(HETERO)ARYL SULFONAMIDE COMPOUND AND FORMULATION FOR CONTROLLING HARMFUL ORGANISMS

Abstract

A compound represented by formula (I) or a salt thereof, as well as a formulation for controlling harmful organisms, an insecticidal formulation, an acaricidal formulation, a nematicidal formulation, or a formulation for controlling or exterminating endoparasites, containing at least one compound selected from the group consisting of the compounds described above and salts thereof, as an active ingredient.

##STR00001##

In formula (I), Ar.sup.1 is a benzene ring or a 5- to 6-membered heteroaryl ring, R.sup.1 is a C1 to C6 alkyl group, a halogeno group, or the like, n represents the number of R.sup.1 and is 0, 1, 2, or 3, and in the case of n being 2 or more, two or more R.sup.1 may be the same as or different from one another, R.sup.2 is a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, or the like, R.sup.3 is a hydrogen atom, a C1 to C6 alkyl group, a C1 to C6 alkylcarbonyl group, or the like, and AR.sup.2 represents a substituted or unsubstituted heteroaryl group.

Claims

1. A compound represented by formula (I) or a salt thereof: ##STR00033## in formula (I), Ar.sup.1 is a 5- to 6-membered heteroaryl ring, R.sup.1 is a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C2 to C6 alkenyl group, a substituted or unsubstituted C2 to C6 alkynyl group, a hydroxyl group, a substituted or unsubstituted C1 to C6 alkoxy group, a formyl group, a substituted or unsubstituted C1 to C6 alkylcarbonyl group, a carboxyl group, a substituted or unsubstituted C1 to C6 alkoxycarbonyl group, a substituted or unsubstituted C1 to C6 alkylcarbonyloxy group, a mercapto group, a substituted or unsubstituted C1 to C6 alkylthio group, a substituted or unsubstituted C1 to C6 alkylsulfinyl group, a substituted or unsubstituted C1 to C6 alkylsulfonyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C6 to C10 aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted C6 to C10 aryloxy group, a substituted or unsubstituted heteroaryloxy group, a halogeno group, a nitro group, a cyano group, a group represented by —NR.sup.aR.sup.b, a group represented by —(C═O)—NR.sup.cR.sup.d, or a group represented by —O—(C═O)—NR.sup.cR.sup.d, n represents the number of R.sup.1 and is 0, 1, 2, or 3, and in the case of n being 2 or more, two or more R′ may be the same or different from one another, each of R.sup.a and R.sup.b independently represents a hydrogen atom, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C1 to C6 alkylcarbonyl group, or a substituted or unsubstituted C1 to C6 alkoxycarbonyl group, each of R.sup.c and R.sup.d independently represents a hydrogen atom, or a substituted or unsubstituted C1 to C6 alkyl group, R.sup.2 is a C1 to C6 alkyl group, a C1 to C6 haloalkyl group, a C3 to C8 cycloalkyl group, a C3 to C8 halocycloalkyl group, or a C3 to C8 cycloalkyl C1 to C6 alkyl group, or a C3 to C8 halocycloalkyl C1 to C6 alkyl group, R.sup.3 is a hydrogen atom, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C1 to C6 alkyl carbonyl group, a substituted or unsubstituted C1 to C6 alkoxy carbonyl group, a substituted or unsubstituted C1 to C6 alkylsulfonyl group, a substituted or unsubstituted C3 to C8 cycloalkyl group, a substituted or unsubstituted C3 to C8 cycloalkyl carbonyl group, or a substituted or unsubstituted C3 to C8 cycloalkoxy carbonyl group, and Ar.sup.2 represents a substituted or unsubstituted heteroaryl group.

2. (canceled)

3. The compound according to claim 1 or a salt thereof, wherein Formula (I) is Formula (III): ##STR00034## in Formula (III), R.sup.1, R.sup.2, R.sup.3, Ar.sup.2, and n represent the same meanings as those recited in Formula (I).

4. A formulation for controlling harmful organisms, comprising at least one compound selected from the group consisting of the compounds as recited in claim 1 and salts thereof, as an active ingredient.

5. An insecticidal or acaricidal formulation, comprising at least one compound selected from the group consisting of the compounds as recited in claim 1 and salts thereof, as an active ingredient.

6. A nematicidal formulation, comprising at least one compound selected from the group consisting of the compounds as recited in claim 1 and salts thereof, as an active ingredient.

7. A formulation for controlling or exterminating endoparasites, comprising at least one compound selected from the group consisting of the compounds as recited in claim 1 and salts thereof, as an active ingredient.

Description

EXAMPLES

[0439] [Formulations]

[0440] Several examples of formulations for controlling harmful organisms, insecticidal, acaricidal, or nematicidal formulations, endoparasite controlling formulations or parasiticidal formulations of the present invention are described below, but the additives and the addition ratios are not limited to those detailed in these examples, and can be modified over a wide range. The term “parts” in the formulations indicates “parts by weight”.

