DE102006015362A1 - New N-((1H-pyrazol-1-yl)alkyl)(thio)phosphoric acid triamide compounds useful e.g. in the regulation of extracorporeal and/or inhibition of urease catalyzed hydrolysis of urea and nitrification and to reduce the nitrogen loss - Google Patents

Abstract

N-[(1H-Pyrazol-1-yl)alkyl](thio)phosphoric acid triamide compounds (I) and their salt, tautomer, polymorph form and metal complex with urease- and nitrification inhibitory effect, are new. N-[(1H-Pyrazol-1-yl)alkyl](thio)phosphoric acid triamide compounds of formula (I) and their salt, tautomer, polymorph form and metal complex with urease- and nitrification inhibitory effect, are new. X : O or S; R1>-R3>1-8C alkyl, 3-8C cycloalkyl, aryl, alkylsulfonyl, carbamoyl, sulfamoyl, amino, alkylamino, dialkylamino, F, Cl, Br, I, cyano, nitro, sulfo, carbonyl, carboxy, H or OH, where the groups of R1>-R3> are self-substituted; and n : 1-4. Independent claims are included for: (1) the preparation of (I); (2) a composition (A1) comprising (I) and optionally a carrier, stretching agent and/or diluting agent, auxiliary material and optionally further active agents; and (3) a fertilizer composition (FC) comprising urea based material and/or organic fertilizer and (I) and/or (A1). [Image] ACTIVITY : Fertilizer. MECHANISM OF ACTION : None given.

Description

The present invention relates to novel N- (pyrazolylalkyl) (thio) phosphoric triamides, Process for their preparation, compositions containing them and the use of these N- (pyrazolylalkyl) (thio) phosphoric triamides or compositions containing them as a means of regulation or inhibition of enzymatic (urease-catalyzed) urea hydrolysis as well as to inhibit nitrification. The compounds of the invention serve to avoid nitrogen losses when using urea-based Fertilizer, and to reduce the ammonia burden in animal sheds due to a most extensive elimination of urea hydrolysis. The Invention further relates to fertilizer compositions, which N- (pyrazolylalkyl) (thio) phosphoric triamides and a urea-based fertilizer contain.

urea is an original one biogenic metabolite produced by the enzyme urease in ammonia and carbon dioxide is split. The reaction is extraordinary fast and effective and is therefore for N-losses in the application of urea-based fertilizers responsible. These are especially tall if the ground does not have one has sufficient sorption power, to bind the liberated ammonia in the form of ammonium ions. Further losses result from the nitrification of ammonium to nitrate which is easily washed out of the soil or by Denitrification to harmful Greenhouse gases are released into the environment. This is going to agriculture yearly considerable Loss of nitrogen is lost, thus contributing to environmental impact on the other hand require an increased fertilizer requirement.

Furthermore can under unfavorable Climatic conditions and / or when applying to light soils spontaneously high ammonia concentrations in the soil occur, which then additionally the Germination and the emergence of young plants adversely affect.

There Urea the nitrogen fertilizer with the largest percentage of N content and by far the world's dominant N-fertilizer, is the search for workable solutions understandable for reducing nitrogen losses. To reach this goal, is a variety of solutions been proposed. To name in this context are the sour serving of urea prills or granules to produce in this way To be able to trap ammonia by salt formation or coating with substances, whereby urea is released slowed down and thus the resulting Ammonia can be easily "buffered" can.

Also caused the urease-catalyzed urea hydrolysis by cleavage of the in Feces and especially in urine urea in animal sheds to Part considerable ammonia loads, which - apart from an odor nuisance with a correspondingly high concentration - the development and the growth affect the animals negatively.

The N losses from urease-catalyzed hydrolysis of urea and nitrification under unfavorable Conditions, especially in tropical and subtropical climates, up to 50%. To minimize this loss potential, will be As required, several times divided fertilizers are recommended, however for the Farmer as a result of additional Application costs with considerable labor disadvantages and corresponding additional expenses.

options for restriction The nitrogen losses consist in the targeted inhibition of urease-catalyzed Urea hydrolysis on the one hand and nitrification inhibition on the other hand. The application appears in the first case Such substances promising, leading to a urease or nitrification inhibition to lead, being next to the application for fertilization purposes Of course also offers the application to minimize the ammonia load in animal sheds.

