JP2001354659A - New pyrazoline derivative, method for producing the same and pest controlling agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new pyrazoline derivative capable of exhibiting excellent pest controlling effects, low toxicity and low residual properties and a pest controlling agent comprising the pyrazoline derivative. SOLUTION: This new pyrazoline derivative is a compound represented by the following formula (I) specifically, e.g. 4-[4-(4-chlorophenoxy) phenylimino]-1,3-dimethyl-2-pyrazolin-5-one).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel 4- (phenoxy or phenylthio-substituted phenylimino) pyrazolin derivative, a method for producing the same, and a pesticidal agent containing the pyrazoline derivative as an active ingredient.

[0002]

2. Description of the Related Art In recent years, pests have gained resistance due to the long-term use of pesticides, making it difficult to control with conventional pesticides. In addition, some pesticides are highly toxic to humans, and some are disturbing ecosystems due to persistence. Therefore, there is still a need for the development of a new pesticide with low toxicity and low residue.

Hitherto, 4-substituted phenyliminopyrazoline derivatives have been described as bactericides in JP-A-62-28186, and 4-alkylamino-substituted phenyliminopyrazoline derivatives have been described in JP-A-Showa. 63-1151, JP-A-9-30135, JP-A-9
JP-A-31346, JP-A-10-86535, and JP-A-10-62978 each describe a photosensitive material.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have intensively searched for a compound which shows an excellent pest control effect, and has a low toxicity and a low residual property, and has found a group of novel 4-substituted phenyliminopyra. It has been found that zoline derivatives have such an activity. In addition, in each of the above-mentioned publications, it is needless to say that there is no description of these novel compounds themselves, and a description showing the relationship between the conventionally known 4-substituted phenyliminopyrazoline derivatives and pest control activity, Or,
There is no statement suggesting that. Therefore, the object of the present invention is to
Provided is a novel compound which exhibits an excellent pest control effect, has low toxicity to humans and has low residual properties, a method for producing the same, and a pesticide containing the novel compound as an active ingredient. It is in.

[0005]

According to the present invention, there is provided a compound of formula (I):

Embedded image [Wherein, R ¹ and R ² each independently represent a hydrogen atom,
An alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a cyanoalkyl group having 1 to 4 carbon atoms in the alkyl portion, A hydroxyalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 1 to 4 carbon atoms in the alkoxy portion and 1 to 4 carbon atoms in the alkyl portion, and 1 to 4 carbon atoms in the alkylthio portion having carbon atoms in the alkyl portion; An alkylthioalkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms in the alkoxy portion, and 1 to 4 carbon atoms in the alkyl portion.
4 alkoxycarbonylalkyl group, an alkoxy moiety having 1 to 4 carbon atoms and an alkyl moiety having 1 to 4 carbon atoms, an alkyl moiety having 1 to 4 carbon atoms, an aminocarbonylalkyl group and an alkylamino moiety Has 1 to 4 carbon atoms and the alkyl portion has 1 to
4 alkylaminocarbonylalkyl groups, wherein the carbon number of each alkyl moiety in the dialkylamino moiety is independently 1 to 4, and the carbon number of the alkyl moiety in the carbonylalkyl moiety is 1 to 4; An oxiranylalkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted, a benzyl group which may be substituted, or a heterocyclic group which may be substituted; An oxygen atom or a sulfur atom; and R ³ , R ⁴ , R ⁵ , R ⁶ , R
⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are each independently
A hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms,
A haloalkyl group having 1 to 4 carbon atoms, a nitro group, a cyano group,
An alkoxy group having 1 to 4 carbon atoms or an alkylthio group having 1 to 4 carbon atoms], or a salt thereof.

Further, the present invention provides a compound of the formula (II):

Embedded image [Wherein, R ¹ and R ² each independently represent a hydrogen atom,
An alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a cyanoalkyl group having 1 to 4 carbon atoms in the alkyl portion, A hydroxyalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 1 to 4 carbon atoms in the alkoxy portion and 1 to 4 carbon atoms in the alkyl portion, and 1 to 4 carbon atoms in the alkylthio portion having carbon atoms in the alkyl portion; An alkylthioalkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms in the alkoxy portion, and 1 to 4 carbon atoms in the alkyl portion.
4 alkoxycarbonylalkyl group, an alkoxy moiety having 1 to 4 carbon atoms and an alkyl moiety having 1 to 4 carbon atoms, an alkyl moiety having 1 to 4 carbon atoms, an aminocarbonylalkyl group and an alkylamino moiety Has 1 to 4 carbon atoms and the alkyl portion has 1 to
4 alkylaminocarbonylalkyl groups, wherein the carbon number of each alkyl moiety in the dialkylamino moiety is independently 1 to 4, and the carbon number of the alkyl moiety in the carbonylalkyl moiety is 1 to 4; An oxiranylalkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted, a benzyl group which may be substituted, or a heterocyclic group which may be substituted; ¹ and X ² are independently the same or different halogen atoms] and a compound represented by the formula (III):

Embedded image Wherein Z is an oxygen atom or a sulfur atom; and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are each independently , Hydrogen atom, halogen atom,
An alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms]. And a reaction in the presence of a base, wherein the pyrazoline derivative is represented by the formula (I). Further, the present invention relates to a pesticidal composition comprising the pyrazoline derivative represented by the formula (I) or a salt thereof as an active ingredient.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The radicals R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
Specific substituents included in the substituents defined for R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ include the following substituents. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, and s.
-Butyl group or t-butyl group.
Examples of the alkenyl group having 2 to 4 carbon atoms include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group,
1-butenyl group, 2-butenyl group, 3-butenyl group, 1
-Methyl-1-propenyl group, 2-methyl-1-propenyl group, 1-methylallyl group, or 2-methylallyl group. Examples of the alkynyl group having 2 to 4 carbon atoms include an ethynyl group, a 1-propynyl group,
Propynyl group, 1-butynyl group, 2-butynyl group, 3-
Examples thereof include a butynyl group and a 1-methyl-2-propynyl group.

The haloalkyl group having 1 to 4 carbon atoms includes
1 carbon atom substituted by 1 or more halogen atoms
When each of the alkyl groups is a substituted or unsubstituted alkyl group, the halogen atoms may be the same or different. Examples of the haloalkyl group having 1 to 4 carbon atoms include a trifluoromethyl group,
Examples include a chloromethyl group, a dichloromethyl group, a trichloromethyl group, and a chlorodifluoromethyl group. In addition, as a halogen atom, for example, a chlorine atom,
Examples thereof include a bromine atom, a fluorine atom, and an iodine atom.

As the cyanoalkyl group having 1 to 4 carbon atoms, a cyanoalkyl group substituted with 1 or more cyano groups may be used.
There is no particular limitation on the alkyl group, as long as it is an alkyl group of 4 to 4, and examples thereof include a cyanomethyl group and a cyanoethyl group. The hydroxyalkyl group having 1 to 4 carbon atoms is not particularly limited as long as it is an alkyl group having 1 to 4 carbon atoms and substituted with one or more hydroxyl groups. For example, a hydroxymethyl group or hydroxyethyl Groups.

The alkoxyalkyl group having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety is not limited to these, but includes, for example, methoxymethyl, methoxyethyl, ethoxy and the like. Examples thereof include a methyl group and an ethoxyethyl group. The alkylthio moiety has 1 to 4 carbon atoms and the alkyl moiety has 1 to 4 carbon atoms.
Examples of the alkylthioalkyl group 4 include, but are not limited to, a methylthiomethyl group.

The alkoxycarbonyl group having 1 to 4 carbon atoms in the alkoxy moiety is not limited thereto, but includes, for example, a methoxycarbonyl group. Examples of the hydroxycarbonylalkyl group having 1 to 4 carbon atoms in the alkyl portion include, but are not limited to, a hydroxycarbonylmethyl group and a hydroxycarbonylethyl group.
Examples of the alkoxycarbonylalkyl group having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety include, but are not limited to, for example, a methoxycarbonylmethyl group, a methoxycarbonylethyl group,
An ethoxycarbonylmethyl group or an ethoxycarbonylethyl group can be mentioned.

