CS235323B2 - Fungicide and microbicidal agent for protection of plants and technical materials and method of efficient substance production - Google Patents

Abstract

A fungicidal and microbicidal agent to protect plants and technical materials, characterized as being effective the component comprises at least one halopropargylformamide of formula (I) O II H - C - N - CIL · - C = C - Hel (I) AND R in which R represents a hydrogen atom or, respectively, a hydrogen atom / one to five times, equally or differently halogen, nitro, alkyl C 1 -C 4, helogenalkyl with 1 to 5 halogen atoms having from 1 to 4 atoms carbon substituted with phenyl, and Hal represents iodine or bromine.

Description

The present invention relates to a fungicidal and microbicidal plant protection agent and technical materials which contain novel halopropargylformamides as active ingredient.

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

Heavy metal salts of ethylene-1,2-bis-dithiocarbamic acid, especially zinc ethylene-1,2-bis-di-thiocarbamate, have been known for a long time in the agricultural and horticultural field to combat phytopathogenic fungi (cf. R. Wegler, Chemie der Pflanzenschutz- und Schadlingsbekampfungsmittel, Volume 2, page 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. Thus, for example, N- (trichloromethylthio) tetrahydrophthalimide is used in fruit tree and grapevine cultivation to combat fungal diseases (cf. German Patent 887,506 and Angew. Chem. 16, 807 (1964)).

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

In addition, iodopropargyl compounds, such as K-butyl iodopropargylcarbamate, are known as spreading fungicides (cf. DE-OS 3 116 653).

We have now found novel halopropargylformamides of the formula I

O

II

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

H in which

H is hydrogen or optionally one to five times, equally or differently halogen, nitro, C 1 -C 4 alkyl, C 1 -C 5 haloalkyl and C 1 -C 4 haloalkyl,

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

SUMMARY OF THE INVENTION The present invention provides a fungicidal and microbicidal agent for the protection of plants and technical materials, characterized in that it contains at least one halopropargylformemide of the formula I as defined above as an active ingredient.

According to the invention, the novel helogenpropargylformamides of the formula I are obtained by reacting the propargylformamides of the formula II

O

II

H-C-N-CHg-Cg C-H

AND

R (II) wherein

R is as defined above, with halogenating agents in the presence of bases in the diluent at a temperature between -30 and 50 ° C.

The novel halopropargylformamides of the formula I have potent fungidic and bactericidal properties in plant protection. Surprisingly, they have a greater effect than the known compounds.

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

Particularly particularly preferred are compounds of formula (I) wherein R is hydrogen, optionally one to three times, equally or differently nitro, methyl, ethyl, n- and isopropyl, trifluoromethyl substituted with phenyl, and

Hal means iodine and bromine.

For example, the following halogenated propargylformamides may be mentioned individually in addition to the compounds exemplified in the examples: bromopropargylformamide, iodopropargylformanilide,

2-chloroiodopropargylformanilide, 3-chloroiodopropargylformanilide, 4-chloroiodopropargylformanilide 2,3-dichloroiodopropargylformanilide, 2,4-dichloroiodopropargylformanilide, 3,4-dichloroiodopropargylformanilide, 2,4-dichloro odproparloride -metyljodpropargylformanilid 3-metyljodpropargylformanilid 4-metyljodpropargylformanilid, 2,3-dimetyljodpropargylformanilid, 2,6-aimetyljodpropargylformanilid, 2-methyl-6-etyljodpropargylformanilid 3 trifluormetyljodpropargylformanilid-3,5-bis-trifluormetyljodpropargylformanilid 3-nitrojodpropargylformanilid, brompropargylformanilid,

3-chlorobromopropargylformanilide.

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

II NaOH

_HC-NH-CH2-H -CeC j + ₂ ->.

-NaJ

II

HC-NH-CH ₂ -C? C-J

The propargylformamides used as starting materials in the process of the invention are defined by formula II. These compounds are for the most part known or can be prepared by known methods, for example by reacting the corresponding formamide with, for example, potassium tert-butoxide to form the potassium salt of formamide and then reacting with the propargyl halide. However, a primary amine may also be used to react with the propergyl halide in the presence of a base, and the resulting propargylamine is then formulated with formic acid or formic acid ester (cf., for example, Bull. Soc. Chim. Fr. 1967 (2), pp. 588-596). .

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 preferred to use organic solvents which have some ability to dissolve the reactants. Preferably, solvents that contain hydroxyl groups, such as alcohols, are used. Suitable alcohols are, in particular, lower aliphatic alcohols, such as methanol, ethanol, isopropanol, but also di- and polyhydroxy compounds, such as ethylene glycol and polyethylene glycol. Particular preference is given to working in methanol and water.

