JPH10273485A - Diphenylmethyl heterocyclic compound, process for producing the same, and insecticide for agricultural and horticultural use - Google Patents

Abstract

(57) [Summary] PROBLEM TO BE SOLVED: To provide a new useful insecticide for agricultural and horticultural use.
To provide a specific diphenylmethyl heterocyclic compound
Make it an issue. SOLUTION: The diphenylmethyl heterocyclic compound of the present invention
The thing is the following formula Embedded image [Wherein, R¹Represents a halogen atom;^TwoIs C1-4
X represents an alkyl group or a C1-4 haloalkyl group;
Represents a C1-4 alkylene group or an oxygen atom;
Represents an integer of 2; Y¹~ Y^ThreeAre independently nitrogen sources
Child or CR^Three(R ^ThreeAre independently halogen sources
, A C1-4 alkyl group, a C1-4 thioalkyl
Group). ] Is shown.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel diphenylmethyl heterocyclic compound useful as an insecticide for agricultural and horticultural use.

[0002]

BACKGROUND OF THE INVENTION Since the novel diphenylmethyl heterocyclic compound of the present invention is a novel compound, it is not known that it has an insecticidal activity for agricultural and horticultural purposes.

[0003]

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

[0004]

Means for Solving the Problems As a result of investigations to solve the above problems, the present inventors have found that a novel diphenylmethyl heterocyclic compound has a remarkable insecticidal activity for agricultural and horticultural use. Completed the invention. That is, the present invention is as follows. According to a first aspect, the following formula (1):

[0005]

Embedded image

[Wherein, R ¹ represents a halogen atom;
² is an alkyl group having 1 to 4 carbon atoms or 1 carbon atom
X represents 1 to 4 haloalkyl groups; X represents 1 to 4 carbon atoms
Represents an alkylene group or an oxygen atom; n represents an integer of 0 to 2; Y ^{1 to} Y ³ each independently represent a nitrogen atom or CR ³ (R ³ represents each independently a halogen atom, a carbon atom An alkyl group having 1 to 4 carbon atoms or an alkylthio group having 1 to 4 carbon atoms). And a diphenylmethyl heterocyclic compound represented by the formula: The second invention provides the following formula (2):

[0007]

Embedded image

(Wherein R ¹ and R ² have the same meanings as described above; Q represents a hydroxyl group or a halogen atom). A third invention provides the following equation (3):

[0009]

Embedded image

(Wherein R ¹ , R ² , X and n are as defined above; E represents a leaving group) and the following formula (4):

[0011]

Embedded image

(Wherein Y ^{1 to} Y ³ have the same meanings as described above), and a method for producing a diphenylmethyl heterocyclic compound represented by the above formula (1). It is about. The fourth invention relates to an insecticide for agricultural and horticultural use containing the diphenylmethyl heterocyclic compound represented by the above formula (1) as an active ingredient.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
I do. Diphenyl of the target compound represented by the above formula (1)
Methyl heterocyclic compound [Compound (1)]
Phenylmethane compound [compound (2)]
R ¹, R^Two, X, Y¹~ Y^Three, Q, etc. are as follows
You.

[R ¹ ] Examples of R ¹ include a halogen atom. As the halogen atom, a chlorine atom,
Examples include iodine, bromine and fluorine atoms; preferably chlorine atoms. The position of the substituent is not particularly limited; however, it is preferably the 4-position.

[R ² ] R ² represents 1 to 4 carbon atoms.
And an alkyl group having 1 to 4 carbon atoms, but preferably an alkyl group having 1 to 4 carbon atoms in the compound (1) and 1 to 4 carbon atoms in the compound (2). 4 haloalkyl group. Alkyl groups can be straight or branched; preferably C ₂ H ₅ . As the haloalkyl group, alkyl is linear or branched, and a chlorine atom,
Examples thereof include those having an iodine atom, a bromine atom, and a fluorine atom; preferably those having a fluorine atom; and more preferably CF ₃ . [X] X is an alkylene group having 1 to 4 carbon atoms,
Oxygen atoms can be mentioned. Alkylene groups include straight or branched ones;
Preferably it is CH _2. [N] n represents an integer of 0 to 2.

