JPH0436125B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (In the formula, R ₁ and R ₂ are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a halomethyl group, a methoxy group, an ethoxy group, a difluoromethoxy group, or R ₁ and R ₂ represents a methylenedioxy group. A is a group represented by the formula, ,

【formula】

【formula】

[Formula] Here, R ₁ represents a hydrogen atom, a methyl group, a formyl group, or an acetyl group, and X represents a hydrogen atom or a halogen atom. R ₃ represents a hydrogen atom or a fluorine atom,
R ₄ represents a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group. ) The present invention relates to an insecticide and acaricide characterized by containing a novel aromatic alkane derivative represented by the following as an active ingredient, and a method for producing the same. In recent years, research has been widely conducted on analogs with modified chemical structures of pyrethrin, a natural insecticidal ingredient, and the general formula (Here, R ₁ , R ₂ , R ₃ , and R ₄ have the same meanings as above.) In addition to the compound group represented by High insecticidal activity was found in the compound shown. (Japanese Patent Application Laid-open No. 58-201737). The present inventors continued intensive research to search for more useful insecticidal and acaricidal components, and as a result, we found a general formula in which the phenoxy group of the compound represented by the general formula Knowing that the compound represented by I has significantly enhanced insecticidal efficacy compared to the original compound, while its toxicity to warm-blooded animals and seafood is further reduced,
The invention has been completed. The compound represented by the above formula I used as an active ingredient in the present invention is of the general formula V (In the formula, R ₁ and R ₂ are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a halomethyl group, a methoxy group, an ethoxy group, a difluoromethoxy group, or R ₁ and R ₂ represents a methylenedioxy group.) and the general formula (wherein A is a group represented by the formula,