[0441] Formulations for agricultural and horticultural use and formulations for paddy rice are described below.

[0442] (Formulation 1: Water-Dispersible Powder)

[0443] Forty parts of the (hetero)aryl sulfonamide compound of the present invention, 53 parts of diatomaceous earth, 4 parts of a higher alcohol sulfate and 3 parts of an alkylnaphthalene sulfonate salt were mixed together uniformly and then finely pulverized to obtain a water-dispersible powder containing 40% of the active ingredient.

[0444] (Formulation 2: Emulsion)

[0445] Thirty parts of the (hetero)aryl sulfonamide compound of the present invention, 33 parts of xylene, 30 parts of dimethylformamide and 7 parts of a polyoxyethylene alkyl aryl ether were mixed together and dissolved to obtain an emulsion containing 30% of the active ingredient.

[0446] (Formulation 3: Granules)

[0447] Five parts of the (hetero)aryl sulfonamide compound of the present invention, 40 parts of talc, 38 parts of clay, 10 parts of bentonite and 7 parts of sodium alkyl sulfate were mixed together uniformly and then finely pulverized, and the resulting powder was granulated into a granular shape having a diameter of 0.5 to 1.0 mm to obtain granules containing 5% of the active ingredient.

[0448] (Formulation 4: Granules)

[0449] Five parts of the (hetero)aryl sulfonamide compound of the present invention, 73 parts of clay, 20 parts of bentonite, 1 part of sodium dioctylsulfosuccinate and 1 part of potassium phosphate were pulverized and mixed together, water was then added to the resulting powder and thoroughly mixed, and the mixture was granulated and dried to obtain granules containing 5% of the active ingredient.

[0450] (Formulation 5: Suspension)

[0451] Ten parts of the (hetero)aryl sulfonamide compound of the present invention, 4 parts of a polyoxyethylene alkyl aryl ether, 2 parts of sodium polycarboxylate, 10 parts of glycerol, 0.2 parts of xanthan gum and 73.8 parts of water were mixed, and the resulting mixture was subjected to wet pulverizing down to a grain size of not more than 3 microns to obtain a suspension containing 10% of the active ingredient.

[0452] Formulations for endoparasite control and parasiticidal formulations are described below.

[0453] (Formulation 6: Granulated Powder)

[0454] Five parts of the (hetero)aryl sulfonamide compound of the present invention was dissolved in an organic solvent to obtain a solution, the solution was sprayed onto 94 parts of kaolin and 1 part of white carbon, and the solvent was then evaporated under reduced pressure. This type of granulated powder can be mixed with animal feed.

[0455] (Formulation 7: Injection)

[0456] From 0.1 to 1 part of the (hetero)aryl sulfonamide compound of the present invention and 99 to 99.9 parts of peanut oil were mixed together uniformly, and the resulting mixture was then filter-sterilized using a sterilizing filter.

[0457] (Formulation 8: Pour-on Formulation)

[0458] Five parts of the (hetero)aryl sulfonamide compound of the present invention, 10 parts of a myristate ester and 85 parts of isopropanol were mixed together uniformly to obtain a pour-on formulation.

[0459] (Formulation 9: Spot-on Formulation)

[0460] From 10 to 15 parts of the (hetero)aryl sulfonamide compound of the present invention, 10 parts of a palmitate ester and 75 to 80 parts of isopropanol were mixed together uniformly to obtain a spot-on formulation.

[0461] (Formulation 10: Spray-on Formulation)

[0462] One part of the (hetero)aryl sulfonamide compound of the present invention, 10 parts of propylene glycol and 89 parts of isopropanol were mixed together uniformly to obtain a spray-on formulation.

[0463] Examples of the compounds are described below in order to describe the present invention in more detail. However, it should be understood that the present invention is not limited to the examples of the compounds described below.

Example 1

Synthesis of 1,1,1-trifluoro-N-[5-(trifluoromethyl)-2-[3-(trifluoromethyl)pyrazol-1-yl]-3-pyridyl]methanesulfonamide (Compound No. (1-1))

Step 1

3-(Trifluoromethyl)pyrazole→3-Nitro-5-(trifluoromethyl)-2-[3-(trifluoromethyl)pyrazol-1-yl]pyridine

[0464] ##STR00013##

[0465] 3-(Trifluoromethyl)pyrazole in an amount of 0.3 g was dissolved in 7 ml of DMF, and 0.11 g of 60% sodium hydride-containing paraffin was added thereto at 0° C. The mixture was stirred for 10 minutes at 0° C. Subsequently, 0.5 g of 2-chloro-3-nitro-5-(trifluoromethyl)pyridine was added thereto at 0° C. The reaction mixture was warmed to room temperature, and stirred for 30 minutes. The obtained reaction solution was poured into water, and subjected to extraction with ethyl acetate. The obtained organic layer was dried over anhydrous magnesium sulfate, and subjected to filtration. The filtrate was concentrated under reduced pressure. Thereby, a concentrated product was obtained.

