JP3216697B2 - Heterocyclic oxybenzylidene hydrazine compound, process for producing the same, and pesticide for agricultural and horticultural use - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel heterocyclic oxybenzylidenehydrazine compound which is an agricultural and horticultural pesticide useful as an insecticide or the like.

[0002]

DESCRIPTION OF THE PRIOR ART As a heterocyclic oxybenzylidene hydrazine compound related to the present invention, German Patent 27
No. 07776 discloses that bis- and tris (guanylhydrazonium) salts are useful for the purification of polluted water. In addition, Egypt. J. Chem. , 23 , 1
65 (1980) discloses that hydrazone compounds of 4- (6-phenylpyridanyloxy) benzaldehyde or acetophenones can be expected to have herbicidal activity.

[0003] However, the structures of these compounds are different from those of the compounds of the present invention, and no investigation has been made as to whether or not they show usefulness as insecticides or the like.

Therefore, since the heterocyclic oxybenzylidenehydrazine compound of the present invention is a novel compound, it is not known that it has a pest control activity for agricultural and horticultural use which is useful as an insecticide or the like.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel heterocyclic oxybenzylidenehydrazine compound, a process for producing the same, and a pesticidal composition for agricultural and horticultural use which is useful as an insecticide containing the compound as an active ingredient. It is.

[0006]

Means for Solving the Problems As a result of investigations to solve the above problems, the present inventors have found that a novel heterocyclic oxybenzylidenehydrazine compound is useful as a pesticide and the like for agricultural and horticultural pesticides. As a result, the present invention has been found to have a remarkable controlling activity.

That is, the present invention is as follows. According to a first aspect, the following formula (1):

[0008]

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Wherein R ¹ represents an unsubstituted or substituted phenyl group having a halogen atom, an alkyl group having 1 to 4 carbon atoms or a pyrimidinyloxy group;
² represents a hydrogen atom; R ³ is a hydrogen atom, having 2 to 2 carbon atoms.
It represents a five alkoxycarbonyl group or several 2-5 acyl group carbons; or together with the N and R ² and R ^3, -N
Q may form CR ⁴ NR ⁵ R ⁶ (R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms); Q is unsubstituted or substituted A halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms A 6-membered ring having 1 to 3 nitrogen atoms having a haloalkoxy group or an alkylamino group having 1 to 8 carbon atoms. And a heterocyclic oxybenzylidenehydrazine compound represented by the formula:

According to a second aspect of the present invention, there is provided the following equation (2):

[0011]

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(Wherein R ¹ , R ² and R ³ are as defined above) and the following formula (3):

[0013]

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Wherein Q is as defined above; and Z represents a leaving group. The heterocyclic compound represented by the above formula (1) is reacted with the compound represented by the above formula (1). The present invention relates to a method for producing an oxybenzylidenehydrazine compound. A third invention provides the following equation (4):

[0015]

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(Wherein R ¹ and Q are as defined above) and the following formula (5):

[0017]

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Wherein R ⁴ , R ⁵ and R ⁶ have the same meanings as defined above, characterized by the following formula (1a):

[0019]

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Wherein R ¹ , R ⁴ , R ⁵ , R ⁶ and Q
Is as defined above. The present invention relates to a process for producing a heterocyclic oxybenzylidenehydrazine compound represented by the formula (1). A fourth invention provides the following equation (6):

[0021]

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(Wherein R ¹ and Q are as defined above) and the following formula (7):

[0023]

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Wherein R ² and R ³ have the same meanings as defined above, and are reacted with a compound represented by the formula (1). It relates to the manufacturing method. Fifth
The invention of the following formula (6 ′):

[0025]

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(Wherein, R ¹ has the same meaning as in claim 1. Q ′ is a pyrimidinyl group, and has 1 carbon atom as a substituent.)
Represents a pyridyl group having 1 to 4 haloalkyl groups or a triazinyl group having an alkoxy group having 1 to 4 carbon atoms and an alkylamino group having 1 to 8 carbon atoms as substituents. )). The sixth invention provides the following formula (8):

[0027]

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(Wherein R ¹ , R ² and Q are as defined above) and the following formula (9):

[0029]

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Wherein R ⁷ represents an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms;
Represents a leaving group. Wherein the compound represented by the following formula (1b):

[0031]

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(Wherein, R ¹ , R ² , Q and R ⁷ have the same meanings as described above). The present invention relates to a process for producing a heterocyclic oxybenzylidenehydrazine compound represented by the formula: The sixth invention relates to a pesticidal composition for agricultural and horticultural use, comprising the heterocyclic oxybenzylidenehydrazine compound represented by the formula (1) as an active ingredient.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. R ^{1 to} R ³ , represented by a novel heterocyclic oxybenzylidenehydrazine compound [Compound (1)] and a raw material for producing the same [Compounds (2) to (9)], which are target compounds.
Q, Q ', Z and Z' are as follows.

Examples of R ¹ include an unsubstituted or substituted phenyl group having a halogen atom, an alkyl group having 1 to 4 carbon atoms or a pyrimidinyloxy group. As the halogen atom, a chlorine atom, an iodine atom,
Examples thereof include a bromine atom and a fluorine atom; a chlorine atom and a fluorine atom are preferred. The substitution position of the halogen atom is not particularly limited;
3, 4-position and the like.

