NL8502137A - METHOD FOR PREPARING PESTICIDE. - Google Patents

Description

Reg 7329

Process for preparing pesticide.

The invention relates to pesticides and more particularly to pesticides containing 1inaloQ1.

The use of synthetic pesticides or insecticides that are not of natural origin has in many cases become undesirable. Synthetic insecticides can be toxic to the harmful organism as well as to the animals or people who need to be protected against it. Furthermore, the Federal Insecticide, Fungicide and Rodenticide Act, and the Miller Bill have made the registration and use of synthetic insecticides somewhat difficult. Compliance with the regulations 10 requires, among other things, the approval of the authority responsible for the protection of the environment.

Use of so-called natural or organic insecticides is desirable in many other respects. Many of these insecticides have been shown to be safe for humans and animals, for which they are useful. "Organic" components can be extracted from plant material or can be synthesized in many cases.

Numerous organic or natural insecticides as well as insect repellents have been provided over the years. For example, a number of terpenes have been shown to exhibit insecticidal activity. Terpenes are found in plant essences and come in many forms. Terpenes have been discussed by G. I.

Vasechko et al., 'Insecticidal Properties of Some Components of Essential Oils', Dopovidi, Akademiya, Nauk Ukrayin'skoyl / RSR, vol. 32, 1970, biz.

275278 and a summary is given in 'Chemical Abstracts', 81 1117102 D. Terpenes such as borneol and alpha terpineol have been found to be toxic to mealworm larvae of the cockchafer. Another Russian publication discussing terpenes is V.P. Smelyanets, 'Toxicity of Some Terpene Compounds', summarized in 'Chemical Abstracts', 70, 30 35483 (g). Terpene hydrocarbons, including terpineol and bornyl acetate, have also been discussed to be toxic to pine beetles. It is also noted that it is interesting to study these compounds and those often found in other essences - menthol, linalool, borneol and acetates thereof. Smelyanets 35 further says that the results of the tests indicate that terpene compounds have a varying effect on harmful insects of A r - Λ 't * 7 V "-' j U / · ƒ v, fli - ^ /» ** • \ l V -2- \ different species, making it possible in some cases to choose insect-attracting compounds and in other cases insect-repelling compounds, without harming beneficial insects. is as an insect-killing ingredient in a pesticide described in U.S. Patent 4,379,168 The prior art has not recognized the benefits of providing a pesticide with linaldol as an active active ingredient.

According to the present invention, linaldol has been found to be an extremely effective pesticide, larvacide and ovacide which can be used in a number of pesticide formulations. Linalcol has been shown to be effective in killing insects, including fleas, houseflies and mosquitoes, eggs and larvae of various insects, ticks, spider mites and spider mite eggs. Linalcol which is also known as 15 lily of the valley essence, is highly acceptable for household use. Linalol can conveniently be obtained by distillation of various flower oils. Other distillation fractions can be used separately for other applications.

On the other hand, even preferably, synthesized linalcol can be used. Synthesized linalcol provides the cost benefits and the assurance that other distillation fractions are absent. Linalcol can be synthesized appropriately while still providing an "organic" formulation. Linalcöl combines very well with other ingredients of the various insecticide forms provided in accordance with the present invention.

Linalcöl has not previously been considered a suitable insecticidal material, despite its known utility for other purposes.

French Patent Application 2,375,311, laid open to public inspection, entitled "Sublimable composition containing adamantane and process for its preparation as well as use in the manufacture of molded articles" relates to a sublimable composition containing a volatile, sublimable solid material. It has been reported that to protect fabrics against moths, linalcöl 35 can be used in addition to other compounds. Linalcöl has been said to be an essence that repels or repels insects, such as citronella. The repellent property is thus recognized, but not the insecticidal property. The 8502137- -3-

French Patent 2,036,339 entitled "Stabilized Insecticidal Compositions" describes an insecticide based on phosphoric acid esters used as an insecticide. LinaloaL has been discussed as a terpene alcolhol and has been useful as a stabilizer to delay the decomposition of the phosphoric acid esters.

LinaloaL has also been shown to attract some insects such as the silkworm and cotton leafworm larvae, while Linalol is relatively ineffective as a mosquito repellant; D.L.J. Opdyke (ed.) 'Monsgraphs on Fragrance Raw Materials', biz. 501 (Perga-10 mon Press; New York, N.Y., 1979).

The use of linaloaL as an insecticide has not been reported anywhere in the art.

It is therefore an object of the present invention to provide new insecticidal compositions containing linalol 15.

It is also an object of the present invention to provide flea kill sprays and shampoos containing linaloaL.

