JPS62212335A - 2-aryl-2-methylpropyl ether derivative and insecticide containing said derivative as active component - Google Patents

Abstract

NEW MATERIAL:The 2-aryl-2-methylpropyl ether derivative of formula I (X is F, Cl or Br). EXAMPLE:3-Phenoxybenzyl 2-(4-difluorobromomethoxyphenyl)-2-methylpropyl ether. USE:An insecticide. An excellent compound having high insecticidal activity and broad insecticidal spectrum, exhibiting remarkable effect against lepidopterous vermin and useful especially in agricultural field. PREPARATION:A compound of formula I wherein X is Br can be produced by reacting the phenol derivative of formula III with CF2Br2 in a polar solvent such as 1,3-dimethyl-2-imidazolinone in the presence of a base such as KOH. Reaction of the product with HF gives another compound of formula I wherein X is F. The other compound of formula I wherein X is Cl can be produced by reacting the phenol derivative of formula III with CF2BrCl.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to 2-aryl-2-methylpropyl represented by the general formula (I) (wherein X represents a fluorine, chlorine or bromine atom). This invention relates to ether derivatives and insecticides containing them as active ingredients.

The compounds of the present invention are useful in various industrial fields, particularly in the agricultural field, and among these are useful as insecticides.

[Conventional technology]

From many years of research and development into insecticides, many drugs1
Examples include organochlorine insecticides such as DDT and BHC.

Organophosphorus insecticides such as parathion and malathion, and carbamate insecticides such as carverin and methomyl have been developed and put into practical use, and these insecticides have played an extremely important role in improving agricultural production. In recent years, the use of these insecticides has been regulated due to problems such as residue, accumulation, and environmental pollution, and some insecticides have become resistant to insect pests due to long-term use.

Pyrethroid insecticides have been developed and put into practical use because they have low toxicity to humans, are easily decomposed in the natural environment, have little residue, and have non-toxic decomposition products. However, some insect pests that are resistant to pyrethroid insecticides have appeared, and there is a demand for the development of new agents with excellent insecticidal properties.

[Problems to be solved by the present invention]

An object of the present invention is to provide an excellent insecticidal compound having a new structure, a wide insecticidal spectrum, and high insecticidal activity even against resistant pests, in order to solve the problems of the prior art.

[Means and Effects for Solving the Problems] In order to solve the above problems, the present inventors have conducted extensive studies on 2-aryl-2-methylpropyl ether derivatives, and have found that the general formula (I) (in the formula, It was discovered that the 2-aryl-2-methylpropyl ether derivative represented by (X has the above meaning) has a wide insecticidal spectrum and very strong insecticidal activity, and the present invention was completed. 2-71J-Lou 2-
It is known that methylpropyl ether derivatives have insecticidal activity (Japanese Unexamined Patent Publication No. 72928/1983). In this document, physical property values and biological activity data against various pests were described for Compound (n), which has a primary structure as a compound similar to the compound of the present invention.

However, for the very active compound of the present invention represented by general formula (I), neither physical property values nor insecticidal activity data were described.

That is, 2-aryl-2 represented by general formula (I)
-Methylpropyl ether derivative is a new compound discovered for the first time by the present inventors.

In general formula (I), represents a substituent or a fluorine, chlorine or bromine atom.

Compounds (Ia) and (Ib) represented by general formula (I)
The compounds of the present invention (IC) and (IC) can be easily produced from compound (g) by the following method.

(Ia) 011) Nigahamamo (Ib) (IC) That is, a polar compound such as dimethylformamide (DMFJ or 1,3-dimethyl-2-imidazolidinone (DMj)) is added to the phenol derivative represented by the general formula (1). Hydrogenation in a solvent) In the presence of a base such as IJ or potassium t-butoxide, dibromodifluoromethane or chlorobromodifluoromethane is reacted to form the compound (IaJ or (Ib)) (References;
Tetrahedron Letters.

19B1.323.1997J. The compound thus obtained (
Ia) is a compound (
IC) (Reference: JP-A-58-128374)
be able to.