Alkyl groups can be straight or branched; preferably CH ₃ . The substitution position of the alkyl group is not particularly limited; preferably, it is at the 2,3,4-position. Examples of the pyrimidinyloxy group include those having a linear or branched alkoxy group having 1 to 4 carbon atoms; preferably, a 4,6-dimethoxy-2-pyrimidinyloxy group. And although the substitution position of a pyrimidinyloxy group is not specifically limited; Preferably, it is 4-position.

As R ² , a hydrogen atom can be mentioned. Examples of R ³ include a hydrogen atom, an acyl group having 2 to 5 carbon atoms, and an alkoxycarbonyl group having 2 to 5 carbon atoms. Examples of the acyl group include straight-chain or branched ones;
H ₃ .

The alkoxycarbonyl group may be straight-chain or branched; preferably, it is COOC ₂ H ₅ . R ² and R ³ together with N are -N
= CR ⁴ NR ⁵ R ⁶ can also be formed. R ⁴ , R
^{Examples of 5} and R ⁶ each include an independent alkyl group having 1 to 4 carbon atoms.

The alkyl group for R ⁴ , R ⁵ and R ⁶ may be straight-chain or branched; preferably CH ₃ .

Examples of Q include a substituted or unsubstituted 6-membered ring having 1 to 3 nitrogen atoms. Examples of the 6-membered ring include a pyrimidinyl group, a pyridyl group, and a triazinyl group. The pyrimidinyl group is preferably a 4-pyrimidinyl group or a 2-pyrimidinyl group.

The pyridyl group is preferably a 2-pyridyl group. The triazinyl group is preferably a 1,3,5-triazinyl group. Pyrimidinyl group,
Examples of the substituent in the pyridyl group and the triazinyl group include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 1 to 4 carbon atoms. Haloalkyl group having 1 to 1 carbon atoms
Examples include four haloalkoxy groups and an alkylamino group having 1 to 8 carbon atoms. The details of this substituent are as follows.

Examples of the halogen atom include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; a chlorine atom is preferred. As the alkyl group, there may be mentioned a straight or branched; preferably CH _3. The alkylthio group, there may be mentioned those having a straight-chain or branched alkyl group; preferably SCH _3.

The alkoxy group for the substituent may be straight-chain or branched; preferably, OCH ₃ and OC ₂ H ₅ . Examples of the haloalkyl group include those in which alkyl is linear or branched and having a halogen atom such as a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom; preferably having 1 to 4 carbon atoms. And having a fluorine atom; more preferably CF ₃ .

Examples of the haloalkoxy group include those in which alkoxy is straight or branched and has a halogen atom such as a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; From 1 to 4 and a fluorine atom; more preferably —OCHF ₂ . The alkylamino group preferably has two linear or branched alkyl groups having 1 to 4 carbon atoms; more preferably a dimethylamino group.

As the substituent in the pyrimidinyl group,
Preferred are a halogen atom, an alkyl group, an alkylthio group, an alkoxy group, a haloalkyl group and a haloalkoxy group. And the substituent in the 4-pyrimidinyl group is preferably a halogen atom, an alkyl group, an alkylthio group, an alkoxy group or a haloalkyl group;
The substituent in the pyrimidinyl group is preferably an alkoxy group, a haloalkyl group, an alkyl group, a haloalkoxy group, or a halogen atom.

The substituent in the pyridyl group is preferably a haloalkyl group or a halogen atom. The substituent in the triazinyl group is preferably an alkoxy group or an alkylamino group.

Q ′ is a pyrimidinyl group, a pyridyl group having a haloalkyl group having 1 to 4 carbon atoms as a substituent, an alkoxy group having 1 to 4 carbon atoms and an alkylamino having 1 to 8 carbon atoms as a substituent. And a triazinyl group having a group. As the pyrimidinyl group, haloalkyl group and alkylamino group for Q ′,
When Q ′ is a pyrimidinyl group, R ¹ is preferably unsubstituted or a halogen atom as a substituent, having 1 to 1 carbon atoms.
When Q ′ is a pyridyl group having a haloalkyl group, R ¹ is preferably a phenyl group having a halogen atom as a substituent; and Q ′ is an alkoxy group having 4 halogen groups or a pyrimidinyloxy group. In the case of a triazinyl group having a group and an alkylamino group, R ¹ is preferably a phenyl group having a halogen atom as a substituent.

Z is a leaving group and is not particularly limited, and examples thereof include a halogen atom, an alkylsulfonyl group, an alkylthio group, an arylsulfonyl group, an aralkylsulfonyl group and a trialkylamino group; A halogen atom and an alkylsulfonyl group; more preferably a chlorine atom and a methanesulfonyl group.

Z ′ is a leaving group and is not particularly limited. Examples thereof include a halogen atom, an acyloxy group, an alkylthio group, an arylthio group, an imidazole group, an alkoxy group,
Examples thereof include a phenoxy group and the like; preferably a halogen atom and an acyloxy group; and more preferably an acyloxy group. The compound (1) of the present invention also includes geometric isomers and mixtures thereof.

