JP5047588B2 - Quinoline derivatives and agricultural and horticultural insecticides comprising the same - Google Patents

Description

  The present invention relates to a quinoline derivative and an agricultural and horticultural insecticide comprising the same as an active ingredient.

  Various compounds having a controlling action have been developed in the past. For example, WO98 / 055460 (Patent Document 1) discloses quinoline derivatives having bactericidal activity, but does not describe any insecticidal activity of these derivatives. JP-A-3-128355 (Patent Document 2) and US Pat. No. 4,168,311 (Patent Document 3) disclose quinoline derivatives having insecticidal activity. However, the compounds described in these publications differ from the quinoline derivative represented by the formula (I) described later in the structure of the substituent at the 6-position of quinoline.

  The present inventors have previously found that a 4-quinolinol derivative having a substituted phenoxy group at the 6-position and a substituent at the 5-, 7-, or 8-position has excellent insecticidal activity ( WO 2006/013896 (Patent Document 4)).

However, there still exists a need for excellent agricultural and horticultural insecticides, particularly agricultural and horticultural insecticides having excellent insecticidal activity against low-sensitivity insect species such as thrips and pest control species.
WO98 / 055460 publication JP-A-3-128355 U.S. Pat. No. 4,168,311 WO2006 / 013896

  The present inventors have now found that a novel quinoline derivative has a remarkable insecticidal activity, particularly an excellent insecticidal activity against low-sensitivity insect species such as thrips and pest control species. The present invention is based on such knowledge.

  An object of the present invention is to provide a novel quinoline derivative having excellent insecticidal activity according to one embodiment.

  Furthermore, another object of the present invention is to provide an agricultural and horticultural insecticide comprising the novel quinoline derivative according to the present invention.

（式中、
Ｒ₁は、炭素数１〜４のアルキル基、炭素数３または４の環状アルキル基、炭素数２〜４のアルケニル基、または基−ＯＲ_５若しくは基−ＳＲ_５(ここで、Ｒ_５は炭素数１〜４のアルキル基を表す。）を表し、
Ｒ_２、Ｒ_３およびＲ_４は、それぞれ独立して、炭素数１〜４のアルキル基を表す。）。 Further, the novel quinoline derivative according to the present invention is a compound represented by the following formula (I) and an acid addition salt acceptable in agriculture and horticulture:

(Where
R ₁ is an alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 or 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or a group —OR ₅ or a group —SR ₅ (where R ₅ is carbon Represents an alkyl group of formulas 1 to 4, and
R ₂ , R ₃ and R ₄ each independently represents an alkyl group having 1 to 4 carbon atoms. ).

  Moreover, the agricultural and horticultural insecticide according to the present invention comprises, as an active ingredient, a quinoline derivative represented by the above formula (I) or an acid addition salt acceptable in agriculture and horticulture.

Detailed description of the invention

The compound represented by the formula (I) The alkyl group having 1 to 4 carbon atoms represented by R ₁ in the formula (I) may be linear or branched. Specific examples thereof include methyl Group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group and t-butyl group, preferably methyl group and i-propyl group. In addition, examples of the cyclic alkyl group having 3 or 4 carbon atoms represented by R ₁ include a cyclopropyl group and a cyclopropylmethyl group, and preferably a cyclopropyl group.

Examples of the alkenyl group having 2 to 4 carbon atoms represented by R ₁ in the formula (I) include a vinyl group, (1- or 2-) propenyl group, and (1-, 2- or 3-) butenyl group, Vinyl group.

In the formula (I), R ₁ represents a group —OR ₅ or a group —SR _5, and the alkyl group having 1 to 4 carbon atoms represented by R ₅ may be linear or branched. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group and a t-butyl group, preferably a methyl group. .

The alkyl group having 1 to 4 carbon atoms represented by R ₂ , R ₃ and R ₄ in formula (I) may be linear or branched, and specific examples thereof include a methyl group, ethyl Group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group or t-butyl group, preferably methyl group or ethyl group.

In a preferred embodiment of the present invention, R ₁ is an alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 or 4 carbon atoms, or a group —OR ₅ (where R ₅ is an alkyl group having 1 to 4 carbon atoms). And a compound of formula (I) wherein R ₂ , R ₃ and R ₄ are each independently a methyl group or an ethyl group.

  The compounds of formula (I) according to the invention may be in the form of agricultural and horticultural acid addition salts, examples of which are hydrochlorides, nitrates, sulfates, phosphates or acetates. It is done.

