JP7569031B2 - Pyridine-based fluorine-containing aromatic compound, its method of manufacture and pest control agent containing the same as an active ingredient - Google Patents

Description

The present invention relates to a novel pyridine-based fluorine-containing aromatic compound, a method for producing the compound, and a pest control agent containing the compound as an active ingredient.

Pyriproxyfen has been used as an insecticide that has insect juvenile hormone-like activity, and has been put to practical use to control insects of the orders Coleoptera, Lepidoptera, Hemiptera, Orthoptera, Diptera, Thysanoptera, Crypoptera, and Isoptera, as well as mites such as spider mites (see, for example, Patent Document 1).

Tokuho 5-64140

However, the number of pests resistant to pyriproxyfen is increasing, and compounds with better pest control efficacy are needed.

In view of the above situation, the present inventors conducted extensive research to find a compound with superior pest control efficacy, and discovered that the compound represented by the following formula (I) has extremely excellent juvenile hormone-like activity, leading to the present invention.

［式中、Ｒはハロゲン原子を表わし、ｎは１～３の整数を表わす。ｎが２または３を表わす場合、個々のＲは同一または相異なる。※は不斉炭素を表わす。］で示されるピリジン系含フッ素芳香族系化合物（以下、本発明化合物という）、その製造方法ならびに本発明化合物を有効成分として含有する有害生物防除剤および本発明化合物の有効量を有害生物または有害生物の生息場所に施用することを特徴とする有害生物の防除方法を提供するものである。 That is, the present invention provides:
(Formula I)

[wherein R represents a halogen atom, and n represents an integer of 1 to 3. When n represents 2 or 3, each R may be the same or different. * represents an asymmetric carbon.] (hereinafter referred to as the compound of the present invention), a method for producing the compound, a pest control agent containing the compound of the present invention as an active ingredient, and a method for controlling pests, which comprises applying an effective amount of the compound of the present invention to pests or to their habitats.

Compounds of the present invention are significantly different from conventional insecticides in that they have extremely excellent juvenile hormone-like activity against insects. In other words, they exhibit effects such as inhibiting metamorphosis into adults, inhibiting egg hatching, and sterilizing adults. As a result, compounds of the present invention act primarily as growth regulators, sterilizers, ovicides, or growth inhibitors against various pests, including those that are resistant to existing insecticides, such as agricultural, forestry, and horticultural pests, stored grain pests, and sanitary pests, and can exert a high control effect.

［式中、Ｒはハロゲン原子を表わし、ｎは１～３の整数を表わす。ｎが２または３を表わす場合、個々のＲは同一または相異なる。※は不斉炭素を表わす。］
で示される含フッ素アルコール系化合物と、
式（ＩＩＩ）

［式中、Ｘはフッ素原子または塩素原子を表わす。］
で示される２－ハロゲン置換ピリジン系化合物とを反応させることにより製造することができる。 The compound represented by formula (I) can be prepared, for example, by the following method.
That is, formula (II)

[In the formula, R represents a halogen atom, and n represents an integer of 1 to 3. When n represents 2 or 3, each R may be the same or different. * represents an asymmetric carbon.]
and a fluorine-containing alcohol compound represented by the formula:
Formula (III)

[In the formula, X represents a fluorine atom or a chlorine atom.]
The compound can be produced by reacting a 2-halogen-substituted pyridine compound represented by the following formula:

The reaction is preferably carried out under basic conditions, more specifically in the presence of an acid binder (acid scavengers). Suitable acid binders (acid scavengers) include, for example, alkali metals such as metallic sodium, alkyl lithium reagents, alkali metal hydrides such as sodium hydride, alkali metal amides, and alkali hydroxides.

The reaction is preferably carried out without a solvent or in an inert solvent, and examples of such inert organic solvents include dimethylformamide, dimethylsulfoxide, tetrahydrofuran, dimethoxyethane, toluene, and mixtures of two or more of these.

If necessary, a phase transfer catalyst such as an ammonium salt (such as triethylbenzylammonium chloride or tetra-n-butylammonium bromide) may be added to the reaction system. In this case, water can also be used as the solvent.

The reaction time is not particularly limited, but is usually within the range of 5 minutes to 72 hours.
The reaction temperature is usually in the range of −20° C. to 100° C. (however, when the boiling point of the solvent used is lower than 100° C., −20° C. to the boiling point of the solvent), and preferably in the range of −5° C. to 100° C. (however, when the boiling point of the solvent used is lower than 100° C., −5° C. to the boiling point of the solvent).

In the reaction, the molar ratio of the fluorine-containing aromatic compound represented by formula (II) to the pyridine compound represented by formula (III) is usually 1:0.5-10, preferably 1:0.8-2.0.
The compounds obtained by the above-mentioned production methods can be purified by means of recrystallization, column chromatography and the like, if necessary.

［式中、Ｒはハロゲン原子を表わし、ｎは１～３の整数を表わす。ｎが２または３を表わす場合、個々のＲは同一または相異なる。］ The raw material compound represented by the formula (II) can be produced, for example, by reacting a fluorine-containing phenoxyphenol represented by the formula (IV) with propylene oxide in the presence of an alkali hydroxide salt and a tetrabutylammonium salt.
(IV)

[In the formula, R represents a halogen atom, and n represents an integer from 1 to 3. When n represents 2 or 3, each R is the same or different.]

［式中、Ｒはハロゲン原子を表わし、ｎは１～３の整数を表わす。ｎが２または３を表わす場合、個々のＲは同一または相異なる。］ The halogen-substituted fluorine-containing phenoxyphenol compound represented by formula (IV) is novel and can be produced by the method shown below. The synthesis scheme is shown below.

