt. -% of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid based on the total weight of the composition.

In the following preferred embodiments, the term "2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate" is referred to as "DMPSA and/or a derivative thereof", and "2- (dimethyl-1H-pyrazol-1-yl) succinic acid" is referred to as "DMPSA". All of these preferred embodiments are optionally also preferably combined with the above pH values of the composition of greater than 7, preferably 8 to 12.

In a preferred embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to greater than 40 to 45 wt% DMPSA, based on the total weight of the composition.

In a preferred embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 41 to 46 wt% DMPSA, based on the total weight of the composition.

In a preferred embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 42 to 47 wt.% DMPSA, based on the total weight of the composition.

In a preferred embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 43 to 48 wt.% DMPSA, based on the total weight of the composition.

In a preferred embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 44 to 49 wt% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 45 to 50 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 46 to 51 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 47 to 52 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 48 to 53 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 49 to 54 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 50 to 55 wt% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 51 to 56 weight percent DMPSA based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 52 to 57 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 53 to 58 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 54 to 59 weight percent DMPSA based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 55 to 60 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 56 to 61 wt% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 57 to 62 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 58 to 63 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 59 to 64 weight percent DMPSA based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 60 to 65 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 61 to 66 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 62 to 67 weight percent DMPSA based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 63 to 68 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 64 to 69 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 65 to 70 wt.% DMPSA, based on the total weight of the composition.

In another preferred embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to greater than 40 to 43 wt% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 41 to 44 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 42 to 45 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 43 to 46 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 44 to 47 weight percent DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 45 to 48 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 46 to 49 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 47 to 50 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 48 to 51 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 49-52 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 50 to 53 wt% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 51 to 54 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to from 52 to 55 wt% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 53 to 56 weight percent DMPSA based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 54 to 57 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 55 to 58 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 56 to 59 weight percent DMPSA based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 57 to 60 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 58 to 61 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 59 to 62 weight percent DMPSA based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 60 to 63 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 61 to 64 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 62 to 65 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 40 to 65 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 42 to 63 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 45 to 60 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 40 to 60 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 40 to 55 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 40 to 50 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 45 to 65 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 45 to 55 wt% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 50 to 65 wt.% DMPSA, based on the total weight of the composition.

In another embodiment, the total amount of DMPSA and/or derivatives thereof in the composition corresponds to 50 to 60 wt.% DMPSA, based on the total weight of the composition.

As mentioned above, these DMPSA concentrations are preferably achieved at a pH of the composition of greater than 7, preferably from 8 to 12. More preferably, the pH is from 8.5 to 11.5, especially from 9 to 11, which can be adjusted by the amount of ammonia in the composition, as explained further below.

In a particularly preferred embodiment, compositions having the parameters of Table C are preferred according to the invention.

Watch C

pH measured in Water, i.e. aqueous compositions

With respect to the above-described embodiments involving compositions having alkaline pH values and/or certain DMPSA concentrations, it is further preferred that the compositions are obtained by using ammonia in an amount such that the molar ratio of ammonia to 2- (dimethyl-1H-pyrazol-1-yl) succinic acid is from 2:1 to 10:1, preferably from 2:1 to 5: 1. In particular, such a ratio preferably establishes an acidic pH value as defined above. It is to be understood that this ratio relates to the components before any acid-base reaction occurs. Thus, after the chemical equilibrium in the composition is established, the molar ratio relates to the total amount of ammonia and ammonium relative to the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, 2- (dimethyl-1H-pyrazol-1-yl) hydrogen succinate and 2- (dimethyl-1H-pyrazol-1-yl) succinate.

Thus, in a preferred embodiment, the molar ratio of (a) ammonia and ammonium to (b)2- (dimethyl-1H-pyrazol-1-yl) succinic acid, 2- (dimethyl-1H-pyrazol-1-yl) hydrogen succinate and 2- (dimethyl-1H-pyrazol-1-yl) succinate is from 2:1 to 10:1, preferably from 2:1 to 5: 1.

Thus, in a particularly preferred embodiment, compositions having the parameters of Table D are preferred according to the invention.