Of the Use of urease inhibitors is an effective way the extraordinary under normal conditions Rapidly extending enzymatic urea hydrolysis significantly slow it down. By the delay This enzyme reaction can be the fertilizer of nitrogen undecomposed into deeper soil layers.

In order to are ammonia losses due to the sorption potential of the above Soil layers, unlike on the soil surface, almost impossible. Furthermore In this way, urea and urea-containing fertilizers can be made easy To apply soil sites lossless.

In animal sheds, the emission of ammonia from manure and animal excrement by addition of a urease inhibitor can be effectively restricted.

Out the view of lossless and thus environmentally friendly storage and application of organic fertilizers such as manure or manure the use of urease and nitrification inhibitors is a suitable measure, around the fertilizer and thus fertilization efficiency of manure to increase, and the environmental impact of ammonia emissions or nitrate shift to minimize in the groundwater.

Out The literature is known to be specific organic, as well inorganic compounds urease-catalyzed urea hydrolysis to stave off (see S. Kiss, M. Simihăian, Improving Efficiency of Urea Fertilizers by Inhibiting of Soil Urease Activity, Kluwer Academic Publishers (2002)).

With the discovery of phosphoric acid ester diamides ( DD 122 177 ) compounds have been found which are extremely effective urease inhibitors. Similarly effective is a series of derivatives of phosphoric triamide, including the main body (cf., for example, US Pat. US 4,540,428 . US 4,676,822 . US 4,696,693 . US 4,537,614 . US 4,517,004 . EP 0 119 487 ), of which the N- (n-butyl) thiophosphoric triamide (NBTPT) has been commercialized as the only representative so far (AGROTAIN International, product name Agrotain ^® ).

at closer examination of these substances it turns out that some are relatively susceptible to hydrolysis, especially their duration of action and thus their applicability considerably limited is. For another, they are sometimes only in low yield or obtainable by means of complex manufacturing processes, so that a justifiable economy is not given. About that In addition, many compounds only disproportionately high application rates sufficient urease-inhibiting effect.

Although the above-mentioned N- (n-butyl) thiophosphoric triamide (NBTPT) is a good urease inhibitor, it has only limited stability in combination with urea-based fertilizers. This active ingredient is therefore usually used as a liquid formulation Agrotain ^® , which is mixed with solid urea-based fertilizers or dissolved in Füssigdüngern in these immediately before the fertilizer application, which is extremely uneconomical. On fertilizer granules also a uniform drug distribution can hardly be guaranteed so. In addition, NBTPT fails under anaerobic conditions in rice cultivation, ie precisely where the highest nitrogen losses and ammonia emissions occur, since the formation of the oxygen analogue of NBTPT and thus of the actual urease inhibitor is not or only slowly possible (see Fertilizer Research 42, 251 (1995)). Studies on the use of NBTPT as a slurry stabilizer have shown that NBTPT has little effect or effects only at an unacceptable cost-benefit ratio (see Transactions of the Am Soc. Of Aricult. Eng. (ASAE) 48 (2) , 787 (2005); J. Environm. Qual. 34 (3), 1119 (2005)).

Further, the application of some of the mentioned Compounds affecting disadvantages are that they are another Have migration behavior as urea. This will be the inhibitor separated from the substrate urea, which can lead to impairment of enzyme inhibition. Possible But it is also that originally effective Urea inhibitors, when in contact with soil, have their inhibitory effect by reaction with soil components or fixation to lose them.

Next N losses from uncontrolled urease-catalyzed hydrolysis the urea is ammonium or urea-based when used fertilizer Nitrogen in the form of nitrate lost by leaching or Displacement into deeper soil layers deprived of plant nutrition becomes. About that can out these N losses still increased when in the course of rapid nitrification of ammonium ions relatively large Amounts of nitrate are formed, which in turn by incipient Denitrification can be converted into molecular nitrogen and so also for the vegetable diet unavailable are. Denitrification also produces nitrogen oxides, which act as climate gases burden the environment. Due to the lower mobility of ammonium ions Compared to nitrate ions, ammonium ions stay longer in the Ground and thus longer available to plants. To eliminate or slow down the nitrification process offers the use of nitrification inhibitors.

