HU191124B - Fungicide emulsions containing alpha-/2-chlorophenyl/-alpha-/4-chlorophenyl/-5-pyrimidine-methanol as active agent - Google Patents

Abstract

Fungicide compsn. contains 10-30 wt.% alpha-(2-chlorophenyl) -alpha- (4-chlorophenyl) -5-pyrimidine-methanol, 60-70 wt.% solvent consisting of one polar and one apolar solvent, and 5-15 wt.% of a mixt. of ethoxylated alkyl-aryl-ether, ethoxylated vegetable oil and alkyl-aryl-sulphonate.

Description

The present invention relates to an emulsion-forming fungicidal composition comprising α- (2-chlorophenyl) -α- (4-chlorophenyl) -5-pyrimidine-methanol (hereinafter referred to as fenarimol).

Fungicide preparations containing fenarimol are effective against apple powdery mildew and scab, stone fruit fungus, grape vine powder, currant and cumin against powdery mildew, parsley against powdery mildew and salsify against monilia.

Formulations of the active ingredient fenarimol are most often used in combination with other fungicidal (mainly anti-rumen) agents. This is intended to broaden the spectrum of action and to simplify pest control technology.

It is known that 5-substituted pyrimidine-methanol compounds were prepared by Sperber (U.S. Patent No. 2,727,895). The fungicidal activity of the pyrimidine compounds was discovered by Margot (U.S. Patent No. 2,839,446). No. 714,003. The Belgian patent discloses the plant fungicidal and growth regulating activity of the 5-pyrimidine-methanol series. No. 1,218,623. U.S. Patent No. 4,463,123 also discloses the preparation of substituted 5-pyrimidine derivatives. The synthesis of some analogs is described in detail, in a recipe-like manner, together with a description of the physical properties. For drug formulation, EC and WP are mentioned without the active ingredient designation.

Among N-containing heterocyclic compounds substituted by BeneficI (Eli Lilly) with afluoroalkoxyphenyl, herbicides, fungicides and plant growth regulators have been found, depending on the species and location of the substituents (U.S. Patent No. 3,967,949). Among the compounds prepared are

5-Pyrimidine-methanol analogues include, in addition to the fluoroalkoxyphenyl group, alkyl, cycloalkyl, phenyl, and the like. they contain a substituted phenyl group as the α-substituent. In the above-mentioned patent specification, and subsequently in Re 29 367, In addition, biological test results were reported. Among the derivatives is

5-Pyrimidine-methanol analogs have been used for soybean meadow grass. No. 2,272,079. French and 4,110,099; In US patents, Benefiel describes the preparation and biological assay of a further 5-pyrimidine-methanol derivative substituted by a fluoroalkoxyphenyl group.

The use of the fungicidal agent containing the active ingredient fenarimol is disclosed in U.S. Pat. No. 2,852,121. See the description in the GDR. According to the disclosure, wettable powder formulations with a content of 0.5 to 99% by weight of the active ingredient are proposed in formulation formulations. In the case of aqueous suspensions, the active ingredient content may be varied from 2 to 60% by weight. Granules are prepared with a particle size of 0.05 to 2 mm for an active ingredient content of 1 to 25% by weight and 0.05 to 0.5 mm for microgranules.

The preparation of a water-emulsifiable liquid is also recommended. The amount of active ingredient in these formulations is not related.

It appears from the foregoing that fenarimol-containing formulations were prepared in powder form only and with a relatively low active ingredient content (12% w / w) as an emulsion spray. (The Pesticid Manual 7 Th. Ed. P. 257)

It is an object of the present invention to provide a high active ingredient emulsion formulation in a simple manner.

It has been found that fenarimol, when dissolved in a pair of apolar and polar solvents, mixed with an ethoxylated hydrocarbon mixture and an alkylaryl sulfonate emulsifier, can be converted to a high active ingredient stable emulsion formulation (EC).

