Bipyridine compound and use of same for noxious arthropod control

Abstract

A bipyridine compound having an excellent controlling effect against noxious arthropods is provided. In particular, a bipyridine compound of formula (I) or an N-oxide thereof is provided in which the variable groups are as described in the specification. Also provided are compositions containing the bipyridine compound or an N-oxide thereof, and methods of using such compounds and compositions to control noxious arthropods. ##STR00001##

Claims

1. A bipyridine compound represented by formula (I) or an N-oxide thereof: ##STR00098## wherein: L represents a single bond or an oxygen atom, and when L represents an oxygen atom, m represents 2; R.sup.1 represents a C1-C10 chain hydrocarbon group substituted with one or more halogen atoms, a (C1-C5 alkoxy)C2-C5 alkyl group substituted with one or more halogen atoms, a (C1-C5 alkylsulfanyl)C2-C5 alkyl group substituted with one or more halogen atoms, a (C1-C5 alkylsulfinyl)C2-C5 alkyl group substituted with one or more halogen atoms, a (C1-C5 alkylsulfonyl)C2-C5 alkyl group substituted with one or more halogen atoms, a (C3-C7 cycloalkyl)C1-C3 alkyl group substituted with one or more substituents selected from Group G, or a C3-C7 cycloalkyl group substituted with one or more substituents selected from Group G; R.sup.2 represents a C1-C6 alkyl group optionally substituted with one or more halogen atoms; R.sup.3 represents a C1-C6 chain hydrocarbon group optionally substituted with one or more substituents selected from Group B, a phenyl group optionally substituted with one or more substituents selected from Group D, a 5 or 6 membered aromatic heterocyclic group optionally substituted with one or more substituents selected from Group D, a OR.sup.12, a NR.sup.11R.sup.12, a NR.sup.11aR.sup.12a, a NR.sup.24NR.sup.11R.sup.12, a NR.sup.11C(O)R.sup.13, a NR.sup.24NR.sup.11C(O)R.sup.13, a NR.sup.11C(O)OR.sup.14, a NR.sup.24NR.sup.11C(O)OR.sup.14, a NR.sup.11C(O)NR.sup.15R.sup.16, a NR.sup.24NR.sup.11C(O)NR.sup.15R.sup.16, a N?CHNR.sup.15R.sup.16, a N?S(O).sub.xR.sup.15R.sup.16, a S(O).sub.yR.sup.15, a C(O)OR.sup.17, a C(O)NR.sup.11R.sup.12, a cyano group, a nitro group, or a halogen atom; q is 0, 1, 2, or 3, and when q is 2 or 3, a plurality of R.sup.3 may be identical or different; R.sup.6 represents a C1-C6 alkyl group optionally substituted with one or more halogen atoms, a OR.sup.18, a NR.sup.18R.sup.19, a C(O)OR.sup.25, a OC(O)R.sup.20, a cyano group, a nitro group, or a halogen atom; p is 0, 1, 2, or 3, and when p is 2 or 3, a plurality of R.sup.3 can be identical or different; R.sup.11, R.sup.17, R.sup.18, R.sup.19, R.sup.20, R.sup.24 and R.sup.25 represent independently of each other a hydrogen atom, or a C1-C6 chain hydrocarbon group optionally substituted with one or more halogen atoms; R.sup.12 represents a hydrogen atom, a C1-C6 chain hydrocarbon group optionally substituted with one or more halogen atoms, a C1-C6 alkyl group substituted with one substituent selected from Group F, or a S(O).sub.2R.sup.23; R.sup.23 represents a C1-C6 chain hydrocarbon group optionally substituted with one or more halogen atoms, or a phenyl group optionally substituted with one or more substituents selected from Group D, R.sup.11a and R.sup.12a combine together with a nitrogen atom to which they are attached to form a 3 to 7 membered nonaromatic heterocyclic group, wherein the 3 to 7 membered nonaromatic heterocyclic group represents aziridine, azetidine, pyrrolidine, imidazoline, imidazolidine, piperidine, tetrahydropyrimidine, hexahydropyrimidine, piperazine, azepane, oxazolidine, isooxazolidine, 1,3-oxazinane, morpholine, 1,4-oxazepane, thiazolidine, isothiazolidine, 1,3-thiazinane, thiomorpholine, or 1,4-thiazepane, and the 3 to 7 membered nonaromatic heterocyclic group is optionally substituted with one or more substituents selected from Group E; R.sup.13 represents a hydrogen atom, a C1-C6 chain hydrocarbon group optionally substituted with one or more halogen atoms, a C3-C7 cycloalkyl group optionally substituted with one or more halogen atoms, a (C3-C6 cycloalkyl)C1-C3 alkyl group optionally substituted with one or more halogen atoms, a phenyl group optionally substituted with one or more substituents selected from Group D, or a 5 or 6 membered aromatic heterocyclic group optionally substituted with one or more substituents selected from Group D; R.sup.14 represents a C1-C6 chain hydrocarbon group optionally substituted with one or more halogen atoms, a C3-C7 cycloalkyl group optionally substituted with one or more halogen atoms, a (C3-C6 cycloalkyl)C1-C3 alkyl group optionally substituted with one or more halogen atoms, or a phenyl C1-C3 alkyl group, wherein the phenyl group in the group is optionally substituted with one or more substituents selected from Group D; R.sup.15 and R.sup.16 represent independently of each other, a C1-C6 alkyl group optionally substituted with one or more halogen atoms; n is 0, 1 or 2; m is 0, 1 or 2; x is 0 or 1; y is 0, 1 or 2; Group B is selected from the group consisting of a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, a C3-C6 alkenyloxy group optionally substituted with one or more halogen atoms, a C3-C6 alkynyloxy group optionally substituted with one or more halogen atoms, a C1-C6 alkylsulfanyl group optionally substituted with one or more halogen atoms, a C1-C6 alkylsulfinyl group optionally substituted with one or more halogen atoms, a C1-C6 alkylsulfonyl group optionally substituted with one or more halogen atoms, a C3-C6 cycloalkyl group optionally substituted with one or more halogen atoms, a cyano group, a hydroxy group, and a halogen atom; Group D is selected from the group consisting of a C1-C6 chain hydrocarbon group optionally substituted with one or more halogen atoms, a hydroxy group, a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, a C3-C6 alkenyloxy group optionally substituted with one or more halogen atoms, a C3-C6 alkynyloxy group optionally substituted with one or more halogen atoms, a sulfanyl group, a C1-C6 alkylsulfanyl group optionally substituted with one or more halogen atoms, a C1-C6 alkylsulfinyl group optionally substituted with one or more halogen atoms, a C1-C6 alkylsulfonyl group optionally substituted with one or more halogen atoms, an amino group, a NHR.sup.21, a NR.sup.21R.sup.22, a C(O)R.sup.21, a OC(O)R.sup.21, a C(O)OR.sup.21, a cyano group, a nitro group, and a halogen atom, wherein R.sup.21 and R.sup.22 represent independently of each other a C1-C6 alkyl group optionally substituted with one or more halogen atoms; Group E is selected from the group consisting of a C1-C6 chain hydrocarbon group optionally substituted with one or more halogen atoms, a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, a C3-C6 alkenyloxy group optionally substituted with one or more halogen atoms, a C3-C6 alkynyloxy group optionally substituted with one or more halogen atoms, a halogen atom, an oxo group, a hydroxy group, a cyano group, and a nitro group; Group F is selected from the group consisting of a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, a NHR.sup.21, a NR.sup.21R.sup.22, a cyano group, a phenyl group optionally substituted with one or more substituents selected from Group D, a 5 or 6 membered aromatic heterocyclic group optionally substituted with one or more substituents selected from Group D, a C3-C7 cycloalkyl group optionally substituted with one or more halogen atoms, and a 3 to 7 membered nonaromatic heterocyclic group optionally substituted with one or more substituents selected from Group C; Group C is selected from the group consisting of a C1-C6 chain hydrocarbon group optionally substituted with one or more halogen atoms, a C1-C6 alkoxy group optionally substituted with one or more halogen atoms, a C3-C6 alkenyloxy group optionally substituted with one or more halogen atoms, a C3-C6 alkynyloxy group optionally substituted with one or more halogen atoms, and a halogen atom; Group G is selected from the group consisting of a halogen atom, and a C1-C6 haloalkyl group.

