DE2223467A1 - AGENTS FOR CONTROLLING PHYTOPATHOGENIC FUNGI AND DISCARRANTING RODENTS AND RURAL - Google Patents

Description

FARBENFABRIKEN BAYER AG LEVERK US EN'Bayerweik Central area Patents, trademarks and licenses

Slr / HM II a

Preparations for combating phytopathogenic fungi and for deterring rodents and ruminants

The present invention relates to the use of some known aminoalkyldithiocarbamic acids as fungicides and for repelling rodents and ruminants.

Dithiocarbamates are already in the form of their salts and disulfides known for a long time as fungicides. Heavy metal salts, e.g. the zinc and manganese salts obtained from alkylene-bis-dithiocarbamic acids. Also the salts, e.g. the zinc salts, of -uP-amino-alkyl-dithiocarbamic acids are previously described as fungicides (see e.g. German Auslegeschriften 1 023 921 and 1 094 729). However, these previously known active ingredients are inadequate because of them Spectrum of activity to combat cereal diseases Can only be used to a limited extent. As part of the development of new seed dressings against cereal diseases,

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which should replace the toxicologically questionable mercury-containing agents are the previously known active ingredients Not based on dithiocarbamate, mainly because of its lack of or inadequate action against Helminthosporium species universally usable.

It is also already known that zinc dimethyl dithiocarbamate and tetramethyl thiuram disulfide can be used to repel rodents and ruminants. These two active ingredients have gained considerable importance in practice (JF Welch, Proceedings Third Vertebrate Pest Conf., San Francisco, 1967, pp. 36-40). However, the effect is not always satisfactory , especially against ruminants.

It has now been found that the partially known aminoalkyldithiocarbamic acids of the formulas

ti \ +) ti

H ₂ N-AIk-NH-C-SH or H ₃ N-AIk-NH-CS

(Ia) (Ib)

in which

Alk stands for an alkylene radical with 2 to 6 carbon atoms,

have strong fungicidal properties and also have a good deterrent effect on rodents and ruminants.

The importance of the active ingredients lies in the previously unknown fungicidal effect of the compounds on the Pathogens of various cereal diseases, in particular

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compared to Helminthosporium species. According to the previous ones Experience with dithiocarbamate fungicides known from the prior art is the newly discovered effect surprised. Furthermore, surprisingly, the repellent effect of the active ingredients which can be used according to the invention is higher than those of the well-known rodent and ruminant repellants tetramethyl thiuram disulfide and zinc dimethyl dithiocarbamate, The substances that can be used according to the invention thus represent an enrichment of technology.

The aminoalkyldithiocarbamic acids to be used according to the invention are clearly characterized by the formulas (Ia) and (Ib). The radical "Alk" is branched or unbranched saturated alkylene group with two to six carbon atoms. Examples are: 2-aminoethyl-dithiocarbamic acid

2-aminopropyl-dithiocarbamic acid "

3-aminopropyl dithiocarbamic acid
1-aminopropyl- (2) -dithiocarbamic acid 3-aminobutyl-dithiocarbamic acid
4-aminobutyl-dithiocarbamic acid
5-aminopentyl dithiocarbamic acid
6-aminohexyl-dithiocarbamic acid.

The substances that can be used according to the invention are largely known (see, for example, Ber. £, 241 (1872); JJ5, 3351 (1922), Hoppe-Seylers Zeitschrift f. Phys. Chem. 180 , 202 (1929)) '. If they have not yet been described in detail, they can be produced by customary processes known from the literature. They are usually obtained by the action of equimolar amounts of carbon disulfide on diaminoalkanes in diluents such as water, alcohols, hydrocarbons, ethers, etc. at normal temperature. "

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The active ingredients according to the invention are highly fungitoxic Effect on and are characterized by a wide range of effects. Their low toxicity to warm blooded animals and Their good tolerance for higher plants allows their use as a pesticide against fungal infections Diseases. They do not damage crop plants in the concentrations required to control the fungi. Fungitoxic agents are used in crop protection to control fungi from various classes of fungi, such as Archimycetes, Phycomycetes, Ascomycetes, Basidiomycetes and Fungi imperfecti.

So they show a good action against seed-borne fungi, such as Ustilago avenae, Fusarium nivale, Helminthosporium and against soil-dwelling fungi, such as Rhizoctonia species, Fusarium species, Py t nium species, Phytophthor-a species, Verticillium alboatrum, Thielaviopsis basicola and Corticium rolfsii.

The active ingredients are therefore particularly suitable for soil treatment and seed dressing.

Furthermore, as already stated, the compounds according to the invention have a deterrent effect against harmful ones shark-like animals and rodents, such as hares and rabbits (Leporidae) and squirrel-like (Sciuroidae), pocket rats (oeomyoidae) and mouse-like species (Muroidae), to which essentially the dormouse-like (Muscardinidae) and the mice (Muridae) count.

