GB2163651A - Linalool pesticide - Google Patents

Abstract

Pesticidal compositions include linalool as an active toxic ingredient in a range of 0.1% to 95% by weight. Linalool may be combined in a vehicle solution with surfactants, synergists, and various alcohols to provide different forms of pesticidal products.

Description

SPECIFICATION Linanool pesticide The present invention relates to pesticides and more particularly to pesticides comprising linalool.

Use of synthetic pesticides or insecticides which are not naturally occurring has become undesirable in many instances. Synthetic insecticides may be toxic to both the pest and to animals or people to be protected from the pest. Further, the Federal Insecticide, Fungicide and Rodenticide Act and the Miller Bill have made registration and use of synthetic insecticides a somewhat difficult. Compliance with regulations requires, among other things, Environmental Protection Agency approval.

Use of so-called natural or organic insecticides is desirable in many other respects. Many of these insecticides have been found out to be safe to humans and the animals whom they are to benefit. "Organic" components may be extracted from vegetable matter or they may in many instances be synthesized.

Various organic or natural insecticides and insect repellants have been provided over the years.

For example, a few terpenes have been found to have insecticidal activity. Terpenes are found in essential oils of plants and come in many forms. Terpenes are discussed in G.l. Vasechko et al., Insecticidal Properties of Some Components of Essential Oils, Dopovidi, Akademiya, Nauk Ukrayins'koyl RSR, Volume 32, 1970 pp. 275278 and abstracted at Chemical Abstracts, 81 1117102D. Terpenes such as borneol and alpha terpineol were found to have toxicity for cockchafer mealworm larvae. Another Russian publication discussing terpenes is V.P. Smelyanets, Toxicity of Some Terpene Compounds, abstracted at Chemical Abstracts, 70 35483(9).

Toxicity of hydrocarbons for different pine bugs was discussed for terpenes, including terpineol, bornyl acetate. The article states that "it was of interest to make a study of these compounds, and of those frequently encountered in other essential oils-menthol, linalool, borneol, and their acetates. Smelyanets et al., further states that "the results of the experiments indicate that terpene compounds exert a dissimilar influence on harmful insects of various species; this yields the possibility of selecting, for some, attractants, and for others-repellants, without causing harm to useful insects." The terpene, D-limonene, is disclosed as an insect killing ingredient in a pesticide in United States Patent 4,379,168 issued 5 April 1983.The art has not recognised advantages of providing a pesticide having linalool as the effective active ingredient.

In accordance with the present invention, it has been found that linalool is an extremely effective pesticide, larvacide and ovacide which may be used in a number of pesticide compositions. It has been found to be effective in killing insects, including fleas, house flies and mosquitoes, various insect eggs and larvae, ticks, spider mites and spider mite eggs. Linalool, also known as lily of the valley essential oil, is highly acceptable for domestic use. Linalool can be conveniently obtained by distillation from various oils from flowers. Other distillation fractions may be used separately for other utility.

Alternatively, and preferably, synthesized linalool can be used. Synthesized linalool provides advantages in terms of cost and in certainty of absence of other distillation fractions. It may conveniently be synthesized while still providing an "organic" formulation. Linalool combines well with other ingredients of the different forms of insecticide provided in accordance with the present invention.

Linalool has not previously been regarded as a suitable insecticide material despite its recognised utility for other purposes. Published French Patent Application, Publication No. 2,375,311, entitled "Sublimible Composition Containing Adamantane and Process of Preparing an Application to the Fabrication of Moulded Objects" is directed towards a sublimible composition containing a volatile, sublimible solid. It is stated therein that to protect clothes against moths, one can utilise linalool amongst other compounds. Linalool is taught as an essential oil which is insect repeilant, such as citronella. The repellant property is recognised but not an insecticidal property. French Patent No. 2,036,339 entitled Stabilised Insecticide Compositions, issued to J.R.Geigy S.A. on 15 December 1970, discloses insecticide based on phosphoric esters utilised as an insecticide.

Linalool, which is discussed as a terpene alcohol, is taught to be useful as a stabiliser to slow the decomposition of the phosphoric esters.

Linalool has also been found to be attractive to some insects such as the silkworm and cotton leafworm larvae, while being relatively ineffective as a repellant for the mosquito, D.L.J. Opdyke (ed.) Monographs on Fragrance Raw Materials, p. 501 (Pergamon Press; New York, N.Y., 1979).

Use of linalool as an insecticide has been avoided in the prior art.

It is therefore an object of the present invention to provide novel insecticidal compositions comprising linalool.

It is an object of the present invention to provide flea killing sprays and shampoos comprising linalool.

It is also an object of the present invention to provide an effective composition for killing insects, insect larva and insect eggs, and other pests, including ticks, ants, flea eggs, flea larvae, and mosquitoes.

It is another object of the present invention in one form to provide a linalool insecticide having utility in treating areas of fire ant infestation.