2. The bipyridine compound according to claim 1, wherein R.sup.2 represents an ethyl group.

3. The bipyridine compound according to claim 1, wherein R.sup.1 represents a C1-C10 fluoroalkyl group.

4. The bipyridine compound according to claim 1, wherein R.sup.1 represents a C1-C10 fluoroalkyl group having two or more fluoro atoms.

5. The bipyridine compound according to claim 1, wherein R.sup.1 represents a C1-C10 perfluoroalkyl group.

6. The bipyridine compound according to claim 1, wherein L represents a single bond.

7. The bipyridine compound according to claim 1, wherein q is 0 or 1, and R.sup.3 represents a halogen atom, or a C1-C6 alkyl group optionally substituted with one or more halogen atoms.

8. The bipyridine compound according to claim 1, wherein: R.sup.1 represents a C1-C10 fluoroalkyl group, R.sup.2 represents an ethyl group, R.sup.3 represents a halogen atom, or a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and R.sup.6 represents a halogen atom, or a C1-C6 alkyl group optionally substituted with one or more halogen atoms.

9. The bipyridine compound according to claim 1, wherein: R.sup.1 represents a C1-C10 perfluoroalkyl group, R.sup.2 represents an ethyl group, R.sup.3 represents a halogen atom, or a C1-C6 alkyl group optionally substituted with one or more halogen atoms, and p is 0.

10. The bipyridine compound according to claim 1, wherein: R.sup.1 represents a C1-C10 perfluoroalkyl group, R.sup.2 represents an ethyl group, and p and q are independently of each other 0.

11. A bipyridine compound represented by formula (100): ##STR00099## wherein: A represents a S(O).sub.j; R.sup.101 represents a C2-C10 haloalkyl group, or a (C1-C5 alkoxy) C2-C5 alkyl group substituted with or more halogen atoms, R.sup.102 represents a C1-C6 alkyl group optionally substituted with one or more halogen atoms, R.sup.103, R.sup.104, R.sup.105, R.sup.106, R.sup.107, and R.sup.108 represent independently of each other a hydrogen atom, a halogen atom, or a C1-C6 alkyl group optionally substituted with one or more halogen atoms, j is 0, 1, or 2; and k is 0, 1, or 2.

12. The bipyridine compound according to claim 11, wherein: R.sup.101 represents a C2-C10 fluoroalkyl group substituted with two or more fluoro atoms, or a (C1-C5 alkoxy) C2-C5 alkyl group substituted with two or more halogen atoms, R.sup.102 represents an ethyl group, R.sup.103, R.sup.104, R.sup.105, R.sup.106, R.sup.107, and R.sup.108 represent independently of each other a hydrogen atom.

13. A composition for controlling a harmful arthropod comprising the bipyridine compound according to claim 1 and an inert carrier.

14. A method for controlling a harmful arthropod which comprises applying an effective amount of the bipyridine compound according to claim 1 to a harmful arthropod or a habitat where a harmful arthropod lives.

Description

EXAMPLES

(1) Hereinafter, the present invention is explained in more detail by using Preparation example, Formulation example, and Test example, however, the present invention should not be limited to these examples.

(2) First, with respect to the preparation of the compound A, the Preparation example is shown.

Preparation Example 1-1

(3) To a mixture of 1.6 M butyl lithium-hexane solution 100 mL, and 160 mL of THE were added dropwise a mixture of ethyl methyl sulfone 23 g and THF 20 mL at ?78? C. The reaction mixtures were raised gradually to 0? C. and were then re-cooled to ?78? C. To the reaction mixtures was added dropwise a mixture of 5-fluoro-2-cyanopyridine 20 g and THF 20 mL at ?78? C. The mixtures were raised gradually to room temperature, and to the reaction mixtures was added 2N hydrochloric acid, and the mixtures were stirred for 30 minutes. The resulting mixtures were extracted with ethyl acetate and the organic layers were washed with saturated brine. The organic layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the compound 1 below 40 g.

(4) ##STR00076##
.sup.1H-NMR (CDCl.sub.3) ?: 8.57 (1H, d), 8.19 (1H, dd), 7.62-7.55 (1H, m), 4.97 (2H, s), 3.30 (2H, q), 1.47 (3H, t).

Preparation Example 1-2

(5) To a mixture of oxalyl chloride 11 mL and chloroform 86 mL was added dropwise DMF 10 mL under ice-cooling. The mixtures were stirred for 30 minutes under ice-cooling, and to the mixtures was then added dropwise butyl vinyl ether 33 mL. The mixtures were raised to room temperature, and stirred for two hours, and to the mixtures was then added a mixture of the compound 1 10 g, triethylamine 42 mL and chloroform 30 mL under ice-cooling. The mixtures were raised to room temperature, and then stirred for one hour. The resulting mixtures was added to a saturated aqueous ammonium chloride solution and extracted with chloroform. The resulting organic layers were washed with water and saturated brine, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was diluted with ethanol 30 mL and thereto was added 28% aqueous ammonia solution 10 mL at room temperature. The mixtures were heated at 60? C. with stirring for 2.5 hours, and then stood to cool to room temperature. Thereto was added saturated aqueous sodium carbonate solution, and the mixtures were extracted with ethyl acetate. The resulting organic layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was subjected to a silica gel column chromatography to obtain the compound 2 below 9.4 g.

(6) ##STR00077##
.sup.1H-NMR (CDCl.sub.3) ?: 8.88 (1H, dd), 8.52-8.46 (2H, m), 7.87 (1H, dd), 7.62-7.54 (2H, m), 3.86 (2H, g), 1.38 (3H, t).

Preparation Example 1-3

(7) To a mixture of the compound 2 9.4 g and NMP 120 mL was added sodium hydrogen sulfide n hydrate 8.3 g at room temperature. The mixtures were heated at 100? C. with stirring for three hours. To the resulting reaction mixtures were added ethyl acetate 200 mL and concentrated hydrochloric acid under ice-cooling to adjust pH to 4, and the mixtures were stirred for 30 minutes. The resulting mixtures were extracted with ethyl acetate. The organic mixtures were dried over anhydrous sodium sulfate, and concentrated under reduced pressure. To the crude mixtures was added 10% aqueous potassium carbonate solution 50 mL room temperature, and the mixtures were stirred at room temperature for five hours. To the resulting mixtures was added water 100 mL, and the mixtures were extracted with ethyl acetate. The organic layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residues were subjected to a silica gel column chromatography to obtain the compound 3 below 7.6 g.

(8) ##STR00078##
.sup.1H-NMR (CDCl.sub.3) ?: 8.88 (1H, dd), 8.67 (1H, dd), 8.49 (1H, dd), 8.00 (1H, dd), 7.83 (1H, d), 7.56 (1H, dd), 3.88 (2H, g), 1.36 (3H, t).

