JP2000344767A - Oxadiazoline derivative and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new oxadiazoline compound having a strong insecticidal activity, hardly causing damage to plants by the compound, having only slight toxicity to human beings and beasts, fish and natural enemy or the like, and having safety. SOLUTION: This new compound is expressed by formula I, wherein R1 is a 1-6C (halo)alkyl; (n) is 0-2; X is NR2R3, wherein R2 and R3 are each H or a (pyridyl substituted)1-6C alkyl or the like; R5 is a (substituted)alkyl or the like; R8 is a (substituted)phenyl or the like; A is nitrogen or the like and; B is nitrogen or the like and is e.g. 1-(2,6-dichloro-4- trifluoromethylohenyl)-3- 4-(N,N-dimethylcarbamoly)-Δ2-1,2,4-oxadiazolin-3-yl}-5- isopropoxymethyleneamino-4-trifluoromethylsulfinylpyrazole. The compound of formula I is obtained by reacting a compound of formula II e.g. with an acylating agent or an alkylating agent, if necessary, in the presence of an adequate acid or basic catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel oxadiazoline derivative and a pesticide containing the same.

[0002]

2. Description of the Related Art A large number of synthetic compounds having a pest control effect have been used as insecticides, most of which are organic phosphates, carbamates, organic chlorine-containing compounds or pyrethroid compounds. Belongs to On the other hand, a 1-arylpyrazole derivative in which the 3-position of the pyrazole ring is a hydrogen atom, an alkyl group, a cycloalkyl group, a halogenoalkyl group, a cyano group, a nitro group, a halogen atom, a carbamoyl group or a thiocarbamoyl group shows insecticidal activity. Have been reported (Japanese Unexamined Patent Publication No.
JP-A-2-22865, JP-A-62-207259, JP-A-5-148240, JP-A-2-282366,
JP-A-5-86054 and JP-A-7-500319).

[0003]

However, even though these pyrazole derivatives have high insecticidal activity, they are highly toxic to humans and fish, and sometimes exhibit toxicity to natural enemies of pests.
At present, satisfactory effects have not always been obtained in practical use, such as excessive persistence in soil and the like.

[0004]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have made intensive studies for many years in order to find an insecticide having a completely different structure from the conventionally used insecticides. As a result, it was found that the novel oxadiazoline derivative represented by the formula [I] or a salt thereof has a surprisingly strong insecticidal activity, and furthermore, has almost no phytotoxicity to plants, and furthermore, has no toxicity to humans and animals, It has low toxicity to natural enemies and is safe. further,
The present inventors have conducted intensive studies based on these findings, and as a result, completed the present invention. That is, the present invention provides (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 with 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 An optionally substituted acyl group, R ⁸ is
(1) halogen, (2) a C _1-6 haloalkyl group, (3) a C _1-6 haloalkoxy group or (4) a phenyl group optionally substituted with a C _1-6 haloalkyl group, and A is a nitrogen atom Or

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

Embedded image (Hereinafter sometimes abbreviated as compound [I]) or a salt thereof, (2) the compound or a salt thereof according to the above (1), wherein R ¹ is a trifluoromethyl group, 3) X represents a respectively -NR ² R ³ (R ² and R ³ a hydrogen atom or a C _1-6 alkyl group) or -N
化合物 CHOR ⁴ (R ⁴ represents a C _1-6 alkyl group) or a compound thereof according to the above (1), or (4) wherein X is —N
The compound or a salt thereof according to the above (1), wherein H ₂ or —N ＝ CHOR ⁴ (R ⁴ represents a C _1-6 alkyl group),
(5) have R ⁵ is an optionally substituted carbamoyl group (1) or a salt thereof according to claim, (6) R ⁵
There (1) C _1-6 1 to 3 or an optionally substituted C _1-6 alkyl group with an alkoxy, (2) (i) C 1-6 alkyl with one or 2
C _2-10 alkanoyl optionally substituted with 1 to 3 substituents selected from amino optionally substituted, (ii) C _1-6 alkoxy, (iii) phenyl and (iv) halogen Group, (3) C _4-10 cycloalkanoyl group, (4) C
_3-10 alkenylcarbonyl group, (5) benzoyl group, (6)
(i) C _1-6 alkyl _optionally substituted with a substituent selected from phenyl, halogen and an amino group optionally substituted with C _1-6 alkyl, (ii) C _3-9 cycloalkyl,
(iii) C _2-6 alkenyl, (iv) C _2-6 alkynyl, (v) phenyl, (vi) amino optionally substituted by 1 or 2 C _1-6 alkyl, (vii) cyclic amino, (viii) a carbamoyl group optionally substituted by one or two substituents selected from hydroxyl and (ix) C _1-6 alkoxy,
(7) cyclic amino-carbonyl group, (8) C _1-6 alkoxy-
(8) The compound according to the above (1), which is a carbonyl group or (9) a formyl group, or a salt thereof; (7) the compound according to the above (1), wherein R ⁸ is a trifluoromethyl group, or a salt thereof; But

Embedded image (9) The compound according to the above (1) or a salt thereof,
B is a nitrogen atom, or a salt thereof of (1) above, wherein, (10) X is (indicating each R ² and R ³ a hydrogen atom or a C _1-6 alkyl group) -NR ² R ^3, - N = C
HOR ⁴ (R ⁴ represents a C _1-6 alkyl group) or -N =
CHNR ⁶ R ⁷ (R ⁶ and R ⁷ each represent a hydrogen atom or a C _1-6 alkyl group), R ⁸ represents a trifluoromethyl group, and A represents

Embedded image A compound or a salt thereof according to the above (1), wherein B represents a nitrogen atom, (11) X is —NR ² R ³ (R ² and R ³ each represent a hydrogen atom or a C _1-6 alkyl group) Or the compound or a salt thereof according to the above (10), wherein -N = CHOR ⁴ (R ⁴ represents a C _1-6 alkyl group);
1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl)
-Δ ² -1,2,4-oxadiazolin-3-yl}-
The compound according to the above (1), which is 5-isopropoxymethyleneamino-4-trifluoromethylsulfinylpyrazole or a salt thereof, or a salt thereof, (13) 1-
(2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl)-
Delta ^{2-1,2,4-oxadiazolin-3-yl}} -5
-Ethoxymethyleneamino-4-trifluoromethylsulfinylpyrazole or a salt thereof according to the above (1) or a salt thereof, (14) 1- (2,6-dichloro-4-trifluoromethylphenyl) -5 The above-mentioned (1), which is -ethoxymethyleneamino-3- {4- (morpholinocarbonyl) -Δ ² -1,2,4-oxadiazolin-3-yl} -4-trifluoromethylsulfinylpyrazole or a salt thereof. Or a salt thereof, (15) 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-
3- {4- isobutyryl - [delta ^{2-1,2,4-oxadiazolin-3-yl}} -4-trifluoromethyl methylsulfinyl pyrazole, or a compound or a salt thereof of (1) above, wherein a salt thereof, ( 16) A pesticide comprising the compound according to (1) or a salt thereof, (17) a pesticide according to (16), wherein the pesticide is an insecticide;
8) Use of the compound described in the above (1) or a salt thereof as an insecticide.

