CS235323B2 - A fungicidal and microbicidal agent for the protection of plants and technical materials and a method of producing the active ingredient - Google Patents

Abstract

Fungicidal and microbicidal agent for the protection of plants and technical materials, characterized in that it contains as an active ingredient at least one halopropargylformamide of the general formula I O II H - C - N - CIL· - C = C - Hel (I), I R in which R represents a hydrogen atom or optionally / one to five times, identically or differently, a halogen, a nitro group, an alkyl group with 1 to 4 carbon atoms, a haloalkyl group with 1 to 5 halogen atoms and. with 1 to 4 carbon atoms substituted by a phenyl group, and Hal represents iodine or bromine.

Description

The present invention relates to a fungicidal and microbicidal composition for the protection of plants and technical materials, which contains novel halopropargylformamides as an active ingredient.

Furthermore, the invention relates to a process for the preparation of these novel halopropargylformamides and their use as fungicides and microbicides.

Salts of ethylene-1,2-bis-dithiocarbamic acid with heavy metals, in particular zinc ethylene-1,2-bis-dithiocarbamate, have been known for a long time in agriculture and horticulture for controlling phytopathogenic fungi (cf. R. Wegler, Chemie der Pflanzenschutz- und Schadlingsbekampfungsmittel, vol. 2, p. 65, Springer-Verleg Berlin/Heidelberg/New York (1970)).

Furthermore, it has long been known to use compounds containing N-trihalomethylthio groups as fungicides in agriculture and horticulture. For example, N-(trichloromethylthio)tetrahydrophthalimide is used in practice in fruit tree cultivation and in grape cultivation to combat fungal diseases (cf. German Patent Specification 887,506 and Angew. Chem. 16, 807 (1964)).

Furthermore, inorganic copper compounds are known which have a broad spectrum of fungicidal effects (cf. K. H. Biichel, Pflanzenschutz und Schedlingsbekampfung, pp. 121 and 122, Georg Thieme Verlag Stuttgart).

In addition, iodopropargyl compounds, such as N-butyl iodopropargyl carbamate, are known as fungicides applied by painting (cf. DE-OS 3,116,653).

New halopropargylformamides of the general formula I have now been found

O

II

H - C - K - CHg - C = C - Hal (I)

H in which

H represents a hydrogen atom or optionally one to five times, identically or differently, with halogen, nitro, alkyl with 1 to 4 carbon atoms, haloalkyl with 1 to 5 halogen atoms and phenyl substituted with 1 to 4 carbon atoms,

Hal stands for iodine or bromine, which have strong fungicidal and bactericidal effects in the protection of plants and technical materials.

The subject of the present invention is a fungicidal and microbicidal composition for the protection of plants and technical materials, which is characterized in that it contains as an active ingredient at least one halopropargylformamide of the above-mentioned and defined general formula I.

According to the present invention, novel halogenopropargylformamides of the general formula I are obtained by reacting propargylformamides of the general formula II

O

II

H - C - N - CHg - C g C - H

AND

R (II), in which

R has the above meaning, with halogenating agents in the presence of basic substances in a diluent at a temperature between -30 and 50 °C.

The novel halopropargylformamides of formula I have strong fungicidal and bactericidal properties in plant protection. Surprisingly, they have a higher effect than previously known compounds.

The compounds of the invention represent a valuable enrichment of the state of the art due to the numerous possibilities for their advantageous biological use.

Very particularly preferred are compounds of the general formula I in which r is hydrogen, optionally one to three times, identically or differently, by a nitro group, a methyl group, an ethyl group, an n- and isopropyl group, a trifluoromethyl group substituted by a phenyl group and

Hal stands for iodine and bromine.

