WO2002000022A1 - Composition for inhibiting feeding of weevils - Google Patents

Composition for inhibiting feeding of weevils Download PDF

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Publication number
WO2002000022A1
WO2002000022A1 PCT/SE2001/001458 SE0101458W WO0200022A1 WO 2002000022 A1 WO2002000022 A1 WO 2002000022A1 SE 0101458 W SE0101458 W SE 0101458W WO 0200022 A1 WO0200022 A1 WO 0200022A1
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Prior art keywords
methyl
compound
composition
active compound
present
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PCT/SE2001/001458
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French (fr)
Inventor
Jan Löfqvist
Fredrik Schlyter
Hans-Erik HÖGBERG
Olof Smitt
Kristina SJÖDIN
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Forskarpatent I Syd
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Priority to PL36050201A priority Critical patent/PL360502A1/en
Priority to EP01944068A priority patent/EP1294229A1/en
Priority to AU66509/01A priority patent/AU6650901A/en
Priority to CA002413508A priority patent/CA2413508A1/en
Publication of WO2002000022A1 publication Critical patent/WO2002000022A1/en

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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
    • C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
    • C07C49/713—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups a keto group being part of a six-membered ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
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    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/24—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients to enhance the sticking of the active ingredients
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    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
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    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • A—HUMAN NECESSITIES
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    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aldehyde or keto groups, or thio analogues thereof, directly attached to an aromatic ring system, e.g. acetophenone; Derivatives thereof, e.g. acetals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/20—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom three- or four-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/277—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups

Definitions

  • Neem oil is, however, not equally active against all insects and has turned out to have a limited effect against Hylobius abietis and H. pales.
  • the gnawing inhibiting compound is present in a bound form to a substance of the group of zeolites, cyclodextrines, homogenous porous microspheres, spherical vesicles, hollow fibres, such as textile fibres (wool) capillaries of synthetic material (polymers), starch, and polymer films, optionally in combination with a carrier and/or adhering agent, whereby the gnawing inhibiting compound is present in an amount of 1 to 10 % by weight.
  • a dry round flask (argon atmosphere) comtaining activated chips of magnesium was provided with 31 ml of dry Et 2 O.
  • 15 g (78 mmol) of n-octyl bromide (dried K 2 CO 3 , distilled prior to use) were added dropvwise simultaneously with refluxing the mixture gently.
  • the Grignard reagens formed was then added dropwise to another round flask (argon atmosphere) containing a stirred solution of 1.1 g (5.8 mmol) of Cul in 77 ml of dry THF at -30 °C followed by addition of 10 g (42 mmol) the silylether-epoxide (prepared as described above).
  • the resulting mixture was allowed to reach room temperature during 15 hrs stirring and was quenched by adding 400 ml of NH C1
  • (5R)-5-[(lR/S)-l-Hydroxy-l-methyl-decyl]-2-methyl-cyclohex-2-enone Prepared in accordance with the same procedure as (5R)-5-[(lR/S)-l-Hydroxy-l-methyl-hexyl]-2-methyl-cyclohex-2-enone, described above. It was distilled using bulb to bulb distillation, 220 °C (heating chamber)/0.4 mbar. This provided the diastereomers ( ⁇ 1:1 mixture) as a weakly yelow syrup.
  • Method B 1 mol of a suitable aromathic aldehyde dissolved in 200 ml of ethanol (95%). 1.25 mol NaOH or KOH dissolved in 250 ml of ethanol and 250 ml of H 2 O were charged to the solution. The solution was cooled -10 °C and 1.4 mol propanal or acetaldehyde, alternatively, were charged slowly at room temperature, during the charging the temperature was never allowed to exceed 20 °C. The solution was allowed to stand at room temperature. The reaction was disrupted by neutralizing the reaction mixture using -200 ml 6 M of HCl and was extracted twice using ether, the organic phases were washed with NaHCO 3s H 2 O and finally with saturated salt solution and was dried using MgSO 4 . The resulting oil or crystals, alternatively, after filtration, was purified by means of distillation and/or chromatography or recrystallization, alternatively.
  • CE8 3-(2-Methoxyphenyl)-propanal-2-ene Prepared in accordance with method B using 2- methoxybensaldehyde, NaOH and distilled acetaldehyde. The reaction was disrupted 1 hr after finishing the charging o the acetaldehyde. Crystals having 96% GC-purity were obtained after distillation and MPLC chromatography using ether/pentane (1:9), bp 101 °C/0.5 mbar (litt. 128-130 °C/0.6 mmHg) 4 , mp 43-46 °C (litt. 45-46 °C) 5 .

Abstract

The present invention relates to a Composition containing a gnawing inhibiting compound and intended to be applied on conifer saplings, in particular pine saplings, to prevent weevil to attack the young stem, wherein the gnawing inhibiting compound is present in a bound form to a substance of the group of zeolites, cyclodextrines, homogenous porous microspheres, spherical vesicles, hollow fibres, such as textile fibres (wool) capillaries of synthetic material (polymers), starch, and polymer films, optionally in combination with a carrier, whereby the gnawing inhibiting compound is present in an amount of 1 to 10 % by weight, as well as gnawing inhibiting compounds.

Description

TITLE
COMPOSITION FOR INHIBITING FEEDING OF WEEVILS .
DESCRIPTION Technical field
The present invention relates to a composition comprising a gnawing inhibiting compound intended to be applied on conifer saplings, in particulr pine saplings in order to prevent pine weevil to attach the young stem, as well as gnawing inhibiting compounds.
The object ofthe present invention is to obtain a composition intended to be applied on conifer saplings in order to prevent damages caused by gnawing on the young plant stem caused by pine weevil (Hylobius abietis).
Background ofthe invention The pine weevil is the pest insect causing the most serious damages in Swedish forestry. Witliout any treatment ofthe newly planted pine and spruce saplings up to 80% of these young saplings can become killed by the weevil gnawing for feeding itself on the cortex. An estimated yearly cost of these damages is 0.5 to 2 billion Swedish Crowns only in Sweden depending on the amount and the concentration of weevils.
