BENZYLPROPARGYLETHER AS NITRIFICATION INHIBITORS

Abstract

The present invention relates to the use of compounds of formula (I) for reducing nitrification and to compositions comprising the compounds of formula (I) and to agricultural mixtures comprising at least one compound of formula (I) and at least one fertilizer. Furthermore, the present invention relates to 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 a compound of formula (I) or a composition comprising a compound of formula (I).

Claims

1.-15. (canceled)

16. A compound of formula I ##STR00076## or a stereoisomer, salt, tautomer or N-oxide thereof, wherein R.sup.1 and R.sup.2 are independently of each other selected from the group consisting of H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.4-alkoxy-C.sub.1-C.sub.4-alkyl C.sub.1-C.sub.6-alkoxy, C.sub.2-C.sub.6-alkenyloxy, C.sub.2-C.sub.6-alkynyloxy, wherein the C-atoms may in each case be unsubstituted or may carry 1, 2 or 3 identical or different substituents R.sup.e; C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkenyl, heterocyclyl, aryl, hetaryl, C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.8-cycloalkenyl-C.sub.1-C.sub.6-alkyl, heterocyclyl-C.sub.1-C.sub.6-alkyl, aryl-C.sub.1-C.sub.6-alkyl, and hetaryl-C.sub.1-C.sub.6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may in each case be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents R.sup.a; A is phenyl, wherein said phenyl ring may be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents R.sup.A; wherein R.sup.A is selected from the group consisting of CN, halogen, NO2, OR.sup.b, NR.sup.cR.sup.d, C(Y)R.sup.b, C(Y)OR.sup.b, C(Y)NR.sup.cR.sup.d, S(Y).sub.mR.sup.b, S(Y).sub.mOR.sup.b, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio, wherein the C-atoms may in each case be unsubstituted or may carry 1, 2 or 3 identical or different substituents R.sup.e; C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.8-cycloalkenyl, heterocyclyl, aryl, hetaryl, C.sub.3-C.sub.8-cycloalkyl-C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.8-cycloalkenyl-C.sub.1-C.sub.6-alkyl, heterocyclyl-C.sub.1-C.sub.6-alkyl, aryl-C.sub.1-C.sub.6-alkyl, and hetaryl-C.sub.1-C.sub.6-alkyl, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1, 2, 3, 4, or 5 identical or different substituents R.sup.a; and wherein R.sup.a is selected from CN, halogen, NO.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl and C.sub.1-C.sub.4-alkoxy; or two substituents R.sup.a on adjacent C-atoms may be a bridge selected from CH.sub.2CH.sub.2CH.sub.2CH.sub.2, OCH.sub.2CH.sub.2CH.sub.2, CH.sub.2OCH.sub.2CH.sub.2, OCH.sub.2CH.sub.2O, OCH.sub.2OCH.sub.2, CH.sub.2CH.sub.2CH.sub.2, CH.sub.2CH.sub.2O, CH.sub.2OCH.sub.2, O(CH.sub.2)O, SCH.sub.2CH.sub.2CH.sub.2, CH.sub.2SCH.sub.2CH.sub.2, SCH.sub.2CH.sub.2S, SCH.sub.2SCH.sub.2, CH.sub.2CH.sub.2S, CH.sub.2SCH.sub.2, S(CH.sub.2)S, and form together with the C atoms, to which the two R.sup.a are bonded to, a 5-membered or 6-membered saturated carbocyclic or heteocyclic ring; R.sup.b is selected from H, C.sub.1-C.sub.6-alkyl, C.sub.2-C.sub.4-alkenyl, C.sub.2-C.sub.4-alkynyl, C.sub.1-C.sub.4-haloalkyl, phenyl and benzyl; 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; or R.sup.c and R.sup.d together with the N atom to which they are bonded form a 5- or 6-membered, saturated or unsaturated heterocycle, which may carry a further heteroatom being selected from O, S and N as a ring member atom and wherein the heterocycle may be unsubstituted or may carry 1, 2, 3, 4, or 5 substituents which are independently of each other selected from halogen; R.sup.e is selected from CN, halogen, 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; Y is O or S; and m is 0, 1 or 2.

17. The compound of claim 16, wherein the radicals R.sup.a, R.sup.b, R.sup.c, R.sup.d, and R.sup.e are defined as follows: R.sup.a is selected from halogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkoxy, or two substituents R.sup.a on adjacent C-atoms may be a OCH.sub.2CH.sub.2O bridge or a O(CH.sub.2)O bridge; R.sup.b is selected from H, C.sub.1-C.sub.6-alkyl, phenyl and benzyl; 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 R.sup.e is selected from halogen and C.sub.1-C.sub.4-alkyl.

18. The compound of claim 16, wherein in said compound of formula I, R.sup.1 and R.sup.2 are independently of each other selected from the group consisting of H, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-alkynyloxy, aryl-C.sub.1-C.sub.6-alkyl, and hetaryl-C.sub.1-C.sub.6-alkyl, wherein preferably at least one of R.sup.1 and R.sup.2 is H.

19. The compound of claim 16, wherein in said compound of formula I, A is phenyl, wherein said phenyl ring is unsubstituted or carries 1, 2, or 3 identical or different substituents R.sup.A.