The compound of the present invention represented by the general formula (1) is useful for sanitary pests such as flies, mosquitoes, and cockroaches, as well as for Hemiptera (Hemiptera) such as the brown planthopper, brown planthopper, brown planthopper, black-bottomed planthopper, whitefly, green peach aphid, etc.
1ptera) Pests, Lepidoptera, such as the Japanese armyworm moth, diamondback moth, fall armyworm, armyworm, North fall armyworm, and cabbage butterfly.epi4tera] Pests, Coleoptera, such as the rice weevil, and the rice weevil.
) It is also effective against agricultural pests such as pests, house pests such as termites, bark insects, and 9 other pests. It is particularly effective against lepidopteran pests. When the compound of the present invention is actually applied, it can be used alone without adding other ingredients, but it is generally used as a pesticidal agent by blending it with a carrier. The compounds of the present invention can be formulated into emulsions, irrigation agents, powders, granules, fine granules, oils, aerosols, etc. without any special conditions and by methods well-known in the art industry in accordance with general agricultural chemicals. It can be adjusted to any desired dosage form, such as poison bait, and can be used for various purposes depending on the purpose.

The term "carrier" as used herein means a synthetic or natural inorganic or organic substance that is incorporated to help the active ingredient reach the area to be treated and to facilitate storage, transport, and handling of the active ingredient compound. do.

Suitable solid carriers include clays such as montmorillonite and kaolinite, inorganic materials such as diatomaceous earth, clay, talc, vermiculite, gypsum, calcium carbonate, silica gel, and ammonium sulfate, and vegetable organic materials such as soybean flour, sawdust, and wheat flour. Examples include substances and urea.

Suitable liquid carriers include aromatic hydrocarbons such as toluene, xylene and cumene, paraffinic hydrocarbons such as kerosene and mineral oil, halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloroethane, and ketones such as acetone and methyl ethyl keto7. , ethers such as dioxane and tetrahydrofurano, alcohols such as methanol, ethanol, propatool, and ethylene glycol, dimethylformamide, dimethyl sulfoxide, and water.

Furthermore, in order to enhance the efficacy of the compound of the present invention, the following auxiliaries may be used individually or in combination depending on the purpose, taking into consideration the dosage form of the preparation, the application situation, etc.゛For the purpose of emulsification, dispersion, spreading, wetting, binding, stabilization, etc., water-soluble bases such as phosphogenine sulfonate, aniono surfactants such as alkylbenzene sulfonate, alkyl sulfate, polyoxyalkylene Alkyl ether, polyoxyalkylene alkylaryl ether, polyoxyalkylene alkyl amine, polyoxyalkylene alkyl amide, polyoxyalkylene alkyl thioether, polyoxyalkylene fatty acid ester, glycerin fatty acid ester, nrubitan fatty acid ester, polyoxyalkylene nrubitan fatty acid ester, Examples include nonionic surfactants such as polyoxypropylene polyoxyethylene block polymers, lubricants such as calcium stearate and wax, stabilizers such as isopropylhydrodiene phosphate, and others such as methylcellulose, carboxymethylcellulose, casein, and gum arabic.

However, these components are not limited to the above.

Furthermore, by using two or more of these compounds of the present invention in combination, it is possible to express more excellent insecticidal power, and it is also possible to express more superior insecticidal power by combining two or more kinds of compounds, and by using other physiologically active substances such as allethrin, N-(chrysanthemoylmethyl)-3, 4,5,6-ketone hydrophthalimide, 5-befjyl-3-furylmethyl chrysanthemate, 6-nerphenoxypenzyl chrysanthemate, 5-propargylfurfuryl chrysanthemate, and other known cyclopropane compounds Acid ester, 3-phenoxy/dimethyl-2,2-dimethyl-3-(2,2-dichlorovinyl)-
Cycloclopane-1-carboxylate, 3-phenoxy-α-cyanobenzyl 2,2-dimethyl-5-(2,
2-dichlorovinylnocyclopropane-1-carboxylate, 6-7 dinoxy α-cyanopenzyl 2,2
Synthetic pyrethroids such as -dimef-3-(2,2-schif' lomopinylnocyclopropane-1-carboxylate, 3-7 dynoxy α-cyanobenzyl α-inpropyl-4-chlorophenylacetate, and various types thereof) Isomers or pyrethrum extract, 0,0-diethyl-〇-(5-oxo-2-phenyl-211-pyridazin-6-yl) phosphorothioate (Mitsui Toatsu Chemical registered trademark Offnac J, 0,0-dimethyl-〇- (2,2
-dichlorovinyl j phos 7-'-) (DDVP J,
0.0-dimethyl-0(3-)f-4-nitrophenyl) phosphorothioate, diazinon, 0,0-dimethyl-0-,4-cyanophenyl phosphorothioate, 0.0-dimethyl-5-(α-(ethoxy phosphorodithioate, 2-methoxy-4
H-1, 3,2-benzodioxaphosphorine-2-sulfide, organophosphorus insecticides such as 0-ethyl-〇-4-cyanophenylphosphonothioate, 1-naphthyl N-
Methyl carbamate (NAOJ, m-tolyl N-methylcarbuff-) (MTMO), 2-dimethylamino-5
, 6-dimethylpyrimidin-4-yl-dimethylcarbamate (bilimer), 3.4-dimethylphenyl N-methylcarbamate, 2-impropoxyphenyl N-methylcarbamate, etc., carbamate insecticides, 6-phenoxybenzyl 2 -(4-/lorophenyl J-2-methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl J-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-ethoxyphenyl J- 2-, J thylpropyl ether, 3-
Arylpropyl ether insecticides such as phenoxy-4-fluorobenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether, 1-(3-phenoxyphenyl J-4-(4-chlorophenyl)-4-methyl Pentane, 1-(3-phenoxy-4-fluorophenyl)-4-(4-chlorophenyl)-4-methylpentane, 1-(3-phenoxyphenyl-4=(4-
ethoxyphenyl)-4-methylpentane, 1-(3-
Aromatic alkane-based insecticides such as 7-dinoxy-4-fluorophenyl J-4-(4-ethoxyphenyl)-4-methylpentane, other insecticides, acaricides or fungicides, nematicides, herbicides agent, plant growth regulator, fertilizer, BT
By mixing it with pesticides, insect hormones, other agricultural chemicals, etc., it is possible to create a multipurpose composition with even greater efficacy, and a synergistic effect can also be expected. The compound of the present invention is stable against light, heat, oxidation, etc., but if necessary, it may be added with an antioxidant or an ultraviolet absorber, such as BHT (2,6-di-t-butyl-phenol J, BHA (butylhydroxyanisole)). By adding an appropriate amount of phenol derivatives and bisphenol derivatives such as, phenyl-α-naphthylamine, phenyl-β-naphthylamine, arylamines such as a condensate of phenetidine and aceto, or benzophenol compounds as stabilizers, A composition with more stable effects can be obtained.