Preferred specific examples of the compound represented by the formula (I) according to the present invention are as follows (note that the following compound numbers correspond to the compound numbers in the examples).
2-Ethyl-7-methoxy-4-methoxycarbonyloxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Quinoline (Compound No. 1),
7-Ethoxy-2-ethyl-4-methoxycarbonyloxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Quinoline (Compound No. 2),
4-acetyloxy-2-ethyl-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline (Compound No. 3),
4-Cyclopropylcarbonyloxy-2-ethyl-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -Quinoline (compound no. 4),
2-Ethyl-7-methoxy-3-methyl-4-methylthiocarbonyloxy-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Quinoline (Compound No. 5),
4-Allylcarbonyloxy-2-ethyl-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Quinoline (Compound No. 6),
2-Ethyl-4-isopropyloxycarbonyloxy-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -Quinoline (compound no. 7),
4-acetyloxy-2,3-dimethyl-7-methoxy-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline (compound No. 8), or 3-ethyl-7-methoxy-4-methoxycarbonyloxy-2-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin- 6-yloxy) -quinoline (Compound No. 9).

Production of Compound of Formula (I) The compound of formula (I) can be preferably produced by the method of Scheme I below according to the method described in JP-A-3-128355.

That is, a compound represented by the following formula (II) is reacted with a reagent represented by formula (III) or formula (IV) in the presence or absence of a base, and a substituent is converted as necessary. Can be synthesized. In scheme I, R _{1 to} R ₄ represent the same meaning as defined above. Examples of the base include organic amines such as triethylamine and pyridine, and inorganic alkalis such as sodium carbonate, potassium carbonate, and sodium hydride.

上記反応において出発物質である式（ＩＩ）の化合物は、公知の方法であるJ.Am.Chem.Soc.70,2402(1948)またはTetrahedron Lett.27,5323(1986)に準じて、以下のスキームＩＩの方法により製造することが出来る。スキームＩＩ中、Ｒは炭素数１〜４のアルキル基を表し、Ｒ_２〜Ｒ_４は、上で定義したものと同一の意味を表す。 Scheme I

The compound of the formula (II) which is the starting material in the above reaction is prepared by the following method according to J. Am. Chem. Soc. 70, 2402 (1948) or Tetrahedron Lett. 27, 5323 (1986). It can be produced by the method of Scheme II. In Scheme II, R represents an alkyl group having 1 to 4 carbon atoms, and R _{2 to} R ₄ have the same meaning as defined above.

さらに式（Ｖ）の化合物は、以下のスキームＩＩＩに沿って式（ＶＩＩ）の化合物におけるニトロ基を還元することにより製造することが出来る。 Scheme II

Furthermore, the compound of the formula (V) can be produced by reducing the nitro group in the compound of the formula (VII) according to the following scheme III.

式（ＶＩＩ）の化合物は、式（ＶＩＩＩ）の化合物と式（ＩＸ）の化合物とから、以下のスキームＩＶの方法により製造することが出来る。すなわち、一般に入手可能な式（ＶＩＩＩ）のフェノール誘導体および式（ＩＸ）のニトロ化合物を、塩基存在下または塩基非存在下で反応させ、式（ＶＩＩ）のジフェニルエーテル誘導体を合成する。ここで、Ｘは塩素、臭素、ヨウ素、フッ素のようなハロゲン原子を表す。 Scheme III

The compound of the formula (VII) can be produced from the compound of the formula (VIII) and the compound of the formula (IX) by the method of the following scheme IV. That is, a generally available phenol derivative of formula (VIII) and a nitro compound of formula (IX) are reacted in the presence or absence of a base to synthesize a diphenyl ether derivative of formula (VII). Here, X represents a halogen atom such as chlorine, bromine, iodine, or fluorine.

Scheme IV

Use of Compound / Agricultural Horticultural Insecticide The compound of the formula (I) according to the present invention exhibits an excellent control effect against various pests. The compound group represented by the formula (I) according to the present invention exhibits a death rate of 90% or more with respect to Frankliniella occidentalis at a concentration of 1 ppm or less. According to the description of WO2006 / 013896 (Patent Document 4), it is considered by those skilled in the art that the compound group of the formula (I) exhibits a death rate of 90% or more despite such a low concentration. It is understood as a marked improvement in effect.

  Therefore, according to the present invention, there is provided an agricultural and horticultural insecticide comprising, as an active ingredient, a compound of formula (I) or an agriculturally and horticulturally acceptable acid addition salt thereof.

