WO2001045508A1

WO2001045508A1 - Use of at least one fatty acid polydialkanol diamides in combination with quinic acid and/or shikimic acid for pest control

Info

Publication number: WO2001045508A1
Application number: PCT/EP2000/012498
Authority: WO
Inventors: Franz Bencsits
Original assignee: Biolink Technologies Ag
Priority date: 1999-12-21
Filing date: 2000-12-11
Publication date: 2001-06-28
Also published as: DE19961812A1; AU2007701A

Abstract

The invention relates to the use of at least one fatty acid polydialkanol diamide of formula (I) R?1-CO-NR2R2¿, where R1 = a fatty acid group and each R2 = a polyalkanol group, whereby both R2 groups can be the same or different, in combination with quinic acid and/or shikimic acid, for pest control.

Description

Use of at least one fatty acid polydialkanolamide in combination with quinic acid and / or shikimi acid for pest control

The present invention relates to the use of at least one fatty acid polydialkanolamide in combination with quinic acid and / or shikimic acid for pest control

Pesticides are substances that are designed to render pests and harmful organisms harmless. These can also be called insecticides, i.e. as pesticides, which are particularly effective against insects.

Chemically, a distinction is first made between natural and synthetic insecticides. Natural insecticides include pyrethroids, redoids and alkaloids (eg nicotine) as well as N-isobutylamides of unbranched unsaturated fatty acids and endotoxins isolated from bacteria. The synthetic insecticides can be divided into inorganic and organic compounds. The inorganic insecticides include arsenic preparations, cryolite, fluorosilicates, sodium fluoride, hydrogen cyanide, hydrogen phosphide and sulfuryl fluoride. The organic insecticides include, for example, the classes of chlorinated hydrocarbons, for example DDT, Aldπn, Dieldππ, chlordane, lindane, heptachlor and combat chlorine, phosphoric acid esters, such as, for example, Paration (E 605), carbamates, for example carbaryl, carbofuran or propoxur, synthetic pyrethroids, for example Allethπn, Cyfluthπn or Permethnn as well as acylureas, amidines, dinitrophenols, thiocyanates, ziπnorgaπische connections as well as phenylpyrrazoles and nitroguanidme For most of the above mentioned insecticides a negative judgment has meanwhile been made, since these substances have strong adverse effects prohibited The chlorinated hydrocarbons are often very resistant and accumulate due to Their good fat solubility mostly in the adipose tissue of warm-blooded animals. Common disadvantages of all these natural and synthetic insecticides are, on the one hand, their varying levels of toxicity to humans as well as birds and small rodents, which are present in all substances, and, on the other hand, the ability of the pests to resist resistance to different species in a rapid generation change Developing active ingredients Even with the most careful treatment method, it can never be ruled out that individual specimens, which are not fatal, get insecticide doses and detoxify quickly through enzymatic oxidation and pass on this property in the genetic information to their offspring and the subsequent populations are then immune to the insecticide (become resistant)

This effect can be alleviated by adding so-called synergists, such as the well-known carcinogenic piperonyl butoxide, or highly toxic phosphoric acid esters or carbamates. These, in turn, as explained above, are to be handled with caution due to their toxicity

An interesting class of substances for "natural" insecticides are organic nitrogen-containing compounds. For example, US-A-4263321 describes the ovicidal effect of certain fatty acid amides which are substituted with low molecular weight alcohols on the nitrogen atom. Dan A Wolfenbarger, MJ Lukefahr and WL Lowry also describe that The effectiveness of synthetic insecticides can be increased by adding alkanolamides (Journal of economic entomology, Vol 60, No. 4, page 902). AT-B-404310 describes that substances based on ethanolamide have insecticidal effects. A possible compound for use is coconut fatty acid polydiethanolamide

However, the alkanolamides tested as a pure substance show practically no ovicidal or larvicidal activity, and the use of the

Coconut fatty acid polydiethanolamids require relatively high drug concentrations to be effective

Accordingly, the present invention seeks to provide an effective pesticide based on substances based on nature to provide the lowest toxicological risk This pesticide should be safe for humans and their living environment (pets, food, contaminated surfaces and objects) even with excessive misuse, non-persistent, i.e. quickly and without the formation of harmful metabolites, and should be biodegradable Do not allow target animals to develop resistance even when using non-lethal doses. In addition, despite these requirements, a sufficiently long duration of action should be provided to completely eradicate pest infestation

This object is achieved through the use of a fatty acid polydialkanolamide of the general formula

