WO1994008954A1 - Semicarbozones arthropodicides - Google Patents

Semicarbozones arthropodicides Download PDF

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Publication number
WO1994008954A1
WO1994008954A1 PCT/US1993/009475 US9309475W WO9408954A1 WO 1994008954 A1 WO1994008954 A1 WO 1994008954A1 US 9309475 W US9309475 W US 9309475W WO 9408954 A1 WO9408954 A1 WO 9408954A1
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WO
WIPO (PCT)
Prior art keywords
compounds
oil
compound
pests
ether
Prior art date
Application number
PCT/US1993/009475
Other languages
English (en)
Inventor
Du Pont De Nemours And Company E.I.
Original Assignee
Lahm, George, Philip
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 Lahm, George, Philip filed Critical Lahm, George, Philip
Priority to AU52994/93A priority Critical patent/AU5299493A/en
Publication of WO1994008954A1 publication Critical patent/WO1994008954A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
    • C07C281/06—Compounds containing any of the groups, e.g. semicarbazides
    • C07C281/08—Compounds containing any of the groups, e.g. semicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. semicarbazones
    • C07C281/12—Compounds containing any of the groups, e.g. semicarbazides the other nitrogen atom being further doubly-bound to a carbon atom, e.g. semicarbazones the carbon atom being part of a ring other than a six-membered aromatic ring
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane

Definitions

  • TITLE ARTHROPODICIDAL SEMICARBAZONES This invention pertains to substituted semicarbazones useful as broad spectrum arthropodicides, particularly for control of pests of the Orders Lepidoptera and Coleoptera.
  • WO 90/07495 generically discloses the compounds of the present invention.
  • the present invention comprises the racemic mixture, individual enantiomers and optically active mixtures of the enantiomers of the compounds as well as their agriculturally suitable salts.
  • This oil (78 g) was dissolved in methanol (200 mL) and treated with a 35% solution of sodium hydroxide in water (200 mL) and the resulting suspension heated to reflux for 4 h.
  • the mixture was poured into water (200 mL) and washed once with ether (200 rnL).
  • the aqueous phase was acidified to a pH of 2 with concentrated hydrochloric acid and then extracted with ether (3 x 200 mL).
  • the combined organic phases were dried over magnesium sulfate, filtered and concentrated under reduced pressure.
  • the resulting oil was dissolved in xylenes (300 mL) and heated to reflux for 18 h. After cooling to room temperature, the mixture was concentrated under reduced pressure to give 55.3 g of an oil.
  • This oil 55.3 g was added in three portions over 30 min to 610 g of mechanically stirred polyphosphoric acid (PPA) heated to 60°C. The mixture was then heated to 100°C for 1.5 h. After cooling to 60°C, ice was added and the mixture washed with toluene (2 x 300 mL). The combined organic phases were washed with saturated aqueous sodium bicarbonate solution (100 mL) and saturated aqueous sodium chloride solution (100 mL), dried over magnesium sulfate, filtered and concentrated under reduced pressure.
  • PPA polyphosphoric acid
  • Lithium diisopropylamide (LDA) was prepared by combining 7.0 mL (50 mmol) of diisopropyl amine and 100 mL of tetrahydrofuran. To this mixture cooled to approximately -78°C was added via a syringe 20.0 mL of n-BuLi (2.5 M in hexane). The reaction mixture was stirred for approximately 3 min and 6.5 g of ethyl valerate (7.4 mL, 50 mmol) was added dropwise. The reaction mixture was stirred for an additonal 3 min and then 8.0 g of 3-chlorobenzylchloride (V, 50 mmol) was added dropwise.
  • LDA Lithium diisopropylamide
  • the reaction mixture was allowed to warm to -10°C over 30 min, quenched by adding 100 mL of 0.2 ⁇ HC1 and then partitioned between water and diethyl ether. The ether layer was washed twice with water, dried over magnesium sulfate, filtered and concentrated under reduced pressure to yield 14.2 g of a yellow oil.
  • the oil was purified by chromatography on silica gel eluting with 2.5% ethyl acetate in hexane to yield a mixture of products by thin layer chromatography (silica gel, 5:95 ethyl acetate:hexane).
  • the oil (2.07 g) was combined with 40 mL of methanol, 10 mL of water and 3.0 mL of 50% aqueous sodium hydroxide. This mixture was heated to reflux and allowed to reflux overnight. The methanol was removed under reduced pressure, and the residue partitioned in diethyl ether and water. The ether layer was washed with water and the combined water layers were acidified, extracted 3 times with diethyl ether. The ether layers were combined, dried over magnesium sulfate, filtered and concentrated under reduced pressure. The resulting oil was dissolved in carbon tetrachloride and reconcentrated under reduced pressure to yield 1.58 g of a yellow oil. H NMR was consistent with the acid.
  • This oil (1.58 g) dissolved in a small amount of toluene was added with stirring to 30 g of polyphosphoric acid (PPA) heated to 60°C. The mixture was then heated to 115°C for 1.5 h. After cooling, the reaction was quenched with 60 mL of water and partitioned between water and toluene. The organic layer was washed with 5.0% sodium bicarbonate, dried over magnesium sulfate, filtered and concentrated under reduced pressure to yield 1.35 g of a yellow oil.
  • PPA polyphosphoric acid
  • Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent.
  • Useful formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High strength compositions are primarily used as intermediates for further formulation.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up 100 weight percent.
  • Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill.
  • Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., 1988, pp 251-259.
  • Suspensions are prepared by wet-milling; see, for example, U.S. 3,060,084.
  • Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques.
  • Compound I 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • the compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term “arthropods” includes insects, mites and nematodes) which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests.
  • all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, junveniles and adults of the Phylum Nematoda.
  • the compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes.
  • the compounds are active against southern corn rootworm (Diabrotica undecimpunctata howardi), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite (Tetranychus urticae), fall armyworm (Spodopterafrugiperda), black bean aphid (Aphis fabae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatellafurcifera), green leafhopper (Nephotettix cincticeps), brown planthopper (Nilaparvata lugens), small brown planthopper (Laodelphax striatellus), rice stem borer (Chilo suppressalis), rice leafroller (Cnaphalocrocis medinalis), black rice stink bug (S
  • Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis; Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus calif ornicus and Brevipalpus obovatus; Eriophyid
  • Compounds of this invention can also be mixed with one or more other insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellants, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • insecticides such as avermectin B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlorpyrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, metha-midophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, t
  • Arthropod pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or both of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • the present invention further comprises a method for the control of foliar and soil inhabiting arthropods and nematode pests and protection of agronomic and/or nonagronomic crops, comprising applying one or both of the compounds of Formula I and ⁇ , or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • a preferred method of application is by spraying.
  • granular formulations of these compounds can be applied to the plant foliage or the soil.
  • Other methods of application include direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others.
  • the compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like.
  • the compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
  • a preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, and synergists and other solvents such as piperonyl butoxide often enhance compound efficacy.
  • the rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/ square meter may be sufficient or as much as 150 mg/square meter may be required.
  • Test units each consisting of an 8-ounce (230 mL) plastic cup containing a layer of wheat germ diet, approximately 0.5 cm thick, were prepared.
  • Ten third- instar larvae of fall armyworm (Spodopterafrugiperda) were placed into a cup.
  • a solution of the test compound (acetone/distilled water 75/25 solvent) was sprayed into the cups, a single solution per set of three cups. Spraying was accomplished by passing the cups, on a conveyer belt, directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.5 pounds of active ingredient per acre (about 0.55 kg/ha) at 30 p.s.i. (207 kPa).
  • the cups were then covered and held at 27°C and 50% relative humidity for 72 h, after which time both Compounds I and ⁇ gave 100% mortality.
  • Test A The test procedure of Test A was repeated for efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens) except that mortality was assessed at 48 h after which time both Compounds I and II gave 100% mortality.
  • Test units each consisting of an 8-ounce (230 mL) plastic cup containing 1 sprouted corn seed, were prepared. A set of three test units was sprayed as described in Test A with a solution of Compound I. After the spray on the cups had dried, five third-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardi) were placed into each cup. A moistened dental wick was inserted into each cup to prevent drying and the cups were then covered. The cups were then held at 27°C and 50% relative humidity for 48 h, after which time both Compounds I and II gave 100% mortality.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On décrit les composés suivants, I: 2-(2-éthyl-4-fluoro-2,3-dihydro-1H-inden-1-ylidène)-N-[(4-trifluorométhoxy)phényl]hydrazinecarboxamide et II: 2-(5-chloro-2,3-dihydro-2-propyl-1H-inden-1-ylidène)-N-[(4-trifluorométhoxy)phényl]hydrazinecarboxamide, des compositions les contenant et leur utilisation pour lutter contre les arthropodes.
PCT/US1993/009475 1992-10-19 1993-10-12 Semicarbozones arthropodicides WO1994008954A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU52994/93A AU5299493A (en) 1992-10-19 1993-10-12 Arthropodicidal semicarbazones