Preparation Example 1-4

(9) To a mixture of the compound 3 1.0 g, potassium carbonate 990 mg, hydroxymethane sulfinic acid dihydrate 1.1 g, and NMP 10 mL was added 2,2,2-trifluoroethyl trifluoromethane sulfonate (hereinafter, referred to as Compound 4) 830 mg under ice-cooling. The reaction mixtures were stirred at room temperature for two hours. To the resulting mixtures was added saturated aqueous sodium hydrogen carbonate solution at room temperature, and the mixtures were extracted with ethyl acetate. The organic layers were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residues were subjected to a silica gel column chromatography to obtain. the compound S-1 below 1.0 g.

(10) ##STR00079##
.sup.1H-NMR (CDCl.sub.3) ?: 8.90-8.88 (1H, m), 8.70 (1H, d), 8.51-8.49 (1H, m), 7.98 (1H, dd), 7.83 (1H, d), 7.58 (1H, dd), 3.88 (2H, q) , 3.50 (2H, q) , 1.38 (3H, t).

Preparation Example 2

(11) The compound S-4 below was prepared by using 2,2,3,3, -pentafluoropropyl trifluoromethane sulfonate instead of the compound 4 according to the similar method to that described in Preparation Example 1-4.

(12) ##STR00080##
.sup.1H-NMR (CDCl.sub.3) ?: 8.89 (1H, dd), 8.71 (1H, d), 8.50 (1H, dd), 7.98 (1H, dd), 7.83 (1H, dd), 7.58 (1H, dd), 3.88 (2H q), 3.50 (2H, t), 1.38 (3H, t).

Preparation Example 3

(13) To a mixture of the compound S-1 680 mg and ethyl acetate 5 mL was added 70% mCPBA 700 mg under ice-cooling. The mixtures were stirred for twenty four hours under ice-cooling. To the resulting reaction mixtures were added saturated aqueous sodium hydrogen carbonate solution and aqueous sodium sulfite solution, and the mixtures were extracted with ethyl acetate. The organic layers were dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residues were subjected to a silica gel column chromatography to obtain the compound S-2 below 410 mg and the compound S-3 below 250 mg.

(14) The compounds that were prepared by the similar method to Preparation Example 3 and their physical property values are shown below.

(15) Compound represented by formula (400):

(16) ##STR00081##
wherein R.sup.1 and m represent any combination indicated in Table 18.

(17) TABLE-US-00018 TABLE 18 Compound R.sup.1 m S-2 CF.sub.3CH.sub.2 1 S-3 CF.sub.3CH.sub.2 2 S-5 CF.sub.3CF.sub.2CH.sub.2 1 S-6 CF.sub.3CF.sub.2CH.sub.2 2
Compound S-2
.sup.1H-NMR (CDCl.sub.3) ?: 8.94-8.89 (2H, m), 8.52 (1H, dd), 8.23 (1H, dd), 8.06 (1H, dd), 7.63 (1H, dd), 3.86 (2H, q), 3.79-3.53 (2H, m), 1.40 (3H, t).
Compound S-3
.sup.1H-NMR (CDCl.sub.3) ?: 9.16 (1H, d), 8.93 (1H, dd), 8.52 (1H, dd), 8.41 (1H, dd), 8.08 (1H, d), 7.66 (1H, dd), 4.03 (2H, q), 3.85 (2H, q), 1.40 (3H, t).
Compound S-b 5
.sup.1-NMR (CDCl.sub.3) ?: 8.93-8.91 (2H, m), 8.52 (1H, dd), 8.24 (1H, dd), 8.07 (1H, dd), 7.64 (1H, dd), 3,87 (2H, q), 3.74-3.59 (1H, m), 3.54-3.43 (1H, m), 1.40 (3H, t).
Compound 8-6
.sup.1H-NMR (CDCl.sub.3) ?: 9.19 (1H, d), 8.93 (1H, dd), 8.53 (1H, dd), 8.43 (1H, dd), 8.09 (1H, dd), 7.66 (1H, 3.94 (2H, t), 3.86 (2H, q), 1.41 (3, t).

Preparation Example 4

(18) A mixture of the compound 3 1.0 g, tetrakis(dimethylamino)ethylene 1.2 mL and DMF 4 mL was stirred under trifluoroiodomethane under ice-cooling for three hours. To the resulting mixtures was added saturated aqueous sodium hydrogen carbonate solution, and the mixtures were extracted with ethyl acetate. The organic layers were washed with water, and dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residues were subjected to a silica gel column chromatography to obtain the compound S-7 below 930 mg.

(19) ##STR00082##
.sup.1H-NMR (CDCl.sub.3) ?: 8.91 (1H, dd), 8.83 (1H, d), 8.51 (1H, dd), 8.17 (1H, dd), 7.92 (1H, dd), 7.61 (1H, dd), 3.88 (2H, q), 1.39 (3H, t).

(20) The compounds that were prepared by the similar method to Preparation Example 4 and their physical property values are shown below.

(21) Compound represented by formula (500):

(22) ##STR00083##
wherein R.sup.1 and R.sup.2 represent any combination indicated in Table 19.

(23) TABLE-US-00019 TABLE 19 Compound R.sup.1 R.sup.2 S-10 CF.sub.3CF.sub.2 CH.sub.3CH.sub.2 S-12 CF.sub.3CF.sub.2CF.sub.2 CH.sub.3CH.sub.2 S-13 CF.sub.3CF.sub.2CF.sub.2CF.sub.2 CH.sub.3CH.sub.2
Compound S-10
.sup.1H-NMR (CDCl.sub.3) ?: 8.91 (1H, dd), 8.82 (1H, d), 8.51 (1H, dd), 8.16 (1H, dd), 7.92 (1H, dd), 7.61 (1H, dd), 3.88 (2H, q), 1.39 (3H, t).
Compound S-12
.sup.1H-NMR (CDCl.sub.3) ?: 8.91 (1H, dd), 8.83 (1H, d), 8.51 (1H, dd), 8.17 (1H, dd), 7.92 (1H, dd), 7.61 (1H, dd), 3.88 (2H, q), 1.39 (3H, t).
Compound S-13
.sup.1H-NMR (CDCl.sub.3) ?: 8.91 (1H, dd), 8.83 (1H, d), 8.51 (1H, dd), 8.17 (1H, dd), 7.92 (1H, d), 7.61 (1H, dd), 3.88 (2H, q), 1.39 (3H, t).

Preparation Example 5

(24) To a mixture of the compound S-7 720 mg and ethyl acetate 10 mL was added 70% mCPEA 770 mg under ice-cooling. The reaction mixtures were raised to room temperature, and stirred for twenty four hours. To the resulting mixtures were added saturated aqueous sodium hydrogen carbonate solation and aqueous sodium sulfite solution, and the mixtures were extracted with ethyl acetate. The organic layers were dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residues were subjected to a silica gel column chromatography to obtain the compound S-8 below 160 mg and the compound S-9 below 90 mg and the compound N-1 below 120 mg.

(25) The compounds that were prepared by the similar method to Preparation Example 5 and their physical property values are shown below.

