STABILISED FORMULATIONS CONTAINING PROTHIOCONAZOLE WITH A LOW 2-(1-CHLOROCYCLOPROPYL)-1-(2-CHLOROPHENYL)-3-(1H-1,2,4-TRIAZOL-1-YL)PROPAN-2-OL CONTENT

Abstract

The invention relates to storage-stable prothioconazole-containing formulations having a particularly low content of 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-( H-1,2,4-triazol-1-yl)propan-2-ol based on organic vinyl compounds, to a process for their preparation, to a method for controlling phytopathogenic fungi in crop protection and to their use as crop protection agents.

Claims

1. A formulation, comprising a) prothioconazole and b) at least one compound of formula (IV) ##STR00018## where n=0-24; optionally 2-16; optionally 4-14; and optionally 8-12: R.sub.1H, C.sub.1-C.sub.6-alkyl, CN, Cl, Br, F, optionally H, C.sub.1-C.sub.4-alkyl, ptionally H, methyl; and optionally H; XCOO, CONR.sub.3R.sub.4, S, SO.sub.2, O and COS; preferably COO, CONR.sub.3R.sub.4, S, O and COS; optionally COO, CONR.sub.3R.sub.4; and optionally COO; R.sub.2(CH.sub.2).sub.m, (CH.sub.2O).sub.m, (C.sub.2H.sub.4O).sub.m, (C.sub.4H.sub.6O).sub.m, optionally (CH.sub.2).sub.m, (CH.sub.2O).sub.m, (C.sub.2H.sub.4O).sub.m, (C.sub.3H.sub.6O).sub.m; optionally (CH.sub.2O).sub.m, (C.sub.2H.sub.4O).sub.m, (C.sub.3H.sub.6O).sub.m; and optionally (CH.sub.2O).sub.m, T=H, sulfate, phosphate, C.sub.1-C.sub.3-alkyl, OH, SH, sulfone; ptionally H, sulfate, sulfone, OH, phosphate; optionally H, sulfate, OH; and particularly optionally H and OH; R.sub.3H, C.sub.1-C.sub.6-alkyl, C.sub.3-C.sub.6-cycloalkyl, C.sub.6-C.sub.10-aryl, ptionally H, C.sub.1-C.sub.4-alkyl, C.sub.5-C.sub.6-cycloalkyl, phenyl, optionally H, methyl and phenyl; and optionally H; R.sub.4H, methyl, ethyl, propyl, (CH.sub.2).sub.m, (CH.sub.2O).sub.m, (C.sub.2H.sub.4O).sub.m, (C.sub.3H.sub.6O).sub.m, (C.sub.4H.sub.8O).sub.m; optionally H, methyl, ethyl, propyl, (CH.sub.2).sub.m, (CH.sub.2O).sub.m, (C.sub.2H.sub.4O)m, (C.sub.3H.sub.6O).sub.m; more optionally H, methyl, ethyl, propyl, (CH.sub.2O).sub.m, (C.sub.2H.sub.4O).sub.m, (C.sub.3H.sub.6O).sub.m; and particularly optionally H, methyl, ethyl, propyl, (CH.sub.2O).sub.m, and R.sub.3 is different from R.sub.4, and m=0-100, optionally 2-50, optionally 5-25, and optionally 8-12; where the formulation is free from compounds according to formula (I) ##STR00019## in which n is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 15 or 18, and additionally free from glycoside surfactants having a 9-decenoyl radical, where for XCNR.sub.3R.sub.4 and m=0 T is not present.

2. The formulation as claimed in claim 1, wherein in formula (IV) n=2-16; R.sub.1H, C.sub.1-C.sub.4-alkyl, XCOO, CONR.sub.3R.sub.4, S, O and COS; R.sub.2(CH.sub.2).sub.m, (CH.sub.2O).sub.m, (C.sub.2H.sub.4O).sub.m, (C.sub.3H.sub.6O).sub.m; T=H, sulfate, sulfone, OH, phosphate; R.sub.3H, C.sub.1-C.sub.4-alkyl, C.sub.5-C.sub.6-cycloalkyl, phenyl; R.sub.4H, methyl, ethyl, propyl, (CH.sub.2).sub.m, (CH.sub.2O).sub.m, (C.sub.2H.sub.4O).sub.m, (C.sub.3H.sub.6O).sub.m; and R.sub.3 is different from R.sub.4, and m=0-50.

3. The formulation as claimed in claim 1, wherein in formula (IV) n=8-12: R.sub.1H; XCOO, R.sub.2(CH.sub.2O).sub.m, T=H and OH; m=8-12.

