NZ272326A

NZ272326A - Insecticidal composition comprising methyl 10-undecylenate and another insecticidal substance

Info

Publication number: NZ272326A
Application number: NZ272326A
Authority: NZ
Inventors: Catherine Regnault-Roger; Henri-Jean Caupin
Original assignee: Atochem Elf Sa
Priority date: 1994-06-14
Filing date: 1995-06-12
Publication date: 1996-02-27
Also published as: FI952894A0; NO952320L; CA2151553A1; EP0695502A1; JPH0840808A; CN1114856A; AU2165895A; FI952894A; FR2720897A1; NO952320D0; BR9502788A; KR960000025A

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £72326 I | Priority Date(s): 3. hi. < -oTjplEie Specification Filed: ..I3>IW.}3.$ ::iQGs: (6) Publication Date: ^.,^..F.E8..]$SS • .0. Journal No: Mc».\ Patents Form No. 5 Our Ref: JB204786 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION N.Z. PATENT OFF ICE 12 J UN 1995 IHSECTICIDAL COMPOSITIONS BASED ON METHYL UHt)ECYLENATE UNDI We, ELF ATOCHEM S.A., a French company of 4 & 8 Couxs Michelet, La Defense 10 - Cedex 42, 92800 Puteaux, France hereby declare the invention, for which We pray that a patent may be granted to us and the method by which it is to be performed, to be particularly described in and by the following statement: PT0524853 - 1 - 2 - 272321 Insecticidal compositions based on methyl uwdecvlenate It is already known that methyl 10-undecylenate of formula CH2 = CH-(CH2)8"CO-CH3 (!) denoted hereinbelow by the abbreviation Cll, has an action which makes it possible to control insects on wool (Chemical Abstracts, vol. 98, No. 25, Columbus, Ohio, U.S.-20 June 1986). However, it has now been found that an insecticidal composition comprising an insecticidal substance other than Cll is considerably more active when Cll is added thereto. Cll has an attractant effect, such that the composition comprising both an insecticidal substance other than Cll and Cll has a synergy effect, Cll attracting the insects and immobilizing them in proximity to the other fast-action insecticide. The attractant effect makes it possible to mask the repellent effect of the other insecticidal substances. An antifeedant activity is added thereto, along with inhibition of reproduction by lowering fertility, and an ovicidal and larvicidal effect limiting the replenishment of the generations, all of the effects combining to reduce the flow of insects. The invention applies most particularly to the control of insects that destroy stored foodstuffs, such as Coleoptera and aphids. It is moreover recommended to add a polyphenol to a composition of Cll and of an insecticide other than Cll and other than a polyphenol. Polyphenols which are advantageously used are those of formula —| — r2 (I) in which Rjlz Rj and R3, which are identical or different, are a hydrogen atom, a hydroxyl or a lower alkoxy, at least two of Rlr R2 and K3 being other than a hydrogen atom, R4 is a hydrogen atom, Rs is a hydrogen atom, a hydroxyl, an alkoxy or a glycosides, or R4 and R5 together form an additional valenC« bond between the carbon atoms which bear them, R6 is a hydrogen atom, R<7 is a hydroxyl, lower alkyl or phenyl, optionally mono-, di- or trisubstitut^d with lower alkyl, lower alkoxy or hydroxyl ra-dicals, or Rg and Ry together form a divaleajt radical of formula joined by the oxygen atom to tfr« carbon atom bearing R4. The term lower alkyl or alkoxy refers to linear or branched radicals having from 1 to 6 carbon atoms and, preferably, from 1 to 4 carbon atoms. Among these polyphenols, there may in particular be mentioned catechins, flavanoneff, flavones, flavanonols, flavonols and other flavonoi&s of monomeric forms or of associated forms as dimers or polymers. There may in particular be mentioned caffeic acid, ferulic acid, gallic acid, and other phenolic acidLs derived from cinnamic acid or from benzoic acid, catecb-in., quercetin, rutin and naringin. Rutin, caffeic acid afl-d naringin are highly attractant and bring about a strong- inhibition of the natural motor functions o£ the insects and are consequently very particularly preferred, The attractant effect of polyphenol.? is such that they increase the consumption of the toxic mixture by the - 4 - insects, by allowing the effective concentrations of each of the insecticidal compounds to be