JPH0465805B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to the general formula () [Wherein, Ar is unsubstituted or a halogen atom, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkenyl group, lower haloalkenyl group, lower alkoxy lower Alkyl group, lower haloalkenyloxy group, lower alkynyloxy group, lower alkoxy lower alkoxy group, lower alkoxycarbonyl group, lower haloalkoxycarbonyl group, lower cycloalkoxy group, phenyl group, phenoxy group, cyano group or methylenedioxy group It represents a substituted phenyl group, and when it has a plurality of substituents, these groups may be the same or different. R ¹ and R ² represent a methyl group, R ³ represents a group (), (In the formula, R represents a hydrogen atom or a fluorine atom.)] and 0-(2,2-dichlorovinyl)0,0-dimethylphosphate (DDVP). ), 0-(4-methylthiophenyl)0,0-di-
(n-propyl) phosphate (propaphos), 0,0-dimethyl 0-(3-methyl 4-methylthiophenyl) phosphorothioate (MPP), 0,0-dimethyl 0-(3-methyl-4-nitrophenyl) phosphorothioate ( MEP), 0-(3,5,6-trichloro-2-pyridine)
0,0-diethyl phosphorothioate (chlorpyrifos), 0,0-diethyl 0-(2-isopropyl-6
-Methyl-4-pyrimidinyl) phosphorothioate (diazinon), 0,0-diethyl 2,3-dihydro-3-oxo-2-phenyl-6-pyridazinyl phosphorothioate (pyridafenethione), 0-(4- Bromo-2-chlorophenyl)0-
Ethyl S-(n-propyl)phosphorothiolate (prophenofos), 0,0-dimethyl S-(N-methylcarbamoylmethyl)phosphorodithioate (dimethoate), S-(N-formyl-N-methylcarbamoyl) Methyl 0,0-dimethylphosphorodithioate (formothion), 0-(2,4-dichlorophenyl)0-ethyl-S-propolphosphorodithioate (prothiophos), 0,S-dimethyl N-acetylphosphoramide Thiolate (acephate) or 0,0-dimethyl 2,2,2-trichlor-1
The present invention relates to an insecticidal/acaricidal composition containing one or more of -hydroxyethylphosphonate (DEP). [Prior Art and Problems to be Solved by the Invention] Conventionally, various types of insecticides have been used to exterminate harmful animals in the fields of agriculture, forestry, horticulture, and epidemic prevention. For example, parathion, malathion, MEP,
Organophosphorus insecticides such as MPP, DDVP, DEP, EPN, CYP, PAP, acephate, thiometone, dimethoate, diazinon, DMPT, pyridafentione, chlorpyrifos; NAC, CPMC,
Carbamate insecticides such as MTMC, MIPC, BPMC, PHC, XMC, pirimicarb, menmyl, cartap; organochlorine insecticides such as DTT, lindane, chlordane, aldrin; natural insecticides such as pyrethrin, Delis, nicotine sulfate, etc. be. Some of these insecticides are fast-acting, systemic,
Although there are many products that have excellent properties such as low gas emissions and low toxicity, they are not satisfactory in all aspects such as insecticidal efficacy, insecticidal spectrum, residual efficacy, toxicity to humans, livestock and aquatic animals, and chemical damage to crops. do not have. Furthermore, as a result of the long-term use of these pesticides, pests that are highly resistant to these insecticides have appeared in various places. For example, planthoppers and leafhoppers, which are rice pests, diamondback moths, which are vegetable pests, houseflies, which are sanitary pests, and spider mites, which damage various crops, have developed particularly strong drug resistance. Some agents are beginning to lose their usefulness. Furthermore, the introduction of large amounts of these drugs into fields has caused problems such as environmental pollution of soil and rivers, and accumulation in living organisms. desired. [Means and effects for solving the problem] As a result of intensive studies to solve the above problem, the present inventors have found that a new compound represented by the general formula () has excellent insecticidal and acaricidal activity. Although these requirements can be met even when the compound is used alone, by applying a mixture of this compound and one or more types of organophosphorus insecticides and acaricides, compared to when applied alone. Not only will the insecticidal spectrum be expanded, but the insecticidal effect will increase synergistically to increase pest control efficiency, and at the same time, the amount of application in actual use can be reduced. It has been found that the risk of That is, the present invention provides general formula () [Wherein, Ar is unsubstituted or a halogen atom, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkenyl group, lower haloalkenyl group, lower alkoxy lower Alkyl group, lower haloalkenyloxy group, lower alkynyloxy group, lower alkoxy lower alkoxy group, lower alkoxycarbonyl group, lower haloalkoxycarbonyl group, lower cycloalkoxy group, phenyl group, phenoxy group, cyano group or methylenedioxy group It represents a substituted phenyl group, and when it has a plurality of substituents, these groups may be the same or different. R ¹ and R ² represent a methyl group, R ³ represents a group (), (In the formula, R represents a hydrogen atom or a fluorine atom.)] and 0-(2,2-dichlorovinyl)0,0-dimethylphosphate (DDVP). ), 0-(4-methylthiophenyl)0,0-di-
