US20050070576A1 - Methods and compositions for controlling pests - Google Patents

Methods and compositions for controlling pests Download PDF

Info

Publication number
US20050070576A1
US20050070576A1 US10/477,057 US47705704A US2005070576A1 US 20050070576 A1 US20050070576 A1 US 20050070576A1 US 47705704 A US47705704 A US 47705704A US 2005070576 A1 US2005070576 A1 US 2005070576A1
Authority
US
United States
Prior art keywords
alkyl
alkenyl
arylalkyl
haloalkyl
dihaloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/477,057
Other languages
English (en)
Inventor
Robert Spooner-Hart
Albert Basta
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Western Sydney
BioProspect Ltd
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of US20050070576A1 publication Critical patent/US20050070576A1/en
Priority to US12/134,035 priority Critical patent/US7820209B2/en
Priority to US12/782,125 priority patent/US20100227009A1/en
Assigned to BIOPROSPECT LIMITED, UNIVERSITY OF WESTERN SYDNEY reassignment BIOPROSPECT LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BASTA, ALBERT HABIB, SPOONER-HART, ROBERT NEIL
Priority to US13/431,726 priority patent/US20120184625A1/en
Priority to US14/250,187 priority patent/US9474270B2/en
Priority to US15/332,364 priority patent/US20170035048A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • A01N35/08—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 at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—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 at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
    • 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
    • A01N37/18—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 the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/04—Pteridophyta [fern allies]; Filicophyta [ferns]
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/10—Apiaceae or Umbelliferae [Carrot family], e.g. parsley, caraway, dill, lovage, fennel or snakebed
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/12—Asteraceae or Compositae [Aster or Sunflower family], e.g. daisy, pyrethrum, artichoke, lettuce, sunflower, wormwood or tarragon
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/22—Lamiaceae or Labiatae [Mint family], e.g. thyme, rosemary, skullcap, selfheal, lavender, perilla, pennyroyal, peppermint or spearmint
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/28—Myrtaceae [Myrtle family], e.g. teatree or clove
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/08—Magnoliopsida [dicotyledons]
    • A01N65/36—Rutaceae [Rue family], e.g. lime, orange, lemon, corktree or pricklyash
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/40—Liliopsida [monocotyledons]
    • A01N65/42—Aloeaceae [Aloe family] or Liliaceae [Lily family], e.g. aloe, veratrum, onion, garlic or chives
    • 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
    • A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
    • A01N65/40—Liliopsida [monocotyledons]
    • A01N65/48—Zingiberaceae [Ginger family], e.g. ginger or galangal
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K36/00—Medicinal preparations of undetermined constitution containing material from algae, lichens, fungi or plants, or derivatives thereof, e.g. traditional herbal medicines
    • A61K36/18—Magnoliophyta (angiosperms)
    • A61K36/185—Magnoliopsida (dicotyledons)
    • A61K36/61—Myrtaceae (Myrtle family), e.g. teatree or eucalyptus

