EP4037484A1

EP4037484A1 - Pesticide synergist sx-pyr

Info

Publication number: EP4037484A1
Application number: EP20797014.6A
Authority: EP
Inventors: Denis Mbonimpa
Original assignee: Jeunen Carlo
Current assignee: Jeunen Carlo
Priority date: 2019-10-05
Filing date: 2020-10-05
Publication date: 2022-08-10
Also published as: WO2021064252A1; CA3156449A1; BE1027622A1; BE1027622B1; WO2021064252A9

Abstract

The present invention relates to a composition and to the production and use of said composition. Pesticide synergist composition comprising, inter alia, (1) a proteolytic enzyme (or a mixture of proteolytic enzymes), (2) a polyphenol compound (or a mixture of polyphenol compounds chosen from hydrolysable tannins), (3) a compound chosen from triglycerides (or a mixture thereof), (4) a phase change inhibitor chosen from ethanol, isopropyl alcohol, benzyl alcohol and a mixture thereof, (5) an enzyme stabiliser chosen from organic peroxides, (6) a non-ionic surfactant, (7) an essential oil chosen from melaleuca alternifolia and quinquenervia essential oils, (9) a simple reagent such as ascetic acid and citric acid to modify/stabilise the ph. The present invention can be in the form of a concentrate or an emulsion further comprising pyrethrins and pyrethroids (i) and (ii) and a mixture thereof. The composition is intended, when used, to manage the resistance linked to the mechanism of insects, detoxify insecticides and improve the efficacy of pesticides, in particular certain insecticides such as pyrethrins and pyrethroids (i) and (ii).

Description

SX-PYR PESTICIDE SYNERGIST

FIELD OF THE INVENTION

The present invention relates to a composition as well as the production of this composition and the use of this composition.

The invention relates to a formulation characterized by the simultaneous presence of supramolecular complexes based on pyrethrins, pyrethroids (I) and (II) and a synergist of pesticides in particular pyrethrins and pyrethroids (I) and (II). One of the two components has insecticidal, acaricidal, fungicidal or vermicidal activity while the other component has synergistic activity when combined with the first components, and enhances its effectiveness. The active substance is chosen from pyrethroids (I) and (II) in which hydrogen atoms 1, 2 or 3 are present. The synergist substance has a composition of fatty acids, saturated, monounsaturated, polyunsaturated associated with a cysteine protease, for example papain associated with a polyphenolic composition comprising hydrolyzable tannins ((or gallic or ellagic tannins) and flavonoids, such as flavanols, one can quote quercetin (C15 H10 07) These new compositions improve the action of certain insecticides such as (natural pyrethrum and pyrethroids) and, on the other hand, have an inhibitory activity of certain genes in resistant mosquitoes. These same genes code for "biodegradation enzymes": proteins which can inactivate toxic substances, that is to say pesticides, and thus make mosquitoes and certain harmful parasites resistant to insecticides. ssociée with a phenol derivative such as: 1,3- (methylenedioxy) phenol, 5-hydroxy-1,3-benzodioxole, containing at least one aromatic or non-aromatic carbocyclic ring. The invention also relates to the process for preparing said formulation and its use in the activities described above. One of the distinctive characteristics identified as having a surprising technical effect is the involvement in the present invention of a polyphenol from the tannin family, associated with a molecule identified and innovative in this application, whereas usually the polyphenols of the tannin family. family tannins are only soluble in water, ethanol, acetone, and methyl alcohol. Among the components of the synergist, this composition is involved in the process of protecting pyrethrins and pyrethroids (I) and (II ⁰ against their detoxification by insects. BACKGROUND OF THE INVENTION

The invention relates to a formulation characterized that it is a synergist of pyrethroids and pyrethroids and consequently the invention is also characterized by the combined presence of supramolecular complexes based on pyrethrins, pyrethroids (I) and the synergist of the present invention. invention. One of the two components has insecticidal, acaricidal, fungicidal or vermicidal activity while the other component has synergistic activity when combined with the first components, and enhances its effectiveness. The biologically active substance is selected from the following classes of chemicals: besides at least one approved pyrethroids selected from the group consisting of: pyrethrins and pyrethroids (I) and (II), described as follows: permethrin, deltamethrin, tetramethrin, cypermethrin and the various mixtures of isomers which are derived from it, and in particular α-cypermethrin and asymethrin, esbiothrin, kadethrin, acrynathrin, cyhalothrin and the various mixtures of isomers which are derived from it. derived from, and in particular l-cyhalothrin, cyfluthrin, tralomethrin, fluvalinate, fenvalerate, S-fenvalerate or (lR, cis) 2,2-dimethyl 3 - [(Z) 2- (methoxycarbonyl) ethenyl ] cyclopropane carboxylate of (S) a-cyano 3-phenoxy benzyl However, pyrethroids in which are present hydrogen atoms 1,2, or 3.

The synergist substance is present as a composition of fatty acids, saturated, monounsaturated, polyunsaturated, chosen from short chain fatty acids, C (6: 0), C (8: 0), C (10: 0), C (12: 0), C (14: 0), medium chain fatty acids, C (16: 0 w9), C (17: 0), C (18: 0), C (18: lw9), C (18: lw7), C (18: 2 LA), and long chain fatty acids, C (20: 0), C (20: lwll), C (20: lw9), C (24: 0), characterized in that it is associated with a cysteine protease and a polyphyletic composition comprising hydrolyzable tannins (or gallic or ellagic tannins) and flavonoids, such as flavanols, mention may be made of quercetin (C15H10O7). These new compositions improve the action of certain insecticides such as (natural pyrethrum and pyrethroids) and, on the other hand, have an inhibitory activity, of certain insecticides such as (natural pyrethrum and pyrethroids) and also have an inhibitory activity, of certain genes in resistant mosquitoes. These same genes code for protein biodegradation enzymes that inactivate toxic substances and thus make mosquitoes and some pests resistant to insecticides. This composition is combined with a phenol derivative such as: l, 3- (methylenedioxy) phenol, 5-hydroxy-1,3-benzodioxole, stabilizer of proteolytic enzymes, containing at least one aromatic or non-aromatic carbocyclic ring.

The synergist substance has a fatty acid composition, saturated, monounsaturated, polyunsaturated, selected from short chain fatty acids, C (6: 0), C (8: 0), C (10: 0), C (12 : 0), C (14: 0), medium chain fatty acids, C (16: 0 w9), C (17: 0), C (18: 0), C (18: lw9), C (18 : lw7), (C18: 2 LA), C (18: 3) and long chain fatty acids, C (20: 0), C (20: lwll), (C20: lw9), C (20: 4 ), C (24: 0).

The present invention relates to a novel synergistic composition of pesticides containing as active principle a proteolytic enzyme, ie a cysteine protease, and a polyphenolic compound or a mixture of polyphenolic compounds consisting of hydrolyzable tannins ((gallic or ellagic tannins) or flavonoids, such as flavonols, we can cite quercetin and may contain a triglyceride or a mixture of triglycerides, we can cite (sesame, cottonseed, coconut, paraffin, sunflower, soybean, rapeseed or corn oil, preferably a sesame oil, cottonseed oil, or else methylated rapeseed oil), combined with a phase change inhibitor chosen from ethanol, isopropyl alcohol, benzyl alcohol, and their mixture; and a protein stabilizer, preferably hydrogen peroxide.

The present invention is characterized by one of the compositions which allows the rapid penetration of the insecticide towards the nervous system of the pests, due to the simultaneous presence of short-chain fatty acid, among which, there may be mentioned a combination of fatty acids such as: C (6: 6), C (8: 0), C (10: 0), C (12: 0), C (14: 0).

The present invention is also characterized by its antioxidant role vis-à-vis insecticides and thereby prolongs the persistence of pyrethrins and pyrethroids (I) and (II) by the action of one of its components of. medium chain fatty acids among which there may be mentioned, C (16: lw9), C (16: lcisw7).

This composition, which is both anti-oxidant, occurs at the initiation stage. In vivo, oxygenases (enzymes allowing oxidation) such as lipoxygenase and cyclooxgenase, allow the synthesis of eicosanoids, leukotrienes for the first, prostaglandins for the second, from arachidonic acid C (20: 4) and C ( 18: 3)

The synergist of the present invention is involved in the process of combating the detoxification of pyrethrins and pyrethroids (I) and (II) by insects. Mosquitoes and insects that destroy crops and are resistant to insecticides participate in an increased production of detoxifying enzymes: "Esterases are enzymes naturally produced by all mosquitoes: they degrade organophosphate insecticides, they are biodegradation enzymes". Insects generally produce proteins that make it possible to inactivate toxic substances, even after treatment, insects presumed dead can sometimes come back to life thanks to their enzymes which continue to detoxify the insecticides ingested.

