Thioether compounds as nitrification inhibitors

Abstract

Provided herein are a use of thioether compounds of formula I as nitrification inhibitors, and agricultural mixtures and compositions including the thioether compounds.

Claims

1. At least one thioether compound of formula I.sup.1, ##STR00143## or a stereoisomer thereof, a salt thereof, a tautomer thereof, or an N-oxide thereof as nitrification inhibitor, wherein R.sup.1 and R.sup.2 are independently selected from the group consisting of H and C.sub.1-C.sub.2-alkyl; and wherein R.sup.3 is selected from the group consisting of (i) C(═N—OH)R.sup.a and C(═N—R.sup.x)NR.sup.cR.sup.d; wherein R.sup.a is selected from the group consisting of H and C.sub.1-C.sub.2-alkyl; R.sup.c and R.sup.d are independently selected from the group consisting of H and C.sub.1-C.sub.2-alkyl; and R.sup.x is ##STR00144## wherein § marks the connection to the atom to which R.sup.x is bonded; and wherein V, W, Y, and Z each represent CH, and X is selected from the group consisting of CH and CR.sup.y, wherein R.sup.Y is selected from the group consisting of halogen, CN, C.sub.1-C.sub.2-alkyl, and C.sub.1-C.sub.2-alkoxy; and wherein m is one of 0, 1, and 2; p is one of 1 and 2.

