MXPA98008761A - Fungicide sales - Google Patents

Abstract

The combination of pyrimethanil with an organic acid having a volatility of less than 2 Pa at 20 ° C is described, which results in a product having valuable physical and biological properties

Description

FUNGICIDE SALTS DESCRIPTION OF THE INVENTION This invention relates to compounds having fungicidal activity. Pyrimethanil is a known fungicide, which has the chemical name 2-anilino-4,6-dimethylpyrimidine. However, it has a relatively high vapor pressure which restricts its use. We have found that the combination of pyrimethanil with certain acids confers certain advantages to the compound. According to the invention, there is provided a product obtained by the combination of pyrimethanil with an organic acid, selected from the long chain fatty acids, such as oleic acid and palic acid, saccharin, sulfonic acids such as camphorsulfonic acid, salicylic acid and jasmonic acid. It is generally preferred that the acid be present in at least one stoichiometric amount and in this case a salt is usually formed between the pyrimethanyl and the acid. The excess acid can be an advantage, for example in a molar ratio of acid to pyrimethanil of up to 2: 1. Certain pyrimethanyl salts are novel and useful, and the invention also includes the pyrimethanyl salts with an organic acid having a volatility of less than 2 Pa at 20 ° C. As stated above an advantage of the products of the invention, it is in particular that they have a reduced vapor pressure as compared to free pyrimethanil, which increases the persistence of the compound on the crop that is to be protected from attack by mushrooms.

Reduced volatility also reduces fungicide levels in the atmosphere. In many cases the products have reduced phytotoxicity to certain plants. In some cases the salts have increased activity compared to free pyrimethanil.

Another advantage is that the products have physical and chemical properties, which often make them suitable to provide better formulations than free pyrimethanil. For example, the free pyrimethanil product with oleic acid is liquid, which provides formulation advantages compared to free pyrimethanil, which is a solid. The products are used to combat diseases for which pyrimethanil can be used, for example Botrytis spp., Especially B. cinerea, Venturia spp., Altenaria spp., And Monolinia fructigena. However, salt can also extend useful activity to diseases such as molds and particularly the powdery mildew of cereals (Erysiphe graminis) and glume spot . { Leptosphaeria nodorum).

The invention is illustrated in the following examples.

Example 1 A solution of pyrimethanil (1.0 g), toluene (50 ml) and oleic acid (1.42 g) were allowed to stand overnight at room temperature. Toluene was evaporated under reduced pressure for pyrimethanil oleate, as an oil (compound 1) NMR data: CDC13 scale d 0.9 (3H, t, CH3) 1.25-1.42 (20H,, 10xCH2) 1.62-1.76 (2H, m, CH2) 1.95-2.1 (4H, m, 2xCH2) 2.34-2.42 (8H, m, 2xCH3, CH2) 5.3-5.42 (2H, m, CH = CH) 6.47 OH, s, pyrimidine CHL 7.0 (OH, t, ArH) 7.32 (2H, t, ArH) 7.72 (2H, d, ArH) 8.67 (OH, br s, NH) Example 2 A solution of camphorsulfonic acid (1.25 g) in ethanol (10 ml) was slowly added to a solution of pyrimethanil (1 g) in toluene (20 ml) and the mixture was allowed to stand for 30 minutes at room temperature. The mixture was evaporated under reduced pressure and the residue was recrystallized from a mixture of diisopropyl ether and ethyl acetate to give pyrimethanyl camphorsulfonate, mp 166-7 ° C (Compound 2).

