DD202376A5 - FUNGICIDE BZW. BACTERICIDAL AGENTS - Google Patents

Abstract

The invention relates to fungicidal or bactericidal agents containing as active ingredient a complex metal compound of ethylene-1,2-bis (dithiocarbamidsaeure) and 8-hydroxyquinoline of the formula I.

Description

Fungicides or bactericidal agents

Field of application of the invention:

The invention relates to fungicidal or bactericidal agents,

as

Active ingredient containing a complex metal compound of ethylene-1,2-bis (dithiocarbamic acid) and 8-hydroxyquinoline,

Characteristic of the known technical solutions:

The non-phytotoxic salts and complex metal compounds of ethylene-1,2-bis- (dithiocarbamic acid) are known fungicidal active ingredients commonly used in crop protection. bis (dithiocarbamate) (US Pat. No. 2,317,765), the manganese-ethylene-1,2-bis- (dithiocarbamate) with polymer structure (US Pat. No. 2,504,404), the complex of this last compound containing 20 % manganese and 2 , 5% zinc (GB-PS 996 264; Mancozeb) and the zinc-ethylene-1,2-bis- (dithiocarbamate) (US-PS 2 457 674).

It is known that the salts of 8-hydroxyquinoline and its complex with copper and iron have a fungicidal and bactericidal action, which is why these compounds

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as active ingredient of fungicides or bactericides are used (G. From; Re Path., Veg., 23_, 131/1936 /; A. Albert and co-workers: Srit, 3rd exptl Path 34,119 / 1963 /), but is the Availability of these compounds limited because of the phytotoxic effect of S-hydroxyquinoline. The potassium S-hydroxyquinoline sulfate is used in medicine for disinfecting.

The interaction of the dithiocarbamate derivatives and the various complex-forming compounds has been the subject of numerous investigations (see, for example, Gy Matolcsy and his colleagues: Pestic., 2, 229-231 / 1971 /).

Object of the invention:

The aim of the invention was the provision of agents with improved fungicidal or bactericidal action.

Explanation of the essence of the invention:

Surprisingly, it has now been found that the complex metal compounds of A'thylen-1,2-bis (dithiocarbamic acid) and 8-hydroxyquinoline with mixed ligand have a strong fungicidal or bactericidal action and are therefore used as active ingredient of agricultural fungicides or bactericides can, wherein the effect of the previously mentioned fungicidal or bactericidal agents containing complexes of identical ligands containing as active ingredient, is exceeded by the effect of the inventive agents. The favorable properties of the known complexes are combined with each other, whereby the harmful side effects of the known complexes are reduced.

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in the new complex metal compounds with different ligands, the metal may be any divalent cation which is not phytotoxic in use. As examples, mention may be made of calcium, manganese, copper, iron, zinc and tin.

The presumed structure of said complex compounds of ethylene-1,2-bis (dithiocarbamic acid) and 8-hydroxyquinoline can be described with good approximation by the general formula (I).

In this formula, Me represents any divalent metal cation, and the bonds, shown as a dashed line, represent the delocalization bonds ♦

The novel complex metal compound can be prepared by suitably adding to an aqueous solution containing any water-soluble salt, suitably an alkali metal salt, preferably the sodium salt of ethylene-1,2-bis (dithiocarbamic acid), and any water-soluble salt of 8-hydroxyquinoline Alkali metal salt, preferably the sodium salt, in an equivalent amount, ie in the molar ratio of 1: 2, the aqueous solution of a readily water-soluble salt of a corresponding metal, preferably the solution of a halide or sulfate, is added, wherein the complex metal compound as an insoluble precipitate precipitates out of the solution.

The metal set can be used in an equivalent amount, i. based on 1 mole of ethylene-1,2-bis (dithiocarbamic acid), in an amount of 2 moles, or in slight excess.

The active ingredient content of the agent may be 0.01 to 95% by weight , preferably 0.5 to 80 % , depending on the purpose.

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The new compounds can be used for crop protection, as well as for the protection of various materials against harmful fungi and bacteria, such as z.3. used for the protection of wooden structures, stables, warehouses or stored products.

The use of the agent for crop protection according to the invention can z.3. as a soil disinfectant, as a mordant, as a thickening agent, which is suitable for the direct treatment of plants, as pollinating agents, as a means of spreading, as granules, etc., take place. The protection of various materials can be realized so that the material to be protected is coated or impregnated with the agent, by z.3. the agent is mixed with a dye to provide surface protection.

The agent according to the invention can therefore z.3. be formulated as a dusting, spray, suspension, dispersion, paste or granules. The agent is prepared in a known manner, i. the active ingredient is mixed with a solid or liquid carrier and / or a diluent and / or surfactants.