2. A method for reducing nitrification, the method comprising: applying a composition comprising a compound of Formula (I), or a stereoisomer, a salt, a tautomer, or N-oxide thereof, to a locus where nitrification occurs, wherein ##STR00145## R.sup.1 and R.sup.2 are independently selected from the group consisting of H and C.sub.1-C.sub.2-alkyl; R.sup.3 is selected from the group consisting of: (i) C(═O)R.sup.a, C(═O)OR.sup.a, C(═O)NR.sup.cR.sup.d, C(═N—OH)R.sup.a, C(═N—OH)NR.sup.cR.sup.d, C(═N—R.sup.b)R.sup.a, C(═N—R.sup.b)NR.sup.cR.sup.d, C(═N—R.sup.x)R.sup.a, or C(═N—R.sup.x)NR.sup.cR.sup.d; (ii) C.sub.1-C.sub.8-alkyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.2-C.sub.8-alkenyl, C.sub.3-C.sub.8-cycloalkenyl, or C.sub.2-C.sub.8-alkynyl, wherein the C-atoms of these groups optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, OR.sup.a, NO.sub.2, NR.sup.cR.sup.d, NR.sup.b(C═O)R.sup.a, C(═O)R.sup.a, C(═O)OR.sup.a, C(═O)NR.sup.cR.sup.d, S(O).sub.nR.sup.a, and S(O).sub.nNR.sup.cR.sup.d; (iii) C.sub.6-C.sub.14-aryl, C.sub.5-C.sub.14-hetaryl, C.sub.6-C.sub.14-aryl-C.sub.1-C.sub.2-alkyl, or C.sub.5-C.sub.14-hetaryl-C.sub.1-C.sub.2-alkyl, wherein the aromatic moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, R.sup.x, OR.sup.a, SR.sup.a, NR.sup.cR.sup.d, NR.sup.b(C═O)R.sup.a, NR.sup.b(C═O)NR.sup.cR.sup.d, C(═O)R.sup.a, C(═O)OR.sup.a, C(═O)NR.sup.cR.sup.d, S(O).sub.nR.sup.a, S(O).sub.nNR.sup.cR.sup.d, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-alkylen-OR.sup.a, C.sub.1-C.sub.4-alkylen-NR.sup.cR.sup.d, C.sub.6-C.sub.10-aryl, C.sub.6-C.sub.10-aryl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-hetaryl, C.sub.5-C.sub.10-hetaryl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-carbocyclyl, C.sub.5-C.sub.10-carbocyclyl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-heterocyclyl, and C.sub.5-C.sub.10-heterocyclyl-C.sub.1-C.sub.2-alkyl, wherein the C.sub.6-C.sub.10-aryl, C.sub.5-C.sub.10-hetaryl, C.sub.5-C.sub.10-carbocyclyl, and C.sub.5-C.sub.10-heterocyclyl moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, OH, SH, NH.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-dialkylamino, and C.sub.1-C.sub.4-haloalkyl; and (iv) C.sub.5-C.sub.14-carbocyclyl, C.sub.5-C.sub.14-carbocyclyl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.14-heterocyclyl, or C.sub.5-C.sub.14-heterocyclyl-C.sub.1-C.sub.2-alkyl, wherein the heterocyclyl rings optionally carry 1, 2, 3, 4, or 5 heteroatoms selected from the group consisting of O, S, and N, of which S and/or N are optionally oxidized, and wherein the carbocyclic or heterocyclic rings optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of ═O, ═S, halogen, CN, R.sup.x, OR.sup.a, SR.sup.a, NO.sub.2, NR.sup.cR.sup.d, NR.sup.b(C═O)R.sup.a, NR.sup.b(C═O)NR.sup.cR.sup.d, C(═O)R.sup.a, C(═O)OR.sup.a, C(═O)NR.sup.cR.sup.d, S(O).sub.nR.sup.a, S(O).sub.nNR.sup.cR.sup.d, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-alkylen-OR.sup.a, C.sub.1-C.sub.4-alkylen-NR.sup.cR.sup.d, C.sub.6-C.sub.10-aryl, C.sub.5-C.sub.10-hetaryl, C.sub.5-C.sub.10-hetaryl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-carbocyclyl, C.sub.5-C.sub.10-carbocyclyl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-heterocyclyl, and C.sub.5-C.sub.10-heterocyclyl-C.sub.1-C.sub.2-alkyl, wherein the C.sub.6-C.sub.10-aryl, C.sub.5-C.sub.10-hetaryl, C.sub.5-C.sub.10-carbocyclyl, and C.sub.5-C.sub.10-heterocyclyl moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, OH, SH, NH.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-dialkylamino, and C.sub.1-C.sub.4-haloalkyl; R.sup.a is selected from the group consisting of H, C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-haloalkyl, C.sub.2-C.sub.8-alkenyl, C.sub.2-C.sub.8-alkynyl, and C.sub.5-C.sub.10-hetaryl or C.sub.6-C.sub.10-aryl, wherein the C.sub.5-C.sub.10-hetaryl or C.sub.6-C.sub.10-aryl moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, OH, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.5-C.sub.6-hetaryl and C.sub.6-aryl, wherein said C.sub.5-C.sub.6-hetaryl and C.sub.6-aryl moieties optionally carry 1, 2, 3, 4, or 5 substituents selected from the group consisting of halogen, CN, OH, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, and C.sub.2-C.sub.4-alkynyl; R.sup.b is selected from the group consisting of H, C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.8-alkynyl, and C.sub.6-C.sub.10-aryl; R.sup.c and R.sup.d are independently of each other selected from the group consisting of H, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.6-C.sub.10-aryl, and C.sub.5-C.sub.10-hetaryl; or R.sup.c and R.sup.d together with the N-atom to which they are bonded form a 5- to 6-membered, saturated or unsaturated heterocycle, which optionally carries a further heteroatom selected from the group consisting of O, S, and N as a ring member atom, of which S and/or N are optionally oxidized, and wherein the heterocyclic ring optionally carries 1, 2, 3, 4, or 5 substituents, which are independently selected from the group consisting of halogen, CN, OH, NO.sub.2, C.sub.1-C.sub.4 alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.4-haloalkoxy; R.sup.x is ##STR00146## V, W, X, Y, and Z are independently selected from the group consisting of N, CH and CR.sup.y, R.sup.Y is selected from the group consisting of halogen, CN, NO.sub.2, OH, SH, NH.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-dialkylamino, and C.sub.1-C.sub.4-haloalkyl; m is 0, 1, or 2; n is 0, 1, or 2; and p is 0, 1, or 2.

