DE1001854B - Fungicides - Google Patents

Description

Fungicides It is known that acylazophenols have a good effect as an irritant against seed diseases. It has now been found that quinone oxime acylhydrazones, which in most cereal diseases the first-mentioned compounds in their Does not have an effect with mushrooms that cause rash diseases, like them Legumes, beets, maize, flax, cotton, etc. infested, an extraordinarily fungicide Develop an effect that is far superior to the acylazophenols mentioned above. the In the simplest case, effective compounds are used in the form of seed dressings.

Quinone oxime acylhydrazones are to be understood as meaning compounds of the general formula (HO-N = R_N = NH-X-) nRi. Here IZ stands for a mononuclear or polynuclear quinoid radical, R1 for hydrogen or an organic radical (in the case of n = 2 or 3, R1 stands for any radical of a di- or tricarboxylic acid, sulfonic acid, etc.), where the radical R1 just as R can be substituted or unsubstituted. R is linked to X directly or via a heteroatom such as 0, N or S. X means the 'group and n stands for an integer. These compounds are prepared by processes known per se, e.g. B. by condensation 'of quinone monoximes or nitrosophenols with mono- or polycarboxylic acid mono- or polyhydrazides, with thiocarboxylic acid hydrazides, sulfonic acid hydrazides, semicarbazides, thiosemicarbazides, aminoguanidines, etc.

To combat emergent diseases, metal-free Substances such as tetramethylithiuram disulfide or 2,3-dichloro-naphthoquinone-1,4 are used. While these compounds contain at least 50% active ingredient Setting must be used are quinone oxime acylhydrazones, e.g. B. the quinone oxime benzoyl hydrazone, in the case of legumes in 10 to 15%, in the case of beets even in 2.5% and the same application rate effective. In the latter case, the 2.5 ° /, setting is shown of the hydrazone of a stain containing 2.20 /, Hg as phenyl-Hg-acetate, likewise with the same application rate, at least equivalent. So here is the first Occurrence that the fungicidal effect of an organic mercury compound of a metal-free substance is also achieved in the order of magnitude. For seed dressing the quinone oxime acylhydrazones are diluted individually or in the usual way used according to the known pickling process. You can also use other fungicides or insecticides are mixed, additives of bird repellants or contain those products that improve their solubility or spreadability or have a beneficial influence on their usability in some other way.

The following experiments with multicircular sugar beets were carried out on one Seeds carried out that were naturally infected with root blight pathogens. As a germination medium compost was used, which also contained soil fungi that caused root burns. The germination temperatures were kept at 10 to 15 °. By these factors were Conditions created that are considered special for the development of healthy plants are unfavorable to look at.

In the experiments on legumes, the naturally infected seeds (Peas and Böhneri) laid out in compost soil after the usual dressing, which contained fungi pathogenic for legume seanlings, and at temperatures around 10 ° irri cultivated greenhouse. The temperature conditions are for peas and special extremely unfavorable for beans, as it is well known that bubbling diseases are particularly common occur strongly when the germination rate is due to such low temperatures is greatly delayed.

Example 1 A dry stain containing 2.5% quinone oxime benzoyl hydrazone in addition to extenders and conditioning agents, was 6 g per kg Multi-germ sugar beet seeds applied. When 100 beet clusters were sown, the result was 84 emergence points emerged from which 152 beet plants developed. Of these only 8 plants perished from root burns within 4 weeks. Under completely similar experimental conditions and with simultaneous approach of the'Versuche brought treated with a commercially available dry pickle containing 2.2% mercury Seeds from 100 balls laid out, 68 emergence points with 134 beet plants, from which perished 46 plants over a period of 4 weeks. The same seed gave untreated 56 emergence sites with 106 plants, of which 40 plants demolished within 4 weeks Succumb to root burn.

Example 2 The same containing 2.50/0 quinone oxime benzoyl hydrazone In a further experiment carried out in the same way, pickling was obtained from 100 beet clumps 74 emergence sites with 170 plants, of which only 10 subsequently died. To the treatment of the seeds with the Hb dressing resulted in 62 emergence points with 120 plants received, of which 60 were received. Untreated seeds resulted in 46 emergence points with 72 plants, of which 52 died.

The use of a dressing containing 100 % quinone oxime benzoyl hydrazone resulted in 80 emergence points with 172 plants in the same test series, all of which were still healthy even after 4 weeks. A 300/0 setting of the dry stain with the same active ingredient did not result in germ suppression with the same application rate. The substance is therefore completely compatible with the seeds.

Example 3 Peas seed was .gebeizt / Chinonoximbenzoylhydrazon containing mordant dry 2 g per kg with a 150 and cultured as described above. After 24 days, 70 healthy plants were obtained from 100 peas. A commercially available Hg dressing yielded 45 healthy plants, while untreated seeds yielded only 20 healthy plants.

Example 4 Out of 100 laid out beans labeled with a 10 "/, quinone oxime benzoyl hydrazone dry stain containing 2 g per kg were treated after a test duration of 24 days 92 healthy and 2 diseased plants preserved. The commercially available Hg stain resulted in im 81 healthy and 8 diseased plants in the same experiment. The untreated seeds brought only 3 plants emerged.

Example 5 Wheat seeds were grown with 5 g of wheat stone brandy spores per kg artificially infected in the usual way and then with a 5 0/0 quinone oxime benzoyl hydrazone containing dry stain treated 2 g per kg. In the spore germination test, which was carried out after the by Gassner was carried out, resulted in the non-pickled Seed almost complete spore germination, while the treated seed only a few spores germinated.

