DELAYED RELEASE FORMULATION OF NITRIFICATION INHIBITORS

Abstract

The invention relates to a composition comprising a) zeolitic imidazolate framework ZIF-8; and b) Compounds of formula (I) or a stereoisomer, salt, tautomer or N-oxide thereof, wherein the variables have a meaning as defined in the main body of the text. It also relates to a method for fertilization comprising treatment with the composition. Other objects are the use of ZIF-8 for reducing the evaporation rate of Compounds of formula (I); a method for production of the composition as defined comprising step a) of adsorbing Compounds of formula (I) on ZIF-8; and the use of the composition for producing granules comprising Compounds of formula (I) and a fertilizer.

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Claims

1. A composition comprising a) zeolitic imidazolate framework ZIF-8; and b) a compound of formula (I) ##STR00040## or a stereoisomer, salt, tautomer or N-oxide thereof, wherein the variables have the following meaning: R.sup.1, R.sup.2 are independently 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, which groups are unsubstituted or substituted by one or more, same or different R.sup.e; or 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, hetaryl-C.sub.1-C.sub.6-alkyl, phenoxy, or benzyloxy, wherein the cyclic moieties are unsubstituted or substituted by one or more, same or different R.sup.a; A phenyl, which is unsubstituted or substituted with one or more, same or different R.sup.A; R.sup.A CN, halogen, NO.sub.2, 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, which groups are unsubstituted or substituted by one or more, same or different R.sup.e; or 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, hetaryl-C.sub.1-C.sub.6-alkyl, phenoxy, benzyloxy, wherein the cyclic moieties are unsubstituted or substituted by one or more, same or different R.sup.a; R.sup.a CN, halogen, NO.sub.2, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-haloalkyl, or C.sub.1-C.sub.4-alkoxy; or two substituents R.sup.a on adjacent C-atoms form a bridge 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 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 or benzyl; R.sup.c, R.sup.d are independently of each other H, C.sub.1-C.sub.4-alkyl, or 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, wherein the heterocycle is unsubstituted or substituted with one or more, same or different halogen atoms; R.sup.e CN, 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; Y O or S; and m 0, 1 or 2.

2. The composition according to claim 1, wherein the variables of the compound of formula (I) have the following meaning: R.sup.a 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 are a OCH.sub.2CH.sub.2O bridge or a O(CH.sub.2)O bridge; R.sup.b H, C.sub.1-C.sub.6-alkyl, phenyl and benzyl; R.sup.c, R.sup.d are independently H, C.sub.1-C.sub.4-alkyl, or C.sub.1-C.sub.4-haloalkyl; and R.sup.e halogen and C.sub.1-C.sub.4-alkyl.

3. The composition according to claim 1, wherein the variables of the compound of formula (I) have the following meaning: R.sup.1, R.sup.2 are independently H, C.sub.2-C.sub.6-alkynyl, C.sub.2-C.sub.6-alkynyloxy, aryl-C.sub.1-C.sub.6-alkyl, or hetaryl-C.sub.1-C.sub.6-alkyl; wherein least one of R.sup.1 and R.sup.2 is H.

4. The composition according to claim 1, wherein the variables of the compound of formula (I) have the following meaning: A phenyl, which is unsubstituted or one or more, same or different R.sup.A; and R.sup.A 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, or benzyloxy, wherein the cyclic moieties are unsubstituted or substituted with one or more, same or different R.sup.a.

5. The composition according to claim 1, wherein the variables of the compound of formula (I) have the following meaning: R.sup.1, R.sup.2 are H; and A is phenyl, which is substituted with Cl.

6. The composition according to claim 1, wherein the weight ratio of the compound of formula (I) to ZIF-8 is from 1:10 to 2:1.

7. The composition according to claim 1 comprising a fertilizer.

8. The composition according to claim 7, wherein the fertilizer is an organic, or inorganic ammonium-containing fertilizer, or a urea-containing fertilizer.

9. A method for fertilization, comprising treating plant propagation material, 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 the composition as defined in claim 1.

10. The method according to claim 10, wherein the plant propagation material, the plant and/or the locus or soil or soil substituents where the plant is growing or is intended to grow is additionally treated with a fertilizer.

11. A method for reducing the evaporation rate of the compound of formula (I) comprising the use of ZIF-8.

12. A method for producing the composition as defined in claim 1 comprising a step a) of adsorbing the compound of formula (I) on the metal-organic-framework ZIF-8.

13. The method according to claim 12 comprising a step b) of co-granulating the compound of formula (I) adsorbed on ZIF-8 with a fertilizer, wherein the composition is in the form of granules.