As the compound (1), compounds obtained by combining the above-mentioned various substituents can be mentioned, and from the viewpoint of the efficacy, the following are preferable. (a) The compound wherein R ¹ is a phenyl group, R ² and R ³ together with N form —N ＝ C (CH ₃ ) N (CH ₃ ) ₂ , and Q is a pyrimidinyl group. (b) A compound wherein R ¹ is a phenyl group, R ² and R ³ together with N form —N ＝ C (CH ₃ ) N (CH ₃ ) ₂ , and Q is a pyridyl group. (c) The compound wherein R ¹ is a phenyl group, R ² and R ³ are hydrogen atoms, and Q is a pyrimidinyl group. (d) R ¹ is a phenyl group, R ² is a hydrogen atom,
A compound wherein R ³ is an alkoxycarbonyl group having 2 to 5 carbon atoms and Q is a pyrimidinyl group. (e) R ¹ is a phenyl group, R ² is a hydrogen atom,
R ³ is an alkoxycarbonyl group having 2 to 5 carbon atoms,
A compound in which Q is a triazinyl group.

(F) A compound wherein R ¹ is a phenyl group, R ² is a hydrogen atom, R ³ is an alkoxycarbonyl group having 2 to 5 carbon atoms, and Q is a pyridyl group. (g) The compound wherein R ¹ is a phenyl group, R ² and R ³ together with N form —N ＝ C (CH ₃ ) N (CH ₃ ) ₂ , and Q is a triazinyl group. (h) R ¹ is a phenyl group, R ² is a hydrogen atom,
A compound wherein R ³ is an acyl group having 2 to 5 carbon atoms and Q is a pyrimidinyl group.

The preferred combination (a)
As R ^{1 to} R ³ and Q of the compound (1) shown by (h), the preferable ones and the more preferable ones described in the above description can be exemplified. These specific compounds (1) include compounds 1 to 10, 12 to 14, 16, 17, 19, 20, and 2 described in Tables 3 to 9 described below.
2 to 24, 26, 28, 29, 33, 35 to 38, 4
6, 49 to 53, 56.

Compound (1) was prepared by the following Production Method 1,
2, 3, or 4. [Production Method 1] As described below, the reaction is carried out by reacting compound (2) with compound (3) in a solvent in the presence of a base.

[0053]

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(Wherein R ^{1 to} R ³ , Z and Q have the same meanings as described above). The type of solvent is not particularly limited as long as it does not directly participate in the reaction. , Chlorinated or unchlorinated aromatics, aliphatics, alicyclics such as, xylene, methyl naphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, trichloroethylene, cyclohexane Hydrocarbons of the formula; ethers such as diethyl ether, tetrahydrofuran, dioxane, etc .; ketones, such as acetone, methyl ethyl ketone; alcohols, such as methanol, ethanol, ethylene glycol, etc .; N, N-dimethylformamide, N , N-dimethylacetamide, etc. Amides; nitriles such as acetonitrile, propionitrile and the like; organic bases such as triethylamine, pyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] undec-7-ene and the like 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; and mixtures of the above-mentioned solvents.

The amount of the solvent used is such that the compound (2) is 1-80.
% By weight;
70% by weight is preferred. The type of the base is not particularly limited, and for example, triethylamine, pyridine, 4-
Organic bases such as N, N-dimethylaminopyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] undec-7-ene, sodium methoxide,
Examples thereof include alkali metal alkoxides such as sodium ethoxide, and inorganic bases such as sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, and potassium carbonate.

The amount of the base to be used is 0.001 to 5 times the molar amount of the compound (2). The reaction temperature is not particularly limited, but is within a temperature range from room temperature to the boiling point of the solvent to be used; a temperature of the boiling point or lower is preferable. The reaction time varies depending on the above-mentioned concentration and temperature;
Time.

The amount of the starting compound used is 0.5 to 2 moles of the compound (3) with respect to the compound (2); preferably 0.8 to 1.5 moles. Compound (2) can be usually synthesized by dehydration-condensing compound (10) and compound (7) as shown below. Alternatively, compound (2a) [in compound (2), R ² and R ³
Used for the synthesis of the compound (1a) in which -N = CR ⁴ NR ⁵ R ⁶ is formed together with N]
The compound (11) can be produced by dehydrating and condensing 0) with hydrazine and reacting this with the compound (5).

[0058]

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(Wherein, R ^{1 to} R ⁶ are as defined above). Compound (5) is an amide acetal,
n. , 641 , 1 (1961), and some of them can be used as commercial products. Compound (5) was prepared using compounds 1 to 5, 7, 10, 13 to 18, 25, 28, and 4 shown in Tables 3 to 9 described below.
Compound (5) consisting of substituents R ^{4 to} R ⁶ corresponding to 6, 56 can be mentioned [Compounds (5) ₁ to (5)
₅ , (5) ₇ , (5) ₁₀ , (5) ₁₃ to (5) ₁₈ , (5)
₂₅ , (5) ₂₈ , (5) ₄₆ and (5) ₅₆ . For example,
In compound (5) ₁ , R ^{4 to} R ^{6 in the} formula represented by compound (5) are methyl groups. ]

[0060] Compound (7) may, for example, R ² is at H, R
^{When 3} is an alkoxycarbonyl group, fu
r Practische Chemie [2] 70 ,
276, and can be used as a commercial product. As the compound (7), compounds 1 to 5 shown in Tables 3 to 9 described below
Compound (7) consisting of substituents R ² and R ³ corresponding to 6
[Compounds (7) ₁ to (7) are referred to as ₅₆ . For example, compound (7) ₁ is a compound represented by the formula (7), wherein R ² and R ³ together with N are -N = C (C
H ₃ ) N (CH ₃ ) ₂ . ].