The aminocarbonylalkyl group having 1 to 4 carbon atoms in the alkyl moiety is not limited thereto, but includes, for example, an aminocarbonylmethyl group or an aminocarbonylethyl group. Examples of the alkylaminocarbonylalkyl group having 1 to 4 carbon atoms in the alkylamino moiety and 1 to 4 carbon atoms in the alkyl moiety include, but are not limited to, for example, a methylaminocarbonylmethyl group or an ethylaminocarbonyl A methyl group can be mentioned. The carbon number of each alkyl moiety in the dialkylamino moiety is independently 1
Examples of the dialkylaminocarbonylalkyl group having 1 to 4 carbon atoms of the alkyl portion in the carbonylalkyl portion include, but are not limited to, a dimethylaminocarbonylmethyl group or a diethylaminocarbonylmethyl group. Can be.

The oxiranylalkyl group having 1 to 4 carbon atoms in the alkyl portion is not limited thereto, but includes, for example, an oxiranylmethyl group or an oxiranylethyl group.

"A phenyl group which may be substituted"
The term means an unsubstituted phenyl group or a phenyl group which may be substituted with one or more same or different substituents. Similarly, "a benzyl group which may be substituted" refers to an unsubstituted benzyl group, or
A benzyl group which may be substituted with one or more same or different substituents.

The substituent in the phenyl or benzyl group which may be substituted includes a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom or an iodine atom), a cyano group, a nitro group, a hydroxyl group, Carbon number 1
To 4 alkyl groups (e.g., methyl group, ethyl group, n-
Propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, or t-butyl group),
4, an alkoxy group (for example, a methoxy group or an ethoxy group), a dioxyalkylene group having 1 to 4 carbon atoms [for example,
A dioxymethylene group (together with a benzene ring,
A 2-methylenedioxybenzene, or a dioxyethylene group (together with a benzene ring,
-Benzodioxane), an alkylthio group having 1 to 4 carbon atoms (for example, a methylthio group or an ethylthio group), an acyloxy group having 2 to 4 carbon atoms (for example, an acetoxy group or a propionyloxy group), and having 1 carbon atom To 4 haloalkyl groups (for example, chloromethyl group, dichloromethyl group, trichloromethyl group, trifluoromethyl group, dichlorofluoromethyl group, or chlorodifluoromethyl group); Fluoromethoxy group), a haloalkylthio group having 1 to 4 carbon atoms (for example, trifluoromethylthio group), and a group selected from the group consisting of a phenyl group.

"Heterocyclic group which may be substituted" means an unsubstituted heterocyclic group or a heterocyclic group which may be substituted with one or more same or different substituents. . The substituent in the optionally substituted heterocyclic group is a halogen atom (for example, a chlorine atom,
Bromine, fluorine, or iodine), nitro,
An alkyl group having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-propyl, i-propyl, n-butyl,
i-butyl group, s-butyl group, or t-butyl group), an alkoxy group having 1 to 4 carbon atoms (for example, methoxy group or ethoxy group), and a haloalkyl group having 1 to 4 carbon atoms (for example, trifluoromethyl Group) means a group selected from the group consisting of:

The "heterocyclic group" in the "optionally substituted heterocyclic group" is a nitrogen atom, an oxygen atom, and / or
Or a 5- to 6-membered saturated or unsaturated cyclic hydrocarbon group having one or more sulfur atoms (hereinafter referred to as a heterocyclic group), or an oxo derivative thereof, or the heterocyclic group or an oxo derivative thereof. It means a benzo-fused heterocycle composed of one or more benzene rings. Examples of the heterocyclic group include the following structural formulas:

Embedded image (Wherein, A is an oxygen atom or a sulfur atom), or 1,1-dioxotetrahydrothien-3-yl.

The groups X ¹ and X ² each independently represent a halogen atom, for example, a chlorine atom, a bromine atom, a fluorine atom,
Or an iodine atom.

The pyrazoline derivative of the present invention has geometric isomers (ie, Z-form and E-form) at the CＣN bond in the 4-imino group of the pyrazolone ring.
The pyrazoline derivative of the present invention includes a Z form, an E form, and a mixture thereof.

The salts of the pyrazoline derivative of the present invention include:
Salts with inorganic or organic acids are included. As the acid addition salt, for example, hydrochloride, sulfate, methanesulfonate, or p-toluenesulfonate, and further, a dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, maleic acid, or fumaric acid And salts with monocarboxylic acids such as acetic acid, propionic acid and butyric acid.

In the preferred pyrazoline derivative of the present invention, R ¹ and R ² in the formula (I) each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a haloalkyl having 1 to 4 carbon atoms. Z is an oxygen atom or a sulfur atom; R ³ , R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or a group having 1 to 1 carbon atoms. 4 alkoxy groups; and
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, The compound is an alkoxy group having 1 to 4 carbon atoms or an alkylthio group having 1 to 4 carbon atoms.

The more preferred pyrazoline derivative of the present invention is
The conductor is represented by R in the formula (I). ¹And R^TwoBut each
Independently of each other, a hydrogen atom or a carbon number of 1 to 4 (more preferably
Is an alkyl group having 1 or 2 carbon atoms; Z is an oxygen atom
Or a sulfur atom (more preferably an oxygen atom);
^Three, R^Four, R^Five, And R⁶Is a hydrogen atom; and
R ⁷, R⁸, R⁹, R^Ten, And R¹¹One substituent in
(More preferably, a substituent bonded to the 4-position) is halogen
An atom (more preferably a chlorine atom);⁷, R⁸, R
⁹, R^Ten, And R¹¹The remaining four substituents in are hydrogen atoms
A compound that is a child.

As typical examples of the pyrazoline derivative represented by the formula (I) according to the present invention, the structures of the compounds represented by the compound numbers 1 to 336 are shown in the following Tables 1 to 3.
In the column of the group “R ^{3 to} R ⁶ ” in Tables 1 to 3, the position and type of the substituent on the benzene ring are described. At this time, the ring carbon atom bonded to the nitrogen atom of the imino group is 1
Rank. Group R ³ to R ^{6 (i.e., R 3, R 4, R} 5, and R ⁶⁾ If all the groups are hydrogen atom, "H"
Notation. When at least one of the groups R ^{3 to} R ⁶ is a substituent other than a hydrogen atom, its position and type are described, and the hydrogen atom is omitted. For example, "2-Cl"
Is that one of the groups R ^{3 to} R ⁶ is a chlorine atom (Cl), the remaining three groups are hydrogen atoms, and the chlorine atom (Cl) is bonded to the 2-position of the benzene ring. To indicate that “3-Cl, 5-Cl” means that two of the groups R ^{3 to} R ⁶ are chlorine atoms (Cl), the remaining two groups are hydrogen atoms, and each chlorine atom (Cl ) Indicates that they are bonded to the 2- and 4-positions of the benzene ring, respectively.

Similarly, the groups "R ^{7 to} R ⁷ " in Tables 1 to 3
^In the column " ¹¹ ", a ring carbon atom bonded to the group Z (that is, an oxygen atom or a sulfur atom) is the 1-position. When all the groups R ^{7 to} R ¹¹ (that is, R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ ) are hydrogen atoms, the group is represented by “H”. When at least one of R ^{7 to} R ¹¹ is a substituent other than a hydrogen atom, its position and type are described, and the hydrogen atom is omitted. For example, "4-Cl"
Is that one of the groups R ^{7 to} R ¹¹ is a chlorine atom (Cl), the remaining three groups are hydrogen atoms, and the chlorine atom (Cl) is bonded to the 4-position of the benzene ring. To indicate that In Tables 1 to 3, "Me" means a methyl group.

Each of the compounds Nos. 1 to 288 shown in Table 1 has the formula (Ia):

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R
⁹ , R ¹⁰ , R ¹¹ and Z have the same meanings as described above).