decreased. These polyphenols are natural substances of plant origin which are found in the daily food supply and which 5 are, by definition, biodegradable and non-toxic for mammals at dosee effective on insects. When combined with another insecticidal substance which is itself also biodegradable and non-toxic and preferably natural, polyphenols thus make it possible to constitute an 10 insecticidal composition which is not harmful to the environment. For this reason, according to a preferred embodiment of the composition according to the invention, the insecticidal substance other than Cll is a terpene. Terpenes are hydrocarbons of the aliphatic and cyclanic 15 series, the constitution of which is expressed by the formulae obtained by assembling isoprene units. It is possible to use C10H16 acyclic terpene hydrocarbons having the structure of 2,6-dimethyloctane, C10H16 true terpene hydrocarbons and C15H24 sesquiterpene hydrocarbons. 20 Monocyclic terpenes and bicyclic terpenes are especially preferred. Among the terpenes, menthane, limonene, cymene, terpinen.es, eugenol, pinene, sabinene and carene may be mentioned. The terpenes may bear an alcohol function, such as linalool, menthol or terpineol, a 25 ketone function, such as menthone, carvone, thujone and camphor, an aldehyde function, such as safranal, geranial, cynamaldehyde and cuminaldehyde, or a phenol function, such as thymol and carvacrol, and may be methoxylated, such as anethole, eugenol, estragol and 30 borneol. Eugenol, terpineol and carvacrol are most particularly preferred, and, to a lesser extent, thymol, linalool, anethole, arminaldehyde, cynamaldehyde and cymene. A conventional insecticidal substance is combined 35 with Cll, alone or to which a polyphenol has been added, such as fatty acids and derivatives which are carboxylic acids in which the aliphatic chain is sufficiently long to impart a lipophilic nature thereto, this chain generally consisting of 10 to 20 carbon atoms and being 2723 saturated or mono- or polyunsaturated. The fatty acids may be used in free form, in salified form, it being possible for the cation to be an alkali metal or ah alkaline-earth metal, in esterified form, generally with an aliphatic alcohol, or in the form of a glyceride such as a mono-, a di- or a triglyceride. It is also possible to combine with Cll, as insecticidal substance, a carbamate, a pyrethroid, an organophosphorous compound or an organochlorine compound. Another insecticide is preferably combined with the Cll-terpene couple. The insecticidal substance(s) other than Cll/Cll weight ratio is preferably between 1/1000 and 1/10. When a ternary composition containing Cll, a polyphenol and an insecticide other than Cll and other than a polyphenol is used, the Cll + polyphenol/insecticide other them Cll and other than polyphenol weight ratio is between 1/1000 and 1/10 and the Cll/polyphenol ratio is between 0.1 and 10. The composition is obtained by mixing the constituents together. The insecticidal composition according to the invention makes it possible not only to control actual insects, but also relates more generally to the entire sub-kingdom of Metazoa and, in particular, the phylum of arthropods, among which are featured the Arachnida, for example Tetranychus urticae, family Trombididae, order Acari. However, the preferred target class is that of the Insecta among which are featured (classification according to Balachowsky, 1962) the order of Blattida, in particular: genus Blatella, species B. germanica, B. orientalis (cockroaches), genus Ectobius species E. lapponicus (forest cockroach) . The order of Hymenoptera, in particular *family Formicidae (ants), genus Camponotus, species C. femoratus, C. ligna-perda (carpenter ant), genus Formica, species F. polyctena (russet ant), F. fusca, 27 - 6 - * family Myrcidae, genus Myrmica, species M. rubra (red ant), genus Monomorium, species K. pharaonis (pharaoh ant) . 