WO2002015691A1 - Use for conifer sapling protection against insect attack - Google Patents
Use for conifer sapling protection against insect attack Download PDFInfo
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- WO2002015691A1 WO2002015691A1 PCT/SE2001/001811 SE0101811W WO0215691A1 WO 2002015691 A1 WO2002015691 A1 WO 2002015691A1 SE 0101811 W SE0101811 W SE 0101811W WO 0215691 A1 WO0215691 A1 WO 0215691A1
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- Prior art keywords
- methyl
- hydrogen
- optionally
- propanoate
- hydroxy
- Prior art date
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- 0 *C(*C(*)C1=C(*)C(*)C(*)C(*)=C1*)C(O*)=O Chemical compound *C(*C(*)C1=C(*)C(*)C(*)C(*)=C1*)C(O*)=O 0.000 description 1
- HDTRQBZBZCEUDQ-UHFFFAOYSA-N CC(Cc1ccccc1)C(OC)=C Chemical compound CC(Cc1ccccc1)C(OC)=C HDTRQBZBZCEUDQ-UHFFFAOYSA-N 0.000 description 1
- XPRVBYSCJOFAFY-UHFFFAOYSA-N COC(C(C(c1ccccc1)Br)Br)=O Chemical compound COC(C(C(c1ccccc1)Br)Br)=O XPRVBYSCJOFAFY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/734—Ethers
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
-
- 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
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
Definitions
- the present invention relates to the use of at least one compound for conifer sapling protection against insect attack. It also relates to the use of a composition for conifer sapling protection against insect attack. Finally, it relates to a compound of formula (I)-
- the pine weevil is, therefore, one of the economically most important insects in Sweden.
- the species is known as a serious noxious insect in large parts of Europe and Asia. In North America there are some closely related species with a similar way of living (Hylobius pales, Hylobius congener, ⁇ Pachylobius picivorus).
- the present invention relates to the use of certain cinnamate and/or phenylpropanoate derivatives for conifer sapling protection against insect attack. It also relates to the use of a composition for conifer sapling protection against insect attack. Finally, it relates to a compound of formula (I).
- One object of the present invention is the use of at least one compound for conifer sapling protection against insect attack, wherein the insect species belong to the beetle (Coleoptera) family Curculionidae (including subfamilies Curculioninae and Scolyti- nae), particularly species of the genera Hylobius, Pachylobius and Hylastes, specifically the species Hylobius abietis, Hylobius pinastri, Hylobius pales, Hylobius congener, Pachylobius picivorus, Hylastes brunneus and Hylastes cunicularius, character- ised in that the compounds are selected from the following compounds with formula I:
- R-i, R.2, R 3 , R 4 , and R 5 each independently stand for
- Ci-Ce-alkyl group - a Ci-Ce-alkyl group; - a C 2 -C 6 -alkenyl group;
- - halogen preferably bromo
- R ⁇ 5 and R 7 each independently stand for - methylene
- Ci-C 6 -alkyl group preferably methyl, and optionally one hydrogen
- Ci-C 6 -alkyl group preferably methyl, ethyl, n-propyl, isopropyl, 1-butyl or 2- butyl; - a C 2 -C 6 -alkenyl group;
- ⁇ stands for a single or a double carbon-carbon bond; as well as esters and salts thereof.
- Another object of the present invention is the use of a composition for conifer sapling protection against insect attack, wherein the insect species belong to the beetle (Cole- optera) family Curculionidae (including subfamilies Curculioninae and Scolytinae). particularly species of the genera Hylobius, Pachylobius and Hylastes, specifically the species Hylobius abietis, Hylobius pinastri, Hylobius pales, Hylobius congener, Pachylobius picivorus, Hylastes brunneus Bind Hylastes cunicularius, characterised in that it comprises at least one of the following compounds with Formula I:
- Ri, R 2 , R 3 , R4, R5. R5. R7. Rs. a d ⁇ are as defined above, pure or in a solvent, with or without a suitable carrier such as wood, cellulose, wood-flour, straw, cork, cane, lignin, lignocellulose, rubber, gum, leather or skin, milled carbon, fats or waxes of animal, vegetable, or synthetic origin, natural resins of animal or vegetable origin, plastic, organic polymers such as polyvinyl acetate, polyacrylates, polyvinyl chloride, chlorinated polyethylene, polyols such as polyethylene glycol, synthetic or natural latexes, silicone polymers or resins, silicates, pumice, silica, or any mixture thereof.
- a suitable carrier such as wood, cellulose, wood-flour, straw, cork, cane, lignin, lignocellulose, rubber, gum, leather or skin, milled carbon, fats or waxes of animal, vegetable, or synthetic
- Preferred compounds are those of Formula I with the exception of methyl 3',4'- dimethoxycinnamate.
- Another object of the invention is a compound of Formula I, wherein R 3 is methoxy; Ri, R 2 , R4, and R 5 are hydrogen; R ⁇ and R 7 are both two hydrogens; and R 8 is isopro- pyl.
- a suitable solvent is selected from the group consisting of Ci-C ⁇ -alkohols and C ⁇ -C 6 - alkyl esters of a C ⁇ -C 6 -alkanoic acid, preferably methyl acetate and methanol.
- Ci-C ⁇ -a-kyl refers to a saturated, straight or branched chained alkyl radical containing from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, 1 -butyl, 2-butyl, t-butyl, n-pentyl, n-hexyl, etc;
- any alkyl containing 1, 2, 3, 4, 5, or 6 carbon atoms could be used.