The insecticide of the compound of the present invention contains 0.0001 to 95% of the compound.
Weight officer, preferably o. ooi to 50% by weight. To apply the insecticide of the present invention, the active ingredient is generally 0.0
1 to 5000 ppm, preferably 0.1 to 100
Preferably, it is used at a concentration of 0 ppm. In addition, the application amount per 10A is 300% with general active ingredients! i to 11.

〔Example〕

The present invention will be explained in more detail by reference examples, synthesis examples, formulation examples, and test examples.

Example i 3-phenoxybenzyl 2-4-hydroxyphenyl-2-methylpropyl ether (compound (I)
)) Synthesis (1) 3-phenoxybenzyl 2-(3-chloro-4-
Ethoxyphenyl-2-methylpropyl ether 10
Add 0g of potassium hydroxide, 25J of 97% potassium hydroxide to 300g of 1,3-dimethyl-2-imidazolidinone, and stir at 150°C.
Stirred for 88 hours. After cooling to room temperature, it was poured into water, acidified with concentrated hydrochloric acid, and extracted with benzene. After washing the benzene solution with water and drying, the benzene was distilled off under reduced pressure, and the resulting oily residue was purified by column chromatography (silica gel, developing solvent: benzene) to obtain 3-phenoxypencyl 2-( 3-Chloro-4-hydroxyphenyl)-2-methylpropyl ether 45.6.j9 (mp.

68-b (2) 3-phenoxybenzyl 2-(5-
Chloro-4-hydroxyphenyl)-2-methylpropyl ether 20.09.95 Sodium thihydroxide 2.6
7ji and 5% pct-a (50chi water-containing product) 1,
Add 09 to 80% methanol 100ml 1Vc, hydrogen pressure 2
Stirring was carried out at a rate of 0 to 30 kg/ff1G and a temperature of 100° C. for 6 hours.

After cooling, the catalyst was removed by filtration and thoroughly washed with benzene. The solvent was distilled off under reduced pressure, diluted hydrochloric acid was added, and the mixture was extracted with benzene. After washing the benzene solution with water and drying,
Benzene was distilled off under reduced pressure to obtain the desired 3-phenoxybenzyl 2-(4-hydroxyphenyl)-2-methylpropylnitrate/L/18, 2 g (mp, 69.2~
7 Q, Q℃] and Tco.

