NO136128B - FUNGICID AVERAGE. - Google Patents

Description

The object of the invention is a fungicidal agent which

is characterized in that it contains 2-(0,0-diethyl-thionophosphoryl)-5-methyl-6-carbethoxypyrazolo-(1,5a)-pyrimidine

mixed with

a) 2-Methoxycarbonylamino-benzimidazole

or with

b) 1-(N-butylcarbamoyl)-2-methoxycarbonyl-amino-benzimidazole

in that the quantity ratio between the active compounds is from 10:1 to 1:10, preferably 5=1 to 1:5"

The compound of formula I is known from BRD, off.

font 1.5^5.790. It is used as a fungicide, especially against powdery mildew. The compounds of formula II and III are likewise known as fungicides (II: US Patent No. 3,010,968, III: Dutch al-

but available application no. 6,706,331).

It has now been found that the mixture of a compound I with II or III shows not only an additive, but a synergistic effect against plant pathogenic fungi. The synergistic effect occurs at mixing ratios between 10:1 and 1:10, especially between 5" and 1:5.

With them. active substance mixtures according to the invention allow. the same effects as with the individual components can already be achieved at lower concentrations. When using the present mixtures, the risk of resistance formation is also considerably reduced, as observed from the use of benzimidazole compounds.

The effective substance mixtures according to the invention can be used with advantage against numerous plant pathogenic fungi, especially against true powdery mildew fungi as well as against other Ascomyzetes and Fungi imperfecti. Mention should be made, for example, of Venturia inaequalis, the cause of apple scab, Podosphaera leucotricha, the cause of downy mildew on apples and Botrytis cinerea, the cause of gray mold on fruit.

The agents according to the invention, in the correct dosage, work prophylactically as well as curatively. They are particularly suitable for fighting resp. prevention of fungal attacks on living plants, e.g. fruit and nursery crops, ornamental plants, vegetables, bush and berry fruit, cereal and seed plants, potatoes, etc.

The agents can be used in the form of spray powders, dust, granules, preferably, however, in the form of dispersions in paraffinic or vegetable oils or suitable higher-boiling liquid organic dispersants such as ethers and esters, preferably phthalic acid esters, e.g. phthalic acid dioctyl ester. The active substance I can be incorporated into such dispersions suitably dissolved in aromatic solvents.

When preparing spray powders and dusts, the active substance I is first adsorbed on adsorbable fine carriers such as synthetic silicic acids, diatomaceous earth, bentonites and then ground together with one of the active substances II and III, additional carriers as well as dispersing, wetting and adhesive agents. When making dust, appropriate talc such as calcium silicates and clay can be used as carriers.

Granules are suitably prepared by wetting granular inert carriers such as quartz sand with a solution of the active substance I in a higher-boiling solvent such as higher-boiling aromatic fractions, ketones such as isophorone, preferably in the presence of an emulsifier and stabilizers, and on the thus moistened sand brings for adhesion one of the active substances II or III in finely ground form, the granules being dried at the same time. However, one can also proceed in such a way that one adsorbs a solution of the active substance in absorbent granulated carriers such as attapulgite and on these granules a ground product of one of the active substances II or III is brought to stick.

Suitable dispersants in the spray powder are sodium salts of dinaphthyl methanesulfonic acid, dialkylnaphthalene sulfonic acid or oleylmethyl tauride, alkali and alkaline earth salts of lignin sulfonic acids, the sodium salt of sulforaic acid esters. Sodium dodeoylbenzene sulphonates or polyethylene or polypropylene glycols adsorbed on synthetic silicic acids can be used as wetting agents. Suitable adhesives are partially saponified polyvinyl acetates, polyvinyl alcohols, polyvinyl pyrrolidones, carboxyethyl celluloses, hydroxyethyl celluloses and plant gums.

For the formulation of liquid dispersions, the following organic dispersants are taken into account: O-acyl and nonylphenol polyglycol ether, triisobutylphenol polyglycol ether, castor polyglycol ether or -ester, preferably in the presence of a calcium salt of dodecylbenzenesulfonic acid. Depending on the chain length of the mentioned polyglycol ethers or -esters, these substances are suitable as dispersants more or less well in paraffinic oils in vegetable oils and other organic liquid dispersants.

Due to the higher boiling point and the organic dispersant, the dispersions are preferably suitable for application by the Ultra-Low-Volume method, as they are formulated in such a way that they can not only be mixed diluted in water, but also with additional organic liquids such as fractions of panafin oils without the active substances being degraded.

Due to better handling and flowability, the dispersions contain between 10-40 weight/S, preferably 20-25$ of the active substance combination. The spray powder can contain up to 70%, the granules up to 2-20%, dust .2-1056 of the active substance combination.

