DD161132A1 - MEANS FOR PRESERVING FODDER TO BE STORED - Google Patents

Abstract

The invention relates to improved means for preserving feeds to be stored, in particular cereals, maize and potatoes, based on 2-ethylhex-2-en-1-al (A). According to the invention they contain as additional active ingredients 2-ethylhexan-1-ol (B) and / or 1-acetoxy-2-ethyl-hexa-1,3-diene (C). The weight ratios of the components A: B are 1: 1 to 20: 1A: C 1: 1 to 20: 1 and A: B: C 8: 1: 1 to 20: 1: 1.

Description

Means for the preservation of stored feed Field of application of the invention

The invention relates to improved means for the preservation of stored feed, in particular of cereals, corn and potatoes. , ,

Characteristic of the known technical solutions

It is known to use lower aliphatic aldehydes and their derivatives for the preservation of food and feed (DD-PS 122 327, JP-PS 7 325 922, DE-PS 23 54 385). It is also known to use 2-alkyl-substituted alk-2-en-1-ale for pest control (DD-PS 143 023).

However, the effect of this compound is not always fully satisfactory at low application rates and its duration of action is inadequate in various cases. In addition, these aldehydes have a relatively high selectivity to certain types of microorganisms, thereby restricting broad application of the agents.

It is also known that some alcohols of the aliphatic series have a microbicidal action. Thus, such compounds in mixtures with lower aliphatic aldehydes, such as formaldehyde or glycoaxal, used in disinfectants (DE-PS 25 16 670). The mentioned combinations, however, as well as the individual active ingredients have various disadvantages. These agents have often insufficient microbicidal activity against various types of microorganisms, require for the inhibition or destruction of pests relatively high application rates and can cause quality impairments in the biological products to be preserved. , '....-

As expected, however, disinfectants are only suitable for their specific application due to their properties and often fail because of the insufficient in interaction with agricultural products antimicrobial activity against specific types of microorganisms, especially at low concentration levels. Inadequate lasting effects, quality impairments and residue-toxicological loads are further disadvantages when applied to food and feed.

Known and proven preservatives on the basis of organic acids such as propionic acid, sorbic acid or benzoic acid, disadvantageous in addition to their risk of corrosion for transport and application facilities only at relatively high dosages on a sufficient preservation effect. '

Object of the invention

The aim of the invention is to develop new means for the preservation of feed, which are improved in their antimicrobial activity and long-term effects.

Explanation of the essence of the invention

This object is achieved in that the means for preserving stored feed,

in particular of cereals, maize and potatoes, on the basis of 2-ethylhex-2-en-1-al (A) in addition to customary excipients and carriers as additional active ingredients 2-ethylhexan-1-ol (B) and / or 1- Acetoxy-2-ethyl-hexa-1,3-diene (C). there

can the weight ratios of the components.

A: B = 1: 1 to 20: 1

A: C = 1: 1 to 20: 1 and

A: B: C = 8: 1: 1 to 20: 1: 1

be.

This is to be described as extremely surprising since a combination of 2-ethylhex-2-en-1-al with a number of other aliphatic alcohols having antimicrobial properties such as n-propanol, ethylene glycol, ethylene glycol monobutyl ether, propane-1,2-diol, Propane-1,3-diol, butane-1,3-diol or triethylene glycol, does not give an increase in antimicrobial efficacy, but in some cases even blends the alcohols for this purpose

is. ·

The preservatives of the invention show a greatly increased antimicrobial effectiveness, which is significantly better than the expected additive effect of the individual components. In addition, a broadening of the spectrum of action and an extension of the duration of action is achieved with them.

The agents of the invention show excellent activity against fungal harmful organisms, yeasts, bacteria and protozoa. Compared to insects and mites and their ice age they show a medium to good effect. They do not damage or affect the products to be treated at the required concentrations and are of low water toxicity.

The effect of the agents occurs both on the surface and in the interior of the biological objects and their processed products.