3. The method according to claim 2, wherein: R.sup.1 and R.sup.2 are H; and p is 1 or 2.

4. The method according to claim 2, wherein: R.sup.3 is selected from the group consisting of: (i) C(═O)R.sup.a, C(═N—OH)R.sup.a, or C(═N—R.sup.x)NR.sup.cR.sup.d; (ii) C.sub.1-C.sub.8-alkyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.2-C.sub.8-alkenyl, or C.sub.2-C.sub.8-alkynyl, wherein the C-atoms of these groups optionally carry 1, 2, or 3 identical or different substituents selected from the group consisting of halogen and CN; (iii) C.sub.6-C.sub.14-aryl, C.sub.5-C.sub.14-hetaryl, C.sub.6-C.sub.14-aryl-C.sub.1-C.sub.2-alkyl, and C.sub.5-C.sub.14-hetaryl-C.sub.1-C.sub.2-alkyl, wherein the aromatic moieties optionally carry 1, 2, or 3 identical or different substituents selected from the group consisting of halogen, CN, R.sup.x, OR.sup.a, SR.sup.a, NO.sub.2, NR.sup.cR.sup.d, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.6-C.sub.10-aryl, C.sub.6-C.sub.10-aryl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-hetaryl, C.sub.5-C.sub.10-hetaryl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-carbocyclyl, C.sub.5-C.sub.10-carbocyclyl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-heterocyclyl, and C.sub.5-C.sub.10-heterocyclyl-C.sub.1-C.sub.2-alkyl, wherein the C.sub.6-C.sub.10-aryl, C.sub.5-C.sub.10-hetaryl, C.sub.5-C.sub.10-carbocyclyl, and C.sub.5-C.sub.10-heterocyclyl moieties optionally carry 1, 2, or 3 identical or different substituents selected from the group consisting of halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.4-haloalkyl; and (iv) C.sub.5-C.sub.14-carbocyclyl, C.sub.5-C.sub.14-carbocyclyl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.14-heterocyclyl, or C.sub.5-C.sub.14-heterocyclyl-C.sub.1-C.sub.2-alkyl, wherein the heterocyclyl rings optionally carry 1, 2, or 3 heteroatoms selected from the group consisting of O, S, and N, of which S and/or N are optionally oxidized, and wherein the carbocyclic or heterocyclic rings optionally carry 1, 2, or 3 identical or different substituents selected from the group consisting of ═O, ═S, halogen, CN, R.sup.x, OR.sup.a, SR.sup.a, NO.sub.2, NR.sup.cR.sup.d, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.6-C.sub.10-aryl, C.sub.6-C.sub.10-aryl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-hetaryl, C.sub.5-C.sub.10-hetaryl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-carbocyclyl, C.sub.5-C.sub.10-carbocyclyl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-heterocyclyl, and C.sub.5-C.sub.10-heterocyclyl-C.sub.1-C.sub.2-alkyl, wherein the C.sub.6-C.sub.10-aryl, C.sub.5-C.sub.10-hetaryl, C.sub.5-C.sub.10-carbocyclyl, and C.sub.5-C.sub.10-heterocyclyl moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.4-haloalkyl; R.sup.a is selected from the group consisting of H, C.sub.1-C.sub.4-alkyl, and C.sub.1-C.sub.4-haloalkyl; R.sup.c and R.sup.d are independently selected from the group consisting of H, C.sub.1-C.sub.4-alkyl, and C.sub.1-C.sub.4-haloalkyl; R.sup.x is ##STR00147## V, W, X, Y, and Z are independently selected from the group consisting of N, CH and CR.sup.y; and R.sup.Y is selected from the group consisting of halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-dialkylamino, and C.sub.1-C.sub.4-haloalkyl.

5. The method according to claim 2, wherein: R.sup.3 is selected from the group consisting of: (i) C(═N—OH)R.sup.a or C(═N—R.sup.x)NR.sup.cR.sup.d; (ii) C.sub.2-C.sub.4-alkynyl; (iii) C.sub.6-C.sub.10-aryl, C.sub.5-C.sub.10-hetaryl, C.sub.6-C.sub.10-aryl-C.sub.1-C.sub.2-alkyl, or C.sub.5-C.sub.10-hetaryl-C.sub.1-C.sub.2-alkyl, wherein the aromatic moieties optionally carry 1, 2, or 3 identical or different substituents selected from the group consisting of halogen, CN, R.sup.x, OR.sup.a, SR.sup.a, NR.sup.cR.sup.d, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.6-aryl, and C.sub.5-C.sub.6-hetaryl, wherein the C.sub.6-aryl and C.sub.5-C.sub.6-hetaryl moieties optionally carry 1, 2, or 3 identical or different substituents selected from the group consisting of halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.4-haloalkyl; and (iv) C.sub.5-C.sub.10-heterocyclyl, wherein the heterocyclyl ring optionally carries 1, 2, or 3 heteroatoms selected from the group consisting of O, S, and N, of which S and/or N are optionally oxidized, and wherein the heterocyclic ring optionally carries 1, 2, or 3 identical or different substituents selected from the group consisting of ═O, halogen, CN, R.sup.x, OR.sup.a, SR.sup.a, NR.sup.cR.sup.d, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.6-aryl, and C.sub.5-C.sub.6-hetaryl, wherein the C.sub.6-aryl and C.sub.5-C.sub.6-hetaryl moieties optionally carry 1, 2, or 3 identical or different substituents selected from the group consisting of halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.4-haloalkyl; R.sup.a is selected from the group consisting of H and C.sub.1-C.sub.4-alkyl; R.sup.c and R.sup.d are independently selected from the group consisting of H and C.sub.1-C.sub.4-alkyl; R.sup.x is ##STR00148## V, W, Y, and Z are CH, X is selected from the group consisting of CH and CR.sup.y; and R.sup.Y is selected from the group consisting of halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio, and C.sub.1-C.sub.4-dialkylamino.