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US96275392A 1992-10-19 1992-10-19
US7/962,753921019 1992-10-19

Publications (1)

Publication Number Publication Date
WO1994008954A1 true WO1994008954A1 (fr) 1994-04-28

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5608109A (en) * 1993-12-08 1997-03-04 Nihon Nohyaku Co., Ltd. Insecticidal hydrazine derivatives
US6465700B1 (en) * 1997-02-05 2002-10-15 Boulder Scientific Company Coupling reactions of 2-substituted, 7-haloindenes with aryl substituents to produce metallocene catalyst ligands
EP1280756A2 (fr) * 2000-05-08 2003-02-05 Boulder Scientific Company Synthese d'acide 2-halobenzyl alcanoique
CN102584639A (zh) * 2011-12-22 2012-07-18 山东京博控股股份有限公司 对三氟甲氧基苯胺基甲酰肼的合成方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990007495A1 (fr) * 1988-12-27 1990-07-12 E.I. Du Pont De Nemours And Company Arthropodicides a base de semicarbazone a substitution

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990007495A1 (fr) * 1988-12-27 1990-07-12 E.I. Du Pont De Nemours And Company Arthropodicides a base de semicarbazone a substitution

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5608109A (en) * 1993-12-08 1997-03-04 Nihon Nohyaku Co., Ltd. Insecticidal hydrazine derivatives
US6465700B1 (en) * 1997-02-05 2002-10-15 Boulder Scientific Company Coupling reactions of 2-substituted, 7-haloindenes with aryl substituents to produce metallocene catalyst ligands
EP1280756A2 (fr) * 2000-05-08 2003-02-05 Boulder Scientific Company Synthese d'acide 2-halobenzyl alcanoique
EP1280756A4 (fr) * 2000-05-08 2005-09-28 Boulder Scient Co Synthese d'acide 2-halobenzyl alcanoique
CN102584639A (zh) * 2011-12-22 2012-07-18 山东京博控股股份有限公司 对三氟甲氧基苯胺基甲酰肼的合成方法

Also Published As

Publication number Publication date
AU5299493A (en) 1994-05-09

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