When using the preservative according to the invention, mold growth and associated mycotoxin formation in storage goods containing high moisture content are prevented during storage and thus losses and quality losses are avoided. Such products to be treated may include, for example, corn, corn, rice, soybeans and meal, broad beans, field beans, peas, sunflowers, lupines or rape seeds. Furthermore, raw potatoes, intermediate products of the sugar industry, compound feed, green fodder, feed silage, molasses, fishmeal

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Another noteworthy advantage of the agents according to the invention lies in their favorable toxicological properties. There are no disadvantageous residue problems to be expected, since the main body of the active ingredients used are present as naturally occurring compounds in the harvested products.

The preparation of the corresponding active compounds 2-ethylhex-2-en-1-al, 2-ethylhexan-1-ol and 1-acetoxy-2-ethylhexane-1,3-diene is known and has been described in the literature (Houben-Weyl: "Methods of organic chemistry," Bd.VII / 1 and Bd. V / 1 a CH-PS 313 998, US-PS 2866 813, DE-PS 11 46 871).

Of the active compound combinations according to the invention, depending on the type of application and field of application, formulations such as solutions, suspensions, emulsion concentrates, pastes, aerosol sprays or solid preparations can be prepared in a known manner. For this they are mixed with the usual additives such as water, liquid organic solvents, complexing agents, foam inhibitors, Anoxidantien'oder high molecular weight compounds. To improve the wetting action and the ability to penetrate into the harvest-moist products to be treated, the addition of cationic, anionic or nonionic surfactants is expedient. The formulations generally contain between 90.0 and 99.9% by weight of the active compound combinations according to the invention.

The compositions of the invention are particularly advantageous in closed spaces such as warehouses, outdoor storage with tarpaulin or foil cover, silos, containers, means of transport or the like can be used. The application rate of the agents according to the invention depends on the specific application and can be varied within a substantial range depending on the nature of the product to be preserved. In general, the required amounts of active ingredient are 1 to 15 g per kg of material to be treated. As is known, the application can be carried out by spraying, spraying, pouring, dipping, pickling or cold misting.

The following examples serve to explain the microbicidal activity and to illustrate the fields of application of the agents according to the invention. ,

embodiment Example 1:

Mucor mucedo - 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 certain amount of spleen mycelium, which by spore runoff with SISLER medium and a precultivation time of this suspension is 0.23 mg / ml. Then the active ingredients dissolved in dimethylformamide are added (final dimethylformamide concentration: 1%). After 3 hours, the growth measurement takes place in the photometer. Using a calibration curve, the mushroom substance values corresponding to the extinction values are determined

 The evaluation is carried out by calculating the percentage growth inhibition for the respective active ingredients.

Table I: Growth inhibition of fungi (Mucor mucedo)

Growth inhibition in% Concentration: 10 mg / l

2-ethylhex-2-en-1-al 2-ethylhexan-1-ol 1 -acetoxy-2-ethyl-hexa-1,3-diene

2-ethylhex-2-en-1-al 2-ethylhexan-1-ol 2-ethylhex-2-en-1-al 2-ethylhexan-1-ol

1-acetoxy-2-ethyl-hexa-1,3-diene 2-ethylhex-2-en-1-al + i-acetoxy-2-ethyl-hexa-1,3-diene 2-ethylhex-2-ene 1-al + 2-ethylhexan-1-ol + 1-acetoxy-2-ethyl-hexa-1,3-diene

(1: 1) 26 (10: 1) 23 (4: 1) 28 (20: 1) 25

(8: 1: 1)

Example 2: Fusarium, oxysporum test

The active ingredients are allowed to act in culture tubes on Fusarium oxysporum. The growth of 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 pellet, obtained by spore-leaching with SISLER medium and a pre-culturing time of 15 hours at 17 ^C C. The initial dry weight of this suspension is 0.18 mg / ml. Then, the drug dissolved in dimethylformamide is added (final dimethylformamide concentration: 1%). After 5 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.