(n-propyl) phosphate (propaphos), 0,0-dimethyl 0-(3-methyl-4-methylthiophenyl) phosphorothioate (MPP), 0,0-dimethyl 0-(3-methyl-4-nitrophenyl) phosphorothioate (MEP), 0-(3,5,6-trichloro-2-pyridine)
0,0-diethyl phosphorothiate (chlorpyrifos), 0,0-diethyl 0-(2-isopropyl-6
-Methyl-4-pyrimidinyl) phosphorothioate (diazinon), 0,0-diethyl 2,3-dihydro-3-oxo-2-phenyl-6-pyridazinyl phosphorothioate (pyridafenethione), 0-(4- Bromo-2-chlorophenyl)0-
Ethyl S-(n-propyl)phosphorothiolate (prophenofos), 0,0-dimethyl S-(N-methylcarbamoylmethyl)phosphorodithioate (dimethoate), S-(N-formyl-N-methylcarbamoyl)
Methyl 0,0-dimethylphosphorodithioate (formothion), 0-(2,4-dichlorophenyl)0-ethyl-S-propylphosphorodithioate (prothiophos), 0,S-dimethyl N-acetylphosphoramidothio acephate or 0,0-dimethyl 2,2,2-trichlor-1
This is an insecticidal/acaricidal composition containing one or more of -hydroxyethylphosphonate (DEP). Among the compounds represented by the general formula (), representative ones are shown in Table 1.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[R ⁴ is a group () (In the formula, R represents the above meaning)]

Let the aldehyde of or use the general formula () Aldehyde represented by and general formula () When condensing a ketone represented by , the reaction is carried out in the presence of a basic or acidic catalyst as a condensing agent, without a catalyst, or in an inert solvent. Condensing agents include alkali hydroxide, alkali carbonate, alkali alcoholate, potassium cyanide, alkali acetate, zinc chloride and acetyl chloride, sulfuric acid, hydrohalic acid, aluminum halide, phosphorus oxychloride, triphenylaluminum, alumina, orthophosphorus. Sodium oxide, barium oxide, salts of organic amines, amines, ion exchange resins, etc. can be used, and basic catalysts are preferred. As the inert catalyst, water, alcohol, ether, benzene, acetic acid, etc. can be used. In some cases, β-oxyketones or β-haloketones may be obtained by the reaction of the above ketone and aldehyde, but these can be easily synthesized by general formula () or () by dehydration or dehydrohalogenation.
α,β-unsaturated carbonyl compounds can be obtained. ()or() (In the formula, Ar, R ¹ , R ² and R ⁴ represent the above-mentioned meanings.) The α,β-unsaturated carbonyl compound of (In the formula, Ar, R ¹ , R ² and R ³ have the above-mentioned meanings) It is also possible to obtain an aromatic alkane derivative represented by do. ( ) or (
Chem., 29 , 116 (1964). and (In the formula, Ar, R ¹ , R ² and R ⁴ represent the above-mentioned meanings.) By obtaining this mixture and further ring-forming it, the aromatic alkone derivative of the general formula () is obtained in good yield. be able to. The ketone () or () used as a raw material is prepared by reacting the corresponding nitrile with methylmagnesium halide (CRHauser et al, J.Org.
Chem., 15 , 359 (1950) or by reacting methyllithium with the corresponding carboxylic acid. The aldehyde () used as a raw material reduces the corresponding nitrile (J.Am, Chem.Sec., 86 ,
1085 (1964)) and by reducing the corresponding acid chloride (Org. Reactions, 4 , 362
(1948). Also,
They can also be produced by oxidizing the corresponding alcohol. (Helvetica Chimica
Acta, 54 , 868 (1971)). Also, the general formula () (In the formula, Ar, R ¹ and R ² have the above meanings) and the general formula () or ()

【formula】

[Formula] (In the formula, R ³ and R ⁴ represent the above-mentioned meanings, R ⁵ represents an alkyl group or a phenyl group, and R ⁶ represents an alkyl group.) When reacting with a compound represented by the following, an inert solvent is used. The reaction is carried out at -70°C to 100°C in the presence of Inert solvents include ether, dichloromethane, THF, DMF, DMSO, HMPA,
Benzene, alcohol, dimethic cellosolve, etc. can be used. Compounds of general formula () or () are
^{R 4 CHX} _or ^{R 3 _} _{_} ^{_ _} (representing meaning) can be easily obtained by matching. In the general formula (), when the substituent of the Ar group is an alkoxy group, haloalkoxy group, haloalkenyloxy group, etc., another easy-to-obtain alkoxy derivative is hydrolyzed to obtain a hydroxy derivative, and then reacted with the corresponding halide. It is also possible to obtain the desired object. An example of the production route is shown below using a reaction formula. (In the formula, R ⁷ and R ⁸ represent an optionally substituted alkyl group, alkenyl group, alkyl group, etc.). In the compound of general formula () obtained by the above method, Ar is an unsubstituted or halogen atom,
Lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkenyl group, lower haloalkenyl group, lower alkoxy lower alkyl group, lower haloalkenyloxy group, lower alkenyloxy represents a phenyl group substituted with a group, a lower alkoxy lower alkoxy group, a lower alkoxycarbonyl group, a lower haloalkoxycarbonyl group, a lower cycloalkoxy group, a phenyl group, a phenoxy group, a cyano group or a methylenedioxy group, and multiple substituents These groups may be the same or different. Specific examples of the Ar group are shown below, but are not limited to the examples. That is, phenyl group, 4-
Methylphenyl group, 3,4-dimethylphenyl group, 4-trifluoromethylphenyl group, 3-methylphenyl group, 3-trifluoromethylphenyl group, 4-chlorophenyl group, 3,4-dichlorophenyl group, 4 -nitrophenyl group, 4-methylthiophenyl group, 4-methoxyphenyl group, 3,
4-dimethoxyphenyl group, 3,4-methylenedioxyphenyl group, 4-difluoromethylthiophenyl group, 4-trifluoromethylthiophenyl group, 4-cyanophenyl group, 4-fluorophenyl group, 4-bromophenyl group group, 3,4-difluorophenyl group, 3,4-dibromophenyl group, 4
-Chloro-3-fluorophenyl group, 3-chloro-4-fluorophenyl group, 3-chloro-4-methylphenyl group, 3-bromo-4-chlorophenyl group, 4-difluorotoxyphenyl group, 3,4
-bis(difluoromethoxy)phenyl group, 4-
Trifluoromethoxyphenyl group, 3,4-bis(trifluoromethoxy)phenyl group, 4-methoxy-3,5-dimethylphenyl group, 4-tert-butylphenyl group, 4-ethylphenyl group, 4-isopropyl Phenyl group, 4-isopropenylphenyl group, 4-vinylphenyl group, 4-
(2,2-dichlorovinyl)phenyl group, 4-chloro-3-methylphenyl group, 3-bromo-4-
Fluorophenyl group, 3-fluoro-4-bromophenyl group, 4-fluoro-3-methylphenyl group, 3-fluoro-4-methylphenyl group, 3-
Bromo-4-methylphenyl group, 3,4-ethylphenyl group, 3,4-diisopropylphenyl group, 3-ethyl-4-methylphenyl group, 4-isopropyl-3-methylphenyl group, 4-allylphenyl group, 4-ethoxycarbonyl group phenyl group, 4-ethoxyphenyl group, 3,5-dichloro-4-methylphenyl group, 4-propargylphenyl group, 3-methoxy-4-methylphenyl group,
4-methoxymethylphenyl group, 4-(1-chloroethylene-1-yl)phenyl group, 4-(2-
chloroallyl) phenyl group, 4-methoxycarbonylphenyl group, 3-nitro-4,5-dimethylphenyl group, 3-ethoxy-4-bromophenyl group, 3-chloro-4-methoxyphenyl group, 4-
Bromo-3-chlorophenyl group, 3,4-(di-
tertiarybutyl) phenyl group, 4-ethyl-
3-methylphenyl group, 4-tert-butyl-3-methylphenyl group, 4-(1,1,2,2
-tetrafluoroethoxy)phenyl group, 4-
(2,2-dichlorovinyloxy)phenyl group,
4-(2,2,2-trifluoroethoxy) phenyl group, 4-pentafluoroethoxy phenyl group, 4-(chlorodifluoromethoxy) phenyl group, 4-(chlorofluoromethoxy) phenyl group,
4-(dichlorofluoromethoxy)phenyl group,
4-(1,1-difluoroethoxy)phenyl group,
4-(1,2,2-trichloro-1,2-difluoroethoxy)phenyl group, 4-(2-bromo-
1,1,2,2-tetrafluoroethoxy) phenyl group, 4-(2-propynyloxy) phenyl group, 4-(1-propynyloxy) phenyl group,
4-allyloxyphenyl group, 4-ethynyloxyphenyl group, 4-(2-chloroethynyl)phenyl group, 4-(n-propoxy)phenyl group, 4
-isopropoxyphenyl group, 4-cyclopentyloxyphenyl group, 4-(n-amyloxy)
Phenyl group, 4-isobutoxyphenyl group, 4-
Iodophenyl group, 4-vinyloxyphenyl group,
4-biphenyl group, 4-(n-butoxy)phenyl group, 4-(sec-butoxy)phenyl group, 4-phenoxyphenyl group, 4-(2-fluoroethoxycarbonyl)phenyl group, 4-(1, 1, 2,
2-tetrafluoroethoxycarbonyl) phenyl group, 4-(2-iodo-1,1-difluoroethoxy) phenyl group, 4-cyclohexyloxyphenyl group, 3-chloro-4-ethoxyphenyl group, 4-ethoxymethyl Phenyl group, 4-(1-
ethoxyethyl)phenyl group, 4-(1-methoxyethyl)phenyl group, 4-ethoxy-3-methylphenyl group, 4-(2-methylpropenyl)phenyl group, 4-(1,2,2-trichlorovinyloxy) Phenyl group, 3,4-diethoxyphenyl group, 4-ethynyl phenyl group, 4-ethoxy-
3,5-dimethylphenyl group, 4-ethoxy-3
-Methoxyphenyl group, 4-ethylthiophenyl group, 4-(2,2,2-trifluoroethoxycarbonyl)phenyl group, 4-(1-ethylvinyl)
Phenyl group, 4-(1-methyl-1-propenyl)
Phenyl group, 4-(1,2-dichlorovinyloxy)
Phenyl group, 4-(2,3-dichloroallyloxy)
Phenyl group, 4-(2-iodo-1-fluorovinyloxy) phenyl group, 4-(2-fluoroethoxy) phenyl group, 4-(2-chloro-1,1-
difluoroethoxy) phenyl group, 4-(2-chloro-1-fluorovinyloxy) phenyl group, 4
-isopropylthiophenyl group, 4-(2,2-
dichloro)-1,1-difluoroethoxy)phenyl group, 4-(2,2-dichloro-1-fluorovinyloxy)phenyl group, 4-(1,1,2,2
-tetrafluoroethoxy) phenyl group, 3-chloro-4-ethoxyphenyl group, 4-ethylthio group, 3-ethoxyphenyl group, 4-allyloxyphenyl group, 4-(2,2-dichlorovinyloxy)
Examples include phenyl group, 4-(1,1,1-trifluoroethoxy)phenyl group, and the like. Next, the method for producing these aromatic chalcane derivatives will be explained in more detail with reference to synthesis examples. Synthesis Example 1 Synthesis of 1-(3-phenoxyphenyl)-4-(4-methylphenyl)-4-methylpetane Synthesis was performed according to the following sequence. (1) 1-(3-phenoxyphenyl)4-(4-methylphenyl)-4-methyl-2- and 1-