- C ⁇ -C 6 -alky ⁇ all subgroups thereof are contemplated such as C ⁇ -C 5 -alkyl, CrC 4 -alkyl, -Cs-alkyl, C r C 2 -alkyL C 2 -C 6 -alkyl, C 3 -C 6 -alkyl, C 2 -C 5 - alkyl etc;
- C 2 -C 6 - lkenyl refers to an unsaturated, straight or branched chained alkenyl radical containing from 2 to 6 carbon atoms, such as vinyl, 1- ⁇ ropenyl, 2- propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, etc;
- any alkyl containing 2, 3, 4, 5, or 6 carbon atoms could be used.
- C 2 -C 6 -alkenyl For parts of the range "C 2 -C 6 -alkenyl" all subgroups thereof are contemplated such as C 2 -C 5 -alkenyl, C 2 -C 4 -alkenyl, C 2 -C 3 -alkenyl, C 2 -C 6 -alkenyl, C 3 -C 6 -alkenyl, C 4 -
- CrC ⁇ -alkoxy For parts of the range "CrC ⁇ -alkoxy" all subgroups thereof are contemplated such as C ⁇ -C 5 -alkoxy, C ⁇ -C 4 -alkoxy, C ⁇ -C 3 -alkoxy, C 1 -C 2 -alkoxy, C2-C 6 -alkoxy, C 3 -C 6 - alkoxy, QrCs-alkoxy etc; d) the term “C 2 -C 6 -alkenoxy” refers to an unsaturated, straight or branched chained alkenoxy radical containing from 2 to 6 carbon atoms, such as vinyloxy, 1- propenoxy, 2-propenoxy, 1-butenoxy, 1-pentenoxy, 1-hexenoxy, etc; Thus, any alkyl containing 2, 3, 4, 5, or 6 carbon atoms could be used.
- C 2 -C 6 -alkenoxy For parts of the range "C 2 -C 6 -alkenoxy" all subgroups thereof are contemplated such as C 2 -C 5 -alkenoxy, C 2 -C 4 -alkenoxy, C 2 -C 3 -alkenoxy, C 2 -C 6 -alkenoxy, C 3 -C 6 - alkenoxy, C 4 -C 5 -alkenoxy etc; e) the term “C ⁇ -C 6 -alcohol” refers to a saturated, straight or branched alkyl alkohol and containing 1-6 carbon atoms, such as methanol, ethanol, n-propanol, isopropa- nol, n-butanol, tert-butanol, n-pentanol, n-hexanol, etc; and f) the term "C ⁇ -C 6 -alkyl ester of a Ci-C 6 -alkanoic acid
- esters and salts of the compounds according to the invention are included within the scope of the invention.
- esters of the compounds are intended e.g. methyl, ethyl, n-propyl, isopropyl, 1-butyl, tert-butyl and n- pentyl esters.
- salts of the compounds are intended in particular environmentally acceptable acid and base addition salts.
- environmentally acceptable acid addition salts are intended to be any non-toxic organic or inorganic acid addition salt of the base compounds with the formula I.
- suitable inorganic acids hydrochloric acid, hydrobromic acid, sulphuric acid, phosphoric acid and acid metal salts such as sodium monohydrogen ortophosphate and potassium hydrogensulphate.
- illustrative organic acids that form suitable salts are mono-, di- and rricarboxylic acids.
- acids examples include acetic acid, glycolic acid, lactic acid, pyruvic acid, malonic acid, succinic acid, glutaric acid, fumaric acid, malic acid, tartaric acid, citric acid, ascorbic acid, maleic acid, hydroxymaleic acid, benzoic acid, hydroxybenzoic acid, phenylacetic acid, cinnamic acid, salicylic acid, 2-phenoxybenzoic acid, and sulphonic acids such as p-toluenesulphonic acid, methanesulphonic acid and 2-hydroxyethane- sulphonic acid.
- Such salts could either be in hydrated or anhydrous form.
- the acid addition salts of these compounds are generally water soluble and different hydrophilic organic solvents and, that compared to the free base forms thereof, generally display higher melting points.
- the expression "environmentally acceptable base salts" are intended to be any non- toxic organic or inorganic base addition salt of the base compounds with the formula I.
- illustrative inorganic bases that form suitable salts are alkali and earth alkali metal hydroxides and carbonates such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, calcium hydroxide, calcium carbonate, magnesium hydroxide, magnesium carbonate and ammonia.
- Examples of illustrative organic bases that form suitable salts are methylamine, dimethylamine, trimethylamine and picoline. Either mono- or dibasic salts could be formed with such compounds.
- the base addition salts of these compounds are generally water soluble and different hy- drophilic organic solvents and, that compared to the free base forms thereof, generally display higher melting points.
- Methyl ⁇ -m ethyl -3-phenyl14 Methyl ⁇ , ⁇ -dibromo-3-phenyl- propanoate (Methyl 2-methyl-3- propanoate (Methyl 2,3-dibromo- phenylpropanoate) 3 -phenylpropanoate)
- Compound No. 1 could be purchased from Aldrich, Sigma-Aldrich Sweden AB, Sol- kraftsvagen 14C, 135 70 Sweden with catalogue No. 11,237-2.
- Compound No. 10 could be purchased from Lancaster, Lancaster Synthesis Ltd., Newgate, White Lund, Morecambe, Lancashire LA3 3DY, UK with catalogue No. 5310.
- Table 1 is given CAS numbers for compounds No. 2-9, 11-17, and 19-21. CAS numbers marked with an asterisk (*) are those preferred by Beilstein.
- Compound No. 18 could be prepared as follows:
- insects used for the experiments was the pine weevil (Hylobius abietis) taken from then natural environment, i e coniferous forests.