R ¹ -CO-NR ² R ²

wherein R ^{1 represents} a fatty acid residue and R ² each represents a polyalkanol residue, where the two residues marked with R ² may be the same or different, dissolved in combination with quinic acid and / or shikimic acid for pest control.The quinic acid and / or the shikimic acid act in this combination as a synergist This allows the concentrations of fatty acid polydialkanolamide used to be drastically reduced compared to the sole use of the amide

The fatty acid residue denoted by R ¹ in the above formula is any fatty acid residue. The fatty acid in R ¹ can be a saturated and / or unsaturated and / or unbranched and / or branched acid. Examples of these are valenic acid, caproic acid, onanthic acid, caprylic acid, perlagonic acid, capric acid , Ecansaure, Lauπnsaure, Tπdecansaure, Myπstinsaure, pentadecanoic acid, palmitic acid, heptadecanoic acid, Steaπnsaure, nonadecylic acid, Arachmsaure, behenic acid, Lignoceπnsaure, Cerotmsaure, Me ssinsaure, palmitoleic acid, oleic acid, erucic acid, sorbic acid, linoleic acid, Lmolensaure, Elaeosteaπnsaure, arachidonic acid, Clupanodonsaure and docosahexaenoic Preferred Fatty acids are fatty acids with 12 to 24 carbon atoms, especially with an even carbon number, Lauπnsaure, Myπstinsaure, Palmitinsaure, oleic acid, Erucasaure and Linolsaure, as well as the mixtures of fatty acids called coconut fatty acid and sunflower fatty acid. Coconut fatty acid denotes a mixture of fatty acids with even carbon number in the following mixture ratio

The following mixture is to be understood as sunflower fatty acid

C ₁₄ less than 0.5%,

C ₁₆ 3 to 10%,

Ciβ monounsaturated 14 to 65%,

Cι ₈ unsaturated 20 to 75%,

Ciß triple unsaturated,

C ₂₀ and C ₂₀ monounsaturated, less than 2.7% overall

Coconut fatty acid is particularly preferred

The two radicals denoted by R ² , which can be the same or different, are oligomers or polymers which are composed of alkane oxide units.These radicals are therefore chains which are composed of alkylene units connected to oxygen atoms. Examples of these alkylene units are methylene, ethylene, propylene, butylene , Pentylene These may optionally be substituted. There may be several different types of alkylene units in the radicals. Preferred radicals represented by R ² can be represented by the following formula

- ((CH ₂ ) nO) _m - ((CH ₂ ) _o O) _p -H where n and o each independently represent 1, 2, 3 or 4, m is greater than 1 and p is 0, 1 or greater than 1

N and o are preferably 2 or 3 m is preferably 10 to 500, particularly preferably 20 to 50 If p is not 0, p is preferably 10 to 500, particularly preferably 20 to 50 Both radicals R ² are preferably the same

Preferred fatty acid polydialkanolamides are coconut fatty acid polydiethanolamides, sunflower fatty acid polydiethanolamides and the polydipropanolamides of these compounds

The substances used according to the invention are characterized by a surprisingly good insecticidal action and, at the same time, negligible toxicity. The LD50 value (rate, oral) of fatty acid polydiethaπolamides is over 5,000 mg / kg body weight, while this value is significantly lower in conventional pesticides (1 -Naphthylmethylcarbamat 300 mg / kg, Lindane 88 mg / kg, Dieldπn 56 mg / kg) Another advantage over all other known insecticides is the good water solubility of the pesticide used according to the invention, since it also means the use of toxicologically and ecologically questionable formulation ingredients and auxiliaries , such as halogenated organic solvents, hydrocarbons and emulsifiers, can be completely dispensed with, which entails the following advantages in particular when it comes to pest control in agriculture and horticulture

1) complete absence of phytotoxicity on parts of the plant containing chlorophyll, as occurs again and again as a result of the action of emulsifiers in all other agents, which in turn triggers crop failures and the death of perennial crop plants,

2) Complete, rapid biodegradation without harmful formation of metabolites. Thus, the pesticide used according to the invention can be used without risk and without any impairment and risk potential on air, earth and water. At the same time, any risk from contamination of field and garden crops to fruit-eaters, such as people and animals, be excluded 3) no development of resistance, so that use in minimum dosage is always guaranteed. Thus, no change of active substance is necessary when resistant populations occur

Also new is the mechanism of action of the pesticides used in accordance with the invention, since fatty acid polydialkanolamides and quinic acid or shikimiaure are neither nerve poisons nor acetylcholinesterase inhibitors, but act directly on the water balance of the pests as pure contact and feeding poisons In the digestive tract, they affect the bacteria responsible for the metabolism of the insects, so that their metabolic activity comes to a standstill. On the other hand, the water-containing body fluid is very quickly displaced from the bodies, so that the pests dry up and die