The compound (10) can be produced, for example, from the corresponding carboxylic acid phenol ester by freeze-transfer reaction, and some of them can be used as commercial products.

As the compound (2), there can be mentioned a compound (2) comprising substituents R ^{1 to} R ³ corresponding to the compounds ¹ to 56 shown in Tables 3 to 9 described below [Compound (2)
₁ to (2) ₅₆ . For example, in the compound (2) ₁ , R ^{1 in the} formula represented by the compound (2) is a 4-chlorophenyl group, and R ² and R ³ are N and —N ＝ C (CH ₃ ) N.
(CH ₃ ) ₂ . ].

In the compound (3), for example, Z is an alkyls
In the case of a rufonyl group, J. Org. Chem. ,2
8, 2945 (1962).
Produced by a method such as oxidation of
Can be built. As the compound (3), the following table
From the substituent Q corresponding to the compounds 1 to 56 shown in 3 to 9
[Compound (3)]
₁~ (3)₅₆Called. For example, compound (3)₁Is
Q in the formula represented by the compound (3) is 5-chloro-6-
It is a methyl-4-pyrimidinyl group. ]

[Production Method 2] Compound (1a) [Compound (1)
Wherein R ² and R ³ together with N are -N = CR ⁴ NR ⁵
In the case where R ⁶ is formed (R ^{4 to} R ⁶ have the same meanings as described above), compound (4) and compound (5) are mixed with or without a solvent as shown below. The reaction is performed by reacting.

[0065]

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(In the formula, R ¹ , R ^{4 to} R ⁶ and Q have the same meanings as described above.) The type of the solvent is not particularly limited as long as it does not directly participate in the reaction. Chlorinated or non-chlorinated aromatics and aliphatics, such as, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloroethane, trichloroethylene, cyclohexane, Alicyclic hydrocarbons; Ethers such as diethyl ether, tetrahydrofuran, dioxane, etc .; Alcohols such as methanol, ethanol, ethylene glycol and the like or hydrates thereof; N, N-dimethylformamide, N, N-dimethyl Amides such as acetamide; acetonitrile,
Nitriles such as propionitrile; triethylamine, pyridine, N, N-dimethylaniline, 1,8
Organic bases such as -diazabicyclo [5.4.0] undec-7-ene; 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; and mixtures of the above solvents.

The amount of the solvent used is such that the compound (4) is
Weight percent can be used; however, 10
~ 70% by weight is preferred. The reaction temperature is not particularly limited, but is in a temperature range from room temperature to 200 ° C; preferably 50 to 150 ° C. The reaction time varies depending on the concentration and temperature described above; it is usually 0.1 to 100 hours; preferably 0.3 to 24 hours.

The amount of the starting compound to be used is 0.5 to 50 times the molar amount of the compound (5) relative to the compound (4); preferably 0.8 to 10 times the molar amount. If necessary, a catalyst for the reaction may be, for example, a mineral acid such as hydrochloric acid, sulfuric acid or nitric acid; an organic acid such as formic acid, acetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid or p-toluenesulfonic acid; Acid addition salts of amines such as hydrochloride and triethylamine hydrochloride can be used in an amount of 0.001 to 1 mol based on Compound (4).

Compound (4) can be produced by reacting compound (6) with hydrazine as shown below in the same manner as in the usual synthesis of hydrazone.

[0070]

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(Wherein, R ¹ and Q have the same meanings as described above.) Compound (6) is produced by reacting compound (10) with compound (3) as shown below. Can be.

[0072]

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(In the formula, R ¹ , Z and Q have the same meanings as described above.) As the compound (6), the substituents R ¹ and R ¹ corresponding to the compounds ¹ to 56 shown in Tables 3 to 9 described below and Compound (6) comprising Q [compounds (6) ₁ to (6)
_{Called 56} . For example, compound (6) ₁ is compound (6)
R ^{1 in the} formula represented by the formula is a 4-chlorophenyl group, Q
Is a 5-chloro-6-methyl-4-pyrimidinyl group. ].

Among the compounds (6) thus obtained, the compound (6 ′) [for example, the compound (6) described in Tables 1 and 2 below) is a novel substance. [Production Method 3] Compound (6) and compound (7) are reacted in the absence or presence of a solvent as shown below.

[0075]

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(In the formula, R ^{1 to} R ³ and Q have the same meanings as described above.) As the type of the solvent, the same one as described in Production method 2 can be used. The solvent may be used in such an amount that the compound (6) is used in an amount of 0.5 to 80% by weight; preferably, 0.5 to 70% by weight.

The reaction temperature is not particularly limited, but is from room temperature to
In the temperature range of 200 ° C; preferably 50-150
° C. The reaction time varies depending on the concentration and temperature described above; it is usually 0.1 to 100 hours; preferably 0.3 to 24 hours. The amount of the starting compound to be used is 0.5 to 50 times mol of compound (7) relative to compound (6); preferably 0.8 to 10 times mol.