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

Possible halogenating agents are elemental halogenates and halogenates. Halogens are formed by adding halogen to the above alkaline solutions, but may also be prepared from the halogen before the halogenation reaction and the alkali (b) may then be added to the halogenated substance. In particular, iodine and bromine can be mentioned,

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

The process according to the invention can be carried out, for example, as follows:

The propargylformamide of the formula II is introduced in one of the abovementioned diluents and a molar to three times the molar amount of alkali, preferably 1.5 times the molar amount, are added. Thereafter, at least molar amounts of halogenating agent are added in portions (excess of this reagent does not provide any benefit) and the reaction mixture is further stirred at temperatures from 0 to 20 ° C. The reaction was monitored by thin layer chromatography. Treatment of the reaction mixture after completion of the reaction is carried out by conventional methods, for example by precipitation of the reaction product with water or by extraction.

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

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

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

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

The good tolerability of the active substances by plants at the concentrations necessary to combat fungal diseases makes it possible to treat the above-ground parts of plants, seedlings and seeds, as well as the soil.

As plant protection agents, the active compounds according to the invention can be used with a particularly good result in combating Leptosphaeria nodorum and Fusarium nivale in cereals, against Venturia in apples and against Xanthomonas oryzae in rice. In addition, the broad fungicidal effect of the non-agar plate test should be mentioned. At the appropriate dose, the compounds also have acaricidal effects.

The active substances can be converted into the customary formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granulates, aerosols, natural and synthetic substances impregnated with the active substance, small particles coated with polymeric substances and seed coatings, as well as flammable additives such as smoke cartridges, smoke jars, smoke spirals and others, as well as means for application by the so-called ULV process and means applied in the form of a warm mist.

These compositions are prepared in a known manner, for example by mixing the active ingredient with fillers, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. reagents. If water is used as a filler, it is also possible to use, for example, organic solvents as co-solvents. Basically suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexanone or paraffins, for example 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 dimethylsulfoxide, and water. By liquefied gaseous fillers or carriers is meant those liquids which are gaseous at normal temperature and pressure, for example aerolar propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

Suitable solid carriers are, for example, natural stone meal, such as kaolins, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic stone meal, such as highly disperse silica, alumina and silicates. Suitable solid carriers for the preparation of granulates are crushed and fractionated natural stone materials such as limestone, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells , corn sticks and tobacco stalks.

Suitable emulsifiers and / or foaming agents are, for example, non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g.

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

In addition, these compositions may contain coloring agents such as inorganic pigments, for example iron oxide, titanium dioxide and ferrocyanide blue, and organic dyes such as alizarin dyes, azo dyes and metallic phthaloxyanine dyes, as well as trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The 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 compounds according to the invention may be present in concentrated formulations or in various forms of administration in admixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, avian protective agents, growth agents, plant nutrients and means for improving soil structure.

The active compounds may be administered as such, in the form of concentrates or dosage forms which have been prepared by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. Application is carried out in a conventional manner, for example by watering, dipping, spraying, fogging, evaporating, injection, suspension, coating, dusting, sprinkling, dry pickling, wet pickling, wet pickling, suspension pickling or incrustation.

In the treatment of plant parts, the concentrations of the active ingredient in the dosage forms can vary widely. They are generally between 1 and 0.000 1% by weight, preferably between 0.5 and 0.001% by weight.

In the treatment of seed, generally 0.001 to 50 g of active ingredient per kg of seed, preferably 0.01 to 10 g of active ingredient per kg of seed, is required.

In soil treatment, a concentration of active compound of from 0.00001 to 0.1% by weight, preferably from 0.0001 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.

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

Technical materials to be protected by the active compounds according to the invention from microbial alteration and decomposition are, for example, adhesives, glues, papers and cartons, textiles, leather, wood, paints, cleaning agents, cooling and lubricating agents, sealants and plastic products masses that can be dropped or decomposed by microorganisms. The materials to be protected may also include parts of production facilities, such as cooling water circuits and cooling lubricants, the desired function of which may be adversely affected by microorganisms. The active compounds according to the invention can advantageously be used for the protection of adhesives, paper, cardboard, films, paints, wood and longer.

Microorganisms that can cause degradation or alteration of technical materials are for example bacteria, fungi, yeasts, algae and other mucilaginous 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 fungal-like fungi such as wood-destroying fungi and wood-coloring fungi.

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

Alternaria such as Alternaria tenuis,

Aspergillus like Aspergillus niger,

Aureobasidium, such as Aureobasidium pullulans,

Chaetomium, like Chaetomium globosum,

Coniophora, like Coniophora cerebella,

Lentinus, like Lentinus tigrinus,

Penicillium, like Penicillium glaucum,

Polyporus, like Polyporus versicolor,

Sclerophoma, like Sclerophoma pityophila,

Trichoderma such as Trichoderma viride.

