WO1987006429A1 - Pesticides photoactifs d'azole - Google Patents

Pesticides photoactifs d'azole Download PDF

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Publication number
WO1987006429A1
WO1987006429A1 PCT/US1987/000842 US8700842W WO8706429A1 WO 1987006429 A1 WO1987006429 A1 WO 1987006429A1 US 8700842 W US8700842 W US 8700842W WO 8706429 A1 WO8706429 A1 WO 8706429A1
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WO
WIPO (PCT)
Prior art keywords
thiazole
phenyl
thien
thienyl
methylthien
Prior art date
Application number
PCT/US1987/000842
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English (en)
Inventor
Kathryn Ann Lutomski
Susan Ellen Burkart
Richard Benton Phillips
David Michael Roush
Ignatius Joseph Turchi
Original Assignee
Fmc Corporation
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 Fmc Corporation filed Critical Fmc Corporation
Priority to KR1019870701259A priority Critical patent/KR900000566B1/ko
Publication of WO1987006429A1 publication Critical patent/WO1987006429A1/fr
Priority to DK689387A priority patent/DK689387A/da

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • 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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • This invention is in the field of heterocyclic organic chemical compounds which contain an azole nucleus. More particularly, the invention includes certain oxazole and thiazole compounds per se, agricul ⁇ tural compositions containing the novel compounds, and the method of using a broad class of such compounds to control agricultural pests such as insects, acarids and nematodes.
  • agricul ⁇ tural compositions containing the novel compounds and the method of using a broad class of such compounds to control agricultural pests such as insects, acarids and nematodes.
  • toxic mechanisms initiated by light play an important role in natural control of certain pest populations.
  • photoactive agents as insecticides has been advanced.
  • Such photosensi- tizers typically display insecticidal activity by catalyzing the electronic triplet to singlet conversion of molecular oxygen. The excited singlet oxygen behaves as a super oxidizing agent, destroying the insect tissues which it contacts, hence killing the insect.
  • oxazole/thiazole compounds of the following structural formula are photodynamic insecticides and acaricides, as well as nematicides:
  • W is selected from O and S;
  • R_ is selected from optionally substituted thienyl and optionally substituted phenyl;
  • R. is selected from hydrogen, halogen, lower alkyl, lower haloalkyl, thienyl, tri(lower alkyl)silyl, and optionally substituted phenyl;
  • R_ is selected from hydrogen, lower alkyl, optionally substituted thienyl, or optionally substituted phenyl; provided, however, that at least one of R-, and R- is an optionally substituted thienyl group, and R. is other than hydrogen when one of R- and R-. is unsubstituted thienyl and the other of R-, and R-. is unsubstituted phenyl.
  • Substituents which optionally may be carried by phenyl include one or more of the following, indepen- dently selected: hydrogen, halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, cyano, dialkylamino, phenyl, pyridyl, thienyl, lower alkyl- sulfonyloxy, thiobenzoyl, phenylsulfonyloxy, nitro, or
  • Thienyl optionally may carry a substituent indepen ⁇ dently selected from: hydrogen, halogen, lower alkyl, lower hydroxyalky1, lower alkylthio, lower haloalkyl- thio, lower alkylsulfonyl, lower haloalkenylthio, thienyl, tri(lower)alkylsilyl, or lower alkoxycar- bonyl.
  • a substituent indepen ⁇ dently selected from: hydrogen, halogen, lower alkyl, lower hydroxyalky1, lower alkylthio, lower haloalkyl- thio, lower alkylsulfonyl, lower haloalkenylthio, thienyl, tri(lower)alkylsilyl, or lower alkoxycar- bonyl.
  • W is as defined above; - is selected from the group consisting of phenyl, naphthyl, 2,2-difluoro-l,3-benzodioxyl, phenyl substituted with at least one substituent selected from halogen, lower alkyl, lower haloalkyl, cyano, lower alkoxy, lower haloalkoxy, di(lower)alkylamino, phenylthiocarbonyl, or phenylsulfonyloxy, thienyl, and thienyl substituted with a substituent selected from halogen, lower alkyl, or thienyl; R. is selected from the group consisting of hydrogen, tri(lower)alkylsilyl, phenyl, halophenyl, and thienyl;
  • R_ is selected from the group consisting of hydrogen, lower alkyl, phenyl, phenyl substituted with at least one substituent selected from halogen, lower alkyl, lower haloalkyl, lower alkoxy, phenyl, or nitro, thienyl, and thienyl substituted with a substituent selected from lower alkyl, halogen, lower hydroxyalkyl, lower haloalkyl, lower alkylsulfonyl, lower halo- alkenylthio, lower alkoxycarbonyl, or tri(lower)alkyl- silyl.