Another object of the present invention is to provide an effective composition for killing insects, insect larvae and eggs, and other pests including ticks, ants, flea eggs and larvae, and mosquitoes. Yet another object of the present invention is to provide a linalool based insecticide useful for treating areas of ant infestation.

It is also another object of the present invention to provide an insecticide useful against spider mites.

Another object of the present invention is to provide forms of linaloaL insecticide using alcohol, synergists and / or surfactants to enhance activity.

In summary, according to the present invention, insecticidal compositions containing linalol are provided. Depending on the preparation and the form, linalol can form from 0.1 to 95% of the preparation. Other forms may also include shampoos containing water, synergists, and / or sprays containing synergists and / or alcohol, or alcohol and water.

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The means by which the above objects and features of novelty are achieved are set out in detail in the claims set out at the end of this description. The invention will be further elucidated in the following description, both with regard to the embodiment and the method of application.

LinaloöL occurs naturally in more than 200 oils from flowers, wood, leaves and herbs. It is found in Ceylon cinnamon, sassafras, orange blossom, bergamot, Artemsia 10 balchanorum, ylang ylang, rosewood, and other oils. Linalol is also known as coriandrol or 3,7-dimethyl-1,6-octadien-3-ol. This structure provides a remarkably and surprisingly different insecticidal activity compared to other terpenes which have the same general formula C ^ q ^ IS ^. LinaloöL is usually used as an aromatizing agent and as a perfume. LinaloöL is also known as the scent of lily of the valley.

Linalol can be obtained directly by fractional distillation of vegetable products. It can also be obtained synthetically from monocyclic terpenes. It can be distilled from commercially available d-limonene. As used herein, commercially available d-limonene refers to a commonly available form containing on the order of 95% pure d-limonene and about 7 other constituent oils.

In its pure form, Linalool is a viscous liquid. LinaloöL can be combined with various carriers. LinaloöL is soluble in many alcohols and combinations of alcohol and water. As used herein, alcohol refers to ethanol unless otherwise noted. Alcohol is a useful solvent for spray purposes. For use as an insecticidal shampoo, for example, as a flea shampoo in dogs or cats, linalol can be dispersed in a liquid using surfactants. Linalol can be combined with carriers for numerous known useful insecticide preparations to form suitable products such as sprays, dips, shampoos and the like. When used as a spray, the spray is formulated to be used in undiluted form and sprayed onto the fur of dog or feline animals or other animal species. A pumpable spray or an aerosol spray can be provided for use in plants or household applications as well as in veterinary use. Shampoos are on usual. . Λ · V '· - «- 5 - mode used.

Linalool insecticides can be formulated in concentrations from about 0.1 to about 95%, the remainder of the composition consisting of an inert diluent or carrier, including conventional carriers, surfactants, stabilizers, perfumes and the like. Linalool can be combined with other insecticides and / or synergists in an inert carrier medium.

In the discussion of the invention and also in the claims, all percentages, amounts and ratios are given in weight unless otherwise indicated.

According to an embodiment of the invention, the linalool insecticide is included in a shampoo base. The shampoos of this invention comprise about 0.5 to about 10% by weight of linalool. The presently preferred shampoo base contains about 20-70% surfactant or eraser, which may be any suitable surfactant of the anionic, cationic, nonionic or amphoteric type. It is also preferable to include in the shampoo base about 0.01-5% of an emollient, which may be any emollient suitable for use in treating animal fur; about 0.01-5% lanolin oil or a lanolin derivative; and about 0.01-10% of a foaming amide, which may be a coconut diethanolamide. The rest of the shampoo base consists of water and, if desired, materials for otherwise desired functions, such as perfumes, detergents, thickeners, stabilizers, emulsifiers, preservatives, antioxidants, etc. These shampoo preparations are especially effective for killing fleas and ticks.

According to another embodiment of the invention, the linaloSL insecticide is used in an animal dip liquid. A dip concentrate can be prepared containing from about 10 to about 90% linaloSl 30 along with a surfactant such as Tween 80, Sponto 232T , Sponto 234T, Tween 20 or similar anionic or non-ionic surfactants. Dip concentrates according to the invention may also contain a solvent, such as xylene or other aromatic solvents, aliphatic solvents, mineral oils or water. The dip concentrate is diluted with water to form a dip with about 0.3-2.5% linalole and preferably 0.3-1.5% linalole, most preferably about 0.3 to about 1.0% linalole. The diluted dip preparation has been found to be an effective insecticide when used as an X; ! !? / - * i - 6 - · used for destroying ant heaps or as a spray for closed places.