Table D

The aqueous composition as defined above is particularly advantageous for the transport of the active ingredient 2- (dimethyl-1H-pyrazol-1-yl) succinic acid as nitrification inhibitor. The acidic formulation can further advantageously be used in combination with an alkali-sensitive fertilizer.

In certain embodiments, the present invention therefore also relates to a method of applying an aqueous composition as defined herein to soil or a soil substitute in which plants are growing or are intended to grow.

The aqueous composition may be applied in combination with at least one fertilizer or with a lag time, preferably a lag time of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.

Aqueous compositions having a pH of 7 or less may preferably be applied in combination with alkali sensitive fertilizers such as ammonium containing fertilizers.

Aqueous compositions having a pH greater than 7 may preferably be applied in combination with acid sensitive fertilizers such as carbonate containing fertilizers.

The compositions of the present invention are suitable as nitrification inhibitors. In one embodiment, the compositions of the present invention are used as nitrification inhibitors.

In one embodiment, the composition of the invention is applied or sprayed in and/or on the soil and preferably applied in and/or on the soil in the furrow and/or as side application and/or as broadcast application together with at least one fertilizer, one ammonium containing fertilizer and/or one urea containing fertilizer.

In another preferred embodiment, the composition of the invention can be used as a nitrating agent, in combination with the following, and/or as an additive, and/or as a coating material for fertilizers, preferably in combination with or for the following: ammonium-and/or urea-containing fertilizers, more preferably in combination or for use as follows: an ammonium-and/or urea-containing fertilizer selected from solid and liquid mineral fertilizers and organic fertilizers, most preferably in combination or for use as follows: ammonium-and/or urea-containing fertilizers selected from ammonium nitrate, calcium ammonium nitrate, ammonium sulphate nitrate, calcium nitrate, diammonium phosphate, monoammonium phosphate, ammonium thiosulphate, calcium cyanamide, NPK fertilizers, NK fertilizers, NP fertilizers, UAN (urea ammonium nitrate solution), manure and/or urea, particularly preferably in combination or for use as follows: calcium ammonium nitrate, ammonium sulfate and/or ammonium sulfate nitrate. In another preferred embodiment, the composition of the invention can be used as nitrification inhibitor in combination with: an ammonium-and/or urea-containing fertilizer selected from ammonium nitrate, calcium ammonium nitrate, ammonium sulphate nitrate, diammonium phosphate, monoammonium phosphate, ammonium thiosulphate, NPK fertilizer, NK fertilizer, NP fertilizer, UAN (urea ammonium nitrate solution), manure and urea. The fertilizer may be in crystalline, granular, compacted, granulated or ground form, preferably in granular form.

In another embodiment, the composition of the invention may be applied in or on a nitrogen-containing fertilizer by: the compositions according to the invention in liquid or solid form are mixed with the fertilizers or incorporated into the latter by granulating, compacting or pelleting, by adding them to the corresponding fertilizer mixtures or to the slurries or melts. Preferably, the composition of the invention is applied to the surface of an existing granular, pressed or pelletized form of nitrogen-containing fertilizer, for example by spraying, powder application or dipping. Other adjuvants such as adhesion promoters or coating materials may also be used. Suitable devices for carrying out the application are, for example, trays, drums, mixers or fluidized bed devices, but the application can also be carried out on a conveyor belt or at the discharge point thereof or by means of a pneumatic solids conveyor. It may also be treated last with an anti-caking and/or anti-dust agent. The composition of the invention can be used in fertilisation with an ammonium-and/or urea-containing fertilizer. Preferably on agricultural or horticultural land.

Fertilizers can be used, processed, combined, treated, coated and/or melted with the compositions of the present invention.

In one embodiment, the compositions of the present invention are preferably applied to the plants by spraying the soil and/or foliage. Here, application can be carried out by conventional spraying techniques using, for example, water as carrier, using spray quantities of from about 50 to 1000l/ha (for example 300-400 l/ha). The compositions of the present invention may also be applied by low or ultra low volume methods or in the form of microparticles. The compositions of the present invention may be applied pre-or post-emergence or with the seeds of the crop plants. The compositions of the present invention may also be applied by applying seeds of crops pretreated with the compositions of the present invention.