Individually, for example, in addition to the compounds mentioned in the examples, the following halopropargylformamides can be mentioned: bromopropargylformamide, iodopropargylformanilide,

2- chloroiodopropargylformanilide, 3-chloroiodopropargylformanilide, 4-chloroiodopropargylformanilide 2,3-dichloroiodopropargylformanilide, 2,4-dichloroiodopropargylformanilide, 3,4-dichloro-iodopropargylformanilide, 3,5-dichloroj odpropargylformanilide, 2,4,6-trichloro-j odpropargylformanilide, 2-methyliodopropargylformanilide, 3-methyliodopropargylformanilide, 4-methyliodopropargylformanilide, 2,3-dimethyliodopropargylformanilide, 2,6-aimethyliodopropargylformanilide, 2-methyl-6-ethyliodopropargylformanilide, 3-trifluoromethyliodopropargylformanilide, 3,5-bis-trifluoromethyliodopropargylformanilide, 3-nitroiodopropargylformanilide, bromopropargylformanilide,

3- Chlorbromopropargylformanilide.

The course of the reaction in the process according to the invention can be illustrated by the following reaction scheme using, for example, propargylformamide and iodine as starting materials:

1 l NaOH

HC-NH-CH ₂ -CeC-H + j ₂ ->.

-NaJ

II

HC-NH-CH ₂ -CsC-J

The propargylformamides which are used as starting materials in carrying out the process according to the invention are defined by formula II. These compounds are for the most part known or can be prepared by known processes, for example by reacting the corresponding formamide, for example, with potassium tert-butoxide to form the potassium salt of the formamide and then reacting it with the propargyl halide. However, it is also possible to use a primary amine in the presence of a base for the reaction with the propargyl halide and the propargylamine formed is then formylated by the action of formic acid or by the action of a formic acid ester (cf. for example Bull. Soc. Chim. Fr. 1967 (2), pp. 588 to 596).

Halogenating agents, which are further used as starting materials, such as halogen, are readily available products on the market.

Suitable diluents for the process according to the invention are water and polar organic solvents. Suitable polar organic solvents are those which are inert under the reaction conditions. It is preferable to use organic solvents which have a certain ability to dissolve the reactants. Solvents which contain hydroxyl groups, such as alcohols, are preferably used. Suitable alcohols are primarily lower aliphatic alcohols, such as methanol, ethanol, isopropanol, but also di- and polyhydroxy compounds, such as ethylene glycol and polyethylene glycol. The process is particularly preferably carried out in methanol and water.

Suitable basic substances are alkali metal and alkaline earth metal hydroxides, but alkali metal hydroxides such as sodium hydroxide or potassium hydroxide are preferably used.

Elemental halogens and halogenates are suitable halogenating agents. Halogenates are formed by adding halogen to the above-mentioned alkaline solutions, but they can also be prepared from halogen and alkali before the halogenation reaction and then added to the halogenated substance. Iodine and bromine are particularly suitable.

The reaction temperature can range from -30 to +50°C, but is preferably carried out at a temperature of from 0 to 20°C.

The process according to the invention can be carried out, for example, in the following manner:

Propargylformamide of formula II is introduced in one of the diluents mentioned and a molar amount of alkali is added, preferably 1.5 times the molar amount. Then at least a molar amount of halogenating agent is added in portions (an excess of this agent does not bring any advantages) and the reaction mixture is further stirred at temperatures from 0 to 20 ° C. The reaction is monitored by thin layer chromatography. The reaction mixture is worked up after the reaction is completed by conventional methods, for example by precipitation of the reaction product with water or by extraction.

The active ingredients according to the invention have a strong fungicidal and microbicidal effect and can be used for practical purposes to combat undesirable microorganisms in plant protection.

The active substances are suitable for use as plant protection agents and as microbicidal agents for the protection of technical materials.

Fungicidal agents are used in plant protection to combat fungi from the classes Plasmodiophoromycetes, Oomyoetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes.

Bactericidal agents are used in plant protection to combat fungi Pseudomonadacae Rhizobiaceae, Enterobacteriaoeae, Corynebacteriaceae and Streptomycetaceae.

The good compatibility of active ingredients with plants in the concentrations necessary to combat fungal diseases allows the treatment of above-ground parts of plants, seedlings and seeds, as well as soil.