When the composition according to the invention is formulated to be used as a spray for pets and their environment, such as their lying area, carpets and furniture, the concentration of linaloaL is about 0.1-15%, with preference being about 1 to about 5%, and most preferably a concentration of about 1 to about 2% is used. The rest of this spray preparation can be a solution of water and denatured alcohol.

Carpet sprays of the invention can be suitably formulated as a concentrate containing about 1 to 10% linalool. A preferred concentrate contains about 10% linalool, 40% Witconate P10-59 and 50% Witconol NP100. For use as a spray, this concentrate can be diluted to obtain the desired final concentration of about 0.5 to about 2.0% linalool. Usually the concentrate is formulated to be diluted with about 10-20 parts of water . Witconate and Witconol are trade names of Witco Chemical Company. Witconate P10-59 is an anionic surfactant which is an amine salt of dodecylbenzene sulfonic acid. Witconol 20 NP100 is a non-ionic surfactant which is a nonyphenol polyethylene glycol ether.

Aerosol preparations containing linaloaL as a pesticide have been found to be particularly effective against fleas. In aerosol formulations, linaloaL can be used in an amount from about 1 to about 15%, with otherwise about 8 to about 20% propane and further 1,1,1-trichlorethane. A preferred formulation contains linaloaL at a concentration of about 10% with 2.5% piperonyl butoxide as a synergistic agent, about 14% propane as a propellant, about 32% methylene chloride as a solvent and a co-propellant, and the balance 1.1 , Ι-ΒΟ trichlorethane as an additional solvent and co-propellant.

Shampoos

Linalool is very efficient in a number of shampoo preparations with an insecticidal effect. In the following examples, various shampoo components are used, along with the toxic substances. The commonly available shampoo bases can be used. An example of a suitable shampoo base includes:, - * h Λ Λ »9 atf * w λ:«) 1 *** / v * «-a» ί V / "" "likii - 7 - # Ir 20-70 % surfactant, e.g. triethanolamine lauryl sulfate (40% active) by weight 0.01-5% lanolin derivative 0.01-5% emollient 5 0.01-10% amide 0-10% thickener

Balance: water, stabilizers, preservatives.

Other anionic surfactants such as sodium lauryl sulfate, sodium alpha olefin sulfonate, ammonium lauryl sulfate and similar surfactants can be used in place of triethanol amine lauryl sulfate. Amphoteric surfactants can be used in place of or in conjunction with an anionic surfactant. Furthermore, non-ionic surfactants can be used in place of or in conjunction with anionic surfactants.

The lanolin derivative used in the above exemplary shampoo formulation may be lanolin oil, which is the liquid fraction of whole lanolin obtained by physical means or any of the ethoxylated polymers of whole lanolin products such as Lanogel 41, Lanogel 21 (both products of Robinson-Wagner Chemical Company) or Ethoxylan 50 (product of Malstrom Chemical Company).

Any emollient such as glycerine, isopropyl myristate or Finesolv TN can be used in these shampoo preparations. Flnesolv 25 TN is a benzoate alcohol with twelve to fifteen carbon atoms and is available from Finetex, Ine.

The amide used in the exemplary composition may be Marsamid 50 (product of AZS Chemical Company), a coconut diethanolamide or other coconut diethanolamide products such as, for example, Monamid 1509-ADD (trade name of Mona Chemical Company) or Emid 6515 (trade name of Emery Chemical Company).

An optional thickener used may be Methocel 65HG, a methyl cellulose product from Dow Chemical Company; hydroxypropylmethylcellulose or similar products, such as the hydroxyethyl-35 cellulose compounds, Cellosize from Union Carbide or Natrosol 250 from Hercules Powder Company.

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Example I

A shampoo was provided containing 1 wt% linalcci. contained in a shampoo base. When used in laboratory animals, that shampoo resulted in almost instant flea killing, for example in about 10 minutes. The linalol had a quick insecticidal effect and the hair was easy to continue to brush.

The shampoo base used in this example was as follows: 50% triethanolamine lauryl sulfate (40% active) 5% amide 10 2.5% glycerine 2.5% lanolin derivative 1.0% stabilizer Balance: water

In this shampoo base, the triethanolamine lauryl sulfate used in this example was available under the tradename Standapol T, an anionic surfactant which is a product of Henkel Corp. The amide was Marsamid 50, a product of AZS Chemical Company, and the lanolin derivative in this example was Lanogel 41, a product of Robinson-Wagner Chemical Company. In this shampoo base 20 was provided as stabilizer Tween 80, a nonionic polyoxyalkalene derivative of hexitol anhydride partial long chain fatty esters, a product of ICI Americas, Inc.

References to a "shampoo base" in the following examples refer to the shampoo base formulation of this example 25 I.