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Table: Growth inhibition of fungi (Fusarium oxysporum)

Growth inhibition in%. ι

Concentration: 50 mg / l

2-ethylhex-2-en-1-al. , · 65

2-ethylhexane-i-ol., 43 '

1-acetoxy-2-ethyl-hexa-1,3-diene 62

2-ethylhex-2-en-1-al-i-

2-ethylhexan-1-ol (1: 1) 74

2-ethylhex-2-en-1-al +

2-ethylhexan-1-ol (10: 1) 71

2-ethylhex-2-en-1-al +

1-Acetoxy-2-ethyl-hexa-1,3-diene (4: 1) 69

2-ethylhex-2-en-1-al +

1-acetoxy-2-ethyl-hexa-1,3-diene. (20: 1) 67

2-ethylhex-2-en-1-al +

2-ethylhexan-1-ol +

1-Acetoxy-2-ethyl-hexa-1,3-diene (8: 1: 1) OO 70

Example 3: Candida utilis test

The active ingredients are allowed to act in culture tubes on Candida utilis. 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 15 hours precultivation time in a modified SISLER medium (2% glucose). The initial dry weight of this suspension is 0.06 mg / ml. For this purpose, the active ingredients dissolved in dimethylformamide are added (dimethylformamide final concentration: 1%). 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.

TABLE III Growth inhibition of yeast cultures (Candida utilis test)

Growth inhibition in% Concentration: 50 mg / l

2-ethylhex-2-en-1-al36

2-ethylhexane-T-ol 41 -

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

2-ethylhex-2-en-1-al +

2-ethylhexan-1-ol (1: 1) 52

2-ethylhex-2-en-1-al +

2-ethylhexan-1-ol, (4: 1) 52

2-ethylhex-2-en-1-al + '. ;

2-ethylhexan-1-ol '(10: 1) 47

2-ethylhex-2-en-1-al + '

1-Acetoxy-2-ethyl-hexa-1,3-diene (4: 1) 54

2-ethylhex-2-en-1-al +

1-Acetoxy-2-ethyl-hexa-1,3-diene (20: 1) 51

2-ethylhex-2-en-1-al +

2-ethylhexan-1-ol +

1-Acetoxy-2-ethyl-hexa-1,3-diene (8: 1: 1) 54

Example 4: Candida albicans test

The active ingredients are allowed to act in culture tubes on Candida albicans. The growth of the yeast 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 15 hours precultivation in a MILLER medium (3% glucose). The initial dry weight of this suspension is 0.09 mg / ml. Then the active ingredients dissolved in dimethylformamide are added (final dimethylformamide concentration: 1%). After 5 hours, the growth measurement takes place in the photometer. The yeast dry substance values corresponding to the extinction values are determined on the basis of a calibration curve. The evaluation is carried out by calculating the percentage growth inhibition for the respective active substance. * *

-4- 231 116 Table IV: Growth inhibition of yeast cultures (Candida albicans test)

Growth inhibition in% Concentration: 50 mg / l

1-ethylhex-2-en-1-al 25

2-Ethyihexan-1-ol

1-acetoxy-2-ethyl-hexa-1,3-diene 34

2-ethylhex-2-en-1-al +

2-ethylhexan-1-ol (1: 1) '35

 2-ethylhex-2-en-1-al +

2-ethylhexane-i-ol. (4: 1) 35

2-ethylhex-2-en-1-al + 2-ethylhexan-1-ol (10: 1) 32

1-Acetoxy-2-ethyl-hexa-1,3-diene (10: 1) 39

2-ethylhexan-1-ol +

1-Acetoxy-2-ethyl-hexa-1,3-diene (8: 1: 1) 36

Example 5: 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 gfobdispersen system in a photometer. The tubes are filled with a certain amount of bacterial suspension which has grown after 15 hours fermentation time in glucose nutrient broth at 22 ° C. The starting dry weight suspension is 0.16 mg / ml. Then, the active ingredients dissolved in dimethylformamide are added (dimethylformamide final 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 ingredients.