As nitrification inhibitors, in addition to dicyandiamide (DCD), for example, substituted pyrazoles ( DD 131 063 . US 3,635,690 ), Triazoles (DE-OS 18 04 994, US 3,697,244 . US 3,701,645 ) but also drug combinations based on pyrazole compounds and dicyandiamide ( DD 227 957 ) or triazole derivatives and dicyandiamide (WO 95/22 515).

Although DCD is a cost-effective nitrification inhibitor, but must in very high application rates ap be plied to achieve a good effect. In addition, DCD is easily washed out in the soil under appropriate conditions. Pyrazole and triazole derivatives are more effective nitrification inhibitors than DCD. However, they are sometimes more expensive to produce, have a high volatility or show insufficient hydrolysis stability.

to comprehensive minimization of nitrogen losses during use of urea-based fertilizers Thus, both the use of urease inhibitors and of Nitrification inhibitors necessary.

In US 5,364,438 are described new liquid nitrogen fertilizers containing dissolved nitrogen in the form of urea and other nitrogen nutrients also shares of N- (n-butyl) thiophosphoric triamide (NBTPT) and dicyandiamide (DCD). Granulated urea-based fertilizers with NBTPT and DCD are used in US 5,352,265 claimed. The disadvantages of DCD have already been mentioned. Investigations have also shown that urease and nitrification inhibitors can not be arbitrarily combined with each other, since under certain conditions, the additional application of a nitrification inhibitor urease inhibitor may adversely affect the intended reduction of ammonia losses (NBTPT / DCD: Biol. Fertil., Soils 36 129 (2002)). This finding is also reflected in the yields, which were partly at the level of the sole urea fertilization used as a comparison (NBTPT / Carbid: Biol. Fertil., Soils 22, 89, (1996)).

If, in addition to the urease inhibitor, a nitrification inhibitor is also used as the nitrogen stabilizer, this of course also affects the price of the fertilizer, since higher costs are incurred for the production / procurement of the active ingredients, for storage, for different active substance formulations, etc. It is therefore more advantageous to use only one active substance which has both a urease and nitrification-inhibiting action. In the patent US 4,932,992 Thiophosphoric triamide is proposed as such a nitrogen stabilizer. However, this shows only at an extremely high and thus unfeasible practice rate of 20% based on the nitrogen content of the fertilizer a good effect and is also still hydrolyzed stable. In addition, certain 1,2,4-thiadiazole derivatives also show a urease- and nitrification-inhibiting action (WO 2005/007636). Apart from the only moderate inhibition effects, the production costs of these compounds are relatively high.

Of the It is an object of the present invention to provide such compounds for the Practice available to put in the application with fertilizer or other urea-based fertilizers are capable of enzyme-catalyzed urea hydrolysis such a measure too restrict, that resulting nitrogen losses in the form of ammonia almost impossible or the ammonia load in animal sheds by spontaneous decomposition of urea is significantly reduced. The new connections are next to the urease-inhibiting effect simultaneously inhibit nitrification, to further improve N utilization in urea-based mineral fertilizers as well as in manure to reach. The new nitrogen stabilizers are said to go beyond that already have a sufficient inhibitory effect at low application rates, thus an economic Application guaranteed is.

These Tasks are performed according to the invention the provision and use of N- (pyrazolylalkyl) (thio) phosphoric triamides as nitrogen stabilizers with the in claims 1 or 2 defined structures solved.

It that is surprisingly demonstrated that chemical linking of N-alkyl (thio) phosphoric triamides (as urease inhibitors) with pyrazole derivatives (as nitrification inhibitors) to N - [(1H-pyrazol-1-yl) alkyl] (thio) phosphoric triamides, the original Effect of the two components is largely retained.

Next a sufficient hydrolysis resistance and low volatility are the novel N- (pyrazolylalkyl) (thio) phosphoric triamides Furthermore technically trouble-free and cost-effective can be produced from simple starting materials. The novel N- (pyrazolylalkyl) (thio) phosphoric triamides are as well with common ones Process easily in urea or urea-based fertilizers einarbeitbar, whereby an efficient spreading together with the fertilizer possible is. They are both sufficiently water-soluble and well oil-soluble, which was also unpredictable.