Step 2

3-Nitro-5-(trifluoromethyl)-2-[3-(trifluoromethyl)pyrazol-1-yl]pyridine→5-(Trifluoromethyl)-2-[3-(trifluoromethyl)pyrazol-1-yl]pyridin-3-amine

[0466] ##STR00014##

[0467] The concentrated product obtained in Step 1 was dissolved in 8.4 ml of isopropyl alcohol, and 2.7 ml of water, 0.54 g of iron powder, and 0.13 g of ammonium chloride were added thereto at room temperature. The reaction mixture was stirred for 40 minutes under reflux conditions. The reaction mixture was cooled to room temperature. Subsequently, ethyl acetate was added thereto. The obtained reaction solution was subjected to filtration through celite. The filtrate was concentrated under reduced pressure to obtain a concentrated product. A saturated aqueous solution of sodium hydrogencarbonate was added to the concentrated product. Subsequently, the mixture was subjected to extraction with ethyl acetate. The obtained organic layer was washed with a saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate, and filtrated. The obtained filtrate was concentrated under reduced pressure, and thereby, a concentrated product was obtained. The obtained concentrated product was purified by column chromatography with silica gel. Thereby, 0.20 g of the target product was obtained (yield: 29%, 2 steps).

[0468] The .sup.1H-NMR of the obtained target product is shown below.

[0469] .sup.1H-NMR (400 MHz, CDCl.sub.3): δ 8.66 (d, 1H), 8.04 (s, 1H), 7.33 (d, 1H), 6.73 (d, 1H), 5.81 (brs, 2H).

Step 3

5-(Trifluoromethyl)-2-[3-(trifluoromethyl)pyrazol-1-yl]pyridin-3-amine→1,1,1-Trifluoro-N-[5-(trifluoromethyl)-2-[3-(trifluoromethyl)pyrazol-1-yl]-3-pyridyl] methanesulfonamide

[0470] ##STR00015##

[0471] 5-Trifluoromethyl-2-[3-(trifluoromethyl)pyrazol-1-yl]pyridin-3-amine in an amount of 0.19 g, and 0.10 g of trimethylamine were dissolved in 8 ml of chloroform, and 0.27 g of anhydrous trifluoromethanesulfonic acid was dropwise added thereto at 0° C. The reaction mixture was warmed up to room temperature, and stirred for 5 hours at room temperature. The obtained reaction solution was concentrated under reduced pressure, and water was added to the obtained concentrated product. The organic layer thereof was extracted with ethyl acetate. The obtained organic layer was washed with a saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate, and filtrated. The filtrate was concentrated under reduced pressure. The obtained concentrated product was purified by column chromatography with silica gel. Thereby, 0.17 g of the target product was obtained (yield: 62%).

[0472] The .sup.1H-NMR of the obtained target product is shown below.

[0473] .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ 8.45 (dd, 1H), 8.28 (d, 1H), 8.15 (d, 1H), 6.88 (d, 1H).

[0474] Examples of the (hetero)aryl sulphonamide compounds of the present invention produced by the same methods as those described in the above Examples are shown in Table 1 to Table 3. Table 2 indicates the substituents of the compounds represented by Formula (I-1), and Table 3 indicates the substituents of the compounds represented by Formula (I-2). The physical data of the compounds are described in the column of “Physical property”. In the tables, “Me” indicates a methyl group, “Et” indicates an ethyl group, “cPr” indicates a cyclopropyl group, and “Ph” indicates a phenyl group.

TABLE-US-00001 TABLE 1 Compound Physical No. Structure property 1-1  [00016] m.p. 270-272° C. 1-2  [00017] amorphous 1-3  [00018] m.p. 242-249° C. 1-4  [00019] m.p. 234-255° C. 1-5  [00020] m.p. 286-292° C. 1-6  [00021] viscous oil 1-7  [00022] m.p. 142-144° C. 1-8  [00023] viscous oil 1-9  [00024] m.p. 290° C. up 1-10 [00025] m.p. 114-134° C. 1-11 [00026] m.p. 69-70° C. 1-12 [00027] m.p. 89-90° C. 1-13 [00028] m.p. 85-86° C. 1-14 [00029] m.p. 148-149° C. 1-15 [00030] m.p. 94-95° C.