(26) Compound represented by formula (600):

(27) ##STR00084##
wherein R.sup.1, A.sup.1, A.sup.2 and m represent any combination indicated in Table 20]

(28) TABLE-US-00020 TABLE 20 Compound R.sup.1 m A.sup.1 A.sup.2 S-8 CF.sub.3 1 N N S-9 CF.sub.3 2 N N S-11 CF.sub.3CF.sub.2 1 N N N-1 CF.sub.3 0 N.sup.+O.sup.? N N-2 CF.sub.3CF.sub.2 0 N.sup.+O.sup.? N N-3 CF.sub.3CF.sub.2 0 N N.sup.+O.sup.? N-4 CF.sub.3CF.sub.2 0 N.sup.+O.sup.? N.sup.+O.sup.?
Compound S-8
.sup.1H-NMR (CDCl.sub.3) ?: 8.96 (1H, d), 8.93 (1H, dd), 8.53 (1H, dd), 8.32 (1H, dd), 8.09 (1H, dd), 7.65 (1H, dd), 3.87 (2H, q), 1.40 (3H, t).
Compound S-9
.sup.1H-NMR (CDCl.sub.3) ?: 9.20 (1H, d), 8.95 (1H, dd), 8.55-8.52 (1H, m), 8.50-8.47 (1H, m), 8.16-8.13 (1H, m), 7.68 (1H, dd), 3.86 (2H, q), 1.41 (3H, t).
Compound S-11
.sup.1H-NMR (CDCl.sub.3) ?: 8.97-8.92 (2H, m), 8.53 (1H, dd), 8.32 (1H, dd), 8.10 (1H, dd), 7.65 (1H, dd), 3.90-3.82 (2H, m), 1.40 (3H, t).
Compound N-1
.sup.1H-NMR (CDCl.sub.3) ?: 8.99-8.93 (1H, m), 8.49 (1H, d), 8.41-8.36 (1H, m), 7.73-7.60 (2H, m), 748 (1H, d), 3.74-3.52 (2H, m), 1.36 (3H, t).
Compound N-2
.sup.1H-NMR (CDCl.sub.3) ?: 8.97-8.94 (1H, m) , 8.48 (1H, s), 8.39-8.36 (1H, m), 7.72-7.62 (2H, m), 7.48 (1H, dd), 3.74-3.48 (2H, m), 1.41-1.31 (3H, m).
Compound N-3
.sup.1H-NMR (CDCl.sub.3) ?: 8.88 (1H, d), 8.52-8.49 (1H, m), 8.15 (1H, dd), 7.99-7.95 (1H, m), 7.76 (1H, dd), 7.54 (1H, dd), 3.49-3.42 (2H, m), 1.35-1.28 (3H, m).
Compound N-4
.sup.1H-NMR (CDCl.sub.3) ?: 8.55-8.51 (1H, m), 8.51-8.45 (1H, m), 7.93-7.87 (1H, m), 7.67-7.56 (2H, m), 7.53 (1H, dd), 3.35-3.19 (2H, m) 1.32-1.22 (3H, m).

Preparation Example 6-1

(29) A mixture of 2-bromo-5-methoxypyridine 1.5 g, 3-fluoro-2-(tributylstannyl)pyridine 4.6 g, tetrakis triphenylphosphine palladium (0) 920 mg, copper(I) iodide 300 mg and anhydrous lithium chloride 500 mg and toluene 27 mL was heated under reflux with stirring for seven hours. The resulting reaction mixtures were stood to cool to room temperature, and aqueous sodium hydrogen carbonate solution was added thereto, and the mixtures were extracted with ethyl acetate. The organic layers were washed successively with water and saturated brine, and dried over anhydrous sodium sulfate, and the organic layers were concentrated under reduced pressure. The obtained residues were subjected to a silica gel column chromatography to obtain the compound 5 below 510 mg.

(30) ##STR00085##
.sup.1H-NMR (CDCl.sub.3) ?: 8.57-8.54 (1H, m), 8.51-8.49 (1H, m), 7.96 (1H, dd), 7.56-7.49 (1H, m), 7.35-7.28 (2H, m), 3.94-3.91 (3H, m).

Preparation Example 6-2

(31) To a mixture of the compound 5 510 mg, sodium hydride (oil, 60 %) 110 mg and DMF 5 mL was added dropwise ethanethiol 200 ?L under ice-cooling. The mixtures were raised to room temperature and then stirred for four hours. To the resulting reaction mixtures was added saturated aqueous sodium hydrogen carbonate solution, and the mixtures were extracted with ethyl acetate. The organic layers were washed successively with water and saturated brine and concentrated under reduced pressure.

(32) The obtained residues were diluted with chloroform, and thereto was added mCPBA (70 %) 1.4 g. The reaction mixtures were stirred at room temperature for ten hours. To the resulting reaction mixtures were added sodium sulfite and saturated aqueous sodium hydrogen carbonate solution successively, and then extracted with chloroform. The organic layers were washed with saturated sodium hydrogen carbonate and dried over anhydrous sodium sulfate, and the organic layers were concentrated under reduced pressure. The obtained residues were subjected to a silica gel column chromatography to obtain the compound 6 below 490 mg.

(33) ##STR00086##
.sup.1H-NMR (CDCl.sub.3) ?: 8.86 (1H, dd), 8.48 (1H, dd, 8.31 (1H, d), 7.83 (1H, d), 7.51 (1H, dd) , 7.36 (1H, dd), 3.94-3.87 (5H, m), 1.37 (3H, t).

Preparation Example 6-3

(34) To a 1.0 M boron tribromide dichloromethane solution 5 mL was added the compound 6 490 mg under ice-cooling. The mixtures were raised to room temperature, and stirred for two days. To the resulting reaction mixtures was added saturated aqueous sodium hydrogen carbonate solution under ice-cooling, and the mixtures were extracted with chloroform. The organic layers were washed successively with water and saturated brine and dried over anhydrous sodium sulfate, and the organic layers were concentrated under reduced pressure. The resulting residues were subjected to a silica gel column chromatography to obtain the compound 7 below 300 mg.

(35) ##STR00087##
.sup.1H-NMR (CDCl.sub.3) ?: 8.86 (1H, dd), 8.50 (1H, dd), 8.12 (1H, d), 7.67 (1H, d), 7.54 (1H, dd), 7.08 (1H, dd), 6.64 (1H, br s), 3.94 (2H, q), 1.39 (3H, t).

Preparation Example 6-4

(36) To a mixture of the compound 7 300 mg, 2,6-lutidine 240 mg, and chloroform 4 mL was added trifluoromethanesulfonic anhydride 380 mg under ice-cooling. The reaction mixtures were stirred under ice-cooling for ten minutes. To the resulting reaction mixtures was added saturated aqueous sodium hydrogen carbonate solution, and the mixtures were extracted with chloroform. The organic layers were dried over anhydrous sodium hydrate, and concentrated under reduced pressure. The obtained residues were subjected to a silica gel column chromatography to obtain the compound O-1 below 430 mg.

(37) ##STR00088##
.sup.1H-NMR (CDCl.sub.3) ?: 8.90 (1H, dd), 8.61 (1H, d), 8.51 (1H, dd), 7.97 (1H, d) 7.81 (1H, dd), 7.61 (1H, dd), 3.84 (2H, q) , 1.39 (3H, t).

Preparation Example 7

(38) The compound O-2 was prepared by using 2,2,2-trifluoroethane sulfonic chloride instead of trifluoromethanesulfonic anhydride according to a similar method to that described in Preparation Example 6-4.

(39) ##STR00089##
.sup.1H-NMR (CDCl.sub.3) ?: 8.90 (1H, dd), 8.60 (1H, d), 8.51 (1H, dd), 7.96 (1H, d), 7.83 (1H, dd), 7.60 (1H, dd), 4.17-4.08 (2H, m), 3.86 (2H, q), 1.38 (3H, t).

(40) A compound represented by formula (204):

(41) ##STR00090##
[wherein R.sup.201, R.sup.202, R.sup.203, R.sup.204, R.sup.205, n and m represent any combination indicated in Table 21 to Table 23 below.] may be prepared according to the above-mentioned method.