Pentene, (a) 5.3 g of 2-(4-methylphenyl)-2-methyl-3-butanone in 50 ml of ethanol, 3-
Phenoxybenzaldehyde 6.0g, KOH6.0
g was added thereto, and the mixture was stirred at room temperature for 1 hour and 20 minutes. Then, after pouring the reaction mass into 30 ml of water,
Extracted with benzene. After washing the benzene solution with water and drying, the solvent was distilled off under reduced pressure to obtain crude 1-
(3-phenoxyphenyl)-4-(4-methylphenyl)-4-methyl-1-pentene-
10.4 g of 3-one was obtained. Next, it was purified by column chromatography (silica gel 250 g, developing solvent benzene) to obtain purified 1-(3-phenoxyphenyl)-4-(4-methylphenyl)-4-methyl-1-pentene-3. −on
6.8g was obtained. n ^20.3 _D 1.6121 ν ^Neat _nax (cm ^-1 ); 1680, 1650, 1570, 1485,
1240, 1055 δ ^CCl4 _TMS (ppm); 1.47 (s, 6H), 2.32 (s, 3H
),
6.3-7.6 (m, 15H (b) After adding 1.4 g of lithium aluminum hydride to 10 ml of dry ether, aluminum chloride
A solution of 9.7 g/20 ml of ether was carefully added dropwise. Then, a solution of 7.4 g of 1-(3-phenoxyphenyl)-4-(4-methylphenyl)-4-methyl-1-penten-3-one/10 ml of ether obtained in (a) was added dropwise, and the mixture was stirred for 30 minutes. The mixture was heated to reflux. Ethyl acetate and then water were added dropwise to the reaction mass while cooling, followed by extraction with benzene. After washing the benzene solution with water and drying, the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (150 g of silica gel, developing solvent: benzene-hexane (1:2)).
-(3-phenoxyphenyl)-4-(4-methylphenyl)-4-methyl-2-pentene (50%), 1-(3-phenoxyphenyl)-4
-(4-methylphenyl)-4-methyl-1-
3.6 g of a mixture of pentene (50%) was obtained. n ^20.2 _D 1.5882 ν ^Neat _nax (cm ^-1 ); 1590, 1500, 1495, 1455,
1255, 1225, 980, 825, 700 δ ^CCl4 _TMS (ppm); 1.32 (s, 6H×1/2), 1.36 (
s,
6H×1/2), 2.28(s, 3H×1/2), 2.31(1,
3H x 1/2), 2.43 (d, J = 7.1Hz, 2H x 1/2: equivalent to the methylene proton of 1-pentene) 3.32 (2, J = 5.7Hz, 2H x 1/2: equivalent to the methylene proton of 2-pentene) (equivalent to methylene proton) 5.5-6.4 (m, 2H), 6.6-7.4 (m, 13H) (2) 1-(3-phenoxyphenyl)-4-(4-
methylphenyl)-4-methylpentane 1-(3-phenoxyphenyl)-4-(4-
methylphenyl)-4-methyl-2-pentene (50%), 1-(3-phenoxyphenyl)-4-
1.9 g of a mixture of (4-methylphenyl)-4-methyl-1-pentene (50%) was added to 30 ml of ethyl acetate.
After dissolving in the solution, 0.4 g of 5% Pd-C was added, and the mixture was stirred at room temperature under a hydrogen pressure of 20 Kg/cm ² G for 3 hours. After the reaction was completed, Pd-C was filtered off, and ethyl acetate was distilled off under reduced pressure. The residue was purified by column chromatography (50 g of silica gel, developing solvent: benzene-hexane (1:2)) to obtain the desired 1-(3-phenoxyphenyl)-4-(4- 1.8 g of methylphenyl)-4-methylpentane was obtained. n ^20.0 _D 1.5710 ν ^Neat _nax (cm ^-1 ); 1595, 1495, 1260, 1225, 820,
700 δ ^CCl4 _TMS (ppm); 1.24 (s, 6H), 1.0~1.7 (m,
4H)
2.25 (s, 3H), 2.42 (t, J=7.5Hz,
2H), 6.55-7.25 (m, 13H) Synthesis Example 2 Synthesis of 1-(3-phenoxyphenyl)-4-(3-trifluoromethylphenyl)-4-methylpentane Synthesized according to the following sequence . (1) 1-(3-phenoxyphenyl)-4-(3-
trifluoromethylphenyl)-4-methyl-
2- and 1-Pentene (a) 4.3 2-(3-trifluorophenyl)-2-methyl-3-butanone in 30 ml ethanol
g, 3.7 g of 3-phenoxybenzaldehyde,
1.0 g of KOH was added, and the mixture was stirred at room temperature all day and night. After discharging the reaction mass into 300 ml of water, it was extracted with benzene, the extraction station was washed with water, and after drying, the solvent was distilled off under reduced pressure to obtain 7.5 g of a residue. The residue was subjected to column chromatography (silica gel
210g, purified with developing solvent: benzene),
Preliminary 1-(3-phenoxyphenyl)-4-(3
5.9 g of -trifluoromethylphenyl)-4-methyl-1-penten-3-one was obtained. n ^19.8 _D 1.5820 ν ^eat _nax (cm ^-1 ); 1690, 1610, 1590, 1580,
1490, 1460, 1330, 1240, 1165, 1125,
1075, 1060, 1000, 980, 805, 705, 695 (b) 0.71 g of lithium aluminum hydride was added to 10 ml of dry ethereal, and a solution of 5.0 g of anhydrous aluminum chloride/20 ml of dry ether was added dropwise thereto. After finishing the dropping, 1-(3-
A solution of 4.4 g (phenoxyphenyl)-4-(3-trifluoromethylphenyl)-4-methyl-1-penten-3-one in 20 ml of dry ether was added dropwise and the mixture was heated to reflux for 30 minutes. While cooling with ice water, ethyl acetate and water were added dropwise to the reaction mass in this order to complete the reaction.