As plant protection agents, the active ingredients according to the invention can be used with particularly good results to combat Leptosphaeria nodorum and Fusarium nivale in cereals, Venturia in apple trees and Xanthomonas oryzae in rice. Furthermore, it is necessary to mention the broad fungicidal effect in the agar plate test. At the appropriate dose, the compounds also have acaricidal effects.

Active substances can be converted into conventional products such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic substances impregnated with the active substance, small particles coated with polymeric substances and seed coatings, as well as products with incendiary additives such as smoke cartridges, smoke cans, smoke spirals and others, as well as products for application using the so-called ULV process and products applied in the form of warm fog.

These compositions are prepared in a known manner, for example by mixing the active ingredient with fillers, i.e. with liquid solvents, liquefied gases under pressure and/or solid carriers, optionally using surface-active agents, i.e. emulsifiers and/or dispersants and/or foaming agents. In the case of using water as filler, it is possible to use, for example, organic solvents as auxiliary solvents. Liquid solvents that are suitable in principle are: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexanone or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol, as well as their ethers and esters, and ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, highly polar solvents, such as dimethylformamide and dimethyl sulfoxide, as well as water. Liquefied gaseous fillers or carriers are liquids which are gaseous at normal temperature and pressure, for example aerosol propellants, such as halogenated hydrocarbons, as well as butane, propane, nitrogen and carbon dioxide.

Suitable solid carriers include, for example, natural stone flours, such as kaolins, aluminas, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone flours, such as highly dispersed silicic acid, alumina and silicates. Suitable solid carriers for the preparation of granules include crushed and fractionated natural stone materials, such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules made from inorganic and organic flours and granules made from organic material, such as sawdust, coconut shells, corn cobs and tobacco stalks.

Suitable emulsifiers and/or foaming agents include, for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates, and dispersants include, for example, lignin, sulfite waste liquors and methyl cellulose.

The compositions of the invention may contain adhesives such as carboxymethylcellulose, natural and synthetic powdered, granular or latex polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.

Furthermore, these compositions may contain dyes, such as inorganic pigments, for example iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthaloxyanine dyes, as well as trace elements, for example salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Concentrates generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90% by weight of active ingredient.

The active ingredients according to the invention can be present in concentrated compositions or in various application forms in a mixture with other known active ingredients, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth promoters, plant nutrients and soil structure improvers.

The active ingredients can be applied as such, in the form of concentrates or in application forms prepared from them by further dilution, such as directly usable solutions, emulsions, suspensions, powders, pastes and granules. The application is carried out in the usual manner, for example by pouring, dipping, spraying, misting, evaporation, injection, suspension, coating, dusting, sprinkling, dry pickling, damp pickling, wet pickling, suspension pickling or encrustation.

When treating parts of plants, the concentrations of active ingredient in the application forms can vary within a wide range. They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

When treating seeds, 0.001 to 50 g of active ingredient per 1 kg of seed is generally required, preferably 0.01 to 10 g of active ingredient per 1 kg of seed.

In soil treatment, a concentration of active ingredient of from 0.000 01 to 0.1% by weight, preferably from 0.000 1 to 0.02% by weight, is generally required at the point where the effect is to be achieved.

The compounds according to the invention are also suitable for the protection of technical materials.

Technical materials within the scope of the present invention are products which do not occur naturally but are made from natural or synthetic starting materials. The products to be protected within the scope of the present invention are technical materials which can be attacked by microorganisms and/or can be decomposed by microorganisms.

Technical materials to be protected by the active ingredients according to the invention against microbial change and decomposition are, for example, adhesives, glues, paper and cardboard, textiles, leather, wood, paints, cleaning agents, cooling and lubricating agents, sealants and plastic products that can be damaged or decomposed by microorganisms. The materials to be protected also include parts of production equipment, such as cooling water circuits and cooling lubricants, the required function of which can be adversely affected by microorganisms. The active ingredients according to the invention can be advantageously used to protect adhesives, paper, cardboard, films, paints, wood and more.