To the hares and rabbits, for example, the wild rabbit (Oryctolagus cuniculus) belongs, to the squirrel-like eg the ground squirrel (Citellus citellus) and the ground squirrel (Citellus lateralis) and to the pocket rats eg the mountain pocket gopher (Thomomys talpoides). The common dormouse, for example, includes the dormouse (glis glis). The mice essentially comprise Le A 14 392 - 4 -

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in the group of long-tailed mice (Murinae), the rats (Rattusspec.), such as the house rat (Rattus rattus) and the brown rat (Rattus norvegicus); the house mice (Mus spec), such as Mus musculus; j η of the group of hamster-like (Cricetinae) _; the European hamster (Gricetus cricetus) and in the group of short-tailed mice (Microtinae), for example, the field mouse (Microtus arvalis), the earth vole (Microtus agrestis) and the large vole (Arvicoia terrestris).

The substances according to the invention also deter harmful ruminants (ruminantia), the most important groups of which are the Deer (Cervidae) and the horned animals (Bovidäe) are to be mentioned.

The deer include, for example, the roe deer (Capreolus capreolus), the Virginia deer (Odocoileus spec.), The fallow deer (Dama dama), the elk (Cervus canadensis) and the red deer (Cervus elaphus). Among the horned animals belong to the group of Chamois-like (Rupicaprinae) especially the sheep (Ovis spec) and goats (Capra, spec).

The active ingredients according to the invention can be converted into the customary formulations, such as solutions, emulsions, Suspensions, powders, pastes and granulates. These are produced in a known manner, e.g. by mixing the active ingredients with extenders, i.e. liquid solvents, pressurized liquefied gases and / or solids Carriers, if necessary using surface-active substances Agents, that is to say emulsifiers and / or dispersants. In the case of using water as an extender For example, organic solvents can also be used as auxiliary solvents be used. The main liquid solvents that can be used are: aromatics, such as xylene, toluene, Benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,

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Chlorethylene or methylene chloride, aliphatic ^ hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols such as butanol or glycol and their Ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, e.g. aerosol propellants such as halogenated hydrocarbons, e.g., freon; as solid carrier materials: natural rock flour, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite, or diatomaceous earth, and synthetic rock powder, such as highly dispersed silica, aluminum oxide and silicates; as emulsifier: non-ionic and anionic Emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g., alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, and aryl sulfonates; as a dispersant: e.g. lignin, sulphite waste liquors and methyl cellulose,

The active ingredients according to the invention can be present in the formulations as mixtures with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth substances, Plant nutrients and soil structure improvers.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90 #.

The active ingredients can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions,

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Suspensions, powders, pastes and granules will. The application happens in the usual way, e.g. by pouring, spraying, spraying, dusting, scattering, dry pickling, wet pickling or encrusting. Furthermore can the active ingredients or their formulations (preparations) are used for seed treatment.

To develop a deterrent ~ (Eepellent-) effect can also the use of the active ingredients according to the invention, their formulations and the use forms produced therefrom, as usual, e.g. also by seed treatment, by spraying, dusting or Spreading of suitable active ingredient preparations on by rodents and / or browsing by ruminants (game browsing) endangered plants or parts of plants, through soil treatment, through smoking in rooms or underground Buildings, by applying deterrent coverings and barriers above or below ground as well as by impregnation Rodent and / or ruminant endangered materials such as wood, paper, rubber and plastics.

In the treatment of seeds, amounts of active ingredient are generally used from 0.1 g to 10 g per kg of seed, preferably 0.? up to 5 g required. Amounts of active ingredient are used for soil treatment from 1 to 500 g per cubic meter of soil, preferably 10 to 200 g, is required.

Spray liquors or pastes to achieve coatings that repel rodents and ruminants, for example on endangered plants or parts of plants, generally contain between 0.1 and 20 percent by weight of active ingredient, preferably between 0.5 and 10 %. Materials that are soaked with the active ingredients should have an active ingredient concentration in the surface layer from about 0.1 to 5 percent by weight.

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The versatile application possibilities go out of the the following usage examples:

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Example A:

Seed dressing test / streak disease in barley (• name-related mycosis)

To produce a suitable dry dressing agent, the active ingredient is stretched with a mixture of the same Parts by weight of talc and kieselguhr to a finely powdered mixture with the desired active ingredient concentration.