In another embodiment, the composition of the invention may be applied by treating seeds. The treatment of seed includes essentially all procedures (seed dressing, seed coating, seed dusting, seed soaking, seed coating, seed multilayer coating, seed encrusting, seed dipping and seed pelleting) well known to those skilled in the art based on the compositions of the invention and their compounds. The compositions of the present invention may be applied at this point with or without dilution.

The term "seed" includes all types of seeds, such as corn, seeds, fruits, tubers, seedlings and the like. The preferred term seed herein describes corn and seed. The seed used may be a seed of the above-mentioned useful plant, but may also be a seed of a transgenic plant or a plant obtained by a conventional breeding method.

The term "fertilizer" is understood to mean a compound applied to promote the growth of plants and fruits. Fertilizers are typically applied through soil (to be taken up by the plant roots), through soil substitutes (also to be taken up by the plant roots), or through foliar feed (to be taken up by the leaves). The term also includes mixtures of one or more different types of fertilizers as described below.

The term "fertilizer" can be subdivided into several categories, including: a) organic fertilizers (consisting of plant/animal matter), b) inorganic fertilizers (consisting of chemicals and minerals) and c) urea-containing fertilizers.

The organic fertilizer includes fertilizers such as liquid fertilizer, semi-liquid fertilizer, biogas manure, manure or straw manure, slurry, liquid manure, sewage sludge, earthworm manure, peat, seaweed, compost, sewage and guano. Green manure crops (field crops) are also commonly grown to add nutrients (especially nitrogen) to the soil. The prepared organic fertilizer comprises compost, blood meal, bone meal and seaweed extract. Other examples are enzymatically digested protein, fish meal and feather meal. Decomposing crop residues from the previous years is another source of fertility.

Inorganic fertilizers are typically manufactured by chemical methods (such as the Haber-Bosch process) that also use natural deposits, but chemically modify them (e.g., concentrating triple superphosphate). The natural inorganic fertilizer comprises sodium chilean nitrate, ore phosphate, limestone, potassium sulfate fertilizer, potassium chloride fertilizer and raw potassium fertilizer.

Typical solid fertilizers are in crystalline, granular or granular form. Typical nitrogen-containing inorganic fertilizers are ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, calcium nitrate, diammonium phosphate, monoammonium phosphate, ammonium thiosulfate and calcium cyanamide.

The inorganic fertilizer may be an NPK fertilizer. "NPK fertilizers" are inorganic fertilizers formulated at suitable concentrations and contain a combination of the 3 main nutrients nitrogen (N), phosphorus (P) and potassium (K) and usually also S, Mg, Ca and trace elements. "NK fertilizers" contain two main nutrients nitrogen (N) and potassium (K) and usually also S, Mg, Ca and trace elements. "NP fertilizers" contain two major nutrients nitrogen (N) and phosphorus (P) and usually also S, Mg, Ca and trace elements.

In particular embodiments, the urea-containing fertilizer may be urea formaldehyde, UAN, urea sulphur, stabilized urea, urea based NPK fertilizer or urea ammonium sulphate. Also included is the use of urea as a fertilizer. In the case of using or providing a urea-comprising fertilizer or urea, it is particularly preferred that a urease inhibitor as defined above may be added or that they may be additionally present, or that they are used simultaneously or in combination with a urea-comprising fertilizer.

The fertiliser may be provided in any suitable form, for example as coated or uncoated particles, in liquid or semi-liquid form, as a sprayable fertiliser or via drip irrigation or the like.

A wide range of materials can be provided for coated fertilizers. The coating may be applied, for example, to a granular or granular nitrogen (N) fertilizer or a multi-nutrient fertilizer. Urea is commonly used as the base material for most coated fertilizers. However, the invention also includes other base materials for coating fertilizers, any of which is as defined herein. In some embodiments, elemental sulfur may be used as a fertilizer coating. The coating may be performed by spraying the molten S onto the urea granules and then applying a sealing wax to close cracks in the coating. In another embodiment, the S layer may be covered with an organic polymer layer, preferably a thin organic polymer layer. In another embodiment, the coated fertilizer is preferably a physical mixture of coated and uncoated fertilizer.

Other coated fertilizers included may be provided by reacting a resin-based polymer on the surface of the fertilizer particle. Another example of providing a coated fertilizer includes the use of a low permeability polyethylene polymer in combination with a high permeability coating.

