DE943730C - Fungicidal substances - Google Patents

Description

Organic mercury compounds used as fungicides in horticulture, in the protection of Textiles and surfaces against sponge formation and in the treatment of fungi and bacteria infections are known to be active. In this context are phenyl mercuri acetate and phenyl mercuri naphthenate have already been used successfully.

Also heavy metal salts and among these copper, lead and mercury salts of oxyquinoline are considered known fungicidal substances. Water-insoluble soaps, especially those from Alkaline earth or heavy metals, reacted with water-insoluble oxyquinoline salts of alkaline earths or Heavy metals. There are also compounds of mercury salts with aromatic or heterocyclic salts Bases used for the destruction of animal and vegetable pests. As a seed dressing agent are heavy metal compounds, especially mercury and bismuth compounds of the ao 8-oxy-quinolines known.

It has been found that phenyl-mercury derivatives of 8-oxy-quinoline and those 8-oxy-quinolines which contain at least 1 halogen atom in the carbocyclic nucleus, in their fungicidal properties the previously ag known organic mercury compounds far

surpass. The new compounds are phenyl-mercuri-S-oxy-quinolinates general formula

-X Y

OH

where X and Υ represent hydrogen or halogen. It include monohalogenated derivatives such as 5-bromo-8-oxy-quinoline, and the halogenated 8-oxy-quinolines, such as 5,7-dichloro-8-oxy-quinoline, 5, 7-dibromo-8-oxyquinoline and s-chloro ^ -iodo-S-oxy-quinoline, to these Links.

These are compounds in which a phenyl mercuri group, i.e. a phenyl mercury group linked to the halogenated 8-oxy-quinoline group. With the previously known In mercury compounds, the mercury was in the form of sulfate or chloride bound to an 8-OxychinoHn group before.

The new substances can be produced, for example, by mixing phenyl mercury hydroxide or its salt with an organic carboxylic acid and 8-oxy-quinoline or an 8-oxy-quinoline, which contains at least 1 halogen atom in the carbocyclic nucleus in a solvent in which these compounds are at least partially soluble. The phenyl mercury salt of an organic carboxylic acid is preferably one with a monocarboxylic acid, with salts of saturated monocarboxylic acids, which are highly volatile are preferred,

for example phenyl mercury acetate and phenyl mercury propionate.

No protection is sought for the establishment of the connections in the present application.

The table below shows results obtained with phenyl mercuri-8-oxy-quinolinate were compared with similar data for phenyl mercuric acetate and phenyl mercuric naphthenate, two well-known fungicides.

To achieve these results, 2/ ₀ % solutions or dispersions of the compounds in a solvent, consisting of 80 percent by volume of diacetone alcohol and 20 percent by volume of a mixture consisting of equal parts of water and a condensation product of octylphenol with 8 molecules of ethylene oxide, were first prepared and then diluted with water to the desired concentration. 0.015 ^cm x ³ of such a solution or dispersion was placed as circular drops 1.5 mm in diameter on a microscope slide and allowed to dry. Then a suspension of spores of a selected fungus was prepared in which about 30,000 spores per cm ^{3 were} contained. 0.04 cm ^{3 of} this suspension was added to the dried drop residue. The slide was then left to act for 24 hours and the percentage of spores killed was determined by counting.

The concentration of the compound tested was then plotted against the percentage killed spores and from the diagram obtained that concentration is determined which is the killing of Causes 50 and 95% of the spores. These values are given as LD 50 and LD 95 in the table below.

Table I.

link

Venturia
inaequalis

Sclerotinia
fructigena

Botrytis cinerea

Fusarium sp.

Phenyl mercuri-8-oxy-quinolinate.

Phenyl mercury acetate

Phenyl mercury naphthenate.

0.000025
0.0002

0.00011
0.0003

0.00037
0.00056

0.000025
0.0002

0.00034
0.0009

0.00012
0.00083

0.00005

0.0001

0.00027 0.00034

0.00043 0.00088

0.00008

0.0002

0.00017 0.00068

0.000067 0.00030

It can be seen that there is a considerable difference between the LD 50 and LD 95 values for the quinolinate (LD = lethal dose). The corresponding values for the other two mercury fungicides show smaller differences. From the so-called LD 50 and LD 95 values can be in bacteriology those amounts of substance by extrapolation determine which are necessary for a ioo ° / ₀ owned destruction of spores. Usually an excess over the value thus determined is then used in practice. This amount of substance actually used - also called field dose - is only ten times the LD 95 value for the new compounds, while 20 times the LD 95 value must be used for the phenyl mercuric acetates. In absolute numbers, this means that usually only the third part of the amount required when using phenyl mercuriacetate is required when using the new compounds.

