FR2520197A1 - ETHION AND PYRETHROID-BASED INSECTICIDE AND ACARICIDE COMPOSITIONS AND PROCESS FOR TREATING ARTHROPODIC VEGETABLES USING THE SAME - Google Patents

Abstract

THE INVENTION CONCERNS INSECTICIDE AND ACARICIDE COMPOSITIONS PRESENTING A SYNERGY EFFECT CONTAINING, AS ACTIVE MATERIAL, AN ASSOCIATION OF ETHION AND A PYRETHROID, SUCH AS CYPERMETHRIN. THEY ARE MORE PARTICULARLY INTENDED FOR THE FIGHT AGAINST PHYTOPHAGUS MITES THAT BECOME RESISTANT TO ORGANOPHOSPHORUS PESTICIDES.

Description

The present invention relates to insecticidal and acaricidal compositions

  with a synergistic effect for the control of arthropod pests It also concerns a method of treating plants against arthropods, more particularly

against phytophagous mites.

  It is known to use pestici-

  organophosphates for the control of arthropod pests of crops Among these compounds the ethion, has been used for a long time successfully for the fight against

phytophagous mites.

  It is recalled that the ethion is the active ingredient of formula (I):

C 2 H 5 O -C 2 H 5

P-S-CH-S-P (I

C - / -C 2 H 50

  whose chemical name is bis- (dithiophosphate 0,0 diethyl-

  This compound is also known under the common name of diethion. In the present text, it will be described in US Pat. No. 2,873,228.

  systematically designated by the common name "ethion".

  For a long time, organophosphorus pesticides

  have been used successfully as insecticides and acarici

  in agriculture In recent years, the appearance and development of mite strains has been observed

  phytophages that have become resistant to organophosphorus

  phorés The fight against these mites resistant to pestici-

  organophosphates have led farmers to increase the doses of the treatments and consequently the cost of these treatments, with despite this often disappointing results and an increase of the residues on the plants

processed.

252 '0197

  It is also known to use as insecticides

  and / or acaricides in agriculture a class of compounds

  These compounds are generally known as pyrethroids, described in US Pat. Nos. 3,835,178 and 3,996,244. These compounds generally exhibit excellent insecticidal activity, but their acaricidal activity.

  is generally considered insufficient.

  It has now been found, and this is the subject of the present invention, that the combination of certain pyrethroids with the ethion makes it possible to significantly improve the acaricide activity, especially with respect to visions of phytophagous mites that have become

  resistant to organophosphorus pesticides This improvement

  ration is all the more surprising when they are used

  pyrethroids alone have practically no acaricidal activity, at the doses used on these same

  mite strains This synergistic effect will be better explained

  with reference to the examples illustrating this

patent application.

  The present invention relates first of all to

  synergistic insecticidal and acaricidal compositions

  born to be used for the fight against arthropods

  pests, characterized in that they

  have as an active ingredient an association of ethion and a pyrethrum with the general formula (II):

R -C-O-CH

GOLD _ '

  in which: R represents a hydrogen atom or the cyano radical, R 1 represents the dimethyl-2,2- (2,2-dichloro) radical;

  > t v Xnyc) oyclor_ "j '' 'rî D di thy 1,2 -' (ibr

  mo-2,2 vinyl) -3-cyclopropyl-1, the 2,2-dimethyl radical

  (2-methylpropenyl-1) -3-cyclopropyl-1 or the radical:

(4-chlorophenyl) -1-isobutyl-1.

  The pyrethroids according to formula (II) often exist in different isomeric, optical or geometric forms, optionally in mixtures with one another. For the purpose of the present text, the term "pyrethroids according to formula (II)" encompasses the various isomeric forms of

  these compounds as well as their mixtures.