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 C _2-10 alkanoyl group optionally substituted with 1 to 3 halogen atoms, (3) C _4-10 cycloalkanoyl group, (4) C _3-10
An alkenylcarbonyl group, (5) a benzoyl group, (6) a substituent selected from the group _{consisting of} phenyl, halogen, and an amino group optionally substituted by 1 or 2 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 or (9) formyl.

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
Examples of the haloalkyl group include the same as the C _1-6 haloalkyl group exemplified for R ¹ above. 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 Or a carbamoyl group or a cyclic amino-carbonyl group selected from (9) 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 '' represents (1) a C _1-9 alkyl-carbonyl group or (2)
A carbamoyl group which may be substituted by 1 or 2 C _1-6 alkyl].

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 1 or 2 C _1-6 alkyl].

The salt of the compound [I] of the present invention may be any salt that is pharmaceutically acceptable. 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. Alkaline earth metals, such as
An inorganic base such as ammonia, for example, an organic base such as pyridine, collidine, triethylamine, and triethanolamine is used. 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, Sulfuric acid, salts of inorganic acids such as perchloric acid or for example, formic acid, acetic acid, tartaric acid, malic acid, citric acid,
Salts of organic acids such as oxalic acid, succinic acid, benzoic acid, picric acid, methanesulfonic acid and p-toluenesulfonic acid are used. Compound [I] may form an inner salt, which is also included in the present invention.

The compound [I] of the present invention or a salt thereof, and the compound [II] used as a raw material for producing the compound [I] or a salt thereof shown below are described in WO97 / 28126.
Or a method analogous thereto. Generally, a compound (I
The compound [I] of the present invention or a salt thereof can be synthesized by reacting I] with an acylating agent or an alkylating agent in the presence of a suitable acid or base catalyst as required. Examples of the acylating agent used in such a reaction include carboxylic acid halides (eg, acetyl chloride, propionyl bromide, etc.), carbamoyl halides (eg, chloride
N, N-dimethylcarbamoyl, N, N-diethylcarbamoyl chloride, etc.), halogenocarbonate (eg, methyl chlorocarbonate, phenylchlorocarbonate, etc.), dialkyl dicarbonate (eg, di-tert-butyl dicarbonate, dimethyl dicarbonate, etc.) ), Carboxylic anhydride (eg, acetic anhydride, propionic anhydride, etc.)
A publicly known acylating agent such as the above can be used. Examples of the alkylating agent used in such a reaction include alkyl halides (eg, methyl iodide, ethyl bromide, etc.), alkyl sulfonates (eg, methyl methanesulfonate, p-
Ethyl toluenesulfonate, methyl trifluoromethanesulfonate, etc.), dialkyl sulfate (eg, dimethyl sulfate,
Known alkylating agents such as diethyl sulfate and the like, and trialkyl orthoformate (eg, trimethyl orthoformate, triethyl orthoformate and the like) can be used. In this reaction, the amount of the acylating agent or the 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, sodium ethylate, sodium methylate, potassium tert.
Alkoxides of alkali metals such as -butoxide and the like; organic bases such as triethylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine, N, N-dimethylaniline and the like, for example, potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, carbonate Inorganic bases such as sodium hydrogen, potassium hydrogen carbonate, sodium hydride and the like 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 is preferably 0.1 to 20 equivalents. Examples of the acid catalyst used in this reaction 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, and oxalic acid And organic protonic acids such as succinic acid, benzoic acid, trifluoroacetic acid and p-toluenesulfonic acid, and Lewis acids such as aluminum chloride, ferric chloride, zinc chloride, titanium tetrachloride and boron trifluoride. 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.
Preferably it is 0.1 to 20 equivalents. 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 usually about -50 to 200C, and the reaction time is generally about 0.1 to 96 hours. When compound [I] is obtained as a free compound, it can be converted into a salt as described above, and when obtained in the form of a salt, it can be converted into a free compound 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],
Alternatively, it may be used 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 of the alkyl group, the aforementioned R
Examples are the same as the substituents of 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 are bonded 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 the present 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 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. 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 described above.

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 with the carboxylic acid derivative represented by the formula 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).

[0028] Reaction formula (D) is a compound [IIa] is reacted with phosgene or an equivalent thereof, and intermediates [VI], to which R ^5d R ^5e NH [R ^5d, R ^5e is as defined above Show. Is reacted with an amine represented by the formula [VI
1] is shown. In the compound [IIa], B
Can be produced according to the method described in the above-mentioned WO 97/28126. Phosgene, trichloromethyl chloroformate (diphosgene), bistrichloromethyl carbonate (triphosgene) and the like are used as phosgene or its equivalent used in this reaction. 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 the reaction for producing the compound [X] by reacting the compound [IX] with formaldehyde or its equivalent. 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] is 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 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. The compound [I] of the present invention and a salt thereof are effective in controlling sanitary pests, plant and animal parasites, and exhibit a strong insecticidal action when applied to animals and plants infested with pests. Further, the compound [I] of the present invention and a salt thereof are safe and advantageous as a pest control agent for sanitary use, livestock industry, pets, horticulture, and agriculture, for example, having little phytotoxicity to plants and low toxicity to fish. It also has various properties.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION When a compound [I] or a salt thereof is used as an agrochemical, particularly as an insecticide, one or more of the general forms of agrochemicals, that is, one or more compounds (preferably One or more, three or less) as an active ingredient is dissolved or dispersed in an appropriate liquid carrier as an active ingredient, or mixed or adsorbed with an appropriate solid carrier, and an emulsion, liquid, microemulsion, flowable, oil, Used as wettable powders, powders, granules, fine granules, seed coating agents, smokers, tablets, microcapsules, sprays, EW, ointments, baits and the like. These preparations may be used if necessary, for example, emulsifiers, suspensions,
Spreading agents, penetrants, wetting agents, mucilage agents, stabilizers and the like may be added, and can be prepared by a method known per se.

