USE OF N-SUBSTITUTED PYRROLIDONES TO PROMOTE THE PENETRATION OF AGROCHEMICAL ACTIVE AGENTS

Abstract

Use of N-substituted pyrrolidones to promote the penetration of agrochemical active agents. The use of one or more N-substituted pyrrolidones of the formula (I),

##STR00001##

wherein R signifies a linear or branched, saturated alkyl group with 3 to 6 carbon atoms, wherein in the alkyl group, hydrogen H can be substituted by a methoxy group OCH3, and wherein 1 to 6 hydrogens H of the pyrrolidone ring can be substituted by methyl CH3, to promote the penetration of agrochemical active agents in plants or in non-plant-based harmful organisms is described.

Claims

1. A method for promotion of penetration of at least one active agrochemical ingredient into a plant or into a non-plant harmful organism comprising the step of contacting the plant with a composition comprising at least one N-substituted pyrrolidone of the formula (I) ##STR00005## in which R is a linear or branched, saturated alkyl group having 3 to 6 carbon atoms, where one hydrogen H in the alkyl group may be replaced by a methoxy group OCH.sub.3, and where 1 to 6 hydrogens H in the pyrrolidone ring may be replaced by methyl CH.sub.3.

2. The method as claimed in claim 1, wherein the at least one N-substituted pyrrolidone of the formula (I) is selected from the group consisting of N-(n-butyl)-2-pyrrolidone, N-(isobutyl)-2-pyrrolidone, N-(tert-butyl)-2-pyrrolidone, N-(n-pentyl)-2-pyrrolidone, N-(methyl-substituted butyl)-2-pyrrolidone, ring methyl-substituted N-(propyl)-2-pyrrolidone, ring methyl-substituted N-(butyl)-2-pyrrolidone and N-(methoxypropyl)-2-pyrrolidone.

3. The method as claimed in claim 1, wherein the N-substituted pyrrolidone of the formula (I) is N-(n-butyl)-2-pyrrolidone.

4. The method as claimed in claim 1, wherein the at least one N-substituted pyrrolidone of the formula (I) is in a crop protection composition comprising a) 1% to 90% by weight of the at least one N-substituted pyrrolidone of the formula (I) and b) 1% to 90% by weight of at least one active agrochemical ingredient.

5. The method as claimed in claim 1, wherein the at least one N-substituted pyrrolidone of the formula (I) is used in a crop protection composition comprising a) 1% to 50% by weight, of at least one N-substituted pyrrolidone of the formula (I) and b) 1% to 90% by weight of at least one active agrochemical ingredient.

6. The method as claimed in claim 1, wherein the at least one N-substituted pyrrolidone of the formula (I) is used in a tankmix additive containing 1% to 90% by weight of at least one N-substituted pyrrolidone of the formula (I) and additionally at least one additive and optionally water.

7. The method as claimed in claim 1, wherein the at least one N-substituted pyrrolidone of the formula (I) is used in a crop protection composition in the form of an aqueous spray liquor.

8. The method as claimed in claim 7, wherein the at least one N-substituted pyrrolidone of the formula (I) is used in a crop protection composition in the form of an aqueous spray liquor comprising a) 0.001% to 99% by weight, of the at least one N-substituted pyrrolidone of the formula (I) and b) 0.001% to 10% by weight, of at least one active agrochemical ingredient.

9. The method as claimed in claim 1, wherein the at least one active agrochemical ingredient is selected from the group consisting of systemic active agrochemical ingredients.

10. The method as claimed in claim 1, wherein the at least one active agrochemical ingredient is selected from the group consisting of active agrochemical ingredients having a log P value <4.5.

11. The method as claimed in claim 1, wherein the at least one active agrochemical ingredient is selected from the group consisting of strobilurin fungicides, azoxystrobin, pyraclostrobin, pycoxystrobin, fluoxastrobin, oryzastrobin, picoxystrobin, trifloxystrobin, azole fungicides, preferably prothioconazole, tebuconazole, cyproconazole, difeconazole, metconazole, propiconazole, tetraconazole, tricyclazole and further active ingredients, preferably fluxapyroxad, boscalid, bitertanol, prochloraz, thiophanate, chlorothalonil, dimethomorph, fenpropimorph, spiroxamine, trifluralin, metribuzin, saflufenacil, fenoxaprop-ethyl, acetolachlor, S-metolachlor, pendimethalin, pinoxaden, fluroxypyr, imidacloprid, thiacloprid, thiamethoxam, clothianidin, acetamiprid, emamectin benzoate, lambda-cyhalothrin, pymetrozine, chloantraniliprole, gibberellic acid, benzylaminopyrin, trinexapac-ethyl, etephon, thidiazuron and mixtures thereof.

12. The method as claimed in claim 11, wherein the at least one active agrochemical ingredient is selected from the group consisting of strobilurin fungicides, further active ingredients, and mixtures thereof.

13. The method as claimed in claim 12, wherein the at least one active agrochemical ingredient is selected from the group consisting of azoxystrobin, pyraclostrobin, fluoxastrobin, trifloxystrobin, prothioconazole, tebuconazole, fluxapyroxad, bitertanol, prochloraz, chlorothalonil, fenpropimorph, trifluralin, metribuzin, saflufenacil, fenoxaprop-ethyl, pendimethalin, imidacloprid, thiacloprid, thiamethoxam, acetamiprid, gibberellic acid, benzylaminopyrin and mixtures thereof.

14. The method as claimed in claim 1, wherein the at least one active agrochemical ingredient i selected from the group consisting of insecticides from the pyrethroid family.

15. The method as claimed in claim 1, wherein the at least one active agrochemical ingredient n selected from the group consisting of fenpicoxamid, bixafen, isopyrazam, fluopyram, penthiopyrad and abamectin.

16. (canceled)

17. The method as claimed in claim 1 wherein the penetration of the at least one active agrochemical ingredient into the plants or into the non-plant harmful organisms, takes place at least for some time at a temperature of not more than 25 C.