For dressing, barley seeds that are naturally contaminated by Helminthosporium gramineum are shaken with the dressing in a sealed glass bottle. ^{The seeds are exposed to a temperature of 4 °} C. in moist compost soil in closed Petri dishes in the refrigerator for 10 days. The germination of the barley and possibly also of the fungal spores is initiated. Subsequently sown the pregerminated barley grain 2 χ 50 2 cm deep in Fruhstorfer Einheitsrerde and cultivated in a greenhouse at temperatures of about 18 ⁰ C in seed boxes which are exposed 16 hours a day light. The typical symptoms of streak disease develop within 3 to 4 weeks.

After this time, the number of diseased plants is determined as a percentage of the total emerged plants. Of the The less plants are diseased, the more effective the active ingredient.

Active ingredients, active ingredient intake and number of sick people Plants are shown in the table below:

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Tabel

Seed dressing test / streak disease
the barley

Active ingredient active ingredient application number strips

amount in mg / kg of diseased plants Seed in $> of the total number of emerged plants

unpickled - 26.4

200 15.5

600 17.2

(known) ¹²⁰ ° ⁹ ' ²

H ₅ ) ₂ N- (CH ₂ ) ₃ -NH-CS-S_7 ₂ Zn ² ^ g * η \%

1200 16 ^ 0

(known)

NH ₀ - (CH ₀ K-NH-CS-SH 200 3.0

^{from 4} 600 0.0

φ 5- β

H ₃ N-CH ₂ -CH ₂ -NH-CS 600 6.2

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Example B;

Seed dressing test / sinew it heaven (seed-borne mycosis)

Stretched to produce a suitable dry pickling agent the active ingredient with a mixture of equal parts by weight of talc and diatomaceous earth to a finely powdered Mixture with the desired concentration of active ingredient.

For dressing, rye seeds that are naturally contaminated by Fusarium nivale are shaken with the dressing in a "sealed glass bottle. The seeds are sown with 2 x 100 seeds in seed boxes 1 cm deep in Pruhstorfer standard soil. The young plants develop in climatic chambers at 10 ^° C., 95 ° relative humidity and diffuse daylight illumination and show the typical symptoms of snow mold within the first 3 weeks. ' * '

After this time, the number of fusarium plants is determined as a percentage of the total emerged plants. Of the The active ingredient is the more effective the fewer plants are diseased.

Active ingredients, active ingredient application rates and number of sick people Plants are shown in the table below:

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Tabel
Seed dressing test / snow mold

Active ingredient active ingredient expenditure - number of fusarium

amount in mg / kg plants in # seed of the total

run plants

unpickled - 12.1

H ₁ -) ^ N- (CH ₉ U-NH-CS-SJ? Zn 600 8.6

^ά ° ^dd * ^d 1200 8.2

(known)

600 0.0

1200 0.0

β 2 θ

H ^ N-CH ₉ -CH ₉ -NH-CS 600 1.1

⁵ ^ 1200 0.5

N- (CH ₂ J ₆ -NH-CS "600 0.5

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Example C;

Seed dressing test / oat burn (seed-borne mycosis)

Stretched to produce a suitable dry pickling agent the active ingredient with a mixture of equal parts by weight of talc and diatomaceous earth to a finely powdered Mixture with the desired concentration of active ingredient.

For dressing, oat seeds, which are naturally contaminated with oat brandy (Ustilago avenae), are shaken with the dressing in a sealed glass bottle. The seeds are sown with 2 × 100 seeds in seed boxes 2 cm deep in a mixture of 1 part by volume of Fruhstorfer standard soil and 1 part by volume of quartz sand. The boxes are set up in the greenhouse at a temperature of about 18 ^° C., kept normally moist and exposed to light for 16 hours a day. After 10-12 weeks the oats will flower and show healthy and diseased panicles (fire panicles).

After this time, the diseased panicles are determined as a percentage of the total developed panicles. $ 0 means none diseased panicles are present, $ 100 means all Panicles are diseased. The active ingredient is all the more effective fewer diseased panicles have emerged.

Active ingredients, active ingredient application rates and number of sick people Panicles are shown in the table below:

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Tabel

Seed dressing test / oat burn

Active ingredients Active ingredient concentration in
mg / kg of seed

Number of Brandrispen in ia the total excluded. formed panicles

unpickled

(C ₀ Hc) ₀ N -CH ₉ -CH ₀ -CH ₀ -NH-CS 900

7.8 5.3

(known from German Offenlegungsschrift 1,693,179)

H, N -CH ₂ -CH ₂ -NH-CS

900

0.0

H ₅ N- (CH ₂ J ₆ -NH-CS

900

0.0

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Example D:

Deterrent test / deer mouse

Experimental animal: North American deer vole

(Peromyscus maniculatus) Solvent: acetone
Active ingredient concentration in the test feed: 2 fo

To produce a suitable preparation of active ingredient, 2 parts by weight of active ingredient are dissolved in as little as possible Amount of the above-mentioned solvent, this solution is intimately mixed with 98 parts by weight of seed wheat and leaves that Evaporate solvents.

