DE1001854C2 - Fungicides - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

PATENT 1 001 REGISTRATION DAY:

NOTICE DERREMELDDNG DND ADSING THE LEGAL LETTERING:

ADDITION OF THE PATENT LETTERING:

kl. 451 3/01

INTERNAT. KL. A 01 Il FEBRUARY 25, 1953

JANUARY 31, 1957 JULY 4, 1957

agrees with the exposition

1 001 854 (F 11178 IVa / 451)

It is known that acylazophenols have a good effect as a dressing agent against seed diseases. It was now found that quinone oximacy! hydrazones, which are present in the Most cereal diseases do not achieve the first-mentioned compounds in their effect, in the case of emergence diseases Causing fungi, such as those affecting legumes, beets, maize, flax, cotton, etc., are extraordinary Develop fungicidal effect which 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 compounds of the general formula

(HO-N = R = N-NH-X-J _n R ₁

be understood. Here R stands for a mononuclear or polynuclear quinoid radical, R ₁ for hydrogen or an organic radical (in the case of η = 2 or 3, R ₁ stands for a corresponding radical of a di- or tricarboxylic acid, sulfonic acid, etc.), where the R ₁ radical, like R, can be substituted or unsubstituted. R ₁ is linked to X directly or via a heteroatom such as O, N or S. X represents the group of fungicides

Patented for:

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

IO

or

or - C - or - S -

Il / \

NH OO

and η stands for an integer. These compounds are prepared by methods 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.

Metal-free substances such as tetramethylthiuram disulfide or 2, S-dichloro-naphthoquinone-1,4 are already used today to combat emergence diseases. But while these compounds must be used in at least 50 ° / ₀ medicated setting are Chinonoximacylhydrazone such. B. the Chinonoximbenzoylhydrazon effective in legume in 10 to 15 ° / _o sodium, in beets even at 2.5 ° / ₀ hydrochloric setting and the same application rate. In the latter case, the 2, S ° / ₀ setting indicates strength of the hydrazone of 2.2 ° / o Hg as phenyl mercury acetate-containing stains, also at the same application rate, equivalent to the least. This is the first case in which the fungicidal effect of an organic mercury compound is achieved by a metal-free substance in the order of magnitude. For dressing seeds, the quinone oxime acylhydrazones are used alone or diluted in the usual way according to the known dressing processes. They can also be mixed with other fungicides or insecticides, additives from vogelfraß-Dr. Ewald Urbschat, Cologne-Mülheim, and Dr. Paul-Ernst Frohberger, Odenthal (Cologne district), have been named as the inventor

contain obstructive substances or such products that improve their solubility or distributability or have a beneficial influence on their usability in other ways.

The following experiments with multi-germ sugar beets were carried out on seeds that were caused by root blight of course was infected. Compost soil was used as the germination medium, which is also root burn Containing soil fungi that cause it. The germination temperatures were kept at 10 to 15 °. Through these factors were conditions. created for the development of healthy plants should be viewed as particularly unfavorable.

In the experiments on legumes, the naturally infected seeds (peas and beans) were found in the how usually carried out dressing laid out in compost soil, which contained pathogenic fungi for legume seedlings, and cultivated at temperatures around 10 ° in the greenhouse. The temperature conditions are for peas and Particularly unfavorable for beans, as it is well known that bubbling diseases are particularly prevalent, when the rate of germination is severely retarded by such low temperatures.

45

example 1

A Trockenbeize containing 2.5 ° / ₀ Chinonoximbenzoylhydrazon addition to extenders and conditioning means, was charged with 6 g per kg applied to multigerm sugar beet seed. When 100 beet clusters were sown, 84 emergence points resulted from which 152 beet plants developed. Of these, only 8 plants took root within 4 weeks.

■ brand based. Under completely identical test conditions and with the tests being started at the same time

709 573/385

brought seeds treated with a commercial dry dressing containing 2.2% mercury from 100 laid out Clusters of 68 casseroles with 134 beet plants, of which 46 plants perish over a period of 4 weeks went. The same seed, untreated, gave 56 emergence sites with 106 plants, of which within 4 weeks 40 plants succumbed to the root burn.

Example 2

The same stain containing 2.5% quinone oxime benzoyl hydrazone resulted in a further one carried out analogously Experiment from 100 beet balls 74 emergence points with 170 plants, of which only afterwards 10 died. After the seeds had been treated with the Hg dressing, 62 run-up places with 120 plants were made received, of which 60 were received. Untreated seeds resulted in 46 emergence sites with 72 plants, of which 52 died.

The use of a stain containing 10% quinone oxime benzoyl hydrazone gave the same result Test series 80 emergence points with 172 plants, all of which were still healthy even after 4 weeks. A 30% adjustment of the dry stain with the same active ingredient resulted in the same application rate no germ depression. The substance is therefore completely compatible with the seeds.

Example 3

Pea seeds were made with. a 15% quinone oxime benzoyl hydrazone containing pickling 2 g per kg dry pickled and cultivated as described above. After 24 days 70 healthy plants were obtained from 100 peas. A commercially available Hg stain produced 45 healthy plants, while untreated seeds yielded only 20 healthy plants.

Example 4

Out of 100 laid out beans with a dry dressing containing 10% quinone oxime benzoyl hydrazone 2 g per kg were treated, 92 healthy and 2 diseased plants were obtained after a test duration of 24 days. The commercially available Hg stain produced 81 healthy and 8 diseased plants in the same experiment. The untreated Seeds only produced 3 plants.

