DD260859A1 - PROCESS FOR THE PREPARATION OF NEW MEANS FOR THE CONTROL OF THE MILK VARROAJACOBSONI - Google Patents

Abstract

The invention relates to a process for the preparation of new agents for combating the mite Varroa jacobsoni on bee colonies. According to the invention, the active compounds are 0.0-diethyl-O- (3-Br-4-methyl-coumarin-7-yl) -thionophosphoric acid esters, copper chelates of acetoacetic ester or acetylacetone or acetic acid with extenders and / or solvents, emulsifiers and / or or dispersants mixed. This new product makes it possible to expand the application methods for bee treatment. It can be fed to the bees and also allows the wetting of the bees with the agent according to the invention without having to accept a reduction in the effect. Likewise, the agent provides mite treatment within the hatched brood. The agent is well bee-compatible and acts almost quantitatively in the concentrations according to the invention.

Description

: C = O.

^HG C \ ^ ^C V / ^GH

H₃C. -C--O ^ "^) = C-O-G₂H₅

or copper chelate of the acetylacetone of the formula GH ₃

3 o'c

<ΐ \ /^σΗ (IV)

CH ο CH ο

or copper chelate of acetic acid of the formula (V) [Cu (CH ₃ COO) ₂ .H ₂ O] ₂

are mixed with extenders and / or solvents, emulsifiers and / or dispersants by known methods and diluted in use with water.

2. The method according to claim 1, characterized in that in the preparation of 11 of the new composition 2 to 35g of the active ingredients (I) or (II) and 0.02 to 0.6 g of the copper chelates of the formulas (III), (IV) or (V) with the remaining amount of extenders and / or solvents, emulsifiers and / or dispersants.

3. The method according to claim 1 and 2, characterized in that are used as the solvent alcohols, glycols, ketones, polyglycols or sulfoxides and as emulsifiers or dispersants Alkylarylpolyglykolether, protein hydrolysates and / or natural products.

Field of application of the invention

The invention relates to a process for the preparation of new agents for combating the mite Varroa jacobsoni Oudemans on normally developed bee colonies.

Characteristic of the known state of the art

The mite Varroa jacobsoni parasitises not only on adult bees, drones and queen bees, but also on their larvae and pupae. It lives on the hemolymph of the bees and thereby causes their weakening and early mortality. Untreated infested peoples collapse in the 3rd or 4th year of infestation. By weakening the bees due to parasitism infestation by viruses and bacteria is favored. Immediate damage is the reduction of the yield of honey, wax, propolis, pollen and bee venom; a multiple indirect damage is caused especially in the entomophilic crops by reducing the pollination.

Worldwide, the Varroa mite has found an unstoppable spread in a few years.

According to DE-PS 3420751, DD-PS 241 686 and 229920 and EP-PS 164629, the active ingredient, 0.0-diethyl-O- (3-chloro-4-methylcoumarin-7-yl) -thiophosphorsäureester in low application rate Used to combat mites.

In these agents, however, shows disadvantageous that a sufficient effect can only be achieved after pouring, sprinkling or spraying on the bees. In addition, it is necessary to use these agents several times to achieve a good effect. When administered in feed solutions, the effect is reduced, so that this type of application is not suitable for these agents.

Known methods for combating this mite are the pollinating or smoking of bee colonies with bees contracted contact acacia, thermotherapy, as well as biotechnical procedures of beekeepers. Disadvantages of these methods are the great amount of manual and time-consuming work, the high use of active ingredient, the necessary multiple use, as well as the unease of the bee colonies when carrying out these control methods. Also to be mentioned are the risk to bees for bee and beekeepers during fumigation and dusting with contact acacia and the limited control success of <90% in all these treatments. Furthermore, according to DE-PS 3341017, DD-PS 229920 and EP-PS 0144721 the control of the mites with the help of systemically acting agents by dusting, watering, sprinkling or spraying or by feeding in sugar solutions to the bees. Disadvantage of these methods is the high application rate of 0.5-0.6 g of active ingredient per colony of bees to fight the Varroa jacobsoni well, as this amount moves just below the toxic limit for bees.

All described methods of control only work outside of the hatched brood.

Object of the invention

The object of the invention is to find a method for a new, bee-friendly, highly effective means for controlling the mite Varroa jacobsoni.

Explanation of the essence of the invention

The object of the invention is to find a method for the preparation of novel means of controlling the Varroa mite, which is easy to use.

This object is achieved in that the active substances of the formula I or II,

where Hal = Cl I or Hal = Br II and copper chelate of the acetoacetic ester of the formula

or copper chelate of the acetylacetone of the formula

IV

or copper chelate of the acetic acid of the formula

₂ [Cu (CH ₃ COO) ₂ · H ₂ O] V

are mixed with extenders and / or solvents, emulsifiers and / or dispersants by known methods and diluted in use with water.

For the preparation of 11 of the new composition, 2 to 35 g of the active compounds I or II and 0.02 to 0.6 g of Kupferchelateder of the formulas III, IV or V with the appropriate amount of the extenders and / or solvents, emulsifiers and / or dispersants mixed.

