DD222471A3 - ACTIVE COMBINATION FOR INHIBITION BZW. REGULATION OF NITRIFICATION OF AMMONIUM NITROGEN IN CULTURED BODIES - Google Patents

Abstract

The invention relates to active ingredient combinations for inhibiting or regulating the nitrification of ammonium nitrogen in Kultursoeden. The aim of the invention is a better utilization of the fertilizer nitrogen. The object of the invention is to find active substance combinations which have a synergistic effect in terms of inhibiting or regulating the nitrification of ammonium nitrogen in the soil. The object is achieved according to the invention in that a pyrazole compound, this can be pyrazole itself, a substituted pyrazole or a corresponding pyrazolium salt and dicyandiamide in Mischungsverhaeltnissen of 1:10 to 1: 400 was combined. The active ingredient combinations can be used in agriculture and forestry before, simultaneously with or after Duengerapplikation in application rates of 2 to 60 kg of active ingredient / ha.

Description

Combination of active substances for inhibiting or regulating the nitrification of ammonium nitrogen in cultivated soils ,

Field of application of the invention

The invention relates to the use of drug combinations for inhibiting or regulating the nitrification of ammonium nitrogen, in particular from mineral and organic fertilizers, in cultivated soils. ¹

Characteristic of the known technical solutions

Ammonium nitrogen is subject in the soil in a relatively short time of microbial conversion via the intermediate of nitrite nitrogen to nitrate nitrogen

This nitrification is significantly influenced by the temperature, the soil moisture, the pH and the biological activity of the soil. Nitrate nitrogen, in contrast to ammonium nitrogen, is not sorbed by the sorption carriers of the soil, clay and humus. The consequence of this is that nitrate nitrogen during the winter half-year and in heavy rainfall or intensive irrigation also during the summer half-year, especially on lighter soils, the leaching is subject. The leaching losses can average up to 20 % of the fertilizer nitrogen per year. The leached nitrogen does not work

1äÄUQ.1983 * llll5-7

^ ₂

R. A,

Formula I

where in formula IR, and F? 2 independently of one another can be hydrogen, methyl, halogen or nitro, R _{3 can be} hydrogen, methyl or halogen and hydrogen, nitro and CXR ₄ and herein X is either oxygen or sulfur, R. Alkyl- / alkenyl-, aryl- and / or cyclohexyl radicals substituted amino- or sulfonamido group, an optionally substituted by alkyl and / or aryl radicals ureido or thioureido, an optionally substituted by alkyl and / or aryl radicals hydroxylamino or hydrazino or is an optionally substituted alkoxy or Aroxyrest, with dicyandiamide corresponding to the general formula II

NH

H ₂ NC-NHCN '

Formula II

be combined, wherein in a mixing ratio of 1: 1 to 1: 400, preferably 1:10 to 1: 100 (pyrazole: dicyandiamide), synergistic improvements compared to the individual effects occurred. The dicyandiamide is the synergist to said pyrazoles, as could be demonstrated by the results of different structural variants.

ι _t

For the nutrition of crops lost, but it also comes to the enrichment of nitrate nitrogen in groundwater. In connection with the drinking water supply, this can lead to damage to health in humans and animals.

In addition to the leaching losses occur annually significant gaseous nitrogen losses by denitrification of nitrate nitrogen.

It is already known that substituted pyrazoles (WP 131.063 and WP 133.088 and US Pat. No. 3,494,757) as well as their azolium salts (US Pat. No. 3,635,690 and OP-P 72-47,182 and DP-P 72-47,183 inter alia Dicyandiamide (Amberger, A "and other journal Arable and Pflanzenbau 148 pp. 198-204 and pp. 239-246, 1979) inhibit nitrification.

Object of the invention

The aim of the invention is to increase the economic benefits of nitrogen fertilization by inhibiting or regulating the nitrification.

Explanation of the essence of the invention

The object of the invention is. To find active agent combinations that aufwei.sen synergistic effect in terms of inhibiting or regulating the nitrification of Ammoniumstickstof.f in the soil and thus allow more economical use of the individual active ingredients. '

The object is achieved in that substituted pyrazoles of the general formula I and / or their azolium salts.