18. A crop protection composition comprising a) 1% to 90% by weight of at least one N-substituted pyrrolidone of the formula (I) ##STR00006## in which R is a linear or branched, saturated alkyl group having 3 to 6 carbon atoms, where one hydrogen H in the alkyl group may be replaced by a methoxy group OCH.sub.3, and where 1 to 6 hydrogens H in the pyrrolidone ring may be replaced by methyl CH.sub.3, and b) 1% to 90% by weight of at least one active agrochemical ingredient, wherein component b) is selected from the group consisting of fungicides, bactericides, insecticides, acaricides, nematicides, plant growth regulators, plant nutrients, repellents, molluscicides and rodenticides, wherein the crop protection composition is in the form of a dispersible concentrate (DC); an emulsion concentrate (EC); an oil-in-water emulsion (EW); an emulsion for seed treatment (ES); a flowable concentrate for seed treatment (FS); a water-in-oil emulsion (EO); an oil dispersion (OD); a suspoemulsion (SE); a water-soluble concentrate (SL) or a capsule suspension (CS).

19. The crop protection composition as claimed in claim 18, comprising 1% to 50% by weight, of component a), and 1% to 90% by weight, by weight of component b.

20. A crop protection composition in the form of an aqueous spray liquor comprising a) 0.001% to 99% by weight, of at least one N-substituted pyrrolidone of the formula (I) ##STR00007## in which R is a linear or branched, saturated alkyl group having 3 to 6 carbon atoms, where one hydrogen H in the alkyl group may be replaced by a methoxy group OCH.sub.3, and where 1 to 6 hydrogens H in the pyrrolidone ring may be replaced by methyl CH.sub.3, and b) 0.001% to 10% by weight, of at least one active agrochemical ingredient selected from the group consisting of fungicides, bactericides, insecticides, acaricides, nematicides, plant growth regulators, plant nutrients, repellents, molluscicides and rodenticides, wherein the crop protection composition is in the form of a dispersible concentrate (DC); an emulsion concentrate (EC); an oil-in-water emulsion (EW); an emulsion for seed treatment (ES); a flowable concentrate for seed treatment (FS); a water-in-oil emulsion (EO); an oil dispersion (OD); a suspoemulsion (SE); a water-soluble concentrate (SL) or a capsule suspension (CS).

21. The crop protection composition as claimed in claim 20, wherein the content of component b) is less than 0.05 g/L, and the content of component A) is especially less than 0.1% by weight, based on the total amount of the spray liquor.

22. The crop protection composition as claimed in claim 18, wherein component b) is selected from the group consisting of fungicides, insecticides, nematicides and plant growth regulators.

Description

EXAMPLES

[0241] Penetration Test (Penetration into Plants)

[0242] In this test, the penetration of active ingredients through enzymatically isolated cuticles of apple or pear tree leaves was measured.

[0243] Leaves that had been cut in the fully developed state off apple trees of the Golden Delicious variety or pear trees were used. The cuticles were isolated by [0244] first filling leaf disks labeled on the underside with dye and formed by punching by means of vacuum infiltration with a pectinase solution (0.2% to 2% strength) buffered to a pH of between 3 and 4, [0245] then adding sodium azide and [0246] leaving the leaf disks thus treated to stand until dissolution of the original leaf structure and until detachment of the noncellular cuticles.

[0247] All that were used thereafter were the cuticles of the top sides of the leaves that were free of stomata and hairs. They were repeatedly washed alternately with water and a buffer solution of pH 7. The clean cuticles obtained were finally applied to Teflon platelets, and smoothed and dried with a gentle air stream.

[0248] In the next step, the cuticle membranes thus obtained were placed into stainless steel diffusion cells (=transport chambers) for membrane transport studies. For this purpose, the cuticles were placed with tweezers at the midpoint onto the edges of the diffusion cells that had been coated with silicone grease and closed with a likewise greased ring. The arrangement had been chosen such that the morphological outer face of the cuticles faced the outside, i.e. the air, while the original inner face faced the interior of the diffusion cell. The diffusion cells were filled with water or with a mixture of water and solvent.

[0249] To determine penetration, 9 L in each case of a spray liquor of the composition specified in the examples was applied to the outer face of a cuticle.

[0250] CIPAC water was used in each of the spray liquors.

[0251] After the spray liquors had been applied, the water was allowed to evaporate in each case, then the chambers were each turned around and they were placed into thermostated baths, while air at a defined temperature and air humidity was blown onto the outer face of the cuticle. The penetration that set in took place at a relative air humidity of 60% and a set temperature as specified. The active ingredient penetration was measured by means of high-performance liquid chromatography (HPLC).

[0252] As apparent from the examples adduced in tables 1 to 20, the presence of N-(n-butyl)-2-pyrrolidone leads to a considerable increase in uptake compared to the formulations where N-(n-butyl)-2-pyrrolidone is absent. The alternatives to N-(n-butyl)-2-pyrrolidone used are examples of commercial feedstocks for formulations.

[0253] The values for % penetration reported in the tables which follow report what percentage of the amount of substance applied to the plant penetrates into the plant. The values reported are averages.

[0254] The abbreviations used in the tables have the following meaning:

[0255] 20 SG: short form of Mospilan 20 SG

[0256] Calypso SC 480: commercial formulation of thiacloprid

[0257] Custodia SC 320: commercial formulation of azoxystrobin and tebuconazole

[0258] DAT: days after treatment

[0259] DF75: short form of Dimetric DF75

[0260] Dimetric DF75: commercial formulation of metribuzin

[0261] DMSO: dimethyl sulfoxide

[0262] EC 540: commercial formulation of trifluralin

[0263] Galaster BL97: butyl lactate

[0264] Genagen NBP: NBP (neat)

[0265] Mospilan 20 SG: commercial formulation of acetamiprid

[0266] n: number of treatments and accompanying measurements

[0267] NBP: N-(n-butyl)-2-pyrrolidone

[0268] NMP: N-methylpyrrolidone

[0269] Orkestra SC 500: commercial formulation of fluxapyroxad and pyraclostrobin

[0270] RT: room temperature (23 to 25 C.)

