Use of N-functionalized alkoxy pyrazole compounds as nitrification inhibitors

Abstract

The present invention relates to the use of novel nitrification inhibitors of formula (I), which are N-functionalized alkoxy pyrazole compounds. Moreover, the invention relates to the use of compounds of formula (I) as nitrification inhibitors, i.e. for reducing nitrification, as well as agrochemical mixtures and compositions comprising the nitrification inhibitors of formula (I).

Claims

1. An N-functionalized alkoxy pyrazole compound of formula I ##STR00022## or a salt, stereoisomer, tautomer, or N-oxide thereof for use as a nitrification inhibitor, wherein R.sup.1 is H, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, benzyl, allyl, CHR.sup.aC(═O)OR.sup.b, CHR.sup.aC(═O)NR.sup.bR.sup.c, or phenyl, wherein said phenyl group is unsubstituted or substituted by one or more, same or different substituents R.sup.x; R.sup.2 is halogen, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, benzyl, allyl, propargyl, or phenyl, wherein said phenyl group is unsubstituted or substituted by one or more, same or different substituents R.sup.x; R.sup.N is CHR.sup.aC(═O)OR.sup.b, CHR.sup.aC(═O)NR.sup.bR.sup.c, CH(C(═O)OR.sup.b)CH.sub.2(C(═O)OR.sup.b); C(═O)R.sup.d, or CHR.sup.aNR.sup.e(C═O)R.sup.f; and wherein R.sup.a is H, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.3-C.sub.8-cycloalkyl, phenyl, or phenyl-C.sub.1-C.sub.2-alkyl; R.sup.b is H, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.3-C.sub.8-cycloalkyl, phenyl, or phenyl-C.sub.1-C.sub.2-alkyl; R.sup.c is H, C.sub.1-C.sub.4-haloalkyl, or phenyl; R.sup.d is H, C.sub.1-C.sub.8-alkyl, C.sub.2-C.sub.8-alkenyl, C.sub.2-C.sub.8-alkynyl, phenyl, or phenyl-C.sub.1-C.sub.2-alkyl, wherein these groups are unsubstituted or substituted by a group COOH; R.sup.e is H, C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.8-cycloalkyl, or C.sub.6-C.sub.10-aryl; R.sup.f is H, or C.sub.1-C.sub.4-alkyl; R.sup.x is halogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy, or C.sub.1-C.sub.4-haloalkoxy; n is 0, 1, or 2.

2. The compound of claim 1, wherein R.sup.1 is C.sub.1-C.sub.6-alkyl, benzyl, allyl.

3. The compound of claim 1, wherein n is 0; or n is 1, and R.sup.2 is C.sub.1-C.sub.3-alkyl or phenyl.

4. The compound of claim 1, wherein R.sup.a is H; R.sup.b is H or C.sub.1-C.sub.4-alkyl; R.sup.c is H or C.sub.1-C.sub.4-alkyl; R.sup.d is C.sub.1-C.sub.3-alkyl; R.sup.e is H; R.sup.f is H or CH.sub.3.

5. A method for reducing nitrification, comprising treating a plant growing on soil or soil substituents and/or the locus or soil or soil substituents where the plant is growing or is intended to grow with at least one compound of formula I as defined in claim 1.

6. The method of claim 5, wherein the plant and/or the locus or soil or soil substituents where the plant is growing or is intended to grow is additionally provided with a fertilizer.

7. The method of claim 6, wherein the application of said compound of formula I and of said fertilizer is carried out simultaneously or with a time lag.

8. The method of claim 7 wherein the time lag is 1 day, 2 days, 3 days, 1 week, 2 weeks, or 3 weeks.

9. The method of claim 5, wherein said plant is an agricultural plant, a vegetable; sorghum; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or in a genetically modified form.

10. The method of claim 9 wherein the agricultural plant or vegetable is selected from the group consisting of wheat, barley, oat, rye, soybean, corn, potatoes, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice, spinach, lettuce, asparagus, and cabbages.

11. An agrochemical mixture comprising (i) at least one fertilizer; and (ii) at least one compound of formula I as defined in claim 1.

12. The agrochemical mixture of claim 11, wherein said fertilizer is a solid or liquid ammonium-containing inorganic fertilizer, a solid or liquid organic fertilizer, or an urea-containing fertilizer.