  • At least one of R_ and R_ is an optionally substituted thienyl group, preferably an optionally substituted 2-thienyl group, and R. is other than hydrogen when one of R_ and R_ is unsubstituted thienyl and the other of R trash and R_ is unsubstituted phenyl.
  • halo or halogen when employed herein mean fluorine, chlorine or bromine.
  • lower modifying "alkyl,” “alkoxy,” and the like means a straight or branched hydrocarbon chain of 1-6, prefer ⁇ ably 1-4, carbon atoms; "halo,” “hydroxy,” etc. coupled with another term means one or more hydrogen atoms has been replaced by halogen or hydroxy, respectively.
  • the thiazoles are preferred, and, in the most active compounds, R. is hydrogen.
  • R- be a 5-substituted thienyl substituent.
  • pesticides include the following compounds: 5-(5-methylthien-2-yl)-2-(4-trifluoro- methylphenyl)thiazole, 5-(5-methylthien-2-yl)-2-[3,5- bis(trifluoromethyl)phenyl]thiazole, 2-(4-fluoro- phenyl)-5-(thien-2-yl)thiazole, 2-(4-chlorophenyl)- 5-(thien-2-yl)thiazole, 2-(4-trifluoromethylphenyl)-5- (thien-2-yl)thiazole, 5-(5-chlorothien-2-yl)-2- (4-fluorophenyl)thiazole, 2-(4-methylphenyl)-5- (5-methylthien-2-yl)thiazole, 2-(5-methylthien- 2-yl)-5-(thieri-2-yl)thiazole, 2,5-bis(5-chlorothien-2- yl)thiazo
  • the active compounds of this invention can be pre ⁇ pared by elementary modification of synthesis tech ⁇ niques known in the art. Attention is directed, e.g., to U.S. 4,024,156, J. Am. Chem. Soc. , 71, 2473 (1949), Synth. Comm., 14, 1 (1984), and U.S. 4,153,703.
  • Preparation of the oxazole/thiazole compounds of this invention is illustrated by the following specific examples. In general, the compounds were characterized by melting point, elemental analysis, and absorption spectra.
  • Example 1 5-(5-Methylthien-2-yl)-2-(4-trifluoromethyl ⁇ phenyl)thiazole
  • a warm solution of 5-methyl-2-acetylthiophene (20.1 g, 0.14 mole) in chloroform (100 ml) was added to a stirred, refluxing mixture of copper (II) bromide (48.0 g, 0.22 mole) in ethyl acetate (100 ml). After com ⁇ plete addition the resultant mixture was heated at reflux for 2.5 hours. The mixture was cooled slightly and filtered. An additional 31.9 g (0.14 mole) of copper(II) bromide was added to the filtrate, and the mixture was heated at reflux for 1.5 hours. The mix ⁇ ture was cooled and filtered. The filtrate was evap- orated under reduced pressure yielding 32.1 g of
  • Example 2 5-(5-Methylthien-2-yl)-2-[3,5-bis(trifluoro- methyl)phenyl]thiazole
  • 2-amino-l-(5-methylthienyl)ethanone hydrochloride 2.6 g, 0.014 mole
  • 3,5- bis(trifluoromethyl)benzoyl chloride 3.8 g, 0.014 mole
  • 2N sodium hydroxide solution (13.7 ml) yielded 4.6 g of N-[2-(5-methylthienyl)-2-oxoethyl]- 3,5-bis(trifluoromethyl)benzamide as a solid.
  • Example 11 2-(4-Methylphenyl)-5-(thien-2-yl)thiazole To a stirred mixture of 4-methyl-N-[2-(thien-2-yl)- 2-oxoethyl]benzamide (3.01 g, 0.0116 mole) in approxi ⁇ mately 20 mL of pyridine was added phosphorous penta- sulfide (5.16 g, 0.0116 mole). After complete addi ⁇ tion the mixture was heated at reflux for 2.5 hours. The hot mixture was poured into ice water forming a precipitate. This precipitate was collected by filtration.
  • the filter cake was dissolved in methylene chloride and was subjected to column chromatography on silica gel, eluting with methylene chloride, producing yellow solid. This solid was recrystallized from ethanol to yield 0.96 g of 2-(4-methylphenyl)-5-( hien- 2-yl)thiazole, mp 85.5-86.5°C.
  • the mixture was washed in succession with an aqueous, saturated, sodium bicarbonate solution, water, and an aqueous, saturated, sodium chloride solution.
  • a thin layer chromatograph of the organic phase indicated that starting material remained.
  • the washed organic phase was diluted with methylene chloride, and an additional 1.7 grams of m-chloroperoxybenzoic acid was added.
  • This mixture was stirred and heated at reflux until only one spot was seen by thin layer chro ato- graphy. Approximately 100 mL of an aqueous 10% sodium sulfate solution was added, and the mixture was stirred for about 15 minutes.
  • Example 50 4-Phenyl-2-(thien-2-yl)thiazole To a stirred solution of 2-thiophenethiocarboxamide (1.56 g, 0.0109 mole) in ethanol (50 mL) was added 2-bromoacetophenone (2.19 g, 0.0110 mole). After complete addition the mixture was heated at reflux for two hours, then was allowed to cool to room temperature and stir for approximately 18 hours. The solvent was removed from the reaction mixture by evaporation under reduced pressure, leaving an oil which solidified.