As far as test results are available, they show that the new compounds do not exert any phytotoxic effects on fruits in the concentrations used. They have very low solubility in water and are therefore not easily washed off by water from the objects to which they have been applied.

It has been found that the new compounds, especially phenyl mercuri-8-oxy-quinolinate, are very valuable Substances for the protection of textile materials

pose against the attack of various fungi, especially to protect materials that contain vegetable fibers, such as cotton, flax, jute and hemp, contain or consist of. The phenyl mercuri compounds can be formed in situ, them but can also be used in solution or in dispersion. It is therefore possible to use a textile material to first impregnate with a solution of a phenylmercuri salt, such as phenyl mercuri acetate, set the intake of a fixed amount with the help of scrolling rollers and that impregnated material obtained with or without drying by a solution of 8-oxy-quinoline or halogen-substituted 8-oxyquinoline, for example in solution of a lower aliphatic alcohol, too to lead. The following example describes this mode of operation according to the invention.

Example ι

A boiled flax canvas is first moved through a solution containing 336 parts by weight of phenyl mercuric acetate in 20,000 parts by volume of water. The uptake of liquid was adjusted _{to 50 ° / 0} by moving the canvas between rollers. The impregnated fabric obtained was then passed through a second solution which contained 145 parts by weight of 8-oxy-quinolonium potassium sulfate in 10,000 parts by volume of water. After the excess solution had been squeezed off, the fabric was washed out and dried.

Finished phenyl-mercuri-8-oxy-quinolinate is usually applied in the form of the solution or the suspensions. There is a very useful way of working involves first producing a melt with stearic acid amide and then with the one obtained Product to produce a solution or dispersion in an organic solvent. Suitable Solvents are petroleum hydrocarbons and their mixtures. Describe the examples below this side of the invention.

Example 2

ι Part of phenyl mercuri-S-oxy-quinolinate was made with 3 parts of stearic acid amide melted together and the mixture was allowed to cool. A wax-like one Substance was obtained. This substance could easily be found in petroleum-hydrocarbon fractions, for example one with a boiling range from 60 to 160 °.

Cotton cloth was impregnated with such solutions of various concentrations. The recording was adjusted to 50% of the cloth weight. The product was then dried. When the crowd was insufficient in absorbed phenyl mercuri compound on the cloth, so treatment became repeatedly until the desired amount has been absorbed. Similar impregnations were made performed with other known fungicidal substances. The obtained samples of cotton cloth were then inoculated with an agar suspension of spores of a selected species of fungus and for 84 days Let ripening, whereupon the tensile strength was determined. The following table shows the Minimum concentration for a loss in tensile strength of no more than 5%.

Table II

Chaetomium
Globosum

Aspergillus
Niger

0 / / 0

Penicillium Roquefortii Thorn.

Phenyl mercuri-S-oxy-quinolinate

Phenyl mercury acetate

Copper 8-oxy-quinolinate

. 0.002
0.002
2.0

0.003
0.002
1.0

0.02

o, 5 0.8

Example 3

A heavy cotton fabric with a weight of 1.086 kg / m ² was obtained in a solution containing 0.32 percent by weight of that obtained by melting together phenyl mercuri-s-chloro-y-iodo-S-oxy-quinolinate with three times the amount by weight of stearic acid amide contained a wax-like product dissolved in mineral spirits, impregnated. The fabric was immersed for 30 minutes and then moved by rollers to set a liquid uptake of 50 percent by weight. The impregnated fabric was dried at room temperature and then covered with dirt. No reduction in tensile strength was found after 6 months.

Example 4

An impregnation mixture was prepared by dissolving 3624 g of the wax-like substance from Example 2 in 453 kg of mineral spirits. Real hemp yarns were immersed at 25 ^0, placed by rolling on a weight uptake of 2O ° / ₀ and then at 35 ° dried. Very useful fishing nets were made with the treated thread.

Phenyl mercuri-S-oxy-quinolinate and its halogenated Derivatives have also proven to be valuable additives to paints in order to make them fungicidal To give properties. The finished quinolinate was mixed with the pigment materials and this then in a known manner with the dye base

and the solvents brought together. Based on the weight of the pigment substances can usually 0.1 to 0.2%, generally not more than 0.5%, quinolinate can be added, although higher Concentrations - if desired - are applicable.

The following examples show typical compositions of colors. Many other Compilations in the sense of the general information of the invention are of course possible.