- compositions are prepared by incorporating the compounds in a suitable matrix.
- a solvent is used to transfer the compounds into the matrix.
- a 50 mM solution in methyl acetate was applied on the pine bark, except for compound No. 12, wherein a 50 mM solution in methanol were used.
- compound No. 11 both solutions were used.
- Example 1 Test of gnawmg-inhibiting effect of substances applied on pine bark.
- This treatment was compared with seedlings similarly treated with the same methanol/AGS mixture without the active substance and also with untreated seedlings.
- a randomised block design was used with each of the 80 blocks containing one seedling of each of the three treatments. The distance between seedlings within a block was about 0.5 m and the dis- tance between blocks about 2 m.
- the seedlings were planted on a fresh clear-cutting 13 kmNNE Uppsala, Sweden, on 11 June 1999. The amount of pine weevil feeding was recorded for each seedling after 19 and 36 days.
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Abstract
The present invention relates to the use of at least one compound of formula (I) for conifer sapling protection agains insect attack. It also relates to the use of a composition for conifer sapling protection against insect attack. Finally, it relates to a compound of formula (I).
Description
Use for conifer sapling protection against insect attack
The present invention relates to the use of at least one compound for conifer sapling protection against insect attack. It also relates to the use of a composition for conifer sapling protection against insect attack. Finally, it relates to a compound of formula (I)-
Background of the invention
The pine weevil, Hylobius abietis, kills through its gnawing on the bark a large proportion of the conifer saplings that are planted after felling. The damage costs Swedish forestry hundreds of millions Swedish crowns yearly (Weslien 1998). The pine weevil is, therefore, one of the economically most important insects in Sweden. The species is known as a serious noxious insect in large parts of Europe and Asia. In North America there are some closely related species with a similar way of living (Hylobius pales, Hylobius congener, ά Pachylobius picivorus).
The damage by the pine weevil could to a certain degree be reduced by a fallow period, soil scarification and regeneration beneath shelterwood trees. The fallow period should be avoided because of production loss and problems with competing vegetation. Soil scarification and regeneration beneath shelterwood are silvicultural methods that currently are further developed, and that in many areas could be included as a part of the management of the pine weevil problem (Orlander & Nordlander 1998). However, further protection of the saplings is needed in most places. Different ways of me- chanical protection are presently tested but there is not yet any method really working in practice (Orlander & Petersson 1998).
Since a long time, the pine weevil problem has mainly been managed by immersion or spraying the saplings with a relatively persistent insecticide (Langstrom 1998). At pre- sent, the synthetic pyrethroid permetiirin is allowed for this purpose in Sweden. However, the Swedish National Chemicals Inspectorate has the intention to prohibit this
treatment of saplings after the year 2004 because of environmental reasons. Possibly the other Nordic countries will also follow this example. Therefore, it is very urgent to find alternatives to protection treatment with insecticides.
Some alternatives to insecticides have been described in the literature such as insect repellents and the use thereof. For example, Viktorov-Nabokov (1980) describes methyl-4-hydroxybenzoate as a blood sucking mosquito repellent. SE 7709013-2 describes the use of a composition comprising halogen substituted phenols and phenol ethers designed for conifer sapling protection against noxious insects. No publications describe the use of the compounds according to the invention for conifer sapling protection against insect attack, wherein the insect species belong to the beetle (Coleop- tera) family Curculionidae.
There is strong evidence that plants have evolved defense systems against herbivores and pathogenes, and that these systems to a large extent are based on the production of secondary metabolites (Rosenthal 1986, Harborne 1988 and references cited therein, Sunnerheim-Sjδberg, 1991, Daurade-Le Vaguresse et al. 1992, Suga et al. 1993). Even high priority food plants produce defense compounds against herbivores - otherwise the plant would risk to be overbxowsed. So, although the polyphagous pine weevil pre- fers pines to a multitude of other plant species (Eidmann 1974), pines can be expected to contain antifeedants against pine weevils. However, different species of pines and different parts of a pine tree may contain varying amounts of defense compounds.
Comparative tests have shown that pine weevils feed less on bark from Lodgepole pine, Pinus contorta L, than on bark from Scots pine, P. sylvestris Dougl., and this result promoted us to look for compounds possessing antifeedant activity derived from P. contorta. Scots pine is the most abundant pine in Sweden, while Lodgepole pine has been introduced from North America and planted on large areas in northern Sweden. Bioassays of fractionated extracts of Lodgepole pine bark showed strong gnawing- inhibitory effect for a fraction containing mainly compounds no. 1 and 15. Further bioassays showed that these compounds, as well as several similar substances, have a
significant gnawmg-inhibiting effect. The toxicity of these substances is low. The risk of resistance development towards the substances is insignificant due to the fact that saplings constitute a small part of the pine weevil diet (Nordlander 1998).
Summary of the invention
The present invention relates to the use of certain cinnamate and/or phenylpropanoate derivatives for conifer sapling protection against insect attack. It also relates to the use of a composition for conifer sapling protection against insect attack. Finally, it relates to a compound of formula (I).