Next, extraction was carried out with benzene, the extract was washed with water, dried, and the solvent was distilled off under reduced pressure to leave a residue.
4.4g was obtained. The residue was purified by column chromatography (100 g of silica gel, developing solvent: benzene-hexane (12)) to obtain 1-(3-phenoxyphenyl)-4-(3-trifluoromethylphenyl). )-4-methyl-2-pentene (70
%), 1-(3-phenoxyphenyl)-4-
(3-Trifluoromethylphenyl)-4-methyl-1-pentene (30%) mixture at 2.2
I got g. n ^19.8 _D 1.5517 ν ^Neat _nax (cm ^-1 ); 1590, 1500, 1305, 1260,
1220, 1175, 1140, 1080, 705, 675 δ ^CCl4 _TMS (ppm); 1.40 (s6H), 2.45 (d, J=6.9Hz, 2H×30/100, 1-
(equivalent to methylene proton of pentene) 3.31 (d, J = 4.8Hz, 2H x 70/100, 2-
(equivalent to methylene proton of pentene) 3.5-6.4 (m, 2H), 6.45-7.6 (m, 13H) (2) 1-(3-phenoxyphenyl)-4-(3-
Trifluoromethylphenyl)-4-methylpentane 1-(3-phenoxyphenyl)-4-(3-trifluoromethyphenyl) in 25 ml of ethyl acetate
-4-methyl-2-pentene (70%), 1-(3
1.2 g of a mixture of -phenoxyphenyl)-4-(3-trifluoromethylphenyl)-4-methyl-1-pentene (30%) and 40 g of 5% Pd-C were added, and the mixture was heated to 20 Kg/cm ² G with hydrogen. The mixture was stirred at 65°C for 3 hours. After the reaction was completed, Pd-C was filtered off, and the solvent was distilled off under reduced pressure to obtain 1.2 g of a residue. The residue was subjected to column chromatography (silica gel
25g, developing solvent: benzene-hexane (1:
2)) to obtain 1-(3-phenoxyphenyl)-4-(3-trifluoromethylphenyl).
0.8 g of -4-methylpentane was obtained. n ^19.5 _D 1.5373 ν ^Neat _nax (cm ^-1 ); 1580, 1480, 1330, 1245, 1210
,
1160, 1120, 1170, 695, 680 δ ^CCl4 _TMS (ppm); 1.31 (s, 6H), 1.1~1.8 (m,
4H), 2.47 (t, J = 6.6Hz, 2H), 6.6-7.6 (m, 13H) Synthesis Example 3 1-(3-phenoxy-4-fluorophenyl)
-Synthesis of -4-(4-ethoxyphenyl)-4-methylpentane Synthesis was performed according to the following sequence. (1) 1-(3-phenoxy-4-fluorophenyl)-4-(4-ethoxyphenyl)-4-methyl-2- and 1-pentene (a) 2-(4-ethoxyphenyl)- Using 6.2 g of 2-methyl-3-butanone and 6.5 g of 3-phenoxy-4-fluorobenzaldehyde, the same procedure as in (1)-(a) of Synthesis Example 2 was carried out to obtain 12.0 g of a residue. Column chromatography (200 g of silica gel, developing solvent: benzene) Purify 1-(3-phenoxy-4-fluorophenyl)-4-(4-ethoxyphenyl)-4-methyl-1-pentene -3-on
5.8g was obtained. n ^19.7 _D 1.5900 ν ^Neat _nax (cm ^-1 ); 1690, 1610, 1590, 1510,
1490, 1290, 1270, 1250, 1210, 1185,
1120, 1060, 820, 750, 690 (b) 1-(3-phenoxy-4-fluorophenyl)-4-(4-ethoxyphenyl)-4-methyl-1-pentene- obtained in (a) 3-on
Using 4.1 g, the same treatment as in (1)-(b) of Synthesis Example 2 was carried out to obtain a residue of 3.9 g. The residue was subjected to column chromatography (silica gel 8.0
g, developing solvent: benzene-hexane (2:
3)) to obtain 1-(3-phenoxy-4-
fluorophenyl)-4-(4-ethoxyphenyl)-4-methyl-2-pentene (45%),
1.44% of a mixture of 1-(3-phenoxy-4-fluorophenyl)-4-(4-ethoxyphenyl)-4-methyl-1-pentene (55%)
I got g. n ^20.1 _D 1.5745 ν ^Neat _nax (cm ^-1 ); 1610, 1585, 1510, 1490,
1290, 1270, 1245, 1210, 1180, 1115,
1045, 965, 825, 690 δ ^CCl4 _TMS (ppm); 1.2 to 1.5 (m, 3H x 3), 2.39 (d, J = 7.1Hz, 2H x 55/100; 1-
(equivalent to methylene proton of pentene) 3.27 (d, J = 5.0Hz, 2H x 45/100; 2-
equivalent to the methylene proton of pentene), 3.8
~4.1 (m, 2H), 5.4~6.3 (m, 2H), 6.5~
7.4 (m, 12H) (2) 1-(3-phenoxy-4-fluorophenyl)-4-(4-ethoxyphenyl)-4-methylpentane 1-(3-phenoxy-4-fluorophenyl) -4-(4-ethoxyphenyl)-4-methyl-2-pentene (45%), 1-(3-phenoxy-4-fluorophenyl)-4-(4-ethoxyphenyl)-4-methyl -1-pentene (55
%) was reduced and treated according to Synthesis Example 2 (2). 1.0g of residue was obtained and the column
Purified by chromatography (20 g of silica gel, developing solvent: benzene-hexane (2:3)) to obtain 1-(3-phenoxy-4-fluorophenyl)-4-(4-ethosyphenyl)-4-methyl. 0.80 g of pentane was obtained. n ^20.0 _D 1.5578 ν ^Neat _nax (cm ^-1 ); 1585, 1510, 1490, 1290, 1270
,
1240, 1210, 1180, 1115, 1045, 820, 750,