Example 5

A dye carrier was made by dissolving 5 parts by weight of zinc resin and 12 parts of a commercially available one Alkyd resin made in 13 parts of ethyl acetate. This dye carrier was made up of 15 parts Grind Lithopone and 0.03 parts of phenyl mercuri-8-oxyquinolate.

Example 6 ^r

An aqueous emulsion of low viscosity polyvinyl chloride was emulsified with a polyvinyl acetate which had been partially saponified with 2% sulfuric acid. 200 parts this emulsion was made by grinding with 50 parts of titanium white, which 0.2 part of phenylmercuri-8-oxy-quinolinate, previously dissolved in 10 parts of propylene glycol, had been added, pigmented.

Example 7

The following ingredients were married together, until a completely uniform substance was obtained: 25.4 kg dry purple brown, 25.4 kg Parisian White, 127 kg baryta, 9.54 kg linseed oil base varnish, 3.53 kg base varnish, 9.08 kg raw linseed oil, 1.13 kg a mixture of 25 percent by weight phenyl

mercuri-8-oxy-quinoline and 75 percent by weight stearic acid amide,

The fungicidal activity of dyes containing phenylmercuri-8-oxy-quinoline is very remarkable, and an amount as small as 0.01% by weight, based on the non-volatile components of the paint, is sufficient to produce remarkable fungicidal properties. The following test illustrates this. Pieces of filter paper with a diameter of 9 cm were immersed in a series of paints which contained varying amounts of fungicidal components, then allowed to drain and dried until the paint hardened (usually at least ι ~ week). The pieces of paper were then placed on Petri dishes containing Saboreaud's agar medium such that 1.25 cm of medium was left along the edges of the pieces of filter paper. The medium used was then inoculated with Aspergillus niger at four equally distant points and a further inoculation was carried out in the center of the filter paper. The dishes were then left for 20 days at 26 ⁰ to the action. It was then determined the minimum amount of anti-pesticide that a growth of the cultures over the. Prevents the edges of the paper from coming out. Typical results obtained using compounds of the invention commonly used for the same purpose and commercial preparations are shown below.

link Minimal
concentration
% Phenyl mercuri-S-oxy-quinolate
Phenyl mercury naphthenate ...
Oil-soluble koppquinolinate 0, OX
0.25
4.0

In the case of phenyl mercuri-8-oxy-quinonate a zone of inhibition 2 mm wide was obtained when the paint was 0.031 percent by weight based on the non-volatile constituents. A complete inhibition of the growth on the petri dishes was found on the same basis with paints containing 0.5 percent by weight of the same substance contained.

The compounds can be used in the form of sprays to control parasitic fungi will. In Table I it has been shown that good control of Venturia inaequalis (apple fungus disease) can be carried out by using the compounds of the invention. One A large number of tests have been carried out on apple trees of the Worcester Pearxnain, Cox's Orange, Pippin and Bramley's Soedling every fourteen days, beginning in early April, with one Spray were injected, the 0.004 ° / ,, phenylmercuri-8-oxy-quinolinate contained. Spraying was continued for 2 months. Parallel tests were carried out with lime sulfur as the most reliable commercial means of combating parasites. Leaves, flowers and fruits were given to the present checked by mushrooms. There could be no local difference "in the tendency to Püzinfection or the degree of fungal disease of the fruit in eight distant places in the southern one Half of England can be established. The spray agent used was obtained as follows:

A 2% solution of phenyl mercuri-8-hydroxyquinoline was prepared in a mixture of 8o ° / ₀ diacetone alcohol and 2O ° / ₀ of a mixture containing equal parts of water and a condensation product of octylphenol with 8 molecules of ethylene oxide are contained. This solution was diluted to adjust the concentration required.

The new compounds can be used as a seed disinfectant in finely divided form with finely divided solid carriers such as bleaching earth, kieselguhr, bentonite, lime and talc, be mixed.

Claims (5)

PATENT CLAIMS: r. Use of phenyl mercuri-8-oxy-quinolinates the general formula Hg- OH -X
-Y where X and Y represent hydrogen or halogen, as fungicidal substances. 2. Use of the compounds according to claim ι for the impregnation of textile materials including vegetable fibers. 3. "Application of the compounds according to claim ι in the form of additives to dyes.- 4. Use of the compounds according to claim ι in the form of an aqueous dispersion as Protective preparations for horticultural purposes, in particular. as a spray with the addition of a wetting agent. 5. Use of the compounds according to claim ι for the treatment of seeds after mixing in finely divided form with finely divided solid carriers, such as fuller's earth, Diatomite, bentonite, lime, talc. Referred publications:
German Patent Nos. 469 202, 572 126;
U.S. Patent No. 2,561,380. © 609510 5.56