4. The formulation as claimed in claim 1, wherein in formula (IV) n=7: R.sub.1H; XCOO; T=H; m=0.

5. The formulation as claimed in claim 1, wherein the compound IV is selected from the group consisting of 9-decenoic acid, 9-decenoate ester having n EO groups (EOC.sub.2H.sub.4O), where n=8, 9, 10, 11 and optionally n=10; C10-17 DMAPA-amides ##STR00020## C10-20 DMAPA amine-oxides ##STR00021## and C10-24: sulfobetaines. ##STR00022##

6. The formulation as claimed in claim 1, wherein the proportion of component b) is 1% by weight to 50% by weight.

7. The formulation as claimed in claim 1, wherein the proportion of component a) is 1% by weight to 50% by weight.

8. The formulation as claimed in claim 1, wherein this formulation comprises as least one of the following components: c) c1: non-ionic dispersant/emulsifier, c2: ionic dispersant/emulsifier d) one or more other active agrochemical ingredients different from a) e) one or more solvents including OD carriers f) one or more carriers (WGs, and also Aerosils for SC/TK/WG) g) one or more of: g1: organic thickeners g2: inorganic thickeners h) one or more further additives and auxiliaries.

9. The formulation as claimed in claim 8, comprising a nonionic (c1) and/or anionic (c2) emulsifier.

10. The formulation as claimed in claim 8, wherein said one or more active agrochemical ingredients d) are one or more active insecticidal or fungicidal ingredients.

11. The formulation as claimed in claim 8, wherein the further active agrochemical ingredient d) is bixafen.

12. The formulation as claimed in claim 10, comprising not more than 5% by weight of water.

13. A process for preparing the formulation as claimed in claim 1 comprising mixing components a) and b) and optionally one or more further additives.

14. A method of controlling one or more harmful organisms, comprising contacting the harmful organisms, a habitat, one or more hosts, optionally plants and seed, and/or soil, an area and/or an environment in which said organisms grow or could grow, and/or one or more materials, plants, seeds, soil, surfaces or spaces which are to be protected from attack or infestation by organisms that are harmful to plants, with an effective amount of the formulation as claimed in claim 1.

15. The use of the formulations as claimed in claim 1 for protection of plants including seed, and/or optionally useful plants, from infestation by one or more harmful organisms.

16. The formulations as claimed in claim 1 for control of one or more organisms that are harmful to plants, optionally phytopathogenic harmful fungi, insects, arachnids, nematodes and harmful plants.

17. The formulation as claimed in claim 15, wherein the harmful organisms are phytopathogenic harmful fungi.

18. An emulsion obtainable by mixing water with the formulation as claimed in claim 1, wherein the mixing ratio of water to emulsion concentrate is from 1000:1 to 1:1.

Description

EXAMPLES

Feedstocks Used

[0245] The terms used in the examples below have the following meanings:

TABLE-US-00003 prothioconazole PTZ (Bayer AG) Synperonic F127 propylene oxide/ethylene oxide (PO-EO) block polymer (Croda) Soprophor 4D384 tristyrylphenol ethoxylate sulfate ammonium salt (Solvay) citric acid polybasic organic acid Rhodopol 23 xanthan derivative (Solvay) Silcolapse 411 silicone defoamer (Solvay) Silfoam SE 2 silicone defoamer (Wacker) glycerol antifreeze Proxel GXL preservative (biocide, Proxel) Kaolin TEC1 aluminum hydrosilicate Sipernat 22S precipitated silica Sokalan K30 polyvinylpyrrolidone, nonionic dispersant Solvesso 200 ND mineral oil, ExxonMobil, naphthalene-free Calsogen 4814 calcium dodecylbenzenesulfonate in 2-ethylhexanol (about 40%), Clariant Emulsogen 3510 nonionic surfactant, n-butyl-PO-EO block oxalkylate, Clariant Lucramul CO30 nonionic emulsifier, castor oil ethoxylated, Levaco Chemicals, DE Rhodocal 60BE calcium dodecylbenzenesulfonate in 2-ethylhexanol (about 40%), Solvay EL400 ethoxylated (40EO) castor oil, Croda Aerosil 972 hydrophobic finely divided silicic acid, Evonik Soprophor 796/P nonionic emulsifier, ethoxylated propoxylated tristyrylphenol, Solvay SAG1572 aqueous emulsion of polydimethylsiloxane Momentive Hallcomid 1025 dimethyldecenamide Stepan Genagen 4296 dimethyldecanamide Clariant Agnique KE 3308 dimethyldecanamide BASF 9-decenoic acid Sigma-Aldrich (CAS number: 14436-32-9) limonene Sigma-Aldrich, available as various isomers under the following CAS numbers 5989-27-5 [(D)-(+)- limonene], 5989-54-8 [(S)-()-limonene], 138-86-3 [dipentene unspecified], 7705-14-8 [()- limonene], 6876-12-6 [trans-1-methyl-4- (methylvinyl)cyclohexene