Today the saplings are protected using permethrin, a pyrethroid which is allowed for use on exemption up to 1999, inclusive, for different types of plants. Permethrin prevents the weevil to gnaw the cortex ofthe saplings. Permethrin is, however, an environmental poisson having a high toxicity to aquatic organisms.
Normally, insects prefer to feed on one or a few plant species. The selection is often controlled by scent and taste substances. The positive ones, i.e. those that tempt gnawing are called stimulants, the negative ones, i.e. those that deter from gnawing are called "antifeedants". The weevil is polyphag, i.e. it can feed on a number of plants species on a clearing but prefer conifer cortex. If one could direct the weevil away from the conifers large amounts of or large concentrations of weevil will not play any essential role.
The weevil is an insect living on the soil surface where it looks for feed gnaw. Normally, it does not climb the young saplings but gnawing takes place within the area, which the weevil reaches on the stem - and around the same - from the soil surface.
Another way of inhibiting the gnawing is to treat the plants using a wax. This means a mere mechanical protection. However, the wax is difficult to apply as it is required that the wax is liquid which leads to increased temperatures which in turn can be a risk to the young saplings..
Other mechanical protections, which have been proposed, are latex and different types of casings or tubes of polymers. All mechanical protections, however, suffer from the drawback that they require a complicated application and are connected with high costs.
In a number of plant-insect systems specific gnawing inhibitors have been described as an indispensable part ofthe natural defence provided by the plant. The most well known example is the tree Azadiractica indica, which was early known as active against many insects. More variants are available today and an extract ofthe seed capsules ofthe tree ("neem oil") is used in green houses. Neem oil is, however, not equally active against all insects and has turned out to have a limited effect against Hylobius abietis and H. pales.
Anti gnawing agents have been proposed in order to prevent or inhibit the feed gnaw by weevils. The desire is hereby that the protection to the conifer saplings shall rest at least two seasons, until the young sapling has obtained a cortex thick enough to stand an attack. The requirements on such anti gnawing agents are that they shall be low volatile, have a high stability at temperatures of up to 70oC and to UN-light as well as have a low toxicity to humans and animals.
A model compound which has been tested is carvon, which has turned out to be efficient against the weevil by inhibiting the feed gnaw. It has, however, turned out that the gnawing inhibiting effect is of short duration if the compound is brushed directly onto he sapling. The reason is that carvone is volatile at low temperatures and thus evaporates away from the saplings treated
Thus a problem exists to solve, viz. to obtain gnawing inhibiting compounds and then not only carvone, to remain on a treated saplings during two or more growing seasons and thereby stand climate strains such as precipitation, cold, heat and sun light (UN -light).
Description ofthe present invention
It has now turned out possible to be able to solve this problem by means ofthe present invention which is characterized in that the gnawing inhibiting compound is present in a bound form to a substance of the group of zeolites, cyclodextrines, homogenous porous microspheres, spherical vesicles, hollow fibres, such as textile fibres (wool) capillaries of synthetic material (polymers), starch, and polymer films, optionally in combination with a carrier and/or adhering agent, whereby the gnawing inhibiting compound is present in an amount of 1 to 10 % by weight.
Further characteristics are evident from the accompanying claims.
By means of the present invention it is obtained that the gnawing inhibiting compound can be efficiently bound to the young sapling for a considerable time, such as two to three seasons. This means that the antagonistic compound, a gnawing inhibitor, is enclosed more or less in a tight casing.
With bound form is meant above, that the active compound is physically bound to the polymer or another substance according to the group above, either by a binding in or by inclusion. At zeolites the active compound is absorbed in to the zeolite skeleton, at cyclodextrine the active compound is bound or enclosed at a molecular level, at homogenous porous microspheres the active compound is present enclosed in a polymer casing (example of such microspheres is Dynospheres T-12). Dynospheres are compact particles manufactured of 98% of polystyrene, and 2% of divinyl benzene as a cross-linking agent and having a density of 1.05 g/cm3. At vesicles the active compound is enclosed in a casing. Spherical vesicles can consist of spherical polymer particles , whereby the microspheres consist of a polymer shell which encloses a gas which gas at heating allows the polymer shell to expand more than 40 times and thereby allows enclosure of liquid or solid compound. Phospholipid vesicles can also be suitable as carrier ofthe active compound whereby the vesicles being filled with active compound are slurried in an aqueous phase such as a suspension provided with latex, where the latex has a binding capability to the treated sapling. In the actual microspheres or vesicles the amount of active compound is very high and can be up to 90% by weight, more commonly up to 50 % by weight. In a formulation ready-to-use in composition being sprayable or brushable the active compound is normally 1 to 10 % by weight, but can reach 10 to 20 % by weight.
Test carried out shows that a micro-encapsulation having a diameter of 200 μ is eaten by the weevil and can pass the gastro-intestinal tract.
At use the composition is slurried in an aqueous medium ad is sprayed onto the saplings, alternatively the saplings can be dipped in such a slurry. Normally it is preferred spraying ofthe parts ofthe stem subject to the attack ofthe weevil in order to minimise the amount of foreign material on the plant, and to minimise the amount of active compound and binding polymer from a cost and environmental point of view.
The aqueous medium may suitably be provided with a latex emulsion, which has a binding ability to the stems ofthe young saplings in such a way that the active compound in its combination remains on the stem.
The active compound can also be oil bound such as bound in linseed oil, in particular raw linseed oil, which hardens or also in so called boiled linseed oil.
The antagonistic compound can also be incorporated in a polymer laminate which is wound around the conifer sapling, whereby, when the weevil bites through the outermost film meets the antagonistic compound and is restrained from further gnawing attempts in the area of the first bite. Encapsulation of active compound can thereby be carried out in simple way by having a layer ofthe laminate being provided with the active compound whereupon a second covering layer is added to the first layer and is adhered or heat sealed thereto. One ofthe layers can thereby have an adhering layer for the adhesion to a substrate such as the actual conifer sapling.