Definitions

  • THIS INVENTION relates generally to methods and compositions for controlling pests. More particularly, the present invention relates to pest-controlling compositions comprising as active ingredients one or more ⁇ -diones, particularly ⁇ -diketones and ⁇ -triketones, and to the use of these compositions inter alia for preventing, eradicating, destroying, repelling or mitigating harmful, annoying or undesired pests including insects, arachnids, helminths, molluscs, protozoa and viruses.
  • the present invention further relates to processes of preparing ⁇ -diones by de novo synthesis or from natural sources such as volatile oil-bearing plants from families including Alliaceae, Apiaceae, Asteraceae, Cannabinaceae, Lamiaceae, Pteridaceae, Myrtaceae, Myoporaceae, Proteaceae, Rutaceae and Zingiberaceae.
  • Triketones have been used for many years as herbicides for the control of undesired vegetation.
  • Herbicidal triketones have been described, for example, in EP-A-338992, EP-A-336898, U.S. Pat. No. 4,869,748, EP-A-186118, EP-A-186119, EP-A-186120, U.S. Pat. No. 4,202,840, U.S. Pat. No. 4,695,673, U.S. Pat. No. 4,780,127, U.S. Pat. No. 4,921,526, U.S. Pat. No. 5,006,150, U.S. Pat. No. 5,545,607, U.S. Pat. No. 5,925,795, U.S. Pat.
  • herbicidal triketones are inter alia Sulcotrione (MIKADO®) whose chemical designation is 2-(2-chloro-4-methanesulfonylbenzoyl)-1,3-cyclohexandione, 2-(4-methylsulfonyloxy-2-nitrobenzoyl)-4,4,6,6-tetramethyl-1,3-cyclohexane dione; 3-(4-methylsulfonyloxy-2-nitrobenzoyl)-bicyclo-[3,2,1]octane-2,4-dione; 3-(4-methylsulfonyl-2-nitrobenzoyl)-bicyclo-[3,2,1]octane-2,4-dione; 4-(4-chlor
  • the instant invention is predicated in part on the discovery that ⁇ -diones, particularly ⁇ -diketones and ⁇ -triketones, such as those obtainable from volatile oil-bearing plants including plants from the families Alliaceae, Apiaceae, Asteraceae, Cannabinaceae, Lamiaceae, Pteridaceae, Myrtaceae, Myoporaceae, Proteaceae, Rutaceae and Zingiberaceae, exhibit significant pesticidal, especially insecticidal, arachnicidal, helminthicidal and/or molluscicidal activity.
  • This discovery has been reduced to practice in novel pest-controlling compositions and methods for their preparation and use, as described hereinafter.
  • FIG. 1 shows the structures relating to the major constituents of the published Myrtaceae essential oils.
  • FIG. 2 is a representation of a GC-MS trace of E. cloeziana oil.
  • FIG. 3 is a tabular and graphical representation showing 1 H NMR data recorded on a fraction (F4) obtained from silica gel chromatography of E. cloeziana oil and the structure of the major and minor isomers of the compound deduced from these data.
  • FIG. 4 is a diagrammatic representation showing various tautomeric forms of an isolated ⁇ -triketone compound in solution (CDCl 3 ).
  • One aspect of the present invention contemplates the use of a ⁇ -dione compound, particularly a ⁇ -diketone or a ⁇ -triketone compound, in the preparation of a composition for controlling harmful, annoying or undesired pests, said compound being represented by the general formula (I) wherein
  • Heterocyclic systems can be optionally attached to a moiety other than those set forth above via a carbon atom or a heteroatom of R 1 to R 11 .
  • Preferred compounds represented by formula (1) are ⁇ -diketones and especially preferred are ⁇ -triketones.
  • alkyl refers to linear or branched chains.
  • haloalkyl refers to an alkyl group substituted by at least one halogen.
  • haloalkoxy refers to an alkoxy group substituted by at least one halogen.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • aryl refers to aromatic carbocyclic ring systems such as phenyl or naphthyl, anthracenyl, especially phenyl.
  • aryl is C 6 -C 14 with mono, di, tri, tetra and penta substitution containing OR 2 , F, Cl, Br, I, NO 2 , CF 3 , COR 1 , NR 4 R 5 , SO 2 R 2 , SR 2 .
  • heterocycle refers to a saturated, unsaturated, or aromatic carbocyclic group having a single ring, multiple fused rings (for example, bicyclic, tricyclic, or other similar bridged ring systems or substituents), or multiple condensed rings, and having at least one heteroatom such as nitrogen, oxygen, or sulfur within at least one of the rings.
  • heteroaryl refers to a heterocycle in which at least one ring is aromatic. Any heterocyclic or heteroaryl group can be unsubstituted or optionally substituted with one or more groups, as defined above.
  • bi- or tricyclic heteroaryl moieties may comprise at least one ring, which is either completely, or partially, saturated.
  • Suitable heteroaryl moieties include, but are not limited to oxazolyl, thiazaoyl, thienyl, furyl, 1-isobenzofuranyl, 2H-pyrrolyl, N-pyrrolyl, imidazolyl, pyrazolyl, isothiazolyl, isooxazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyradazinyl, indolizinyl, isoindolyl, indoyl, indolyl, purinyl, phthalazinyl.
  • an element means one element or more than one element.
  • a preferred carbocyclic ring formed by Q is an optionally substituted cyclohexanedione.
  • Such compounds may exist in a number of tautomeric forms.
  • X and Y are each oxygen, and B is hydrogen
  • the compounds of formula II may exist as one or more of the structural formulae shown below.
  • flavesone analogues contemplated by the present invention include, but are not restricted to, compounds having the following structural formulae, wherein the structural formula of flavesone is shown for comparative purposes:
  • Non-limiting examples of isoleptospermone analogues contemplated by the present invention include, but are not restricted to, compounds having the following structural formulae, wherein the structural formula of isoleptospermone is shown for comparative purposes:
  • Non-limiting examples of leptospermone analogues contemplated by the present invention include, but are not restricted to, compounds having the following structural formulae, wherein the structural formula of leptospermone is shown for comparative purposes:
  • Non-limiting examples of jensenone analogues contemplated by the present invention include, but are not restricted to, compounds having the following structural formulae, wherein the structural formula of jensenone is shown for comparative purposes:
  • Preferred ⁇ -diones represented by formula (IV) are tasmanone (1-isobutroyl-4-methoxy-3,5,5-trimethylcyclohex-3-en-2,6-dione), agglomerone (1-isobutroyl-4-methoxy-5,5-dimethylcyclohex-3-en-2,6-dione), lateriticone (1-valeroyl-4-methoxy-3,5,5-trimethylcyclohex-3-en-2,6-dione), isolateriticone (1-isovaleroyl-4-methoxy-3,5,5-trimethylcyclohex-3-en-2,6-dione and platyphyllol (6,6-dimethyl-2-acetyl-5-methoxycyclohex-4-ene-1,3-dione), including analogues and derivatives thereof.
  • Non-limiting examples of tasmanone analogues contemplated by the present invention include, but are not restricted to, compounds having the following structural formulae, wherein the structural formula of tasmanone is shown for comparative purposes:
  • More specifically unsaturation, epoxides and thioexpoxides may exist at positions designated by H (or G) connected to F (or E) or F (or E) connected to C (or D).
  • a four-membered ring forming a part of a bicyclic structure may exist at positions designated by H (or G) connected to C (or D).
  • Preferred ⁇ -diones represented by formula (V) are angustione (1-acetyl-3,5,5-trimethylcyclohex-2,6-dione), dehydroangustione (1-acetyl-3,5,5-trimethylcyclohex-3-en-2,6-dione) and xanthostemone (1-isobutroyl-5,5-dimethylcyclohex-3-en-2,6-dione), including their analogues and derivatives.
  • angustione analogues contemplated by the present invention include, but are not restricted to, compounds having the following structural formulae, wherein the structural formula of angustione is shown for comparative purposes:
  • dehydroangustione analogues include, but are not restricted to, compounds having the following structural formulae, wherein the structural formula of dehydroangustione is shown for comparative purposes:
  • Non-limiting examples of xanthostemone analogues include, but are not restricted to, compounds having the following structural formulae, wherein the structural formula of xanthostemone is shown for comparative purposes:
  • Derivatives of the above compounds include, but are not restricted to, ethoxylate derivatives, propoxylate derivatives, hydrates, aldehyde derivatives, ester derivatives, ether derivatives, alcohol derivatives, phenol derivatives, amine derivatives, other biologically or chemically equivalent substances, and any combination of two or more of the foregoing.
  • salts of the above compounds including mono-valent salts (e.g., sodium, potassium) and di-valent metal salts (e.g. calcium, magnesium, iron or copper) and ammonium salts (e.g., isopropyl ammonium, trialkyl and tetraalkylammonium salts).
  • mono-valent salts e.g., sodium, potassium
  • di-valent metal salts e.g. calcium, magnesium, iron or copper
  • ammonium salts e.g., isopropyl ammonium, trialkyl and tetraalkylammonium salts.
  • the compounds according to any one of formulae (I)-(V) can be prepared according to methods analogous to those known in the art for the preparation of ⁇ -diones. Exemplary methods are disclosed for example in EP-A-338992, EP-A-336898, U.S. Pat. No. 4,202,840, U.S. Pat. No. 4,869,748, EP-A-186118, EP-A-186119, EP-A-186120, U.S. Pat. No. 4,695,673, U.S. Pat. No. 4,780,127, U.S. Pat. No. 4,921,526, U.S. Pat. No. 5,006,150, U.S. Pat. No. 5,545,607, U.S. Pat. No.
  • compounds of formula (IV) can be prepared according to a second representative procedure, as follows: 3-methoxy-2,4,4-trimethylcyclohex-2-en-1,5-dione 4 (1 mole eq) (commercially available) and benzoyl cyanide are dissolved in anhydrous dichloromethane and cooled to 0° C. under an atmosphere of nitrogen. To the cooled solution is added anhydrous finely powdered zinc chloride (1.1 mole eq.) followed by slow addition of triethylamine (1.2 mole eq). The reaction mixture is stirred at room temperature for 5-6 h and then poured into 2 M hydrochloric acid.
  • the compounds of formula (V) can be prepared according to a second representative procedure, as follows: 4,4-dimethyl-1,3-cyclohexanedione 7 (1 mole eq) (commercially available) and benzoyl cyanide are dissolved in anhydrous dichloromethane and cooled to 0° C. under an atmosphere of nitrogen. To the cooled solution is added anhydrous finely powdered zinc chloride (1.1 mole eq) followed by slow addition of triethylamine (1.2 mole eq). The reaction mixture is stirred at room temperature for 5-6 h and then poured into 2 M hydrochloric acid. The mixture is partitioned and the dichloromethane layer washed with 5% sodium carbonate.