The proposed combinations have the advantage that they have a higher residual effect and the application rate can be significantly reduced without the, positive effect is lost. This results in lower cost of ownership, lower burden on the ecological system and the possibility of earlier application of nitrogen fertilizers.

The combinations of the invention may be used in admixture with or in conjunction with solid or liquid mineral or organic fertilizers containing urea and / or ammonia and / or ammonium nitrogen, and may also be in the form of a solid or liquid concentrate, e.g. Water, or in admixture with a solid, ground or granulated excipient.

The combinations according to the invention can also be used together with other agrochemicals, such as. As pesticides and soil conditioners and applied with other agrotechnical measures.

The combinations are expediently shortly before, simultaneously with or shortly after the application of the fertilizer. . '. , medium applied at an application rate of 0.2 to 100 kg of active ingredient / ha, preferably 0.5 to 60 kg per hectare.

When used together with a solid or liquid fertilizer, they may be used at from 0.1 to 50% by weight, but preferably from 1 to 30% by weight of the fertilizer nitrogen.

· Ι

The following examples serve to illustrate the invention without limiting it.

Table 1 gives an overview of the biological activity of individual representatives of said pyrazoles

of the general formula I, while Table 2 shows the differential residual effect.

Based on this, individual derivatives were selected for combination with dicyandiamide, and it was the stated aim of this invention to prove, by means of the following examples (Tables 3-9), that a synergistic effect improvement is achieved by the combination with dicyandiamide, regardless of the structural type of the pyrazole derivative reflected in an increased residual effect ·

example 1

Substituted pyrazoles of the general formula I or their azolium salts are distinguished by a high initial effect, as the results in Table 1 show.

To test the initial effect 16 ppm (based on soil mass) of the respective pyrazole were added to a humorous sandy loam soil.

The nitrogen source was ammonium sulfate (20 mg N / 100 g soil). After humidifying the soil to 50 % of the maximum water capacity, it was incubated at 20 ⁰ C and determines the nitrate or nitrite nitrogen formed after 14 days. The reported inhibition of nitrification in percent is calculated as follows:

a - b % inhibition = - = -. 100

a = nitrite and nitrate content of the control b = nitrite and nitrate content of the sample, with active substance c = nitrite and nitrate content of the soil used

Table 1:

Percent inhibition of nitrification by substituted pyrazoles of formula I after 14 days of incubation.

Ser. No. ν ^z / R ₁ R ₂ ^R 3 % Inhibition 1 OC ₂ H ₅ CgH ₅ CH ₃ H 8.4 2 C0 (4-N0 ₂ -Phen) C ₂ H ₅ CH ₃ H '100 '' 3 H Chg-Phen H H 86 4 OC ₂ H ₅ CH ₃ CH ₃ CH ₃ 85 5 CONH ₂ CH ₃ H H 100 6 COOC ₂ H ₅ CH ₃ H H' 100 7 CS-Phen CH ₃ H H 96 8th H CH ₃ ; ' CH ₃ H 81 9 OC ₂ H ₅ CH ₃ H H 92 10 C0 (2-N0g-phen) ¹ ι CH ₃ H H ' 92 11 C0 (4-N0G-phen) CH ₃ H   H 96 12 CONHg CH ₃ CH ₃ H 100 13 C0N (CH _{3) 2,} CH ₃ CH ₃ H 80 14 CONH (3-CF ₃ -Phen) CH ₃ . H H 100 15 C0NH (4-Cl-phen) CH ₃ H H 100 16 CSNH-Phe.n CH ₃ H H 100 17 / CSNHCH ₃ CH ₃ H H 95 18 C00 (4-N0 ₂ -Phen) CH ₃ H H 100 19 CH ₂ OH CH ₃ H H 100 20 CSNHCH ₃ 3-Cl-phen H H 100 21 OCgH ₅ CH ₃ Cl H 75

