JP2001158785A - Agrochemical composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an agrochemical composition having an excellent controlling effect. SOLUTION: This insecticidal composition comprises a compound of formula [I] [R1 is a 1-6C alkyl group or a 1-6C haloalkyl group; n is an integer of 0 to 2; X is NR2R3 (R2 and 3 are each H or a 1-6C alkyl group which may be substituted with pyridyl), N=CHOR4 (R4S is a 1-6C alkyl group), N=CHR6R7 (R6 and R7 are each H or 1-6C alkyl) or the like; R5 is an alkyl] group or an acyl group which may be substituted, respectively; R8 is a halogen, a 1-6C haloalkyl group, a 1-6C haloalkoxy group or a phenol group which may be substituted with the 1-6C haloalcyl group; A is N or =CR9 (R9 is Cl or CN); B is N or CH] or its salt and another agrochemical active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition comprising an oxadiazoline derivative represented by the formula [1] or a salt thereof and another pesticidal active ingredient, which has excellent insecticidal action or insecticidal fungicidal action.

[0002]

2. Description of the Related Art The oxadiazoline derivative represented by the formula [I] used in the present invention is a compound having an excellent insecticidal action by itself (Japanese Patent Application No. 11-151959). In addition, WO 97/28126 reports arylpyrazole derivatives that are themselves excellent in insecticidal activity.

[0003]

In recent years, environmental pollution by various chemical substances has been regarded as a global problem, and there is a social demand to minimize the release of chemical substances into the environment. In the field of agriculture, various methods for controlling pests other than chemical substances, such as creation of genetically modified crops, control of pests by natural enemies, and physical control are being studied.
However, pest control methods using substances other than these chemicals have many problems, such as control of only specific pests and instability, and the necessity of control with chemicals has not yet been reduced.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies with the aim of reducing the pesticide application from the viewpoint of environmental pollution and the like. As a result, the oxadiazoline derivative represented by the formula [I] and other The pesticides in combination with the pesticide active ingredient, each exhibit a higher effect than expected when used alone, for that reason, it is possible to reduce the amount of application or the number of applications, and found that the present invention It was completed. That is, the present invention relates to [1] Formula [I]

Embedded image [Wherein, R ¹ represents a C _1-6 alkyl group or a C _1-6 haloalkyl group, n represents 0, 1 or 2, and X represents (1) -NR ² R
³ (R ² and R ³ each represent a hydrogen atom or a C _1-6 alkyl group optionally substituted with pyridyl), (2)-
N = CHOR ⁴ (R ⁴ represents a C _1-6 alkyl group), (3)-
N = CHNR ⁶ R ⁷ (R ⁶ and R ⁷ each represent a hydrogen atom or a C _1-6 alkyl group), (4) —N ＝ CHAr (A
r represents a phenyl group which may be substituted by a substituent selected from hydroxyl and a C _1-3 alkoxy group) or (5) a pyrrolyl group; and R ⁵ represents an optionally substituted alkyl group or a substituted R ⁸ represents an acyl group which may be
A represents a phenyl group which may be substituted with (1) halogen, (2) C _1-6 haloalkyl group, (3) C _1-6 haloalkoxy group or (4) C _1-6 haloalkyl group; Or

Embedded image (R ⁹ represents a chlorine atom or a cyano group), B is a nitrogen atom or

Embedded image An oxadiazoline derivative represented by
Compound [I]) or a pesticidal composition containing a salt thereof and another pesticidal active ingredient, [2] an oxadiazoline derivative or a salt thereof and another pesticidal active ingredient in a weight ratio of 1 : The composition according to the above [1], which is contained at a ratio of 0.25 to 1:20; [3] the insecticidal composition according to the above [1], wherein the other pesticidal active ingredient is an insecticidal ingredient; The insecticidal component is clothianidin, and the oxadiazoline derivative or a salt thereof and clothianidin are each in a weight ratio of 1:
[5] The composition according to the above [3], wherein the composition has a ratio of 0.25 to 1: 4, [5] the insecticidal component is nitenpyram, and an oxadiazoline derivative or a salt thereof and nitenpyram are each 1: 0 in weight ratio. .25 to 1: 4 as described above.
[3] The composition according to [3], wherein the insecticidal component is cartap hydrochloride, which contains the oxadiazoline derivative or a salt thereof and cartap hydrochloride in a weight ratio of 1: 1 to 1:10, respectively. The composition according to the above [3], wherein the insecticidal component is bensultap, and the oxadiazoline derivative or a salt thereof and bensultap are each in a weight ratio of 1: 1 to 1: 1.
The composition according to the above [3], which is contained at a ratio of 1:10,
[8] The composition according to the above-mentioned [3], wherein the insecticidal component is pyraclofos, and the oxadiazoline derivative or a salt thereof and pyraclofos are each contained in a weight ratio of 1: 1 to 1:10, [9] The above wherein the other pesticide active ingredient is a bactericidal ingredient
The composition according to [1], wherein the [10] oxadiazoline derivative is 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl)
-Δ ² -1,2,4-oxadiazolin-3-yl}-
5-isopropoxymethyleneamino-4-trifluoromethylsulfinylpyrazole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4-
(N, N-dimethylcarbamoyl) -Δ ² -1,2,4
-Oxadiazolin-3-yl} -5-ethoxymethyleneamino-4-trifluoromethylsulfinylpyrazole and 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-3-
{4- (morpholinocarbonyl) -Δ ² -1,2,4-
The composition according to the above [1], wherein the composition is selected from oxadiazolin-3-yl} -4-trifluoromethylsulfinylpyrazole, [11] Formula [I]

Embedded image [Wherein, R ¹ represents a C _1-6 alkyl group or a C _1-6 haloalkyl group, n represents 0, 1 or 2, and X represents (1) -NR ² R
³ (R ² and R ³ each represent a hydrogen atom or a C _1-6 alkyl group optionally substituted with pyridyl), (2)-
N = CHOR ⁴ (R ⁴ represents a C _1-6 alkyl group), (3)-
N = CHNR ⁶ R ⁷ (R ⁶ and R ⁷ each represent a hydrogen atom or a C _1-6 alkyl group), (4) —N ＝ CHAr (A
r represents a phenyl group which may be substituted by a substituent selected from hydroxyl and a C _1-3 alkoxy group) or (5) a pyrrolyl group; and R ⁵ represents an optionally substituted alkyl group or a substituted R ⁸ represents an acyl group which may be
A represents a phenyl group which may be substituted with (1) halogen, (2) C _1-6 haloalkyl group, (3) C _1-6 haloalkoxy group or (4) C _1-6 haloalkyl group; Or

Embedded image (R ⁹ represents a chlorine atom or a cyano group), B is a nitrogen atom or

Embedded image Wherein the oxadiazoline derivative represented by the formula or a salt thereof is used in combination with another pesticidal active ingredient; [12] Formula [I]

Embedded image [Wherein, R ¹ represents a C _1-6 alkyl group or a C _1-6 haloalkyl group, n represents 0, 1 or 2, and X represents (1) -NR ² R
³ (R ² and R ³ each represent a hydrogen atom or a C _1-6 alkyl group optionally substituted with pyridyl), (2)-
N = CHOR ⁴ (R ⁴ represents a C _1-6 alkyl group), (3)-
N = CHNR ⁶ R ⁷ (R ⁶ and R ⁷ each represent a hydrogen atom or a C _1-6 alkyl group), (4) —N ＝ CHAr (A
r represents a phenyl group which may be substituted by a substituent selected from hydroxyl and a C _1-3 alkoxy group) or (5) a pyrrolyl group; and R ⁵ represents an optionally substituted alkyl group or a substituted R ⁸ represents an acyl group which may be
A represents a phenyl group which may be substituted with (1) halogen, (2) C _1-6 haloalkyl group, (3) C _1-6 haloalkoxy group or (4) C _1-6 haloalkyl group; Or

Embedded image (R ⁹ represents a chlorine atom or a cyano group), B is a nitrogen atom or

Embedded image A method for enhancing the insecticidal effect of the oxadiazoline derivative [I] or a salt thereof, comprising using an oxadiazoline derivative represented by the following formula or a salt thereof in combination with another agricultural chemical active ingredient; and [13] R ¹ represents a trifluoromethyl group, n represents 1, R ⁵ represents an acetyl group, R ⁸ represents a trifluoromethyl group, and A represents ＣCCl—.
When B is ＣＨCH—, X is not —N ＝ CHOC ₂ H ₅ , wherein the composition according to the above item [1], the insecticidal method according to the above item [11], or the insecticide method according to the above item [12]. The present invention relates to a method for enhancing the insecticidal effect.

The compound [I] or a salt thereof may have a geometrical isomer and / or a stereoisomer, and the present invention includes each of the isomers and a mixture of the isomers. Examples of the C _1-6 alkyl group represented by R ¹ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.
Butyl and the like. Examples of the C _1-6 haloalkyl group represented by R ¹ include chloromethyl, fluoromethyl, bromomethyl, 2-chloroethyl, dichloromethyl, trichloromethyl, trifluoromethyl, 2,2,2
C _1-6 substituted with 1 to 10 (preferably 1 to 5) halogens (eg, fluorine, chlorine, bromine, iodine) such as trifluoroethyl, pentafluoroethyl, heptafluoropropyl, and nonafluorobutyl. An alkyl group is used. n represents 0, 1 or 2, with 1 being particularly preferred. R ¹ is preferably a C _1-6 such as a trifluoromethyl group.
Haloalkyl groups are preferred. Examples of the C _1-6 alkyl group in the “C _1-6 alkyl group optionally substituted with pyridyl” in R ² and R ³ include the C _1-6 exemplified in the aforementioned R ¹
_{The same as the 1-6} alkyl group can be mentioned. Pyridyl includes 2-, 3- or 4-pyridyl groups.
Such a pyridyl group may have one or two C _1-6 alkyl groups.
May be replaced. R ² and R ³ are each preferably a hydrogen atom or a methyl group, and particularly preferably, both are hydrogen atoms. As the C _1-6 alkyl group in R ^4, R ⁶ and R ^7, the same as the C _1-6 alkyl groups exemplified above R ¹ can be mentioned. R ⁴ is preferably a C _1-6 alkyl group, particularly preferably an ethyl group or an isopropyl group. R ⁶ and R ⁷ are preferably C _1-6 alkyl such as methyl. C which may be substituted on the phenyl group of Ar
_{Examples of the 1-3} alkoxy group include methoxy, ethoxy, propoxy, isopropoxy and the like. Particularly, methoxy is preferred. The phenyl group of Ar may be substituted with 1 to 3 substituents selected from hydroxyl and C _1-3 alkoxy groups. Ar is especially 3-methoxy-4
-Hydroxyphenyl groups are preferred. Examples of the pyrrolyl group for X include a 1-, 2- or 3-pyrrolyl group. The X, -NR ² R ³ among the above (R ² and R ³ is as defined above) or -N = CHOR ⁴
(R ⁴ has the same meaning as described above), particularly —NH ₂
Or -N = CHOR ⁴ (R ⁴ is as defined above) are preferred.

The alkyl group of the optionally substituted alkyl group represented by R ⁵ includes C _1-6 exemplified for R ¹ above.
The same as the alkyl group can be mentioned. Examples of the substituent of the alkyl group include a hydroxyl group, an amino group, a mono- or di-C _1-6 alkylamino group (eg, methylamino, ethylamino, propylamino, dimethylamino,
A C _1-6 alkoxy group (eg, methoxy, ethoxy, propoxy, isopropoxy, butoxy, etc.), a C _1-4 alkylthio group (eg, methylthio, ethylthio, n-propylthio, isopropylthio, butylthio, etc.), Examples include a halogen atom (eg, fluorine, chlorine, bromine, iodine), a carboxyl group, a nitro group, a cyano group, and the like. As the substituent, a C _1-6 alkoxy group is particularly preferred. The number of substitutions is 1 to 6, preferably 1 to 3 within the range that can be substituted. Examples of the acyl group of the optionally substituted acyl group represented by R ⁵ include an acyl group having 1 to 20 carbon atoms derived from a carboxylic acid,
For example, (1) formyl, (2) alkanoyl group, preferably alkanoyl group having 2 to 10 carbon atoms (eg, acetyl, propionyl, butyryl, isobutyryl, pentanoyl,
C _1-9 alkyl-carbonyl groups such as hexanoyl, heptanoyl, pivaloyl), (3) cycloalkanoyl group,
Preferably a cycloalkanoyl group having 4 to 10 carbon atoms (eg, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, etc.), (4) an alkenylcarbonyl group, preferably an alkenylcarbonyl group having 3 to 10 carbon atoms (eg, Acryloyl, allylcarbonyl, isopropenylcarbonyl, isobutenylcarbonyl, 1-methylallylcarbonyl, cinnamoyl, etc.), (5) alkynylcarbonyl group, preferably an alkynylcarbonyl group having 3 to 7 carbon atoms (eg, propargylcarbonyl, 2 -Butynylcarbonyl, 3-butynylcarbonyl, 3-pentynylcarbonyl, etc.), (6) an arylcarbonyl group, preferably an aryl-carbonyl group having 6 to 14 carbon atoms (eg, benzoyl, 1-naphthoyl, 2-na (7) an alkoxycarbonyl group, preferably an alkoxy-carbonyl group having 1 to 6 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl) , Tert-butoxycarbonyl, etc.), (8) aryloxycarbonyl group, preferably an aryloxy-carbonyl group having 6 to 14 carbon atoms (eg phenoxycarbonyl group), (9) aralkylcarbonyl group, preferably having 7 to 14 carbon atoms. 19 Aralkyl-
Carbonyl group (eg, phenyl-C _1-4 alkylcarbonyl such as benzylcarbonyl, phenethylcarbonyl, phenylpropylcarbonyl, naphthyl-C such as benzhydrylcarbonyl and 1-naphthylethylcarbonyl)
_1-4 alkylcarbonyl, etc.), (10) aralkyloxycarbonyl groups, preferably aralkyloxycarbonyl group 19 from 7 carbon atoms (e.g., benzyloxycarbonyl,
Phenyl-C _1-4 alkyloxycarbonyl such as phenethyloxycarbonyl and phenylpropyloxycarbonyl), (11) carbamoyl group, (12) cyclic aminocarbonyl group (eg, 1-pyrrolidinocarbonyl, piperidinocarbonyl, morpholinocarbonyl Thiomorpholinocarbonyl, 1-perhydroazepinylcarbonyl, etc.).

When the acyl group is an alkanoyl group, an alkenylcarbonyl group or an alkynylcarbonyl group, 1 to 6 (preferably 1 to 3) hydroxyl groups, amino groups, mono- or di-C _1- as substituents. ₆ alkylamino groups (eg, methylamino, ethylamino, propylamino, dimethylamino, diethylamino, etc.), C _1-6
Alkoxy groups (eg, methoxy, ethoxy, propoxy,
Isopropoxy, butoxy, etc.), C _1-6 alkylthio group (eg, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, etc.), halogen atom (eg, fluorine, chlorine, bromine, iodine), carboxyl group, It may have a nitro group, a cyano group, a phenyl group and the like. When the acyl group is a cycloalkanoyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkylcarbonyl group or an aralkyloxycarbonyl group, 1 to 5 (preferably 1 to 3) hydroxyl groups are substituted. , Amino group,
Mono- or di-C _1-6 alkylamino group (eg, methylamino, ethylamino, propylamino, dimethylamino, diethylamino, etc.), C _1-6 alkoxy group (eg,
Methoxy, ethoxy, propoxy, isopropoxy, butoxy, etc.), C _1-6 alkylthio group (eg, methylthio,
Ethylthio, n-propylthio, isopropylthio, n-
Butylthio, etc.), halogen atoms (eg, fluorine, chlorine, bromine, iodine), carboxyl groups, nitro groups, cyano groups,
Phenyl group, C _1-6 alkyl group (eg, methyl, ethyl, n
-Propyl, isopropyl, n-butyl, isobutyl, s
ec-butyl, tert-butyl, etc.), C _2-6 alkenyl group (eg, vinyl, allyl, 1-propenyl, 1-butenyl, 2-butenyl, etc.), C _2-6 alkynyl group (eg, ethynyl, 1- Propynyl, propargyl, 1-butynyl, etc.). When the acyl group is a carbamoyl group, one or two (1) C _1-6 alkyl groups (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert.
-Butyl, etc.), (2) C _3-9 cycloalkyl group (eg, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.), (3) C _2-6 alkenyl group (eg, vinyl, allyl, 1-propenyl, 1 -Butenyl, 2-butenyl, etc.), (4) C _2-6 alkynyl group (eg, ethynyl, 1-propynyl, propargyl, 1-butynyl, etc.), (5) hydroxyl group, (6) C _1-6 alkoxy group (Eg, methoxy, ethoxy, propoxy, isopropoxy, butoxy, etc.),
(7) amino group, (8) mono- or di-C _1-6 alkylamino group (eg, methylamino, ethylamino, propylamino, dimethylamino, diethylamino, etc.), (9) cyclic amino group (eg, 1 -Pyrrolidino, piperidino, morpholino, 4-methyl-1-piperazino, etc.) or (10) a phenyl group, and the substituent is a cyclic amino group (for example, 1-pyrrolidino) together with a nitrogen atom to be bonded. , Piperidino, morpholino, thiomorpholino, 4-methyl-
1-piperazino). Further, the substituent may be a hydroxyl group, an amino group, a mono- or di-C
_1-6 alkylamino group (e.g., methylamino, ethylamino, propylamino, dimethylamino, diethylamino, etc.), C _1-6 alkoxy group (e.g., methoxy, ethoxy,
Propoxy, isopropoxy, butoxy, etc.), C _1-6 alkylthio group (eg, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, etc.), halogen atom (eg, fluorine, chlorine, bromine, iodine), phenyl It may be substituted with 1 to 6 (preferably 1 to 3) substituents selected from a group, a carboxyl group, a nitro group and a cyano group. As R ⁵ , an alkyl group which may be substituted, an alkanoyl group which may be substituted, a cycloalkanoyl group which may be substituted, an alkenylcarbonyl group which may be substituted, Preferred are an arylcarbonyl group, an optionally substituted alkoxycarbonyl group, and an optionally substituted carbamoyl group, and more preferably an optionally substituted carbamoyl group. In particular, (1) C _1-6 1 to 3 amino optionally substituted by C _1-6 alkyl group with an alkoxy, (2) C _1-6 alkyl with one or two optionally substituted amino, C _1-6 alkoxy, phenyl or a _C2-10 alkanoyl group optionally substituted by 1 to 3 halogen atoms, (3) _C4-10 cycloalkanoyl group, (4) _C3-10
An alkenylcarbonyl group, (5) a benzoyl group, (6) a substituent selected from phenyl, halogen, and an amino group optionally substituted by one or two C _1-6 alkyl groups.
One or two optionally substituted C _1-6 alkyl, C _3-9 cycloalkyl, C _2-6 alkenyl, C _2-6 alkynyl, phenyl, C _1-6 alkyl may be substituted. Amino, cyclic amino (eg, pyrrolidino, piperidino), carbamoyl group optionally substituted by one or two hydroxyl or C _1-6 alkoxy, (7) cyclic amino-carbonyl group (eg, pyrrolidinocarbonyl, piperidi Carbonyl, 1-perhydroazepinylcarbonyl, 4-methyl-1-piperazinylcarbonyl, morpholinocarbonyl), (8) _C1-6 alkoxy-carbonyl group or (9) formyl group.

