WO1987006429A1

WO1987006429A1 - Photoactive azole pesticides

Info

Publication number: WO1987006429A1
Application number: PCT/US1987/000842
Authority: WO
Inventors: Kathryn Ann Lutomski; Susan Ellen Burkart; Richard Benton Phillips; David Michael Roush; Ignatius Joseph Turchi
Original assignee: FMC Corp
Current assignee: FMC Corp
Priority date: 1986-04-30
Filing date: 1987-04-14
Publication date: 1987-11-05
Anticipated expiration: 1988-10-30
Also published as: GR870672B; IL82341A0; KR900000566B1; KR880701237A; CN87103235A; AU7301587A

Abstract

Oxazole and thiazole compounds of formula (I) are photodynamic insecticides and acaricides as well as nematicides, wherein W is selected from O and S; R2 is selected from optionally substituted thienyl and optionally substituted phenyl; R4 is selected from hydrogen, lower alkyl, lower haloalkyl, thienyl, tri(lower alkyl)silyl, and optionally substituted phenyl; R5 is selected from optionally substituted thienyl and optionally substituted phenyl; at least one of R2 and R5 is an optionally substituted thienyl group, and R4 is other than hydrogen when R4 and R5 are each substituted phenyl or thienyl.

Description

PHOTOACTIVE AZOLE PESTICIDES

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. There is increasing scientific evidence that toxic mechanisms initiated by light play an important role in natural control of certain pest populations. In the last few years the concept of using 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.

According to the present invention, oxazole/thiazole compounds of the following structural formula are photodynamic insecticides and acaricides, as well as nematicides:

wherein 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

-C₄H₄-, -OC(X)₂0-, -OCF₂CF₂-, or -OC(CH.-)₂CH₂-,

-OCX₂CX-,0- bridging adjacent ring positions, wherein X is hydrogen, fluoro or methyl.

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.

More particularly the invention provides pesticidal compounds of the foregoing structural formula in which

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„ and R_ is unsubstituted phenyl.

The terms "halo" or "halogen" when employed herein mean fluorine, chlorine or bromine. The term "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. Among the aforesaid compounds, the thiazoles are preferred, and, in the most active compounds, R. is hydrogen. Furthermore, it is preferred that R- be a 5-substituted thienyl substituent.

Specific preferred 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)thiazole, 5-(5-methylthien-2-yl)-2-(thien-2-yl)- thiazole, 2-(5-chlorothien-2-yl)-5-(5-methyl- thien-2-yl)thiazole, and 2-(2,2-difluoro-1,3- benzodioxol-5-yl)-5-(5-methylthien-2-yl)thiazole.

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

2-bromo-l-(5-methylthien-2-yl)ethanone as a dark liquid. A mixture of 2-bromo-l-(5-methylthien-2-yl)ethanone (30.0 g of the aforesaid dark liquid) and hexamethylene tetramine (21.0 g, 0.15 mole) in chloroform (500 ml) was stirred at room temperature for three days. The solvent was removed from the reaction mixture by evap¬ oration under reduced pressure, leaving a dark residue. This residue was stirred in warm methylene chloride. Diethyl ether was added slowly to the mix¬ ture, causing a solid to precipitate. After being cooled for several hours, the solid was collected by filtration. The filter cake was rinsed with diethyl ether and was dried under reduced pressure yielding

43.1 g of l-[2-oxo-2-(5-methylthienyl)ethyl]-3,5,7-

3 7 triaza-l-azoniatricyclo-[3,3,l,l ' ]decane bromide (mp 141^βC dec).

A mixture of l-(2-oxo-2-(5-methylthienyl)ethyl]- 3,5,7-triaza-l-azoniatricyclo[3,3,1,1 3'7]decane bromide (41.7 g, 0.12 mole) and concentrated hydro¬ chloric acid (50 ml) in ethanol (200 ml) was stirred at room temperature for approximately 18 hours, forming a precipitate. This precipitate was collected by filtra¬ tion and dried under reduced pressure to yield 26.3 g of a solid. The filtrate was reduced in volume by evaporation to about 100 ml. Diethyl ether was added, causing more precipitate to form. This precipitate was collected by filtration and dried under reduced pres¬ sure, yielding 9.0 g of 2-amino-l-(5-methylthienyl)- ethanone hydrochloride.