Examples of the liquid carrier (solvent) used include water, alcohols (eg, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, ethylene glycol, etc.), 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, methyl naphthalene, etc.), halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, etc.), acid amides (eg, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), Solvents such as esters (eg, ethyl acetate, butyl acetate, fatty acid glycerin ester, etc.) and nitriles (eg, acetonitrile, propionitrile, etc.) are suitable, and these are one kind or two or more (preferably one or more, three or less) ) Can be mixed at an appropriate ratio and used as appropriate.

As the solid carrier (diluting / extending agent), vegetable powders (eg, soybean powder, tobacco powder, flour, wood flour, etc.),
Mineral powders (for example, clays such as kaolin, bentonite and acid clay, talcs such as talc powder and lauric powder, silicas such as diatomaceous earth and mica powder), alumina, sulfur powder, activated carbon and the like are used. One type or two or more types (preferably one type or more and three types or less) can be mixed at an appropriate ratio and used as appropriate. 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. Alcohol,
Petroleum jelly, white petrolatum, liquid paraffin, lard, various vegetable oils, lanolin, dehydrated lanolin, hardened oil, resins, etc., or two or more (preferably one or more, three or less), or various surfactants shown below What added the agent etc. is used suitably.

Surfactants used as emulsifiers, spreading agents, penetrants, dispersants and the like include soaps, if necessary,
Polyoxyethylene alkyl aryl ethers (e.g.,
Neugen (trade name), EA 142 (E-A142 (trade name)); manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Nonal (trade name);
Toho Chemical Co., Ltd.], alkyl sulfates [eg, Emar 10 (trade name), Emar 40 (trade name); Kao Corporation
Manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), alkyl sulfonates [eg, Neogen (trade name), Neogen T (trade name);
Neoperex; manufactured by Kao Corporation), polyethylene glycol ethers [eg, Nonipol 85 (trade name), Nonipol 100 (trade name), Nonipol 160 (trade name); manufactured by Sanyo Chemical Co., Ltd.], polyhydric alcohol esters Non-ionic and anionic surfactants such as, for example, Tween 20 (trade name) and Tween 80 (trade name; manufactured by Kao Corporation) are appropriately used. In addition, the compound [I] or a salt thereof and, for example, other kinds of insecticides (pyrethroid insecticides, organophosphorus insecticides, carbamate insecticides, neonicotinoid insecticides, natural insecticides, etc.), acaricides , Nematicides, herbicides, phytohormones, plant growth regulators,
A bactericide (for example, a copper-based bactericide, an organochlorine-based bactericide, an organic sulfur-based bactericide, a phenol-based bactericide, etc.), a synergist, an attractant, a repellent, a pigment, a fertilizer, and the like are appropriately used. It is also possible.

The content of the compound [I] or a salt thereof in the agricultural chemical composition (pesticide) of the present invention is usually about 0.1 to 80% by weight, preferably about 1 to 2% by weight, based on the total amount of the composition.
It is about 0% by weight. Specifically, when used in emulsions, solutions, wettable powders (eg, wettable powders) and the like, it is usually about 1%.
About 80% by weight, preferably about 1-20% by weight. When used in oils, powders and the like, it is usually about 0.1 to 50% by weight, preferably about 0.1 to 20% by weight. When used as granules, it is usually about 5 to 50% by weight, preferably about 1 to 20% by weight. The other pesticidal active ingredients (eg, insecticides, herbicides, acaricides and / or fungicides) incorporated in the pesticidal composition of the present invention are usually about 1 to about the total amount of the preparation.
It is used in an amount of about 80% by weight, preferably about 1 to 20% by weight. The content of additives other than the above active ingredients is
The amount is usually about 0.001 to 99.9% by weight, preferably about 1 to 99% by weight, although it depends on the kind or content of the pesticidal active ingredient or the dosage form of the preparation. More specifically, based on the total amount of the composition, the surfactant is usually about 1 to 20% by weight, preferably about 1 to 15% by weight, the flow aid is about 1 to 20% by weight, and the carrier is about 1 to 20% by weight. It is preferred to add 1 to 90% by weight, preferably about 1 to 70% by weight. Specifically, in the case of producing a liquid preparation, the surfactant is usually added in an amount of about 1 to 20% by weight, preferably 1 to 10% by weight.
Preferably, about 20 to 90% by weight of water is added. Emulsions, wettable powders (eg, granule wettable powders) and the like are appropriately diluted and increased with water or the like (for example, about 100 to
(5,000 times) and spray.