Detailed description of the invention
One object of the present invention is the use of at least one compound for conifer sapling protection against insect attack, wherein the insect species belong to the beetle (Coleoptera) family Curculionidae (including subfamilies Curculioninae and Scolyti- nae), particularly species of the genera Hylobius, Pachylobius and Hylastes, specifically the species Hylobius abietis, Hylobius pinastri, Hylobius pales, Hylobius congener, Pachylobius picivorus, Hylastes brunneus and Hylastes cunicularius, character- ised in that the compounds are selected from the following compounds with formula I:
Formula I
wherein
R-i, R.2, R3, R4, and R5 each independently stand for
- hydrogen;
- hydroxy;
- a Ci-Ce-alkyl group; - a C2-C6-alkenyl group;
- a Cι-C6-alkoxy group, preferably methoxy or 1-butoxy;
- a C2-C6-alkenoxy group;
- halogen, preferably bromo;
R<5 and R7 each independently stand for - methylene;
- one or two hydrogens;
- one hydroxy and optionally one hydrogen;
- one Ci-C6-alkyl group, preferably methyl, and optionally one hydrogen;
- one C2-C6-alkenyl group, and optionally one hydrogen; - one halogen, preferably bromo, and optionally one hydrogen; R8 stands for
- hydrogen;
- a Ci-C6-alkyl group, preferably methyl, ethyl, n-propyl, isopropyl, 1-butyl or 2- butyl; - a C2-C6-alkenyl group;
~ stands for a single or a double carbon-carbon bond; as well as esters and salts thereof.
Another object of the present invention is the use of a composition for conifer sapling protection against insect attack, wherein the insect species belong to the beetle (Cole- optera) family Curculionidae (including subfamilies Curculioninae and Scolytinae). particularly species of the genera Hylobius, Pachylobius and Hylastes, specifically the species Hylobius abietis, Hylobius pinastri, Hylobius pales, Hylobius congener, Pachylobius picivorus, Hylastes brunneus Bind Hylastes cunicularius, characterised in that it comprises at least one of the following compounds with Formula I:
Formula I
wherein
Ri, R2, R3, R4, R5. R5. R7. Rs. a d ~ are as defined above, pure or in a solvent, with or without a suitable carrier such as wood, cellulose, wood-flour, straw, cork, cane, lignin, lignocellulose, rubber, gum, leather or skin, milled carbon, fats or waxes of animal, vegetable, or synthetic origin, natural resins of animal or vegetable origin, plastic, organic polymers such as polyvinyl acetate, polyacrylates, polyvinyl chloride, chlorinated polyethylene, polyols such as polyethylene glycol, synthetic or natural latexes, silicone polymers or resins, silicates, pumice, silica, or any mixture thereof.
Preferred compounds are those of Formula I with the exception of methyl 3',4'- dimethoxycinnamate.
Another object of the invention is a compound of Formula I, wherein R3 is methoxy; Ri, R2, R4, and R5 are hydrogen; R^ and R7 are both two hydrogens; and R8 is isopro- pyl.
A suitable solvent is selected from the group consisting of Ci-Cδ-alkohols and Cι-C6- alkyl esters of a Cι-C6-alkanoic acid, preferably methyl acetate and methanol.
As used in this application: a) the term "Ci-Cό-a-kyl" refers to a saturated, straight or branched chained alkyl radical containing from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, 1 -butyl, 2-butyl, t-butyl, n-pentyl, n-hexyl, etc;
Thus, any alkyl containing 1, 2, 3, 4, 5, or 6 carbon atoms could be used. For parts of the range "Cι-C6-alkyι" all subgroups thereof are contemplated such as Cι-C5-alkyl, CrC4-alkyl, -Cs-alkyl, CrC2-alkyL C2-C6-alkyl, C3-C6-alkyl, C2-C5- alkyl etc; b) the term "C2-C6- lkenyl" refers to an unsaturated, straight or branched chained alkenyl radical containing from 2 to 6 carbon atoms, such as vinyl, 1-ρropenyl, 2- propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, etc; Thus, any alkyl containing 2, 3, 4, 5, or 6 carbon atoms could be used. For parts of the range "C2-C6-alkenyl" all subgroups thereof are contemplated such as C2-C5-alkenyl, C2-C4-alkenyl, C2-C3-alkenyl, C2-C6-alkenyl, C3-C6-alkenyl, C4-
C5-alkenyl etc; c) the term "Ci-Cδ-alkoxy" refers to a saturated, straight or branched chained alkoxy radical containing from 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, 1-butoxy, 2-butoxy, t-butoxy, n-pentoxy, n-hexoxy, etc; Thus, any alkoxy containing 1, 2, 3, 4, 5, or 6 carbon atoms could be used.
For parts of the range "CrCβ-alkoxy" all subgroups thereof are contemplated such as Cι-C5-alkoxy, Cι-C4-alkoxy, Cι-C3-alkoxy, C1-C2-alkoxy, C2-C6-alkoxy, C3-C6- alkoxy, QrCs-alkoxy etc; d) the term "C2-C6-alkenoxy" refers to an unsaturated, straight or branched chained alkenoxy radical containing from 2 to 6 carbon atoms, such as vinyloxy, 1- propenoxy, 2-propenoxy, 1-butenoxy, 1-pentenoxy, 1-hexenoxy, etc; Thus, any alkyl containing 2, 3, 4, 5, or 6 carbon atoms could be used. For parts of the range "C2-C6-alkenoxy" all subgroups thereof are contemplated such as C2-C5-alkenoxy, C2-C4-alkenoxy, C2-C3-alkenoxy, C2-C6-alkenoxy, C3-C6- alkenoxy, C4-C5-alkenoxy etc; e) the term "Cι-C6-alcohol" refers to a saturated, straight or branched alkyl alkohol and containing 1-6 carbon atoms, such as methanol, ethanol, n-propanol, isopropa- nol, n-butanol, tert-butanol, n-pentanol, n-hexanol, etc; and f) the term "Cι-C6-alkyl ester of a Ci-C6-alkanoic acid " refers to a saturated, straight or branched alkyl ester and containing 1-6 carbon atoms of a saturated, straight or branched alkanoic acid and containing 1-6 carbon atoms, such as methyl formiate,
ethyl formiate, isopropyl formiate, methyl acetate, ethyl acetate, ethyl propanoate, ethyl butyrate, ethyl valerate, ethyl hexanoate, etc.