According to the invention, fenarimol is dissolved in the apolar-polar solvent mixture with stirring at room temperature. After dissolution, the stock solution is filtered, the surfactant forming the anionic / nonionic emulsifier system is added and the composition is homogenized by stirring.

As the solvent pair, we use non-polar and polar solvents in which the weight ratio of the solvents to each other is 1: 0.6: 1.7,

They can be used as apolar solvents, benzene homologues such as benzene, toluene, xylene.

Polar solvents: ketones, preferably acetone, valain formamide, N-methylpyrrolidone-2, γ-butyrolactone, dimethylformamide, dimethylsulfoxide.

Of the surfactants that promote emulsification in water, anionic / nonionic mixtures have proven to be most preferred. These include various ethoxylated hydrocarbons, such as ethoxylated ethers and vegetable solvents, and alkylaryl sulfonates.

The active ingredient content of the composition may vary from 10 to 30% by weight, depending on the solvent pair and emulsifier used.

The following examples illustrate the composition of the invention.

EXAMPLE 7 An Equal Mixture of Phenarimol Containing Wt% Phenarimol Wt% Xylene Wt% Dimethylformamide% 15 to 20 Ethoxylated Phenyl Acrylic Ether, Ethoxylated Alkyl Aryl Ether, Ethoxylated Vegetable Oil and Alkylaryl Sulfonate.

Example 2 Preparation containing by weight fenarimol 30% by weight fenarimol by weight 1: 1 by weight mixture of xylene: N-methyl-2-pyrrolidone by weight is the surfactant of Example I.

Example 3 Preparation containing by weight of fenarimol 20% by weight of fenarimol 30% by weight of dinyltylformamide 45% by weight of toluene is the surfactant mixture of Example I.

EXAMPLE 4 A mixture containing by weight of fenarimol, by weight, a mixture of phenarimol and xylene: dimethylformamide in a weight ratio of 1: 1 is the surfactant mixture of Example I.

The formulations in the Examples meet the requirements for the use of culminating agents. (MSZ-080218 / 1-79, MSZ-08 0218 / 2-80, MSZ-08 0494-81, MI-080169-80.) The samples have good cold tolerance, - 15 When stored at 0 ° C, it does not freeze, no crystallization occurs. At 54 ° C for 2 weeks in the so-called accelerated storage test, the active substance content of the formulations is not reduced by gas chromatography. There is no deterioration in quality during cyclic heat storage.

The emulsion stability of the samples prepared according to the above examples was not precipitated with a suitable dilution of 0.1 wt. The diluted samples were compared to a 0.1% standard aqueous solution of Rubigan 12 EC. The spray formulation of the formulations in the examples listed above has better stability than the spray formulation of Rubigan 12 EC.

Biological tests

The emulsion formulations containing 30% by weight of the active ingredient are tested in the greenhouse for its phololoxicylation and fungicidal activity.

For the sake of comparability, the data obtained with the standard Rubigan 12 EC used in the tests is also reported.

Λ Phytoloxicity studies were performed on cucumber plants and apple inagon in a greenhouse.

Example 5

Effect of Phenarimoin preparations on cucumber plants

Készítmény Formulations of Example 2 (A) and Example 4 (B) were tested on cucumber plants.

Table 1 shows the result.

Rubigan 12 EC at the highest concentration used is phytotoxic: this is not the case with the compositions of the invention.

Table 7

Phytotoxic effect of phenarimol preparations on cucumber plants in a greenhouse

preparation Concentration pg / ml agent side effect Rubigan 12 EC 1000 LONG AGO. 4+ Rubigan 12 EC 500 mild REG Rubigan 12 EC 250 mild REG Rubigan 12 EC 125 - Rubigan 12 EC 62.5 Rubigan 12 EC 31.25 - "A" 30 EC 1000 mild REG "A" 30 EC 500 mild REG “A 30 EC 250 - "A" 30 EC 125 - "A" 30 EC 62.5 - "A" 30 EC 31.25 - "B" 30 EC 1000 LONG AGO "B" 30 EC 500 mild REG "B" 30 EC 250 - "B" 30 EC 125 - "B" 30 EC 62.5 - "B" 30 EC 31.25 -

Note: REG - Regulatory effect (leaf distortion, retardant effect), + + - phytotoxicity '(levclszlcrisis).