Representative examples of insecticides, acaricides, and fungicides which can be used by mixing with the compound [I] of the present invention or a salt thereof are shown below. EPN (EPN), acephate (acephat)
e), isoxathion, isofenphos, isoprocarb, etrimfos, oxydeprofo
s), quinalphos, cadsaphos (cadus)
afos), chlorethoxyfos, chlorpyrifos, chlorpyrifos-methyl, chlorophenvinphos (chl
orofenvinphos), salithion, cyanophos, disulfoton, dimethoate, sulprofo
s), diazinon, thiometone
on), tetrachlorvinphos,
Tebupirimfos (tebupirimfos), trichlorfon (tr
ichlorphon), nailed (naled), bamidion (vam)
idothion), pyraclophos, pyridafenthion, pyrimiphos-methyl, fenitrothion
ion), fenthion, fentoate (p
henthoate), fosthiazate, butathiofos, prothiofo
s), propaphos, profenophos (prof
enofos), phosalone, phosiaceat (f
osthiazate), marathon (malathion), methidathion (methidathion), metolcarb (metolcarb), monocrotophos, BPMC (BPMC), X
MC (XMC), alanicarb (alanycarb), ethiofencarb (ethiofencarb), carbaryl (carbaryl),
Carbosulfan, carbofuran (car
bofuran), xylylcarb, cloethocarb, thiodicarb,
Triazemate, pirimicarb (pirimi)
carb), phenoxycarb, fenothiocarb, furathioca
rb), propoxur, bendiocarb, benfuracarb, methomil, metrin, acrinathri
n), imiprothrin, ethofenprox, cycloprotrin
hrin), sigma-cypermethr
in), cyhalothrin (cyhalothrin), cyfluthrin (c
yfluthrin), cypermethrin (cypermethrin), silafluofen (silafluofen), tefluthrin (tefluth
rin), deltamethrin (deltamethrin), tralomethrin (tralomethrin), fenvalerate (fenvalerat)
e), fenpropathrin, flucythrinate, fluvali
nate), flufenenoprox, fluproxyfen, flumethrin (flume)
thrin), praletrin (prallethrin), beta-cyfluthrin (beta-cyfluthrin), benfluthrin (benfl
uthrin), permethrin, acetamiprid, imidacloprid
d), cartap, thiocycla
m), nitenpyram, clothianidin (c
lotianidine), tefuranidine, AKD
-1022 (AKD-1022), thiamethoxam (thiomethox)
am), bensultap, avermectin, emamectin benzoate (emamecti)
n-benzoate), clofentezine (clofentezine), chlorfluazuron (chlorfluazuron), cyromazine (cy
romazine), diafenthiuron,
Dienochlor, dichlorvos
os), diflubenzuron (diflubenzuron), spinosyn (spynosyn), sulfuramide (sulfluramid), teflubenzuron (teflubenzuron), tebufenozide (teb)
ufenozide), tebufenpyrad (tebufenpyrad), hydroprene, vaniliprole (vanili)
prole), pymetrozine, pyridaben, pyriproxyfe
n), pyrimidifen, fipronil, fenazaquin, fenpyroximate, fluazuron (fluaz)
uron), flucycloxuron, flufenoxuron, buprofezin (bu
profezin), hexaflumuron (hexaflumuron), hexthiazox (hexythiazox), milbemycin (mil
bemycin), methoxadiazone, lufenuron, levamisol,
Chlorphenapyr, NC-184 (NC
-184), etoxazole, IBP (IB
P), ampropylfos, edifenphos, chlorthiophos
s), tolclofos-methyl, fosetyl, ipconazole,
Imazalil, imibenconazole (imiben)
conazole), etaconazole, epoxiconazole, cyproconazole (c
yproconazole), dicononazole (diniconazole), difenoconazole (difenoconazole), tetraconazole (tetraconazole), tebuconazol (tebuconazol)
e), triadimenol, triadimefon, triticonazol
e), triforine, bitertanol (bi
tertanol), biniconazole (viniconazole), fenarimol (fenarimol), fenbuconazole (fenbucona)
zole), fluotrimazole, fluconazole-cis, fursilazole, flusilazole, flutriafol, bromuconazole, propiconazole, hexaconazol
e), pefurazoate, penconazole, microbutanil (myclobutanil),
Metconazole, carbendazine (cab)
endazin), debacarb, prothiocarb, benomyl, mane
b), TPN (TPN), isoprothiola (isoprothiola)
ne), iprodione, iminoctadine (i
minoctadine-albesil), iminoctadine acetate (imino
ctadine-triacetate), etirimol (ethirimol), etridiazole (etridiazole), oxadixyl (oxa)
dixyl), oxycarboxin, oxolinic acid, offrace (ofurac)
e), kasugamycin, carboxin, captan, clozylacon, clobeniazone (chlobenthiazon)
e), cyprodinil, cyprodinil, cypram
rofuram), dietofencarb, dichlofluanid, dicromedin
lomezine), zineb (zineb), dimethylimole (dimethi)
rimol), dimethomorph, dimefluazole, thiabendazole
azole), thiophenate-methy
l), thifluzamide, tecloftalam, triazoxide, triclamide, tricyclazole
lazole), tridemorph (tridemorph), triflumizole, and validamycin A (validamyci)
n A), hymexazol, pyracarbolid, pyrazophos, pyrifenox, pyrimethanil
l), pyroquilon, ferimzone
zone), fenpiclonil, fenpropidin, fenpropimorph
opimorph), fthalide, furametpyr, furalaxyl, fluazinam, furcarbani
l), fluquinconazole, fludioxonil, flusulfamide (flusu)
lfamide), flutolanil, butiobate, prochloraz, procymidone, probenazole
le), benalaxyl, benodanil (benod)
anil), pencuron (pencycuron), microzoline (myclozolin), metalaxyl (metalaxyl), metsulfovax (metsulfovax), methofloxam (methf)
uroxam), mepanipyrim, mepronil, kresoxim-methy
l), azoxystrobin, SSF-
126 (SSF-126), carpropamid