(42) TABLE-US-00021 TABLE 21 Compound A R.sup.201 n m R.sup.203 R.sup.204 R.sup.205 S-12 CF.sub.2H 2 0 H H H S-13 CF.sub.2HCH.sub.2 2 0 H H H S-14 CF.sub.3CH.sub.2 2 0 H H H S-15 CCl.sub.3CH2 2 0 H H H S-16 CF.sub.2HCF.sub.2 2 0 H H H S-17 CClFHCF.sub.2 2 0 H H H S-18 CF.sub.3CH.sub.2CH.sub.2 2 0 H H H S-19 CF.sub.2HCF.sub.2CH.sub.2 2 0 H H H S-21 CF.sub.3CFHCF.sub.2 2 0 H H H S-22 CF.sub.3CFHCF.sub.2 2 1 H H H S-23 CF.sub.3CFHCF.sub.2 2 2 H H H S-24 CH.sub.3CH.sub.2CH.sub.2 2 0 H H H S-25 C(CF.sub.3).sub.2(CH.sub.3)CH.sub.2 2 0 H H H S-26 CF.sub.3CFHCF.sub.2CH.sub.2 2 0 H H H S-26 CF.sub.3CFHCF.sub.2CH.sub.2 2 1 H H H S-26 CF.sub.3CFHCF.sub.2CH.sub.2 2 2 H H H S-27 CF.sub.3CF.sub.2CF.sub.2CH.sub.2 2 0 H H H S-28 CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2 2 0 H H H S-29 CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2 2 0 H H H S-30 CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2 2 0 H H H S-31 CF(CF.sub.3).sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2 2 0 H H H S-32 CF.sub.2HCF.sub.2CF.sub.2CF.sub.2CH.sub.2 2 0 H H H S-33 CF.sub.2HCF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2 2 0 H H H S-34 CF.sub.3OCFHCF.sub.2 2 0 H H H S-35 CF.sub.3OCFHCF.sub.2 2 1 H H H

(43) TABLE-US-00022 TABLE 22 Compound A R.sup.201 n m R.sup.203 R.sup.204 R.sup.205 S-36 CF.sub.3OCFHCF.sub.2 2 2 H H H S-37 CF.sub.3CH.sub.2OCH.sub.2CH.sub.2 2 0 H H H S-41 CF.sub.2H 2 0 H CF.sub.3 H S-42 CF.sub.3 2 0 H CF.sub.3 H S-43 CF.sub.2HCH.sub.2 2 0 H CF.sub.3 H S-44 CCl.sub.3CH.sub.2 2 0 H CF.sub.3 H S-45 CF.sub.2HCF.sub.2 2 0 H CF.sub.3 H S-46 CClFHCF.sub.2 2 0 H CF.sub.3 H S-47 CF.sub.3CF.sub.2 2 0 H CF.sub.3 H S-48 CF.sub.3CH.sub.2CH.sub.2 2 0 H CF.sub.3 H S-49 CF.sub.2HCF.sub.2CH.sub.2 2 0 H CF.sub.3 H S-50 CF.sub.3CFHCF.sub.2 2 0 H CF.sub.3 H S-51 CF.sub.3CF.sub.2CF.sub.2 2 0 H CF.sub.3 H S-52 CF.sub.3CF.sub.2CF.sub.2 2 1 H CF.sub.3 H S-53 CF.sub.3CF.sub.2CF.sub.2 2 2 H CF.sub.3 H S-54 C(CF.sub.3).sub.2(CH.sub.3)CH.sub.2 2 0 H CF.sub.3 H S-55 CF.sub.3CFHCF.sub.2CH.sub.2 2 0 H CF.sub.3 H S-56 CF.sub.3CFHCF.sub.2CH.sub.2 2 1 H CF.sub.3 H S-57 CF.sub.3CFHCF.sub.2CH.sub.2 2 2 H CF.sub.3 H

(44) TABLE-US-00023 TABLE 23 Compound A R.sup.201 n m R.sup.203 R.sup.204 R.sup.205 S-58 CF.sub.3CF.sub.2CF.sub.2CF.sub.2 2 0 H CF.sub.3 H S-59 CF.sub.3CF.sub.2CF.sub.2CF.sub.2 2 1 H CF.sub.3 H S-60 CF.sub.3CF.sub.2CF.sub.2 2 2 H CF.sub.3 H S-61 CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2 2 0 H CF.sub.3 H S-62 CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2 2 0 H CF.sub.3 H S-63 CF.sub.3CF.sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2 2 0 H CF.sub.3 H S-64 CF(CF.sub.3).sub.2CF.sub.2CF.sub.2CH.sub.2CH.sub.2 2 0 H CF.sub.3 H S-65 CF.sub.2HCF.sub.2CF.sub.2CF.sub.2CH.sub.2 2 0 H CF.sub.3 H S-66 CF.sub.2HCF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2CH.sub.2 2 0 H CF.sub.3 H S-67 CF.sub.3OCFHCF.sub.2 2 0 H CF.sub.3 H S-68 CF.sub.3OCFHCF.sub.2 2 1 H CF.sub.3 H S-69 CF.sub.3OCFHCF.sub.2 2 2 H CF.sub.3 H S-70 CF.sub.3CH.sub.2OCH.sub.2CH.sub.2 2 0 H CF.sub.3 H

(45) A compound represented by formula (301):

(46) ##STR00091##
[wherein, R.sup.201, R.sup.202, R.sup.203, R.sup.204, R.sup.205, and n represent any combination indicated in Table 24 to Table 25 below.]

(47) may be prepared according the similar method to hose described above.

(48) TABLE-US-00024 TABLE 24 Compound A R.sup.201 n R.sup.203 R.sup.204 R.sup.205 O-3 CF.sub.2H 2 H H H O-4 CF.sub.2HCH.sub.2 2 H H H O-5 CF.sub.2HCF.sub.2 2 H H H O-6 CF.sub.3CF.sub.2 2 H H H O-7 CF.sub.3CF.sub.2CF.sub.2 2 H H H O-8 CF.sub.3CF.sub.2CF.sub.2CF.sub.2 2 H H H O-9 CF.sub.3CF.sub.2CF.sub.2CF.sub.2CF.sub.2 2 H H H

(49) TABLE-US-00025 TABLE 25 Compound A R.sup.201 n R.sup.203 R.sup.204 R.sup.205 O-10 CF.sub.2H 2 H CF.sub.3 H O-11 CF.sub.2HCH.sub.2 2 H CF.sub.3 H O-12 CF.sub.2HCF.sub.2 2 H CF.sub.3 H O-13 CF.sub.3CF.sub.2 2 H CF.sub.3 H O-14 CF.sub.3CF.sub.2CF.sub.2 2 H CF.sub.3 H O-15 CF.sub.3CF.sub.2CF.sub.2CF.sub.2 2 H CF.sub.3 H O-16 CF.sub.2CF.sub.2CF.sub.2CF.sub.2CF.sub.2 2 H CF.sub.3 H

(50) Next, the formulation examples of the compound A are shown below. The parts represents part by weight unless otherwise specified.

Formulation Example 1

(51) Into a mixture of 35 parts of xylene and 35 parts of DMF, 10 parts of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16 is mixed, and then 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzene sulfonate are added, followed by mixing them to obtain each formulation.

Formulation Example 2

(52) Four (4) parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic hydrated silicon oxide fine powder and 54 parts of diatomaceous earth are mixed, and further 20 parts of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16 is added, followed by mixing them to obtain each wettable powders.

Formulation Example 3

(53) To 2 parts of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16, 1 part of synthetic hydrated silicon oxide fine powder, 2 parts of lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay are added, followed by mixing, granulation with granulator and forced-air drying to obtain each granular formulation.