  According to another aspect of the present invention, the method comprises applying an effective amount of the compound represented by the formula (I) or an agriculturally and horticulturally acceptable acid addition salt to a plant or soil. A method for controlling agricultural and horticultural pests is provided.

  According to another aspect of the present invention, there is provided use of a compound represented by the formula (I) or an agriculturally and horticulturally acceptable acid addition salt as an agricultural and horticultural insecticide.

The insect species that the compound represented by the formula (I) shows a controlling effect are lepidopterous pests (for example, moths such as Spodoptera litura, Shirothyomojiyoto, Ayayoto, Yotoga, Tamanayaga, Trichopulcia, Heliotis, Helicoberpa, etc., Common moths such as Japanese corn borer, European corn borer, Hymadara noiga, Shibatatsuga, Watanogaiga, Noshimemadaranoga, etc. , Limantria, Euprocutis, etc., Suga, etc., Scots, such as cotton beetle, Hitriga, such as American white starfish, Hirosukoga, etc. For example, aphids such as peach aphid and cotton aphid, planthoppers such as Japanese brown planthopper, brown planthopper and white-tailed planthopper, leafhoppers such as leafhopper leafhopper, red-bellied leafhopper, red-headed beetle, chabaenokamemushi, minamiaokamemushi, etc. Whitefly whitefly, silver leaf whitefly, etc., scale insects such as stag beetle, staghorn beetle, pheasant, etc. Scarabidae, Scarabaeidae, Scarabae, and the like, Kisojimi beetle, cucumber potato beetle, Colorado potato potato beetle, Western corn rootworm, Southern cornle Worms such as worms, rice beetles, blue-spotted beetles, sinkworms, epilacunas such as Amanita tenshito, etc. Mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, mites, etc. Eye pests (e.g., houseflies, house moss, anopheles, chironomids, black flies, larvae, sand flies, sand flies, legumes, tomato leaf flies, leaf leaf flies such as leaf flies, fruit flies, fruit flies, flies , Butterflies, flyfish, abs, hornflies, etc.), thrips pests (for example, Thrips thrips, Thrips thrips, Thrips thrips, Thrips thrips, Thrips thrips, Thrips thrips, Parasitoids) Insects (e.g. root-knot nematodes, nectar nematodes, cyst nematodes, aferencoides such as rice scented nematodes, pine wood nematodes, etc.)
In particular, it exhibits an excellent control effect against thrips of the order Thrips, preferably the citrus thrips.

  When the compound of formula (I) is used as an agricultural and horticultural insecticide, the compound of formula (I) may be used as it is, but the compound represented by formula (I) is a suitable solid carrier, liquid carrier, gas Emulsions, EW agents, solutions, suspensions, wettable powders, granule wettable powders, powders, DL powders, powders, etc., mixed together with surfactants, dispersants, and other formulation adjuvants , Granules, tablets, oils, aerosols, flowables, dry flowables, microcapsules and the like.

Examples of the solid carrier include talc, bennite, clay, kaolin, diatomaceous earth, vermiculite, white carbon, calcium carbonate, acid clay, silica sand, silica, zeolite, perlite, attapulgite, pumice, ammonium sulfate, sodium sulfate, urea, and the like. .

  Examples of the liquid carrier include alcohols such as methanol, ethanol, n-hexanol, ethylene glycol, and propylene glycol; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as n-hexane, kerosene, and kerosene; Aromatic hydrocarbons such as toluene, xylene and methylnaphthalene, ethers such as diethyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, nitriles such as acetonitrile and isobutyronitrile, dimethylformamide and dimethylacetamide Examples include acid amides, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, and water.

  Examples of the gaseous carrier include LPG, air, nitrogen, carbon dioxide gas, dimethyl ether and the like.

  Surfactants and dispersants include, for example, alkyl sulfates, alkyl (aryl) sulfonates, polyoxyalkylene alkyl (aryl) ethers, polyhydric alcohol esters, lignin sulfonates, alkyl sulfosuccinates, Formalin condensates of alkyl naphthalene sulfonates, polycarboxylates, POE polystyryl phenyl ether sulfates and phosphates, POE / POP block polymers and the like can be mentioned.

  Furthermore, examples of the adjuvant for formulation include carboxymethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, xanthan gum, pregelatinized starch, gum arabic, polyethylene glycol, liquid paraffin, calcium stearate, and antifoaming agent, preservative and the like. .

  The carriers, surfactants, dispersants, and adjuvants can be used alone or in combination as required.

  The content of the active ingredient in the preparation is not particularly limited, but is preferably 1 to 75% by weight for the emulsion, 0.3 to 25% by weight for the powder, 1 to 90% by weight for the wettable powder, and 0 for the granule. .5-10% by weight.