It should be noted that both E- and Z-isomers of the compounds, optical isomers, as well as mixtures thereof, and all isotopes are included within the scope of the invention. By the expression "isotopes" is meant all compounds with naturally occurring isotopes such as all possible deuterium and 13C-isotopes of the compounds according to the invention.
It should be noted that both esters and salts of the compounds according to the invention are included within the scope of the invention. As examples of esters of the compounds are intended e.g. methyl, ethyl, n-propyl, isopropyl, 1-butyl, tert-butyl and n- pentyl esters. As examples of salts of the compounds are intended in particular environmentally acceptable acid and base addition salts.
The expression "environmentally acceptable acid addition salts" are intended to be any non-toxic organic or inorganic acid addition salt of the base compounds with the formula I. Examples of illustrative inorganic acids that form suitable salts are hydrochloric acid, hydrobromic acid, sulphuric acid, phosphoric acid and acid metal salts such as sodium monohydrogen ortophosphate and potassium hydrogensulphate. Examples of illustrative organic acids that form suitable salts are mono-, di- and rricarboxylic acids. Examples of such acids are acetic acid, glycolic acid, lactic acid, pyruvic acid, malonic acid, succinic acid, glutaric acid, fumaric acid, malic acid, tartaric acid, citric acid, ascorbic acid, maleic acid, hydroxymaleic acid, benzoic acid, hydroxybenzoic acid, phenylacetic acid, cinnamic acid, salicylic acid, 2-phenoxybenzoic acid, and sulphonic acids such as p-toluenesulphonic acid, methanesulphonic acid and 2-hydroxyethane- sulphonic acid. Such salts could either be in hydrated or anhydrous form. The acid addition salts of these compounds are generally water soluble and different hydrophilic organic solvents and, that compared to the free base forms thereof, generally display higher melting points.
The expression "environmentally acceptable base salts" are intended to be any non- toxic organic or inorganic base addition salt of the base compounds with the formula I. Examples of illustrative inorganic bases that form suitable salts are alkali and earth alkali metal hydroxides and carbonates such as sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, calcium hydroxide, calcium carbonate, magnesium hydroxide, magnesium carbonate and ammonia. Examples of illustrative organic bases that form suitable salts are methylamine, dimethylamine, trimethylamine and picoline. Either mono- or dibasic salts could be formed with such compounds. The base addition salts of these compounds are generally water soluble and different hy- drophilic organic solvents and, that compared to the free base forms thereof, generally display higher melting points.
Examples of compounds with Formula I are listed below i e the compounds 1-21.
1. Ethyl cinnamate 2. Propyl cinnamate
(Ethyl 3-ρhenylpropenoate) (n-propyl 3-phenylpropenoate)
3. Isopropyl cinnamate 4. 1 -butyl cinnamate (isopropyl 3-phenylpropenoate)
5. 2-butyl cinnamate 6. Methyl 2',3'-dimethoxy- cinnamate
7. Methyl 2',4'-dimethoxy- 8. Methyl 3',4'-dimethoxy- cinnamate cinnamate
9. Methyl 3',5'-dimethoxy- 10. Methyl 3-phenylpropanoate cinnamate
11. Methyl 3-(4'-methoxy- 12. Methyl 3-(4'-hydroxy-3' phenyl)propanoate methoxyphenyl)propanoate
15. Ethyl α,β-dibromo-3-phenyl- 16. Methyl 3-(2'-methoxy- propanoate (Ethyl 2,3-dibromo- phenyl)propanoate 3 -phenylpropanoate)
17. Methyl 3-(3'-methoxy- 18. Isopropyl 3-(4'-methoxy- phenyl)propanoate phenyl)propanoate
21. Methyl 3-(4'-(l-butoxy)- phenyl)propanoate
Compound No. 1 could be purchased from Aldrich, Sigma-Aldrich Sweden AB, Sol- kraftsvagen 14C, 135 70 Stockholm with catalogue No. 11,237-2. Compound No. 10 could be purchased from Lancaster, Lancaster Synthesis Ltd., Newgate, White Lund, Morecambe, Lancashire LA3 3DY, UK with catalogue No. 5310. In Table 1 is given CAS numbers for compounds No. 2-9, 11-17, and 19-21. CAS numbers marked with an asterisk (*) are those preferred by Beilstein. Compound No. 18 could be prepared as follows:
Isopropyl 3-(4'-hydroxyphenyl)propanoate (Registry Number: 116144-68-4) was reacted with methyl iodide in acetone/potassium carbonate to give isopropyl 3-(4'- methoxyphenyl)propanoate (Compound No. 18). The product was verified with NMR. 1H NMR δ 1.21 (6H, d, J =6.4 Hz), 2.55 (2H, t, J = 7.8 Hz), 2.88 (2H, t, J = 7.8 Hz), 3.78 (3H, s), 5.00 (IH, sept, J = 6.4 Hz), 6.82 (2H, d, J = 8.7 Hz) and 7.12 (2H, d, J = 8.7 Hz).
Table 1. CAS numbers for compounds No. 2-9, 11-17, and 19-21.
By the expression "comprising" we understand including but not limited to. Thus, other non-mentioned substances, additives or carriers may be present.
The invention will be illuminated by the following Examples, which are only intended to illuminate and not restrict the invention in any way.