The halogen for R ⁸ includes fluorine, chlorine, bromine and iodine. As the C _1-6 haloalkyl group for R ⁸ include the same C _1-6 haloalkyl groups exemplified above for R ^1. Examples of the C _1-6 haloalkoxy group for R ⁸ include chloromethoxy, fluoromethoxy, bromomethoxy, 2-chloroethoxy, dichloroethoxy, trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, and pentafluoro Halogen such as ethoxy, heptafluoropropoxy, nonafluorobutoxy (eg, fluorine, chlorine, bromine,
A C _1-6 alkoxy group substituted by 1 to 10 (preferably 1 to 5) with iodine) is used. Particularly, trifluoromethoxy is preferable. C in the "C _1-6 haloalkyl phenyl group which may be substituted with group" of R ⁸ _1-6
As the haloalkyl group, those similar to the C _1-6 haloalkyl group exemplified for R ¹ can be mentioned. The number of substituents in the phenyl group is 1 to 5, preferably 1 to 3. Particularly, a phenyl group which may be substituted with 1 to 3 trifluoromethyl groups is preferable. Especially for A

Embedded image Is preferred. B is particularly preferably a nitrogen atom.

Compound (I) is represented by the formula

Embedded image [In the formula, n represents 0, 1 or 2, X ′ represents -NH ₂ , -N =
CHOR ⁴ '(R ⁴ ' represents a C _1-6 alkyl group) or-
N = CHNR ⁶ 'R ⁷ ' (R ⁶ 'and R ⁷ ' are each C _1-6
R ⁵ ′ represents (1) a C _1-6 alkyl group optionally substituted with C _1-6 alkoxy, (2) a mono- or di-C _1-6 alkylamino, phenyl, C _1-9 alkyl-carbonyl group which may be substituted with 1 to 3 substituents selected from C _1-6 alkoxy and halogen, (3) benzoyl group, (4) C _4-10 cycloalkanoyl group, (5) C _3-10 alkenylcarbonyl group optionally substituted by 1 or 2 phenyl, (6) formyl group, (7) C _1-6 alkoxy-
Carbonyl group, (8) C _1-6 alkyl, C _2-6 alkenyl,
Substituted with one or two substituents selected from C _2-6 alkynyl, phenyl, benzyl, mono- or di-C _1-6 alkylamino, hydroxyl, C _1-6 alkoxy, C _3-9 cycloalkyl and piperidino A carbamoyl group or (9) a cyclic amino-carbonyl group selected from pyrrolidinocarbonyl, piperidinocarbonyl, 1-perhydroazepinylcarbonyl, 4-methyl-1-piperazinylcarbonyl and morpholinocarbonyl Is preferable].

A more preferred compound [I] has the formula

Embedded image [Wherein, n represents 0, 1 or 2, X ″ represents —NH ₂ or —N ＝ CHOR ⁴ ″ (R ⁴ ″ represents a C _1-6 alkyl group)
R ⁵ ″ is (1) a C _1-9 alkyl-carbonyl group, (2) C
_A carbamoyl group which may be substituted by one or two _1-6 alkyl groups or (3) a morpholinocarbonyl group].

Further preferred compounds [I] include compounds of the formula

Embedded image [Wherein, n represents 0, 1 or 2, and X ″ ′ represents —NＮCHO
R ⁴ '' a '(R ^4' '' represents a C _1-6 alkyl group), R 5 ^'''
Represents a carbamoyl group which may be substituted by one or two C _1-6 alkyls].
Compound as [I] 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N- dimethylcarbamoyl) - [delta ^{2-1,2,4-oxadiazoline} - 3-yl} -5-isopropoxymethyleneamino-4-trifluoromethylsulfinylpyrazole,
1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl)
-Δ ² -1,2,4-oxadiazolin-3-yl}-
5-ethoxymethyleneamino-4-trifluoromethylsulfinylpyrazole and 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-3- {4- (morpholinocarbonyl)-
Δ ² -1,2,4-oxadiazolin-3-yl｝ -4
-Trifluoromethylsulfinylpyrazole or salts thereof are particularly preferred.

The salt of the compound [I] may be any salt which is acceptable in agrochemical chemistry. That is, when the molecule has an acidic group such as a carboxyl group or a sulfo group, a salt with a base may be formed. Examples of the base include alkali metals such as sodium, potassium and lithium, calcium and magnesium. And inorganic bases such as ammonia, and organic bases such as pyridine, collidine, triethylamine and triethanolamine. When the molecule has a basic group such as an amino group in the molecule, a salt with an acid may be formed. Examples of the acid include hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, Salts of inorganic acids such as sulfuric acid, perchloric acid or the like or formic acid, acetic acid, tartaric acid, malic acid, citric acid, oxalic acid, succinic acid, benzoic acid, picric acid, methanesulfonic acid, p
-Salts of organic acids such as toluenesulfonic acid are used. Compound [I] may form an inner salt, which is also included in the present invention.

The compound [I] or a salt thereof, and the compound [II] used as a starting material for producing the compound [I] or a salt thereof shown below can be prepared by the method described in WO 97/28126 or a method analogous thereto. Can be manufactured. In general, compound [I] or a salt thereof is synthesized by reacting compound [II] as a raw material with an acylating agent or an alkylating agent in the presence of an appropriate acid or base catalyst as required. Can be. Examples of the acylating agent used in such a reaction include carboxylic acid halides (eg, acetyl chloride, propionyl bromide, etc.), carbamoyl halides (eg, N, N-dimethylcarbamoyl chloride, N, N-diethylcarbamoyl chloride, etc.),
Halogeno carbonate (eg, methyl chlorocarbonate, phenyl chlorocarbonate, etc.), dialkyl dicarbonate (eg, dite dicarbonate)
Known acylating agents such as rt-butyl, dimethyl dicarbonate, etc.) and carboxylic anhydrides (eg, acetic anhydride, propionic anhydride, etc.) can be used. Examples of the alkylating agent used in such a reaction include alkyl halides (eg, methyl iodide, ethyl bromide, etc.) and alkyl sulfonates (eg, methyl methanesulfonate, ethyl p-toluenesulfonate, methyl trifluoromethanesulfonate, etc.) Known alkylating agents such as dialkyl sulfate (eg, dimethyl sulfate, diethyl sulfate, etc.) and trialkyl orthoformate (eg, trimethyl orthoformate, triethyl orthoformate, etc.) can be used. In this reaction, the amount of the above-mentioned acylating agent or alkylating agent is not particularly limited, and a large excess may be used as a solvent. Examples of the base catalyst used in this reaction include, for example, alkali metal alcoholates such as sodium ethylate, sodium methylate and potassium tert-butoxide, for example, triethylamine, diisopropylethylamine, pyridine,
Organic bases such as -dimethylaminopyridine, N, N-dimethylaniline, for example, potassium carbonate, sodium carbonate,
Inorganic bases such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium bicarbonate and sodium hydride can be used. The amount of the base to be used is not particularly limited as long as it does not adversely affect the reaction, and a large excess can be used also as a solvent, but preferably 0.1 to 2
It is 0 equivalent. As the acid catalyst used in this reaction, for example, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, inorganic protic acids such as sulfuric acid, for example, formic acid, acetic acid, tartaric acid,
Malic acid, citric acid, oxalic acid, succinic acid, benzoic acid,
Organic protonic acids such as trifluoroacetic acid and p-toluenesulfonic acid, and Lewis acids such as aluminum chloride, ferric chloride, zinc chloride, titanium tetrachloride and boron trifluoride are used. The amount of the acid catalyst used in the reaction is not particularly limited as long as it does not adversely affect the reaction, and a large excess can be used as a solvent, but is preferably 0.1 to 20 equivalents. This reaction can be performed using a suitable solvent. Such solvents include reaction substrates,
There is no particular limitation as long as it does not give a by-product by reacting with the reaction reagent and the product, but it is desirable to dissolve both the reaction substrate and the reaction reagent. Examples of such a solvent include aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, and esters such as methyl acetate, ethyl acetate, ethyl formate and ethyl propionate. , Acetone, ketones such as methyl ethyl ketone, ethers such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran and dioxane; nitriles such as acetonitrile and propionitrile; acid amides such as dimethylformamide and dimethylacetamide , Sulfoxides such as dimethylsulfoxide, sulfones such as sulfolane, phosphoric amides such as hexamethylphosphoramide, and halogenated compounds such as dichloromethane, chloroform, 1,2-dichloroethane and carbon tetrachloride. Gen hydrocarbons, pyridine, picoline, lutidine,
Aromatic amines such as quinoline, a mixed solvent thereof, water, and a mixed solvent of these and water are used. The reaction temperature is usually about -50 to 200C, and the reaction time is generally about 0.1 to 96 hours. When the compound [I] is obtained as a free compound, a salt as described above, and when the compound [I] is obtained in a salt form, as a free compound,
Each can be converted according to a conventional method. When the compound contained in the compound [I] is used as a raw material for producing another kind of the compound [I], it may be used as it is or as a salt. When other raw materials can be salts as described above, they can be used not only free but also as salts. Therefore, the starting compounds and products used in the following production methods include salts thereof (for example, salts with acids as described in the above compound [I]). Compound [I] or a salt thereof can be specifically produced by the following method.

[Reaction formula (A)]

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[Reaction formula (B)]

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[Reaction formula (C)]

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[Reaction formula (D)]

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[Reaction formula (E)]

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[Reaction formula (F)]

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[Reaction formula (G)]

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[Reaction formula (H)]

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[Reaction formula (I)]

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[Reaction formula (J)]

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In the above reaction formulas (A) to (J), A, B,
X, n, R ¹ , R ⁴ , R ⁵ and R ⁸ are as defined above,
^5a is an ^optionally substituted C _1-9 alkyl group, an _optionally substituted C _3-9 cycloalkyl group, an _optionally substituted C _2-6 alkenyl group, an optionally substituted phenyl group , A C _1-6 alkoxy group or mono- or di-C
_1-6 alkylamino group, R ^5b is an ^optionally substituted C _1-9 alkyl group, an _optionally substituted C _3-9 cycloalkyl group, an _optionally substituted C _2-6 alkenyl group R ^5c , R ^5f and R ^5g each represent an optionally substituted C _1-6 alkyl group; m represents 1 or 2; R ^5d and R ^5e each represent hydrogen; An atom, an optionally substituted C _1-6 alkyl group, an _optionally substituted C _3-9 cycloalkyl group, an _optionally substituted C _2-6 alkenyl group, an optionally substituted C _{2 Represents a -6} alkynyl group, an optionally substituted phenyl group, a mono- or di-C _1-6 alkylamino group, a cyclic amino group, a hydroxyl group, a C _1-6 alkoxy group, or cyclic with a nitrogen atom to be bonded Shows an amino group. ^Optionally substituted C in R ^5a and R ^5b
Examples of the alkyl group of the _1-9 alkyl group include methyl,
Ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n
eo-pentyl, 1-ethylpropyl, 1-propylbutyl, n-hexyl, n-heptyl, n-octyl, n-nonyl and the like. As the substituent for the alkyl group, the aforementioned R
Examples are the same as the substituents for the optionally substituted alkyl group exemplified in ⁵ . The number of substitutions is 1 to 6, preferably 1 to 3 within the range that can be substituted. As the ^optionally substituted C _1-6 alkyl group for R ^5c , R ^5d , R ^5e , R ^5f and R ^5g, the same as the aforementioned optionally substituted alkyl group for R ⁵ can be mentioned. Examples of the substituent of the phenyl group of R ^5a , R ^5b , R ^5d and R ^5e include the same substituents as those of the acyl group (arylcarbonyl group) in R ⁵ . The number of substituents is 1 to 5 (preferably 1 to 3).
^Examples of the C _1-6 alkoxy group for R ^5a , R ^5d and R ^5e include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and the like. As the C _1-6 alkyl in the mono- or di-C _1-6 alkylamino group for R ^5a , R ^5d and R ^5e , the same alkyl groups as those exemplified for the aforementioned R ¹ can be mentioned. Examples of the cycloalkyl group of the ^optionally substituted C _3-9 cycloalkyl group in R ^5a , R ^5b , R ^5d and R ^5e include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. Examples of the alkenyl group of the ^optionally substituted C _2-6 alkenyl group in R ^5a , R ^5b , R ^5d and R ^5e include, for example, vinyl, allyl, 1-propenyl, 1-butenyl,
2-butenyl and the like. Examples of the alkynyl group of the ^optionally substituted C _2-6 alkynyl group in R ^5d and R ^5e include ethynyl, 1-propynyl, propargyl, 1-butynyl and the like. Examples of the cyclic amino group for R ^5d and R ^5e include 1-pyrrolidino, piperidino, morpholino, 4-methyl-1-piperazino and the like. The cycloalkyl group, alkenyl group, alkynyl group, and cyclic amino group described above are a hydroxyl group, an amino group, a mono- or di-C _1-6 alkylamino group (eg, methylamino, ethylamino, propylamino, dimethylamino , Diethylamino, etc.), C _1-6 alkoxy group (eg, methoxy, ethoxy, propoxy, isopropoxy, butoxy, etc.), C _1-6 alkylthio group (eg, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio) Etc.), halogen atoms (eg, fluorine, chlorine, bromine, iodine), phenyl groups, carboxyl groups, nitro groups and cyano groups
It may be substituted with up to 6 (preferably 1 to 3) substituents. Examples of the cyclic amino group shown together with the nitrogen atom to which R ^5d and R ^5e bind include 1-pyrrolidino, piperidino, morpholino, 4-methyl-1-piperazino and the like.

In the reaction formula (A), the compound [II] is ^converted to R ^5a CO 2
L [L may be substituted with 1 to 3 halogen atoms such as a halogen atom (eg, fluorine, chlorine, bromine, iodine), an acyloxy group (formyloxy group; acetoxy group, propionyloxy group, trifluoroacetoxy group, etc.) C _1-6
Alkyl-carbonyloxy group; C _1-10 acyloxy group such as C _1-6 alkoxy-carbonyloxy group such as methoxycarbonyloxy and t-butoxycarbonyloxy)
And the like. The reaction of producing a compound [III] by reacting with an acylating agent represented by the formula Compound (I
I] not only serves as a raw material for this reaction, but also has excellent insecticidal activity. Preferred examples of the compound [II] include, for example, 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-3-
(Delta ^{2-1,2,4-oxadiazolin-3-yl)} -
4-trifluoromethylsulfinylpyrazole, 1-
(2,6-dichloro-4-trifluoromethylphenyl) -3- (Δ ² -1,2,4- oxadiazoline -3
-Yl) -5- (n-propoxymethyleneamino) -4
-Trifluoromethylthiopyrazole, 1- (2,6-
Dichloro-4-trifluoromethylphenyl) -3-
(Delta ^{2-1,2,4-oxadiazolin-3-yl)} -
5- (n-propoxymethyleneamino) -4-trifluoromethylsulfonylpyrazole and the like. In this reaction, the amount of the above-mentioned acylating agent is not particularly limited, and a large excess may be used as a solvent, but it is preferably about 0.8 to 5 equivalents. For the purpose of accelerating the reaction and reducing by-products, good results may be obtained by allowing a base to coexist or acting before and after the reaction. Examples of such base include alcoholates of alkali metals such as sodium ethylate, sodium methylate, potassium tert-butoxide and the like, and organic bases such as triethylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine and N, N-dimethylaniline. Bases, for example, inorganic bases such as potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride and the like can be used. The amount of the base used is not particularly limited as long as it does not adversely affect the reaction, and a large excess can be used also as a solvent. This reaction can be performed using a suitable solvent. Such solvents include:
There is no particular limitation as long as it does not give a by-product by reacting with the reaction substrate, the reaction reagent and the product, but it is desirable to dissolve both the reaction substrate and the reaction reagent. Such solvents include, for example, pentane, hexane, heptane,
Aliphatic hydrocarbons such as petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, esters such as methyl acetate, ethyl acetate, ethyl formate, ethyl propionate, ketones such as acetone and methyl ethyl ketone, and diethyl ether Ethers such as dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran and dioxane; nitriles such as acetonitrile and propionitrile; acid amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethyl sulfoxide; and sulfolane. Sulfones, phosphoric amides such as hexamethylphosphoramide, dichloromethane, chloroform, 1,2-dichloroethane, halogenated hydrocarbons such as carbon tetrachloride, pyridine, picoline,
Aromatic amines such as lutidine and quinoline, a mixed solvent thereof, water, and a mixed solvent of these and water are used. The reaction temperature is generally about -50 to 200C, preferably about -30 to 150C. The reaction time is generally about 0.1-96 hours, preferably 0.1-72 hours.
Hours, more preferably about 0.1 to 24 hours. The obtained compound is separated and purified by a method known per se, for example, concentration, concentration under reduced pressure, liquid conversion, phase transfer, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc. May be used as a raw material for the reaction.

The reaction formula (B) shows that the compound [II] is ^converted to R ^5a CO 2
₂ H [R ^5a is as defined above. The reaction of producing a compound [IV] by reacting a carboxylic acid derivative represented by the formula [1] with a dehydrating condensing agent is shown. As the dehydrating condensing agent used in this reaction, a known dehydrating condensing agent such as DCC (dicyclohexylcarbodiimide), carbonyldiimidazole, BOP reagent (benzotriazol-1-yloxy-tris (dimethylamino) phosphonium hexafluorophosphate) is used. Can be The amount used is not particularly limited, but is preferably 0.8 to 5 equivalents. The amount of the carboxylic acid derivative used in this reaction is not particularly limited, and a large excess can be used as a solvent, but it is usually about 0.8 to 5 equivalents.

The reaction formula (C) shows that the compound [II] is ^converted to R ^5c NCO
[R ^5c is as defined above. The reaction of producing a compound [V] by reacting with an isocyanate derivative represented by the following formula: The amount of the isocyanate derivative used in this reaction is not particularly limited, and a large excess may be used as a solvent, but is preferably about 0.8 to 5 equivalents. For the purpose of accelerating the reaction and reducing by-products, good results may be obtained by allowing a base to coexist or acting before and after the reaction. The kind and amount of the base are the same as those in the reaction formula (A).

In the reaction formula (D), the compound [IIa] is reacted with phosgene or an equivalent thereof to obtain an intermediate [VI], in which R ^5d R ^5e NH [R ^5d and R ^5e have the same meanings as described above. Show. Reaction of the amine represented by the compound [VI
1] is shown. In the compound [IIa], B
Can be produced according to the method described in WO 97/28126. As phosgene or its equivalent used in this reaction, phosgene, trichloromethyl chloroformate (diphosgene), bistrichloromethyl carbonate (triphosgene) and the like are used. The amount used is not particularly limited,
Preferably it is 0.3 to 5 equivalents. Intermediate [VI] is separated by a means known per se, for example, concentration, concentration under reduced pressure, liquid conversion, phase transfer, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc., after purification, or as a reaction mixture. It may be used as a raw material for the next reaction. The amount of the amine represented by R ^5d R ^5e NH used in this reaction is not particularly limited, and a large excess can be used as a solvent, but it is usually about 0.8 to 5 equivalents.