The preparation containing the compound [I] of the present invention or a salt thereof is specifically exemplified by, for example, Eurydema rugo.
sum), rice stink bug (Scotinophara lurida), stag beetle (Riptortus clavatus), Nashigumbai (Ste
phanitis nashi), Japanese brown planthopper (Laodelphax striate)
llus), brown planthopper (Nilaparvata lugens), black leafhopper (Nephotettix cincticeps), mosquitoes (Unaspis yanonensis), soybean aphid (Aphis g
lycines) and Aphid aphid (Lipaphiserysim)
i), radish aphid (Brevicoryne brassicae), cotton aphid (Aphis gossypii), peach peach aphid (M
yzus persicae), Potato beetle aphid (Aulac
orthum solani), Aphis spiraec
ola), whiteflies (Bemisia tabaci), whiteflies (Trialeurodes vaporariorum),
(Sogatella furcifera), Leafhopper (Em
poasca onukii), Pseudococus c
omstocki), the orange scale insect (Planococcus citr)
i), Hemiptera pests such as Icerya purchasi, Icerya purchasi, Platya stali, and Eysarcoris parvus, for example, Spodoptera litura, Plutella xylos
tella), white butterfly (Pieris rapae crucivora), Japanese squid (Chilo supppressalis),
tographa nigrisigna), tobacco moth (Helicoverpa assult)
a), armyworm (Pseudaletia separata), armyworm (Mam
estra brassicae), and the apple snail, Adoxophye
s orana fasciata), Watanomeiga (Notarcha derogat)
a), Coleoptera (Cnaphalocrocis medinalis), Potato moth (Phthorimaea operculella), Aedes aegypti (Chilo polychrysus), Sankameiga (Typoryza incer)
tulas), Japanese armyworm (Spodoptera exigua), Kabulaya (Agrotis segetum), Tamanayaga (Agrotis ipsi)
lon), tobacco moth (Heliothis armigera), tobacco bad worm (Heliothis virescens), ball worm (Heliot
his zea), Naranga aenescens, European corn borer (Ostrinia nubilalis), Atomeiga (Ostrinia furnacalis), rice beetle (Parnara)
guttata), chanococcus terrestris (Adoxophyes sp.),
Chanohosoga (Caloptilia theivora), Kinmonhosoga
(Phyllonorycter ringoneella), peach sink moth (Carpo
sina niponensis)
sta) and other lepidopteran insect pests, for example,
pilachna vigintioctopunc tata), turtle beetle (Aulacop
horafemoralis) and the beetle beetle (Phyllotreta strio)
lata), rice weevil (Oulema oryzae), rice weevil (Echinocnemus squameus), rice weevil (Lissor
hoptrus oryzophilus), Weevil weevil (Anthonomus gr
andis), Callosobruchus chinensis,
Weevil weevil (Sphenophorus venatus), beetle
(Popillia japonica), Douganebuui (Anomala cupr)
ea), corn rootworm (Diabrotica spp.), Colorado potato beetle (Leptinotarsa decemlineata), click beetle (Agriotes spp.), tobacco beetle (Lasiod
erma serricorne) and the beetle beetle (Anthrenus)
verbasci) and Tribolium castaneu
m), fly bark beetle (Lyctus brunneus), stalk beetle (Anoplophora malasiaca), pine bark beetle (To
beetles such as housefly (Muscpiniperda)
a domestica), Culex pipiens (Culex popiens pallens),
Bullflies (Tabanus trigonus), onions (Delia ant
iqua), flies (Delia platura),
pheles sinensis) and rice leaf fly (Agromyza oryza)
e), rice leaf fly (Hydrellia griseola), rice leaf fly (Chlorops oryzae), rice fly (Dacus cu
curbitae), medfly (Ceratitis capitat)
a), dipteran pests such as the beetle leaf fly (Liriomyza trifolii), for example, Tososama locust (Locusta migratoria), Kera (Gryllotalpa africana), Oxya yezoen
sis), Orthoptera (Oxya japonica) and other Orthoptera pests, for example, Thrips tabaci, Thrips palmi (Thrips parmi), Citrus yellow thrips (Frankliniella occidentalis), Rice thrips (Bal
iothrips biformis) and Thrips palmi (Scirtot
hrips dorsalis)
(Athalia rosae) and other hymenopteran pests such as German cockroaches (Blattella germanica) and black cockroaches (Periplanet)
a fuliginosa) and the cockroach (Periplaneta japonic)
a), cockroaches (Periplaneta americana) and other cockroach family pests such as the spider mite (Tetranychus urtica)
e), red mite (Panonychus citri), red mite
(Tetranychus kanzawai)
cinnabarinus), apple spider mite (Panonychus ulmi), citrus red mite (Aculops pelekassi),
(Polyphagotarsonemus latus), spider mite (Rhizoglyphus e
chinopus) and other mite pests, for example, rice squirrel nematode (Aphelenchoides besseyi), sweet potato nematode (Meloidogyne incognita), Kitanegusuresuto (Pratylenchus penetrans), strawberry messenger (N
othotylenchus acris) and other nematodes, termites (Copto
termesformosanus), termites (Reticulitermes s)
peratus), Japanese termite (Odontotermes formosanu)
s), and particularly effective in controlling pests such as termites such as termites (Cryptotermes domesticus).

The preparation containing the compound [I] or a salt thereof of the present invention can be used in the field of veterinary disease treatment and the livestock industry, and in vertebrates such as humans, cattle, sheep, goats,
It can be used to control arthropods and parasites that are internal and / or external to pigs, poultry, dogs, cats, fish, etc., and maintain public health. For example, among the parasites, ticks (Ixodes spp.), Bovine ticks (Boophilus spp.)
p. (eg, Boophilus microplus)),
Acarly ticks (Amblyomma spp.), Ibo ticks (H
yalomma spp.), Rhipicephalus spp.
(Eg Rhipicephalus appendiculatus), tick mites (Haemaphysalis spp.), Ticks (dermacentor)
spp.), Ornithodoros spp. (eg Orn
ithodoros moubata)), Wandering spider (Dermahyssus gallina)
e), Dermatophagoids (Sarcoptes spp. (eg, Sarcoptes scabiei)), Dermatophagoids (Psoroptes spp.), Dermatophagoides (Chorio)
ptes spp.), Demodex mites (Demodex spp.), tsutsugamushi (Eutrombicula spp.), Aedes (Aedes sp.)
p.), Anopheles spp., House flies (Musca spp.), Bullflies (Hypoderma spp.), Flies (Gasterophilus spp.), Blackflies (Simulium)
spp.), green turtles (Triatoma spp.), lice (Phth
iraptera (e.g., Damalinia spp., Linognathus sp.
p.)), fleas (Ctenocephalides spp.), house ants (monomorium pharaonis) and nematodes [eg, ciliate nematodes (eg, Nippostrongylus brasiliensis, Trichost)
rongylus axei, Trichostrongylus colubriformis),
Trichinella spiralis (e.g., Trichinella spiralis), torsion stomach (Haemonchuscontortus), nematozils (e.g., N
ematodirus battus, Ostertag
a circumcincta), couperias (Cooperia spp.),
Dwarf tapeworm (Hymenolepis nana)].

The pesticidal composition containing the compound [I] of the present invention or a salt thereof has excellent insecticidal activity, has very low toxicity, is safe, and can be used as an excellent pesticidal composition (pesticide). . And the pesticidal composition of the present invention can be used in the same manner as the conventional pesticidal composition, and as a result, it can exhibit more excellent effects than conventional products.
For example, the pesticidal composition of the present invention is 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 exterminated by contacting or ingesting the above-mentioned pests (such as pests). Can be. In another embodiment, for example, the arthropod or parasite parasitic on the vertebrate is controlled by administering the pesticidal composition of the present invention to the inside (in the body) or the outside (body surface) of the vertebrate. Can be. More specifically, for example, the pesticidal composition of the present invention is used for treating a target pest with, for example, seed treatment, nursery box treatment, planting hole treatment, root plant treatment, soil mixing treatment, foliage spraying, stem injection, poison breeding. It can be used for smoke, irrigation, underwater application in paddy fields, etc. The application rate can be varied in a wide range according to the application time, application place, application method, etc., but generally about 0.3 g to 3 g of active ingredient (compound [I] or its salt) per hectare. It is desirable that the application be such that the weight is 5,000 g, preferably about 50 g to 1,000 g. When the pesticidal composition of the present invention is a wettable powder, the final concentration of the active ingredient is about 0.1 to 1,000.
It may be used after being diluted so as to be in the range of preferably 10 to 500 ppm.