  • aqueous carbonate phase is then acidified with hydrochloric acid and extracted with methylene chloride and dried (Na 2 SO 4 ). The solvent is removed and the residue subjected to SiO 2 column chromatography (hexane/ethyl acetate) affording 1-benzoyl-3,3,5-trimethylcyclohexan-2,6-dione 8. (W. J. Michaely and G. W. Kraatz, EP-B-135191).
  • Dehydroangustione and xanthostemone derivatives are simply derived from dehydrogenation of angustione derivatives, for example, by treatment of 1-benzoyl-3,3,5-trimethylcyclohexan-2,6-dione 8 with palladium on charcoal in methanol, which thereby affords 1-benzoyl-3,5,5-trimethylcyclohex-3-en-2,6-dione 9 (Scheme 5).
  • Metal salts (enolates) of the above compounds can be prepared by the reaction of triketone derivatives with the corresponding metal hydroxides suspended in methanol or ethanol.
  • Trialkylammonium salts can be prepared by the reaction of triketone derivatives (e.g., 3) with trialkylamines in a chlorinated solvent such as dichloromethane.
  • Tetraalkylammonium salts can be prepared by adding a halogenated tetraalkylammonium salt to a metal salt in dichloromethane, which precipitates the metal halide removed by filtration. The pure material is obtained by evaporation of the filtrate.
  • the present inventors have discovered that the ⁇ -diones of the invention can be obtained from natural sources and, in particular, from volatile oil-bearing organisms. Accordingly, in another aspect, the present invention encompasses the use of a ⁇ -dione compound, particularly a ⁇ -diketone or a ⁇ -triketone compound, obtainable from a volatile oil-bearing organism, including an analogue or derivative thereof, in the preparation of a pesticidal composition for controlling harmful, annoying or undesired pests.
  • the present invention contemplates the use of any volatile oil-bearing organism that produces ⁇ -diones, preferably the ⁇ -diones according to any one of formulae (I)-(V), and especially ⁇ -diketones and/or ⁇ -triketones, for the preparation of the pesticidal compositions of the invention.
  • Preferred volatile oil-bearing organisms are volatile oil-bearing plants including, but not restricted to, plants from the families Alliaceae, Apiaceae, Asteraceae, Cannabinaceae, Lamiaceae, Pteridaceae, Myrtaceae, Myoporaceae, Proteaceae, Rutaceae and Zingiberaceae.
  • the volatile oil-bearing plant is selected from genera of the Myrtaceae family including, but not limited to, Angophora, Austromyrtus, Backhousia, Baeckea, Callistemon, Corymbia, Darwinia, Eucalyptus, Kunzea, Leptospermum, Melaleuca, Syzygium and Xanthostemon.
  • compositions of the present invention may contain as active ingredients substantially purified ⁇ -diones or crude ⁇ -dione-containing extracts obtained from a volatile oil-bearing organism, preferably a volatile oil-bearing plant.
  • Volatile oils also known in the art as essential oils, typically comprise a volatile mixture of esters, aldehydes, alcohols, ketones and terpenes, which can be prepared from botanical materials or plant cell biomass from cell culture. Volatile oils can be prepared by subjecting botanical materials to a distillation process, for example. A number of different procedures can be used for distillation.
  • plant matter e.g., foliage, stems, roots, seeds, bark etc
  • steam distillation is used to break down the cells of the plant to release the oil.
  • the steam is then condensed and the oil phase is separated from the aqueous phase to obtain the volatile oil.
  • solvent extraction is known to those of skill in the art and it will be understood, in this regard, that the present invention is not limited to the use or practice of any one particular method of extracting volatile oils.
  • the compositions comprise naturally-occurring compounds derived from a volatile oil-bearing organism.
  • the pesticidal composition of the invention comprises one or more ⁇ -dione active compounds, particularly ⁇ -diketone- and/or ⁇ -triketone-active compounds, that are derived from the volatile oil of a volatile oil-bearing organism.
  • the composition may optionally contain a naturally-occurring carrier and/or other naturally-occurring additives.
  • Naturally-occurring additives contemplated by the present invention include natural antioxidants, which can be used advantageously to reduce the effect of oxidation of the compounds of the invention.
  • An example of a suitable naturally-occurring antioxidant is ⁇ -tocopherol.
  • Other additives, such as naturally-occurring stabilisers, are also contemplated, which may desirably be added to improve the stability and shelf life of the composition.
  • suitable natural stabilisers include gum arabic, guar gum, sodium caseinate, polyvinyl alcohol, locust bean gum, xanthan gum, kelgum, and mixtures thereof.
  • the naturally-occurring compounds derived from a volatile oil may be modified or derivatised to improve, for instance, their shelf-life, stability, activity and/or bioavailability.
  • the compounds of the present invention are useful for controlling harmful, annoying or undesired pests. They may be used singularly or in combination with other pest-controlling compounds of the invention.
  • controlling is meant preventing, combating, eradicating, destroying, repelling, or mitigating pests or increasing the mortality or inhibiting the growth and/or development of pests.
  • the term “pest” is used herein in its broadest sense and includes within its scope insects, arachnids (e.g. acari, spiders), helminths (e.g., nematodes), molluscs, protozoa (e.g., Plasmodium sp.
  • Paramecium sp. viruses (e.g., herpesviruses) and the like.
  • Suitable applications for such control include, but are not limited to, combating and/or eradicating infestations by pests in animals (including humans) and/or plants (including trees) and/or stored products, which includes the administration to the animal or site of an effective quantity of a compound of the invention.
  • a “pesticidally-effective” amount is the amount of active compound that is effective for increasing the mortality or decreasing the growth of a significant number of pests.
  • a “pest-repelling” effective amount is the amount of active compound that is noxious to, and/or induces behavioural changes in, a significant number of pests. The effective amount will vary depending upon the taxonomic group of pest exposed to the active compound, the formulation of the composition, and other relevant factors. It is expected that the amount will fall in a relatively broad range that can be determined through routine trials.
  • the compounds of the present invention can be used as pesticides, such as but not limited to insecticides, arachnicides, anti-helminthics, molluscicides antivirals, antiprotozoals and the like, or as pest repellents including repellents of insects, arachnids, helminths, molluscs, protozoa and viruses.
  • the compounds of the present invention are used in the control of insects, arachnids, helminths or molluscs.
  • the compounds can be applied as formulations containing the various adjuvants and carriers known to or used in the industry for facilitating bioavailability, stability and dispersion. The choice of formulation and mode of application for any given compound may affect its activity, and selection will be made accordingly.
  • a pest-controlling compound of the invention can be compounded with appropriate inert carriers and additives in an appropriate ratio by means of dissolving, separating, suspending, mixing, impregnating, adsorbing or precipitating operation to formulate into oil formulations, emulsifiable concentrates, wettable powders, flowables, granules, powders, dusts, solutions, suspensions, emulsions, controlled-release forms such as microcapsules, aerosols or fumigants.
  • the compounds of the present invention can be mixed with a solid carrier, liquid carrier or gas carrier, optionally together with a surfactant and other adjuvants useful for such formulations.
  • the compounds of the invention can be used in an amount from about 0.00005% to about 90% by weight as contained in these formulations as their active component.
  • the term “about” refers to a quantity, level, value or amount that varies by as much as 30%, preferably by as much as 20%, and more preferably by as much as 10% to a reference quantity, level, value or amount.
  • the formulations will usually comprise as their principal active ingredient from about 0.0001% to about 90%, preferably from about 0.0001% to about 50%, more preferably from about 0.0005% to about 10%, even more preferably from about 0.0005% to about 5%, even more preferably from about 0.0005% to about 1% and still even more preferably from about 0.001% to about 0.5% by weight of the extract.
  • the formulations will usually comprise as their principal active ingredient from about 0.00005% to about 90%, preferably from about 0.0001% to about 50%, more preferably from about 0.0005% to about 10%, even more preferably from about 0.001% to about 5% and still even more preferably from about 0.001% to about 1% by weight of the substantially purified ⁇ -dione.
  • substantially purified is meant a compound which has been separated from components that naturally accompany it.
  • a compound is substantially pure when at least 60%, more preferably at least 75%, more preferably at least 90%, and most preferably at least 99% of the total material (by volume, by wet or dry weight, or by mole percent or mole fraction) in a sample is the compound of interest. Purity can be measured by any appropriate method, e.g., by chromatography or HPLC analysis.
  • solid carriers useful in preparing the formulations are clays including kaolin clay, diatomite, water-containing synthetic silicon oxide, bentonite, Fubasami clay, and acid clay; talcs; ceramics; inorganic minerals such as Celite, quartz, sulfur, active carbon, calcium carbonate and hydrated silica; and chemical fertilisers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride, these solid carriers being finely divided or granular.
  • liquid carriers examples include water, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and methylnaphthalene, aliphatic hydrocarbons such as hexane, cyclohexane, kerosene and light oil, esters such as ethyl acetate and butyl acetate, nitriles such as acetonitrile and isobutyronitrile, ethers such as diisopropyl and dioxane, acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide, halogenated hydrocarbons such as dichloromethane, trichloroethane and carbon tetrachloride, dimethyl sulfoxide, and fish oils, mineral oils, plant derived oils such as canola oil,