【formula】

【formula】

[Formula] Here, R ₅ represents a hydrogen atom, a methyl group, a formyl group, or an acetyl group, and X represents a hydrogen atom or a halogen atom. R ₃ is a hydrogen atom or a fluorine atom, R ₄
represents a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group. ) is reacted with the general formula (Here, R ₁ , R ₂ , A, R ₃ , and R ₄ have the same meanings as above.) It can be prepared by obtaining an unsaturated carbonyl compound represented by the following and reducing the obtained ketone. . The reaction is carried out in a suitable solvent, optionally in the presence of a catalyst, and optionally under heating. In addition, when A is the general formula, there are geometric isomers based on the double bond of the vinyl group, and those obtained by ordinary synthesis methods are mixtures of these, but each of these is of course included in the present invention. It will be done. Representative examples of the compound represented by the above formula I are shown below, but the present invention is of course not limited to these. 1-(3-anilino-4-fluorophenyl)-
4-Methyl-4-(4-ethoxyphenyl)pentane n ²⁰ D1.5740 1-{3-(4-fluoro-N-methylanilino)}phenyl-4-methyl-4-(3,4-dichlorophenyl)pentane n ²⁰ _D 1.5753 1-{3-(1-phenylvinyl)}phenyl-
4-Methyl-4-(4-difluoromethoxyphenyl)pentane n ²⁰ _D 1.5709 1-{3-(2-phenylvinyl)}phenyl-
4-Methyl-4-(3,4-methylenedioxyphenyl)pentane n ²⁰ _D 1.5732 1-{3-(4-chloro-N-formylanilino)-4-fluoro}phenyl-4-methyl-4
-(4-tert-butylphenyl)pentane
n ²⁰ _D 1.5786 1-{3-(4-Methyl-N-acetylanilino)}phenyl-4-methyl-4-(4-methoxyphenyl)pentane n ²⁰ _D 1.5798 1-{3-(1-phenyl-2-chlorovinyl)
-4-fluoro}phenyl-4-methyl-4-
(3-chloro-4-trifluoromethylphenyl)
Pentane n ²⁰ _D 1.5761 1-[3-{2-(4-trifluoromethylphenyl)vinyl}-6-fluoro]phenyl-4-
Methyl-4-(3,4-dimethylphenyl)pentane n ²⁰ _D 1.5744 1-(3-anilino)phenyl-4-methyl-
4-(4-difluoromethoxyphenyl)pentane n ²⁰ _D 1.5732 1-{3-(N-methylanilino)-4-fluoro}phenyl-4-methyl-4-(4-ethoxyphenyl)pentane n ²⁰ _D 1.5759 1-[3-{1-(4-fluorophenyl)vinyl}-4-fluoro]phenyl-4-methyl-4
-(4-chlorophenyl)pentane n ²⁰ _D 1.5710 1-[3-{1-(4-methylphenyl)-2-bromovinyl}]phenyl-4-methyl-4-(3-
Fluoro-4-ethylphenyl)pentane n ²⁰ _D
1.5775 1-[3-2-(4-chlorophenyl)vinyl}
-5-fluoro]phenyl-4-methyl-4-
(3-Methoxy-4-chloromethylphenyl)pentane n ²⁰ _D 1.5763 1-{3-(2-phenylvinyl)-4-fluoro}phenyl-4-methyl-4-(4-ethoxyphenyl)pentane n ²⁰ _D 1.5718 1-{3-(4-trifluoromethyl-N-methylanilino)}phenyl-4-methyl-4-(3-
Methyl-4-bromophenyl)pentane n ²⁰ _D
1.5784 1-{3-(4-promo-N-acetylanilino)-6-fluoro}phenyl-4-methyl-4
-(4-isopropylphenyl)pentane n ²⁰ _D
1.5786 1-[3-{1-(4-trifluoromethylphenyl)vinyl}]phenyl-4-methyl-4-
(3,4-methylenedioxyphenyl)pentane
n ²⁰ _D 1.5749 1-{3-(1-phenyl-2-chlorovinyl)}
Phenyl-4-methyl-4-(4-ethoxyphenyl)pentane n ²⁰ _D 1.5723 1-[3-{1-(4-chlorophenyl)-2-fluorovinyl}-5-fluoro]phenyl-4-
Methyl-4-(3-bromo-4-chlorophenyl)
Pentane n ²⁰ _D 1.5790 1-[3-{2-(4-methylphenyl)vinyl}]phenyl-4-methyl-4-(4-difluoromethoxyphenyl)pentane n ²⁰ _D 1.5722 1-[3-{2-(4-fluorophenyl)vinyl}]phenyl-4-methyl-4-(4-chlorophenyl)pentane n ²⁰ _D 1.5718 1-{3-(4-methylanilino)-5-fluoro}phenyl-4-methyl-4-(3-propyl-4-fluorobromomethylphenyl)pentane
n ²⁰ _D 1.5781 1-{3-(N-formylanilino)}phenyl-4-methyl-4-(4-chlorophenyl)pentane n ²⁰ _D 1.5748 The compound used as an active ingredient in the insecticide and acaricide of the present invention is a new compound, and it can be used at room temperature. It is solid or liquid and is generally easily soluble in organic solvents. Therefore, insecticides and acaricides for spraying can be used as emulsions, oils, powders, wettable powders, aerosols, etc. They can also be mixed with wood flour or other suitable bases to be used as fumigation agents such as mosquito coils. It can be used as an insecticide and acaricide. Also, when used as a so-called electric mosquito repellent, in which the active ingredient is dissolved in an appropriate organic solvent and soaked in a mount, or dissolved in an appropriate solvent and heated and evaporated with an appropriate heating element, it can be used in the same way as a mosquito coil. Shows excellent effects. The compound of the present invention is more stable to light than conventional pyrethroids, has a broader spectrum of insecticidal and acaricidal properties, has low toxicity, low toxicity to fish, and is inexpensive, so it is better than conventional organic phosphorus agents. It can be used as an agricultural and horticultural insecticide and acaricide in place of organochlorine insecticides. The insecticide and acaricide of the present invention can be used for flies,