The synergist used according to the invention is (1 R, 3R, 4S, 5R) -1, 3,4,5-tetrahydroxycyclohexane carboxylic acid with the empirical formula C ₇ H ₁₂ O ₈ , hereinafter simply called quinic acid and / or 3,4,5- Tπhydroxy-1-cyclohexenecarboxylic acid, the dehydrated form of quinic acid, hereinafter called shikimic acid

Quinic acid can be obtained by known processes from its natural occurrence in China, various types of quinona, potato beans, sugar beets, meadow hay, gooseberries and blackberries as well as leaves of blueberries and cranberries. The extraction is usually carried out by leaching and conversion. Likewise, quinic acid can be synthetically produced and used

The pesticide used according to the invention can either be in pure form or in a conventional mixed form.For example, the active ingredients can be used as a solution in water. The fatty acid polydialkanolamide and quinic acid and / or shikimic acid are preferably used in a mixing ratio of 100 0.01 to 1 1, preferably 50 0.1 to 2 1 and particularly preferably from 20 0.1 to 5 1 A ratio of 10 1 is particularly preferred Solutions of fatty acid dialkanolamide and quinic acid and / or shikimic acid in water are preferably used. Effective amounts of fatty acid polydialkanolamide are in the range from 10 to 0.01% by weight. Effective amounts of quinic acid and / or shikimic acid are in the range from 0.0001 to 2. 0% by weight are preferred in each case solutions with contents of fatty acid polydialkanolamide of 1 to 2% by weight, 0.1 to 0.2% by weight and 0.01 to 0.02% by weight and a corresponding content of quinic acid and / or Shikimisaure in the range of 0.01 to 0.02% by weight, 0.001 to 0.002% by weight and 0.0001 to 0.0002% by weight. Instead of water, another harmless solvent can be used, such as mono- or polyvalent linear or branched lower alcohols, such as ethanol, isopropanol or glycine. These substances can also be present in mixtures with water. 1,2-propylene glycol or ethylene diglycol can also be used

Furthermore, it is also possible to formulate fatty acid polydialkanolamides as ointments, pastes, creams, spray solutions or in almost solid form. Such formulations can be chosen in accordance with the intended mode of application. The customary formulation auxiliaries can be used

Ointments are gels of plastic deformability that are applied for topical application to the skin or mucous membranes to be protected. Creams are ointments with a particularly soft consistency that contain large amounts of water. Pastes are those ointments in which powdery components, usually in larger amounts Amount suspended are water-rich creams can also be provided on the basis of hydrogels and / or oil-water emulsions. The customary means and processes are used for the preparation of these ointments, creams and pastes, since no penetration and absorption of the active substances take place in the use according to the invention should be omitted, the auxiliaries usually used in this regard. The usual ointment, paste and cream bases are hydrocarbons, such as petroleum jelly, piastibase, lipogels, such as waxes (e.g. beeswax, walrus, wool wax), fats (e.g. pork lard, hardened peanut oil, halbsynthet ische fats), hydrogels, such as inorganic, such as Aerosil or bentonite, or organic, such as strong, and Polyethyleπglycolgele and Silicone gels (silicone oils, solidified with Aerosil or calcium stearate). The pesticides used according to the invention can also be in the form of preparations suitable for sprinkling or sprinkling

The auxiliaries commonly used in the formulations described above are, for example, fillers, binders or thickeners, flow regulators, adsorbents or drying agents, solvents, anti-foaming agents, salt formers, buffers, gel formers, film formers, lubricants, mold release agents or sorbents, and auxiliaries which take on special functions can, for example antioxidants, preservatives, and odor-correcting agents as well as colorants

Furthermore, the pesticide used according to the invention can also be present in combination with substances which serve as attractants or feed substances for insects.This can be in the form of so-called insect traps, the pests being attracted first by the feed or attractants and then by the contact or the Absorption of the active ingredients as pesticides are killed

Representative examples of commonly used auxiliaries are sugars and sugar alcohols, macromolecular auxiliaries, such as starches, for example corn starch, rice starch, potato starch or wheat starch, cyclodextine, gelatin, tragacanth, pectin, cellulose, methyl cellulose, methyl hydroxypropyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, methyl hydroxyl cellulose, ethyl cellulose, Cellulose acetate phthalate, polyacrylates, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acids, such as carbopoles, macrogels, polyethylene glycols, polyethylene oxides, surface or surface-active auxiliaries, talc, white clay, kaolin, bentonite, titanium dioxide, calcium hydrogenphosphate, calcium carbonate, sodium and silicon dioxide, and non-dispersing agents, silicon dioxide, and non-silicon dioxide colorants, highly disperse odorants