  • the active compounds In the normal use of the pesticidal azole compounds of the present invention, the active compounds usually will not be employed free from admixture or dilution, but ordinarily will be used in a suitable formulated composition compatible with the method of application and comprising an insecticidally, acaricidally, or nematicidally effective amount of active compound.
  • the active compounds of this invention like most pesti ⁇ cidal agents, may be blended with the agriculturally acceptable surface-active agents and carriers normally employed for facilitating the dispersion of active ingredients, recognizing the accepted fact that the formulation and mode of application of a pesticide may affect the activity of the material.
  • the present active compounds may be applied, for example, as sprays, dusts, or granules to the area where pest control is desired, the type of application varying of course with the pest and the environment.
  • the active compounds of this invention may be formulated as granules of large particle size, as powdery dusts, as wettable powders, as emulsifiable concentrates, as solutions, and the like.
  • Granules may comprise porous or nonporous parti ⁇ cles, such as attapulgite clay or sand, for example, which serve as carriers for the active compounds.
  • the granule particles are relatively large, a diameter of about 400-2500 microns typically.
  • the particles are either impregnated with the active compound from solu ⁇ tion or coated with the active compound, adhesive sometimes being employed.
  • Granules generally contain 0.05-10%, preferably 0.5-5%, active ingredient as the pesticidally effective amount.
  • Dusts are admixtures of the active compounds with finely divided solids such as talc, attapulgite clay, kieselguhr, pyrophyllite, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, flours, and other organic and inorganic solids which act as carriers for the insecticide, acaricide, or nematicide. These finely divided solids have an average particle size of less than about 50 microns.
  • a typical dust formulation useful for controlling insects, acarids, or ne atodes contains 1 part of active compound, such as 5-(5-methylthien-2-yl)-2-(4- trifluoromethylphenyl)thiazole, and 99 parts of talc.
  • the active compounds of the present invention may be made into liquid concentrates by dissolution or emulsification in suitable liquids and into solid con- centrates by admixture with talc, clays, and other known solid carriers used in the pesticide art.
  • the concentrates are compositions containing, as a pesti- cidally effective amount, about 5-50% active compound and 95-50% inert material, which includes surface- active dispersing, emulsifying, and wetting agents, but even higher concentrations of active ingredient may be employed experimentally.
  • the concentrates are diluted with water or other liquids for practical application as sprays, or with additional solid carrier for use as dusts.
  • a typical 50% wettable powder formulation would consist of 50.0% (wt/wt) of 5-(5-methylthien-2-yl)-2- [3,5-bis(trifluoromethy1)phenyl]thiazole, 22.0% attapulgite diluent, 22.0% kaolin diluent, and 6.0% sodium salts of sulfonated Kraft lignin emulsifier.
  • Typical carriers for solid concentrates include fuller's earth, clays, silicas, and other highly absorbent, readily wetted inorganic diluents.
  • a solid concentrate formulation useful for controlling insects, acarids, or nematodes contains 1.5 parts each of sodium lignosulfonate and sodium laurylsulfate as wetting agents, 25 parts of 5-(5-methylthien-2-yl)-2-[3,5-bis(trifluoromethyl)- phenyl]thiazole, and 72 parts of attapulgite clay.
  • Manufacturing concentrates are useful for shipping low melting products of this invention.
  • Such concen ⁇ trates are prepared by melting the low melting solid products together with one percent or more of a solvent to produce a concentrate which does not solidify on cooling to the freezing point of the pure product or below.
  • Useful liquid concentrates include the emulsifiable concentrates, which are homogeneous liquid or paste compositions readily dispersed in water ⁇ or other liquid carriers. They may consist entirely of the active com ⁇ pound with a liquid or solid emulsifying agent, or they may also contain a liquid carrier such as xylene, heavy aromatic naphthas, isophorone and other relatively nonvolatile organic solvents. For application, these concentrates are dispersed in water or other liquid carriers and normally applied as sprays to areas to be treated.