Table 1: Continuation

No. Z ^R l R ₂ ^R 3 % Inhibition 22 CO-Phen CH ₃ Cl H 89 23 H CH ₃ br H 85 24 _H (D CH ₃ Cl H 88 25 H CH ₃ H OC ₂ H ₅ 92 26 H CH ₃ H H 100 27 C0 (2-N0 ₂ -Phen) CH ₃ H ^CH 3 98 28 H CH ₃ H CH ₃ 98 29 CH ₂ OH tert.C ₄ H _g H H 80 30 C0 (4-N0 ₂ -Phen) nC ₃ H _y H H 89 31 CO (4-NO ₂ -Phen) CH ₃ CH ₃ H 90 32 C0 (4-N0 ₂ -Phen) H H H 100 33 • H C ₂ H ₅ CH ₃ H 85 34 H < ² > CH ₃ H H 35 _H (3) CH ₃ H H 99 (1) hydrochloride (2) sulfate (3) phosphate

Example 2

The experimental batch corresponds to that in Example 1. described, wherein the active ingredient concentration was 5 x 10 ~ mol / 100 g of soil and was used as N-source urea.

To determine the residual effect, the samples were made variable according to the inhibitory effect of the compounds.

After logarithmic transformation of the sum of the specific nitrate or nitrite contents and the incubation time in days, the measured values could be calculated by means of linear regression. ,

From the determined regression lines, the t ₅₀ values were determined, which represent the time in days after which 50 % of the fertilizer nitrogen in the soil is nitrified.

The tc> y value represents a statistically assessable biological effect parameter. The difference between your t Q value of the test variant represents the delay of the nitrification process caused by the active substance. ''''.'.

As Table 2 indicates, depending on the substituent matrix of the formula I, the substituted pyrazoles show a strongly differentiated residual action.

Table 2: Residual effect of substituted pyrazoles according to formula I.

No. ^{z R} i. ^CH 3 ^CH 3 R ₂ ^R 3  "50 ^t 50 ⁽¹⁾ _r w 40 1 C0 (4-N0 ₂ -Phen) CH ₃ ) CH ₃ ^CH 3 H H 32.1 31.3 to 33.0 .9783 45 2 C0 (4-N0 ₂ -Phen) CH ₃ C0 (3-N0 ₂ -4-Br-Phen) CH ₃ ^CH 3 Cl H 19.9 19.3 to 20.9 .9606 30 3 C0 (4-N0 ₂ -Phen) ^CH 3 CONH ₂ ^CH 3 CH ₃ H 26.6 24.2 to 28.8 .9390 30 4 ' C0 _(T 4 N0 ₂ phen) CH ₃ CONHCH ₃ CH ₃ br H 8.2 8.0-8.4 .9665 30 5 C0 (4-N0 ₂ -Phen) CH ₃ CON- (CH ₃ ) CONHCh ₃ CH ₃ CH ₃ CH ₃ 8.7 7.2 to 10.5 .7332 40 6 C0 (4-N0 ₂ -Phen) CH ₃ CONH-CyCLC ₆ H ₁₁ CH, H CH ₃ 8.8 8.4- 9.1 .9644 30 7 C0 (4-N0 ₂ -Phen) H CONH-Phen H H 11.4 11.1 to 11.8 .9614 45 8th H CH ₃ CSNHCH ₃ H H 32.0 29.7 to 34.6 .8806 35 9 H ^CH 3 CSNHCH, Cl H 24.8 24.3 to 25.3 .9109 45 10 H CH ₃ CH = CH ^CH 3 H 10.5 10.3 to 10.7 .9820 42 11 H n · -C ₃ H ₇ H H 9.1 8.8- 9.3 .9860 35 12 H iC ₄ H _g H H 8.7 8.4- 9.0 .9810 30 13 C0 (2-Cl-phen) H H 31.9 31.1 to 32.7 .9680 40 14 C0 (4-CH ₃ S0 ₂ -Phene H H 31.2 30.7 to 31.7 .9739 35 15 H H 28.2 27.7 to 28.7 .9706 45 16 H H 32.7 31.9 to 33.5 .8807 25 17 H H 11.0 10.7 to 11.3 .9222 45 18 H H 30.6 30.0 to 31.0 .9087 30 19 H H 7.4 7.2-7.6 .9471 45 20 H H 24.8 24.5 to 25.1 0.9700 50 21 H H 32.1 31.1 to 33.2 .9107 45 22 CH, H 26.4 26.1 to 26.9 .9327