In particular embodiments, the composition and/or thickness of the fertilizer coating may be adjusted to control, for example, the rate of nutrient release for a particular application. The nutrient release duration of a particular fertilizer may vary from weeks to months, for example.

The coated fertilizer may be provided as a Controlled Release Fertilizer (CRF). In particular embodiments, these controlled release fertilizers are fully coated N-P-K fertilizers that are homogeneous and generally exhibit a predetermined long-term release. In other embodiments, CRF may be provided as a blended controlled release fertilizer product that may contain coated, uncoated, and/or slow release components. In some embodiments, these coated fertilizers may additionally comprise micronutrients. In particular embodiments, these fertilizers may exhibit a predetermined longevity, for example in the case of N-P-K fertilizers.

Additional possible examples of CRF include combination release fertilizers. These fertilizers typically exhibit a predetermined release combination (e.g., high/normal/low) and a predetermined longevity. In exemplary embodiments, the fully coated N-P-K, Mg and micronutrients may be delivered in a combined release fashion.

Also possible are double coating methods or coated fertilizers based on programmed release.

In other embodiments, the fertilizer mixture may be provided as a slow release fertilizer or may comprise or contain a slow release fertilizer. The fertilizer may for example be released over any suitable period of time, for example over a period of 1-5 months, preferably up to 3 months. Typical examples of ingredients of slow release fertilizers are IBDU (isobutylene diurea), e.g. containing about 31-32% nitrogen, of which 90% is water insoluble; or UF, a urea-formaldehyde product containing about 38% nitrogen, of which about 70% can be provided as water-insoluble nitrogen; or CDU (crotonodiurea) containing about 32% nitrogen; or MU (methylene urea) containing about 38-40% nitrogen, 25-60% of which is typically cold water insoluble nitrogen; or MDU (methylene diurea) containing about 40% nitrogen, less than 25% of which is cold water insoluble nitrogen; or MO (hydroxymethyl urea) containing about 30% nitrogen, which can be used in solution generally; or DMTU (dimethylene triurea) containing about 40% nitrogen, wherein less than 25% is cold water insoluble nitrogen; or TMTU (trimethylene tetraurea), which may be provided as a component of the UF product; or TMPU (trimethylene pentaurea), which may also be provided as a component of the UF product; or UT (urea triazone solution) which typically contains about 28% nitrogen. The fertilizer mixture may also be a long-term nitrogen-containing fertilizer comprising a mixture of acetyleneurea and at least one other organic nitrogen-containing fertilizer selected from the group consisting of methyleniurea, isobutylenediurea, crotylenediurea, substituted triazinones, 1, 3-diaminoformylurea (triuret), or mixtures thereof.

Any of the above fertilizers or fertilizer forms may be suitably combined. For example, the slow release fertilizer may be provided as a coated fertilizer. They may also be combined with other fertilizers or fertilizer types. The same applies to the presence of the composition of the invention, which may be adapted to the form and chemical nature of the fertilizer and may therefore provide for its release to be accompanied by the release of the fertilizer, for example at the same time or at the same frequency.

The term "fertigation" as used herein relates to the application of a fertilizer, optionally a soil amendment and optionally other water-soluble products together with water to a plant or a locus where the plant is growing or is intended to grow or a soil substitute as defined below via an irrigation system. For example, liquid fertilizer or dissolved fertilizer can be provided directly to the plant or to the locus where the plant is growing or is intended to grow via fertigation. Likewise, the compositions of the present invention may be provided to plants or to the locus where plants are growing or are intended to grow via fertigation. The fertiliser and the composition of the invention may be provided together, for example dissolved in the same charge or charge of material to be irrigated (typically water). In other embodiments, the fertilizer and the composition of the invention may be provided at different time points. For example, the composition of the present invention may be applied dropwise first, followed by dropwise application of the composition, or preferably, the composition of the present invention may be applied dropwise first, followed by dropwise application of the composition. The time interval of these activities follows the time interval described above for applying the fertilizer and the composition of the invention, for example a time interval of 0.25 hours to 30 days, preferably 0.5 hours to 14 days, in particular 1 hour to 7 days, or 1.5 hours to 5 days, even more preferably 2 hours to 1 day. It is also possible to drip the fertilizer and the composition of the invention repeatedly, either together or intermittently, for example every 2 hours, 6 hours, 12 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days or more.