The reaction formula (E) shows that the compound [II] is ^converted to R ^5f Hal
[Wherein, R ^5f has the same meaning as described above, and Hal represents a halogen atom (eg, fluorine, chlorine, bromine, iodine). With an alkyl halide represented by the formula (VIII)
Shows the reaction for producing R ^5f Hal used in this reaction
The amount of the alkyl halides represented by is not particularly limited,
Although a large excess can be used as the solvent, it is usually used in an amount of about 0.1.
8 to 5 equivalents. For the purpose of accelerating the reaction and reducing by-products, good results may be obtained by allowing a base to coexist or acting before and after the reaction. The kind and amount of the base are the same as those in the reaction formula (A).

The reaction formula (F) shows a reaction for producing the compound [X] by reacting the compound [IX] with formaldehyde or an equivalent thereof. As formaldehyde or its equivalent used in this reaction, formaldehyde, paraformaldehyde and the like are used. The amount used is not particularly limited, and a large excess can be used as a solvent.
Preferably it is 0.8 to 15 equivalents. Accelerate the reaction,
Good results may be obtained by coexisting an acid or acting before and after the reaction for the purpose of reducing by-products. Such acid catalysts include, for example, inorganic protic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, and sulfuric acid, for example, formic acid, acetic acid, tartaric acid, malic acid, citric acid, oxalic acid, succinic acid, Organic protonic acids such as benzoic acid, trifluoroacetic acid and p-toluenesulfonic acid, and Lewis acids such as aluminum chloride, ferric chloride, zinc chloride, titanium tetrachloride and boron trifluoride are used. The amount of the acid catalyst used in the reaction is not particularly limited as long as it does not adversely affect the reaction, and a large excess can be used as a solvent.

The reaction formula (G) shows a reaction for producing the compound [XII] by oxidizing the compound [XI] with an oxidizing agent. As the oxidizing agent used in this reaction, for example, hydrogen peroxide,
Peracetic acid, perbenzoic acid, m-chloroperbenzoic acid, sodium metaperiodate, ozone, selenium dioxide, chromic acid,
An oxidizing agent such as bromine, N-bromosuccinimide, iodosylbenzene, or t-butyl hypochlorite is used.
The amount to be used is not particularly limited, and a large excess can be used as a solvent, but the amount is preferably 0.8 to 5 equivalents.

The reaction formula [H] shows that the compound [XIII] can be converted to CH (O
The reaction for producing a compound [XIV] by reacting with a trialkyl orthoformate represented by R ⁴ ) ₃ is shown. The amount of the trialkyl orthoformate used in this reaction is not particularly limited, and a large excess can be used as a solvent, but it is preferably 0.8 to 15 equivalents. For the purpose of accelerating the reaction and reducing by-products, good results may be obtained by coexisting an acid or acting before and after the reaction. Such acid catalysts include, for example, inorganic protic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, and sulfuric acid, for example, formic acid, acetic acid, tartaric acid, malic acid, citric acid, oxalic acid, succinic acid, Organic protonic acids such as benzoic acid, trifluoroacetic acid, methanesulfonic acid and p-toluenesulfonic acid, and Lewis acids such as aluminum chloride, ferric chloride, zinc chloride, titanium tetrachloride and boron trifluoride are used. The amount of the acid catalyst used in the reaction is not particularly limited as long as it does not adversely affect the reaction, and a large excess can be used as a solvent.

The reaction formula [I] is obtained by converting the compound [XV] to vanillin.

Embedded image (Me represents a methyl group), and the compound [XVI]
Shows the reaction for producing The amount of vanillin used in this reaction is not particularly limited, and a large excess can be used as a solvent, but it is preferably 0.8 to 15 equivalents. For the purpose of accelerating the reaction and reducing by-products, good results may be obtained by coexisting an acid or acting before and after the reaction. Such acid catalysts include, for example, inorganic protic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, and sulfuric acid, for example, formic acid, acetic acid, tartaric acid, malic acid, citric acid, oxalic acid, succinic acid, Organic protonic acids such as benzoic acid, trifluoroacetic acid, p-toluenesulfonic acid, aluminum chloride, ferric chloride, zinc chloride,
Lewis acids such as titanium tetrachloride and boron trifluoride are used. The amount of the acid catalyst used in the reaction is not particularly limited as long as it does not adversely affect the reaction, and a large excess can be used as a solvent.

In the reaction formula [J], the compound [XV] is reacted with 2,5-dimethoxytetrahydrofuran to give the compound [XVI
I] is shown. 2,5 used in this reaction
The amount of -dimethoxytetrahydrofuran is not particularly limited, and a large excess can be used as a solvent, but it is preferably 0.8 to 15 equivalents. For the purpose of accelerating the reaction and reducing by-products, good results may be obtained by coexisting an acid or acting before and after the reaction. Such acid catalysts include, for example, inorganic protic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid, and sulfuric acid, for example, formic acid, acetic acid, tartaric acid, malic acid, citric acid, oxalic acid, succinic acid, Organic protonic acids such as benzoic acid, trifluoroacetic acid and p-toluenesulfonic acid, and Lewis acids such as aluminum chloride, ferric chloride, zinc chloride, titanium tetrachloride and boron trifluoride are used. The amount of the acid catalyst used in the reaction is not particularly limited as long as it does not adversely affect the reaction, and a large excess can be used as a solvent.

Each of the reactions of the reaction formulas (B) to (J) can be carried out using an appropriate solvent. Such solvents include:
The same one as described above in the reaction formula (A) is used. The temperature used for each reaction of the reaction formulas (B) to (J) is usually about -50 to 200C, preferably about -200C.
30-150 ° C. The reaction time is generally about 0.1 to
96 hours, preferably about 0.1 to 72 hours, more preferably about 0.1 to 24 hours. Reaction formulas (B) to (J)
The compound obtained in each of the above reactions may be separated and purified by a means known per se described in the reaction formula (A), or may be used as a reaction mixture as a starting material for the next reaction.

Compound [I] and salts thereof are used as sanitary pests,
It is effective for controlling plant and animal parasites and shows strong insecticidal action by treating plants and animals with pests. In addition, compound [I] and salts thereof have a safe and advantageous property as a pesticide for sanitary use, livestock industry, pets, horticulture, and agriculture, such as low phytotoxicity to plants and low toxicity to fish. Has both. The following pesticidal active ingredients, acaricidal active ingredients, bactericidal active ingredients, and the like, which are used in combination with the compound [I] or a salt thereof, and which are the other components that can be contained in the insecticidal composition of the present invention, are as follows. No.

Insecticidal active ingredients: EPN (EPN), acephate, isoxathion, isofenphos, isoprocarb (isoprocarb)
carb), etrimfos, oxydeprofos, quinalphos, cadusafos, chlorethos
xyfos), chlorpyrifos, chlorpyrifos-methyl, chlorofenvinphos, salithion
ion), cyanophos (cyanophos), disulfoton (disu)
lfoton), dimethoate, sulprofos, diazinon, thiometon, tetrachlorvinphos
inphos), tebupirimfos (tebupirimfos), trichlorphon (trichlorphon), nailed (naled), vamidothion (vamidothion), pyraclophos (pyraclopho)
s), pyridafenthion, pyrimiphos-methyl, fenitrothion, fenthion, phenthoate, butathiofo
s), prothiofos, propafos
phos), profenofos, hosalon (ph
osalone), fosthiazate, marathon (malathion), methidathion (methidathion), metolcarb (metolcarb), monocrotoph (monocrotoph)
os), BPMC (BPMC), XMC (XMC), alanycarb, ethiofencar
b), carbaryl, carbosulfan (car
bosulfan), carbofuran, xylylcarb, cloethocarb,
Thiodicarb (tridicarb), triazemate (triaza)
mate), pirimicarb (pirimicarb), phenoxycarb (fenoxycarb), fenothiocarb (fenothiocar)
b), furathiocarb, propoxur, bendiocarb, benfuracarb, methomil,
Acrinathrin, imiprothrin (imi
prothrin), ethofenprox,
Cycloprothrin, sigma-cypermethrin, cyhalothrin (cy
halothrin), cyfluthrin (cyfluthrin), cypermethrin (cypermethrin), silafluofen (silafluo)
fen), tefluthrin, deltamethrin, deltamethrin, tralomethrin,
Fenvalerate, fenpropathrin, flucythrina
te), fluvalinate, flufenenoprox, fluproxyfen
oxyfen), beta-cyfluthrin
n), benfluthrin, permethrin, acetamiprid, imidacloprid, cartap
p), thiocyclam, nitempiram (nit
enpyram), clothianidine, tefuranidine, AKD-1022 (AKD-102)
2), thiomethoxam, bensultap, avermectin, emamectin-benzoate, chlorfluazuron, cyromazine
zine), diafenthiuron, dichlorvos, diflubenzuron
zuron), spinosyn (spynosyn), teflubenzuron (teflubenzuron), tebufenozide (tebufenozid)
e), hydroprene, vaniliprole, pymetrozine, pyriproxyfen, fipronil
onil), flufenoxuron, buprofezin, hexaflulumon
uron), milbemycin, lufenuron, chlorphenapyr,
NC-184 (NC-184)

Acaricidal active ingredient: Clofentezine (clof
entezine), dienochlor, tebufenpyrad, pyridaben,
Hexythiazox, fenazaquin (f
enazaquin), fenpyroximat
e), etoxazole, amitraz (amitr
az), bromopropylate, fenbutatin oxide, pyrimidifen, BPPS (propargite), tebufenpyrad, kelofen (dicofol), N
BA-9761 (NBA-9761)

Bactericidal active ingredients: IBP (IBP), ampropylfos, edifenphos
s), chlorthiophos, tolclofos-methyl, fosety
l), ipconazole, imazalil (ima)
zalil), imibenconazole, etaconazole, epoxyconazole (e
poxiconazole), cyproconazol
e), diniconazole, difenoconazole, tetraconazole
onazole), tebuconazole (tebuconazole), triadimenol (triadimenol), triadimefon (triadim
efon), triticonazole, triforine, bitertano
l), viniconazole, fenarimol, fenbuconazol
e), fluotrimazole, fluconazole-cis, flusilazole (fl
usilazole), Flutriafol, Bromconazole, Propiconazole
piconazole), hexaconazole, pefurazoate, penconazole
nazole), microbutanil (myclobutanil), metconazole (metconazole), carbendazi (cabendazi)
n), debacarb, prothiocarb (proth
iocarb), benomyl, maneb, T
PN (TPN), isoprothiolane,
Iprodione, iminoctazine
adine-albesil), iminoctadin acetate
e-triacetate), ethirimol, etridiazole, oxadixy
l), oxycarboxin, oxolinic acid, ofurace, kasugamycin, carboxi
n), captan, capzillacon (clozylaco)
n), cllobenthiazone, cyprodinil, cyprodinil, cyprofuram, dietofencarb, dichlofluanid, diclomezine,
Zineb (zineb), dimethirimol (dimethirimol), dimethomorph (dimethomorph), dimefluazole (dime
fluazole), thiabendazole, thiophenate-methyl, thifluzamide, tecloftalam
m), triazoxide, triclamide (t
riclamide), tricyclazole, tridemorph, triflumizole
mizole, validamycin A, hymexazol, pyracarbolide
lid), pyrazophos, pyrifenox, pyrimethanil, pyroquilon, ferimzone,
Fenpiclonil, fenpropidin, fenpropimorp
h), fthalide, furametopil
pyr), furalaxyl, fluazinam (fl
uazinam), furcarbanil, fluquinconazole, fludioxonil (f
ludioxonil), Flusulfamide, Flutolanil, Butiobat
e), prochloraz, procymidone (pro
cymidone), probenazole (probenazole), benalaxyl (benalaxyl), benodanil (benodanil), pencyclone (pencycuron), microzoline (myclozoli)
n), metalaxyl, metsulfovax, methfuroxam, mepanipyrim, meproni
l), kresoxim-methyl, azoxystrobin, SSF-126 (SS
F-126), carpropamid, acibenzolar-S-methyl

The above "other pesticide active ingredients" are all known pesticide active ingredients. Other pesticidal active ingredients may contain one or more (preferably one or more, three or less) types in the composition. Here, when the "other pesticidal active ingredient" is a bactericidal active ingredient, the composition of the present invention is referred to as a composition having both insecticidal and bactericidal actions, a so-called insecticidal bactericidal composition, When the "active ingredient" is an acaricidal active ingredient, the composition according to the invention is suitably referred to as a composition having both insecticidal and acaricidal action, a so-called insecticidal and acaricidal composition. In the composition of the present invention, an insecticidal active ingredient and a bactericidal active ingredient are particularly preferable among the above-mentioned pesticidal active ingredients. As the insecticidal active ingredient, particularly, clothianidin [1- (2-chlorothiazol-
5-ylmethyl) -3-methyl-2-nitroguanidine],
Nitenpyram [(E) -N- (6-chloro-3-pyridylmethyl) -N-ethyl-N'-methyl-2-nitrovinylidenediamine], cartap hydrochloride [1,3-bis (carbamoylthio) -2 -(N, N-dimethylamino) propane hydrochloride], bensultap [S, S'-2
-Dimethylaminotrimethylene = di (benzenethiosulfonate)], pyraclofos [(RS)-[O-1-
(4-Chlorophenyl) pyrazol-4-yl] = O-
Ethyl = S-propyl = phosphorothioate] and the like are preferably used. Examples of the fungicidally active compound include soil treatment agents for rice, seed treatment agents, or carbopropamide, diclocymet, probenazole, tricyclazole, pyroquinone, isoprothiolane, acibenzol-S-methyl as surface application agents, and carpropamide as foliar spray agents. Diclosimet, probenazole, tricyclazole, pyroquinone, isoprothiolane, acibenzol-S-methyl, validamycin A, ferimzone, fusalide and the like are preferably used. Validamycin A, ferimzone, fusalide and the like are particularly preferably used.

Hereinafter, preferred embodiments of the present invention will be described. (1) An insecticidal composition containing the compound [I] or a salt thereof and clothianidin. (2) An insecticidal composition containing compound [I] or a salt thereof and nitenpyram. (3) An insecticidal composition containing the compound [I] or a salt thereof and cartap hydrochloride. (4) An insecticidal composition containing compound [I] or a salt thereof and bensultap. (5) An insecticidal composition containing compound [I] or a salt thereof and pyraclofos. (6) An insecticidal and fungicidal composition containing the compound [I] or a salt thereof and validamycin A. (7) An insecticidal fungicidal composition containing the compound [I] or a salt thereof and ferimzone. (8) An insecticidal and fungicidal composition containing the compound [I] or a salt thereof and fusalide. In an insecticidal composition containing compound [I] or a salt thereof and nitenpyram, nitenpyram is formed into an inclusion complex with cyclodextrin such as Toyoderin P (trade name) for the purpose of improving the stability of the composition. May be contained in the product. These compositions may further contain one or more (preferably one or more and three or less) other pesticidal active ingredients (for example, the above-described insecticidal active ingredient, acaricidal active ingredient, and fungicidal active ingredient).
For example, compound [I] or a salt thereof, validamycin,
Insecticidal and bactericidal compositions containing ferimzone and fthalide.

The composition of the present invention may be used as an insecticide, an insecticidal acaricide,
When used as a pesticide preparation such as an insecticide fungicide, a form that can be taken by a general pesticide, that is, the compound [I]
Or one or more (preferably one or more and three or less) of salts thereof and one or two or more (preferably one or more and three or less) of other pesticidal active ingredients as an active ingredient in a liquid suitable for the intended use. Dissolving or dispersing in a carrier, or mixing or adsorbing with a suitable solid carrier, wettable powder, aqueous suspension, emulsion, liquid, UL
V, powder, granule, tablet, jumbo, paste, foam, aerosol, microcapsule, seed coating, fumigant, smoke, stick for crop irrigation, oil, etc. . These preparations may be used if necessary, for example, ointment bases, emulsifiers, suspending agents, spreading agents, penetrants, wetting agents, dispersants, stabilizers, binders, flow aids, anti-caking agents, flocculants, Antioxidants, suspending agents, antifoaming agents, antifreezing agents, preservatives, moisture removing agents, ultraviolet absorbers, ultraviolet scattering agents, coloring agents, suspension stabilizers and the like may be added as appropriate, and methods known per se Can be prepared. That is, it can be produced by uniformly mixing the compound [I] or a salt thereof, other pesticidal active ingredients, a liquid carrier or a solid carrier, and the above-mentioned various additives. For example, the emulsion may contain the compound [I]
Alternatively, it can be produced by uniformly mixing and dissolving a salt thereof, another agricultural chemical active ingredient, an emulsifier, an organic solvent and the like. For example, granules, water dispersible granules and the like, compound (I) or a salt thereof,
It can be produced by uniformly mixing and granulating other pesticidal active ingredients, dispersants (surfactants), binders, extenders (or solid carriers), and the like. For example, powder (such as DL powder)
The compound [I] or a salt thereof, other agrochemical active ingredients, a bulking agent (or a solid carrier) and the like can be uniformly mixed and pulverized. For example, a flowable agent is produced by mixing and dispersing components such as the compound [I] or a salt thereof, other pesticidal active ingredients and a dispersant using a stirrer, and wet-milling using a dyno mill or the like. For example, jumbo drugs
The compound [I] or a salt thereof, other pesticidal active ingredients, dispersants (surfactants), binders, suspending agents, extenders (or solid carriers) and the like can be uniformly mixed and granulated.

Examples of the liquid carrier (solvent, organic solvent) used include water, alcohols (eg, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, etc.) and ketones (eg, acetone, methyl ethyl ketone, etc.). ), Ethers (eg, dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), aliphatic hydrocarbons (eg, kerosene,
Kerosene, fuel oil, machine oil, etc.), aromatic hydrocarbons (eg, benzene, toluene, xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, etc.), acid amides (Eg, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), esters (eg, ethyl acetate, butyl acetate, fatty acid glycerin ester, etc.), nitriles (eg, acetonitrile, propionitrile, etc.)
Such solvents are suitable, and these can be used alone or in combination of two or more (preferably one or more, three or less) in an appropriate ratio.

Examples of the solid carrier (diluent / extender) include vegetable powders (eg, soybean powder, tobacco powder, flour, wood flour, etc.),
Mineral powders (for example, clays such as kaolin, bentonite, sepiolite and acid clay, talcs such as talc powder and laurite powder, silicas such as diatomaceous earth and mica powder, lactose, ammonium sulfate, urea, sodium bicarbonate, sodium thiosulfate, phosphorus Water-soluble substances such as disodium hydrogen oxyoxide, sodium acetate, sodium carbonate, etc.), calcium carbonate, alumina, sulfur powder, activated carbon, etc. are used, and one or more of these (preferably one or more, three or less) are suitable. It can be used by mixing at an appropriate ratio. Examples of the ointment base include polyethylene glycol, pectin, polyhydric alcohol esters of higher fatty acids such as glyceryl monostearate, cellulose derivatives such as methylcellulose, sodium alginate, bentonite, and higher alcohols such as glycerin. One or more (preferably one or more, three or less) of polyhydric alcohols, petrolatum, white petrolatum, liquid paraffin, lard, various vegetable oils, lanolin, dehydrated lanolin, hardened oils, resins, etc. One or two or more (preferably one or more and four or less) of various surfactants are appropriately used.