Microorganisms that can cause the degradation or alteration of technical materials are, for example, bacteria, fungi, yeasts, algae and other slime-like organisms. The substances according to the invention preferably have a strong and broad action against fungi and bacteria, and this fungicidal action also includes an action against mold-type fungi, such as wood-destroying fungi and wood-staining fungi.

For example, microorganisms of the following genera can be mentioned:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Aureobasidium, such as Aureobasidium pullulans,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora cerebella,

Lentinus, as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride.

Depending on the intended use, the substances according to the invention can be converted into conventional formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. These formulations can be produced in a manner known per se, for example by mixing the active ingredients with a carrier selected from the group of liquid solvents and/or solid carriers, optionally using surface-active agents such as emulsifiers and/or dispersants, and in the case of extenders, organic solvents can optionally be used as auxiliary solvents.

Organic solvents for the active ingredients can be, for example, alcohols, such as lower alcohols, preferably ethanol or isopropanol or benzyl alcohol, ketones, such as acetone or methyl ethyl ketone, liquid hydrocarbons, such as gasoline fractions, chlorinated hydrocarbons, such as 1,2-dichloroethane.

The microbicidal compositions according to the invention generally contain 10 to 100% by weight, preferably 50 to 80% by weight, of halopropargylformamides as active ingredients.

The concentration of the substances according to the invention used depends on the type and occurrence of the microorganisms to be controlled, as well as on the composition of the material to be protected. The optimum amount to be applied can be determined by a series of tests. In general, the concentrations used are in the range of 0.001 to 5% by weight, preferably 0.01 to 1% by weight, based on the material to be protected.

The new active ingredients according to the invention may also be present in a mixture with other known active ingredients. For example, the following active ingredients may be mentioned: benzimidazolyl carbamates, trihalogenomethylthioderivatives, such as N-fluorodichloromethylthiophthalimide and N,N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio)sulfamide, formaldehyde-releasing compounds, such as hemiformals, phenol derivatives, such as p-chloro-m-cresol, 2-phenylphenol, (2,2'-dihydroxy-5,5-dichloro)diphenylmethane, dithiocarbamates, thiazolylbenzimidazole, isothiazolone and benzisothiazolone derivatives, dinitrile tetrachloroisophthalic acid, mercaptobenzothiazole, mercaptopyridine.

Examples illustrating the method of producing the active ingredient:

Example!

H - C - N - CH ₂ - C = C - J g (0.2 mol) of propargylformanilide is dissolved in 600 ml of methanol and a solution of 10 g (0.25 mol) of sodium hydroxide in 30 ml of water is added at 0 to 5 °C. Then 5'1 g (0.2 mol) of iodine is added in several portions over the course of one hour at 0 °C and the reaction mixture is stirred for a further 4 hours at 0 °C. The thin-layer chromatogram now shows that the starting material has reacted completely. For work-up, the reaction mixture is stirred into a mixture of 2 liters of ice water and 10 ml of 40% sodium bisulfite solution (to decolorize iodine residues), and crystallization begins after some time. The crystalline product is filtered off with suction, washed with water and dried. The yield is 44 g (77% of theory) of beige-colored crystals of N-iodopropargyl-N-formylanilide. After recrystallization from ethanol, the product melts at 78 °C.

The starting material used in Example 1 is prepared as follows:

g (0.8 mol) of formanilide is dissolved in 400 ml of tetrahydrofuran and 90 g (0.8 mol) of potassium tert-butoxide in 400 ml of tetrahydrofuran is added to the solution. After the exothermic reaction has subsided (salt formation), the reaction mixture is concentrated to dryness on a rotary evaporator. The residue is added in portions at a temperature of 0 to 5 °C to a solution of 60 g (0.8 mol) of propargyl chloride in 500 ml of dimethylformamide, after which the mixture is slowly warmed to room temperature and stirred for another 20 hours until complete conversion is achieved according to the thin-layer chromatogram. The reaction mixture is concentrated, extracted with a mixture of methylene chloride and water, the organic phase is separated, concentrated and distilled in vacuo. The fraction boiling in the range of 105 to 120 °C/200 Pe is represented by propargyl formanilide. The yield is 96 g (75% of theory). The product can be used for the reaction with iodine without further purification.