<< Table 1 >> Numbers R ¹ R ² Z R ³ -R ⁶ R ⁷ -R ¹¹ 1 HHOHH2MeHOHH3MeMeOHH4HMeOHHH5MeMe O 3-Cl, 5-Cl H 6 Me Me O 2-CN H 7 Me Me O 2-NO 2, 5-Cl H 8 Me Me S H H 9 H H O H 2-Cl 10 Me H O H 2 -Cl 11 Me Me O H 2- Cl 12 H Me O H 2-Cl 13 Me Me O 3-Cl, 5-Cl 2-Cl 14 Me Me O 2-NO 2, 5-Cl 2-Cl 15 Me Me O2-CN2-Cl16MeMeSH2-Cl17HHOH3-Cl18MeHOH3-Cl19MeMeOH3-Cl20HMeOH3-Cl21MeMe _{O 2-NO 2, 5-} Cl 3-Cl 22 Me Me O 3-Cl, 5-Cl 3-Cl 23 Me Me O 2-CN 3-Cl 24 M MeSH3-Cl25HHOH4-Cl26MeHOH4-Cl27MeMeOH4-Cl28HMeOH4-Cl29MeMeO2-CN4-Cl30Me Me S H 4-Cl 31 Me Me O 2-NO 2, 5-Cl 4-Cl 32 H H O 3-Cl, 5-Cl 4-Cl 33 Me H O 3-Cl, 5-Cl 4-Cl 34 MeMeO3-Cl, 5-Cl4-Cl35H MeO3-Cl, 5-Cl4-Cl36MeMeS3-Cl, 5-Cl4-Cl37HHOH2-Cl, 4-Cl38MeHOH2-Cl, 4-Cl39MeMeOH2-Cl, 4-Cl40MeMeO2-CN2-Cl, 4-Cl41HMeOH2-Cl, 4-Cl 42 Me Me O 2 -NO 2, 5-Cl 2-Cl, 4-Cl 43 Me Me O 3-Cl, 5-Cl 2-Cl, 4-Cl 44 Me Me S H 2-Cl, 4 -Cl 45 H H O H 3-Cl, 4-Cl 46 Me HO H 3-Cl, 4-Cl 47 Me Me OH 3-Cl, 4-Cl 48 Me Me O 2-CN 3-Cl, 4-Cl 49 H Me OH 3-Cl, 4-Cl _{50 Me Me O 2-NO 2} , 5-Cl 3-Cl, 4-Cl 51 Me Me O 3-Cl, 5-Cl 3-Cl, 4-Cl 52 Me Me S H 3-Cl, 4-Cl 53 HHOH3-Cl, 5-Cl54MeHOH3-Cl, 5-Cl55MeMeOH3-Cl, 5-Cl56HMeOH3-Cl, 5-Cl57MeMe O 2-CN 3-Cl, 5-Cl 58 Me Me O 2-NO 2, 5-Cl 3-Cl, 5-Cl 59 Me Me O 3-Cl, 5-Cl 3-Cl, 5-Cl 60 Me MeSH3-Cl, 5-Cl61HHOH2-Cl, 4-Cl, 6-Cl62MeHOH2-Cl, 4-Cl, 6-Cl63MeMeOH2-Cl , 4-Cl, 6-Cl64HMeOH2-Cl, 4-Cl, 6-Cl65MeMeO2-CN2-Cl , 4-Cl, 6-Cl 66 Me Me O 2-NO 2, 5-Cl 2-Cl, 4-Cl, 6-Cl 67 Me Me S H 2-Cl, 4-Cl, 6-Cl 68 H H O H 2-Br 69 Me H O H 2-Br 70 Me Me O H 2-Br 71 H Me O H 2-Br 72 Me Me O 2-CN 2-Br 73 Me Me O 2-NO 2, 5- Cl2-Br74MeMeSH2-Br75HHOH3-Br76MeHOH3-Br77MeMeOH3-Br78HMeOH3-Br79MeMeO2- CN 3-Br 80 Me Me O 2-NO 2, 5-Cl 3-Br 81 Me Me S H 3-Br 82 H H O H 4-Br 83 Me H O H 4-Br 84 Me Me O H 4- Br 85 H Me O H 4- Br 86 Me Me O 2-CN 4-Br 87 Me Me O 2-NO 2, 5-Cl 4-Br 88 Me Me S H 4-Br 89 H H O H 2-F 90 Me H O H 2-F 91 Me Me O H 2-F 92 H Me O H 2-F 93 Me Me O 2-CN 2-F 94 Me Me O 2-NO 2 , 5-Cl2-F95MeMeSH2-F96HHOH3-F97MeHOH3-F98MeMeOH3-F99HMeOH3-F100MeMe O 2-CN 3-F 101 Me Me O 2-NO 2, 5-Cl 3-F 102 Me Me S H 3-F 103 H H O H 4-F 104 Me H O H 4-F 105 Me Me O H 4-F 106 H Me O H 4-F 107 Me Me O 2-CN 4-F 108 Me Me O 2-NO 2, 5-Cl 4-F 109 Me Me S H 4-F 110 H H O H 2-F, 3-F111MeHOH2-F, 3-F112MeMeOH2-F, 3-F113HMeOH2-F, 3-F114MeMeO2-CN 2-F 3-F 115 Me Me O 2 -NO 2, 5-Cl 2-F, 3-F 116 Me Me S H 2-F, 3-F 117 H H O H 2-F, 4-F 118 Me H O H2-F, 4-F119MeMeOH H2-F, 4-F120HMeOH H2-F, 4-F121MeMeO2-CN2-F, 4-F122MeMeO _{2-NO 2, 5-Cl} 2-F, 4-F 123 Me Me S H 2-F, 4-F 124 H H O H 2-F, 5-F 124 Me H O H 2-F, 5- F125MeMeOH2-F, 5-F126HMeOH2-F, 5-F127MeMeO2-CN2-F, 5-F128MeMeSH2-F, 5- F129HHOH2-F, 6-F130MeHOH2-F, 6-F131MeMeOH2-F, 6-F132HMeOH2-F, 6-F133 Me Me O 2-CN 2- F, 6-F 134 Me Me O 2-NO 2, 5-Cl 2-F, 6-F 135 Me Me SH 2-F, 6-F 136 H HO H 3-F, 4-F 137 Me HO H 3-F, 4-F 138 Me Me OH 3-F, 4-F 139 H Me OH 3-F, 4-F 140 Me Me O 2-CN 3-F, 4-F 141 Me Me O 2-NO 2, 5-Cl 3-F, 4-F 142 Me Me S H 3-F, 4 -F143HHOH3-F, 5-F144MeHOH3-F, 5-F145MeMeOH3-F, 5-F146HMeOH3-F, 5-F 147 Me Me O 2-CN 3 -F, 5-F 148 Me Me O 2-NO 2, 5-Cl 3-F, 5-F 149 Me Me S H 3-F, 5-F 150 H H O H 2-F, 3-F, 4-F151MeHOH2-F, 3-F, 4-F152MeMeOH2-F, 3-F, 4-F153HMeOH2- F, 3-F, 4- F 154 Me Me O 2-CN 2-F, 3-F, 4-F 155 Me Me O 2-NO 2, 5-Cl 2-F, 3 F, 4-F156MeMeSH2-F, 3-F, 4-F157HHOH2-F, 3-F, 5-F158MeHOH2-F, 3-F, 5-F159MeMeOH2-F, 3-F, 5-F160HMeOH2-F, 3-F, 5-F161MeMeO2-CN2-F, 3-F, 5-F 162 Me Me O 2 -NO 2, 5-Cl 2-F, 3-F, 5-F 163 Me Me S H 2-F, 3-F, 5-F 164 H H O H 2-F , 4-F, 5-F165MeHOH2-F, 4-F, 5-F166MeMeOH2-F, 4-F, 5-F167HMeOH2-F, 4 -F, 5-F 168 Me Me O 2-CN 2-F, 4-F, 5-F 169 Me Me O 2-NO 2, 5-Cl 2-F, 4-F, 5-F 170 Me Me SH2-F, 4-F, 5-F171HHOH3-F, 4-F, 5-F172MeHOH3-F, 4-F, 5-F173MeMeOH 3-F, 4-F 5-F 174 H Me O H 3-F, 4-F, 5-F 175 Me Me O 2-CN 3-F, 4-F, 5-F 176 Me Me O 2-NO 2, 5-Cl 3 -F, 4-F, 5- F 177 Me Me S H 3-F, 4-F, 5-F 178 H H O H 2-Cl, 5-CF 3 179 Me H O H 2-Cl, 5- _{CF 3 180 Me Me O H 2} -Cl, 5-CF 3 181 H Me O H 2-Cl, 5-CF 3 182 Me Me O 2-CN 2-Cl, 5-CF 3 183 Me Me O 2-NO _{2, 5-Cl 2-Cl} , 5-CF 3 184 Me Me S H 2-Cl, 5-CF 3 185 H H O H 3-CF 3, 4-Cl 186 Me H O H 3-CF 3, 4 -Cl 187 Me Me O H 3- CF 3, 4-Cl 188 H Me O H 3-CF 3, 4-Cl 189 Me Me O 2-CN 3-CF 3, 4-Cl 190 Me Me O 2-NO _{2, 5-Cl 3-CF} 3, 4-Cl 191 Me Me S H 3-CF 3, 4-Cl 192 H H O H 2-Me 193 e H O H 2-Me 194 Me Me O H 2-Me 195 H Me O H 2-Me 196 Me Me O 2-NO 2, 5-Cl 2-Me 197 Me Me S H 2-Me 198 H H O H 3-Me 199 Me H O H 3-Me 200 Me Me O H 3-Me 201 H Me O H 3-Me 202 Me Me O 2-CN 2-Me 203 Me Me O 2-NO 2, 5-Cl 3-Me204MeMeSH3-Me205HHOH4-Me206MeHOH4-Me207MeMeOH4-Me208HMeOH4-Me209MeMeO2-CN 4-Me 210 Me Me O 2 -NO 2, 5-Cl 4-Me 211 Me Me S H 4-Me 212 H H O H 2-Me, 4-Cl 213 Me H O H 2-Me, 4-Cl 214 MeMeOH2-Me, 4-Cl215HMeOH2-Me, 4-Cl216MeMeSH2-Me, 4-Cl21 7 Me Me O 2-CN 2 -Me, 4-Cl 218 Me Me O 2-NO 2, 5-Cl 2-Me, 4-Cl 219 H H O 3-Cl, 5-Cl 2-Me, 4- Cl220MeHO3-Cl, 5-Cl2-Me, 4-Cl221MeMeO3-Cl, 5-Cl2-Me, 4-Cl222HMeO3-Cl, 5-Cl2- Me, 4-Cl223MeMeO2-CN2-Me, 4-Cl224MeMeS3-Cl, 5-Cl2-Me, 4-Cl225HHOH2-OMe226MeHOH 2-OMe 227 Me Me O H 2-OMe 228 H Me O H 2-OMe 229 Me Me O 2-CN 2-OMe 230 Me Me O 2-NO 2, 5-Cl 2-OMe 231 Me Me S H 2 -OMe 232 HHOH3-OMe233MeMeHOH3-OMe234MeMeOH3OMe235HMeOH3-OMe236MeMeO2-CN3-OMe237Me _{e O 2-NO 2, 5} -Cl 3-OMe 238 Me Me S H 3-OMe 239 H H O H 4-OMe 240 Me H O H 4-OMe 241 Me Me O H 4-OMe 242 H Me O H 4-OMe 243 Me Me O 2 -CN 4-OMe 244 Me Me O 2-NO 2, 5-Cl 4-OMe 245 Me Me S H 4-OMe 246 H H O H 2-SMe 247 Me H O H 2 -SMe 248 Me Me O H 2- SMe 249 H Me O H 2-SMe 250 Me Me O 2-CN 2-SMe 251 Me Me O 2-NO 2, 5-Cl 2-SMe 252 Me Me S H 2- SMe253HHOH3-SMe254MeHOH3-SMe255MeMeOH3-SMe256HMeOH3-SMe257MeMeO2-CN3-SMe258MeMeO2-NO _{2, 5-Cl 3-SMe} 259 Me Me S H3-SMe260HHOH4-SMe261MeMeHOH4-SMe262MeMeOHH4-SMe263HMeOHH4-SMe264MeMeO2-CN4-SMe265MeMeO _{2-NO 2, 5-Cl} 4-SMe 266 Me Me S H 4-SMe 267 H H O H 2-NO 2 268 Me H O H 2-NO 2 269 Me Me O H 2-NO 2 270 H Me O _{H 2-NO 2 271 Me Me} O 2-CN 2-NO 2 272 Me Me O 2-NO 2, 5-Cl 2-NO 2 273 Me Me S H 2-NO 2 274 H H O H 3-NO 2 275 Me H O H 3-NO 2 276 Me Me O H 3-NO 2 277 H Me O H 3-NO 2 278 Me Me O 2-CN 3-NO 2 279 Me Me O 2-NO 2, 5-Cl _{3-NO 2 280 Me Me S} H 3-NO 2 281 H H O H 4-NO 2 282 Me H O H 4 _{NO 2 283 Me Me O H 4} -NO 2 284 H Me O H 4-NO 2 285 Me Me O 3-Cl, 5-Cl 4-NO 2 286 Me Me O 2-CN 4-NO 2 287 Me Me O 2-NO ₂ , 5-Cl 4-NO ₂ 288 Me MeSH 4-NO ₂