In addition to sanitary pests such as mosquitoes and cockroaches, organophosphate and carbamate resistant leafhoppers, planthoppers, stinkbugs, armyworms, diamondback moths, tobacco moths, bean weevils, nocturnal moths, cabbage moths, chestnut beetles, leafhoppers, aphids, scale insects, etc. It is extremely useful for controlling agricultural pests, such as grain pests such as brown elephant, and mites. Furthermore, the compound of the present invention has significantly reduced toxicity to fish compared to conventional pyrethroids, making it possible to use it as an insecticide for paddy rice. In addition, the insecticides and acaricides of the present invention include N-octylbicycloheptenedicarboximide (trade name MGK-264) and a mixture of N-octylbicycloheptenedicarboximide and an arylsulfonate salt (tradename MGK-264).
5026), cinepirin 500, octachlorodipropyl ether, piperonyl ptoxide, etc., the insecticidal effect can be further enhanced. In addition, other insecticides may be used in addition to the insecticides and acaricides of the present invention, such as organic phosphorus agents such as fenitrothion, DDVP, diazinon, propaphos, and pirdafuenthione, carbamate agents such as NAC, MTMC, BPMC, and PHC, pyrethrin, and allethrin. ,
phthalthrin, flamethrin, phenothrin,
Conventional pyrethroid insecticides such as permethrin, cypermethrin, decametrin, fuenvalerate, fuenpropanate, insecticides or acaricides such as cartap, chlorphenamidine, methomyl, fungicides, nematicides, herbicides By mixing , plant growth regulators, fertilizers, and other agricultural chemicals, a highly effective multipurpose composition can be obtained, and labor savings and synergistic effects among the drugs can be fully expected. Next, examples of synthesizing compounds used as active ingredients in the present invention will be shown. Ketones of the general formula are easily synthesized, for example, according to FIG. 1, as described in JP-A-58-201737. On the other hand, the aldehyde of the general formula is an intermediate of the alcohol component constituting the pyrethroid ester, and can be easily obtained by a known method.
However, when A is the formula, it is preferable to react in a manner that protects the double bond and then convert it back to its original form. Synthesis Example 1 Synthesis of 1-(3-anilino-4-fluorophenyl)-4-methyl-4-(4-ethoxyphenyl)pentane (a) 2-methyl-2-(4-ethoxyphenyl) −
Add 4.2 g of 3-butanone and 4.3 g of 3-anilino-4-fluorobenzaldehyde to 50 ml of ethanol.
4.0 KOH was added, and the mixture was stirred at room temperature for 2 hours. Then, the reaction solution was poured into 200ml of water,
Extracted with benzene. The benzene solution was washed with saturated saline and dried over sulfur salt. The oily substance obtained by distilling off benzene under reduced pressure is converted into silica gel.
Purified by 100g column chromatography,
1-(3-anilino-4-fluorophenyl)-
4-methyl-4-(4-ethoxyphenyl)-1
-5.7 g of penten-3-one were obtained. (b) Add 1.0 g of lithium aluminum hydride to 10 ml of dry ether, then add aluminum chloride.
A solution of 7.0 g dissolved in 20 ml of ether was carefully added dropwise. Then, the 1-(3-anilino-4-fluorophenyl)-4-methyl- obtained in (a)
4-(4-ethoxyphenyl)-1-pentene-
A solution of 5.5 g of 3-one dissolved in 10 ml of ether was added dropwise over 20 minutes, and the mixture was further refluxed for 1 hour. While cooling, ethyl acetate and then water were added dropwise to the reaction solution to decompose excess lithium aluminum hydride, followed by extraction with benzene. The benzene solution was washed with water, dried, and then the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (100 g) to obtain 1-(3-anilino-4-fluorophenyl)-4. -Methyl-4-(4-ethoxyphenyl)-2-pentene and 1-(3-anilino-4-fluorophenyl)
-4-methyl-4-(4-ethoxyphenyl)-
4.1 g of a mixture of 1-pentene was obtained. (c) After dissolving 3.7 g of the pentene mixture obtained in (b) in 30 ml of ethyl acetate, 0.5 g of 5% PD-C was added.
The mixture was stirred at room temperature under a hydrogen pressure of 20 kg/cm ² G for 4 hours. After the reaction was completed and PD-C was separated, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography using 80 g of silica gel to obtain the desired 1-