  • surfactants are alkylsulfuric acid esters, alkylsulfonic acid salts, alkylarylsulfonic acid salts, alkyl aryl ethers and polyoxyethylene adducts thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, sorbitane monolaurate, alkylallyl sorbitane monolaurate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, lignin sulfonate, and sulfuric acid ester salts of higher alcohols. These surfactants may be used alone or in combination.
  • adjuvants for the formulations such as binders and dispersants
  • binders and dispersants examples include casein, gelatin, polysaccharides such as starch, gum arabic, cellulose derivatives and alginic acid, lignin derivatives, bentonite, sugars and water-soluble synthetic high-molecular-weight substances such as polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylic acids.
  • stabilisers examples include PAP (acid isopropyl phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), synergists such as piperonyl butoxide, vegetable oils, mineral oils, fish oils, surfactants and fatty acids or esters thereof.
  • PAP acid isopropyl phosphate
  • BHT 2,6-di-tert-butyl-4-methylphenol
  • BHA mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol
  • synergists such as piperonyl butoxide, vegetable oils, mineral oils, fish oils, surfactants and fatty acids or esters thereof.
  • Emulsifying agents that may be used are suitably one or more of those selected from non-ionic or anionic emulsifying agents.
  • non-ionic emulsifying agents include, but are not restricted to, polyoxyethylenealkylphenylether, polyoxyethylenealkylether, polyethyleneglycol fatty ester, sorbitan fatty ester, polyoxyethylene sorbitan fatty ester, polyoxyethylenesorbitol fatty ester, polyoxyethylenepolyoxypropylenealkylether.
  • anionic emulsifying agents include alkyl sulphates, polyoxyethylenealkylether sulphates, sulfosuccinates, taurine derivatives, sarcosine derivatives, phosphoric esters, alkylbenzenesulfonates and the like.
  • These emulsifying agents may be used in an amount of 5 to 20 weight parts per 100 weight parts of the compositions of the present invention.
  • Formulation thus obtained can be used solus or diluted, for example, with water or other diluent.
  • the formulations can be used also as admixtures with other pesticides such as insecticides, arachnids, anti-helminthics, molluscicides, herbicides, plant growth regulators, synergists, soil improvers, baits and the like, or can be used simultaneously with such agents without mixing.
  • the pest-controlling compounds of the invention can be combined with other naturally derived bioactive compounds or extracts such as neem or its components, derris, pyrethrum; microbial extracts such as avermectins or streptomycins; with synthetic insecticides, acaricides, molluscicides, anti-helminthics; anti-protozoals, antivirals or with microorganisms having insecticidal, acaricidal, molluscicidal, anti-helminthic anti-protozoal or antiviral activity e.g., bacteria such as Bacillus thuringiensis, Bacillus popillae , entomogenous fungi such as Metarhizium spp., Verticillium lecanii , nematodes such as Steinernema spp and Heterorhabditis .
  • the pest-controlling compounds of the invention can be combined with synergist
  • the compound of the invention When used as an agricultural pesticide, the compound of the invention is preferably applied usually in an amount of 0.01 to 500 g/100 m 2 .
  • an emulsifiable concentrate, wettable powder or flowables are used as diluted with water, the compound is applied usually at a concentration of 0.1 to 1000 ppm, preferably 1 to 500 ppm.
  • the granular or dust can be applied without dilution.
  • the amount or concentration of application although exemplified above, can be suitably increased or reduced according to the type of preparation, time, place, method of application, kind of pest and extent of harm or annoyance suffered.
  • the invention also contemplates the use of the above described ⁇ -dione compounds in pest repellent, particularly insect repellent, compositions.
  • Repellent compositions contemplated by the present invention include those that are noxious to, and/or induce behavioural changes in, a pest.
  • the latter compositions suitably comprise an activity including, but not restricted to, an antifeedant activity, an oviposition deterrent activity and an insect growth regulatory activity.
  • Insect repellent compositions in various dosage forms can be prepared by blending the above-described ⁇ -dione compounds as active ingredients with a base of cosmetics or pharmaceuticals, which are usually applied to human bodies or animals. They can be formulated in, for example, lotions, aerosols, milky lotions, creams or the like. These compounds can be further incorporated with other insect repellents, antioxidants, UV-absorbers, humectants or other additives.
  • the above compounds or the above-prepared compositions of the present invention can be applied directly to human bodies or animals.
  • substrates such as sheets, films, nets, timber or the like, which have preliminarily been treated with the above compounds or compositions by means of application, impregnation or blending, can also be used.
  • the quantity of the above compounds to be formulated in the noxious-insect repellents depends upon the dosage form, usage or other conditions. Suitable dosages may be selected from about 0.1% to about 90% by weight.
  • a method for controlling harmful, annoying or undesired pests comprising exposing said pests to a pest-controlling effective amount of a composition comprising a ⁇ -dione compound as broadly described above.
  • Preferred embodiments of this type include exposing said pests to a pesticidally effective amount or a pest-repelling effective amount of said composition.
  • compositions and methods of the present invention may be applied to pests including, but not restricted to, insects, arachnids, helminths, molluscs, protozoa and viruses.
  • pests including, but not restricted to, insects, arachnids, helminths, molluscs, protozoa and viruses.
  • suitable insects include those:
  • Arachnids contemplated by the present invention include, but are not limited to, spiders and scorpions and especially mites such as phytophagous mites (Acari), such as Aculops lycopersicae, Aculops pelekassi, Aculus Louendali, Brevipalpus phoenicis, Bryobia praetiosa, Eotetranychus carpini, Eutetranychus banksii, Eriophyes sheldoni, Oligoinychus pratensis, Panonychus ulmi, Panonychus citri, Phyllocoptruta oleivora, Polyphagotarsonenmus latus, Tarsonemuspallidus, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranchus pacificus, Tetranychus urticae , ticks, such as Amblyomma americanum, Amblyomma variegatum, Argas per
  • Helminths falling within the scope of the present invention may be selected from cestodes such as fish tapeworm, pork tapeworm, beef tapeworm, and dwarf tapeworm; trematodes such as from the genera Metagonimus and Heterophyes ; and nematodes such as but not limited to filariid, ascarid, strongyle and trichostrongyle nematodes of the genera Acanthocheilonema, Aelurostrongylus, Ancylostoma, Angiostrongylus, Ascaris, Brugia, Bunostomum, Dictyocaulus, Dioctophyme, Dipetalonema, Dirofilaria, Dracunculus, Filaroides, Lagochilascaris, Loa, Mansonella, Muellerius, Necator, Onchocerca, Parafilaria, Parascaris, Protostrongylus, Setaria, Stephanofilaria, Strongyloides, Strongylus, Thelazia, Toxascaris
  • Suitable molluscs include those of the Gastropoda class examples of which include snails, slugs, conchs, and whelks.
  • Protozoa may be selected for example from Plasmodia, Toxoplasma, Leishmania, Trypanosoma, Giardia, Entamoeba, Acanthamoeba, Nagleria, Hartmanella, Balantidium, Babesia, Cryptosporidium, Isospora, Microsporidium, Trichomonas or Pneumocystis species.
  • Viruses may be selected from RNA viruses or DNA viruses, which include but are not limited to Human Immunodeficiency Virus (HIV), Poliovirus , Influenza virus, Rous Sarcoma virus, Flaviviruses such as Japanese encephalitis, Influenza virus, Respiratory Syncytial Virus, Hepatitis virus, Parvovirus, Rotavirus , Coronavirus, Adenovirus and Herpesviruses such as Papillomavirus and Epstein-Barr virus.
  • HIV Human Immunodeficiency Virus
  • Poliovirus Poliovirus
  • Influenza virus Rous Sarcoma virus
  • Flaviviruses such as Japanese encephalitis, Influenza virus, Respiratory Syncytial Virus, Hepatitis virus, Parvovirus, Rotavirus , Coronavirus, Adenovirus and Herpesviruses such as Papillomavirus and Epstein-Barr virus.
  • the present invention also extends to methods for producing resistance in plants to pests including, but not limited to, insects, arachnids, helminths, molluscs, protozoa and viruses by crossing a plant expressing a ⁇ -dione compound according to the invention with pest susceptible lines. Crossing a ⁇ -dione-producing plant into a pest susceptible background would produce a resistant plant with a high level of pest resistance. Plants that could be made pest resistant include, but are not limited to, dicotyledonous plants, especially trees and more especially members of the Myrtaceae family. For example E. cloeziana commonly known as Gympie Messmate is one of the many Eucalyptus species grown for hard wood production.
  • Suitable ⁇ -dione-producing plants may be selected from the families Alliaceae, Apiaceae, Asteraceae, Cannabinaceae, Lamiaceae, Pteridaceae, Myrtaceae, Myoporaceae, Proteaceae, Rutaceae and Zingiberaceae.
  • the volatile oil-bearing plant is selected from genera of the Myrtaceae family including, but not limited to, Angophora, Austromyrtus, Backhousia, Baeckea, Callistemon, Corymbia, Darwinia, Eucalyptus, Kunzea, Leptospermum, Melaleuca, Syzygium and Xanthostemon.
  • Preferred 16-dione-producing plants are Leptospermum mornsonii, Eucalyptus bensonii, Eucalyptus megacornuta, Eucalyptus pilularis, Eucalyptus cornuta, Eucalyptus baxteri, Eucalyptus macrorhyncha, Eucalyptus cloeziana, Melaleuca cajuputi, Eucalyptus jensenii, Backhousia angustifolia and Leptospennum scoparium .
  • a particularly preferred ⁇ -dione-producing plant is Eucalyptus cloeziana.
  • plant includes reference to whole plants, plant organs (e.g., leaves, stems, roots, etc.), seeds and plant cells and progeny of same.
  • Plant cell as used herein includes, without limitation, seeds suspension cultures, embryos, meristematic regions, callus tissue, leaves, roots, shoots, gametophytes, sporophytes, pollen, and microspores.