With active compound is meant herein every gnawing inhibiting compound that inhibits the feed gnaw ofthe weevil. The present invention further relates to active, gnawing inhibiting compounds according to the set up below comprising three different basic structures.
Compound type I
0-3
Figure imgf000008_0001
Figure imgf000008_0005
Compound type II = H or alkyl
Figure imgf000008_0002
R2 can e
Figure imgf000008_0003
ach independently be methoxy and/or two R2 groups X = O, S, or R3 in neighbouring positions can be R3 = either methyl, ethyl, isopropyl together methylene dioxy. The n and/or butyl localized substituents can be localized in in positions 1, 2 and/or 3 positions 1, 2, 3, and/or 4 m = 1, 2 or 3 n= 1, 2, 3, and/or 4
Compound type III
X can be OH or CHO
Figure imgf000008_0004
Compound type I
Examples:
Figure imgf000009_0001
Cn-epox DHCnOH
Figure imgf000009_0002
Figure imgf000009_0003
Compound type II
Examples:
Figure imgf000010_0001
Figure imgf000010_0002
CE11 CE14
Figure imgf000010_0003
Figure imgf000010_0004
#40 #55 Compound type III
Examples:
Figure imgf000011_0001
#51 #18 (BHT) #3 #47
Figure imgf000011_0002
#19 Hq (Juglon) #8(BHA)
Figure imgf000011_0003
#22
Figure imgf000011_0004
B11
Figure imgf000011_0005
#14 #45 INDEX OF SUBSTANCES
Figure imgf000012_0001
Figure imgf000013_0001
*The commercial chemicals are bought from Aldrich. Denominations are their catalogue numbers from the 2000-2001 catalogue.
API in the table above has been determined in accordance with the following.
In order fulfil the need for testing small amounts of synthetic compounds and extracts a micro feeding test was developed. Alternative substrates for testing of gnawing inhibiting compounds with regard to weevil, Hylobius abietis, was searched for, as host plant - twigtest consumes too large amounts of compound for routine testing of series of synthetic compounds or extracts or their fractions. Furthermore, the twig cortex consumption a long time for exposure and determination. A simple set-up consisting of 5 x 5 mm pieces of thin layer chromatography plates was made. They were used in pair for the choice of biotest, attached to a strip of double adhesive tape in a 9 cm Petri dish. After application of 1.5 μl of 10 % solutions and evaporation ofthe solvent, each plate obtained a 5 μl amount of 1 M of succrose in water as feeding stimulant. A 1 day starvation which is enough for the twig test replaced a 6-7 days of starvation which gave a significant death prior to or after the test. The test period is 4 hrs, the plates and the animals were kept at +25°C, 65% RH, 2000 lux and 20:4 light: dark cycle. The correlation of biological non-eating activity with that ofthe twig test was excellent, which shows a good accuracy.
For a simple comparison between different types of feeding tests, AntiFeedantlndex, AFI, was used:
Amount fed at Control - Amount fed at Treatment
AFI =
Amount fed at Control + Amount fed at Treatment
An API = 1 indicates a total protection against feeding (feed intake) (maximal anti-gnaw effect), an AFI = 0 is no effect, while an API = -1 indicates perfect feed stimulation (i.e., gnawing).
EXPERIMENTALPART - SYNTHESIS
Commercially available chemicals have been used as delivered. Dry Et2O was obtained by distillation from LiAlH4 under argon atmosphere. Dry THF was obtained by distillation from a blue solution of K and bensophenone under an argon atmosphere. Preparative liquid chromatography (MPLC) aims at "straight-phase" chromatography on SiO2 (230-400 mesh). Boiling points have not been corrected. !H och 13C NMR spectra derive from a Brulcer Avance 250 instrument having 25 °C testtemperature,
CDCI3 as solvent and TMS as internal reference. FT-IR spectra was obtained using a Perkin Elmer 16 PC instrument. Mass spektrometry derives from a Varian 3800 GC connected to a Varian 2000 MS (ion trap detector) in El or CI (CH3CN as chemical ionization gas) mode. COMPOUND TYPE I
Figure imgf000015_0001
DHCnOH
(5R)-(l-Hydroxy-l-methyl-ethyl)-2-methyl-cyclohex-2-enone. Prepared in accordance with the method described by: Bϋchi, G.; Wϋest, H. J Org. Chem. 1979, 44, 546. Purified by means of bulb to bulb distillation, 155-160 °C (heating chamber)/0.3 mbar. Complementary data: lR NMR (250.13 MHz) δ 6.78 (m, 1 H), 2.62 (m, 1 H), 2.46 (m, 1 H), 1.97-2.32 (m, 3 H), 1.77 (m, 3 H), 1.24 (s, 3 H), 1.22 (s, 3 H); 13C NMR (62.9 MHz): δ 200.5, 145.4, 135.1, 71.5, 46.1, 39.6, 27.3, 27.2, 27.0, 15.6; MS in accordance with: An, J.; Bagnell, L.; Cablewski, T.; Strauss, C.R.; Trainor, R.W. J.Org.Chem. 1997, 62, 2505.
Figure imgf000015_0002
Cn-epox
(5R)-2-Methyl-5-[(lR/S)-l-methyl-oxiranyl]-cyclohex-2-enone. Prepared in accordance with the method described by: Baldwin, j. E.; Broline, B. J. Am. Chem. Soc. 1982, 104, 2865. Purified by means of distillation, bp 87-90 °C/0.7 mbar. Isomer mixture was carried over to the next step without separation. Complementary data: IR (undiluted, KBr) 2975, 2925, 1675, 1450, 1435, 1385, 1365, 1110 cm"1; l3C NMR (62.9 MHz) δ 198.9, 198.8, 144.1, 143.9, 135.7, 135.6, 58.0, 57.9, 53.0, 52.4, 41.4, 40.8, 40.4, 40.0, 27.9, 27.8, 19.1, 18.4, 15.7; MS (CI) m/z (rel. int.) 167 (M + H , 10), 149 (40), 109 (100).