The present invention acts against the phenomena of habituation of pests (insects) and particularly mosquitoes resistant to pyrethroids by its action linked to the presence of long-chain fatty acids, among which there may be mentioned two isomers such as: C (20: lwll), C (20: lw9). The action they generate accelerates the speed of action of the insecticide by quickly reaching the target, ie here the synaptic space. It must therefore quickly enter the insect's body and circulate in its internal environment. The compositions of the invention are characterized by the action of preventing esterases produced by mosquitoes, from trapping or metabolizing insecticides, before they can inhibit acetylcholinesterase (ACE) in the synapses.

Differences in the properties of Ace (acetylcholinesterase) from mosquitoes with this form of resistance and from susceptible mosquitoes can be detected by the following test:

Experimental protocol TESTS N ° -l: Sensitive and resistant mosquitoes.

Product-tested: the insecticide Propoxur (Baygon).

Experimental protocol TESTS N ° -2: Sensitive and resistant mosquitoes.

Product-tested: Insecticide -NILO-PYR whose composition contains: 2.5 g / L of pyrethrins and 12.5 g / L of the “SYNERGIST OF THE COMPOSITION OF THE PRESENT“ INVENTION-SX-PYR ”l ° the mosquito is crushed (or the larva) and the ground material is homogenized in an Eppendorf tube with a buffer solution (20 mM tris, pH 7, containing 1% Triton X-100). After centrifugation at 10,000g for 2 minutes, the supernatant (which contains the ACE) is collected and distributed in the wells (A) and (B) of a plate (100 microliters in each well),

2 ° one then adds in each well either 10 microliters of a concentrated insecticide solution (pyrethrum-based products at 10-2 M), Baygon, a brand of pesticides produced by SC Johnson well (B), and 10 microliters of alcohol, well (A.) The plate is left for 15 minutes at room temperature (this time is sufficient to allow the possible action of the insecticide),

3 ° determination of the catalytic activity of ACE (acetylcholinesterase): 100 microliters of a solution containing acetylcholine (2.5 mM) and 0.2 mM of DTNB (dinitro- 2-benzoic). The intensity of the coloration is evaluated by measuring the optical density (the optical density increases with the coloration) If the enzyme is active, the products of the hydrolysis of acetylcholine react with the DTNB to give a substance which shows an absorption peak for radiations of 412 nm. It is therefore possible to follow the course of the reaction by spectrophotometry.

Experimental protocol TESTS N ° -l: Sensitive and resistant mosquitoes Product-TEST: the insecticide Propoxur (Baygon).

The graphs below in Figure 6 show the change in optical density for 10 min in each well, for 8 susceptible mosquitoes and 8 resistant mosquitoes (on the y-axis: intensity of the optical density; on the x-axis: time

Observations:

Sensitive individuals

The esterase production by susceptible mosquitoes is very low, insufficient to prevent the insecticide Propoxur (Baygon) from working.

Resistant individuals

Observations: analysis of the results for resistant mosquitoes: the slope of the curves reflecting the change in optical density is almost the same in the wells with or without insecticide. It can therefore be concluded that the ACE of resistant mosquitoes is completely insensitive to the insecticide Propoxur (Baygon).

On the other hand, the slope of the line reflecting the change in optical density in the absence of insecticide is markedly lower in resistant mosquitoes than in susceptible mosquitoes. The Ace of resistant mosquitoes is therefore less active and less effective than that of sensitive mosquitoes. The reduction in activity of the resistant enzyme compared to the sensitive enzyme is about 60%. This is one aspect of the cost of resistance. Experimental protocol TESTS N ° -2: Sensitive and resistant mosquitoes Product TESTE -NILO-PYR whose composition contains: 2.5 g / L of pyrethrins and 12.5 g / L of the "SYNENERGIST OF THE PRESENT" INVENTION-SX-PYR "

Observations in Figure 7: Analysis of the results for sensitive and resistant mosquitoes: compared to the control wells (A), the change in the optical density of the wells where the insecticide (B) NILO- has been added. PYR is almost zero (horizontal line). Ace was therefore inactivated by the insecticide NILO-PYR.

The compositions of this invention inhibit the overproduction of detoxifying enzymes produced by resistant mosquitoes. (Illustration in Figure 7 - Test- N ° 2)

The present invention is characterized by the property of causing, at a very low dose, the dissociation of a large quantity of esterases produced by insects and more particularly by resistant mosquitoes. The compositions of the present invention disrupt the increased production of esterase in resistant insects and make the target acetylcholinesterase (ACE) more sensitive to the insecticide. Esterases are enzymes naturally produced by insects; they hydrolyze the ester bonds, in particular those of the molecules of the OP insecticides.

The compositions of the invention are characterized by the action of preventing esterases produced by mosquitoes, from trapping or metabolizing insecticides, before they can inhibit acetylcholinesterase (ACE) in the synapses.

The compositions of the invention allow the insecticide to penetrate into the resistant mosquito organism and to circulate in its internal environment, to cause the dysfunction of its nervous system and to act on its target, the acetylcholine esterase enzyme ( Ace, present at the level of cholinergic synapses and having the role of hydrolysis of the neurotransmitter acetylcholine).

Synergists are chemicals which do not have pesticidal effects but which improve the pesticidal properties of other chemicals. Piperonyl Butoxide (PBO) is defined as a synergist used in many pesticides. Piperonyl Butoxide (PBO) can be added in phytosanitary formulations containing pyrethrins or more generally compounds of the pyrethroid family. After ingestion by insects, PBO inhibits the secretion of certain enzymes and potentiates the insecticidal properties of the plant protection product. PBO has harmful effects on human endocrine functions and on the environment. Today, the analyzes and results of the Casdar Sécurbio show that piperonyl butoxide, used as a synergist for insecticides (natural pyrethroids and synthetic pyrethroids), is present in plant (cereals) and animal (meat) production in the form of a residue (intact substance). This is not a phytosanitary product, but is considered by Articles 25 and 26 of EC Regulation No. 1107/2009 and as such was not subject to a maximum residue limit (MRL). Products containing piperonyl butoxide (PBO) The CNAB in France, on December 8, 2015, decided to ban all products containing PBO in organic farming within the following deadlines: Removal of the AB mention on product labeling concerned for sale and distribution as of March 31, 2017. End of use of stock on September 30, 2017. ”Products containing PBO will be withdrawn from the guide as of September 30, 2017. Products containing PBO are marked with 'an asterisk in the guide.

Synergistic products have been described in Patent WO 2011154434 A2, Pesticide mixtures comprising isoxazoline derivatives and in patent: WO2007101547A2 * 21 Feb. 2007 Sep 13, 2007 Bayer Cropscience Ag Synergistic combinations of active ingredients

In the article by Corbel et al, "Dinotefuran: A Potential Nicotinic Insecticide Against Resistant Mosquitoes" published in J. Med. Entomol. 41 (4): 712.717 (2004), Dinotefur has been proposed as an insecticidal agent for mosquito nets. In this article, Dinotefuran was shown to have a lethal effect on mosquitoes of the species Anopheles gambiae, Aedes aegypti and Culex quinquefasciatus. Also for the VKPR (also called VKPER) mosquito strain of An, gambiae, which has the mutation for resistance to pyrethroid knockdown, Dinotefuran has been shown to have a lethal effect.

Resistance to neonicotinoids is now quite widespread in target populations of crop pests. In Spain, resistance to imidacloprid in the tobacco whitefly was discovered in 1996; in the United States the Colorado beetle pests of potato crops have shown resistance to the same insecticide since 1997 (Millar and Denholm, 2007). Fortunately, neonicotinoids have only been used on mosquitoes on an experimental basis, which limits their impact on the selection of resistance in these vectors.

The chemical product becomes totally ineffective, which induces real problems, whether in agriculture or in LAV, since there is then no more means of regulate harmful populations. Today, resistance has been observed in the majority of disease vector species around the world. (Carnevale and Robert, 2009).

Mosquitoes and insects that destroy crops and are resistant to insecticides participate in an increased production of detoxifying enzymes: "Esterases are enzymes naturally produced by all mosquitoes: they degrade organophosphate insecticides, they are biodegradation enzymes". Insects generally produce proteins that make it possible to inactivate toxic substances, even after treatment, insects presumed dead can sometimes come back to life thanks to their enzymes which continue to detoxify the insecticides ingested.

However, for an insecticide to be effective it must be able to reach its target, ie here the synaptic space. It must therefore enter the insect's organism and circulate in its internal environment. Resistance to OP insecticides and carbamates can therefore be explained by mechanisms that prevent these insecticides from reaching their target, or by a lower sensitivity of the target (Ace).