The invention further relates to processes for the preparation of the N- (pyrazolylalkyl) (thio) phosphoric triamides according to the invention as defined in claim 3, compositions containing these N- (pyrazolylalkyl) (thio) phosphoric triamides as defined in claim 4, a fertilizer composition as defined in claims 5 or 6 and the uses defined in claims 7 to 11.

Further advantageous and / or preferred embodiments of the invention are the subject of the dependent claims.

in der:
X = Sauerstoff oder Schwefel;
n = 1, 2, 3 oder 4
R¹, R², R³ = unabhängig voneinander Wasserstoff, C₁-C₈-Alkyl, C₃-C₈-Cycloalkyl, Aryl, Alkylsulfonyl, Fluor, Chlor, Brom, Iod, Cyano, Nitro, Sulfo, Carbonyl, Carboxy, Carbamoyl, Sulfamoyl, Amino, Alkylamino, Dialkylamino, Hydroxy
bedeuten.The N - [(1H-pyrazol-1-yl) alkyl] (thio) phosphoric acid triamides according to the invention as urease and nitrification inhibitor inhibitors have the general formula (I):

in the:
X = oxygen or sulfur;
n = 1, 2, 3 or 4
R ¹ , R ² , R ³ = independently of one another hydrogen, C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl, aryl, alkylsulfonyl, fluorine, chlorine, bromine, iodine, cyano, nitro, sulfo, carbonyl, carboxy , Carbamoyl, sulfamoyl, amino, alkylamino, dialkylamino, hydroxy
mean.

The radicals R ¹ -R ³ may optionally be substituted independently and independently of one another with one or more of the abovementioned groups.

It also includes the invention salts, tautomers, polymorphic forms and metal complexes of compounds of the general formula (I) which have a urease and / or have nitrification-inhibiting effect.

Of course it will the skilled person the radicals given in the general formula (I) or select groups, that is not impossible molecules arise, e.g. chemically or sterically impossible.

The mentioned below Alkyl groups of the corresponding carbon number can be straight chain or branched and monounsaturated or polyunsaturated.

in the The following will sometimes be used to avoid unnecessary redundancy for the sake of simplicity, only the term "alkyl group" or "cycloalkyl group" etc. is used, however, in each case the corresponding unsaturated groups should be included.

Of the Term "alkyl" refers yourself, in any combination with any other group, in particular to an alkyl group containing 1 to 8 carbon atoms has, e.g. a methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, tert-butyl, amyl, isoamyl, n-hexyl, 2,2-dimethylbutyl or n-octyl group.

Of the Term "heteroalkyl" refers with regard to the alkyl moiety on an above-defined alkyl group, but should also a corresponding heteroalkenyl or heteroalkynyl group in which one or more carbon atoms are replaced by at least replaced an oxygen, nitrogen, phosphorus or sulfur atom are.

Of the Term "aryl" refers refers to an aromatic cyclic group containing one or more Has rings, and is formed by a skeleton, the 6 bis Contains 10 ring carbon atoms. Of course you can in the case of multiple rings one or more rings completely or partially hydrogenated (an example of which is the 1,2,3,4-tetrahydro-naphthalen-1-yl group). Furthermore an aryl group may be represented by alkyl or heteroalkyl groups (respectively as defined above). Examples are a phenyl, Naphthyl, indene, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 4-carboxyphenylalkyl or 4-hydroxyphenyl group.

Of the Term "cycloalkyl" or "carbocyclic" refers on a saturated or partially unsaturated, cyclic, optionally branched, group containing one or more rings which has a scaffold which contains 3 to 8 carbon atoms, e.g. a cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl, tetralin, cyclopentenyl or cyclohex-2-enyl group.

It It should again be noted that all of the above defined Groups both with themselves and with others of the ones defined above Groups can be substituted.