It is an object of the present invention as well to provide an insecticide having utility against spider mites.

It is a further object of the present invention to provide forms of linalool insecticide in which alcohol, synergists and/or surfactants are utilised to enhance activity.

Thus, the present invention in its broadest form comprises linalool for use as an insecticide.

The invention also extends to insecticidal compositions comprising linalool. Depending on the composition and form, linalool may comprise from 0.1% to 95% of the composition. Other forms may also include shampoos including water, synergists, and/or sprays which may include synergists and/or alcohol, or alcohol and water.

Linalool occurs naturally in more than 200 oils from flowers, wood, leaves and herbs. It is found in oils of Ceylon's cinnamon, sassafrass, orange flower, bergamot, Artemsia balchanorum, ylang ylang, rosewood and other oils. Linalool is also known as coriandrol or 3,7-dimethyl-1,6octadiene-3-ol. This structure provides for significant and surprisingly different insecticidal activity from other terpenes having the same generic formula of C10H18O. Linalool is commonly used as a flavouring agent and a perfume. Linalool is also known as lily of the valley scent.

Linalool may be obtained directly by fractional distillation from vegetable products. It can also be obtained by synthesizing from monocyclic terpenes. It can be distilled from commercial dlimonene. As used herein, commercial d-limonene refers to a commonly available form which may comprise on the order of 95% pure d-limonene and approximately seven other component oils.

Linalool in its pure form is a viscous liquid. It may be combined with various vehicles. It is soluble in many alcohols and alcohol-water combinations. As used herein, alcohol, unless otherwise specified, refers to ethanol. Alcohol is a useful solvent for spray purposes. For use as an insecticidal shampoo, as for example, a dog or cat flea shampoo, linalool may be dispersed in liquid with surfactant. It is combinable with vehicles for many known useful insecticidal compositions to form useful products such as sprays, dips, shampoos and the like. In employment of a spray, the spray is formulated to be used in an undiluted form and directed onto the hair of a canine, feline or other animal. Pump or aerosol spray may be provided for use on plants or in home application as well as for veterinary use. Shampoos are used in a conventional manner.

Linalool insecticides may be formulated in concentrations ranging from about 0.1% to about 95%, with the remainder of the said composition being an inert vehicle or carrier, including conventional vehicles, surfactants, stabilisers, perfumes and the like. Linalool may be formulated with other insecticides and/or synergists in an inert carrier medium.

In one embodiment of the invention, the linalool insecticide is formulated in a shampoo base.

The shampoos of the present invention comprise about 0.5% to about 10% linalool. The presently preferred shampoo base contains about 20-70 percent surfactant or emulsifier which may be any suitable surfactant of the anionic, cationic, non-ionic or amphoteric type. It is also preferred to incorporate in the shampoo base about 0.01-5% of an emollient which may be any emollient suitable for use on the coats of animals; about 0.01-5% lanolin oil or a lanolin derivative; and about 0.01-10% of an amide foam builder which may be a coconut diethanolamide. The remainder of the shampoo base is water and, if desired, materials for other desired functions, such as perfumes, detergents, thickening agents, stabilizers, emulsifiers, preservatives, antioxidents, etc. These shampoo compositions are particularly effective in kiling fleas and ticks.

In another embodiment of the invention, the linalool insecticide is used in an animal dip. A dip concentrate may be prepared containing about 10% to about 90% linalool together with a surfactant, e.g. an anionic or non-ionic surfactant such as Tween (Registered Trade Mark) 80; Sponto (Registered Trade Mark) 232T; Sponto 234T; Tween 20, or similar anionic and non-ionic surfactants. Also, dip concentrates of this invention may contain a solvent e.g. an aromatic solvent, such a xylene, or other aromatic solvents, aliphatic solvents, mineral spirits, or water.

The dip concentrate is preferably diluted with water to form a dip with a range of 0.3% to 2.5% linalool and, preferably, 0.3% to 1.5% linalool, and most preferably, about 0.3% to about 1.0%.

It has been found that the diluted dip composition is an effective insecticide when applied to fire ant mounds, or when used as a yard spray.

With the composition of the present invention formulated for use as a spray for application to domestic animals, and their environment such as bedding, carpets and furniture, the concentration of linalool is preferably from about 0.1% to 15% with about 1% to about 5% preferred, and a range of about 1% to about 2% being presently most preferred. The remainder of this spray composition may be a solution of water and denatured alcohol.