In the following examples, some typical formulations should be mentioned: Example 1: A dispersion in paraffin oils is obtained when you mix grind the following mixture in a friction ball mill:

15.0% by weight active substance II

3.0 weight$ active substance I

0.07 wt$ epichlorohydrin

7.50 wt$ nonylphenol polyglycol ether 3>25 wt? triisobutylphenol polyglycol ether 2.65 wt$ calcium dodecylbenzenesulfonate 0.70 wt$ castor oil polyglycol ether resp. -ester 8.33 wt$ xylene

58.80 weight/S paraffinic oil.

Example 2: A spray powder of both active substances is composed as follows:

30.0% by weight active substance II

15.0 weight$ active substance I

7.5 wt% paraffinic aromatic oil (Mobilsol F, .

Mobil Oil AG)

37.0 wt% finely dispersed silicic acid

5.0 weight/? sodium dinaphthalene disulfonic acid 2.0 wt/2 dibutylnaphthalene disulfonic acid sodium 0.5 wt/2 epichlorohydrin

2.0 wt/2 partially saponified polyvinyl acetate

1.0 wt$ polypropylene glycol.

Example 3; A sand granulate with 5.75% total active substance of the following composition is obtained according to the method described above: 91.275% by weight of quartz sand (0.3 - 1 mm grain size) is moistened with. a solution of 0.75 wt% of active substance

I in 0.75 wt$ aromatic oil "(Mobilsol F, Mobil Oil AG) and 0.025 wt$ epichlorohydrin. On the moistened sand, one rolls in a mixer 7.20 wt/2 of a 7<0>/2-ig

finely ground active ingredient II with silicic acid as carrier. Example 4:- Comparative substance.

Active substance II 50$ spray powder.

50 wt% active substance II

5 wt$ of sodium diethylmethanesulfonic acid

2 wt$ dibutylnaphthalene sulphonic acid sodium

2 wt% partially saponified polyvinyl acetate

1 wt$ polypropylene glycol

19 wt-/» skimmed milk powder

11 wt/2 synthetic finely dispersed silicic acid. Example 5 - Comparative substance.

Active substance In 30$ emulsion concentrate.

30.0 weight$ active substance I

5.5 wt% castor polyglycol ether

4.5 wt$ phenylsulfonate-Ca 0.5 wt$ epichlorohydrin

59.5 wt$ xylene.

Example I.

Cucumber plants, which were grown in pots in greenhouses, were heavily infected in the second leaf stage with a conidia suspension of cucumber powdery mildew (Erysiphe cichoriacearum D.C.) and grown for one day in a humidity chamber at 95 - 100$ relative humidity and a temperature of 20°C. They then entered a greenhouse which was set at a temperature of 22°C. After a period of 5 days, the thus infected plants were treated with the combinations of active substance I (formula I) and active substance II (formula II) listed in Table I. It was observed that a good wetting of the plants was achieved. After drying of the spray coating, the plants were returned to the greenhouse and observed after an incubation period until the untreated controls showed a clearly visible powdery mildew coating. Then the assessment took place. Powdery mildew attack was assessed with the naked eye. As a benchmark for fungal attack, it was used by the Biologischen Bundesanstalt in Braun -schweig set up a scheme of 1-9 (see below). The assessment of the sunergistic effect of the active substance combination took place according to the method of Horsfall or Sakai. (Horsfall J.G., "Fungicides and their Action", Chronica Botanica 19^5, ( Walham, Mass.), page 239 ff- resp. Sakai et al., 1951 II "Insect Toxi-cological Studies in the Joint Toxic Action of Insecticides between Contact Insecticides", Boty-K agaku 16 (1951), 130-140).

Example II.

In the same way as under example I, experiments were carried out with mixtures of compounds I with compound III. The results of these tests are shown in the following table

II.

Example III. ,

In a field experiment, a mixture of one part active substance I and 2 parts active substance II in a total concentration of 0.04/5 was compared with the individual components and with 0.05$

(active substance) binapacryl (4,6-dinitro-2,6-butylphenol-beta-dimethylacrylate) against apple scab (Podosphaera leucotricha Salm.) applied to apple trees of the Jonathan type ten times at intervals of 14 days each time. The amount of spray liquid was approx. 2000 litres/ha per spraying. The assessment (extraction) of the Triebspitz attack with powdery mildew took place after the end of the vegetation in late autumn.

Table VI shows the percentage of downy mildew-affected terminal buds from a total sample of 200 drift tips per three.

Claims (1)

Fungicidal agent, characterized in that it contains 2-(0,0-diethyl-thionophosphoryl)-5-methyl-6-carb-ethoxypyrazolo-(1,5a)-pyrimidine in mixture with a) 2-methoxycarbonylamino-benzimidazole or with b) 1-(N-butylcarbamoyl)-2-methoxycarbonyl-amino-benz- imidazole in that the quantity ratio between the active compounds is from 10:1 to 1:10, preferably 5:1 to 1:5-