AGROCHEMICAL ADJUVANT CONTAINING 2-OXO-1,3-DIOXOLAN-4 CARBOXYLATES

Abstract

The present invention relates to a method for preparing a tank mix, which comprises the step of contacting a pesticide formulation, water, and a tank mix adjuvant which comprises a carbonate of the formula (I); to a pesticide formulation comprising the tank mix adjuvant; to a method of controlling phytopathogenic fungi and/or undesired vegetation and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the tank mix or the pesticide formulation is allowed to act on the respective pests, their environment or the plants to be protected from the respective pest, on the soil and/or on undesired plants and/or the crop plants and/or their environment; and to a use of the tank mix adjuvant for increasing the efficacyl of a pesticide.

Claims

1.-14. (canceled)

15. A method for preparing a tank mix, which comprises the step of contacting a pesticide formulation, water, and a tank mix adjuvant which comprises a carbonate of the formula (I) ##STR00017## where R.sup.a is a C.sub.1-12 alkyl, or a n-valent radical derived by abstraction of the OH groups of an n-valent polyol and which is substituted by n minus 1 carbonate groups of the formula (II) ##STR00018## where n is from 2 to 4 and the polyol is an aliphatic polyol comprising 2 to 10 carbon atoms.

16. The method of claim 15, wherein R.sup.a is a linear, or branched C.sub.1-10 alkyl, the index n is 2 or 3, and the polyol is an aliphatic polyol comprising 2 to 8 carbon atoms.

17. The method of claim 15, wherein R.sup.a is methyl, ethyl, n-butyl, iso-butyl, n-hexyl, branched octyl, branched decyl, or n is 2, the polyol is 1,2-ethanediol, 1,4-butanediol or 2,2-dimethyl-1,3-propanediol.

18. The method of claim 15, wherein the tank mix contains from 0.005 to 2.0 wt % of the tank mix adjuvant.

19. The method of claim 15, wherein the tank mix adjuvant contains at least 50 wt % of the carbonate of the formula (I).

20. The method of claim 15, wherein the tank mix has a pH value of up to 9.0.

21. The method of claim 15, wherein the pesticide formulation comprises from 5 to 60 wt % of the pesticide.

22. The method of claim 15, wherein the weight ratio of the pesticide to the carbonate of the formula (I) is from 1:1 to 1:100.

23. The method of claim 15, wherein the tank mix adjuvant is essentially free of pesticides.

24. A pesticide formulation comprising a pesticide and a tank mix adjuvant which comprises a carbonate of the formula (I) ##STR00019## where R.sup.a is a C.sub.1-12 alkyl, or a n-valent radical derived by abstraction of the OH groups of an n-valent polyol and which is substituted by n minus 1 carbonate groups of the formula (II) ##STR00020## where n is from 2 to 4 and the polyol is an aliphatic polyol comprising 2 to 10 carbon atoms.

25. The formulation of claim 24, wherein the pesticide is present in dissolved form.

26. The formulation of claim 24, in form of a liquid.

27. The formulation of claim 24, wherein the weight ratio of the pesticide to the carbonate of the formula (I) is from 1:1 to 1:100.

28. The formulation of claim 24, wherein R.sup.a is a linear, or branched C.sub.1-10 alkyl, the index n is 2 or 3, and the polyol is an aliphatic polyol comprising 2 to 8 carbon atoms.

29. The formulation of claim 24, wherein R.sup.a is methyl, ethyl, n-butyl, iso-butyl, n-hexyl, branched octyl, branched decyl, or n is 2, the polyol is 1,2-ethanediol, 1,4-butanediol or 2,2-dimethyl-1,3-propanediol.

30. A method of controlling phytopathogenic fungi, and/or undesired vegetation, and/or undesired insect or mite attack, and/or for regulating the growth of plants, the formulation of claim 24, or a tank mix comprising the formulation, is allowed to act on the respective pests, their environment or the plants to be protected from the respective pest, on the soil, and/or on undesired plants, and/or the crop plants, and/or their environment.