[0271] SC320: short form of Custodia SC 320

[0272] SC480: short form of Calypso SC 480

[0273] SC500: short form of Orkestra SC 500

[0274] EC 18: commercial formulation of abamectin (emulsion concentrate)

[0275] SC 200: commercial formulation of rynaxypyr (suspension concentrate)

[0276] Acceptor medium: solution of forchlorfenuron in a water/diethylene glycol medium

[0277] Prothioconazole x % RW: prothioconazole powder with active ingredient content x % by weight

[0278] Genagen PA: dimethylpelargonamide

[0279] Genagen 4296: dimethyldecanamide

[0280] Agsolex 08: N-octylpyrrolidone

[0281] Solvesso 200 ND: mixture of aromatic hydrocarbons

[0282] Emulsogen 3510: alkylated copolymers of ethylene oxide and propylene oxide

[0283] Synergen 848: alkylated copolymers of ethylene oxide and propylene oxide

[0284] Synergen W03: alkylsulfosuccinate, Na salt in hydrocarbons

[0285] Synergen W09: alkylsulfosuccinate, Na salt in white oil

[0286] Genapol X 090: isotridecyl alcohol with 9 ethylene oxide units

[0287] Emulsogen MTP 070: alkylated copolymers of ethylene oxide and propylene oxide

[0288] Emulsogen EL 300: castor oil with 30 ethylene oxide units

[0289] Emulsogen EL 360: castor oil with 36 ethylene oxide units

[0290] Momentive SAG 1571: polydimethylsiloxane emulsion

[0291] Trinexapac Ethyl x % RW: trinexapac-ethyl powder with active ingredient content x % by weight

[0292] Hostaphat 1306: isotridecyl phosphate with 6 ethylene oxide units

[0293] Emulsogen ELO 200: modified castor oil ethoxylates

[0294] Synergen SOC: tankmix adjuvant

[0295] MSO: sunflower oil methyl ester

Example 1: Penetration Tests with Metribuzin at 10 C. in Pear

[0296]

TABLE-US-00001 TABLE 1 Penetration results after 6 hours and after 2 days of example 1 Metribuzin % metribuzin % metribuzin Formulation/test substance concentration (g/L) penetration at penetration at in the aqueous spray liquor Active in the aqueous 10 C. in pear 10 C. in pear Example (% by wt.) ingredient spray liquor after 6 h//n = 5-7 after 2 DAT//n = 5-7 1-1 Dimetric DF75 metribuzin 2.25 0.57 1.28 1-2 DF75/NMP (0.1) metribuzin 2.25 0.48 1.25 1-3 DF75/NMP (0.5) metribuzin 2.25 0.83 3.51 1-4 DF75/DMSO (0.1) metribuzin 2.25 0.28 1 1-5 DF75/DMSO (0.5) metribuzin 2.25 0.64 2.02 1-6 DF75/NBP (0.1) metribuzin 2.25 1.88 3.54 1-7 DF75/NBP (0.3) metribuzin 2.25 8.93 11.64 1-8 DF75/NBP (0.5) metribuzin 2.25 16.88 21.05

Procedure for Examples 1-1 to 1-8

[0297] The formulation (Dimetric DF75 or DF75) was diluted with water, such that the dilution contained a metribuzin concentration of 4.50 g/L. By mixing this diluted formulation with the appropriate amount of test substance (NMP, DMSO or NBP) in water, the desired concentration of test substance (0.1% by weight, 0.3% by weight or 0.5% by weight) and the active agrochemical ingredient metribuzin (2.25 g/L) in the aqueous spray liquor was established. Penetration through isolated pear cuticles was measured at a temperature of 10 C. after 6 h and after 2 days after application (2 DAT).

[0298] The tests of examples 2 to 17 and 20 to 22 were conducted analogously to example 1, but taking account of the data and conditions specified in tables 2 to 20.

Example 2: Penetration Tests with Metribuzin at Room Temperature in Pear

[0299]

TABLE-US-00002 TABLE 2 Penetration results after 6 hours and after 2 days of example 2 Metribuzin % metribuzin % metribuzin Formulation/test substance concentration (g/L) penetration at penetration at in the aqueous spray liquor Active in the aqueous RT in pear RT in pear Example (% by wt.) ingredient spray liquor after 6 h//n = 5-7 after 2 DAT//n = 5-7 2-1 Dimetric DF75 metribuzin 2.25 2.93 26.81 2-2 DF75/NMP (0.1) metribuzin 2.25 1.82 7.61 2-3 DF75/NMP (0.5) metribuzin 2.25 5 15.84 2-4 DF75/DMSO (0.1) metribuzin 2.25 1.82 6.9 2-5 DF75/DMSO (0.5) metribuzin 2.25 0.94 5.47 2-6 DF75/NBP (0.1) metribuzin 2.25 3.43 13.46 2-7 DF75/NBP (0.3) metribuzin 2.25 8.78 18.14 2-8 DF75/NBP (0.5) metribuzin 2.25 18.6 32.41

Example 3: Penetration Tests with Metribuzin at 10 C. in Pear

[0300]

TABLE-US-00003 TABLE 3 Penetration results after 6 hours and after 2 days of example 3 Metribuzin % metribuzin % metribuzin Formulation/test substance concentration (g/L) penetration at penetration at in the aqueous spray liquor Active in the aqueous 10 C. in pear 10 C. in pear Example (% by wt.) ingredient spray liquor after 6 h//n = 5-7 after 2 DAT//n = 5-7 3-1 Dimetric DF75 metribuzin 2.25 0.1 1.14 3-2 DF75/isophorone (0.1) metribuzin 2.25 0.27 1.87 3-3 DF75/isophorone (0.3) metribuzin 2.25 0.24 1.54 3-4 DF75/isophorone (0.5) metribuzin 2.25 0.45 4.13 3-5 DF75/NBP (0.1) metribuzin 2.25 0.86 1.86 3-6 DF75/NBP (0.3) metribuzin 2.25 6.63 11.45 3-7 DF75/NBP (0.5) metribuzin 2.25 14.7 20.79

Example 4: Penetration Tests with Azoxystrobin at 10 C. in Apple

[0301]