  • a typical 50 gram per liter emulsifiable concen- trate formulation would consist of 5.90% (wt/wt) of 5-(5-methylthien-2-yl)-2-(4-trifluoromethylphenyl)- thiazole; as emulsifiers: 1.80% of a blend of the calcium salt of dodecylbenzene sulfonate and a nonionic 6-molar ethylene oxide condensation product of nonyl- phenol, 2.70% of a blend of the calcium salt of dodec ⁇ ylbenzene sulfonate and a nonionic 30-molar ethylene oxide condensation product of nonylphenol, 1.50% of a nonionic paste of polyalkylene glycol ether; and 88.10% refined xylene solvent.
  • Typical surface-active wetting, dispersing, and emulsifying agents used in pesticidal formulations include, for example, the alkyl and alkylaryl sul- fonates and sulfates and their sodium salts; alkylamide sulfonates, including fatty methyl taurides; alkylaryl polyether alcohols, sulfated higher alcohols, poly- vinyl alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition products of such esters; and the addi- tion products of long-chain mercaptans and ethylene oxide.
  • alkyl and alkylaryl sul- fonates and sulfates and their sodium salts alkylamide sulfonates, including fatty methyl taurides
  • alkylaryl polyether alcohols sulfated higher alcohols, poly- vinyl alcohols
  • polyethylene oxides
  • the surface-active agent when used, normally comprises about 1-15% by weight of the insecticidal, acaricidal, or nematicidal composition.
  • Other useful formulations include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as acetone or other organic solvents.
  • An insecticidally, acaricidally, or nematicidally effective amount of active compound in an insecticidal, acaricidal, or nematicidal composition diluted for application is normally in the range of about 0.001% to about 8% by weight.
  • spraying and dusting compositions known in the art may be used by substituting the active compounds of this invention into compositions known or apparent in the art.
  • the insecticidal, acaricidal, or nematicidal compositions of this invention may be formulated with other active ingredients, including other insecticides, nematicides, acaricides, fungicides, plant growth regulators, fertilizers, etc.
  • other active ingredients including other insecticides, nematicides, acaricides, fungicides, plant growth regulators, fertilizers, etc.
  • an insecticidally, acaricidally, or nematicidally effective amount of azole compound be applied to the locus where control is desired.
  • Such locus may, e.g., be the pests themselves, plants upon which the pests feed, or the pest habitat.
  • an insecticidally, acaricidally, or nematicidally effective amount will be about 50 to 750 g per hectare, preferably 150 g to 500 g per hectare.
  • the azole compounds were tested for insecticidal and acaricidal activity under near ultraviolet light (wavelength 320-400 nanometers) at an intensity of
  • Leaves infested with adult twospotted spider mites (Tetranychus urticae) were removed from culture plants and cut into segments containing 50-75 female mites. Each segment was placed on the upper leaf surface of a whole pinto bean (Phaseolus vulgaris) plant. After the mites had migrated to the under surfaces of the leaves, the leaf segments used to infest were removed and each plant sprayed with test chemical as described above. After the plants had dried, the entire plant and pot were placed in * metal .trays in a hood. A supply of water in the tray kept the plants turgid. Tests were conducted against both susceptible and phosphate resistant strains.
  • the azole compounds were evaluated for nematicidal activity against the root-knot nematode (Meloidogyne incognita) using aqueous acetone solutions or 5 weight percent dust formulations made up as follows and ground to fine powders:
  • Soil so infested was used for soil-incorporated nematicidal studies within 2 days of preparation.
  • the infested soil was treated with formulations to be tested for nematicidal activity by incorporating the formulation in the soil at 25 ppm or less (weight active compound in mg/soil volume in liters). Young tomato or cucumber plants were planted in this treated, infested soil in three-inch pots. Check plants were planted in the same manner, except untreated, infested soil was used.
  • the formulation base, without active ingredient, was added to infested soil separately and tomato plants grown therein to detect the effects, if any, of chemicals in the formulation base.
  • Azole compounds of this invention were also tested and found to be effective against southern corn rootworm (Diabrotica undecimpunctata howardi) and the free-living nematode Caenorhabditis elegans. Activity against the latter is indicative of anthelmintic activity.
  • TSM-R Twospotted spider mite - resistant
  • TSM-S Twospotted spider mite .- susceptible

