DD295518A5 - BIOZIDE MEDIUM - Google Patents

Abstract

The invention relates to biocidal agents having fungicidal, insecticidal and acaricidal activity, which can be used to combat unwanted or damaging mites, insects and fungi in agricultural and agricultural crops and in the storage of agricultural products or their processing products. The object of developing new agents having high activity, a broad spectrum of activity and a sufficiently long duration of action is achieved according to the invention by the use of 2-ethylhex-2-en-1-al-sec-butylazomethine as active ingredient. {Biocidal agent; Fungicide; Insecticide; acaricide; mushrooms; Insects; mites; Agriculture; Horticulture; Stock protection; 2-ethylhex-2-en-1-al-sec-butyl-azomethine}

Description

Field of application of the invention

The invention relates to biocidal agents for controlling harmful fungi, mites and insect species in agricultural and horticultural crops and in the storage of agricultural products and their processed products

Characteristic of the known state of the art

It is known to use lower ahphatische aldehydes and their derivatives for the preservation of food and feed (DD-PS 122327, DE-PS 2354385, JP-PS 7325922) Furthermore, it is known 2 alkyl-substituted alk-2 en-1-alezur pest control (DD Furthermore, azomethines of aliphatic aldehydes with various primary aliphatic and aromatic amines are described as antimicrobial compounds (ZbI Bakt Hyg, I Abt Orig B167, 224-233, 1978).

Azomethines of sec-butylamine with aliphatic ketones or aromatic aldehydes are proposed for controlling Penicillium infestation on citrus fruits (Pestic. Sei 15 [1983], 220-228). However, the action of these compounds is not always fully satisfactory at low application rates and their duration of action is in many cases In addition, the said compounds have a relatively high selectivity towards certain types of microorganisms, which severely restricts their broad application for use as biocidal agents. Tested agents for controlling storage and hygiene disorders based on methyl or ethyl bromide, hydrogen cyanide, phosphine, acrylonitrile Ethylene oxide, sulfur dioxide, isothiocyanates, trichloroacetonitrile, etc. also have a high warm-blood toxicity and a low MAK value. In addition, these agents often have an unpleasant pungent odor and cough and mucous membrane irritancy In addition, when used regularly, there is a risk of the development of resistant fungus, insect or mite strains, thereby jeopardizing effective control in low-cost means

Object of the invention

The aim of the invention is to provide novel biocidal compositions with improved active and application properties for the protection of agricultural products as well as for use in agricultural and horticultural crops against harmful fungal, mite and insect species

Explanation of the essence of the invention

The invention has for its object to develop new biocidal agents for crop protection in agriculture and for use in agricultural and horticultural crops, which have high activity, a broad spectrum of activity and a sufficiently long duration of action and based on large-scale Ausgangsprodukkte and simple synthesis processes can be produced

To solve this problem, biocidal agents are proposed which are characterized in that they contain 2-ethylhex-2-en-1-al-sec-butylazomethine as active ingredient as well as conventional auxiliaries and carriers. Surprisingly, it has been found that the biocidal compositions of the invention have a broad spectrum of activity They are able to exert or inhibit fungal organisms and animal pests via the gas phase, too. They do not damage or prevent the products to be treated at the required concentrations. The use as an alternative to known active substances reduces the risk of the formation of resistant fungal organisms. , Insect or mite trunks No adverse effects on humans and the environment are to be expected since the active substance according to the invention is readily biodegradable