[Y] Y ^{1 to} Y ³ together with two nitrogen atoms form a 5-membered ring; each of Y ¹ to Y ³ independently represents a nitrogen atom or CR ³ . R ³ is each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms,
An alkylthio group having 1 to 4 carbon atoms can be mentioned. Examples of the halogen atom in R ³ include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; preferably a chlorine atom. Examples of the alkyl group for R ³ include linear or branched ones; preferably CH ₃ . The alkylthio group for R ³ may be a straight-chain or branched one; preferably, SCH ₃ . Preferred 5-membered rings include H as shown in Table 1 below.
Heterocycles such as et1-5 can be mentioned; more preferably Het1-4.

[0017]

[Table 1]

As the compound (1), the above-mentioned various substituents
Can be mentioned as a combination of
Preferred from the viewpoint is as follows. (1) R¹Is a 4-halogen atom, R^TwoIs the number of carbon atoms
X is an alkyl group having 1 to 4 carbon atoms, and X is an alkyl group having 1 to 4 carbon atoms.
A alkylene group, n is 0, and (Y¹~ Y^ThreeAnd two
5-membered ring formed with the nitrogen atom of
some stuff. (2) R¹Is a 4-halogen atom, R^TwoIs the number of carbon atoms
1 to 4 haloalkyl groups, X is an oxygen atom,
n is 2 and (Y¹~ Y^ThreeFormed with and two nitrogen atoms
Is a Het1 type. As shown in (1) and (2), which consist of these preferred combinations
R of the compound (1) ¹, R^Two, X, n and (Y¹~ Y
^ThreeAnd a five-membered ring formed by two or three nitrogen atoms)
Are the preferred ones described in the above description, and more preferred.
Preferred examples can be illustrated.

The compound (2) preferably includes those having R ¹ , R ² and Q corresponding to the above-mentioned compound (1); more preferred are the following: . (1) R ¹ is a 4-halogen atom, R ² is a haloalkyl group having 1 to 4 carbon atoms, and Q is a hydroxyl group. (2) R ¹ is a 4-halogen atom, R ² is a haloalkyl group having 1 to 4 carbon atoms, and Q is a halogen atom. [Production method of compound (1)] The compound (1) can be synthesized by reacting the compound (3) with the compound (4) in the absence or in a solvent as shown below. If necessary, a base catalyst or an acid catalyst can be used.

[0020]

Embedded image

Where R ¹ , R ² , X, n, E and Y ¹
To Y ³ have the same meaning as described above. The leaving group (E) is not particularly limited, and examples thereof include a hydroxyl group, a halogen atom, an alkylsulfonyloxy group, and an aralkylsulfonyloxy group. The type of the solvent is not particularly limited as long as it does not directly participate in the present reaction, and examples thereof include chlorinated or non-chlorinated aromatic, aliphatic, alicyclic hydrocarbons, ethers, and ketones. , Alcohols or hydrates thereof, amides, nitriles, organic bases, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide, and mixtures of the above-mentioned solvents.

The chlorinated or unaromatic aromatic, aliphatic and alicyclic hydrocarbons include benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, and chloride. Methylene, chloroform, dichloroethane, trichloroethylene, cyclohexane and the like can be mentioned. Examples of ethers include diethyl ether, tetrahydrofuran, dioxane, and the like. Examples of ketones include acetone and methyl ethyl ketone. Examples of alcohols include methanol, ethanol, ethylene glycol and the like.

Examples of the amide include N, N-dimethylformamide and N, N-dimethylacetamide. Nitriles include acetonitrile,
Propionitrile and the like can be mentioned. Examples of ketones include acetone and methyl ethyl ketone. As the organic base, triethylamine,
Pyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] undec-7-ene and the like can be mentioned.

The amount of the solvent used is such that the compound (1)
80% by weight; preferably 1-70% by weight. Examples of the type of the base catalyst include triethylamine, pyridine, 4-N, N-dimethylaminopyridine, N, N-dimethylaniline, 1,4-diazabicyclo [2.2.2] octane, and 1,8-diazabicyclo [ 54.0] Organic bases such as undec-7-ene; alkali metal alkoxides; alkoxides such as sodium methoxide, sodium ethoxide, potassium-t-butoxide; sodium hydride, potassium hydride, sodium amide; Sodium hydroxide, potassium hydroxide,
Inorganic bases such as potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate; and lithium diisopropylamide and bistrimethylsilyllithium amide.