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Des composés d'oxazole et de thiazole sont des insecticides ainsi que des acaricides et des nématicides photodynamiques ayant la formule (I) dans laquelle W est sélectionné entre O et S; R2 est sélectionné entre un thiényle éventuellement substitué et un phényle éventuellement substitué; R4 est sélectionné parmi l'hydrogène, alkyle inférieur, haloalkyle inférieur, thiényle, tri(alkyle inférieur)silyle, et phényle éventuellement substitué; R5 est sélectionné entre un thiényle éventuellement substitué et un phényle éventuellement substitué; au moins un élément parmi R2 et R5 est un groupe thiényle éventuellement substitué, et R4 est autre qu'hydrogène lorsque R4 et R5 sont chacun phényle ou thiényle substitués.
PCT/US1987/000842 1986-04-30 1987-04-14 Pesticides photoactifs d'azole WO1987006429A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1019870701259A KR900000566B1 (ko) 1986-04-30 1987-04-14 광활성 아졸 살충제
DK689387A DK689387A (da) 1986-04-30 1987-12-29 Photoaktive azol-pesticider

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US908,754 1978-05-23
US85788386A 1986-04-30 1986-04-30
US857,883 1986-04-30
US90875486A 1986-09-17 1986-09-17

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Publication Number Publication Date
WO1987006429A1 true WO1987006429A1 (fr) 1987-11-05

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Application Number Title Priority Date Filing Date
PCT/US1987/000842 WO1987006429A1 (fr) 1986-04-30 1987-04-14 Pesticides photoactifs d'azole