TABLE-US-00004 TABLE 4 Penetration results after 6 hours and after 3 days of example 4 Azoxystrobin % azoxystrobin % azoxystrobin Formulation/test substance concentration (g/L) penetration at penetration at in the aqueous spray liquor Active in the aqueous 10 C. in apple 10 C. in apple Example (% by wt.) ingredients spray liquor after 6 h//n = 5-7 after 3 DAT//n = 5-7 4-1 Custodia SC 320 azoxystrobin and 0.45 0.21 0.88 tebuconazole 4-2 SC320/NMP (0.1) azoxystrobin and 0.45 0 0.72 tebuconazole (=undetectable) 4-3 SC320/NMP (0.5) azoxystrobin and 0.45 0 0.61 tebuconazole 4-4 SC320/NBP (0.1) azoxystrobin and 0.45 0 0.46 tebuconazole 4-5 SC320/NBP (0.5) azoxystrobin and 0.45 0.32 3.04 tebuconazole

[0302] For penetration tests on tebuconazole at 10 C. in apple see example 6

Example 5: Penetration Tests with Azoxystrobin at Room Temperature in Apple

[0303]

TABLE-US-00005 TABLE 5 Penetration results after 6 hours and after 3 days of example 5 Azoxystrobin % azoxystrobin % azoxystrobin Formulation/test substance concentration (g/L) penetration at penetration at in the aqueous spray liquor Active in the aqueous RT in apple RT in apple Example (% by wt.) ingredients spray liquor after 6 h//n = 5-7 after 3 DAT//n = 5-7 5-1 Custodia SC 320 azoxystrobin and 0.45 0.54 3.61 tebuconazole 5-2 SC320/NMP (0.1) azoxystrobin and 0.45 0.47 2.47 tebuconazole 5-3 SC320/NMP (0.5) azoxystrobin and 0.45 1.28 8.76 tebuconazole 5-4 SC320/NBP (0.1) azoxystrobin and 0.45 0.33 1.43 tebuconazole 5-5 SC320/NBP (0.5) azoxystrobin and 0.45 5.06 13.85 tebuconazole

[0304] For penetration tests on tebuconazole at room temperature in apple see example 7

Example 6: Penetration Tests with Tebuconazole at 10 C. in Apple

[0305]

TABLE-US-00006 TABLE 6 Penetration results after 6 hours and after 3 days of example 6 Tebuconazole % tebuconazole % tebuconazole Formulation/test substance concentration (g/L) penetration at penetration at in the aqueous spray liquor Active in the aqueous 10 C. in apple 10 C. in apple Example (% by wt.) ingredients spray liquor after 6 h//n = 5-7 after 3 DAT//n = 5-7 6-1 Custodia SC 320 azoxystrobin and 0.75 0.37 0.91 tebuconazole 6-2 SC320/NMP (0.1) azoxystrobin and 0.75 0.12 1.55 tebuconazole 6-3 SC320/NMP (0.5) azoxystrobin and 0.75 0.12 3.85 tebuconazole 6-4 SC320/NBP (0.1) azoxystrobin and 0.75 0.06 2.14 tebuconazole 6-5 SC320/NBP (0.5) azoxystrobin and 0.75 7.01 18.17 tebuconazole

[0306] For penetration tests on azoxystrobin at 10 C. in apple see example 4

Example 7: Penetration Tests with Tebuconazole at Room Temperature in Apple

[0307]

TABLE-US-00007 TABLE 7 Penetration results after 6 hours and after 3 days of example 7 Tebuconazole % tebuconazole % tebuconazole Formulation/test substance concentration (g/L) penetration at penetration at in the aqueous spray liquor Active in the aqueous RT in apple RT in apple Example (% by wt.) ingredients spray liquor after 6 h//n = 5-7 after 3 DAT//n = 5-7 7-1 Custodia SC 320 azoxystrobin and 0.75 2.54 22.72 tebuconazole 7-2 SC320/NMP (0.1) azoxystrobin and 0.75 3.67 20.73 tebuconazole 7-3 SC320/NMP (0.5) azoxystrobin and 0.75 9.2 71.3 tebuconazole 7-4 SC320/NBP (0.1) azoxystrobin and 0.75 4.27 12.41 tebuconazole 7-5 SC320/NBP (0.5) azoxystrobin and 0.75 30.4 79.6 tebuconazole

[0308] For penetration tests on azoxystrobin at room temperature in apple see example 5

Example 8: Penetration Tests with Fluxapyroxad at 10 C. in Apple

[0309]

TABLE-US-00008 TABLE 8 Penetration results after 1 day and after 3 days of example 8 Formulation/ Fluxapyroxad % fluxapyroxad % fluxapyroxad test substance concentration penetration at penetration at in the aqueous (g/L) in the 10 C. in apple 10 C. in apple spray liquor Active aqueous after 1 DAT // after 3 DAT // Example (% by wt.) ingredients spray liquor n = 5 7 n = 5 7 8-1 Orkestra SC 500 fluxapyroxad and 0.285 0.12 0.25 pyraclostrobin 8-2 SC500/isophorone (0.3) fluxapyroxad and 0.285 0 0.23 pyraclostrobin 8-3 SC500/NBP (0.3) fluxapyroxad and 0.285 1.45 3.0 pyraclostrobin

Example 9: Penetration Tests with Fluxapyroxad at Room Temperature in Apple

[0310]

TABLE-US-00009 TABLE 9 Penetration results after 1 day and after 3 days of example 9 Formulation/ Fluxapyroxad % fluxapyroxad % fluxapyroxad test substance concentration penetration at penetration at in the aqueous (g/L) in the RT in apple RT in apple spray liquor Active aqueous after 1 DAT // after 3 DAT // Example (% by wt.) ingredients spray liquor n = 5 7 n = 5 7 9-1 Orkestra SC 500 fluxapyroxad and 0.285 1.99 3.84 pyraclostrobin 9-2 SC500/isophorone (0.3) fluxapyroxad and 0.285 1.01 3.16 pyraclostrobin 9-3 SC500/NBP (0.3) fluxapyroxad and 0.285 10.14 21.39 pyraclostrobin

Example 10: Penetration Tests with Pyraclostrobin at 10 C. in Pear

[0311]