Carpet sprays embodying the present invention may be conveniently formulated as a concentrate comprising about 1% to 20% linalool. A preferred concentrate contains about 10% linalool, 40% of an anionic surfactant, e.g. an alkyl aryl sulphonic acid surfactant such as Witconate P1059 and 50% of a non-ionic surfactant e.g. alkyl phenol polyethylene glycol ether such as Witconol NP100. For use as a spray, this concentrate may be diluted to obtain the desired final concentration of about 0.5% to about 2.0% linalool. Usually the concentrate is formulated for dilution with about 10 to 20 parts water. "Witconate" and "Witconol" are trade marks of Witco Chemical Company. Witconate P10-59 is an anionic surfactant which is an amine salt of dodecylbenzene sulphonic acid. Witconol NP100 is a non-ionic surfactant that is a nonylphenol polyethylene glycol ether.

Aerosol formulations embodying linalool as a pesticide have been found to be particularly effective against fleas. In aerosol compositions, linalool may be used in a range of from about 1% to about 15% with the remainder about 8% to about 20% propane and the balance 1, 1, 1, trichlorethane. In a preferred formulation, the linalool is provided at about 10% concentration with 2.5% piperonyl butoxide as a synergist; about 14% propane as a propellant; about 32% methylene chloride, as a solvent and co-propellant; and the balance 1, 1, 1 trichlorethane, as an additional solvent and co-propellant.

Linalool is highly effective in a number of insectidical shampoo compositions. In the following examples, various shampoo components are used with the toxicant. Commonly available shampoo bases may be used. An exemplary suitable shampoo base comprises.

20-70% surfactant, e.g. triethanolamine lauryl sulphate (40% active) by weight 0.01-05% lanolin derivative 0.01-05% emollient 0.01-10% amide 0-10% thickening agent Balance: water, stabilizers, preservatives.

Other anionic surfactants such as sodium lauryl sulphate, sodium alpha olefin sulphonate, ammonium lauryl sulphate, and similar surfactants may be usd in lieu of triethanolamine lauryl sulphate. Amphoteric surfactants may be used instead of, or in conjunction with, an anionic surfactant. Further, nonionic surfactants may be used in place of, or in conjunction with, anionic surfactants.

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

In these shampoo formulations, any emollient, such as glycerine, isopropyl myristate or Finesolv TN may be used. Finesolv TN is a benzoate alcohol having twelve to fifteen carbon atoms and it is available from Finetex, Inc.

The amide employed in the exemplary shampoo formulation may be a coconut diethanolamide such as Marsamid 50 (a product of AZS Chemical Company) or other coconut diethanolamide products such as Monamid 1509-ADD (Registered Trade Mark of Mona Chemical Company) or Emid 6515 (Registered Trade Mark of Emery Chemical Company).

The thickening agent, if used, may be a methylcellulose, e.g. Methocel 65HG, a product of Dow Chemical Company; a hydroxypropyl methycellulose or similar compounds, such as the hydroxyethyl celluloses, e.g. Cellosize QP of Union Carbide or Natrosol 250 of Hercules Powder Company.

The invention may be put into practice in various ways and a number of specific embodiments will be described to illustrate the invention with reference to the accompanying examples.

In all discussion of the invention and in the claims, all percentages, proportions and ratios of parts are by weight unless otherwise indicated.

EXAMPLES I to VII These relate to shampoos.

EXAMPLE I A shampoo is provided comprising 1% lanalool by weight in a shampoo base. In use on test animals it provided flea kill almost instantly, e.g. in approximately three minutes. The linalool had rapid insecticidal effect and the hair remained easy to brush.

The shampoo base used in this Example is: 50% Triethanolamine lauryl sulphate (40% active) 5% Amide 2.5% Glycerine 2.5% Lanolin derivative 1.0% Stabilizer Balance: Water.

In this shampoo base, the triethanolamine lauryl sulphate used in this Example is available under the trade mark Standapol T, an anionic surfactant which is a product of Henkel Corp. The amide is Marsamid 50, a product of AZS Chemical company, and the lanolin derivative of this Example is Lanogel 41, a product of Robinson-Wagner Chemical Company, As a stabilizer, we provided in this shampoo base Tween 80, a nonionic polyoxyalkene derivative of hexitol anhydride partial long chain fatty esters, a product of ICI Americas, Inc. "Tween" is a registered trade mark of ICI Americas, Inc.

References to a "shampoo base" in the following Examples refer to the shampoo base composition of this Example I.

EXAMPLE II A shampoo is provided comprising 1% linalool, 5.3% d-limonene and the balance shampoo base.

The flea kill remained fast, but this Example did not lather as well as the formulation of Example I. The composition was perceived to be substantially odourless.

EXAMPLE lil This shampoo comprised 0.5% linalool and 3.0% d-limonene in a shampoo base. The killing time for fleas was longer in this example, but nonetheless was under ten minutes. Lathering characteristics of the shampoo were not adversely affected and the odour was perceived to be pleasant.

EXAMPLE IV Higher percentages of linalool were also utilised. In this example, the shampoo comprised 5 percent linalool, 38% water and 57% shampoo base.

EXAMPLE V A further modification of the formulae for linalool containing shampoos to provide desirable fragrance properties of citrus oils comprises a shampoo formulated as follows: 5% linalool 0.25% citric acid 0.25% "Fresh lime" fragrance (Available from Arylessence Inc.).

