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CN-122029140-A - Pyrazole derivatives as dual function urease and nitrification inhibitors

CN122029140ACN 122029140 ACN122029140 ACN 122029140ACN-122029140-A

Abstract

Dual function urease and nitrification inhibitor compositions and methods for inhibiting hydrolysis of urea and nitrification of ammonia in soil are disclosed. Also disclosed are methods of preparing dual function urease and nitrification inhibitors and/or compositions containing the dual function urease and nitrification inhibitors.

Inventors

  • Fahan Ahmed Pasha
  • Vino Viswanat
  • RAVI HEGDE
  • Balamurugan Widjayakumar
  • Khalid Abdullah Alba Hili

Assignees

  • 沙特基础工业公司农业营养素

Dates

Publication Date
20260512
Application Date
20240715
Priority Date
20230911

Claims (15)

  1. 1. A method of inhibiting urease activity and nitrification of ammonia, the method comprising applying to soil, crops and/or fertilizer a dual urease and nitrification inhibitor and/or a composition comprising the dual urease and nitrification inhibitor, wherein the dual urease and nitrification inhibitor have a structure represented by formula I: Wherein: x is sulfur or oxygen; r is a moiety having a structure represented by formula II or formula III: Either (or) or (b) And (C) sum R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 and R 10 are each independently H, substituted or unsubstituted C1 to C9 alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted saturated heterocycle, substituted or unsubstituted unsaturated heterocycle, substituted or unsubstituted aryl, hydroxy (-OH), methoxy (-OCH 3 ), ethoxy (-OC 2 H 5 ), nitro (-NO 2 ), amino (-NH 2 ), or halogen.
  2. 2. The method of claim 1, wherein the composition further comprises at least one nitrogen fertilizer component.
  3. 3. The method of claim 2, wherein the at least one nitrogen fertilizer component comprises urea, an ammonium salt, or anhydrous ammonia, or any combination thereof.
  4. 4. A method according to any one of claims 1 to 3, wherein the composition further comprises at least one additional nitrification inhibitor, wherein the additional nitrification inhibitor preferably comprises clomazone, dicyandiamide, ammonium thiosulfate, methyl 3- (4-hydroxyphenyl) propionate, 1, 9-decanediol, potassium azide, 2-amino-4-chloro-6-methylpyrimidine, sulfathiazole, 4-amino-1, 2, 4-triazole, 2, 4-diamino-6-trichloromethyl-s-triazine, potassium ethylxanthate, guanylthiourea, 4-nitrotrichlorotoluene, 4-methanesulfonyl trichlorotoluene, sodium trithiocarbonate, mercury phenylacetate, 3, 4-dimethylpyrazole phosphate, or sorghum, or any combination thereof.
  5. 5. The method of any one of claims 1 to 4, wherein the composition further comprises at least one additional urease inhibitor, wherein the additional urease inhibitor preferably comprises tri-N- (N-butyl) thiophosphates or tri-N- (N-propyl) thiophosphates, or a combination thereof.
  6. 6. The method of any one of claims 1 to 5, wherein the method increases Nitrogen Use Efficiency (NUE) of the crop.
  7. 7. The method of any one of claims 1 to 6, wherein the dual urease and nitrification inhibitor are (i) distributed throughout the fertilizer, (ii) coated on the fertilizer, and/or (iii) encapsulated.
  8. 8. The method of any one of claims 1 to 7, wherein R is pyrazole or-N (CH 3 ) 2 ;R 1 is H or methyl; R 2 is methyl, N-propyl or N-butyl; R 3 is H; R 4 is H; R 5 is H; R 6 is H; R 7 is H; R 8 is H; R 9 is methyl, and R 10 is methyl.
  9. 9. The method of claim 8, wherein the dual urease and nitrification inhibitor have a structure represented by formula IV, formula V, or formula VI: ; Either (or) or (b) 。
  10. 10. A fertilizer composition comprising: dual urease and nitrification inhibitors having a structure represented by formula VII: Wherein: R is a moiety having a structure represented by formula VIII or formula IX; ; And (C) sum R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 and R 10 are each independently H, substituted or unsubstituted C1 to C9 alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted saturated heterocycle, substituted or unsubstituted unsaturated heterocycle, substituted or unsubstituted aryl, hydroxy (-OH), methoxy (-OCH 3 ), ethoxy (-OC 2 H 5 ), nitro (-NO 2 ), amino (-NH 2 ) or halogen, and Optionally, one or more of the following: An additional inhibitor comprising an additional urease inhibitor and/or an additional nitrification inhibitor; Solid and/or liquid carrier, and/or At least one nitrogen (N), phosphorus (P) and/or potassium (K) fertilizer component.
  11. 11. The fertilizer composition of claim 10, wherein: The additional nitrification inhibitor comprises clomazone, dicyandiamide, ammonium thiosulfate, methyl 3- (4-hydroxyphenyl) propionate, 1, 9-decanediol, potassium azide, 2-amino-4-chloro-6-methylpyrimidine, sulfathiazole, 4-amino-1, 2, 4-triazole, 2, 4-diamino-6-trichloromethyl-s-triazine, potassium ethylxanthate, guanylthiourea, 4-nitrotrichlorotoluene, 4-methylsulfonyl trichlorotoluene, sodium trithiocarbonate, mercury phenylacetate, 3, 4-dimethylpyrazole phosphate, or sorghum, or any combination thereof, and/or The additional urease inhibitor includes N- (N-butyl) thiophosphoric triamide or N- (N-propyl) thiophosphoric triamide, or a combination thereof.
  12. 12. The fertilizer composition of any one of claims 10 or 11, wherein the solid and/or liquid carrier comprises plaster of paris, flour, chalk, starch, gluten, kaolin, bentonite, colloidal silica, distillers dried grains and solubles thereof, lignin, synthetic polymers, waxes, chitin, glycosaminoglycans, pectins, hyaluronic acid, chondroitin sulfate, dermatan sulfate, alginic acid, polymannuronate, polyguluronic acid, polyglucuronate, amylose, amylopectin, callose, chitosan, polygalactomannan, dextran, xanthan gum, keratan sulfate, mgO, caO, bone flour, rice husk 、CaCO 3 、Na 2 CO 3 、K 2 CO 3 、KH 2 PO 4 、NaHCO 3 、MgCO 3 、 alcohol, water, liquid buffers, chelating agents, or any combination thereof.
  13. 13. The fertilizer composition of any one of claims 10-12, wherein the at least one nitrogen (N), phosphorus (P), and/or potassium (K) fertilizer component comprises at least one nitrogen fertilizer component.
  14. 14. The fertilizer composition of any one of claims 10-13, wherein R is pyrazole or-N (CH 3 ) 2 ;R 1 is H or methyl; R 2 is methyl, N-propyl or N-butyl; R 3 is H; R 4 is H; R 5 is H; R 6 is H; R 7 is H; R 8 is H; R 9 is methyl, and/or R 10 is methyl.
  15. 15. The fertilizer composition of any one of claims 10-14, wherein the dual urease and nitrification inhibitor have a structure represented by formula IV, formula V, or formula VI ; Either (or) or (b) 。