Further, if necessary, as a catalyst for the reaction,
In addition to those described in Production Method 2, a Lewis acid such as a boron trifluoride-ether complex is added to Compound (6) at a concentration of 0.0
01 to 1 mol can be used. [Production method 4] Compound (1b) [in compound (1), R
^{In the case where 3} represents an alkoxycarbonyl group having 2 to 5 carbon atoms or an acyl group having 2 to 5 carbon atoms (R ¹ and R ² are as defined above), The reaction is carried out by reacting the compound (8) with the compound (9) without or in a solvent.

[0079]

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(Wherein R ¹ , R ² , R ⁷ , Z ′ and Q
Is as defined above. As the type of the solvent, the same one as described in Production method 1 can be used. The amount of the solvent to be used may be such that the amount of the compound (8) is 0.5 to 80% by weight; it is preferably 0.5 to 70% by weight.

The reaction temperature is not particularly limited.
Within the temperature range of 00 ° C; preferably between 0 and 100 ° C. The reaction time varies depending on the above concentration and temperature; it is usually 0.1 to 100 hours;
3 to 24 hours. The amount of the starting compound to be used is 0.5 to 50 times mol of compound (9) relative to compound (8); preferably 0.8 to 10 times mol.

A base can be used if necessary. The type of the base is not particularly limited, and for example, triethylamine, pyridine, 4-N, N-dimethylaminopyridine, N, N-dimethylaniline, 1,8
Organic bases such as -diazabicyclo [5.4.0] undec-7-ene, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate , Sodium bicarbonate, potassium carbonate and the like.

The amount of the base to be used is 0.001 to 5 moles compared to Compound (8). Compound (8) can be prepared in the same manner as in the normal synthesis of hydrazone, as follows.
And a hydrazine compound (12).

[0084]

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(Where R¹, R^TwoAnd Q are as defined above.
It is. As the compound (8), the compounds shown in Tables 3 to 9 below
8, 9, 11, 12, 19 to 24, 26, 27, 29 to
Substituent R corresponding to 45, 47, 48, 50 to 55¹,
R^TwoAnd a compound (8) consisting of Q
[Compound (8) ₈, (8)₉, (8)₁₁, (8)₁₂,
(8)₁₉~ (8)_{twenty four}, (8)₂₆, (8)₂₇, (8)₂₉~
(8)₄₅, (8)₄₇, (8)₄₈, (8)₅₀~ (8)₅₅When
Name. For example, compound (8)₈Represents a compound (8)
R in the formula¹Is a 4-chlorophenyl group, R^TwoBut
Hydrogen atom, Q is 4,6-dimethyl-2-pyrimidinyl group
It is. ].

As the compound (9), a commercially available product can be used, or it can be produced by a method known in the literature.

As the compound (9), compounds 8, 9, 11, 12, 19 to 24, 26, and
Compounds (9) having an R ⁷ moiety described in the substituent R ³ corresponding to 27, 29 to 45, 47, 48, 50 to 55 [compounds (9) ₈ , (9) ₉ ,
(9) ₁₁ , (9) ₁₂ , (9) ₁₉ to (9) ₂₄ , (9) ₂₆ ,
(9) ₂₇ , (9) _29- (9) ₄₅ , (9) ₄₇ , (9) ₄₈ ,
(9) ₅₀ to (9) ₅₅ . For example, compound (9) ₈
In the formula, R ^{7 in the} formula represented by the compound (9) is an ethoxy group. ].

The target compound produced as described above
(1) is the usual method such as extraction, concentration, filtration, etc.
Post-treatment, recrystallization and various chromatographic
It can be appropriately purified by a known means such as a fee.
As the compound (1), the compounds shown in Tables 3 to 9 described below
Compounds 1 to 56 [for example, compounds
1 represents R in the formula represented by the compound (1)¹Is 4-k
Lolophenyl group, R^TwoAnd R^ThreeAnd N together with -N = C (C
H_Three) N (CH _Three)_TwoAnd Q is 5-chloro-6-
It is a methyl-4-pyrimidinyl group. ].

The pests in agricultural and horticultural activities which are controlled by the compound (1) of the present invention include agricultural and horticultural insect pests such as Hemiptera (Orthoptera, leafhoppers, aphids,
Whiteflies, etc.), lepidopterans (armyworms, such as Spodoptera litura), moths, locust beetles, scabbards, sink beetles, cabbage beetles, etc., Coleoptera (e.g., beetles, weevil, chrysomelids, beetles, etc.),
Acarina (red spider mite of the spider mite family, spider mite, etc., citrus spider mite, etc.)], sanitary pests (eg, flies, mosquitoes, cockroaches, etc.), and grain storage pests (e.g., black beetles, etc.). Corn rootworm, root-knot nematode, pine wood nematode, spider mite and the like in soil can be mentioned, and agricultural and horticultural pathogens (for example, wheat rust, barley powdery mildew, cucumber downy mildew, rice blast,
Tomato blight etc.).

The agricultural and horticultural pesticidal composition of the present invention has a particularly remarkable insecticidal effect, and contains one or more compounds (1) as an active ingredient. Compound (1) is
It can be used alone, but usually by a usual method,
Carriers, surfactants, dispersants, adjuvants, etc. are blended (for example, prepared as compositions such as powders, emulsions, fine granules, granules, wettable powders, oily suspensions, and aerosols). Is preferred.

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea; hydrocarbons (kerosene, mineral oil, etc.), and aromatic hydrocarbons Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water, etc .; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection), and the like.