[0045]

Next, the present invention will be described in more detail with reference to Reference Examples, Examples and Test Examples. Elution in column chromatography in Examples and Reference Examples was performed by TLC
(Thin Layer Chromatography). In TLC observation,
Kieselgel 60F254 (70-230 mesh) manufactured by Merck was used as a TLC plate, a solvent used as an elution solvent in column chromatography was used as a developing solvent, and a UV detector was used as a detection method. Silica gel for column is Kieselgel 6 also manufactured by Merck
0 (70-230 mesh) was used. The NMR spectrum shows proton NMR, using Bruker AC-200P (200 MHz) using tetramethylsilane as an internal standard.
It was measured with a mold spectrometer, and all δ values were shown in ppm. When a mixed solvent is used as the developing solvent, the numerical values shown in parentheses are the volume mixing ratios of the respective solvents. The abbreviations used in the following Examples, Reference Examples and Tables have the following meanings. Me: methyl group, Et: ethyl group, Ph: phenyl group, Pr-n (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 t-Bu): tert-butyl, s: singlet,
br: broad (broad), brs: broad singlet (broad singlet), d: doublet, t: triplet, q: quartet, qu: quintet (quintuple), sep: septet (seventuple), m: multiplet , Dd: double doublet, dt: double triplet, J: coupling constant, Hz: hertz,
%: Weight%, mp: melting point, room temperature is about 15 to 2
Means 5 ° C.

[0046]

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.
g (14.8 mmol) of 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-3- (Δ 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 ℃

[0049]

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)

[0050]

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).
Recrystallized 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)

[0051]

Example 1 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)

[0052]

Example 2 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)

[0053]

Example 3 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)

[0054]

Example 4 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)

[0055]

EXAMPLE 5 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,
2,4-oxadiazolin-3-yl) -4-trifluoromethylsulfinylpyrazole 300 mg (0.557 mmol)
A solution of 5 ml of THF was added dropwise over 5 minutes under ice cooling, and the mixture was stirred 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 = 7Hz), 1.19 (3H, t, J = 7H
z), 3.30 (4H, q, J = 7Hz), 4.08 (2H, m), 5.48 (1H, d, J = 1H
z), 5.55 (1H, d, J = 1Hz), 7.72 (2H, m), 8.58 (1H, s)

[0056]

Example 6 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. 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)

[0057]

Example 7 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) in 15 ml of acetonitrile, 0.8 ml (11 mmol) of a 37% aqueous solution of formalin, acetic acid 3
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 washed three times with 40 ml of a saturated aqueous sodium bicarbonate 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)

[0058]

Example 8 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)

[0059]

Example 9 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. It 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)

[0060]

Example 10 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)

[0061]

Example 11 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. It 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)

[0062]

Example 12 5-Amino-1- (2,6-dichloro-
4-trifluoromethylphenyl) -3- {4- (N,
N- diethylcarbamoyl) - [delta ^{2-1,2,4-oxadiazolin-3-yl}} -4-trifluoromethyl methylsulfinyl pyrazole carbonate bistrichloromethyl (BTC) 113mg (0.38mmol) was dissolved 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)

[0063]

Example 13 1- (2,6-Dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-diethylcarbamoyl) -Δ 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 = 7H
2. z), 1.23 (3H, t, J = 6 Hz),
27 (4H, q, J = 7 Hz), 4.16 (2H,
q, J = 6 Hz), 5.64 (2H, s), 7.
74 (2H, s), 8.04 (1H, s)

[0064]

Example 14 1- (2,6-Dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl) -Δ 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) was dissolved in 5 ml of THF and added dropwise, followed by stirring 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)

[0065]

Example 15 1- (2,6-Dichloro-4-trifluoromethylphenyl) -3- {4- (N-ethyl-N-
Methylcarbamoyl) -Δ ² -1,2,4-oxadiazolin-3-yl} -5-ethoxymethyleneamino-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)

[0066]

Example 16 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. NMR (CDCl ₃ , δ) 0.82 (3H, t, J = 7H)
z), 1.14 (6H, t, J = 7 Hz), 1.
58 (2H, m), 3.30 (4H, q, J = 7H
z), 3.99 (2H, m), 5.48 (1
H, d, J = 1 Hz), 5.55 (1H, d, J =
1 Hz), 7.72 (2H, m), 8.61
(1H, s)

[0067]

Example 17 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 mmol
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 ℃ 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)

[0068]

Example 18 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.
After the reaction solution was concentrated under reduced pressure, it was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 4: 1), and 485
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)

[0069]

Example 19 1- (2,6-Dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-diethylcarbamoyl) -Δ ² -1,2,4-oxadiazoline-3 -Yl} -5-dimethylaminomethyleneamino-4
-Trifluoromethylsulfinyl pyrazole 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. Then, after stirring for 30 minutes under ice-cooling and for 12 hours at room temperature, 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 ℃ NMR (CDCl 3, δ} ) 1.14 (6H, t, J = 7.2H
z), 2.78 (3H, s), 3.07 (3
H, s), 3.30 (4H, q, J = 7 Hz),
5.47 (1H, d, J = 1 Hz), 5.54
(1H, d, J = 1 Hz,), 7.66-7.71
(2H, m), 8.65 (s, 1H)

[0070]

Example 20 1- (2,6-Dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl) -Δ 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)-
Delta ^{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)

[0071]

Example 21 1- (2,6-Dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl) -Δ 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)

[0072]

Example 22 1- (2,6-Dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl) -Δ 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)

[0073]

Example 23 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)

[0074]

Example 24 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 give 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)

[0075]

Example 25 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, 100 mg of 3-chloroperbenzoic acid (mCPBA) (0.579 m
mol) in dichloromethane (5 ml) was added dropwise, and the mixture was stirred under ice cooling for 18 hours. 10 ml of saturated aqueous sodium hydrogen carbonate solution was added to the reaction 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 Examples 1 to 25 are shown in Tables 1 to 36 below, including the compounds obtained in the above Examples.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

[Table 4]

[0081]

[Table 5]

[0082]

[Table 6]

[0083]

[Table 7]

[0084]

[Table 8]

[0085]

[Table 9]