A stirred suspension of 2-amino-l-(5-methylthienyl)- ethanone hydrochloride (3.0 g of a mixture containing approximately 60% 2-amino-l-(5-methylthienyl)ethanone hydrochloride) in methylene chloride (100 ml) was cooled in an ice bath. To this cold mixture was added 4-(trifluoromethyl)benzoyl chloride (2.8 g, 0.013 mole), followed by the slow addition of a 2N solution of sodium hydroxide (9.4 ml). After complete addition, the mixture was stirred at room temperature for three days. The mixture was washed first with an aqueous 5% hydrochloric acid solution, followed by water. The organic phase was dried over anhydrous magnesium sul- fate and filtered. The filtrate was evaporated under reduced pressure, yielding 3.9 g of N-[2-(5-methylthi- enyl)-2-oxoethyl]-4-trifluoromethylbenzamide as a solid. A small portion was recrystallized from ethanol for analysis, .p. 182-183°C.

To a stirred suspension of Lawesson's Reagent (2.3 g, 0.0057 mole) in approximately 40 ml of toluene was added a mixture of N-[2-(5-methylthienyl)-2-oxoethyl]- 4-trifluoromethylbenzamide (3.0 g, 0.011 mole) in toluene (35 ml). After complete addition the reaction mixture was heated at reflux for approximately four hours, then was allowed to cool to room temperature and stirred for two days. The solvent was removed from the reaction mixture by evaporation under reduced pressure, leaving an oil. The oil was dissolved in a small amount of methylene chloride and purified by column chromatography on silica gel, eluting with methylene chloride, yielding 1.0 g of 5-(5-methylthien-2-yl)-2- (4-trifluoromethylphenyl)thiazole as a solid, m.p. 150-152^βC.

Example 2 5-(5-Methylthien-2-yl)-2-[3,5-bis(trifluoro- methyl)phenyl]thiazole In a manner similar to Example 1, the reaction of 2-amino-l-(5-methylthienyl)ethanone hydrochloride (2.6 g, 0.014 mole) in methylene chloride (75 ml) with 3,5- bis(trifluoromethyl)benzoyl chloride (3.8 g, 0.014 mole) and 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. In a manner similar to Example 1, the reaction of N-[2-(5-methylthienyl)-2-oxoethyl]-3,5-bis(trifluoro- methyl) benzamide (4.0 g, 0.01 mole) in toluene (100 ml) with a suspension of Lawesson's Reagent (2.0 g, 0.005 mole) in toluene (100 ml) yielded 1.0 g of 5-(5- methylthien-2-yl)-2-[3,5-bis(trifluoromethyl)phenyl]- thiazole as a solid, m.p. 119.5-121°C.

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.

Example 31 2-(4-Methylphenyl)-5-(5-methylthienyl-2-yl)- thiazole

Under a dry nitrogen atmosphere, a solution of 2-(4-methylphenyl)-5-(thien-2-yl)thiazole (0.17 g, 0.00066 mole) in dry tetrahydrofuran (15 mL) was cooled to -78^βC. To this solution was added n-butyl lithium (0.40 mL of a 1.3 M solution in hexanes). After com¬ plete addition the reaction mixture was stirred at -78°C for approximately one hour. Methyl iodide (0.1 g, 0.0007 mole) was added, followed by the addi¬ tion of dimethyl sulfate (0.027 g, 0.00021 mole). The resultant mixture was stirred and allowed to gradually warm to room temperature. To this was added an aqueous saturated ammonium chloride solution. After stirring for a brief period of time the mixture was extracted with methylene chloride. The extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 0.22 g of a yellow solid, mp 108-110°C. The NMR spectrum indicated the yellow solid was a mixture which con¬ tained 85% 2-(4-methylphenyl)-5-(5-methylthien-2-yl)- thiazole and 15% 2-(4-methylphenyl)-5-(thien-2-yl)- thiazole.

Example 40 2-(4-Fluorophenyl)-5-(5-methylsulfonylthien-

2-yl)thiazole To a stirred solution of 2-(4-fluorophenyl)-5-(5- methylthiothien-2-yl)thiazole (1.07 g, 0.0035 mole) in methylene chloride (50 mL) was added dropwise a solution of m-chloroperbenzoic acid (1.7 g, 0.0084 mole) in methylene chloride (25 mL) . After complete addition the mixture was stirred at room temperature for approximately 18 hours. Approximately 100 mL of an aqueous 10% sodium sulfate solution wa's added, and the mixture was stirred for about 15 minutes. 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. Thus 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. This mixture was washed in suc¬ cession with an aqueous, saturated sodium bicarbonate solution, water, and an aqueous, saturated, sodium chloride solution. The washed organic phase was evap- orated under reduced pressure, leaving a solid resi¬ due. This residue was purified by column chromato- graphy on silica gel, elution with methylene chloride: ethyl acetate (19:1), to yield 0.59 g of 2-(4-fluoro- phenyl)-5-(5-methylsulfonylthien-2-yl)thiazole as a solid, mp 183-184°C.