We know of research based on the activity of the pancreas which produces proteolytic enzymes, mainly trypsin and chymotrypsin, which are essential for the proper digestion of proteins. Some plants contain similar enzymes, which are also able to break down protein molecules. This is the case, for example, with papain which comes from papaya (Carica papaya, caricaceae family) and bromelain which is obtained from pineapple (Ananas comosus, bromeliad family). Whether they are from animal or plant sources, proteolytic enzymes have in common that they participate in the process of protein digestion.

The compositions of the invention comprise at least one natural substance which is a sulfhydril protease (RS-H) which comes from the latex and from the fruit of papaya and is part of the family of peptidase C1: “papain”. Papain consists of a single polypeptide chain with three disulfide bonds which gives it good stability. And a group necessary for the activity of the sulfhydril enzyme, the Polypeptide chain is also formed of 212 amino acid residues. This chain is folded into two groups, an inactive part and the other active, this one is represented by the oxidized sulfhydril groups essentially present in the CYS 25. The alpha helix As for it has the C = 0 bond directed towards the 'propeller axis, while the Hydrogens are in antiparallel conformation, they are then directed towards the nuclei of the layers. It therefore has an active Cysteine nucleophilic site at position 25 which attacks the peptide bond. Structure of papain and shown in Figure 1, a cysteine protease.

Physical and kinetic properties.

SUMMARY OF THE INVENTION

The invention relates to a composition of a synergist of pesticides containing as active ingredients (1) a proteolytic enzyme or a mixture of proteolytic enzymes, preferably cysteine proteases, (2) and a polyphenolic compound chosen from hydrolyzable tannins (or gallic or ellagic tannins) and flavonoids, such as flavonols, there may be mentioned quercetin, (3) and a triglyceride chosen from among sesame, cottonseed, coconut, paraffin, sunflower, soybean and rapeseed oil , corn, methylated rapeseed), (4) a phase change inhibitor selected from ethanol, benzyl alcohol, and a mixture thereof; (5) a protein stabilizer, we can cite hydrogen peroxide, (6) a nonionic surfactant, we can cite coconut glucoside; (7) an essential oil chosen from the essential oils of melaleuca Alternifolia and quinquenervia, (8) a simple reagent such as acetic acid and citric acid to modify / stabilize the pH of the composition of the invention. Said composition is intended in its use for the management of resistance linked to the mechanisms of insects to detoxify insecticides and the improvement of the effectiveness of pesticides and certain insecticides such as (natural pyrethrum and pyrethroids (I) and (II )). One of the sources of the appearance of resistance is linked to the overproduction of detoxifying enzymes by certain insects; By slowing down this overproduction, the present invention makes it possible to limit the multiplication of these resistant strains and its use brings about a benefit for human health through formulations less concentrated in active substance, and therefore more favorable toxicological classifications; By reducing the amounts of insecticides required, it is possible to lower the levels of insecticide residues in treated storage seeds. The present invention relates to a composition of a synergist of pesticides which can also be provided in the form of a concentrate or an emulsion containing pyrethrins (extract of pyrethrum flowers), pyrethrinoids (I) and (II ) and their mixture.

The compositions of the present invention have been the subject of research focused on the action of hydrolyzable tannins which are plant substances of the polyphenol family, of plant origin and which have the ability to precipitate proteins.

The present invention is a composition combining, inter alia, a proteolytic enzyme (papain) and a polyphenolic compound (tannic acid).

1. Synergistic composition of pyrethrins and pyrethroids (I) and (II) having a fatty acid composition, saturated, monounsaturated, or polyunsaturated, which are chosen from fatty acids with short chains, C (6: 0), C (8 : 0), C (10: 0), C (12: 0), C (14: 0), medium chain fatty acids, C (16: 0 w9), C (17: 0), C (18 : 0), C (18: lw9), C (18: lw7), C (18: 2 LA), and long chain fatty acids, C (20: 0), C (20: lwll), C ( 20: lw9), C (24: 0), characterized in that it is associated with a cysteine protease and a polyphenolic composition or a mixture of polyphenolic compounds consisting of hydrolyzable tannins or gallic or ellagic tannins and flavonoids , such as flavanols, there may be mentioned quercetin (C15H10O7). These new compositions improve the action of certain insecticides such as (natural pyrethrum and pyrethroids) and, on the other hand, have an inhibitory activity, of certain insecticides such as (natural pyrethrum and pyrethroids) and also have an inhibitory activity, of certain genes in resistant mosquitoes. These same genes code for protein biodegradation enzymes that inactivate toxic substances and thus make mosquitoes and some pests resistant to insecticides. This composition is combined with a phenol derivative such as: l, 3- (methylenedioxy) phenol, 5-hydroxy-l, 3-benzodioxole, stabilizer of proteolytic enzymes, containing at least one aromatic or non-aromatic carbocyclic ring. 2. Composition according to Claim 1, characterized in that the said cysteine protease is chosen from fig tree ficin, papaya papain, pineapple bromelain, asclepias protease (Asclepias speciosa), euphorbaine protease. (E. cerifera), solanaïne (S. Eleagnifoldium), pomirine (Maclura pomiera) and Mexican (Pileus mexicanus).

3. Composition according to the preceding claim, characterized in that said selected cysteine protease is papain.

4. Composition according to any one of the preceding claims, characterized in that the compound, the cysteine protease, is present in a proportion of between 1 to 90%, by weight relative to the total weight of the composition. 5. Composition according to any one of the preceding claims, characterized in that the compound, the cysteine protease, is present in a proportion of between 1 to 10%, by weight relative to the total weight of the composition.

6. Composition according to any one of the preceding claims, characterized in that the said polyphenolic compound is chosen from flavonoids, carnosic acid, carnosol, (2,5-dihydroxyphenyl) carboxylic acids and (2,5 - substituted carboxylic dihydroxy phenyl) allylenes, and their derivatives, esters or amides of caffeic acid and tannic acid. 7. Composition according to Claim 1, characterized in that the said selected polyphonic compound is tannic acid.

8. Composition according to any one of the preceding claims, characterized in that the polyphenolic compound is present in a proportion of between 1 and 10% by weight relative to the total weight of the composition.

9. Composition according to any one of the preceding claims, characterized in that the polyphenolic compound is present in a proportion of between 0.1 and 1% by weight relative to the total weight of the composition.

10. Composition according to any one of the preceding claims, characterized in that the composition contains a triglyceride chosen from (sesame, cottonseed, coconut, paraffin, sunflower, soybean, rapeseed or but of preferably sesame oil, cottonseed oil, or methylated rapeseed oil).

11. Composition according to any one of the preceding claims, characterized in that the said selected triglyceride is sesame oil.

12. Composition according to the preceding claims, characterized in that they contain, 0, 1 to 800g / L of fatty acids (C (6: 0), C (8: 0), C (10: 0), C ( 12: 0), C (14: 0), medium chain fatty acids, C (16: 0 w9), C (17: 0), C (18: 0), C (18: lw9), C ( 18: lw7), (C18: 2 LA), C (18: 3) and long chain fatty acids, C (20: 0), C (20: lwll), (C20: lw9), C (20: 4), C (24: 0).), Associated with 0.1 to 100g of tannic acid, and 1 to 250g (+) - 4-Isopropenyl-l-methylcyclohexene, (+) - Isopropenyl-4 methyl-1 cyclohexene, D-Isopropenyl-4 methyl-1 cyclohexene, (D) -Limonene and further the present compositions may contain from 0.1 to 10 g / L of citric acid, and from 0.1 to 10 g / L of acetic acid.

13. Composition according to claim 1, characterized in its use as a synergist of pesticides in combination with pyrethroids such as: permethrin, bifenthrin, deltamethrin, tefluthrin, tetramethrin, cypermethrin and the various mixtures of isomers which are therein. derived from, and in particular α-cypermethrin and asymethrin, esbiothrin, kadethrin, acrynathrin, cyhalothrin and the various mixtures of isomers which are derived therefrom, and in particular l-cyhalothrin, cyfluthrin, tralomethrin, fluvalinate, fenvalerate, S-fenvalerate or (lR, cis) 2,2-dimethyl 3 - [(Z) 2- (methoxycarbonyl) ethenyl] cyclopropane carboxylate of (S) a-cyano 3 -phenoxy benzyl.

14. The compositions according to the preceding claims are used in a combination with pesticides, in an amount of 0.1 to 900 g / L of the composition according to the preceding claims, preferably 30 to 45 g / L of the composition according to the preceding claims. preceding claims, in a composition containing from 1 to 900 g / L of deltamethrin, preferably from 1 to 15 g / L of deltamethrin.