Table V: Growth inhibition of bacteria (Pectobacterium carotovorum test)

Growth inhibition in% Concentration: 100 mg / l

2-ethylhex-2-en-i-al / 30

2-ethylhexan-1-ol 30

1-acetoxy-2-ethyl-hexa-1,3-diene 40

2-ethylhex-2-en-1-al +

2-ethylhexan-1-ol (1: 1) 36

2-ethylhex-2-en-1-al +,

2-ethylhexan-1-ol (4: 1) 38

2-ethylhex-2-en-1-al +, ~. -

2-ethylhexan-1-ol. (10: 1) 36

2-ethylhex-2-3n-1-al + ·

i-acetoxy-ethyl-hexa-1S-diene (4: 1) 49

2-ethylhex-2-en-1-al +

1-Acetoxy-2-ethyl-hexa-1,3-diene (20: 1) 42

2-ethylhex-2-en-1-al +

2-ethylhexan-1-ol +

1-Acetoxy-2-ethyl-hexa-1,3-diene (8: 1: 1) 47

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Example 6: Cereal preservation

Each 300g wheat (W _F = 25%) are placed in 800 ml glass jars. The active ingredients are added to the glass inner wall by means of a measuring pipette. The closed with a screw-on vessels are then shaken several times to achieve a sufficient distribution of the active ingredients. They are then stored in a climate chamber at 30 ⁰ C for 3 months in the dark. Each trial is repeated in triplicate. The evaluation of the mold infestation on the cereal grains is carried out by laying out 100 grains per test variant in petri dishes (d = 10 cm) with malt agar nutrient medium. After four days of incubation at 30 ⁰ C, the infested grains are counted. Percentage mold growth is calculated from the number of infested grains versus the total number of cereal grains.

Table IV: Prevention of mold infestation in feed grain

(1: 1) Wirkstoffauf Mold wall quantity in infested in (1: 1) ml / kg % Untreated control - 100 2-ethylhex-2-en-1-al (1: 1) ' 1. 95 2-ethylhex-2-en-1-al 2 80 2-ethyl hexane-1-ol (1: 1) 1 100 2-ethyl hexane-1-ol 2 92 1-acetoxy-2-ethyl-hexa-1,3-diene (1: 1) 1 85 1-acetoxy-2-ethyl-hexa-1,3-diene 2 76 Formaldehyde + (1: 1) I 2-ethyl hexane-1-ol 1 95 Formaldehyde + (1: 1) 2-Ethyihexan-1-ol 3 19 Glyoxal + (4: 1) 2-ethyl hexane-1-ol 1 99 Glyoxal + (4: 1) 2-ethyl hexane-1-ol 3 34 2-ethylhex-2-en-1-al + (4: 1) _ i .._ . _:. ... 2-ethyl hexane-1-ol 1 85. ' 2-ethylhex-2-en-1-al + (10: 1) " 2-ethyl hexane-1-ol 2 8th 2-ethylhex-2-en-1-al + (10: 1) 2-ethyl hexane-1-ol 3 0 2-ethylhex-2-en-1-al + 2-ethyl hexane-1-ol (4: 1) 1 ν 76 2-ethylhex-2-en-1-al + 2-ethyl hexane-1-ol 2 3 2-ethylhex-2-en-1-al + (4: 1) 2-ethyl hexane-1-ol 3 0 2-ethylhex-2-en-1-al + 2-ethyl hexane-1-ql (20: 1) 2 15 2-ethylhex-2-en-1-al + 2-ethyl hexane-1-ol 3 4 2-ethylhex-2-en-1-al + (20: 1) 1-acetoxy-e-ethyl hexa-1,3-diene 2 55 2-ethylhex-2-en-1-al + (8: 1: 1) 1-acetoxy-2-ethyl- hexa-1,3-diene 3 7 2-ethylhex-2-en-1-al + (8: 1: 1) 1-acetoxy-2-ethyl hexa-1,3-diene 2 68 2-ethylhex-2-en-1-al + 1-acetoxy-2-ethyl- hexa-1,3-diene 3 9 2-ethylhex-2-en-1-al + 2-ethylhexan-1-ol + 1-acetoxy-2-ethyl-hexa-1,3-diene 2 4 2-ethylhex-2-en-1-al + 2-ethylhexan-1-ol + 1-acetoxy-2-ethyl-hexa-1,3-diene 3 0

Example 7: Corn Preservation

The active substances mixed with 0.1% by mass of emulsifier (alkylphenyl polyglycol ether) are mixed and, by uniform spraying, each 100% of maize (Wc = 34%) is taken up in accordance with oenorTi.cöhi ^ i, "- n ..," u ": - ι: ~ > - »

-O- £ .0 I I IO I

treated corn covered with polyethylene film to prevent evaporation losses. Then the corn is at 18

stored at 20 ⁰ C for one month.

