DD161129A1 - MICROBICIDE MEDIUM - Google Patents

Abstract

The invention relates to microbicidal agents which can be used in crop and storage protection. As active ingredient they contain enol acylates of alk-2-en-1-alene, preferably 1-acetoxy-2-ethyl-hexa-1,3-diene, alone or in combination with 2-ethylhex-2-en-1-al. The weight ratio between the enolacylates and the aldehyde can be 1: 1 to 1:10.

Description

-2- 231 114

Dimethylformamide dissolved active ingredient added (dimethylformamide final concentration: 1%). After 3 hours, the growth measurement takes place in the photometer. Using a calibration curve, the mushroom 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 substance.

Table I: Mocor mucedo test

Growth inhibition in% concentration 5 x 10 ^-4 mol / l

2-ethylhex-2-enal (known) 49

1-acetoxy-hexa-1,3-diene - 51

1-acetoxy-2-ethyl-hexa-1,3-diene 86

1-acetoxy-2-ethylbuta-1,3-diene 88

1-acetoxy-2-methyl-penta-1,3-diene 46

1-Benzoxy-2-ethyl-hexa-1,3-diene '84

1-propionoxy-2-ethyl-hexa-1,3-diene 61 1-acetoxy-2-ethyl-hexa-1,3-diene +

2-ethylhex-2-enal (1: 1). :. 91

Example 2:

Fusarium oxysporum test

The active ingredients are allowed to act in culture tubes on Fusarium oxysporum. The growth of the fungi is determined by absorbance measurements in the coarsely disperse system in a photometer. The tubes are filled with a certain amount of germ cell produced by spore-leaching with SISLER medium and a pre-culturing time of 15 hours at 17 ° C. The initial dry weight of this suspension is 0.18 mg / ml. Then the active ingredient dissolved in dimethylformamide is added (final dimethylformamide concentration: 1%). After 5 hours, the growth inhibition takes place in the photometer. Using a calibration curve, the mushroom 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 substance.

Table: Fusarium oxysporum - test

Growth inhibition in% concentration 5 x 10 " ⁴ mol / l

2-ethyl-hex-2-enal (known) 95 -

i-acetoxy-hexa-1S-diene 49

1-acetoxy-2-ethyl-hexa-1,3-diene 91

1-acetoxy-2-ethylbuta-1,3-diene 60

1-acetoxy-2-methyl-penta-1,3-diene 61

1-Benzoxy-2-ethyl-hexa-1,3-diene 49

1-propionoxy-2-ethyl-hexa-1,3-diene 58

Example 3: Botrytis cinerea test

The active ingredients are allowed to act in culture tubes on Botrytis cinerea. The growth of the fungi is determined by absorbance measurements in the coarsely disperse system in a photometer. The tubes are filled with a certain amount of seed zygula obtained by spore-leaching with SISLER medium and a pre-cultivation time of 6 hours at 22 to 24 ° C and 15 hours at 7 ° C. The initial dry weight of this suspension is 0.25 mg / ml. Then, the drug dissolved in dimethylformamide is added (final dimethylformamide concentration: 1%). After 6 hours, growth inhibition occurs in the photometer. Using a calibration curve, the mushroom 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 substance.

Table III: Botrytis cinerea test

Growth inhibition in% Concentration 5 χ 10 ^-4 mol / l

2-ethylhex-2-enal (known) 48

1-acetoxy-hexa-1,3-diene 29

1-acetoxy-2-ethyl-hexa-1,3-diene 88

i-acetoxy-ethyl-buta-1-diene ^ 86

1-Acetoxy-2-methyl-pehta-1,3-diene 51 l-benzoyl-2-ethyl-hexa-1,3-diene '81

l-Propionoxy-2-ethyl-hexa-1,3-diene 26 l -acetoxy-2-ethyl-hexa-1,3-diene +

> -Ethylhex-2-enal (1: 1) 72

-3- £ 6Λ 114s

Example 4:

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 15 hours precultivation in glucose broth at 22 ° C. The initial dry weight of this suspension is 0.04 mg / ml. Then, the drug dissolved in dimethylformamide is added (final dimethylformamide concentration: 1%). After 6 hours, the bacterial growth is measured in MAYER broth using 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 substance.

Table IV: Pectobacterium carotovorum test

Growth inhibition in% concentration 10 ~ ³ mol / l

2-ethylhex-2-enal (known) 20,

1-acetoxy-hexa-1,3-diene 35

1-acetoxy-2-ethyl-hexa-1,3-diene 45

1-acetoxy-2-ethylbuta-1,3-diene 25

1-acetoxy-2-methyl-penta-1,3-diene 40

1-Benzoxy-2-ethyl-hexa-1,3-diene 75 1 -acetoxy-2-ethyl-hexa ^: 1,3-diene +

2-ethylhex-2-enal (1: 1) 58.