It is important to ensure that the active substance is evenly distributed homogeneously when an effective use according to the intended use is to be carried out. The carrier and / or the diluent material may be a solid or liquid, natural or artificial material. The surfactants may primarily have a non-tognogenic or anionogenic character; they have a wetting effect, emulsifying effect, or suspending effect, and they must be com comatible with the active ingredient.

For the production of pollinators, wettable powders and granules can be used as a solid carrier, 2.3. Talc, koaline, bentonite, dolomite, silica, zaolite, silica gel or silicate. The active ingredient is mixed with these and the mixture is ground to appropriate particle size. As a liquid carrier or diluent material, mineral oil fractions, vegetable oils, silicones, aliphatic, cyclic and aromatic hydrocarbons and their derivatives, in the first row cyclic and aromatic hydrocarbons, for example, cyclohexanone, cyclohexanol, Senzoly toluene, xylene; chlorinated hydrocarbons; strong polar solvents e.g. Dimethylformamide or dimethyl sulfoxide; also be used water.

As surface-active substances are alkyl aryl sulphonates, z.3. Alkyl naphthalene sulphonates, sulphated alcohols, derivatives of polyethylene glycol esters and ethers, alky-'E-arylpolyglycol ethers> polyglycol fatty acid esters, carboxymethylcellulose, condensates of naphthalene sulphonic acid and formaldehyde, lignin sulphonic acid, adducts of alkyl phenols and ethylene oxide, fatty acid esters of polyvalent ones Alcohols and ethylene oxide, phenolsulphonic acid-urea-formaldehyde condensates, fatty acid polyethyleneglycol esters and adducts of alkylamines and thiols with ethylene oxide.

Treatment with the new agent, optionally after dilution of the agent of high drug content immediately prior to use, e.g. with water, can in usual meadow, z.3. be done by sprinkling, atomization, pollination, sprinkling, spread or pickling. The agents according to the invention may, if appropriate, also be admixed with other crop protection agents, or the agent according to the invention may also be used together with other crop protection agents. In case of use as soil disinfectant, it may e.g. a fertilizer and to treat the damage of

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Trees are mixed with a treeworm tea. EXEMPLARY EMBODIMENTS:

The invention will be explained in more detail below with reference to the embodiments without restricting them to them.

example 1

Preparation of the complex metal compound of zinc, ethylene-1,2-bis (dithiocarbamic acid) and 8-hydroxyquinoline in a molar ratio of 2: 1: 2

An aqueous solution of 6Og (1Hole) of ethylenediamine and 30 g (2MoI) of sodium hydroxide is weighed into a flask equipped with recirculation condenser, mechanical stirrer and metering device. With stirring, 152 g (2 mol) of carbon disulfide are added, in such a way that the temperature does not rise above 35 C. Stirring is continued until a homogeneous, orange-yellow solution is obtained instead of the initially two-phase liquid mixture. 290 g (2 mol) of 8-hydroxyquinoline are dissolved in a solution of 80 g of NaOH in 720 ml of water, and the resulting solution of sodium 8-hydroxyquinolinate is added to the disodium 1,2-bis-benzene prepared in the above manner. (dithiocarbamate) solution added. Thereafter, a solution of 272 g (2 mol) of zinc chloride in 1000 ml of water is added to the reaction mixture, and it is stirred continuously for a further 30 minutes. The solid phase is separated and washed with water until free from sodium chloride. Thereafter, the product at a temperature of max. 70 C dried.

The product obtained 614.5 g (97.6 %) of a pale yellow powder whose melting point is at 337 ⁰ C (decomposition).

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H , 9 3 N S A Γ / / ύ 2 ,1 8th , 9 20 2 C- / 0 3 A 19

Composition: C calculated: 42,0 qfound: 39,8

In the following examples, the preparation of some representatives of the agent according to the invention will be described.

Example 2

Means for treating the damaged surfaces of tree-like plants

Due to the natural or artificial damage of tree-like plants often enter pathogenic bacteria and fungi in the plant structure. Therefore, it is useful if the serving to cover the wound preparation contains an active ingredient which has a bactericidal and fungicidal action. With the help of the new active ingredient such preparations can be prepared in a simple way.

a) From the finely ground active substance according to Example 1, the fraction with a particle size of <5, un with the aid

separated from seven. Of this, 50 g are suspended in some white spirit and the suspension is added with vigorous stirring 1000 g of enamel. The resulting means for treatment of tree wounds should be well stirred before use and applied without dilution with a brush on the damaged surface.

b) 100 g of finely ground active substance according to Example 1, 1000 g are added by heating softened Baumwundenteer, whereupon the mixture is allowed to solidify. Its use is done in the usual way.