Depending on the purpose of use, the substances according to the invention can be converted into the customary formulations such as solutions, emulsions, suspensions, powders, pastes and granules. These compositions can be prepared in a manner known per se, for example by mixing the active compounds 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, they may optionally use organic solvents as co-solvents.

Organic solvents for the active compounds 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 ingredient.

The concentration of the substances to be used depends on the type and prevalence 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 novel active compounds according to the invention may also be present in admixture with other known active compounds, for example the following active compounds; benzimidazolylcarbamates, trihalomethylthioderivatives such as N-fluorodichloromethylthiophthalimide and N, N-dimethyl-N'-phenyl-N '- (fluorodichloromethylthio) sulfamide, formaldehyde cleaving compounds such as hemiformals, phenol derivatives such as p-chloro-m-cresol, 2 -phenylphenol, (2,2'-dihydroxy-5,5-dihloro) diphenylmethane, dithiocarbamates, thiazolylbenzimidazole, isothiazolone and benzisothiazolone derivatives, tetrachloroisophthalic acid dinitrile, mercaptobenzothiazole, mercaptopyridine.

Examples illustrating the method of manufacture of 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 0 to 5 ° C is added. 30 ml water. At 0 DEG C., 5.1 g (0.2 mol) of iodine was added in several portions over one hour, and the reaction mixture was further stirred at 0 DEG C. for 4 hours. Now the thin layer chromatogram shows that the starting material has completely reacted. For working-up, the reaction mixture is stirred into a mixture of 2 liters of ice water and 10 ml of a 40% sodium bisulfite solution (to decolorize the iodine residues), after which time crystallization begins. The crystalline product is filtered off with suction, washed with water and dried. Yield: 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 was 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 are added. After the exothermic reaction (salt formation) has subsided, the reaction mixture is concentrated to dryness on a rotary evaporator. The residue is added in portions at 0 to 5 ° C to a solution of 60 g (0.8 mol) of propargyl chloride in 500 ml of dimethylformamide, then the mixture is slowly warmed to room temperature and stirred for 20 hours until a thin layer chromatogram is obtained. to complete conversion. The reaction mixture is concentrated, extracted with methylene chloride / water, the organic phase is separated, concentrated and distilled under vacuum. The fraction boiling in the range of 105 to 120 ° C / 200 Pe is represented by propargylformanilide. Yield: 96 g (75% of theory). The product can be used for reaction with iodine without further purification.

Example 2

O

(a) H - α - NH - CH ₂ - C = C - J / g (0,5 mol) of propargylformamide is dissolved in 1 liter of methanol and a solution of 25 g (0,6 mol) is added at 0 ° C. of sodium hydroxide in 80 ml of water and at the same temperature 130 g (0.5 mol) of iodine are added portionwise. The reaction mixture is stirred for a further 4 hours at 0 DEG C. and then stirred in a solution of 5 ml of a 40% sodium bisulphite solution in 2 liters of water, extracted three times with 300 ml of methylene chloride each time, the organic phase is separated. and thicken. The crude product (45 g) was chromatographed on a silica gel column using ethyl acetate as the eluent. 31 g (57% of theory) of light crystals of iodopropargylformamide are obtained, which, after recrystallization from water, melt at 86-88 ° C.

The propargylformamide used in Example 2 was prepared as follows:

b) hc-nh-ch ₂ -c = c-h

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

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

O

II

H - C - N - CH ₂ - C = C - Hal (I)

R

Example number

Hal Melting point (° C)

Yield (% of theory) up to 80 ch ₃

ch ₃ h ₃ c— (o ch ₃ ch ₃ d ³ ch ₃

C1 to 84 to 87 to 90 to 90

Example number R

Cl ^C '- < A

Cl ci- (O

Cl

Cl

Cl

NO

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

104 to 106 27 to 84

117 to 119 16

Br oil, n [deg.] = 1.582 4,885

1

Example number K

Hal

Melting point <° C)

Yield (% of theory)

Br 58-60 63

Cl

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

O u

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

I ·

R

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

, 548 0 6 9

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

CH ₃ , 502> 0 98 ^c 2 ^H 5

12 '

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

Yield (% of theory) <0

1.532 8 cf ₃ (O ei 54

107 to 108/80

Cl

C1 to 46 to 53 to 74 to 73

Cl to 80 to 71 to 72

Cl

Ozci

H Melting point (° C) Boiling point (° C / Pa) «In O Λ, refractive index ίηβ j Yield (% of theory) -AND 82 to 83 68 no ₂ 114 to 116 31