Examples
Experimental
Insects. The insects used for the experiments was the pine weevil (Hylobius abietis) taken from then natural environment, i e coniferous forests.
Preparation of gnawing-inhibiting compositions. The compositions are prepared by incorporating the compounds in a suitable matrix. When the compounds are not solu- ble in the matrix a solvent is used to transfer the compounds into the matrix. A 50 mM solution in methyl acetate was applied on the pine bark, except for compound No. 12, wherein a 50 mM solution in methanol were used. For compound No. 11, both solutions were used.
Example 1 - Test of gnawmg-inhibiting effect of substances applied on pine bark.
For each test, 40 pine weevils (20 females + 20 males) were used placed in separate Petri dishes provided with a piece of a pine twig enveloped in aluminium foil. In the foil, two holes with a diameter of 5 mm were punched, whereby the underlying bark was exposed. One of the two surfaces exposed was treated with 100 μl of a 50 mM solution of the substance that was tested, and the other surface was treated with the same amount of solvent alone (control). After 6 and 24 hours, respectively, it was recorded whether the pine weevil had started to eat on the treated and untreated surface, respectively. In Table 2 the gnawing-inhibiting effect is shown by means of the fol- lowing index:
(C+T) , wherein C is the number of control surfaces with gnawing and T is the number of treated surfaces with gnawing. It was tested if there was a statistic significant difference between treatment and control with a chi2-test of a 2x2 table (not con- tinuity corrected): *=p<0.05, **=p<0.01, ***=φ<0.001.
Table 2. Test of gnaw g-iri biting effect of substances applied on pine bark (methyl acetate used as a solvent when nothing else is stated).
Example 3 - Field test with 80 saplings
The antifeedant effect of ethyl 2, 3 -dibromo-3 -phenylpropanoate (compound No. 15) applied on stems of Norway spruce seedlings was assessed in a field test. The active
substance was dissolved in methanol and to this solution a liquid wax (AGS 3512 Ultra, Trion Tensid AB, Uppsala, Sweden) was added in the proportion 3:1 (methanol: AGS), giving 0,056 g of active substance per mL of the final mixture. About 2 mL of this mixture (containing 0.11 g of active substance) was applied on each seedling in a way that it completely covered the lower half of the stem. This treatment was compared with seedlings similarly treated with the same methanol/AGS mixture without the active substance and also with untreated seedlings. A randomised block design was used with each of the 80 blocks containing one seedling of each of the three treatments. The distance between seedlings within a block was about 0.5 m and the dis- tance between blocks about 2 m. The seedlings were planted on a fresh clear-cutting 13 kmNNE Uppsala, Sweden, on 11 June 1999. The amount of pine weevil feeding was recorded for each seedling after 19 and 36 days.
The application of ethyl 2,3 -dibromo-3 -phenylpropanoate (compound No. 15) on spruce seedlings significantly reduced the amount of pine weevil feeding on the stems (Table 3). After 5 weeks the damage level was 4 times higher on control seedlings treated with methanol/AGS without the active substance and 3 times higher on untreated seedlings. Thus, methanol/AGS alone tended to increase damage, but this effect was counteracted when the active substance was added.
Table 3. Pine weevil feeding in the field on seedlings treated with ethyl 2,3-dibromo- 3 -phenylpropanoate (compound No. 15) and on control seedlings of two different types. Column means followed by the same letter are not significantly different at the 5 % level (ANOVA (GLM Proα, SAS) of log-transformed data followed by Tukey's HSD test).
References
DAURADE-LE VAGUERESSE M.H. and BOUNIAS M. 1992. Response du β- glucosyle de Lalcool coniferylique du Pinus sylvestris a l'inoculation du Cerato- cystis bruneociliata au liber. Can. J. For. Res. 22:1184-1191. EIDMANN H. N. 1974, Hylobius Schδnh. In: Schwenke, W. Die Forstshadlinge Eu- ropas. 2 Kafer, p 275-293. Hamburg. HARBORNE J.B. 1988. Introduction to Ecological Biochemistry. 3d ed. Academic Press, London. LANGSTROM, B. 1998. Varfδr ar snytbaggen fortfarande ett problem? Kungliga
Skogs- och Lantbruksakademiens Tidskrift 137(15):23-33. NORDLANDER, G. 1998. Vad kan vi gora at snytbaggeproblemet? Kungliga Skogs- och Lantbruksakademiens Tidskrift 137(15):35-41.
ROSENTHAL G.A. 1986. The chemical defenses of higher plant. Scientific American
254, 76-81. SUGA T., OHTA S., MUNESADA K., IDE N., KURAKAWA M., SHIMIZU M. and OHTA E. 1993. Endogenous pine wood nematodical substances in pines, Pinus massoniana, P. strobus and . palustris. Phytochemistry 33:1395-1401
SUNNERHEIM-SJOBERG K. 1991. Chemical Studies of Secondary Metabolites in Betula and Pinus - with Emphasis on Defence Against Mammalian Herbivores. Thesis. Department of Chemistry. University of Agricultural Sciences, Uppsala.
VIKTOROV-NABOKOV, O.V.; KOVALENKO, L. G.; MALEVANNAYA, Z. A.; SKRYNIK, E. M.; SHOLUDCHENKO, L. I. 1980. Effect of substituents in a series of benzoic acid esters and amides on repellence with respect to blood-sucking mosquitoes. Fiziol. Akt. Veshchestva, 12:96-98. WESLIEN, J. 1998. Vad kostar snytbaggeskadorna? Kungliga Skogs- och Lantbruksakademiens Tidskrift 137(15): 19-22.