[In the formula, R represents a halogen atom, and n represents an integer from 1 to 3. When n represents 2 or 3, each R is the same or different.]

The following is an example of the preparation of the compound of the present invention: Proton NMR spectrum was measured using a JEOL 500 MHz system.
Production Example 1
1-[3-Fluoro-4-(3-fluorophenoxy)phenoxy]-2-(2-pyridyloxy)-propane [compound (1)] was synthesized according to the route described below.

1) Synthesis of 3-fluoro-4-(3-fluorophenoxy)anisole 2 mL of dimethylformamide was placed in a reaction vessel, to which 1.05 g of 3-fluorophenol, 1.44 g of 4-bromo-3-fluoroanisole, 1.16 g of potassium carbonate, 73 mg of cuprous chloride, and 73 mg of cuprous iodide were added, and the mixture was stirred at 150°C for 8 hours under a nitrogen stream. The reaction solution was poured into 10 mL of ice-cooled 5% hydrochloric acid, and extracted twice with 30 mL of ethyl acetate. The ethyl acetate layers were combined, washed with saturated sodium bicarbonate water and then with saline, and then dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the mixture was purified by silica gel column chromatography to obtain 276 mg of 3-fluoro-4-(3-fluorophenoxy)anisole.
<NMR data>
7.22 (1H, tt), 7.05 (1H, t), 6.76 (1H, d), 6.68 to 6.74 (3H, m), 6.60 (1H, dt), 3.80 (3H, s),

2) Synthesis of 3-fluoro-4-(3-fluorophenoxy)phenol 2 mL of dichloromethane was placed in a reaction vessel, and 276 mg of 3-fluoro-4-(3-fluorophenoxy)anisole was cooled to -70°C while stirring and dissolving, and 2 mL of boron tribromide (1M solution) was added to the reaction vessel, followed by stirring for 12 hours. The reaction solution was poured into 5 mL of ice-cooled 5% hydrochloric acid, and extracted twice with 20 mL of ethyl acetate. The ethyl acetate layers were combined, washed with saline, and then dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, 250 mg of 3-fluoro-4-(3-fluorophenoxy)phenol was obtained. This was used in the next reaction without purification.
<NMR data>
7.22 (1H, tt) 7.00 (1H, t), 6.58 to 6.75 (5H, m),

3) Synthesis of 1-[3-fluoro-4-(3-fluorophenoxy)phenoxy]-2-propanol 2.5 mL of toluene was placed in a reaction vessel, and 250 mg of 3-fluoro-4-(3-fluorophenoxy)phenol was dissolved therein, followed by the addition of a solution of 180 mg of sodium hydroxide dissolved in 0.5 mL of water. 0.50 mL of propylene oxide and 80 mg of tetrabutylammonium bromide were further added and stirred for 12 hours. 20 mL of ethyl acetate and 20 mL of saturated saline were added to the reaction solution and the mixture was separated. The aqueous layer was further extracted with 20 mL of ethyl acetate. The ethyl acetate layers were combined, washed with 30 mL of saturated saline, and then dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the mixture was purified by silica gel column chromatography to obtain 201 mg of 1-[3-fluoro-4-(3-fluorophenoxy)phenoxy]-2-propanol.
<NMR data>
7.22 (1H, dt) 7.06 (1H, t), 6.67 to 6.78 (4H, m), 6.60 (1H, dt), 4.20 (1H, m), 3.92 (1H, dd), 3.79 (1H, dd), 1.29 (3H, d),

4) Synthesis of 1-[3-fluoro-4-(3-fluorophenoxy)phenoxy]-2-(2-pyridyloxy)-propane [Compound (1)] 3 mL of dimethylformamide was placed in a reaction vessel, 201 mg of 1-[3-fluoro-4-(3-fluorophenoxy)phenoxy]-2-propanol and 0.15 mL of 2-fluoropyridine were added and stirred to dissolve, and 64 mg of sodium hydride (60%) was added under ice cooling, and then stirred at room temperature for 12 hours. The reaction solution was poured into 15 mL of ice water and extracted twice with 20 mL of ethyl acetate. The ethyl acetate layers were combined, washed with 20 mL of saturated saline, and dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the mixture was purified by silica gel column chromatography to obtain 139 mg of 1-[3-fluoro-4-(3-fluorophenoxy)phenoxy]-2-(2-pyridyloxy)-propane [Compound (1)].
<NMR data>
8.15 (1H, dd), 7.58 (1H, m), 7.21 (1H, dt), 7.03 (1H, t),
6.87 (1H, dd), 6.83 (1H, dd), 6.67-6.76 (4H, m), 6.59 (1H, dt), 5.58 (1H, m), 4.18 (1H, dd), 4.07 (1H, dd), 1.48 (3H, d)

Production Example 2
1-[3-Fluoro-4-(4-fluorophenoxy)phenoxy]-2-(2-pyridyloxy)-propane [compound (2)] was synthesized according to the following route.

