DK158697B - APPLICATION OF ACARICIDE AGENTS TO TREAT MEAD INFECTIONS IN TREATING OVERVIEWING MEAD EGGS - Google Patents

Description

DK 158697B

The invention relates to the use of acaricidal agents of the kind set forth in claim 1.

The acaricidal agents in question are essentially known per se from DK Patent No. 154500 and IT Patent Application Nos. 26205 A / 80 and 21003 A / 80.

When evaluating the acaricidal activity of a compound that is active against mite eggs, one must distinguish between the ovicidal activity against the summer eggs and the ovicidal activity against the wintering eggs.

10 In fact, some midge species overwinter in the egg stage, and these overwintering eggs are less sensitive to pesticides than summer eggs. This is due to the dormant stage associated with embryonic life as well as the batri which the winter egg chorion, which is more resistant than the summer-15 egg chorion, presents to the pentation of the active substance.

Various acaricidal compounds are known, some of which are active against midsummer eggs and others active against pups or adult mites. However, due to the particular characteristics of the wintering eggs of mites, most of the known acaricidal compounds appear to be inactive in this species of eggs. However, the compounds known to have some activity against wintering eggs of mites are only partially active and only for the very short period of time close to the hatching of the eggs. Winter control of mites is usually carried out using formulations of phosphoric acid esters (especially Parathion) in mineral oils. In this case, too, the effectiveness of such formulations is not complete, and is achieved only by treating simultaneously with the hatching of the eggs.

In the short period during which such treatment may be 2

DK 158697B

to be useful, there are often adverse meteorological conditions. A treatment that precedes the previously stated period proves to be extremely effective on winter eggs because, as previously stated, they are particularly resistant to pesticide penetration. On the other hand, delayed treatment can produce such phenomena as phytotoxicity because the plants in the advanced vegetative state are sensitive to many mineral oils.

The availability of specific products active against overwintering eggs would allow the application of tea treatments only in winter, eliminating the difficulties previously stated, while offering the advantage of not damaging numerous insect species that are useful for controlling 15 mites (predatory insects). From a practical point of view, it can also be stated that the possibility of protecting the crops from mite attacks in winter, ie. for a period of time in which work on the farm is limited, represents an additional, undoubted benefit.

As far as the applicant is aware, there are no specific acaricidal compounds on the market that are effectively active against the overwintering eggs of mites.

In IT Patent Application Nos. 21003 A / 80 and Nos. 26205 A / 80, hydroquinone dieters have been described, all of which correspond to the following general formula: R - ° '(o) -O- (CH2) mX-'CH2 ) nV (I> wherein:.

R represents either C ^-C ^ alkyl or C ^-C ^ alkenyl; X represents an oxygen atom, a -CH = CH- or a -C = C- group; 30 m and n (equal or different) represent a positive integer from 1 to 4; 3

DK 158697B

Y represents an OH or SH group, a -O-R 2 or 1 -S-R group or a -O-C-R group

II

Wherein R: represents a C ^-C ^ alkyl, alkenyl or alkynyl, whereas R ^ represents a C ^-C ^ alkyl, C ^-C ^ cycloalkyl or phenyl.

The compounds of formula (I) disclosed in the prior Italian patent applications exhibit acaricidal activities that are effective both against adult mites and against their summer eggs.

Moreover, these compounds possess a practically negligible toxicity to warm-blooded animals and fish, and even at high doses, they exhibit no phytotoxicity to the most diverse agricultural crops.

It is an object of the invention to provide an application of compounds for controlling mite infections in the treatment of the overwintering eggs of mites, whereby the control is more effective than has hitherto been possible.

The use according to the invention is characterized by that of claim 1.

Thus, according to the invention, it has surprisingly been found that certain agents known per se exhibit a fully satisfactory acaricidal activity against overwintering mite eggs which have hitherto been considered to be highly resistant to acaricides.

It is well known from US Patent No. 4061683 diphenyl ether derivatives for the control of individuals of the order acarina. The study of those of this US patent 4

DK 158697B

However, known compounds were limited to the treatment of larvae or pupae, with no description being given of the use of these known compounds for the control of wintering mite eggs. Furthermore, it may be noted that in Table 2, later described in this specification, a comparison is made between a compound of the US patent (shown as compound A) and some of the compounds which are within the scope of the invention.

Thus, it has been found in accordance with the invention that some of the compounds of formula I have a particularly high acaricidal activity against the overwintering eggs of mites. These compounds may be combined under the limiting formula (II) of claim 1.