[0086]

[Table 10]

[0087]

[Table 11]

[0088]

[Table 12]

[0089]

[Table 13]

[0090]

[Table 14]

[0091]

[Table 15]

[0092]

[Table 16]

[0093]

[Table 17]

[0094]

[Table 18]

[0095]

[Table 19]

[0096]

[Table 20]

[0097]

[Table 21]

[0098]

[Table 22]

[0099]

[Table 23]

[0100]

[Table 24]

[0101]

[Table 25]

[0102]

[Table 26]

[0103]

[Table 27]

[0104]

[Table 28]

[0105]

[Table 29]

[0106]

[Table 30]

[0107]

[Table 31]

[0108]

[Table 32]

[0109]

[Table 33]

[0110]

[Table 34]

[0111]

[Table 35]

[0112]

[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 (CD
Cl ₃ , δ) 1.17 (6H, t, J = 7Hz), 1.90 (6H, d, J = 6Hz), 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)

[0114]

Example 26 Compound no. 1-5 (20% by weight), xylene (75% by weight), and polyoxyethylene glycol ether (Nonipol 85 (trade name)) (5% by weight) are mixed well to prepare an emulsion.

[0115]

Example 27 Compound no. 1-5 (30% by weight), sodium lignin sulfonate (5% by weight), polyoxyethylene glycol ether (Nonipol 85 (trade name)) (5% by weight), white carbon (30% by weight), clay (30% by weight) %) Is mixed well to produce a wettable powder.

[0116]

Example 28 Compound no. 1-5 (3% by weight), white carbon (3% by weight) and clay (94% by weight) are mixed well to produce a powder.

[0117]

Example 29 Compound no. 1-5 (10% by weight), sodium ligninsulfonate (5% by weight), clay (8
5% by weight), well mixed with water, kneaded well, and then granulated and dried to produce granules.

[0118]

Example 30 Compound no. 1-5 (1.275% by weight), Cartap (2.2% by weight), white carbon (0.5% by weight), and clay (96.025% by weight) are mixed well to produce an insecticide powder. .

[0119]

Example 31 Compound no. 1-5 (1.275% by weight), validamycin (0.33% by weight), white carbon (0.5% by weight) and clay (97.895% by weight) are mixed well to produce an insecticide fungicide powder. I do.

[0120]

Example 32 Compound no. 20-11 (5.5% by weight), NK98147TX (polyoxyethylene allyl phenyl ether, calcium salt of alkylbenzene sulfonic acid, mixture of aromatic hydrocarbons (Solvesso 100 (trade name))) (7% by weight), N-methylpyrrolidone (AG
SOREX1 (brand name)) (87.5%)
An emulsion was prepared.

[0121]

Example 33 Compound no. 20-11 (5.5% by weight), polyoxyethylene alkyl allyl ether (Neugen EA177 (trade name)) (2% by weight), silica
Alumina mixture (Aerosil COK84 (trade name))
(2% by weight), xanthan gum (Roadpol 23 (trade name)) (0.1% by weight), ethylene glycol (7% by weight), silicone emulsion defoamer (Antihome E-
20) (0.2% by weight), butyl paraben (0.1% by weight), ion-exchanged water (83.1% by weight),
A flowable agent was manufactured.

[0122]

[Test Example 1] Insecticidal effect on rice borer (Chilosuppressalis) The test compound (of the compound obtained in the above example) was applied to the foliage of rice seedlings of 2-3 leaf stage (6/7 plants / planted) grown in a nursery box. No.) 5 mg of tween 20
Dissolve in 0.5 ml of acetone containing (trade name)
20 ml / pot was sprayed with a spray gun to a predetermined concentration (100 ppm) with 00-fold diluted dyne water. After the drug solution dries, put the rice seedlings in test tubes (φ: 3cm, h: 20c
m) together with tap water (5 ml), 10 larvae of the third instar larvae of the larva were released and placed in an incubator (27 ° C.). The mortality was calculated by the following formula, and the degree of damage to rice seedlings was determined according to the following criteria. The results are shown in [Table 37]. Mortality rate (%) = (number of dead insects / number of test insects) × 100 Damage degree 0: Almost no damage is observed 1: Very slight (about 1/10 or less of untreated area) damage is observed 2: Less than about 1/2 of the untreated section is observed. 3: More than about 1/2 of the untreated section is observed. 4: The same level of damage as the untreated section is observed.

[Table 37] Comp. No. Mortality (%) Degree of damage 1-2 100 0 1-5 100 0 1-7 100 0 1-26 100 0 2-5 100 0 2-8 100 0 3-5 100 0 4-4 100 0 4-5 100 0 4-6 100 0 5-5 100 0 6-5 100 07-4 100 100 7-7 100 100 7-6 100 0 8-4 100 0 8-5 100 0 8-6 100 0 9-5 100 0 10-5 100 0 11-5 100 0 11-26 100 0 12-5 100 0 13-5 100 0 14-5 100 0 15-5 100 0 16-5 100 0 17-26 100 0 18-5 100 0 20-2 100 0 20-4 100 0 20-5 100 0 20-6 100 0 20-7 100 0 20-10 100 0 20-11 100 0 20-12 100 0 20-13 100 0 20-14 100 0 20-15 100 0 20-25 100 0 20-26 100 0 20-27 100 0 21-4 100 0 21-5 100 0 21-6 100 0 21-7 100 0 21-8 100 0 21-9 100 0 21-10 100 0 21-11 100 0 21-12 100 0 21-13 100 0 21-14 100 0 21-15 100 0 21-25 100 0 21-26 100 0 21-27 100 0 22-4 100 0 22-5 100 0 22-6 100 0 22-10 100 0 22-11 100 0 22-12 100 0 22-13 100 0 22-14 100 0 22-15 100 0 22-26 100 0 22-27 100 0 23-27 100 0 24-5 100 0 24- 27 100 0 26-26 100 0 27-2 100 0 27-4 100 0 27-5 100 0 27-6 100 0 27-8 100 0 27-11 100 0 27-16 100 0 27-17 100 0 27- 18 100 0 27-20 100 0 27-23 100 0 27-26 100 0 28-8 100 0 28-11 100 0 28-14 100 0 28-17 100 0 28-20 100 0 28-23 100 0 28- 26 100 0 29-2 100 0 29-5 100 0 29-8 100 0 29-11 100 0 29-14 100 0 29-17 100 0 29-20 100 0 29-23 100 0 29-26 100 0 30- 2 100 0 30-5 100 0 30-8 100 0 30-11 100 0 30-14 100 0 30-17 100 0 30-20 100 0 30-23 100 0 30-26 100 0 31-2 100 0 31-10 100 0 31-11 100 0 31-12 100 0 31-13 100 0 31-14 100 0 31-15 100 0 31-16 100 0 31-17 100 0 31-18 100 0 31-19 100 0 32-2 100 0 32-5 100 0 32-8 100 0 32-11 100 0 32-14 100 0 32-17 100 0 32-20 100 0 32-23 100 0 32-26 100 0 33-2 100 0 33-5 100 0 33-8 100 0 33-11 100 0 33-14 100 0 33-17 100 0 33-20 100 0 33-24 100 0 34-2 100 0 34-5 100 0 4-8 from 100 0 34-10 100 0 34-11 100 0 34-12 100 0 35-1 100 0 35-2 100 0 35-3 100 0 Table 37], compound [I] of the present invention is excellent It was found to be an excellent compound having an insecticidal action and having no harm to food.