20. The compound of claim 16, wherein in said compound of formula I, if present, R.sup.A is selected from the group consisting of halogen, NO.sub.2, NR.sup.cR.sup.d, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1 or 2 identical or different substituents R.sup.a, wherein R.sup.a and R.sup.c and R.sup.d are as defined in claim 16.

21. A composition comprising at least one compound claim 16 and at least one carrier.

22. An agrochemical mixture comprising (i) at least one fertilizer; and (ii) at least one compound of claim 16.

23. 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 a compound of claim 16.

24. The method of claim 22, 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.

25. The method of claim 22, wherein the application of said nitrification inhibitor and of said fertilizer is carried out simultaneously or with a time lag, preferably an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.

26. The agrochemical mixture of claim 22, wherein said fertilizer is an solid or liquid ammonium-containing inorganic fertilizer such as an NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate; an solid or liquid organic fertilizer such as liquid manure, semi-liquid manure, biogas manure, stable manure and straw manure, worm castings, compost, seaweed or guano, or an urea-containing fertilizer such as urea, formaldehyde urea, urea ammonium nitrate (UAN) solution, urea sulphur, stabilized urea, urea based NPK-fertilizers, or urea ammonium sulfate.

27. The method of claim 23, wherein said plant is an agricultural plant selected from the group consisting of wheat, barley, oat, rye, soybean, corn, potatoes, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, and rice; a vegetable plant selected from the group consisting of spinach, lettuce, asparagus, cabbages, and sorghum; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or in a genetically modified form.

28. The method of claim 23, wherein the radicals R.sup.a, R.sup.b, R.sup.c, R.sup.d, and R.sup.e are defined as follows: R.sup.a is selected from halogen, C.sub.1-C.sub.2-alkyl, C.sub.1-C.sub.2-alkoxy, or two substituents R.sup.a on adjacent C-atoms may be a OCH.sub.2CH.sub.2O bridge or a O(CH.sub.2)O bridge; R.sup.b is selected from H, C.sub.1-C.sub.6-alkyl, phenyl and benzyl; 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 R.sup.e is selected from halogen and C.sub.1-C.sub.4-alkyl.

29. The method of claim 23, wherein in said compound of formula I, R.sup.1 and R.sup.2 are independently of each other selected from the group consisting of H, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-alkynyloxy, aryl-C.sub.1-C.sub.6-alkyl, and hetaryl-C.sub.1-C.sub.6-alkyl, wherein preferably at least one of R.sup.1 and R.sup.2 is H.

30. The method of claim 23, wherein in said compound of formula I, A is phenyl, wherein said phenyl ring is unsubstituted or carries 1, 2, or 3 identical or different substituents R.sup.A.

31. The method of claim 23, wherein in said compound of formula I, if present, R.sup.A is selected from the group consisting of halogen, NO.sub.2, NR.sup.cR.sup.d, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.6-alkylthio, phenoxy and benzyloxy, wherein the cyclic moieties may be unsubstituted or may carry 1 or 2 identical or different substituents R.sup.a, wherein R.sup.a and R.sup.c and R.sup.d are as defined in claim 16.

Description

EXAMPLES

Example 1

[0558] The compounds of the invention have been tested as follows in terms of the inhibition of nitrification:

[0559] 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.

[0560] 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. Measurements were taken with a Tecan plate Reader at 540 nm wavelength.

[0561] The results of the measurements (with a dose of 10 ppm) were that all compounds 1-1 to 1-22 as shown in Table 1 above, supra demonstrated an inhibition of ≧10% compared to a control (DMSO only). Futhermore, the compounds 1-23 to 1-33 as shown in Table 1 above (with a dose of 5±1 ppm), supra demonstrated an inhibition of 15% compared to a control (DMSO only). 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

[0562] The results for the compounds tested with a dose of 10 ppm are provided in the following Table 1.1. In each case, the best inhibition value (IN) obtained for a compound is provided.

TABLE-US-00002 TABLE 1.1 No. Compound IN 1-1 [00042] 15 1-2 [00043] 48 1-3 [00044] 11 1-4 [00045] 15 1-5 [00046] 27 1-6 [00047] 10 1-7 [00048] 11 1-8 [00049] 57 1-9 [00050] 20 1-10 [00051] 14 1-11 [00052] 12 1-12 [00053] 15 1-13 [00054] 10 1-14 [00055] 56 1-15 [00056] 58 1-16 [00057] 11 1-17 [00058] 10 1-18 [00059] 10 1-19 [00060] 15 1-20 [00061] 10 1-21 [00062] 20 1-22 [00063] 11

Comparative Example 1.2

[0563] For comparative purposes phenylacetylene was tested under the same conditions as outlined above with a dose of 10 ppm. The following inhibition value was obtained.

TABLE-US-00003 TABLE 1.2 Comp. Ex.1.2 Structure IN Phenylacetylene [00064] 7

Example 1.3

[0564] The results for the compounds tested with a dose of 5±1 ppm are provided in the following Table 1.3. In each case, the best inhibition value (IN) obtained for a compound is provided.

TABLE-US-00004 TABLE 1.3 No. Compound IN 1-23 [00065] 18 1-24 [00066] 18 1-25 [00067] 87 1-26 [00068] 69 1-27 [00069] 59 1-28 [00070] 88 1-29 [00071] 37 1-30 [00072] 25 1-31 [00073] 18 1-32 [00074] 53 1-33 [00075] 24