Example II

A shampoo was provided which contained 1% linalool and 5.3% d-limonene and otherwise consisted of shampoo base.

Flea killing remained rapid, but this example 30 foamed less well than the preparation of example I. The preparation, incidentally, was found to be substantially odorless.

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Example III

This shampoo contained 0.5% linalooL and 3.0% d-limonene in a shampoo base. The time taken to kill the fleas was longer in this example, but nevertheless was less than 10 minutes. The foam properties of the shampoo were not adversely affected and the smell was experienced as pleasant.

Example IV

Higher percentages of linalooL were also used. In this example, the shampoo contained 5% linalool, 38% water and 57% shampoo base.

10 Example V

A further modification of the preparations for linalool-containing shampoos to provide the desired scent properties of citrus oils included a shampoo composition composed as follows: 5% linalool 0.25% citric acid 0.25% 'fresh lime' fragrance (available from Arylessence Ine .)

The rest of this preparation consisted of the shampoo base of Example I diluted with water in a ratio of 70% shampoo base to 30% water.

Example VI

94% of a solution, half water and half shampoo base, was combined with 5% linalool and 1% methanol. The resulting shampoo preparation was found to be an effective insecticide when applied to animal fur.

Example VII

An effective insecticidal activity was also achieved with a shampoo consisting of 1% linaloSl, 5% d-limonene and before r. s f. ? 1? 7

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Sprays to be pumped

A pumpable spray is a liquid for use in a hand-held reservoir for direct spraying or spraying onto an animal's fur 5 as well as spraying nearby lying areas, carpets and other surfaces. For direct application to the animal, a spray of the liquid may be sprayed onto the animal's fur. The saturation dose depends on the size and hair length. When used, the spray preparation is sprayed onto the animal's fur and 10 remains there. Killing of the fleas takes place both at the direct contact of the spray with the fleas and at the contact of the fleas with the wetted coating or with linalool vapors. It has been found that ethanol is a suitable carrier solution to be dissolved with linalool and sprayed and left on the coating after the ethanol has evaporated. In the following examples, ethanol is provided in the form of a specially denatured alcohol, in particular SDA-40.

SDA-40 contains 0.47 liters of t-butyl alcohol and 43 g of either 1) brucine alkaloid, 2) brucine sulfate NF IX, 3) quassine or 4) any combination of two or three of these denaturing agents per 378 liters of ethanol . SDA-40 is only slightly denatured. Diluted ethanol can also be used, other denatured alcohols can be used. Saturated alcohols, other than ethanol, can also be a solvent for linalool; however, ethanol is preferred.

Example VIII

A highly effective pumpable insecticidal spray was obtained containing 5% linalool and 95% solution of water and SDA-40 in a ratio of three parts water to seven parts SDA-40 by weight.

Initial and long-term lethality over a 24 hour period was provided at saturation levels of 25, 50 and 75%. Saturation levels are subjective measures of how much an animal's skin is wetted with spray.

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Example IX

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Effective insecticidal activity was also achieved with 5% linalool and 95% SDA-40.

Example X.

Effective insecticidal activity was achieved by using 1% linalool and 99% denatured ethanol, namely SDA-40.

Example XI

1% linalool was also effective in a formulation, the remaining 99% of which was water and SDA-40 in a weight ratio of 3-7.

Example IX

Linalool can also be used with other terpenes that have * k toxic properties, as illustrated in Examples XII and XIII,

Example XII

A spray was provided containing 1% linalool, 1% alpha-terpineol and 98% SDA-40. At nominal saturation levels, for example 50% i for a given hair length, a quick kill was achieved in less than 10 minutes. However, the odor was stronger than that of the formulations of Examples X and XI.

Example XIII

A pumpable spray was provided containing 0.5% linaloSl, 5.43% d-limonene and 94.07% SDA-40. Effective killing was provided and the preparation was found to have a good odor on examination.

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Example XIV

The amount of linalool was reduced and the amount of SDA-40 was reduced in a pumpable spray consisting of 1% linalool, 5.43% d-limonene and 93.57% SDA-40. In this case too, report 5 can be made of good killing power and a good smell.

Example XV

The preparation of Example XIV was redone except that 0.5 wt% SDA-40 was removed and replaced with Vita Cos 535, a form of wheat germ glycerides. Vita Cos is a trade name of Wickhen 10 Products Ine. Both effective killing power and a pleasant odor were observed. In addition, the animals' skin retained a good shine when brushed after drying the spray.