TABLE-US-00010 TABLE 10 Penetration results after 1 day and after 3 days of example 10 Formulation/ Pyraclostrobin % pyraclostrobin % pyraclostrobin test substance concentration penetration at penetration at in the aqueous (g/L) in the 10 C. in pear 10 C. in pear spray liquor Active aqueous after 1 DAT // after 3 DAT // Example (% by wt.) ingredients spray liquor n = 5 7 n = 5 7 10-1 Orkestra SC 500 fluxapyroxad and 0.566 0.04 0.12 pyraclostrobin 10-2 SC500/NMP (0.3) fluxapyroxad and 0.566 0.05 0.29 pyraclostrobin 10-3 SC500/DMSO (0.3) fluxapyroxad and 0.566 0.02 0.06 pyraclostrobin 10-4 SC500/NBP (0.3) fluxapyroxad and 0.566 3.77 5.45 pyraclostrobin

Example 11: Penetration Tests with Pyraclostrobin at Room Temperature in Pear

[0312]

TABLE-US-00011 TABLE 11 Penetration results after 1 day and after 3 days of example 11 Formulation/ Pyraclostrobin % pyraclostrobin % pyraclostrobin test substance concentration penetration at penetration at in the aqueous (g/L) in the RT in pear RT in pear spray liquor Active aqueous after 1 DAT // after 3 DAT // Example (% by wt.) ingredients spray liquor n = 5 7 n = 5 7 11-1 Orkestra SC 500 fluxapyroxad and 0.566 0.56 2.18 pyraclostrobin 11-2 SC500/NMP (0.3) fluxapyroxad and 0.566 2.51 9.65 pyraclostrobin 11-3 SC500/DMSO (0.3) fluxapyroxad and 0.566 0.72 2.62 pyraclostrobin 11-4 SC500/NBP (0.3) fluxapyroxad and 0.566 13.43 29.44 pyraclostrobin

Example 12: Penetration Tests with Thiacloprid at 10 C. in Pear

[0313]

TABLE-US-00012 TABLE 12 Penetration results after 6 hours and after 2 days of example 12 Formulation/ Thiacloprid % thiacloprid % thiacloprid test substance concentration penetration at penetration at in the aqueous (g/L) in the 10 C. in pear 10 C. in pear spray liquor Active aqueous after 6 h // after 2 DAT // Example (% by wt.) ingredients spray liquor n = 5 7 n = 5 7 12-1 Calypso SC 480 thiacloprid 0.3 0.2 0.2 12-2 SC480/NMP (0.1) thiacloprid 0.3 0.16 0.24 12-3 SC480/NMP (0.3) thiacloprid 0.3 0.13 0.4 12-4 SC480/NMP (0.5) thiacloprid 0.3 0.36 0.68 12-5 SC480/DMSO (0.1) thiacloprid 0.3 0 0.2 12-6 SC480/DMSO (0.3) thiacloprid 0.3 0 0.11 12-7 SC480/DMSO (0.5) thiacloprid 0.3 0.06 0.17 12-8 SC480/NBP (0.1) thiacloprid 0.3 2.16 2.78 12-9 SC480/NBP (0.3) thiacloprid 0.3 18.25 20.96 12-10 SC480/NBP (0.5) thiacloprid 0.3 27.29 31.53

Example 13: Penetration Tests with Thiacloprid at Room Temperature in Pear

[0314]

TABLE-US-00013 TABLE 13 Penetration results after 6 hours and after 2 days of example 13 Formulation/ Thiacloprid % thiacloprid % thiacloprid test substance concentration penetration at penetration at in the aqueous (g/L) in the RT in pear RT in pear spray liquor Active aqueous after 6 h // after 2 DAT // Example (% by wt.) ingredients spray liquor n = 5 7 n = 5 7 13-1 Calypso SC 480 thiacloprid 0.3 0.04 0.59 13-2 SC480/NMP (0.1) thiacloprid 0.3 0.08 0.54 13-3 SC480/NMP (0.3) thiacloprid 0.3 0.51 1.25 13-4 SC480/NMP (0.5) thiacloprid 0.3 1.02 2.69 13-5 SC480/DMSO (0.1) thiacloprid 0.3 0.14 1.33 13-6 SC480/DMSO (0.3) thiacloprid 0.3 0.01 0.54 13-7 SC480/DMSO (0.5) thiacloprid 0.3 0 0.44 13-8 SC480/NBP (0.1) thiacloprid 0.3 2.16 3.52 13-9 SC480/NBP (0.3) thiacloprid 0.3 23.37 29.85 13-10 SC480/NBP (0.5) thiacloprid 0.3 34.8 44.33

Example 14: Penetration Tests with Thiacloprid at 10 C. in Apple

[0315]

TABLE-US-00014 TABLE 14 Penetration results after 1 day and after 3 days of example 14 Formulation/ Thiacloprid % thiacloprid % thiacloprid test substance concentration penetration at penetration at in the aqueous (g/L) in the 10 C. in apple 10 C. in apple spray liquor Active aqueous after 1 DAT // after 3 DAT // Example (% by wt.) ingredients spray liquor n = 5 7 n = 5 7 14-1 Calypso SC 480 thiacloprid 0.3 0.31 0.77 14-2 SC480/isophorone (0.1) thiacloprid 0.3 0.31 0.76 14-3 SC480/isophorone (0.3) thiacloprid 0.3 0.14 0.44 14-4 SC480/isophorone (0.5) thiacloprid 0.3 0.31 0.85 14-5 SC480/NBP (0.1) thiacloprid 0.3 0.83 1.34 14-6 SC480/NBP (0.3) thiacloprid 0.3 6.89 8.57 14-7 SC480/NBP (0.5) thiacloprid 0.3 18.57 20.77

Example 15: Penetration Tests with Thiacloprid at Room Temperature in Apple

[0316]