With regard to the use as pest control or repellant on human skin, the formulations produced can also contain skin-care constituents, as long as there is no adverse effect on the effectiveness as Anti-pollution or control agent is exerted. The above-mentioned formulations can be produced in the devices commonly used for this purpose. The so-called depot forms or slow-release forms are particularly preferred. The active ingredient is inserted into a matrix of a material which slowly decomposes under the influence of the environmental conditions The active ingredient is released slowly, so that long-lasting effectiveness is ensured. The auxiliaries or manufacturing processes to be used for this are known to the person skilled in the art

The following examples illustrate the invention. The coconut fatty acid poly-diethanolamide used was a commercial product from HENKEL KGaA called COMPERLAN PD

1. Examples of pesticides (PAT) with synergist quinic acid in 10 times lower concentration

(I) 0.002 wt% coconut fatty acid polydiethanolamide 0.0002 wt% quinic acid

99.9978% by weight of water

(II) 0.02% by weight coconut fatty acid polydiethanolamide 0.002% by weight quinic acid

3.0% by weight 1, 2,3-propanπol (Glyceπn) 96.978% by weight water

(III) 0.2% by weight of coconut fatty acid diethaolamide 0.02% by weight of quinic acid

17.98% by weight of water

0.20% by weight carbopol (cross-linked acrylic acid polymer)

81.6% by weight 1, 2.3 propanole (Glyceπn) 1.A. Examples of pesticides (TP) without synergist in 10 times higher concentrations than PAT (I) to (IV)

(I) 0.20 wt% coconut fatty acid polydiethanolamide 99.80 wt% water

(II) 2.00% by weight of coconut fatty acid polydiethanolamide 3.00% by weight of 1,3,3-propanetriol (glycerol) 95.00% by weight of water

(III) 20.00% by weight coconut fatty acid polydiethanolamide 10.00% by weight water

0.20% by weight Carbopol (crosslinked acrylic acid polymer) 69.80% by weight 1,3,3-propanetriol (glycerol)

1.B. Reference products used (REF)

(I) 0.20 wt% methomyl (carbamate) 99.80 wt% water

(II) 0.50 wt% chlorpyriphos 0.37 wt% neopynamine 1.95 wt% methoxychlor 97.18 wt% water

(III) 20.00% by weight deltamethrin 10.00% by weight water 0.20% by weight Carbopol

69.80% by weight 1, 2,3-propanetriol

(IV) Commercial product containing 30.00% by weight of diethyltoluamide (AUTAN ^® ) 2. Use in vegetable plants

2.a. PAT (I) and TP (I) were compared to REF (I) in 2 greenhouses on 200 vegetable plants (white cabbage, savoy, cauliflower, kohlrabi and stalks), which differed greatly with white fly (Aleyrodes proletella) and aphids (Aphididae) Species were infected, tested

The amount of water was 200 ml, the entire surface was wet. Results with PAT (I) and TP (I) as well as with the use of REF (I), all plants were free of infection after 1, 4, 7 and 14 days

2 B. PAT (I) and TP (I) were compared to REF (I) with 20 strong mit Spinπ mites

(Panonynchus ulmi) infected begonias in a quantity of 20 ml (always 1 ml per plant) applied to the entire surface of the wet

The results for PAT (I) and TP (I) as well as for REF (I) were all

Plants free of infestation after 1, 4, 7 and 14 days

The evaluations of the phytotoxic phenomena after product use

(Leaf margin discoloration, necrosis, etc.) showed the value 0 (no visible changes) for REF (I) for all ratings for PAT (I) and TP (I) on the 5-part scale

Value 1 (slight discoloration on leaves or bleeding)

The results show that the pesticide used according to the invention unexpectedly shows at least the same effect as the market product REF (I), but without having its risks to the health of users and plants

3. Use on insects

3.a. PAT (II) and TP (II) were used in the same amount as REF (II) in the laboratory test as a spray to combat the following pests (adults and metamorphoses). A) Musca domestica - common housefly

B) Blatelia germanica - German cockroach

C) Lasius niger - black garden ant

D) Ixodes rizinus - Holzbock (tick)

E) Tineola bisselliella - clothes moth

For the experiments, 30 pests of flying pests A) and E) were placed in gauze-hung cages measuring 1x1x1 m and sprayed with 1 ml PAT (II) and TP (II) and REF (II). Animals that were unable to fly on the ground were evaluated after 1, 5, 10 and 20 minutes and after 24 hours the mortality or resuscitation rate (recovery) was evaluated.