##STR00031##

TABLE-US-00002 TABLE 2 Com- pound Physical No. (R.sup.1).sub.n R.sup.2 R.sup.3 Ar.sup.2 property 2-1 4-Br CF.sub.3 H 1H-benzo[d]imidazol-2-yl m.p. 220° C. up 2-2 4-Br CF.sub.3 SO.sub.2CF.sub.3 1H-benzo[d]imidazol-2-yl m.p. 180-182° C. 2-3 5-CF.sub.3 CF.sub.3 H 5,6-Cl.sub.2-1H-benzo[d]imidazol-2-yl m.p. 220° C. up 2-4 5-CF.sub.3 CF.sub.3 H 5-Cl-7-COOMe-1H-benzo[d]imidazol-2-yl m.p. 220° C. up 2-5 5-CF.sub.3 CF.sub.3 SO.sub.2CF.sub.3 5-CF.sub.3-1H-benzo[d]imidazol-2-yl amorphous 2-6 5-CF.sub.3 CF.sub.3 H 5-CF.sub.3-1H-benzo[d]imidazol-2-yl m.p. 220° C. up 2-7 5-CF.sub.3 CF.sub.3 H 4,5-F.sub.2-7-COOMe-1H-benzo[d]imidazol- m.p. 220° C. up 2-yl 2-8 5-CF.sub.3 CF.sub.3 H 5,6-F.sub.2-1H-benzo[d]imidazol-2-yl m.p. 220° C. up 2-9 4,5-F.sub.2 CF.sub.3 H 5,6-F.sub.2-1H-benzo[d]imidazol-2-yl m.p. 220° C. up 2-10 5-CF.sub.3 CF.sub.3 H 5-Cl-benzo[d]oxazol-2-yl m.p. 131-133° C. 2-11 5-CF.sub.3 CH.sub.2CF.sub.3 H 5,6-F.sub.2-1H-benzo[d]imidazol-2-yl m.p. 220° C. up 2-12 5-CF.sub.3 CF.sub.3 H 1H-pyrazol-1-yl m.p. 110-112° C. 2-13 4-CF.sub.3 CF.sub.3 H 1H-pyrazol-1-yl m.p. 220° C. up 2-14 5-CF.sub.3 Et H 5,6-F.sub.2-1H-benzo[d]imidazol-2-yl m.p. 220° C. up 2-15 5-CF.sub.3 CF.sub.3 H 3-(4-Br—Ph)-1H-1,2,4-triazol-1-yl amorphous 2-16 5-CF.sub.3 CF.sub.3 H 4-(4-Cl—Ph)-1H-pyrazol-1-yl m.p. 140-142° C. 2-17 5-CF.sub.3 Et H 3-(4-Br—Ph)-1H-1,2,4-triazol-1-yl m.p. 221-223° C. 2-18 5-CF.sub.3 CF.sub.3 H 3-(4-Cl—Ph)-1H-pyrazol-1-yl m.p. 143-145° C. 2-19 5-CF.sub.3 CF.sub.3 H 4-Br-1H-pyrazol-1-yl m.p. 103-105° C. 2-20 5-CF.sub.3 CF.sub.3 H 3-(3,4-F.sub.2—Ph)-1H-pyrazol-1-yl m.p. 157-159° C. 2-21 5-CF.sub.3 CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl amorphous 2-22 5-CF.sub.3 CF.sub.3 H 3-(4-CF.sub.3—Ph)-1H-pyrazol-1-yl m.p. 136-138° C. 2-23 5-CF.sub.3 CF.sub.3 H 5-CF.sub.3-1,3,4-oxadiazol-2-yl m.p. 270° C. up 2-24 5-CF.sub.3 CF.sub.3 H 3-Me-1,2,4-oxadiazol-5-yl m.p. 90-91° C. 2-25 5-CF.sub.3 CF.sub.3 H 3-(4-Cl—Ph)-1,2,4-oxadiazol-5-yl m.p. 130-132° C. 2-26 4-Br CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 169-171° C. 2-27 5-CF.sub.3 CF.sub.3 H 5-(4-Cl—Ph)-1,2,4-oxadiazol-3-yl m.p. 85-87° C. 2-28 5-CF.sub.3 CF.sub.3 H 5-(thiophen-2-yl)-1,2,4-oxadiazol-3-yl m.p. 113-115° C. 2-29 5-CF.sub.3 CF.sub.3 H 5-CF.sub.3-1,2,4-oxadiazol-3-yl m.p. 183-185° C. 2-30 5-CF.sub.3 CF.sub.3 H 5-.sup.cPr-1,2,4-oxadiazol-3-yl m.p. 100-102° C. 2-31 4-Br Me H 3-CF.sub.3-1H-pyrazol-1-yl viscous oil 2-32 4-(2-Cl-4-CF.sub.3-Ph) Me H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 121-123° C. 2-33 5-CF.sub.3 CF.sub.3 H 3-(4-Cl—Ph)-4-Me-1H-pyrazol-1-yl m.p. 121-123° C. 2-34 5-CF.sub.3 CF.sub.3 H 4-CF.sub.3-1H-imidazol-2-yl m.p. 154-156° C. 2-35 5-CF.sub.3 CF.sub.3 H 6-CF.sub.3-pyridin-2-yl m.p. 83-84° C. 2-36 5-CF.sub.3 CF.sub.3 H 5-CF.sub.3-pyridin-2-yl m.p. 121-123° C. 2-37 5-CF.sub.3 CF.sub.3 H 6-CF.sub.3-pyridin-3-yl m.p. 197-199° C. 2-38 5-CF.sub.3 CF.sub.3 H 2-CF.sub.3-pyrimidin-5-yl m.p. 105-107° C. 2-39 5-CF.sub.3 CF.sub.3 H 5-Me-thiazol-2-yl m.p. 122-124° C. 2-40 5-CF.sub.3 CF.sub.3 H 4-Me-thiazol-2-yl m.p. 82-83° C.