The compounds I according to the invention can be obtained by analogous application of known processes where X, n, R ¹ -R ^{3 have} the meaning described above. The (1H-pyrazol-1-yl) alkylamines used as starting materials can be obtained by reacting 1H-pyrazoles with chloroalkylamines (cf., for example, Patent PL 93771 ). If the resulting isomeric 3- and 5-substituted pyrazole derivatives are not separated, the two isomers are also obtained in the further reaction. In the synthesis of the compounds according to the invention corresponding to equations (1) and (2), the use of mixtures of isomers as starting materials disregarded the occurrence of isomers with respect to the position of the R ¹ and R ³ substituents. If desired, the particular isomers may be separated by the usual methods known to those skilled in the art.

• a) (1H-Pyrazol-1-yl)alkylamine oder deren Hydrochloride mit Phosphorylchlorid (POCl₃) oder Thiophosphorylchlorid (PSCl₃), gegebenenfalls in Anwesenheit eines organischen Lösungsmittels und einer Hilfsbase, bei Temperaturen von 0 bis 150°C, gegebenenfalls unter Schutzgasatmosphäre, entsprechend Gleichung (1) zu N-(Pyrazolylalkyl)phosphorsäureamiddichloriden des Typs (A) umsetzt, wobei Verbindungen (A) mit X = S alternativ auch durch Schwefelung der entsprechenden Sauerstoffderivate erhalten werden können,
  
• b) die in Stufe a) gebildeten Verbindungen des Typs (A) mit Ammoniak oder wässriger Ammoniaklösung, gegebenenfalls in einem inerten organischen Lösemittel, bei Temperaturen von -80 bis 30°C entsprechend Gleichung (2) zum gewünschten Endprodukt (I) reagieren lässt:
  

Preferably, the preparation of N- (pyrazolylalkyl) (thio) phosphoric triamides is carried out in such a way that

• a) (1H-pyrazol-1-yl) alkylamines or their hydrochlorides with phosphoryl chloride (POCl ₃ ) or thiophosphoryl chloride (PSCl ₃ ), optionally in the presence of an organic solvent and an auxiliary base, at temperatures of 0 to 150 ° C, optionally under a protective gas atmosphere , according to equation (1) to N- (pyrazolylalkyl) phosphoric acid amide dichloride of the type (A) is reacted, wherein compounds (A) with X = S can alternatively be obtained by sulfurization of the corresponding oxygen derivatives,
  
• b) reacting the compounds of type (A) formed in stage a) with ammonia or aqueous ammonia solution, optionally in an inert organic solvent, at temperatures of -80 to 30 ° C. in accordance with equation (2) to give the desired end product (I):
  

The N- (pyrazolylalkyl) (thio) phosphoric triamides according to the invention or compositions containing them, if suitably substituted at the Pyrazolrest a for Practical issues have good inhibitory effect, thereby reducing the slow down enzymatic urea hydrolysis or nitrification or temporarily can turn off, that nitrogen losses as part of fertilization measures using organic and / or mineral urea-containing nitrogen fertilizer a minimum be reduced or the occurrence of harmful or more annoying Ammonia concentrations in animal husbandry due to urea degradation is excluded in animal excreta.

there it is irrelevant whether the effect of the N- (pyrazolylalkyl) (thio) phosphoric triamides according to the invention or compositions containing them on fertilizer or preventive activities extends to avoid high ammonia concentrations in animal sheds.

The Compounds of the invention are preferably used together with urea-based fertilizers, preferably in an amount of 0.01 to 10 wt .-%, based on the weight of the urea-based fertilizer applied or in animal stables added to existing animal excretions. It is for example in the context of fertilization measures irrelevant, whether they are superficial before on the fertilizer applied, incorporated or dissolved in common or acceptable Period separated from urea-containing fertilizers are applied.

One further subject of the invention are therefore compositions those used in the invention N- (pyrazolylalkyl) (thio) phosphoric triamides and a urea-based contain mineral and / or organic fertilizer.

to Use as nitrogen stabilizers, for example for lowering the nitrogen losses during fertilization with fertilizer urea or urea-based fertilizers or to reduce the ammonia load from the manure or the animal excrement in animal stables can be According to the invention suitable compounds be applied or applied in various ways.