Examples of surfactants and dispersants which can be used to improve the performance of the agent, such as adhesion to animals and plants, absorption, and dispersion, emulsification, and spreading of drugs include alcohol sulfates and alkyls. Sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like can be mentioned. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as an auxiliary agent.

In the preparation of the present preparation, the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in appropriate combination according to the respective purposes.
When the compound (I) of the present invention is formulated, the concentration of the active ingredient is usually from 1 to 50% by weight in the emulsion, and usually from 0.3 to 0.3 in the powder.
25 to 25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils and 0.1 to 5% by weight for aerosols. is there.

These preparations can be diluted to an appropriate concentration and sprayed on the foliage of plants, soil, or the surface of paddy fields, or applied directly to various uses depending on the purpose.

[0095]

The present invention will be specifically described below with reference to examples. Note that these examples do not limit the scope of the present invention. Example 1 Synthesis of Compound (6) (1) Synthesis of 4-chloro-4 '-(4,6-dimethyl-2-pyrimidinyloxy) benzophenone [Compound (6) ₆ ]

4-Chloro-4'-hydroxybenzophenone (3.3 g), 2-chloro-4,6-dimethylpyrimidine (2.0 g) and potassium carbonate (3.0 g) were
Suspended in N, N-dimethylformamide (30 ml),
The mixture was heated and stirred at 70 to 80 ° C. for 10 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water was added, the target compound was extracted with ethyl acetate, washed with 2N sodium hydroxide, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. did.

The obtained oil was subjected to silica gel column chromatography (Micro Sphere Gel D).
-150-60A, toluene: ethyl acetate = 6: 1 elution), and the obtained crystals were washed with hexane to obtain 3.4 g of the target compound as a pale yellow powder. (2) Synthesis of compound (6) According to the method described in the above (1), R in the following Tables 3 to 9
Another compound (6) consisting of a combination of ¹ and Q was synthesized.

The compounds (6 ') among the compounds (6) synthesized as described above and their physical properties are shown in Tables 1 and 2.

[0099]

[Table 1]

[0100]

[Table 2]

Example 2 Synthesis of Compound (1) (1) 4-Chloro-4 '-(5-chloro-6-methyl-4
Synthesis of -pyrimidinyloxy) benzophenone 1-dimethylaminoethylidenehydrazone [compound 1] According to Production Method 1, it was synthesized as follows.

4-Chloro-4'-hydroxybenzophenone 1-dimethylaminoethylidenehydrazone (0.
7 g), 4,5-dichloro-6-methylpyrimidine (0.4 g) and potassium carbonate (0.5 g) were added to N, N
Suspended in dimethylformamide (20 ml), 70-
The mixture was heated and stirred at 80 ° C. for 8 hours. After completion of the reaction, the mixture was cooled to room temperature, water was added, the target compound was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure.

The obtained oil was purified by silica gel column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 10: 1) and crystallized with hexane to give the target compound as pale yellow crystals. .4
g was obtained.

(2) 4-chloro-4 '-(5-trifluoromethyl-2-pyridyloxy) benzophenone 1-
Synthesis of dimethylaminoethylidenehydrazone [compound 2] According to Production Method 1, it was synthesized as follows. 4-chloro-4′-hydroxybenzophenone 1-dimethylaminoethylidenehydrazone (0.7 g), 2-chloro-
5-Trifluoromethylpyridine (0.5 g) and potassium carbonate (0.4 g) were suspended in N, N-dimethylformamide (15 ml), and the mixture was heated and stirred at 70 to 80 ° C. for 8 hours.

After the completion of the reaction, the reaction mixture was cooled to room temperature, and water was added.
The target compound was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 20: 1).
Purification by elution) yielded 0.6 g of the target compound as a yellow oil.

(3) 4-chloro-4 '-(4,6-dimethoxy-2-pyrimidinyloxy) benzophenone 1-
Synthesis of dimethylaminoethylidenehydrazone [compound 3] According to Production Method 1, it was synthesized as follows. 4-chloro-4'-hydroxybenzophenone 1-dimethylaminoethylidenehydrazone (0.7 g), 4,6-dimethoxy-2-methanesulfonylpyrimidine (0.6 g)
And potassium carbonate (0.4 g) were suspended in N, N-dimethylformamide (15 ml) and heated and stirred at 70 to 80 ° C. for 8 hours.

After completion of the reaction, the mixture was cooled to room temperature, water was added,
The target compound was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 20: 1).
Purification by elution) yielded 0.4 g of the target compound as a yellow oil.

(4) 4-chloro-4 '-(4-methoxy-
Synthesis of 6-trifluoromethyl-2-pyrimidinyloxy) benzophenone 1-dimethylaminoethylidenehydrazone [compound 4] According to Production Method 1, it was synthesized as follows. 4-chloro-4'-hydroxybenzophenone 1-dimethylaminoethylidenehydrazone (0.54 g), 4-methoxy-6-trifluoromethyl-2-methanesulfonylpyrimidine (0.50 g) and potassium carbonate (0.5 g)
Was suspended in N, N-dimethylformamide (15 ml) and heated and stirred at 70 to 80 ° C. for 6 hours.

After the completion of the reaction, the mixture was cooled to room temperature, water was added,
The target compound was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 15: 2).
Purification by elution) yielded 0.15 g of the target compound as yellow crystals.