Example 5

Wheat seeds were artificially infected in the usual way with 5 g of wheat stone brandy spores per kg then treated with a dry stain containing 5% quinone oxime benzoyl hydrazone, 2 g per kg. in the Spore germination experiment, following that given by Gassner Method was carried out, resulted in almost complete spore germination in the non-dressed seed, while in the treated seed only sporadically Spores germinated.

Similar results were obtained when using quinone oxime formylhydrazone, quinone oxime acetylhydrazone, Quinone oxime cyanoacetyl hydrazone, di-quinone oxime oxallyl hydrazone, Quinone - oxime - ρ - chlorbenzoyl - 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 infected with Phythium de Baryanum contaminated compost soil inserted. The temperature during the test period is between 10 and 20 °. The compounds are stretched with talc and used as a dry dressing agent:

IO Quinone oxime Conc
tration expense
crowd
in g / kg After 4 weeks healthy
plant Tangles Active ingredient Carbonic acid- Seeds healthy
Casserole
put after sowing * 5 ethyl ester from 100 110 hydrazone 86 Quinone oxime 5% 6th 50 Carbonic acid- 15% 6th 48 methyl ester 150 ²⁰ hydrazone 132 Quinone oxime 5% 6th 72 Carbonic acid- 15% 6th 52 phenyl ester 104 hydrazone
«Σ 130 5% 6th 50 15% 6th 62

Example 7

Use of quinone oxime benzoyl hydrazone as a floor disinfectant against down-to-earth

fungal seedling diseases

Unheated 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, part was at a layer height of 10 cm with 2 g per m ² . and another part with 10 g per m ^{2 of} quinone oxime benzoyl hydrazone mixed uniformly. 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 m ² resulted in 24 healthy plants from 100 seeds, and treatment with 10 g per m ² ensured the emergence of 58 healthy plants.

45

Example 8

Use as active ingredients in sprays
to combat grain rust

In the table below are the numbers of Infestation assessment of two tests with different active ingredients as a spray against brown rust of the Wheat (Puccinia triticina) compiled.

Working method: Young wheat plants of the Peragis variety Guarantors were raised in pots. After the first sheet was fully developed, it was marked with a Uredospore suspension containing 0.1% agar infected. After the spores have dried on, after about 3 hours, the plants were sprayed with sprays containing 0.1 or 0.3% active ingredient and 0.3% of a wetting agent contained. The plants pretreated in this way were for 48 hours in a humid chamber at 18 to 20 ° and 95% rel. Humidity set up and then under normal greenhouse conditions at Temperatures of 18 to 20 ° continued to be cultivated. The infestation classification was carried out 12 days after the infection, where the infestation number 0 is completely free from infestation and the infestation number 4 is dense population of the first infected Leaves means. The figures given in the tables represent the average infestation of 10 plants in each case.

After the rust infection sprayed with active ingredient concentration in the spray liquor in ° / ₀

Infestation number

for the

Rust attack

(0 to 4 after

12 days)

water

Wetting sulfur (as a comparison medium) J — CO —NH-N = <

CH ₃ NH - CH ₂

CO

> = NOH

NH - Ν =

CH, -NH-

CH ₂ -CO-NH-N =

= ΝΌΗ HS-C-:

Il s

XH,

CH ₃

0.3

0.1 0.3

0.1 0.3

0.1 0.3

2.5 0.0

0.0 0.1

0.2 0.4

0.6 0.3

Example 9

Use as active ingredients in spraying agents for spraying tests against powdery mildew on oats (Erysiphe fighting cereal mildew. graminis). The trials were like

The table below shows the results given in Example 8.

25th

After the powdery mildew infection, sprayed with

water

CO - NH - N =

CO - NH τ- Ν =

NH-N =

= N0H

= NONa

= NOH active ingredient concentration
tration in
the spray liquid in ° / ₀

0.1
0.3

0.1
0.3

0.1
0.3

Infestation number for powdery mildew infestation (0-4

after 10 days)

1.5 0.5

0.1

1.0 0.5

0.6 0.4

example

A dry stain containing 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 it was the number of healthy seedlings given in the table (labeled B) received 4 weeks after sowing.

The table also contains information about the results that are achieved when the sugar beet seeds is not pickled.

running spots (labeled A) and healthy plants ⁵ The compounds have the following constitutions:

Connection 1

Connection 2

NH-N = <> = NOH

+ HCl

L J-CH ₂ -CO-NH-N =

= NOH

Compound 3 CH CH

CH C —CO —NH-N = <

> = NOH

TabeUe

connection Conc
tration A. B. Connection 1
unpickled
Connection 2
unpickled
Connection 3
unpickled 5%
15%
5% 57
15th
56
41 ■
74
28 125
23
118
76
154
40

IO

Claims (1)

Claim: " Fungicides containing quinone oxime acylhydrazones of the general formula (HO - N = R = N- NH- X) _n R ₁ , in which: R = mononuclear or polynuclear quinoid radical, R ₁ = H or an organic radical, where R and R _{1 can} optionally be substituted, X = -C-, —C—, —C— or - S—, Ii Ii Ii y \ O S NH OO η is an integer from 1 to 3 and in which R _{1 is} linked to X directly or via a heteroatom such as O, N or S. © 609 763'285 1.57 7O9i 5737385 6. 57