5 But especially *the order of Diptera, with the families of Drosophilidae, genus Drosophila (example: species D. melanogaster, common fruit fly, D. auraria), family of the Muscidae, genus Musca, species 10 M. domestica (housefly), family of the Trypetidae, genus Ceratitis, species C. capitata (Mediterranean fruit fly), family Culicidae, genus Culex, C. pipiens (mosquito) or other mosquitoes, example: Aedes aegypti yellow 15 fever vectors. ♦order of the Coleoptera, sub-order Polyphaga, with the super-families Cucujoidea including the families of Coccinellidae, sub-family of the Epilachninae (phytophagous larvae 20 of fruit and vegetables), species E. chrysomelina, E. varivestis, E. similis, family of the Mordellidae, genus Mordellistena, M. parvula (pest of sunflower and hemp), family Tenebrionidae, 25 - genus Tribolium, species Tribolium castaneum, T. confus\im (pests of grain and flower of wheat and barley type), genus Tenebrio, species T. molitor, T. obscurus F (dark mealworm) , 30 - Super-family Bostrychoidea including the family of the Bostrychidae, (genus Rhizopertha, R. dominica (lesser grain borer), super -family Scarabaeoidae, for exan^>le family Scarabaeidae, sub-family Rutelinae, genus Popillia, 35 P. japonica (Japanese beetle). Super-family Phytophagoidea, including: family Bruchidae, sub-family Bruchinae, * genus Acanthoscelides, species A. obtectus (bean weevil), * genus Bruchus, species Bruchus lentis (lentil weevil), * genus Callosobruchus, species C. maculatus (cowpea weevil), C. chinensis (adzuki bean weevil), sub-family Amblycerinae, * genus Zabrotes, species Z. fasciatus (vegetable weevil), family Chrysomelidae, sub-family Crysomelidae, genus Leptinotarsa, species L. decemlineata (Colorado potato beetle), family Curculonidae, sub-family Tanymecinae, genus Tanymecus, species T. palliatus (beet leaf weevil), sub-family Curculioninae, tribe Trichiini, genus Tychius, species T. quinque-punctatus (vegetable weevil), T. fasciatus, tribe of the Calandini, genus Sitophilus, species S. granarius, S. oryzae, S. zeamais (wheat, rice and corn weevil) . Order of the Lepidoptera: Sub-order of the Heteroneura, - sub-division Heterocera, ♦♦♦including the super-family: Pyraloidea, for example: family Pyralidae, - sub-family Pyraustinae, genus Ostrinia, species: Ostrinia nubilalis Hb (European corn borer), genus Loxostege, species L. sticticalis (beet webworm), genus Evergestis, species E. frumentalis (cabbageworm) , - sub-family Galleriinae, genus Ephestia, species E. cautella, E. kuenhniella (flour moth), - super-family Noctuoidea, for example: family Noctuidae, group Trifides, 27 - 8 - - sub-family Amphipyrinae, - genus Sesamia, species Sesamia nonagrioides Lef. (corn borer), - genus Spodoptera, 5 species Spodoptera litura Fab., Spodoptera littoralis Bois du Val (cluster caterpillar, fruit and vegetable pest), sub-family Melicleptriinae, genus Helicoverpa (or Heliothis), 10 species E. zea Hb., Super-family Tineoidea, for example: family Gelichiidae including: genus Sitotroga, species Sitotroga cerealla OL. (grain moth). 15 The composition according to the invention may be used to protect crops in the open field. The composition according to the invention is applied at a rate of 100 to 1000 grams per hectare. The compositions may also be formulated for 20 domestic use, an example of which formulation is given below: a spray container 650 ml in total volume, filled to a useful volume of 500 ml, has a net weight of 300 grams and contains: 250 grams 0.4 grams 0.5 grams 0.1 gram 0.5 gram 1.5 grams 0.025 gram 47 grams - propellant (butane) 25 - polyphenol - Cll terpenes fragrance surface-active agent 30 - viscosity agent 50% ethanol This composition is prepared in the following way: an aqueous-alcoholic solution at a concentration of 50% by weight is prepared, in which the surfactants 35 (10 EO ethoxylate of undecylenic acid and 10 EO ethoxy-late of ricinoleic acid) are dissolved, followed by the Cll, the polyphenols, the terpenes and the fragrance; the mixture is emulsified and em aqueous solution of viscosifying gum is then added thereto. The spray containers are filled with 50 grains of this emulsion, to which are added 250 g of butane or of another propellant gas. (EO refers to ethylene oxide). It is also possible to use the compositions for external or internal protective coatings (all fields, for example: electricity, light construction for land or water use) and all fields of packaging, especially food packaging intended for foodstuffs and also for agronomic use: encapsulation of biopesticides, small containers for plant seedlings, and multi-purpose biodegradable polymer films. The experiments which follow illustrate the invention. 