  The agricultural and horticultural insecticide according to the present invention can be mixed or used in combination with other insecticides, fungicides, acaricides, herbicides, plant growth regulators, fertilizers and the like. Examples of drugs that can be mixed or used together include those described in the Pesticide Manual (published by The British Crop Protection Council 13th edition) and Shibuya Index (published by SHIBUYA INDEX 10th edition, 2005, published by SHIBUYA INDEX RESEARCH GROUP). Can be mentioned.

  More specifically, the insecticides used include acephate, dichlorvos, EPN, fenitrothion, fenamifos, prothiofos, profenfos, pyraclofos, Organophosphate compounds such as chlorpyrifos-methyl, diazinon, methomyl, thiodicarb, aldicarb, oxamyl, propoxur, carbaryl ), Fenobucarb, ethiofencarb, fenothiocarb, pirimicarb, carbofuran, carbamate compounds such as benfuracarb, cartap, thiocyclam Nereistoxin derivatives Organochlorine compounds such as dicofol, tetradifon, permethrin, tefluthrin, cypermethrin, deltamethrin, cyhalothrin, fenvalerate, fulvalerate Such as fluvalinate, etofenprox, pyrethroid compounds such as silafluofen, diflubenzuron, teflubenzuron, flufenoxuron, chlorfluazuron, chlorfluazuron Benzoylurea compounds, juvenile hormone-like compounds such as metoprene, and other compounds such as buprofezin, hexythiazox, amitraz, chlordimeform, pyridaben, fenpyroxy Mate (fenpyroxymate), pyrimidifen (pyrimidifen), tebufenpyrad (tebufenpyrad), fluacrypyrim (fluacrypyrim), acequinocyl (acequinocyl), fipronyl, etoxazole (ethoxazole), imidacloprid (imidacloprid), metroidin Bifenazate, spirodiclofen, chlorfenapyr, pyriproxyfen, indoxacarb, pyridalyl, or spinosad, avermectin, milbemycin ), Organometallic compounds, dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds, and hydrazine compounds. Furthermore, the compound of the present invention can be used in combination or in combination with a microbial pesticide such as a BT agent, an entomopathogenic virus agent and the like.

  Examples of the bactericides used include azoxystrobin, kresoxym-methyl, trifloxystrobin and other strobilurin compounds, mepanipyrim, pyrimethanil, cyprodinil ) Anilinopyrimidine-based compounds such as triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, microbutanyl azole compounds such as myclobutanil, cyproconazole, tebuconazole, hexaconazole, prochloraz, simeconazole, and quinoxalines such as quinomethionate Compounds, maneb, zineb, mancozeb, polycarbamate, dithiocarbamate compounds such as propineb, phenyl carbamate compounds such as diethofencarb, chlorothalonil ), Organochlorine compounds such as quintozene, benomyl, thiophanate-methyl, benzimidazole compounds such as carbendazole, metalaxyl, oxadixyl, and olase ( ofurace), benalaxyl, furalaxyl, phenylamide compounds such as cyprofuram, sulfenic acid compounds such as dichlofluanid, cupric hydroxide, oxy Copper-based compounds such as oxine-copper, Isoxazole compounds such as hydroxyisoxazole, organophosphorus compounds such as fosetyl-aluminium, tolclofos-methyl, captan, captafol, N-halogenothioalkyl compounds such as folpet, procymidone, iprodione, dicarboximide compounds such as vinchlozolin, flutolanil, mepronil, etc. Benzanilide compounds, morpholine compounds such as fenpropimorph, dimethomorph, phenthin hydroxide, organotin compounds such as fenthin acetate, fludioxonil (fludioxonil), fenpiclonil Anopirole compounds, other fthalide, fluazinam, cymoxanil, triforine, pyrifenox, fenarimol, fenpropidin, pencicuron, cyazofamide ( cyazofamid), iprovalicarb, and benchthiavalicarb-isopropyl.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples.

Reference example 1
Synthesis of 2,2,3,3-tetrafluoro-6- (2-methoxy-4-nitrophenoxy) -2,3-dihydrobenzo-1,4-dioxin 1-chloro-2-methoxy-4-nitrobenzene .6 g, N, N-dimethylacetamide 3.2 ml, 2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-ol 0.72 g and potassium carbonate 0.34 g The mixture was heated and stirred at 130 to 140 ° C. for 17 hours. The reaction mixture was poured into a mixture of ethyl acetate and water and extracted with ethyl acetate. The ethyl acetate layer was washed with brine and then concentrated under reduced pressure to give 1.2 g of the title compound.