Each of the compounds Nos. 289 to 312 shown in Table 2 has the formula (Ib):

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R
⁹ , R ¹⁰ , R ¹¹ and Z have the same meanings as described above).

<< Table 2 >> Number R ¹ R ² Z R ³ -R ⁶ R ⁷ -R ¹¹ 289 HHOHH290MeHOHH291MeMeOHH292292MeOHH293MeMe S H H 294 Me Me O 2 -NO 2, 4-OMe H 295 H H O H 2-Cl 296 Me H O H 2-Cl 297 Me Me O H 2-Cl 298 H Me O H 2-Cl 299 Me Me S H 2-Cl 300 Me Me O 2-NO 2, 4-OMe 2-Cl 301 H H O H 3-Cl 302 Me H O H 3-Cl 303 Me Me O H 3-Cl 304 H Me O H 3-Cl 305 Me Me S H 3-Cl 306 Me Me O 2-NO 2, 4-OMe 3-Cl 307 H H O H 4-Cl 308 Me H O H 4-Cl 309 Me Me O H 4-Cl 310 H Me O H 4-Cl 311 Me Me S H 4-Cl 312 Me Me O 2-NO 2, 4-OMe 4-Cl

Each of the compounds Nos. 313 to 336 shown in Table 3 has the formula (Ic):

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R
⁹ , R ¹⁰ , R ¹¹ and Z have the same meanings as described above).

<< Table 3 >> No. R ¹ R ² Z R ³ -R ⁶ R ⁷ -R ¹¹ 313 HHOOHH314 MeHOHH315 MeMeOHH 316 HMeOHHH317 MeMe S H H 318 Me Me O NO 2, 4-OMe H 319 H H O H 2-Cl 320 Me H O H 2-Cl 321 Me Me O H 2-Cl 322 H Me O H 2-Cl 323 Me Me S H 2-Cl 324 Me Me O NO 2, 4-OMe 2-Cl 325 H H O H 3-Cl 326 Me H O H 3-Cl 327 Me Me O H 3-Cl 328 H Me O H 3-Cl 329 Me Me S H 3-Cl 330 Me Me O NO 2, 4-OMe 3-Cl 331 H H O H 4-Cl 332 Me H O H 4-Cl 333 Me Me O H 4-Cl 334 H Me O H 4 -Cl 335 Me MeSH 4-Cl 336 Me Me ONO ₂ , 4-OMe 4-Cl

The pyrazoline derivative of the present invention is not limited thereto, but can be synthesized, for example, by the production method of the present invention. In the production method of the present invention, the reaction formula (1):

Embedded image(Where R¹, R^Two, R^Three, R^Four, R^Five, R⁶, R⁷, R⁸, R
⁹, R^Ten, R¹¹, X¹, X ^Two, And Z are as defined above
Based on the formula (I)
Synthesizing derivatives. That is, represented by the above formula (II)
4,4-dihalogeno-2-pyrazolin-5-one compound
And a phenoxy-substituted anili represented by the formula (III).
With a phenyl derivative or a phenylthio-substituted aniline derivative
The reaction is performed in the presence of a group.