  As pyrethroids corresponding to formula (II), mention may be made, for example, of the following compounds:

  (RS) -alpha-cyano-3-phenoxybenzyl (1RS) -cis, trans-3-

  (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, the common name of which is cypermethrin,

  3-Phenoxybenzyl (1 RS) cis, trans-3- (2,2-dichlorovinyl) -

  2,2-dimethylcyclopropanecarboxylate, the common name of which is permethrin,

  (S) -alpha-cyano-3-phenoxybenzyl (LR) -cis-3- (2,2-dibro)

  movinyl) -2,2 dimethylcyclopropanecarboxylate whose common name is decamethrin, and which is also called deltamethrin,

  (RS) -alpha-cyano-3-phenoxybenzyl (RS) -2- (4 chlorophenyl)

  nyl) -3-methylbutyrate, the common name of which is fenvalerate.

  For the purpose of this text, the word "association" refers not only to ready-to-use combinations (that is, prepared in advance and intended to be used after dilution) but also extemporaneous mixtures of the two active ingredients ( that is to say

  mixtures prepared just prior to application to

considered).

  The present invention relates more particularly to

  compositions comprising from 0.01 to 100 parts by weight of pyrethroid (II) per 100 parts by weight of ethion and preferably from 0.1 to 10 parts by weight. vvvvvg -a G; i

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  As the pyrethroid (II), cypermethrin is preferably used. In addition to the combination constituted by the ethion and the pyrethroid according to formula (II), the compositions according to the invention generally comprise an inert, solid or liquid support (or diluent) which is acceptable in agriculture. If necessary, these compositions also contain one or more surfactants, which are also agriculturally acceptable and, if appropriate, also other additives which are also agriculturally acceptable, such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, agents and the like. penetration,

  stabilizers, sequestering agents and, if necessary,

  other known active ingredients with properties

  pesticides (especially insecticides, acaricides or fungicides)

  des) or with properties promoting plant growth.

  Generally, the compositions according to the invention comprise from 0.001 to 95% by weight of the combination of active ingredients, that is to say of the entire ethion + pyrethroid. By the term "carrier" in the present description, is meant any organic or inorganic, natural or synthetic material with which the combination of active ingredients is itself associated to facilitate its application to crops or on the ground, or to facilitate storage or handling This support is usually inert and

  acceptable in agriculture especially for the treated crop.

  The carrier (or diluent) can be a solid or a

liquid.

  As solid supports, there may be mentioned clays, natural or synthetic silicates; natural silicas such as, for example, diatomaceous earths; magnesium silicates, such as talc, and fucidates.

2 "20,207

  for example, attapulgites and vermiculites; silicates

  such as, for example, kaolinites, montmorillonite

  lonites and micas; calcium carbonate; sulphate

  calcium; synthetic silicates of calcium or alumina

  minium; natural or synthetic resins such as for example polyvinyl chloride, polymers and copolymers of styrene, solid polychlorophenols; waxes such as for example beeswax and the

  paraffin; solid fertilizers such as superphos

  phate, etc. As liquid carriers, there may be mentioned in particular water; alcohols such as for example isopropanol and glycols; ketones such as, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; the ethers; aromatic or paraffinic hydrocarbons such as, for example, benzene, toluene, xylenes, fractions or petroleum cuts, kerosene; mineral oils; halogenated hydrocarbons, for example carbon tetrachloride,

  perchlorethylene or trichloroethane, or possibly

  liquefied gases are often used.

  of these different liquid media.

  The surfactant may be emulsifying, dispersing

  For example, polyacrylic acid salts,

  salts of lignosulphonic acid, salts of phenolsul-

  or fatty acids or fatty amines, substituted phenols (especially alkylphenols or arylphenols), salts of derived from

  taurine (in particular alkyltaurates), phospho-

  of polyoxyethylated alcohols or phenols the presence

  at least one surfactant is generally required

  bblue iulsqut lu buppuur L iner The rles L not soluble in

  water, and that the agent vector of the application is water.

  The compositions according to the invention can be

  in quite diverse forms, solid or liquid.

  As forms of solid compositions, mention may be made of powders for dusting or dispersion (with an active matter content of up to 90%). As forms of liquid or intended compositions

  to constitute liquid compositions during the application

  the solutions, in particular the

  water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or powders), mates.