- 10 Table 2: Continuation

I -Prl '- »r -v - ^ (I) ·

_No. .1 2 ^K 3 ^Έ 50 50

23 CSNH-Phen CH ₃ HH 32.8 32.1-33.5 0/9536 40

24, CSCH ₂ CH = CH ₂ . , CH ₃ HH 32.2 32.0-32.5 0.9511 30

25 C0 (4-N0 ₂ -phen) C ₃ H ₅ CH ₃ H 10.4 10.2 to 10.6 0.9812 45

26 C0 (4-N0 ₂ -Phen) n-CjH-, HH 8.8 8.4- 9.2 0.9622 45

Urea untreated (control) 8.1 7.9-8.3 0.9762 30

V ^ confidence interval for = 0.05

ν 'correlation coefficient ^' number of measuring points

Example 3

The experimental procedure and evaluation corresponds to that described in Examples 1 and 2.

The combinations of 3-methylpyrazole and dicyandiamide according to the invention were added in the soil in a mixing ratio of 1: 1 to 1: 400 with different absolute active substance concentrations. Concentration series of the 3-methylpyrazole (0.3-1.5 ppm) and of the dicyandiamide (8-60 ppm) served as comparison.

As Table 3 indicates, prolonged residual effects are achieved by the combinations of 3-methylpyrazole (Compound No. 3, Table 2) with dicyandiamide throughout the mixing range, depending on the absolute drug concentration.

       '..' · '- 12 -

Table 3: Residual effect of 3-methylpyrazole, dicyandiamide and their combinations

3-Methyl dicyan-mixture pyrazole diamide ratio (ppm) ' (ppm) /

(Days)

0.30 _; , , 0 1 - 30.7 29 ^ 4- 3.2.1 .9320 12- 0.44 O 1 - - 38.2 36.1-40.4 .9127 12 0.67 \ 0 1 mm ..; 5i o 49.7 to 52.4 .8876 15 1.00 1 - 81.6 80.4- 82.7 .9518 20 1.50 0 1 - 89.3 88.0-90.6. .9794 24 O 8.0 ^Λ 1 - 25.9 24,7- 27,1 .8987 20 O '; 12.0 1 - _ 36,9 36.1-37.8 .9534 24 O 18.0 1 - 39.7 39.0- 40.3 .9764 24 O 27.0 1 - 48.8 48.3-49.3 0.9806 20 O 40.0 1 - 65.7 64.8-66.6 .9579 20 O 60.0 1 •1 74.8 74.1-75.5 .9673 20 0.50 0.5 ' 1 4.4 55.8 54.9- 56.7 .8849 20 0,90 ' 4.0 1 : 4.4 83.5 82.1- 84.9 .9608 20 1.35 1 : 4.5 90.1 88.4- 91.8 .9543 12 0.60 2.7 1 : 4.5 60.1 58.9-61.3 .9474 32 0.40 1.8 1 : 20 ; 39.6 39.1-40.2 0.9793, 24 0.25 5.0> 1 : 20 39.3 38.5- 40.2 .9549 24 0.40 8.0 1 : 20 47.2 46.2-48.3 .9503 20 0.60 12.0 : 22 94.1 91.8-96.6 .9285 16 0.90 20.0 : 80 111.0 108.7 to 113.3 ^ .9142 12 0.20 16.0 53.3 51.9- 54.7 .9154 16 0.13 10.5 : 80 45.2 44.3-46.2 0.9525 24 0.30 24.0 : 89 .. 88.6 87.2-90.0 .9969 24 0.45 40.0 : 358 114.5 112.8 to 116.3 .9723 18 0.067 24.0 360 45.3 .45,6-47,0 .9800 18 0.10 36.0 360 67.4 66.2-68.6 .9610 20 0.15 54.0 : 364 94.9 92.9-96.9 .9631 19 0,044 16.0 : 400, 42.2. 41.7- 42.7 .9797 24 0,025 Λ 16.0 41.3 40.8- 41.8 .9810 20 \ 'Urea untreated 13.4 12.8-14.0 .9763 14

The combination effect is said to be synergistic if it is better than the equivalent effect calculated from the two individual effects of the mixing partners or if the dose required for a given effect is less than that calculated (Groeger et al., Pharmazie 36_ (1981) p. 87).