14. The method according to claim 13, wherein the temperature in step b) is from 50 C. to 150 C.

15. (canceled)

Description

EXAMPLES

[0183] ZIF-8 was purchased as Basolite Z1200 from SigmaAldrich.

[0184] Zeolite Beta was purchased from Alfa Aesar.

[0185] Compound A: 1-chloro-4-(prop-2-ynoxymethyl)benzene (corresponding to compound 1-15 in Table A).

Working Example 1: Compound a on ZIF-8

[0186] ZIF-8 powder (10 g) was placed in a porcelain dish. The ZIF-8 powder was in the activated stage with virtually nothing adsorbed in the pores of the material. Compound A (3 g, below 2% impurities) was slowly added at 20 to 25 C. to the manually agitated ZIF-8 powder over a period of 15 minutes to result in Sample A containing 23 wt % of Compound A based on the total weight of Sample A.

Working Example 2: Compound a on ZIF-8 at Different Loadings

[0187] ZIF-8 was loaded with Compound A as described in Working Example 1 with different amounts of Compound A, thereby resulting in the Samples B-H of Table 1.

TABLE-US-00002 TABLE 1 Loading of ZIF-8 with different amounts of Compound A in [wt %] Sample B Sample C Sample D Sample E Sample F Loading [wt %] relative 16.6 28.6 37.5 44.4 50 to the total weight of the sample Sample G Sample H Loading [wt %] relative 54.5 58.3 to the total weight of the sample

Comparative Working Example 1: Compound a on Zeolite Beta

[0188] Zeolite Beta powder (10 g) were placed in a porcelain dish. The zeolite Beta powder was in the activated stage with virtually nothing adsorbed in the pores of the material. Compound A (3 g, below 2% impurities) was slowly added at 20 to 25 C. to the manually agitated zeolite Beta powder over a period of 15 minutes to result in Sample K containing 23 wt % of Compound A based on the total weight of Sample K.

Example-1: Volatility Measurement at 35 C.

[0189] Five beakers B1-B5 were prepared containing samples as specified in Table 2

TABLE-US-00003 TABLE 2 Samples in Beakers 1-5. B 1 B 2 B 3 B 4 B 5 Compound A ZIF-8 Sample A (8.7 g Zeolite Sample K (8.7 g (2 g) (6.7 g) containing 2 g Beta containing 2 g of Compound A) (6.7 g) of Compound A)

[0190] All 5 beakers were mounted in an oil bath such that half of the beakers were immersed. The temperature of the oil bath was set to 35 C. During the heating process, the beakers were periodically taken out of the oil bath, dried, and weighted. The total mass of the beaker with samples was noted and compared to the initial weight of the beakers with samples. The weight loss attributed to Compound A was calculated from the total weight loss of the sample by taking the loading of the respective sample with Compound A into account. A comparison of the weight loss of Compound A, and the whole sample weight loss in the all 5 beakers after 23 hours at 35 C. was shown in the Table 3.

TABLE-US-00004 TABLE 3 Weight loss of samples in [%] relative to the initial weight. Sample B1 B2 B3 B4 B5 Weight loss of 4.22 0.27 26.48 Compound A Total sample 4.22 0.14 0.05 1.10 6.07 weight loss

Example-2: Volatility Measurement at 60 C.

[0191] Five beakers B1-B5 were prepared and treated as described in Example-1 with the differences that the oil bath was set to 60 C. and that the weight loss was recorded after 32 hours. Table 4 showed a comparison of the weight loss Compound A, and the whole sample weight loss in the all 5 beakers after 32 hours at 60 C.

TABLE-US-00005 TABLE 4 Weight loss of samples in [%] relative to the initial weight. Sample B1 B2 B3 B4 B5 Weight loss of 37.97 0.83 41.78 Compound A Total sample 37.97 0.10 0.19 5.69 9.58 weight loss

Example-3: Volatility Measurement at 100 C.

[0192] Five beakers B1-B5 were prepared and treated as described in Example-1 with the differences that the oil bath was set to 100 C. and that the weight loss was recorded after hours. Table 5 showed a comparison of the weight loss Compound A, and the whole sample weight loss in the all 5 beakers after hours at 100 C.

TABLE-US-00006 TABLE 5 Weight loss of samples in [%] relative to the initial weight. Sample B1 B2 B3 B4 B5 Weight loss of 68.82 1.87 44.69 Compound A Total sample 68.82 0.49 0.44 8.64 10.20 weight loss

Example-4: Volatility Measurement at 60 C. with Different Loading for 24 or 72 Hours

[0193] Five beakers B6-B10 were prepared containing samples as specified in Table 6.