Example 5: Cereal preservation

Active ingredient: 90 parts by mass

Emulsifier: 5 parts by weight Alkylphenylpolyglykolether '.

5 parts by weight of alkylbenzenesulfonic acid (butylammonium salt)

For the desired active ingredient concentration, the necessary amount of active ingredient and the stated amount of emulsifier are mixed and applied by uniform spraying of harvest-moist corn (wheat, W _F = 25.0%). The treated grain is filled in quantities of 400g in polyethylene foil bags and hermetically sealed. The cereal is then stored at a temperature of 25 ° C for 7 weeks. The evaluation of the mold infestation on the cereal grains is carried out by laying out 100 grains per test variant in petri dishes with malt agar nutrient medium. After 72 hours of incubation, the spoiled grains are counted. The mold infestation in percent is calculated from the number of spoiled grains compared to the total number of cereal grains. - '

Table V: Prevention of mold on feed grains

Active ingredient on mold wall quantity in case in g / kg wheat % - 100 0.2 80 0.3 11 0.2 6 0.3 0 0.3 0 0.3 0

Untreated Control 2-Ethyihex-2-enal (known) 2-Ethylhex-2-enal (known) 1-Acetoxy-2-ethyl-hexa-1,3-diene 1-Acetoxy-2-ethyl-1,3-diene 1-Acetoxy-2-ethyl-hexa-1,3-diene + 2-ethylhex-2-enal (1: 1) 1-acetoxy-2-ethyl-hexa-1,3-diene + 2-ethylhex-2 enal (1: 4)

Example 6: Potato preservation

Active ingredient: 90 parts by weight ·

Emulsifier: 7.5 parts by weight of alkylbenzenesulfonic acid (butylammonium salt) 2.5 parts by weight of alkylphenyl polyglycol ether

11 g of the specified emulsion concentrate are mixed with 100 ml of water and 2 kg of raw potato chips are treated by pouring. The potato carving I are then filled into 40 cm tall cylindrical vessels and stored for 5 months. ,

The evaluation took place according to the following rating scheme:

0 unchanged, no fungal and bacterial attack

1 mold on the surface

2 complete spoilage

Table VI: Prevention of mold growth in feed potatoes

Untreated Control 1-Acetoxy-2-ethyl-hexa-1,3-diene i-Acetoxy-2-methyl-penta-i, 3-diene i-Benzoxy-2-ethyl-hexa-1,3-diene-1-acetoxy 2-ethyl-hexa-i, 3-diene + 2-ethylhex-2-enal (1: 4)

Bonitur 1 month 3 months 5 months !Week - - 2 0 - 0 0 0 ~ 0 0 0 0 0 0 0 0

Example 7: Potato preservation

Raw potatoes are washed and then sliced. Immediately after crushing, but before introduction into the silo, 0.5 l / t of active ingredient is uniformly applied to the potato chips. After 7 weeks of storage, the following levels of feed were achieved compared to potatoes preserved with benzoic acid.

Table VII: Potato preservation (comparative example)

information active substance 1-acetoxy-2-ethyl-I in g / kg benzoic acid hexa-1,3-diene feed (known) 428 dry matter 404 .11 Raw ash 8th 25 crude protein 22 15 Raw fiber> 14 12 Digestible crude protein 10 267 EF _R 252 14 VRP ₅ 12 321, EF _S 303 4.4 PH value 4.5

Examples:

Apple Storage -

Active ingredient: 80 parts by mass. "''. '

Emulsifier: 5 parts by weight of alkyl phenyl polyglycol ether. '.

5 parts by weight of alkylbenzenesulfonic acid (butylammonium salt) Solvent: 10 parts by weight of n-propanol

To prepare a suitable preparation of active compound, the ingredients are mixed and the concentrate is diluted with water to the desired active ingredient concentration. In each case 5 apples of the "Gelber Köstlicher" variety are provided on the fruit equator with 2 opposite stains of about 5 mm diameter and 5 mm depth The inoculation is carried out by introducing an exciter suspension of Penicillium expansum into the artificial wound with the aid of a brush. After 4 hours of incubation, the treatment is carried out by immersing the apples in the preparation of active ingredient, each variant being repeated five times, after 10 days of storage in foil bags at 25 ° C. the development of rot is scored Efficiency of means in percent according to ABBOTT WG [%] = (percent infestation untreated contr. -Proc. Infestation mean var.) Χ 100

proc. Infestation unbeh. Control calculated.