As surfactants used as emulsifiers, spreading agents, penetrants, wetting agents, dispersants, etc., as nonionic surfactants, for example, soaps, polyoxyethylene alkyl ethers (Newcalgen) D1504, Neugen ET65, Neugen ET83, Neugen ET157
), Polyoxyethylene alkyl allyl ethers (Neugen EA92, Neugen EA142, etc.), polyoxyethylene alkyl phenyl ethers, polyoxyethylene nonyl phenyl ethers (Nonipol 20,
Nonipol 100, etc.), polyoxyethylene polyoxypropylene ethers, polyoxyethylene distyrenated phenyl ether (Neugen EA87, Neugen EA
177, etc.) polyoxyethylene alkyl esters (ionet MO20, ionet MO600, etc.), sorbitan fatty acid esters (reodol SP-S10, rheodol TW-S20, etc.), polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide Polymers (Newpole PE64), higher fatty acid alkanolamides, alkylmaleic acid copolymers (Demol EP), polyhydric alcohol esters (Tween 20, Tween 80, etc.) and the like are used, and as a cationic surfactant, For example, alkylamine salts, quaternary ammonium salts and the like are used. As anionic surfactants, for example, naphthalene sulfonic acid polycondensate metal salt, naphthalene sulfonic acid formalin condensate (Neucalgen FS4 ), Alkyl naphthalene sulfonates (such as Solpol 5115), metal compounds such as lignin sulfonic acid metal salts, alkyl allyl sulfonates, alkyl allyl sulfonate sulfates, sodium polystyrene sulfonate, metal polycarboxylates, polyoxy For example, there may be used ammonium ethylene histyl phenyl ether sulfate, higher alcohol sulfonate, higher alcohol ether sulfonate, dialkyl sulfosuccinate (such as Newcalgen EP70P), and higher fatty acid alkali metal salt. Examples of the stabilizer include a compound having an epoxy group, an antioxidant [eg, dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA), tetrakis [3- (3,5-di-ter
[t-butyl-4-hydroxyphenyl) propionyloxymethyl] methane (Irganox 1010), DL-tocopherol, propyl gallate, erythorbic acid, sodium erysorbate, isopropyl citrate, etc.], phosphoric acid, PAP auxiliary agent (isopropyl acid phosphate Fate), cyclodextrin (Toyoderin P), tall oil fatty acid (hator fatty acid), and the like, and these are used alone or in combination of two or more (preferably one or more and three or less) at an appropriate ratio. can do. As the binder, dextrin, pregelatinized starch, polyvinyl alcohol, gum arabic, sodium alginate,
Polyvinylpyrrolidone, glucose, sucrose, mannitol, sorbitol, and the like are used, and one or more of them (preferably one or more, three or less) can be used as appropriate by mixing at an appropriate ratio. As the fluidity aid, a PAP aid (eg, isopropyl acid phosphate), talc, or the like is used, and these may be used alone or in a combination of two or more (preferably one or more, three or less) at an appropriate ratio. can do. As the anti-caking agent, white carbon, diatomaceous earth, magnesium stearate, aluminum oxide, titanium dioxide and the like are used, and these may be used alone or in combination of two or more (preferably one or more and three or less) in an appropriate ratio. It can be used as appropriate. As a flocculant, liquid paraffin, ethylene glycol, diethylene glycol, triethylene glycol, isobutylene polymer (eg, IP solvent)
And the like, and one or more of them (preferably one or more and three or less) may be mixed at an appropriate ratio and used as appropriate. Antioxidants include dibutylhydroxytoluene, 4,4-thiobis-6-tert-butyl-3-methylphenol, butylhydroxyanisole, paraoctylphenol, mono (or di or tri) (a-methylbenzyl) phenol , 2,6-di-
tert-butyl-4-methylphenol, tetrakis [3
-(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane or the like is used,
These can be used singly or as a mixture of two or more (preferably one or more and three or less) at an appropriate ratio. The floating agent is used particularly for producing a jumbo agent, and a powder base having a specific gravity of 1 or less (preferably 1 to 0.5) is preferable. The powder base preferably has a particle diameter of 600 μm or less, preferably 600 μm to 10 μm. In the case of inorganic substances, natural glass is fired to form one or more independent air bubbles therein. For example, perlite composed of perlite or obsidian, shirasu balloon (trade name) composed of shirasu, vermiculite composed of vermiculite, or the like, and a fine hollow phyllite (aluminosilicate-based phyllite) obtained by similarly firing (Product name). In addition, organic materials include higher fatty acids such as stearic acid and palmitic acid that are solid at ordinary temperature, higher alcohols such as stearyl alcohol, and paraffin wax, which are generally called waxy substances. Therefore, it is difficult for water to penetrate, the pesticidal active ingredient may be entrapped in the waxy substance for a long time, and it may be difficult to disperse the substance in water. Therefore, it is preferably used by mixing with the above-mentioned glassy hollow body. As an antifoaming agent, a silicon-based antifoaming agent (for example,
Antihome E20) and the like can be used, and one or more of them (preferably one or more and three or less) can be mixed and used at an appropriate ratio. As the antifreezing agent, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin and the like are used, and these can be used alone or in combination of two or more (preferably one or more, three or less) at an appropriate ratio. . As the preservative, butyl paraben, potassium sorbate and the like are used, and these can be used alone or in a combination of two or more (preferably one or more and three or less) at an appropriate ratio. As the water removing agent, anhydrous gypsum, silica gel powder and the like are used, and these are one kind or two or more kinds (preferably one kind or more, three kinds or less).
Can be mixed at an appropriate ratio and used as appropriate. As the ultraviolet absorber, 2- (2'-hydroxy-5'-
Methylphenyl) benzotriazole, 2-ethoxy-
2′-methyloxalic acid bisanilide, dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate and the like are used. Two or more (preferably one or more and three or less) may be mixed at an appropriate ratio and used as appropriate. As the ultraviolet scattering agent, titanium dioxide or the like is used, and these can be used as appropriate by mixing one kind or two or more kinds (preferably one kind or more and three kinds or less) at an appropriate ratio. As the coloring agent, cyanine green G, Erio green B400, or the like is used, and these can be used alone or in a combination of two or more (preferably one or more and three or less) at an appropriate ratio. Examples of the suspension stabilizer include polyvinyl alcohol (such as Gohsenol GH17), clay minerals (such as Kunipia F, VEEGUM R), and silicon dioxide (such as Aerosil COK84), and one or more of these (preferably one or more). , Three or less) in an appropriate ratio and used as appropriate. Jumbo, powders, granules, wettable powders, wettable powders and the like may be used by being packaged in a water-soluble film in a unit of 20 to 200 g for easy application. Examples of the water-soluble film include polyvinyl alcohol, carboxymethylcellulose, starch, gelatin, polyvinylpyrrolidone, polyacrylic acid and its salts, pullulan (trade name: starch-based polysaccharide), and paogen (trade name: thermoplastic water-soluble polymer). No. In addition to the compound [I] or a salt thereof, and other pesticidal active ingredients (eg, insecticidal active ingredients, acaricidal active ingredients, fungicidal active ingredients, nematicidal active ingredients, herbicidal active ingredients, etc.), for example, plant hormone agents , Plant growth regulators, synergists (eg, piperonyl butoxide), attractants,
It is also possible to mix a repellent, a pigment, a fertilizer, and the like and use it as appropriate.

The content of the compound [I] or a salt thereof in the composition of the present invention is usually about 0.1 to 80% by weight, preferably about 1 to 20% by weight, based on the total amount of the composition. Specifically, for example, when used in emulsions, solutions, wettable powders (eg, water-dispersible granules), aqueous suspension preparations, microemulsions, and the like, usually about 1 to 80% by weight,
Preferably, about 1 to 20% by weight is appropriate. For example, when used in oils, powders and the like, usually about 0.1 to 5
About 0% by weight, preferably about 0.1 to 20% by weight is appropriate. For example, when used in granules, tablets, jumbo and the like, the amount is usually about 0.5 to 50% by weight, preferably about 1 to 20% by weight.

In the composition of the present invention, the compound [I] or a salt thereof and the other pesticidal active ingredient are each in a weight ratio of 1: 0.
It is preferable to contain in a ratio of 25 to 1:20. In particular,
When the other pesticidal active ingredient is a pesticidal active ingredient, the compound [I] or a salt thereof and the pesticidal active ingredient are each in a weight ratio of 1: 0.25 to 1:20, preferably 1: 0.5.
１ ： 1: 10 is preferred. When the other pesticidal active ingredient is an acaricidal active ingredient, the compound [I] or a salt thereof and the acaricidal active ingredient are each in a weight ratio of 1: 0.25 to 1: 0.25.
It is preferably contained in a ratio of 1:20, preferably 1: 0.5 to 1:10. When the other pesticidal active ingredient is a fungicidal active ingredient, the compound [I] or a salt thereof and the fungicidal active ingredient are each in a weight ratio of 1: 0.25 to 1:20, preferably 1: 1 to 1:10. It is preferred to contain. More specific preferred embodiments are shown below. (1) Compound [I] or a salt thereof and clothianidin in a weight ratio of 1: 0.25 to 1: 4, preferably 1:
An insecticidal composition containing 0.5 to 1: 2. (2) Compound [I] or a salt thereof and nitenpyram in a weight ratio of 1: 0.25 to 1: 4, preferably 1: 1, respectively.
An insecticidal composition containing 0.5 to 1: 2. (3) Compound [I] or a salt thereof and cartap hydrochloride in a weight ratio of 1: 1 to 1:10, preferably 1: 5.
Insecticidal compositions containing 殺 1:10. (4) Compound [I] or a salt thereof and bensultap in a weight ratio of 1: 1 to 1:10, preferably 1: 5 to 1
An insecticidal composition containing 1:10. (5) Compound [I] or a salt thereof and pyraclofos in a weight ratio of 1: 1 to 1:10, preferably 1: 3 to 1
An insecticidal composition containing 1:10. (6) An insecticidal fungicidal composition comprising the compound [I] or a salt thereof and validamycin A in a weight ratio of 1: 0.25 to 1: 4, preferably 1: 0.5 to 1: 2. (7) Compound [I] or a salt thereof and ferimzone are each in a weight ratio of 1: 2 to 1:20, preferably 1: 4 to
An insecticidal fungicidal composition containing 1:10. (8) Compound [I] or a salt thereof and fusalide in a weight ratio of 1: 2 to 1:20, preferably 1: 4 to 1:
An insecticidal fungicidal composition containing the composition at a ratio of 10. The content of the additives other than the above-mentioned active ingredients varies depending on the kind or content of the pesticidal active ingredient or the dosage form of the preparation, but is usually about 0.001 to 99.9% by weight, preferably about 1 to 99% by weight. It is about. More specifically, the surfactant is usually about 1 to 30% by weight, preferably about 1 to 15% by weight, and the flow aid is about 1 to 2% by weight based on the total amount of the composition.
It is preferred to add about 0% by weight and about 1 to 90% by weight of the carrier, preferably about 1 to 70% by weight. In particular,
In the case of preparing a liquid preparation, the surfactant is usually about 1 to 20% by weight, preferably about 1 to 10% by weight, and water is added to about 2% by weight.
It is preferable to add 0 to 90% by weight. When preparing an emulsion, it is desirable to add a surfactant in an amount of usually 1 to 30% by weight, preferably 2 to 15% by weight, and an organic solvent. When producing a water dispersible granule, the surfactant is usually 0.1 to
It is desirable to add 10% by weight, preferably 0.5 to 5% by weight, 0.1 to 15% by weight of a binder, preferably 0.5 to 5% by weight, and an extender such as lactose, ammonium sulfate or clay. When producing granules, the surfactant is usually 0.1
10 to 10% by weight, preferably 0.5 to 5% by weight, the stabilizer 0.1 to 10% by weight, preferably 0.5 to 5% by weight,
It is desirable to add a bulking agent such as clay. When producing a jumbo agent, the surfactant is usually 0.1 to 15% by weight, preferably 0.5 to 5% by weight, and the binder is 0.5 to 1% by weight.
0% by weight, preferably 0.5-5% by weight;
It is desirable to add a filler such as 5 to 40% by weight, preferably 1 to 20% by weight, such as clay. The wettable powder (e.g., wettable powder for granules) is preferably diluted with water or the like when used, and then appropriately diluted (e.g., about 100 to 5,000 times) and sprayed.

The composition of the present invention has good insecticidal and acaricidal activity against many kinds of pests (including arthropods other than insects) while having good safety against mammals and crops. Has bactericidal activity. Examples of pests to which the composition of the present invention is used include, but are not limited to, the following. Centipedes, geese,
Millipods of the double-legged class, Coleoptera brassicae, Coleoptera: Collembolae, Staphylinidae, Orthoptera cockroaches, Grasshoppers, Locusts, Kera, Isoptera termites , Lepidoptera earwigs, Coleoptera chatters, Ciliophora lice, whiteflies, Hemiptera stinkbugs, planthoppers, leafhoppers, aphids, whiteflies, scale insects, cicadas, Psyllids, thrips of the order Thysanoptera, mosquitoes of the order Diptera, flies, flies, flies, flies of the order Coleoptera, weevils weevil, chrysomelidae,
Beetles, kisui, bark beetles, beetle beetles, beetles, ladybirds, hymenoptera ants, paper wasps, hornets, wasps, lepidopteran pedestrians, white butterflies, swallowtail butterflies, minoga, yaga Mosses, Himehamakigai, Omanagai, Meigata, Suga, Hosoga, Hamoguriga, Sagamori,
Singing moths, Iragas, Atogekogaga, Kibaga,
Geometrids, mites, moths, moths,
Sparrows. Furthermore, it can also be used for mollusk slugs and snails.

The compositions of the present invention may also be used in the field of veterinary disease treatment and in the livestock industry, and in and / or in vertebrates such as humans, cattle, sheep, goats, pigs, poultry, dogs, cats and fish. Alternatively, it can be used to control external arthropods and parasites and maintain public health. For example, among the parasites, ticks (Ixodes spp.), Bovine ticks (Boophilus spp. (Eg, Boophilus spp.
microplus))), Acarina ticks (Amblyomma sp.)
p.), Ixodid ticks (Hyalomma spp.), Carrion ticks (Rhipicephalus spp. (eg Rhipicephalus appendi)
culatus)), tick mites (Haemaphysalis spp.), ticks (dermacentor spp.), Kazuki mites (Ornith
odoros spp. (for example, Ornithodoros moubata)), mites (Dermahyssus gallinae), sarcoptic mites (Sarcoptes)
spp. (for example, Sarcoptes scabiei)), sarcophaga spider mite (Psoroptes spp.), Scarab mite (Chorioptes spp.), acne mite (Demod)
ex spp.), chiggers (Eutrombicula spp.), falcons (Aedes spp.), anopheles (Anopheles sp.)
p.), house flies (Musca spp.), bullflies (Hypode
rma spp.), horseflies (Gasterophilus spp.), blackflies (Simulium spp.), turtles (Triatoma spp.),
Lice (Phthiraptera (eg Damalinia spp., Linog
nathus spp.)), fleas (Ctenocephalides spp.), house ants (monomorium pharaonis) and nematodes [eg, hairy nematodes (eg, Nippostrongylus brasiliensi)
s, Trichostrongylusaxei, Trichostrongylus colubrifo
rmis), Trichinella spiralis (eg, Trichinella spiralis), Tortoise stomach (Haemonchus contortus), Nematodirus (eg, Nematodirus battus), Ostertagia circumcincta, Cooperia (Cooper)
ia spp.), dwarf tapeworm (Hymenolepis nana)] and the like.

The composition of the present invention has excellent insecticidal activity due to the compound [I] or a salt thereof, and also has insecticidal activity, acaricidal activity, fungicidal activity, etc. possessed by other pesticidal active ingredients. It is extremely safe and can be used as an excellent pesticide composition. For example, the composition of the present invention can be sprayed on a paddy field, a field, an orchard, a non-agricultural land, a house, or the like by a method known per se, and can be controlled by contacting or ingesting the above-mentioned insect pests (such as insect pests). it can. In another embodiment, for example, the composition of the present invention is administered to the inside (inside the body) or outside (body surface) of the above-described vertebrate to control arthropods and parasites that infest the vertebrate. it can. As a method for specifically applying the composition of the present invention, it can be used in the same manner as a general method for applying pesticides. The preparations of the individual components can be mixed and used at the time of application. Examples of application of such preparations are foliage application, ULV application, soil application, soil irrigation, water surface application, soil admixture, floor soil admixture, nursery box treatment, stock plant treatment, lateral application, trunk irrigation, stem application, seed application Examples include, but are not limited to, dressing, seed soaking, poison bait, fertilizer mixing, irrigation water mixing, and the like.
The composition of the present invention can be used in combination with natural enemy microorganism preparations, combined with natural enemy organisms (natural enemy insects such as parasitic bees and predatory beetles, predatory mites, parasitic nematodes, entomopathogenic microorganisms, etc.), and used with insect pheromones. Combination, use with genetically modified crops,
IPM when used alone, such as in combination with inducers or repellents
(Integrated Pest Management) It is suitable for the promotion of the program. However, the composition of the present invention or the mixed use of the single preparation at the time of application can be mixed or used together with these control means, and can contribute to the promotion of the IPM program. it can. In the case of cabbage cultivation, for example, communication disruption using pheromones or pest control using natural enemy insects, such control measures are known to have little or no effect when the density of the pests to be controlled is high. ing. In a field where the composition of the present invention was subjected to soil treatment at the time of cabbage transplantation and the Japanese moth was suppressed to a low density, the above-mentioned compound was used when the residual effect of the compound [I] or a salt thereof or other pesticidal active ingredients was almost lost. When communication disruption or natural enemy insects are used, the effect of the communication disruption or natural enemy insects becomes more certain, and long-term reliable control becomes possible. In the case of communication disturbance using pheromones or control using natural enemy insects, the growth of pests other than the target pest may become a problem. In such a situation, by applying the composition according to the present invention, it is possible to suppress the growth of target pests that are problematic in communication disturbance or control using natural enemy insects,
Better overall control can be provided.

The application rate of the composition of the present invention can be varied in a wide range according to the timing of application, the place of application, the method of application, and the like. The sum of other pesticidal active ingredients) is about 0.3 g to 3,000 g, preferably about 50 g to 1.0 g.
Desirably, the application is made to be 00 g. When the composition of the present invention is a wettable powder, the final concentration of the active ingredient is about 0.1 to 1,000 ppm, preferably about 10 to 50 ppm.
What is necessary is just to dilute and use it so that it may be in the range of 0 ppm.