TABLE-US-00007 TABLE 6 Samples in Beakers 6-10. B6 B7 B8 B9 B10 Sample B (6 g Sample C (7 g Sample D (8 g Sample E (9 g Sample F (10 g containing 1 g containing 2 g containing 3 g containing 4 g containing 5 g of Compound A) of Compound A) of Compound A) of Compound A) of Compound A)

[0194] All 5 beakers B6-B10 were mounted in an oil bath such that half of the beakers were immersed. The temperature of the oil bath was set to 60C. During the heating process, the beakers were periodically taken out of the oil bath, dried, and weighted. The total mass of the beaker with samples was noted and compared to the initial weight of the beakers with samples. The weight loss attributed to Compound A was calculated from the total weight loss of the sample by taking the loading of the respective sample with Compound A into account. A comparison of the weight loss of Compound A, and the whole sample weight loss in the all 5 beakers after 24 and 72 hours at 60 C. was shown in the Table 7.

TABLE-US-00008 TABLE 7 Weight loss of samples in [%] relative to the initial weight after 24 and 72 hours. Sample B6 B7 B8 B9 B10 Weight loss of 1.38 0.11 7.59 6.76 6.99 Compound A after 24 hours Total sample 0.23 0.03 2.86 3.01 3.49 weight loss after 24 hours Weight loss of 1.17 0.46 15.21 16.62 18.1 Compound A after 72 hours Total sample 0.19 0.13 5.72 7.40 9.05 weight loss after 72 hours

Example-5: Volatility Measurement at 60 C. with Different Loading for 24 or 72 Hours

[0195] Five beakers B11-B15 were prepared containing samples as specified in Table 8.

TABLE-US-00009 TABLE 8 Samples in Beakers 11-15. B11 B12 B13 B14 B15 Sample E (9 g Sample F (10 g Sample G (11 g Sample H (12 g Compound A containing 4 g containing 5 g containing 6 g containing 7 g (7 g) of Compound A) of Compound A) of Compound A) of Compound A)

[0196] All 5 beakers B11-B15 were mounted in an oil bath such that half of the beakers were immersed. The temperature of the oil bath was set to 60C. During the heating process, the beakers were periodically taken out of the oil bath, dried, and weighted. The total mass of the beaker with samples was noted and compared to the initial weight of the beakers with samples. The weight loss attributed to Compound A was calculated from the total weight loss of the sample by taking the loading of the respective sample with Compound A into account. A comparison of the weight loss of Compound A, and the whole sample weight loss in the all 5 beakers after 24 and 72 hours at 60 C. was shown in the Table 9.

TABLE-US-00010 TABLE 9 Weight loss of samples in [%] relative to the initial weight after 24 and 72 hours. Sample B11 B12 B13 B14 B15 Weight loss of 6.66 7.06 5.80 4.92 9.02 Compound A after 24 hours Total sample 2.96 3.53 3.17 2.87 9.02 weight loss after 24 hours Weight loss of 16.64 18.01 16.64 14.47 26.99 Compound A after 72 hours Total sample 7.40 9.01 9.08 8.44 26.99 weight loss after 72 hours

Example 6: Nitrogen Retention in Field Trials

[0197] An area of sandy soil, previously untreated with fertilizer or other agricultural products near the field station Limburgerh of, was treated as follows. Drainage pipes of 20 cm in length and 12 cm diameter were inserted 10 cm deep into the soil. A treatment as indicated in a line of Table 10 was added on top of the soil under which a pipe was buried. At the beginning of the experiment and after three weeks, the pipes were dug out of the soil with its content, the content emptied into a bag and frozen on site. The soil was then analyzed for NH.sub.4-nitrogen content in the laboratory according to the following method: Samples were defrosted for 24 h, then sieved through a 5-6 mm mesh sieve. 200 g of the thus homogenized samples were put into 1 L plastic bottles and 600 mL of a K.sub.2S.sub.4 solution (1% (w/w) K.sub.2SO.sub.4 in water) were added. The samples were then shaken for 2 h end over end. The solution was filtered to remove the soil and 50 mL of the filtrate retained for analysis in a Continuous Flow Analyzer for NH.sub.4-nitrogen content.

TABLE-US-00011 TABLE 10 Field trial results Incorpora- NH.sub.4- tion Depth nitrogen Treatment (cm) Timepoint (kg/ha) none 3 weeks after application 0 Ammonium Sulfate 0 At time of application 75 Ammonium Sulfate 0 3 weeks after application 8 Ammonium Sulfate + 0 3 weeks after application 50 Sample A Ammonium sulfate + 0 3 weeks after application 8 Compound A Ammonium Sulfate + 0 3 weeks after application 30 MOF