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.

This solid was suspended in water and extracted twice with methylene chloride. The extracts were combined, dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure to yield 2.48 g of 4-phenyl-2-(thien-2-yl)thiazole as a solid, mp 51-53°C.

Example 63

4-(4-Chlorophenyl)-2-(5-chlorothien-2-yl)-

5-(4-methylphenyl)thiazole Under a dry nitrogen atmosphere 2-bromo-2-(4- methylphenyl)-l-(4-chlorophenyl)ethanone (4.5 g, 0.014 mole) and 5-chloro-2-thiophenethiocarboxamide (2.5 g, 0.014 mole) were heated at 110°C for 2.5 hours. The mixture was cooled and subjected to column chromato- graphy on silica gel, eluting with diethyl ether:n_- hexane (5:95), leaving a solid. Recrystallization of this solid from ethanol yielded 0.68 g of 4-(4-chloro- phenyl)-2-(5-chlorothienyl-2-yl)-5-(4-methylphenyl)- thiazole, mp 103.35-104.5^βC. Example 92

2,5-Di(thien-2-yl)oxazole A stirred mixture of N-[2-oxoethyl-2-(thien-2-yl)]- 2-thiophenecarboxamide (2.02 g, 0.0080 mole) and phos¬ phorus oxychloride (30 mL) was heated at reflux for approximately 18 hours. The mixture was allowed to cool and was poured slowly into ice water. After complete addition the aqueous mixture was stirred to destroy all residual phosphorus oxychloride and then was extracted twice with methylene chloride. The extracts were combined, dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure, leaving a solid residue. This solid was purified by chromatography, eluting with methylene chloride:n-hexane (50:40), to yield 1.42 g of 2,5-bis(thien-2-yl)oxazole, mp 64.5-66°C.

Additional azole compounds within the scope of this invention are prepared by similar techniques and are listed in Table 1.

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. Thus, 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 (also called wettable powders) 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. Many other types of useful surface-active agents are available in commerce. 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. Many variations of 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. In using the composi¬ tions to control insects, acarids, or nematodes, it is only necessary that 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. When the locus is soil, e.g., soil in which agricultural crops are or will be planted, the active compound may be applied to and optionally incorporated into the soil. For most applications, 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 pesticidal activity of the active compounds whose preparation is described above was evaluated as follows:

The azole compounds were tested for insecticidal and acaricidal activity under near ultraviolet light (wavelength 320-400 nanometers) at an intensity of

2 1600-2400 microwatts/cm using test procedures adapted to the various organisms in the test. Regard¬ less of the organism, foliage of whole plants or foliage removed from whole plants was sprayed to runoff with a 10% acetone-0.25% octylphenoxypolyethoxyethanol- water solution containing up to 200 ppm of the test compound.

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.

In tests utilizing the Mexican bean beetle (Epilachna varivestis) or the cabbage looper (Trichoplusia ni), the pinto bean test plants were sprayed with test chemical and allowed to dry as pre¬ viously described. Each test plant was cut off at the soil line and the stem was pushed through a small diameter hole punched in the bottom of an eight ounce waxed container. Ten first instar Mexican bean beetle or cabbage looper larvae were counted into each container. Each container was covered with a glass petri dish and, with the plant stem protruding from the bottom, placed on a holding rack which allowed the stem to remain in water throughout the exposure period. The test results were collected and recorded at the end of a 24 hour or 48 hour exposure period. These data appear in Table 2. In contrast to the results shown in Table 2, in the absence of ultraviolet irradi- ation, at application rates of 1000 ppm, the compounds generally failed to kill the insects and acarids.