15. The compositions according to the preceding claims are used diluted in water and applied using a sprayer; one can for example dilute 100 ml of this composition in 5 liters of water. We can thus effectively treat 100 m2 of surface (treatment against crawling insects). When it is desired to treat surfaces against flying insects, 65 ml of the composition described above can be diluted in 5 liters of water. When it is desired to carry out nebulization treatments, 700 ml of the above composition can be diluted in 9 liters of petroleum solvent and apply the solution obtained at the rate of 500 ml of solution per hectare. When it is desired to treat interior spaces, it is possible to dilute from 500 ml to 1000 ml of the composition described above in 4 liters of petroleum solvent and apply 250 ml of the solution thus obtained to treat 1000 m3 of interior space.

16. The compositions according to the preceding claims are used in combination with pesticides; one can for example quote a combination in a proportion of 0.1 to 900 g / L of the final composition, preferably from 300 to 450 g / L of the final composition, in a composition containing from 1 to 900 g / L of tralomethrin , preferably from 1 to 144 g / L of tralomethrin.

17. The compositions according to the preceding claims are used in combination with pesticides; for example, mention may be made of a combination, by virtue of 0.1 to 900 g / L of the composition, preferably from 30 to 45 g / L of the final composition, in a composition containing from 1 to 900 g / L of tralomethrin, preferably from 1 to 15 g / L of tralomethrin.

18. The compositions according to the preceding claims are used in combination with pesticides; one can for example cite a combination by reason of 0.1 to 900 g / L of the final composition, preferably from 60 to 190 g / L of the final composition, in a composition containing from 1 to 900 g / L of Acrinathrin , preferably from 1 to 30g / L of Acrinathrin.

19. The compositions according to the preceding claims are used in combination with pesticides; one can for example quote a combination in a proportion of 0.1 to 900 g / L of the final composition, preferably from 30 to 45 g / L of the final composition, in a composition containing from 0.1 to 900 g / L of Cyfluthrin, preferably 0.1 to 15 g / L of Cyfluthrin.

20. The compositions according to the preceding claims are used in combination with pesticides; one can for example quote a combination in a proportion of 0.1 to 900 g / L of the final composition, preferably from 130 to 200 g / L of the final composition, in a composition containing from 0.1 to 900 g / L of Cypermethrin, preferably from 1 to 66g / L of Cypermethrin.

21. The compositions according to the preceding claims are used in combination with pesticides; one can for example quote a combination in a proportion of 0.1 to 900 g / L of the final composition, preferably from 300 to 500 g / L of the composition final, in a composition containing from 0.1 to 900 g / L of permethrin, preferably del60 g / L of permethrin.

22. The compositions according to the preceding claims are used in combination with pesticides; one can for example cite a combination by virtue of 0.1 to 900 g / L of the substance of the invention, preferably from 300 to 500 g / L of the substance of the invention, in a composition containing from 1 to 900 g / L of Bifenthrin, preferably from 1 to 160 g / L of Bifenthrin.

23. The compositions according to the preceding claims are used in combination with pesticides; one can for example quote a combination in a proportion of 0.1 to 900 g / L of the final composition, preferably from 15 to 30 g / of the final composition, in a composition containing from 0.1 to 500 g / L of pyrethrins (pyrethrum extract), preferably from 0.1 to 30g / L of pyrethrins.

The compositions according to certain preceding claims can be used against the rice weevil (Sitophilus oryzae) is a species of coleopteran insects of the family Curculionidae, with a cosmopolitan distribution. This pest insect is so called because the female lays her eggs in the seeds of cereals and particularly rice, in particular causing damage to stocks. It is classified according to some authors in the family of Curculionidae or in that of Dryophthoridael., Sitotroga cerealella (alucite of cereals or moth of cereals, Angoumoise moth of grain, Angoumois moth) is a species of insects of the order Lepidoptera (Tinéidae family), with a cosmopolitan distribution. It is a pest insect that attacks cereal grains (corn, wheat, barley, rice, etc.) both in the ears in the field and in storage stores (granaries, silos, etc.). It is found in all temperate to warm and tropical regions of the world, counter Sitotroga The grain nasturtium (Rhyzopertha dominica) is a cosmopolitan beetle insect species of the Bostrichidae family. It belongs to the monotypic genus Rhyzopertha.

It is a major pest of stored grain, against flying insects such as flies and mosquitoes and crawling insects such as cockroaches, lice, fleas and ants, as well as in the control of wood pests.

The compositions according to the preceding claim are also used for the destruction of the flying or crawling insects mentioned above in spatial treatment outside for the treatment of urban spaces, as well as in spatial treatment inside buildings. or dwellings.

The compositions according to any preceding claim are used for fight against bedbugs, fleas, lice, ticks and mites; ectoparasites living on the human body and in his clothing and bedding. There are many species of blood-sucking fleas, lice, ticks and mites. Lice are parasites of humans that live on their body or in their clothes, while bedbugs are often found gorging themselves with blood on humans or pets. Bedbugs, which are also found in other furniture, get their blood meal by biting humans. Some mites, eg scabies agents, are parasites of the skin, preventing infestations with fleas (Ctenocephalides canis, and against Ctenocephalides felis). ; one can for example cite a combination by reason of 0.1 to 900 g / L of the composition the final composition, preferably 100 g / L of the final composition, in a composition containing from 0.1 to 900 g / L Permethrin, preferably 15 g / L Permethrin.

24. The compositions of the invention are characterized in that they may contain from 0.1 to 25 g / L of deltamethrin, preferably from 5 to 15 g / L of deltamethrin.] 28. The compositions of the invention are characterized in that they can contain from 0.1 to 155 g / L of tralomethrin, preferably from 100 to 155 g / L of tralomethrin.

25. The compositions of the invention are characterized in that they can contain from 0.1 to 20 g / L of cyalothrin, preferably from 10 to 15 g / L of cyalothrin.

26. The compositions of the invention are characterized in that they can contain from 0.1 to 35 g / L of Acrinathrin, preferably from 20 to 30 g / L.

27. The compositions of the invention are characterized in that they contain from 1 to 25 g / L of cyfluthrin, preferably from 15 to 20 g / L of cyfluthrin.

28. The compositions of the invention are characterized in that they contain from 1 to 75 g / L of Cypermethrine, preferably from 10 to 70 g / L.

29. The compositions of the invention are characterized in that they contain from 1 to 200 g / L of bifenthrin, preferably from 100 to 160 g / L of bifenthrin.

30. The compositions of the invention are characterized in that they contain from 1 to 200 g / l of permethrin, preferably from 100 to 160 g / L of permethrin. 31. The compositions of the invention are characterized in that they contain from 0.1 to 200 g / l of Tefluthrin. This composition is intended for the fight, among others, against the 3 main underground pests of cereals which are wireworms, ground beetle and gray fly. This composition has a very high vapor pressure, which gives it a greater persistence of action than the other molecules, for optimal efficiency until after winter.

BRIEF DESCRIPTION OF THE FIGURES Fig. 1: Structure of papain, a cysteine protease.

Fig. 2: Model of Sierbert et al. 1996. In this model, polyphenols can attach proteins at both ends and proteins have a limited number of binding sites. Three types of interactions are described according to the phenol / protein ratio; A: at equal ratio a maximum network is observed; B: in excess of protein, phenols can only bind 2 proteins. C: In excess of phenol, all the sites of the protein are saturated with phenol and the bridging of two proteins is made more difficult. Adapted from Siebert et al. 1996 [124].

Fig. 3: The esterase production by susceptible mosquitoes is very low, insufficient to prevent the insecticide from working. In some resistant strains, the production of esterases in much greater quantities is the mechanism behind the resistance. It is therefore not a qualitative change (efficiency of esterases) but a quantitative change (the increase in the quantity of esterases produced can be considerable, up to representing 6 to 10% of the total proteins of insect). Fig. 4: Sensitive mosquito Fig. 5: Mosquito resistant

Fig. 6: Observations: Susceptible individuals The production of esterases by susceptible mosquitoes is very low, insufficient to prevent the insecticide Propoxur (Baygon) from working. Resistant individuals Observations: analysis of the results for resistant mosquitoes: the slope of the curves reflecting the evolution of the optical density is almost the same in the wells with or without insecticide. It can therefore be concluded that the ACE of resistant mosquitoes is completely insensitive to the insecticide Propoxur (Baygon).

Fig. 7: Observations: Analysis of the results for sensitive and resistant mosquitoes: compared to the control wells (A), the change in the optical density of the wells where the insecticide (B) NILO-PYR has been added is almost zero (horizontal line). Ace was therefore inactivated by the insecticide NILO-PYR. DETAILED DESCRIPTION OF THE INVENTION

The present invention refers to the model proposed by Siebert et al. in 1996 [124] after studies of the interaction of catechin and tannic acid on several peptides (gelatin, gliadin, lysozyme, papain, or synthetic polypeptide), through light scattering studies. This is a binding mechanism based once again on hydrophobic interactions. On the one hand, nonpolar amino acids can interfere with the formation of complexes by promoting the folding of the hydrophobic regions of the molecule inward, thus making them inaccessible. Alternatively, these same amino acids can promote the formation of complexes, if they act by cooperating with an adjacent proline residue to increase the activity of the binding site. Other amino acids can act sterically or electrostatically on complexation [124]. This system takes this time into consideration the tannin-protein ratios (Figure 2).