[0124]

The compound [I] (oxadiazoline derivative) of the present invention or a salt thereof has excellent insecticidal activity and extremely low fish toxicity. Therefore, an agricultural chemical (pesticide) containing the compound [I] of the present invention or a salt thereof is
It can protect agricultural products from pests and contribute to the development of agriculture.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Atsuo Akayama 2-3-3 Higashi, Tsukuba-shi, Ibaraki Prefecture, No. 202 Lissiell Tsukuba 202 72) Inventor Toshiyuki Kiji 3-12-1, Matsushiro, Tsukuba, Ibaraki Prefecture Takeda Matsushiro Residence 308 F-term (Reference) 4C063 AA01 AA03 BB01 CC58 DD04 DD22 EE03 4H011 AC01 AC02 AC03 AC04 BA01 BB10 BC01 BC03 BC07 BC18 BC20 DA02 DA14 DA15 DA16 DD03 DE16 DG05

Claims (18)

[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 with 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 An optionally substituted acyl group, R ⁸ is
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 Or a salt thereof. 2. The compound according to claim 1, wherein R ¹ is a trifluoromethyl group, or a salt thereof. 3. X is -NR ² R ³ (R ² and R ³ each represent a hydrogen atom or a C _1-6 alkyl group) or -N =
The compound according to claim 1, which is CHOR ⁴ (R ⁴ represents a C _1-6 alkyl group) or a salt thereof. Wherein X is -NH ₂ or -N = CHOR ⁴ (R ⁴
_{Represents a} C _1-6 alkyl group) or a salt thereof. ^5. The compound according to claim 1, wherein R ⁵ is an optionally substituted carbamoyl group, or a salt thereof. 6. R ⁵ is (1) a C _1-6 alkyl group optionally substituted with 1 to 3 C _1-6 alkoxy, and (2) (i) 1 or 2 C _1-6 alkyl groups. Optionally substituted amino, (ii)
C _1-6 alkoxy, (iii) C _2-10 alkanoyl group optionally substituted by 1 to 3 substituents selected from phenyl and (iv) halogen atom, (3) C _4-10 cycloalkanoyl group It is substituted with (4) C _3-10 alkenylcarbonyl group, (5) a benzoyl group, (6) (i) phenyl, halogen and C _1-6 alkyl with a substituent selected from amino group which may be substituted C _1-6 alkyl, (ii) C _3-9 cycloalkyl, (iii) C _2-6 alkenyl, (iv) C _2-6 alkynyl, (v) phenyl, (vi) C _1-6 Amino optionally substituted by 1 or 2 alkyl, (vii) cyclic amino, (vii
i) a carbamoyl group optionally substituted by one or two substituents selected from hydroxyl and (ix) C _1-6 alkoxy, (7) cyclic amino-carbonyl group, (8) C _1-6 alkoxy-carbonyl The compound according to claim 1, which is a group or a (9) formyl group, or a salt thereof. 7. The compound according to claim 1, wherein R ⁸ is a trifluoromethyl group, or a salt thereof. (8) A is The compound according to claim 1, which is or a salt thereof. 9. The compound according to claim 1, wherein B is a nitrogen atom, or a salt thereof. 10. wherein X is -NR ² R ³ (R ² and R ³ each represent a hydrogen atom or a C _1-6 alkyl group), - N = C
HOR ⁴ (R ⁴ represents a C _1-6 alkyl group) or -N =
CHNR ⁶ R ⁷ (R ⁶ and R ⁷ each represent a hydrogen atom or a C _1-6 alkyl group), R ⁸ represents a trifluoromethyl group, and A represents And the compound or a salt thereof according to claim 1, wherein B represents a nitrogen atom. 11. X is --NR ² R ³ (R ² and R ³ each represent a hydrogen atom or a C _1-6 alkyl group) or --N
The compound according to claim 10, wherein ＝ CHOR ⁴ (R ⁴ represents a C _1-6 alkyl group) or a salt thereof. 12. A 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl) -Δ ² -1,2,4-oxadiazoline-3 -Yl} -5-isopropoxymethyleneamino-4
The compound according to claim 1, which is -trifluoromethylsulfinylpyrazole or a salt thereof, or a salt thereof. 13. A 1- (2,6-dichloro-4-trifluoromethylphenyl) -3- {4- (N, N-dimethylcarbamoyl) -Δ ² -1,2,4-oxadiazoline-3 The compound according to claim 1, which is -yl} -5-ethoxymethyleneamino-4-trifluoromethylsulfinylpyrazole or a salt thereof. 14. A 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-
3- {4- (morpholinocarbonyl) -Δ ² -1,2,
The compound according to claim 1, which is 4-oxadiazolin-3-yl} -4-trifluoromethylsulfinylpyrazole or a salt thereof, or a salt thereof. 15. A 1- (2,6-dichloro-4-trifluoromethylphenyl) -5-ethoxymethyleneamino-
3 or a salt thereof according to claim 1, which is a {4-isobutyryl - [delta ^{2-1,2,4-oxadiazolin-3-yl}} -4-trifluoromethyl methylsulfinyl pyrazole. 16. An agricultural chemical comprising the compound according to claim 1 or a salt thereof. 17. The pesticide according to claim 16, wherein the pesticide is an insecticide. 18. Use of the compound according to claim 1 or a salt thereof as an insecticide.