The evaluation of the results shown in Table 3 by this isobolene method is shown in the table. The stated specific dose results from the Korizentrationsreihen the individual compounds or combinations for a given effect (t ₅₀ value = 90 days). The evaluation of the synergism is carried out by indicating the percentage of drug savings compared to the dose determined according to the model described above. ,

Table 4: Percentage drug savings over the equivalence model calculated dose (isobolic method) for t _5Q = 90 days of the combination of 3-methylpyrazole and dicyandiamide

Substance/ im trying him for equivalence % one combination average dose model determined gespar · (Ppm) Dose (ppm) th dose 3-methylpyrazole 1.5 _ 1: 5 7.0 7.6 8th 1:25 11.5 25.4 55 1: 100 24 54.6 56 1: 400 50 77,2 35 dicyandiamide 90 -. ' -

14 example 4 ,

  *

Following the combination matrix (Table 3) shown in Example 3, the corresponding 1-carbamoyl-3-methylpyrazole (Compound No. 16, Table 2) / dicyandiamide combinations were tested,

Evaluation of the obtained tcg values by the isobolene method yielded the percentage of active substance shown in Table 5. ·

Table 5:

Percentage drug savings over equivalent-dose (isobolic method) for t _5Q - 90 days combination of l-carbamoyl-3-methylpyrazole and dicyandiamide

Substance / in trial he combination mediated dose (ppm) '. 1.6 Equivalent dose model (ppm) % saved dose 1-carbamoyl-3-methylpyrazole 8.1 - - 1 ; 5 12.0 7.6 6 1:25 23.8 25.4 53 1: 100 '52.0 54.6 56 1: 400 90.0 77,2 33 dicyandiamide - -

Example 5

S-Methyl ^ -chloropyrazole (Compound No. 9, Table 2) or l-Methylthiocarbamoyl-S ^ -dimethylpyrazole were combined with dicyandiamide in the mixing ratios of 1:25, 1:50 and 1:75 (pyrazole: dicyandiamide) and the Residual effect compared to the pure active ingredients determined. For this purpose, the active ingredients or combinations were mixed with a loamy sandy soil in the specified mixing ratios and absolute concentrations of active ingredient. The N-source was urea (20 mg N / 100 g soil). The experimental procedure and the calculation of the percentage inhibition of the nitrification process corresponds to those described in Example 1. As Table 6 shows, synergistic improvements are also achieved by these structural types.

Table 6: Residual action of 3-methyl-4-chloropyrazole,

of the l-methylthiocarbamoyl-S ^ -dimethylpyrazols, the dicyandiamides and the combinations between the two pyrazoles and dicyandiamide

Substance / _ % inhibition after days Incubation Combination ^μρ 14 28 42 56 70

3-methyl-4-chloropyrazole 0.5 100 88 64 35 12 1:25 ¹⁰ \ 100 ioo 95 77 45 1:50 10 100 100 93 73 43 1: 75 10 100 100 96 74 42 1-methyl'thi-carbamoyl-3,4-dimethylpyrazole 0.5 100 90 67 40 20 1 ? 25 10 100 100 97 80 50 1:50 10 100 100 95 85 48 1: 75 10 100 100 93 74 45 dicyandiamide 10 - 95 65 35 8th 0 15 98 78 45 35 20 20 100 95 89 87 52

Example 6 .

In the same mixing ratios as in Example 5, 3-methylpyrazole, 1-carbamoyl-5-methylpyrazole and 3-methylpyrazole sulfate were combined with dicyandiamide. The experimental procedure and evaluation is only changed by using as N-source slurry (20 mg total N / 100 g soil). The results achieved are shown in Table 7. As with the use of nitrogen fertilizers, the addition of

Combinations according to the invention to the organic fertilizer, the synergistic effect improvement regardless of the structural type of the pyrazole clearly pronounced.