[0052]

Now, the present invention will be described in further detail with reference to Reference Examples, Examples and Test Examples. Elution in the column chromatography of the reference example was performed by TLC (Th
in Layer Chromatography)
Under observation by In TLC observation, TL
As a C plate, Kieselgel 60F254 (70 to 230 mesh) manufactured by Merck, as a developing solvent, a solvent used as an elution solvent in column chromatography, and as a detection method, a UV detector was used. The silica gel for the column is Kieselgel 60, also manufactured by Merck.
(70-230 mesh) was used. The NMR spectrum shows proton NMR, which was measured with a Bruker AC-200P (200 MHz) spectrometer using tetramethylsilane as an internal standard, and all δ values were shown in ppm.
When a mixed solvent is used as a developing solvent, the numerical values shown in parentheses indicate the volume mixing ratio of each solvent. The abbreviations used in the following Reference Examples and Tables have the following significance. M
e: methyl group, Et: ethyl group, Ph: phenyl group, P
rn (or n-Pr): n-propyl, Pr-i
(Or i-Pr or ⁱ Pr): isopropyl,
Bu-n (or n-Bu): n-butyl, Bu-i
(Or i-Bu): isobutyl, Bu-s (or s-Bu): sec-butyl, Bu-t (or tB)
u): tert-butyl, s: singlet, br: broad (broad), brs: broad singlet (broad singlet), d: doublet, t: triplet,
q: quartet, qu: quintet (quintuple), s
ep: septet (7-fold line), m: multiplet, d
d: double doublet, dt: double triplet,
J: coupling constant, Hz: hertz,%: weight%, m
p: melting point, room temperature means about 15 to 25 ° C.

[0053]

[Example]

Reference Example 1 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-3
- (Δ ² -1,2,4- oxadiazolin-3-yl)
-4-trifluoromethylsulfinylpyrazole 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (Δ ² -1,2,4-oxadiazolin-3-yl)- 31.6 g (65.4 mmol) of 4-trifluoromethylsulfinylpyrazole is dissolved in 315 ml (1.89 mmol) of triethyl orthoformate, 1.25 g (6.54 mmol) of p-toluenesulfonic acid monohydrate is added, and the mixture is stirred at 40 ° C for 4 hours. did. After the reaction, triethyl orthoformate was distilled off under reduced pressure, n-hexane and a small amount of chloroform were added to the residue, and the mixture was thoroughly rubbed. The resulting crystals were collected by filtration, dried, and dried to give 7.94.
g (14.8 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-3- (delta ^{2-1,2,4-oxadiazolin-3-yl)} - 4-trifluoromethylsulfinylpyrazole was obtained as colorless crystals. After concentrating the filtrate, acetonitrile
200 ml and 50 ml of water were added, 0.5 ml of 1.2 N hydrochloric acid was added, and the mixture was allowed to stand at room temperature for 30 minutes. After concentration under reduced pressure, a mixed solvent of n-hexane / acetone was added and the mixture was rubbed well. The resulting crystals were collected by filtration, dried, and further treated with 21.1 g (39.2 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl). ) -5-ethoxymethyleneamino-3- (delta ^{2-1,2,4-oxadiazolin-3-yl)} -4-trifluoromethyl sulfinyl pyrazole. 82% yield. mp. 186-187 ° C NMR (CDCl ₃ , δ) 1.20 (3H, t, J = 7Hz), 4.08 (2H, m), 5.21
(1H, br), 5.44 (1H, s), 5.49 (1H, s), 7.75 (1H, s),
7.76 (1H, s), 8.50 (1H, br)

Using the same method, the following compounds were synthesized. 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (Δ ² -1,2,4-oxadiazoline-
3-yl) -5- (n-propoxymethyleneamino)-
4-trifluoromethylthiopyrazole mp. 106-107 ° C

1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (Δ ² -1,2,4-oxadiazolin-3-yl) -5- (n-propoxymethyleneamino) -4-trifluoromethylsulfonylpyrazole mp. 111-112 ° C

[0056]

Reference Example 2 5-amino-1- (2,6-dichloro-4)
-Trifluoromethylphenyl) -3- (N ¹ -ethyl-
N ² -Hydroxyamidino) -4-trifluoromethylsulfinylpyrazole 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (5-methyl-1,2,4-
Oxadiazol-3-yl) -4-trifluoromethylsulfinylpyrazole (10.1 g, 20.5 mmol) in 100 ml
After dissolving in THF, 5.58 g (40.9 mmol) of zinc chloride and 1.76 g (41.9 mmol) of sodium borohydride were added. After stirring at room temperature for 5 days, the reaction mixture was poured into 150 ml of water. Ethyl acetate 1
00 ml was added, and the resulting precipitate was filtered using Celite. The filtrate was washed twice with 100 ml of a saturated saline solution, dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a yellow-brown amorphous. This was subjected to silica gel column chromatography (ethyl acetate: hexane = 1: 2) to give 6.45.
g (13.0 mmol) of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (N ¹ -ethyl-N ² -hydroxyamidino) -4-trifluoromethylsulfinylpyrazole. Obtained as a pale yellow amorphous. 63% yield. NMR (CDCl ₃ , δ) 1.15 (3H, t, J = 7Hz), 3.47-3.62 (2H, m),
5.07 (1H, t, J = 6.3Hz), 5.14 (2H, br), 7.24 (1H, br),
7.80 (2H, s)

[0057]

Reference Example 3 1- (2,6-Dichloro-4-trifluoromethylphenyl) -5-dimethylaminomethyleneamino-3- (Δ ² -1,2,4-oxadiazoline-3-
Yl) -4-trifluoromethylsulfinylpyrazole 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (Δ ² -1,2,4-oxadiazolin-3-yl ) -4-trifluoromethylsulfinylpyrazole 0.91 g (1.89 mmol), toluene 10 ml, N, N-dimethylformamide dimethyl acetal 0.56 ml (purity 90%; 3.79 mmol) was further added, and the mixture was stirred at 80 ° C. for 4 hours. . The solvent was distilled off, and the colorless oil obtained was subjected to silica gel column chromatography (ethyl acetate: chloroform = 1: 10).
Recrystallize with a mixed solvent of hexane and 0.56 g (1.03 mmol) of 1
-(2,6-dichloro-4-trifluoromethylphenyl) -5-dimethylaminomethyleneamino-3- (Δ ²
-1,2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole was obtained as colorless crystals. Yield 55% mp. 171~173 ℃ NMR ( CDCl 3, δ) 2.79 (3H, s), 3.08 (3H, s), 5.24 (br, 1
H), 5.41 (1H, dd, J = 1Hz, 3Hz,), 5.47 (1H, dd, J = 1Hz, 3H
z), 7.70-7.74 (2H, m), 8.56 (1H, s)

[0058]

Reference Example 4 5-amino-1- (2,6-dichloro-4)
- trifluoromethylphenyl) -3- (4-diisopropoxy-methyl - [delta ^{2-1,2,4-oxadiazolin-3-yl)} -4-trifluoromethylsulfonyl pyrazole 5-amino-1- (2 1.00 g (2.01 mmol) of 2,6-dichloro-4-trifluoromethylphenyl) -3- (Δ ² -1,2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfonylpyrazole It was dissolved in 5 ml of triisopropyl. 20 mg of paratoluenesulfonic acid monohydrate was added to the reaction solution, and the mixture was stirred at 90 ° C for 34 hours.
The reaction solution was subjected to silica gel column chromatography (n-hexane: acetone = 5: 1) to obtain pale yellow crystals. The obtained crystals were recrystallized from petroleum ether-acetone to give 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (4-diisopropoxymethyl-Δ ² as colorless crystals. 360 mg (0.57 mmol) of -1,2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfonylpyrazole was obtained. Yield 29% mp. 173-176 ° C NMR (CDCl ₃ + DMSO-d ₆ , δ) 1.10 (6H, d, J = 6Hz), 1.11 (6H,
d, J = 6Hz), 3.85 (2H, sep, J = 6Hz), 5.54 (2H, s), 5.66
(1H, s), 6.58 (2H, br), 7.80 (2H, d, J = 0.5Hz)

[0059]

Reference Example 5 3- (4-acetyl-Δ ² -1,2,4-
Oxadiazolin-3-yl) -1- (2,6-dichloro-4-trifluoromethylphenyl) -5-methoxymethyleneamino-4-trifluoromethylsulfinylpyrazole 1- (2,6-dichloro-4- (Trifluoromethylphenyl) -5-methoxymethyleneamino-3- (Δ ² −
520 mg (1.00 mmo of 1,2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole
l) was suspended in 10 ml of acetonitrile. Pyridine 82 mg (1.04 mmol) was added to the reaction solution, and acetic anhydride 106 mg (1.04 mmol)
Of acetonitrile was added dropwise at room temperature, and
Stir for 18 hours. 4-Dimethylaminopyridine 1
27 mg (1.04 mmol) was added, and the mixture was further stirred at room temperature for 5 hours.
The reaction solution was concentrated under reduced pressure, and the concentrated residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate =
5: 1), 530 mg of colorless crystals were obtained. The crystals were recrystallized from ethyl acetate-n-hexane to give 3- (4
-Acetyl-Δ ² -1,2,4-oxadiazoline-3
-Yl) -1- (2,6-dichloro-4-trifluoromethylphenyl) -5-methoxymethyleneamino-4-
400 mg of trifluoromethylsulfinylpyrazole (0.
70 mmol) were obtained. Yield 70% mp. 126-127 ° C NMR (CDCl ₃ , δ) 2.14 (3H, s), 3.70 (3H, s), 5.82 (1H,
d, J = 3Hz), 6.01 (1H, d, J = 3Hz), 7.78 (2H, m), 8.64 (1
H, s)

[0060]

Reference Example 6 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-3
-(4-propionyl- [Delta] ² -l, 2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole 1- (2,6-dichloro-4-trifluoromethylphenyl) -5- Ethoxymethyleneamino-3- (Δ ² −
1,2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole 550 mg (1.02 mmol
l) was suspended in 10 ml of acetonitrile. Pyridine 0.09 ml (1.23 mmol), propionic anhydride 0.157 ml (1.2
3 mmol), 4-dimethylaminopyridine (DMAP) 150
mg (1.23 mmol) was added, and the mixture was stirred at room temperature for 4 hours. The reaction solution was concentrated under reduced pressure, and the concentrated residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 2:
1), a colorless liquid was obtained. The liquid was crystallized from isopropyl ether-petroleum ether to give 1- (2,
6-dichloro-4-trifluoromethylphenyl) -5
-Ethoxymethyleneamino-3- (4-propionyl-
Δ ² -1,2,4-oxadiazolin-3-yl) -4
-440 mg of trifluoromethylsulfinylpyrazole
(0.74 mmol) was obtained. Yield 72% mp. _{114~115 ℃ NMR (CDCl 3, δ} ) 1.07 (3H, t, J = 7Hz), 1.22 (3H, t, J = 7H
z), 2.37 (2H, m), 4.12 (2H, m), 5.81 (1H, d, J = 3Hz), 6.0
2 (1H, d, J = 3Hz), 7.76 (2H, m), 8.61 (1H, s)

[0061]

Reference Example 7 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-3
-(4-methylcarbamoyl- [Delta] ² -l, 2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole 1- (2,6-dichloro-4-trifluoromethylphenyl) -5 -Ethoxymethyleneamino-3- (Δ ² −
1,2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole 550 mg (1.02 mmol
l) was suspended in 10 ml of acetonitrile. 0.124 ml (2.04 mmol) of methyl isocyanate was added to the reaction solution, and the mixture was stirred at room temperature for 45 hours. 0.285 ml of triethylamine (2.04 mmo
l), 0.124 ml (2.04 mmol) of methyl isocyanate was added,
Stirred at room temperature for another 24 hours. The reaction solution was concentrated under reduced pressure,
The concentrated residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to obtain a pale yellow liquid. The liquid ethyl acetate - was crystallized with petroleum ether, as colorless crystals of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-3- (4-methylcarbamoyl - [delta ² -1 , 2,4
370 mg (0.62 mmol) of -oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole was obtained. Yield 61% mp. 115-116 ° C NMR (CDCl ₃ , δ) 1.21 (3H, t, J = 7Hz), 2.75 (3H, d, J = 5H
z), 4.11 (2H, m), 5.83 (1H, d, J = 2Hz), 6.13 (1H, d, J = 2
Hz,), 7.22 (1H, m), 7.80 (2H, m), 8.56 (1H, s)

[0062]

[Reference Example 8] 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (4-diethylcarbamoyl - [delta ^{2-1,2,4-oxadiazolin-3-yl)} -
5-ethoxymethyleneamino-4-trifluoromethylsulfinylpyrazole bistrichloromethyl carbonate (BTC) 56.2 mg (0.189 mmol) as T
It was dissolved in 5 ml of HF and cooled on ice. Pyridine 0.0496m in the reaction solution
l (0.613 mmol) was added and the mixture was stirred at room temperature for 1 hour. 1 in the reaction solution
- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino -3- (Δ ² -1,
300 mg (0.557 mmol) of 2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole
A solution of 5 ml of THF was added dropwise over 5 minutes under ice cooling, followed by stirring at room temperature for 1 hour. After the reaction, 0.115 ml of diethylamine (1.11 m
mol) and stirred at room temperature for 6 hours. The precipitated crystals were removed by filtration, the filtrate was concentrated under reduced pressure, and the concentrated residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 3: 1) to give 1- (2,6-dichloro- as colorless crystals. 4-trifluoromethylphenyl) -3- (Δ ² -4
-Diethylcarbamoyl-1,2,4-oxadiazolin-3-yl) -5-ethoxymethyleneamino-4-trifluoromethylsulfinylpyrazole in 220 mg (0.3
4 mmol). Yield 62% mp. 107-108 ° C NMR (CDCl ₃ , δ) 1.14 (6H, t, J = 7H
2. z), 1.19 (3H, t, J = 7 Hz),
30 (4H, q, J = 7 Hz), 4.08 (2H,
m), 5.48 (1H, d, J = 1 Hz), 5.
55 (1H, d, J = 1 Hz), 7.72 (2
H, m), 8.58 (1H, s)

[0063]

[Reference Example 9] 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (4-dimethylamino-acetyl - [delta ^{2-1,2,4-oxadiazolin-3-yl)}
-5-ethoxymethyleneamino-4-trifluoromethylsulfinylpyrazole 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-3- (Δ ² −
1,2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole 500 mg (0.93 mmol
l) was suspended in 10 ml of acetonitrile. Hydrochloric acid N, N
-Dimethylglycine 127mg (0.93mmol), BOP reagent 410mg
(0.93 mmol) and 0.26 ml (1.86 mmol) of triethylamine were added, and the mixture was stirred at room temperature for 55 hours. The reaction solution was concentrated under reduced pressure, and the concentrated residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to remove colorless crystals by 270.
mg was obtained. The crystals propyl ether - was recrystallized from hexane, as colorless crystals of 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (4-dimethylamino-acetyl - [delta ^2-1,2,4- Oxadiazoline-3
-Yl) -5-ethoxymethyleneamino-4-trifluoromethylsulfinylpyrazole in 150 mg (0.24 mmo
l) Got it. Yield 26% mp. 135 ° C NMR (CDCl ₃ , δ) 1.22 (3H, t, J = 7Hz), 2.11 (6H, s), 2.95
(1H, d, J = 14Hz), 3.40 (1H, d, J = 14Hz), 4.11 (m, 2H), 5.
60 (1H, d, J = 4Hz), 6.11 (1H, d, J = 4Hz), 7.76 (2H, m), 8.
72 (1H, s)

[0064]

Reference Example 10 5-amino-1- (2,6-dichloro-
4-trifluoromethylphenyl) -3- (4-ethyl-Δ ² -1,2,4-oxadiazolin-3-yl)-
4-trifluoromethylsulfinylpyrazole 1.0 g of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (N1-ethyl-N2-hydroxyamidino) -4-trifluoromethylsulfinylpyrazole (2.0 mmol) was dissolved in 15 ml of acetonitrile, and 0.8 ml (11 mmol) of a 37% aqueous solution of formalin was added.
Drops were added, and the mixture was heated under reflux for 7 hours. After the reaction, 60 ml of ethyl acetate was added, and the mixture was added three times with 40 ml of a saturated aqueous sodium hydrogen carbonate solution, and 20 ml of a saturated saline solution
And washed twice. After drying over anhydrous magnesium sulfate, the solvent was distilled off to obtain a pale yellow amorphous. This was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 3: 1), and 500 mg (0.98 mmol) of 5-
Amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (4-ethyl - [delta ² -1,2,4
-Oxaziazolin-3-yl) -4-trifluoromethylsulfinylpyrazole was obtained as a colorless amorphous. Yield 49%. NMR (CDCl ₃ , δ) 1.14 (3H, t, J = 7Hz), 3.4-3.7 (2H, m),
5.18 (2H, br), 5.38 (2H, d, J = 7Hz), 7.82 (2H, s)

[0065]

[Reference Example 11] 3- (4-acetyl - △ ² -1,2,4
-Oxadiazolin-3-yl) -1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-4-trifluoromethylsulfinylpyrazole 1- (2,6-dichloro-4 -Trifluoromethylphenyl) -5-ethoxymethyleneamino-3- (Δ ² −
0.89 g (1.7 mm) of 1,2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole
ol) in 10 ml of acetonitrile, 0.21 g (1.72 mmol) of 4-dimethylaminopyridine, 0.16 ml of acetic anhydride (1.7 m
mol) and stirred at room temperature for 2.5 hours. After the reaction, the solvent was distilled off, and 70 ml of ethyl acetate was added. 2 with 20 ml of saturated aqueous sodium bicarbonate
It was washed twice with 30 ml of saturated saline. After drying over anhydrous magnesium sulfate and evaporating the solvent, a pale yellow amorphous was obtained. This was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 2: 1), and the obtained colorless crystals were recrystallized from chloroform-n-hexane.
160mg of (0.27mmol) 3- (4- acetyl - [delta ² -1,
2,4-oxadiazolin-3-yl) -1- (2,6
-Dichloro-4-trifluoromethylphenyl) -5-
Ethoxymethyleneamino-4-trifluoromethylsulfinylpyrazole was obtained as colorless crystals. Yield 16%. mp. 116-118 ° C NMR (CDCl ₃ , δ) 1.22 (3H, t, J = 7Hz), 2.14 (3H, s), 4.2
0-4.25 (2H, m), 5.83 (1H, d, J = 3Hz), 6.01 (1H, d, J = 3Hz),
7.76-7.80 (2H, m), 8.60 (1H, s)

[0066]