Dip

A dip can be provided in which an animal can be bathed. The dip is preferably provided as a concentrate containing from about 10% to about 90% linalool with about 90% to about 10% surfactants, which may contain any anionic or nonionic surfactant in strong to be diluted with water to prepare the dip preparation. A preferred dilution is 30 to 120cm 3 concentrate per 3.78 liters of water. The desired dilution will vary depending on the concentration of linalool in the concentrate. Dilution of the concentrate should yield a final concentration of linalool from about 0.3 to about 2.5%, preferably from about 0.3 to about 1.5%, and most preferably from about 0.3 to 1.0 % when used for treating animals. Stored in a diluted form for long periods of time, lasting several months, can lead to some loss of activity.

Example XVI

A dip concentrate was provided containing 10% linalool, 75% 30 d-limonene and 15% Tween 80. Tween 80 is a surfactant, which makes the terpene oils miscible with water. When diluted as 3502137 ♦ * - 13 - described herein, by mixing 30 to 60cm3 with 3.78 liters of water, the solution remained clear. Highly effective flea-killing power was obtained along with satisfactory drying properties.

Other surfactants can be used instead of Tween 80. Tween is a trade name of ICI Americas, Inc., for a nonionic polyoxyalkylene derivative of hexitol, anhydride, partial long chain fatty acid esters.

Example XVII

An insecticidal dip concentrate was also prepared containing 90% linalool and 10% Tween 80. Highly effective insecticidal dip compositions were obtained by diluting that concentrate in proportions of about 30 to 60 cm 3 per 3.78 liters of water.

Example XVIII

15 · A linalool dip concentrate can also be obtained with a smaller concentration of linalool. A dip concentrate was provided containing 5% linalool, 10% Tween 80, 30% Farnesol and 55% castor oil. Since the Farnesol component functions as a perfume as well as an insecticide, the dilution ratio can be the same as in previous dip examples with effective results.

Carpet sprays

Insecticide and pesticide application can take place in a carpet spray. Carpets may contain fleas and other harmful organisms ->% nisms. In the following examples preparations for 25 concentrates are provided. Before use, each concentrate can be diluted as needed to obtain the final spray concentration, usually in a ratio of 10 to 1 or 20 to 1 by weight with water for application to a carpet. The diluted concentration is preferably from about 0.5 to about 2.0% linalool in the 30 spray formulations. The degree of saturation required per carpet is somewhat analogous to what applies to animals. The length and density of the carpet are a measure of the amount of spray required.

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Example XIX

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A carpet spray concentrate was provided containing 10% linalol, 10% alpha terpineol, 40% Witconate P10-59 and 40% Witconol NP-100. P10-59 is the amine salt of dodecylbenzene sulfonic acid.

NP-100 includes nonylphenol polyethylene glycol ether. At dilution as shown above, the sprays obtained were found to be effective insecticides.

Example XX

A spray having an effective insecticidal effect was provided, doubling the amounts of terpene compounds in Example XIX while proportionally reducing the remaining components present. In the examples described above, the most effective terpene species, in the case of a combination of terpenes, was found to be linalol.

Table A

Fleas deposited on a wet treated surface (% dead + immobile) 5 10 15 20 60 treatment min. Min. Min. Min. Min.

20 linalool solution 97% 97% 100% 100% 100% control (H20) 00000

The percentage shown is an addition of the dead fleas and those that have become immobile (fleas on their side and unable to move). There were 27 to 36 fleas per 25 treatment. All compounds were used at a final concentration of 0.7% linalol (starting solutions of linalol prepared with 90% linalol and 10% Tween 80 and then diluted at a ratio of 28.4 grams per 3.78 liters or 1: 128).

As shown in Table B below, linalol 30 can be effective in varying concentrations. In these experiments, starting preparations were prepared with 90% toxic substance and 10% Tween 80. The starting solutions were diluted with water to obtain 0 ° C! O / - 15 - of the various concentrations described below, 1cm3 was applied to filter paper in Petri dishes and flea larvae were placed on the wet paper. There were ten larvae for each treatment.

Table B

5 Toxicity of linalool to flea larvae (% dead)

Time after the start of the test_ 5 10 15 30 min. Min. Min. Min.

10% Linalool 70 70 100 100 10 5% Linalool 30 80 100 100 2.5% Linalool 10 30 90 100 1% Linalool 10 30 60 100

Toxicity of the water-based sprays to adult houseflies and mosquitoes It has been found that a wide concentration range can also be used for the linalool insecticide in the form of an effective spray for killing adult houseflies and mosquitoes.

A starting solution of linalol was prepared with 90% linalol and 10% Tween 80. The starting solution was diluted with water to obtain insecticidal concentrations of 10%, 5% and 2.5%.

The adult insects were placed in cylindrical cardboard boxes fitted with mesh lids. The insecticide was sprayed through the gauze using a glass chromatogram sprayer. In order to simulate open chamber conditions, the insects were transferred to dry filter paper in Petri dishes 3-5 minutes after spraying. By doing this they were removed from the slightly moist reservoir in which the spraying had been carried out.

