LU83799A1 - ACARICIDAL COMPSOTIONS ACTING AGAINST HIBERNATED EGGS - Google Patents

Abstract

A method and compositions for combatting mite infestations on useful plants, by treating the hibernating (or over-wintering) eggs with a compound of the general formula: <IMAGE> in which R' represents an alkyl group having from 8 to 11 carbon atoms, R'' represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, an allyl group or a <IMAGE> group, in which R<2> represents an alkyl group having from 1 to 4 carbon atoms, a cycloalkyl having from 3 to 6 carbon atoms or a phenyl group.

Description

"

Miticide compositions acting against hibernating eggs,

The present invention relates to a method for combating infestations of plants useful by mites and more particularly relates to a method for combating these infestations by treating moth eggs in hibernation with compounds belonging to the diethers class. 'hydro-quinone ,. Furthermore, the invention relates to compositions containing the above-mentioned compounds and acting against hibernating moth eggs.

When evaluating the acaricidal activity of a compound acting against moth eggs, a distinction should be made between ovicidal activity against summer eggs and ovicidal activity against hibernating eggs.

15 Indeed, some species of hibernate mites are born at the egg stage and these hibernating eggs are less sensitive to pesticides than summer eggs. This characteristic is due to the state of rest of embryonic life ^ as well as to the barrier which the chorion of the egg (which is more resistant than that of summer eggs) opposes the penetration of the active substance .

Various acaricidal compounds are known, some of which act against the eggs of summer mites, while others act against moths or adult mites. However, due to the special characteristics of moth eggs in hibernation, most of the known miticide compounds have been found to be inactive vis-à-vis eggs of this type.

Other compounds have been found to be active only partially and exclusively during the very short period close to hatching of the eggs. We ef— *; 2 “l usually perform winter control of mites using formulations of phosphoric esters (in particular, Parathion) in mineral oils. Likewise, in this case, the effectiveness of these formulations is never complete and it is only achieved by carrying out a treatment in coincidence with the hatching of the eggs.

During the short period during which such treatment can be useful, atmospheric conditions are very often harmful. A treatment carried out before the aforementioned period proves to be ineffective on winter eggs because, as indicated above, these eggs are particularly resistant to the penetration of the pesticide. On the other hand, delayed treatment can give rise to phytotoxicity phenomena, since at an advanced vegetative stage, plants are sensitive to many mineral oils.

If specific products were available which act against hibernating eggs, treatments could be carried out in the middle of winter, thus eliminating the abovementioned difficulties, while at the same time benefiting from the advantage of not harming many species of insects useful for the control of mites (predatory insects). In addition, from a practical point of view, the possibility of protecting crops against attacks by mites in winter, * that is to say during a period during which l; agricultural work is limited, undoubtedly an additional advantage.

To the knowledge of the Applicant, there is no specific acaricidal compound commercially acting against moth eggs in hibernation.

In Italian patent applications Nos. 21ΟΟ3 A / 80 and 26205 A / 80, diethers 3 of hydroquinone have been described which may fall within the framework of the following general formula: R_0 - ^) ^ 0- (CH2). .-X- (CH2) n-ï (I) in which

R represents an alkyl group or an alkenyl group at yClg J

X represents an oxygen atom, a group -CH = CH-10 or a group -C = C- ·, m and n (which may be identical or different) each represent an integer from 1 to 4 5 * Y represents an OH, SH, -0-R1, -S-R1 or 15 -0-C-R2 group

II

0 where R * represents a C 1 -C 4 alkyl group, an alkenyl group or a C 2 -C 4 alkynyl group, 2 ^ 4 while R “represents a C 1 -C 4 alkyl group, a C 1 -C 4 cycloalkyl group or a phenyl group.

The compounds of formula (i) which have been described in the aforementioned Italian patent applications, exert acaricidal activities both against adult mites and their summer eggs.

In addition, the aforementioned compounds have practically negligible toxicity towards warm-blooded animals and fish, while, even in high doses, they are characterized by the absence of any phytotoxicity towards against the most widespread agricultural crops · Now, the Applicant has found that certain compounds of formula I were endowed with a particularly strong acaricidal activity against the 35 moth eggs in hibernation. These compounds may fall within the framework of the following restricted formula: * 4 vant e: R '- 0- (CH2) 3 ~ C ^ C-CH2-0-R "(II) 5 in which R * represents a Cn-C alkyl group, „: o 11 R11 represents a hydrogen atom, an alkyl group

AT

in C 1 -C 4, an allyl group or a group -C-R 4 O 2 in which R represents an alkyl group in a C 1 -C 4 cycloalkyl group or a phenyl group.