Solvents may be, for example, alcohols, glycols, ketones, polyglycols or sulfoxides. As emulsifiers or dispersants preferably alkylaryl polyglycol ethers or protein hydrolysates and natural products are used as emulsifiers. Concentrates are used between 1 to 10 ml for use in a normally developed colony of bees.

Surprisingly, these agents could be used as a potent agent against the mite Varroa jacobsoni both after stirring in water for spraying, sprinkling or watering the bees, as well as after being stirred into sugar or bee-high feed solutions for feeding to bees. It is thus optionally possible for the beekeeper to administer these agents by wetting a part of the bee colony or preferably by introducing them into the feed solution during stimulus or winter feeding.

The social exchange of bees among bees causes a uniform distribution among all members of a bee colony. The active substances reach the outside sucking parasites via the hemolymph. Surprisingly for the expert was that the new agent can also be introduced into the feed solution without having to accept a reduction in the effect of having to accept.

In comparison to the prior art, novel applications of the active substance mixtures continue to emerge when these solid feeds which serve as pollen substitutes are added.

In this way it is possible during the breeding season in the spring to target the larvae of the bees with the agents that are supplied by the bees before the honeycombs are covered with active feed. The amounts of active ingredients required for this purpose are low because the early larval stages of the Varroa mite are characterized by high sensitivity to these agents. This form of treatment is well suited to supplement the existing modes of application of Varroa mite control agents. The agents are included in the mixture in the following concentrations per kilogram of pollen substitute:

50-1,000 mg of the compounds I or II, preferably 200 mg and up to 17 mg of the compounds III, IV or V, preferably

The pollen substitute and the mixed medium are fed for 14 days each with 50g per day and per person.

Another advantage of the new agent is the high potency, which is significantly better than the already described in the literature means. The addition of the copper complexes results in the formation of a synergistic mixture whose effectiveness is almost qualitative. The type of application is not critical, so that the expert can choose the most favorable for him application without accepting loss of efficacy. The toxicity of the agent is very low in the application concentrations described, the bees are not damaged.

Preferably, the following concentrations are used:

25 to 32 mg of compound I or II

and 0.5 mg of copper chelate complexes of the formula III, IV or V.

embodiments example 1

Process for the preparation of the new composition

The ingredients specified in points a to I are mixed together in the predetermined concentrations.

Where:

I O, O-diethyl-O-O-chloro-A-methylcoumarin-T-y-thionophosphoric acid ester

II O.O-diethyl-O-O-bromo-methylcoumarin-T-yDthionophosphoric acid ester

III copper chelate of the acetoacetic ester

IV Copper chelate of acetylacetone

V copper chelate of acetic acid EO ethylene oxide

3.2 g Il 0.05 g III 100 g Dispersant based on ethoxylated alkylphenol with 12 EO ad 1000 ml Polyethylene glycol 600 3.0 g Il 0.05 g IV 70g Dispersant based on alkylaryl polyglycol ether 30 g anionic emulsifier ad 1000 ml Polyethylene glycol 400 3.2 g I 0.04 g III 100 g Dispersant based on ethoxylated alkylphenol with 12 EO ad 1000 ml Polyethylene glycol 600 3.0 g I 0.04 g IV 50 g Dispersant based on ethoxylated alkylphenol with 55 EO 50 g Emulsifier based on ethoxylated alkylphenol with 5-7 EO ad 1000 ml propylene glycol 3.2 g Il 0.05 g III 40 g ethoxylated ricinoleic alcohol with 20 EO 100 g ethoxylated alkylphenol with 12EO ad 1000 ml dimethyl sulfoxide 3.2 g Il 0.05 g V 100 g Dispersant based on ethoxylated alkylphenol with 12 EO ad 1000 ml Polyethylene glycol 600 32g Il 0.5 g III 20 g Dispersant based on ethoxylated alkylphenol with 55 EO 70 g ethoxylated ricinoleic alcohol with 9 EO ad 1000 ml acetone 30 g I 0.5 g III 100 g Dispersant based on ethoxylated alkylphenol with 12 EO ad 1000 ml acetone 32 g I 0.4 g IV 30 g Dispersant based on ethoxylated alkylphenol with 16 EO 80 g Emulsifier based on ethoxylated alkylphenol with 5-7 EO ad1,000 ml acetone 32 g Il 0.5 g III 100 g Dispersant based on ethoxylated alkylphenol with 12 EO ad 1000 ml dimethyl sulfoxide 32 g Il 0.5 g III 100 g Dispersant based on ethoxylated alkylphenol with 12 EO ad1,000 ml acetone 2.0 g Il 0.033 g III 2.0 g ascorbic acid ad 10 kg soy flour

Of the novel agents mentioned in Example 1, 10 ml and g to 1 ml per normally developed colony of bees are used in the compositions a to f.

Example 2

Determination of bee compatibility The bee compatibility of the active substance combinations is determined in the deposit test to determine the contact effect and in a test to determine the feeding toxicity.