Table VIII: Prevention of rot in apples

Untreated Control 1-Acetoxy-2-ethyl-hexa-1,3-diene 1-Acetoxy-2-ethyl-hexa-1,3-diene

Wirkstoffkonz. Infestation [%] Efficiency [%] in the exchange bath 76.5 [% Mass content] 53.1 30.3 16.9 77.9 0.5 1.0

Claims (2)

-1-231114 5 Claim for the invention:. Microbicidal agents, characterized in that they are in addition to conventional excipients and carriers as active ingredients enol acylates of alk-2-en-1-alene, preferably 1-acetoxy-2-ethyl-hexa-1,3-diene, alone or in combination with Contain 2-ethylhex-2-en-1-al, wherein in the second case, the weight ratio between the enol acylates and the aldehyde can be 1: 1 to 1:10. Microbicidal agents
Field of application of the invention The invention relates to microbicidal agents that can be used in plant and storage protection. Characteristic of the known technical solutions It is known to use a-alkyl-substituted alk-2-en-1-ale and their acetals for pest control (DD-PS 143023). However, these compounds are not always fully satisfactory at low overheads. In addition, the duration of action of these aldehydes is insufficient in various cases. Autoxidation causes the formation of unpleasant-smelling products. Object of the invention The aim of the invention is to develop new microbicidal agents which show a long-lasting effect at low application rates. Explanation of the essence of the invention This object is achieved in that the microbicidal agents in addition to conventional Hiifs- and carriers as active ingredient enol acylates of alk-2-en-1-alene, preferably 1-acetoxy-2-ethyl-hexa-1,3-diene, alone or in combination with 2-ethyl-hex-2-en-1-ol. The weight ratio between the enol acylates and the aldehyde can be 1: 1 to 1:10. The preparation of the enol acylates is known (Hoeben-Weyl, Methods of Organic Chemistry, Volume VII / 1,4.Auflage, .S.442-445). The starting materials are predominantly aldol condensation readily accessible α, / 3-unsaturated aldehydes and organic acid anhydrides. . Surprisingly, the compositions according to the invention show, compared with the known active compounds of the alk-2-en-1-al type, a multiple increased activity while maintaining a broad antimicrobial spectrum. The enolacylates continue to have a significantly extended duration of action. Compared to insects, mites and the ice cream they show a medium to good effect. Their smell is perceived as aromatic pleasant. The compositions according to the invention are outstandingly suitable for controlling hyphae fungi, yeasts, bacteria, viruses and protozoa, but also insects, mites and egg shells. They do not damage crops and crops in the required concentration and are of low toxicity to warm-blooded animals. For these reasons, they are suitable for use as crop protection agents for controlling fungi and bacteria in host-parasite combinations. Another application relates to the prevention of mold growth and associated mycotoxin formation in high moisture agricultural products and processed products of agricultural products used in animal nutrition during storage or intermediate storage. The products to be treated include, for example, wheat, oats, barley, rye, corn, fishmeal, peanuts, soybeans and meal, broad beans, broad beans, field peas, sunflower seeds, rapeseed and rice. Furthermore, potato chips, beet pulp, compound feed, green fodder, feed silage, compressed bale silage, hay, straw, brewer's yeast, spent grains, molasses and pellets for animal nutrition can be treated. Of the active ingredients, formulations such as solutions, emulsion concentrates / wettable powders, granules, microcapsules, aerosol sprays and so on depending on the specific application can be prepared in a known manner. For this purpose, they are mixed with the usual extenders, such as liquid organic solvents and / or solid carriers, optionally with the use of surface-active compounds. Suitable solid carriers are, in particular, ground natural minerals, the kaolins, alumina and talc, or ground synthetic minerals, such as highly disperse silica and silicates. Suitable surface-active substances are commercial emulsifiers and anionic, cationic and nonionic surfactants. By their admixture of agricultural products with high moisture content, especially the penetration capability is facilitated or increased. The formulations generally contain between 0.5 and 95% by weight of active compound, preferably between 5 and 90% by weight. The application is carried out in a known manner, for example by spraying, spraying, pouring, sprinkling or cold misting. The funds are in the field and particularly advantageous in enclosed spaces, such as greenhouses, warehouses, free storage under tarpaulins or films, silos, containers, storage rooms, means of transport and others used. The use concentration of the agents according to the invention depends on the specific application and can be varied within a substantial range. When used as foliar fungicides, the active ingredient concentrations are between 0.2 and 0.0001% by weight, preferably between 0.05 and 0.001% by weight. For the treatment of agricultural products and processed products of agricultural products, such as cereals and animal feed, the amount of active ingredient is highly dependent on the moisture content. A high humidity requires correspondingly higher application rates. In general, the required Wirkstpffmengen amount from 0.1 g to 100 g per kg of grain or feed, preferably from 1 g to 20g. embodiment
Example 1:
Mucormucedo test The active ingredients are allowed to act in culture tubes on Mucor mucedo. The growth of the fungi is determined by absorbance measurements in the coarsely disperse system in a photometer. The tubes are filled with a specific microfilament. by SDorenabschwemmunq with SISLER medium and a Vorkultivierungzeit of