  • the class of plants which can be used in the methods of the invention is generally as broad as the class of higher plants amenable to transformation techniques, including both monocotyledonous and dicotyledonous plants.
  • the present invention contemplates conventional plant breeding methods to transfer the genetic material associated with ⁇ -dione production via crossing and backcrossing. Such methods will comprise the steps of: (1) sexually crossing the ⁇ -dione-producing plant with a plant from a pest susceptible taxon; (2) recovering reproductive material from the progeny of the cross; and (3) growing ⁇ -dione-producing/pest-resistant plants from the reproductive material.
  • the agronomic characteristics of the susceptible taxon can be substantially preserved by expanding this method to include the further steps of repetitively: (1) backcrossing the pest-resistant progeny with pest-susceptible plants from the susceptible taxon; and (2) selecting for expression of a ⁇ -dione (or an associated marker gene) among the progeny of the backcross, until the desired percentage of the characteristics of the susceptible taxon are present in the progeny along with the gene or genes imparting ⁇ -dione activity.
  • taxon herein is meant a unit of botanical classification. It thus includes, genus, species, cultivars, varieties, variants and other minor taxonomic groups which lack a consistent nomenclature.
  • the ⁇ -triketones obtained from selected Myrtaceous volatile oils were shown to have significant insecticidal and/or acaricidal activity.
  • E. cloeziana oil continued to show high potency against both insect tests. This oil exhibited an LD 95 between 0.04-0.20% (depending on formulation and treatment) against two-spotted mite. An LD 95 of 0.10% was observed against 1 st instar lavae of diamond back moth and this rose to 0.78% when tested against 3 rd instar lavae. In additional preliminary investigations with greenhouse thrips ( Heliothrips haemorrhoidalis ), a 0.1% concentration of E. cloeziana oil induced 100% mortality.
  • B. angustifolia M. cajuputi subsp platyphylla and E. cloeziana were then subjected to additional chemical fractionation.
  • the lower insecticidal activity observed in the recollected B. angustifolia (I) was in part attributed to the lower levels of ⁇ -triketone.
  • the level of ⁇ -triketone was elevated by the removal of the more volatile monoterpenes using vacuum distillation.
  • M. cajuputi subsp platyphylla a platyphyllol (64-71%) rich oil (Table 6), which also displayed consistent activity at every stage of processing and formulation.
  • This study investigated the potential of E. cloeziana oil to induce reverse mutations at the histidine locus in the genome of one strain of Salmonella typhimurium TA100 in the presence and absence of a metabolic activation system (mammalian microsomal enzymes, S9 mix).
  • the test sample was dissolved in dimethyl sulfoxide (DMSO).
  • DMSO dimethyl sulfoxide
  • an E. cloeziana oil test sample did not induce an appropriate-fold increase (a 2-fold increase for TA100) in the mean revertants per plate in the tester strain TA100 over the mean revertants per plate of the appropriate vehicle control. Accordingly, the test sample was considered to be non-mutagenic under the conditions of the assay.
  • the acute oral toxicity of E. cloeziana oil was investigated in ten (10) Sprague Dawley Specific Pathogen Free female rats (groups of 2) at doses of 500, 250, 125 and 50 mg/kg.
  • the experimental procedure was based on OECD guidelines for the testing of chemicals, No. 420.
  • Clinical signs of toxicity occurred between one (1) and twenty-four (24) hours after dosing. Both animals in the 500 mg/kg group exhibited subdued behaviour, partial eye closure, slow breathing, reduced motor activity, ataxia followed by death within 24 hours. The animals in the 250 mg/kg group exhibited subdued behaviour, partial eye closure, slow breathing, social isolation, and reduced motor activity, and had returned to normal by 24 hours after dosing. The animals in the 125 mg/kg group exhibited subdued behaviour, partial eye closure, slow breathing, piloerection and reduced motor activity, and had returned to normal by 24 hours after dosing. The animals in the 50 mg/kg group did not show any signs of toxicity during the seven day experimental period.
  • 100 and 200 mg/kg can be selected for a main study as the maximum non-toxic dose, intermediate dose and high dose, respectively.
  • E. cloeziana oil was investigated in thirty (30) Sprague Dawley Specific Pathogen Fee rats (15 males and 15 females) at doses of 50, 100 and 200 mg/kg. These doses were chosen following a dose range finding in the above study. The experimental procedure was based on OECD guidelines for the testing of chemicals, No. 420.
  • the acute NOAEL of E. cloeziana oil was determined to be 50 mg/kg, and the MTD was 200 mg/kg under the conditions of this study.
  • E. cloeziana oil was investigated in ten (10) Sprague Dawley Specific Pathogen Free rats (5 males and 5 females) at a dose of 2000 mg/kg. A preliminary study (SIGHTING) indicated no signs of toxicity at this dose. The experimental procedure was based on OECD guidelines for the testing of chemicals, No. 420.
  • E. cloeziana oil is a non-irritant according to the National Occupational Health and Safety Commission (NOHSC) “Approved Criteria for Classifying Hazardous Substances [NOHSC:1008(1999)]”.
  • NOHSC National Occupational Health and Safety Commission
  • ⁇ -triketones listed in Table 7 were isolated in quantities adequate for insecticidal screening. A minimum of 50 mg of each compound was required. Isoleptospermone and leptospermone were difficult to separate due to their structural similarity as were angustione and dehydroangustione. Consequently, mixtures of these compounds, where one isomer was significantly more abundant, were provided for insecticidal screening as this will still allow for differentiation in observed activity.
  • TMS Two spotted mite
  • Acarina Tetranychus urticae Koch
  • Acarina Tetranychidae
  • potted French beans Phaseolus vulgaris L [Fabales: Fabaceae] in a glasshouse maintained at 25 ⁇ 5° C., 65 ⁇ 5% RH and 14 h D:L photoperiod. Only young females were selected for bioassay.
  • Tomato russet mites (TRM) Aculops lycopersici (Massee) (Acarina: Eriophyidae) were collected from infested tomato plants near Riverstone, NSW.
  • Drug store beetle Sitodrepa panicea (Coleoptera: Anobiidae) were reared on curry powder under laboratory conditions of 25 ⁇ 1° C. and 65 ⁇ 5% RH.
  • the leaf discs were placed with their underside uppermost on moist absorbent cotton wool covered with muslin netting. Water was added to the dishes daily to prevent desiccation of the leaf discs. Five mL aliquots (unless otherwise stated) were applied to each petri dish with a Potter precision spray tower as described by Herron et al (1995). The average mass of solution applied to each dish was calculated to be 3.95 mg/cm 2 . Mortality was recorded 24 h after treatment. Death was recognised by the absence of movement when the test organisms were mechanically stimulated. Data were analysed using SPSS for WindowsTM Version 7. Probit analysis was carried out for dose-mortality data and heterogeneity of regressions was determined by the Pearson chi-squared characteristic.
  • TSM was treated with E. cloeziana oil extract in combination with paraffin oil.
  • E. cloeziana oil extract at levels of 0.1, 0.2, 0.3, 0.4 and 0.5 g were weighed out and each was made up to a weight of 10.0 g with a formulated paraffin oil (BioPest®), which was then sonicated for 10 min.
  • a 1.0% v/v of each blend was prepared by mixing 1.0 mL with distilled water in a 100.0 mL volumetric flask. TSM were transferred to the petri dish following the same standard method Five-mL aliquots were applied to each petri dish and mortality was recorded 24 h after treatment. All blends of E.
  • Lemon leaf discs 2.5 cm diam. were cut from tender young leaves and mounted on moistened absorbent cotton wool in 90 mm petri dish with their adaxial surface uppermost. Each petri dish contained four leaf discs. Uniform early instar nymphs were then transferred with a fine brush to the leaf discs (each containing 8-10 nymphs). A Potter tower was used to apply 5 mL aliquots to each petri dish. A control (solvent and surfactant only) was also included in the assessment. Mortality was assessed 24 h after treatment.
  • E. cloeziana oil extract was prepared using pure acetone as a diluent. From this solution, further serial dilutions were prepared by adding the required amount in acetone. Five mL aliquots of each concentration of E. cloeziana oil extract were dispensed into 500 mL kilner jars. The kilner jars were immediately rotated until dryness to coat the inner surface uniformly with the E. cloeziana oil residue. After complete dryness, 30-50 pupae were transferred to a series of clean uncovered petri dishes(45 mm diam.), one of which was placed inside each jar. The jar mouth was then covered with nylon netting supported by a rubber band. All adult houseflies started to emerge from pupae after 48 h and most emerged within a 3 h period. Flies were fed 5% sugar solution soaked in absorbent cotton wool. Jars were maintained in an incubator at 29° C.
  • Mortality was assessed at the end of the third day (i.e., approx. 72 h) after application of the E. cloeziana oil residues in the kilner jar and the placement of pupae inside the jars. (This comprised 48 h for pupae to emerge and 24 h exposure to E. cloeziana oil residues which were now 48 h old). Flies were observed to die within a few hours after emergence, whereas in the control they remained alive for >48 h after emergence. The total number of adult houseflies that emerged in each kilner jar was counted and their mortality was recorded.
  • Tests were conducted on 10-20 three months old nymphs (mean individual mass 0.2-0.3 g) and replicated three times.
  • One mL of 1.0% E. cloeziana oil extract in acetone was uniformly distributed on 90 mm diam. Whatman No 2 filter paper.
  • a control treatment was also carried out using 1 mL acetone only (ie., minus E. cloeziana oil extract).
  • the required number of cockroaches was transferred inside the kilner jars, and were fed dry dog food. Kilner jar necks were covered with muslin netting supported by rubber bands. Mortality was assessed 24 h after releasing the cockroaches, and death was recognised by the absence of movement when the test animals were mechanically stimulated.