To carry out the deposit test, Petri dishes of 15 cm diameter on the bottom and lid were completely lined with filter paper.

The aqueous preparations prepared with the aid of solvent and disperser are applied evenly to the filter paper (2 ml / 100 cm ² ). After the evaporation of the water 10 working bees have been used per shell. For each concentration of a test agent, 50 test animals were used. The exposure time was 24 hours. The mortality of the bees was determined and the LC ₅₀ value was derived from UTCHFIELD and WILCOXON. The experiments included an untreated control. The temperature during the test was 22 ± 2 ° C. During the observation period

the experimental animals received a 50% sugar solution. To determine the feeding toxicity ad libitum aqueous preparations with 50% sugar content have been offered to the bees over a period of 72 hours in feeding tubes. All other experimental conditions corresponded to those mentioned in the deposit test.

Table 1 shows the results of the determination of the bee toxicity of an active substance combination of Example 1, consisting of II and III (except I).

Table 1

Bee toxicity of a new drug combination

samples

LC ₅₀ contact (deposit test) in mg / 100 cm ²

LC ₅₀ -ad libitum in mg / ml

7.6

1.0

From the obtained LC ₅₀ values, the bee compatibility of the drug combination can be derived.

Example 3

Proof of synergistic efficacy

To check the synergistic activity of the combinations for combating the mite Varroa jacobsoni, the compounds I, II and the metal chelates III, IV or V in the compositions according to Example 1 with Varroa mites

infested working bees have been fed.

This mixture proved to be optimal considering the solubility of the metal complexes. The test substances were dissolved in acetone and diluted 1:10 with 30% honey solution. Depending on the concentration of the active ingredients or the combinations, 20 mite contaminated bees have been used. The volume of the honey-containing honey solution administered per bee was Βμ \. After administration, the test animals were kept individually in test cages at 35 ° C and fed with honey solution. After 72 hours of observation, the live and dead Varroa mites became

counted.

Table 2

Effectiveness of the new agents against the Varroa mite under laboratory conditions

samples

Drug cost in g per bee

Efficiency in%

Il III

II + III I

IV I + IV

0.5

0.0085

0.5 + 0.0085

0.5

0.0086

0.5 + 0.0086

76.3

91.2 69.8

0 88.6

Under practical conditions with a combination of active ingredients consisting of II + III in compositions of Example 1 compared to non-synergized Il and to a liquid and a granular commercial preparation based on the drug Coumaphos 5 bee colonies with 50ml of an aqueous preparation per people by dropping on the bees have been treated along the lattice streets or by feeding 500 ml in 30% sugar solution per colony.

After 7 days was a repeat treatment.

The liquid preparation contained 32 g / l active ingredient, the granules 50g / kg.

Example 4

Effectiveness of the new funds under field conditions

The treatment of bee colonies took place in the fall after Trachtabschluß to a brutal time. The effectiveness has been determined by counting the mites of 200 bees per cane before and after the treatments. The following results were achieved: (Table 3)

Table 3

Effectiveness of the new funds under field conditions

samples

application form

Active ingredient in mg / people

efficiency

Il and III

according to Example 1

Coumaphos liquid preparation Coumaphos granules

dripped

lined

dripped

lined

dripped

lined

dripped

lined

30 + 0.5

30 + 0.5

96.72 92.87 93.55 87.50 91.41 14.58 11.72 77.65

The efficiencies of the combinations of II + III listed in Tables 2 and 3 compared to the prior art agents based on the active ingredient Coumaphos show that the new agent by applicability in both proven forms of application with good bee compatibility by high efficiencies characterized and superior in this respect to the prior art comparative preparations.

Example 5

To prove the effectiveness of the new agents when feeding pollen substitutes, 10 kg of soya flour containing 2 g of the substances I or II and combinations of the substances I and II with the synergistic additives III or IV or V were fed to the bees.

The feed was given at the beginning of breeding. Per person and day 50g of the preparations were fed for a period of 14 days. Depending on the experimental variant, the treatment was carried out by 5 colonies with relatively uniformly strong infestation. The treatment success was determined on the 25th day after the start of feeding. For each bee colony, 50 female workers, who were close to the hatching of the imagines, were removed and examined for infestation with Varroa mites. The following result was achieved:

Table 4

Effectiveness of new remedies after feeding with pollen substitutes based on soya flour

Percentage of infested dolls

9.3 3.3 2.7 2.0 2.0 0.7 1.3

test substance Active ingredient in mg 140 per people 140 control - 140 + 2,3 I 140 + 2,3 Il 140 + 2,3 I + III 140 + 2,3 I + IV Il + III Il + IV

Claims (1)

1. A process for the preparation of novel agents for the control of the mite Varroa jacobsoni on normally developed colonies, characterized in that the active substances of the formula (I) or (II), ^ P ο- ¹ ^ ^ ^ ⁰ (I), where Hai = Cl (II) if Hai = Brist, and copper chelate of the acetoacetic ester of the formula