Example 6

Effect of Fenarimol preparations on apple seeds

The effect of formulations A and B on Example 5 in apple seedling was more favorable in greenhouse than Rubigan 12 EC.

The results are shown in Table 2.

Table 2

Phytotoxic effects of fenarimol preparations ahnamagoncon iiregházhau

preparation Hatóanvag- machine concentration, Side effect pg / ml Rubigan 12 EC Rubigan 12 EC Rubigan 12 EC Rubigan 12 EC Rubigan 12 EC Rubigan 12 EC 1000 REG 500 mild REG 250 125 62.5 .31.25

191,124

preparation bulk chemicals konccntráció, Mg / ml side effect "A" 30 EC 1000 - ¹ "A" 30 EC 500 -. "A" 30 EC 250 - "A" 30 EC 125 - "A" 30 EC 62.5 - "A" 30 EC 31.25 "B" 30 EC 1000 mild REG "B" 30 EC 500 - "B" 30 EC 250 "B" 30 EC 125 - "B" 30 EC 62.5 - "B" 30 EC 31.25 -

Note: REG - Regulatory effect (leaf distortion, retardant effect)

Example 7

Effect of Phenarimol preparations against the pathogen of apple mildew

The fungicidal activity of the formulations "A" and "B" as described in Example 5 against the pathogenic apple mildew (Podosphaera lencotricha) was practically equivalent to the standard Rubigan 12 EC (Table 3). The test was carried out in a greenhouse on apple seedlings.

Table 3

Effect of Phenarimol Preparations on Podosphaera leueotricha in the Greenhouse - Contact, Protect and Preventive Action

preparation Active ingredient- * concentration, Mg / ml % cleaning Untreated control 26 Rubigan 12 EC 500 0 Rubigan 12 EC 250 0 Rubigan 12 EC 125 0 Rubigan 12 EC 62.5 0 Rubigan 12 EC 31.25 0 Rubigan 12 EC 15.62 0 "A" 30 EC 500 0 "A" 30 EC 250 0 "A" 30 EC 125 0 “A 30 EC 62.5 0 "A" 30 EC 31.25 0 "A" 30 EC 15.62 0.12 "B" 30 EC 500 0 "B" 30 EC

Preparation. concentration.

250 0 "B" 30 EC 125 0 "B" 30 EC 62.5 0 "B" 30 EC 31.25 1.0 "B" 30 EC 15.62 4.0

Example 8

Effect of Phenarimol preparations against cucumber powdery mildew »

The effect of the formulations "A" and "B" on the cucumber powdery mildew (Sphaerotheca fuligined) described in Example 5 is shown in Tables 4 and 5. The efficacy corresponds to the fungicidal activity of Rubigan 12 EC. '

The efficacy of the fungicidal compositions of the present invention is also confirmed by field trials in small plots. In these experiments, treatments were performed according to the Rubigan 12 EC technology proposal. No phytotoxic symptoms were observed in either crop.

Table 4

Effect of Phenarimol Preparations against Sphaerotheca fuliginea in the Greenhouse - Contact, Protect, Preventive Mode

preparation bulk chemicals concentration, Mg / ml % Infection Untreated control 74 Rubigan 12 EC 500 0 Rubigan 12 EC 250 0 Rubigan 12 EC 125 0 Rqbigan 12 EC 62.5 1 Rubigan 12 EC 31.25 0 Rubigan 12 EC 15.62 1 "A" 30 EC 500 0 "A" 30 EC 250 0 "A" 30 EC 125 0 "A" 30 EC 62.5 1 "A" 30 EC 31.25 0 , Λ ”30 EC 15.62 2 "B" 30 EC 500 0 "B" 30 EC 250 0 "B" 30 EC 125 0 "B" 30 EC 62.5 0 "B" 30 EC 31.25 3 "B" 30 EC 15.62 2

191,124

Table J.