1) Synthesis of 3-fluoro-4-(4-fluorophenoxy)anisole 2 mL of dimethylformamide was placed in a reaction vessel, to which 908 mg of 4-fluorophenol, 1.25 g of 4-bromo-3-fluoroanisole, 390 mg of sodium methylate, and 135 mg of cuprous chloride were added, and the mixture was stirred at 152°C under a nitrogen stream for 13 hours. The reaction solution was poured into 10 mL of ice-cooled 5% hydrochloric acid, and extracted twice with 30 mL of ethyl acetate. The ethyl acetate layers were combined, washed with saturated sodium bicarbonate water and then with saline, and then dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the mixture was purified by silica gel column chromatography to obtain 280 mg of 3-fluoro-4-(4-fluorophenoxy)anisole.
<NMR data>
6.94-7.02 (3H, m), 6.86-6.89 (2H, m), 6,74 (1H, dd), 6.65 (1Hdq), 3.79 (3H, s)

2) Synthesis of 3-fluoro-4-(4-fluorophenoxy)phenol 7 mL of dichloromethane was placed in a reaction vessel, 280 mg of 3-fluoro-4-(4-fluorophenoxy)anisole was added thereto, and the mixture was cooled to -70°C while stirring and dissolving, and 2 mL of boron tribromide (1M solution) was added thereto, followed by stirring for 12 hours. The reaction solution was poured into 5 mL of ice-cooled 5% hydrochloric acid solution, and extracted twice with 20 mL of ethyl acetate. The ethyl acetate layers were combined, washed with saline, and then dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, 250 mg of 3-fluoro-4-(4-fluorophenoxy)phenol was obtained. This was used in the next reaction without purification.
<NMR data>
6.85-6.99 (5H, m), 6.69 (1H, dd), 6.57 (1H, dq),

3) Synthesis of 1-[3-fluoro-4-(4-fluorophenoxy)phenoxy]-2-propanol 2.5 mL of toluene was placed in a reaction vessel, 250 mg of 3-fluoro-4-(4-fluorophenoxy)phenol was added to it, and after stirring and dissolving, a solution of 188 mg of sodium hydroxide dissolved in 0.5 mL of water was added. Further, 0.50 mL of propylene oxide and 66 mg of tetrabutylammonium bromide were added and stirred for 12 hours. 20 mL of ethyl acetate and 20 mL of saturated saline were added to the reaction solution and the liquids were separated. The aqueous layer was further extracted with 20 mL of ethyl acetate. The ethyl acetate layers were combined, washed with 30 mL of saturated saline, and then dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the mixture was purified by silica gel column chromatography to obtain 249 mg of 1-[3-fluoro-4-(4-fluorophenoxy)phenoxy]-2-propanol.
<NMR data>
6.86-6.99 (5H, m), 6.76 (1H, dd), 6.66 (1H, dq), 4.19 (1H, m), 3.91 (1H, dd), 3.77 (1H, dd), 1.29 (3H, d)

4) Synthesis of 1-[3-fluoro-4-(4-fluorophenoxy)phenoxy]-2-(2-pyridyloxy)-propane [Compound (2)] 3 mL of dimethylformamide was placed in a reaction vessel, and 230 mg of 1-[3-fluoro-4-(4-fluorophenoxy)phenoxy]-2-propanol and 159 mg of 2-fluoropyridine were added and dissolved therein. 66 mg of sodium hydride (60%) was then added under ice cooling and stirred at room temperature for 12 hours. The reaction solution was poured into 15 mL of ice water and extracted twice with 20 mL of ethyl acetate. The ethyl acetate layers were combined, washed with 20 mL of saturated saline, and dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the product was purified by silica gel column chromatography to obtain 221 mg of 1-[3-fluoro-4-(4-fluorophenoxy)phenoxy]-2-(2-pyridyloxy)-propane [Compound (2)].
<NMR data>
8.14 (1H, d), 7.56 (1H, dt), 6.95 (3H, m), 6.86 (3H, m), 6.82 (1H, dd), 6.74 (1H, d), 6.69 (1H, br.d)), 5.58 (1H, mm), 4.18 (1H, dd), 4.05 (1H, dd) ), 1.47 (3H, d)

Production Example 3
1-[3-Fluoro-4-(3,5-difluorophenoxy)phenoxy]-2-(2-pyridyloxy)-propane [compound (3)] was synthesized according to the following route.

1) Synthesis of 3-fluoro-4-(3,5-difluorophenoxy)anisole 803 mg of 3,5-difluorophenol, 1.0 g of 4-bromo-3-fluoroanisole, 320 mg of sodium carbonate, 414 mg of potassium carbonate, and 100 mg of cuprous chloride were added to a reaction vessel and stirred at 165°C under a nitrogen stream for 12 hours. The reaction solution was poured into 10 mL of ice-cooled 5% hydrochloric acid solution and extracted twice with 30 mL of ethyl acetate. The ethyl acetate layers were combined, washed with saturated sodium bicarbonate solution and then with saline, and dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the mixture was purified by silica gel column chromatography to obtain 282 mg of 3-fluoro-4-(3,5-difluorophenoxy)anisole.
<NMR data>
7.06 (1H, t), 6.75 (1H, dd), 6.69 (1H, dq), 6,48 (1H, tt), 6.40 (2H, dd), 3.81 (3H, s),

2) Synthesis of 3-fluoro-4-(3,5-difluorophenoxy)phenol 5 mL of dichloromethane was added to a reaction vessel, 282 mg of 3-fluoro-4-(3,5-difluorophenoxy)anisole was added thereto, and the mixture was cooled to -70°C while stirring and dissolving, and 1.7 mL of boron tribromide (1M solution) was added, followed by stirring for 12 hours. The reaction solution was poured into 5 mL of ice-cooled 5% hydrochloric acid solution, and extracted twice with 20 mL of ethyl acetate. The ethyl acetate layers were combined, washed with saline, and then dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, 260 mg of 3-fluoro-4-(3,5-difluorophenoxy)phenol was obtained. This was used in the next reaction without purification.
<NMR data>
7.01 (1H, t) 6.71 (1H, dd), 6.62 (1H, dq), 6,47 (1H, tt), 6.41 (2H, dd),