  Emulsifiable or soluble concentrates include

  Most often, 10 to 80% by weight of the combination of active ingredients, emulsions or solutions ready for application, also called slurries, containing, for their part, 0.001 to 20% by weight of the combination of active ingredients Ei In addition to the solvent, the emulsifiable concentrates may contain, when necessary, 2 to 20% by weight of suitable additives, such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, colorants, adhesives For example, here is the composition of some concentrates In the following A represents the ethion and B cypermethrin: combination of active ingredients (A / B = 2.4) 150 g / 1 calcium alkylarylsulfonate 30 g / 1 alkylphenol oxyethylated with 10 molecules of ethylene oxide 50 g / l aromatic solvent (petroleum fraction) qs 1 liter For example, here is the composition of another emulsifiable concentrate according to the invention: combination of active ingredients (A / B = 4.5) 500 g / l al Kyialryisulunace of calcium 40 g / i 7. alkylphenol oxyethylated to 10 molecules of ethylene oxide 60 g / 1 cyclohexanone 100 g / 1 aromatic solvent (petroleum fraction) qspi From these concentrates, emulsions of any desired concentration can be obtained by dilution with water, which are particularly suitable for application.

on crops.

  Wettable powders (or powders to be sprayed)

  are usually prepared in such a way that they

  contain from 20 to 95% of active ingredient, and usually contain, in addition to the solid support, from 0 to 5% of a wetting agent, from 3 to 10% of a dispersing agent, and

  when necessary, from 0% to 10% of one or more

  and / or other additives, such as penetration agents,

  adhesives, or anti-caking agents, dyes, etc. By way of example, here are various compositions of wettable powders: combination of active ingredients

(A / B = 10) 30%

  Calcium lignosulfonate (deflocculant) 5% Calcium alkyl aryl sulphonate (anionic wetting agent) 1% Anti-caking silica 30% Kaolin (filler) 34% Another composition of 40% spraying powder uses the following constituents: combination of active ingredients (A / B = 100) 400 g sodium dibutylnaphthylsulphonate 50 g condensation product in 3/2/1 proportions of naphthalenesulfonic acid of phenolsulphonic acid and at a rate of 100 g, 252 t 1 7 kaolin 120 g Anti-caking silica 400 g Another composition of powder to be sprayed uses the following constituents: combination of active ingredients (A / B = 6.66) 250 g calcium lignosulfonate 45 g mixture of champagne perononderal chalk and hydroxyethylcellulose 19 g sodium dibutylnaphthalenesulfonate 15 g silica 250 g kaolin 421 g Another composition of 10% spraying powder uses the following constituents: combination of active ingredients (A / B = 200) 100 g mixture of sod salts saturated fatty acid sulphate 30 g

  condensation product of naphthalene

  sulphonic and formaldehyde 50 g silica 100 g kaolin 720 g To obtain these powders to be sprayed or wettable powders, intimately mix the active ingredients

  in appropriate mixers with the additive substances

  In this way, sprayable powders are obtained, the wettability and suspension of which are advantageous. they can be suspended with water at any desired concentration and this suspension can be used very advantageously especially for application on

the leaves of the plants.

  As already mentioned, dispersions and emul-

  aqueous solutions, for example compositions obtained from

  3 using water with a wettable powder or concentrate

  The emulsifiable compounds according to the invention are included in the general scope of the compositions which can be used in the present invention.

  The emulsions may be of the water-in-water type

  oil or oil-in-water and they can have a

  thick consistency like that of a "mayonnaise".

  For an application called very low volume (ULV),

  with a spray of very fine droplets,

  solutions of the two active ingredients in soil

  suitable solutions, and these solutions are applied at a rate of about 1 to 5 liters / hectare As an example, here is the composition of an ULV solution according to the invention combination of active ingredients (A / B = 10) 200 g / 1 aromatic solvent (petroleum fraction) qsp 1 liter

  The invention furthermore relates to a method of treating

  plants against arthropods

  tures and more particularly against phytoplasmic mites

  phages such as spider mites This process is characterized

  in that it consists in applying to these plants a quantity

  effective use of a composition containing as a material

  activates an association of ethion and a pyrethroid answering

  Formula (II) The term "effective amount" means an amount sufficient to control and destroy arthropods present on or adjacent to these plants. For the method of treatment according to the invention, aqueous dispersions or emulsions, for example compositions obtained

  by diluting with water a wettable powder or a concentrate

  emulsifiable previously described can also be used for this treatment a very low volume solution

  (ULV) as previously described.