685 8 δ ^CCl4 _TMS (ppm); 1.22 (s, 6H), 1.36 (t, J=
6.9
Hz, 3H), 2.39 (t, J=7.7Hz, 2H), 3.91
(q, J=6.9Hz, 2H), 1.0~1.7 (m, 4H),
6.5-7.4 (m, 12H) Synthesis Example 4 1-(3-phenoxyphenyl)-4-(3,4
-Methylenedioxyphenyl)-4-methylpentane Synthesis was performed according to the following sequence. (1) 1-(3-phenoxyphenyl)-4-(3,
4-Methylenedioxyphenyl)-4-methyl-1- and 2-pentene (a) 2-(3,4-methylenedioxyphenyl)
-2-methyl-3-butanone 10g, 3-phenoxybenzaldehyde 9.6g, ethanol
A mixture of 50 ml and 2 g of KOH was stirred at 60°C for 30 minutes. Then pour the reaction mass into 300 ml of water,
Benzene was extracted, the benzene layer was washed with water, dried, and the solvent was distilled off under reduced pressure to obtain 23 g of a residue. The residue was separated by column chromatography (silica gel, developing solvent: benzene), and purified 1-(3-phenoxyphenyl)-4-
(3,4-methylenedioxyphenyl)-4-
15.3 g of methyl-1-penten-3-one was obtained. n ^19.9 _D 1.6208 ν ^Neat _nax (cm ^-1 ); 1705, 1620, 1600, 1590,
1515, 1495, 1460, 1250, 1080, 1070,
1050, 940, 825, 690 δ ^CCl4 _TMS (ppm); 1.43 (s, 6H), 5.85 (s, 2H
)
6.36-7.70 (m, 14H) (b) 1-(3-phenoxyphenyl)- obtained in (a)
4-(3,4-methylenedioxyphenyl)-
12 g of 4-methyl-1-penten-3-one was treated according to Synthesis Example 1-(b) to give 1-(3
-phenoxyphenyl)-4-(3,4-methylenedioxyphenyl)-4-methyl-2-
Pentene (40%), 1-(3-phenoxyphenyl)-4-(3,4-methylenedioxyphenyl)-4-methyl-1-pentene (60%)
2.0g of the mixture was obtained. n ^20.0 _D 1.5966 ν ^Neat _nax (cm ^-1 ); 1600, 190, 1510, 1495, 1455
,
1250, 1220, 1050, 945, 820, 700 δ ^CCl4 _TMS (ppm); 1.2-1.3 (m, 6H), 2.39 (d, J = 5.9Hz, 2H x 60/100; 1-
equivalent to the methylene proton of pentene) 3.29 (d, J = 5.4Hz, 2H x 45/100; 2-
equivalent to the methylene proton of pentene), 5.4
~6.4 (m, 4H), 6.5 ~ 7.4 (m, 12H) (2) 1-(3-phenoxyphenyl)-4-(3,
4-methyledioxyphenyl)-4-methylpentane 1-(3-phenoxyphenyl) obtained from (1)-(b)
-4-(3,4-methylenedioxyphenoxy)
A mixture of -4-methyl-1- and 2-pentene was treated according to Synthesis Example 1-(2), and quantitatively 1-(3-phenoxyphenyl)-4-(3,
4-methylenedioxyphenyl)-4-methylenepentetane was obtained. n ^20.0 _D 1.5824 ν ^Neat _nax (cm ^-1 ); 1570, 1490, 1475, 1430, 1235
,
1200, 1150, 1095, 1025, 925, 800, 740,
680 δ ^CCl4 _TMS (ppm); 1.70-1.70 (m, 4H), 1.23 (s
,
6H), 2.46 (t, 2H), 5.28 (s, 2H), 6.5-7.4 (m, 12H) Synthesis Example 5 1-(3-phenoxyphenyl)-4-(4-methoxyphenyl)- Synthesis of 4-methylpentane Synthesis was performed according to the following sequence. (1) 1-(3-phenoxyphenyl)-4-(4-
methoxyphenyl)-4-methyl-1- and 2-pentene (a) 2-(4-methoxyphenyl)-2-methyl-3-butanone 10 g, 3-phenoxybenzaldehyde 33.7 g, methanol 80 ml,
A mixture of 4.0 g of KOH was reacted at 40° C. for 2 hours each. The following treatment was performed according to Synthesis Example 1-(1)-(a), and 1-(3-phenoxyphenyl)-4
25 g of -(methoxyphenyl)-4-methyl-1-penten-3-one was obtained. n ^20.2 _D 1.6094 ν ^Neat _nax (cm ^-1 ); 1680, 1600, 1575, 1480,
1230, 1050, 880, 825, 750, 685 δ ^CCl4 _TMS (ppm); 1.44 (s, 6H), 3.69 (s, 3H
),
6.34-7.61 (m, 15H), (b) 1-(3-phenoxyphenyl)- obtained in (a)
4-(4-methoxyphenyl)-4-methyl-
23.7 g of 1-penten-3-one was treated according to Synthesis Example 1-(1)-(b) to obtain 1-(3-phenoxyphenyl)-4-(4-methoxyphenyl)-4. -Methyl-2-pentene (40%), 1
9.0 g of a mixture of -(3-phenoxyphenyl)-4-(4-methoxyphenyl)-4-methyl-1-pentene (60%) was obtained. n ^19.7 _D 1.5948 ν ^Neat _nax (cm ^-1 ); 1620, 1590, 1520, 1500,
1450, 1255, 1220, 1190, 1040, 835, 700 δ ^CCl4 _TMS (ppm); 1.20-1.40 (m, 6H) 2.40 (d, J = 6.5Hz, 2h, ×60/100; 1-
equivalent to the methyle proton of pentene) 3.28 (d, J = 5.6Hz, 2H, ×40/100; 2-
(equivalent to methylene proton of pentene) 3.6 to 3.8 (m, 3H), 5.2 to 6.4 (m, 2H),
6.6-7.4 (m, 13H) (2) 1-(3-phenoxyphenyl)-4-(4-
1-(3-phenoxyphenyl)-4 obtained from methoxyphenyl)-4-methylpentane (1)
-(4-methoxyphenyl)-4-methyl-2-
Synthesis of a mixture of and 1-pentene Example 1-
(2), and quantitatively determined 1-(3-phenoxyphenyl)-4-(4-methoxyphenyl).