The base used in the production method of the present invention is not limited to these, but includes, for example, alkali metals (for example, lithium, sodium or potassium) and alkaline earth metals (for example, magnesium). ),
Alkali metal alkoxides (eg, sodium methoxide, sodium ethoxide, or potassium t-butoxide), alkaline earth metal alkoxides (eg, calcium methoxy ethoxide), alkali metal hydrides (eg, sodium hydride) Or potassium hydride), alkali metal carbonates (eg, potassium carbonate or sodium carbonate), alkaline earth metal carbonates (eg, magnesium carbonate or calcium carbonate), alkaline earth metal hydrides (eg, hydrogenation) Calcium), alkali metal organometallic compounds (eg, methyllithium, ethyllithium, butyllithium, sec
-Butyllithium, tert-butyllithium, or benzyllithium), organometallic compounds of alkaline earth metals, organic Grignard reagents (eg, methyl magnesium iodide, ethyl magnesium bromide, or n-butyl magnesium bromide), Organic copper compounds prepared from a monovalent copper salt and an organic metal compound of an alkali metal or an alkaline earth metal or a Grignard reagent, alkali metal amides (for example, lithium diisopropylamide), alkaline earth metal amides, Or organic amines (eg, triethylamine, pyridine, 4-
Dimethylaminopyridine, N, N-dimethylaniline,
Or 1,8-diazabicyclo [5.4.0] undec-
7-ene), and these bases can be used alone or as a mixture of two or more bases.

The solvent which can be used in the reaction step of the production method of the present invention or the purification step of the product obtained by the production method of the present invention is 4,4-dihalogeno represented by the above formula (II). Although it is not particularly limited as long as it is an inert organic solvent that does not react with the -2-pyrazolin-5-one compound and the phenoxy-substituted aniline derivative or the phenylthio-substituted aniline derivative represented by the formula (III), for example, Aromatic hydrocarbons (for example,
Benzene, toluene, xylene, or methylnaphthalene), aliphatic hydrocarbons (eg, pentane, hexane, or heptane), alicyclic hydrocarbons (eg, cyclohexane or methylcyclohexane), chlorinated hydrocarbons (eg, Methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethane, or chlorobenzene), amides (eg, N, N-dimethylformamide, N, N-dimethylacetamide, or N-methyl-2-pyrrolidinone) , Ethers (diethyl ether, dimethoxyethane, diethylene glycol, dimethyl ether, diisopropyl ether, tetrahydrofuran, diglyme, dioxane, or petroleum ether), lower alkanols (eg, methyl alcohol, ethyl alcohol 1-methyl alcohol, or 1,1-dimethylethyl alcohol), water, carbon disulfide, acetonitrile, nitromethane, ethyl acetate, acetic acid, propionic acid, pyridine, methyl sulfoxide, or hexamethylphosphoric amide; One of these solvents can be used alone, or two or more solvents can be used as a mixture. As the inert organic solvent, dissolves the substrate, does not react with the substrate or product, benzene, toluene, xylene, cyclohexane, methylene chloride, chloroform, carbon tetrachloride,
It is preferable to use chlorobenzene, diethyl ether, dimethoxyethane, dimethyl ether, tetrahydrofuran, or dioxane.

It is preferable that all the reactions in the production method of the present invention are carried out in a solvent or a solvent mixture. Also,
As the solvent mixture, a solvent composition that can be mixed uniformly can be used, but a solvent composition composed of two or more solvents that do not form a uniform layer with each other can be used. In the latter case, it is appropriate to add a phase transfer catalyst such as a conventional quaternary ammonium salt or crown ether as the base to the reaction system.

In the reaction step of the production method of the present invention or the purification step of the product obtained by the production method of the present invention, when the use of an acid is preferred, the present invention is not limited thereto. , An inorganic acid (eg, hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, or sulfuric acid), an organic acid (eg, formic acid, acetic acid, butyric acid, or p-toluenesulfonic acid), or a Lewis acid (eg, , Boron trifluoride, aluminum chloride, or zinc chloride), and these acids can be used alone or as a mixture of two or more acids.

In the production method of the present invention, generally, 0 to 160
C. (preferably 50-100.degree. C.) at a reaction temperature of 4,4-dihalogeno-2-pyrazolin-5-one compound represented by the formula (II) and phenoxy substitution represented by the formula (III). An aniline derivative or a phenylthio-substituted aniline derivative is reacted with the above-mentioned inert organic solvent in the presence of a base for 1 hour.
By reacting for up to 6 hours (preferably 1 to 1.5 hours), the pyrazoline derivative represented by the formula (I) can be synthesized. The pyrazoline derivative represented by the formula (I) is usually obtained in the form of a mixture of isomers. If further purification is required, the purification may be performed, for example, by silica gel column chromatography or recrystallization. Can be.

As the inert organic solvent, the solvents exemplified above as suitable solvents, ie, benzene, toluene, xylene, cyclohexane, methylene chloride, chloroform,
When carbon tetrachloride, chlorobenzene, diethyl ether, dimethoxyethane, dimethyl ether, tetrahydrofuran, or dioxane is used, usually 0 to 16
The reaction can be performed at a temperature of 0 ° C, preferably 50 to 100 ° C. The reaction time in this case is 30 minutes to 6 minutes.
Time, preferably 1 to 1.5 hours.
Further, in this reaction, it is preferable to use triethylamine, potassium carbonate, sodium carbonate, or pyridine as a base.

The 4,4-dihalogeno-2-pyrazolin-5-one compound represented by the formula (II) used in the production method of the present invention can be obtained, for example, by the following reaction scheme (2):

Embedded image (Wherein R ¹ , R ² , X ¹ , and X ² have the same meanings as described above). This production method is known, and for example, for 4,4-dibromo-1,3-dimethyl-2-pyrazolin-5-one, Japanese Patent Publication No.
-99402.

That is, 1,3 represented by the above formula (IV)
The halogenation agent is added dropwise to the -disubstituted-2-pyrazolin-5-one compound in water or an organic solvent with stirring, and the mixture is reacted at room temperature for 0.1 to 24 hours to obtain a compound represented by the formula (II). 4,4-dihalogeno-2-pyrazolin-5-one compound can be obtained. Examples of the reaction solvent include water, aromatic hydrocarbons (eg, benzene, toluene, xylene, or methylnaphthalene), petroleum ethers, and aliphatic hydrocarbons (eg, pentane, hexane,
Or heptane), alicyclic hydrocarbons (eg, methylcyclohexane), chlorinated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, tetrachloroethane, or chlorobenzene). it can. As the halogenating agent, for example, N
-Chlorosuccinimide, 1,3-dichloro-5,5-
Dimethylhydantoin, trichloroisocyanuric acid, N
- bromosuccinimide or bromine (Br ₂₎ can be cited, N- bromosuccinimide is preferred. Further, the amount of the halogenating agent used is 1, 1 represented by the formula (IV).
It is usually 2 to 3 mol, preferably 2 to 2.5 mol, per 1 mol of the 3-disubstituted-2-pyrazolin-5-one compound.

1,3-disubstitution represented by the formula (IV-1)
The 2-pyrazolin-5-one compound [having a tautomeric relationship with the 1,3-disubstituted-5-hydroxypyrazole compound represented by the formula (IV-2)] is, for example, as described in the reaction formula (3). :

Embedded image [Wherein, R ¹² and R ¹³ are a hydrogen atom at the same time, or together form an ethoxymethylene group (= CH—O
Assumed to be C ₂ H ₅ group), R ¹⁴ is an alkyl group having 1 or 2 carbon atoms, R ¹ is as defined above. R ²¹ has the same meaning as R ² when R ¹² and R ¹³ are a hydrogen atom at the same time; and when R ¹² and R ¹³ together form an ethoxymethylene group, Number 1
To 2 alkoxy groups]. This manufacturing method is described, for example, in J. prakt. C
hem. , 110, 153 (1925); Org.
Chem. 27, 994 (1962), or
No. 53971.