Figure imgf000016_0001
DHCnOH
(lR/S,5R)-2-Methyl-5-[(lR/S)-l-methyl-oxiranyl]-cyclohex-2-enol. 3.11 g (18.7 mmol) ofthe epoxide (prepared as described above) were stirred into 25 ml MeOH and were then added (little by little) with an excess of NaBH4 under a 10 min period. The mixture was stirred for 2hrs at room temperature and was then added with 20 ml of ice water and 15 ml of 0.2 N HC1 (aq) and was extracted using 10 x 10 ml Et2O. The organic phase was dried using MgSO , evaporated, and purified (MPLC chromatography, 75 g SiO2 with EtOAc/c-hexane as eluent) which gave 2.67 g (85%) ofthe isomers ofthe title as a weakly yellowish syrup (mixture of diastereomers). The isomer mixture was carried to the next step without further separation. 1H NMR (250.13 MHz, main isomers) δ 5.45 (m, 1 H), 4.16 (m, 1 H), 2.52-2.70 (m, 2 H), 1.87-2.25 (m, 2 H), 1.74 (m, 3 H), 1.28 (2 x s, 2 x 3 H); 13C NMR (62.9 MHz, main isomers) δ 136.9, 136.8, 123.0, 122.7, 70.3, 70.1, 59.0, 58.9, 53.3, 52.7, 39.9, 39.2, 35.2, 35.1, 27.8, 27.6, 19.0, 18.9, 18.6, 17.9; MS (CI, main isomer) m/z (rel. int.) 151 (15), 93 (100).
Figure imgf000016_0002
TrimethyI-[(lR/S,5R)-2-methyl-5-{(lR/S)-l-methyl-oxiranyl}-cyclohex-2-enyloxy]-silane. 1.87 g (11.1 mmol) ofthe epoxy-alcohol (prepared as described above) were stirred in 35 ml of DMF and were then provided with 2.25 g (22.3 mmol) Et3N. 2.0 g (18 mmol) of TMSC1 were then added whereupon the mixture was stirred for 3 hrs (room temperature). 50 ml of H2O were then added to the reaction mixture which was extracted using 3 x 50 ml of Et O, dried over Na2SO4 and evaporated. The resulting oil was purified using MPLC chromatography, 70 g of SiO2 and EtOAc/c-hexane as eluent, which provided 2.37 g (89%) ofthe above mentioned isomer as a weakly yellowish oil (diastereomer mixture). The mixture of isomers was brought to the next step without further separation. 1H NMR (250.13 MHz, main isomers) δ 5.45 (m, 1 H), 4.19 (m, 1 H), 2.52-2.66 (m, 2 H), 1.85-2.14 (m, 2 H), 1.65 (s, br, 3 H), 1.27 (s, 3 H), 1.26, (s, 3 H), 0.15 (s, 9 H), 0.14 (s, 9 H); 13C NMR (62.9 MHz, main isomers) δ 137.0, 136.9, 123.0, 122.7, 70.9, 70.7, 58.8, 58.7, 53.6, 52.6, 40.3, 39.3, 35.5, 35.3, 27.8, 27.7, 26.9, 19.5, 19.4, 18.6, 17.5, 0.3 (2Cs); MS (CI, mainly isomer) m/z (rel. int.) 241 (M + H", 5), 223 (5), 183 (20), 151 (50), 93 (100).
Figure imgf000017_0001
Trimethyl-[(lR/S,5R)-2-methyl-5-{(lR/S)-l-hydroxy-l-methyl-hexyI}-cyclohex-2-enyloxy]-silane.
0.34 g (1.8 mmol) of Cul in a dry round flask (argon atmosphere) were provided with 5 ml of dry THF, whereupon the stirred mixture was cooled to -72 °C (bath temp.). 12 ml of 1.6 M rc-BuLi (19 mmol) were added dropwise to the flask for a 5 min period. After 5 rnin 3.45 g (14.4 mmol) ofthe silylether- epoxide (preparared as described above) were added to the solution whereupon the mixture was allowed to reach 0 °C in 2.5 hrs. The reaction mixture was quenched by adding 20 ml of NH C1 (saturated, aq), 80 ml H2O were added and was extracted using 3 x 100 ml of Et2O. The organic phases were combined, washed sequentially using 75 ml of H2O, 75 ml of saturated sodium chloride solution , dried using Na SO4 and was evaporated which provided 3.59 g of a weakly yellow oil which was brought to the next step without further purification. !H NMR (250.13 MHz, raw product, main isomers) δ 5.50 (m, 1 H), 4.21 ( , 1 H), 1.85-2.02 (m, 2 H), 1.69 (s, br, 3 H), 1.20-1.58 (m, 10 H), 1.16, (s, 3 H), 1.12 (s, 3 H), 0.89-0.99 (m, 4 H), 0.18 (s, 9 H); 13C NMR (62.9 MHz, raw product, main isomers) δ 136.6, 136.3, 123.8, 123.6, 73.8, 73.7, 71.4, 42.3, 41.7, 40.3, 39.3, 34.4, 33.8, 32.5 (2Cs), 27.1, 26.2, 24.3, 23.4, 23.2, 22.9, 22.7 (2Cs), 19.5 (2Cs), 14.1 (2Cs), 0.3 (2Cs); MS (El, main isomer) m/z (rel. int.) 298 (M , 5), 280 (30), 209 (50), 181 (100), 137 (35).
Figure imgf000018_0001
Trimethyl-[(lR/S,5R)-2-methyI-5-{(lR/S)-l-hydroxy-l-methyI-decyI}-cyclohex-2-enyloxy]-silane.