The remainder of this composition comprises 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 of half water and half shampoo base was combined with 54% linalool and 1% methanol. The resulting shampoo composition was found to be an effective insecticide when applied to the coats of animals.

EXAMPLE VII Insecticidal efficacy was also achieved with a shampoo comprising 1% linalool, 5% d-limonene and the remainder shampoo base.

EXAMPLES VIII to XV These relate to pump sprays.

A pump spray is a liquid for use in a hand-held container for spraying directly on the coat of an animal, and also spraying bedding, carpets, and other environmental surfaces. For direct application to the animals, a mist of the liquid may be sprayed on an animal's hair. The saturation dose is dependent upon size and hair length. In use, a spray composition is sprayed onto the animal's coat and remains there. Killing of fleas occurs both upon direct contact of the spray on fleas as well as contact of fleas with the wetted coat or with linalool vapours. It is found that ethanol provides a suitable vehicle in which to dissolve linalool and carry it as a spray and for leaving linalool on the coat 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 comprises 1/8 gallon (US) (0.47 litres) ter-butyl alcohol and 1-1/2 adv. ounces (42.5 grams) of either 1) brucine alkaloid, 2) brucine sulphate NF IX, 3) quassin or, 4) any combination of two or of three of those denaturants per 100 gallons (US) (387.5 litres) of ethanol. SDA-40 is only slightly denatured. Diluted ethanol could also be used. Other denatured alcohols may be used.

Saturated alcohols other than ethanol may also comprise a solvent for linalool; however, ethanol is preferred.

EXAMPLE VIII A highly effective insecticidal pump spray was provided comprising 5% linalool and 95% of a solution of water and SDA-40 in the ratio of 3 parts water to 7 parts SDA-40 by weight. Initial killing power and prolonged killing power over a 24-hour period was provided at saturation levels of 25%, 50% and 75%. The saturation levels are subjective measures of the degree to which an animal's coat is wetted with spray.

EXAMPLE IX Insecticidal efficacy was also achieved with 5% linalool and 95% SDA-40.

EXAMPLE X Insecticidal efficacy was achieved utilising 1% linalool and 99% denatured ethanol, namely, SDA-40.

EXAMPLE Xl 1 percent linalool was also effective in a composition in which the remaining 99% was water and SDA-40 in weight ratio of 3 to 7, respectively.

EXAMPLE XII Linalool can also be used with other terpenes which have toxicant properties as illustrated in Examples XIII and XIV.

EXAMPLE XIII A spray was provided comprising 1% linalool, 1% alpha terpineol and 98% SDA-40. At nominal saturation levels, e.g. for a given hair length, a fast kill, namely, under 10 minutes, was provided. Odour was stronger than that provided for Examples X and Xl, however.

EXAMPLE XIV A pump spray was provided comprising 0.5% linalool, 5.43% d-limonene and 94.07% SDA40. Effective kill was provided and the composition was perceived by testers to have a good odour.

EXAMPLE XV The amount of linalool was increased and the amount of SDA-40 was decreased in a pump spray consisting of 1% linalool, 5.43% d-limonene and 93.57% SDA-40. Again, good kill and good odour were reported.

EXAMPLE XVI The composition of Example XV was duplicated with the exception that 0.5% by weight SDA40 was removed and replaced with Vita Cos 535, a form of wheat germ glycerides. Vita Cos is a trade mark of Wickhen Products, Inc. Both effective kill and pleasant odour were reported.

Additionally, the animals' coats were left with a good shine when brushed out after drying of the spray.

EXAMPLES XVII to XIX These all relate to dips.

A dip may be provided in which an animal may be bathed. The dip is preferably provided as a concentrate containing from about 10% to about 90% linalool, with about 90% to about 10% surfactant which may be any anionic or non-ionic surfactant. The concentrate may be highly diluted in water to prepare the dip composition. A preferred dilution is 1 to 4 fluid ounces (US) (29.6 to 118.3 cc) concentrate per gallon (US) (3.875 litres) of water, i.e 7.6 to 30.5 ccs per litre). The desired dilution will vary based on the concentration of linalool in the concentrate.

Dilution of the concentrate should achieve a final concentration of linalool of about 0.3% to about 2.5%, preferably from about 0.3% to about 1.5% and most desirably from about 0.3% to about 1.0% for application to the animal. Storage in diluted form over a long period of time, e.g.

several months, may result in some loss of activity.

EXAMPLE XVII A dip concentrate was provided comprising 10% linalool, 75% d-limonene and 15% Tween 80. The Tween 80 is a surfactant rendering the terpene oils miscible in water. When diluted, as described herein, by admixing 1 to 2 fluid ounces (29.6 to 59.2 cc) in a gallon (US) of water (3.876 litres) (i.e 7.6 to 15.2 cc/l) the solution stayed clear. Highly effective flea kills were reported along with satisfactory drying characteristics.