Examples of the type of acid catalyst include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid; and organic acids such as formic acid, acetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid monohydrate. Acid addition salts of amines such as pyridine hydrochloride and triethylamine hydrochloride; metal halides such as titanium tetrachloride, zinc chloride, ferrous chloride and ferric chloride; and boron trifluoride etherate. it can. The amount of the base catalyst or the acid catalyst to be used is 0.001 to 1-fold the molar amount of the compound (3). The amount of the starting compound used is such that the compound (4) is 0.5 to 50-fold the molar amount of the compound (3); preferably 0.8 to 10 times.
It is twice the mole.

The reaction temperature is not particularly limited, but may be from 0 to 2
00 ° C; preferably between room temperature and 100 ° C. The reaction time varies depending on the above concentration and temperature, but is usually 0.1 to 100 hours; preferably 0.3 to 24 hours.
Time. For example, as shown below, when the leaving group E is a hydroxyl group, the compound (3 ′) is a compound (3 ′) corresponding to the corresponding benzophenone according to the method described in JP-A-9-3038. It can be produced by reducing (5).

[0027]

Embedded image (In the formula, R ¹ , R ² , X and n are as defined above.)

The compound (3 ″) in which the leaving group E is a halogen atom and an alkylsulfonate group can be produced from the corresponding hydroxyl compound (3 ′) by a known method. When it is a chloro group, it is described in J. Org. Chem. 14, 706 (1949).
And by reacting with a chlorinating agent such as thionyl chloride, as shown below.

[0029]

Embedded image

Compound (4) can be produced by a known method if a commercially available product cannot be used. For example, various pyrazoles are described in "The Che
mystery of Heterocyclic Che
history ”, IntersciencePubli
shers, New York, 1967, vol. 22,
It can be produced by the method described on pages 81 to 137 and the like. After completion of the reaction, the target compound (1) produced as described above is subjected to ordinary post-treatments such as extraction, concentration and filtration, and if necessary, by known means such as recrystallization and various types of chromatography. It can be appropriately purified.

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.), lepidoptera (armyworms such as Spodoptera litura), moths, leaf snails, pygmy moths, sink beetles, white butterfly, etc., Coleoptera (e.g., Tenebrion beetles, weevil, chrysomelids, beetles), mites ( Corn spider mites such as red mites and red spider mites, and spider mites of the family Scarabaeidae), sanitary pests (eg, flies, mosquitoes, cockroaches, etc.), stored pests (e. G. Root worms, root-knot nematodes, pine wood nematodes, ticks and the like can be mentioned. The agricultural and horticultural insecticide of the present invention contains, as an active ingredient, at least one specific compound falling under the category of compound (1).

The compound (1) can be used as it is, but usually, a carrier, a surfactant,
It is preferable to use a dispersant, an auxiliary agent and the like compounded (for example, prepared as a composition such as powder, emulsion, fine granule, granule, wettable powder, oily suspension and aerosol).

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.), aromatic carbon 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, improvement of 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 production of the present agent, the above-mentioned carrier, surfactant, dispersant, and auxiliary can be used alone or in appropriate combination according to the respective purposes. When the compound (1) of the present invention is formulated, the concentration of the active ingredient is usually 1 to 50% by weight for emulsions, usually 0.3 to 25% by weight for powders, and usually 1 to 90% for wettable powders.
% By weight, 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. These preparations can be diluted to an appropriate concentration and applied to various uses by spraying them on plant foliage, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0035]

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 (1) (1) Synthesis of 1- [4-chloro-4 ′-(ethylthiomethyl) diphenylmethyl] pyrazole [Compound 1] 4-chloro-4 ′-(ethylthiomethyl ) Diphenylmethyl chloride (0.8 g), pyrazole (0.8 g)
Was dissolved in acetonitrile (5 ml) and heated under reflux for 4 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with toluene. Wash the toluene solution with saturated saline,
After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Micro Sphere Gel D-150-6).
0A, toluene: ethyl acetate = 10: 1) to give the target compound as a colorless oil in 0.7%.
g was obtained.

(2) Synthesis of other compound (1) in Table 2 According to the method described in (1), other compound (1) in Table 2 was synthesized. Compounds 4 to 6 represent any of the following three types of five-membered rings.

[0037]

Embedded image

Table 2 shows the compound (1) synthesized as described above and its physical properties.