  • a 0.3576 g of 85% ai of E. cloeziana oil extract was dissolve in pure acetone as a diluent to give approximately 0.304% concentration stock solution. From this solution, further serial dilutions 0.152, 0.076, 0.0043 and 0.00215 were prepared by adding the required amount in acetone. Aliquots (2.5 mL) of each concentration of E. cloeziana oil extract were dispensed into 500 mL kilner jars with total internal surface area as 286.53 cm 2 . The kilner jars were immediately rotated to coat the inner surface uniformly with the E. cloeziana oil extract residue, until dry.
  • E. cloeziana oil extract against TSM was Her assessed under greenhouse conditions. French bean plants were grown in 15 cm diam. plastic pots in an insecticide-free glasshouse maintained at 27° C., RH 65% and natural light. Plants were used when they reached the two true-leaf stage (ie., before trifoliate leaves appeared). One plant was maintained in each pot (i.e., two leaves/pot). Twenty gravid TSM females were then transferred with a fine brush to the upper surface of each leaf. Mites were left to settle for 4 h before treatment, during which time they usually settled on the lower leaf surfaces. E.
  • cloeziana oil extract at a concentration of 0.07% as well as a blank control were prepared using the same procedures described above for the laboratory bioassays.
  • a 400 mL hand sprayer was used to apply the pesticide evenly to all aerial surfaces of the plants, to run-off. Each treatment was replicated four times. The mortality was assessed 24 h after treatment. The results were recorded as mean percent mortality with standard deviation. These results revealed that the mean percent mortality in E. cloeziana oil extract treatment and control were 92.19 ⁇ 6.39 and 0.25 ⁇ 0.46, respectively.
  • E. cloeziana oil extract was efficacious against all pests tested namely TSM, TRM, GHT, aphids, termites, houseflies, American cockroaches, whitefooted ants adult mosquitoes, ash whitefly, drug store beetle and snails. It was also toxic to honeybees.
  • E. cloeziana oil extract against arthropods.
  • the test organisms used were termites, Nasutitermes walkeri.
  • a Whatman No 2 filter paper (90 mm diam.) was immersed in distilled water five seconds and left to drain excess water before placing it on the bottom of a 90 mm diam. petri dish, to provide moisture for termite workers during the experimental period.
  • a 1.0% E. cloeziana oil solution was prepared in pure acetone. One mL was uniformly spread on a second filter paper, which was allowed to air dry on a sheet of aluminium foil. It was then placed under the lid of the petri dishes containing the moist filter paper on their base.
  • E. cloeziana oil extract has highly significant fumigant effects on termites.
  • One hundred percent mortality was recorded in all replicates of the E. cloeziana oil treatment whereas no mortality occurred in any of the control (acetone only) replicates.
  • Concentrated natural emulsifiable concentrate spray (4.4%) - I Ingredient Parts E. cloeziana extract 4.4 Pyrethrins 7.4 Emulsifier: e.g. t-octylphenoxypolyethoxyethanol, 14.7 polyoxyethylenesorbitan, organosilicate Solvent: e.g. ethyl alcohol, isopropyl alcohol etc 73.5
  • Concentrated emulsifiable concentrate spray (44%) Ingredient Parts E. cloeziana extract 22.0 Platyphyllol (natural or synthetic) 22.0 Emulsifier: e.g. t-octylphenoxypolyethoxyethanol, 34.0 polyoxyethylenesorbitan, organosilicate Solvent: e.g. ethyl alcohol, isopropyl alcohol etc 22
  • Natural ready to use insecticide spray Ingredient Parts E. cloeziana extract 0.3 Lavender oil 1.0 Emulsifier: e.g. t-octylphenoxypolyethoxyethanol, 1.0 polyoxyethylenesorbitan, organosilicate Solvent e.g. ethyl alcohol, isopropyl alcohol etc 40 Carrier: Water 57.7
  • Oil-based natural spray concentrate Ingredient Parts E. cloeziana extract 10.0 Petroleum oil 89.0 Emulsifier: e.g. t-octylphenoxypolyethoxyethanol, 1.0 polyoxyethylenesorbitan, organosilicate
  • Concentrated emulsifiable concentrate spray (10%) Ingredient Parts E. cloeziana extract 10.0 Permethrin 10.0 Piperonyl butoxide 28.0 Emulsifier: e.g. t-octylphenoxypolyethoxyethanol, 31.0 polyoxyethylenesorbitan, organosilicate Solvent e.g. ethyl alcohol, isopropyl alcohol etc 21
  • Molluscidal dust Ingredient Parts E. cloeziana extract 2 Anti-caking agent (e.g. silica gel) 2 Emulsifier: e.g. t-octylphenoxypolyethoxyethanol, 3 polyoxyethylenesorbitan, organosilicate Inert carrier (talc, kaolin, diatomaceous earth) 93
  • Anti-caking agent e.g. silica gel
  • Emulsifier e.g. t-octylphenoxypolyethoxyethanol, 3 polyoxyethylenesorbitan, organosilicate Inert carrier (talc, kaolin, diatomaceous earth) 93
  • Aerosol insecticidal and acaricidal spray Ingredient Parts E. cloeziana extract 1.0 Piperonyl butoxide 0.9 Propellent hydrocarbon 98.1
  • Emulsifier e.g. t-octylphenoxypolyethoxyethanol, 1.0 polyoxyethylenesorbitan, organosilicate Solvent: e.g. ethyl alcohol, isopropyl alcohol etc 5.0 Tannic acid 1.0 Carrier e.g. water 92.8
  • Concentrated natural emulsifiable concentrate spray (4.4%) - II Ingredient Parts Melaleuca cajeputi extract 8.8 Pyrethrins 7.4 Emulsifier: e.g. t-octylphenoxypolyethoxyethanol, 14.7 polyoxyethylenesorbitan, organosilicate Solvent: e.g. ethyl alcohol, isopropyl alcohol etc 69.1
  • Ready-to-use miticide spray - III Ingredient Parts 99% Tasmanone 0.09 Emulsifier: e.g. t-octylphenoxypolyethoxyethanol, 1.0 polyoxyethylenesorbitan, organosilicate Solvent: e.g. ethyl alcohol, isopropyl alcohol etc 5 Tannic acid 1.0 Carrier e.g. water 92.91
  • Concentrated natural emulsifiable concentrate spray (4.4%) - III Ingredient Parts 99% Tasmanone 4.0 Pyrethrins 7.4 Emulsifier: e.g. t-octylphenoxypolyethoxyethanol, 14.7 polyoxyethylenesorbitan, organosilicate Solvent: e.g. ethyl alcohol, isopropyl alcohol etc 73.9
  • Ready-to-use miticide spray - IV Ingredient Parts 99% Platyphyllol 0.09
  • Emulsifier e.g. t-octylphenoxypolyethoxyethanol, 1.0 polyoxyethylenesorbitan, organosilicate Solvent: e.g. ethyl alcohol, isopropyl alcohol etc 5 Tannic acid 1.0 Carrier e.g. water 92.91
  • Concentrated natural emulsifiable concentrate spray (4.4%) - IV Ingredient Parts 99% Platyphyllol 4.0 Pyrethrins 7.4 Emulsifier: e.g. t-octylphenoxypolyethoxyethanol, 14.7 polyoxyethylenesorbitan, organosilicate Solvent: e.g. ethyl alcohol, isopropyl alcohol etc 73.9
  • an intra-specific Eucalyptus cross breeding technique will employ the following protocol. This begins with the selection of supreme individuals as parent stock. Within a selected parent stock having superior pest resistant characteristics (e.g., E. cloeziana ) male and female trees are identified for cross-pollination experiments. Pollen is harvested from the male trees and either stored or directly transferred to the female trees if flowering is synchronous. Emasculation is undertaken to preclude extraneous pollination occurring and flowers are often bagged as a further precaution. Seed set and subsequent embryo development proceeds over the ensuing 12-24 months and F1 seeds are collected at full maturation.
  • superior pest resistant characteristics e.g., E. cloeziana
  • Seeds are then germinated to produce seedlings that are subjected to detailed analysis to assess the transfer of traits from parent to progeny. If the F1 progeny show a desirable mix of phenotypic traits these progeny can be used to vegetatively propagate the new variety. If the F1 progeny show some improvement in the selected phenotypic traits, but further improvement is required selected F1 progeny can be back-crossed either within the F1 progeny or with one of the parent trees to produce an F2 progeny using the methodology outlined above. This iterative process can be continued ad infinitum until the desired characteristics are achieved.
  • Eucalyptus camaldulensis displays 14 natural hybrid crosses including E. camaldulensis XE. robusta, E. camaldulensis X E. alba, E. camaldulensis X E. cladocalyx, E. camaldulensis X E. bigalaterita, E.
  • camaldulensis X E. tereticornis E. camaldulensis X E. blakelyi, E. camaldulensis X E. dwyeri, E. camaldulensis X E. rudis, E. camaldulensis X E. ovata, E. camaldulensis X E. bridgesiana, E. camaldulensis X E. viminalis, E. camaldulensis X E. largiflorens, E. camaldulensis X E. melliodora, E. camaldulensis X E. leucoxylon; 15 manipulated hybrids including E.
  • Eucalyptus globulus displays 15 natural hybrids including E. globulus XE. barberi, E. globulus XE. brookeriana, E. globulus XE. ovata, E. globulus XE. kitsoniana, E. globulus XE. goniocalyx, E. globulus XE. nortonii, E.
  • globulus X E. cypellocarpa E. globulus X E. pseudoglobulus, E. globulus X E. bicostata, E. globulus XE. johnstonii, E. globulus XE. viminalis, E. globulus XE. cordata, E. globulus XE. rubida, E. globulus XE. urnigera, E. globulus XE. perriniana and 13 successful manipulated hybrids including E. globulus X E. urophylla, E. globulus X E. grandis, E. globulus XE. robusta, E.
  • Eucalyptus grandis displays 4 natural hybrids including E. grandis XE. urophylla, E.
  • Corymbia henryi/variegata/maculata/citriodora complex displays 14 natural hybrids including C. citriodora X C catenaria, C. citriodora X C. variegata, C. citriodora X C. maculata, C. maculata X C. gummifrea, C. maculata X C. intermedia, C. maculata X C. citriodora, C. maculata X C. variegata, C. variegata X C. bloxsomeri, C. variegata X C.
  • Eucalyptus cloeziana displays only 1 natural hybrid E. cloeziana X E. acmenoides.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Natural Medicines & Medicinal Plants (AREA)
  • Agronomy & Crop Science (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • Mycology (AREA)
  • Botany (AREA)
  • Pest Control & Pesticides (AREA)
  • Chemical & Material Sciences (AREA)
  • Alternative & Traditional Medicine (AREA)
  • Medical Informatics (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Catching Or Destruction (AREA)
US10/477,057 2001-05-08 2002-05-08 Methods and compositions for controlling pests Abandoned US20050070576A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US12/134,035 US7820209B2 (en) 2001-05-08 2008-06-05 Methods and compositions for controlling pests
US12/782,125 US20100227009A1 (en) 2001-05-08 2010-05-18 Methods and compositions for controlling pests
US13/431,726 US20120184625A1 (en) 2001-05-08 2012-03-27 Methods and compositions for controlling pests
US14/250,187 US9474270B2 (en) 2001-05-08 2014-04-10 Methods and compositions for controlling pests
US15/332,364 US20170035048A1 (en) 2001-05-08 2016-10-24 Methods and compositions for controlling pests