The evaluation of the mold infestation on the corn kernels is carried out by laying out 100 grains per test variant in petri dishes (d = 10 cm) with malt agar nutrient medium. After three days of incubation at 3O ⁰ C infested grains are counted. The mold infestation in percent is calculated from the number of infested grains in relation to the total number

Corn kernels.

Table VII: Prevention of mold infestation in feed maize

Wirkstoffauf mold wall quantity in case in ml / kg % Untreated control - 100 2-ethylhex-2-en-1-al 10 6 2-ethyl hexane-1-ol 10 85 1-acetoxy-2-ethyl-hexa-1,3-diene 10 14

2-ethylhex-2-en-1-al + 2-ethylhexan-1-ol (1: 1)

2-ethylhex-2-en-1-al + 2-ethylhexan-1-ol (4: 1)

2-ethylhex-2-en-1-al + 2-ethylhexan-1-ol, (10: 1)

2-ethylhex-2-en-1-al + 1-acetoxy-2-ethyl-hexa-1,3-diene (4: 1) 2-ethylhex-2-en-1-al + .1-acetoxy-2 ethyl 1-hexa-1,3-diene (20: 1) 2-ethyl-hex-2-en-1-a I + 2-ethylhexan-1-ol + 1-acetoxy-2-ethyl-hexa-1, 3-dien (8: 1: 1)

10 10 10 10 10

10

Example 8:

Potato preservation -. -

Active ingredient: 90.0 parts by weight

7.5 parts by weight of alkylbenzenesulfonic acid-butyl-amrrionium salt. '2.5 parts by weight Alkylphenylpolyglykolether.

11 g of the specified emulsion concentrate are mixed with 10OmI of water and appiiziert per 2kg raw Kärtoffelschnitzeln by pouring. The treated potato chips are then filled into 40 cm tall cylindrical vessels and stored for five months. The evaluation follows the following rating scheme:

0 = unchanged, no mold attack

1 = mold on the surface.

2 = complete spoilage

Table VIII: Prevention of Mold Infestation on Feed Potatoes

Bonita week

month

months

5 months

Unsupported Control Benzoic acid (known) 2-Ethylhex-2-en-1-aj 2-Ethylhexan-1-ol 1 -acetoxy-2-ethyl-1-hexa-1,3-diene

2 2 2 2 0 1 1 2 0 0 1 1 0 1 1 2

2-ethylhex-2-en-1-al +

2-ethylhexan-1-ol (1: 1)

2-ethylhex-2-en-1-al +

2-ethylhexan-1-ol (10: 1)

2-ethylhex-2-en-1-al + 1-acetoxy-2-ethyl

hexa-1,3-diene (4: 1)

2-ethylhex-2-en-1-al + 1-acetoxy-2-ethyl-I

hexa-1,3-diene (20: 1)

2-ethylhex-2-en-1-al + 2-ethylhexan-1-ol +.

1-acetoxy-2-ethyl-hexa-

1,3-diene (4: 2: 4)

Claims (2)

-1- 231 116 1 Invention claims:. 1. A means for preserving stored feed, in particular of cereals, corn and potatoes, on the basis of 2-ethylhex-2-en-1-al (A), characterized in that they in addition to conventional excipients and carriers as additional Active ingredients 2-ethylhexane-1-oil (B) and / or 1-acetoxy-2-ethyl-hexa-1,3-diene (C). 2. Means according to item!, Characterized in that the weight ratios of the components A: B = 1: 1 to 20: 1 A: C = 1: 1 to 20: 1 and '. A: B: C = 8: 1: 1 to 20: 1: 1 be.