In another preferred embodiment, the fertilizer may be applied first to the soil or plant and then the composition of the invention, or preferably, the composition of the invention may be applied first to the soil or plant and then the fertilizer. The time interval of these activities follows the time interval described above for applying the fertilizer and the composition of the invention, for example a time interval of 0.25 hours to 30 days, preferably 0.5 hours to 14 days, in particular 1 hour to 7 days, or 1.5 hours to 5 days, even more preferably 2 hours to 1 day. It is also possible to apply the fertilizer and the composition of the invention repeatedly, either together or intermittently, e.g. every 2 hours, 6 hours, 12 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days or more.

In a particularly preferred embodiment, the fertilizer is an ammonium-containing fertilizer and/or a urea-containing fertilizer.

The invention also relates to an agrochemical mixture comprising at least one fertilizer and the composition according to the invention.

The agrochemical mixture according to the invention can comprise a fertilizer as defined above and the composition according to the invention. In other embodiments, the agrochemical mixture of the present invention may comprise at least one or more than one fertilizer as defined above, for example 2, 3,4, 5, 6, 7, 8, 9, 10 or more different fertilizers (including inorganic, organic and urea-containing fertilizers) and the composition of the present invention.

The agrochemical mixture may comprise, in addition to at least one fertilizer and the composition of the present invention, other ingredients, compounds, active compounds or compositions, and the like. For example, the agrochemical mixture may additionally comprise or be based on a carrier, for example an agrochemical carrier, preferably an agrochemical carrier as defined herein. In other embodiments, the agrochemical mixture may further comprise at least one additional pesticide compound. For example, the agrochemical mixture may additionally comprise at least one further compound selected from herbicides, insecticides, fungicides, growth regulators, biopesticides, urease inhibitors, nitrification inhibitors and denitrification inhibitors.

In particular embodiments, the treatment may be performed during all suitable growth stages of the plant as defined herein. This treatment can be performed during the main growth phase of the BBCH, for example.

The term "BBCH major growth stage" relates to the extended BBCH standard, which is a system that uniformly encodes a phenoiomorphic growth stage of all monocotyledonous and dicotyledonous plant species, in which the entire developmental cycle of the plant is subdivided into longer lasting developmental stages that can be clearly identified and differentiated. The BBCH standard uses a decimal coding system, which is divided into primary and secondary growth phases. The abbreviation BBCH is derived from the Federal Biological Research Centre for Agriculture and Forestry (Germany), the Bundesportenamt (Germany) and the chemical industry.

In one embodiment, the present invention relates to a method of reducing nitrification comprising treating a plant growing on soil or a soil substitute and/or a locus where the plant is growing or is intended to grow with a composition of the present invention during a Growth Stage (GS) between the plants GS00-GS > BBCH 99, preferably between the plants GS00-GS 65 BBCH (e.g., when fertilizing after harvest of apples in autumn).

In one embodiment, the present invention relates to a method for reducing nitrification, comprising treating a plant growing on soil or a soil substitute and/or a locus where the plant is growing or is intended to grow with a composition of the present invention at a Growth Stage (GS) between GS00-GS 45 of the plant, preferably between GS00-GS 40BBCH of the plant.

In a preferred embodiment, the present invention relates to a method for reducing nitrification, comprising treating a plant growing on soil or a soil substitute and/or the locus where the plant is growing or is intended to grow with a composition according to the invention at an early Growth Stage (GS) of the plant, in particular GS00-GS 05, or GS00-GS 10, or GS00-GS 15, or GS00-GS 20, or GS00-GS 25 or GS00-GS 33 BBCH. In a particularly preferred embodiment, the method of reducing nitrification comprises treating the plants growing on the soil or soil substitute and/or the locus where the plants are growing or are intended to grow with the composition of the invention during the growth phase including GS 00.

In another particular embodiment of the invention, the composition of the invention is applied to the plant growing on the soil or soil substitute and/or the locus where the plant is growing or is intended to grow, at a growth stage between GS00-GS 55 BBCH of the plant.

In another embodiment of the invention, the composition of the invention is applied to the plant growing on the soil or soil substitute and/or the locus where the plant is growing or is intended to grow, at a growth stage between the plants GS00-GS 47 BBCH.