Example 2

O

a) H - á - NH - CH ₂ - C = C - J / g (0.5 mol) of propargylformamide is dissolved in 1 liter of methanol and to this solution is added at 0 °C a solution of 25 g (0.6 mol) of sodium hydroxide in 80 ml of water and at the same temperature 130 g (0.5 mol) of iodine is added in portions. Then the reaction mixture is stirred for another 4 hours at 0 °C, after which it is stirred into a solution of 5 ml of 40% sodium bisulfite solution in 2 liters of water, extraction is carried out three times with 300 ml of methylene chloride each time, the organic phase is separated, dried with sodium sulfate and concentrated. The crude product in a yield of 45 g is chromatographed on a silica gel column using ethyl acetate as eluent. 31 g (57% of theory) of light crystals of iodopropargylformamide are obtained, which melt at 86-88°C after recrystallization from water.

Propargylformamide, used in Example 2, is prepared as follows:

b) hc-nh-ch ₂ -c = c- h

45 g (1 mol) of freshly distilled fortnamide are introduced into 600 ml of dimethylformamide and 172 g (1.25 mol) of potassium carbonate and 186 g (2.5 mol) of chloropropyne are added and the reaction mixture is heated. The exothermic reaction, which begins at about 80 to 90 °C, is maintained at 100 °C with gentle cooling and the reaction mixture is then stirred for 15 hours at 100 °C. The reaction mixture is now concentrated on a rotary evaporator and the residue is fractionated by column chromatography on silica gel using ethyl acetate as eluent. 42 g (56% of theory) of a light liquid are obtained which can be distilled at 120 to 125 °C/2000 Pa,

In a manner analogous to that described in Examples 1 and 2 above, the following halopropargylformamides of general formula 1 are obtained.

O

II

H - C - N - CH ₂ - C = C - Hal (I)

R

Example number

Hal Melting point (°C)

Yield (% theory) up to 80 ch ₃

ch ₃ h ₃ c—(o ch ₃ ch ₃ d ³ ch ₃

Cl up to 84 up to 87 up to 90 up to 90

Example number R

Cl ^C '-<A

Cl ci-(O

Cl

Cl

Cl

NO

Hal Melting point Yield (°C) (% of theory) up to 81 up to 89 32 up to 81 up to 81 33 up to 102 43

104 to 106 27 to 84

117 to 119 16

Br oil, n^°= 1.582 4 85

1

Example number K

Hall

Melting point (<°C)

Yield (% of theory)

Br 58 to 60 63

Cl

The propargylformamides of formula II, which serve as starting materials, are prepared in an analogous manner to that described in examples 1b) and 2b):

About

H-C-N-CH, -C=C-H (II)

I ·

R

Melting point (°C) Yield Boiling point (°C/Pa) (% theory) Refractive index Cjijj J <o>43 to 45 69 ch ₃

,547 0 6 9

158/1 200 58 to 54 82 from ^CH 3 (o>— to 59 32 ch ₃

_CH3,502 > ⁰ 98 ^c2H5

12'

Melting point (°C) Boiling point (°C/Pa) Refractive index

Yield (% theory) <0

1.532 8 cf ₃ (O eí 54

107 to 108/80

Cl

Cl to 46 to 53 to 74 to 73

Cl to 80 to 71 to 72

Cl

Ozzie

H Melting point (°C) boiling point (°C/Pa) «v O Λ , refractive index ίηβ j Yield (% of theory) —A 82 to 83 68 no ₂ 114 to 116 31

In the following examples, which illustrate biological efficacy, the compounds listed above are used as comparators:

CH ₂ - NH

Zinc (A)

CH ₂ - NH

C - S

II with

x Cu(OH) ₂ x CuCl ₂ x H ₂ 0 nC ₄ H ₉ -NH-CO-CH ₂ (C) (D)

Example A

Leptosphaeria nodorum (wheat) test / protective effect

Solvent: .00 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable active agent, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test the protective effect, young plants are sprayed with the active preparation until wet. After the spray layer has dried, the plants are sprayed with a suspension of Leptosphaeria nodorum conidia. The plants are left for 48 hours at a temperature of 20 °C and 100% relative humidity in an incubation chamber.