Thus, according to the invention, there is provided a method for combating mite infestation of beneficial plants by which the method of treating wintering (hibernal) eggs of mites with compounds of formula II, either as such or in the form of suitable agents.

The effectiveness of the compounds of formula II against overwintering eggs is satisfactory for practical application in the agricultural field. In fact, the compounds of formula II have a high acaricidal activity against the overwintering eggs, even at fairly low doses.

When applied correctly to contact all of the mite eggs, these compounds exert a virtually complete acaricidal effect and, as a result, the plants remain in an uninfected state for a long period of time (even for 2 months after period, during which the eggs would otherwise hatch), enabling the treatment to be postponed to the adult mites, which can significantly

DK 158697 B

5 may occur later as a result of other infections of another origin.

The known products used against the winter eggs of mites (e.g., mineral oils to which phosphoric acid esters have been added), in addition to exhibiting the aforementioned disadvantages of use, have no complete activity, and thus To achieve the same results you need to perform at least two additional spring treatments with acaricidal products.

10 For practical applications in agriculture, the compounds of formula II were used in the form of suitable mixtures for the main purpose of obtaining the best possible distribution of the product so as to reach all the mite eggs, often present on plant parts, 15 which are difficult to reach .

The above agents may contain, in addition to one or more of the compounds of formula II, as an active ingredient an inert carrier and a surfactant.

The choice of the carrier (carrier) and of the additives depends on the type of formulation required.

Suitable formulations are the emulsifiable concentrates consisting of the active ingredient, of a liquid carrier such as an organic solvent, and of 25 surfactants. Examples of organic solvents which may be used in the above mixtures are aromatic or alkyl aromatic hydrocarbons such as xylene or other commercial mixtures of alkyl aromatic hydrocarbons, alcohols such as butyl or isoamyl alcohol, ketones such as ethyl amyl ketone or cyclohexanone. · 6

DK 158697B

Examples of surfactants which may be used in the above compositions are alkylbenzene sulfonates, polyoxyethylated alkyl phenols, polyoxyethylated vegetable oils, polyoxyethylated fatty acids glycerides, polyoxyethylated sorbitan oleate or mixtures thereof.

In the above compositions, the constituents may be present in the following quantities: A - active ingredient (compound of formula II) 0.5-50 wt% 10 B - organic solvent 30-80 wt% C - surfactant 0.5-20 weight-%

It is known that mineral oils exhibit some activity against the overwintering eggs of mites. However, such activity, which is not particularly pronounced, derives essentially from a physical activity because the indicated oils can cover the mite eggs with a very thin film, thereby preventing exchanges of gaseous components so that even often causing the death of the undeveloped mite.

20

Thus, it is possible that mineral oils which function as a carrier medium, but which at the same time also act as an active substance, can also be added to the compositions described above:

The appropriate mineral oils are the commercial oils having a content of non-sulfonated substances greater than or equal to 80%. The solvents and surfactants that can be used are those listed above.

In these mixtures, the constituents may be present in the following amounts:

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7 A - Compound of Formula II 0.5 - 30% by weight B Mineral Oil 40 - 80% by weight C - Organic solvent 5 - 30% by weight D - Surfactant 0.5 - 20% by weight in all cases where a particular situation should require, to the mixtures or formulations to which the use according to the invention is directed, also to add other active substances useful for winter control of other plant infections and diseases.

These active substances may include insecticides, but above all fungicides.

The intermediate species which can be effectively controlled at the stage corresponding to wintering eggs, in the application to which the invention is directed, belong in particular to the Tetranychidae family, the genera Panonychus, Bryobia and Oligonychus.

Among these species, the most important in terms of the spread of the damage inflicted on the plants and in the wide spread in all temperate areas is Panonychus 20 ulmi, which almost everywhere exhibits a high level of resistance to the various pesticides due to the intense chemical attack to which this species is systematically exposed.

The amount of active substance to be distributed to ensure an effective effect against the overwintering eggs of mites may vary depending on various factors. Usually amounts between 0.1 and 3 kg / ha are perfectly satisfactory.

The preparation of the agents to which the use according to the invention is directed does not require any particular method.

8

DK 158697B

The active ingredient (compound of formula II), the solvent and the surfactant are mixed without any preferred order at room temperature. To this mixture is added the mineral oil, 5 if necessary.

To better illustrate the invention, some examples are set forth below.

EXAMPLE 1

Preparation of Acaricidal Mixtures 10 Representative examples of acaricidal mixtures are reported in the following Table 1.