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AUPR4842A AUPR484201A0 (en) 2001-05-08 2001-05-08 Pesticidal compositions
AUPR4842 2001-05-08
PCT/AU2002/000569 WO2002089587A1 (en) 2001-05-08 2002-05-08 Methods and compositions for controlling pests

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2002/000569 A-371-Of-International WO2002089587A1 (en) 2001-05-08 2002-05-08 Methods and compositions for controlling pests

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/134,035 Continuation US7820209B2 (en) 2001-05-08 2008-06-05 Methods and compositions for controlling pests

Publications (1)

Publication Number Publication Date
US20050070576A1 true US20050070576A1 (en) 2005-03-31

Family

ID=3828836

Family Applications (6)

Application Number Title Priority Date Filing Date
US10/477,057 Abandoned US20050070576A1 (en) 2001-05-08 2002-05-08 Methods and compositions for controlling pests
US12/134,035 Expired - Lifetime US7820209B2 (en) 2001-05-08 2008-06-05 Methods and compositions for controlling pests
US12/782,125 Abandoned US20100227009A1 (en) 2001-05-08 2010-05-18 Methods and compositions for controlling pests
US13/431,726 Abandoned US20120184625A1 (en) 2001-05-08 2012-03-27 Methods and compositions for controlling pests
US14/250,187 Expired - Lifetime US9474270B2 (en) 2001-05-08 2014-04-10 Methods and compositions for controlling pests
US15/332,364 Abandoned US20170035048A1 (en) 2001-05-08 2016-10-24 Methods and compositions for controlling pests

Family Applications After (5)

Application Number Title Priority Date Filing Date
US12/134,035 Expired - Lifetime US7820209B2 (en) 2001-05-08 2008-06-05 Methods and compositions for controlling pests
US12/782,125 Abandoned US20100227009A1 (en) 2001-05-08 2010-05-18 Methods and compositions for controlling pests
US13/431,726 Abandoned US20120184625A1 (en) 2001-05-08 2012-03-27 Methods and compositions for controlling pests
US14/250,187 Expired - Lifetime US9474270B2 (en) 2001-05-08 2014-04-10 Methods and compositions for controlling pests
US15/332,364 Abandoned US20170035048A1 (en) 2001-05-08 2016-10-24 Methods and compositions for controlling pests

Country Status (8)

Country Link
US (6) US20050070576A1 (ja)
EP (1) EP1392119B1 (ja)
JP (1) JP4651267B2 (ja)
AT (1) ATE505082T1 (ja)
AU (2) AUPR484201A0 (ja)
DE (1) DE60239738D1 (ja)
NZ (1) NZ529414A (ja)
WO (1) WO2002089587A1 (ja)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050008714A1 (en) * 2003-04-24 2005-01-13 Essam Enan Compositions and methods for controlling insects
US20050214267A1 (en) * 2004-03-19 2005-09-29 Essam Enan Compositions and methods for controlling insects related to the octopamine receptor
US20060057178A1 (en) * 2002-05-09 2006-03-16 Scimetrics Limited Corp. Novel pest control methods
US20060263403A1 (en) * 2003-04-24 2006-11-23 Essam Enan Compositions and methods for controlling insects involving the tyramine receptor
US20080020078A1 (en) * 2006-07-17 2008-01-24 Essam Enan Compositions and methods for controlling insects
WO2008003007A3 (en) * 2006-06-27 2008-05-22 Univ Vanderbilt Compositions and methods for treating parasitic infections
US20090099135A1 (en) * 2007-01-16 2009-04-16 Tyratech, Inc. Pest control compositions and methods
US20100055208A1 (en) * 2005-11-28 2010-03-04 Ayhan Gokce Insecticidal Compositions and Uses Thereof
US20120128648A1 (en) * 2009-07-28 2012-05-24 The Energy And Resources Institute (Teri) Novel Biopesticide Compositions And Method For Isolation And Characterization Of Same
US20160255833A1 (en) * 2007-09-25 2016-09-08 Keygene N.V. Plant volatiles
US11712039B2 (en) 2017-07-07 2023-08-01 Bio-Gene Technology Limited Control of resistant pests
US11800866B2 (en) * 2018-04-06 2023-10-31 Bio-Gene Technology Unlimited Methods for control of pests

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2002950436A0 (en) * 2002-07-29 2002-09-12 George John Orban Insect repellant
US20060008491A1 (en) * 2002-09-03 2006-01-12 Leach David N Eremophilone and eremophilone derivatives for pest control
WO2005121114A2 (en) * 2004-06-07 2005-12-22 Glycom Aps 1,5 and 1,4-anhydroketoses, methods for the preparation of 1,5-and 1,4-anhydroketoses, intermediates, and uses of 1,5-and 1,4-anhydroketoses
CN1796351A (zh) 2004-12-29 2006-07-05 吴久鸿 毛叶假鹰爪素，其制法和抗肿瘤和艾滋病的应用
NZ590535A (en) * 2008-08-08 2012-11-30 Chemipreneur Ltd Fractionation and modification of natural essential oils containing beta-triketones
US8575450B2 (en) * 2009-04-09 2013-11-05 Cornell University Methods and compositions for acylsugars in tomato
US8932654B2 (en) * 2009-05-15 2015-01-13 Ecoflora Agro S.A.S. Swinglea glutinosa leaves derived material in combination with avermectins for control of acari
CN105341009A (zh) * 2015-10-30 2016-02-24 广西金神农生态农业科技开发有限公司 用于沃柑的无公害环保农药
EP3471710A4 (en) * 2016-06-21 2019-12-18 University of Canberra ANTIPARASITIC COMPOSITIONS AND METHODS
EP3648602A4 (en) * 2017-07-07 2020-12-02 Bio-Gene Technology Limited PEST CONTROL SYSTEM
CN109169566B (zh) * 2018-11-15 2023-06-09 桂林医学院 一种野外诱捕蜱虫装置
CZ309288B6 (cs) * 2020-04-22 2022-07-20 Výzkumný ústav rostlinné výroby, v. v. i Synergicky působící směs využitelná jako prostředek na ochranu rostlin před škůdci a chorobami
CN113994981A (zh) * 2021-12-02 2022-02-01 宜宾樟之美生物科技有限公司 一种含蓝桉尾油成分的驱虫杀菌剂及其制备方法
WO2023245257A1 (en) * 2022-06-24 2023-12-28 Bio-Gene Technology Limited Improved pesticidal compositions and pest control methods

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4797150A (en) * 1986-06-09 1989-01-10 Stauffer Chemical Company Certain 2-(2-substituted benzoyl)-1,3,5-cyclohexanetriones
US4853028A (en) * 1986-06-30 1989-08-01 Stauffer Chemical Company Certain 2-(2-substituted benzoyl)-1,3-cyclohexanediones
US5411728A (en) * 1993-03-03 1995-05-02 Robertet S.A. Use of derivatives of 6,6-dimethyl-2-acylcyclohex-4-en-1,3-diones in the sun protection sector of the cosmetics industry, preparations containing these derivatives, novel derivative and process for the production thereof
US5416061A (en) * 1991-04-17 1995-05-16 Rhone-Poulenc Agriculture Ltd. Herbicidal combinations of bromoxynil with selected 2-benzoylcyclohexane-1,3-diones
US6054137A (en) * 1997-12-19 2000-04-25 Societe L'oreal S.A. Promoting epidermal renewal with phloroglucinol
US6218579B1 (en) * 1997-11-27 2001-04-17 Zeneca Limited Process for the preparation of acylated cyclic 1,3-dicarbonyl compounds
US6291400B1 (en) * 1987-03-19 2001-09-18 Zeneca Limited Herbicidal compounds
US6444216B2 (en) * 1997-06-30 2002-09-03 Stratacor, Inc. Natural insect repellent

