DD249620A1 - MICROBICIDE MEDIUM - Google Patents

Abstract

The invention relates to microbicidal agents for use in plant and storage protection, in particular for the control of phytophathogenic fungi and bacteria. The aim of developing new agents with favorable properties with regard to microbicidal activity, spectrum of action, plant compatibility and warm-blood toxicity is achieved according to the invention by using ammoniocarboxylic acid alkylamide salts of general formula I as active ingredients. The microbicidal agents are particularly suitable for the protection of crop plants against soil and leaf parasites which are not to be underestimated in their economic extent. The meaning of R, R1, R2, R3, R4, X and n can be taken from the description. Formula I

Description

Field of application of the invention

The invention relates to microbicidal agents that can be used to control harmful microorganisms in crop and storage protection.

Characteristic of the known technical solutions

It is known to use a large number of quaternary ammonium compounds for controlling unwanted microorganisms, in particular fungi and bacteria (H. Horn, M. Privora and W. Weuffen, Handbook of Disinfection and Sterilization, Vol. 1-3, Berlin 1974). However, the previously known agents have no lasting and uniformly strong action. In addition, occur at higher use concentrations, as z. B. for killing phytopathogenic fungi are required to phytotoxic damage. It is also known that the agents in use with microbicidal properties, such as i.a. Fungicides from the group of oxathiin derivatives (carboxin, oxycarboxin), the benzimidazoles (benomyl) or the morpholine derivatives (tridemorph), in many cases an undesirably high selectivity to fungal harmful organisms, which can lead to the increased occurrence of other phytopathogenic pathogens. In addition, the use of such agents in some phytopathogens resistance formation, whereby the control of pathogens is greatly complicated.

It is also known that the use of such agents containing as active ingredients metal salts of Dithiocarbaminsäurederivaten, organotin compounds, N-Trichlormethylthio compounds or copper salts, is associated with a number of disadvantages, with primarily relatively high application rates, insufficient duration of action and heavy residue burden are called.

Object of the invention

The aim of the invention is to provide new microbicidal agents with good activity and broad spectrum of action with good

Plant lability η and low warm-blood toxicity on the basis of large-scale starting materials and simple synthesis processes to develop.

Explanation of the essence of the invention

The object of the invention is achieved in that the microbicidal agents in addition to the usual excipients and carriers as active ingredients contain at least one Ammonio-carboxylic acid alkylamide salt of the general formula I,

R ₁ R ~ E

R ₂ -Ii- (CH ₂ ) _n -CH-C-NH-R ₄ 3T,

R ₃ '

in which R is hydrogen or a methyl radical,

R 1, R ₂ and R ₃ , which may be the same or different,

Methyl, ethyl, allyl or benzyl radicals or the

R ₁ R ₂ R3N®-grouping pyridinium,

R _{4 is} a straight-chain or branched alkyl radical having at least 6 to 24 carbon atoms, Χ ^{θ is} a chloride, bromide or methosulfate anion and

mean.

Surprisingly, it has been found that the ammonium-carboxylic acid-N-alkylamide salts of the general formula I according to the invention have excellent microbicidal properties and are particularly suitable for controlling phytopathogenic fungi and bacteria. They have a microbicidal spectrum of activity which is very favorable for practical purposes, in order to protect crops and vegetable stocks. The agents are not phytotoxic because their microbicidal activity is sufficient in plant compatible concentrations.

A particularly preferred embodiment of the microbicidal agents contains as active ingredients trimethylammonio-acetic acid, dodecyl, tetradecyl, hexadecyl or octadecylamidchlorid according to the formula

(H ₃ C) ₃ N 1 CH ₂ -CO-NH-C ₁₀ H ₂₁ ZC ₁₂ H ₂₆ ZC ₁₄ H ₂₉ ZC ₁₆ H ₃₃ ZC ₁₈ H ₃₇ Ci ' ³ .

As the alkylamide derivatives of the natural product betaine, the active compounds according to the invention have a low toxicity to warm-blooded animals

The agents according to the invention can be used to combat fungi which occur on plants or parts of plants (flowers, fruits, seeds, foliage, stems, tubers, roots). The salts of the general formula I are also suitable as mordants for the treatment of seed and plant cuttings for protection against fungal infections and can be used against occurring in the soil phytopathogenic fungi.

The compositions according to the invention are suitable for controlling phytopathogenic fungi which are not to be underestimated in their economic extent, for example Erysiphe, Botrytis, Phytophthora, Pythium, Fusarium, Mucor and Alternaria species. The active ingredients, with their broad microbicidal spectrum of activity, also have different bactericidal activity, which at the same time achieves a suppression of the growth of bacterial species.