A dry round flask (argon atmosphere) comtaining activated chips of magnesium was provided with 31 ml of dry Et2O. To this stirred mixture 15 g (78 mmol) of n-octyl bromide (dried K2CO3, distilled prior to use) were added dropvwise simultaneously with refluxing the mixture gently. The Grignard reagens formed was then added dropwise to another round flask (argon atmosphere) containing a stirred solution of 1.1 g (5.8 mmol) of Cul in 77 ml of dry THF at -30 °C followed by addition of 10 g (42 mmol) the silylether-epoxide (prepared as described above). The resulting mixture was allowed to reach room temperature during 15 hrs stirring and was quenched by adding 400 ml of NH C1
(saturated, aq), 800 ml of H2O were then added and extracted using 3 x 250ml of Et2O. The organic phases were combined, dried using Na2SO4 and evaporated which provided 15.3 g of a weakly yellow oil which was brought to the next step without further purification.
Figure imgf000018_0002
(lR/S,5R)-2-Methyl-5-[(lR/S)-l-hydroxy-l-methyl-hexyl]-cyclohex-2-enol. 3.59 g ofthe raw product (mono silylether protected diol prepared in accordance with above) were stirred in 60 ml of MeOH with 0.17 g (1.0 mmol) of TsOH at room temperature over night. After 15 hrs MeOH was evaporated and the resulting oil was purified using flash chromatography, 80 g SiO2 with EtOAc/c- hexane, 30%, as eluent, which provided 2.47 g (76% for tvδ. steg) of a diastereomer mixture as a thick oil. An analytical sample was distilled bulb to bulb, 200 °C (heating chamber)/0.85 mbar. The isomer mixture was brought to the next step without further separation. 1H NMR (250.13 MHz, main isomers) δ 5.49 (m, 1 H), 4.17 (m, 1 H), 1.88-2.26 ( , 3 H), 1.76 (s, br, 3 H), 1.20-1.55 (m, 10 H), 1.15 (s, 3 H), 1.12 (s, 3 H), 0.89 (t, 3 H, J= 7 Hz); 13C NMR (62.9 MHz, main isomers) δ 136.6, 136.4, 123.9, IS
123.7, 74.0, 79.9, 71.0, 42.0, 41.8, 40.2, 39.7, 34.3, 33.8, 32.5, 32.4, 27.0, 26.3, 24.3, 23.6, 23.3, 23.0, 22.7 (2Cs), 18.8, 14.1 (2Cs); MS (El, main isomer) m/z (rel. int.) 193 (10), 137 (55), 115 (35), 109 (45), 93 (90), 79 (100).
Figure imgf000019_0001
(lR/S,5R)-2-Methyl-5-[(lR/S)-l-hydroxy-l-methyl-decyl]-cyclohex-2-enol. Prepared using the same procedure as (lR/S,5R)-2-Methyl-5-[(lR/S)-l-hydroxy-l-mehtyl-hexyl]-cyclohex-2-enol, descibed above.
Figure imgf000019_0002
B2
(5R)-5-f(lR/S)-l-Hydroxy-l-methyl-hexyl]-2-methyl-cyclohex-2-enone. 1.1 g (4.9 mmol) ofthe diol (prepared as described above) were stirred in 10 ml of CH2C12 with 7.1 g (74 mmol) of MnO2 (90%, dried at 140 °C, stored in an exicator) 2.5 days at room temperature. This resulted in a not fully completed turnover. The mixture was then filtered through a celite cake, evaporated, and the resulkting oil was pvxrified using MPLC chromatography, 15 g of SiO2 with EtOAc/c-hexane as eluent, and was finally distilled using bulb to bulb distillation.175 °C (heating chamber)/0.6 mbar. This gave 0.52 g (47%) ofthe diastereomers (-1:1 mixture) as a weakly yellow syrup. IR (undiluted, KBr) 3465, 2935, 2870, 1660, 1450, 1370 cm'1; 1H NMR (250.13 MHz) δ 6.77 (m, 1 H), 2.57 (m, 1 H), 2.05-2.43 (m, 4 H), 1.78 (m, 3 H), 1.40-1.54 (m, 2 H), 1.20-1.40 (m, 6 H), 1.17 (s, 3 H), 1.16 (s, 3 H), 0.89 (t, 3 H, J= 7 Hz); 13C NMR (62.9 MHz) δ 200.5, 200.3, 145.4, 145.1, 135.2 (2Cs), 73.3 (2Cs), 44.0, 43.9, 40.2, 40.0, 39.5, 39.0, 32.4 (2Cs), 27.1, 26.7, 24.2, 24.1, 22.6 (2Cs), 15.6 (2Cs), 14.0 (2Cs); MS (El) m/z (rel. int.) 207 (5), 153 (10), 135 (10), 115 (40), 110 (100), 95 (70).
Figure imgf000020_0001
B34
(5R)-5-[(lR/S)-l-Hydroxy-l-methyl-decyl]-2-methyl-cyclohex-2-enone. Prepared in accordance with the same procedure as (5R)-5-[(lR/S)-l-Hydroxy-l-methyl-hexyl]-2-methyl-cyclohex-2-enone, described above. It was distilled using bulb to bulb distillation, 220 °C (heating chamber)/0.4 mbar. This provided the diastereomers (~1:1 mixture) as a weakly yelow syrup. IR (xmdiluted, KBr) 3470, 2925, 2855, 1665, 1455, 1370 cm"1; Η MR (250.13 MHz) δ 6.77 (m, 1 H), 2.56 (m, 1 H), 2.05-2.43 (m, 4 H), 1.77 (m, 3 H), 1.40-1.54 (m, 2 H), 1.18-1.38 (m, 16 H), 1.16 (s, 3 H), 1.15 (s, 3 H), 0.88 (t, 3 H, J= 7 Hz); 13C NMR (62.9 MHz) δ 200.6, 200.5, 145.6, 145.3, 135.1 (2Cs), 73.1 (2Cs), 44.1, 44.0, 40.2, 40.0, 39.5, 39.0, 31.9 (2Cs), 30.3 (2Cs), 29.6 (4Cs), 29.3 (2Cs), 27.2, 26.7, 24.1 (2Cs), 23.6 (2Cs), 22.7 (2Cs), 15.6 (2Cs), 14.1 (2Cs); MS (El) m/z (rel. int.) 264 (5), 171 (20), 153 (5), 135 (5), 110 (100), 95 (45).