  Advantageously, this treatment according to the invention

  is performed using a composition whose composition

  tion rate and dose are such that the ethion is

  applied at a rate of 100 g / ha to 5,000 g / ha and the pyrene

  LiHruiu, (iie t úi :: UI, da 0, i y / 0, m O uu / Hà, a and ', vau ,, or ,, li 1 ,,

  indicated above, the compositions preferably include

Z 521 197

  from 0.01 to 100 parts of pyrethroid (preferably

  cypermethrin) per 100 parts of ethion.

  The compositions and the treatment method according to the invention can be used to protect against arthropods different types of perennial or annual crops such as in particular: annual crops of temperate climate or tropical climate (cereals, potatoes, beets, tobacco, cotton, soybean, sugar cane, etc.) vegetable or tropical crops orchards floral and ornamental crops,

  this list is not limiting.

  The compositions and the method according to the invention are mainly used for the fight against phytophagous mites, against which they exhibit a synergistic effect as shown by the examples described.

  below They can also be used advantageously

  for the control of different classes of phytophagous insects, such as, for example, Homoptera,

  Coleoptera, Lepidoptera, and Diptera.

  The examples below illustrate the invention without

however, limit it.

  Example 1: Greenhouse tests on mites (Tetranychus urticae) Aqueous dispersions of ethion are prepared,

  cypermethrin and the ethion + cypermethrin combination.

  These dispersions are then diluted with distilled water

  to obtain the desired concentrations.

  Bean plants, at the stage "2 leaves trifo-

  related, "King of the Belgians" are contaminated with strains of mites "Tetranychus urticae" considered resistant to organophosphorus pesticides and cypermethrin 4 e uui'a S plauntse b aricotiu a e, dspri N aueusvdbe b UL

  each of the bean plants an aqueous dispersion containing

2? 20 '197

  ln the active ingredient or combination of active ingredients at the dose under consideration (4 trials / dose) a control plant is treated with distilled water containing no active ingredient. Just before the treatment, a leaflet is taken from each bean plant. Using a brush, the dust mites on each leaflet are dropped on a white paper. The mites are then crushed on the paper to allow a visual assessment of the number of mites. mites present on each leaflet before treatment The treated plants and the control plant are kept in a greenhouse under the usual conditions of temperature, lighting and humidity. 21 days after the treatment, a leaflet is taken from each bean plant. Using a brush, the mites on each leaflet are dropped on a white paper and crushed on the paper. The mites on each leaf are then evaluated. leaflet The percentage of mortality relative to the control plant treated with distilled water without active ingredient is thus determined. The results are as follows: NO test cypermethrin ethion% mortality g / hl g / hl

1 15 O O%

2 O 12.5 0%

3 O 25 0%

4 O 50 95%

5 5 12.5 100%

6 5 25 100%

7 10 12.5 100%

8 10 25 100%

  The results result from the sythetic syndrome resulting from the combination of cypermethrin and

2 20197

  In particular, it will be observed that the combination of g / hl of cypermethrin with 12.5 g / hl of ethion results in a mortality of 100% whereas the cypermethrin used alone at 15 g / hl does not cause any mortality and that it is the same for the ethion, used alone, at the dose of 25 g / hl. Example 2: Outdoor test on mites (Panonychus

  ulmi) with repetitive treatments.

  The test is performed on an apple orchard of starking variety, about twenty years old and arranged in

different plots.

