USE OF A SUBSTITUTED THIAZOLIDINE COMPOUND AS NITRIFICATION INHIBITOR

Abstract

The invention relates to novel nitrification inhibitors of formula I, which are substituted thiazolidine 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. A substituted thiazolidine compound of formula I ##STR00013## or a salt, stereoisomer, tautomer, N-oxide, or S-oxide thereof for use as a nitrification inhibitor, wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently of each other selected from H, halogen, 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-haloalkoxy, C.sub.2-C.sub.6-alkenyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.1-C.sub.4-alkylsulfonyl, benzyl, and phenyl, wherein said groups are unsubstituted or substituted by one or more, same or different substituents R.sup.x; or R.sup.1 and R.sup.2 or R.sup.3 and R.sup.4 together form ═O; and wherein R.sup.N is H, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, benzyl, allyl, propargyl, or phenyl, wherein said groups are unsubstituted or substituted by one or more, same or different substituents R.sup.y; CHR.sup.aC(═O)OR.sup.b, CHR.sup.aC(═O)O.sup.−-Q.sup.+, CHR.sup.aC(═O)R.sup.d, CHR.sup.aC(═O)NR.sup.bR.sup.c, C(═O)R.sup.d, C(═O)OR.sup.b, C(═O)NR.sup.bR.sup.c, CHR.sup.aOR.sup.b, C(═O)(CH.sub.2).sub.2C(═O)OR.sup.b, or CSNR.sup.bR.sup.c; R.sup.a is H, halogen, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.1-C.sub.4-haloalkyl, C.sub.3-C.sub.6-cycloalkyl, phenyl, or phenyl-C.sub.1-C.sub.2-alkyl; R.sup.b is H, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl, aryl, phenyl, or phenyl-C.sub.1-C.sub.2-alkyl; R.sup.c is H, C.sub.1-C.sub.6-alkyl, C.sub.1-C.sub.6-alkoxy, C.sub.3-C.sub.6-cycloalkyl, aryl, phenyl, or phenyl-C.sub.1-C.sub.2-alkyl; R.sup.d is H, C.sub.1-C.sub.3-alkyl, C.sub.1-C.sub.6-haloalkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, phenyl, phenyl-C.sub.1-C.sub.2-alkyl, hetaryl, or hetaryl-C.sub.2-C.sub.3-alkenyl, wherein these groups are unsubstituted or substituted by one or more, same or different substituents selected from halogen, OH, OCH.sub.3, and CH.sub.3; R.sup.x is halogen, OH, 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-haloalkoxy, C.sub.1-C.sub.6-alkylthio, C.sub.1-C.sub.6-alkylcarbonyl, or C.sub.1-C.sub.6-alkylcarboxy; R.sup.y is halogen, OH, 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-haloalkoxy, or phenyl; and Q.sup.+ is selected from the group consisting of Na.sup.+, K.sup.+, Ca.sup.2+, and NH.sub.4.sup.+.

2. The compound of claim 1, wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently of each other selected from H, halogen, and C.sub.1-C.sub.4-alkyl; R.sup.N is H, C.sub.1-C.sub.4-alkyl, benzyl, allyl, propargyl, phenyl, CHR.sup.aC(═O)OR.sup.b, CHR.sup.aC(═O)O.sup.−-Q.sup.+, CHR.sup.aC(═O)NR.sup.bR.sup.c, CHR.sup.aC(═O)R.sup.d, C(═O)R.sup.d, or C(═O)(CH.sub.2).sub.2C(═O)OR.sup.b; R.sup.a is H, C.sub.1-C.sub.4-alkyl; R.sup.b is H, C.sub.1-C.sub.4-alkyl; R.sup.c is H, C.sub.1-C.sub.4-alkyl; R.sup.d is H, C.sub.1-C.sub.3-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, phenyl, or phenyl-C.sub.1-C.sub.2-alkyl, hetaryl, or hetaryl-C.sub.2-C.sub.3-alkenyl, wherein these groups are unsubstituted or substituted by one or more, same or different substituents selected from halogen, OH, OCH.sub.3, and CH.sub.3; Q.sup.+ is selected from the group of Na.sup.+, K.sup.+, Ca.sup.2+, and NH.sub.4.sup.+.

3. The compound of claim 1, wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are H; R.sup.N is H, C.sub.1-C.sub.3-alkyl, or C(═O)R.sup.d; R.sup.d is H, C.sub.1-C.sub.3-alkyl, C.sub.2-C.sub.6-alkenyl, C.sub.2-C.sub.6-alkynyl, phenyl, or phenyl-C.sub.1-C.sub.2-alkyl, hetaryl, or hetaryl-C.sub.2-C.sub.3-alkenyl, wherein these groups are unsubstituted or substituted by one or more, same or different substituents selected from halogen, OH, OCH.sub.3, and CH.sub.3.

4. The compound of claim 1, wherein the substituted thiazolidine compound of formula I is present in the form of a salt with different acids, selected from the group consisting of H.sub.3PO.sub.4, H.sub.2SO.sub.4, HNO.sub.3, HBr, and HCl.

5. 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.

6. An agrochemical mixture comprising (i) at least one fertilizer; and (ii) at least one com-pound of formula I as defined in claim 1.

