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. A thioether compound of formula I ##STR00143## or a stereoisomer, salt, tautomer or N-oxide thereof as nitrification inhibitor, wherein R.sup.1 and R.sup.2 are independently selected from H and C.sub.1-C.sub.2-alkyl; and wherein R.sup.3 is (i) C(O)R.sup.a, C(O)OR.sup.a, C(O)NR.sup.cR.sup.d, C(NOH)R.sup.a, C(NOH)NR.sup.cR.sup.d, C(NR.sup.b)R.sup.a, C(NR.sup.b)NR.sup.cR.sup.d, C(NR.sup.x)R.sup.a, or C(NR.sup.x)NR.sup.cR.sup.d; or (ii) C.sub.1-C.sub.5-alkyl, C.sub.3-C.sub.5-cycloalkyl, C.sub.2-C.sub.5-alkenyl, C.sub.3-C.sub.5-cycloalkenyl, or C.sub.2-C.sub.5-alkynyl, wherein the C-atoms of these groups may in each case be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, OR.sup.a, NO.sub.2, NR.sup.cR.sup.d, NR.sup.b(CO)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; or (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 may in each case be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents selected from halogen, CN, R.sup.x, OR.sup.a, SR.sup.a, NR.sup.cR.sup.d NR.sup.b(CO)R.sup.a, NR.sup.b(CO)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 may in each case be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents selected from 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; or (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 may carry 1, 2, 3, 4, or 5 heteroatoms being selected from O, S, and N, of which S and/or N may optionally be oxidized, and wherein the carbocyclic or heterocyclic rings may in each case be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents selected from O, S, halogen, CN, R.sup.x, OR.sup.a, SR.sup.a, NO.sub.2, NR.sup.cR.sup.d, NR.sup.b(CO)R.sup.a, NR.sup.b(CO)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.1i-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.00-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 may in each case be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents selected from 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; or and wherein R.sup.a is H, C.sub.1-C.sub.5-alkyl, C.sub.1-C.sub.5-haloalkyl, C.sub.2-C.sub.5-alkenyl, C.sub.2-C.sub.5-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 may in each case be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents selected from 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 may be unsubstituted or may carry 1, 2, 3, 4, or 5 substituents selected from 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 H, C.sub.1-C.sub.4-alkyl, C.sub.3-C.sub.5-cycloalkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.5-alkynyl, or C.sub.6-C.sub.10-aryl; and 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.5-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 may carry a further heteroatom being selected from O, S, and N as a ring member atom, of which S and/or N may optionally be oxidized, and wherein the heterocyclic ring may be unsubstituted or may carry 1, 2, 3, 4, or 5 substituents, which are independently selected from 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; and wherein R.sup.x is ##STR00144## wherein marks the connection to the atom to which R.sup.x is bonded; and wherein V, W, X, Y, and Z are independently selected from N, CH and CR.sup.y, wherein 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; and wherein m is 0, 1, or 2; n is 0, 1, or 2; and p is 0, 1, or 2.

2. The thioether compound of claim 1, wherein in the compound of formula I R.sup.1 and R.sup.2 are H; and p is 1 or 2.

3. The thioether compound of claim 1, wherein in the compound of formula I R.sup.3 is (i) C(O)R.sup.a, C(NOH)R.sup.a, or C(NR.sup.x)NR.sup.cR.sup.d; or (ii) C.sub.1-C.sub.5-alkyl, C.sub.3-C.sub.5-cycloalkyl, C.sub.2-C.sub.5-alkenyl, or C.sub.2-C.sub.5-alkynyl, wherein the C-atoms of these groups may in each case be unsubstituted or may carry 1, 2, or 3 identical or different substituents selected from halogen and CN; or (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 may in each case be unsubstituted or may carry 1, 2, or 3 identical or different substituents selected from 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 may in each case be unsubstituted or may carry 1, 2, or 3 identical or different substituents selected from halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.4-haloalkyl; or (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 may carry 1, 2, or 3 heteroatoms being selected from O, S, and N, of which S and/or N may optionally be oxidized, and wherein the carbocyclic or heterocyclic rings may in each case be unsubstituted or may carry 1, 2, or 3 identical or different substituents selected from O, S, halogen, CN, R.sup.x, OR.sup.a, SR.sup.a, NO.sub.2, NR.sup.cR.sup.dC.sub.1i-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 may be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents selected from 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 wherein R.sup.a is H, C.sub.1-C.sub.4-alkyl, or C.sub.1-C.sub.4-haloalkyl; and 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, and C.sub.1-C.sub.4-haloalkyl; and wherein R.sup.x is ##STR00145## wherein marks the connection to the atom to which R.sup.x is bonded; and wherein V, W, X, Y, and Z are independently selected from N, CH and CR.sup.y, wherein 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.