##STR00032##

TABLE-US-00003 TABLE 3 Compound Physical No. (R.sup.1).sub.n R.sup.2 R.sup.3 Ar.sup.2 property 3-1 3-CF.sub.3 CF.sub.3 H 3-COOMe-1H-pyrazol-1-yl m.p. 270° C. up 3-2 3-CF.sub.3 CF.sub.3 H 3-C(═O)NH.sup.iPr-1H-pyrazol-1-yl m.p. 270° C. up 3-3 3-CF.sub.3 CF.sub.3 H 3-(4-Cl-phenyl)-1H-pyrazol-1-yl m.p. 184-186° C. 3-4 3-CF.sub.3 Me H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 158-160° C. 3-5 3-CF.sub.3 CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 184-186° C. 3-6 3-Cl CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 277-281° C. 3-7 3-CF.sub.3 CF.sub.3 Me 3-CF.sub.3-1H-pyrazol-1-yl m.p. 83-88° C. 3-8 3-CF.sub.3 CH.sub.2CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 81-85° C. 3-9 — CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 266-267° C. 3-10 3-Me CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 260-264° C. 3-11 3-CF.sub.3 CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 60-64° C. 3-12 2-Cl CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 243-245° C. 3-13 3-I CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 98-101° C. 3-14 3-CN CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 285° C. up 3-15 2-Me CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 235-243° C. 3-16 2-(6-CF.sub.3-pyridin-3-yl) CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 285° C. up 3-17 3-CF.sub.3 CCl.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 151-153° C. 3-18 2-OMe CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl viscous oil 3-19 4-Me CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 110-112° C. 3-20 2-CF.sub.3 CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl amorphous 3-21 3-CF.sub.3 CF.sub.3 H 1H-pyrazol-1-yl m.p. 234-238° C. 3-22 3-CF.sub.3 CF.sub.3 H 3-Cl-1H-pyrazol-1-yl m.p. 272-274° C. 3-23 3-CF.sub.3 CF.sub.3 H 3-.sup.tBu-1H-pyrazol-1-yl m.p. 94-96° C. 3-24 3-CF.sub.3 CF.sub.3 H 3-Br-1H-pyrazol-1-yl m.p. 89-90° C. 3-25 3-CF.sub.3 CF.sub.3 H 3-I-1H-pyrazol-1-yl m.p. 104-106° C. 3-26 3-CF.sub.3 CF.sub.3 H 3-CF.sub.3-5-CF.sub.3-1H-pyrazol-1-yl viscous oil 3-27 3-CF.sub.3 CF.sub.3 H 4-F-1H-pyrazol-1-yl m.p. 103-104° C. 3-28 3-CF.sub.3 CF.sub.3 H 4-Cl-1H-pyrazol-1-yl m.p. 87-88° C. 3-29 3-CF.sub.3 CF.sub.3 H 4-Br-1H-pyrazol-1-yl m.p. 102-103° C. 3-30 3-CF.sub.3 CF.sub.3 H 4-CF.sub.3-1H-pyrazol-1-yl m.p. 92-94° C. 3-31 3-CF.sub.3 CF.sub.3 H 4-CN-1H-pyrazol-1-yl m.p. 116-118° C. 3-32 3-CF.sub.3 CF.sub.3 H 5-Me-1H-pyrazol-1-yl n.sub.D(22.0° C.) 1.4964 3-33 3-CF.sub.3 CF.sub.3 H 4-CF.sub.3-1H-imidazol-1-yl viscous oil 3-34 2-C(═O)NH.sub.2 CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 202-206° C. 3-35 2-(2-Cl-4-CF.sub.3- CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl viscous oil phenyl) 3-36 2-CN CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 290° C. up 3-37 3-CF.sub.3 CH.sub.2CF.sub.2CH.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl m.p. 104-105° C. 3-38 3-CF.sub.3 CF.sub.3 H 3-CF.sub.3-4-Br-1H-pyrazol-1-yl m.p. 106-108° C. 3-39 3-CF.sub.3 CF.sub.3 H 3-CF.sub.3-5-Me-1H-pyrazol-1-yl n.sub.D(21.6° C.) 1.4534 3-40 2-SMe CF.sub.3 H 3-CF.sub.3-1H-pyrazol-1-yl n.sub.D(18.4° C.) 1.5191 3-41 3-CF.sub.3 CF.sub.3 H 1-CH.sub.2CF.sub.3-1H-pyrazol-4-yl viscous oil 3-42 3-CF.sub.3 CF.sub.3 SO.sub.2CF.sub.3 1-CH.sub.2CF.sub.3-1H-pyrazol-4-yl m.p. 119-120° C. 3-43 3-CF.sub.3 CF.sub.3 H 3-CF.sub.3-5-.sup.tBu-1H-pyrazol-1-yl m.p. 73-74° C. 3-44 3-CF.sub.3 CF.sub.3 H 3-CN-1H-pyrazol-1-yl m.p. 83-84° C. 3-45 3-CF.sub.3 CF.sub.3 H 3-SOCF.sub.3-1H-pyrazol-1-yl m.p. 220° C. up 3-46 3-CF.sub.3 CF.sub.3 H 3-CF.sub.3-4-Br-5-Me-1H-pyrazol-1-yl n.sub.D(21.0° C.) 1.4952 3-47 3-CF.sub.3 CF.sub.3 H 6-CF.sub.3-pyridin-2-yl m.p. 92-93° C. 3-48 3-CF.sub.3 CF.sub.3 H 1-CH.sub.2CF.sub.3-1H-pyrazol-3-yl m.p. 135-136° C. 3-49 3-CF.sub.3 CF.sub.3 H 3-CF.sub.3-5-NH.sub.2-1H-pyrazol-1-yl m.p. 81-83° C.