-4-Methylpentane was obtained. n ^19.8 _D 1.5774 ν ^Neat _nax (cm ^-1 ); 1610, 1580, 1515, 1485, 1250
,
1215, 1180, 1035, 825, 755, 690 δ ^CCl4 _TMS (ppm); 0.88-1.73 (m, 4H), 1.26 (s
,
6H), 2.46 (t, 2H), 3.73 (s, 3H), 6.6-7.4 (m, 13H) Synthesis Example 6 1-(3-phenoxy-4-fluorophenyl)
Synthesis of -4-(4-methoxyphenyl)-4-methylpentane (1) 2-(4-methoxyphenyl)-2-methyl-
3-butanone 7.6g, 3-phenoxy-4-fluorobenzaldehyde 8.5g, methanol 30g
ml and 2 g of KOH was stirred at 60°C for 2 hours to react. The reaction mass was treated according to Synthesis Example 1-(1)(a) to obtain 1-(3-phenoxy-4-fluorophenyl)-4-(4-methoxyphenyl).
5g of -4-methyl-1-penten-3-one
I got it. n ^19.7 _D 1.6058 ν ^Neat _nax (cm ^-1 ); 1680, 1605, 1580, 1420, 1290
,
1270, 1250, 1205, 1180, 1105, 1060,
1030, 980, 825, 745, 680 δ ^CCl4 _TMS (ppm); 1.45 (s, 6H), 3.74 (s, 3H)
,
6.26-7.61 (m, 14H), 1-(3-phenoxy-4-fluorophenyl-4-(4-methoxyphenyl)-4) obtained above
-Methyl-1-penten-3-one (4.2 g) was treated according to Synthesis Example 1-(1)-(b), and 1-(3
-phenoxy-4-fluorophenyl)-4-
(4-methoxyphenyl)-4-methyl-2-pentene (50%), 1-(3-phenoxy-4-fluorophenyl)-4-(4-methoxyphenyl)
-Mixture of 4-methyl-1-pentene (50%)
2.8g was obtained. n ^19.9 _D 1.5764 ν ^Neat _nax (cm ^-1 ); 1605, 1585, 1510, 1490, 1290
,
1270, 1245, 1210, 1180, 1110, 1035, 825,
680 δ ^CCl4 _TMS (ppm); 1.2-1.4 (m, 6H), 2.38 (d, J = 6.8Hz, 2H x 50/100; equivalent to methylene proton of 1-pentene) 3.40 (d, J = 5.6Hz, 2H×50/100; equivalent to methylene proton of 2-pentene) 3.6 to 3.8 (m, 3H), 5.2 to 6.3 (m, 2H), 6.5
~7.4 (m, 12H) (2) 1-(3-phenoxy-4-fluorophenyl)-4-(4-methoxyphenyl)-4 obtained in (1)
-Synthesis of a mixture of methylpentene Example 1-(2)
1-(3-phenoxy-4-
Fluorophenyl)-4-(4-methoxyphenyl)-4-methylpentane was quantitatively obtained. n ^20.0 _D 1.5642 ν ^Neat _nax (cm ^-1 ); 1620, 1600, 1520, 1500, 1430
,
1285, 1260, 1220, 1195, 1175, 1125,
1040, 835, 755, 695 δ ^CCl4 _TMS (ppm); 0.92-1.67 (m, 4H), 1.22 (s
,
6H), 2.39 (t, 2H), 3.68 (s, 3H), 6.5-7.4 (m, 12H) Synthesis Example 7 1-(3-phenoxyphenyl)-4-(4-chlorophenyl-4-methyl Synthesis of pentane An equivalent mixture of α,α-dimethyl-(4-chlorophenyl)acetaldehyde and 3-phenoxyacetophenone was reacted according to Synthesis Example 2, and 1-(3-phenoxyphenyl)- 4-(4-
chlorophenyl)-4-methylpentane was obtained. n ^20.2 _D 1.5786 ν ^Neat _nax (cm ^-1 ); 1600, 1520, 1500, 1430, 1300,
1285, 1220, 1170, 1125, 1020, 830, 755,
695 δ ^CCl4 _TMS (ppm); 0.98-1.72 (m, 4H), 1.26 (s,
6H), 2.42 (t, 2H), 6.67-7.40 (m, 12H) Synthesis Example 8 Synthesis of 1-(3-phenoxyphenyl)-4-(4-isopropoxyphenyl)-4-methylpentane (1) 1-(3-phenoxyphenyl)-4-(4-
5.0 g of methoxyphenyl)-4-methylpetane,
A mixture of 30 ml of 47% aq HBr and 30 ml of acetic acid was heated under reflux for 8 hours. The reaction mass was poured into water and extracted with benzene. Wash the benzene layer with water, dry it,
The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, developing solvent: benzene) to obtain 1-(3-phenoxyphenyl)-4-(4-hydroxyphenyl). enyl)-4-
4.2g of methylpentane was obtained. n ^19.4 _D 1.5870 ν ^Neat _nax (cm ^-1 ); 3400, 1610, 1580, 1515, 1485
,
1440, 1240, 1210, 825, 755, 690, 675 δ ^CCl4 _TMS (ppm); 1.00-1.68 (m, 4H), 1.20 (s
,
6H), 2.43 (t, 2H), 5.52 (broad s, 1H)
6.56-7.38 (m, 13H) (2) 1-(3-phenoxyphenyl)-4 obtained in (1)
-(4-hydroxyphenyl)-4-methylpentane 0.5 g, K ₂ CO ₃ 1.5 g, isopropyl bromide 3
130 ml, a mixture of 20 ml of dimethylformamide
The reaction was allowed to proceed at a temperature of 2 hours with stirring. The reaction mass was poured into water and extracted with benzene. The benzene layer was washed with water, dried, and the solvent was distilled off under reduced pressure.