  Cypermethrin is used in the form of an aqueous emulsion containing 2 g / hl of cypermethrin, obtained by diluting with water an emulsifiable concentrate having the following composition: cypermethrin 100 g ethoxylated alkylphenol 50 g calcium alkylaryl sulphonate 30 g petroleum cutting (aromatic solvent) qs 100 ml The ethion is used in the form of an aqueous emulsion containing 75 g / hl of ethion, obtained by diluting with water the emulsifiable concentrate sold under the trademark Rhodocide and having the following composition: ethion 500 g mixture of anionic and nonionic surfactants 80 g oxyethylated castor oil 30 g diisopropylbenzene qs 100 ml By mixing the two emulsifiable concentrates described above and by diluting the mixture obtained with water, an emulsion containing the association

  of the two active ingredients at the rate of 2 g / hl

thrine and 75 g / hl of ethion.

  Using these emulsions, seven treatments are carried out

  successive installments, on the following dates: 8 April (T 1), 24 v 1 rn) t T & illet T) p pul -T June (T 5), 16 June (T 6) and 8 July (T 7) by pul-

2 E 2 '0197

  at a flow rate of about 1000 1 / ha, with four

repetitions for each dose.

  Fifteen days after the first treatment (date T 1 + T 5) is taken on each plot corresponding to a dose of an active ingredient 25 leaves; the number of live mites present is counted and the average number is calculated

of mites for a leaf.

  The same survey is performed six days after each treatment T 2, T 3, T 4, T 5, T 6 and 19 days after treatment T 7 The results are reported in

the table below.

r- 0% r- i ub Cj

  NUMBER OF LIVE MITES BY SHEET

  Date Taken Cypermethrin ethion Iypermethrin <2 cf / hl of no (2 g / hl) <75 g / hl) + raised treated ethion (75 g / hl)

T + 15 10.6 16 16 9.4

T 2 + 6 8.7 7.4 3.2 3.4

T 3 + 6 15.2 16.4 4.3 3.5

T 4 + 6 26.4 35.1 7.5 4.9

T 5 + 6 68.5 86.7 21.8 2.7

T 6 + 6 52.8 96.6 30.1 l 6.5

T 7 + 19 622 1357 1098 284

M-1

2 "C 197

  - It is observed that cypermethrin used alone at the

  dose of 2 g / hl does not have any acariological activity in this test.

  cide, and even, that the number of mites present in the

  trials treated with cypermethrin is often much higher than

  This phenomenon is probably due to the action of cypermethrin on insects, competitors and / or predators of mites, which indirectly promotes the proliferation of the latter. It is also observed that the ethion, used alone at 75 g / hl has only a weak acaricidal activity, and that, according to the last of the measurements (Date T + 19), it also seems to indirectly favor the proliferation of the mites (number of mites greater than that of the control) It is finally observed that the association cypermethrin + ethion present

  in all cases, an excellent acaricidal activity.

  Example 3: Outdoor test on various parasites with

repetitive treatments.

  This test is carried out in the same apple orchard and according to the same method as in example 2, in

  using the same compositions and carrying out the

  on the dates indicated in this example N 02 The insecticidal activity is then evaluated with regard to the following parasites: a) Operophtera brumata (defoliating caterpillars) Fifteen days after the T 1 treatment, the number of live caterpillars on the buds and one

  calculates the number of live caterpillars per 100 buds.

  The results are as follows: untreated control: 10.3 cypermethrin (2 g / hl): 1.6 ethion (75 g / hl): cypermethrin + ethion (2 + 75 g / hl): 0.3 b) Dysaphis plantaginea (aphids): Ten days after treatment T is counted in

  (v) uilui 4 uu 11 i Iu I Ib 1 of the OL'4 U puú uu

  s 3 ui It is the number of scaffolding x Luu ar U é site and one thus determines the number of attacked twigs

52.0197

  The results are as follows: untreated control: 82.6 cypermethrin (2 g / hl): 2,3 ethion (75 g / hl): O cypermethrin + ethion (2 + 75 g / hl): O c Eriosoma lanigerum (woolly adelgid) Twenty days after T 7 treatment, the number of attacked twigs and the number of unaffected twigs are counted and the% of twigs attacked are evaluated. The results are as follows: untreated control 24.7% cypermethrin (2 g / hl) 81.7% ethion (75 g / hl) 4.7% cypermethrin + ethion 1.7% Example 4: Outdoor test on mites (Panonychus ulmi) with a single treatment This test is carried out on an orchard of apple trees

  Golden variety aged about 20 years.