That is, the compound represented by the formula (IV) is heated by heating the compound represented by the formula (V) and the substituted hydrazine derivative represented by the formula (VI) in a reaction solvent. , 3-Disubstituted-2-pyrazolin-5-one compounds can be obtained. As the reaction solvent, for example, water,
Aromatic hydrocarbons (eg, benzene, toluene, xylene, or methylnaphthalene), aliphatic hydrocarbons (eg, pentane, hexane, or heptane), alicyclic hydrocarbons (eg, methylcyclohexane), or chlorine Hydrocarbons (eg, methylene chloride, chloroform,
Carbon tetrachloride, 1,2-dichloroethane, tetrachloroethane, or chlorobenzene).

The methods for synthesizing the substituted hydrazine derivative represented by the above formula (VI) are described in many documents as shown below. For example, reaction formula (4):

Embedded image (Wherein X ³ is a hydroxyl group or a halogen atom;
Is a phenyl group, and R ¹ has the same meaning as described above). , 4 (2), 957 or Tetrahedron Lett [TELEAY] 4
731 (1978).

Further, the reaction formula (5):

Embedded image (Wherein THF refers to tetrahydrofuran). Org. Chem. [JOCEA
H] 46 (26) 5413 (1981). Also, the reaction formula (6):

Embedded image (Where Et means an ethyl group) is described in Chem. Ber [CHBEAM] 102,308
8 (1969).

The reaction formula (7):

Embedded image (Wherein Am represents an amyl group and Ph is a phenyl group), the synthesis method based on Chem. Ber [CH
BEAM] 86, 1073 (1953). Further, the reaction formula (8):

Embedded image The synthesis method based on Chem. Ber [CHBEA
M] 95,680 (1962) or Chem. Ber
[CHBEAM] 97, 49 (1964).

The above formula (III) used in the production method of the present invention
The phenoxy-substituted aniline derivative or phenylthio-substituted aniline derivative represented by, for example, Rec. Tra
v. Chim. , 80, 1075 (1961) or SU
With reference to the specification of Japanese Patent No. 170,526, a reaction formula (9):

Embedded image (Wherein, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ ,
R ¹¹ and Z have the same meanings as described above). That is, by heating a compound represented by the formula (VII) in a reaction solvent with a reducing agent or in a reaction solvent in the presence of a reducing agent and a catalytic amount of an acid, the compound represented by the formula (III) The phenoxy-substituted aniline derivative or phenylthio-substituted aniline derivative represented by the formula (1) can be obtained. Examples of the reducing agent include sodium sulfide, iron, tin (II) chloride, and hydrazine.

The phenoxynitrobenzene derivative or the phenylthionitrobenzene derivative represented by the compound (VII) can be obtained, for example, by using the reaction formula (10):

Embedded image (Wherein X ⁴ is a halogen atom, and R ³ , R ⁴ , R ⁵ , R
⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and Z have the same meanings as described above) or reaction formula (11):

Embedded image (Wherein X ⁵ is a halogen atom, and R ³ , R ⁴ , R ⁵ , R
⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and Z have the same meanings as described above). These production methods are described, for example, in JP-B-41-6355,
Or Synth Commun [SYNCVC] 13
(4), 335 (1983) [Copper (I), p.
henylacetylide, pyridine (A
nhyd. )].

That is, in the reaction formula (10), the nitrobenzene derivative represented by the formula (VIII) and the halogen-substituted benzene derivative represented by the formula (IX) are heated in the presence of a base. And the compound represented by the formula (VII) can be obtained. The reaction formula (1)
In 1), the halogen-substituted nitrobenzene derivative represented by the formula (X) and the phenol derivative or thiophenol derivative represented by the formula (XI) are heated in the presence of a base to form the compound represented by the formula (VII). ) Can be obtained. Examples of the base used in these reactions include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, and sodium hydride.

The pyrazoline derivative represented by the formula (I) according to the present invention exhibits pest control activity and is therefore useful as an active ingredient of a pesticide. The pest to which the pest control agent of the present invention containing the pyrazoline derivative represented by the formula (I) or a salt thereof according to the present invention as an active ingredient is not limited, For example, a harmful nematode or a harmful insect (that is, a harmful insect) can be mentioned.

Examples of the harmful nematodes include root-knot nematodes and Senorabditis elegans.

Examples of the harmful insects include, for example, Hemiptera pests (eg, black leafhoppers, brown planthoppers, brown planthoppers, scutellaria aphids, peach aphids, cotton aphids, locust aphids, green stink bugs, and dipteran insects), dipteran insects ( For example, house flies, Aedes aegypti, Culex pipiens or Culex pipiens), lepidopteran pests (for example, blue-tailed beetle, Spodoptera litura, Awanomeiga, Konaga, Nikameichu,
Or Coleoptera), Coleoptera pests (e.g., adzuki beetle, weevil, scorpion beetle, brown beetle, colorado potato beetle, or rice weevil), or Orthoptera pests (e.g., German cockroach, cockroach, keratella, grasshopper, yamato termite) House termite). The pest control agent of the present invention is preferably applied to nematodes or dipteran pests (especially mosquitoes).

The pesticidal composition according to the present invention may contain, if necessary, a carrier or diluent (particularly a carrier or diluent conventionally used in pesticidal compositions).
Conventionally known various forms, for example, emulsions, wettable powders, aqueous solvents,
It can be used in the form of granules, fine granules, granules, powders, coatings, spray preparations, aerosol preparations, microcapsule preparations, or fumigation preparations. In producing these preparations, various surfactants can be used for emulsification, dispersion, suspension, or foaming. As the surfactant, for example, a nonionic surfactant (for example,
A polyoxyethylene alkyl ether, a polyoxyethylene alkyl ester, or a polyethylene sorbitan alkyl ester), or an anionic surfactant (for example,
Alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, allyl sulfonate, or lignin sulfite).

As the diluent or carrier, for example, various organic solvents, various aerosol propellants, various natural minerals, and / or various synthetic compounds can be used. Examples of the organic solvent include benzene, xylene, ethylbenzene, chlorobenzene, alkylnaphthalene, chloroethylene, cyclohexanone, methylethylketone,
Methyl isobutyl ketone, alcohols, cellosolves, dimethylformamide, dimethylsulfoxide, acetonitrile, or mineral oil fractions can be mentioned. Examples of the aerosol propellant include propane, butane, halogenated hydrocarbon, nitrogen, and carbon dioxide.

The pesticidal composition of the present invention includes, but is not limited to, the pyrazoline derivative represented by the formula (I), but is usually about 0.1 to 95% by weight, preferably about 0.1% by weight. It can be contained in an amount of 5 to 90% by weight. The pesticidal agent of the present invention can be used without dilution or after dilution with an appropriate carrier or water.
When used after dilution, the concentration of the pyrazoline derivative represented by the formula (I) is usually about 0.0001 to 90% by weight, preferably 0.001 to 10% by weight. can do.

The pyrazoline derivative of the formula (I) according to the present invention is placed in a place where pests need to be controlled, in an amount effective for controlling the pests (optionally together with a suitable carrier or diluent). In addition, the pests can be controlled by supplying and treating the pests in a dosage form suitable for controlling the pests.

[0055]

EXAMPLES The present invention will be described below in more detail with reference to Examples, which do not limit the scope of the present invention.
In the following abbreviations for NMR, "s" means a singlet, "d" means a doublet, "m" means a multiplet, and "br" means blow- Means

Production Example 1 << 4- [4- (4-chlorophenoxy) phenylimino] -1,3-dimethyl-2-pyrazolin-5-one [Compound No. 27; Hereinafter, the compound (2)
7)] In this production example, the reaction formula (12):

Embedded image (Where Me is a methyl group and Et is an ethyl group), the following operation is carried out to obtain the title compound [the compound represented by the formula (Ia) (R ¹ and R ² =
_{CH 3, Z = O, R} 3 ~R 6 = H, R 7 ~R 11 = 4-C
l)] was synthesized.