13. The agrochemical mixture of claim 12 wherein the fertilizer is selected from the group consisting of an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate, ammonium phosphate, liquid manure, semi-liquid manure, biogas manure, stable manure, straw manure, worm castings, compost, seaweed guano, urea, formaldehyde urea, anhydrous ammonium, urea ammonium nitrate (UAN) solution, urea sulphur, urea based NPK-fertilizers, and urea ammonium sulfate.

14. A composition for use in reducing nitrification comprising at least one compound of formula I as defined in claim 1 and at least one carrier.

15. A method for treating a fertilizer, comprising applying a nitrification inhibitor as defined in claim 1 to the fertilizer.

Description

EXAMPLES

Example 1

(1) The compounds of the invention have been tested as follows in terms of the inhibition of nitrification:

(2) 100 g soil is filled into 500 ml plastic bottles (e.g. soil sampled from the field) and is moistened to 50% water holding capacity. The soil is incubated at 20° C. for two weeks to activate the microbial biomass. 1 ml test solution, containing the compound in the appropriate concentration (usually 0.3 or 1% of nitrogen N), or DMSO and 10 mg nitrogen in the form of ammoniumsulfate-N is added to the soil and everything mixed well. Bottles are capped but loosely to allow air exchange. The bottles are then incubated at 20° C. for 0 and 14 days.

(3) For analysis, 300 ml of a 1% K.sub.2SO.sub.4-solution is added to the bottle containing the soil and shaken for 2 hours in a horizontal shaker at 150 rpm. Then the whole solution is filtered through a filter (Macherey-Nagel Filter MN 807′%). Ammonium and nitrate content is then analyzed in the filtrate in an autoanalyzer at 550 nm (Merck, AA11).

(4) The inhibition (NI @ a specified concentration) is calculated as follows:

(5) $\text{inhibition in \%}=\frac{\begin{array}{c}(\mathrm{NO}3-N_{wi\mathrm{thout}\mathrm{NI}\mathrm{at}\mathrm{end}\mathrm{of}\mathrm{incubation}}-\\ \mathrm{NO}3-N_{\mathrm{with}\mathrm{NI}\mathrm{at}\mathrm{end}\mathrm{of}\mathrm{incubation}})\end{array}}{\left(\mathrm{NO}3-N_{wi\mathrm{thout}\mathrm{NI}\mathrm{at}\mathrm{end}\mathrm{of}\mathrm{incubation}}-\mathrm{NO}3-N_{\mathrm{at}\mathrm{beginning}}\right)}\times 100$

(6) The following compounds of general formula I.1(i) have been tested.

(7) ##STR00019##

(8) TABLE-US-00011 No. R.sup.1 R.sup.N NI* @ 1% NI* @ 0.3% 1 C.sub.2H.sub.5 C(═O)CH.sub.3 63.7 26.6 2 CH.sub.3 C(═O)CH.sub.3 63.8 34 3 benzyl C(═O)CH.sub.3 21.2 — *In each case the best obtained NI value is provided (only compounds with values >20).
Further, the following compounds of general formula I.3(i) have been tested.

(9) ##STR00020##

(10) TABLE-US-00012 No. R.sup.1 R.sup.N NI* @ 1% NI* @ 0.3% 4 CH.sub.3 C(═O)CH.sub.3 73.3 35.4 5 CH.sub.3 C(═O)OC(CH.sub.3).sub.3 37.8 — *In each case the best obtained NI value is provided (only compounds with values >20).
Further, the following compounds of general formula I.3(i) have been tested.

(11) ##STR00021##

(12) TABLE-US-00013 NI* @ NI* @ No. R.sup.1 R.sup.2 R.sup.N 1% 0.3% 6 CH.sub.3 CH.sub.3 C(═O)CH.sub.3 90.7 75.7 7 C.sub.2H.sub.5 CH.sub.3 CH.sub.2OH 74.2 57.9 8 CH.sub.3 CH.sub.3 CH(C(═O)OH)CH.sub.2(C(═O)OH) 53.0 — 9 C.sub.2H.sub.5 CH.sub.3 CH(C(═O)OH)CH.sub.2(C(═O)OH) 42.7 — *In each case the best obtained NI value is provided (only compounds with values >20).