ORLANDER, G. & NORDLANDER, G. 1998. Skarmar, markberedning och andra skogsskδtselatgarder - kan de minska snytbaggeskadorna? Kungliga Skogs- och Lantbruksakademiens Tidskrift 137(15):59-69. ORLANDER, G. & PETERSSON, M. 1998. Mekaniska skydd. Kungliga Skogs- och Lantbruksakademiens Tidskrift 137(15):43-50.
Claims
1. Use of at least one compound for conifer sapling protection against insect attack, wherein the insect species belong to the beetle (Coleoptera) family Curculionidae (including subfamilies Curculioninae and Scolytinae), particularly species of the genera Hylobius, Pachylobius and Hylastes, specifically the species Hylobius abietis, Hylobius pinastri, Hylobius pales, Hylobius congener, Pachylobius picivorus, Hylastes brunneus and Hylastes cunicularius, characterised in that the compounds are selected from the following compounds with formula I:
Formula I
wherein Ri, R2, R3, R4, and R5 each independently stand for
- hydrogen;
- hydroxy;
- a Ci-Cβ-alkyl group;
- a C2-C6-alkenyl group; - a Cι-C6-alkoxy group;
- a C2-C6-alkenoxy group;
- halogen;
Rό and R7 each independently stand for
- methylene; - one or two hydrogens; - one hydroxy and optionally one hydrogen;
- one Cι-C6-alkyl group and optionally one hydrogen;
- one C2-C6~alkenyl group and optionally one hydrogen;
- one halogen and optionally one hydrogen; R8 stands for
- hydrogen;
- a Ci-Cβ-alkyl group;
- a C2-C6-alkenyl group; stands for a single or a double carbon-carbon bond; as well as esters and salts thereof.
2. Use of a composition for comfer sapling protection against insect attack, wherein the insect species belong to the beetle (Coleoptera) family Curculionidae (including subfamilies Curculioninae and Scolytinae), particularly species of the genera Hylo- bius, Pachylobius and Hylastes, specifically the species Hylobius abietis, Hylobius pinastri, Hylobius pales, Hylobius congener, Pachylobius picivorus, Hylastes brunneus and Hylastes cunicularius, characterised in that it comprises at least one of the following compounds with Formula I:
Formula I
wherein
R R2, R3, R4, and R5 each independently stand for - hydrogen; - hydroxy;
- a CrC6-alkyl group;
- a C2-C6-alkenyl group;
- a Cι-C6-alkoxy group; - a C2-C6-alkenoxy group;
- halogen; e and R7 each independently stand for
- methylene;
- one or two hydrogens; - one hydroxy and optionally one hydrogen;
- one Cι-C6-alkyl group and optionally one hydrogen;
- one C2-C6-alkenyl group and optionally one hydrogen;
- one halogen and optionally one hydrogen; R8 stands for - hydrogen;
- a Cr -alkyl group;
- a C2-C6-alkenyl group; stands for a single or a double carbon-carbon bond; as well as esters and salts thereof, pure or in a solvent, with or without a suitable car- rier.
3. Use according to claim 1-2, characterised in that the compounds are selected from the following compounds with Formula I:
Formula I
wherein R R2, R3, R4, and R5 each independently stand for
- hydrogen;
- hydroxy;
- a Ci-C6-alkoxy group;
- a C2-C6-alkenoxy group; - halogen;
Re and R7 each independently stand for
- methylene;
- one or two hydrogens;
- one hydroxy and optionally one hydrogen; - one Ci-C6-alkyl group and optionally one hydrogen;
- one C2-C6-alkenyl group and optionally one hydrogen;
- one halogen and optionally one hydrogen; R8 stands for
- a Cι-C6-alkyl group; - a C2-C6-alkenyl group; stands for a single or a double carbon-carbon bond; as well as esters and salts thereof.
4. Use according to claim 1-3, characterised in that the compounds are selected from the following compounds with Formula I:
Formula I
wherein
Ri, R2, R3, R4, and R5 each independently stand for
- hydrogen;
- hydroxy;
- a Cι-C6-alkoxy group;
- bromo;
Re and R7 each independently stand for
- one or two hydrogens;
- one hydroxy and optionally one hydrogen;
- one Cι-C6-alkyl group and optionally one hydrogen;
- one bromo and optionally one hydrogen; R8 stands for
- a Cr -alkyl group; stands for a single or a double carbon-carbon bond; as well as esters and salts thereof.
5. Use according to claim 1-4, characterised in that the compounds are selected from the following compounds with Formula I:
Formula I
wherein
Rls R2, R3, R4, and R5 each independently stand for hydrogen, hydroxy, methoxy, 1- butoxy, and bromo;
Re and R each independently stand for one or two hydrogens, one hydroxy and optionally one hydrogen, one methyl and optionally one hydrogen, and one bromo and optionally one hydrogen; R8 stands for methyl, ethyl, n-propyl, isopropyl, 1 -butyl or 2-butyl; stands for a single or a double carbon-carbon bond; as well as esters and salts thereof.