1st experiment; insecticidal and attractant power of Cll. Two separate compartments each 465 cm3 in volume are connected by a glass tube 1.5 cm in cross-section and 10 cm in length. The product whose activity is to be tested is placed in the first compartment and the insects whose sensitivity is to be studied are placed in the second compartment. The glass tube described above permits circulation of the insects and of the gases. In this experiment, a fumigation chamber, which the insects are prevented from accessing by means of a grille and which contains 4.43 mg (5 /il) of methyl undecylenate (Cll) impregnated on Whatman paper No. 1, is placed in the first compartment (A) . A population of insects consisting of 20 adult individuals of AcanthoBcelidea obtectus Say (Bruchidae, Coleoptera) bean weevil, Phaaeolus vulgaris L develops in the second compartment (B). After 4h, 20% of the insects are found in compartment A, 50% after 5 hours, 60% after 8 hours and 70% after 24 hours. This proportion subsequently remains stable. All of the insects remain alive for the first 12 hours, but it is observed that 20% of dead insects are found in the compartment containing the fumigation chamber after 24 hours, whereas, after 48 hours, 30% of dead insects are found in compartment A and 10% in compartment B. The experiments performed with the control batch contain no dead insects and the migration 2723 is significantly different: 30% of insects in compartment A and 70% in compartment B. For a control compound, the distribution is equal between the two compartments (50%/50%) and no deaths are counted. A second type of experiment is performed according to the reverse arrangement: the insects are placed in compartment A containing the fumigation chamber and the number of insects fleeing this compartment and seeking refuge in compartment B are counted. 80% of the insects remain in the first compartment and only 20% have migrated into the other compartment after 4 hours, the proportion remaining stable for the subsequent 48 hours. 20% of dead insects are counted in compartment A after 24 hours. The ethoxy control compound causes no deaths, the distribution of the insects being 50%/50% in the compartments, as above. All of these observations make it possible to deduce that Cll has attractant and insecticidal power. The insects move to or remain in the compartment containing the compound Cll. The inhalatory toxicity causes the death of insects which have been attracted and which are in proximity to the fumigation chamber, but also after diffusion of the vapours into the other compartment. 2nd experiment: inhalatory toxicity on Acanfciioscelides obtectus, Coleoptera, beam weevil. Three population series of 20 Acanthoscelides obtectus insects, bean weevil, are each placed in am experimental chamber in confined atmosphere (volume 106 cm3). The experimental chamber contains a fumigation chamber (volume ratio: 40/1) closed off by a grille amd in which chamber the insecticidal compounds, alone or as binary or ternary combinations, are deposited on Whatman paper. The number of dead insects is counted after 24 h. 1.05 mg of cinnaunaldehyde, to which are added 50 mg of naringin, gives rise to 23% of dead insects, amd the addition of 0.66 mg of Cll increases this proportion to 70%. The presence of Cll reinforces the toxicity of the binary mixture in question. 3rd experiment: toxicity on rose-grain aphid, Meto-polophiurn dirhodum, Aphis. The aphids are placed in the experimental chamber described above, on their support, a Triticum aestivum wheat seedling. 0.53 mg of eugenol and 50 mg of naringin are introduced into the fumigation chamber; 25% of dead insects are counted after 24 h, while this proportion increases to 56% in the presence of 8.86 mg of Cll and to 82.5% with 17.7 mg. The presence of Cll increases the insecticidal power. 