(3-anilino-4-fluorophenyl)-4-
3.5 g of methyl-4-(4-ethoxyphenyl)pentane was obtained. Synthesis Example 2 1-[3-{1-(4-methylphenyl)-2-bromovinyl}]phenyl-4-methyl-4-(3-fluoro-4-ethylphenyl)
Synthesis of pentane (a) 4.3 g of 2-methyl-2-(3-fluoro-4-ethylphenyl)-3-butanone and 3-(4-
Dissolve 4.5 g of methyl-α-methoxybenzyl)benzaldehyde in 30 ml of methanol, and add KOH3.0
g was added thereto, and the mixture was reacted at 60°C for 2 hours. Next, the reaction solution was poured into 200 ml of ice, and Synthesis Example 1-
1-[3-(4-methyl-α-
methoxybenzyl) phenyl-4-methyl-
4-(3-fluoro-4-ethylphenyl)-1
-5.6 g of penten-3-one were obtained. (b) After adding 1.2 g of lithium aluminum hydride to 15 ml of dry ether, a solution of 6.5 g of aluminum chloride in 20 ml of ether was added dropwise. Then, 1-{3-(4-methyl-α-methoxybenzyl)}phenyl-4-methyl-4 obtained in (a)
-(3-fluoro-4-ethylphenyl)-1-
A solution of 5.3 g of penten-3-one dissolved in 10 ml of ether was added dropwise over 30 minutes, and the reaction was further carried out under reflux for 1 hour, followed by treatment according to Synthesis Example 1-(b). (4-Methyl-α-methoxybenzyl)}phenyl-4-methyl-4-(3-fluoro-4-ethylphenyl)-2-pentene and 1-{3-(4-methyl-α-methoxybenzyl)}phenyl 3.8 g of a mixture of -4-methyl-4-(3-fluoro-4-ethylphenyl)-1-pentene was obtained. (c) After dissolving 3.4 g of the pentene mixture obtained in (b) in 30 ml of ethyl acetate, it was hydrogenated and reduced in the same manner as in Synthesis Example 1-(c) using 5% PD-C as a catalyst.
-{3-(4-methyl-α-methoxybenzyl)}
Phenyl-4-methyl-4-(3-fluoro-
3.7 g of 4-ethylphenyl)pentane was obtained. (d) The compound obtained in (c) was reacted with BBr in methylene chloride according to a conventional method to demethylate the α-methoxybenzyl moiety, and then oxidized with chromic acid to form 1-{3-(4 -methyl-benzoyl)}phenyl-4-methyl-4-(3-fluoro-4
-ethylphenyl)pentane was obtained. (e) To a stirred solution at 20°C of 4.0 g of (bromomethyl)triphenylphosphonium bromide in 50 ml of ether containing piperidine was added 0.8 g of BuLi in hexane over 15 minutes and then
Stir for hours. Cool the mixture to −70°C,
A solution of 3.8 g of the compound obtained in step d dissolved in 20 ml of ether was added dropwise. After reacting at −70° C. for 1 hour and at room temperature overnight, water was added to separate the ether layer.
100g of silica gel was added to the residue obtained after distilling off the solvent.
Purify by column chromatography to obtain the desired 1-[3-{1-(4-methylphenyl)
-2-bromovinyl}] phenyl-4-methyl-4-(3-fluoro-4-ethylphenyl)
3.6 g of pentane was obtained. Synthesis Example 3 1-{3-(2-phenylvinyl)}
Synthesis of phenyl-4-methyl-4-(3,4-methylenedioxyphenyl)pentane (a) 4.2 g of 2-methyl-2-(3,4-methylenedioxyphenyl)-3-butanone and 3 -(Dimethoxymethyl)benzaldehyde 3.7 was dissolved in methanol 30ml, KOH 2.0g was added and treated in the same manner as in Synthesis Example 2-(a) to obtain 1-{3-(dimethoxymethyl)}phenyl-4-methyl. -4-
5.1 g of (3,4-methylenedioxyphenyl)-1-penten-3-one was obtained. (b) Synthesis of the compound obtained in (a) Example 1-(b), (c)
The reaction was carried out in the same manner as above to obtain 1-{3-(dimethoxymethyl)}phenyl-4-methyl-4-(3,4-methylenedioxyphenyl)pentane. (c) Dissolve the compound obtained in (b) in ethanol and P
-Deacetalized in the presence of TsOH to 1-
(3-formylphenyl)-4-methyl-4-
(3,4-methylenedioxyphenyl)pentane was obtained quantitatively. 3.0 g of this compound was reacted with benzyl-triphenylphosphonium salt by Wittetsu reaction to obtain the desired 1-{3-(2-phenylvinyl)}phenyl-4-methyl-4-
3.2 g of (3,4-methylenedioxyphenyl)pentane was obtained. Next, the results of test results to clarify the superiority of the composition provided by the present invention will be shown. Test Example 1 Insecticidal test by spraying A 0.2% white light solution of the compound of the present invention (A), a white light solution of 0.2% and 0.8% Cinepirin 500 (B), a white light solution of 0.1% and phthalthrin 0.1% (C), The falling and turning rate of houseflies was calculated for each 0.2% white light solution of phthalthrin and compound (A), the relative effectiveness of the test agent was calculated, and the mortality rate after 24 hours was calculated as follows. be.