Reference Example 12 5-amino-1- (2,6-dichloro-
4-trifluoromethylphenyl) -3- {4- (N,
N-Diethylcarbamoyl) -Δ ² -1,2,4-oxadiazolin-3-yl} -4-trifluoromethylthiopyrazole 318 mg (1.07 mmol) of bistrichloromethyl carbonate (BTC) in THF
It was dissolved in 6 ml and cooled on ice. 255 mg of pyridine (3.22
mmol) and stirred at room temperature for 30 minutes. To the reaction solution of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (delta ^{2-1,2,4-oxadiazolin-3-yl)} -4-trifluoromethylthio Pyrazole
A solution of 1.00 g (2.15 mmol) in 6 ml of THF was added dropwise under ice cooling, and the mixture was stirred at the same temperature for 30 minutes. After the reaction, 472 mg of diethylamine (6.
45 mmol), and the mixture was stirred under ice cooling for 3 hours and then at room temperature for 3 hours. The mixture was poured into 100 ml of ice water and extracted with 100 ml of ethyl acetate. After drying over anhydrous magnesium sulfate and concentration, the obtained residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 1: 1) to give 370 mg (0.65 mmol).
The title compound was obtained as colorless crystals of l). Yield 30% mp. 81-83 ° C NMR (CDCl ₃ , δ) 1.16 (6H, t, J = 7Hz), 3.30 (4H, q, J = 7H
z), 4.34 (2H, s), 5.51 (2H, s), 7.76 (2H, s)

[0067]

Reference Example 13 1- (2,6-Dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-diethylcarbamoyl) -Δ ² -1,2,4-oxadiazoline-3 -Yl} -5-ethoxymethyleneamino-4-trifluoromethylthiopyrazole 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-diethylcarbamoyl) - [delta ^{2-1,2,4-oxadiazoline} -
3-yl} -4-trifluoromethylthiopyrazole 37
0 mg (0.65 mmol) was dissolved in 3 ml of triethyl orthoformate.
Add 50 mg of paratoluenesulfonic acid monohydrate to the reaction solution,
Stirred at room temperature for 3 hours. The reaction solution was concentrated under reduced pressure, and the obtained residue was subjected to silica gel column chromatography (n
-Hexane: ethyl acetate = 2: 1) to give the title compound as colorless crystals (290 mg, 0.47 mmol). Yield 72% mp. 93-95 ° C NMR (CDCl ₃ , δ) 1.26-1.14 (9H, m), 3.30 (4H, q, J = 7H
z), 4.13 (2H, q, J = 7Hz), 5.55 (2H, s), 7.70 (2H, s), 8.
33 (1H, s)

[0068]

Reference Example 14 5-amino-1- (2,6-dichloro-
4-trifluoromethylphenyl) -3- {4- (N,
N- dimethylcarbamoyl) - [delta ^{2-1,2,4-oxadiazolin-3-yl}} -4-trifluoromethyl methylsulfinyl pyrazole carbonate bistrichloromethyl (BTC) 615mg (2.07mmol) was dissolved in THF
It was dissolved in 12 ml and cooled on ice. Pyridine 492 mg (6.2
2 mmol) and stirred at room temperature for 30 minutes. To the reaction solution of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (delta ^{2-1,2,4-oxadiazolin-3-yl)} -4-trifluoromethyl A solution of 2.00 g (4.15 mmol) of sulfinylpyrazole in 12 ml of THF was added dropwise under ice cooling, and the mixture was stirred at the same temperature for 30 minutes. After the reaction, 1.12 g (12.4 mmol) of a 50% aqueous dimethylamine solution was added, and the mixture was stirred for 1 hour under ice cooling. The mixture was poured into 100 ml of ice water and extracted with 100 ml of ethyl acetate. Drying over anhydrous magnesium sulfate and concentration gave 2.26 g (4.08 mmol) of the title compound as colorless crystals. Yield 98% mp. 207.0-207.5 ° C NMR (CDCl ₃ , δ) 2.93 (6H, s), 5.14 (2H, s), 5.46 (1H,
d, J = 2Hz), 5.52 (1H, d, J = 2Hz), 7.78 (2H, s)

[0069]

Reference Example 15 5-amino-1- (2,6-dichloro-
4-trifluoromethylphenyl) -3- {4- (N,
N-Diethylcarbamoyl) -Δ ² -1,2,4-oxadiazolin-3-yl−-4-trifluoromethylsulfinylpyrazole 113 mg (0.38 mmol) of bistrichloromethyl carbonate (BTC) in THF
It was dissolved in 10 ml and cooled on ice. 0.0923 ml of pyridine in the reaction solution
(1.14 mmol), and the mixture was stirred at room temperature for 30 minutes. To the reaction solution of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (delta ^{2-1,2,4-oxadiazolin-3-yl)} -4-trifluoromethyl A solution of 500 mg (1.04 mmol) of sulfinylpyrazole in 5 ml of THF was added dropwise under ice cooling, and the mixture was stirred at room temperature for 1 hour. After the reaction, 0.322 ml (3.11 mmol) of diethylamine was added, and the mixture was stirred at room temperature for 15.5 hours. The precipitated crystals were removed by filtration, and the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography (n-
Hexane: ethyl acetate = 2: 1) to obtain colorless crystals. This was recrystallized from a mixed solvent of n-hexane and ethyl acetate to give 26
0 mg (0.45 mmol) of the title compound was obtained as colorless crystals. Yield 43% mp. 98.0-99.0 ° C NMR (CDCl ₃ , δ) 1.13 (6H, t, J = 7Hz), 3.30 (4H, q, J = 7H
z), 5.13 (2H, s), 5.43 (1H, d, J = 1Hz), 5.50 (1H, d, J = 1)
Hz), 7.78 (2H, s)

[0070]

[Reference Example 16] 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N- diethylcarbamoyl) - [delta ^{2-1,2,4-oxadiazoline} -3 -Yl} -5-ethoxymethyleneamino-4-trifluoromethylsulfonylpyrazole 119 mg (0.401 mmol) of bistrichloromethyl carbonate (BTC) in TH
F was dissolved in 10 ml and cooled on ice. 0.0974 ml of pyridine in the reaction solution
(1.20 mmol) and 1- (2,6-dichloro-4-).
Trifluoromethylphenyl) -5-ethoxymethyleneamino -3- (Δ ² -1,2,4- oxadiazoline -
A solution of 400 mg (0.803 mmol) of 3-yl) -4-trifluoromethylsulfonylpyrazole in 5 ml of THF was added dropwise under ice cooling, and the mixture was stirred at the same temperature for 2 hours. After the reaction, diethylamine
Dissolve 0.332 ml (3.21 mmol) in 5 ml of THF and add
Stirred at room temperature for 30 minutes. The reaction solution was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 1: 1) to obtain 130 mg (0.20 mmol) of the title compound as colorless crystals. Yield 25% mp. 105.5-106.5 ° C NMR (CDCl ₃ , δ) 1.17 (6H, t, J = 7Hz), 1.23 (3H, t, J = 6H
z), 3.27 (4H, q, J = 7Hz), 4.16 (2H, q, J = 6Hz), 5.64 (2H,
s), 7.74 (2H, s), 8.04 (1H, s)

[0071]

[Reference Example 17] 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N- dimethylcarbamoyl) - [delta ^{2-1,2,4-oxadiazoline} -3 -Yl｝ -5-ethoxymethyleneamino-4-trifluoromethylsulfinylpyrazole bistrichloromethyl carbonate (BTC) 91.2 mg (0.310 mmol) as T
It was dissolved in 5 ml of HF and cooled on ice. 0.0751 ml of pyridine in the reaction solution
(0.929 mmol), and the mixture was stirred at room temperature for 1 hour. Further 1-
(2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino -3- (Δ ² -1,
500 mg (0.929 mmol) of 2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole
A solution of 5 ml of THF was added dropwise under ice cooling, and the mixture was stirred at room temperature for 1 hour. After the reaction, 0.167 ml of 50% aqueous dimethylamine solution (1.86 mm
ol) in 5 ml of THF was added dropwise and stirred at room temperature for 3.5 hours. The reaction solution was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 2: 1) to obtain 210 mg (0.34 mmol) of the title compound as a colorless amorphous. Yield 37% NMR (CDCl ₃ , δ) 1.20 (3H, t, J = 7Hz), 2.94 (6H, s), 4.1
0 (2H, m), 5.51 (1H, d, J = 2Hz), 5.58 (1H, d, J = 2Hz), 7.
72 (2H, m), 8.56 (1H, s)

[0072]

Reference Example 18 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N-ethyl-N-
Methylcarbamoyl) - [delta ^{2-1,2,4-oxadiazolin-3-yl}} -5-ethoxymethylene-amino-4
-Trifluoromethylsulfinylpyrazole bistrichloromethyl carbonate (BTC) 138 mg (0.47 mmol) in THF
It was dissolved in 3 ml and cooled on ice. Pyridine 111 mg (1.40
mmol), and the mixture was stirred under ice cooling for 30 minutes. Furthermore, 1- (2,
6-dichloro-4-trifluoromethylphenyl) -5
- ethoxymethyleneamino -3- (Δ ² -1,2,4-
A solution of 500 mg (0.93 mmol) of oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole in 3 ml of THF was added dropwise under ice-cooling, and the mixture was stirred at the same temperature for 30 minutes. After the reaction,
110 mg (1.86 mmol) of ethyl methylamine was added to 1 ml of THF
, And added dropwise, followed by stirring at room temperature for 21 hours. The mixture was poured into 100 ml of ice water and extracted with 100 ml of ethyl acetate. After drying over anhydrous magnesium sulfate and concentration, the residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate =
3: 1), 100 mg (0.16 mmol) of the title compound was obtained as a colorless amorphous. Yield 17% mp. 113-114 ° C NMR (CDCl ₃ , δ) 1.14 (3H, t, J = 7Hz), 1.20 (3H, t, J = 7H
z), 2.93 (3H, s), 3.31 (2H, q, J = 7Hz), 4.30-3.90 (2H,
m), 5.50 (1H, s), 5.57 (1H, s), 7.72 (2H, s), 8.58 (1H,
s)

[0073]

REFERENCE EXAMPLE 19 1- (2,6-Dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-diethylcarbamoyl) -Δ ² -1,2,4-oxadiazoline-3 -Yl} -5-isopropoxymethyleneamino-4
-Trifluoromethylsulfinylpyrazole bistrichloromethyl carbonate (BTC) 85.3 mg (0.287 mmol)
It was dissolved in 10 ml of HF and cooled on ice. Pyridine 0.0769m in the reaction solution
l (0.951 mmol) was added dropwise, and 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-isopropoxymethyleneamino-3- (Δ ² -1,2,4-oxadiazoline- A solution of 500 mg (0.905 mmol) of 3-yl) -4-trifluoromethylsulfinylpyrazole in 5 ml of THF was added dropwise under ice-cooling, and the mixture was stirred at room temperature for 1 hour. The reaction solution was cooled on ice, and 0.192 ml (1.86 mmol) of diethylamine was added to 5 ml of T
Dissolved in HF and added dropwise, and stirred at room temperature for 22.5 hours. The reaction solution was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 2:
1), 240 mg (0.37 mmol) of the title compound was obtained as a colorless liquid. Yield 41% NMR (CDCl ₃ , δ) 0.82 (3H, t, J = 7Hz), 1.14 (6H, t, J = 7H
z), 1.58 (2H, m), 3.30 (4H, q, J = 7Hz), 3.99 (2H, m), 5.
48 (1H, d, J = 1Hz), 5.55 (1H, d, J = 1Hz), 7.72 (2H, m),
8.61 (1H, s)

[0074]

Reference Example 20 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-
3- {4- pivaloyl - [delta ^{2-1,2,4-oxadiazolin-3-yl}} -4-trifluoromethyl methylsulfinyl pyrazole 1- (2,6-dichloro-4-trifluoromethylphenyl) -5 -Ethoxymethyleneamino-3- (Δ ² −
1,2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole 500 mg (0.929 mmo
l) was suspended in 10 ml of acetonitrile. 0.142 ml (1.02 mmol) of triethylamine and 0.166 ml of pivaloyl chloride were added to the reaction solution.
(1.02 mmol), 5 mg of 4-dimethylaminopyridine,
Stirred at room temperature for 4 days. The reaction solution was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 3: 1) to give 220 mg (0.35 mmol) of the title compound as colorless crystals. Yield 38% mp. 133.5-134.0 ° C NMR (CDCl ₃ , δ) 1.21 (3H, t, J = 7Hz), 1.28 (9H, s), 4.1
1 (2H, m), 5.71 (1H, d, J = 2Hz), 5.88 (1H, d, J = 2Hz), 7.
72 (1H, s), 7.73 (1H, s), 8.54 (1H, s)

[0075]

Reference Example 21 3- {4- (t-butoxycarbonyl)
-Δ ² -1,2,4-oxadiazolin-3-yl}-
1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-4-trifluoromethylsulfinylpyrazole 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxy Methyleneamino-3- (Δ ² −
538 mg (1.00 mmo of 1,2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole
l) was dissolved in 10 ml of acetonitrile, and 0.097 ml (1.20 mmol) of pyridine and Di-t-butyldicarbona were stirred at room temperature.
270 mg (1.2 mmol) of te were added. Further, 147 mg (1.20 mmol) of 4-dimethylaminopyridine was added, and the mixture was stirred at room temperature for 2 hours.
The reaction solution was concentrated under reduced pressure, and then subjected to silica gel column chromatography (n-hexane: ethyl acetate = 4: 1).
mg (0.76 mmol) of the title compound were obtained as a colorless amorphous. Yield 76% NMR (CDCl ₃ , δ) 1.22 (3H, t, J = 7Hz), 1.45 (9H, s), 3.9
8-4.26 (2H, m), 5.73 (1H, d, J = 2Hz), 5.78 (1H, d, J = 2H
z), 7.72-7.78 (2H, m), 8.61 (1H, s)

[0076]

REFERENCE EXAMPLE 22 1- (2,6-Dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-diethylcarbamoyl) -Δ ² -1,2,4-oxadiazoline-3 -Yl} -5-dimethylaminomethyleneamino-4
-Trifluoromethylsulfinylpyrazole bistrichloromethyl carbonate (BTC) 0.14 g (0.47 mmol) in THF
After dissolving in 5 ml and cooling with ice, 0.13 ml (1.62 mmol) of pyridine was added. The mixture was stirred at room temperature for 35 minutes, and 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-dimethylaminomethyleneamino-3- dissolved in 5 ml of THF was added thereto.
(Delta ^{2-1,2,4-oxadiazolin-3-yl)} -
0.45 g of 4-trifluoromethylsulfinylpyrazole
(0.84 mmol) was added dropwise under ice cooling. After the dropwise addition, the mixture was stirred at room temperature for 1 hour, and 0.18 ml (1.74 mmol) of diethylamine was injected under ice cooling. Thereafter, the mixture was stirred for 30 minutes under ice-cooling and for 12 hours at room temperature. Then, 0.09 ml (0.86 mmol) of diethylamine was added, and the mixture was further stirred at room temperature for 1.5 hours. 20 ml of water and 20 ml of saturated saline were added, and the mixture was extracted with 40 ml of ethyl acetate. The ethyl acetate layer was washed with saturated saline (20 ml × 2) and dried over anhydrous magnesium sulfate. The solvent was distilled off, and the obtained reaction mixture was subjected to silica gel column chromatography (ethyl acetate: hexane = 1: 1).
And purified. The crystals obtained after the silica gel column were washed with ethyl acetate: hexane = 1: 5 and recrystallized from a mixed solvent of ethyl acetate-hexane (20 ml) to give 0.30 g (0.47 mmol) of the title compound as colorless crystals. Yield 57% mp. 156-158 ° C NMR (CDCl ₃ , δ) 1.14 (6H, t, J = 7.2Hz), 2.78 (3H, s),
3.07 (3H, s), 3.30 (4H, q, J = 7Hz), 5.47 (1H, d, J = 1Hz),
5.54 (1H, d, J = 1Hz,), 7.66-7.71 (2H, m), 8.65 (s, 1H)

[0077]

[Reference Example 23] 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N- dimethylcarbamoyl) - [delta ^{2-1,2,4-oxadiazoline} -3 -Yl} -5-isopropoxymethyleneamino-4
-Trifluoromethylsulfinylpyrazole 516 mg (2.71 mmol) of triisopropyl orthoformate, 50 mg of p-toluenesulfonic acid monohydrate, 500 mg (0.90 mmol) of 5-amino-
1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl)
-Δ ² -1,2,4-oxadiazolin-3-yl}-
After reacting the mixture of 4-trifluoromethylsulfinylpyrazole at room temperature for 1 hour, 1.2 g (6.3 mmol)
Was added, and the mixture was further stirred for 18 hours. After further stirring at reflux for 10 hours, 100
The mixture was poured into ml of ice water and extracted with 100 ml of ethyl acetate. Drying over anhydrous magnesium sulfate and concentration gave a yellow oil. This was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 1: 1),
240 mg (0.39 mmol) of colorless crystals 1-
(2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl)-
Δ ² -1,2,4-oxadiazolin-3-yl} -5
-Isopropoxymethyleneamino-4-trifluoromethylsulfinylpyrazole was obtained. 43% yield. _{mp.114-116 ℃ NMR (CDCl 3, δ} ) 1.10 (3H, d, J = 6Hz), 1.23 (3H, d, J = 6Hz),
2.95 (6H, s), 4.84 (1H, qu, J = 6Hz), 5.51 (1H, d, J = 2Hz), 5.59
(1H, d, J = 2Hz), 7.73 (2H, s), 8.56 (1H, s)

[0078]

[Reference Example 24] 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N- dimethylcarbamoyl) - [delta ^{2-1,2,4-oxadiazoline} -3 -Yl} -5- (4-hydroxy-3-methoxyphenyl) methyleneamino-4-trifluoromethylsulfinylpyrazole 300 mg (1.97 mmol) of vanillin, 40 mg
P-toluenesulfonic acid monohydrate, 730 mg (1.
32 mmol) of 5-amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4-
(N, N-dimethylcarbamoyl) -Δ ² -1,2,4
After reacting a mixture of -oxadiazolin-3-yl} -4-trifluoromethylsulfinylpyrazole and 30 ml of toluene at 90 ° C for 5 hours and further at reflux for 9 hours, 3
The mixture was poured into 0 ml of ice-cooled saline and extracted with 50 ml of ethyl acetate. Drying over anhydrous magnesium sulfate and concentration gave a brown oil. This was subjected to silica gel column chromatography (n-hexane: acetone =
2: 1), 240mg (0.39mmol yellow crystals as 1- (2,6-dichloro-4-trifluoromethylphenyl of)) -3- {4- (N, N- dimethylcarbamoyl) - [delta ² -1 , 2,4-oxadiazolin-3-yl} -5- (4-hydroxy-3-methoxyphenyl)
Methyleneamino-4-trifluoromethylsulfinylpyrazole was obtained. Yield 30%. _{mp.174-175 ℃ NMR (CDCl 3, δ} ) 2.96 (6H, s), 3.83 (3H, s), 5.54 (1H, d, J = 2
Hz), 5.62 (1H, d, J = 2Hz), 6.18 (1H, s), 6.93 (1H, d, J = 8Hz),
7.19 (1H, d, J = 2Hz), 7.32 (1H, dd, J = 1.8Hz, 8.2Hz), 7.70-7.
72 (1H, m), 7.76-7.77 (1H, m), 9.08 (1H, s)