7. The method of claim 9, wherein said compound of formula I is used in combination with a fertilizer.

8. The method of claim 9, 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.

9. 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.

10. The method of claim 9, 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.

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

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

13. The agrochemical mixture of claim 6, wherein said fertilizer is a solid or liquid ammonium-containing inorganic fertilizer; a solid or liquid organic fertilizer, or a urea-containing fertilizer.

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

15. The method of claim 11 wherein the time lag is an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks, or 3 weeks

16. The agrichemical mixture of claim 13 wherein the fertilizer comprises 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, or urea ammonium sulfate.

17. The method of claim 14 wherein the plant 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, or cabbages, each in its natural or in a genetically modified form.

Description

EXAMPLES

[0581] The compounds of the invention have been tested as follows in terms of the inhibition of nitrification:

[0582] 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.

[0583] 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).

[0584] The inhibition (NI® a specified concentration) is calculated as follows:

[00001]$\mathrm{inhibition}\mathrm{in}\%=\frac{\begin{array}{c}(\mathrm{NO}3-N_{\mathrm{without}\mathrm{NI}\mathrm{at}\mathrm{end}\mathrm{of}\mathrm{incubation}}-\\ \mathrm{NO}3-N_{\mathrm{with}\mathrm{NI}\mathrm{at}\mathrm{end}\mathrm{of}\mathrm{incubation}})\end{array}}{\left(\mathrm{NO}3-N_{\mathrm{without}\mathrm{NI}\mathrm{at}\mathrm{end}\mathrm{of}\mathrm{incubation}}-\mathrm{NO}3-N_{\mathrm{at}\mathrm{beginning}}\right)}\times 100$

[0585] The following compounds of general formula I, wherein R.sup.1 and R.sup.2 are in each case H, have been tested.

##STR00012##

TABLE-US-00002 NI* NI* NI* No. R.sup.3 R.sup.4 R.sup.N @ 3% @ 1% @ 0.3% 1 H H H 83.5 47   — 2 H H C(═O)phenyl- 67.9 73.1 34.8 m(OCH.sub.3) 3 H H C(═O)—CH.sub.2- 71.1 55.3 26.6 phenyl 4 H H C(═O)CH.sub.3 68.7 32.3 — 5 H H C(═O)phenyl-pCl 67 30.7 — 6 CH.sub.3 CH.sub.3 H 57.5 — — 7 H H C(═O)phenyl- 57.4 27.5 19.8 p(OCH.sub.3) 8 H H C(═O)phenyl- 55 — — 3,4-di-OCH.sub.3 9 H H C(═O)phenyl-mBr 49 — — 10 H H C(═O)phenyl 48.4 — — 11 H H CH.sub.3 39.9 — — 12 H H C(═O)-3-methyl-2- 39 — — benzofuranyl

[0586] Synthesis of the Tested Compounds:

[0587] Cmpd 1: 1,3-Thiazolidine-2-thione., CAS-Nr. 96-53-7. This substance is commercially available and has been purchased. It exists in equilibrium with its tautomer 2-mercapto-2-thiazoline.

[0588] Cmpd. 2: 3-(3-Methoxybenzoyl)-2-thiazolidinethione, CAS-No. 462069-01-8. This substance is commercially available and has been purchased.

[0589] Cmpd. 3: 3-(Phenylacetyl)-2-thiazolidinethione, CAS-No. 65439-58-9. This compound has been prepared as described in Synlett, (15), 2351-2352; 2003.

[0590] Cmpd. 4: 3-Acetylthiazolidine-2-thione, CAS-No. 76397-53-0. This substance is commercially available and has been purchased.

[0591] Cmpd. 5: 3-(4-Chlorobenzoyl)-2-thiazolidinethione, CAS-No. 65439-57-8. This compound has been prepared as described in Pige Huagong, 19(1), 19-22; 2002.

[0592] Cmpd. 6: 4,4-Dimethyl-2-thiazolidinethione, CAS-No. 1908-88-9. This compound has been prepared as described in Tetrahedron, 67(41), 7971-7976; 2011. It exists in equilibrium with its tautomer 4,4-dimethyl-2-mercaptothiazoline.

[0593] Cmpd. 7: 3-(4-Methoxybenzoyl)-2-thiazolidinethione, CAS-No. 134821-22-0. This compound has been prepared as described in Pige Huagong, 19(1), 19-22; 2002.

[0594] Cmpd. 8: 3-(3,4-Dimethoxybenzoyl)-2-thiazolidinethione, CAS-No. 111427-22-6. This substance is commercially available and has been purchased.

[0595] Cmpd. 9: 3-(3-Bromobenzoyl)-2-thiazolidinethione, CAS-No. 872587-20-7. This substance is commercially available and has been purchased.

[0596] Cmpd. 10: 3-Benzoyl-2-thiazolidinethione, CAS-No. 70326-37-3. This substance is commercially available and has been purchased.

[0597] Cmpd. 11: 3-Methyl-2-thiazolidinethione, CAS-No. 1908-87-8. This substance is commercially available and has been purchased.

[0598] Cmpd. 12: 3-[(3-Methyl-2-benzofuranyl)carbonyl]-2-thiazolidinethione, CAS-No. 880844-66-6. This substance is commercially available and has been purchased.