Reference example 2
Synthesis of 3-methoxy-4- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) phenylamine 1.28 g of iron powder, ethanol 4.5 ml, distilled water 1.8 ml and 35% hydrochloric acid 0.0096 ml were heated to reflux. Subsequently, 2,2,3,3-tetrafluoro-6- (2-methoxy-4-nitrophenoxy) -2,3-dihydrobenzo-1,4-dioxin dissolved in 1.4 ml of ethanol (Reference Example 1) 1.2 g was added dropwise and heated to reflux for 2.5 hours. After cooling to room temperature, sodium bicarbonate water was added and filtered. The filtrate was concentrated under reduced pressure, and ethyl acetate and brine were added for liquid separation. The ethyl acetate layer was washed with brine and concentrated under reduced pressure to give 1.1 g of the title compound.

Reference example 3
Synthesis of 6- (2-ethoxy-4-nitrophenoxy) -2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin 1-chloro-2-ethoxy-4-nitrobenzene .58 g, N, N-dimethylacetamide 3 ml, 2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-ol 0.65 g and potassium carbonate 0.3 g 130- The mixture was heated and stirred at 140 ° C. for 14.5 hours. After cooling, the reaction solution was poured into a mixture of ethyl acetate and water and extracted with ethyl acetate. The ethyl acetate layer was washed with brine and then concentrated under reduced pressure to give 1.12 g of the title compound.

Reference example 4
Synthesis of 3-ethoxy-4- (2,2,3,3-tetrafluoro-2,3-dihydro-benzo-1,4-dioxin-6-yloxy) phenylamine 1.15 g of iron powder, 4 ml of ethanol, 1.6 ml of distilled water and 0.009 ml of 35% hydrochloric acid were heated to reflux. Subsequently, 6- (2-ethoxy-4-nitrophenoxy) -2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin dissolved in 1.2 ml of ethanol (Reference Example 3) 1.12 g was added dropwise and heated to reflux for 2 hours. After cooling to room temperature, sodium bicarbonate water was added and filtered. The filtrate was concentrated under reduced pressure, and ethyl acetate and brine were added for liquid separation. The ethyl acetate layer was washed with brine and concentrated under reduced pressure to give 1.03 g of the title compound.

Synthesis example 1
2-Ethyl-7-methoxy-4-methoxycarbonyloxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Synthesis of quinoline (compound 1) 3-methoxy-4- (2,2,3,3-tetrafluoro-2,3-dihydro-benzo-1,4-dioxin-6-yloxy in 30 ml of xylene ) 1.04 g of phenylamine (Reference Example 2), 1.09 g of methyl 2-methyl-3-oxopentanoate and 0.57 g of p-toluenesulfonic acid were heated to reflux for 14 hours. After cooling, the mixture was extracted with ethyl acetate, and the ethyl acetate layer was concentrated under reduced pressure. The precipitated crystals were collected by filtration and 1.19 g of 2-ethyl-4-hydroxy-7-methoxy-3-methyl-6- (2 , 2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline. Next, 12 ml of dimethylacetamide was added to 1.19 g of the obtained crystals, and 0.24 g of 60% sodium hydride and 0.51 g of methyl chloroformate were added at 0 ° C. After stirring at room temperature for 1 hour, the reaction solution was poured into a mixture of water and ethyl acetate, and extracted with ethyl acetate. The ethyl acetate layer was washed with brine and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (BW300 manufactured by Fuji Silysia Chemical Ltd., solvent n-hexane / ethyl acetate) to obtain 0.67 g of the title compound.

Synthesis example 2
7-Ethoxy-2-ethyl-4-methoxycarbonyloxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Synthesis of quinoline (compound 2) 3-Ethoxy-4- (2,2,3,3-tetrafluoro-2,3-dihydro-benzo-1,4-dioxin-6-yloxy in 30 ml of xylene ) 1.05 g of phenylamine (Reference Example 4), 1.0 g of methyl 2-methyl-3-oxopentanoate and 0.56 g of p-toluenesulfonic acid were heated to reflux for 8 hours. After cooling, the precipitated crystals were collected by filtration, washed with n-hexane and aqueous sodium bicarbonate, and 1.3 g of 7-ethoxy-2-ethyl-4-hydroxy-3-methyl-6- (2,2,3,3- Tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline was obtained. Next, 12 ml of dimethylacetamide was added to 1.3 g of the obtained crystals, and 0.25 g of 60% sodium hydride and 0.54 g of methyl chloroformate were added at 0 ° C. After stirring at room temperature for 1.5 hours, the reaction mixture was poured into a mixture of aqueous sodium hydrogen carbonate and ethyl acetate, and extracted with ethyl acetate. The ethyl acetate layer was washed with brine and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (BW300 manufactured by Fuji Silysia Chemical Ltd., solvent n-hexane / ethyl acetate) to obtain 0.73 g of the title compound.