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:

Azole compound (100% active basis) 5 parts Base 95 parts

96%-attapulgite clay 2%-highly purified sodium lignosulfonate (100%)

2%-powdered sodium alkylnaphthalenesulfonate (75%) The formulations were tested for activity against root-knot nematode as follows:

Samples of root-knot nematode inoculum were processed for nematodes by using the Caveness and

Jensen centrifugal-sugar flotation extraction technique [Caveness, F.E. and Jensen, H.J., "Modification of the Centrifugal Flotation Technique for the Isolation and Concentration of Nematodes and their Eggs from Soil and Plant Tissue", Proc. Helm. Soc., Washington, 22, 87-89 (1955)] and mixed with additional steam-sterilized sandy soil so that there were 600 to 800 root-knot nematode larvae and eggs per pot of soil (three inch diameter each, containing approximately 300 g soil). Depending on the total amount of nematode infested soil needed, mixing was accomplished by use of a cement mixer for 5 minutes or a V-shaped rotary mixer for 60 seconds.

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.

At the end of two weeks the roots of all plants were examined and evaluated for galling in comparison to untreated check plants. The results of the tests were expressed in terms of "Percent Control" and appear in Table 3.

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.

TABLE 1 Additional Examples

Ex. Name mp ( °C)

3 2-Phenyl-5-(thien-2-yl)thiazole 73-74

4 2-(2-Fluorophenyl)-5-(thien-2-yl)- 92-93.5 thiazole

5 2-(2-Trifluoromethylphenyl)-5- oil (thien-2-yl)thiazole

6 2-(3-Fluorophenyl)-5-(thien-2-yl)- 89-90 thiazole

7 2-(3-Trifluoromethylphenyl)-5- 102-103 (thien-2-yl)thiazole

8 2-(4-Fluorophenyl)-5-(thien-2-yl)- 120.5-122 thiazole

9 2-(4-Chlorophenyl)-5-(thien-2-yl)- 145.5-147 thiazole

10 2-(4-Bromophenyl)-5-(thien-2-yl)- 151-152 thiazole

12 2-[4-(l,l-Dimethylethyl)phenyl]-5- 78.5-80 (thien-2-yl)thiazole

13 2-(4-Trifluoromethylphenyl)-5- 152-153.5 (thien-2-yl)thiazole

14 2-(4-Cyanophenyl)-5-(thien-2-yl)- 189.5-191 thiazole

15 2-(4-Methoxyphenyl)-5-(thien-2-yl)- 108.5-110 thiazole

16 2-(4-Pentoxyphenyl)-5-(thien-2-yl)- 98-99 thiazole

17 2-[4-(2-Bromo-l,l,2,2-tetrafluoro- 90.5-91.5 ethoxy)phenyl]-5-(thien-2-yl)- thiazole

18 2-(4-Dimethylaminophenyl)-5-(thien- 136.5-138 2-yl)thiazole Ex . Name mp ( ° C )

19 5-(Thien-2-yl)-2-(4-thiobenzoyl- 125.5-127 phenyl)thiazole

20 2-[4-(Phenylsulfonyloxy)phenyl]-5- 165-166.5 (thien-2-yl)thiazole

21 2-(2,4-Difluorophenyl)-5-(thien- 114.5-116 2-yl)thiazole

22 2-(3,4-Dichlorophenyl)-5-(thien- 151.5-153 2-yl)thiazole

23 2-[3,5-bis(Trifluoromethyl)phenyl]- 126.5-127.5 5-(thien-2-yl)thiazole

24 2-(4-Fluorophenyl)-5-(3-methyl- 56.5-57.5 thien-2-yl)thiazole

25 5-(5-Chlorothien-2-yl)-2-(4-fluoro- 128.5-129.5 phenyl)thiazole

26 2-(4-Bromophenyl)-5-(5-chlorothien- 162-163.5 2-yl)thiazole

27 5-(5-Chlorothien-2-yl)-2-[4-(l,l- 162-163 dimethylethyl)phenyl]thiazole

28 2-(4-Fluorophenyl)-5-(5-methyl- 123-124 thien-2-yl)thiazole

29 2-(4-Chlorophenyl)-5-(5-methyl- 150.5-152 thien-2-yl)thiazole

30 2-(4-Bromophenyl)-5-(5-methyl- 156-157.5 thien-2-yl)thiazole

32 2-(2,4-Difluorophenyl)-5-(5-methyl- 100.5-101.5 thien-2-yl)thiazole

33 2-(2,4-Dichlorophenyl)-5-(5-methyl- 140.5-142 thien-2-yl)thiazole

34 2-(3,4-Dichlorophenyl)-5-(5-methyl- 170.5-172 thien-2-yl)thiazole

35 2-[4-(2-Bromo-l,l,2,2-tetrafluoro- 125.5-127 ethoxy)-3-chlorophenyl]-5-(5-methyl- thien-2-yl)thiazole Ex . Name mp ( ° C )