  From the emulsifiable concentrates described in Example 2, these aqueous emulsions containing respectively either cypermethrin alone (3 g / hl) or

  ethion alone (75 g / hl) is the association ethion + cyper-

Methrin (75 g / hi + 3 g / hi)

  As a comparison product, the tetra-

  sul, acaricide of the trade and an aqueous suspension is prepared containing 40 g / hl of this product, by diluting with

  water a wettable powder at 20% tetrasul.

  These emulsions or dispersions are carried out

  May 15 (date T-O) treatment by spraying,

with a flow of 1500 1 / ha.

  Immediately prior to treatment, the number of live mites present on 25 leaves of

  each parcel and calculate the average for a leaf.

  The same reading is taken respectively 3 days, 7 days and 1, Lc 4 _ r, SnT I YTTT =, SC, T 7 ') / The results are reported in the table below: EVOLUTION OF THE NUMBER ACAIRIENS (Average / leaf) Date of control tetrasul Cypermethrin ethion Cypermethrin (3 g / hl) reported no 40 g / hl 3 g / hl, 75 g / hl + treated ethion (75 g / hl)

T-O 8.5 8.4 8.6 7.3 7.7

T + 3 6.3 2.2 0.3 0.3 0.1

T + 7 18.3 7.6 9 8.5 1.0

T + 17 36 24.5 34 32.5 10.8

ol- 1c> r- 1-4

E 2 '0197

  It is observed that, according to the last of the surveys carried out, the combination cypermethrin + ethion has a

  excellent acaricidal activity, superior to that of

  comparison, and that, when used alone, at the same dose as in the combination, cypermethrin and ethion lead to very similar results.

  of those observed in the case of the untreated control.

Claims (7)

  1) Insecticidal and acaricidal composition for use in the control of arthropod pests of crops, characterized in that it contains as   active ingredient an association of ethion and pyrethroid Thyroid of formula: R 1-C-O-H Q (II) II I 0 R   in which: R represents a hydrogen atom or the cyano radical,   R 1 represents the dimethyl-2,2- (2,2-dichloro) radical;   vinyl) -3-cyclopropyl-1, the 2,2-dimethyl radical   (2,2-dibromo-vinyl) -3-cyclopropyl-1, the dimer radical   thyl-2,2- (2-methylpropenyl) -3-cyclopropyl-1 or   radical: (4-chlorophenyl) -1-isobutyl-1.   2) Composition according to claim 1) characterized in that it comprises from 0.01 to 100 parts of pyrethroid per 100 parts of ethion.   3) Composition according to one of claims 1) and 2)   characterized in that the pyrethroid is selected from cypermethrin, permethrin, decamethrin and fenvalerate. 4) Composition according to claim 3) characterized in that   that the pyrethroid is cypermethrin.   Composition according to one of claims 1) to 4)   characterized in that it further comprises an inert carrier acceptable in agriculture and optionally a surfactant.   C 5 o) Frjuu: I drew Lte: m L-i iujes v yulu% u, t'ule i Us arthro-   pests pests crop and especially against phytophagous mites characterized in that it consists in applying to these plants an effective amount of a   composition containing as an active ingredient an association   an ethion and a pyrethroid of the formula: R 1 -C-O-CH GOLD_   in which R 1 and R 1 have the same meaning as in claim 1).   7) Process according to claim 6) characterized in that the pyrethroid is chosen from cypermethrin,   permethrin, decamethrin and fenvalerate.   8) Method according to claim 7) characterized in that   the pyrethroid is cypermeth Yine.   9) Method according to one of claims 6) to 8) characteristics   in that the treatment is carried out by means of a   composition, the constitution and dose of which   the ethion is applied at a rate of 5 000 g / ha and the pyrethroid at a rate of 0.1 to 500 g / ha and that the weight ratio of pyrethroid / ethion is between 0.0001 and 1.   10) Method according to claim 9) characterized in that the weight ratio pyrethroid / ethion is between 0.001 and 0.1.