In order to simplify the scope of Table 1, the following abbreviations have been used.

a.i. = active ingredient; the following compounds of formula II have been used as active ingredient:

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9 1) ch3- (ch2) 9.0- (o). o-ch2-ch2-ch2-c = c-ch2-o-ch3 2) ch3- (ch2) i0-oh (o) - * 0-ch2-ch2-.ch2-c = c-ch2-0-ch3 3) ch3- (ch2) 7-0- <g> - o-ch2-ch2-ch2-c = c-ch2-o-ch-ch3 4) ch3- (ch2) o-ch2-ch2-ch2-c = c-ch2-o-ch3 5) ch3- (ch2) 7-0- ^ o) - o-ch2-ch2-ch2-c = c-ch2-o-ch2-ch3 6) ch3- (ch2) 9 -o- ^ O ^ o-ch2-ch2-ch2-c = c-ch2-oh 7) ch3- (ch2) 9-0- ^ O ^ 0-ch2-ch2-ch2-c = c-ch2-0 -c- o 8) ch3- (ch2) 9-o - ^^) - o-ch2-ch2-ch2-c = c-ch2-oc-ch3 o 9) ch3- (ch2) 9-o ^ O > - o-ch2-ch2-ch2-c = c-ch2-oc-ch (ch3) 2 o 10) ch3- (ch2) 9-o. ^ q ^ o - ch2-ch2-ch2 ^ chc-ch2 -o-ch2-ch = ch2 10

DK 158697B

solvents

Sol 1 = xylene, commercially available mixtures are used

Sol 2 = isobutyl alcohol Sol 3 = cyclohexanone.

Mineral oils MO 1 = Mineral oil with a content of non-sulfonable substances of 905o or more M0 2 = Mineral oil with a content of non-sulphonatable substances of 805o or more.

Surfactants

Acid 1 = Mixture of polyoxyethylated nonylphenyl (7 moles of ethylene oxide per mole of substrate), polyoxyethylated sorbitan oleate (20 moles of ethylene oxide per mole of substrate) and calcium dodecylbenzenesulfonate in the 4.9: 2.1: 3 ratio.

Acid 2 = Mixture of polyoxyethylated nonylphenyl (7 ETO) and sorbitan oleate (20 ETO) in a 5: 3 ratio.

Acid 3 = Mixture of polyoxyethylated nonylphenol (7 ETO) 20 and sorbitan oleate (20 ETO) in the ratio 7: 3.

11

DK 158697B

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DK 158697B

The mixtures reported in Table 1 are prepared by simply mixing the ingredients at room temperature. The mixtures containing mineral oils have been prepared by mixing the oil with the mixture 5 of the other ingredients.

EXAMPLE 2

Determination of acaricidal activity on winter eggs of Pa-nonychus ulmi.

Twigs heavily infected with P. ulmi have been cut 10 in the fall from apple trees that are propelled in an orchard that is naturally infected with mites.

The twigs have then been kept outdoors under natural conditions.

Working in an unheated environment during the winter, small parts were cut out from the twigs on which the eggs were particularly concentrated, and for each of these parts the number of eggs which showed clear vitality was spoken, removed all damaged eggs and eggs whose hatching status was uncertain.

20 With each of the compounds tested, suitable mixtures and formulations were prepared, and with each of them treated by spraying twenty twigs, containing a total of 800-1000 eggs.

After drying, the twigs were kept outdoors under a natural cover until the end of the sample.

The results were assessed several days after completion of hatching of eggs in the blank (portion 13).

DK 158697B

infected twigs treated only with a hydroacetonic solution [cf. note b to Table 2] and a surfactant) by counting the un hatched eggs in comparison to the eggs present before treatment, and by taking the un hatched 5 eggs into the blank.

Following the same method, infected twigs have also been treated with a commercial agent containing Parathion in mineral oil.

In the following Table 2, the 10 activity data against winter eggs reported by Panonychus ulmi have been reported by some agents used according to the invention and by some known agents.

Because a certain number of mite eggs, both in the trial and in the blank, can be altered or missing for natural, not 15 defined reasons, the results have been expressed in the form of activity classes instead of percent values which would not be suitable for the practical nature of the experiment, as follows: ++++ = practically complete acaricidal activity 20 +++ = high activity ++ = partial activity + = negligible or any activity Based on the values given in Table 2, it can be seen The agents used according to the invention exhibit a high activity against winter eggs of mites.