[0475] Among the compounds shown in Table 1, Table 2, and Table 3, the .sup.1H-NMR data of the compounds having a viscous oil property or amorphous property are shown below.

[0476] Compound No. (1-2): .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ 9.29 (s, 1H), 8.34 (d, 1H), 8.17 (d, 1H).

[0477] Compound No. (2-5): .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ 8.33 (s, 1H), 8.02 (m, 1H), 7.93 (m, 1H), 7.79 (s, 1H), 7.47 (d, 1H), 7.12 (d, 1H).

[0478] Compound No. (2-15): .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ 9.32 (s, 1H), 8.00 (d, 2H), 7.84 (m, 2H), 7.67 (d, 2H), 7.23 (d, 1H).

[0479] Compound No. (2-21): .sup.1H-NMR (400 MHz, DMSO-d.sub.6): δ 8.59 (s, 1H), 7.82 (s, 1H), 7.66 (d, 1H), 7.19 (d, 1H), 6.88 (s, 1H).

[0480] Compound No. (2-31): .sup.1H-NMR (400 MHz, CDCl.sub.3): δ 8.58 (s, 1H), 7.89 (s, 1H), 7.67 (d, 1H), 7.56 (m, 2H), 6.81 (d, 1H).

[0481] Compound No. (1-6): .sup.1H-NMR (400 MHz, MeOH-d.sub.4): δ 8.92 (s, 1H), 8.17 (d, 1H), 7.34 (d, 1H), 6.79 (s, 1H).

[0482] Compound No. (1-8): .sup.1H-NMR (400 MHz, MeOH-d.sub.4): δ 8.61 (d, 1H), 8.07 (d, 1H), 7.63 (d, 1H), 6.79 (d, 1H).

[0483] Compound No. (3-18): .sup.1H-NMR (400 MHz, MeOH-d.sub.4): δ 8.61 (s, 1H), 7.92 (d, 1H), 6.92-6.89 (m, 2H), 4.01 (s, 3H).

[0484] Compound No. (3-20): .sup.1H-NMR (400 MHz, MeOH-d.sub.4): δ 8.48 (d, 1H), 8.24 (d, 1H), 7.74 (d, 1H), 6.81 (d, 1H).

[0485] Compound No. (3-26): .sup.1H-NMR (400 MHz, MeOH-d.sub.4): δ 8.53 (d, 1H), 8.44 (d, 1H), 7.40 (s, 1H).

[0486] Compound No. (3-33): .sup.1H-NMR (400 MHz, MeOH-d.sub.4): δ 8.91 (s, 1H), 8.53 (dd, 1H), 8.29-8.26 (m, 2H).

[0487] Compound No. (3-35): .sup.1H-NMR (400 MHz, MeOH-d.sub.4): δ 8.71 (dd, 1H), 8.26 (d, 1H), 7.93-7.89 (m, 3H), 7.77 (m, 1H), 6.94 (d, 1H).

[0488] Compound No. (3-41): .sup.1H-NMR (400 MHz, CDCl.sub.3): δ 9.02 (s, 1H), 8.24 (s, 1H), 8.23 (s, 1H), 7.90 (s, 1H), 4.82 (q, 2H).

[0489] [Biological Testing]

[0490] The test examples described below demonstrate that the (hetero)aryl sulfonamide compounds of the present invention are useful as the active ingredient in a formulation for controlling harmful organisms. The unit “parts” is based on weight.

[0491] (Preparation of Test Emulsion)

[0492] Five parts of the (hetero)aryl sulfonamide compound of the present invention, 93.6 parts of dimethylformamide and 1.4 parts of a polyoxyethylene alkyl aryl ether were mixed together and dissolved to obtain an emulsion (I) containing 5% of the active ingredient.