That is, 4-chlorophenoxyaniline (0.81 g, 3.7 mmol) was added to 30 m of dry benzene.
and triethylamine (0.78 g, 3.7 × 2.1 mmol) was added to the resulting solution with stirring at room temperature.
Then, 5 ml of a dry benzene solution of 4,4-dibromo-1,3-dimethyl-2-pyrazolin-5-one (1 g, 3.7 mmol) was added dropwise. Then, under heating and reflux,
A time reaction was performed. After allowing to cool, triethylamine hydrobromide precipitated from the reaction solution was separated by filtration, the benzene layer was washed with water, dried over anhydrous sodium sulfate, and benzene was distilled off under reduced pressure. The residue was purified by silica gel column chromatography [elution solvent: mixed solvent of ethyl acetate and n-hexane (ethyl acetate: n-hexane = 1: 2)] to give the title compound (yield = 0.9 g, yield = 75). %) As a red solid. Melting point: 72-74 ° C IR KBr cm ^-1 : 1680, 1470, 1240 ¹ H-NMR (60 MHz, CDCl ₃ , δ): 2.1
(3H, S, pyrazoline ring 3-position —CH ₃ ), 3.2 (3
H, S, pyrazoline ring _{N-CH 3), 6.8 (} 4H,
d, J = 9 Hz), 7.16 (2H, d, J = 9H)
z), 7.55 (2H, d, J = 9 Hz)

Test Example 1 << Effect of controlling Aedes aegypti larvae >> 4- [4- (4-chlorophenoxy) phenylimino] -1,3-dimethyl-2-pyrazolin-5 produced in Production Example 1 above
-One [compound (27)] Aedes aegypti (Aede)
saegypti) was evaluated for its control effect on larvae. A solution of 24 μg of the compound (27) in dimethyl sulfoxide (DMSO) (6 μl) was added to a 96-well test plate (8
× 12), and water was added to each well to a final volume of 2.0 ml. DMSO is 1% of the final volume.
Was not exceeded. Next, an aqueous solution of about 3rd instar larvae of Aedes aegypti was added to each well and kept at room temperature for 24 hours.

Twenty-four hours later, the number of larvae swimming in response to this stimulus was evaluated in three steps by gently tapping the plate and comparing to the control: 3: The number of individuals swimming in response to the stimulus The number of individuals swimming in response to the stimulus in the control group decreased to 30% or less. 2: The number of individuals swimming in response to the stimulus exceeds 30% and 70% of the number of individuals swimming in response to the stimulus in the control group
Decreased to below. 1: The number of individuals swimming in response to the stimulus is greater than or equal to 70% of the number of individuals swimming in response to the stimulus in the control group. Compound (27) is “3”
Activity.

Test Example 2 << Effect of Control of Larvae of Senorabuditis elegans >> 4- [4- (4-chlorophenoxy) phenylimino] -1,3-dimethyl-2 produced in Production Example 1 above
Concentration of pyrazolin-5-one [compound (27)] 10
Senorabditis elegance in ppm (Caen
orhabditiselegans) to control larvae. Test medium (mixture of Na22 medium and M9 buffer) in a 96-well micro test plate
125 μl of a compound (27) in DMSO solution (concentration =
(4000 ppm) 0.75 μl. The Na22 medium was NaCl (3 g), agar (17 g),
Peptone (2.5 g) and distilled water (976 mL) were mixed and subjected to high pressure sterilization, followed by CaCl ₂ (1 mol / L) 1.
mL, uracil (2 mg / mL) 1 mL, cholesterol (5 mg / mL, ethanol), MgSO ₄ (1 mo
1 / L) 1 mL and potassium phosphate buffer (pH 6)
This is a medium supplemented with 25 mL. The composition of the M9 buffer was Na ₂ HPO ₄ (6 g), KH ₂ PO ₄ (3 g), N
_{aCl (5g), MgSO 4 ·} 7H 2 O (0.25g),
And distilled water (1000 mL). Next, an aqueous solution containing Senolabuditis elegance (about 90 head / 10
(0 μl) 175 μl was added and kept at 20 ° C. for 7 days.

By comparing the size of the population 7 days after the drug treatment with the size of the population immediately after the start of the test, the following three levels were evaluated: 3: The size of the population 7 days after the drug treatment was , 1.2 times or less the size of the population immediately after the start of the test. 2: The size of the population 7 days after the drug treatment was larger than 1.2 times the size of the population immediately after the start of the test and was 2 times or less. 1: The size of the population 7 days after drug treatment was larger than twice the size of the population immediately after the start of the test. Compound (27) showed the activity of "3".

Test Example 3 << Effect of controlling root-knot nematode against larvae >> 4- [4- (4-chlorophenoxy) phenylimino] -1,3-dimethyl-2-pyrazolin- produced in Production Example 1 above
Meloidogyne incogn at a concentration of 10 ppm of 5-one [compound (27)]
By testing the control effect of ita) on larvae, it was confirmed that it was effective.

The following Reference Production Examples 1 to 5 are intended to illustrate a method for producing a starting compound that can be used in the production method of the present invention. Reference Production Example 1 << Synthesis of 1,3-dimethyl-5-hydroxypyrazole >> In this Reference Production Example, the reaction formula (13):

Embedded image By performing the following operation on the basis of the above, the title compound [the compound represented by the formula (IV-2) (R ¹ and R ² ＣC
H ₃ )]. The reaction formula is described in prakt.
Chem. , 110, 153 (1925) or J.A. Or
g. Chem. , 27, 994 (1962)].

Specifically, methylhydrazine (22.2)
g, 0.48 mol) of acetoacetic acid methyl ester (61.5 g, 0.48 mol) in 100 ml of an aqueous solution.
× 1.1 mol) was added. At this time, heat was generated. Then, it stirred under heating at 95-100 degreeC for 4 hours. Subsequently, the reaction solution was cooled with water, and water in the reaction solution was distilled off under reduced pressure. Since the residue solidified and was in a state where it was difficult to take out, acetone was added and the solid was collected by filtration while crushing. A part of the crude product (yield = 34.7 g, yield = 64.6%) was purified by silica gel column chromatography to obtain the title compound as a white solid. Furthermore, benzene recrystallization is also possible. Melting point: 119 to 120 ° C (literature value: 117 ° C) ¹ H-NMR (60 MHz, CDCl ₃ , δ): 2.03
_{(3H, CH 3), 3.06} (2H, S, CH 2), 3.
16 (3H, S, N- CH 3)

Reference Production Example 2 << Synthesis of 4,4-dibromo-1,3-dimethyl-2-pyrazolin-5-one >> In this Reference Production Example, the reaction formula (14):

Embedded image (Where Me is a methyl group), the following operation is carried out to obtain the title compound [compound represented by formula (II) (R ¹ and R ² ＣＨCH ₃ , X ¹ and X ² = B
r)] was synthesized.

That is, the 5 prepared in Reference Production Example 1
-Hydroxy-1,3-dimethylpyrazole (10 g,
0.089 mol) was dissolved in 150 ml of water, and bromine (25.1 g, 0.1 mL) was added to the resulting solution while stirring under ice cooling.
(089 × 1.75 mol) was added dropwise and reacted at room temperature for 12 hours with stirring. The resulting reaction solution was diluted with ethyl acetate 1
The mixture was extracted three times with 00 ml, and the organic layer was washed with saturated saline and dried over anhydrous sodium sulfate. Then, ethyl acetate was distilled off to obtain an oily substance, which was subjected to vacuum distillation to obtain 13 g (yield = 54%) of the title compound as a red oily substance. The residue in the vacuum distillation was further purified by silica gel column chromatography [a mixed solvent of ethyl acetate and n-hexane (ethyl acetate: n-hexane = 1: 5)] to obtain 4 g of the title compound. Together with 13 g of the title compound obtained above, a total yield of 17 g (yield =
70.8%). Boiling point: 85 to 88 ° C. (1 mmHg) IR NaCl liquid film cm ⁻¹ : 1720, 655 ¹ H-NMR (60 MHz, CDCl ₃ , δ): 2.35
(3H, S, pyrazoline ring third place -CH _3), 3.40
(3H, S, pyrazoline ring N-CH ₃₎

Reference Production Example 3 << Synthesis of 3-trifluoromethyl-1-methyl-5-hydroxypyrazole >> In this Reference Production Example, the reaction formula (15):

Embedded image (Where Et is an ethyl group), the following operation was carried out to obtain the title compound [compound represented by formula (IV-2) (R ¹ = CH ₃ , R ² = CF ₃ )] Was synthesized. The reaction formula is described in prakt. Chem. , 11
0,153 (1925) or J.A. Org. Chem. ,
27, 994 (1962).