Formulation Example 4

(54) Into an appropriate amount of acetone, 1 part of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16 is mixed, and then 5 parts of synthetic hydrous silicon oxide fine powder, 0.3 parts of isopropyl acid phosphate and 93.7 parts of kaolin clay are added, followed by mixing stirring thoroughly and removal of acetone from the mixture by evaporation to obtain each of powder formulation.

Formulation Example 5

(55) A mixture of 35 parts of polyoxyethylene alkyl ether sulfate ammonium salt and white carbon (weight ratio of 1:1), 10 parts of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16, and 55 parts of water are mixed, followed by finely grounding by a wet grinding method to obtain each flowable formulation.

Formulation Example 6

(56) Into a mixture of 5 parts of xylene and 5 parts of trichloroethane, 0.1 parts of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16 is dissolved, and the resulting mixture is then mixed with 89.9 parts of kerosene to obtain each oil solution.

Formulation Example 7

(57) Into 0.5 mL of acetone, 10 mg of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16 is dissolved and the solution is added dropwise to 5 g of a solid feed powder for an animal (solid feed powder for rearing and breeding CE-2, manufactured by CLEA Japan, Inc.), followed by mixing the resulting mixture uniformly, and then by drying them by evaporation of acetone to obtain each poison bait.

Formulation Example 8

(58) Into an aerosol can, 0.1 part of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16 and. 49.9 parts of Neothiozole (Chuo Kasei Co., Ltd.) are placed. After mounting an aerosol valve, 25 parts of dimethyl ether and 25 parts of LPG are filled, followed by shaking and further mounting an actuator to obtain an oily aerosol.

Formulation Example 9

(59) A mixture of 0.6 part of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16, 0.01 part of BHT (2,6-di-tert-butyl-4-methylphenol), 5 parts of xylene, 3.39 parts of deodorized kerosine and 1 part of an emulsifier {Rheodol MO-60 (registered trademark of Kao Corporation)} and 50 parts of distilled water are filled into an aerosol container, and a valve part is attached. Then, 40 parts of a propellant (LPG) is filled therein through the valve under pressure to obtain an aqueous aerosol.

Formulation Example 10

(60) Zero point one (0.1) parts of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16 are mixed into 2 mL of propylene glycol, and the resulting solution is impregnated into a ceramic plate having a size of 4.0 cm?4.0 cm and a thickness of 1.2 cm, to obtain thermal fumigants.

Formulation Example 11

(61) Five (5) parts of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16, and 95 parts of ethylene-methyl methacrylate copolymer (the ratio of the methyl methacrylate in the copolymer: 10 weight %), Acryft (registered by trademark) WD 301, manufactured by Sumitomo Chemical Co. Ltd.) are melted and kneaded with a closed type pressure kneader, and the resulting kneaded product is extruded from an extrusion molding machine through a molding die to obtain a rod-shaped molded product having a length of 15 cm and a diameter of 3 mm.

Formulation Example 12

(62) Five (5) parts of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16, and 95 parts of plasticized polyvinyl chloride resin are melted and kneaded with a closed type pressure kneader, and the resulting kneaded product is extruded from an extrusion molding machine through a molding die to obtain a rod-shaped molded product having a length of 15 cm and a diameter of 3 mm.

Formulation Example 13

(63) One hundred (100) mg of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16, 68.75 mg of lactose, 237.5 mg of corn starch, 43.75 mg of microcrystalline cellulose, 18.75 mg of polyvinylpyrrolidone, 28.75 mg of sodium carbomethyl starch and 25 mg of magnesium stearate are mixed, and the resulting mixture was compressed to an appropriate size to obtain a tablet.

Formulation Example 14

(64) Twenty five (25) mg of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16, 60 mg of lactose, 25 mg of corn starch, 6 mg of carmellose calcium and an appropriate amount of 5% of hydroxypropyl methylcellulose are mixed, and the resulting mixture are filled into a hard shell gelatin capsule or a hydroxypropyl methylcellulose capsule to obtain capsules.

Formulation Example 15

(65) To 100 mg of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16, 500 mg of fumaric acid 2,000 mg of granulated sugar, 13,000 mg of sorbitol (70% solution), 100 mg of Veegum K (manufactured by Vanderbilt. Co.), 35 mg of perfume and 500 mg of coloring agent, a distilled water is added so that a final volume is set to be 100 mL, followed by mixing them to obtain a suspension for oral administration.

Formulation Example 16

(66) Into a mixture of 5% by weight of an emulsifier, 3% by weight of benzyl alcohol and 30% by weight of propylene glycol, 5% by weight of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16 is dissolved, and phosphate buffer is added thereto so that a pH of the solution is set to be 6.0 to 6.5, and water is added as the rest parts to obtain the solution for oral administration.

Formulation Example 17

(67) To a mixture of 57% by weight of fractional distillated palm oil and 3% by weight of polysorbate 85, 5% by weight of aluminum distearate is added, and heated to disperse it. The resulting mixture is cooled to room temperature, and 25% by weight of saccharin is dispersed in an oil vehicle. Ten (10) % by weight of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16 is divided thereto to obtain a paste for oral administration.

Formulation Example 18

(68) Five (5) % by weight of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16 is mixed with 95% by weight of limestone filler, followed by a wet granulation of the resulting mixture to obtain a granule for oral administration.

Formulation Example 19

(69) Into 80 parts of diethylene glycol monomethyl ether, 5 parts of any one of compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16 is dissolved, and 15 parts of propylene carbonate is added thereto, and the resulting mixture is mixed to obtain a spot-on solution.

Formulation Example 20

(70) Into 70 parts of diethylene glycol monomethyl ether, 10 parts of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16 is dissolved, and 20 parts of 2-octyldodecanol is added thereto, and the resulting mixture is mixed to obtain a pour-on solution.

Formulation Example 21

(71) To 0.5 parts of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16, 60 parts of Nikkol (registered by trademark) TEALS-42 (manufactured by Nikko Chemical Co. Ltd.: 42% of aqueous solution of lauryl sulfuric acid triethanol amine) and 20 parts of propylene glycol are added, and the resulting mixture is mixed with stirring thoroughly, and 19.5 parts of water is then added thereto and the resulting mixture is further mixed with stirring thoroughly to obtain ahydrogenous solution of shampoo formulation.

Formulation Example 22

(72) Zero point fifteen (0.15)% by weight of any one of the compounds to S-70, N-1 to N-4, and O-1 to O-16, 95% by weight of animal feed, as well as 4.85% by weight of a mixture of dibasic calcium phosphate, diatomaceous earth, aerosol and carbonate (or chalk) are mixed with stirring thoroughly to obtain a premix for animal feed.

Formulation Example 23

(73) Seven point two (7.2) g of any one of the compounds S-1 to S-70, N-1 to N-4, and O-1 to O-16, and 92.8 of Hosco (registered trademark) S-55 (manufactured by Maruishi Pharmaceuticals) are melted and mixed at 100? C., and the resulting mixture was poured into a suppository mold, followed by performing a cooling solidification to obtain a suppository.

(74) Next, Test Examples are used to show an efficacy of the compound A on controlling harmful arthropods.

Test Example 1

(75) Each of the compounds S-1, S-2, S-3, S-4, S-5, S-6, S-7, S-8, S-9, S-10, N-1, N-4, O-1 and O-2 was made to a formulation according to a similar method to that described in the Formulation Example 5 and was then diluted with water so that the active ingredient concentration was set to 500 ppm to prepare each of the diluted solution.

(76) Cucumber seedling (on the developmental stage of the first true leaf) was planted a polyethylene cup and 30 heads of cotton aphid (Aphis gossypii) (all stages of life) were released onto the leaves of the cucumber and allowed to stand for 1 day. The diluted solutions 20 mL were sprayed into the seedling.