(5) Synthesis of 4-chloro-4 '-(4,6-dimethyl-2-pyrimidinyloxy) benzophenone 1-dimethylaminoethylidenehydrazone [compound 7] According to Production Method 2, it was synthesized as follows. . 4-chloro-4 ′-(4,6-dimethyl-2-pyrimidinyloxy) benzophenone hydrazone (0.8 g) and N,
N-dimethylacetamide dimethyl acetal (0.
The mixture of 6 g) was heated at reflux for 6 hours.

After completion of the reaction, the reaction mixture was cooled to room temperature, water was added,
The target compound was extracted with toluene, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by silica gel column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 4: 1) to obtain 0.4 g of the objective compound as yellow crystals.

(6) 4-chloro-4 '-(4,6-dimethyl-2-pyrimidinyloxy) benzophenone N'-
Synthesis of ethoxycarbonylhydrazone [compounds 8 and 9] According to Production Method 3, it was synthesized as follows. 4-chloro-4 '-(4,6-dimethyl-2-pyrimidinyloxy) benzophenone (0.6 g), ethyl carbazate ((0.6 g)) and a catalytic amount of boron trifluoride-ether complex (100 ml) and dehydrated by heating.

After completion of the reaction, the reaction mixture was cooled to room temperature, water was added,
The target compounds 8 and 9 were extracted with toluene, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil is subjected to silica gel column chromatography [Micro Sphere Gel D-150].
-60 A, toluene: ethyl acetate = (6: 1)-
(4: 1) elution] to obtain 0.2 g of each of the target compounds 8 and 9 as colorless crystals.

(7) 4-chloro-4 '-(4-methyl-6
Synthesis of -trifluoromethyl-2-pyrimidinyloxy) benzophenone 1-dimethylaminoethylidenehydrazone [compound 46] According to Production Method 1, it was synthesized as follows. 4-chloro-4'-hydroxybenzophenone 1-dimethylaminoethylidenehydrazone (0.8 g), 4-methyl-
6-trifluoromethyl-2-methanesulfonylpyrimidine (0.7 g) and potassium carbonate (0.5 g)
Suspended in N, N-dimethylformamide (15 ml),
The mixture was heated and stirred at 70 to 80 ° C for 6 hours.

After completion of the reaction, the reaction mixture was cooled to room temperature, water was added,
The target compound was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to silica gel column chromatography (Wakogel C-200, toluene: ethyl acetate = 20: 1).
Purification by elution) gave 0.8 g of the target compound as a viscous oil.

(8) 4-chloro-4 '-(4-methoxy-
6-trifluoromethyl-2-pyrimidinyloxy) benzophenone N'-acetylhydrazone [compound 50
And 51] According to Production Method 4, the following compounds were synthesized. 4-chloro-4 '-(4-methoxy-6-trifluoromethyl-
2-Pyrimidinyloxy) benzophenone hydrazone (0.45 g) and triethylamine (0.13 g) were dissolved in chloroform (20 ml), and acetic anhydride (0.13 g) dissolved in chloroform (5 ml) was added under ice-cooling. For 2 hours.

After completion of the reaction, water was added, the target compound was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil is subjected to silica gel column chromatography (Wakogel C-20).
0, toluene: ethyl acetate = 20: 1 elution) to give the target compound as a white powder in 0.00.0% each.
6 g were obtained.

(9) Synthesis of other compounds (1) in Tables 3 to 9 According to the methods described in the above (1) to (8), other compounds (1) in Tables 3 to 9 were synthesized. did. Tables 3 to 10 show the compounds synthesized as described above and their physical properties.

[0119]

[Table 3]

[0120]

[Table 4]

[0121]

[Table 5]

[0122]

[Table 6]

[0123]

[Table 7]

[0124]

[Table 8]

[0125]

[Table 9]

[0126]

[Table 10]

Example 3 [Preparation of preparation] (1) Preparation of granule 5 parts by weight of compound 1, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neoperex powder (trade name; manufactured by Kao Corporation) And 2 parts by weight of sodium ligninsulfonate were uniformly mixed, and then kneaded by adding a small amount of water, and then granulated and dried to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound 1, 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of Neoperex powder (trade name, manufactured by Kao Corporation) and Demol (trade name) Name; manufactured by Kao Corporation) and 0.5 parts by weight,
Then, it was ground to obtain a wettable powder.

(3) Preparation of Emulsion To 20 parts by weight of compound 1 and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name; manufactured by Sanyo Chemical Industries) was added, mixed uniformly, and dissolved to obtain an emulsion. .

(4) Preparation of powder 5 parts by weight of compound 1, 50 parts by weight of talc and kaolin 4
5 parts by weight were uniformly mixed to obtain a powder.

Example 4 [Efficacy Test] (1) Efficacy Test for Conger Compounds (1) prepared according to Example 2 and shown in Tables 3 to 9
Each hydration agent in water containing a surfactant (0.01%).
It was diluted to 0 ppm, and cabbage leaf pieces (5 × 5 cm) were immersed in each of these chemical solutions for 30 seconds, placed in each plastic cup one by one, and air-dried.

Next, 10 cup moths (3rd instar larvae) were released into each of these cups, covered, left in a constant temperature room at 25 ° C., and two days later, the number of live and dead insects in each cup was counted and killed. Insect rates were determined. The insecticidal effect was evaluated in four stages (A: 100%, B: less than 100 to 80%, C: 80) depending on the range of the mortality.
-60%, D: less than 60%).