COMPOUND TYPE II
Method A
1 mol of a suitable aromathic aldehyde was dissloved in 200 ml of ethanol (95%).1.4 mol of propanal were charged to the solution. The solution was cooled to -10 °C and 1.25 mol of NaOH or KOH, alternatively, dissolved in 250 ml of ethanol and 250 ml of H2O were charged slowly at room temperature, during charging the temperature was never allowed to exceed 20 °C. The solution was allowed to stand in room temperature. The reaction was disrupted by neutralizing the reaction mixture using -200 ml 6 M of HC1 and was extracted twice using ether, the organic phases were washed using NaHCO3, H2O and finally using a saturated salt solution and was dried using MgSO4. The resulting oil or crystals, alternatively, after filtration and roller evaporation was purified by means of distillation, chromatography or recrystallization, alternatively.
Method B 1 mol of a suitable aromathic aldehyde dissolved in 200 ml of ethanol (95%). 1.25 mol NaOH or KOH dissolved in 250 ml of ethanol and 250 ml of H2O were charged to the solution. The solution was cooled -10 °C and 1.4 mol propanal or acetaldehyde, alternatively, were charged slowly at room temperature, during the charging the temperature was never allowed to exceed 20 °C. The solution was allowed to stand at room temperature. The reaction was disrupted by neutralizing the reaction mixture using -200 ml 6 M of HCl and was extracted twice using ether, the organic phases were washed with NaHCO3s H2O and finally with saturated salt solution and was dried using MgSO4. The resulting oil or crystals, alternatively, after filtration, was purified by means of distillation and/or chromatography or recrystallization, alternatively.
,CHO w }
#40
2-Methyl-3-(-2-furanyl-5-methyl)-propanal-2-ene. Prepared in accordance with method A using 5- methylfuranal, NaOH and propanal. The reaction was disrupted after 2 hrs when the charging of 'NaOH was finished. An oil having 96% GC-purity was obtained after distillation, bp 111-113 °C/3-4 mmHg (litt. 118 °C/10 mHg)1. 1H NMR (250.13 MHz) δ 9.46 (s, 1 H), 6.96 (s, 1 H), 6.69 (d, 1 H, J = 3.1 Hz), 6.19 (d, 1 H, J= 3.1 Hz), 2.39 (s, 3 H), 2.09 (s, 3 H); MS (El) m/z (rel. int.) 150 (M+, 90), 135 (55), 121 (30), 77 (90).
Figure imgf000021_0001
#54
2-Methyl-3-(2-methoxyphenyl)-propanal-2-ene. Prepared in accordance with method A using 2- methoxybensaldehyde, NaOH and propanal. RThe reaction was disrupted after 5 hrs when the charging of NaOH was finished. An oil having 92% GC-purity was obtained after distillation, bp 94- 98 °C/0.3 mbar (litt. 128 °C/4.25 mmHg)2. 1H MR (250.13 MHz) δ 9.62 (s, 1 H), 7.60 (s, br, 1 H), 7.35-7.48 (m, 2 H), 6.94-7.04 (m, 2 H), 3.89 (s, 3 H), 2.02 (d, 3 H, J= 0.6 Hz); MS (El) m/z (rel. int.) 176 (M\ 25), 161 (10), 145 (100), 133 (15), 77 (20).
Figure imgf000022_0001
B5 alt. CE7
2-Methyl-3-(4-methoxyphenyl)-propanal-2-ene. Prepared in accordance with method B using 4- methoxybensaldehyde, NaOH and propanal. The reaction was disrupted after 1 hr when the charging of propanal was finished. An oil having 92 % GC-purity was obtained after distillation, bp 110-111 °C/0.6 mbar (litt. 101-102 °C/0.1 mmHg)3. IR (undiluted, KBr) 2840, 1675, 1620, 1515, 825 cm"1; 1H NMR (250.13 MHz) δ 9.59 (s, 1 H), 7.58 (m, 2 H), 7.24 (s, br, 1 H), 7.02 (m, 2 H), 3.92 (s, 3 H), 2.13 (d, 3 H, J=1.2 Hz); 13C NMR (62.9 MHz) δ 195.5, 160.7, 149.8, 136.2, 132.0, 128.0 (2Cs), 114.2 (2Cs), 55.4, 10.9; MS (El) m/z (rel. int.) 176 (M1-, 100), 161 (20), 145 (50), 133 (15), 108 (30), 78 (25).
Figure imgf000022_0002
CE8 3-(2-Methoxyphenyl)-propanal-2-ene. Prepared in accordance with method B using 2- methoxybensaldehyde, NaOH and distilled acetaldehyde. The reaction was disrupted 1 hr after finishing the charging o the acetaldehyde. Crystals having 96% GC-purity were obtained after distillation and MPLC chromatography using ether/pentane (1:9), bp 101 °C/0.5 mbar (litt. 128-130 °C/0.6 mmHg)4, mp 43-46 °C (litt. 45-46 °C)5. IR (KBr) 3000, 2840, 1675, 1485, 1465, 1135, 750 cm'1; 1H NMR (250.13 MHz) δ 9.69 (d, 1 H, J= 7.8 Hz), 7.84 (d, 1 H, J= 15.9 Hz), 7.56 (dd, 1 H, J-- 7.5, 1.3 Hz), 7.42 (m, 1 H), 6.99 (m, 2 H), 6.79 (dd, 1 H, J= 7.8, 15.9 Hz), 3.92 (s, 3 H); 13C NMR (62.9 MHz) δ 194.6, 158.3, 148.2, 132.7, 129.1, 128.9, 123.0, 120.9, 111.3, 55.6; MS (El) m/z (rel. int.) 162 ( T", 30), 147 (15), 131 (100), 119 (35), 77 (20).