36 2-(3,5-Dichlorophenyl)-5-(5-methyl- 150-152 thien-2-yl)thiazole

37 2-(4-Fluorophenyl)-5-[5-(1-hydroxy- 120-121.5 2-methylpropyl)thien-2-yl]thiazole

38 2-(4-Fluorophenyl)-5-[5-(1-hydroxy- 152-153 2,2-dimethylpropyl)thien-2-yl]- thiazole

39 2-(4-Fluorophenyl)-5-(5-methylthio- 102-103 thien-2-yl)thiazole

41 2-(4-Fluorophenyl)-5-(5-trifluoro- 86-87 methylthiothien-2-yl)thiazole

42 2-(4-Fluorophenyl)-5-[5-(3,4,4- 69-70.5 trifluoro-3-butenylthio)thien-

2-yl]thiazole

43 2-(4-Fluorophenyl)-5-(5-trimethyl- 141-142.5 silylthien-2-yl)thiazole

44 2-(4-Trifluoromethylphenyl)-5- 100-101 (5-trimethylsilylthien-2-yl)- thiazole

45 2-(4-Fluorophenyl)-4-trimethyl- 63-65 silyl-5-(5-trimethylsilylthien-

2-yl)thiazole

46 2-Phenyl-4-(thien-2-yl)thiazole 70.5-72

47 5-(5-Chlorothien-2-yl)-2-(naphth- 120.5-121.5 1-yl)thiazole

48 5-(5-Chlorothien-2-yl)-2-Cnaphth- 163.5-164.5 2-yl)thiazole

49 2-Pentafluorophenyl-5-(5-methyl- 130.5-132 thien-2-yl)thiazole

51 5-Phenyl-2-(thien-2-yl)thiazole 95-96

52 4-(4-Chlorophenyl)-2-(thien-2-yl)- 87-88 thiazole

53 5-(4-Fluorophenyl)-2-(thien-2-yl)- 138-140 thiazole Ex. Name mp ( °C)

54 5-(4-Chlorophenyl)-2-(thien-2-yl)- 171-172.5 thiazole

55 5-Methyl-4-phenyl-2-(thien-2-yl)- 111-112 thiazole

56 4, 5-Diphenyl-2-(thien-2-yl)thiazole 121-122

57 4-(4-Chlorophenyl)-5-phenyl-2- 111-112 (thien-2-yl)thiazole

58 4-(4-Chlorophenyl)-2-(5-chloro- 118-119 thien-2-yl)-5-phenylthiazole

59 4-(4-Chlorophenyl)-2-(5-methyl- 117-118 thien-2-yl)-5-phenylthiazole

60 4,5-bis(4-Chlorophenyl)-2-(thien- 94-96 2-yl)thiazole

61 4,5-bis(4-Chlorophenyl)-2-(5- 131.5-133 chlorothien-2-yl) hiazole

62 4-(4-Chlorophenyl)-5-(4-methyl- 154-155 phenyl)-2-(thien-2-yl)thiazole

64 4-(4-Chlorophenyl)-5-(4-methyl- 96.5-98 phenyl)-2-(5-methylthien-2-yl)- thiazole

65 2,5-Di(thien-2-yl)thiazole 91-92

66 2-(5-Chlorothien-2-yl)-5-(thien- 103.5-105 2-yl)thiazole

67 2-(5-Methylthien-2-yl)-5-(thien- 105.5-107.5 2-yl)thiazole

68 2-(5-Chlorothien-2-yl)-5-(3-methyl- 86-87 thien-2-yl)thiazole

69 2,5-bis(5-Chlorothien-2-yl)thiazole 122-123.5

70 5-(5-Chlorothien-2-yl)-2-(5-methyl- 103.5-104.5 thien-2-yl)thiazole

71 5-(5-Methylthien-2-yl)-2-(thien-2- 120.5-122 yl)thiazole Ex. Name mp ( °C)