Other surfactants may be substituted for Tween 80. Tween is a registered trade mark of ICI Americas, Inc., for nonionic polyoxyalkylene derivative of hexitol anhydride partial long chain fatty acid esters.

EXAMPLE XVIII An insecticidal dip concentrate was also prepared comprising 90% linalool and 10% Tween 80. Highly effective insecticidal dip compositions were produced by diluting this concentrate at ratios from about 1 fluid ounce (29.6 cc) to about 2 fluid ounces (59.2 cc) per gallon (US) of water (3.875 litres) (i.e 7.6 to 15.2 cc/l).

EXAMPLE XIX Linalool dip concentrate may also be provided in reduced linalool concentration. A dip concentrate was provided comprising 5% linalool, 10% Tween 80, 30% Fernesol and 55% castor oil.

Since the Farnesol component functions as both a perfume and as an insecticide, the range of dilution may be the same as in prior dip examples with effective results.

EXAMPLES XX and XXI These relate to carpet sprays.

Insecticidal and pesticidal utility is found in a carpet spray. Carpets may harbour fleas and other pests. In the following example, formulations are provided for concentrates. At the time of application each concentrate may be diluted 10 to 1, or 20 to 1, by weight with water for application to a carpet. The diluted concentration preferably ranges from about 0.5 percent to about 2.0 percent linalool in the spray compositions. Degree of required saturation per carpet is somewhat analogous to that for animals. Length and density of the carpet dictate the amount of spray required.

EXAMPLE XX A carpet spray concentrate was provided comprising 10% linalool, 10% alpha-terpineol, 40% Witconate P10-59 and 40% Witconol NP-100. P10-59 comprises the amine salt of dodecyl benzene sulphonic acid. NP-100 comprises nonylphenol polyethylene glycol ether. When diluted as provided above, the resulting sprays were found to be effective insecticides.

EXAMPLE XXI Insecticidally effective spray was provided wherein the amounts of terpene compounds in Example XX were doubled with proportional reductions in the other components identified. In the above-described examples, the most active species of terpene where there is a combination of terpenes has been found to be the linalool.

Table 1 below gives data on the contract effect of linalool on fleas.

TABLE 1 FLEAS PUT ON WET TREATED SURFACE (Percentage Mortality Plus Immobility 5 10 15 20 60 Treatment min. min. min. min. min.

Linalool solution 97% 97% 100% 100% 100% Control (H2o) 0 0 0 0 0 The percentage given in Table 1 is the sum of mortality and immobility (fleas on their side and can't walk). There were 27 to 36 fleas per treatment. All compounds were used at a final concentration of 0.7% linalool (stock solutions of linalool made up with 90% linalool and 10% Tween 80 and then diluted at 1 fluid ounce (29.6 cc) per gallon (US) (3.875 litres) or 1:128).

As illustrated in Table 2 below, linalool may be effective in varying concentrations. In tests of the present exemplification, stock formulations are made up with 90% toxicant and 10% Tween 80. The stock solutions were diluted with water to obtain the various concentrations described below. 1 millilitre was put on filter paper in petri dishes, and flea larvae were put on the wet paper. There were 10 larvae for each treatment.

TABLE 2 TOXICITY OF LINALOOL TO FLEA LARVAE (Percent Mortality) Time After Start of Test 5 10 15 30 min. min. min. min.

10% Linalool 70 70 100 100 5% Linalool 30 80 100 100 2.5 % Linalool 10 30 90 100 1% Linalool 10 30 60 100 EXAMPLES XXlla, b and c TOXICITY OF WATER BASE SPRAYS AGAINST ADULT HOUSE FLIES AND MOSQUITOES It has been found that a wide range of concentration may also be used for a linalool insecticide as an effective spray for killing adult house flies and mosquitoes.

A stock solution of linalool was prepared with 90% linalool plus 10% Tween 80. The stock was diluted with water to obtain 10%, 5%, and 2.5% concentrations of the insecticide.

The adult insects were placed in cylindrical cartons with screen lids. The insecticide was sprayed through the screen using a glass chromotagram sprayer. To simulate open room conditions, 3 to 5 minutes after spraying the insects they were transferred to dry filter paper in petri dishes. By doing this, they were removed from the slightly moist spray container.

There were 10 house flies used for each treatment and 7 to 10 mosquitoes per treatment.

The results are set forth in Table 3.

TABLE 3 TESTS AGAINST ADULT HOUSE FLIES AND MOSQUITOES WITH LINALOOL SPRAYS Stock solutions for linalool were prepared with 10% Tween 80 and 90% toxicant. The desired concentrations of toxicant for the following tests were then obtained by dilution of the stock solution with water.