[0493] For the control, 93.6 parts of dimethylformamide and 1.4 parts of a polyoxyethylene alkyl aryl ether were mixed together and dissolved to obtain an emulsion (II).

[0494] The insect mortality rate and the nematode mortality rate were calculated using the following equations.

Insect mortality rate(%)=(number of dead insects/number of test insects)×100 Nematode mortality rate(%)=(number of dead nematodes/number of test nematodes)×100

Test Example 1

[0495] Efficacy Test Against Mythimna separata

[0496] First, 0.8 g of a commercially-available artificial feed (Insecta LFS, manufactured by Nosan Corporation) and 1 μl of the emulsion (I) were mixed well, and thereby, a test feed was obtained. Subsequently, 0.2 g of the test feed was placed in each of the treatment areas of a plastic test container (volume: 1.4 ml). Subsequently, two second-instar larvae of Mythimna separata were inoculated into each treatment area, and a plastic lid was placed on the test container to prevent the larvae from escaping. The closed container was placed in a thermostatic chamber at 25° C. On the 5.sup.th day therefrom, the insect mortality rate and the amount of feed consumed were checked. The test was repeated.

[0497] In addition, for a control area, the insect mortality rate and the amount of feed consumed were checked in the same manner as that described in Test Example 1, with the exception of replacing the emulsion (I) with the emulsion (II).

[0498] Efficacy tests against Mythimna separata were conducted for the compounds of Compound Nos. 1-13, 2-3, 2-5, 2-6, 2-8, 2-9, 2-14, 2-15, 2-16, 2-17, 2-18, 2-22, 2-25, 2-36, 3-8, 3-46, and 3-47. For all of the compounds, the insect mortality rate against Mythimna separata was 100%, and the amount of feed consumed was 10% or less of the amount of feed consumed in the control area. It can be seen that the (hetero)aryl sulfonamide compounds of the present invention are effective against Mythimna separata.

Test Example 2

[0499] Efficacy Test against Spodoptera litura

[0500] The emulsion (I) was diluted with water to achieve a concentration of the compound of the present invention of 125 ppm. Cabbage leaves were soaked in the diluted liquid for 30 seconds. These cabbage leaves were then placed in a Petri dish, and five second-instar larvae of Spodoptera litura were released into the Petri dish. The Petri dish was placed in a thermostatic chamber at a temperature of 25° C. and a humidity of 60%. Mortality was investigated 6 days after larvae release, and the mortality rate was calculated. The test was repeated.

[0501] Efficacy tests against Spodoptera litura were conducted for the compounds of Compound Nos. 2-5, 2-6, 2-8, 2-17, and 2-18. All of the compounds exhibited a mortality rate against Spodoptera litura of 80% or more.

Test Example 3

[0502] Efficacy Test Against Plutella xylostella

[0503] The emulsion (I) was diluted with water to achieve a concentration of the compound of the present invention of 125 ppm. Cabbage leaves were soaked in the diluted liquid for 30 seconds. These cabbage leaves were then placed in a Petri dish, and five second-instar larvae of Plutella xylostella were released into the Petri dish. The Petri dish was placed in a thermostatic chamber at a temperature of 25° C. and a humidity of 60%. Mortality was investigated 3 days after larvae release, and the mortality rate was calculated. The test was repeated.

[0504] Efficacy tests against Plutella xylostella were conducted for the compounds of Compound Nos. 2-5, 2-6, 2-8, 2-14, 2-17, and 2-18. All of the compounds exhibited a mortality rate against Plutella xylostella of 80% or more.

Test Example 4

[0505] Efficacy Test Against Caenorhabditis elegans (In Vitro Test) A suspension containing about 50 mixed instars of Caenorhabditis elegans per 0.2 mL was dispensed into each well of a 96-well microplate, at a rate of 200 μL of the suspension per well. Subsequently, a solution of the compound of the present invention dissolved in DMSO at a concentration of 10,000 pm was added thereto in an amount of 1.0 μL of the DMSO solution of the compound mentioned above per well. The 96-well microplate was allowed to stand for 2 days at 25° C. Subsequently, mortality was investigated, and the nematode mortality rate was calculated. Observation was performed for 10 seconds, and those individuals that showed no movement during the 10-second observation were deemed to be dead. The test was repeated.

[0506] Efficacy tests against Caenorhabditis elegans were conducted for the compounds of Compound Nos. 2-3, 2-4, 2-6, 2-7, 2-8, 2-9, 2-10, 2-15, 2-16, and 2-29. All of the compounds exhibited a nematode mortality rate against Caenorhabditis elegans of 80% and more.

Test Example 5

[0507] Efficacy Test Against Meloidogyne incognita (In Vitro Test)

[0508] A suspension containing about 50 second-instar larvae (L2) of Meloidogyne incognita per 0.2 mL was dispensed into each well of a 96-well microplate, at a rate of 200 μL of the suspension per well. Subsequently, a solution of the compound of the present invention dissolved in DMSO at a concentration of 10,000 pm was added thereto in an amount of 1.0 μL of the DMSO solution of the compound mentioned above per well. The 96-well microplate was allowed to stand for 2 days at 15° C. Subsequently, mortality was investigated, and the nematode mortality rate was calculated. Observation was performed for 10 seconds, and those individuals that showed no movement during the 10-second observation were deemed to be dead. The test was repeated.