Indeed according to Siebert et al. Each protein has a fixed number of tannin binding sites, and tannins would have two (or more) protein-binding ends. Thus, for an equal concentration of tannins and proteins, a maximum network is observed corresponding to large colloids in excess of proteins. Polyphenols can only bind two proteins and form smaller particles. And in excess of tannins, all of the protein sites are saturated with tannins. Accessing a tannin already attached to one protein at the site of another protein is therefore more difficult, thus making bridging impossible. This results in the formation of particles of smaller sizes.

There are 2 kinds of esterases in mosquitoes called A and B. (Esterases (A) preferentially use alpha NA, and esterases B act preferentially on beta NA.). This action prevents the insecticide from entering and circulating in the insect's body, and therefore from reaching its target. This is a mechanism of detoxification by metabolization of the insecticide.

Evidence of increased esterase production in resistant mosquitoes: The amount of esterases produced by a mosquito can be assessed by the filter paper test. Principle of the experimental protocol applied to the mosquito population of the Montpellier region (including mosquitoes resistant and sensitive to insecticides): mosquitoes collected on a filter paper are crushed, then the following reagents are added:

• a mixture of two substrates on which the esterase acts by cutting them,

• a reagent which colors red one of the products obtained. The results obtained are presented in the document opposite (each box corresponding to a mosquito).

Carrying out the test in the laboratory.

The chromogenic substrate is a mixture of alpha-naphthyl acetate (alpha NA) and beta-naphthyl acetate (beta NA). Strictly speaking, only one of the 2 can be used, but usually it is a mixture of the 2, in a 1: 1 ratio. The esterase cuts these two substrates, releasing alpha (or beta) naphthol, which then segregates. stains in the presence of Fast Garnet GBC (powder to be added to the staining buffer). The product plus Fast Garnet gives a red precipitate, which gives color on the filter paper. Once the mosquito has been crushed on the paper, the revelation takes place between 5 and 15 minutes, if all the reagents are ready. Esterases (A) preferentially use alpha NA, and Esterases (B) act preferentially on beta NA

• DETECTION OF INCREASED ESTERASE ACTIVITY IN THE MOSQUITO BY A FILTER PAPER TEST (Figure 3).

Location of esterase production in mosquitoes Esterases can be demonstrated by an immunofluorescence technique (Figure 4-5).

Demonstration of esterase B1 by immunofluorescence in a mosquito sensitive to OP insecticides and in a resistant mosquito. The basic fluorescence intensity results in a blue flow, a higher fluorescence results in a color varying from yellow to red according to its increasing intensity. (La Recherche, n ° 234, July / August 1991).

The genes encoding esterases are not expressed in all the tissues of the insect; this expression takes place above all in the wall of the digestive tract, the sub-hypodermic skin cell zone and the cerebral and thoracic ganglia, the first two tissues constituting the main routes of penetration of the insecticide into the body, the latter containing the target insecticides.

The mechanisms that make the target less sensitive to the insecticide: acetylcholinesterase mutations (ACE) Some mosquitoes owe their resistance to OP insecticides and carbamates to a change in the spatial structure of their molecules of Ace, the target of insecticides , change which numbs the Ace to the action of these insecticides. The compositions of the invention are characterized by the action of preventing esterases produced by mosquitoes, from trapping or metabolizing insecticides, before they can inhibit acetylcholinesterase (ACE) in the synapses.

One of the sources of the appearance of resistance is linked to the overproduction of detoxifying enzymes by certain insects. By slowing down this overproduction, the present invention makes it possible to limit the multiplication of these resistant strains.

The present invention particularly has the property of inhibiting the enzyme produced by the insect and therefore of preventing the attachment of the substrate to the active site of the insecticide by attaching itself in its place, or causing deformation of the insecticide. enzyme that makes it inactive. This composition, which is both anti-oxidant, occurs at the initiation stage. In vivo, oxygenases (enzymes allowing oxidation) such as lipoxygenase and cyclooxgenase, allow the synthesis of eicosanoids, leukotrienes for the first, prostaglandins for the second, from arachidonic acid C (20: 4) and C ( 18: 3).

The compositions of the invention contain, among the amino acids, a catalytic triad (i.e. at least three catalytic residues) containing a serine (0.1 to 4.8 g / L), a histidine (0.1 to 1.5 g / L) and aspartic acid (0.5 to 22.9 g / L), glutamic acid (0.1 to 10 g / L), important for the hydrolysis of biodegrading enzymes produced by insects.

The compositions of the invention are characterized by the formation of a covalent bond between the biodegradation enzyme produced by insects and the inhibitor according to the reaction mechanism: The synergist substance has a fatty acid composition, saturated, monounsaturated, polyunsaturated, chosen from short chain fatty acids, C (6: 0), C (8: 0), C (10: 0), C (12: 0), C (14: 0), fatty acids with medium chain, C (16: 0 w9), C (17: 0), C (18: 0), C (18: lw9), C (18: lw7), (C18: 2 LA), C (18: 3) and long chain fatty acids, C (20: 0), C (20: lwll), (C20: lw9), C (20: 4), C (24: 0), which synergistically cause the dysfunction of the nervous system of insects and to act on the target, the enzyme acetylcholine esterase (Ace, present at the level of cholinergic synapses and having the role of hydrolysis neurotransmitter acetylcholine).

The compositions of the invention relate to a novel synergistic composition of pesticides containing as active principle a proteolytic enzyme containing cysteine or a mixture of proteolytic enzymes containing cysteine among which there may then be mentioned papain associated with a fatty acid composition, saturated, monounsaturated. , polyunsaturated, which can be chosen from fatty acids with short chains: C (6: 0), C (8: 0), C (10: 0), C (12: 0), C (14: 0), medium chain fatty acids, C (16: 0 w9), C (17: 0), C (18: 0), C (18: lw9), C (18: lw7), (C18: 2 LA), C (18: 3) and long chain fatty acids, C (20: 0), C (20: lwll), (C20: lw9), C (20: 4), C (24: 0).

Experimental protocol TESTS N ° -l: Sensitive and resistant mosquitoes. Product-tested: the insecticide Propoxur (Baygon).

Experimental protocol TESTS N ° -2: Sensitive and resistant mosquitoes. Product- tested: Insecticide -NILO-PYR whose composition contains: 2.5 g / L of pyrethrins and 12.5 g / L of the “SYNERGIST OF THE COMPOSITION OF THE PRESENT“ INVENTION- SX- PYR ”l ° the mosquito is crushed (or the larva) and the ground material is homogenized in an Eppendorf tube with a buffer solution (20 mM tris, pH 7, containing 1% Triton X-100). After centrifugation at 10,000g for 2 minutes, the supernatant (which contains the ACE) is collected and distributed in the wells (A) and (B) of a plate (100 microliters in each well),

2 ° one then adds in each well either 10 microliters of a concentrated solution of insecticide (10-2 M pyrethrum-based products), Baygon, a brand of pesticides produced by SC Johnson wells (B), and 10 microliters of alcohol, well (A.) The plate is left for 15 minutes at ambient temperature (this time is sufficient to allow the possible action of the insecticide),

Experimental protocol TESTS N ° -l: Sensitive and resistant mosquitoes Product-TEST: the insecticide PropoxuriBavaonJ.

The graphs below show the change in optical density over 10 min in each well, for 8 susceptible mosquitoes and 8 resistant mosquitoes (on the y-axis: intensity of the optical density; on the x-axis: time On the other hand, the slope of the right showing the change in optical density in the absence of insecticide is markedly lower in resistant mosquitoes than in susceptible mosquitoes.The Ace of resistant mosquitoes is therefore less active and less effective than that of susceptible mosquitoes. The reduction in activity of the resistant enzyme relative to the sensitive enzyme is about 60%, which is one aspect of the cost of resistance (Figure 6).

Experimental protocol TESTS N ° -2: Sensitive and resistant mosquitoes Product TESTE -NILO-PYR whose composition contains: 2.5Q / L of oyrethrins and 12.5 a / L of the "SYNENERGIST OF THE PRESENT" INVENTION-SX-PYR "

The compositions of this invention inhibit the overproduction of detoxifying enzymes produced by resistant mosquitoes. (Illustration above-Test-No.2 Figure 7)

Acetylcholiesterase hydrolysis

ArAtvI hnlinp »nhnlino A r state A The present invention is characterized by the property of causing, at a very low dose, the dissociation of a large quantity of esterases produced by insects and more particularly by resistant mosquitoes.