Effect of Phenarithnol preparations against Sphaerotheca fuliginea in the greenhouse - contact, protective, preventive mode of action

preparation bulk chemicals concentration, pg / ml % Infection Untreated control 67 Rubigan 12 EC 100 0 Rubigan 12 EC 50 0 Rubigan 12 EC 25 0 Rubigan 12 EC 12.5 1 Rubigan 12 EC 6.25 2 Rubigan 12 EC 3.16 0 “A 30 EC 100 0 "A" 30 EC 50 0 "A" 30 EC 25 3 “A 30 EC 12.5 3 "A" 30 EC 6.25 7 "A" 30 EC 3.12 3 "B" 30 EC 100 0 "B" 30 EC 50 1 "B" 30 EC 25 2 "B" 30 EC 12.5 2 "B" 30 EC 6.25 7 "B" 30 EC 3.12 8

Example 9

Effect of Phenarimol Preparations on Jonathan Plantation

The efficacy of preparations A and B as described in Example 5 against Podoshpaera leucohicea was tested on Jonathan plantations. The cultivation method is Hungaria Hedge. The results are shown in Table 6.

Table 6

Effect of Phenarimol Preparations on Podosphaera leucotricha in the Field

preparation Dose, 1 / ha % Infection untreated 46 Rubigan 12 EC 0,072 11 "A" 30 EC 0,072 13 "B" 30 EC 0,072 9

Example 10

Effect of Fenarimol preparations on Starkíng plantation

The formulations "A" and "/ B" described in Example 5 suppressed the appearance of Venturia ináequalis (the apple rotting agent) similarly to Rubin 12 EC (Table 7). The experiments were carried out in the Starking plantation.

Table 7

Effect of fenarimol preparations on Venturia inaequalis in the open field

preparation Dose, L / ha Infection rate% untreated _ 30 Rubigan 12 EC 0,072 5 “A 30 EC 0,072 3 B 30 EC 0.07 7

Example 11

Effect of phenarimol preparations on vineyards

The inhibitory activity of the formulations "A" and "B" described in Example 5 against Uncinulla necator is standard. Table 8 shows the results of the experiment on high cordon plantations of the Red tramini variety.

Table 8

Effect of Phenarimol Preparations on Uncinulla necator in the Field preparation Dose, 1 / ha % Infection untreated _ 32 Rubigan 12 EC 0,036 9 "A" 30 EC 0,036 7 "B" 30 EC 0,036 11

The compositions of the present invention can be prepared in a simple manner. The formulations are stable and have good emulsion forming properties. The product has a high active ingredient content and is therefore well suited for aerial control in large scale plants, but is also suitable for use in home gardens and small farms with other pesticides.

Claims (3)

Claims 1. The active ingredient is α- (2-chlorophenyl) -α- (4-chlorophenyl) - Phenyl) - 5 - pyrimidine - methanol fungicidal emulsions characterized in that α - (2 - chlorophenyl!) - α - (4-chlorophenyl) -5-pyrimidine-methanol 10-30% by weight, 60-75% by weight, 1: (0.6-1.7) by weight of apolar carbocyclic alkyl having up to 10 carbon atoms a pair of solvents consisting of aromatic and polar solvents having from 1 to 4 carbon atoms dialkylformamide or from 1 to 4 carbon atoms alkyl pyrrolidone and from 5 to 15% by weight of ethoxylated phenyl alkyl aryl ether having from 15 to 20 ethoxylated ethoxylated alkyl aryl ether, a mixture of ethoxylated vegetable oil and alkylaryl sulfonate. Composition according to claim 1, characterized in that the apolar solvent comprises xylene, 3. The composition of claim 1 wherein the polar solvent is dimethylformamide.