δ0D” (pI) mJ: 1.29 (6H
, s), 3.36 (21-1, s), MS 4.38 (2H, s), 5.07 (IH, s), 6.
6-7.4 (15H, m) Elemental analysis value: 0uH2403 0H Calculated value (@ 79.28 6.94 Measured value (To) 79.41 6.87 Low enoxybenzyl 2-(4-hydroxyphenyl J- 21.6 g of 2-methylpropyl ether and 1 potassium t-butoxide
3.97 to 1,6-dimethyl-2-imidazolidino 71
A solution dissolved in 20 m/l of dibromodifluoromethane, 80 g/l of dibromodifluoromethane, 5 g/l of 3-dimethyl-2-imidazolidinone,
The mixture was added dropwise to the mixed solution over 30 minutes with stirring while maintaining the temperature at 50 to 60°C, and was further maintained at the same temperature for 6 hours.

It was poured into water and extracted with toluene. The toluene solution was washed over dilute hydrochloric acid, water and dried. Toluene was distilled off under reduced pressure to obtain 294 g of an oily residue. The obtained oily residue was purified by column chromatography (silica gel, 600 g, developing solvent: toluene-hexane (1:1)),
The desired 3-phenoxybenzyl 2-(4-difluorobromomethoxyphenyl)-2-/tylpropyl ether 12.4I was obtained.

n ” 1.5545 neat −1 νmax ((:m J:1260,1230,12
05,1150°1110.1020 2%04H (ppm): 1.55 (6H,S),
3.37 (2H,s), 4.39 (2H,sJ,
6.78-7.4 (131-1°m) Mass spectrometry (El, MaSSJ: m/z 264.
477(M3-phenoxybenzyl 2-(4-hydroxyphenyk)-2-)-F-rubropylether 4.3.9-Potassium t-butoxide 2.8,! ? and 1,3-dimethyl-2-imidazolidinone 50II
Il was charged to a 200ml autoclape. Next, 10.17 g of chlorobromodifluoromethane was charged at room temperature, and the temperature was gradually raised to 65°C. After keeping at the same temperature for 5 hours, it was cooled to room temperature. The reaction solution was poured into water and extracted with toluene. After washing the toluene solution with water and drying, toluene was distilled off under reduced pressure, and the resulting oil was subjected to column chromatography (silica gel, developing solvent: toluene-hexane).
2:3)) to obtain the desired 6-phenoxybenzyl 2
-(4-difluorochloromethoxyphenyl)-2-methylpropyl ether 2.8I was obtained.

δ0C' (ppm): t s s (6H, S
), 3.39 (2H,s), MS 4.36 (21-1,s), 6.75-7.45
(13H.

m) Mass spectrometry (E(! Mass): m/z 219,4
1.30.9 of 32(6-phenoxybenzyl 2-44-difluorobromomethoxyphenyl)-2-methylpropyl ether was dissolved in 1 oml of Improvyl ether. Add hydrofluoric acid-pyridine (Pirid) to this solution.
inium Poly(hydrogen fluor
ide) and then 0.5 ml of mercuric oxide.
g was added. After stirring at room temperature for 5 hours, the mixture was poured into water and extracted with hexane.

The hexa/solution was washed with a dilute aqueous solution of sulfur hydroxide and water in that order, dried, and then the hexane was distilled off under reduced pressure.

1.10 g of the obtained oily residue was purified by column chromatography (silica gel, 40.9, developing solvent: toluene-hexane (2:3)) to obtain the desired 3-phenoxybenzyl 2-(4-). (lifluoromethoxyphenyl)-
2-Methylpropyl ether 105I was obtained.

nD 1,5312 1 part maX (Cm J:1270,1220,117
5.1120δ s U) I) mJ : 1.51 (
6H,S ), 3.34 (2H,S ), 4.36
(2H,s), 6.78~7.36 (13H,m
J mass spectrometry (EI Mass): m/z 203.
416 (M5 order k) The composition of the present invention will be specifically explained by giving examples of formulations.

Formulation Example 1 An emulsion was obtained by uniformly stirring and mixing 20 parts of the compound of the present invention, 10 parts of Sorbol 3558 (trade name of Toho Chemical Co., Ltd. J), 0 parts of Kishi 2 Fufu, and 1 or more parts.

Formulation Example 2 20 parts of the compound of the present invention, 2 parts of sodium alkylnaphthalene sulfonate, 5 parts of sodium lignin sulfonate, 5 parts of white carbon, and 68 parts of diatomaceous matter were uniformly stirred and mixed to obtain a wettable powder. Formulation Example 3 Six parts of the compound of the present invention were dissolved in acetone, and the acetone was evaporated while mixing with 97 parts of clay to obtain a powder.

Formulation Example 4 6 parts of the compound of the present invention, 2 parts of sodium ligninsulfonate, and 1 or more parts of 95 parts of bentonite were uniformly pulverized and mixed, water was added and kneaded, and the mixture was granulated and dried to obtain granules.