Another noteworthy advantage of the active compounds according to the invention lies in their favorable toxicological properties.

There are no detrimental backbones, as some of the active ingredients are present as natural compounds in plants.

Furthermore, the good water solubility of the active ingredients enables simple forms of application of the agents. The compositions according to the invention are absorbed well by plants or parts of plants and in some cases have a systemic effect.

The preparation of the novel ammonio-carboxylic acid alkylamide salts of the general formula I can be carried out in a simple manner by known synthesis principles by tertiary amines in which R ₁ , R ₂ and R _{3 have} the meaning given in the general formula I, with halogen-substituted carboxylic acid derivatives such as chloroacetic acid chloride, Chloressigsäuremethyl- or ethyl, / 3-bromopropionate and .beta.-bromo propionsäu computationally dichloride reacted and the thus obtained quaternary salts with primary amines, wherein the alkyl group is as defined in the general formula I for R ₄ has to be reacted. It is also possible to obtain by other manufacturing processes to the specified under the general formula I drugs.

The anions X® listed in the general formula I of the ammonium-carboxylic acid alkylamide salts are not decisive for the microbicidal action.

The microbicidal compositions according to the invention are prepared by mixing or grinding active compounds of the general formula I with suitable carriers, if appropriate with the addition of inert dispersants or solvents.

Thus, formulations such as solutions, aerosols, wettable powders, pastes, emulsions, dusts, scattering agents, granules, microcapsules, etc., can be prepared in a known manner. The formulations may contain additives such as surface active compounds, adhesives and adhesives and dispersants.

The formulations of the agents according to the invention generally contain between 0.1 and 95% by weight of the active ingredients, preferably between 5 and 90%.

The active compounds according to the invention can be used in the form of their formulations or the use forms prepared therefrom by further dilution. The application is carried out in a known manner, for example by pouring, spraying, spraying or spreading. The application rates depend on the specific application and are generally between 0.2 and 2 kg of active ingredient per hectare.

The examples which follow are intended to further illustrate the invention and to demonstrate the microbicidal action of the active ingredients used according to the invention for the purposes of the present invention.

embodiments

example 1

The preparation of the active substances of the microbicidal agents according to the invention will be explained in more detail in the following example:

N-Alni-N, N-dimethyl-ammonio-acetic acid-tetradecylamide chloride (H ₂ C = CH-CH ₂ -N® (CH ₃ ) ₂ -CH ₂ -CONH-C ₁₄ H ₂₉ Cl ^e ) 850g (10 Mol) allyldimethylamine, prepared according to DD-WP 136497, are initially charged in a reaction vessel. 1 085g (10 mol) of methyl chloroacetate is added dropwise thereto. During the dropwise addition the temperature rises slowly and is maintained by occasional cooling between 60 and 7O ⁰ C. The resulting N-AHyl- ^ N-dimethyl-ammonioessigsäuremethylesterchlorid is clearly transparent and viscous after quantitative conversion, which is achieved after about 30 min. The reaction product

is added by dropwise addition with 2133g (10 mol) of liquefied tetradecylamine, such that the exothermic reaction of amide formation can be maintained at a reaction temperature of 70 to 80 ⁰ C. After about 30 minutes, the reaction is complete, and the product is obtained in quantitative yield of pH 7

 In an analogous procedure, the other active ingredients of the microbicidal agents according to the invention are also accessible.

Example 2

Torulopsis candida test

The active ingredients are allowed to act in culture tubes on Torulopsis Candida. Growth is determined by absorbance measurements in the coarsely disperse system in a photometer.

The tubes are filled with a certain amount of yeast suspension, which has grown after 15h Vorkultivierungszeit in MILLER medium. The initial dry weight of this suspension is 0.05 mg / ml. Thereafter, the active ingredients dissolved in ethanol (final ethanol concentration 1%) are added.

After 5 hours, the growth measurement takes place in the photometer. Using a calibration curve, the yeast dry matter values corresponding to the extinction values are determined and the percentage growth inhibition determined therefrom. From the testing of a concentration series, the ED ₅₀ values are determined (Table A).

Example 3

Pectobacterium carotovorum test

The active ingredients are allowed to act in culture tubes on Pectobacterium carotovorum. The growth of the bacteria is determined by absorbance measurements in the coarsely disperse system in a photometer.

The tubes are filled with a certain amount of bacterial suspension, which has grown after 15h Vorkultivierungszeit in glucose broth at 22 ° C. The initial dry weight of this suspension is 0.22 mg / ml. Thereafter, the active ingredients dissolved in ethanol are added (final ethanol concentration 1%). After 5 hours, the bacterial growth in the MAYER medium is measured by means of a photometer. By means of a calibration curve, the bacterial dry substance values corresponding to the extinction values are determined. The evaluation is carried out by calculating the percentage growth inhibition for the respective active substances and the ED ₅₀ values (Table B).