Specifically, methylhydrazine (5 g,
Trifluoroacetoacetic acid ethyl ester (20 g, 0.108 mol) in a 25 ml aqueous solution.
08 mol) was added. At this time, heat was generated. Thereafter, the mixture was stirred for 5 hours while heating at 95 ° C to 100 ° C. Subsequently, the mixture was allowed to stand under water cooling, and the precipitated solid was collected by filtration and washed with water to obtain a crude product of the title compound in a crude yield of 15.3 g (yield = 91.6%). In addition, the crude product was
l and 25 ml of water to give the title compound (yield = 11 g, yield = 65.8%).
Was obtained as a white solid. Melting point: 177-178 ° C IR KBr cm ^-1 : 2950-2460,156
5,1395,1340,1280,1225,116
0,1118,980,760 ¹ H-NMR (60 MHz, d ₆ -DMSO, δ): 3.
59 (3H, S, N- CH 3), 5.69 (1H, S,
Pyrazole ring 4-position H), 11.55 (1H, br, pyrazole ring 5-position OH)

By repeating the above operation of this Reference Production Example using hydrazine instead of methylhydrazine, 3-trifluoromethyl-5-hydroxypyrazole [formula (IV-2) Compound (R ¹ = H, R ²
= CF ₃ )].

Reference Production Example 4 << Synthesis of 1-methyl-5-hydroxypyrazole hydrochloride >> In this Reference Production Example, the reaction formula (16):

Embedded image (In the formula, Et is an ethyl group), the following operation is carried out to obtain the title compound [compound represented by formula (IV-2) (R ¹ = CH ₃ , R ² = H) ] Was synthesized. The above reaction formula is disclosed in JP-A-62-53971.

Specifically, ethoxymethylenemalonic acid di
Ethyl ester (10.8 g, 50 mmol) was added to ethanol
And cooled to 0 ° C. Reaction temperature 5
Hydrazine (2.3 g, 5 g).
(0 mmol) in ethanol. Drip end
Thereafter, the mixture was stirred at room temperature for 1 hour and then refluxed for 8 hours. solvent
Was distilled off, and 20 ml of 35% hydrochloric acid was added to the residue.
Hydrolyzed at reflux. Distill off water and add more benzene.
The title compound was obtained by azeotropic dehydration and drying.
72 g (yield = 100%) were obtained as a solid.¹ H-NMR (60 MHz, d₆-DMSO, δ): 3.
5 (3H, S, N-CH _Three), 5.3 (1H, d, J =
2 Hz, pyrazole ring 4-position H), 7.1 (1H, d, J)
= 2 Hz, pyrazole ring 3-position H)

Reference Production Example 5 << 4,4-dibromo-1-methyl-2-pyrazolin-5
Synthesis of -one >> In this Reference Production Example, the reaction formula (17):

Embedded image (In the formula, Et is an ethyl group), the following operation is carried out to obtain the title compound [the compound represented by the formula (II) (R ¹ = CH ₃ , R ² = H, X ¹ And X ² = B
r)] was synthesized. In the reaction formula (17), N
The dibromination reaction is carried out using -bromosuccinimide (NBS), but bromine can be used instead of NBS.

Specifically, 1-methyl-5-hydroxypyrazol hydrochloride (2 g,
14.8 mmol) in 50 ml of chloroform,
To this, triethylamine (1.5 g, 14.8 mmol)
l) was added and stirred until the solids dissolved. Then, at room temperature, NBS (5.42 g, 14.8 × 2.05 mmol)
l) was added and stirred for 1 hour. Subsequently, 50 mL of water was added to the reaction solution for partition, and the chloroform layer was washed with saturated saline and dried over anhydrous sodium sulfate. After evaporating the solvent under reduced pressure, 3.27 g of the title compound was obtained as a crude product. This was purified by silica gel column chromatography to give 2.19 g of the title compound.
(Yield = 45.6%) was obtained as colorless crystals. Melting point: 66-68 ° C IR KBr cm ^-1 : 3030, 1690, 137
0,890,875 ¹ H-NMR (60 MHz, CDCl ₃ , δ): 3.35
(3H, S, N-CH 3), 7.46 (1H, S, pyrazole ring 3-position H)

[0074]

Industrial Applicability The novel pyrazoline derivative of the present invention exhibits high pest control activity and is useful as an active ingredient of a pest control agent.

Claims (4)

[Claims] 1. A compound of formula (I): [Wherein, R ¹ and R ² each independently represent a hydrogen atom,
An alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a cyanoalkyl group having 1 to 4 carbon atoms in the alkyl portion, A hydroxyalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 1 to 4 carbon atoms in the alkoxy portion and 1 to 4 carbon atoms in the alkyl portion, 1 to 4 carbon atoms in the alkylthio portion and An alkylthioalkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms in the alkoxy portion, and 1 to 4 carbon atoms in the alkyl portion.
4 alkoxycarbonylalkyl group, an alkoxy moiety having 1 to 4 carbon atoms and an alkyl moiety having 1 to 4 carbon atoms, an alkyl moiety having 1 to 4 carbon atoms, an aminocarbonylalkyl group and an alkylamino moiety Has 1 to 4 carbon atoms and the alkyl portion has 1 to
4 alkylaminocarbonylalkyl groups, wherein the carbon number of each alkyl moiety in the dialkylamino moiety is independently 1 to 4, and the carbon number of the alkyl moiety in the carbonylalkyl moiety is 1 to 4; An oxiranylalkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted, a benzyl group which may be substituted, or a heterocyclic group which may be substituted; An oxygen atom or a sulfur atom; and R ³ , R ⁴ , R ⁵ , R ⁶ , R
⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are each independently
A hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms,
A haloalkyl group having 1 to 4 carbon atoms, a nitro group, a cyano group,
A C1-4 alkoxy group or a C1-4 alkylthio group], or a salt thereof. 2. In the above formula (I), R ¹ and R ² are
Each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a haloalkyl group having 1 to 4 carbon atoms; Z is an oxygen atom or a sulfur atom; R ³ , R ⁴ , R ⁵ , and R ⁶
Are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, or an alkoxy group having 1 to 4 carbon atoms; and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are Each independently represents a hydrogen atom, a halogen atom, a carbon number of 1 to 4;
The pyrazoline derivative according to claim 1, which is an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, an alkoxy group having 1 to 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms. 3. A compound of formula (II): [Wherein, R ¹ and R ² each independently represent a hydrogen atom,
An alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, an alkynyl group having 2 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a cyanoalkyl group having 1 to 4 carbon atoms in the alkyl portion, A hydroxyalkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group having 1 to 4 carbon atoms in the alkoxy portion and 1 to 4 carbon atoms in the alkyl portion, and 1 to 4 carbon atoms in the alkylthio portion having carbon atoms in the alkyl portion; An alkylthioalkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms in the alkoxy portion, and 1 to 4 carbon atoms in the alkyl portion.
4, an alkoxycarbonylalkyl group having 1 to 4 carbon atoms and an alkyl moiety having 1 to 4 carbon atoms, an aminocarbonylalkyl group having 1 to 4 carbon atoms in the alkyl moiety, an alkylamino moiety Has 1 to 4 carbon atoms and the alkyl portion has 1 to
4 alkylaminocarbonylalkyl groups, wherein the carbon number of each alkyl moiety in the dialkylamino moiety is independently 1 to 4 and the carbon number of the alkyl moiety in the carbonylalkyl moiety is 1 to 4 dialkylaminocarbonylalkyl group, An oxiranylalkyl group having 1 to 4 carbon atoms, a phenyl group which may be substituted, a benzyl group which may be substituted, or a heterocyclic group which may be substituted; ¹ and X ² are independently the same or different halogen atoms] and a compound represented by the formula (III): Wherein Z is an oxygen atom or a sulfur atom; and R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are each independently , Hydrogen atom, halogen atom,
An alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a nitro group, a cyano group, an alkoxy group having 1 to 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms]. And reacting in the presence of a base. The method for producing a pyrazoline derivative represented by the formula (I) according to claim 1, wherein 4. A pesticidal composition comprising the pyrazoline derivative represented by the formula (I) according to claim 1 or a salt thereof as an active ingredient.