Synthesis example 3
4-acetyloxy-2-ethyl-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline Synthesis of (Compound 3) 2-Ethyl-4-hydroxy-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3- synthesized in Synthesis Example 1 100 mg of dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline was dissolved in 1 ml of N, N-dimethylformamide, 11 mg of 60% sodium hydride was added under ice cooling, and the mixture was stirred for 1 hour. To this, 20 μl of acetyl chloride was added and stirred for 1 hour, and further stirred at room temperature for 3 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (Mega Bond Elut SI (Varian) 10 mL, solvent: n-hexane / ethyl acetate) to obtain 51 mg of the title compound.

Synthesis example 4
4-Cyclopropylcarbonyloxy-2-ethyl-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) Synthesis of quinoline (compound 4) 2-ethyl-4-hydroxy-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2, synthesized in Synthesis Example 1 100 mg of 3-dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline was dissolved in 1 ml of N, N-dimethylformamide, 11 mg of 60% sodium hydride was added under ice cooling, and the mixture was stirred for 1 hour. To this was added 28 μl of cyclopropanecarbonyl chloride, and the mixture was stirred for 1 hour, and further stirred at room temperature for 3 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (Mega Bond Elut SI (Varian) 10 mL, solvent: n-hexane / ethyl acetate) to obtain 20 mg of the title compound.

Synthesis example 5
2-Ethyl-7-methoxy-3-methyl-4-methylthiocarbonyloxy-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Synthesis of quinoline (Compound 5) 2-ethyl-4-hydroxy-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3 ) synthesized in Synthesis Example 1 -Dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline (100 mg) was dissolved in 1 ml of N, N-dimethylformamide, 11 mg of 60% sodium hydride was added under ice cooling, and the mixture was stirred for 1 hour. To this was added 30 μl of methylchlorothioformate and stirred for 1 hour, and further stirred at room temperature for 3 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (Mega Bond Elut SI (Varian) 10 mL, solvent: n-hexane / ethyl acetate) to obtain 30.5 mg of the title compound.

Synthesis Example 6
4-Allylcarbonyloxy-2-ethyl-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Synthesis of quinoline (Compound 6) 2-ethyl-4-hydroxy-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3 ) synthesized in Synthesis Example 1 -Dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline (100 mg) was dissolved in 1 ml of N, N-dimethylformamide, 11 mg of 60% sodium hydride was added under ice cooling, and the mixture was stirred for 1 hour. To this, 30 μl of allylcarbonyl chloride was added and stirred for 1 hour, and further stirred at room temperature for 3 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (Mega Bond Elut SI (Varian) 10 mL, solvent: n-hexane / ethyl acetate) to obtain 59.7 mg of the title compound.

Synthesis example 7
2-Ethyl-4-isopropyloxycarbonyloxy-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -Synthesis of quinoline (Compound 7) 2-Ethyl-4-hydroxy-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2, synthesized in Synthesis Example 1 100 mg of 3-dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline was dissolved in 1 ml of N, N-dimethylformamide, 11 mg of 60% sodium hydride was added under ice cooling, and the mixture was stirred for 1 hour. To this, 300 μl of a 1.0 M toluene solution of isopropyl chloroformate was added and stirred for 1 hour, and further stirred at room temperature for 3 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crude product was purified by silica gel chromatography (Mega Bond Elut SI (Varian) 10 mL, solvent: n-hexane / ethyl acetate) to obtain 80 mg of the title compound.

Synthesis Example 8
4-acetyloxy-2,3-dimethyl-7-methoxy-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline (compound 8) Synthesis of 3-methoxy-4- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) phenylamine in 33 ml of xylene ( Reference Example 2) 1.1 g, 1.02 g of ethyl 2-methylacetoacetate and 0.61 g of p-toluenesulfonic acid were heated to reflux for 7 hours. After cooling and concentration under reduced pressure, n-hexane was added, and the precipitated crystals were collected by filtration and 1.36 g of 2,3-dimethyl-4-hydroxy-7-methoxy-6- (2,2,3,3- Tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline was obtained. Next, 30 ml of acetic anhydride was added to the obtained 1.36 g of crystals, heated at 130 to 135 ° C. for 3 hours, and then heated to reflux for 1 hour. The reaction mixture was concentrated under reduced pressure, ethyl acetate was added, and the mixture was washed with brine. Thereafter, the solvent was concentrated under reduced pressure, and the resulting compositional organism was purified by silica gel chromatography (BW300 manufactured by Fuji Silysia Chemical Ltd., solvent: n-hexane / ethyl acetate) to obtain 0.31 g of the title compound.