House Flies: Example 10%-All immobile at one minute, 100 immobile at 5 minutes and 100% mortality at 5 XXlla minutes.

Example 5%-80% immobile at 2 minutes, 100 percent paralysed at 10 minutes, partial recovery XXllb by 30 percent which buzzed around on their backs at 30 to 60 minutes, but all eventually died.

Mosquitoes: Example 10%-lnstant "knock down", 100% never move and are dead immediately.

XXlla Example 5%-lnstant "knock down", 100% do not move or recover.

XXllb Example 2.5%-50% still move after 15 minutes.

XXlle EXAMPLES XXIII and XXIV These relate to fire ant treatment.

Linalool is useful in treatment of fire ant mounds.

The surprising effectiveness against fire ants is particularly important in view of the fact that widely used fire ant insecticides have been recently disapproved by the Environmental Protection Agency. Broadly speaking, a fire ant is one of the genus Solenopsis, which is a fiercely stinging, omnivorous ant. While generally unknown in the northern United States, they are native to the southern United States, and their area of penetration has been increasing. Provision of a natural fire ant treatment, as in the following examples, is particularly useful.

EXAMPLE XXIII A dip concentrate was prepared according to Example XVII. In use, the concentrate was diluted in the proportion of 1 fluid ounce (29.6 cc) to one-half gallon (US) of water (1.94 litres) (i.e 15.3 cc/l). One-half gallon (1.94 litres) of the mixture was poured on an average sized fire ant mound (e.g. 10 inches (25 cm) in diameter by 6 inches (15 cm). Insects touched by the liquid were highly agitated and began to evacuate the mounds. No living adults were found after 48 hours.

EXAMPLE XXIV A dip concentrate was prepared according to Example XVIII and the concentrate was then diluted in the proportion of 1 fluid ounce to 1/2 gallon of water (15.3 cc/l). 1/2 gallon (1.94 litres) of this dilute mixture was poured on an average size fire ant mound as in Example XXIII.

As in the case of XXIII, no living adult fire ants were found after 48 hours.

EXAMPLE XXV This relates to a flea ovicide.

Linalool has been found to be effective with respect to flea eggs.

A spray was provided with linalool in a concentration of 0.5% in solvent (5.0% ethanol) and vehicle (0.1% Tween 80 in water). The eggs were placed in carpet squares. The spray was applied to carpet squares until the carpet was damp to the touch. The carpet squares were examined for live larvae at 11 days after treatment and for adult fleas at 24 days. In each case 50 eggs of 1-16 hours of age were placed in each square. Neither live larvae nor adult fleas were found. The linalool spray prevented the flea eggs from developing.

Table 4 below compares the toxicity of d-limonene and linalool to flea eggs.

TABLE 4 COMPARATIVE TOXICITY OF 1% D-LIMONENE and 1% LINALOOL TO FLEA EGGS IN CARPET Number of Eggs Put in Carpet Percent Adult Squares Treatment Emergence 50 1.0 percent d-limonene 68 48 1.0 percent linalool 0 50 Control - untreated 62 57 Control - water treatment 72 The formulations above were toxicant in a carrier consisting of 0.1 percent Tween 80 and the remainder was H2O.

EXAMPLES XXVI and XXI These relate to spider miticides.

Linalool has been found effective in killing spider mites and spider mite eggs.

EXAMPLE XXVI A spray was formulated comprising 0.1% linalool, and 0.1% Tween 80 in a water solution.

The spray was applied to leaves which were cut from insect infested plants and put in petri dishes. The leaves were sprayed with a fine mist of the insecticide. A 100% mortality of spider mite eggs was achieved.

EXAMPLE XXI A spray was provided comprising 0.5% linalool, and 0.1% Tween 80 in a water solution.

When applied as in Example XXVI, 100% mortality of spider mites was achieved.

It has been found that linalool at 1% or less has minimal phytotoxicity, and has little or no adverse effect on plants.

EXAMPLES XX VIII and XIX These relate to the use of synergists.

The toxicity of linalool with respect to adult fleas can be enhanced by combination with synergists such as sesame oil or piperonyl butoxide. At concentrations of 0.25% to 0.5% of the synergist, the percentage of linalool may be reduced very substantially with no reduction in insecticidal efficacy as illustrated in examples XXVIII and XXIX.

EXAMPLE XX VIII A spray comprising 0.2% linalool and 0.5% sesame oil in SDA-40 was provided and found to be effective when used in accordance with Example IX above.

EXAMPLE XXIX A pump spray with SDA-40 was prepared in accordance with Example IX above and comprising 0.2% linalool and 0.5% piperonyl butoxide. 100% mortality against adult fleas was achieved.

The effectiveness of these additional components with linalool is further illustrated in Table 5.

TABLE 5 TOXICITY OF LINALOOL SYNERGIZED WITH SESAME OIL OR PIPERONYL BUTOXIDE TO ADULT FLEAS Mortality at these intervalsa 5 10 15 20 60 24 Treatment min. min. min. min. min. hrs.