Example 4

Agar plate test with mushroom species of different taxonomic position

The fungicidal activity of the agents against the test fungi Phytophthora cactorum, Botrytis cinerea, Fusarium oxysporum, Alternaria solani, Mucor mucedo and Trichophyton mentagro.phytes is conventionally inhibited as radial inhibition of the fungi on malt agar nutritive medium (2% malt) in Petri dishes Incubation temperature of 25 ⁰ C determined by the active ingredients after dissolving in dimethylformamide and diluting with water are added to the liquid Ag ar so that the desired drug concentration in the medium is achieved. The DMF content does not exceed 0.5%. The measurements are made when the controls without any additional agent have grown through to 70 to 90% of the shell diameter. The evaluation is carried out by calculating the percentage growth inhibition of the respective agents compared to the controls without added funds and determination of the ED ₅₀ values (Table C).

Example 5

Test against Phytophthora infestans on tomato leaf disks

The active ingredients are dissolved in a little DMF and distilled with dist. Water to the desired concentration in the gradation 100,50,10, 1 ju.g / ml set.

To perform the test, leaf disks are punched out of adult leaves of tomato plants.

The zoospore suspension needed for the infection is produced by flushing fungal turf from tuber halves of susceptible potato varieties.

The treatment with the active ingredients and the infection are carried out simultaneously by adding certain active substance concentrations to the zoospore suspension of Phytophthora infestans and, after shaking, pouring these mixtures onto the leaf disks laid out in petri dishes. After 2 hours, the supernatant liquid is poured off. The dishes are stored at 15 to 20 ⁰ C under exposure. After 3 to 4 days, the evaluation is carried out by determining the proportion of necrotic leaf area per leaf disc. From the testing of a concentration series, the infection inhibition is determined as ED ₅₀ and ED ₉₀ value (Table D).

Examples

Test against Erysiphe graminis on barley leaf pieces

4 cm long leaf pieces of spring barley (variety "Astacus") are shaken with a conidia suspension of the fungus for 2 h in water at 2O ⁰ C with the addition of the active ingredients, and then incubated for 7 days in moist chambers under light exposure.

To assess the effect of the reduction in the number of pustules over the controls without adding funds. The

Evaluation is carried out by determining the ED ₅₀ values (Table E).

Example 7

In vivo test against Phytophtora infestans on tomato plants

The active ingredients formulated in a conventional manner as wettable powders are sprayed onto the leaves of tomato plants ("Harzfeuer" variety) in the 2-4-leaf stage in a graduated concentration of the spray mixture After the spray coating has dried on, the infection is carried out with a zoospore suspension of Phytophthora infestans for 1 day in a moist chamber at 17 to 19 ^c Cunddanach6 days under good growth conditions, after which the infestation is determined (Table F), using the following rating scheme as the benchmark for the effectiveness of the means:

1 = 75 to 100% infestation

2 = 25 to 75% infestation.

3 = 5 to 25% infestation

4 = 0 to 5% infestation.

Table A: Growth Inhibition of Yeasts (Torulopsis Candida)

ED ₅₀ -WeH (^ g / ml)

Trimethyl-ammonio-acetic acid

tetradecylamide chloride 8

N-AlII-N, N-dimethyl-ammonio-acetic acid tetradecylamide chloride 30

N-Allyl-N, N-dimethyl-ammonio-acetic acid (hexadecyl / octadecyl) -amide-chloride 80

3- (N-Al IyI-N, N-dimethy! -Monomonopropionic acid dodecylamide chloride 80

2- (N-Allyl-N, N-dimethyl-ammonio) -propionic acid-tetradecylamide bromide 78

Ν, Ν-Diallyl-N-methyl-ammonio-acetic acid hexadecylamide chloride 44

Table 8: Growth inhibition of bacteria (Pectobacterium carotovorum)

ED ₅₀ -WeH (/ μg / ml)

Trimethyl-ammonio-acetic acid *

tetradecylamide chloride 120

N-Allyl-N, -dimethyl-ammonio-acetic acid tetradecylamide chloride 100

N-Allyl-N, N-dimethyl-ammonio-acetic acid hexadecylamide chloride 90

3- (N-Al IyI-N, N-dimethyl-ammonio o) -propionic acid dodecylamide 75

Triallyl-ammonio-acetic acid tetradecylamide chloride 80

Table C: Growth inhibition of fungi in agar plate assay

ED ₅₀ value (Mg / ml)