The Compounds of the invention can as nitrogen stabilizers in the urea or in urea-containing fertilizer before or during The granulation can be incorporated from the molten phase. Furthermore you can she on the surface the urea or Fertilizer granules applied or liquid urea-containing fertilizers be added. After all is the addition of nitrogen stabilizers to organic urea-containing fertilizers like manure or manure possible. About that can out the compounds of the invention also in addition for the application of urea-based fertilizers in a pre- or downstream work step can be applied separately on the field. The compounds of the invention can in pure form as pulverfömiger Fabric, granules or melt, aqueous Solution or as a special formulation, mixed with the usual and known in the art Auxiliary, carrier and extenders or a combination of these agents become. It is irrelevant whether the active ingredient in liquid Shape as z. B. solution, Emulsion or suspension or in solid form as dusts or dispersible powder is formulated. Wettable powders, emulsifiable Concentrates and suspension concentrates usually contain but not necessarily, surfactants, e.g. B. a Wetting, dispersing, emulsifying or suspending agents. The respective formulation methods correspond to the state of Technique and are known in the art.

The compounds, compositions and fertilizers according to the invention can be used, for example, in and for fertigation. By fertigation is meant the targeted supply of nutrients with the irrigation water, which can be applied eg by drip irrigation, spraying or sprinkling. The plants receive only the amount of water required for optimal growth, so that no excess water is produced. Lack of vertical water movement in the soil beneath the rooting zone virtually eliminates nutrient leaching losses. Drip irrigation, spraying or sprinkling with nitrogen stabilizers can take place, for example, after fertilization or together with the fertilizer. Of course, there is no limitation to aqueous solutions or other formulations. For example, sprayable suspensions of fine particles may also be used. Insofar let's be an example EP 1 378 499 and WO2004 / 013253.

The The present invention will now be apparent from the following examples without restriction and thus explained by way of illustration only.

Examples

example 1

General rule

To a solution of 0.05 mol of PSCl ₃ in 50 ml of THF at 0 ° C-5 ° C with stirring, a solution of 0.05 mol of the corresponding (1H-pyrazol-1-yl) alkylamine and 0.05 mol of triethylamine dropped into 50 ml of THF. The mixture is then allowed to warm to room temperature, stirred for a further 30 minutes and then at 50 ° C. for a further 30 minutes. After filtering off the triethylammonium chloride, the filtrate is concentrated in vacuo. The residual oil is washed twice with hexane, dissolved in 100 ml of chloroform and added dropwise at -30 ° C to about 100 ml of liquid ammonia. The reaction mixture is allowed to stand overnight at room temperature. After filtering off the ammonium chloride, the filtrate is concentrated in vacuo. The residual crude product is washed with ether. For further purification, the crude product can be flash chromatographed on silica gel with ethyl acetate.

Example 2

N- [3- (3 (5) -methyl-1H-pyrazol-1-yl) propyl] triamide

In analogy to Example 1, 3- (3 (5) -methyl-1H-pyrazol-1-yl) propylamine is obtained by flash chromatography as N- [3- (3 (5) -methyl-1H-pyrazol-1-yl)]. propyl] triamide.
Yield: 40
¹ H-NMR (DMSO-d ₆ ): δ [ppm] = 1.85 (m, 2H); 2.11 (s, 1.8H); 2.22 (s, 1.2H); 2.76 (m, 2H); 3.84 (s, 4H); 3.91 (m, 1H); 4.03 (t, 2H); 5.93 (d, 0.6H); 5.95 (d, 0.4H); 7.24 (d, 0.4H); 7.54 (d, 0.6H)
³¹ P-NMR (DMSO-d ₆ ): δ [ppm] = 59.8 ppm (m)

Example 3

N- [3- (3, (5) -methyl-1H-pyrazol-1-yl) ethyl] triamide

In analogy to Example 1, 3- (3 (5) -methyl-1H-pyrazol-1-yl) ethylamine is obtained by flash chromatography as N- [3- (3-methyl-1H-pyrazol-1-yl) ethyl] thiophosphoric triamide (only 1 isomer isolated).
Yield: 23
¹ H-NMR (DMSO-d ₆ ): δ [ppm] = 2.13 (s, 3H); 3.15 (m, 2H); 3.88 (s, 4H); 3.93 m (1H); 4.07 (t, 2H); 5.96 (d, 1H); 7.54 (d, 2H)
³¹ P-NMR (DMSO-d ₆ ): δ [ppm] = 59.8 ppm (m)