The active ingredient according to the invention is suitable, for example, for combating fungal harmful organisms such as Ascomycetes, Basidiomycetes or lower fungi, especially Aspergillus or Penicillium species, Fusarium oxysporum, Botrytis cinerea and Fusarum sp. From animal pests such as Myzus persicae, Trialeurodes vaporanorum and Tetranychus urticae Protective products such as Oryzaephilus surinamensis, Sitophilus grananus, Sitophilus oryzae, Ephistia elutella, Tribolium confusum and the hygienic pathogens Musca domestica, Culex pipiens and Blattella germanica can be controlled. Products to be treated can be Apfel B apple, oranges, mandarins, lemons, grapefruits, cereals, maize, rice, Soybeans and meal, broad beans, field beans, field peas, sunflowers, lupines or rape seed may also include raw potatoes, sugar industry intermediates, compound feeds, green fodder, feed silage, molasses, fishmeal or pellets for animal feed be delt

The preparation of the active ingredient 2-ethylhex-2-en-1-al-sec-butylazomethine according to the invention can be carried out in a simple manner by methods known per se from 2-ethylhex-2-en-1-al and sec-butylamine (Orgamkum, VEB German publishing house of the sciences, 15 edition, Berlin 1977, S 481)

The erfmdungsgemaße active ingredient can be incorporated into liquid, pasty and solid preparations and depending on the specific application in particular as a solution, emulsion concentrate, paste, powder, granules or in microencapsulated form are used. The assembly can be by mixing or grinding of 2-ethylhex-2 en-1-al-sec-butylazomethine with conventional additives, such as suitable carriers, dispersants and solvents, water softeners, complexing agents, foam inhibitors, antioxidants or high molecular weight compounds done in the packaging is also the adjustment of solutions to a specific, the application purpose corresponding pH Value included In order to improve the wetting effect and the entrainment potential, the products to be treated are useful in the addition of cationic, anionic or nonionic surfactants

The formulations of the active ingredient according to the invention generally contain between 0.5 and 95% by weight of 2 ethylhex-2-ene-1-al-sec-butylazomethine. The active ingredient according to the invention can be used in the form of its formulations or the use forms prepared therefrom by further dilution biocidal agent 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 treated. In general, the required amounts of active ingredient 0.1 to 15 g per kg of treated material. The application can by spraying, spraying, pouring, dipping, pickling By evaporating the biocidal compositions of the invention, a particularly good effect on the gas phase unfolds is particularly advantageous that can be achieved at suitable dosages in combined Bekampfungserfolg against fungal harmful organisms and animal pests The biocidal compositions according to the invention are advantageously used in closed rooms, such as warehouses, free-standing shelves with tarpaulin or foil cover, silos, containers, means of transport, greenhouse facilities and in beekeeping systems for controlling insecticidal mites. The following examples serve to illustrate the invention

Exemplary embodiments

example 1

Agar plate test with fungi by gas phase application of the agents

The fungicidal activity against the test fungi is determined as inhibiting the radial growth of the fungi on malt agar nutritive medium (2% malt) in Petri dishes (diameter 9 cm) at an incubation temperature of 25 ° C by applying the active ingredients through the gas phase. 4 open Petri dishes each become placed in containers of defined volume (approx. 2 liters) The malt agar plates are inoculated with a mycelium piece of 1 cm diameter for non-sporulating fungi or with a capillary drop of a spore suspension of the sporulating fungi After application of the active ingredients by means of a microliter syringe on the inside the glass vessel is closed tightly with a lid. The growth measurements are made when the controls without active ingredient are 90% of the shell diameter, depending on the growth rate of the fungi 3 to 7 days are necessary. The evaluation is carried out by calculating the percentage growth for each of the active substances compared to those without added active substances (Tables A and B).