Formulation Example 5 0.1 part of the compound of the present invention, 0.5 part of piperonyl ptoxide
and 994 parts of white kerosene were uniformly dissolved and mixed to obtain an oil agent.

Formulation Example 6 04 parts of the compound of the present invention, 2.0 parts of viberonyl ptoxide, and 7.6 parts of deodorized kerosene are uniformly dissolved and mixed, filled into an aerosol container, and an injection pulp is attached. 90 parts of gas was filled under pressure to obtain an aerosol.

Formulation Example 7 Add 0.5 parts of BHTo to the compounds o and osg of the present invention, dissolve in an appropriate amount of chloroform, and prepare 2.5 Cm x 1.5
cm.

A fiber composition heated on an electric heating plate was obtained by uniformly adsorbing it on the surface of asbestos having a thickness Q of 3 cm.

Formulation Example 8 1 part of the compound of the present invention, 5 parts of sugar, 50 parts of wheat bran, 2 parts of rice bran
0 parts and 24 parts of wheat flour were uniformly mixed, an appropriate amount of water was added and kneaded, and the mixture was granulated and dried to obtain a poison bait.

Formulation Example 9 10 parts of the compound of the present invention, 20 parts of a 10% polyvinyl alcohol aqueous solution, and 5 parts of xylene were uniformly stirred and mixed, and then 65 parts of water was added and stirred again to obtain a flowable agent.

Next, in order to clarify that the compound of the present invention has excellent insecticidal activity, it will be specifically explained in the following test examples.

In addition, using compound (II) as a control compound, 0 (compound described in JP-A-57-72928) Si1 row 1
6.5 ml of the diluted emulsion of the test compound prepared in Formulation Example 1 was applied to 4 to 5 paddy rice seedlings on a turntable, and immediately after air-drying, the area was covered with a wire mesh cylinder. We released 20 female adult brown planthoppers there, and
The insects were placed in a constant temperature room at 5℃ and the mortality rate was investigated after 48 hours.
child.

The median lethal concentration was determined using Finney's simple calculation formula. The results are shown in Table 1.

Table 1 Test compound LO511 value (laJ 3.1 μEm (lb) 2.5 (lcJ 1.2 Control compound (II) 14 The test compound was prepared in an acetate/solution of a specified concentration and applied to the ventral thorax of a female German cockroach. 1μE was added dropwise.The treated insects were transferred to a waist-height Petri dish and kept in a constant temperature room at 25℃.After 24 hours, the mortality rate was investigated.60 insects were tested for each concentration, using Finny's simple calculation formula. The median lethal dose was determined using

The results are shown in Table 2.

Table 2 (Ia) 0.064 μg
/ head (IcJ o, ds.

The diluted emulsion prepared according to Formulation Example 1 was sprayed on the soybean surface of the potted plant on a tar/table until the chemical liquid was slightly splattered.After air-drying, the treated leaves were cut and transferred to a plastic cup. Release 10 larvae each,
It was housed in a constant temperature room at 25°C. After 48 hours, the mortality rate was examined. The test was performed in triplicate and with two replicates.
) was used to calculate the median lethal concentration.

The results are shown in Table 3.

Table 5 (laJ 3.4
ppm (IC) 2.7 Control Compound (II) 14 The test compound was prepared as a solution with a predetermined concentration, and 32 μl of the test compound was added dropwise to the back of the thorax of an adult female leafhopper, and the 0-treated insects were added to a paddy rice seedling. Transfer to a wire mesh cylinder and heat at 25℃.
They were housed in a constant temperature room. After 24 hours, the mortality rate was examined. 45 cows were sampled for each concentration mouth, Finney (F'1nn
The median lethal dose was determined using the simple formula of y).

The results are shown in Table 4.

Table 4 (IC) α39 Control Compound (II) 1.6 [Effects of the Invention] As is clear from the above explanation, the 2-aryl-2-methylpropyl ether derivative represented by the general formula (1) according to the present invention is an excellent compound with high insecticidal power and a wide insecticidal spectrum.

Maγko, 2− represented by the general formula (+) related to the present invention
Pesticides containing aryl-2-methylpropyl ether derivatives have excellent properties and are useful as insecticides.

Claims (3)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) 2-aryl-2-methylpropyl ether derivative represented by (In the formula, X represents a fluorine, chlorine or bromine atom) . (2) The 2-aryl-2-methylpropyl ether derivative according to claim (1), wherein in the general formula (I), X is a fluorine atom. (3) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) 2-aryl-2-methylpropyl ether derivative represented by (In the formula, X represents a fluorine, chlorine or bromine atom) An insecticide characterized by containing as an active ingredient.