Synthesis Example 9
3-ethyl-7-methoxy-4-methoxycarbonyloxy-2-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Synthesis of quinoline (compound 9) 3-methoxy-4- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) in 33 ml of xylene 1.1 g of phenylamine (Reference Example 2), 1.0 g of ethyl 2-ethyl-3-oxobutanoate and 0.61 g of p-toluenesulfonic acid were heated to reflux for 7 hours. After cooling and concentration under reduced pressure, n-hexane was added, and the precipitated crystals were collected by filtration and 1.17 g of 3-ethyl-4-hydroxy-7-methoxy-2-methyl-6- (2,2,3,3). 3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline was obtained. Next, 40 ml of dimethylformamide was added to 1.17 g of the obtained crystals, and 0.24 g of 55% sodium hydride and 0.51 g of methyl chloroformate were added at 0 ° C. After stirring at room temperature for 2 hours, the reaction mixture was poured into a mixture of brine and ethyl acetate, and extracted with ethyl acetate. The ethyl acetate layer was washed with brine and concentrated under reduced pressure. The obtained composition was purified by silica gel chromatography (BW300 manufactured by Fuji Silysia Chemical Ltd., solvent n-hexane / ethyl acetate) to obtain 0.61 g of the title compound.

The structures and ¹ H-NMR data of the compounds synthesized above were as shown in Tables 1 and 2.

Formulation Example 1 [wettable powder]
Compound 1 30% by weight
30% by weight of clay
Diatomaceous earth 35% by weight
Calcium lignin sulfonate 4% by weight
Sodium lauryl sulfate 1% by weight
The above components were mixed uniformly and pulverized to obtain a wettable powder.

Formulation Example 2 [Dust]
Compound 1 2% by weight
60% clay
Talc 37% by weight
Calcium stearate 1% by weight
The said component was mixed uniformly and the powder agent was obtained.

Formulation Example 3 [Emulsion]
Compound 1 20% by weight
N, N-dimethylformamide 20% by weight
Solvesso 150 (ExxonMobil Co., Ltd.) 50% by weight
10% by weight of polyoxyethylene alkyl aryl ether
The above ingredients were uniformly mixed and dissolved to obtain an emulsion.

Formulation Example 4 [Granule]
Compound 3 5% by weight
Bentonite 40% by weight
Talc 10% by weight
43% by weight clay
2% by weight calcium lignin sulfonate
The above components were uniformly pulverized and mixed, water was added and kneaded well, and then granulated and dried to obtain granules.

Formulation Example 5 [Flowable Agent]
Compound 3 25% by weight
POE polystyryl phenyl ether sulfate 5% by weight
Propylene glycol 6% by weight
Bentonite 1% by weight
Xanthan gum 1% aqueous solution 3% by weight
PRONAL EX-300 (Toho Chemical Co., Ltd.) 0.05% by weight
ADDAC 827 (Kay Kasei Co., Ltd.) 0.02% by weight
59.93% by weight of water

  After premixing the whole amount of the above formulation excluding 1% xanthan gum aqueous solution and an appropriate amount of water, it was pulverized by a wet pulverizer. Thereafter, a 1% aqueous solution of xanthan gum and the remaining water were added to the obtained pulverized product to obtain a 100% by weight flowable agent.

Test Example 1: Plutella xylostell control test A test gun diluted to a predetermined concentration with 50% acetone water (added 0.05% Tween20) to a cabbage tree disc with a diameter of 5.0 cm in a plastic cup. Sprayed and air dried. In the cup, 5 long-tailed moths were released, covered and kept in a constant temperature room at 25 ° C. Three days after the treatment, the mortality of the larvae was observed and the mortality rate was calculated. As a result, the compounds in Table 2 showed a death rate of 90% or more at a concentration of 5 ppm or less.