The compositions of the present invention disrupt the increased production of esterase in resistant insects and make the target acetylcholinesterase (ACE) more sensitive to the insecticide. Esterases are enzymes naturally produced by insects; they hydrolyze the ester bonds, in particular those of the molecules of the OP insecticides.

The present invention particularly has the property of inhibiting the enzyme produced by the insect and therefore of preventing the attachment of the substrate to the active site of the insecticide by attaching itself in its place, or causing deformation of the insecticide. enzyme that makes it inactive.

The compositions of the invention contain, among the amino acids, a catalytic triad (i.e. at least three catalytic residues) containing a serine (0.1 to 4.8 g / L), a histidine (0.1 to 1.5 g / L) and aspartic acid (0.5 to 22.9 g / L), glutamic acid (0.1 to 10 g / L), important for the hydrolysis of the biodegradation enzymes produced by insects.

The compositions of the invention are characterized by the formation of a covalent bond between the biodegradation enzyme produced by insects and the inhibitor according to the reaction mechanism:

E + I _, ^► EI

K, jii% f) afë i 20l? I

The compositions of the invention may contain one or more proteolytic enzymes (bromelain, ficin). In addition to the classic proteases (fig tree ficin, papaya papain, pineapple bromelain), we can mention asclepainc (Iselcpius speciosa), euphorhaine (E. cernera), sufanahie (S. eleagnifouliutri) , pontirite (llaclura pam (will) and mexicautc (lMeus mexicattus).

The compositions of the invention relate to a novel synergistic composition of pesticides containing as active principle a proteolytic enzyme containing cysteine or a mixture of proteolytic enzymes containing cysteine, among which may then be mentioned papain.

A more particular subject of the compositions of the invention is a novel composition of a synergist of pesticides, characterized in that it contains a cysteine protease of formula (I) or a mixture of compounds of formula (I) Formula (I) ) cysteine and D or S (-) - cysteine

The first step in the reaction mechanism catalyzed by cysteine proteases is the deprotonation of the thiol group, carried by the cysteine residue of the active site, by the basic side chain of a neighboring amino acid, usually a histidine residue. The next step is the nucleophilic attack of the carbon atom constituting the carbonyl of the substrate by the sulfide anion of deprotonated cysteine. The N-terminal fragment of the substrate is then released, while the histidine residue returns to its deprotonated state and an intermediate between the enzyme and the rest of the substrate is covalently formed through a thioester bond. This thioester bond is then hydrolyzed, which releases both the C-terminal fragment of the substrate and the regenerated enzyme in its active form. In a very recent work, CAREY (51 bis) proved, using Raman resonance spectrography, that the active site of papain reorganizes after a certain time after its action on a protein substrate; recent work on soy proteins, high value food products, showed us that papain could have an action on the performance of these foods, by increasing the proportion of free amino groups, gelation is prevented, but on the other hand , the stability of the emulsion is reduced; the enzymatic action must therefore be controlled. The present invention is characterized by one of the compositions which allows the rapid penetration of the insecticide towards the nervous system of the pests, due to the simultaneous presence of short-chain fatty acid, among which, there may be mentioned a combination of fatty acids such as: C (6: 6), C (8: 0), C (10: 0), C (12: 0), C (14: O). This composition, which is both anti-oxidant, occurs at the initiation stage. In vivo, oxygenases (enzymes allowing oxidation) such as lipoxygenase and cyclooxgenase, allow the synthesis of eicosanoids, leukotrienes for the first, prostaglandins for the second, from arachidonic acid C (20: 4) and C ( 18: 3) The synergist of the present invention is involved in the process of combating the detoxification of pyrethrins and pyrethroids (I) and (II) by insects.

The compositions of the invention contain one or more polyphenolic compounds consisting of hydrolyzable tannins ((gallic or ellagic tannins) or flavonoids, such as flavonols, there may be mentioned quercetin. The compositions of the invention may contain one or more of the triglycerides that may be mentioned (sesame, cottonseed, coconut, paraffin, sunflower, soybean, rapeseed or corn oil, preferably sesame oil , cotton, or methylated rapeseed oil.

The compositions of the invention may contain one or more pyrethroids as well as other insecticidal products, such as organophosphorus compounds, organochlorines, carbamates, as well as other acaricidal, fungicidal and herbicidal products.

The present invention relates to a synergistic composition of pesticides among insecticides, it can contain pyrethrinoids (I) and (II), mention may be made of: permethrin, bifenthrin, deltamethrin, tetramethrin, cypermethrin and various mixtures of 'isomers which result therefrom, and in particular a-cypermethrin and asymethrin, esbiothrin, kadethrin, acrynathrin, cyhalothrin and the various mixtures of isomers which result therefrom, and in particular the l-cyhalothrin, cyfluthrin, tralomethrin, fluvalinate, fenvalerate, S-fenvalerate or (lR, cis) 2,2-dimethyl 3 - [(Z) 2- (methoxycarbonyl) ethenyl] cyclopropane carboxylate of (S ) a-cyano 3-phenoxy benzyl.

The compositions of the invention may also contain a phase change inhibitor chosen from ethanol, isopropyl alcohol, benzyl alcohol, and their mixture or (+) - 4-Isopropenyl-1-methylcyclohexene, (+ ) - Isopropenyl-4 methyl-1 cyclohexene, D-Isopropenyl-4 methyl-1 cyclohexène, (D) - limonene.

The present invention brings about a benefit for human health through formulations which are less concentrated in active substance, and therefore more favorable toxicological classifications.

The compositions of the present invention combined with pesticides greatly reduce the amounts of insecticides required and make it possible to lower the levels of insecticide residues, for example, in storage seeds treated with insecticides.

The compositions of the invention exhibit a power of management of the resistance of insects to OP insecticides and to carbamates and could, at the level of the WHO, be part of the resistance management program, centered on the study of the mosquito. C. pipiens and in particular to vectors of endemic diseases such as Anopheles.

The compositions of the invention are characterized by the fact that they respect the environment by reducing the contributions of insecticides in the biocidal formulations by 30 to 40%, they reduce the risk of transferring a large quantity of insecticide residues into the environment.

A more particular subject of the invention is a synergist for pesticides which is more respectful of man and the environment; according to the following toxicological and ecotoxicological information: Acute toxicity (oral): Not classified. Acute toxicity (dermal): Not classified. Acute toxicity (inhalation): Not classified. Skin corrosion / irritation: Not classified. Additional information: Based on available data, the classification criteria are not met. Germ cell mutagenicity Not classified. Additional information: Based on available data, the classification criteria are not met. Carcinogenicity: Not classified. Additional information: Based on available data, the classification criteria are not met. Reproductive toxicity: Not classified. Additional information: Based on available data, the classification criteria are not met. Specific target organ toxicity (single exposure): Not classified.

Additional information: Based on available data, the classification criteria are not met. Specific target organ toxicity (Repeated exposure): Not classified. Additional information: Based on available data, the classification criteria are not met. Aspiration hazard: Not classified. Acute aquatic toxicity: Not classified. Chronic aquatic toxicity: Not classified. Acute aquatic toxicity: Not classified. Chronic aquatic toxicity: Not classified. Persistence and degradability: Not established. Bioaccumulative potential: Not established. Mobility in soil: No additional information available.

A more particular subject of the invention is the compositions presented in the form of emulsifiable concentrates or concentrates to be diluted.

The compositions of the invention may contain most of the pesticides, but are naturally of greater interest as a synergist for pyrethroids (I) and (II) and pyrethrins which degrade rapidly under the effect of light and of the heat.

A particular subject of the present invention is a synergist of pesticides containing as active ingredients a proteolytic enzyme containing cysteine or a mixture of proteolytic enzymes containing cysteine, preferably papain and a polyphenolic compound among hydrolyzable tannins ((or gallic or ellagic tannins). mention may be made of tannic acid, and among triglycerides, mention may be made of sesame oil, a phase change inhibitor, mention may be made of ethanol, among organic peroxides, preferably hydrogen peroxide; said composition is intended in its use and for the management of resistance linked to the mechanisms of insects to detoxify insecticides and to improve the efficiency of certain insecticides such as (natural pyrethrum and pyrethroids (I) and (II) The present invention relates to compositions containing pyrethrins and pyrethrinoids (I) and (II) and their mixture.