In the following examples, which illustrate biological activity, the following compounds are used as comparative agents:

CH ₂ - NH

Zn (A)

CH ₂ - NH

C - S

II p

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

Example A

Test for Leptosphaeria nodorum (wheat) / protective effect

Solvent: .00 parts by weight. dimethylformamide

Emulsifier: 0.25 parts by weight. of an alkylaryl polyglycol ether

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

In order to test the protective effect, young plants are sprayed until moistened with the active preparation. After the spray layer has dried, the plants are sprayed with Leptosphaeria nodorum conidia suspension. The plants are kept for 48 hours at 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 air humidity of about 80%.

days after inoculation, the test is evaluated.

In this test, for example, the compounds of the following examples show a clear superiority in efficacy over the prior art: 5, 7, 6, 9, 12, 13,

14, 15 and 16.

The results are shown in Table A below:

TableA

Test for Leptosphaeria nodorum (wheat) / protective effect

Active substance

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

Disease attack in% of untreated control

WITH

CH ₂ -NH-CS.

: Zn

0,025 100

CHj

CH ₀ -NH-CS · a

S (Known)> C = 0 (5)

0.025 12.5: h ₂ -c = cj

Active substance

Concentration effective Infestation of the substance in the spray disease suspension in% in% of untreated control

0.025 12.5

(6)

0.025 12.5

CF,

C = 0

CH ₂ -C =CJ

0.025 15.0 b-

(12)

0.025 16.3

(13)

0.025 12.5

Cl i '

Active substance

Concentration of effective Infestation of the substance in the spray disease suspension in% in% of the untreated control

04)

0.025 0.0

C = O ⁽¹⁵⁾ Cl-CH2-CsC-J

0.025 18.8

Example Β

Fusarium nivale (rye) test / seed treatment

The active substances are applied in the form of dry mordant. The dressing agent is prepared by mixing the active ingredient with stone flour and grinding to a finely powdered mixture which ensures uniform distribution of the active ingredient on the seed surface.

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

The rye is sown at a rate of 2 x 100 grains 1 cm deep into the standard soil and grown in a greenhouse at a temperature of about 10 ° C and at a relative air humidity of about 95% in seeding boxes exposed daily to light for 15 hours.

Even for 3 weeks after sowing, plants are evaluated for signs of snow mold.

In this test, for example, the compounds of the following Examples show a clear superiority in efficacy over the prior art: 5 and 9.

The results of this test are shown in Table B below:

TableB

Fusarium nivale (rye) test / seed treatment

Active substance

Amount of active substance used in mg / kg of seed

Diseased plants in% of total emerging plants not infested

16.8

S ll

(known) (A)

600

10.4

H

(5)

500

1.3

Active substance Amount of active substance used in mg / kg of seed Diseased plants in% of total plants fy 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. acetone

Emulsifier: 0.3 parts by weight. alkylaryl polyglycol ether

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

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

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

days after inoculation, evaluation of the experiment is performed.

In this test, for example, the compounds of Examples 15, 3 and 17 show a clear superiority over the state of the art.

The results of this test are shown in Table C below:

Table C

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

Active substance

Infestation in% at active compound concentration

0.000 5%

O

II

C0-SC ^c

II o

(known) (B)

Example D

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

Solvent: 121.25 parts by weight. acetone

Emulsifier: 3.75 parts by weight. alkylaryl polyglycol ether

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

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

In this test, for example, the compounds according to the following Examples show a clear superiority in activity compared to the state of the art: 1, 16, 12 and 9.

The results of this test are shown in Table D below:

Table D

Test for Xanthomonas oryzae (bacteriosis) rice / systemic effect

Active substance

Amount used Infestation of the active compound in mg disease per 100 cnr in% of the untreated control

Cu (OH) ₂ xH ₂ xCuC1 ₂ 0 (C) (prior art)

Η. Λ

X (1) —Ni-ch ₂ -cj

12.5

Cl

12.5

Active substance

Amount used Disease of the active substance by disease in mg not 100 crn in% of untreated control

Example E

Action against fungi

Agar prepared from brew wort and peptone is treated with compounds of the invention in graduated concentrations between 1 and 5000 mg / liter of test sample.

After the agar has solidified, the agar samples thus produced are contaminated with pure cultures of the test fungi.

After storage for two weeks at 28 ° C and 60-70% 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 fungal growth of the species used occurred.

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

The test results are shown in Table E below:

Table E

The compounds of 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 trial fungi are listed in the table under the following abbreviations:

PC = Penicillium glaucum

CHG = Chaetomium globosum

AN = Aspergillus niger

TV = Trichodarma 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