5 individually kept deer mice received next to an unpopular one Standard feed provided with 25 treated wheat kernels on each of 3 consecutive days. The number the grains eaten by each animal are recorded daily.

The measure of the deterrent effect is the reduction in moisture, ie the percentage by which the effective consumption (as a percentage of the total amount of wheat available) is reduced compared to the 100% strength which is always to be expected with untreated wheat. 100 ° ß> reduction in crop means that no wheat kernels were eaten at all, so the deterrent effect was complete. The stated values include the test result of all test animals during the entire test.

The active ingredients, the number of individual experiments and the results can be seen from the following table:

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Table deterrent test / deer mouse

Active ingredient

Number of reduction in size, individual attempts in i »

Zinc dimethyldithiocarbamate (known)

51.5

H ₃ N- (CH ₂ J ₄ -NH.CS 62.4

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Example E;

Deterrent test / house mouse

Test animal: white laboratory mouse (Mus musculus) Active ingredient concentration in the test feed: 0.5 i>

To produce an appropriate preparation of active ingredient, 3 parts by weight of active ingredient are mixed with 2.8 parts by weight of highly disperse silica and 4 _{parts by} weight of 2 parts by weight of talc. To prepare the test bait, 1.67 parts by weight of this active ingredient concentrate are intimately mixed with 95 parts by weight of a flour-like standard feed customary for laboratory animal husbandry with the addition of 3-33 parts by weight of methyl cellulose and a little water. 2 spherical bait pellets are formed from 6 g of dry matter and dried for 24 hours at room temperature before the start of the experiment.

These pellets are placed in front of 2 jointly kept white laboratory mice without additional food for 24 hours. Water is behind Available at will. The remnants of the pellets are dried back after the end of the experiment and weighed.

The re-weighed residual amount, expressed as a percentage of the originally used amount, is used as a measure of the deterrent effect. $ 100> deterrent means that nothing at all has been eaten by the pellets.

You active ingredients, the number of attempts and the results can be seen from the following table:

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Tabel

Deterrent test / house mouse

Active ingredient number of quenching under individual seeking ⁿ ^ (mean)

Tetramethylthiuram disulfide

(known) 67.8

H ₅ N- (CH ₂

82.6

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Example F; . .

Enclosure test / Black-tailed deer Test animal: Black-tailed deer (Odocoileus columbiänus)

For the production of a suitable active ingredient preparation 6 parts by weight of active ingredient and 10 parts by weight of a copolymer of methyl methacrylate and butadiene as Adhesion promoter dispersed in 84 parts by weight of water. Biennial Douglas fir seedlings (Pseudotsuga taxifolia) from 18-30 cm in height become whole in the active ingredient preparation immersed. After drying, the plants are completely covered with a thin layer of adhesive containing active ingredients covered and are placed in a 1.01 hectare game reserve planted. Within the open-air enclosure, 10 test plots are set up, each with 20 seedlings are treated with active ingredient, 20 seedlings are available that have been treated with the standard remedy tetramethyl thiuram disulfide (TMTD) and there are 20 seedlings that have not been treated and are used for control ..

The game enclosure is now occupied with 10 black-tailed deer. The test runs until intermediate checks show that there are enough browsing of 60 to 80 $> on the untreated seedlings. Then the mean degree of browsing is determined. $ 100 means that all the seedlings have been bitten, 0 means that none of the seedlings have been bitten.

Active ingredients, dosages, number of treated seedlings and average degree of browsing are shown in the table below emerge:

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Tabel

Enclosure test / black-tailed deer

Active ingredient

Dosage of the active ingredient in the treatment medium in $

Number of those with intermediate treatment rer seedlings bitter

Tetramethylthiuramdi sulfide (known) 200

47.91

untreated Control 200

74.87

I ₃ N- (CH ₂ ) ₄ -NH.CS

200

20.75

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Claims (4)

Claims; . 1) Fungicidal agents and agents for deterring rodents and ruminants, characterized by a content of aminoalkyldithiocarbamic acids of the formula H ₂ N-AIk-NH-C-SH or H ₃ N-AIk-NH-CS ⁰ in which Alk stands for an alkylene radical with 2 to 6 carbon atoms stands. 2) method for combating fungi and for deterring rodents and ruminants, characterized in, that one aminoalkyldithiocarbamic acids according to claim 1 on fungi, rodents and ruminants or their habitat can act. 3) Use of aminoalkyldithiocarbamic acids according to claim 1 for combating fungi and - for deterring rodents and ruminants. 4) Process for the preparation of fungicidal agents and agents for deterring rodents and ruminants, characterized in that aminoalkyldithiocarbamic acids according to claim 1 mixed with extenders and / or surface-active agents. Le A U 592 - 21 - 309047/1104