[0079]

[Reference Example 25] 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N- dimethylcarbamoyl) - [delta ^{2-1,2,4-oxadiazoline} -3 -Yl} -5- (1-pyrrolyl) -4-trifluoromethylsulfinylpyrazole 0.15 ml (1.16 mmol) of 2,5-dimethoxytetrahydrofuran, 27 mg of p-toluenesulfonic acid monohydrate, 550 mg (0 .99 mmol) of 5
-Amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl)-[Delta] ² -l, 2,4-oxadiazoline-3
A mixture of -yl} -4-trifluoromethylsulfinylpyrazole and 12 ml of toluene was reacted at 80 ° C for 3 hours. 50 ml of ethyl acetate was added, and the organic layer was 30 ml.
Was washed three times with a saturated saline solution. After drying over anhydrous magnesium sulfate and concentration, brown crystals were obtained. This was washed with chloroform and 283 mg (0.47 mmol) of light brown crystals of 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl) -Δ ² -1,2,4-oxadiazolin-3-yl} -5- (1-pyrrolyl) -4-trifluoromethyl sulfinyl pyrazole. Yield 47%. _{mp.244-246 ℃ NMR (CDCl 3, δ} ) 2.97 (6H, s), 5.66 (1H, d, J = 2Hz), 5.80 (1
(H, d, J = 2Hz), 6.19 (2H, d, J = 2Hz), 6.89 (2H, t, J = 2Hz), 8.02-
8.04 (1H, m), 8.10-8.13 (1H, m)

[0080]

Reference Example 26 5-amino-1- (2,6-dichloro-
4-trifluoromethylphenyl) -3- {4- (N,
N- dimethylcarbamoyl) - [delta ^{2-1,2,4-oxadiazolin-3-yl}} -4-ethyl-thio pyrazole of bis trichloromethyl the (BTC) 410mg (1.39mmol)
It was dissolved in 20 ml of THF and cooled on ice. 0.3 ml of pyridine in the reaction solution
(3.87 mmol), and the mixture was stirred under ice cooling for 10 minutes. 5-Amino-1- (2,6-dichloro-4-trifluoromethylphenyl) -3- (Δ ² -1,2,4-oxadiazolin-3-yl) -4-ethylthiopyrazole was added to the reaction mixture. A solution of 1.50 g (3.52 mmol) in 10 ml of THF was added dropwise under ice cooling.
Stir for 1.5 hours. After the reaction, dimethylamine 0.94 ml
(10.3 mmol) was added, and the mixture was stirred at room temperature for 2 hours. The reaction solution was concentrated under reduced pressure, and the residue was dissolved in 200 ml of ethyl acetate. 200 ml of saturated saline, 200 ml of 1% hydrochloric acid
Washed with 00 ml and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 3:
1), colorless crystals were obtained. This was washed with n-hexane to obtain 440 mg (0.885 mmol) of the title compound as colorless crystals. Yield 25%. mp.187.0-189.0 ° C NMR (CDCl ₃ , δ) 1.21 (3H, t, J = 7Hz), 2.76 (2H, q, J = 7Hz),
3.05 (6H, s), 4.10 (2H, s), 5.85 (2H, s), 7.75 (2H, s)

[0081]

Reference Example 27 5-amino-1- (2,6-dichloro-
4-trifluoromethylphenyl) -3- {4- (N,
N-dimethylcarbamoyl)-[Delta] ² -l, 2,4-oxadiazolin-3-yl} -4-ethylsulfinylpyrazole 100 mg (0.201 mmol) of 5-amino-1- (2,6-dichloro-4-) Trifluoromethylphenyl) -3- {4-
(N, N-dimethylcarbamoyl) -Δ ² -1,2,4
-Oxaziazolin-3-yl} -4-ethylthiopyrazole was dissolved in 10 ml of dichloromethane and cooled with ice. To the reaction solution, 3-chloroperbenzoic acid (mCPBA) 45 mg (0.258 mm
ol) in 1 ml of dichloromethane was added dropwise, and the mixture was stirred under ice cooling for 2 hours. Saturated aqueous sodium hydrogen carbonate solution
5 ml was added and extracted with 30 ml of chloroform. This was washed with 100 ml of saturated saline and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was subjected to silica gel column chromatography (ethyl acetate) to obtain colorless crystals. This was recrystallized from a mixed solvent of n-hexane and ethyl acetate to obtain 80 mg (0.156 mmol) of the title compound as colorless crystals. Yield 78%. mp.223.0-225.0 ° C NMR (CDCl ₃ , δ) 1.37 (3H, t, J = 7Hz), 3.04 (6H, s), 3.18 (2
(H, q, J = 7Hz), 5.08 (2H, s), 5.77 (2H, s), 7.76 (2H, s)

[0082]

Reference Example 28 5-amino-1- (2,6-dichloro-
4-trifluoromethylphenyl) -3- {4- (N,
N- dimethylcarbamoyl) - [delta ^{2-1,2,4-oxadiazolin-3-yl}} -4-ethylsulfonyl pyrazole 100mg of (0.201 mmol) 5-amino-1- (2,6-dichloro-4- Trifluoromethylphenyl) -3- {4-
(N, N-dimethylcarbamoyl) -Δ ² -1,2,4
-Oxaziazolin-3-yl} -4-ethylthiopyrazole was dissolved in 10 ml of dichloromethane and cooled with ice. To the reaction solution, 3-chloroperbenzoic acid (mCPBA) 100 mg (0.579 m
mol) in dichloromethane (5 ml) was added dropwise, and the mixture was stirred under ice cooling for 18 hours. To the reaction solution was added 10 ml of a saturated aqueous sodium hydrogen carbonate solution, and the mixture was extracted with 30 ml of chloroform. This was washed with 100 ml of saturated saline and dried over anhydrous magnesium sulfate. The mixture was concentrated under reduced pressure to obtain colorless crystals. By recrystallizing this with a mixed solvent of n-hexane-ethyl acetate,
80 mg (0.151 mmol) of the title compound were obtained as colorless crystals. Yield 75%. _{mp.203.0-205.0 ℃ NMR (CDCl 3, δ} ) 1.33 (3H, t, J = 7Hz), 3.01 (6H, s), 3.57 (2
(H, q, J = 7Hz), 5.20 (2H, s), 5.86 (2H, s), 7.78 (2H, s)

Examples of the compounds of the present invention obtained in the same manner as in Reference Examples 4 to 28, including the compounds obtained in the above Reference Examples, are shown in Tables 1 to 36 below.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

[0089]

[Table 6]

[0090]

[Table 7]

[0091]

[Table 8]

[0092]

[Table 9]

[0093]

[Table 10]

[0094]

[Table 11]

[0095]

[Table 12]

[0096]

[Table 13]

[0097]

[Table 14]

[0098]

[Table 15]

[0099]

[Table 16]

[0100]

[Table 17]

[0101]

[Table 18]

[0102]

[Table 19]

[0103]

[Table 20]

[0104]

[Table 21]

[0105]

[Table 22]

[0106]

[Table 23]

[0107]

[Table 24]

[0108]

[Table 25]

[0109]

[Table 26]

[0110]

[Table 27]

[0111]

[Table 28]

[0112]

[Table 29]

[0113]

[Table 30]

[0114]

[Table 31]

[0115]

[Table 32]

[0116]

[Table 33]

[0117]

[Table 34]

[0118]

[Table 35]

[0119]

[Table 36]

The ¹ H-NMR spectra of the oils and amorphous substances in Tables 1 to 36 are shown below. 1) NMR (CDCl ₃ , δ) 1.09 (6H, d, J = 7Hz), 1.25 (3H, t, J = 7H
z), 2.61 (1H, qu, J = 7Hz), 4.16 (2H, q, J = 7Hz), 5.93 (2
H, s), 7.76 (2H, s), 8.37 (1H, s) 2) NMR (CDCl ₃ , δ) 1.10 (6H, d, J = 8Hz), 1.22 (3H, t, J = 7H
z), 2.80 (1H, m), 4.12 (2H, m), 5.81 (1H, d, J = 3Hz), 6.
00 (1H, d, J = 3Hz), 7.76 (2H, m), 8.60 (1H, s) 3) NMR (CDCl ₃ , δ) 0.83 (3H, t, J = 8Hz), 1.08 (3H, d, J = 7H
z), 1.25 (3H, t, J = 7Hz), 1.30-1.80 (1H, m), 2.44 (2H,
q, J = 7Hz), 4.16 (2H, q, J = 7Hz), 5.87 (1H, d, J = 2Hz), 6.
00 (1H, d, J = 2Hz), 7.75 (2H, s), 8.37 (1H, s) 4) NMR (CDCl 3, δ) 1.23 (3H, t, J = 7Hz), 1.31 (9H, s) , 2.
44 (2H, q, J = 7Hz), 4.14 (2H, q, J = 7Hz), 5.84 (2H, s), 7.
71 (2H, s), 8.34 (1H, s) 5) NMR (CDCl ₃ , δ) 1.20 (3H, t, J = 7Hz), 2.94 (6H, s), 4.
10 (2H, m), 5.51 (1H, d, J = 2Hz), 5.58 (1H, d, J = 2Hz),
7.72 (2H, m), 8.56 (1H, s) 6) NMR (CDCl ₃ , δ) 1.10 (3H, d, J = 6Hz), 1.23 (3H, d, J = 6H
z), 2.95 (6H, s), 4.84 (1H, qu, J = 6Hz), 5.51 (1H, d, J = 2H
z), 5.59 (1H, d , J = 2Hz), 7.73 (2H, s), 8.56 (1H, s) 7) NMR (CDCl 3, δ) 1.19 (6H, d, J = 6Hz), 2.92 (6H , s), 4.
94 (1H, qu, J = 6Hz), 5.67 (2H, s), 7.75 (2H, s), 8.00 (1
H, s) 8) NMR (CDCl ₃ , δ) 0.84 (3H, t, J = 7Hz), 1.20-1.40 (2H,
m), 1.5-1.6 (2H, m), 2.95 (6H, s), 4.10 (2H, dt, J = 1H
z, 6.6Hz), 5.58 (2H, s), 7.71-7.72 (2H, m), 8.35 (1H,
s) 9) NMR (CDCl ₃ , δ) 0.82 (3H, t, J = 7Hz), 1.14 (6H, t, J = 7H
z), 1.58 (2H, m), 3.30 (4H, q, J = 7Hz), 3.99 (2H, m),
5.48 (1H, d, J = 1Hz), 5.55 (1H, d, J = 1Hz), 7.72 (2H, m),
8.61 (1H, s) 10) NMR (CDCl ₃ , δ) 0.84 (3H, t, J = 7Hz), 1.16 (6H, t, J = 7
Hz), 1.61 (2H, m), 3.27 (4H, q, J = 7Hz), 4.07 (2H, t, J = 7
Hz), 5.63 (2H, s), 7.74 (2H, s), 8.06 (1H, s) 11) NMR (CDCl ₃ , δ) 1.17 (6H, t, J = 7Hz), 1.90 (6H, d, J = 6
Hz), 3.32 (4H, q, J = 7Hz), 4.93 (1H, qu, J = 6Hz), 5.55
(2H, s), 7.70 (2H, s), 8.29 (1H, s) 12) NMR (CDCl ₃ , δ) 1.12-1.23 (12H, m), 3.28 (4H, q, J = 7
Hz), 4.83-5.05 (1H, m), 5.63 (2H, s), 7.74 (2H, m), 7.99
(1H, s) 13) NMR (CDCl ₃ , δ) 0.84 (3H, t, J = 7Hz), 1.17 (6H, t, J = 7
Hz), 1.25-1.40 (2H, m), 1.49-1.63 (2H, m), 3.32 (4H,
q, J = 7Hz), 4.10 (2H, t, J = 6Hz), 5.55 (2H, s), 7.71 (2
H, s), 8.36 (1H, s) 14) NMR (CDCl ₃ , δ) 0.84 (3H, t, J = 7Hz), 1.17 (6H, t, J = 7
Hz), 1.22-1.36 (2H, m), 1.48-1.59 (2H, m), 3.28 (4H, m
q, J = 7Hz), 4.13 (2H, t, J = 6Hz), 5.64 (2H, s), 7.74 (2
H, s), 8.05 (1H, s) 15) NMR (CDCl ₃ , δ) 1.17 (3H, t, J = 7Hz), 1.26 (3H, t, J = 7
Hz), 2.90 (3H, s), 3.30 (2H, q, J = 7Hz), 4.17 (2H, d, J = 7H
z), 5.65 (2H, s ), 7.75 (2H, s), 8.05 (1H, s) 16) NMR (CDCl 3, δ) 1.26-1.14 (9H, m), 2.93 (3H, s), 3.
33 (2H, q, J = 7Hz), 4.94 (1H, qu, J = 6Hz), 5.57 (2H, s),
7.71 (2H, s), 8.29 (1H, s) 17) NMR (CDCl ₃ , δ) 1.17 (3H, t, J = 7Hz), 1.19 (6H, d, J = 6
Hz), 2.90 (3H, s), 3.29 (2H, q, J = 7Hz), 4.94 (1H, qu, J =
6Hz), 5.66 (2H, s), 7.75 (2H, s), 8.00 (1H, s) 18) NMR (CDCl ₃ , δ) 0.84 (3H, t, J = 7Hz), 1.33-1.14 (5H,
m), 1.57 (2H, qu, J = 6Hz), 2.93 (3H, s), 3.33 (4H, q, J =
7Hz), 4.10 (2H, t, J = 7Hz), 5.57 (2H, s), 7.71 (2H, s),
8.35 (1H, s) 19) NMR (CDCl ₃ , δ) 0.83 (3H, t, J = 7Hz), 1.17 (3H, t, J = 7
Hz), 1.25 (2H, m), 1.55 (2H, m), 2.89 (3H, s), 3.29 (2
(H, t, J = 7Hz), 4.13 (2H, t, J = 7Hz), 5.65 (2H, s), 7.74 (2
H, m), 8.05 (1H, s) 20) NMR (CDCl ₃ , δ) 1.14 (3H, t, J = 7Hz), 3.4-3.7 (2H,
m), 5.18 (2H, br ), 5.38 (2H, d, J = 7Hz), 7.82 (2H, s) 21) NMR (CDCl 3, δ) 1.14 (6H, d, J = 7Hz), 1.23 (3H , t, J = 7
Hz), 2.86 (3H, s), 4.17 (2H, q, J = 7Hz), 4.42 (1H, qu, J =
7Hz), 5.88 (2H, s ), 7.74 (2H, s), 8.03 (1H, s) 22) NMR (CDCl 3, δ) 1.23 (3H, t, J = 7Hz), 1.36 (9H, s),
2.93 (3H, s), 4.07-4.19 (2H, m), 5.56 (2H, s), 7.71 (2
H, s), 8.35 (1H, s) 23) NMR (CDCl ₃ , δ) 1.20 (3H, t, J = 7Hz), 1.35 (9H, s),
2.91 (3H, s), 4.00-4.19 (2H, m), 5.46 (1H, d, J = 2Hz),
5.57 (1H, d, J = 2Hz), 7.71-7.74 (2H, m), 8.60 (1H, s) 24) NMR (CDCl 3, δ) 1.23 (3H, t, J = 7Hz), 1.33 (9H, s),
4.17 (2H, q, J = 7Hz), 5.63 (2H, s), 7.75 (2H, s), 8.06 (1
H, s) 25) NMR (CDCl ₃ , δ) 1.12-1.26 (12H, m), 3.22 (2H, q, J = 7
Hz), 4.00-4.20 (2H, m), 5.48 (1H, d, J = 1Hz), 5.54 (1H,
d, J = 1Hz), 7.72-7.74 (2H, m), 8.59 (1H, s) 26) NMR (CDCl ₃ , δ) 1.20 (3H, t, J = 7Hz), 2.91 (3H, s),
4.03-3.73 (4H, m), 5.16 (1H, q, J = 2Hz), 5.23 (1H, d, J = 2
Hz), 5.48 (2H, d, J = 2Hz), 5.58 (1H, d, J = 2Hz), 5.66-5.
86 (1H, m), 7.74 (2H, s), 8.57 (1H, s) 27) NMR (CDCl ₃ , δ) 1.04 (3H, t, J = 7Hz), 1.14 (3H, t, J = 7
Hz), 1.20 (3H, t, J = 7Hz), 2.85 (2H, m), 3.52 (2H, m),
4.10 (2H, m), 5.66 (1H, d, J = 2Hz), 5.70 (1H, d, J = 2Hz),
7.71 (2H, m), 8.59 (1H, s) 28) NMR (CDCl ₃ , δ) 1.21 (3H, t, J = 7Hz), 3.99-4.26 (2H,
m), 5.75 (1H, d, J = 2Hz), 5.99 (1H, d, J = 2Hz), 7.69 (1H,
brs), 7.79 (2H, m ), 8.51 (1H, s), 9.77 (1H, s) 29) NMR (CDCl 3, δ) 1.21 (3H, t, J = 7Hz), 3.68 (3H, s), 3.99-
4.26 (2H, m), 5.80 (1H, d, J = 2Hz), 6.06 (1H, d, J = 2Hz),
7.81 (2H, m), 8.54 (1H, s), 9.90 (1H, s) 30) NMR (CDCl ₃ , δ) 1.21 (3H, t, J = 7Hz), 3.12 (3H, s),
3.98-4.25 (2H, m), 5.57 (1H, d, J = 3Hz), 5.71 (1H, d, J = 3
Hz), 7.70-7.82 (2H, m), 8.06 (1H, brs), 8.45 (1H, s) 31) NMR (CDCl ₃ , δ) 1.20 (3H, t, J = 7Hz), 1.00-1.50 (4H ,
m), 1.60-1.80 (6H, m), 2.83 (3H, s), 3.70-3.90 (1H, m),
4.00-4.20 (2H, m), 5.48 (1H, d, J = 2Hz), 5.55 (1H, d, J =
2Hz), 7.71-7.74 (2H, m), 8.58 (1H, s) 32) NMR (CDCl ₃ , δ) 1.20 (3H, t, J = 7Hz), 1.60 (6H, br),
3.30-3.40 (4H, m), 4.00-4.20 (2H, m), 5.49 (1H, d, J = 2
Hz), 5.56 (1H, d, J = 2Hz), 7.72-7.75 (2H, m), 8.59 (1
H, s) 33) NMR (CDCl ₃ , δ) 1.20 (3H, t, J = 7Hz), 2.25 (3H, s),
2.38 (4H, t, J = 5Hz), 3.46 (4H, t, J = 5Hz), 4.10 (2H, m),
5.59 (1H, d, J = 2Hz), 5.76 (1H, d, J = 2Hz), 7.73 (2H, m),
8.57 (1H, s) 34) NMR (CDCl ₃ , δ) 1.21 (3H, t, J = 7Hz), 3.42-3.47 (4H,
m), 3.67 (4H, t, J = 5Hz), 4.00-4.20 (2H, m), 5.49 (1H,
d, J = 2Hz), 5.57 (1H, d, J = 2Hz), 7.72-7.77 (2H, m), 8.5
7 (1H, s) 35) NMR (CDCl ₃ , δ) 0.81-1.67 (18H, m), 2.20-2.50 (2H,
m), 3.98-4.27 (2H, m), 5.82 (1H, d, J = 3Hz), 6.00 (1H,
d, J = 3Hz), 7.73-7.81 (2H, m), 8.61 (1H, s) 36) NMR (CDCl ₃ , δ) 0.81-1.67 (20H, m), 2.20-2.50 (2H, m
m), 3.98-4.27 (2H, m), 5.82 (1H, d, J = 3Hz), 6.00 (1H,
d, J = 3Hz), 7.73-7.81 (2H, m), 8.61 (1H, s) 37) NMR (CDCl ₃ , δ) 1.22 (3H, t, J = 7Hz), 1.45-1.74 (4H,
m), 2.55 (1H, m), 4.11 (2H, m), 5.81 (1H, d, J = 3Hz), 6.
04 (1H, d, J = 3Hz), 7.76 (2H, m), 8.62 (1H, s) 38) NMR (CDCl 3, δ) 1.00 (9H, s), 1.22 (3H, t, J = 7Hz) ,
2.25 (1H, d, J = 15.3Hz), 2.31 (1H, d, J = 15.3Hz), 3.99-
4.27 (2H, m), 5.81 (1H, d, J = 3Hz), 5.98 (1H, d, J = 3Hz),
7.73-7.81 (2H, m), 8.62 (1H, s) 39) NMR (CDCl ₃ , δ) 1.21 (3H, t, J = 7Hz), 3.98-4.25 (2H,
m), 5.98 (1H, d, J = 3Hz), 6.05 (1H, d, J = 3Hz), 6.47 (1H,
d, J = 15Hz), 7.27-7.45 (5H, m), 7.63-7.71 (2H, m), 7.7
6 (1H, d, J = 15Hz), 8.58 (1H, s) 40) NMR (CDCl 3, δ) 1.22 (3H, t, J = 7Hz), 3.75 (3H, s),
3.98-4.26 (2H, m), 5.73 (1H, d, J = 2Hz), 5.86 (1H, d, J = 2
Hz), 7.72-7.78 (2H, m), 8.60 (1H, s) 41) NMR (CDCl ₃ , δ) 1.22 (3H, t, J = 7Hz), 1.24 (3H, t, J = 7
Hz), 4.11 (2H, m), 5.73 (1H, d, J = 2Hz), 4.22 (2H, q, J = 7
Hz), 5.76 (1H, d, J = 2Hz), 5.83 (1H, d, J = 2Hz), 7.75 (2
H, m), 8.59 (1H, s) 42) NMR (CDCl ₃ , δ) 1.17-1.29 (9H, m), 3.98-4.27 (2H,
m), 5.00 (1H, 7-fold, J = 6Hz), 5.77 (1H, d, J = 2Hz), 5.8
0 (1H, d, J = 2Hz), 7.72-7.79 (2H, m), 8.59 (1H, s) 43) NMR (CDCl ₃ , δ) 1.22 (3H, t, J = 7Hz), 1.45 (9H, s),
3.98-4.26 (2H, m), 5.73 (1H, d, J = 2Hz), 5.78 (1H, d, J = 2
Hz), 7.72-7.78 (2H, m), 8.61 (1H, s) 44) NMR (CDCl ₃ , δ) 1.24 (3H, t, J = 7Hz), 1.44 (9H, s),
4.17 (2H, q, J = 7Hz), 5.78 (2H, s), 7.76 (2H, m), 8.13
(1H, s) 45) NMR (CDCl ₃ , δ) 1.16 (6H, t, J = 7Hz), 3.32 (4H, q, J = 7
Hz), 3.83 (3H, s), 5.51 (1H, d, J = 1Hz), 5.59 (1H, d, J = 1
Hz), 6.14 (1H, s), 6.93 (1H, d, J = 8Hz), 7.18 (1H, d, J =
2Hz), 7.32 (1H, dd, J = 1.8Hz, 8.2Hz), 7.70-7.80 (2H,
m), 9.12 (1H, s) 46) NMR (CDCl ₃ , δ) 2.92 (6H, s), 4.12 (2H, d, J = 7.0Hz),
5.44 (1H, d, J = 2Hz), 5.53 (1H, d, J = Hz), 6.90 (2H, d, J
= 6Hz), 7.00 (1H, t, J = 7Hz), 7.45 (1H, m), 7.55 (1H, m),
8.40 (2H, d, J = 6Hz) 47) NMR (CDCl ₃ , δ) 1.13 (3H, d, J = 6Hz), 1.20 (3H, d, J = 6
Hz), 2.93 (6H, s), 4.86 (1H, sep, J = 6Hz), 5.50 (1H, d, J
= 2Hz), 5.58 (1H, d, J = 2Hz), 7.47 (2H, m), 8.50 (1H, s) 48) NMR (CDCl 3, δ) 2.99 (6H, s), 5.54 (2H, s) , 5.77 (2
H, brs), 8.17 (1H, m), 8.63 (1H, m)