72 2-(5-Chlorothien-2-yl)-5-(5-methyl- 114-115.5 thien-2-yl)thiazole

73 2, 5-bis(5-Methylthien-2-yl)thiazole 106-107

74 5-(5-Chlorothien-2-yl)-2-([2,2'- 187-188 bithienyl]-5-yl)thiazole

75 2,4-Di(thien-2-yl)thiazole 49-50.5

76 2-(4-Chlorophenyl)-5-(thien-2-yl)- 84-85 oxazole

77 2-(4-Methylphenyl)-5-(thien-2-yl)- 55-57 oxazole

78 2-(4-Fluorophenyl)-5-(3-methyl- 100-101.5 thien-2-y1)oxazole

79 5-(5-Chlorothien-2-yl)-2-(4-fluoro- 97-98.5 phenyl)oxazole

80 5-(5-Methylthien-2-yl)-2-phenyl- 86.5-87 oxazole

81 2-(4-Fluorophenyl)-5-(5-methyl- 86-87 thien-2-yl)oxazole

82 2-(4-Methoxyphenyl)-5-(5-methyl- 73.5-75 thien-2-yl)oxazole

83 5-Phenyl-2-(thien-2-yl)oxazole

84 5-(4-Fluorophenyl)-2-(thien-2- yl)oxazole

85 5-(4-Chlorophenyl)-2-(thien-2-yl)- oxazole

86 5-(4-Methoxyphenyl)-2-(thien-2-yl)- oxazole

87 5-([l,l'-Biphenyl]-4-yl)-2-(thien- 2-yl)oxazole

88 5-(3-Nitrophenyl)-2-(thien-2-yl)- 139-142 oxazole Ex. Name mp ( "C)

89 4,5-Diphenyl-2-(thien-2-yl)oxazole 94-95.5

90 4-(4-Chlorophenyl)-5-phenyl-2- 103.5-105 (thien-2-yl)oxazole

91 4-(4-Chlorophenyl)-5-(4-methyl- 116-117.5 phenyl)-2-(thien-2-yl)oxazole

93 2-(5-Chlorothien-2-yl)-5-(thien- 76.77.5 2-yl)oxazole

94 Ethyl [5-[2-(4-trifluoromethyl- 137-138 phenyl)thiazol-5-yl]thien-2-yl]- carboxylate

95 2-(2,2-Difluoro-l,3-benzodioxol- 120-122 4-yl)-5-(5-methylthien-2-yl)- thiazole

96 2-(2,2-Difluoro-l,3-benzodioxol- 165-169 5-yl)-5-(5-methylthien-2-yl)- thiazole

97 5-(4-Trifluoromethylphenyl)-2- 148-150 (5-methylthien-2-yl)thiazole

TABLE 2

Foliar Testing

Cmpd. Rate Exposure Species (% Kill) of Ex. (ppm) Time (Hr.) CL MBB TSM-R TSM-S

1 100 24 0 100 100

48 100

2 50 24 73 100

50 48 3

200 24 20

3 50 48 97

4 50 24 100 100 200 24 60

5 50 24 23 99 200 24 0

6 50 24 55 100 200 24 80

7 50 24 100 200 24 75

8 100 24 99 50 48 100

9 50 48 100

10 50 24 100 200 24 0

11 100 24 100 50 48 100

12 50 24 100 200 24 85

13 100 24 100 50 48 100

14 50 24 2 200 24 5

15 50 24 100 99 200 24 5 Cmpd. Rate Exposure Species (% Kill) of Ex. (ppm) Time (Hr.) CL MBB TSM-R TSM-S

16 50 24 94 100 200 24 0

17 50 24 100 100 200 24 75

18 50 24 100 200 24 0

19 100 24 3 48 29 200 24 0 48 0

20 50 24 14 200 24 0

21 100 24 100

22 100 24 5 48 100

23 100 24 100

24 100 24 93 50 48 100

25 50 48 100 100

26 50 24 90 200 24 0

27 100 24 92

28 100 24 100 94 200 24 0

29 100 24 97 100

30 50 24 100 200 24 15

31 50 24 97 100 200 24 15

32 100 24 100

33 100 24 95 Cmpd. Rate Exposure Species (% Kill) of Ex. (ppm) Time (Hr.) CL MBB TSM-R TSM-S

34 100 24 ^* 80 96 200 24

35 100 24 93

36 100 24 6 48 87

37 50 24 19 200 24 10

38 50 24 46 200 24

39 50 24 89 100 200 24

40 50 24 14 200 24 0

41 100 24 100 200 24 30

42 100 24 97 98 200 24 35

43 50 24 99 100 200 24 10

44 100 24 97 100 200 24

45 50 24 99 200 24

46 50 48 85

47 50 24 97 200 24 0

48 50 24 99 200 24 0

49 50 24 100 200 24 0

50 100 48 100 Cmpd. Rate Exposure Species (% Kill) of Ex. Time (Hr.) CL MBB TSM-R TSM-S