Example 4

N- [3- (3 (5), 4-dimethyl-1H-pyrazol-1-yl) propyl] triamide

In analogy to Example 1 is obtained from 3- (3 (5), 4-dimethyl-1H-pyrazol-1-yl) propylamine after washing the crude product with ether N- [3- (3,4-dimethyl-1H-pyrazole -1-yl) propyl] thiophosphoric triamide (only 1 isomer isolated).
Yield: 37
¹ H-NMR (DMSO-d ₆ ): δ [ppm] = 1.83 (m, 2H); 1.90 (s, 3H); 2.03 (s, 3H); 2.74 (m, 2H); 3.84 (s, 4H); 3.92 m (1H); 3.97 (t, 2H); 7.36 (s, 1H)
³¹ P-NMR (DMSO-d ₆ ): δ [ppm] = 59.8 ppm (m)

Example 5

N- [3- (4-chloro-3 (5) -methyl-1H-pyrazol-1-yl) propyl] triamide

In analogy to Example 1, 3- (4-chloro-3 (5) -methyl-1H-pyrazol-1-yl) propylamine is obtained after washing the crude product with ether N- [3- (4-chloro-3 (5 ) -methyl-1H-pyrazol-1-yl) propyl] triamide.
Yield: 37%
¹ H-NMR (DMSO-d ₆ ): δ [ppm] = 1.86 (m, 2H); 2.09 (s, 1.8H); 2.22 (s, 1.2H); 2.78 (m, 2H); 3.85 (s, 4H); 3.92 (m, 1H); 4.05 (m, 1H); 7.42 (s, 0.4H); 7.87 (s, 0.6H)
³¹ P-NMR (DMSO-d ₆ ): δ [ppm] = 59.8 ppm (m)

Example 6

exam on urease-inhibiting effect

30 g of soil adjusted to 40% of the maximum water capacity are mixed with 1 ml of urea solution corresponding to 50 mg of urea. At the same time the application of the active ingredient, preferably dissolved in the urea solution. The concentration data for the individual tested active substances in the table below relate to the amount of carbamide nitrogen used in the test. The soil, on the surface of which the urea solution (with and without active ingredient) is applied, is placed in an airtight container into which an original is simultaneously introduced, which captures the ammonia released from the urea as ammonium. By daily rinsing the template and analyzing the NH ₄ -N levels contained, the NH ₃ -N release from the urea is determined.

From the summation of the ammonium amounts in the template, the percentage inhibition of the urea hydrolysis is calculated as a function of time or calculated from these values of the t ₅₀ value.

The t ₅₀ value is the time in days after the start of the experiment at which the inhibition of urea hydrolysis is still 50%.

• ^a) Konz.% HS-N-bez.: Konzentration in Prozent bezogen auf die verwendete Menge an Harnstoffstickstoff
• ^b) Mittelwert verschiedener Versuche

Table 1 gives an overview of the inhibition data of some selected compounds of the invention determined by this method. Table 1: Urease inhibition (t ₅₀ value) after days by N- (pyrazolylalkyl) thiophosphoric triamides

• ^a) conc.% HS-N-mar.: concentration in percent relative to the amount of urea nitrogen used
• ^b) Average of different experiments

Example 7

Testing for nitrification-inhibiting effect

• ^a) Konz.% HS-N-bez.: Konzentration in Prozent bezogen auf die verwendete Menge an Harnstoffstickstoff

100 g of soil adjusted to 50% of the maximum water capacity were mixed with 10 mg of urea-N and the respective active substance with as homogeneous a distribution as possible. The concentration data for the individual tested active substances in the table below relate to the amount of carbamide nitrogen used in the test. The vials prepared in this way are stored under standardized conditions at 20 ° C in a dark climatic chamber. From the time-dependent determination of the conversion of ammonium-N to nitrate nitrogen compared to the variant without inhibitor, the percentage inhibition is determined after 14 days. Table 1: Nitrification inhibition by N- (pyrazolylalkyl) thiophosphoric triamides after 14 days