Figure imgf000023_0001
CE10
2-Methyl-3~(3-methoxy phenyl)-propanal-2-ene. Prepared in accordance with method A using 3- methoxy bensaldehyde, NaOH and propanal. The reaction was disrupted 1 h after finishing the charging of NaOH. An oil having a 99% GC-purity was obtained after distillation and MPLC chromatography EtOAc/cyclohexane (1:4), bp 104-106 °C/0.6 mbar. IR (undiluted, KBr) 3000, 2960, 2835, 2715, 1685, 1595, 1575, 1380, 1170, 1160, 785 cm'1; 1HNMR (250.13 MHz) δ 9.59 (s, 1 H), 7.37 (m, 1 H), 7.25 (s, br, 1 H), 7.13 (d, 1 H, J= 7.5 Hz), 7.05 (m, 1 H), 6.95 (dd, 1 H, J= 8.1, 2.5 Hz), 3.85 (s, 3 H), 2.08 (d, 3 H, J= 1.2 Hz); 13C NMR (62.9 MHz) δ 195.6, 159.6, 149.7, 138.6, 136.4, 129.7, 122.5, 115.4, 115.1, 55.3, 11.0; MS (El) m/z (rel. int.) 176 (M1", 100), 159 (20), 145 (35), 133 (15), 77 (5).
Figure imgf000023_0002
CE11
2-Methyl-3-(2,4-dimethoxy phenyl)-propanal-2-ene. Prepared in accordance with method B using 2,4-dimethoxy bensaldehyde, KOH and propanal. The reaction was disrupted 29 hrs after finishing the charging ofthe propanal. To the oil obtained after working up the reaction cyclohexane was added and the solution was allowed to stand at 5 °C for 2 h, after which time crystals had been formed which were purified by means of recrystrallisation from EtOH to 95% GC-purity. mp 85-87 °C. 1H NMR (250.13 MHz) δ 9.57 (s, 1 H), 7.56 (s, br, 1 H), 7.48 (d, 1 H, J= 8.8 Hz), 6.56 (dd, 1 H, J= 8.8, 2.5 Hz), 6.50 (d, 1 H, J= 2.5 Hz), 3.88 (s, 3 H), 3.86 (s, 3 H), 2.03 (d, 3 H, J-1.2 Hz); 13C NMR (62.9 MHz) δ 195.9, 162.4, 159.3, 144.6, 136.2, 131.2, 117.2, 104.6, 98.3, 55.6, 55.5, 11.1; MS (El) m/z (rel. int.) 206 (M+, 100), 191 (5), 175 (40), 138 (30), 77 (10).
Figure imgf000024_0001
CE14
2-Methyl-3-(3,4-dimethoxy phenyl)-propanal-2-ene. Prepared in accordance with method B using - 3,4-Dimethoxy bensaldehyde, KOH and propanal. The reaction was disrupted after 18 hrs after the charging of propanal was finished. Crystals of >99% GC-purity were obtained after distillation and recrystallisation from EtOH, mp 56-58 °C (litt. 59°C)5. 1H NMR (250.13 MHz) δ 9.55 (s, 1 H), 7.19 (m, 2 H), 7.09 (d, 1 H, J= 1.9 Hz), 6.95 (d, 1 H, J= 8.8 Hz), 3.95 (s, 3 H), 3.93 (s, 3 H), 2.11 (d, 3 H, J = 1.2 Hz); 13C NMR (62.9 MHz) δ 195.4, 150.4, 150.1, 148.9, 136.4, 128.2, 124.1, 113.0, 111.1, 56.0 (2Cs), 11.0; MS (El) m/z (rel. int.) 206 (M+, 100), 191 (25), 175 (30), 163 (30), 147 (10), 107 (25), 91 (25), 77 (20).
References
1. Francke, W.; Reith, W. Liebigs Ann. Chem. 1979, 1.
2. Bogert, T.; Powell, G. Am. Perfumer, 1930, 25, 617. 3. Rustrneier, K.; Breitmeier, E. Angew. Chem. 1980, 92, 841. 4. Cignarella, G.; et al. J. Med. Chem. 1965, 8; 326.
5. Bertram; Kuersten, J. Prakt. Chem. 1985, 51; 316.
6. Dallacker, F.Glombitza, K-W., Lipp, M. Liebigs Ann. Chem. 1961, 24, 67.
COMPOUND TYPE m
Figure imgf000025_0001
#19
2,3-Dipropylhydroquinone. Prepared in accordance with the method described by: Hogberg, H. E. Ada Chem. Scand. 1972, 26, 2752.
Figure imgf000025_0002
#47
2-Propylhydroquinone. Prepared in accordance with the method described by: Cruickshahk, Robinson, J. Chem. Soc. 1938; 2064, 2070.

Claims

1. Composition containing a gnawing inhibiting compound and intended to be applied on conifer saplings, in particular pine saplings, to prevent weevil to attack the young stem, characterized in that the gnawing inhibiting compound is present in a bound form to a substance ofthe group of zeolites, cyclodextrines, homogenous porous microspheres, spherical vesicles, hollow fibres, such as textile fibres (wool) capillaries of synthetic material (polymers), starch, and polymer films, optionally in combination with a carrier, whereby the gnawing inhibiting compound is present in an amount of 1 to 10 % by weight.
2. Composition accrding to claim 1, characterized in that the active compound is presentin a bound form to one or more zeolites.
3. Composition accrding to claim 1, characterized in that the active compound is present in bound form to one or more cyclodextrines.
4. Composition accrding to claim 1, characterized in that the active compound is present in bound form to one or more homogenous porous microspheres.
5. Composition accrding to claim 1, characterized in that the active compound is present in bound form to one or more spherical veiscles.
6. Composition accrding to claim 1, characterized in that the active compound is present in bound form to one or more hollow fibres.
7. Composition accrding to claim 1, characterized in that the active compound is present in bound form to one or more starch derivatives.
8. Composition accrding to claim 1, characterized in that the active compound is present in bound form to one or more capillaries of synthetic material.
9. Composition accrding to claim 1, characterized in that the active compound is present in bound form to one or more polymer films of synthetic or natural origin.
10. Composition accrding to claims 4-9, characterized in that the active compound is up to 90 % by weight of homogenous microsphere or spherical vesicle.
11. Composition accrding to claims 2-3, characterized in that the active compound is up to 30 % by weight ofthe zeolite or cyclodextrine.