[0246] General Preparation of an Aqueous Suspension Concentrate (SC):

[0247] First of all, water is initially charged at room temperature. The active ingredients and the other components are added (in no particular order) with stirring. The mixture is pre-comminuted in a colloid mill, followed by wet grinding using, for example, a bead mill. Finally, the organic thickener is added.

[0248] General Preparation of Water-Dispersible Granules (WG)

[0249] Water is initially charged at room temperature. The active ingredients and the other components are added (in no particular order) with stirring. The mixture is pre-comminuted in a colloid mill, followed by wet grinding using, for example, a bead mill. The TC slurries according to the invention obtained in this manner are processed further to give the WG. Fluidized bed drying is carried out according to the prior art.

[0250] General Preparation of an Emulsion oncentrate (EC)

[0251] The organic solvent is initially charged. All other components are then added (in no particular order) with stirring. Stirring is continued until a clear solution is formed.

[0252] General Preparation of an Organic Dispersion Concentrate (OD):

[0253] First, the organic solvent is initially charged at room temperature. The active ingredients and the other components are added (in no particular order) with stirring. The mixture is pre-comminuted in a colloid mill, followed by wet grinding using, for example, a bead mill.

[0254] Determination of 2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol (Compound III) in Formulations

[0255] 2-(1-Chlorocyclopropyl)-1-(2-chlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propan-2-ol is separated from the formulation constituents on a reverse phase column using an isocratic eluent. After MS/MS detection, the quantitative evaluation is conducted by comparing the peak areas with those of the reference object, using an external standard.

[0256] High-pressure liquid chromatograph: HP 1090

[0257] Sample injection: HP 1090 Autoinjector

[0258] Mass spectrometer: Quattro I, Fisons

[0259] Integration and evaluation: MassLynx from Micromass

[0260] In each case, the samples are, unless indicated otherwise, exposed to light and stored for 4 weeks.

[0261] Example 1: Recipe of a Prothioconazole Emulsion Concentrate Formulation (Storage in the Dark)

TABLE-US-00004 1a % by Component weight 1b prothioconazole 12.75 13.00 bixafen 6.37 6.5 fluopyram 6.37 6.5 Lucramul HOT 5902 7.50 7.50 Lucramul CO 30 7.50 7.50 Soprophor 796/P 5.00 5.00 SAG1572 0.10 0.10 Genagen 4296 (comparison) 54.41 43.90 9-decenoic acid (according to the invention) 10.00 Compound (III) content % by weight Example 1a 0.0037 (comparison) Example 1b 0.0023

[0262] Example 2: Recipe of a Prothioconazole Suspension Concentrate

TABLE-US-00005 2a % by Component weight 2b prothioconazole 45 45 Pluronic PE 10500 6.0 6.0 urea 10 10 defoamer (Momentive SAG1572) 0.1 0.1 Proxel GXL 0.2 0.2 Rhodopol G 0.2 0.2 water 28.5 28.5 water (comparison) 10 9-decenoic acid 10 Compound (III) content % by weight Example 2a 0.0026 (comparison) Example 2b 0.0024

[0263] Example 3: Recipe of a Prothioconazole WG (Waterdispersible Granules, Fluidized Bed Granules)

TABLE-US-00006 3a % by Component weight 3b 3c prothioconazole 50 50 50 Baykanol SL 15 15 15 Oparyl MT 804 1 1 1 Kaolin W 29 29 29 Kaolin W (comparison) 5 5 5 9-decenoic acid 5 9-decenoate ester with 10 EO groups 5 Compound (III) content % by weight Example 3a 0.0094 (comparison) Example 3b 0.0071 Example 3c 0.0077

[0264] Example 4: Recipe of a Prothioconazole WG (Waterdispersible Granules, Prepared as Extrusion Granules)

TABLE-US-00007 3a % by Component weight 3b 3c prothioconazole 50 50 50 Baykanol SL 20 20 20 Pergopak M 5 5 5 NaHCO3 20 20 20 NaHCO3 (comparison) 5 5 5 9-decenoic acid 5 9-decenoate ester with 10 EO groups 5