0.2% linalool 0% 1% 1% 3% 32% 40% 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% 0.5% piperonyl butoxide (control 0% 1% 1% 7% 29% 40% 0.5% sesame oil (control) 0% 0% 0% 0% 0 & 0% 0% a mean values from 2 to 4 replicates.

At one hour after treatment, note from the above these comparative mortality percentages: 0.2% linalool by itself 32% 0.2% linalool with sesame oil 100% 0.2% linalool with piperonyl butoxide 63%.

TOXICITY OF LINALOOL VAPOUR In order to test the toxicity of the linalool vapours to fleas and other insects, a test apparatus was designed wherein the bottom of a vessel of chamber was covered with filter paper and a close fitting cover was placed over the chamber. A hole was drilled in the cover and a very fine mesh wire screen placed over the hole. A glass ring of 3 inches (7.6 cm) in height was placed over the screen and cover placed over the glass ring. The glass ring was sealed to the top of the chamber.

The toxicant compounds were pipetted onto the filter paper and insects or insect eggs were immediately put in the screen chamber. The toxicant used to generate the vapours was formulated in an inert carrier consisting of 5.0% denatured alcohol, 0.1% Tween 80, and the remainder water. The results are given in Table 6 below for adult fleas, in Table 7 for larval fleas and Table 8 for flea eggs.

TABLE 6 TOXICITY OF VAPOURS OF LINALOOL TO ADULT FLEAS (Percent Mortality Plus Immobility) Time No.of 5 10 15 20 60 24 Treatment fleas min. min. min. min. min. hrs.

1% linalool 28 7 7 29 50 100 100 0.2% linalool 25-30 4 4 7 10 57 62 Control (untreated) 31 0 0 0 0 0 0 TABLE 7 TOXICITY OF LtNALOOL tAPOURS TO LARVAL FLEAS Observations at Treatment 24 hours 5.0 percent linalool 100 percent mortality 2.5 percent linalool 100 percent mortality 1.0 percent linalool 100 percent mortality 0.5 percent linalool 100 percent mortality 0.3 percent linalool 100 percent mortality Control of 5.0 percent denatured alcohol No mortality Control - water 3 percent mortality In each of the treatments shown above, there were 25 to 30 larvae placed in the chamber above the screen. As in the previous example, the toxicant formula was linalool at the indicated percentage in an inert carrier comprising 5.0% denatured alcohol, 0.1% Tween 80, with the remainder water.

TABLE 8 TOXICITY OF LINALOOL VAPOURS TO FLEA EGGS (Observations) Treatment 47 hrs. 72 hrs.

1.0 percent linalool 0.7% egg hatch 4.7% egg hatch (1) out of 150 Control - untreated 56% egg hatch 56% egg hatch In the above treatment of flea egs, in each test 50 eggs were placed in the vapour chamber and the above data are the means from three replicates. The formula for the linalool composition used to generate the vapours is the same as that set forth in Table 6 above.

EXAMPLE XXX It has been found that aerosol compositions embodying linalool are effective in killing fleas in a household environment.

LINALOOL AEROSOL 10% Linalool 2.5% Piperonyl Butoxide 32% Methylene Chloride 14% Propane Balance: 1, 1, 1 Trichlorethane In tests of the above aerosol, fleas were placed in open containers 10 ft, 20 ft and 30 ft (3, 6.1 and 9.1 metres) from a release point in an unoccupied residential house. In one test, the percentage kill two hours after the fogger release was 56%, 80% and 84% for the 10, 20, and 30 foot distances, respectively. In a second test at 10, 20 land 30 foot distances, the respective two hour kill rate was 88%, 92% and 96%.

In summary, the present invention provides linalool insecticides, larvacides and ovlcides. Further, the compositions of this invention may be provided in a wide variety of forms at varying concentrations of linalool to provide effective toxicity under different conditions of application and/or for use upon different kinds of insects and other pests.

Further modifications may be made without departing from the spirit of the invention in accordance with the teachings herein.

Claims (37)

1. A pesticide composition consisting essentially of 0.1 to 95% linalool by weight.

2. A pesticide shampoo consisting essentially of from 0.5 percent to 10% linalool in a shampoo base.

3. A shampoo as claimed in Claim 2 consisting essentially of 0.5 to 1.0% linalool.

4. A pesticide pump spray consisting essentially of at least 0.10/0 linalool in a liquid carrier.

5. A composition as claimed in any one of Claims 1 to 4 further comprising piperonyl butoxide.

6. A composition as claimed in any one of Claims 1 to 4 further comprising sesame oil.

7. A spray as claimed in Claim 4, 5 or 6 in which the said carrier comprises ethanol.

8. A spray as claimed in Claim 4, 5, 6 or 7 in which the said carrier comprises water and ethanol in the ratio of about 3 to 7 by weight.