【table】

Test Example 2 Insecticidal test by fumigation A mosquito coil containing 0.5% of the insecticidal ingredient was prepared and tested for its effectiveness in making adult Culex mosquitoes fall and roll over. This experiment was published in Insect Control Science Volume 16 (1951).
The relative effectiveness of the incense stick was calculated according to the method of Nagasawa, Katsuta et al., p. 176, and the results were as follows. The sample drug number is the same as that of the active ingredient example above.

[Table] Test Example 3 Insecticidal test using microdropping method Piperonyl butoxide was added to each of the control compounds (A), (B) and the compound of the present invention in an amount twice the amount of the active ingredient, and an acetone solution of a predetermined concentration was prepared. The compound was applied to the thoracic dorsal plate of adult house flies using a microsyringe, and the relative insecticidal power to the control compound and the synergistic effect with piperonyl butoxide were investigated based on the mortality rate after 24 hours.The results were as follows. be.

[Table] Next, examples of formulation are shown, but the formulation does not require any special conditions similar to general agricultural chemicals, and can be prepared by a method familiar to those skilled in the art. . Reference example 1 White kerosene was added to 0.2 parts of the present compound (1) and the whole
Obtain 0.2% oil solution as 100 parts. Reference Example 2 White kerosene is added to 0.2 parts of the compound (5) of the present invention and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil solution. Reference Example 3 To 20 parts of the compound (7) of the present invention, 10 parts of Solpol SM-200 (registered trademark of Toho Chemical) and 70 parts of xylol were added and mixed and dissolved with stirring to obtain a 20% emulsion. Reference Example 4 0.4 parts of the present compound (9), 0.1 parts of resmethrin, and 1.5 parts of octachlorodipropyl ether were added to refined kerosene.
After dissolving in 28 parts and filling into an aerosol container and attaching a valve part, 70 parts of propellant (liquefied petroleum gas) is pressurized and filled through the valve part to obtain an aerosol. Reference Example 5 0.5 g of the compound (12) of the present invention and 0.5 g of BHT were added to base materials for mosquito coils such as pyrethrum extract lees powder, wood flour, and starch powder.
Mix 99.0g of the mixture uniformly and obtain a mosquito coil by a known method. Reference example 6 Compound of the present invention (16) 0.4g, MGK-5026 1.0g
was uniformly mixed with 98.6 g of a mosquito coil base material to obtain a mosquito coil by a known method. Reference Example 7 0.3 parts of the compound of the present invention (19) and 99.7 parts of clay are thoroughly ground and mixed to obtain a 0.3% powder. Reference Example 8 40 parts of the present compound (22), 35 parts of silica, clay
20 parts of lauryl sulfonate, 3 parts of lauryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder. Test Example 4 5 to 5 on a surface where a large number of green peach aphids appeared
Among the emulsions obtained in Reference Example 3 in a radish field at the 6-leaf stage, each emulsion containing the compounds of the present invention (2), (7), (9), (13), (18), and (21) A solution diluted 1000 times with water was sprayed 100 times per area. Two days later, the parasitism rate was investigated and found that the density had decreased to less than 1/10 of the pre-spraying density in each plot. Test Example 5 Among the emulsions obtained in Reference Example 3, the compound of the present invention
(1), (4), (7), (11) (15), (19) and (23)
of
Fresh leaves were immersed in the 2000-fold diluted solution for about 5 seconds, and after the solution had dried, they were placed in a shear dish, and 10 healthy armyworm larvae were released. The test insects were released twice, once on the day of soaking the fresh leaves, and once 5 days later, and the mortality rate after 24 hours was determined.