Table 7: Residual of unterpfiedlicher pyrazoles, the dicyandiamide and the corresponding combinations with manure as N source in a loamy sandy soil

Substance / combination ppm 14 Inhibition after 28 Incubation 42 ion days 56 3-methylpyrazole 0.5 76 55 .. 21 .0 1:25 10 94 92- 82 63 1:50 10 96 95 82 64 1: 75 10 95 92 88 "58 1-carbamoyl-3-methylpyrazole 0.5 72 36. 19 O 1:25 10 91 85 70 46 1:50, 10 96 94 77 59 1: 75 10 97 94 77 52 3-methylpyrazole sulfate 0.5 84 40 24 O 1 ..':. 25 10 99 97 86 74 1 '' : 50 10 100 98 85 73 1: 75 10 99 57 83 69 Dicyandiamide, 10 86 78 37 O _v 15 98 94 71 .33 . '.. 20 100 100 83 72

- 17 -

Example 7

In Example 7, the results obtained in a sandy soil soil with liquid manure and manure as N-source with the same experimental approach as in Example 6 are shown.

As shown in Tables 8 and 9, although differences in both the residual effect of the pure active ingredients and the combinations in the same soil occur when using manure or manure as the N-source, the synergistic effect improvement is clearly reminiscent in both cases. This also applies to the effect in different soils (see Table 7).

Table 8:

Residual effect of different pyrazoles, the dicyandiamide and the corresponding combinations with liquid manure as N source in a sand rode

Substance/ ppm % Inhibition to incubate ionstagen combination 14 28 42 56 3-methylpyrazole 0.5 100 100 79 25 1:25 10 100 100 100 100 1:50 10 100 100 100 94 1: 75 10 100 100 100 100 1-carbamoyl-3-methylpyrazole 0.5 100 100 78 16 1:25 10 .100 100 100 82 1:50 10 100 100 100 90 1: 75 10 100 · 100 100 95 3-methylpyrazole sulfate 0.5 100 97 45 20 1:25 10 100 100 100 100 1:50 10 100 100 100 99 1: 75 10 100 100 100 88 dicyandiamide 10 100 97 47 O 15 100 100 100 56 20 100 100 100 , 81

Table 9: Residual effect of different pyrazoles, the dicyandiamide and their combinations with Oauche as N-source in a sand rode

Substance/ cathedral % Inhibition g after incubation Stagen 56 combination 14 28 42   23 3-methylpyrazole 0.5 100 99 77 100 1:25. ' 10 100 100. 100 100 1:50 10 100 100 100 100 1: 75  10 ' 100 100 100 29 1-carbamoyl-3-methylpyrazole 0.5 100 100 80 100 1:25. 10 100 100 100 100 1:50 10 100 100 100 100 1: 75 10 100 100 100 23 3-methylpyrazole sulfate 0.5 100 94 77 100 1:25 10 100 ' 100 100 100 1 .:.' 50 10 100 100 100 100 1: 75 10 100 I do 100 25 dicyandiamide 10 100 100 84 95 15 100 100 100 100 20 100 100 100 ^

Claims (1)

invention claim Iu drug combination for the inhibition or control of nitrification in cultivated soils, characterized in that they contain as active ingredient mixtures of pyrazole or substituted pyrazole or pyrazolium salt and dicyandiamide in mixing ratios of 1: 1 to 1: 400. 2f · active ingredient combination according to item 1, characterized in that they are mixed or together with solid or liquid mineral or organic fertilizers containing urea and / or ammonia and / or ammonium nitrogen, in the form of a solid or liquid concentrate or in Geraisch with a solid milled or granulated carrier is used » 3u combination of active ingredients according to item 1, characterized in that it is used before, simultaneously with or after the fertilizer application 4u active ingredient combination according to item 1 and 2, characterized in ⁷ that it comes together with other agrochemicals and / or agro-technical measures to implement '· SU. Active ingredient combination according to items 1 to 4, characterized in that it is applied at an application rate of 0.5 to 100 kg of active ingredient per hectare, but preferably 0.5 to 60 kg per hectare. 6u active ingredient combination according to item 1 and 4, characterized in that it is the fertilizers in amounts of 0.1 to 30 Gewichtsprozententenr, but preferably added 1 to 30 weight percent of the fertilizer nitrogen, applied. Γ " Γ Γ> J Λ