3) Synthesis of 1-[3-fluoro-4-(3,5-difluorophenoxy)phenoxy]-2-propanol 3 mL of toluene was added to a reaction vessel, 260 mg of 3-fluoro-4-(3,5-difluorophenoxy)phenol was added and dissolved, and a solution of 160 mg of sodium hydroxide dissolved in 0.5 mL of water was added to the reaction vessel. 0.27 mL of propylene oxide and 50 mg of tetrabutylammonium bromide were further added and stirred for 12 hours. 20 mL of ethyl acetate and 20 mL of saturated saline were added to the reaction solution and the mixture was separated. The aqueous layer was further extracted with 20 mL of ethyl acetate. The ethyl acetate layers were combined, washed with 30 mL of saturated saline, and then dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the mixture was purified by silica gel column chromatography to obtain 145 mg of 1-[3-fluoro-4-(3,5-difluorophenoxy)phenoxy]-2-propanol.
<NMR data>
7.07 (1H, t), 6.77 (1H, dd), 6.71 (1H, dq), 6,48 (1H, tt), 6.40 (2H, dd), 4.20 (1H, m), 3.93 (1H, dd), 3.79 (1H, dd), 1.28 (3H, d),

4) Synthesis of 1-[3-fluoro-4-(3,5-difluorophenoxy)phenoxy]-2-(2-pyridyloxy)-propane [Compound (3)] 4 mL of tetrahydrofuran was added to a reaction vessel, 145 mg of 1-[3-fluoro-4-(3,5-difluorophenoxy)phenoxy]-2-propanol and 95 mg of 2-fluoropyridine were added thereto, and after stirring and dissolving, 50 mg of sodium hydride (60%) was added under ice cooling and stirred at room temperature for 12 hours. The reaction solution was poured into 15 mL of ice water and extracted twice with 20 mL of ethyl acetate. The ethyl acetate layer was combined, washed with 20 mL of saturated saline, and then dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the mixture was purified by silica gel column chromatography to obtain 134 mg of 1-[3-fluoro-4-(3,5-difluorophenoxy)phenoxy]-2-(2-pyridyloxy)-propane [Compound (3)].
<NMR data>
8.15 (1H, d), 7.56 (1H, dt), 7.04 (1H, t), 6.85, (1H, d), 6.83 (1H, d), 6.75 (1H, d), 6.73 (1H, d), 6.47 (1H, tt), 6.40 (2H, m), 5.58 (1H, m), 4.18 (1H , dd), 4.07 (1H, dd), 1.47 (3H, d)

Production Example 4
1-[3-Fluoro-4-(3,5-dichlorophenoxy)phenoxy]-2-(2-pyridyloxy)-propane [compound (6)] was synthesized according to the following route.

1) Synthesis of 3-fluoro-4-(3,5-dichlorophenoxy)anisole 3 mL of dimethylformamide was added to a reaction vessel, and 1.14 g of 3,5-dichlorophenol, 1.11 g of 4-bromo-3-fluoroanisole, 0.94 g of potassium carbonate, and 163 mg of cuprous chloride were added thereto and stirred for dissolution, followed by stirring at 150°C under a nitrogen stream for 9 hours. The reaction solution was poured into 10 mL of ice-cooled 5% hydrochloric acid, and extracted twice with 30 mL of ethyl acetate. The ethyl acetate layers were combined, washed with saturated sodium bicarbonate water and then with saline, and dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the mixture was purified by silica gel column chromatography to obtain 281 mg of 3-fluoro-4-(3,5-dichlorophenoxy)anisole.
<NMR data>
7.05 (1H, t), 7.02 (1H, t), 6.78 (2H, d), 6,76 (1H, dd), 6.69 (1H, dq), 3.81 (3H, s),

2) Synthesis of 3-fluoro-4-(3,5-dichlorophenoxy)phenol 4 mL of dichloromethane was added to a reaction vessel, 126 mg of 3-fluoro-4-(3,5-dichlorophenoxy)anisole was added thereto, and the mixture was stirred and dissolved, then cooled to -70°C, 1 mL of boron tribromide (1M solution) was added, and the mixture was further stirred for 12 hours. The reaction solution was poured into 5 mL of ice-cooled 5% hydrochloric acid solution, and extracted twice with 20 mL of ethyl acetate. The ethyl acetate layers were combined, washed with saline, and dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, 110 mg of 3-fluoro-4-(3,5-dichlorophenoxy)phenol was obtained. This was used in the next reaction without purification.
<NMR data>
7.02 (1H, t), 7.00 (1H, t), 6.78 (2H, d), 6,72 (1H, dd), 6.62 (1H, dq)

3) Synthesis of 1-[3-fluoro-4-(3,5-dichlorophenoxy)phenoxy]-2-propanol 2 mL of toluene was added to a reaction vessel, 110 mg of 3-fluoro-4-(3,5-dichlorophenoxy)phenol was added to it, and then a solution of 95 mg of sodium hydroxide dissolved in 0.3 mL of water was added. 0.30 mL of propylene oxide and 40 mg of tetrabutylammonium bromide were added and stirred for 12 hours. 20 mL of ethyl acetate and 20 mL of saturated saline were added to the reaction solution and the liquids were separated. The aqueous layer was further extracted with 20 mL of ethyl acetate. The ethyl acetate layers were combined, washed with 30 mL of saturated saline, and then dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the mixture was purified by silica gel column chromatography to obtain 58 mg of 1-[3-fluoro-4-(3,5-dichlorophenoxy)phenoxy]-2-propanol.
<NMR data>
7.05 (1H, t), 7.02 (1H, t), 6,76-6.80 (3H, m), 6.71 (1H, dq), 4.20 (1H, m), 3.92 (1H, dd), 3.80 (1H, dd), 1.28 (3H, d),