Table 11 shows the results.

[0134]

[Table 11]

(2) Efficacy test for Spodoptera litura Compounds (1) prepared according to Example 2 and shown in Tables 3 to 9
Each wettable powder was diluted to 500 ppm with water containing a surfactant (0.01%), soybean leaves were immersed in each of these chemicals for 30 seconds, placed one by one into each plastic cup, and air-dried. did. In each of these cups, ten cutworm armyworms (2nd instar larvae) were released, covered, left in a constant temperature room at 25 ° C., and two days later, the number of live and dead insects in each cup was counted to determine the insecticidal rate.

The results of the evaluation of the insecticidal effect are shown in Table 12 by the four-step evaluation method described in the above (1).

[0137]

[Table 12]

(3) Efficacy test for Pleurotus terrestris (Compound 1) prepared according to Example 2 and shown in Tables 3 to 9
Was diluted to 500 ppm each with water containing a surfactant (0.01%), and 1 ml of each of these chemicals was dripped evenly onto filter paper (diameter 7.8 cm, 1 sheet) in each plastic cup. And air-dried.

In each of these cups, 10 larvae were released, and they were capped. The cups were allowed to stand in a constant temperature room at 25 ° C., and after 5 days, the number of live and dead insects in each cup was counted to determine the killing rate. I asked. The results of the evaluation of the insecticidal effect are shown in Table 13 by the four-step evaluation method described in the above (1).

[0140]

[Table 13]

[0141]

The novel heterocyclic oxybenzylidenehydrazine compound of the present invention has an excellent insecticidal effect.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁷ Identification code FI C07D 239/52 C07D 239/52 239/56 239/56 239/60 239/60 251/34 251/34 N 251/46 251 / 46 A (72) Inventor Takaaki Kuwata 578, Kogushi, Ube-shi, Ube-shi, Yamaguchi 5 Examiner at Ube Research Institute, Ube Industries, Ltd. Shinichi Naito (58) Field surveyed (Int. Cl. ⁷ , DB name) 34 A01N 43/40 101 A01N 43/54 A01N 43/66 C07D 213/64 C07D 239/52 C07D 239/56 C07D 239/60 C07D 251/34 C07D 251/46 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] 1. The following formula (1): Wherein, R ¹ represents a halogen atom an unsubstituted or substituted group, a phenyl group having a C1-4 alkyl group or a pyrimidinyl group carbons; R ² represents a hydrogen atom; R ³ is A hydrogen atom, an alkoxycarbonyl group having 2 to 5 carbon atoms or an acyl group having 2 to 5 carbon atoms;
Alternatively, R ² and R ³ together with N, -N = CR ⁴ NR ⁵
R ⁶ may be formed (R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 4 carbon atoms);
Represents a halogen atom as a substituent or a substituent,
4 alkyl groups, an alkylthio group having 1 to 4 carbon atoms,
C1-C4 alkoxy group, C1-C4 haloalkyl group, C1-C4 haloalkoxy group or C1-C8 alkylamino group having 1-3 nitrogen atoms Represents a 6-membered ring. And a heterocyclic oxybenzylidenehydrazine compound represented by the formula: 2. The following formula (2): (Wherein R ¹ , R ² and R ³ are as defined in claim 1) and a compound represented by the following formula (3): (Wherein Q has the same meaning as described in claim 1; Z represents a leaving group). The compound represented by the formula (1) according to claim 1, wherein A method for producing the indicated heterocyclic oxybenzylidenehydrazine compound. 3. The following formula (4): (Wherein R ¹ and Q are as defined in claim 1) and a compound represented by the following formula (5): (Wherein R ⁴ , R ⁵ and R ⁶ have the same meaning as in claim 1), characterized by reacting with a compound represented by the following formula (1a): (Wherein, R ¹ , R ⁴ , R ⁵ , R ⁶ and Q have the same meanings as described in claim 1). A process for producing a heterocyclic oxybenzylidenehydrazine compound represented by the formula 4. The following formula (6): (Wherein R ¹ and Q are as defined in claim 1) and a compound of the following formula (7): (Wherein, R ² and R ³ have the same meanings as described in claim 1), and are reacted with a compound represented by the formula (1). A method for producing an oxybenzylidene hydrazine compound. 5. The following formula (6 ′): (In the formula, R ¹ has the same meaning as in claim 1. Q ′
Is a pyrimidinyl group, a pyridyl group having a haloalkyl group having 1 to 4 carbon atoms as a substituent or a triazinyl group having an alkoxy group having 1 to 4 carbon atoms and an alkylamino group having 1 to 8 carbon atoms as a substituent Represents ). 6. The following formula (8): (Wherein R ¹ , R ² and Q are as defined in claim 1) and a compound of the following formula (9): (Wherein, R ⁷ represents an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms; Z ′ represents a leaving group). The following formula (1b) is characterized by the following: (Wherein, R ¹ , R ² and Q have the same meanings as described in claim 1; R ⁷ has the same meaning as described above.) A process for producing a heterocyclic oxybenzylidenehydrazine compound represented by the formula: 7. A pest control agent for agricultural and horticultural use comprising the heterocyclic oxybenzylidenehydrazine compound represented by the formula (1) according to claim 1 as an active ingredient.