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KR (1) KR900000566B1 (fr)
CN (1) CN87103235A (fr)
AU (1) AU7301587A (fr)
GR (1) GR870672B (fr)
IL (1) IL82341A0 (fr)
WO (1) WO1987006429A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5668161A (en) * 1994-07-27 1997-09-16 G.D. Searle & Co. Substituted thiazoles for the treatment of inflammation
EP0934937A1 (fr) * 1990-11-30 1999-08-11 Otsuka Pharmaceutical Co., Ltd. Dérivés d'azoles comme inhibiteurs de radicaux superoxyde
WO2000009500A2 (fr) * 1998-08-11 2000-02-24 Nihon Bayer Agrochem K.K. Pyrazoles nematicides
WO2009014287A1 (fr) * 2007-07-26 2009-01-29 Korea Research Institute Of Bioscience And Biotechnology Composition pour tuer des insectes comprenant des composés azole comme ingrédient actif
JP2010536774A (ja) * 2007-08-13 2010-12-02 ダイバージェンス・インコーポレイテッド 線虫を制御するための組成物および方法
WO2014067962A1 (fr) * 2012-10-31 2014-05-08 Bayer Cropscience Ag Nouveaux composés hétérocycliques utilisés comme agents de lutte contre les nuisibles
US9173401B2 (en) 2013-03-15 2015-11-03 Monsanto Technology Llc N-,C-disubstituted azoles and compositions and methods for controlling nematode pests
EP2944636A1 (fr) * 2009-02-10 2015-11-18 Monsanto Technology LLC Procédé et compositions pour le contrôle de nématodes
AU2013203836B2 (en) * 2007-08-13 2016-02-25 Monsanto Technology Llc Compositions and methods for controlling nematodes
US9339035B2 (en) 2010-09-02 2016-05-17 Monsanto Technology Llc Compositions and methods for controlling nematode pests
US10676467B2 (en) 2017-06-30 2020-06-09 Washington University Compositions for binding sphingosine-1-phosphate receptor 1 (S1P1), imaging of S1P1, and methods of use thereof

Citations (1)

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US4153703A (en) * 1977-06-30 1979-05-08 Uniroyal, Inc. Method of controlling insects and acarids with certain aryl-substituted thiazoles

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CHEMICAL ABSTRACTS, Volume 51, No. 21, issued 10 November 1957 (Columbus, Ohio, USA), HAYES et al., "Liquid Scintillators. I. Pulse Height Comparison of Primary Solutes", see 1612d-e, Nucleonics 13, No. 12, 38-41 (1955). *
CHEMICAL ABSTRACTS, Volume 54, No. 10, issued 25 May 1960 (Columbus, Ohio, USA), KERR et al., "Liquid Scintillators, VII. 2,5-Diaryl Substituted Thiazoles as Liquid Scintillator Solutes", see 9891 a-c, J. Org. Chem. 24, 1861-4 (1959). *
CHEMICAL ABSTRACTS, Volume 82, No. 19, issued 12 May 1975 (Columbus, Ohio, USA), CHAUVIN et al., "Chemical Properties of Ring-Substituted Polyheterocycles of the Thienylazole Type", see page 554, column 2, Abstract No. 125314e, Bull. Soc. Chim. Fr. 1974 (9-10, Pt. 2), 2099-104 (Fr). *

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1130017A3 (fr) * 1990-11-30 2001-09-19 Otsuka Pharmaceutical Co., Ltd. Dérivés d'azole et leur utilisation comme inhibiteurs des radicaux superoxydes
EP0934937A1 (fr) * 1990-11-30 1999-08-11 Otsuka Pharmaceutical Co., Ltd. Dérivés d'azoles comme inhibiteurs de radicaux superoxyde
USRE37556E1 (en) 1990-11-30 2002-02-19 Otsuka Pharmaceutical Co., Ltd. Superoxide radical inhibitor
EP1130017A2 (fr) * 1990-11-30 2001-09-05 Otsuka Pharmaceutical Co., Ltd. Dérivés d'azole et leur utilisation comme inhibiteurs des radicaux superoxydes
US5668161A (en) * 1994-07-27 1997-09-16 G.D. Searle & Co. Substituted thiazoles for the treatment of inflammation
US6605730B2 (en) 1998-08-11 2003-08-12 Nihon Bayer Agrochem K.K. Intermediates for nematicidal pyrazoles
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CN87103235A (zh) 1988-06-08
AU7301587A (en) 1987-11-24
GR870672B (en) 1987-09-02
KR880701237A (ko) 1988-07-26
IL82341A0 (en) 1987-10-30
KR900000566B1 (ko) 1990-01-31

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