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Example 5 Preparation of a mordant

300 g of active ingredient according to Example 1, 190 g of talc and 10 g of paraffin oil are stirred in a ball mill for 1 hour and ground. There is obtained 1 kg of agent with an active substance content of SO % , which is expediently used in a dose of 200 g / 100 kg of seed by conventional methods.

Example 4 Preparation of a wettable powder

700 g of active ingredient according to Example 1 and 200 g of kaolin are ground together in a ball mill, then 50 g of sodium salt of a naphthalenesulphonic acid-formaldehyde condensate, 35 g of Zewa-Na and 15 g of Dialkylnaphthalinsulphonsäures sodium salt are added.

There is obtained a spray powder having an active ingredient content of 70 % , from which a thickening agent with an active ingredient gehaöt from 0.5 to 5.0 g / l can be prepared in the usual way with water.

Example 5 Preparation of a liquid suspension

380 g of active ingredient according to Example 1 are mixed together with 110 g of sodium salt of a condensate of phenolsulphonic acid, urea and formaldehyde, further mixed with 30 g of silica gel and 480 g of water. This gives a stable aqueous suspension which can be diluted with 1000 parts by weight of water to a dispersion containing 0.38 g / l of active ingredient.

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The fungicidal and bactericidal action of the agent according to the invention can be seen from the following example.

Example 6 Examination of fungicidal activity in the laboratory

The fungicidal (spore germination-inhibiting) effect of the active compound according to Example 1 was investigated in a drop culture against some important fungus species that are plant-causing. The results are summarized in Table 1. Column "A" contains the concentration that inhibits germination of the conidia by 50 % and column "3" the smallest total inhibitory drug concentration, expressed in g / l.

Table 1

Mushroom type -A-. 3

Coiletotrichum attramentarium 4.1O * "" ⁵ 5.1O ~

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Alternaris tenuis 4.10 5.10 '

Helminthosporium sativum 5.10 "" 5.lO ~ ^r

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3otrytis cinerea 10. 3.10

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Fusatrium cepae 3.10 4.10

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Rhizoctonia sp. 7.10 '5.10

Example 7 Investigation of bactericidal activity in the laboratory

The bactericidal action of the active ingredient according to Example 1 was investigated by mixing an appropriate amount of the active ingredient into a glucose-peptone agar medium

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Then two important plant-pathogenic bacteria were applied to the medium.

The active ingredient can effectively inhibit the growth of bacteria of the strain Xanthomonas vesicatoria and Pseudomonas phaseolicols even at a concentration of 1.6-10 "" g / l.

Example 8 Examination of fungicidal activity on various plants

The fungicidal action of irrigation waters prepared from 70 % active ingredient according to Example 1 containing spray powder was examined in a greenhouse in the following combinations of plants and pathogenic fungi:

Cucumber (Cucumis sativus) - Erysiphe cichoracearum bean (Phaseolus vulgaris) - Uromyces appendiculatus Horse bean (Vicia faba) - Uromyces viciae-fabae Horse bean (Vicia faba) - 3otrytis cinerea Celleria (Apium graveolens) - Septoria apii-graveolentis

The plants were sprinkled with spray solution of various concentrations 24 hours prior to infection. The evaluation was performed on the seventh day due to the spread of fungal infection.

The effect was evaluated with percentage infection, relative to the untreated plant, it can be seen from Table 2.

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Spray solution concentration (ίο)

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Cucumis sativus - Erysiphe eic Phaseolus vulg. - Uromyces app Vicia faba - Uromyces v. Vicia faba - 3otrytis. Apium grav.- Septoria a.g.

0.2 0.1

0.2 .0.1

0.2 0.1

0.2 0.1.

0.2 0.1

18 56

15 18

32

30

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 NH-CH,

CH,

NH-C = -

Contains together with conventional vehicles and / or with surface-active substances.

2, Agent according to point L, characterized in that in the complex metal compound of formula (I) ethylene-1,2-bis (dithiocarbamic acid) 8-hydroxyquinoline and a divalent metal in a molar ratio of 1: 2: 2 are included.

3. Composition according to item 1 or 2, characterized in that it has an active ingredient content of 0.01 to 95 wt. -Jj.

- For this 1 Bl. Formulas -

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CN H-CH ₁ - C Wj-NH-C

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Claims (1)

trfindungsanspruch Fungicidal or bactericidal agent, characterized in that it contains as active ingredient a complex metal compound of ethylene-1,2-bis (dithiocarbanic acid) and 8-hydroxyquinoline, formed with a divalent metal of the formula (I)