31. The method of claim 30, wherein the pesticide is present in dissolved form.

32. The method of claim 30, in form of a liquid.

33. The method of claim 30, wherein the weight ratio of the pesticide to the carbonate of the formula (I) is from 1:1 to 1:100.

34. The method of claim 33, wherein R.sup.a is a linear, or branched C.sub.1-10 alkyl, the index n is 2 or 3, and the polyol is an aliphatic polyol comprising 2 to 8 carbon atoms.

35. The method of claim 34, wherein R.sup.a is methyl, ethyl, n-butyl, iso-butyl, n-hexyl, branched octyl, branched decyl, or n is 2, the polyol is 1,2-ethanediol, 1,4-butanediol or 2,2-dimethyl-1,3-propanediol.

Description

EXAMPLES

[0117] GECA: 4-Methoxycarbonyl-1,3-dioxolan-2-on; substance according to formula (I), wherein R.sup.a is methyl. [0118] GECA-2: 1,2-Ethanediyl-bis(1,3-dioxolane-2-on-4-carboxylate); divalent substance according to formula (a). [0119] BAPMA: N,N-Bis(3-aminopropyl)methylamine [0120] Dicamba-K and Dicamba-BAPMA: Potassium salt and BAPMA salt of Dicamba, respectively. [0121] GL-K: Glyphosate, potassium salt.

Example-1: Preparation of Dicamba Compositions

[0122] Compositions A-F were prepared containing the salts Dicamba-K or Dicamba-BAPMA according to Table 1. Herein, either the Dicamba-BAPMA or the free carbonic acid of Dicamba is premixed with water and the remaining ingredients are added as listed in Table 1.

TABLE-US-00001 TABLE 1 Ingredient (mg/l) A B C D E F Dicamba 188 188 188 — — — Dicamba- — — — 192 192 192 BAPMA KOH 95 95 95 — — — GECA — 1840 — — 1840 — GECA-2 — — 1900 — — 1900 Water To 1 L To 1 L To 1 L To 1 L To 1 L To 1 L

Example-2: Preparation of Glyphosate Compositions

[0123] Compositions G-L were produced as composition a A-F in Example-1, but additionally 370 mg of the potassium salt of glyphosate per liter were added. The ingredients are listed in Table 2.

TABLE-US-00002 TABLE 2 Ingredient (mg/l) G H I J K L Dicamba 188 188 188 — — — Dicamba — — — 192 192 192 BAPMA KOH 95 95 95 — — — GECA — 1840 — — 1840 — GECA-2 — — 1900 — — 1900 GL-K 370 370 370 370 370 370 Water To 1 L To 1 L To 1 L To 1 L To 1 L To 1 L

Example-3: Reduction of the Surface Tension

[0124] The static surface tension of compositions A-F, H-I, K-L was tested by measuring the force on a Wilhelmy-plate. Hereby, the Wilhelmy plate consists of platinum that has been roughened on its surface to allow wetting by the sample. The plate is oriented perpendicular to the surface of the liquid and lowered until it contacts the sample. A thin film forms on both sides of the plate due to the surface tension of the liquid, causing a measurable pulling force on the plate. The mean values of three repetitive measurements are displayed in Table 3.

TABLE-US-00003 TABLE 3 Static surface tension in Composition Ingredients mN/m ± variance σ.sup.2 A Dicamba-K 71.63 ± 0.0582 B Dicamba-K/GECA 69.76 ± 0.0562 C Dicamba-K/GECA-2 56.52 ± 0.0631 D Dicamba-BAPMA 72.35 ± 0.0976 E Dicamba-BAPMA/GECA 70.20 ± 0.0612 F Dicamba-BAPMA/GECA-2 61.34 ± 0.0659 H Dicamba-K/GECA/GL-K 68.35 ± 0.0816 I Dicamba-K/GECA-2/GL-K 59.98 ± 0.0873 K Dicamba-BAPMA/GECA/GL-K 69.90 ± 0.0869 L Dicamba-BAPMA/GECA-2/GL-K 59.05 ± 0.0529 Water Distilled Water 72.51 ± 0.0582

[0125] Upon addition of a carbonate according to formula (I), the static surface tension decreases in all samples compared to the blanks (water and compositions ND).

