HU188111B - Acricide compositions containing hydroquinone-diether derivatives as active agents,against surviveing eggs - Google Patents

Description

FIELD OF THE INVENTION The present invention relates to acaricidal compositions containing hydroquinone diene derivatives as an active ingredient, which can be used effectively against mite infestations of useful plants, particularly overwintered eggs.

To determine the acaricidal activity of a particular sub-ova compound, a distinction should be made between ovicidal activity against summer oviposition and ovicidal activity against overwintering ova.

Certain mite species are able to overwinter in the mite state, and these overwintering eggs are less susceptible to pesticides than summer eggs. This is due, on the one hand, to the slow and relaxed nature of embryonic life and, on the other hand, to the fact that the egg chorion is more resistant to winter eggs than to summer eggs and inhibits the penetration of the active ingredient.

Various acaricidal compositions are known, some of which are effective against the summer eggs of mites, others against neenodes or adult mites. However, due to the special properties of overwintering mites, most of the known acaricides have been shown to be ineffective against this type of egg.

Another group of active ingredients was found to be partially active, but only in the very short period before hatching of the eggs. Winter control of mites usually involves the use of phosphoric ester preparations (mainly Parathion) in mineral oil. The effects of such preparations are never perfect and can only be used effectively if they are used in a timely manner in the course of ovulation.

In the short period during which such treatment may be useful, the weather conditions are often inadequate. The treatment carried out before the aforementioned period is very ineffective against winter eggs, as they are, as mentioned earlier, particularly resistant to the penetration of pesticides. On the other hand, it is. delayed treatment can cause phytotoxicity as it is sensitive to many mineral oils in the advanced vegetative phase of the plant.

If special preparations were available for overwintering eggs, it would be possible to carry out the treatment at any time during the winter, thus avoiding the difficulties listed, without the advantage that many insect species (rabies) useful for mites would not be harmed. . In addition, the possibility of protecting plants from mites in winter, a period when there is little work on the land, is another indisputable advantage.

At present, no acaricidal agent is known which is active against overwintering eggs.

European Patent Application Publication No. 0037092 discloses hydroquinone diethyl derivatives of formula (I). In the general formula (I)

R is C4-C18 alkyl or alkenyl,

X is oxygen, -CH = CH-, or -C = C-, m and n are the same or different and each may be 1, 2, 3 or 4,

Y is -OH, -SH, -O-R ¹ , -S-R ^1, or a) wherein

R ¹ is C 1 -C 4 alkyl or C 2 -C 4 alkenyl or alkynyl,

R ² is C 1 -C 4 cycloalkyl or phenyl.

The compounds of formula (I) according to the above-mentioned Italian patents have acaricidal activity and are active against both adult mites and summer eggs.

In addition, the compounds of formula (I) have very low toxicity in warm-blooded animals and fish, and do not show any phytotoxic activity, even at high doses, as tested in a variety of plants.

Surprisingly, some of the compounds of formula (I) have been found to be extremely effective against overwintering eggs of mites. These compounds are represented by the general formula (II). In the general formula (II)

R 'is C 8 -C 11 alkyl,

R is hydrogen, C1-4 alkyl, allyl or C (O) R ² of formula wherein and ^R2 is C1-4 alkyl, C3-6 cikloalkilcsopo'rt or phenyl.

The present invention therefore relates to an acaricidal composition which is effective primarily against overwintered eggs and which contains as active ingredient one or more compounds of formula II.

The efficacy of the compounds of formula (II) against overwintering eggs exceeds the level required in practice in agriculture; these compounds exhibit very good acaricidal activity even at relatively low doses.

In addition, the compounds of formula (II), when properly applied and delivered to each mite, will have a practically perfect acaricidal action and will, consequently, be free of infections for a long period, up to two months from the time of hatching of the eggs. Thus, it is sufficient to start protection against adult mites much later than usual, when it may be necessary due to re-infection of another origin.

In addition to the disadvantages described above, the conventional methods used for overwintering eggs (for example, treatment with mixtures of mineral oils and phosphoric acid esters) have the disadvantage that they are not perfect, so that at least two spring treatments with some acaricide are required to achieve the same result.

For practical application in agriculture, it is preferable to use the compounds of formula II in the form of suitable preparations; This ensures the best possible distribution of the active ingredient and the delivery of the active ingredient to each egg, including those in hard to reach parts of the plant.

In addition to one or more of the active compounds of formula (II), the compositions of the invention also comprise an inert carrier and optionally a surfactant.

The choice of carrier and other additives will depend on the type of formulation desired.