• ^a) conc.% HS-N-mar.: concentration in percent relative to the amount of urea nitrogen used

Claims (11)

N - [(1H-pyrazol-1-yl) alkyl] (thio) phosphoric triamides of general formula (I):

in which: X = oxygen or sulfur; n = 1, 2, 3 or 4 R ¹ , R ² , R ³ = independently of one another hydrogen, C ₁ -C ₈ -alkyl, C ₃ -C ₈ -cycloalkyl, aryl, alkylsulfonyl, fluorine, chlorine, bromine, iodine, Cyano, nitro, sulfo, carbonyl, carboxy, carbamoyl, sulfamoyl, amino, alkylamino, dialkylamino, hydroxy, where the radicals R ¹ -R ^{3 may} optionally be substituted independently and independently of one another with one or more of the abovementioned groups, and salts , Tautomere, polymorphic forms and metal complexes of compounds of general formula (I), which have a urease and nitrifkationshemmende effect. N- (pyrazolylalkyl) (thio) phosphoric triamides according to claim 1, wherein in formula (I) X = S, n = 3 or 4, R ¹ = methyl, R ² = H, chlorine or methyl and R ³ = H or R ¹ = H, R ² = H, chlorine or methyl and R ³ = methyl. A process for the preparation of the N- (pyrazolylalkyl) (thio) phosphoric triamides according to any one of claims 1 or 2, characterized in that a) (1H-pyrazol-1-yl) alkylamines or their hydrochlorides with phosphoryl chloride (POCl ₃ ) or thiophosphoryl chloride ( PSCl ₃ ), optionally in the presence of an organic solvent and an auxiliary base, at temperatures of 0 to 150 ° C, optionally under a protective gas atmosphere, according to equation (1) to N- (pyrazolylalkyl) phosphoric acid amide dichloride of type (A), wherein compounds (A ) with X = S can alternatively be obtained by sulfurization of the corresponding oxygen derivatives,

and subsequently b) the compounds of type (A) formed in stage a) react with ammonia or aqueous ammonia solution, optionally in an inert organic solvent, at temperatures of -80 to 30 ° C. in accordance with equation (2) to give the desired end product (I) leaves:

Composition, characterized in that at least one N- (pyrazolylalkyl) (thio) phosphoric triamide according to one of the claims 1 or 2 in a sufficient for urease and nitrification inhibition Amount and optionally agricultural and / or physiological acceptable or acceptable or desirable Carrier-, Diluent, Excipients and optionally other active ingredients. Fertilizer composition characterized in that it comprises at least one urea-based mineral and / or organic fertilizer and at least one N- (pyrazolylalkyl) (thio) phosphoric triamide according to one of the claims 1 or 2 and / or a composition according to claim 4 each in one sufficient for Ureaseinhibition or nitrification inhibition Contains quantity. fertilizer composition according to claim 5, characterized in that at least one N- (pyrazolylalkyl) (thio) phosphoric triamide according to one of the claims 1 or 2 in an amount of 0.01 to 10 wt .-%, based on the Weight of urea-based fertilizer, is included. Use of the N- (pyrazolylalkyl) (thio) phosphoric triamides according to one of claims 1 or 2 or the composition of claim 4 for extracorporeal regulation or inhibition of urease-catalyzed urea hydrolysis and nitrification. Use of N- (pyrazolylalkyl) (thio) phosphoric triamides according to one of the claims 1 or 2 or the composition according to claim 4 for lowering the Nitrogen losses during fertilization with fertilizer urea or urea-based mineral and / or organic fertilizers. Use of N- (pyrazolylalkyl) (thio) phosphoric triamides according to one of the claims 1 or 2 or the composition according to claim 4 for reduction the ammonia load from the manure or the animal excrements in animal stables. Use of N- (pyrazolylalkyl) (thio) phosphoric triamides according to one of the claims 1 or 2 or their aqueous solutions or liquid formulations for the stabilization of already applied or still to be carried out urea-based mineral and / or organic fertilizers by downstream or upstream application. Use of N- (pyrazolylalkyl) (thio) phosphoric triamides according to one of the claims 1 or 2 or the composition of claim 4 or the fertilizer compositions according to the claims 5 or 6 in the fertigation and fertigation.