Similar results were obtained using quinone oxime formylhydrazone, Quinone oxime acetyl hydrazone, quinone oxime cyanoacetyl hydrazone, di-quinone oxime oxallyl hydrazone, Quinone oxime p-chlorobenzoyl hydrazone, chloroquinone oxime benzoyl hydrazone, chloroquinone oxime acetyl hydrazone, Quinone oxime p-nitrobenzoyl hydrazone, quinone oxime benzenesulfonic acid hydrazone, quinone oxisemicarbazone i.a.

Example 6 Polynuclear sugar beet seeds infected with Phoma Betae are placed in compost soil contaminated with Phythium de Baryanum. . The temperature during the test period is between 10 and 20 °. The compounds are stretched with talc and used as a dry dressing agent: After 4 weeks Effort-healthy Active ingredient Concentration Amount of casserole healthy tration in g / kg represent plants Seed after sowing of 100 balls Quinone oxime Carbonic 50/0 6 50 110 ethyl ester 150 / ' 6 48 86 hydrazone Quinone oxime Carbonic acid. . SO / 0 6 72 150 methyl ester 15010 6 52 132 hydrazone Quinone oxime Carbonic 50/0 6 50 '104 phenyl ester- 1501, 6 62 130 hydrazone r Example 7 Use of quinone oxime benzoyl hydrazone as a soil disinfectant against soil-borne fungal seedling diseases Unpickled branded peas of the Aldermann variety were sown in ordinary compost soil that was heavily contaminated with phytopathogenic germs. Part of the earth was left untreated, one part was evenly mixed at a layer height of 10 cm with 2 g per m2 and another part with 10 g of 2 quinone oxime benzoyl hydrazone. From 100 peas that were placed in untreated compost soil, only 12 healthy plants emerged, the remaining 88 seedlings rotten in the soil. Treatment of the compost soil with 2 g of quinone oxime benzoyl hydrazone per m2 resulted in 24 healthy plants from 100 seeds, and treatment with 10 g per m2 ensured the emergence of 58 healthy plants.

Example 8 Use as active ingredients in spray compositions for combating of grain rust In the following table are the numbers of the infestation assessment of two experiments with different active ingredients as a spray against brown rust of wheat (Puccinia triticina).

Method of operation: Young wheat plants of the Peragis Garant variety were grown in pots. After the first leaf had fully developed, it was infected with a uredospore suspension containing 0.10 / 0 agar. After the spores had dried on, approximately after 3 hours, the plants were sprayed with sprays containing 0.1 or 0.30 / 0 active ingredient and 0.30 / 0 of a wetting agent. The plants pretreated in this way were for 48 hours in a humid chamber at 18 to 20 ° and 950 /, rel. Set up humidity and then further cultivated under normal greenhouse conditions at temperatures of 18 to 20 °. The infestation classification was carried out 12 days after the infection, the infestation number 0 meaning complete freedom from infestation and the infestation number 4 meaning a dense population of the infected first leaves. The numbers given in the tables represent the average infestation of 10 plants in each case. Active ingredient infestation number concentration for the Sprayed with after the rust infection in the spray / z- rust attack 0 to 4 after broth in% ( 12 days) Water - 2.5 Wetting sulfur (as a comparison agent) 0.3 0.0 CO-NH-N = #> = N OH 0.1 0.0 0- / CH $ 0.3 0.1 _ CHSNH - CH, - CO - NH - N = NOH + HS-CN \ 0.1 0.2 CH, 0.3 0.4 S. CH, -NH- CH, -CO-NH-N = <\ i -:> = NOH + HCl 0.1 0.6 0.3 0.3 Example 9 Use as active ingredients in spray compositions for combating powdery mildew.

The table below shows the results of spray tests against powdery mildew on oats (Erysiphe graminis). The tests were carried out as indicated in Example 8. Active ingredient infestation number concentrate for the After the powdery mildew infection, sprayed with tration in powdery mildew the spray infestation (0-4 brew in % 10 days) Water - 1.5 - @ CO - NH - N NOH 0.1 0.5 0.3 0.1 > - CO - NH - N = # = NONa 0.1 1.0 - 0.3 0.5 @ \ - O-C-NH-N = = NOH 0.3 0.4 O Example 10 A dry dressing which contains the concentrations of compounds 1, 2 or 3 given in the table is applied at 6 g / kg to multi-germinated sugar beet seeds. When 100 beet tubers were sown, the number of healthy emergence points (designated A) and healthy plants (designated B) indicated in the table was obtained 4 weeks after sowing.

The table also contains information about the results, which are achieved if the sugar beet seeds are not dressed.

The compounds have the following constitutions: Tabel Connection Concentrate tration Connection 1. . . . . . . . . . . 5% 57 125 unheated .............. - 15 23 Connection 2. . . . . . . . . . . 150/0 56 118 unheated ......... .. - 41 76 Connection 3. . . . . . . . . . 5%: 74 154 unheated .............. - 28 40

Claims (1)

PATENT CLAIM: Fungicidal agents containing quinone oxime acylhydrazones of the general. Formula (HO-N = R = N-NH-X) nRl, in which: R = mononuclear or polynuclear quinoedr radical, R1 = H or an organic radical, where .R and R1 can optionally be substituted, n is an integer from 1 to 3 and in which R1 is linked to X directly or via a heteroatom such as O, N or S.