30 specimens of mixed metamorphoses of the creeping pests were each placed in tubs measuring 1x1x1 m and sprayed with 1 ml TP (II) and PAT (II) and REF (II).

The evaluation according to the elapsed time only recorded animals lying on their backs, which under the magnifying glass showed no leg or tentacle movements

These test arrangements also showed that, when using the pesticide according to the invention, surprisingly not only a comparable, unexpected effect, but also an effect which was even superior to the commercially available comparative product (REF II), could surprisingly be achieved

4. Long-term trial

4.a. In a long-term trial over 6 months, the effectiveness of a loose permanent spread for cockroach control was carried out Spread 2 ml of TP (III) and PAT (III) and 2 ml of REF (III) each and place them in large acrylic glass tubs (1x1x1 m). In the treated stainless steel tubs, 10 mixed specimens (adults and nymphs) by

Blatella germanica - German cockroach Peπpianeta ameπcana - American cockroach and Blatta oπentalis - Oriental cockroach The treated pan was then removed and kept for further experiments. The contaminated cockroaches were supplied with water and feed in the untreated pan and observed after 5, 10, 30 minutes and 24 hours the animals lying on their backs were paid out and after another 24 hours of observation, the mortality rate was determined as a percentage of the total number of cockroaches used

Blatella Germanica

Peπplaneta ameπcana

Blatta orientalis

Blatella Germanica

Peπplaneta Ameπcana

Blatta Orientalis

This long-term test shows the surprisingly good and long-lasting effect of the pesticide used in accordance with the invention, in particular in its 100% eradication rate of mixed species and stages of cockroaches (leaf odea) even after a storage period of 6 months in comparison to a pyrethroid-containing dissolved piercing agent. that the synergistic effect of quinic acid allows a reduction in the amount of amide. 5. Determination of the defense effect on human skin

5.a. In the course of the general screening, tests were also carried out according to the test specification of the Swiss Tropical Institute in Basel for keeping away from mosquitoes on human skin, which surprisingly produced an effect that was at least comparable to that of a branded product. The right forearm of a test person was exposed on an area of approx. 250 cm ² of the corresponding test substance (PAT (III) and TP III) treated. A quantity of 2 ml of the corresponding test substance was distributed evenly. The treated forearm area was sealed at both ends with a mosquito-tight adhesive tape and a short plastic tube. The untreated hand was covered with a thick glove and thus also served as a control for the biting activity of the test animals. The left forearm was also treated with a reference product (REF IV). About 300 to 400 yellow fever mosquitoes (Aedes aegypti), almost exclusively females, were found in test animals Breeding cage of 40x40x40 cm used

For the test, the forearms and the hand were held one after the other, first the left, then the right, hourly in the cage and during 10 minutes the number of gnats was recorded

(a) tried to pierce the glove (positive control),

(b) approached the treated area closer than 3 cm,

(c) remained on the treated area for more than 2 seconds and

(d) stab the treated area and suck blood b. Results

Test person (1)

Test person (2)

Test person (1)

Test person (2)

For further comparison, the monoethanolamides of lauric acid, myristic acid and palmitic acid, as well as the diethanolamide or the monoethanolamide of coconut fatty acid and the isopropylamide of sunflower fatty acid in combination with quinic acid were also tested. These comparison substances showed practically no activity, which once again clearly underlines that the activity of the substances claimed according to the invention is surprising.

Claims

claims

1. Use of at least one fatty acid polydialkanolamide of the general formula

R ¹ -CO-NR ² R ²

in which R ^{1 represents} a fatty acid residue and R ² each represents a polyalkanol residue, it being possible for the two residues labeled R ^{2 to be the} same or different,

in combination with Chinese acid and / or Shikimisaure for pest control.

2. Use according to claim 1, characterized in that R ^{1 is} a coconut fatty acid residue.

3. Use according to claim 1 or 2, characterized in that a liquid carrier is additionally used.

4. Use according to claim 3, characterized in that the liquid carrier is water, ethanol, isopropanol or 1,2-glycol, individually or in mixtures.

5. Use according to at least one of the preceding claims 1 to 4 in the form of emulsions, dispersions, lotions, creams, gels, pastes or solutions.

6. Use according to at least one of the preceding claims 1 to 5 in flying, creeping, stinging, biting and sucking pests and nuisances.