Hereinafter, Compound (1) is listed in the above table as Comp. No. 20-11.
Compound (2) means Comp. No. 20-5 in the above table, and compound (3) means Comp. No. 30-26 in the above table.

Example 1 Compound (1) 5 parts, clothianidin 8 parts, Neugen EA-177 0.5 parts, Newcalgen FS-42
Parts, Gohsenol GH-17 2 parts, butyl paraben 0.1
Parts, 82.4 parts of water, and thoroughly mixed and dispersed using a high-speed stirrer.
Wet pulverization (1 pass) using glass beads, filling rate 80%, peripheral speed 15 m / s) to obtain a flowable agent.

[0122]

Example 2 5 parts of compound (1), 8 parts of clothianidin, 0.5 part of Neugen EA-177, 0.5 parts of Newcalgen FS-4
1.5 parts, Aerosil COK84 2 parts, Gohsenol GH
-17 2 parts, ethylene glycol 7 parts, Anti-Home E
After sufficiently mixing and dispersing 0.2 parts of -20, 0.1 parts of butylparaben, and 73.7 parts of water with a high-speed stirrer, use a Dynomill (Shinmaru Enterprise, 1.0 mm glass beads, filling rate 80%, peripheral speed 15 m / s). Wet grinding (1 pass)
Then, a flowable agent was obtained.

[0123]

Example 3 1 part of compound (1), 1 part of clothianidin, 0.5 part of Newpol PE-64, dextrin NDS 4
Parts, and 93.5 parts of clay, mix uniformly, add 5 to 10 parts of water, knead, extrude through a 0.8 mmφ screen, and granulate. The obtained granules are dried at 60 ° C. for 1 hour to obtain granules.

[0124]

Example 4 Nitenpyram 20 parts and Toyoderin P 80
A part thereof dissolved in 400 parts of water is spray-dried to obtain a cyclodextrin clathrate A of nitenpyram. Compound (1) 1
Parts, cyclodextrin clathrate A 5 parts, Newcargen EP-70P 2 parts, dextrin NDS 10 parts, clay
After uniformly mixing 82 parts, 5 to 10 parts of water are added and kneaded, and the same operation as in Example 2 is performed to obtain granules.

[0125]

Example 5 Compound (1) 0.2 part, clothianidin 0.15
Part, New Cargen EP-70P2 part, IP solvent
0.2 parts, 1 part of white carbon and 96.45 parts of clay are kneaded uniformly and then pulverized to obtain a DL powder.

[0126]

Example 6 Compound (1) 0.2 part, cyclodextrin clathrate A 1.25 part, Newcargen EP-70P 2 parts, I
0.2 parts of P solvent, 1.5 parts of white carbon, clay
After uniformly kneading 94.85 parts, pulverize to obtain a DL powder.

[0127]

Example 7 Compound (1) 0.2 part, cartap hydrochloride 2
Parts, 1 part of Hartoll fatty acid, 0.2 parts of IP solvent, 1.5 parts of white carbon, and 95.1 parts of clay, and then pulverized to obtain a DL powder.

[0128]

Example 8 Compound (1) 0.2 part, validamycin A 0.3
Parts, 2 parts of ferimzone, 1.5 parts of fusalide, 0.2 parts of IP solvent, 2 parts of Newcargen EP-60P, 1.5 parts of white carbon, 0.05 parts of butylparaben, 3 parts of Newcalgen D-1504, 0.25 parts of Hartolic fatty acid,
After uniformly mixing 89 parts of calcium carbonate, pulverize
L powder is obtained.

Example 9 5 parts of compound (1), 8 parts of clothianidin, 7 parts of Newcalgen 98147TX, and AGSOLEX18
0 parts are uniformly mixed and dissolved to obtain an emulsion.

[0129]

[Test Example 1] Pharmaceutical efficacy against Conaga A solution of each of the compounds shown in [Table 37] (dissolved in acetone or DMF and adjusted with diluted ion-exchanged water) in a 1 / 5000a Wagner pot was irrigated into the planting hole and cabbage was planted. The seedlings were transplanted, and adult adults were released in the house. The number of larvae per strain, which were examined at one week intervals from 3 weeks after drug treatment (from 2nd instar to
Number of terminal larvae) along with the corrected density (ratio to no treatment) [Table 3
7]. As shown in [Table 37], when compound (1) is used as a mixture with clothianidin or nitenpyram, a higher effect is exhibited than when two times the amount of each compound is used alone, and a synergistic effect due to the mixture is obtained. Was observed.

[Table 37]

[0130]

[Test Example 2] Pharmacological activity against Thrips palmi Karny The cucumber seeds treated with each compound shown in [Table 38] (dissolved in acetone or DMF and adjusted with ion-exchanged water) were seeded in a 1 / 5000a Wagner pot. Two weeks after in the house, female adult Thrips palmi were inoculated. The number of larvae per strain examined at one-week intervals from four weeks after the drug treatment is shown in Table 38 together with the corrected density. As shown in [Table 38], when compound (2) is used in combination with clothianidin, a higher effect is exhibited than when two times the amount of each compound is used alone, and a synergistic effect due to the mixture is observed. Was done.

[Table 38]

[0131]

[Test Example 3] Medicinal efficacy against Kobumemeiga In rice at the highest tiller stage grown in a 1 / 5000a Wagner pot, a solution of each compound shown in [Table 39] (compound (1) was dissolved in acetone, and cartap hydrochloride was used. Was adjusted as it was with ion-exchanged water), and the first instar larvae of Kotubomeiga were inoculated at weekly intervals one week after the chemical treatment. The number of surviving insects per strain examined two weeks after each inoculation is shown in Table 39 together with the corrected mortality. However, the corrected mortality rate (%) = (1-the number of larvae in the drug-treated area / the number of larvae in the untreated area) x 100. When the number of larvae in the drug-treated area> the number of larvae in the untreated area, the corrected mortality rate = 0. As shown in Table 39, compounds
By using (3) as a mixture with cartap hydrochloride, a higher effect was exhibited than in the case of using twice the amount of each compound alone, and a synergistic effect by mixing was observed.

[Table 39]

[0132]

[Test Example 4] Pharmaceutical efficacy against Thrips palmi in a tea garden in Makabe-gun, Ibaraki Prefecture, using a backpack-type power sprayer, 300 liters of a diluted solution of the drug shown in [Table 40] / 1
0 ares were sprayed and the number of surviving insects of Thrips palmi Karny was examined by brushing off. The results are shown in [Table 40]. However, the corrected density index = 100 × ((the number of treated insects / the number of untreated insects) / (the number of treated insects before the treatment / the number of untreated insects before the treatment)) Compound (1) 1) 5 parts, ethylene glycol 10 parts, anti-home E-20 0.2 parts, butyl paraben 0.1 parts, Neugen EA-177 2 parts, Neugen E
T-83 1.5 parts, Demol EP 1 part, VEEGUM R
0.5 parts, 1.5 parts of Kunipia F and 78.2 parts of water are sufficiently mixed using a high-speed stirrer, and then wet-pulverized using a Dynomill (Shinmaru Enterprises, 1 mm glass beads, filling rate 80%, peripheral speed 15 m / s). Manufactured by The clothianidin granular water solvent was prepared by uniformly mixing 16 parts of clothianidin, 3 parts of Solpol 5115, 0.15 parts of cyanine green G, and 80.85 lactose for industrial use, and then water was added and kneaded. The kneaded material is processed with a sizing machine (RG-5M, manufactured by Kikusui Seisakusho) to 0.8
After extruding and granulating using a mmφ screen, drying was performed to obtain granules. As shown in [Table 40], when compound (1) is used in combination with clothianidin, a higher effect is exhibited than when two times the amount of each compound is used alone, and a synergistic effect due to the mixture is observed. Was done.

[Table 40]

[0133]

EFFECTS OF THE INVENTION Combining an oxadiazoline derivative represented by the formula [I] with other pesticidal active ingredients has higher effects (control effects such as insecticidal and bactericidal effects) than when each is used alone. That is, a synergistic effect is exhibited, and therefore, it is possible to reduce the pesticide application rate or the number of application times. The insecticidal effect of the oxadiazoline derivative represented by the formula [I] can be enhanced by combining the oxadiazoline derivative represented by the formula [I] with another pesticidal active ingredient.

Claims (12)

[Claims] 1. A compound of the formula [I] [Wherein, R ¹ represents a C _1-6 alkyl group or a C _1-6 haloalkyl group, n represents 0, 1 or 2, and X represents (1) -NR ² R
³ (R ² and R ³ each represent a hydrogen atom or a C _1-6 alkyl group optionally substituted with pyridyl), (2)-
N = CHOR ⁴ (R ⁴ represents a C _1-6 alkyl group), (3)-
N = CHNR ⁶ R ⁷ (R ⁶ and R ⁷ each represent a hydrogen atom or a C _1-6 alkyl group), (4) —N ＝ CHAr (A
r represents a phenyl group which may be substituted by a substituent selected from hydroxyl and a C _1-3 alkoxy group) or (5) a pyrrolyl group; and R ⁵ represents an optionally substituted alkyl group or a substituted R ⁸ represents an acyl group which may be
A represents a phenyl group which may be substituted with (1) halogen, (2) C _1-6 haloalkyl group, (3) C _1-6 haloalkoxy group or (4) C _1-6 haloalkyl group; Or (R ⁹ represents a chlorine atom or a cyano group), B is a nitrogen atom or An insecticidal composition comprising an oxadiazoline derivative represented by the formula or a salt thereof and another pesticidal active ingredient. 2. An oxadiazoline derivative or a salt thereof and another pesticidal active ingredient in a weight ratio of 1: 0.25 to 1: 1, respectively.
The composition according to claim 1, which is contained in a proportion of 20. 3. The insecticidal composition according to claim 1, wherein the other pesticidal active ingredient is an insecticidal ingredient. 4. The composition according to claim 3, wherein the insecticidal component is clothianidin, and the oxadiazoline derivative or a salt thereof and clothianidin are contained in a weight ratio of 1: 0.25 to 1: 4, respectively. 5. The composition according to claim 3, wherein the insecticidal component is nitenpyram, and the oxadiazoline derivative or a salt thereof and nitenpyram are contained in a weight ratio of 1: 0.25 to 1: 4, respectively. 6. The composition according to claim 3, wherein the insecticidal component is cartap hydrochloride, and the oxadiazoline derivative or a salt thereof and cartap hydrochloride are contained in a weight ratio of 1: 1 to 1:10, respectively. . 7. The composition according to claim 3, wherein the insecticidal component is bensultap, and the oxadiazoline derivative or a salt thereof and bensultap are contained in a weight ratio of 1: 1 to 1:10, respectively. 8. The insecticidal component is pyraclophos, which contains an oxadiazoline derivative or a salt thereof and pyraclofos in a weight ratio of 1: 1 to 1:10, respectively.
A composition as described. 9. The composition according to claim 1, wherein the other pesticidal active ingredient is a bactericidal ingredient. 10. An oxadiazoline derivative comprising 1- (2,6
-Dichloro-4-trifluoromethylphenyl) -3-
{4- (N, N- dimethylcarbamoyl) -Δ ² -1,
2,4-oxadiazolin-3-yl {-5-isopropoxymethyleneamino-4-trifluoromethylsulfinylpyrazole, 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl) -Δ ² -1,2,4-oxadiazolin-3-yl} -5-ethoxymethyleneamino-4-
Trifluoromethylsulfinylpyrazole and 1-
(2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-3- {4- (morpholinocarbonyl) - [delta ^{2-1,2,4-oxadiazolin-3-yl}} -4 The composition according to claim 1, which is selected from -trifluoromethylsulfinylpyrazole. 11. A compound of the formula [I] [Wherein, R ¹ represents a C _1-6 alkyl group or a C _1-6 haloalkyl group, n represents 0, 1 or 2, and X represents (1) -NR ² R
³ (R ² and R ³ each represent a hydrogen atom or a C _1-6 alkyl group optionally substituted with pyridyl), (2)-
N = CHOR ⁴ (R ⁴ represents a C _1-6 alkyl group), (3)-
N = CHNR ⁶ R ⁷ (R ⁶ and R ⁷ each represent a hydrogen atom or a C _1-6 alkyl group), (4) —N ＝ CHAr (A
r represents a phenyl group which may be substituted by a substituent selected from hydroxyl and a C _1-3 alkoxy group) or (5) a pyrrolyl group; and R ⁵ represents an optionally substituted alkyl group or a substituted R ⁸ represents an acyl group which may be
A represents a phenyl group which may be substituted with (1) halogen, (2) C _1-6 haloalkyl group, (3) C _1-6 haloalkoxy group or (4) C _1-6 haloalkyl group; Or (R ⁹ represents a chlorine atom or a cyano group), B represents a nitrogen atom or Wherein the oxadiazoline derivative represented by the formula (1) or a salt thereof is used in combination with another pesticidal active ingredient. 12. A compound of the formula [I] [Wherein, R ¹ represents a C _1-6 alkyl group or a C _1-6 haloalkyl group, n represents 0, 1 or 2, and X represents (1) -NR ² R
³ (R ² and R ³ each represent a hydrogen atom or a C _1-6 alkyl group optionally substituted with pyridyl), (2)-
N = CHOR ⁴ (R ⁴ represents a C _1-6 alkyl group), (3)-
N = CHNR ⁶ R ⁷ (R ⁶ and R ⁷ each represent a hydrogen atom or a C _1-6 alkyl group), (4) —N ＝ CHAr (A
r represents a phenyl group which may be substituted by a substituent selected from hydroxyl and a C _1-3 alkoxy group) or (5) a pyrrolyl group; and R ⁵ represents an optionally substituted alkyl group or a substituted R ⁸ represents an acyl group which may be
A represents a phenyl group which may be substituted with (1) halogen, (2) C _1-6 haloalkyl group, (3) C _1-6 haloalkoxy group or (4) C _1-6 haloalkyl group; Or (R ⁹ represents a chlorine atom or a cyano group), B represents a nitrogen atom or Wherein the oxadiazoline derivative or a salt thereof is used in combination with another agricultural chemical active ingredient, thereby enhancing the insecticidal effect of the oxadiazoline derivative or a salt thereof.