Suitable formulations include emulsion 2188 III concentrates, which contain, in addition to the active ingredient, a liquid carrier such as an organic solvent and surfactants. Organic solvents include, for example, aromatic or alkyl aromatic hydrocarbons such as xylene or other commercially available alkyl aromatic hydrocarbon mixtures, alcohols such as butyl or isoamyl alcohol, or ketones such as ethyl amyl ketone or cyclohexanone.

Suitable surfactants for use in the aforementioned formulations include, for example, alkyl benzene sulfonates, polyethoxylated alkyl phenols, polyeloxylated vegetable oils, glycerides of polyethoxylated fatty acids, polyethoxylated sorbitan oleate or mixtures thereof.

The ingredients of the compositions may be used, for example, in the following proportions:

A - active ingredient [compound II] 0.5-50% by weight ",

B - 30 to 80 weight organic solvent, ¹ ',,

C - surfactant 0.5 to 20 wt.

It is well known that mineral oils are to some extent effective against overwintering eggs of mites. However, this effect, which is not very strong, is basically due to physical effects, as these oils form a very thin film on the surface of the mite, thus inhibiting gas exchange and often causing embryo destruction.

Thus, a mineral oil may be added to the composition described above as a carrier, but at the same time it will also act as an active ingredient.

As mineral oils, commercial oils containing 80% or more non-sulfonating components can be used. Solvents and surfactants in such formulations may also be listed above.

For example, formulations containing mineral oil may include:

Ά - 0.5 to 30% by weight of a compound of the formula II

B - mineral oil 40-80% by weight

C - organic solvent 5-30% by weight

D - surfactant 0.5-20% by weight

If required for any specific reason, other active ingredients against other winter plant pests or diseases may be added to the composition of the invention.

These additional active ingredients may also be insecticides, but may be primarily fungicidal.

The compositions of the present invention belong to the family of Tetranychidae, Panonychus, Bryobia and Oligonychus, which are effective in controlling the overwintering oviposition stage.

Panonychus ulmi is the most prominent among the species of the genus listed, due to the extent of the damage caused and its high prevalence in the temperate zone, which is almost everywhere highly resistant to various pesticides, which are subject to intense chemical attack.

The effective amount of active ingredient against overwintering mites depends on a number of factors. Usually 0.1-3 kg ha can be used to achieve a satisfactory result.

The compositions of the present invention are prepared in a manner known per se by mixing the active ingredient of the formula (II), the solvent and the surfactant; neither the order in which the components are added nor the temperature during mixing is important. To this mixture are then added mineral oils, if necessary.

The present invention is illustrated by the following non-limiting examples.

/. example

Preparation of an acrylic preparation

The composition of some of the formulations is shown in Table I, which uses the following abbreviations:

solvents

Sol I = xylene; used commercially available mixtures,

Sol 2 = isobutyl alcohol,

Sol 3 = eiclohexanone.

mineral oils

MO I = 90, mineral oil containing 90 or more non-sulfonating agents,

MO 2 = mineral oil containing 80, or more non-sulfonating agents.

Surfaces tiv

Sur 1 = mixture of nonylphenol ethoxylated with 7 moles of ethylene oxide per mole, sorbitan oleate ethoxylated with 20 moles of ethylene oxide and calcium dodecylbenzene sulfone in a ratio of 4,9: 2,1: 3,

Sur 2 = 7: 3 mixture of nonylphenol ethoxylated with 7 moles of ethylene oxide and 20 moles of ethylene oxide anhydrous sorbitan olea.

Active Ingredients

Each of the compounds (I) to (10) of the formula (II) was used as an active ingredient in formulations 1-9. Thus, each comprises 10 different compositions which differ only in the active ingredient.

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Table 1

The composition of some compositions of the invention

components - _r -, - 1 ——-, ---, -, - Serial number of the preparation First Second Third 4th 5th 6th 7th 8th 9th Active ingredient (% by weight) 20 20 20 10 50 5 5 20 2.5 petroleum MO 1 (% by weight) 80 45 80 MO 2 (weight ^ü / ") - - - - - - 80 - - Solvent Sol 1 (% by weight) 70 80 40 7 7 25 9.5 Sol 2 (% by weight) - 70 - - - - - - - Sol 3 (% by weight) - - 70 - - - - - Surfactant Sur 1 (% by weight) 10 10 10 10 10 Sur 2 (% by weight) - - - - - the 8 - 8 Sur 3 (% by weight) - - - - - - 10 -

The formulations in Table 1 are prepared by simply mixing the components at room temperature. In the preparation of mineral oil formulations, the oil is mixed with a mixture of the other components.