Description

Pyrazole derivatives as dual function urease and nitrification inhibitors Cross Reference to Related Applications The present application claims priority from indian provisional patent application No. 202341048459 filed on day 19, 7, 2023, and european patent application No. EP23196435 filed on day 11, 9, 2023, the entire contents of which are incorporated herein by reference. I. Technical field The present disclosure relates generally to compositions for maintaining or reducing the loss of nitrogen content in soil. In particular, the present invention relates to dual function urease and nitrification inhibitor molecules for fertilizer applications. II background art Nitrogen is one of the most important nutrients for plant growth and production. Nitrogen Utilization Efficiency (NUE) is defined as the ratio of nitrogen uptake by crops to the total input of nitrogen fertilizer. In crops, NUE is very low, with about 50% of the nitrogen fertilizer applied to the crop system being lost to the environment in the form of ammonia (NH 3), nitrate (NO 3-) and nitrous oxide (N 2 O, greenhouse gases). Lower NUEs in agriculture lead to high agricultural production costs, environmental pollution and climate change. These losses are driven mainly by the soil microorganism-catalysed hydrolysis, nitration and subsequent denitrification of urea. Hydrolysis of urea is catalyzed by urease enzymes, which are present in many bacteria, fungi, algae, plants, and also are present in the soil as soil enzymes. These enzymes catalyze the hydrolysis of urea to carbon dioxide and ammonia. Nitrification has traditionally been considered a two-step process in which ammonia (NH 3) is first oxidized to nitrite (NO 2-) by an ammonia oxidizing agent, followed by oxidation to nitrate (NO 3-) by Nitrite Oxidizing Bacteria (NOB). Recent evidence suggests complete nitrification by nitrifying spira (Nitrospira) bacteria present in natural soil environments. Due to the rapid hydrolysis and nitrification of urea in the soil, nitrogen in urea can be rapidly lost. This not only reduces the efficiency of N use, but also leads to climate change and loss of biodiversity by emission of greenhouse gases in the production of excess urea fertilizer. Furthermore, the use of urea in fertilizer mixtures containing other soil nutrients is difficult because urea can react undesirably with other components in the fertilizer, such as organic fertilizers. These reactions can produce moisture, liquefy solid particles or dry mixture products, lead to product caking and loss, and increase the rate at which these adverse reactions occur. See Biskupski et al (EP 2,774,907), and also Achard et al (US 5,409,516). Furthermore, the production of water increases the amount of water that must be removed during the production of urea-containing fertilizers, making the production of these compost difficult and more costly. See Schwob (FR 2,684,372). The world governments have set regulations that require the agricultural sector to reduce its environmental impact. One approach to reducing the impact of agricultural environments involves the use of urease inhibitors and nitrification inhibitors. Urease inhibitors are compounds that can prevent or delay urea hydrolysis, and nitrification inhibitors are compounds that can prevent or delay ammonia nitrification. These inhibitors help reduce the loss of nitrogen from the soil that would be utilized by the plant. However, biological and synthetic urease and nitrification inhibitors are associated with various drawbacks, including instability at high temperature, instability at high or low pH, variable efficacy, difficult application, high cost, environmental pollution, and food safety risks. Disclosure of Invention A solution to at least some of the problems discussed above is disclosed herein. In certain instances, the solution resides in the dual urease and nitrification inhibitors disclosed herein and methods for using the dual inhibitors. Dual inhibitors disclosed herein may include small molecules that are capable of synthesis in certain circumstances. In some cases, the dual urease and nitrification inhibitor have high melting points, which facilitates formulation of the urease and nitrification inhibitor with molten urea at temperatures of about 132 ℃ to 135 ℃ or greater. In some cases, dual urease and nitrification inhibitors are almost non-toxic and are equivalent or more effective than the urease and nitrification inhibitors currently on the market. Dual urease and nitrification inhibitors are useful for a wide variety of soil types, and their temperature and pH ranges are broad. Accordingly, certain aspects of the present disclosure are directed to compositions or compounds that provide reduced hydrolysis of urea and reduced nitrification of ammonium nitrogen, the compositions or compounds comprising dual urease having a structure represented by formula I or formula VII and a nitrification inhibitor: Wherein: x is sulfur or