The object of the present invention is therefore to provide a method for combating infestations of plants useful by mites, this method consisting in treating moth eggs in hibernation with the compounds of formula II either as they are, either in the form of suitable compositions.

A subject of the present invention is also acaricidal compositions acting against hibernating moth eggs and containing, as active ingredient, one or more compounds of formula II.

The effectiveness of the compounds of formula II with respect to hibernating eggs is more than satisfactory for health for practical use in agriculture.

Indeed, the compounds of formula II have a high acaricidal activity against hibernating eggs, even at fairly low doses.

. * In addition, when properly applied to come into contact with all moth eggs, these compounds exert an almost complete miticide action and, therefore, the plants remain free of infestation for a long time (even during two months after the hatching period of the eggs), which makes it possible to delay considerably; treatments against adult mites which may later appear after 1 to 5 following new infestations of a different origin.

In addition to the fact that they have the aforementioned drawbacks during their application, the known products used against moth eggs in hibernation (for example, mineral oils added with phosphoric esters) do not have a complete activity and therefore , to obtain the same results, it is necessary to carry out at least two additional treatments in the spring with acaricide products.

For practical applications in agriculture, it is preferable to use the compounds of formula II in the form of suitable compositions, the main aim envisaged being to obtain the best possible distribution of the product in order to reach all the eggs of mites. which very often come to lodge on hardly accessible parts of the plants.

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

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

Suitable formulations are the emulsifiable concentrates consisting of the active ingredient, a liquid carrier such as an organic solvent, as well as surfactants. Among the organic solvents which can be used in the above compositions, some can be constituted, for example, of aromatic or alkyl-aromatic hydrocarbons such as, for example, xylene or other commercial mixtures of alkyl aromatic hydrocarbons, alcohols such as butyl alcohol or isoamyl alcohol, as well as ketones such as ethyl amyl ketone or cyclohexanone.

Γ 6

Among the surfactants which can be used in the abovementioned compositions, some are constituted, for example, of alkyl benzene sulfonates, of polyoxyethylated alkylphenols, of polyoxyethylated vegetable oils, of glycerides of polyoxyethylated fatty acids , polyoxyethylated sorbitan oleates; or their mixtures.

In the above compositions, the ingredients may be present in the following amounts: A - Active ingredient (compound of formula II) 0.5-50 $ by weight B - Organic solvent 30-80 $ - by weight 15 C - Surfactant 0.5-20 $ by weight.

We know that mineral oils exert a certain activity against hibernating moth eggs. This activity, which is however not very pronounced, is essentially due to an activity of a physical nature, since these oils can coat the eggs of mites with a very thin film, thus preventing gas exchange by even very often causing death. of the embryo.

Therefore, to the compositions described above, it is also possible to add mineral oils which act both as vehicles and as active substances.

'Appropriate mineral oils are the commercially available oils' having a content of non-sulphonable substances greater than or equal to $ 80. The solvents and surfactants which can be used are those mentioned above.

In these compositions, the ingredients can be used! may be present in the following quantities: / i.

7 A - Compound of formula XX 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.

Whenever a special situation demands it, to the compositions or formulations which are the subject of the present invention, it is also possible to add other active substances useful for the winter control of other plant diseases and parasites.

10 ‘These active substances can be in secticides, but mainly fungicides.

The species of mites which can be effectively combated at the stage of hibernating eggs * by the process and the compositions which are the subject of the invention belong to the family of

Tetranychidae, genera: Panonychus, Bryobia and Oligonychus.

Among these species, the most important with regard to the extent of damage inflicted on plants 20 and also with regard to its wide distribution in all temperate regions, is the species Panonychus ulmi which manifests a high degree of resistance almost everywhere. due to the intensive chemical attack to which it is systematically subjected.

The amount of active substance to be distributed to ensure effective action against moth eggs in hibernation, may vary depending on * different factors. As a rule, quantities between 0.1 and 3 kg / ha are perfectly sufficient.