4) Synthesis of 1-[3-fluoro-4-(3,5-dichlorophenoxy)phenoxy]-2-(2-pyridyloxy)-propane [Compound (6)] 1.5 mL of dimethylformamide was added to a reaction vessel, 58 mg of 1-[3-fluoro-4-(3,5-dichlorophenoxy)phenoxy]-2-propanol and 0.05 mL of 2-fluoropyridine were added thereto, and the mixture was cooled on ice while stirring and dissolving. 15 mg of sodium hydride (60%) was added thereto, and the mixture was stirred at room temperature for 12 hours. The reaction solution was poured into 15 mL of ice water, and extracted twice with 20 mL of ethyl acetate. The ethyl acetate layers were combined, washed with 20 mL of saturated saline, and then dried over anhydrous magnesium sulfate. After distilling off the ethyl acetate, the mixture was purified by silica gel column chromatography to obtain 47 mg of 1-[3-fluoro-4-(3,5-dichlorophenoxy)phenoxy]-2-(2-pyridyloxy)-propane [Compound (6)].
<NMR data>
8.16 (1H, dd), 7.61 (1H, dt), 7.03 (1H, t), 7.02 (1H, t) 6.9595 (3H, m) 6.90 (1H, dd), 6.83 (1H, dd), 6.77 (2H, d), 6.73 (1H, ddd), 5.61 (1H, m), 4.18 (1 H, dd), 4.08 (1H, dd), 1.49 (3H, d)

Some of the compounds of the present invention are shown in Table 1.
In addition, the compounds of the present invention have optical isomers based on asymmetric carbons, and these are also included in the present invention.
Table 1. Compound examples

Pests against which the compounds of the present invention are effective include, for example, arthropods such as insects and mites, and specific examples include the following pests:

Lepidoptera pests: moths such as the rice stem borer, rice leaf borer, and Indian meal moth; cutworms such as the common cutworm, armyworm, and cutworm moth; white butterflies such as the cabbage white; tortrix moths such as the smaller tortrix; fruit borer moths, leafminers, tussock moths, grasshoppers, Agrotis spp. such as the turnip cutworm and the cutworm moth; Helicoverpa spp., Heliothis spp., diamondback moth, skipper butterfly, burr moth, brown moth, etc.

Dipteran pests: Culex pipiens pallens, Culex tritaeniorhynchus, and other Culex pipiens, Aedes mosquitoes, Aedes aegypti, Aedes albopictus, and other Anopheles mosquitoes, Chironomids, House flies, Musca domestica, Musca domestica, and other House flies, Blow flies, Flesh flies, Seed flies, Onion flies, and other Flower flies, Fruit flies, Drosophila melanogaster, Moth flies, Flea flies, Horseflies, Black flies, Stable flies, Midges, etc.

Dictyoptera pests: German cockroach, Smoky brown cockroach, American cockroach, Brown cockroach, Oriental cockroach, etc.

Hymenoptera pests: Ants, hornets, ant wasps, sawflies such as turnip sawflies, etc.

Cryptopteran pests Dog fleas, cat fleas, human fleas, etc.

Phthiraptera Pests Body lice, pubic lice, head lice, body lice, etc.

Isoptera pests: Yamato Termite, Formosan Termite, etc.

Hemiptera pests: Planthoppers such as the striate brown planthopper, brown planthopper, and white-backed planthopper, leafhoppers such as the green rice leafhopper and the Taiwanese green rice leafhopper, aphids, stink bugs, whiteflies, scale insects, earwigs, psyllids, etc.

Coleoptera pests: Corn rootworms such as the lesser cut grass beetle, the lesser cut grass beetle, the western corn rootworm, and the southern corn rootworm; scarab beetles such as the lesser cupreous beetle and the lesser chafer beetle; weevils such as the rice weevil, rice water weevil, boll weevil, and azuki bean weevil; meal beetles such as the brown grain beetle and the red flour beetle; leaf beetles such as the rice leaf beetle, the striped flea beetle, and the cucumber beetle; beetles of the Epilachna spp. such as the 200-spot ladybird beetle; flat-headed wood beetles, long-horn beetles, long-horn beetles, and the green leaf staphylococcus beetle.

Thysanoptera pests: Thrips palmi, Thrips occidentalis, Thrips palmi, etc.

Orthoptera pests: mole crickets, grasshoppers

Pests of the order Phthiraptera: Body lice, pubic lice, etc.

Pests of the order Pterygota Formosan Termite, Reticulitermes speratus, Drywood termite, etc.

Mites: House dust mites such as Dermatophagoides farinae and Dermatophagoides pteronyssinus; grain mites such as Acaridae and Aspergillus nigricans; flesh mites such as Dermatophagoides dust mites, Dermatophagoides domestica and Dermatophagoides pedunculata; chigger mites such as Dermatophagoides stag beetle and Dermatophagoides pallidus; dust mites, Flesh mites, House mites, Spider mites such as Tetranychus urticae, Kanzawan red mite, Citrus red mite, and European red mite; ticks such as Haemaphysalis longicornis

When the compound of the present invention is used as an active ingredient of a pest control agent, it may be used as it is without adding any other ingredients, but it is usually mixed with a solid carrier, liquid carrier, gaseous carrier, bait, etc., and if necessary, a surfactant or other formulation auxiliary is added to formulate it into a flowable agent such as an oil solution, emulsion, wettable powder, or water suspension, a granule, powder, aerosol, a heated fumigation agent such as a self-burning type fumigation agent, a chemical reaction type fumigation agent, or a porous ceramic plate fumigation agent, an ULV agent, a poison bait, etc.