The plants are then placed in a greenhouse at a temperature of about 15°C and a relative humidity of about 80%.

days after inoculation, the test is evaluated.

In this test, the compounds according to the following embodiments, for example, show a clear superiority in effectiveness compared to the known state of the art: 5, 7, 6, 9, 12, 13,

14, 15 and 16.

The results are shown in the following Table A:

TableA

Leptosphaeria nodorum (wheat) test / protective effect

Active ingredient

Concentration of active substance in spray suspension in % by weight'

Disease incidence in % of untreated control

WITH

CH ₂ -NH-CS.

:Zn (A)

0.025 100

CHj

CH ₀ -NH-CS·' a

S (known) >C=0 (5)

0.025 12.5 :h ₂ -c=cj

Active ingredient

Concentration of active substance in spray suspension in % in % of untreated control

0.025 12.5

(6)

0.025 12.5

CF,

C=0 (9)

CH2 _- C=CJ

0.025 15.0 b-

(12)

0.025 16.3

(13)

0.025 12.5

Cl i'

Active ingredient

Concentration of active substance in spray suspension in % in % of untreated control Disease attack

04)

0.025 0.0

C=O ⁽¹⁵⁾ ' Cl ^CHj-CsC-J

0.025 18.8

Example B

Fusarium nivale (rye) test / seed treatment

The active ingredients are applied in the form of a dry dressing. The dressing is prepared by mixing the respective active ingredient with stone flour and grinding it into a fine powder mixture, which ensures uniform dispersion of the active ingredient on the surface of the seed.

For pickling, the infected seed is shaken for 3 minutes with the pickling agent in a closed glass bottle.

Rye is sown in quantities of 2 x 100 grains 1 cm deep in standard soil and grown in a greenhouse at a temperature of about 10 °C and a relative humidity of about 95% in seed boxes that are exposed to 15 hours of light per day.

Also, 3 weeks after sowing, the plants are evaluated for symptoms of snow mold.

In this test, the compounds of the following embodiments, for example, 5 and 9, show a clear superiority in efficacy compared to the prior art.

The results of this test are shown in the following Table B:

TableB

Fusarium nivale (rye) test / seed treatment

Active ingredient

Amount of active substance used in mg/kg of seed

Diseased plants as a % of total uninfected plants

16.8

With ll

(known) (A)

600

10.4

H

(5)

500

1.3

Active substance Amount of active ingredient used in mg/kg of seed Diseased plants as % of total plants grown you H \θ=θ -Z (9) 500 2.3 CV ' ^Xx 'ch ₂ -C5J

ExampleC

Test for apple scab (Venturia inaequalis) (apple tree) / protective effect

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable active agent, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

In order to test the protective efficacy, young plants are sprayed with the active preparation until the dew stage. After the spray layer has dried, the plants are inoculated with an aqueous suspension of conidia of the causative agent of apple scab (Venturia inaequalis) and left for 1 day at a temperature of 20 °C and 100% relative humidity in an incubation chamber.

The plants are then exposed in a greenhouse at a temperature of 20°C and a relative humidity of about 70%.

days after inoculation, the experiment is evaluated.

In this test, for example, the compounds of Examples 15, 13, and 17 show a clear superiority in efficacy over the prior art.

The results of this test are shown in the following Table C:

Table C

Test for apple scab (Venturia inaequalis) (apple tree) - protective effect

Active ingredient

Infestation in % at active substance concentration

0.000 5%

O

II

C0-SC ^c, 3

II about

(known) (B)

Example D

Test no Xanthomonas oryzae (bacteriosis) (rice) systemic effect

Solvent: 121.25 parts by weight of acetone

Emulsifier: 3.75 parts by weight of alkylaryl polyglycol ether

To obtain a suitable active agent, 1 part by weight of the active ingredient is mixed with the indicated amount of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

In order to test the systemic properties, the uniform soil in which the young plants are grown is watered with 100 ml of the active agent. 3 days after this treatment, the plants are inoculated with an aqueous suspension of Xanthomonas oryzae by puncture damage. The plants are then left for 14 days until evaluation in a greenhouse at a temperature of 24 to 26 °C and a relative humidity of 70 to 8056.