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4202840A (en) * 1978-09-29 1980-05-13 Stauffer Chemical Company 1-Hydroxy-2-(alkylketo)-4,4,6,6-tetramethyl cyclohexen-3,5-diones
US4780127A (en) * 1982-03-25 1988-10-25 Stauffer Chemical Company Certain 2-(substituted benzoyl)-1,3-cyclohexanediones and their use as herbicides
HU191288B (en) * 1982-03-25 1987-02-27 Stauffer Chemical Co,Us Herbicide preparates consisting 2-/2-substituated-benzoil/-1,3-cyclohexan-dion-derivatives
WO1993024446A1 (en) * 1992-06-02 1993-12-09 The Australian National University Anthelmintic and/or nematocidal compounds
GB9721466D0 (en) * 1997-10-09 1997-12-10 Barrier Hygiene Ltd A pesticidal composition
EP1026159A4 (en) * 1997-10-21 2001-01-10 Otsuka Kagaku Kk 4-ARYL-4- SUBSTITUTED PYRAZOLIDINE-3,5-DIONE DERIVATIVES
EP1062871B1 (en) * 1998-03-12 2007-10-17 Oji Paper Co., Ltd. Bactericides
JP4258053B2 (ja) * 1998-03-12 2009-04-30 王子製紙株式会社 天然物由来殺菌剤
NZ332694A (en) * 1998-11-06 2001-03-30 Coast Biolog Ltd Antimicrobial composition containing manuka oil (leptospermum scoparium) and Australian tea tree oil (melaleuca alternifolia)

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4797150A (en) * 1986-06-09 1989-01-10 Stauffer Chemical Company Certain 2-(2-substituted benzoyl)-1,3,5-cyclohexanetriones
US4853028A (en) * 1986-06-30 1989-08-01 Stauffer Chemical Company Certain 2-(2-substituted benzoyl)-1,3-cyclohexanediones
US6291400B1 (en) * 1987-03-19 2001-09-18 Zeneca Limited Herbicidal compounds
US5416061A (en) * 1991-04-17 1995-05-16 Rhone-Poulenc Agriculture Ltd. Herbicidal combinations of bromoxynil with selected 2-benzoylcyclohexane-1,3-diones
US5411728A (en) * 1993-03-03 1995-05-02 Robertet S.A. Use of derivatives of 6,6-dimethyl-2-acylcyclohex-4-en-1,3-diones in the sun protection sector of the cosmetics industry, preparations containing these derivatives, novel derivative and process for the production thereof
US6444216B2 (en) * 1997-06-30 2002-09-03 Stratacor, Inc. Natural insect repellent
US6218579B1 (en) * 1997-11-27 2001-04-17 Zeneca Limited Process for the preparation of acylated cyclic 1,3-dicarbonyl compounds
US6054137A (en) * 1997-12-19 2000-04-25 Societe L'oreal S.A. Promoting epidermal renewal with phloroglucinol

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7943160B2 (en) 2002-05-09 2011-05-17 Scimetrics Limited Corp. Pest control methods
US20060057178A1 (en) * 2002-05-09 2006-03-16 Scimetrics Limited Corp. Novel pest control methods
US20060263403A1 (en) * 2003-04-24 2006-11-23 Essam Enan Compositions and methods for controlling insects involving the tyramine receptor
US20050008714A1 (en) * 2003-04-24 2005-01-13 Essam Enan Compositions and methods for controlling insects
US8507013B2 (en) 2003-04-24 2013-08-13 Tyratech, Inc. Compositions for controlling insects
US20110003317A1 (en) * 2003-04-24 2011-01-06 Tyratech, Inc. Methods of screening compounds for insect-control activity involving the tyramine receptor
US20050214267A1 (en) * 2004-03-19 2005-09-29 Essam Enan Compositions and methods for controlling insects related to the octopamine receptor
US9271504B2 (en) 2005-11-28 2016-03-01 Board Of Trustees Of Michigan State University Insecticidal compositions and uses thereof
US8202552B2 (en) 2005-11-28 2012-06-19 Board Of Trustees Of Michigan State University Insecticidal compositions and uses thereof
US20100055208A1 (en) * 2005-11-28 2010-03-04 Ayhan Gokce Insecticidal Compositions and Uses Thereof
WO2008003007A3 (en) * 2006-06-27 2008-05-22 Univ Vanderbilt Compositions and methods for treating parasitic infections
CN101478984B (zh) * 2006-06-27 2013-02-20 蒂拉德克公司 治疗寄生虫感染的组合物和方法
US20080145462A1 (en) * 2006-06-27 2008-06-19 Essam Enan Compositions and methods for treating parasitic infections
US8865230B2 (en) 2006-06-27 2014-10-21 Tyratech, Inc. Compositions and methods for treating parasitic infections
US8685471B2 (en) 2006-07-17 2014-04-01 Tyratech, Inc. Compositions and methods for controlling insects
US20080020078A1 (en) * 2006-07-17 2008-01-24 Essam Enan Compositions and methods for controlling insects
US20090099135A1 (en) * 2007-01-16 2009-04-16 Tyratech, Inc. Pest control compositions and methods
US20160255833A1 (en) * 2007-09-25 2016-09-08 Keygene N.V. Plant volatiles
US20120128648A1 (en) * 2009-07-28 2012-05-24 The Energy And Resources Institute (Teri) Novel Biopesticide Compositions And Method For Isolation And Characterization Of Same
US11712039B2 (en) 2017-07-07 2023-08-01 Bio-Gene Technology Limited Control of resistant pests
US11800866B2 (en) * 2018-04-06 2023-10-31 Bio-Gene Technology Unlimited Methods for control of pests

Also Published As

Publication number Publication date
AU2002250738B2 (en) 2008-07-31
US20170035048A1 (en) 2017-02-09
US20080234386A1 (en) 2008-09-25
US7820209B2 (en) 2010-10-26
US20100227009A1 (en) 2010-09-09
EP1392119A1 (en) 2004-03-03
AUPR484201A0 (en) 2001-05-31
EP1392119B1 (en) 2011-04-13
US20120184625A1 (en) 2012-07-19
WO2002089587A1 (en) 2002-11-14
US9474270B2 (en) 2016-10-25
JP2004534021A (ja) 2004-11-11
EP1392119A4 (en) 2004-05-26
JP4651267B2 (ja) 2011-03-16
NZ529414A (en) 2006-10-27
US20140336269A1 (en) 2014-11-13
DE60239738D1 (de) 2011-05-26
ATE505082T1 (de) 2011-04-15

Similar Documents

Publication Publication Date Title
US9474270B2 (en) Methods and compositions for controlling pests
AU2002250738A1 (en) Methods and compositions for controlling pests
US5405612A (en) Hydrophobic extracted neem oil--a novel insecticide
AU2021232737B2 (en) Pest Management
US20230292751A1 (en) Control of resistant pests
US5298251A (en) Fungicide compositions derived from neem oil and neem wax fractions
US5368856A (en) Hydrophobic extracted neem oil-a novel fungicide use
US5356628A (en) Hydrophobic extracted neem oil-a novel fungicide
CZ88098A3 (cs) Prostředky hubení škůdců obsahující rozprašovací granuláty na bázi síry v kombinaci s pyretroidem
WO2023245257A1 (en) Improved pesticidal compositions and pest control methods
NZ760403B2 (en) Control of resistant pests

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: BIOPROSPECT LIMITED,AUSTRALIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SPOONER-HART, ROBERT NEIL;BASTA, ALBERT HABIB;REEL/FRAME:024482/0348

Effective date: 20040303

Owner name: UNIVERSITY OF WESTERN SYDNEY,AUSTRALIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SPOONER-HART, ROBERT NEIL;BASTA, ALBERT HABIB;REEL/FRAME:024482/0348

Effective date: 20040303

Owner name: BIOPROSPECT LIMITED, AUSTRALIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SPOONER-HART, ROBERT NEIL;BASTA, ALBERT HABIB;REEL/FRAME:024482/0348

Effective date: 20040303

Owner name: UNIVERSITY OF WESTERN SYDNEY, AUSTRALIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SPOONER-HART, ROBERT NEIL;BASTA, ALBERT HABIB;REEL/FRAME:024482/0348

Effective date: 20040303