4th experiment: toxicity on Ephestia cautella, Lepidoptera, tropical warehouse moth. The principle of the experimental device remains the same. In the presence o£ 0.21 mg of linalool and 50 mg of naringin, 10% of dead insects are counted after 24 h and 40% after 48 h. The presence of 4.43 mg of Cll makes it possible to take this toxicity to 20% of dead insects for 24 h and to 60% after 48 h. The presence of Cll increases the insecticidal power. All 4 of these experiments show that the addition of Cll to as insecticidal formulation makes it possible to reinforce the insecticidal power of the composition. In addition, its incorporation into a ternary association allows the spectrum of activity to be extended to other insects (Anoploures). It is, moreover, usefully involved as a solvent and a surfactant. 5tb, experiment: synergy with a carbamate. The insecticide chosen is pyrimicarb, which is a selective insecticide, dissolved at a concentration of 50 g/1, and the insect is Acanthoacelidea obtectus Say, Coleoptera phytophagous, beam weevil. The toxicity of methyl undecylenate alone, of the carbamate alone and of an equimolar combination of the two compounds is studied after 24 h. The experiments are performed in a confined medium in 106 cm3 experimental chambers. The results are given in Table I. A synergy between the carbamate and Cll is observed, since their association makes it possible to obtain a higher mortality: the LCS0 of the carbamate and of Cll are 3.16 /il/dm3 and 7.94 /tl/dm3 respectively, whereas that of the equimolar mixture decreases to 2.8 iil/dm3. The results obtained are collated in Table X. Table I: Percentage mortality of Acanthoscelides obtectus in the presence of Cll and carbamate % mortality Deposit Cll Carb. Cll + Carb. (/tl per 100 cm3) (1:1) 0.25 25 40 50 0.5 35 55 55 0.75 40 70 60 1 55 85 75 The association of the two molecules thus makes it possible to reduce the effective doses. 6th experiment: synergie with a pyrethroid. Commercial insecticide corresponds to a solution comprising 0.1 g/1 of pyrethroid, 0.2 g of rotenone and 1.5 g of piperonyl butylate as synergist. The toxicity of the commercial solution on adult insects is determined after 24 h in a confined atmosphere. The toxicity of this solution is low with regard to undecylenic acid. It was thus chosen to compare the toxicities of the pure compounds with an association of the compounds in which the amount of Cll increases (Table II) . Under the same experimental conditions, it is observed that a concentration of 40 /il of pyrethroid solution gives rise to a mortality of 25%, and that addition of Cll enhances the insecticidal power of the pyrethroid solution since the mortality rates are from 25% (for 0.25 /il of Cll: dose below the effective thresh-hold, no synergistic effect) up to 70% for the Cll/pyrethroid combination (1:40 /il) ; a synergistic 2723 effect between the two compounds is observed here also. The results obtained are collated in Table II. Table II: Percentage mortality of Acanthoscelides obtectus in association with pyrethroids Cll Pyxathroida cm5 Cll ♦ Pyr.(vjv)* Dapoait % Deposit % Dapoait % pl/lOOcm3 mortality pl/100ca3 oortiliby )il/100em3 nortality 0.25 25 10 15 0.25:40 25 0.5 35 25 20 0.50:40 35 0.75 40 40 25 0.75:40 45 1 55 ao 50 1.40 70 7th experiment: effect of trixnolecular associations comprising a polyphenol, Cll and another insecticide. The aim of this experiment is to define the effect of the attractant power of compounds on the toxicity of mixtures comprising insecticides. The following experimental device should be used: - a two-compartment apparatus is designed with an overall volume of 1000 cm3. The two compartments are connected by a glass tube. The insects may thus migrate from one compartment to the other. The device is vertical. The atmosphere of the system is confined. - The insects are placed in. a compartment A and the products in the other compartment B. After a given time, the number of insects which have changed compartments is counted, as is the mortality. During the experimental phase, the apparatus is stored in a room subjected to a hygrometry of 65/75% and to a photoperiod of 12 h. of light and 12 h of darkness. A control containing only insects is prepared. The experiment is performed at sub-lethal concentrations in order to examine the various phenomena: attractant effect and enhancement of the toxicity. Results In the control apparatus, the large majority of insects remain in their original compartment (90%). None </div>