These preparations usually contain 0.001 to 95% by weight of the compound of the present invention, depending on the formulation.

Carriers used in formulation include, for example, solid carriers (clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, bentonite, fubasami clay, acid clay, etc.), talcs, ceramics, other inorganic minerals (sericite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, montmorillonite, etc.), chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride, etc.)), etc.), and liquid carriers include water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, phenylxylylethane, etc.). , aliphatic hydrocarbons (hexane, cyclohexane, kerosene, diesel, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N,N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenated hydrocarbons (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, vegetable oils (soybean oil, cottonseed oil, etc.), etc.}, and gaseous carriers, i.e. propellants, include fluorocarbon gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas, etc.

Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylaryl ethers, polyoxyethylated alkylaryl ethers, polyethylene glycol ethers, polyhydric alcohol esters, and sugar alcohol derivatives.

Other formulation adjuvants include adhesives, dispersants and stabilizers, such as casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, etc.), BHT (2,6-di-t-butyl-4-methylphenol) and BHA (a mixture of 2-t-butyl-4-methoxyphenol and 3-t-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or their esters, etc.

Examples of base materials for self-burning fumigants include combustion heat generating agents such as nitrates, nitrites, guanidine salts, potassium chlorate, nitrocellulose, ethyl cellulose, and wood flour; pyrolysis stimulants such as alkali metal salts, alkaline earth metal salts, dichromates, and chromates; oxygen suppliers such as potassium nitrate; combustion enhancers such as melamine and wheat starch; bulking agents such as diatomaceous earth; and binders such as synthetic thickeners.

Examples of base materials for chemically reactive fumigants include heat generating agents such as alkali metal sulfides, polysulfides, hydrosulfides, salt hydrates, and calcium oxide; catalytic agents such as carbonaceous materials, iron carbide, and activated clay; organic foaming agents such as azodicarbonamide, benzenesulfonylhydrazine, dinitropentamethylenetetramine, polystyrene, and polyurethane; and fillers such as pieces of natural fibers and pieces of synthetic fibers.

Examples of substrates for non-heated evaporative agents include thermoplastic resins and paper (filter paper, Japanese paper, etc.).

Examples of the base material for poison bait include bait components such as grain flour, plant essential oils, sugar, and crystalline cellulose, antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, preservatives such as dehydroacetic acid, agents to prevent accidental ingestion such as chili powder and benzethonium benzoate, and pest-attracting flavors such as cheese flavoring, onion flavoring, and peanut oil.

Flowable preparations (suspensions in water or emulsions in water) are generally prepared by finely dispersing 1-75% of a compound in water containing 0.5-15% of a dispersant, 0.1-10% of a suspension aid (e.g., a protective colloid or a compound having thixotropy), or 0-1.0% of a suitable auxiliary (e.g., an antifoaming agent, an antirust agent, a stabilizer, a spreading agent, a penetration aid, an antifreeze agent, an antibacterial agent, an antifungal agent, etc.). It is also possible to prepare a suspension in oil by using an oil in which the compound is hardly soluble instead of water. Examples of protective colloids that can be used include gelatin, casein, gums, cellulose ether, and polyvinyl alcohol. Examples of compounds having thixotropy include bentonite, aluminum magnesium silicate, xanthan gum, and polyacrylic acid.

The preparation obtained in this manner can be used as is or diluted with water etc.

The pest control agent of the present invention can be used in combination with other insecticides, nematicides, soil pest control agents, acaricides, fungicides, herbicides, plant regulators, synergists, fertilizers, soil conditioners, animal feed, etc., or simultaneously without mixing.

Such insecticides or acaricides include the following active ingredients:

Organophosphorus compounds such as fenitrothion, fenthion, diazinon, chlorpyrifos, acephate, methidathion, disulfoton, DDVP, sulprofos, cyanophos, dioxabenzophos, dimethoate, phenthoate, malathion, trichlorfon, azinphos-methyl, monocrotophos, and ethion.

Carbamate compounds such as BPMC, benfuracarb, propoxur, carbosulfan, carbaryl, methomyl, ethiofencarb, aldicarb, oxamyl, and fenothiocarb

Pyrethroid compounds such as etofenprox, fenvalerate, esfenvalerate, fenpropathrin, cypermethrin, permethrin, cyhalothrin, deltamethrin, cycloprothrin, fluvalinate, bifenthrin, 2-methyl-2-(4-bromodifluoromethoxyphenyl)propyl(3-phenoxybenzyl)ether, tralomethrin, silafluofen, d-fenothrin, cyphenothrin, d-resmethrin, acrinathrin, cyfluthrin, tefluthrin, transfluthrin, methofluorothrin, profluthrin, momfluorothrin, dimefluthrin, tetramethrin, allethrin, d-flamethrin, prallethrin, empenthrin, 5-(2-propynyl)furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate

Nitroimidazolidine derivatives, N-cyanoamidine derivatives such as acetamiprid, chlorinated hydrocarbon compounds such as endosulfan, gamma-BHC, 1,1-bis(chlorophenyl)-2,2,2-trichloroethanol, benzoylphenylurea compounds such as chlorfluazuron, teflubenzuron, and flufenoxuron, phenylpyrazole compounds, methoxadiazone, bromopropylate, tetradifon, quinomethionate, pyridaben, fenpyroximate, diafenthiuron, tebufenpyrad, polynactin complex [tetranactin, dinactin, trinactin], pyrimidifen, milbemectin, abamectin, ivermectin, and azadirachtin.