[0039]

[Table 2]

Example 2 [Synthesis of Compound (2)] (1) 4-chloro-4 '-(trifluoromethanesulfonyloxy) diphenylmethyl alcohol [Compound (2-
1)] Synthesis of 4-chloro-4 ′-(trifluoromethanesulfonyloxy) benzophenone (16 g) in methanol (100
ml), sodium borohydride (1 g) was gradually added under stirring at room temperature, and the mixture was further stirred at room temperature for 3 hours.
After completion of the reaction, methanol was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated saline and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 16.5 g of the target compound as a colorless oil.
Obtained. ¹ H-NMR (CDCl ₃ , δ ppm) 2.37 (1H, br.s), 5.81 (1H, s),
7.21 to 7.48 (8H, m)

(2) Synthesis of 4-chloro-4 '-(trifluoromethanesulfonyloxy) diphenylmethyl chloride [compound (2-2)] 4-chloro-4'-(trifluoromethanesulfonyloxy) diphenylmethyl alcohol ( A solution of 16.4 g), thionyl chloride (16 g) and toluene (100 ml) was heated and stirred for 3 hours. After the completion of the reaction, the mixture was poured into water and extracted with toluene. The toluene layer was washed twice with saturated sodium hydrogen carbonate and water twice, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue is subjected to column chromatography (Wakogel C-200, eluted with toluene)
And purified the target compound as a pale yellow oil in 16.2.
g was obtained. ¹ H-NMR (CDCl ₃ , δ ppm) 6.08 (1H, s), 7.18 to 7.49 (8H,
m)

Table 3 shows the compound (2) synthesized as described above and its physical properties.

[0043]

[Table 3]

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, 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 (product) Name; manufactured by Kao Corporation)
Then, it was pulverized to obtain a wettable powder.

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

(4) Preparation of dust 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 Japanese moth Each wettable powder of compound (1) shown in Table 2 prepared according to Example 3 contains a surfactant (0.01%). 300p with water
pm, and the cabbage leaf pieces (5 ×
5 cm) was immersed for 30 seconds, placed one by one in each plastic cup, and air-dried. Next, 10 moths (3rd instar larvae) were released into each of these cups, covered, and allowed to stand in a constant temperature room at 25 ° C. After 2 days, the number of live and dead insects in each cup was counted to determine the mortality. I asked. The insecticidal effect was evaluated in four stages (A: 100%, B: less than 100 to 80) depending on the range of the insecticidal rate.
%, C: less than 80 to 60%, D: less than 60%). Table 4 shows the results.

[0049]

[Table 4]

[0050]

Industrial Applicability The novel diphenylmethyl heterocyclic compound of the present invention has an excellent agricultural and horticultural insecticidal effect.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07C 309/65 C07C 309/65 C07D 231/16 C07D 231/16 249/04 505 249/04 505 249/08 501 501 249/08 501 257/04 257/04 A (72) Inventor Kiyoshi Tsutsuuchi Ube Research Institute, Ube City, Yamaguchi Prefecture, 5-1978 Ube Kogyo Co., Ltd. Ube Laboratory Co., Ltd.

Claims (4)

[Claims] (1) The following formula (1): [In the formula, R ¹ represents a halogen atom; R ² represents an alkyl group having 1 to 4 carbon atoms or a haloalkyl group having 1 to 4 carbon atoms; X represents an alkylene having 1 to 4 carbon atoms. Y represents a group or an oxygen atom; n represents an integer of 0 to 2;
^{1 to} Y ³ are each independently a nitrogen atom or CR ³ (R
³ is independently a halogen atom, 1 to 1 carbon atoms
4 alkyl groups, alkylthio groups having 1 to 4 carbon atoms)
Represents And a diphenylmethyl heterocyclic compound represented by the formula: 2. The following formula (2): (Wherein, R ¹ and R ² have the same meanings as described in claim 1; Q represents a hydroxyl group or a halogen atom). 3. The following formula (3): (Wherein R ¹ , R ² , X and n have the same meanings as in claim 1; E represents a leaving group) and a compound represented by the following formula (4): (Wherein Y ^{1 to} Y 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 a heterocyclic compound. 4. An agricultural and horticultural insecticide comprising the diphenylmethyl heterocyclic compound represented by the formula (1) according to claim 1 as an active ingredient.