52 50 48 100

53 50 48 100

54 50 48 100

55 50 48 99

56 50 48 32

57 50 48 3 100

58 50 24 98 100 24 0

59 50 24 100 100 200 24 5

60 50 24 100 100 24 0

61 50 24 35 100 24 80

62 50 48 17 96 200 48 10 10

63 50 24 2 92 100 24 0

64 50 24 77 200 24 0

65 50 48 10 100 200 48 0

66 50 48 100 100

67 100 24 93 50 48 100

68 50 24 • 100 100 200 24 0

69 50 24 100 100 200 24 0 Cmpd. Rate Exposure Species (% Kill) of Ex. (ppm) Time (Hr. ) CL MBB TSM-R TSM-S

70 50 24 100 100 200 24

71 50 24 100 100 200 24

72 50 24 100 99 200 24

73 50 24 100 100 ^* 24 15

74 50 24 84 200 24 0

75 50 48 98

76 50 48 71

77 50 48 92

78 50 48 100

79 50 • 48 100

80 50 24 87 200 24 15

81 50 24 100 200 24 10

82 50 24 18 200 24 15

83 150 48 100

84 100 48 0

85 100 48 31

86 100 48 0

87 100 48 0

89 50 48 100

90 50 48 10 Cmpd. Rate Exposure Species (% Kill) of Ex. (ppm) Time (Hr.) CL MBB TSM-R TSM-S

91 50 48 86

92 50 48 14 98

93 50 24 59 200 24 0

94 50 48 70 100

95 50 48 0 83

96 50 48 10 100

CL = Cabbage looper

MBB - Mexican bean beetle

TSM-R = Twospotted spider mite - resistant

TSM-S = Twospotted spider mite .- susceptible

TABLE 3 Evaluation Against Root-Knot Nematode

Rate of Compound Application Percent of Ex. (ppm) Control

3 10 99

98

8 10 100

85

9 10 63

25

11 10 100

95 33

24 10 38

75 75

^• 46 . 10 98

63

57 10 0

64 10 100

0

66 10 81

8

71 10 100

25

75 10 98

95

77 10 95

42

79 10 99

68

85 10 81

96

Claims

CLAIMS :

1. A compound characterized by the formula

wherein W is selected from 0 and S; ₂ is selected from 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 halo- alkoxy, di(lower)alkylamino, phenylthiocarbonyl, or phenylsulfonyloxy, thienyl, and thienyl substituted with a substituent seleςted from halogen, lower alkyl, or thienyl; R4 is selected from hydrogen, tri(lower)alkylsilyl, phenyl, halophenyl and thienyl; R5 is selected from hydrogen, lower alkyl, phenyl, phenyl substituted with at least one substituent selected from halogen, lower alkyl, lower halo¬ alkyl, lower alkoxy, phenyl, or nitro, thienyl, and thienyl substituted with a substituent selected from lower alkyl, halogen, lower hydroxyalkyl, lower haloalkylthio, lower alkylsulfonyl, lower haloalkenylthio, lower alkoxycarbonyl, or tri(lower)alkylsilyl; wherein at least one of R₂ and R5 is an optionally substituted thienyl group, and R4 is other than hydrogen when one of R and R5 is unsubstituted thienyl and the other of R₂ and R₅ is unsubstituted phenyl.

2. The compound of claim 1 selected from 5-(5- methylthien-2-yl)-2-(4-trifluoromethylphenyl)thiazole; 5-(5-methylthien-2-yl)-2-[3,5-bis(trifluoromethyl)- phenyl]thiazole; 2-(4-fluorophenyl)-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-(thien-2-yl)thiazole; 2,5-bis(5- chlorothien-2-yl)thiazole; 5-(5-methylthien-2-yl)-2-

(thien-2-yl)thiazole; 2-(5-chlorothien-2-yl)-5-(5- methylthien-2-yl)thiazole; and 2-(2,2-difluoro-l,3- benzodioxol-5-yl)-5-(5-methylthien-2-yl)thiazole.