(77) Cucumber (cv; Sagami-hanjiro-fushinari) was grown in a polyethylene cup until the first true leaf was developed. Approximately 30 heads of cotton aphid (Aphis gossypii) (including the adults and the larvae) was released onto the leaves of the cabbage and next day, the above-mentioned testing drug dilutions 20 mL were sprayed.

(78) After 6 days, the number of the surviving insects that were parasitic on the leaves of the cucumber was examined and the controlling value was calculated by the following equation.
Controlling value (%)={1?(Cb?Tai)/(Cai?Tb)}?100
wherein the symbols in the formula represent the following descriptions.

(79) Cb: Number of the insects before treatment in untreated area;

(80) Cai: Number of the surviving parasitic insects at the time of the investigation untreated area;

(81) Tb: Number of the insects before treatment in treated area;

(82) Tai: Number of the surviving parasitic insects at the time of the investigation in treated area;

(83) Here the untreated area represents an area that was sprayed by a diluted solution of the formulation described in the Formulation Example 5 with out the compound A with water in the same amount as that of the treated area.

(84) As a result, the treated area that was treated with each of the diluted solutions of the compounds S-1, S-2, S-3, S-4, S-5, S-6, S-7, S-8, S-9, S-10, N-1, N-4, O-1 and O-2 respectively showed 90% or greater as the controlling value.

Test Example 2

(85) Each of the compounds S-1, S-2, S-7, S-8, S-9, S-10, N-1, O-1 and O-2 was made to a formulation according to a similar method to that described in the Formulation example 5 and was then diluted with water so that each of the active ingredient concentration was set to 200 ppm to prepare each of the diluted solution.

(86) Cucumber seedling (on the developmental stage of the first true leaf) was planted in a polyethylene cup and 30 heads of cotton aphid (Aphis gossypii) (all stages of life) were released onto the leaves of the cucumber and allowed to stand for 1 day. The diluted solutions 20 mL were sprayed into the seedling.

(87) Cucumber (cv; Sagami-hanjiro-fushinari) was grown in a polyethylene cup until the first true leaf was developed. Approximately 30 heads of cotton aphid (Aphis gossypii) (including the adults and the larvae) was released onto the leaves of the cabbage and next day, the above-mentioned testing drug dilutions 20 mL were sprayed.

(88) After 6 days, the number of the surviving insects that were parasitic on the leaves of the cucumber was examined and the controlling value was calculated by the following equation.
Controlling value (%)={1?(Cb?Tai)/(Cai?Tb)}?100
wherein the symbols in the formula represent the following descriptions.

(89) Cb: Number of the insects before treatment in untreated area;

(90) Cai: Number of the surviving parasitic insects at the time of the investigation in untreated area;

(91) Tb: Number of the insects before treatment in treated area;

(92) Tai: Number of the surviving parasitic insects at the time of the investigation in treated area;

(93) Here the untreated area represents an area that was sprayed by a diluted solution of the formulation described in the Formulation Example 5 without the compound A with water in the same amount as that of the treated area.

(94) As a result, the treated area that was treated with each of the diluted solutions of the compounds S-1, S-2, S-7, S-8, S-9, S-10, N-1, O-1 and O-2 respectively showed 90% or greater as the controlling value.

Test Example 3

(95) Each of the S-1, S-2, S-7, S-8, S-9, S-10, N-1, and O-2 was made to a formulation according to a similar method to that described in the Formulation example 5 and was then diluted with water so that the active ingredient concentration was set to 200 ppm to prepare the diluted solution.

(96) Cucumber seedling (on the developmental stage of the second true leaf) was planted in a polyethylene cup, and the diluted solutions 5 mL were irrigated into the plant foot, and the plants were held at 25? C. in a greenhouse for 7 days. Approximately 30 heads of cotton aphid (Aphis gossypii) (all stages of life) were inoculated onto the cucumber leaves and the plants were held in a greenhouse for additional 6 days, and then the number of the surviving nsects that were parasitic on the cucumber leaves was examined and the controlling value was calculated by the following equation.
Controlling value (%)={1?(Cb?Tai)/(Cai?Tb)}?100
wherein the symbols in the formula represent the following descriptions.

(97) Cb: Number of the insects before treatment in untreated area;

(98) Cai: Number of the surviving parasitic insects at the time of the investigation in untreated area;

(99) Tb: Number of the insects before treatment in treated area;

(100) Tai: Number of the surviving parasitic insects at the time of the investigation in treated area;

(101) Here the untreated area represents an area that was sprayed by a diluted solution of the formulation described in the Formulation Example 5 without the compound A with water in the same amount as that of the treated area.

(102) As a result, the treated area that was treated with each of the diluted solutions of the compounds S-1, S-2, S-7, S-8, S-9, S-10, N-1, O-1 and O-2 respectively showed 90% or greater as the controlling value.

Test Example 4

(103) Each of the compounds S-1, S-2, S-7, S-8, S-9, S-10, N-1, and O-2 was made to a formulation according to a similar method to that described in the Formulation example 5 and was then diluted with water so that each of the active ingredient concentration was set to 500 ppm to prepare each of the diluted solution.

(104) Rice seedling (on the developmental stage of the second true leaf) was planted in a polyethylene cup, and the diluted solutions 10 mL were sprayed. After air drying, 20 heads of 3rd to 4th instar larvae of brown planthopper (Nilaparvata lugens) were released onto the rice leaves and the plants were held at 25? C. in a greenhouse.

(105) After 6 days, the number of the surviving insects that were parasitic on the leaves of the rice was examined and the controlling value was calculated by the following equation.
Controlling value (%)={1?(Cb?Tai)/(Cai?Tb)}?100
wherein the symbols in the formula represent the following descriptions.

(106) Cb: Number of the insects before treatment in untreated area;

(107) Cai: Number of the surviving parasitic insects at the time of the investigation in untreated area;

(108) Tb: Number of the insects before treatment in treated area;

(109) Tai: Number of the surviving parasitic insects at the time of the investigation in treated area;

(110) Here the untreated area represents an area that was sprayed by a diluted solution of the formulation described in the Formulation Example 5 without the compound A with water in the same amount as that of the treated area.

(111) As a result, the treated area that was treated with each of the diluted solutions of the compounds S-1, S-2, S-7, S-8, S-9, S-10, N-1, and O-2 respectively showed 90% or greater as the controlling value.

Test Example 5

(112) Each of the compounds S-1, S-2, S-7, S-8, S-9, S-10, N-1, and O-2 was made to a formulation according to a similar method to that described in the Formulation example 5 and was then diluted with water so that each of the active ingredient concentration was set to 200 ppm to prepare each of the diluted solution.

(113) Rice seedling (on the developmental stage of the second true leaf) was planted in a polyethylene cup, and the diluted solutions 10 mL were sprayed. After air drying, 20 heads of 3rd to 4th instar larvae of brown planthopper (Nilaparvata lugens) were released onto the rice leaves and the plants were held at 25? C. in a greenhouse.

(114) After 6 days, the number of the surviving insects that were parasitic on the leaves of the rice was examined and the controlling value was calculated by the following equation.
Controlling value (%)={1?(Cb?Tai)/(Cai?Tb)}?100
wherein the symbols in the formula represent the following descriptions.

(115) Cb: Number of the insects before treatment in untreated area;

(116) Cai: Number of the surviving parasitic insects at the time of the investigation in untreated area;

(117) Tb: Number of the insects before treatment in treated area;

(118) Tai: Number of the surviving parasitic insects at the time of the investigation in treated area;

(119) Here the untreated area represents an area that was sprayed by a diluted solution of the formulation described in the Formulation Example 5 without the compound A with water in the same amount as that of the treated area.