Claims

<div class="application article clearfix printTableText" id="claims"> 27232 of the insects die. In the apparatus containing 0.5 g of naringin and in that which has 8 (il of Cll, it is observed that 70% of the insects change compartment: both compounds exhibit an 5 attractant power. In the apparatus containing a combination of naringin and Cll, 90% of the insects leave their original compartment A and live in compartment B containing the products. 10 The addition of a molecule from the terpene family, whose toxicity on the insect is known, for example p-cymene (5 fil) which moreover has little attractant power, allows the following count to be obtained (after 22 h): 15 Table III products compartment A % of insects compartment B p-cymene 7C no death 30 p-cymene+naringin 60 no death 40 20 p-cymene+naringin + Cll 30 including 20% of dead insects 70 272526 - 15 - WHAT-WWE CLAIM |S:«

1. Insecticidal composition comprising synergistic amounts of an insecticidal substance other than methyl 10-undecylenate of formula CH2=CH-(CH2)8-CO-CH3 0 characterized in that it comprises a synergistic amount of methyl 10-undecylenate.

2. Composition according to Claim 1, characterized in that It comprises, besides methyl 10-undecylenate and an insecticide other than methyl 10-undecylenate and other than a polyphenol, a polyphenol.

3. Composition according to Claim 2, characterized in that the polyphenol corresponds to the formula (i) R7 in which R1# R2 and R3, which are identical or different, are a hydrogen atom, a hydroxyl or a lower alkoxy, at least two of R1# R2 and R3 being other than a hydrogen atom, R4 is a hydrogen atom, R5 is a hydrogen atom, a hydroxyl, an alkoxy or a glycoside, or R4 and R5 together form an additional valence bond between the carbon atoms which bear them, Re is a hydrogen atom, R7 is a hydroxyl, lower alkyl or phenyl, optionally mono-, di- or trisubstituted with lower alkyl, lower alkoxy or hydroxyl radicals, or Rfi and R7 together form a divalent radical of formula 27 2326 mi joined by the oxygen atom to the carhon atom bearing R4.

4. Composition according to Claim 3, characterized in that the polyphenol is naringin, rutin or caffeic 5 acid.

5. Composition according to one of the preceding claims, characterized in that the insecticidal substance other than methyl 10-undecylenate, comprises a terpene.

6. Composition according to Claim 4, character- 10 ized in that the terpene is eugenol, terpineol, carvacrol, thymol, linalool, anethole, cuminaldehyde, cynamaldehyde or cymene.

7. Composition according to one of Claims 1 to 4, characterized in that the insecticidal substance other 15 than methyl 10-undecylenate, comprises a pyrethroid, a carbamate, an organochlorine compound, an organo-phosphorus compound or a fatty acid.

8. Composition according to one of the preceding claims, characterized in that the weight ratio of the 20 insecticidal substance other than methyl ' 10-undecylenate, to methyl 10-undecylenate is between 1/10 and 1/1000.

9. Composition according to Claim 3, characterized in that the weight ratio between methyl 10-undecyl- 25 enate and the polyphenol is between 0.1 and 10.

10. Composition according to any one of the preceding claims, substantially as herein described.

11. Composition according to claim 1, substantially as described with reference to any one of the Experiments. Elf Atochem S.A. By its Attorneys BALDWIN. SON & CAREY. o/ c~> </div>