In a similar manner, a) pyrimethanyl saccharinate, m.p. 164-5 ° C. (compound 3) b) pyrimethanyl 7-trifluoromethylcarbonate, m.p. 233-5 ° C. (Compound 4) c) 4, 7-dimethoxisaccharinate pyrimethanil, m.p. 187-8 ° C (compound 5) d) 4-chloro-7-methoxisacarinate pyrimethanil, m.p. 244-6 ° C. (compound 6) e) pyrimethanil p-toluenesulfonate, m.p. 200-2 ° C (compound 7) 'f) 2H-l-benzopyran-3-carboxylate, m.p. 126-7 ° C (compound 8) g) pyrimethanyl phenoxyacetate, m.p. 76-8 ° C (compound 9) h) pyrimethanil phenylphosphonate, m.p. 126-8 ° C (compound 10) i) dipyrimethanilic malonate, m.p. 126-8 ° C (compound 11) j) '' dipyrimethanil phthalate, m.p. 144-6 ° C (compound 12) k) pyrimethanyl acid phthalate, m.p. 149-51 ° C (compound 13) Example 3 This example illustrates the relative persistence of the products of the invention in comparison with free anilinopyrimidine. Droplets (5 x 4 μl) of radiolabelled pyrimethanil toluene solutions (0.05% w / v) were applied to microscope coverslips (13 mm diameter), which were placed in Petri dishes. To some of the samples were added various fatty acids in molar proportions of pyrimethanil to acid of 1: 1 and 1: 2. The Petri dishes were left in a room with controlled environment (20 ° C, 16 hours of light) and after two days, the coverslips were removed to determine how much pyrimethanil remained. This was done by transferring the coverslips to scintillation bottles, each containing 10 ml of a dioxane-based scintillation cocktail and measuring the amount of radiation by liquid scintillation counting. The results are as follows: Table 1: Surface recovery of pyrimethanil after 2 days Compound Surface recovery (%) Pyrimethanil + oleic acid (1: 1 molar) 59.5 Pyrimethanil + oleic acid (1: 2 molar) 77.9 Pyrimethanil + lauric acid (1: 1 molar) 66.9 Pyrimethanil + lauric acid (1: 2 molar) 80.1 Pyrimethanilum + myristic acid (1: 1 molar) 71.9 Pyrimethanilum + myristic acid (1: 2 molar) 63.3 Pyrimethanil + palmitic acid (1: 1 molar) 61.6 Pyrimethanil + palmitic acid (1: 2 molar) 71.5 Pyrimethanil 3.1 In a similar manner, the example was repeated by the addition of saccharin to pyrimethanil in the amounts shown (% w / v of the toluene solutions). Surface recovery measurements were taken after 2 and 8 days. The results are as follows: Table 2: Surface recovery of pyrimethanil after 2 days Compound Surface Recovery (%) Pyrimethanil + saccharin (0.05%) 57.9 Pyrimethanil (0.05%) + saccharin (0.1%) 90.3 Pyrimethanil (0.05%) + saccharine (0.2%) 95.8 Pyrimethanil (0.05%) 2.0 * Table 3: Surface recovery of pyrimethanil after 8 days Compound Surface recovery (%) Pyrimethanil (0.05%) + saccharin (0.05%) 43.6 Pyrimethanil (0.05%) + saccharin (0.1%) 80.0 Pyrimethanil (0.05%) + saccharin (0.2%) 94.0 Pyrimethanil (0.05%) 1.1 It will be noted that the addition of the various acids increases the persistence of the pyrimethanil. The compounds of Examples 1 and 2 also demonstrate higher levels of persistence than free pyrimethanil.

Example 4 Powder formulations wettable to 5% of the compounds, were diluted with water to the desired concentration and sprayed on wheat test plants. One day later, parts of the plants were inoculated with appropriate test pathogens and maintained under controlled environmental conditions, adequate to maintain plant development and disease development. After an appropriate time, the degree of infection of the plant was visually estimated. Five replicates were used for each dose of test compound. The results are as follows. The speeds of i. to. (active ingredient) in the tables are based on free pyrimethanil. a) Bo 'tryti s cinerea (evaluated 7 days after inoculation) % control of the disease a Compound No. 5 g i.a./hl 2 g i.a./hl 5 94.4 85.4 6 94.4 88.7 7 91.0 83.1 8 93.2 84.2 9 90.4 75.2 10 94.4 87.6 12 91.0 77.5 Pyrimethanil (15% WP) 85.4 75.2 Scale 78.6 55.0 SCALA is the commercial formulation of SC at 40% pyrimethanil. b) Erysiphe grami ni s f. sp. tri ti ci (evaluated 7 days after inoculation) % disease control a Compound No. 100 g i. to. / ha 25 g i. to. /he has 4 39.7 15.5 8 75.9 27.6 12 51.7 3.4 Pyrimethanil (5% WP) 27.6 3.4 SCALA 0 15.5 c) Leptosphaeria nodorum (evaluated 21 days after inoculation) % disease control a Compound No. 100 g i. to. / ha 25 g i. to. /he has 32.8 15.2 7 22.2 15.2 8 36.4 25.8 12 • 39.9 15.2 Pyrimethanil (5% WP) 11.6 1.0 SCALA 15.2 11.6

Claims (6)

1. A product, characterized in that it is obtained by combining the pyrimethanil with an organic acid, selected from the long chain fatty acids, saccharin, sulfonic acids, salicylic acid and jasmonic acid.

2. Pyrimethanilic salts with an organic acid, characterized in that they have a volatility of less than 2 Pa at 20 ° C.

3. A product according to claim 1, characterized in that the acid is oleic acid.

4. . a salt according to claim 2, characterized in that the acid is oleic acid.

5. A fungicidal composition, characterized in that it comprises a product or salt according to any of the preceding claims, in admixture with an agriculturally acceptable diluent or carrier.

6. A method for combating pathogenic fungi in a site infested or susceptible to being infested with these, characterized in the method because it comprises the application to the site of a product or salt according to any of claims 1 to 4.