9. A pesticide composition comprising a pesticide ingredient consisting essentially of linalool in an amount of at least about 10% by weight with at least about 10% surfactant.

10. A pesticide dip concentrate for preparing a diluted dip for application to animals comprising a pesticide ingredient consisting essentially of linalool in an amount of at least about 10% by weight with at least about 10% surfactant.

11. A pesticide composition spray concentrate having a pesticide ingredient consisting of linalool in concentration of about 1 % to about 20% by weight in a vehicle for rendering the said concentrate miscible in water.

12. A pesticide carpet spray concentrate having a pesticide ingredient consisting of linalool in concentration of about 1% to about 20% by weight in a vehicle for rendering the said concentrate miscible in water.

13. A concentrate as claimed in Claim 11 or Claim 12 in which the said linalool is in a concentration of about 1% to about 10% by weight.

14. A carpet spray consisting essentially of about 0.5% to about 1.0% linalool by weight.

15. A fire ant treatment concentrate comprising 2-20% linalool by weight in an aqueous vehicle.

16. A fire ant insecticide composition consisting essentially of at least 0.1% linalool by weight in solution.

17. A fire ant insecticide composition as claimed in Claim 16 in which the said linalool is in concentration from about 0.3% to about 1.5%.

18. A method of killing pests comprising exposing them to a pesticidal amount of linalool.

19. A method of killing arthropods comprising exposing them to an anthropodicidal amount of linalool.

20. A method of killing insects comprising exposing them to an insecticidal amount of linalool.

21. A method of killing arachnida comprising exposing them to an arachnidacidal amount of linalool.

22. A method of controlling fleas and ticks on the skin and hair of an animal host comprising applying to the said host an effective toxic amount of linalool.

23. A method as claimed in Claim 22 in which the step of applying linalool comprises spraying a composition of linalool in an ethanol vehicle.

24. A method as claimed in Claim 22 in which the step of applying linalool comprises applying a shampoo comprising linalool in a shampoo base and contacting the animal with the said shampoo for up to 15 minutes before rinsing.

25. A method as claimed in Claim 24 which comprises: wetting the said animal with water; applying the said shampoo to the said animal; working the said shampoo into a lather; wetting substantially the entire coat of the said animal with the said lather for a time interval of at least about five minutes, and thereafter rinsing the said lather from the coat of the said animal with water.

26. A method as claimed in Claim 22 in which the said step of applying comprises applying a dip to the said skin and hair.

27. A method as claimed in Claim 26 further comprising the steps of: diluting with water a dip concentrate composition containing linalool as a pesticide in an ampunt ranging from about 10% to about 90% of the total weight of the composition, and an emulsifier in an amount ranging from about 10% to about 90% of the total weight of the said composition, the said water for dilution being added to reduce the concentration of linalool in the dip to a range between about 0.3% and about 1.5% of the total weight of the diluted dip, and bathing the said animal by wetting it completely with the said diluted dip composition.

28. A method for killing house flies and mosquito adults comprising contacting the said flies or mosquitoes with a spray comprising linalool in an effective toxic amount.

29. A method for controlling fire ants comprising placing on a fire ant mound a solution of linalool with an effective toxic amount of linalool.

30. A method for controlling spider mites by contacting the said spider mites with an effective toxic amount of linalool.

31. A method for controlling spider mite eggs by contacting the said spider mite eggs with an effective toxic amount of linalool.

32. A method for controlling flea larvae by contacting the said flea larvae with an effective toxic amount of linalool.

33. A method of killing fleas and ticks in a fabric such as a carpet or rug comprising: spraying onto the fabric a liquid composition to wet such pests, their larvae and eggs, wherein the said liquid composition contains linalool as a pesticide in an amount ranging from about 1% to about 10% of total of the said composition, at least one surfactant in an amount ranging from about 1% to about 10% of the total weight of the said composition, and water in an amount ranging from about 98% to about 80% of the total weight of the said composition.

34. An aerosol composition for killing pests, such as fleas and ticks, comprising: linalool in an amount ranging from about 1% to about 15% of the total weight of the said composition; propane in an amount ranging from about 8% to about 20% of the total weight of the said composition; and aerosol grade 1,1,1 trichlorethane, in an amount ranging from about 65% to about 91% of the total weight of the said composition.

35. An aerosol composition as claimed in Claim 34, in which the said linalool is about 10% of the total weight of the said composition and the said propane is about 14% of the total weight of the said composition, and 1, 1, 1 trichlorethane in an amount comprising the remainder of the said composition.

36. A composition as claimed in Claim 35, further including piperonyl butoxide in an amount of about 2.5% of the total weight of the said composition and methylene chloride in an amount of about 32% of the total weight of the said composition.

37. A pesticide composition as claimed in Claim 1, substantially as specifically described herein with reference to any one of the accompanying examples.