TABLE-US-00015 TABLE 15 Penetration results after 1 day and after 3 days of example 15 Formulation/ Thiacloprid % thiacloprid % thiacloprid test substance concentration penetration at penetration at in the aqueous (g/L) in the RT in apple RT in apple spray liquor Active aqueous after 1 DAT // after 3 DAT // Example (% by wt.) ingredients spray liquor n = 5 7 n = 5 7 15-1 Calypso SC 480 thiacloprid 0.3 0.46 1.48 15-2 SC480/isophorone (0.1) thiacloprid 0.3 0.6 1.62 15-3 SC480/isophorone (0.3) thiacloprid 0.3 0.62 1.71 15-4 SC480/isophorone (0.5) thiacloprid 0.3 0.33 0.87 15-5 SC480/NBP (0.1) thiacloprid 0.3 2.68 4.69 15-6 SC480/NBP (0.3) thiacloprid 0.3 8.86 11.62 15-7 SC480/NBP (0.5) thiacloprid 0.3 31.27 42.15

Example 16: Penetration Tests with Acetamiprid at 10 C. in Apple

[0317]

TABLE-US-00016 TABLE 16 Penetration results after 8 hours and after 1 day of example 16 Formulation/ Acetamiprid % acetamiprid % acetamiprid test substance concentration penetration at penetration at in the aqueous (g/L) in the 10 C. in apple 10 C. in apple spray liquor Active aqueous after 8 h // after 1 DAT // Example (% by wt.) ingredients spray liquor n = 5 7 n = 5 7 16-1 Mospilan 20 SG acetamiprid 0.3 0.6 13.7 16-2 20 SG/NMP (0.1) acetamiprid 0.3 0.6 14.4 16-3 20 SC/NMP (0.3) acetamiprid 0.3 1.4 18.8 16-4 20 SG/NMP (0.5) acetamiprid 0.3 3.6 24.2 16-5 20 SC/DMSO (0.1) acetamiprid 0.3 1.6 15.9 16-6 20 SC/DMSO (0.3) acetamiprid 0.3 1.5 13.4 16-7 20 SG/DMSO (0.5) acetamiprid 0.3 2.8 22.2 16-8 20 SG/isophorone (0.1) acetamiprid 0.3 4.2 18.1 16-9 20 SG/isophorone (0.3) acetamiprid 0.3 4.1 24.1 16-10 20 SG/isophorone (0.5) acetamiprid 0.3 4.5 16.2 16-11 20 SG/Galaster BL97 (0.1) acetamiprid 0.3 5.4 23 16-12 20 SG/Galaster BL97 (0.3) acetamiprid 0.3 5.5 19.3 16-13 20 SG/Galaster BL97 (0.5) acetamiprid 0.3 6.6 22.8 16-14 20 SG/NBP (0.1) acetamiprid 0.3 6.9 22.8 16-15 20 SG/NBP (0.3) acetamiprid 0.3 23.9 48.1 16-16 20 SG/NBP (0.5) acetamiprid 0.3 46.1 57.7

Example 17: Penetration Tests with Trifluralin at 10 C. in Pear

[0318]

TABLE-US-00017 TABLE 17 Penetration results after 1 day and after 3 days of example 17 Formulation/ Trifluralin % trifluralin % trifluralin test substance concentration penetration at penetration at in the aqueous (g/L) in the 10 C. in pear 10 C. in pear spray liquor Active aqueous after 1 DAT // after 3 DAT // Example (% by wt.) ingredients spray liquor n = 5 7 n = 5 7 17-1 EC 540 trifluralin 3.5 0.53 1.31 17-2 EC 540/NMP (0.1) trifluralin 3.5 0.64 1.67 17-3 EC 540/NMP (0.3) trifluralin 3.5 0.56 1.33 17-4 EC 540/NMP (0.5) trifluralin 3.5 0.81 2.06 17-5 EC 540/isophorone (0.1) trifluralin 3.5 0.76 1.97 17-6 EC 540/isophorone (0.3) trifluralin 3.5 0.9 2.29 17-7 EC 540/isophorone (0.5) trifluralin 3.5 0.79 2.13 17-8 EC 540/NBP (0.1) trifluralin 3.5 0.8 1.74 17-9 EC 540/NBP (0.3) trifluralin 3.5 2.43 4.49 17-10 EC 540/NBP (0.5) trifluralin 3.5 3.66 6.19

Example 18: Penetration Tests with Prothioconazole at 10 C. and 20 C. in Pear

[0319] Experiments were conducted with the active ingredient prothioconazole with either Genagen NBP (N-(n-butyl)-2-pyrrolidone) or Emulsogen EL 360 (castor oil ethoxylate).

[0320] The active ingredient was dissolved in acetone/water mixture with a concentration of 2 or 0.75 g/L. The penetration of prothioconazole was measured for pear leaf cuticles. Experiments were conducted with additive systems, firstly with the emulsifier Emulsogen EL 360 as comparison and secondly with Genagen NBP as inventive test with an excess of active ingredient (ratio of active ingredient to additive about 2:1).

[0321] The results of the penetration tests from example 18 are shown in the figure FIG. 1. The results reported are averages from the test results from 5-7 treatments.

[0322] In FIG. 1:

[0323] a prothioconazole (0.75 g/L)+Genagen NBP (0.4 g/L) b prothioconazole (2 g/L)+Genagen NBP (1 g/L) c prothioconazole (0.75 g/L)+Emulsogen EL 360 (0.4 g/L) d prothioconazole (2 g/L)+Emulsogen EL 360 (1 g/L)

[0324] On the x axis of FIG. 1 is plotted the time after application in hours (h).

[0325] On the y axis of FIG. 1 is plotted the proportion of active ingredient that has penetrated through the cuticle of the plant, based on the total amount of active ingredient applied to the plant, in percent (%).

[0326] Penetration was effected first at 10 C. for about one day, then the temperature was increased to 20 C. with relative air humidity constant at about 60%. The concentration of prothioconazole corresponded to values typical in practice (0.75 g/L or 2 g/L prothioconazole). The water from the application droplets had evaporated completely off the leaf cuticle on the macroscopic scale after no later than one hour. With the emulsifier additive Emulsogen EL 360, which remains on the cuticle or leaf surface, there is a significant increase in the amount of the active ingredient that penetrates into the plant or a significant increase in the penetration rate by several times when the temperature is increased from 10 C. to 20 C. Genagen NBP was even more effective with equal use concentrations. This shows that N-(n-butyl)-2-pyrrolidone, even at low use concentrations, can promote penetration sustainably and independently of dissolution properties. This is very favorable for long-term effect or long-term availability, called the residual efficacy, of fungicides and insecticides in particular.