6. Use according to claims 1-5, characterised in that the compounds are selected from the group consisting of: ethyl cinnamate; n-propyl cinnamate; isopropyl cinnamate;
1-butyl cinnamate; 2-butyl cinnamate; methyl 2 ',3 '-dimethoxycinnamate; methyl 2 ' ,4 '-dimethoxycinnamate; methyl 3 ',4 '-dimethoxycinnamate; methyl 3 ',5 '-dimethoxycinnamate; methyl 3-phenylpropanoate; methyl 3-(4'-methoxyphenyl)propanoate; methyl 3-(4'-hydroxy-3 '-methoxyphenyl)propanoate; methyl 2-methyl-3-phenylpropanoate; methyl 2,3-dibromo-3-phenylpropanoate; ethyl 2,3-dibromo-3-phenylpropanoate; methyl 3-(2'-methoxyphenyl)propanoate; methyl 3-(3 '-methoxyphenyl)propanoate; isopropyl 3 -(4 '-methoxyphenyl)propanoate; methyl 3-(3 '-bromo-4'-methoxyphenyl)propanoate; ethyl 3-hydroxy-3-(2'-biOmophenyl)propanoate; and methyl 3-(4'-(l-butoxy)phenyl)propanoate.
7. Use according to claim 1-5, characterised in that the compounds are selected from the following compounds with Formula I:
Formula I
wherein Ri, R2, R , R4, and R5 each independently stand for hydrogen, hydroxy, methoxy, 1- butoxy, and bromo;
Re and R7 each independently stand for one or two hydrogens, one hydroxy and optionally one hydrogen, one methyl and optionally one hydrogen, and one bromo and optionally one hydrogen; R8 stands for methyl, ethyl, n-propyl, isopropyl, 1 -butyl or 2-butyl; stands for a single or a double carbon-carbon bond; as well as esters and salts thereof; with the exception of methyl 3 ',4 '-dimethoxycinnamate.
8. Use according to claims 1-5 and 7, characterised in that the compounds are se- lected from the group consisting of: ethyl cinnamate; n-propyl cinnamate; isopropyl cinnamate; 1 -butyl cinnamate;
2-butyl cinnamate; methyl 2 ',3 '-dimethoxycinnamate; methyl 2 ',4 '-dimethoxycinnamate; methyl 3 ',5 '-dimethoxycinnamate; methyl 3-phenylpropanoate; methyl 3-(4 '-methoxyphenyl)propanoate; methyl 3-(4'-hydroxy-3 '-methoxyphenyl)propanoate; methyl 2-methyl-3-phenylpropanoate; methyl 2,3-dibromo-3-phenylpropanoate; ethyl 2,3-dibromo-3-phenylpropanoate; methyl 3 -(2 '-methoxyphenyl)propanoate; methyl 3-(3 '-methoxyphenyl)propanoate; isopropyl 3-(4'-methoxyphenyl)propanoate; methyl 3 -(3 '-bromo-4'-methoxyphenyl)propanoate; ethyl 3-hydroxy-3-(2'-bromophenyl)propanoate; and methyl 3 -(4 '-( l-butoxy)phenyl)propanoate.
9. Use according to Claim 2-8, characterised in that the suitable carrier is selected from the group consisting of wood, cellulose, wood-flour, straw, cork, cane, lignin, lignocellulose, rubber, gum, leather or skin, milled carbon, fats or waxes of animal, vegetable, or synthetic origin, natural resins of animal or vegetable origin, plastic, organic polymers such as polyvinyl acetate, polyacrylates, polyvinyl chloride, chlorinated polyethylene, polyols such as polyethylene glycol, synthetic or natural latexes, silicone polymers or resins, silicates, pumice, silica, or any mixture thereof.
10. A compound of Formula I
Formula I
wherein R3 is methoxy; Ri, R2, t, and R5 are hydrogen; R^ and R7 are both two hydrogens; and Rg is isopropyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2001282793A AU2001282793A1 (en) | 2000-08-25 | 2001-08-24 | Use for conifer sapling protection against insect attack |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE0003026A SE0003026D0 (en) | 2000-08-25 | 2000-08-25 | Use for conifer sapling protection |
| SE0003026-2 | 2000-08-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2002015691A1 true WO2002015691A1 (en) | 2002-02-28 |
Family
ID=20280798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/SE2001/001811 WO2002015691A1 (en) | 2000-08-25 | 2001-08-24 | Use for conifer sapling protection against insect attack |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2001282793A1 (en) |
| SE (1) | SE0003026D0 (en) |
| WO (1) | WO2002015691A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004002224A1 (en) * | 2002-06-28 | 2004-01-08 | Forskarpatent I Syd Ab | Composition for inhibiting gnawing and feeding by insects and animals intended to be applied on seedlings and trees |
| AP1760A (en) * | 2001-12-06 | 2007-07-18 | Nerviano Medical Sciences Srl | Platinum derivative pharmaceutical formulations. |
| US11136298B2 (en) | 2014-09-08 | 2021-10-05 | Showa Denko K.K. | Method for producing fullerene derivative |
| US11533912B2 (en) * | 2019-11-11 | 2022-12-27 | Institute Of Plant Protection, Gansu Academy Of Agricultural Sciences | Use of cinnamate compounds in the control of fungal diseases of crops |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AP1760A (en) * | 2001-12-06 | 2007-07-18 | Nerviano Medical Sciences Srl | Platinum derivative pharmaceutical formulations. |
| WO2004002224A1 (en) * | 2002-06-28 | 2004-01-08 | Forskarpatent I Syd Ab | Composition for inhibiting gnawing and feeding by insects and animals intended to be applied on seedlings and trees |
| US11136298B2 (en) | 2014-09-08 | 2021-10-05 | Showa Denko K.K. | Method for producing fullerene derivative |
| US11533912B2 (en) * | 2019-11-11 | 2022-12-27 | Institute Of Plant Protection, Gansu Academy Of Agricultural Sciences | Use of cinnamate compounds in the control of fungal diseases of crops |
Also Published As
| Publication number | Publication date |
|---|---|
| SE0003026D0 (en) | 2000-08-25 |
| AU2001282793A1 (en) | 2002-03-04 |
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