In this test, the compounds according to the following embodiments, for example, 1, 16, 12 and 9, show a clear superiority in efficacy compared to the prior art.

The results of this test are shown in the following Table D:

Table D

Test for Xanthomonas oryzae (bacteriosis) of rice / systemic effect

Active ingredient

Amount used Active substance in mg Disease incidence per 100 cnr in % of untreated control

Cu(OH) ₂ xCuC1 ₂ xH ₂ 0 (C) (known)

H. L

X (1) —Ni ch ₂ -c»cj

12.5

Cl

12.5

Active ingredient

Amount used Active substance, disease attack in mg not 100 crn in % of untreated control

Example E

Antifungal effect

Compounds of the invention are incorporated into an agar prepared from brewer's wort and peptone at graded concentrations between 1 and 5,000 mg/liter of test sample.

After the agar has solidified, the agar samples produced in this way are contaminated with pure cultures of experimental fungi.

After two weeks of storage at 28°C and 60 to 70% relative humidity, the experiment is evaluated. The minimum inhibitory concentration (MIC) is the lowest concentration of the substance contained in the ager sample at which no growth of the fungus of the species used occurred.

In this test, the compounds of the following embodiments, for example, show a clear superiority in efficacy compared to the prior art: 11, 12, 13, 15, 17, 18, 5, 7, 14, 3, 4, 6 and 19.

The test results are shown in the following Table E:

Table E

Compounds according to the invention of the general formula are tested

II

HC-N'-CH ₂ -C=CJ

AND

B and for comparison the known compound (D).

53 23

The experimental fungi are listed in the table under the following abbreviations:

PC = Penicillium glaucum

CHG = Chaetomium globosum

AN = Aspergillus niger

TV = Trichoderma viride

AT = Altarnia tenuis

AP = Aurebasidium pullulans

SP = Sclerophoma pityophila

LT = Lentinus tigrinus

PV = Polyporus versicolor

CC = Coniophora cerebella

Test compound

Minimum inhibitory concentration in mg/liter

PO CHG AG TV AT AP SP LT PV CC .Ct

350 50 20 7.5 5 0.5 5 2 0.1 (in ^c fe(12)

50 15 10 3.5 3.50.1 2 2 0.1

100 1 .5 10 1 1 0.1 1 2 0.1 (13) ,CI

^cl “\2/ (15)

3.5 7.5 7.5 2 2 5 1 5 1

15 5 10 1 2 0.5 1.5 1 0.1 (17)

Test compound

Minimum inhibitory concentration in mg/liter

PG CHG AG TV AT AP SP LT PV CC

Claims (3)

SUBJECT OF THE INVENTION 1. A fungicidal and microbicidal agent for the protection of plants and technical materials, characterized in that it contains at least one halopropargylformamide of the formula I as an active ingredient. II H - C - N - CH ₂ - C = C - Hal (I), AND R in which R is hydrogen or optionally one to five times, equally or differently halogen, nitro, C 1 -C 4 alkyl, C 1 -C 5 haloalkyl, C 1 -C 4 haloalkyl, and Hal means iodine or bromine. * · 2. A composition according to claim 1, wherein the active ingredient comprises at least the barley halogenpropsylformamide of formula (I) in which: R is hydrogen, optionally one to three times, equally or differently with chloro, nitro, methyl, ethyl, n- and isopropyl, trifluoromethyl substituted phenyl, and Hal means iodine or bromine, 3. A process according to claim 1, wherein the propargylformamides of the formula II are: H - C - N - GH ₂ - C = C - Η (II), R in which S is as defined in point 1, it acts with halogenating agents in the presence of bases in the diluent at temperatures between -30 to> 0 ° C. Severography, n Price 2,40 Kčs