Repellents include, for example, 3,4-carandiol, N,N-diethyl-m-toluamide, 1-methylpropyl 2-(2-hydroxyethyl)-1-piperidinecarboxylate, p-menthane-3,8-diol, and plant essential oils such as hyssop oil.

Examples of synergists include bis-(2,3,3,3-tetrachloropropyl) ether (S-421), N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (MGK-264), and α-[2-(2-butoxyethoxy)ethoxy]-4,5-methylenedioxy-2-propyltoluene (piperonyl butoxide).

When the compound of the present invention is used as an agricultural pest control agent, the application amount is usually 0.001 g to 500 g per 10 ares, preferably 0.1 to 500 g. When emulsifiable concentrates, wettable powders, flowable agents, etc. are used by diluting them with water, the application concentration is usually 0.00001 to 1000 ppm. Granules, powders, etc. are used as they are without dilution. When used as a pest control agent for quarantine purposes, emulsifiable concentrates, wettable powders, flowable agents, etc. are usually applied by diluting them with water to 0.00001 to 10000 ppm. Oil agents, aerosols, smoke agents, ULV agents, poison bait, etc. are applied as they are.

These application amounts and concentrations vary depending on the type of formulation, application time, application location, application method, type of pest, and damage condition, and can be increased or decreased without adhering to the above ranges.

The present invention will be described in more detail below with reference to formulation examples and test examples, but the present invention is not limited to these examples.

Formulation Example 1 Emulsion 10 parts of any of the compounds (1) to (6) of the present invention are dissolved in 35 parts of xylene and 35 parts of dimethylformamide, and 14 parts of polyoxyethylene styryl phenyl ether and 6 parts of calcium dodecylbenzenesulfonate are added thereto and thoroughly mixed with stirring to obtain a 10% emulsion.

Formulation Example 2 Wettable Powder 10 parts of any of the compounds (1) to (6) of the present invention are added to a mixture of 4 parts of sodium lauryl sulfate, 2 parts of calcium lignosulfonate, 20 parts of synthetic hydrous silicon oxide fine powder and 54 parts of diatomaceous earth, and the mixture is stirred and mixed in a juice mixer to obtain a 20% wettable powder.

Formulation Example 3: Granules 5 parts of any of the present compounds (1) to (6) are added with 5 parts of sodium dodecylbenzenesulfonate, 30 parts of Bentonite Fuji (bentonite, manufactured by Houjun Co., Ltd.) and 60 parts of Shokozan A Clay (kaolin clay, manufactured by Shokozan Kogyosho Co., Ltd.), thoroughly pulverized and mixed, water is added and the mixture is thoroughly kneaded, followed by granulation in an extrusion granulator and drying to obtain 5% granules.

Formulation Example 4: Powder 0.3 parts of any of the present compounds (1) to (6), 3 parts of synthetic hydrous silicon oxide fine powder, 1 part of a flocculant (trade name: Drilles, manufactured by Sankyo Co., Ltd.), and 7.7 parts of clay are thoroughly mixed in a mortar, and then stirred and mixed in a juice mixer. 90 parts of cut clay is added to the resulting mixture, and the mixture is mixed in a bag to obtain a powder.

Formulation Example 5: Powder 0.3 parts of any of the present compounds (1) to (6), 2 parts of fenitrothion as an organophosphorus compound, 3 parts of synthetic hydrous silicon oxide fine powder, 1 part of Drilles B (manufactured by Sankyo Co., Ltd.) as a flocculant, and 7.7 parts of clay are thoroughly mixed in a mortar, and then stirred and mixed in a juice mixer. 90 parts of cut clay is added to the resulting mixture, and the mixture is mixed in a bag to obtain a powder.

Formulation Example 6: Powder 0.3 parts of any of the present compounds (1) to (6), 2 parts of BPMC (O-sec-butylphenyl-N-methylcarbamate) as a carbamate compound, 3 parts of synthetic hydrous silicon oxide fine powder, 1 part of Drilles B (manufactured by Sankyo Co., Ltd.) as a flocculant, and 3.7 parts of clay are thoroughly mixed in a mortar, and then stirred and mixed in a juice mixer. 90 parts of cut clay is added to the resulting mixture, and the mixture is mixed in a bag to obtain a powder.

Formulation Example 7: Powder Formulation 1 part of any of the compounds (1) to (6) of the present invention is dissolved in an appropriate amount of acetone, 5 parts of synthetic hydrous silicon oxide fine powder, 0.3 parts of PAP and 93.7 parts of clay are added thereto, and the mixture is stirred and mixed in a juice mixer. The acetone is removed by evaporation to obtain a 1% powder formulation.

Formulation Example 8: Flowable preparation 10 parts of any of the compounds (1) to (6) of the present invention are added to 40 parts of an aqueous solution containing 6 parts of polyvinyl alcohol and stirred with a mixer to obtain a dispersion, to which 40 parts of an aqueous solution containing 0.05 parts of xanthan gum and 0.1 parts of aluminum magnesium silicate are added, and 10 parts of propylene glycol are further added, followed by gentle stirring and mixing to obtain a 10% suspension in water.