Table A

Effect of 2-ethylhex-2-en-1-al-sec-butylazomethine on fungi in the agar plate test with gas-phase application

Growth inhibition (mol / l)

Mucormucedo Fusanum oxysporum Botrytiscinerea Aspergillus niger Penicillium italicum Penicillium expansum Rhizopus nigricans Phytophthora cactorum

Active substance concentration Wa. (Minor) ιη ° / ί 1 χ 10 "" 82 3 x 10 "* 100 1 x 10 "" 65 3 x 10 "" 100 1 x 10 "" 81 3 x 10 "" 100 1 x 10 "" 97 3 x 10 "" 100 1 x 10 "" 87 3 x 10 "" 100 1 x 10 "" " 95 3 x 10 "" 100 1 x 10 "" 68 3 x 10 "" 100 1 x 10 "" 100

Table B

Effect of 2-ethylhex-2-en-1-al-sec-butylazomethine compared to known agents against fungi in the agar plate assay

with gas-phase application Active substance concentration 1 χ 10 ~ ⁴ mol / l

Growth inhibition in% Aspergillus penictllium

niger expansum

2-ethylhex-2-en-1-al (known) 81 75

sec-butylamine (known) 0 0

2 ethylhex 2 en-1 al sec-butyl azomethine 95 97

Example 2

Storage of citrus fruits

Each citrus fruit is artificially produced with 3 wounds of 5mm diameter and 2mm depth. The inoculation is carried out by introducing fungal spores of Penicillium species of spoiled fruit into the wound by means of a moistened tampon. Then 3 fruits per test variant are applied to watch glasses in 2-I Vessels are put through a dish with water in the vessels, the atmosphere is saturated with water vapor The active ingredients are applied by a 50% solution of the active ingredients in the required amount of active substance per volume of the vessels is applied to the inside of the lid, so that after evaporation of the A thin film of active substance is formed during the solvent

Storage acts on the fruit

After 7 or 20 days of storage at 25 ° C, the development of the cravings is evaluated Based on the birthnotes, the infestation is calculated in% and from this the efficacy of the active ingredients according to ABBOTT is calculated as follows

_ % Infestation (control) -% infestation (trial with active ingredient) % infestation (control)

Table C

Effect of 2-ethylhex-2-en-1-al-sec-butylazomethine in storage of citrus fruits

active substance Efficiency in % concentration shelf life (Minor) 7 days 20 days 1 χ 10 " ⁴ 0 0 3.3x10 " ⁴ 22 0 1 x 10 ~ ⁴ 100 67 3.3x10 "" 100 100

2-ethylhex-2-en-1-al (known) 2-ethylhex-2-en-1-al-sec-butylazomethine

Example 3 Apple Storage

In each case 5 apples of the "Gelber Köstlicher" variety are provided on the fruit equator with 2 opposite punctures of 5 mm diameter and 5 mm depth. Inoculation is carried out by introducing a spore suspension of Penicillium expansum into the artificial wounds with the aid of a brush. The spore suspension is removed by unwinding with Pemcillium expansum overgrown Schragagarrohrchens made with twice 10ml of distilled water After inoculation, the fruits are placed in 5-liter-vials per drug volume required amount of active ingredient is applied by microliter tip at the top of the vessels, so that when you run down the active ingredients easily evaporable Drug film forms The tubes are then sealed and stored at 25 ⁰ C Each variant is scheduled in five replicates After 6 days storage duration, the development of rot is scored Based on the score Boniturn the infestation in% and from the effect the ingredients of ABBOTT are calculated as follows

.., _. , % Infestation (control) -% infestation (trial with active ingredient) WG (%) =

% Infestation (control)

Table D

Effect of 2-ethylhex-2-en-1 al-sec-butylazomethine on storage of apples

Active ingredient efficiency in%

concentration

(Minor)

2-ethylhex-2-en-1-al-sec-butylazomethine 3.3 x 10 " ⁶ 50

1 χ 10 " ⁴ 90

3.3 x 1 (T ⁴ 100

Example 4

Gas-phase test on sensitive and resistant spider mites (Tetranychus urticae) Female spider mites (Tetranychus urticae) from sensitive (S) and resistant (R) laboratory stocks are grown on testis (in 5 repetitions per concentration) on leaf discs of their natural food plant (bean) in hermetisable glass containers ( 21 volumes) of the gas-phase effect of the active substance The preparation is applied to the underside of the cover plate of the glass containers, which are then closed with them. The mortality achieved is checked after 24 or 48 hours by paying off the dead animals