Example-4: Penetration Enhancement of Pesticides in Echinochloa Crus-Galli

[0126] A volume of 1 μl of the compositions A (Dicamba-K), C (Dicamba-K, GECA-2) and I (Dicamba-K, GECA-2, GL-K) was applied on the surface of three plant leaves of Echinochloa crus-galli in triplicates. After drying, the plants were incubated for 3 h at 80% humidity at 20° C. Subsequently, the leaves' surface was washed with water to measure the remaining part of unpenetrated pesticide (Wash). The cuticula was analyzed by applying 50 μl of a solution of 5% cellulose acetate in acetone to the treated positions. After evaporation of the solvent, the cellulose acetate film was removed from the surface and extracted in acetone. The cellulose acetate was precipitated in petrol ether and the supernatant was analyzed (CA). Finally, the washed leaves were homogenized, extracted and the content of active ingredient was determined (Extract). All quantitative measurements were conducted with a UPLC-MS/MS device. Table 4 shows the mean results of these analyses as percentage of the Dicamba concentrations obtained with composition A.

TABLE-US-00004 TABLE 4 Composition Wash [%] CA [%] Extract [%] A 100 100 100 B 14 252 129 C 18 170 172

[0127] Samples B and C, both containing GECA-2, show an increased penetration (Extract) through the cuticula (CA) and a reduced wash-off (Wash) of the pesticide.

Example-5: Biological Efficacy Enhancement of Pesticidal Compositions

[0128] The adjuvant effect was tested in greenhouse trials on (a) Echinochloa crus-galli, Chenopodium album (b) and Abutilon theophrasti (c).

[0129] Plants (a), (b), and (c) were sprayed with compositions D, E*, F*, J, and L*, which were prepared according to Examples 1 and 2, but contained double the concentration of GECA in case of composition E* comared to composition E, and double the concentration of GECA-2 in case of F*, and L* compared to compositions F, and L.

[0130] Plants (a), and (b) were sprayed with compositions A, B*, C*, G, H*, and I*, which were prepared according to Examples 1 and 2, but contained double the concentration of GECA in case of compositions B*, and H*, compared to compositions B, and H, respectively, and double the concentration of GECA-2 in case of C*, and I*, compared to compositions C, and I, respectively. The herbicidal activity was evaluated 14 days after treatment by awarding scores to the treated plants in comparison to the untreated control plants (Tables 5 and 6). The evaluation scale ranges from 0% go 100% activity. 100% activity means the complete death of at least those parts of the plant that are above ground. Conversely, 0% activity means that there were no differences between treated and untreated plants. The effective concentration of Dicamba-BAPMA was 70 g/ha, the effective concentration of GL-K—if present—was 140 g/ha, the effective concentration of GECA, and GECA-2 was 1 L/ha. Herein, the effective concentration means the total mass of active ingredients per treated area.

[0131] The results displayed in Table 5 demonstrate the increased activity of the compositions E*, F* and L* compared to compositions D and J, which do not contain a carbonate compound.

[0132] The results displayed in Table 6 demonstrate the increased activity of the compositions B*, C*, H*, and I* compared to compositions A, and G, which do not contain a carbonate compound.

TABLE-US-00005 TABLE 5 Herbicidal activity [%] of compositions D, E*, F*, J and L* on plant species (a)-(c) (a) (b) (c) D (Dicamba-BAPMA) 0 23 45 E* (Dicamba-BAPMA, GECA) 27 33 57 F* (Dicamba-BAPMA, GECA-2) 45 85 67 J (Dicamba-BAPMA, GL-K) 50 30 43 L* (Dicamba-BAPMA, GECA-2, GL-K 72 85 62

TABLE-US-00006 TABLE 6 Herbicidal activity [%] of compositions A, B*, C* and G, H*, I* on plant species (a)-(b) (a) (b) A (Dicamba-K) 15 62 B* (Dicamba-K, GECA) 43 80 C* (Dicamba-K, GECA-2) 25 85 G (Dicamba-K, GL-K) 43 62 H* (Dicamba-K, GECA, GL-K) 55 75 I* (Dicamba-K, GECA-2, GL-K) 65 92