6. The method according to claim 2, wherein R.sup.3 is selected from the group consisting of (i) C(═N—OH)R.sup.a, and C(═N—R.sup.x)NR.sup.cR.sup.d; (ii) C.sub.3-alkynyl; (iii) C.sub.6-aryl and C.sub.5-C.sub.10-hetaryl; R.sup.a is selected from the group consisting of H, or C.sub.1-C.sub.2-alkyl; R.sup.c and R.sup.d are independently selected from the group consisting of H and C.sub.1-C.sub.2-alkyl; R.sup.x is ##STR00149## V, W, Y, and Z are CH, X is selected from the group consisting of CH and CR.sup.y; and R.sup.Y is selected from the group consisting of halogen, CN, C.sub.1-C.sub.2-alkyl, and C.sub.1-C.sub.2-alkoxy.

7. The method according to claim 2, wherein the composition further comprises a carrier.

8. The method according to claim 2, wherein the composition further comprises a fertilizer.

9. The method according to claim 8, wherein the fertilizer is selected from the group consisting of an ammonium-containing fertilizer; an organic fertilizer; a urea-containing fertilizer, an inorganic fertilizer, a coated fertilizer, a slow-release fertilizer, and combinations thereof, and the fertilizer is a solid or liquid.

10. The method according to claim 2, further comprising applying a fertilizer to the locus where nitrification occurs.

11. The method according to claim 10, wherein the fertilizer is selected from the group consisting of an ammonium-containing fertilizer; an organic fertilizer; a urea-containing fertilizer, an inorganic fertilizer, a coated fertilizer, a slow-release fertilizer, and combinations thereof, and the fertilizer is a solid or liquid.

12. The method according to claim 2, wherein the locus where nitrification occurs is an agricultural location.

13. The method according to claim 2, wherein the locus where nitrification occurs is a field where crops are currently being grown or a field where crops will be grown.

14. The method according to claim 13, wherein the crop 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, cabbages, sorghum, and combinations thereof.

15. The method according to claim 2, wherein said reduction of nitrification occurs in or on a plant, in the root zone of a plant, in or on soil or soil substituents and/or at the locus where a plant is growing or is intended to grow.

16. The method according to claim 2, further comprising applying a fertilizer to the locus where nitrification occurs, wherein the compound of Formula (I) and the fertilizer are applied sequentially or simultaneously, and when the application is sequential, a time lag between applying the fertilizer and the compound of Formula (I) is up to three weeks, and the compound of Formula (I) is applied before or after the fertilizer.

17. The method according to claim 16, wherein the fertilizer is selected from the group consisting of an ammonium-containing fertilizer; an organic fertilizer; a urea-containing fertilizer, an inorganic fertilizer, a coated fertilizer, a slow-release fertilizer, and combinations thereof, and the fertilizer is a solid or liquid.

18. The method according to claim 2, wherein the locus where nitrification occurs is a plant growing on soil, and the plant is selected from the group consisting of (i) an agricultural plant; (ii) a vegetable; (iii) sorghum; (iv) a silvicultural plant; (v) an ornamental plant; and (vi) a horticultural plant; wherein said plant is in its natural form or in a genetically modified form.