Example 19: Microscopy Studies

[0327] Test Procedure:

[0328] The following solutions 1) to 6) were produced:

[0329] Solution 1)

[0330] Solution of 1 g of rynaxypyr in one liter of a mixture of acetone and distilled water at a weight ratio of acetone:distilled water of 30:70.

[0331] Solution 2)

[0332] Solution of 1 g of rynaxypyr in one liter of a mixture of N-(n-butyl)-2-pyrrolidone and distilled water at a weight ratio of N-(n-butyl)-2-pyrrolidone:distilled water of 30:70.

[0333] Solution 3)

[0334] Solution of 1 g of emamectin benzoate in one liter of a mixture of acetone and distilled water at a weight ratio of acetone:distilled water of 30:70.

[0335] Solution 4)

[0336] Solution of 1 g of emamectin benzoate in one liter of a mixture of N-(n-butyl)-2-pyrrolidone and distilled water at a weight ratio of N-(n-butyl)-2-pyrrolidone:distilled water of 30:70.

[0337] Solution 5)

[0338] Solution of 1 g of abamectin in one liter of a mixture of acetone and distilled water at a weight ratio of acetone:distilled water of 30:70.

[0339] Solution 6)

[0340] Solution of 1 g of abamectin in one liter of a mixture of N-(n-butyl)-2-pyrrolidone and distilled water at a weight ratio of N-(n-butyl)-2-pyrrolidone:distilled water of 30:70.

[0341] The procedure as described hereinafter was followed with solutions 1) to 6) (see steps A) to C)): [0342] A) 1 L of the above-described solutions 1) to 6) in each case was applied to silanized glass microscope slides. [0343] B) The solutions were left to stand on the microscope slides at a temperature of 25 C. and 53% relative air humidity over 18 hours, in the course of which drying took place. [0344] C) Thereafter, the microscope slides were assessed and photos were taken at the original edge of the droplets with 400-fold magnification.

[0345] The photos for the active agrochemical ingredient abamectin are shown in FIG. 2A and FIG. 2B, those for the active agrochemical ingredient rynaxapyr in FIG. 3A and FIG. 3B, and those for the active agrochemical ingredient emamectin benzoate in FIG. 4A and FIG. 4B.

[0346] It was found that the respective active agrochemical ingredient had crystallized out of the mixture of acetone and distilled water (see FIG. 2A, FIG. 3A and FIG. 4A) and was thus no longer in a biologically available form. In this crystalline form, the respective active agrochemical ingredient cannot penetrate into non-plant harmful organisms.

[0347] By contrast, it was found that the respective active agrochemical ingredient, even after 18 hours, had not crystallized out of the mixture of N-(n-butyl)-2-pyrrolidone and distilled water, but was still in dissolved form in N-(n-butyl)-2-pyrrolidone (see FIG. 2B, FIG. 3B and FIG. 4B). In this dissolved form, the respective active agrochemical ingredient can penetrate into non-plant harmful organisms.

Example 20: Penetration Tests with Abamectin at 10 C. in Pear

[0348]

TABLE-US-00018 TABLE 18 Penetration results after 1 day and after 2 days of example 20 Formulation/ % abamectin % abamectin test substance Abamectin penetration penetration in the aqueous concentration (+/ SE) at (+/ SE) at spray liquor (g/L) in the 10 C. in pear 10 C. in pear (% by wt.) Active aqueous after 1 DAT // after 2 DAT // Example at 10 C. ingredients spray liquor n = 5 7 n = 5 7 20-1 EC 18 abamectin 0.05 0 0.18 20-2 EC 18/NMP (0.1) abamectin 0.05 0 1.26 20-3 EC 18/NMP (0.3) abamectin 0.05 0 0.79 20-4 EC 18/NMP (0.5) abamectin 0.05 0 1.21 20-5 EC 18/NBP (0.1) abamectin 0.05 1.4 1.52 20-6 EC 18/NBP (0.3) abamectin 0.05 1.2 1.64 20-7 EC 18/NBP (0.5) abamectin 0.05 1.3 2.32

Example 21: Penetration Tests with Rynaxypyr at 10 C. in Pear

[0349]

TABLE-US-00019 TABLE 19 Penetration results after 1 day and after 2 days of example 21 Formulation/ % rynaxypyr % rynaxypyr test substance Rynaxypyr penetration penetration in the aqueous concentration (+/ SE) at (+/ SE) at spray liquor (g/L) in the 10 C. in pear 10 C. in pear (% by wt.) Active aqueous after 6 h // after 2 DAT // Example at 10 C. ingredients spray liquor n = 5 7 n = 5 7 21-1 SC 200 rynaxypyr 0.1 1.17 1.36 21-2 SC 200/NMP (0.1) rynaxypyr 0.1 0.98 1.1 21-3 SC 200/NMP (0.5) rynaxypyr 0.1 1.06 1.25 21-4 SC 200/DMSO (0.1) rynaxypyr 0.1 0.98 1.11 21-5 SC 200/DMSO (0.5) rynaxypyr 0.1 1.05 1.14 21-6 SC 200/Galaster BL 97 (0.1) rynaxypyr 0.1 1.42 1.47 21-7 SC 200/Galaster BL 97 (0.5) rynaxypyr 0.1 1.33 1.26 21-8 SC 200/isophorone (0.1) rynaxypyr 0.1 1.1 1.15 21-9 SC 200/isophorone (0.5) rynaxypyr 0.1 1.14 1.53 21-10 SC 200/NBP (0.1) rynaxypyr 0.1 1.34 2.35 21-11 SC 200/NBP (0.3) rynaxypyr 0.1 6.71 11.53 21-12 SC 200/NBP (0.5) rynaxypyr 0.1 6.04 10.41

Example 22: Penetration Tests with Forchlorfenuron at 10 C. in Pear

[0350]