[0509] Efficacy tests against Meloidogyne incognita were conducted for the compounds of Compound Nos. 1-1, 1-4, 1-11, 1-13, 2-3, 2-8, 2-9, 2-11, 2-15, 2-16, 2-18, 2-19, 2-20, 2-21, 2-22, 2-25, 2-26, 2-34, 2-35, 2-36, 3-3, 3-5, 3-6, 3-8, 3-12, 3-13, 3-20, 3-22, 3-24, 3-25, 3-27, 3-28, 3-29, 3-30, 3-31, 3-33, 3-34, 3-35, 3-37, 3-38, 3-39, 3-43, 3-46, 3-47, and 3-48. All of the compounds exhibited a nematode mortality rate against Meloidogyne incognita of 80% or more.

Test Example 6

[0510] Efficacy Test Against Heterodera glycines (In Vitro Test)

[0511] A suspension containing about 50 second-instar larvae (L2) of Heterodera glycines per 0.2 mL was dispensed into each well of a 96-well microplate, at a rate of 200 μL of the suspension per well. Subsequently, a solution of the compound of the present invention dissolved in DMSO at a concentration of 10,000 pm was added thereto in an amount of 1.0 μL of the DMSO solution of the compound mentioned above per well. The 96-well microplate was allowed to stand for 3 days at 25° C. Subsequently, mortality was investigated, and the nematode mortality rate was calculated. Observation was performed for 10 seconds, and those individuals that showed no movement during the 10-second observation were deemed to be dead. The test was repeated.

[0512] Efficacy tests against Heterodera glycines were conducted for the compounds of Compound Nos. 1-1, 2-3, 2-19, 2-20, 2-21, 2-25, 2-26, 2-34, 3-8, and 3-38. All of the compounds exhibited a nematode mortality rate against Heterodera glycines of 80% or more.

Test Example 7

[0513] Efficacy Test Against Meloidogyne incognita (Club Root Formation Suppression Test)

[0514] The emulsion (I) was diluted with water to achieve a concentration of the compound of the present invention of 125 ppm. A plastic container with a diameter of 5 cm was filled with 7 g of medium, and cucumber seeds were planted therein. The culture medium was irrigated with 1 ml of the above dilution, and then inoculated with 200 eggs of Meloidogyne incognita. The container was then placed in a thermostatic chamber at a temperature of 25° C. and a humidity of 60%, and after 14 days, the roots of the cucumber plants were observed, and the number of club roots formed thereon was counted (treated area).

[0515] In the same manner as that described above with the exception that the culture medium being irrigated with the above dilute liquid was not carried out, the number of club roots formed thereon was counted (untreated area).

[0516] The club root formation suppression ratio (%) was calculated from the number of club roots formed on the roots of the cucumber plants. The test was repeated.

Club root formation suppression ratio(%)=(1−Nt/Nc)×100

[0517] Nt: Total number of club roots formed in treated samples after 14 days after repeating twice

[0518] Nc: Total number of club roots formed in untreated samples after 14 days after repeating twice

[0519] Efficacy tests against Meloidogyne incognita were conducted for the compounds of Compound Nos. 1-1, 2-3, 2-8, 2-9, 2-15, 2-16, 2-18, 2-19, 2-20, 2-21, 2-25, 2-26, 2-34, 2-35, 3-3, 3-5, 3-6, 3-8, 3-12, 3-13, 3-20, 3-22, 3-24, 3-25, 3-27, 3-28, 3-29, 3-30, 3-35, 3-37, 3-38, 3-46, and 3-48. All of the compounds exhibited a club root formation suppression ratio against Meloidogyne incognita of 80% or more.

[0520] Based on the fact that the (hetero)aryl sulfonamide compounds selected randomly from the compounds of the present invention all exhibited the types of effects described above, it can be seen that the condensed heterocyclic compounds of the present invention, including those compounds not exemplified above, have the effects of controlling harmful organisms, and in particular, insecticidal and acaricidal effects or the like. In addition, it can be seen that the compounds of the present invention have the effects of controlling parasites harmful to animals and humans, such as ectoparasites.

INDUSTRIAL APPLICABILITY

[0521] The (hetero)aryl sulfonamide compounds according to the present invention have control activity on harmful organisms, and in particular, have excellent insecticidal, acaricidal and/or nematicidal activity, exhibit excellent safety, and can be advantageously synthesized industrially.

[0522] The formulations for controlling harmful organisms of the present invention can control harmful organisms which are problematic in view of farm products or for hygiene reasons. The formulations for controlling harmful organisms of the present invention exhibit excellent control effects on agriculturally harmful organisms even with a reduced concentration.