This activity is high even when investigated in the form of simple hydroacetonic solutions and it becomes practically complete when used in the form of actual formulations, independent of the presence of a mineral oil.

DK 158697B

14 TABLE 2

Acaricidal activity against P. ulmi winter eggs.

Active Formulation Dose a.i. Acaricide resistance (%) [% min. activity part (a.i.) oil] ·

Compound Hydroacetonic 0.05 ++++ # 1 solution 0.01 +++ EC 20 0.05 ++++ 0.01 ++++ EC 20+ mineral 0.01 [2] ++++ oil

Compound Hydroacetonic 0.05 +++ # 2 solution 0.01 ++

Compound EC 20 0.05 ++++ No. 6 0.01 ++++ EC 20 + Mineral 0.01 [2] ++++ Oil

Compound EC 20 0.05 ++++ No. 9 0.01 ++++ EC 20 + Mineral 0.01 [2] ++++ Oil

Compound EC 20 0.05 ++++ No. 10 0.01 ++++ EC 20 + Mineral 0.01 [2] ++++ Oil

Compound EC 20 0.05 + A (ref.) 0.01 + EC 20 + mineral 0.01 [2] ++ oil

Parathion in Commercial Formula 0.06 [0.96] ++ mineral oil ring

Mineral Oil - [2] _ ++

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15

Notes for Table 2 (a) active ingredients:

The agents containing compounds 1, 2, 6, 9 and 10 have been identified by their formula in Example 1; compound A is a reference compound of the formula: (° y ° - <o) -o-ch 2 -ch 2 -ch 2 -c 5ch (a> according to United States Patent No. 4,061,683;

Parathion is the generic name for the compound 0,0-diethyl-O-p-nitrophenyl phosphorothioate.

Mineral oil ^ is a mineral oil with a content of non-sulfonable substances above 80¾. An emulsion of mineral oil (80% by weight) in water was used in the experiments.

(b) EC 20 means an emulsifiable concentrate (20 wt. 5o) of active ingredient; EC 20 + mineral oil is a mixture made at the moment of treatment.

Hydroacetonic solution is a solution or dispersion of the active ingredient in a water-acetone mixture (acetone 10 wt.

Similar good results have been obtained by using mixtures of Example 1 and containing the other active compounds of Formula II listed in Example 1, both with mineral oil and without.

Claims (11)

Use of acaricidal agents containing as active ingredient one or more hydroquinone dieters of the formula: R 'o -ch 2 -ch 2 -cVc = C-CH 2 -O-R "(11) f 5 wherein R' represents C C ^ alkyl alkyl; R; represents a hydrogen atom, C,-C. alkyl, allyl 2 in ii- or a -C-R group, wherein II 0 2 R represents C 1 -C 4 alkyl, C 1 -C 6 cycloalkyl or phenyl for controlling mite infections by treating the overwintering eggs of mites. Use according to claim 1, characterized in that the acaricidal agents contain a compound of formula II as an active ingredient in addition to inert carriers, surfactants and optionally my real oils. Use according to claim 2, characterized in that the acaricidal agents are in the form of emulsifiable concentrates in which the carrier is an organic solvent. Use according to claim 3, characterized in that the acaricidal agents consist of A - 0.5-50% by weight of formula II B - 30-80% by weight of organic solvent 25 C - 0.5-20% by weight -% surfactant. DK 158697B Use according to claim 3, characterized in that the acaricidal agents consist of A - 0.5-30% by weight compound of formula II B - 40-80% by weight mineral oil 3C - 5-30% by weight organic solvent D - 0.5-20% by weight of surfactant. Use according to claim 4 or 5, characterized in that the organic solvent is alkyl-substituted aromatic hydrocarbons, alcohols or 10 ketones. Use according to claim 4 or 5, characterized in that the surfactant is an alkylbenzenesulfonate, a polyoxyethylated alkylphenyl, a polyoxyethylated vegetable oil, a polyoxyethylated sorbitan oleate or mixtures thereof. Use according to claim 5, characterized in that the mineral oil is a mineral oil with a content of non-sulfonable substances greater than or equal to 80%. Use according to claims 1-8, characterized in that the wintering eggs of mites are treated by distributing an effective amount of the acaricidal agent on the infected area or plants. Use according to claim 9, characterized in that the mites to be controlled belong to the family Tetranychidae, or the genera: Panonychus, Bryobia or Oligonychus. Use according to claim 10, characterized in that the mites that are controlled belong to the species Pananychus ulmi.