Trimethyl-ammonio-phytophtoracactorum

acetic acid tetradecylamid-

chloride

N-allyl-N, N-dimethyl

ammonio-acetic acid hexa

decylamid chloride

3- (N-AIIy-N, N-dimethyl-

ammonioj-propionic acid

dodecylamide chloride

2- (N-allyl-N, N-dimethyl-

ammonio) -propionic acid

tetradecylamid bromide

Pyridinio-acetic acid

(Dodecyl / tetradecyl) -

amide bromide

N-benzyl-N, N-dimethyl-

ammonio-acetic acid

(Dodecyl / tetradecyl) -

amide chloride

For comparison with commercial preparations:

benomyl

Oxycarboxine.

Zineb Phytophthoracactorum

Phytophthora cactorum 8th Trichophyton mentogr. 34 Phytophthora cactorum 10 Botrytis cinerea 9 Alternaria solani 65 Trichophyton mentogr. 40 Phytophthora cactorum 45 Trichophyton mentogr. 73 Phytophthora cactorum 47 Botrytis cinerea 44 Mucormucedo 40 Phytophthora cactorum 52 Botrytis cinerea 92 Mucormucedo 60 iaraten: Phytophtora cactorum 40 Botrytis cinerea 0.4 Mucormucedo 100 Phytophthora cactorum 50 Botrytis cinerea 100 Mucormucedo 100

Table D: Inhibition of infection of Phytophthora infestans on tomato leaf discs

Trimethyl-ammonio-acetic acid

tetradecylamid chloride

N-allyl-N, N-dimethyl-ammonio

acetic acid chloride tetradecylamid

3- (N-Ally-N, N-dimethyl-ammonio) -

propionic acid chloride dodecylamide

2- (N-allyl-N, N-dimethyl ammonio) -

Propionic acid tetradecylamide bromide Pyridinioacetic acid (dodecyl / tetradecyl amide bromide

N-benzyl-N ^ dimethyl-ammonio

acetic acid (docecyl / tetradecyl) -

amide chloride

ED ₅₀ -WeH (/ xg / ml) ED ₉₀ -WeH (, μg / ml) 1.5 4 2.0 13 1.5 4 4 15 4

Table E: Action against Erysiphe graminis on barley leaf pieces

ED ₅₀ -WeH (^ g / ml)

Trimethyl-ammonio-acetic acid

tetradecylamide chloride 1

Triethyl-ammonio-acetic acid

tetradecylamide chloride 0.5

N-allyl-N, N-dimethyl-ammonio-acetic acid

tetradecylamide chloride 0.2

N-Al IyI-N, N-dimethyl-onmonio-acetic acid -

hexadecylamide chloride 0.04

2- (N-Allyl-N, N-dimethyl-ammonio) -propion-

acid tetradecylamide bromide 0.02

Ν, Ν-diallyl-N-methyl-ammonio-acetic acid

hexadecylamide chloride, 2

Pyridinio-acetic acid (dodecyl / tetradecyl) -

amide bromide 2

N-benzyl-N ^ dimethyl-ammonio-acetic acid

(dodecyl / tetradecyl) amide chloride 2

For comparison with commercial preparations:

Tridemorph 0.02

Trimorphamide 0.5

Table F: Action against Phytophthora infestans on tomatoes

drug effectiveness concentration (note taking (^ G / ml) grades) Untreated control 1 Trimethyl-ammonio-acetic acid 1000 4 tetradecylamid chloride 200 4 50 2 N-AlIyI-N, N-dimethylamino on the mono- 1000 4 Essigsäu re-N-tetradecy la mid- 200 3 chloride 50 2 For comparison with the commercial Preparation: Zineb 1000 4 200 3 50 2

Claims (2)

1. Microbicidal agents, characterized in that they contain, in addition to the customary auxiliaries and excipients as active ingredients, at least one ammonium-carboxylic acid alkylamide salt of the general formula I, R ₁ RO ¹ - © in R ₂ -H- (0H ₂ ) _n -OH-0-HH-R ₄ X. in the R is hydrogen or a methyl radical, R ₁ , R ₂ and R ₃ , which may be the same or different, are methyl, ethyl, allyl or benzyl or the R- | R ₂ R ₃ N® pyridinium moiety R _{4 is} a straight-chain or branched alkyl radical having at least 6 to 24 carbon atoms, Χ ^{θ is} a chloride, bromide or methosulfate anion and, η 0 and 1
mean,
contain. 2. Microbicidal agent according to item 1, characterized in that they contain as active ingredients trimethylammonio-acetic acid (C ₁₀ - to C ₁₈ -alkyl) -amide chloride.