In one embodiment of the invention, the composition of the invention is applied to the plants growing on the soil or soil substitute and/or to the locus where the plants are growing or are intended to grow, before and at the time of sowing, before emergence and until harvest (GS00-GS 89 BBCH), or at the Growth Stage (GS) between GS00-GS 65 BBCH of the plants.

In a particularly preferred embodiment, the composition of the invention is used for treating the locus where the plant is intended to grow with the composition of the invention before the plant is planted and/or before the seed of the plant is sown.

Suitable crops are, for example, onions (Allium cepa), pineapples (Ananascomosus), groundnuts (Arachis hybrida), Asparagus (Asparagus officinalis), oats (Avenativa), beets (Beta vulgaris) and American rice (Sorghum), red beans (Sorghum, red beans), red beans (Sorghum), red beans (corn), red beans (Sorghum), red beans (corn), red beans (rice), red beans (corn).

Preferred crops are groundnut (Arachis hypogaea), sugar beet (Beta vulgaris, L.) beet (beet), Brassica napus (Brassica napus, var. napus), kale (Brassicaoleracea), lemon (Citrus limonum), sweet orange (Citrus sinensinsis), coffee chervil (coffee arabica), coffee cherry (coffee carica), coffee cherry (coffee lilac), cotton terrestris (cynomolgus liberans), soybean (Glycine max), cotton terrestris (maize), cotton grass (Gossypium herum), Gossypium sativum (Sorghum viennense), Sorghum vittatum (maize), maize (corn), wheat (maize), maize (corn), wheat (maize), maize (corn), maize (maize).

Particularly preferred crops are cereals, maize, soya, rice, oilseed rape, cotton, potatoes, peanuts or perennial crops.

The mixtures or compositions of the invention may also be used in crops that have been modified by mutagenesis or genetic engineering to provide new traits to plants or to modify traits that are already present.

The term "crop" as used herein also includes plants (crops) that have been modified by mutagenesis or genetic engineering to provide new traits to the plant or to modify an existing trait.

Targeted mutagenesis techniques typically use oligonucleotides or proteins such as CRISPR/Cas, zinc finger nucleases, TA L EN, or meganucleases to achieve a targeted effect.

Genetic engineering typically uses recombinant DNA techniques that are not readily accessible under natural conditions by hybridization, mutagenesis, or natural recombination to produce modifications in the plant genome. One or more genes are typically integrated into the genome of a plant to add or improve a trait. These integrated genes are also referred to in the art as transgenes, and plants comprising such transgenes are referred to as transgenic plants. This plant transformation method typically produces several transformation events that differ in the genomic location into which the transgene has been integrated. Plants comprising a particular transgene at a particular genomic location are often described as comprising a particular "event," the latter being referred to by a particular event name. Traits that have been introduced into plants or modified include herbicide tolerance, insect resistance, increased yield, and tolerance to abiotic conditions, such as drought.

Increased yields are produced by increasing ear biomass using a transgene athb17, e.g., present in corn event MON87403, or by increasing photosynthesis using a transgene bbx32, e.g., present in soybean event MON 87712.

Crops comprising modified oil content have been produced by using transgenes gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb 1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON 87769.

Tolerance to abiotic conditions, particularly drought, by use of the transgene cspB comprised by corn event MON87460 and by use of the soybean event

The transgenic Hahb-4 involved is produced.

Traits are often combined by combining genes in a switching event or by combining different events during a breeding process. Preferred combinations of traits are combinations of herbicide tolerance to different classes of herbicides, insect tolerance to different classes of insects, especially to lepidopteran and coleopteran insects, combinations of herbicide tolerance with one or several types of insect resistance, combinations of herbicide tolerance with increased yield and combinations of herbicide tolerance and abiotic condition tolerance.

Plants comprising individual or stacked traits, as well as genes and events that provide these traits, are well known in the art. For example, detailed information about mutagenized or integrated genes and corresponding events can be obtained from websites of the organizations "International services for the Acquisition of Agri-biological Applications (ISAAA)" (http:// www.isaaa.org/gpmapplavaldatabase) and "Center for Environmental Risk Assessment (CERA)" (http:// CERA-gmc. org/GMcropdatabase) and patent Applications such as EP 3028573 and WO 2017/011288.