(120) As a result, the treated area that was treated with each of the diluted solutions of the compounds S-1, S-2, S-7, S-8, S-9, S-10, N-1, and O-2 respectively showed 90% or greater as the controlling value.

Test Example 6

(121) Each of the compounds S-7, S-8, S-9, S-10, N-1, and O-2 was made to a formulation according to a similar method to that described in the Formulation example 5 and was then diluted with water so that each of the active ingredient concentration was set to 200 ppm to prepare each of the diluted solution.

(122) Rice seedling (two weeks after sowing, on the developmental stage of the second true leaf) was planted in a polyethylene cup, and the diluted solutions 5 mL were irrigated into the plant foot, and the plants were held at 25? C. in a greenhouse for 7 days. Twenty (20) heads of 3rd to 4th instar larvae of brown planthopper (Nilaparvata lugens) were released onto the rice leaves and the plants were held at 25? C. in a greenhouse for additional 6 days, and then the number of the surviving insects that were parasitic on rice leaves was examined and the controlling value was calculated by the following equation.
Controlling value (%)={1?(Cb?Tai)/(Cai?Tb)}?100
wherein the symbols in the formula represent the following descriptions.

(123) Cb: Number of the insects before irrigation in untreated area;

(124) Cai: Number of the surviving parasitic insects at the time of the investigation in untreated area;

(125) Tb: Number of the insects before irrigation in treated area;

(126) Tai: Number of the surviving parasitic insects at the time of the investigation in treated area;

(127) Here the untreated area represents an area that was sprayed by a diluted solution of the formulation described in the Formulation Example 5 without the compound A with water in the same amount as that of the treated area.

(128) As a result, the treated area that was treated with each of the diluted solutions containing the compounds S-7, S-8, S-9, S-10, N-1, and O-2 respectively showed 90% or greater as the controlling value.

Test Example 7

(129) Each of the compounds S-1, S-5, S-7, S-8, S-9, S-10, O-1, and O-2 was made to a formulation according to a similar method to that described in the Formulation example 5 and was then diluted with water so that each of the active ingredient concentration was set to 500 ppm to prepare each of the diluted solution.

(130) A cabbage in the third leaf stage was planted in a polyethylene cup, and thereto was sprayed the diluted solution in ratio 20 mL/cup. After the above-mentioned dilutions were dried, and the stem and leaf thereof was cut and then was stalled in a 50 mL cup, and five heads of cabbage moth (Plutella xylostella) at the second instar larval stages were released into the cup and the cup was covered with the lid. The cup was held at 25? C. and after 5 days, the number of died insects was counted and the mortality of insects was calculated by the following equation.
Mortality of insects (%)=(Number of dead insects/Number of tested insects)?100

(131) As a result, the treated area that was treated with each of the diluted solutions of the compounds S-1, S-5, S-7, S-8, S-9, S-10, O-1, and O-2 respectively showed 80% or greater as the mortality of insects.

Test Example 8

(132) Each of the compounds S-7, S-8, S-9, S-10, and O-2 was made to a formulation according to a similar method to that described in the Formulation example 5 and was then diluted with water so that each of the active ingredient concentration was set to 200 ppm to prepare each of the diluted solution.

(133) A cabbage in the third leaf stage was planted in a polyethylene cup, and thereto was sprayed the diluted solution in a ratio of 20 mL/cup. After the above-mentioned dilutions were dried, and the stem and leaf thereof was cut and then was installed in a 50 mL cup, and five heads of cabbage moth (Plutella xylostella) at the second instar larval stages were released into the cup and the cup was covered with the lid. The cup was held at 25? C. and after 5 days, the number of died insects was counted and the mortality insects was calculated by the following equation.
Mortality of insects (%)=(Number of dead insects/Number of tested insects)?100

(134) As a result, the treated area that was treated with each of the diluted solutions of the compounds S-7, S-8, S-9, S-10, and O-2 respectively showed 80% or greater as the mortality of insects.

Test Example 9

(135) Each of the compounds S-2, S-3, S-7, S-8, and N-1 was made to a formulation according to a similar method to that described in the Formulation example 5 and was then diluted with water so that each of the active ingredient concentration was set to 500 ppm to prepare each of the diluted solution.

(136) The bottom of the polyethylene cup having 5.5 cm diameter was matted with the same size of a filter paper, and 0.7 mL of the diluted solution was added dropwise to the filter paper and 30 mg sucrose as bait was placed in the cup uniformly. Ten (10) heads of female adult housefly (Musca domestica) were released into the polyethylene cup and the cup was covered with the lid. After 24 hours, the life and death of housefly was examined and the number of died insects was counted and the mortality of insects was calculated by the following equation.
Mortality of insects (%)=(Number of dead insects/Number of tested insects)?100

(137) As a result, the treated area that was treated with each of the diluted solutions of the compounds S-2, S-3, S-7, S-8, and N-1 respectively showed 100% as the mortality of insects.

Test Example 10

(138) The compound S-1 was mixed with a mixed solution of acetone and polyoxyethylene sorbitan mono-cocoate (acetone and polyoxyethylene sorbitan mono-cocoate=95 : 5 (weight ratio)) a ratio of 50 ?L of the mixed solution per 1 mg of the compound S-1, and the resulting mixtures were then diluted with ion-exchange water containing 0.03% by volume of shindain (registered trademark, manufactured by Sumitomo Chemical Co. Ltd.) so that the concentration of the compound S-1 was set to 500 ppm to prepare the diluted solution of the compound S-1.

(139) Corns (Xea mays) were sown on a tray overlaid with damped KimWipes (registered trademark). After corns were grown for 5 days, the entire seedling of the corn was immersed into the diluted solution for 30 seconds. After the seedling was dried, two grains of the seedling were installed in a plastic petri dish (90 mm radius), and ten heads of western corn rootworm (Diabrotica virgifera virgifera) at the second instar larval stages were released onto the petri dish and the petri dish was covered with the lid. The petri dish was held at 25? C. and after 5 days, the number of died insects was counted and the mortality of insects was calculated by the following equation.
Mortality of insects (%)=(Number of dead insects/Number of tested insects)?100

(140) Similarly, using the compounds S-2, S-3, S-7, S-10, O-1 and O-2 instead of the compound S-1, the tests were carried out.

(141) As a result, the compounds S-2, S-3, S-4, S-7, S-10, O-1 and O-2 respectively showed 80% or greater as the mortality of insects.

(142) Next, each efficacy against a harmful arthropod of the compound A and the compounds described n JP 2000-26421 A respectively is shown in the below-mentioned comparative experiment.

Comparative Experiment

(143) The comparative experiments were conducted by using the compounds S-1, S-7 and S-8 as the compound A, and the below-mentioned compounds V-7, V-11 and V-12 as the compounds described in JP 2000-26421 A. The results are shown in Table 26. In the Table, each of the Comparative Experiment 2 the Comparative Experiment 3, and the Comparative Experiment 5 represents a comparative experiment that was conducted according to the similar method to that described in Test Example 2, Test Example 3, and Test Example 5, respectively. Here A represents 100%, B represents 90 to 99%, C represents 60 to 89%, D represents 30 to 59% and represents 0 to 29% as a control value.

(144) TABLE-US-00026 TABLE 26 Com- Com- Com- parative parative parative Experi- Experi- Experi- Compound ment 2 ment 3 ment 5 S-1 A B A S-7 A A A S-8 A A A V-7 E E D V-11 E E E V-12 E E E

(145) Industrial Applicability

(146) The compound A shows an excellent control effect against a harmful arthropod.