19. A method for reducing nitrification, the method comprising: applying a composition comprising a compound, or a stereoisomer, a salt, a tautomer, or N-oxide thereof, to a locus where nitrification occurs, wherein the compound is selected from the the group consisting of A-1, A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-11, A-12, A-13, A-14, A-15, A-16, A-17, A-18, A-19, A-20, A-21, A-22, A-23, A-24, A-25, A-26, A-27, A-28, A-29, A-30, A-31, A-32, and A-33 as shown below: TABLE-US-00005 No. Compound A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 A-31 A-32 A-33

20. The method according to claim 19, wherein the compound is selected from the group consisting of A-16, A-17, A-18, A-19, and A-30 as shown below: TABLE-US-00006 No. Compound A-16 A-17 A-18 A-19 A-30

21. An agrochemical mixture comprising (i) at least one fertilizer; and (ii) at least one compound, or a stereoisomer, a salt, a tautomer, or N-oxide thereof, wherein the compound is selected from the group consisting of A-1, A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-11, A-12, A-13, A-14, A-15, A-16, A-17, A-18, A-19, A-20, A-21, A-22, A-23, A-24, A-25, A-26, A-27, A-28, A-29, A-30, A-31, A-32, and A-33 as shown below: TABLE-US-00007 No. Compound A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 A-31 A-32 A-33

22. The agrochemical mixture according to claim 21, wherein the compound is selected from the group consisting of A-16, A-17, A-18, A-19, and A-30 as shown below: TABLE-US-00008 No. Compound A-16 A-17 A-18 A-19 A-30

23. The agrochemical mixture according to claim 21, wherein the fertilizer is selected from the group consisting of an ammonium-containing fertilizer; an organic fertilizer; a urea-containing fertilizer, an inorganic fertilizer, a coated fertilizer, a slow-release fertilizer, and combinations thereof, and the fertilizer is a solid or liquid.