【table】

[Table] Test Example 6 Approximately 200 aphids were infested on one tree one day before applying the insecticidal ingredient to potted fava beans. Among the hydrating agents obtained in Reference Example 8, (3)
(6), (10), (14), (16), (19) and (22) 400
0
The diluted solution was sprayed onto leaves infested with insects using a compressed air spray method (10 ml/pot), and the degree of damage was observed 2 days later. As a result, no increase in the degree of damage was observed in any of the cases. Test Example 7 (1), (5), (8), (12) obtained by Reference Example 7,
Each of the powders (17) and (19) is uniformly sprinkled at a rate of 2 g/m ² on the bottom of a tall glass shear dish with a diameter of 14 cm, and the butter is applied to the wall leaving about 1 cm of the bottom. If you release 10 adult German cockroaches into the container, leave them in contact for 30 minutes, and transfer the cockroaches to a new container, after 3 days, 80.
It was possible to kill more than % of cockroaches. Test Example 8 1 for 4 leaves of potted green beans 5 days after sowing
Infested with 10 female adult spider mites per leaf.
Store in a constant temperature room at 27℃. After 6 days, a medicinal solution prepared by diluting the emulsions (3), (7), (10), (15) and (20) obtained in Reference Example 3 with water to 100 ppm of active ingredient was poured into 10 ml per pot on a turntable. After 10 days of spraying, the number of parasitic spider mites on the plants was investigated. As a result, all of the insecticides and acaricides of the present invention were found to have acaricidal effects superior to the control agents.

【table】

[Table] Test Example 9 Using carp as a control, the test was carried out in accordance with the toxicity test method for fish, Notification Agricultural Policy No. B 2735 (November 25, 1966), and the compounds of the present invention (2), (6), (9) were tested. ), (11),
When the TLm48 (ppm) of (17) and (21) was determined, it was 20 or more in both cases.

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ and R ₂ are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a halomethyl group, a methoxy group, an ethoxy group, a difluoromethoxy group, or R ₁ and R ₂ represents a methylenedioxy group. A is a group represented by the formula, , [Formula] [Formula] [Formula] Here, R ₅ is a hydrogen atom, a methyl group, a formyl group, or an acetyl group, and X is a hydrogen atom. atom or halogen atom.R ₃ is a hydrogen atom or a fluorine atom, R ₄
represents a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group. ) An insecticide and acaricide characterized by containing an aromatic alkane derivative represented by: 2 General formula (In the formula, R ₁ and R ₂ are the same or different, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, a halomethyl group, a methoxy group, an ethoxy group, a difluoromethoxy group, or R ₁ and R ₂ represents a methylenedioxy group.) and the general formula (Wherein, A is a group represented by the formula, [Formula] [Formula] [Formula] where R ₅ is a hydrogen atom, a methyl group, a formyl group,
or an acetyl group, and X represents a hydrogen atom or a halogen atom. R ₃ is a hydrogen atom or a fluorine atom, R ₄
represents a hydrogen atom, a halogen atom, a methyl group or a trifluoromethyl group. ) is reacted with the general formula (Here, R ₁ , R ₂ , A, R ₃ , and R ₄ have the same meanings as above.) A general formula characterized by obtaining an unsaturated carbonyl compound represented by and reducing the obtained ketone. (Here, R ₁ , R ₂ , A, R ₃ , and R ₄ have the same meanings as above.) A method for producing an insecticide or acaricide containing an aromatic alkane derivative represented by the following.