The preparation of the compositions which are the subject of the invention does not require any particular process.

35 | The active ingredient (compound of formula II), the solvent and the surfactant are mixed together.

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8 active at room temperature and without any preferred order. If necessary, add mineral oil to this mixture.

A series of examples 5 will be given below in order to better illustrate the invention.

EXAMPLE 1

Preparation of acaricide compositions.

Representative examples of acaricidal compositions are listed in Table 1 below.

10 In order to simplify the understanding of table 1j, the following abbreviations have been used: i.a, = active ingredient; the following compounds of formula II have been used as an ingredient. active: 1) cV (ch2) 9-o ^ Ô) - o-ch2-ch2-ch2-c = c-ch2-o-ch3 2) ch3- (ch2) i0-0- ^ O ^ 0-ch2- ch2-ch2-c = c-ch2-0-ch3 20 / - \ 3) CH3- (CH2) 7-0- ^ Oy-0-CH2-CH2-CH2-C = C-CH2-0-CH-CH3 3 4) ch3- (ch2) 7-o - <^^ - o-ch2-ch2-ch2-c = c-ch2-o-ch3 25 5) CH3- (CH2) 7-0 ^ y 0-CH2- CH2-CH2-C = C-CH2-0-CH2-CH3

6) CH3- (CH2) 9-0 ^ ô> 0-CH2-CH2 ~ CH2-C = C-CH2-0H

7) CH3- (CH2V0 ^> 0-CH2-CH2-CH2-C = C-CH2-0-C- ^ 0 35 j 81 ch3- (ch2) 9-o - ^ - o-ch2-ch2-ch2- c = c-ch2-oc-ch3. ί ο Λ

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9 9) CH3- (ch2) 9-o / 5V o-ch2-ch2-ch2-csc-ch2-oc-ch (ch3) 2 '-' 0 10) ch3- (CH,) 9-oÆVo-ch2- ch2-ch2-c = c-ch2-o-ch2-ch = ch2 Solvents

Sol 1 = xylol, commercially available mixtures were used

Sol 2 = isobutyl alcohol Sol 3 = cyclohexanone.

Mineral oils. HM 1 = mineral oil with a content of non-sulfonatable substances greater than or equal to $ 90 HM 2 = mineral oil having a content of non-sulfonatable substances greater than or equal to $ 80.

Surfactants ATA 1 = mixture of polyoxyethylated nonylphenol (7 moles of ethylene oxide per mole of substrate), polyoxyethylated sorbitan oleate (20 moles of ethylene oxide per mole of substrate) and dodecyl - calcium benzene sulfonate in the ratio of 4.9: 2.1: 3.

25 ATA 2 = mixture of nonylphenol (7 moles of ethylene oxide) and sorbitan oleate (20 moles of ethylene oxide) polyoxyethylated in the ratio of 5: 3 · * ATA 3 - mixture of nonylphenol (7 moles of ethylene oxide) and sorbitan oleate (20 moles of ethylene oxide) polyoxyethylated in the ratio of 7: 3 ·

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EXAMPLE 2 Determination of the acaricidal activity on eggs of Panonychus ulmi. In hibernation.

10 ‘In autumn, apple twigs heavily infested with Panonychus ulmi eggs were detached from an orchard naturally infested with mites.

The twigs were then stored under natural conditions in the open air.

15 During the winter, working in an unheated environment, twigs were cut out, a small part on which the presence of eggs was particularly concentrated and, for each of these parts, the number was counted. eggs which were clearly alive by disposing of all deteriorated eggs and those whose hatching was uncertain.

With each of the compounds to be tested, suitable compositions and formulations were prepared and, with each, a spray treatment was carried out on 20 parts of twigs comprising, in total, about 800 to 1,000 eggs.

After drying, the twig parts were kept in the open air under shelter under natural conditions until the end of the test.

The results were determined several days after the end of the hatching of the eggs during the control (parts of infested twigs treated only with a hydro-acetone solution and a 35 I surfactant) by counting the number of unhatched eggs. $ compared with the eggs existing before the "7> 4 12 treatment · and taking into account the number of unhatched eggs during the control.

Following the same process, infested twig parts were also treated with a commercial formulation containing Parathion in mineral oil.

Table 2 below summarizes the activity results of certain compounds of the invention and of certain known compounds against eggs of Panony-10 chus ulmi 'in hibernation.