TABLE-US-00020 TABLE 20 Penetration results after 6 h, 1 day and after 3 days of example 22 % % % Formulation/ forchlorfenuron forchlorfenuron forchlorfenuron test substance Forchlorfenuron penetration penetration penetration in the aqueous concentration (+/ SE) at (+/ SE) at (+/ SE) at spray liquor (g/L) in the 10 C. in pear 10 C. in pear 10 C. in pear (% by wt.) Active aqueous after 6 h // after 1 DAT // after 3 DAT // Example at 10 C. ingredient spray liquor n = 5 7 n = 5 7 n = 5 7 22-1 Acceptor medium forchlorfenuron 0.03 2.98 8.22 12.77 22-2 Acceptor medium/NBP (0.01) forchlorfenuron 0.03 9.67 23.2 33.79 22-3 Acceptor medium/NBP (0.05) forchlorfenuron 0.03 21 40.88 53.39

[0351] The results in table 20 demonstrate that the production of high-efficacy spray liquors with a very low active ingredient content (here 0.03 g/L forchlorfenuron) and a very low content of NBP is possible.

Example 23: Formulations with Prothioconazole

[0352] Formulations with the active ingredient prothioconazole in combination with different additives were produced. The compositions of the individual formulations are apparent from table 21 below. It is found that the active ingredient is in dissolved form in high concentration in all formulations.

TABLE-US-00021 TABLE 21 Example Example Example Example Example Example Example Example Constituent 23-1 23-2 23-3 23-4 23-5 23-6 23-7 23-8 Prothioconazole (98.5% RW) [g] 28.88 28.88 Prothioconazole (98% RW) [g] 25.26 25.26 25.26 Prothioconazole (96% RW) [g] 20.19 25.94 30.9 Genagen NBP (tel-quel) [g] 65.51 15 21 44.74 27.49 34.07 32.17 32.11 Genagen PA (tel-quel) [g] 7.5 14.7 1.5 MSO (tel-quel) [g] 15 Genagen 4296 (tel-quel) [g] 1.5 Agsolex 08 (tel-quel) [g] 26.24 20 Solvesso 200 ND (tel-quel) [g] 31.56 Rapeseed oil methyl and ethyl 12.5 15 ester (tel-quel) [g] Rapeseed oil ethyl ester [g] 15 Emulsogen 3510 (tel-quel) [g] 5 5 Synergen 848 (tel-quel) [g] 10 5 5 Synergen W03 (tel-quel) [g] 5 Synergen W09 (tel-quel) [g] 6.8 Genapol X 090 (tel-quel) [g] 2.5 4.5 Emulsogen MTP 070 (tel-quel) [g] 20 Emulsogen EL 300 (tel-quel) [g] 10.5 Emulsogen EL 360 (tel-quel) 15 12.5 15 17.5 17.5 Momentive SAG 1571 (tel-quel) [g] 0.05 0.03 0.01 0.01 Total [g] 100 100 100 100 100 100 100 100 Type.sup.1) 200 EC 250 EC 250 EC 250 EC 250 EC 300 EC 300 DC 300 DC .sup.1) X EC = emulsion concentrate with active ingredient concentration x g/L, X DC = dispersion concentrate with active ingredient concentration x g/L

[0353] Table 21 shows that the use of N-substituted pyrrolidones of the formula I enables the production of highly concentrated active ingredient formulations. The formulations produced were stable and passed the standard FAO tests in respect of emulsifiability and dispersibility. The formulations produced were stable, for example, when stored at 0 C. and 54 C. for two weeks, were redispersible and could be mixed with other substances in the spray liquid without difficulty.

[0354] High active ingredient loadings of 300 g/L were achievable in emulsion concentrates and dispersion concentrates.

[0355] Table 21 also shows that the N-substituted pyrrolidones of the formula I can be used on their own as solvent (example 23-1) or in combination with other solvents.

[0356] The formulations described in table 21 showed a high uptake rate (penetration) that was higher than the standard products on the market.

[0357] In standard products on the market, N,N-dimethyldecanamide is frequently used as penetrant. Table 21 shows that this compound can be used in comparatively low concentration as solvent and/or as crystallization inhibitor in combination with the N-substituted pyrrolidones of the formula I used in accordance with the invention as penetrant to give active ingredient formulations having very high penetration.

Example 24: Formulations with Trinexapac or Abamectin and Acetamiprid

[0358] Formulations with the active ingredient trinexapac-ethyl or with abamectin and acetamiprid were produced in combination with different additives. The compositions of the individual formulations are apparent from table 22 below. It is found that the active ingredients are in dissolved form in high concentration in all formulations.

TABLE-US-00022 TABLE 22 Example Example Example Example Constituent 24-1 24-2 24-3 24-4 Trinexapac-ethyl (97.1% RW) [g] 19.44 19.51 25.84 Abamectin (95% RW) [g] 2.1 Acetamiprid (95% RW) [g] 10.5 Genagen NBP (tel-quel) [g] 9.69 12.49 12.94 50.4 Hostaphat 1306 (tel-quel) [g] 24.42 26.55 Synergen 848 (tel-quel) [g] 5 5 Synergen W03 (tel-quel) [g] 10 Emulsogen MTP 070 (tel-quel) [g] 29.02 31.5 Emulsogen ELO 200 (tel-quel) [g] 10 7 Synergen SOC (tel-quel) [g] 51.22 Triethanolamine (tel-quel) [g] 7.43 4.95 MSO (tel-quel) [g] 10 Water (tel-quel) [g] 5 Total [g] 100 100 100 100 Type.sup.1) 200 EW 200 DC 250 EC 120 EC .sup.1)X EC = emulsion concentrate with active ingredient concentration x g/L; X DC = dispersion concentrate with active ingredient concentration x g/L; X EW = oil-in-water emulsion with active ingredient concentration x g/L

[0359] Table 22 shows that the use of N-substituted pyrrolidones of the formula I enables the production of further highly concentrated active ingredient formulations. The formulations produced were stable and passed the standard FAO tests in respect of emulsifiability and dispersibility. The formulations produced were stable, for example, when stored at 0 C. and 54 C. for two weeks, were redispersible and could be mixed with other substances in the spray liquid without difficulty.

[0360] The formulations described in table 22 showed a high uptake rate (penetration).