Ten house flies were used for each treatment and seven to ten mosquitoes per treatment. The results are shown in Table C below.

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Table C

Tests against adult houseflies and mosquitoes with linalol

Stock solutions for linalol were prepared with 10% Tween 80 and 90% toxic substance. The desired concentrations of toxic substance 5 for the subsequent tests were then obtained by diluting the stock solution with water.

Houseflies: 10% - all flies immobile after 1 minute; 100 immobile after 5 minutes and 100% dead after 5 minutes 10 5% - 80% flying immobile after 2 minutes; 100% paralyzed after 10 minutes. Partial recovery by 30%, who swirled around on their backs after 30 to 60 minutes, but all died eventually.

Mosquitoes: 15 10% - instantly felled, 100% never moved and were dead immediately.

5% - instantly felled, 100% no longer moved or recovered.

2.5% - 50% were still moving after 15 minutes.

20 Treatment of fire ants

Linaloöl'is suitable for treating anthills of fire ants.

The surprising effectiveness against fire ants is particularly important in view of the fact that widely used insecticides for fighting fire ants have recently been rejected by the environmental protection agency. In a broad sense, a fire ant is an ant of the genus Solenopsis, which is a ferocious all-consuming ant. That ant is generally unknown in the northern United States, as it is native to the southern United States, but the area where they are found is expanding.

Providing a natural treatment against fire ants, such as 33021 / β * - 17 - is illustrated in the following examples is of exceptional importance.

Example XXI

A dip concentrate was prepared according to example 16. Before use, the concentrate was diluted in a ratio of 29.5 cm3 to 1.89 liters of water. 1.89 liters of the mixture was poured into an anthill of medium sized fire ants (e.g. 25 cm in diameter by 15 cm). Insects hit by the liquid became highly agitated and began to leave the mounds. No live adult ants were found after 48 hours.

Example XXII

A dip concentrate was prepared according to Example XVII and the concentrate was then diluted in a ratio of 29.5 cm3 to 1.89 liters of water. 1.89 liters of this diluted mixture was poured onto a medium sized anthill of fire ants as in Example 15 XXI. As in the case of Example XXI, no adult fire ants were found after 48 hours.

Flea eggs

Linalool was found to be effective against flea eggs as described in Example XXIII below.

Example XXIII

A spray was provided with linalool at a concentration of 0.5% in solvent (5.0% ethanol) and vehicle (0.1% Tween 80 in water). The eggs were placed on square pieces of carpet. The spray was applied to the carpet until it felt damp. The carpet pieces were examined for live larvae 11 days after treatment and adult fleas after 24 days. In each case, 50 eggs 1-16 hours old were placed on each piece of carpet. No live larvae were found, nor were adult fleas. The linalool spray prevented further development of the flea eggs.

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Table D

Comparative toxicity of 1% D-limonene and 1% linalool for carpet flea eggs% adult 5 Number of eggs laid in flea carpet pieces _Treatment _ from eggs 50 1.0% d-limonene 68 48 1.0% linalool 0 50 control - untreated 62 10 57 control - treated with water 72

The preparations shown above were toxic in a carrier consisting of 0.1% Tween 80 and the remainder of H2O.

Remedy for spider mites

Linaloöl has been shown to be effective in killing spider mites and spider mite eggs.

Example XXIV

A spray was composed of 0.1% linalol and 0.1% Tween 80 in an aqueous solution.

The spray was applied to leaves cut from 20 insect-infected plants and placed in Petri dishes. The leaves were sprayed with a fine mist of the insecticide. There i.

100% mortality of the spider mite eggs was achieved.

Example XXV

A spray was provided consisting of 0.5% linalol and 0.1% Tween 80 in an aqueous solution. When used as in Example XXIV, 100% mortality of spider mites was achieved.

Linalool at a concentration of 1% or less has been found to exhibit minimal phytotoxicity and have little or no adverse effect on plants.

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Synergistic means

The toxicity of linalool can be increased by combination with synergists, such as sesame oil or piperonyl butoxide, against adult fleas. At concentrations of 0.25 to 0.5% 5 of synergistic agent, the percentage of linalool can be very significantly reduced without decreasing insecticidal effectiveness, as shown in Examples XXVI and XXVII,

Example XXVI

A spray consisting of 0.2% linalool and 0.5% sesame oil in SDA-40 was provided and found effective when used as described in Example IX above.

Example XVII

A sprayable pump with SDA-40 was prepared according to example. IX above and contained 0.2% linalool and 0.5% piperonyl butoxide. A 100% mortality against adult fleas was achieved.

