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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• 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)
• Thiazole And Isothizaole Compounds (AREA)
• Plural Heterocyclic Compounds (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

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Cited By (11)

Citations (1)

• 1987
  • 1987-04-14 KR KR1019870701259A patent/KR900000566B1/ko active IP Right Grant
  • 1987-04-14 AU AU73015/87A patent/AU7301587A/en not_active Abandoned
  • 1987-04-14 WO PCT/US1987/000842 patent/WO1987006429A1/en unknown
  • 1987-04-27 IL IL82341A patent/IL82341A0/xx unknown
  • 1987-04-29 GR GR870672A patent/GR870672B/el unknown
  • 1987-04-30 CN CN198787103235A patent/CN87103235A/zh not_active Withdrawn

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