Example 2

Investigation of acaricidal effect on overwintering eggs of Panonychus ulmi

Apple trees cultivated in moths naturally infested with mites were cut off in autumn in branches severely infected with Panonychus ulmi eggs. The branches were then kept outdoors under natural conditions and then, in the winter, in unheated environments, parts of the twigs which had a particularly high number of eggs were slaughtered, and each branch was counted with no doubt live eggs and those with damaged hatching were removed. sure.

Each of the compositions to be tested was sprayed with 20 pieces infected with a total of 800-1000 eggs. After drying, the pieces were kept outdoors under a protective cover under natural conditions until the end of the study.

Results were evaluated a few days after hatching the eggs on the control infected branches (sprayed only with aqueous-acetone solution and surfactant) by counting the number of non-hatching eggs relative to the number of eggs hatched prior to treatment. the number of eggs.

Following the above procedure, infected branches were treated with a commercial formulation containing Parathion and mineral oil.

Table 2 shows the effect of some of the compositions of the invention and some known compounds on overwintering eggs of Panonychus ulmi.

Because a number of eggs have been transformed or destroyed for natural reasons in both experimental and control arms, results are expressed in activity groups instead of percentages that would not adequately represent the experimental result in practical terms. The following groupings are used:

+ + + + practically perfect acaricide effect, + + + high acaricide effect, + + partial acaricide effect, + negligible acaricide effect or ineffective.

It can be seen from the data in Table 2 that the compositions of the present invention are very effective against overwintering eggs of mites.

The active compounds according to the invention are also very effective in simple aqueous-acetone solutions and they are practically perfect in the form of formulations, regardless of the presence of mineral oil.

Table 2

The effect of some of the compositions of the present invention on overwintering eggs of Panonychus ulmi

Active substance (a) Preparation (b) agent The amount (° / o) (Mineral oil) Acaricidal effect (c) Compound (1) Aqueous acetone solution 0.05 0.01 + + + + +++ EC 20 0.05 + + + + o'oi + + + + EC 20 + mineral oil 0.01 [2] + + + +

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Active substance (a) Preparation (b) agent The amount (%) (Mineral oil) Acaricidal effect (c) Compound 2 Aqueous acetone solution 0.05 0.01 + + + ~ ++ Of formula (6) EC 20 0.05 + + + + compound 0.01 + + + + EC 20 + mineral oil 0.01 [2] + + + + (9) EC 20 0.05 + + + + compound 0.01 +++ t EC 20 + mineral oil 0.01 [2] + + + + (10) EC 20 0.05 + + + + compound 0.01 + + + + EC 20 + mineral oil 0.01 [2] + + + + Formula A EC 20 0.05 + compound 0.01 + EC 20 + mineral oil 0.01 [2] ++ Parathion in mineral oil Commercial preparation 0.06 [0.96] ++ petroleum - [2] ++

Notes:

(a) The reference compound of formula A is described in U.S. Patent 4,061,683; the chemical name of Parathion is 0.0-diethyl-O- (p-nitro) phenyl-phosphorothioate;

The mineral oil used was an oil containing more than 80% non-sulfonating agent, and the mineral oil was used as an 80% aqueous emulsion in the experiments.

fb) EC 20 is an emulsion concentrate containing 20% by weight of active ingredient; EC 20 + mineral oil refers to a mixture that is prepared before treatment; an aqueous solution of acetone in the form of a solution or dispersion of the active ingredient in a mixture of water and acetone containing 10% by weight of acetone;

(c) Similarly good results were obtained when using the formulations of Example 1 containing the other active compounds of formula (II) listed in Example 1, with or without mineral oil.

Claims (2)

An acaricidal composition comprising one or more hydroquinone diether derivatives of formula II as an active ingredient R 'is C 8 -C 11 alkyl, R is hydrogen, (C 1 -C 4) -alkyl, allyl or -CO-R ² R ² is C 1 -C 4 alkyl, C 3 -C 5 cycloalkyl or phenyl in an amount of from 0.5 to 50% by weight with 30 to 80% by weight of an inert carrier, preferably an organic solvent, preferably an alkyl aromatic hydrocarbon, alcohol or ketone and / or mineral oil. the non-sulfonating moiety of which is preferably in admixture with 80% or more and optionally 0.5-20% by weight of a surfactant, preferably alkylbenzene sulfonate, (polyoxyoxylated) alkylphenol, vegetable oil, sorbitan oil or a mixture thereof. Acaricidal composition according to claim 1, characterized in that it contains 0.5-30% by weight of active ingredient, 40-80% by weight of mineral oil, 5-30% by weight of organic solvent and 0.5-20% by weight of surfactant.