Table E

Gas phase test on spider mites

phylum Active substance concentration (mol / l) Beh duration (h) Mort (%) S strain 1 x 10 ~ ⁵ 2 x 10 " ⁵ 3 x 10 ~ ⁵ 24/48 24/48 24/48 59/62 68/96 100/100 R strain (Dimethoate-R) 1 χ 10 ~ ⁵ 2 x 10 " ⁵ 3 x 10 ~ ⁵ 48 48 48 63 82 100 R strain (Dichlorvos R) 1 x 10 ~ ⁵ 2 x 10 " ⁵ 3 x 10 ⁵ 48 48 48 69 74 100 R strain (Methamidophos R) 2 x 10 " ⁵ 3x10 ⁵ 48 48 81 100

Example 5

Effect on Sensitive (S) and Tnchlorfon Resistant (R) Houseflies (Musca domestica L) There are 30 adult females each in hermetized glass containers (21 volumes) of the gas phase effect of 2-ethylhex-2-en-1-al-sec-butylazomethine The mortality is determined after 24 hours by paying off the dead animals (application technique see Ex. 1)

Table F

Effect on S and R strains of housefly (Musca domestica L)

phylum Active substance concentration (mol / l) Beh duration (h) Mort (%) S strain (WHO) 1 χ 10 ~ ⁶ 3 x 10 ~ ⁵ 3 x 10 ~ ⁴ 24 24 24 67 84 100 R strain (TCF-R) 3 x 10 ~ " 24 100

Example 6

Effects on sensitive American cockroaches (Penplaneta americana) In each case 5 adult, male animals are placed in glass containers (1 000 ml volume) and these are closed after addition of the active ingredient The active ingredient is applied in liquid form on the inner surface of the container and goes there at room temperature the gas phase over

Table G

Effect on sensitive cockroaches (Periplaneta americana)

Drug duration (h) Mort (%)

concentration (mol / l)

3x10 " ⁴ 2

1 x 10 ~ ⁴ 2

Example 7

Effect on Sensitive White Fly (Trialeurodes vaporanorum) Twenty adult winged individuals are exposed to the test containers (21 volumes) of the gas phase of the active substance described in Example 1. The dead animals are paid after 1 or 2 hours duration of action

Table H Effect on sensitive whitefly Beh.-time (h) Mort. (%) Active substance concentration (mol / l) V ₂ 50/100 30/100 3 χ 10 ~ ⁵ 2 x 10 ~ ⁶

Example 8

Effect on sensitive grain beetles (Sitophilus granarius) and sensitive rice beetles (Sitophilus oryzae) in grain bulk Each 250 adult beetles of the species mentioned are distributed in appropriate repetitions on glass cylinders (600ml volume) with cereal grains (240g / container). The insecticidal agent is introduced into the cereal bulk material with a microliter syringe and distributed in the intermediate spaces over the resulting gas phase. The mortality achieved is determined after the expiry of the desired treatment period by reading the animals and then counting the dead individuals

 The containers are kept in a hermetized condition at room temperature during the test period.

Table I

Effect on sensitive grain beetles and rice beetles

pests Active substance concentration (mol / l) Beh. duration Mort. (%) S.granarius 3x10 " ⁴ '/ 2 86/100 S. oryzae 3 x 10 ^-3 3 x 10 " ³ 2 x 10" ³ 5 3 2 98.5-100 96 92

Claims (3)

1 biocidal agent, characterized in that they contain 2-ethylhex-2-en-1-al-sec-butylazomethin as active ingredient in addition to customary excipients and carriers. 2 method of controlling pathogens characterized in that means according to claim 1 on fungi, insects or mites, or act against these pests, to be protected objects. 3 Use of agents according to claim 1, characterized in that they are used for controlling fungi, insects or mites.