4. The thioether compound of claim 1, wherein in the compound of formula I R.sup.3 is (i) C(NOH)R.sup.a, or C(NR.sup.x)NR.sup.cR.sup.d; or (ii) C.sub.2-C.sub.4-alkynyl; or (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 may in each case be unsubstituted or may carry 1, 2, or 3 identical or different substituents selected from 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 may in each case be unsubstituted or may carry 1, 2, or 3 identical or different substituents selected from halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.4-haloalkyl; or (iv) C.sub.5-C.sub.10-heterocyclyl, wherein the heterocyclyl ring may carry 1, 2, or 3 heteroatoms being selected from O, S, and N, of which S and/or N may optionally be oxidized, and wherein the heterocyclic ring may be unsubstituted or may carry 1, 2, or 3 identical or different substituents selected from 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 may in each case be unsubstituted or may carry 1, 2, or 3 identical or different substituents selected from halogen, CN, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, and C.sub.1-C.sub.4-haloalkyl; or and wherein R.sup.a is H, or C.sub.1-C.sub.4-alkyl; R.sup.c and R.sup.d are independently of each other selected from the group consisting of H and C.sub.1-C.sub.4-alkyl; and wherein R.sup.x is ##STR00146## 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 represents CH or CR.sup.y, wherein 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.

5. The thioether compound of claim 1, wherein in the compound of formula I R.sup.3 is (i) C(NOH)R.sup.a, or C(NR.sup.x)NR.sup.cR.sup.d; or (ii) C.sub.3-alkynyl; or (iii) C.sub.6-aryl or C.sub.5-C.sub.10-hetaryl; and wherein R.sup.a is H, or C.sub.1-C.sub.2-alkyl; R.sup.c and R.sup.d are independently of each other selected from the group consisting of H and C.sub.1-C.sub.2-alkyl; and wherein R.sup.x is ##STR00147## 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 represents CH or 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.

6. 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.

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

8. (canceled)

9. (canceled)

10. A method for reducing nitrification, the method comprising treating a plant growing on at least one of soil, soil substituents, and a locus, soil, and 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.

11. The method of claim 10, further comprising providing the at least one of the plant and the locus, soil, and soil substituents where the plant is growing or is intended to grow with a fertilizer.

12. The method of claim 11, wherein the treating with the compound of formula I and the providing of the fertilizer are carried out simultaneously.

13. A method for treating at least one of a fertilizer and a fertilizer composition, comprising applying a nitrification inhibitor as defined in claim 1 to the at least one of the fertilizer and the fertilizer composition.

14. The agrochemical mixture of claim 7, wherein the fertilizer is selected from the group consisting of a solid ammonium-containing inorganic fertilizer, a liquid ammonium-containing inorganic fertilizer, a solid organic fertilizer, a liquid organic fertilizer, and a urea-containing fertilizer.

15. The method of claim 10, wherein the plant is an agricultural plant, a vegetable, sorghum; a silvicultural plant; an ornamental plant; and a horticultural plant, each in one of a natural and a genetically modified form.

16. At least one of a thioether compound of formula I.sup.1 ##STR00148## a stereoisomer thereof, a salt thereof, a tautomer thereof, and an N-oxide thereof as nitrification inhibitor, wherein R.sup.1 and R.sup.2 are independently selected from H and C.sub.1-C.sub.2-alkyl; and wherein R.sup.3 is at least one of (i) C(NOH)R.sup.a and C(NR.sup.x)NR.sup.cR.sup.d; wherein R.sup.a is at least one 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 ##STR00149## 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 represents at least one 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.

17. The method of claim 12, wherein the application of the compound of formula I and of the fertilizer is carried out with a time lag.

18. The method of claim 17, wherein the time lag is an interval selected from the group consisting of 1 day, 2 days, 3 days, 1 week, 2 weeks, and 3 weeks.

Description

EXAMPLES

Example 1

[0785] 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 m 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 mol ammonium sulfate was added per well as well as 4.8 mg NaClO.sub.3.

[0786] 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 l of the supernatant were placed into a fresh plate and 260 l of a color reaction solution (from Merck Nr 1.11799.0100) were added.

[0787] Measurements were taken with a Tecan plate Reader at 540 nm wavelength.

[0788] 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).

[0789] 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

[0790] 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.

TABLE-US-00002 TABLE 1 No. Compound IN 1-1 [00109] 42 1-2 [00110] 53 1-3 [00111] 68 1-4 [00112] 59 1-5 [00113] 60 1-6 [00114] 59 1-7 [00115] 72 1-8 [00116] 70 1-9 [00117] 67 1-10 [00118] 59 1-11 [00119] 55 1-12 [00120] 52 1-13 [00121] 51 1-14 [00122] 49 1-15 [00123] 48 1-16 [00124] 48 1-17 [00125] 46 1-18 [00126] 44 1-19 [00127] 42 1-20 [00128] 48 1-21 [00129] 69 1-22 [00130] 42 1-23 [00131] 33

Example 1.2

[0791] 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.

TABLE-US-00003 TABLE 2 No. Compound IN 2-1 [00132] 20 2-2 [00133] 20 2-3 [00134] 23 2-4 [00135] 23 2-5 [00136] 24 2-6 [00137] 28 2-7 [00138] 28 2-8 [00139] 38 2-9 [00140] 48 2-10 [00141] 97

Comparative Example 1.3

[0792] 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.

TABLE-US-00004 TABLE 3 Name Structure IN Phenylacetylene [00142] 7