24. A method for treating a fertilizer, the method comprising: applying a compound of Formula (I), or a stereoisomer, salt, tautomer or N-oxide thereof, to the fertilizer, wherein ##STR00226## R.sup.1 and R.sup.2 are independently selected from the group consisting of H and C.sub.1-C.sub.2-alkyl; R.sup.3 is selected from the group consisting of (i) C(═O)R.sup.a, C(═O)OR.sup.a, C(═O)NR.sup.cR.sup.d, C(═N—OH)R.sup.a, C(═N—OH)NR.sup.cR.sup.d, C(═N—R.sup.b)R.sup.a, C(═N—R.sup.b)NR.sup.cR.sup.d, C(═N—R.sup.x)R.sup.a, and C(═N—R.sup.x)NR.sup.cR.sup.d; (ii) C.sub.1-C.sub.8-alkyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.2-C.sub.8-alkenyl, C.sub.3-C.sub.8-cycloalkenyl, or C.sub.2-C.sub.8-alkynyl, wherein the C-atoms of these groups optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, OR.sup.a, NO.sub.2, NR.sup.cR.sup.d, NR.sup.b(C═O)R.sup.a, C(═O)R.sup.a, C(═O)OR.sup.a, C(═O)NR.sup.cR.sup.d, S(O).sub.nR.sup.a, and S(O).sub.nNR.sup.cR.sup.d; (iii) C.sub.6-C.sub.14-aryl, C.sub.5-C.sub.14-hetaryl, C.sub.6-C.sub.14-aryl-C.sub.1-C.sub.2-alkyl, or C.sub.5-C.sub.14-hetaryl-C.sub.1-C.sub.2-alkyl, wherein the aromatic moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents, selected from the group consisting of halogen, CN, R.sup.x, OR.sup.a, SR.sup.a, NR.sup.cR.sup.d, NR.sup.b(C═O)R.sup.a, NR.sup.b(C═O)NR.sup.cR.sup.d, C(═O)R.sup.a, C(═O)OR.sup.a, C(═O)NR.sup.cR.sup.d, S(O).sub.nR.sup.a, S(O).sub.nNR.sup.cR.sup.d, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-alkylen-OR.sup.a, C.sub.1-C.sub.4-alkylen-NR.sup.cR.sup.d, C.sub.6-C.sub.10-aryl, C.sub.6-C.sub.10-aryl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-hetaryl, C.sub.5-C.sub.10-hetaryl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-carbocyclyl, C.sub.5-C.sub.10-carbocyclyl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-heterocyclyl, and C.sub.5-C.sub.10-heterocyclyl-C.sub.1-C.sub.2-alkyl, wherein the C.sub.6-C.sub.10-aryl, C.sub.5-C.sub.10-hetaryl, C.sub.5-C.sub.10-carbocyclyl, and C.sub.5-C.sub.10-heterocyclyl moieties that optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, OH, SH, NH.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-dialkylamino, and C.sub.1-C.sub.4-haloalkyl; and (iv) C.sub.5-C.sub.14-carbocyclyl, C.sub.5-C.sub.14-carbocyclyl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.14-heterocyclyl, or C.sub.5-C.sub.14-heterocyclyl-C.sub.1-C.sub.2-alkyl, wherein the heterocyclyl rings optionally carry 1, 2, 3, 4, or 5 heteroatoms selected from the group consisting of O, S, and N, of which S and/or N may optionally be oxidized, and wherein the carbocyclic or heterocyclic rings optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of ═O, ═S, halogen, CN, R.sup.x, OR.sup.a, SR.sup.a, NO.sub.2, NR.sup.cR.sup.d, NR.sup.b(C═O)R.sup.a, NR.sup.b(C═O)NR.sup.cR.sup.d, C(═O)R.sup.a, C(═O)OR.sup.a, C(═O)NR.sup.cR.sup.d, S(O).sub.nR.sup.a, S(O).sub.nNR.sup.cR.sup.d, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-alkylen-OR.sup.a, C.sub.1-C.sub.4-alkylen-NR.sup.cR.sup.d, C.sub.6-C.sub.10-aryl, C.sub.6-C.sub.10-aryl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-hetaryl, C.sub.5-C.sub.10-hetaryl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-carbocyclyl, C.sub.5-C.sub.10-carbocyclyl-C.sub.1-C.sub.2-alkyl, C.sub.5-C.sub.10-heterocyclyl, and C.sub.5-C.sub.10-heterocyclyl-C.sub.1-C.sub.2-alkyl, wherein the C.sub.6-C.sub.10-aryl, C.sub.5-C.sub.10-hetaryl, C.sub.5-C.sub.10-carbocyclyl, and C.sub.5-C.sub.10-heterocyclyl moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, NO.sub.2, OH, SH, NH.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-dialkylamino, and C.sub.1-C.sub.4-haloalkyl; R.sup.a is selected from the group consisting of H, C.sub.1-C.sub.8-alkyl, C.sub.1-C.sub.8-haloalkyl, C.sub.2-C.sub.8-alkenyl, C.sub.2-C.sub.8-alkynyl; C.sub.5-C.sub.10-hetaryl or C.sub.6-C.sub.10-aryl, wherein the C.sub.5-C.sub.10-hetaryl or C.sub.6-C.sub.10-aryl moieties optionally carry 1, 2, 3, 4, or 5 identical or different substituents selected from the group consisting of halogen, CN, OH, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.5-C.sub.6-hetaryl and C.sub.6-aryl, wherein said C.sub.5-C.sub.6-hetaryl and C.sub.6-aryl moieties optionally carry 1, 2, 3, 4, or 5 substituents selected from the group consisting of halogen, CN, OH, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-haloalkyl, C.sub.2-C.sub.4-alkenyl, and C.sub.2-C.sub.4-alkynyl; R.sup.b is selected from the group consisting of H, C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.8-alkynyl, and C.sub.6-C.sub.10-aryl; R.sup.c and R.sup.d are independently of each other selected from the group consisting of H, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.6-C.sub.10-aryl, and C.sub.5-C.sub.10-hetaryl; or R.sup.c and R.sup.d together with the N-atom to which they are bonded form a 5- to 6-membered, saturated or unsaturated heterocycle, which optionally carries a further heteroatom being selected from the group consisting of O, S, and N as a ring member atom, of which S and/or N are optionally oxidized, and wherein the heterocyclic ring optionally carries 1, 2, 3, 4, or 5 substituents, which are independently selected from the group consisting of halogen, CN, OH, NO.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.4-haloalkoxy; R.sup.x is ##STR00227## V, W, X, Y, and Z are independently selected from the group consisting of N, CH and CR.sup.y, R.sup.Y is selected from the group consisting of halogen, CN, NO.sub.2, OH, SH, NH.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, C.sub.1-C.sub.4-alkylthio, C.sub.1-C.sub.4-dialkylamino, and C.sub.1-C.sub.4-haloalkyl; m is 0, 1, or 2; n is 0, 1, or 2; and p is 0, 1, or 2.