Test Example 2: Silver leaf whitefly (Bemisia tabaci Genn.) Control test Cucumber leaves were cut to a diameter of 6.0 cm and placed on absorbent cotton moistened with water. To this was sprayed 2 mL of the drug diluent using a spray tower. After air drying, it was placed in a plastic cup, 20 adult female silver leaf whitefly were released, and placed upside down in a thermostatic chamber at 25 ° C. Five days after the treatment, the number of live and dead insects was examined, and the death rate was calculated. As a result, the compounds in Table 2 showed a death rate of 90% or more at a concentration of 100 ppm or less.

Test Example 3: Thrips palmi KARNY Control Test Cucumber leaves were cut into 2.5 cm squares and placed on cotton wool moistened with water. To this was sprayed 2 mL of the drug diluent using a spray tower. After air-drying, it was put into a plastic cup, and 10 1st instar Thrips thrips were released and placed in a constant temperature room at 25 ° C. Two days after treatment, the number of live and dead insects was examined, and the death rate was calculated. As a result, the compounds in Table 2 showed a death rate of 90% or more at a concentration of 20 ppm or less.

Test Example 4: Frankliniella occidentalis control test kidney beans were cut to a diameter of 2.8 cm and placed on cotton wool moistened with water on a plastic petri dish. To this, 0.5 mL of the drug dilution was sprayed with a spray gun. After air-drying, 10 first-instar larvae of Citrus thrips were released and placed upside down in a thermostatic chamber at 25 ° C. Three days after treatment, the number of live and dead insects was examined, and the death rate was calculated. As a result, the compounds in Table 2 showed a death rate of 90% or more at a concentration of 1 ppm or less.

Comparative example
The similar compounds disclosed in WO2006 / 013896 were subjected to the test described in Test Example 4, and the results shown in Table 3 below were obtained.

Claims (9)

A compound represented by the following formula (I) or an agriculturally and horticulturally acceptable acid addition salt thereof:

(Where
R ₁ is an alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 or 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or a group —OR ₅ or a group —SR ₅ (where R ₅ is carbon Represents an alkyl group of formulas 1 to 4, and
R ₂ , R ₃ and R ₄ each independently represents an alkyl group having 1 to 4 carbon atoms. ). R ₁ represents an alkyl group having 1 to 4 carbon atoms, a cyclic alkyl group having 3 or 4 carbon atoms, or a group —OR ₅ (wherein R ₅ represents an alkyl group having 1 to 4 carbon atoms);
R ₂ , R ₃ and R ₄ each independently represents a methyl group or an ethyl group,
The compound of claim 1. The compound according to claim 1, wherein the compound represented by the formula (I) is selected from the following compounds or agriculturally and horticulturally acceptable acid addition salts thereof:
2-Ethyl-7-methoxy-4-methoxycarbonyloxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Quinoline,
7-Ethoxy-2-ethyl-4-methoxycarbonyloxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Quinoline,
4-acetyloxy-2-ethyl-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline ,
4-Cyclopropylcarbonyloxy-2-ethyl-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -Quinoline,
2-Ethyl-7-methoxy-3-methyl-4-methylthiocarbonyloxy-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Quinoline,
4-Allylcarbonyloxy-2-ethyl-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Quinoline,
2-Ethyl-4-isopropyloxycarbonyloxy-7-methoxy-3-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -Quinoline,
4-acetyloxy-2,3-dimethyl-7-methoxy-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy) -quinoline, or 3-ethyl-7-methoxy-4-methoxycarbonyloxy-2-methyl-6- (2,2,3,3-tetrafluoro-2,3-dihydrobenzo-1,4-dioxin-6-yloxy)- Quinoline.   An insecticide for agriculture and horticulture, comprising the compound according to any one of claims 1 to 3 or an acid addition salt acceptable in agriculture and horticulture as an active ingredient.   Claims for the control of Lepidoptera, Hemiptera pests, Coleopterous insects, Acarina pests, Hymenoptera pests, Diptera pests, Diptera pests, Thrips pests, or plant parasitic nematodes 4. The agricultural and horticultural insecticide according to 4.   The agricultural and horticultural insecticide according to claim 4 for controlling Frankliniella occidentalis.   A method for controlling agricultural and horticultural pests, comprising applying an effective amount of the compound or the agricultural and horticulturally acceptable acid addition salt thereof according to any one of claims 1 to 3 to a plant or soil. .   The pest is selected from the group consisting of Lepidoptera, Hemiptera, Coleoptera, Mites, Hymenoptera, Diptera, Diptera, Thrips, and plant parasitic nematodes, Item 8. The control method according to Item 7.   The pest control method according to claim 7, wherein the pest is Frankliniella occidentalis.