Use of the compositions of the present invention on crops may result in effects specific to crops comprising certain genes or events. These effects may involve changes in growth behavior or changes in tolerance to biotic or abiotic stress factors. Such effects may include, inter alia, increased yield, increased resistance or tolerance to insects, nematodes, fungi, bacteria, mycoplasma, viruses or viroid pathogens, as well as early vigor, premature or delayed maturation, cold or heat tolerance, and amino acid or fatty acid profile or content changes.

In a likewise preferred embodiment, the present invention relates to a method for improving the nitrification inhibitory effect, wherein seeds, plants or soil are treated with an effective amount of an inventive composition for NI.

The term "NI effective amount" means an amount of a composition of the present invention sufficient to achieve the nitrification inhibitory effect as defined below. Further exemplary information on the amounts to be used, the mode of administration and the appropriate ratios are given below. In any case, the skilled person is well aware of the fact that the amount may vary within wide limits and depends on various factors, such as the climate, the target species, the location, the mode of application, the type of soil, the treated cultivated plant or material and the climatic conditions.

According to the invention, the nitrification inhibition effect is increased by at least 2%, more preferably by at least 4%, most preferably by at least 7%, particularly preferably by at least 10%, more particularly preferably by at least 15%, most particularly preferably by at least 20%, particularly more preferably by at least 25%, particularly most preferably by at least 30%, particularly preferably by at least 35%, particularly more preferably by at least 40%, particularly most preferably by at least 45%, particularly preferably by at least 50%, particularly preferably by at least 55%, particularly more preferably by at least 60%, particularly most preferably by at least 65%, particularly preferably by at least 70%, for example by at least 75%. The nitrification inhibition effect may be increased, for example, usually from 5 to 10%, more preferably from 10 to 20%, most preferably from 20 to 30%. The nitrification inhibition effect can be measured according to example 2 shown below:

the invention is further illustrated by the following examples.

Example (b):

example 1

The aqueous composition according to the invention was prepared according to the following procedure.

A mixture of 25% aqueous ammonia (2-4 equivalents) and water (if needed for lower amounts of DMPSA) was stirred at room temperature. Solid DMPSA (1-3g, 98.9% purity, 3, 4-isomer: 4, 5-isomer ═ 77:23) was added portionwise to reach the indicated amounts and the pH was determined after the solution was formed.

It was tested whether a solution could be obtained. The results are provided in table 1 below.

TABLE 1

Total amount of DMPSA and/or derivatives thereof, calculated as weight% of DMPSA based on the total weight of the composition example 2:

the DMPSA active ingredient assay (hereinafter referred to as "assay DIN EN 17090" a.i.) was carried out according to the Method of DIN EN17090 ("Fertilizers-Determination of nitrile inhibitor DMPSA in modulators-methods using high-performance liquid chromatography (HP L C); German and English edition prEN17090: 2017").

The nitrification inhibiting effect of the aqueous composition according to the present invention has been determined as follows:

100g of soil was filled into a 500ml plastic bottle (e.g., soil sampled from a field) and wetted to about 50% water holding capacity. To the soil was added 10mg of nitrogen in the form of ammonium sulfate-N. The a.i. is added to reach a final concentration of 0.1 or 1% of the applied ammonium-N before the soil is mixed. The bottle was capped but loose to allow air exchange. The bottles were then incubated at 20 ℃ for up to 14 days.

For analysis, 300ml of 1% K₂SO₄The solution was added to a bottle containing soil and shaken in a horizontal shaker at 150rpm for 2 hours. All solutions were then filtered through a Macherey-Nagel filter MN 8071/4. The filtrate was then analyzed for ammonium and nitrate content at 550nm in an automatic analyzer (Merck, AA 11).

A.i. analysis DIN EN17090 was performed on several samples according to the method described above, the results are provided in table 2 below (a.i. analysis). The nitrification inhibitory effect was measured according to the above-described method, and the results are provided in table 3 below (nitrification inhibitory effect). The active ingredient is referred to as "a.i.". The 3, 4-dimethylpyrazole phosphate is referred to as "DMPP".