12. Composition according to one or more of claims 1-10, characterized in that the bound active compound is present in a composition having a carrier containing an emulsion of latex.
13. Composition according to one or more of claims 1-11, characterized in that the bound active compound is present in a composition having a carrier coontaining a wax.
14. Composition according to one or more of claims 1-10, characterized in that the bound active compound is present in a composition having a carrier containing linseed oil.
15. Composition accrding to claims 1-14, characterized in that the active, gnawing inhibiting compound is a compound ofthe general formulae I, II, and/or III, whereby the compound ofthe general formula I is a compound
Figure imgf000028_0001
wherein R1, R2 is -O- (epoxy); Rl is OH, OCH3, OC2H5, or OCO(CH2)nCH3, wherein n is 0-3; R2 is H or (CH2)nCH3, wherein n is 0-8, or
Figure imgf000028_0002
the compound ofthe general formula II is a compound
Figure imgf000028_0003
wherein R1 is H or alkyl, preferably alkyl having 1-4 carbon atoms, and Ar is
Figure imgf000028_0004
wherein R2 is methoxy and/or two R2 groups in neighbouring positions together may form a methylene dioxy, and wherein n can be localised to the positions 1, 2, 3, and/or 4, and wherein n 1, 2, 3, or 4; X is -O-, -S-, or NR3, wherein R3 is methyl, ethyl, isopropyl or butyl localized to the positions 1, 2, and/or 3, and whereby in is 1, 2, or 3;
the compound ofthe general formula III is a compound
Figure imgf000028_0005
-wherein X is OH or CHO; R1, R2. R3, R4, and R5 are the same or different and are H, methyl, ethyl, propyl, isopropyl, n-butyl, tert.-butyl, n-pentyl, allyl, 3,3-dimethylallyl, 1-propenyl, or the group -OR6, wherein R6 is H, methyl, ethyl, propyl and/or isopropyl, or R1 and R2 are a linking chain -CO-CH=CH-CO-, or R1 and R2, R2 and R3, R3 and R4, or R4 and R5 in pair carries each its oxygen which are linked with a methylene bridge (-O-CH2-O).
16. Composition according to claim 15, whereby the gnawing inhibting compound is one or more of
(5R)-( 1 -Hydroxy-1 -methyl-ethyl)-2-methyl-cyclohex-2-enone, 5R)-2-Methyl-5-[(lR/S)-l-methyl-oxiranyl]-cyclohex-2-enone, (li-/S,5R)-2-Methyl-5-[(lR/S)-l-methyl-oxiranyl]-cyclohex-2-enol3 Trimethyl-[(lR/S,5R)-2-methyl-5-{(lR/S)-l-methyl-oxiranyl}-cyclohex-2-enyloxy]-silane, Trimethyl-[( lR/S,5R)-2-methyl-5-{ (1R/S)- 1 -hydroxy- 1 -methyl .hexyl} -cyclohex-2-enyloxy]-silane, Trimethyl-[(lR/S,5R)-2-memyl-5-{(lR/S)-l-hyckoxy-l-me l-decyl}-cyclohex-2-enyloxy]-silane, (lRΛS',5R)-2-Methyl-5-[(lR/S)-l-hydroxy-l-methyl-hexyl]-cyclohex-2-enol, (lR/S,5R)-2-Methyl-5-[(lR/S)-l-hydroxy-l-methyl-decyl]-cyclohex-2-enol, (5R)-5 - [(IRIS)- 1 -Hydroxy- 1 -methyl-heχyl]-2-methyl-cyclohex-2-enone, (5R)-5-[(lR/S)- 1 -Hydroxy- 1 -methyl-decyl]-2-methyl-cyclohex-2-enone, 2-Methyl-3-(-2-furanyl-5-methyl)-propanal-2-ene, 2-Methyl-3-(-2-fiιranyl)-propanal-2-ene, 2-Methyl-3-(2-methoxyphenyl)-propanal-2-ene, 2-Methyl-3-(4-methoxyphenyl)-propanal-2-ene, 3-(2-Methoxyphenyl)-propanal-2-ene, 2-Methyl-3-(3-methoxyphenyl)-propanal-2-ene, 2-Methyl-3-(2,4-dimethoxyphenyl)-propanal-2-ene, 2,3-Dipropylhydroquinone, 2-Propylhydroqx-inone, 3-(2-hydroxi-3-methoxiphenyl)-prop- 1 -ene, 2-(2-hydroxi-5-methoxiphenyl)-2-methylpropane, 3,4-dimethoxyphenyl formaldehyde, 2-(2-hydroxi-3-tert.butyl-5-methylphenyl)-2-methylpropane, 3 -(3 -methoxy-4-hydroxyphenyl)-ρrop- 1 -ene, 2,3,5-trimethylhydroqxιinone, piperonal or 2-methoxyphenyl formaldehyde.
PCT/SE2001/001458 2000-06-26 2001-06-26 Composition for inhibiting feeding of weevils WO2002000022A1 (en)

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CN109020794A (en) * 2018-08-27 2018-12-18 上海华堇生物技术有限责任公司 The preparation method of 3- methoxycinnamic aldehyde
CN109180451A (en) * 2018-08-27 2019-01-11 上海华堇生物技术有限责任公司 The preparation method of 2,3- dimethoxycinnamaldehyde
CN113651682A (en) * 2021-09-23 2021-11-16 八叶草健康产业研究院(厦门)有限公司 Synthetic method of 2-methoxycinnamaldehyde

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CN109020794A (en) * 2018-08-27 2018-12-18 上海华堇生物技术有限责任公司 The preparation method of 3- methoxycinnamic aldehyde
CN109180451A (en) * 2018-08-27 2019-01-11 上海华堇生物技术有限责任公司 The preparation method of 2,3- dimethoxycinnamaldehyde
CN113651682A (en) * 2021-09-23 2021-11-16 八叶草健康产业研究院(厦门)有限公司 Synthetic method of 2-methoxycinnamaldehyde

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