25. The method according to claim 24, wherein: R.sup.1 and R.sup.2 are H; and p is 1 or 2.

26. The method according to claim 24, wherein: R.sup.3 is selected from the group consisting of: (i) C(═N—OH)R.sup.a or C(═N—R.sup.x)NR.sup.cR.sup.d; (ii) C.sub.3-alkynyl; and (iii) C.sub.6-aryl or C.sub.5-C.sub.10-hetaryl; R.sup.a is selected from the group consisting of H and C.sub.1-C.sub.2-alkyl; R.sup.c and R.sup.d are independently selected from the group consisting of H and C.sub.1-C.sub.2-alkyl; R.sup.x is ##STR00228## V, W, Y, and Z are CH, X is selected from the group consisting of CH and CR.sup.y; and R.sup.Y is selected from the group consisting of halogen, CN, C.sub.1-C.sub.2-alkyl, and C.sub.1-C.sub.2-alkoxy.

27. The method according to claim 24, wherein the fertilizer is selected from the group consisting of an ammonium-containing fertilizer; an organic fertilizer; a urea-containing fertilizer, an inorganic fertilizer, a coated fertilizer, a slow-release fertilizer, and combinations thereof, and the fertilizer is a solid or liquid.

28. The method according to claim 24, wherein at least one of the compound of Formula (I) and the fertilizer further comprises a carrier.

29. An agrochemical composition comprising: (i) a compound, or a stereoisomer, a salt, a tautomer, or N-oxide thereof selected from the group consisting of A-1, A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-11, A-12, A-13, A-14, A-15, A-16, A-17, A-18, A-19, A-20, A-21, A-22, A-23, A-24, A-25, A-26, A-27, A-28, A-29, A-30, A-31, A-32, and A-33 as shown below: TABLE-US-00009 No. Compound A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 A-31 A-32 A-33 and (ii) at least one agrochemical carrier.

30. The agrochemical composition of claim 29 wherein the compound is selected from the group consisting of A-16, A-17, A-18, A-19, and A-30 as shown below: TABLE-US-00010 No. Compound A-16 A-17 A-18 A-19 A-30

Description

EXAMPLES

Example 1

(1) The compounds of the invention have been tested as follows in terms of the inhibition of nitrification: Soil was sampled fresh from a field (e.g. Limburgerhof), dried and sieved through a 500 μm sieve. Approximately 200 mg of soil were placed into each well of a 48 well plate. Compounds, or DMSO alone, were added at a concentration of 10 ppm, dissolved in 1% DMSO. 6 μmol ammonium sulfate was added per well as well as 4.8 mg NaClO.sub.3.

(2) Subsequently, the samples were incubated at room temperature for up to 72 hrs. After the incubation period 64 mg KCl were added and mixed. 25 μl of the supernatant were placed into a fresh plate and 260 μl of a color reaction solution (from Merck Nr 1.11799.0100) were added.

(3) Measurements were taken with a Tecan plate Reader at 540 nm wavelength.

(4) The results of the measurements (with a dose of 10 ppm) were that the compounds as shown in Table A supra demonstrated an inhibition of nitrification compared to a control (DMSO only).

(5) Inhibition is calculated as x=% activity compared to control, and converted to 100-x to give the value of inhibition, rather than activity.

Example 1.1

(6) The results for compounds tested with a dose of 10 ppm are provided in the following Table 1. In each case, the best inhibition value (IN) obtained for a compound is provided.

(7) TABLE-US-00002 TABLE 1 No. Compound IN 1-1 09 42 1-2 0 53 1-3 68 1-4 59 1-5 60 1-6 59 1-7 72 1-8 70 1-9 67 1-10 59 1-11 55 1-12 0 52 1-13 51 1-14 49 1-15 48 1-16 48 1-17 46 1-18 44 1-19 42 1-20 48 1-21 69 1-22 0 42 1-23 33

Example 1.2

(8) The results for compounds tested with a dose of 3% a.i./NH are provided in the following Table 2. In each case, the best inhibition value (IN) obtained for a compound is provided.

(9) TABLE-US-00003 TABLE 2 No. Compound IN 2-1 20 2-2 20 2-3 23 2-4 23 2-5 24 2-6 28 2-7 28 2-8 38 2-9 0 48 2-10 97

Comparative Example 1.3

(10) As a reference compound for a known nitrification inhibitor with a terminal alkynyl group, phenylacetylene (U.S. Pat. No. 4,552,581 A) was tested under the same conditions as outlined above with a dose of 10 ppm. The following inhibition value was obtained.

(11) TABLE-US-00004 TABLE 3 Name Structure IN Phenylacetylene 7