The effectiveness of these additional components, * in combination with linaloöl, is further explained in Table E below.

Table E

Toxicity of linalool in combination with sesame oil or piperonyl butoxide to adult fleas

Mortality after the specified time 5 10 15 20 60 24

Treatment Min Min Min Min Min Hours 0.2% Linalool 0% 1% 1% 3% 32% 40% 25 0.2% Linalool + 0.5% Sesame Oil 10% 49% 77% 88% 100 % 100% 0.2% linalool + 0.5% piperonyl butoxide 5% 10% 19% 50% 63% 100% 30 0.5% piperonyl butoxide (control) 0% 1% 1% 7% 29% 40 % 0.5% sesame oil (control) 0% 0% 0% 0% 0% 0% 35 Average values from 2-4 tests Λ -) ·.

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One hour after treatment, the following comparative mortality rates can be juxtaposed from the above figures: 0.2% linalol alone 32% 5 0.2% linalol with sesame oil 100% 0.2% linalol with piperonyl butoxide 63%

Toxicity of linalool vapor

In order to investigate the toxicity of the linalool vapors to fleas and other insects, a test device was designed where the bottom of a tray or chamber was covered with filter paper and a tight-fitting lid was placed over the chamber. A hole was drilled in the lid and a very fine wire mesh was placed over the hole. A 7.50 cm high glass ring was placed over the mesh and a lid was placed over the glass ring. The glass ring was glued to the top of the chamber. The toxic compounds were pipetted onto the filter paper and insects or insect eggs were immediately introduced into the mesh chamber. The toxic substance used to generate the vapors was taken up in an inert support consisting of 5.0% denatured alcohol, 0.1% Tween 80 and the rest from water.

Table F

Toxicity of linaloöl vapors to adult fleas (percent dead + immobile)

Treatment Number of fleas 25 1% linalol 28 28% linalol between 25 and 30 control - untreated 31 time 5 ml. 10 min. 15 min. 20 min. 60 min. 24 hours 77 29 50 100 100 30 4 4 7 10 57 62 0 0 0 0 0 0 1.3 / 9 <

-21-Table G

Toxicity of linalool vapors to flea larvae

Treatment Observations after 24 hours 5.9% linalool 100% dead 5 2.0% linalool 100% dead 1.0% linalool 100% dead 0.5% linalool 100% dead 0.3% linalool 100% dead control with 5, 0% 0% dead 10 denatured alcohol control - water 3% dead

In each of the above treatments, 25 to 30 larvae were placed in the chamber above the mesh. As in the previous example, the toxic preparation consisted of linaloSl in the percentage indicated in an inert carrier consisting of 5.0% denatured alcohol, 0.1% Tween 80 and the balance water.

Table H

Toxicity of linalool vapors to flea eggs (observations) 20 Treatment 48 hours 72 hours 1.0% linalool 0.7% hatch 4.7% hatch (1) from 150 control - untreated 56% hatch egg hatch 56%

In the flea eggs shown above, 50 eggs were introduced into the vapor chamber in each run, and the results shown above are the average of three runs. The linalool recipe used to form the vapors was the same as that shown in Table G.

Insecticide against fleas in the form of aerosol. It has been found that aerosol preparations based on linaloSl. · '·; ; K * s. "M - + -22- are effective for killing fleas in a domestic environment.

Example XXVIII

Linaloöl aerosol 10% linaloöl 5 2.5% piperonyl butoxide 32% methylec chloride 14% propane.

Balance 1.1.1 - trichlorethane

In tests with the aerosol shown above, 10 fleas were placed in open containers at three meters, 6 meters and 9 meters from a drop point in an unoccupied lounge. In one test, the percentage of dead fleas 2 hours after spraying the mist was 56%, 80% and 84% for the distances of 3 meters, 6 meters and 9 meters. In a second test at a distance of 3 meters, 6 meters and 9 meters, the percentage of dead fleas after 2 hours was 88%, 92% and 96%, respectively.

In summary, it can be stated that the present invention provides linalool based insecticides, larvacides and ovicides. Furthermore, the present compositions can be provided in a wide variety of forms with varying concentrations of linalol to provide effective toxicity under various application conditions and / or to be used to control various types of insects and other harmful organisms.

Further changes are possible without departing from the spirit of this invention as set forth herein.