The present invention relates to compositions containing the extract of pyrethrum flowers, the active ingredients of which are pyrethrins (I) and (II). The present invention relates particularly to compositions which contain pyrethroids (I) and (II), we can cite: permethrin, bifenthrin, deltamethrin, tetramethrin, cypermethrin and the various mixtures of isomers which are derived from it, and in particular α-cypermethrin and asymethrin, esbiothrin, kadethrin , acrynathrin, cyhalothrin and the various mixtures of isomers which are derived from it, and in particular l-cyhalothrin, cyfluthrin, tralomethrin, fluvalinate, fenvalerate, S-fenvalerate or (lR, cis) 2,2-dimethyl 3 - [(Z) 2- (methoxycarbonyl) ethenyl] cyclopropane carboxylate of (S) a-cyano 3-phenoxy benzyl. A more particular subject of the invention is the compositions characterized in that they contain from 0.1 to -500 g / l of papain.

Among the compositions of the invention, mention may be made of compositions containing from 1 to 100 g / l of tannic acid. A very specific subject of the invention is a synergistic composition of pesticides characterized in that it contains from 5 to 800 g / l of sesame oil and from 300 to 700 g / l of a phase change inhibitor chosen from among ethanol, isopropyl alcohol, benzyl alcohol and their mixture. As preferred compositions of the invention, mention may be made of compositions characterized in that they contain from 1 to 25 g / L of papain, from 1 to 100 g / L of tannic acid, from 1 to 350 g / L of hydrogen peroxide, from 1 to 700 g / L (Ethanol, isopropyl alcohol, benzyl alcohol and their mixture). Among the latter, mention may be made of those which additionally contain 1 to 400 g / L of coconut glucoside.

Example of compositions according to the invention. EXAMPLE 1 Compositions were prepared containing: [0057]

Compositions similar to that of example (1) were prepared in which 1 to 250g / L of sesame oil were replaced by 1 to 250g (coconut oil or coconut butter), from 1 to 250g of white paraffinic, thence 250g of rapeseed oil, from 1 to 250 g of soybean oil, from there 250 g of sunflower oil or from 1 to 250g of methylated rapeseed oil, in addition the present compositions may contain from 0.1 to 10 g / L of citric acid, and from 0.1 to 10 g / L of acetic acid.

Compositions similar to that of Example (1) were prepared in which 1 to 250 g / L of fatty acids (C (6: 0), C (8: 0), C (10: 0), C ( 12: 0), C (14: 0), medium chain fatty acids, C (16: 0 w9), C (17: 0), C (18: 0), C (18: lw9), C ( 18: lw7), (C18: 2 LA), C (18: 3) and long chain fatty acids, C (20: 0), C (20: lwll), (C20: lw9), C (20: 4), C (24: 0).), Associated with 0.1 to 100g of tannic acid, and 1 to 250g (+) - 4-Isopropenyl-l-methylcyciohexene, (+) - Isopropenyl-4 methyl-1 cyclohexene, D-Isopropenyl-4 methyl-1 cyclohexene, (D) -Limonene and further the present compositions may contain from 0.1 to 10 g / L of citric acid, and from 0.1 to 10 g / L of acetic acid.

Example of compositions according to the invention. EXAMPLE 2 Compositions containing: [0058]

Compositions similar to that of example (2) were prepared in which 1 to 250g / L of sesame oil were replaced by 1 to 250g (coconut oil or coconut butter), from 1 to 250g of white paraffinic, from there 250g of rapeseed oil, from 1 to 250 g of soybean oil, from there 250 g of sunflower oil or from 1 to 250g of methylated rapeseed oil, from 1 to 500g / L (isopropyl alcohol, benzyl alcohol, or their mixture).

The above compositions are used in combination with pesticides; one can for example cite a combination, by virtue of 1 to 900 g / L of the composition of the invention, preferably 30 to 45 g / L of the composition, in a composition containing from 1 to 900 g / L of deltamethrin, of preferably from 1 to 15 g / L of deltamethrin, more precisely 45 g / L of the composition of the invention in a composition containing 15 g / L of deltamethrin.

The above compositions are used diluted and applied using a sprayer; one can for example dilute 100 ml of this composition in 5 liters of water. We can thus effectively treat 100 m2 of surface (treatment against crawling insects). When it is desired to treat surfaces against flying insects, 65 ml of the composition described above can be diluted in 5 liters of water. When it is desired to carry out treatments by nebulization, it is possible to dilute 700 ml of the above composition in 9 liters of petroleum solvent and apply the solution obtained at a rate of 500 ml of solution per hectare. When it is desired to treat interior spaces, it is possible to dilute from 500 ml to 1000 ml of the composition described above in 4 liters of petroleum solvent and apply 250 ml of the solution thus obtained to treat 1000 m3 of interior space. The above compositions are used in combination with pesticides; one can for example quote a combination in proportion of 1 to 900 g / L of the composition of the invention, preferably of 300 to 450 g / L of the composition of the invention, in a composition containing from 1 to 900 g / L of Tralomethrin, preferably from 1 to 144 g / L of Tralomethrin.

The above compositions are used in combination with pesticides; one can for example cite a combination in proportion of 1 to 900 g / L of the composition of the invention, preferably from 30 to 45 g / L of the composition of the invention, in a composition containing from 1 to 900 g / L of Tralomethrin, preferably from 1 to 15 g / L of Tralomethrin.

The above compositions are used in combination with pesticides; one can for example quote a combination by reason of 1 to 900 g / L of the composition of the invention, preferably from 60 to 190 g / L of the composition of the invention, in a composition containing from 1 to 900 g / L of Acrinathrin, preferably 1 to 30g / L of Acrinathrin.

The above compositions are used in combination with pesticides; one can for example cite a combination by virtue of 1 to 900 g / L of the composition of the invention, preferably from 30 to 45 g / L of the substance of the invention, in a composition containing from 1 to 900 g / L of Cyfluthrin, preferably from 1 to 15g / L of Cyfluthrin.

The above compositions are used in combination with pesticides; one can for example cite a combination by virtue of 1 to 900 g / L of the composition of the invention, preferably from 130 to 200 g / L of the substance of the invention, in a composition containing from 1 to 900 g / L of Cypermethrin, preferably from 1 to 66g / L of Cypermethrin.

The above compositions are used in combination with pesticides; one can for example cite a combination by reason of 1 to 900 g / L of the composition of the invention, preferably from 300 to 500 g / L of the composition of the invention, in a composition containing from 1 to 900 g / L of permethrin, preferably 480 g / L of the composition of the invention in a composition containing 160 g / L of permethrin.

The compositions [0066, above,] are intended to fight against bedbugs, fleas, lice, ticks and mites; ectoparasites living on the human body and in his clothing and bedding. There are many species of blood-sucking fleas, lice, ticks and mites. Lice are parasites of humans that live on their body or in their clothes, while bedbugs are often found gorging themselves with blood on humans or pets. Bedbugs, which are also found in other furniture, get their blood meal by biting humans. Some mites, such as scabies, are parasites of the skin.

The substance of the invention is used in combination with pesticides for the treatment and prevention of infestations by fleas (Ctenocephalides canis, Ctenocephalides felis). ; one can for example cite a combination by reason of 1 to 900 g / L of the composition of the invention, preferably of 100 g / L of the composition of the invention, in a composition containing from 1 to 900 g / L of permethrin, preferably 15 g / L of permethrin, from 1 to 300 g / L of N-methylpyrrolidone, from 1 to 200 g / L Miglyol 812, from 1 to 70 g / L of citric acid.

The compositions of the invention are used for the treatment and prevention of infestations by fleas (Ctenocephalides canis, Ctenocephalides felis); they are indicated in their specific use against the target species, for example: The fleas present on the dog are killed in the day following the treatment. A single treatment prevents re-infestation by fleas for four weeks. For the treatment of biting lice (Trichodectes canis). The product has persistent acaricidal and repellent efficacy against tick infestations (Rhipicephalus sanguineus and Ixodes ricinus for four weeks and Dermacentor reticulatus for three weeks). A single treatment ensures a repellent activity (anti-gorging) against sandflies

(Phlebotomus papatasi for two weeks and Phlebotomus perniciosus for three weeks /, against mosquitoes (Aedes aegypti for two weeks and Cul ex pipi ens for four weeks) and against stable flies (Stomoxys calcitrans) 4 weeks.

The above compositions are used in combination with pesticides; one can for example cite a combination by reason of 1 to 900 g / L of the composition of the invention, preferably from 300 to 500 g / L of the composition of the invention, in a composition containing from 1 to 900 g / L of Bifenthrin, preferably from 1 to 160g / L of Bifenthrin. The above compositions are used in combination with pesticides; one can for example cite a combination by reason of 1 to 900 g / L of the substance of the invention, preferably from 15 to 30 g / L of the composition of the invention, in a composition containing from 1 to 900 g / L of Pyrethrins (extract of pyrethrum flowers), preferably from 1 to 30g / L of pyrethrins.