According to calculation

The equation proceeds as follows:

the equations are described in

H. Et al (1973) "Mitterzur Hemmungbzw. Regelung der Nitrfikation von Ammoniumstackstoff in

DDR-Wirtschaftstpatent (German Deutsche Sum. Committee for general Committee) C05C 169727. Cited in Peschke, H. (1985) "Zur Bewertung der inhibierenden Wirkung von Nitrifiziden im Boden", Zbl. Mikrobiol.140, p. 583. 588.

TABLE 2

TABLE 3

The number refers to the number of the aqueous composition as specified in table 1 (further a.i. analysis in table 2).

According to

The equation (see above).

The results in table 3 show that the aqueous composition according to the invention also has a good nitrification inhibiting effect.

Claims

1. An aqueous composition comprising 2- (dimethyl-1H-pyrazol-1-yl) succinic acid and ammonia.

2. An aqueous composition according to claim 1, wherein 2- (dimethyl-1H-pyrazol-1-yl) succinic acid is at least partially present in the form of hydrogen succinate and/or succinate salt.

3. An aqueous composition according to claim 1 or 2, wherein the ammonia is at least partially present in the form of ammonium cations.

4. An aqueous composition according to any one of claims 1 to 3, wherein the aqueous composition is a solution.

5. Aqueous composition according to any of claims 1 to 4, wherein 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, its hydrogen succinate and/or succinate salt is present in the following form:

-2- (3, 4-dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt form;

-in the form of a mixture of isomers comprising

6. The aqueous composition according to any one of claims 1 to 5, wherein the composition is obtained by using ammonia in an amount such that the molar ratio of ammonia to 2- (dimethyl-1H-pyrazol-1-yl) succinic acid is from 1:1 to 10:1, preferably from 2:1 to 6: 1.

7. Aqueous composition according to any of claims 1 to 6, wherein the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present in the composition in an amount corresponding to at least 10 wt. -%, preferably at least 20 wt. -%, based on the total weight of the composition, of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid.

8. Aqueous composition according to any of claims 1 to 7, wherein the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present in the composition in an amount corresponding to 10 to 70% by weight, preferably 20 to 60% by weight, of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, based on the total weight of the composition.

9. An aqueous composition according to any of claims 1 to 8, wherein the pH of the composition is 7 or less, preferably 4 to 6.9.

10. An aqueous composition according to claim 9, wherein the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present in the composition in an amount corresponding to 10-40% by weight, preferably 20-35% by weight, of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, based on the total weight of the composition.

11. The aqueous composition according to claim 9 or 10, wherein the composition is obtained by using ammonia in an amount such that the molar ratio of ammonia to 2- (dimethyl-1H-pyrazol-1-yl) succinic acid is from 1:1 to 2.5:1, preferably from 1.8:1 to 2.5: 1.

12. An aqueous composition according to any of claims 1 to 8, wherein the pH of the composition is greater than 7, preferably 8 to 12.

13. An aqueous composition according to claim 12, wherein the total amount of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid, hydrogen succinate and/or succinate salt is present in the composition in an amount corresponding to more than 40 to 70 wt. -%, preferably more than 40 to 60 wt. -%, of 2- (dimethyl-1H-pyrazol-1-yl) succinic acid based on the total weight of the composition.

14. The aqueous composition according to claim 12 or 13, wherein the composition is obtained by using ammonia in an amount such that the molar ratio of ammonia to 2- (dimethyl-1H-pyrazol-1-yl) succinic acid is from more than 2:1 to 10:1, preferably from 2:1 to 5: 1.

15. Use of an aqueous composition according to any of claims 1 to 14 as nitrification inhibitor in combination with an ammonium-and/or urea-containing fertilizer.

16. Use according to claim 15, wherein the ammonium-and/or urea-containing fertilizer is selected from ammonium nitrate, calcium ammonium nitrate, ammonium sulphate nitrate, diammonium phosphate, monoammonium phosphate, ammonium thiosulphate, NPK fertilizer, NK fertilizer, NP fertilizer, UAN (urea ammonium nitrate solution), manure and urea.

17. Use according to claim 15, wherein the ammonium-and/or urea-containing fertilizer is selected from the group consisting of calcium ammonium nitrate, ammonium sulphate and ammonium sulphate nitrate.