3502137

Claims (30)

A pesticidal composition characterized in that the preparation contains 0.1-95% linalool. 2. Pesticide shampoo, characterized in that the shampoo contains 0.5-10% 5 linalool in a shampoo base. Shampoo according to claim 2, characterized in that the shampoo contains 0.5-1% linalool. Pesticide in the form of a pumpable spray, characterized in that the pesticide contains at least 0.1% linalool in a liquid carrier. A spray according to claim 4, characterized in that the spray additionally contains piperonyl butoxide. A spray according to claim 4, characterized in that the spray additionally contains sesame oil. Spray according to claim 5, characterized in that the carrier comprises ethanol. Spray according to claim 4, characterized in that the carrier comprises water and ethanol in a weight ratio of about 3 to 7. Pesticide dip concentrate for the preparation of a dilute dip for application to animals, characterized in that the concentrate contains 20 pesticide linaloSl in an amount of at least about 10% by weight with at least about 10% surfactant . 10. Pesticide concentrate in the form of a carpet spray, characterized in that the concentrate contains as an insecticidal linalool at a concentration of about 1 to about 20% by weight in a carrier to make the concentrate miscible with water. Concentrate according to claim 10, characterized in that the linalool is present in a concentration of about 1 to about 10% by weight. Carpet spray, characterized in that the spray contains about 0.5 to about 1.0% by weight of linalool. 13. Concentrate for fighting fire ants, characterized in that the concentrate contains 2-20 wt.% Linalool carried in a water. 14. Insecticidal composition for controlling fire ants, characterized in that the composition contains at least 0.1% by weight of linalool in solution. 'ï' - 24 - Insecticidal composition according to claim 14, characterized in that the linalool is present in a concentration of about 0.3 to about 1.5%. 16. Method for controlling fleas and ticks on the skin and hair of a host animal, characterized in that an effective toxic amount of linalool is applied to said animal. Method according to claim 16, characterized in that the application of linalool comprises spraying a preparation of linalool in a carrier of ethanol. A method according to claim 16, characterized in that the step of applying linalool comprises applying a shampoo comprising linalool in a shampoo base, and keeping the animal in contact with said shampoo for a maximum of 15 minutes before rinsing. Method according to claim 18, characterized in that the animal is wetted with water, the shampoo is applied to the animal, the shampoo is rubbed into a foam, practically the entire skin of the animal is moistened with that foam for at least about 5 minutes and the foam from the animal's skin is rinsed off with water. 20. Method according to claim 16, characterized in that the application step comprises applying a dip to the skin and hair. 21. A method according to claim 20, characterized in that the method further comprises the steps of diluting with water a dip concentrate preparation containing linalool as a pesticide in an amount of from about 10 to about 90% of the total weight of the composition and an emulsifier in an amount of from about 10 to about 90% of the total weight of the composition, adding the water used for dilution, to reduce the concentration of 30 linalool in the dip to a value between about 0.3 and about 1.5% of the total weight of the diluted dip and bathing the animal by completely wet the animal with the diluted dip preparation. 22. Method of killing houseflies and adult mosquitoes, characterized in that the flies or mosquitoes are contacted with a spray containing linalol in an effective toxic amount. 23. Method for controlling fire ants, characterized in that 8502137 5- -> - 25 - a solution of linalol containing an effective toxic amount of linalol is applied to an anthill of fire ants. 24. Method for controlling spider mites, characterized in that the spider mites are brought into contact with an effective toxic linalool. A method for controlling spider mite eggs, characterized in that the spider mite eggs are contacted with an effective toxic amount of linalol. 26. Method for controlling flea larvae, characterized in that the flea larvae are contacted with an effective toxic amount of linalool. 27. Method for killing fleas and ticks, characterized in that a liquid preparation is sprayed on a carpet in order to combat the harmful organism, larvae and eggs thereof, the liquid preparation containing linalol as pesticide in an amount from about 1 to about 10% of the total of the composition, at least 1 surfactant in an amount from about 1 to about 10% of the total weight of the composition, and water in an amount from about 98 to about 80% of the total weight of the preparation. 28. Aerosol formulation for killing harmful organisms, such as fleas and ticks, characterized in that the formulation comprises: linalol in an amount of about 1 to about 15% of the total weight of the formulation propane in an amount of about 8 to about 20% of the total weight of the preparation 1,1,1-trichlorethane for aerosol use in an amount of from about 65 to about 91% of the total weight of the preparation. 29. Aerosol formulation according to claim 28, characterized in that the linalol forms about 10% of the total weight of the formulation, propane constitutes about 14% of the total weight of the formulation and 1,1,1-trichlorethane is present in an amount that constitutes the rest of the preparation. The preparation according to claim 29, characterized in that the preparation additionally contains piperonyl butoxide in an amount of about 2.5% of the total weight of the preparation and methylene chloride in an amount of about 32% of the total weight. of the preparation. * / 3 3 7 V. i _ · i 'j J