Formulation Example 9 Oil Solution 0.1 part of any of the compounds (1) to (6) of the present invention is dissolved in 5 parts of xylene and 5 parts of trichloroethane, and the solution is mixed with 89.9 parts of deodorized kerosene to obtain a 0.1% oil solution.

Formulation Example 10: Oil-based aerosol 0.1 part of any of the compounds (1) to (6) of the present invention, 0.2 parts of d-allethrin, 0.1 parts of d-phenothrin, 10 parts of trichloroethane and 59.6 parts of deodorized kerosene are mixed and dissolved, filled into an aerosol container, and a valve is attached. Then, 30 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the valve to obtain an oil-based aerosol.

Formulation Example 11: Aqueous aerosol 0.2 parts of any of the compounds (1) to (6) of the present invention, 0.2 parts of d-allethrin, 0.2 parts of d-phenothrin, 5 parts of xylene, 3.4 parts of deodorized kerosene, and 1 part of an emulsifier {Atmos 300 (emulsifier, registered trademark of Atlas Chemical Co.)} are mixed and dissolved, and 50 parts of pure water are filled into an aerosol container, and 40 parts of a propellant (liquefied petroleum gas) are pressurized and filled through the valve to obtain an aqueous aerosol.

Formulation Example 13: Heat-induced fumigation agent 100 mg of any of the compounds (1) to (6) of the present invention is dissolved in a suitable amount of acetone, and the solution is impregnated into a porous ceramic plate of 4.0 cm×4.0 cm and 1.2 cm thick to obtain a heat-induced fumigation agent.

Next, we will demonstrate by test examples that the compound of the present invention is effective as an active ingredient in a pest control agent.

Test Example 1 (Culture Contamination Test)
House fly Musca domestica Kagawa 2007 strain※2 Larvae (3-4 days old after hatching)
*2: Sumika Technoservice Co., Ltd., successive breeding lines [preparation of test medium]
The compounds (1) to (3), (6) of the present invention and pyriproxyfen were dissolved in acetone to a concentration of 5000 ppm, and then further diluted with acetone to a concentration 100 times the treatment concentration shown in Table 2. 0.1 ml of the diluted solution was mixed with 64 g of pure water, and 32 g of bran-brewer's grains mixed feed and 4 g of MF powder feed were stirred and mixed to prepare an artificial test medium for houseflies.
[Emergence inhibition activity test]
Approximately 100 g of artificial test medium for houseflies was placed in a 200B polycup (diameter 8 cm, height 4 cm) and 50 housefly larvae (Musca domestica Kagawa 2007 strain) aged 3-4 days after hatching were released into the container. The room temperature was kept constant at approximately 25°C during the test, and the number of emerged adults was counted 14 days after the start of the test. This test was repeated three times, and the emergence inhibition rate (%) was calculated using the following formula.
Emergence rate (%) = 100 × number of emerged adults / number of test insects Emergence inhibition rate (%) = 100 × (1 - emergence rate in treated area / emergence rate in blank)

The LC50 values (ppm) of the compound of the present invention and the control pyriproxyfen were calculated using the probit method based on the emergence inhibition rate at each dose, and the results are shown in Table 2.

Table 2. Inhibitory activity against emergence of house fly larvae from the Kagawa 2007 strain

Test Example 2 (Culture medium contamination test method)
Housefly Musca domestica susceptible strain *2 Larva (3-4 days old after hatching)
*2: Sumika Technoservice Co., Ltd.

Preparation of the test medium and the emergence inhibitory activity test were carried out in the same manner as in [0071].

The LC50 values (ppm) of the compound of the present invention and the control pyriproxyfen were calculated using the probit method based on the emergence inhibition rate at each dose, and the results are shown in Table 3.

Table 3. Inhibitory activity against emergence of susceptible house fly larvae

The compound of the present invention has excellent control effects against Hemiptera, Lepidoptera, Diptera, Coleoptera, Dictyoptera, Thysanoptera, Orthoptera, Hymenoptera, Crypteridae, Phthiraptera, and Isoptera, and can be used for various purposes as a pest control agent.

Claims (4)

(Formula I)

[In the formula, R represents a halogen atom, and n represents an integer of 1 to 3. When n represents 2 or 3, each R may be the same or different. * represents an asymmetric carbon.]
A pyridine-based fluorine-containing aromatic compound represented by the formula: (Formula II)

[In the formula, R represents a halogen atom, and n represents an integer of 1 to 3. When n represents 2 or 3, each R may be the same or different. * represents an asymmetric carbon.]
and a fluorine-containing alcohol compound represented by the formula:
(Formula III)

[In the formula, X represents a fluorine atom or a chlorine atom.]
The pyridine-based fluorine-containing aromatic compound according to formula I,

[In the formula, R represents a halogen atom, and n represents an integer of 1 to 3. When n represents 2 or 3, each R may be the same or different. * represents an asymmetric carbon.]
Manufacturing method. (Formula I)

[In the formula, R represents a halogen atom, and n represents an integer of 1 to 3. When n represents 2 or 3, each R may be the same or different. * represents an asymmetric carbon.]
A pest control agent comprising, as an active ingredient, a pyridine type fluorine-containing aromatic compound represented by the formula: (Formula I)

[In the formula, R represents a halogen atom, and n represents an integer of 1 to 3. When n represents 2 or 3, each R may be the same or different. * represents an asymmetric carbon.]
A method for controlling pests (excluding application to humans), which comprises applying an effective amount of a fluorine-containing pyridine aromatic compound represented by the following formula (1):