3. A compound of claim 1 characterized in that R₄ is hydrogen.

4. A compound of claim 3 characterized in that R5 is substituted thienyl. 5. The compound of claim 4,

5-(5-methylthien-2- yl)-2-(4-trifluoromethylphenyl)thiazole. ^•

6. The compound of claim 4, 5-(5-methylthien-2- yl)-2-[3,5-bis(tribromomethyl)phenyl]thiazole.

7. An insecticidal, acaricidal, or nematicidal composition comprising in admixture with an agricul¬ turally acceptable carrier an insecticidally, acarici¬ dally, or nematicidally effective amount of at least one compound characterized by the formula

wherein W is selected from 0 and S;

R is selected from 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 halo- alkoxy, di(lower)alkylamino, phenylthiocarbonyl, or phenylsulfonyloxy, thienyl, and thienyl substituted with a substituent selected from halogen, lower alkyl, or thienyl;

R4 is selected from hydrogen, tri(lower)alkylsilyl, phenyl, halophenyl and thienyl; R5 is selected from hydrogen, lower alkyl, phenyl, phenyl substituted with at least one substituent selected from halogen, lower alkyl, lower halo¬ alkyl, lower alkoxy, phenyl, or nitro, thienyl, and thienyl substituted with a substituent selected from lower alkyl, halogen, lower hydroxyalkyl, lower haloalkyl hio, lower alkylsulfonyl, lower haloalkenylthio, lower alkoxycarbonyl, or tri(lower)alkylsilyl; wherein at least one of R₂ and R5 is an optionally substituted thienyl group, and R₄ is other than hydrogen when one of 2 and R5 is unsubstituted thienyl and the other of R and R5 is unsubstituted phenyl.

8. The composition of claim 7 selected from 5-(5- methylthien-2-yl)-2-(4-trifluoromethylphenyl)thiazole; 5-(5-methylthien-2-yl)-2-[3,5-bis(trifluoromethyl)- phenyl]thiazole; 2-(4-fluorophenyl)-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-(thien-2-yl)thiazole; 2,5-bis(5- chlorothien-2-yl)-thiazole; 5-(5-methylthien-2-yl)-2- (thien-2-yl)thiazole; 2-(5-chlorothien-2-yl)-5-(5- methylthien-2-yl)thiazole, and 2-(2,2-difluoro-l,3- benzodioxol-5-yl)-5-(5-methylthien-2-yl)thiazole.

9. A method for controlling insects, acarids, or nematodes which comprises applying to the locus where control is desired an insecticidally, acaricidally, or nematicidally effective amount of at least one compound characterized by the formula

wherein W is selected from O and S;

R₂ is selected from 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 halo- alkoxy, di(lower)alkylamino, phenylthiocarbonyl, or phenylsulfonyloxy, thienyl, and thienyl substituted with a substituent selected from halogen, lower alkyl, or thienyl; R4 is selected from hydrogen, tri(lower)alkylsilyl, phenyl, halophenyl and thienyl; R5 is selected from hydrogen, lower alkyl, phenyl, phenyl substituted with at least one substituent selected from halogen, lower alkyl, lower halo¬ alkyl, lower alkoxy, phenyl, or nitro, thienyl, and thienyl substituted with a substituent selected from lower alkyl, halogen, lower hydroxyalkyl, lower haloalkylthio, lower alkylsulfonyl, lower haloalkenylthio, lower alkoxycarbonyl, or tri(lower)alkylsilyl; . wherein at least one of R and R5 is an optionally substituted thienyl group, and R4 is other than hydrogen when one of R₂ and R5 is unsubstituted thienyl and the other of R and R5 is unsubstituted phenyl.

10. The composition of claim 9 characterized in that said compound is selected from 5-(5-methylthien-2- yl)-2-(4-trifluoromethylphenyl)thiazole; 5-(5-methyl- thien-2-yl)-2-[3,5-bis(trifluoro ethyl)phenyl]thiazole; 2-(4-fluorophenyl)-5-(thien-2-yl)thiazole; 2-(4-chloro- phenyl)-5-(thien-2-yl)thiazole; 2-(4-trifluoromethyl¬ phenyl)-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- (thien-2-yl)thiazole; 2,5-bis(5-chlorothien-2-yl)- thiazole; 5-(5-methylthien-2-yl)-2-(thien-2-yl)thiazole; 2-(5-chlorothien-2-yl)-5-(5-methylthien-2-yl)thiazole, and 2-(2,2-difluoro-l,3-benzodioxol-5-yl)-5-(5-methyl- thien-2-yl)thiazole.