Since a number of moth eggs (both during testing and control) may be spoiled or missing for undefined natural reasons, the results have been expressed by activity classes rather than by percentages that would not be appropriate for the practicality of the experience, in this case; -H-H- = virtually complete miticide activity +++ - high activity 20 -H- = partial activity + = negligible or no activity.

From the results shown in Table 2, it appears that the compounds of the invention exert a high activity against moth eggs in hibernation.

This activity is high even if the compounds are tested in the form of simple hydro-acetone solutions and becomes practically complete when the compounds are formulated regardless of the presence of a mineral oil.

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Notes to table 2 (a) Active ingredients:

The compounds 1, 2, 6, 9 and 10 according to the invention have been identified by their formula in Example 1; the compound A is a reference compound (comparison) of formula: -0 ^ g) -0-CH2-CH2-CH2-C = CH (A) according to the patent of the United States of America n ° 4.061 .683; Parathion is the common name of the following compound:; 4,0-diethyl-O-p-nitrophenyl phosphorothioate.

15 Mineral oil is a mineral oil with a content of non-sulfonatable substances greater than 80%. In the tests, an emulsion of mineral oil ($ 80 by weight) in water was used.

(b) CE 20 denotes an emulsifiable concentrate at $ 20 20 by weight of active ingredient; CE 20 + mineral oil is a mixture prepared at the time of treatment.

The hydro-acetonic solution is a solution or dispersion of the active ingredient in a mixture of water and acetone (acetone: $ 10 by weight).

(c) Similar results have been obtained using compositions according to Example 1 containing the other active compounds of formula II listed in Example 1, both with and without mined oil - 30 / line.

;

V

Claims (11)

16 1. Miticide compositions suitable for combating mite infestations by treating hibernating moth eggs, characterized in that, as active ingredient, they contain one or more compounds of formula: R "-o ^ Q ^) - o -ch2-ch2-ch2-c = c-ch2-or "(II) 10 in which R * represents an alkyl group in cg" cn JR "represents a hydrogen atom, an alkyl group 2 in C- -C. , an allyl group or a group -CR in * 4 h „* which 0 2 15. represents a C 1 -C 4 alkyl group, a C 1 -C 4 cycloalkyl group or a phenyl group. 2. Miticide compositions according to claim 1, characterized in that they contain a compound of formula II as active ingredient, as well as inert carriers, surface-active agents and optionally mineral oils. 3. Miticide compositions according to claim 2, in the form of emulsifiable concentrates in which the support is an organic solvent. 25 4 · acaricide compositions according to claim 3f, characterized in that they have the following composition; A - Active ingredient (compound of formula II) 0.5-50% "" by weight 30 B - Organic solvent 30-80% - by weight C - Surfactant 0.5 - 20% by weight. 5 C - Organic solvent 5-30 $ by weight D - Surfactant 0.5-20 $ by weight. 5. Miticide compositions according to claim 3, characterized in that they have the following composition: "S.V ·" 17; A - Active ingredient (compound of formula II) 0.5-30 $ by weight B - Mineral oil 40-80 $ by weight 6. Compositions a cari ci des according to claim 10 14 or 5j characterized ^ -: e ;? that the organic solvent is chosen from alkyl aromatic hydrocarbons, alcohols and ketones. 7. Miticide compositions according to claim 4 or 5) characterized in that the surfactant is chosen from alkylbenzene sulfonates, polyoxyethylated alkylphenols, poly-oxyethylated vegetable oils, polyoxyethylated sorbitan oleates and mixtures thereof . 8. Miticide compositions according to claim 51, characterized in that the mineral oil is chosen from mineral oils having a content of non-sulfonatable substances greater than or equal to $ 80. 9. Method for combating infestations of plants useful by mites, characterized in that it consists in treating the eggs of moths in hibernation by distributing, over the infested area of plants, an effective amount of an aca composition -ricide according to claim 1. 10. A method for combating moth infestations according to claim 9, characterized in that the mites to be combated belong to the family Tetranychidae, genera: Panonychus, Bryobia and Oligonychus. 'ï 35 -Γ <_ 9 11. A method for combating infestations by mites according to claim 10, characterized in that the mites to be combated belong to the species Panonychus ulmi. - T ~ 'i * - 1 i