The compositions of the invention can be provided in the usual forms of the agrochemical industry or of the veterinary industry when it is a question of increasing the effectiveness of pesticides and more particularly of pyrethroids (I) and (II) intended in the fight against crop pests, mention may be made, for example, of aphids, and as insecticides against external parasites of animals, insects and mites, using baths, aerosols. They can also be used in shampoos, lotions or creams, to fight against lice in humans, for example.

The compositions of the invention are characterized in that they may contain from 1 to 25 g / L of deltamethrin, preferably from 5 to 15 g / L of deltamethrin.

The compositions of the invention are characterized in that they can contain from 1 to 155 g / L of tralomethrin, preferably from 100 to 155 g / L of tralomethrin.

The compositions of the invention are characterized in that they may contain from 1 to 20 g / L of cyalothrin, preferably from 10 to 15 g / L of cyalothrin.

The compositions of the invention are characterized in that they can contain from 1 to 35 g / L of Acrinathrin, preferably from 20 to 30 g / L.

The compositions of the invention are characterized in that they contain from 1 to 25 g / L of cyfluthrin, preferably from 15 to 20 g / L of cyfluthrin.

The compositions of the invention are characterized in that they contain from 1 to 75 g / L of cypermethrin, preferably from 10 to 70 g / L.

The compositions of the invention are characterized in that they contain from 1 to 200 g / L of bifenthrin, preferably from 100 to 160 g / L of bifenthrin.

The compositions of the invention are characterized in that they contain from 1 to 200 g / l of permethrin, preferably from 100 to 160 g / L of permethrin. The compositions of the invention are characterized in that they additionally contain from 90 to 250 g / l of cyclohexanone or other optional solvent of the ketone or glycol ether type, such as N-methyl pyrrolidone, N-amyl ketone or propylene glycol methyl ether.

Claims

1. Synergistic composition of pyrethrins and pyrethroids (I) and (II) having a fatty acid composition, saturated, monounsaturated, or polyunsaturated, which are chosen from fatty acids with short chains, C (6: 0), C (8 : 0), C (10: 0), C (12: 0), C (14: 0), medium chain fatty acids, C (16: 0 w9), C (17: 0), C (18 : 0), C (18: lw9), C (18: lw7), C (18: 2 LA), and long chain fatty acids, C (20: 0), C (20: lwll), C ( 20: lw9), C (24: 0), characterized in that it is associated with a cysteine protease and a polyphenolic composition or a mixture of polyphenolic compounds consisting of hydrolyzable tannins or gallic or ellagic tannins and flavonoids , such as flavanols, there may be mentioned quercetin (C15H10O7).

2. Composition according to Claim 1, characterized in that the said cysteine protease is chosen from fig tree ficin, papaya papain, pineapple bromelain, asclepias protease (Asclepias speciosa), euphorbaine protease. (E. cerifera), solanaïne (S. Eleagnifoldium), pomirine (Maclura pomiera) and Mexican (Pileus mexicanus).

4. Composition according to any one of the preceding claims, characterized in that the compound, the cysteine protease, is present in a proportion of between 1 to 90%, by weight relative to the total weight of the composition.

5. Composition according to any one of the preceding claims, characterized in that the compound, the cysteine protease, is present in a proportion of between 1 to 10%, by weight relative to the total weight of the composition.

6. Composition according to any one of the preceding claims, characterized in that the said polyphenolic compound is chosen from flavonoids, carnosic acid, carnosol, (2,5-dihydroxyphenyl) carboxylic acids and (2,5 - substituted carboxylic dihydroxy phenyl) allylenes, and their derivatives, esters or amides of caffeic acid and tannic acid.

7. Composition according to Claim 1, characterized in that the said selected polyphonic compound is tannic acid.

10. Composition according to any one of the preceding claims, characterized in that the composition contains a triglyceride chosen from (sesame, cottonseed, coconut, paraffin, sunflower, soybean, rapeseed or corn, preferably sesame oil, cottonseed oil, or methylated rapeseed oil).

12. Composition according to the preceding claims, characterized in that they contain, 0, 1 to 800g / L of fatty acids (C (6: 0), C (8: 0), C (10: 0), C ( 12: 0), C (14: 0), medium chain fatty acids, C (16: 0 w9), C (17: 0), C (18: 0), C (18: lw9),

C (18: lw7), (C18: 2 LA), C (18: 3) and long chain fatty acids, C (20: 0), C (20: lwll), (C20: lw9), C ( 20: 4), C (24: 0).), Associated with 0.1 to 100g of tannic acid, and 1 to 250g (+) - 4-Isopropenyl-l-methylcyclohexene, (+) - Isopropenyl-4 methyl -1 cyclohexene, D-Isopropenyl-4 methyl-1 cyclohexene, (D) -Limonene and furthermore the present compositions may contain from 0.1 to 10 g / L of citric acid, and from 0.1 to 10 g / L acetic acid.

14. The compositions according to the preceding claims are used in a combination with pesticides, in an amount of 0.1 to 900 g / L of the composition according to the preceding claims, preferably 30 to 45g / L of the composition according to the preceding claims, in a composition containing from 1 to 900 g / L of deltamethrin, preferably from 1 to 15 g / L of deltamethrin.

15. The compositions according to the preceding claims are used diluted in water and applied using a sprayer.

16. The compositions according to the preceding claims are used in combination with pesticides; one can for example cite a combination in a proportion of 0.1 to 900 g / L of the composition according to the preceding claims, preferably from 300 to 450 g / L of the composition according to the preceding claims, in a composition containing from 1 to 900 g / L of Tralomethrin, preferably from 1 to 144 g / L of Tralomethrin.

17. The compositions according to the preceding claims are used in combination with pesticides; one can for example cite a combination in a proportion of 0.1 to 900 g / L of the composition according to the preceding claims, preferably from 30 to 45 g / L of the composition according to the preceding claims, in a composition containing from 1 to 900 g / L of Tralomethrin, preferably from 1 to 15 g / L of Tralomethrin.

18. The compositions according to the preceding claims are used in combination with pesticides; one can for example cite a combination by reason of 0.1 to 900 g / L of the composition according to the preceding claims, preferably from 60 to 190 g / L of the composition according to the preceding claims, in a composition containing from 1 to 900 g / L of Acrinathrin, preferably 1 to 30 g / L of Acrinathrin.

19. The compositions according to the preceding claims are used in combination with pesticides; one can for example quote a combination in a proportion of 0.1 to 900 g / L of the composition according to the preceding claims, preferably from 30 to 45 g / L of the composition according to the preceding claims, in a composition containing 0, 1 to 900 g / L of Cyfluthrin, preferably 0.1 to 15 g / L of Cyfluthrin.

20. The compositions according to the preceding claims are used in combination with pesticides; one can for example cite a combination in a proportion of 0.1 to 900 g / L of the composition according to the preceding claims, preferably from 130 to 200 g / L of the composition according to the preceding claims, in a composition containing from 0.1 to 900 g / L of Cypermethrin, preferably from 1 to 66g / L of Cypermethrin.

21. The compositions according to the preceding claims are used in combination with pesticides; one can for example quote a combination in a proportion of 0.1 to 900 g / L of the composition according to the preceding claims, preferably from 300 to 500 g / L of the composition according to the preceding claims, in a composition containing 0.1 at 900 g / L of permethrin, preferably 60 g / L of permethrin.

24. The compositions according to the preceding claims, characterized in that they contain from 0.1 to 25 g / L of deltamethrin, preferably from 5 to 15 g / L of deltamethrin.

25. The compositions according to the preceding claims, characterized in that they contain from 0.1 to 155 g / L of tralomethrin, preferably from 100 to 155 g / L of tralomethrin.

26. The compositions according to the preceding claims, characterized in that they can contain from 0.1 to 20 g / L of cyalothrin, preferably from 10 to 15 g / L of cyalothrin.

27. The compositions according to the preceding claims, characterized in that they can contain from 0.1 to 35 g / L of Acrinathrin, preferably from 20 to 30 g / L.

28. The compositions according to the preceding claims, characterized in that they contain from 1 to 25 g / L of cyfluthrin, preferably from 15 to 20 g / L of cyfluthrin.

29. The compositions according to the preceding claims, characterized in that they contain from 1 to 75 g / L of cypermethrine, preferably from 10 to 70 g / L.

30. The compositions according to the preceding claims, characterized in that they contain from 1 to 200 g / L of bifenthrin, preferably from 100 to 160 g / L of bifenthrin.

31. The compositions according to the preceding claims, characterized in that they contain from 1 to 200 g / l of permethrin, preferably from 100 to 160 g / L of permethrin.

32. The compositions according to the preceding claims, characterized in that they contain from 0.1 to 200 g / l of Tefluthrin.