The residue was subjected to column chromatography (silica
Purified with gel, developing solvent: benzene), and purified with 1-
(3-phenoxyphenyl)-4-(4-isopropoxyphenyl)-4-methylpentane 0.3g
I got it. n ^19.6 _D 1.5682 ν ^Neat _nax (cm ^-1 ); 1605, 1580, 1510, 1485, 1380
,
1245, 1120, 955, 825, 755, 685 δ ^CCl4 _TMS (ppm); 1.02-1.71 (m, 16H), 2.45 (
t,
2H), 4.28-4.56 (m, 1H), 6.57-7.38 (m, 13H) Synthesis Example 9 1-(3-phenoxy-4-fluorophenyl)
-4-(4-difluoromethoxyphenyl)-4
-Synthesis of methylpentane (1) 1 g of 1-(3-phenoxy-4-fluorophenyl)-4-(4-methoxyphenyl)-4-methylpentane was treated according to Synthesis Example 9, and 1- (3-phenoxy-4-fluorophenyl)-4-(4-hydroxyphenyl)-4-
0.6 g of methylpentane was obtained. n ^19.9 _D 1.5760 ν ^Neat _nax (cm ^-1 ); 3360, 1620, 1600, 1520, 1500
,
1435, 1285, 1220, 1130, 840, 760, 700 δ ^CCl4 _TMS (ppm); 1.02-1.67 (m, 4H), 1.21 (s
,
6H), 2.39 (t, 2H), 5.24 (broad s, 1H),
6.52-7.35 (m, 12H) (2) 1-(3-phenoxy-4-fluorophenyl)-4-(4-hydroxyphenyl) obtained in (1)
Chlorodifluoromethane was passed through a mixture of 0.5 g of -4-methylpentane, 1.0 g of KOH, and 20 ml of acetonitrile for 30 minutes while stirring at 60°C. The reaction mass was poured into water and extracted with benzene. The benzene ring was washed with water, dried, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel, developing solvent: benzene) to obtain 1-(3-phenoxy-4-fluoro 0.4 g of phenyl)-4-(4-difluoromethoxyphenyl)-4-methylbentane was obtained. n ^19.6 _D 1.5414 ν ^Neat _nax (cm ^-1 ); 1600, 1520, 1500, 1435, 1395
,
1285, 1220, 1140, 1050, 840, 820, 760,
700 δ ^CCl4 _TMS (ppm); 1.02-1.72 (m, 4H), 1.25 (s
,
6H), 2.42 (t, 2H), 6.39 (t, J=35Hz,
1H), 6.68-7.39 (m, 12H) Synthesis Example 10 1-(3-phenoxy-4-fluorophenyl)
-Synthesis of -4-(4-ethoxyphenyl)-4-methylpentane Synthesis was performed according to the following sequence. (1) 6.4 g of 3-phenoxy-4-fluorobenzyl bromide and 7 ml of triethyl phosphorite
was added, and the mixture was stirred and reacted at 140°C for 7 hours. After cooling, 13.1 g of the reaction mass was subjected to column chromatography (silica gel, developing solvent: benzene) to obtain 6.3 g of diethyl 3-phenoxy-4-fluorobenzylphosphonate. ν ^Neat _nax (cm ^-1 ); 1590, 1515, 1490, 1270, 1250
,
1025, 960, 795 δ ^CCl4 _TMS (ppm); 1.04-1.50 (m, 6H), 2.93 (d
, J.
=21Hz, 2H), 3.70~4.17 (m, 4H), 6.84~
7.38 (m, 8H) (2) 1-(3-phenoxy-4-fluorophenyl)-4-(4-ethoxyphenyl)-4-methyl-1-pentene Sodium hydride (60%) 0.36 g/ Diethyl 3-phenoxy-4-fluorobenzylphosphonate in a solution of 10 ml of dry dimethyl cellosolve.
A solution of 3.0 g/10 ml of dry dimethyl cellosolve was added dropwise and stirred at 50°C for 30 minutes. Thereafter, a solution of 1.55 g of 3-(4-ethoxyphenyl)-3-methyl-butyraldehyde/5 ml of dry dimethyl cellosolve was added dropwise to the mixture, and the mixture was reacted at 50 DEG C. with stirring for 1 hour. The reaction mass was poured into water and extracted with benzene. The organic layer was washed with water, dried over anhydrous sodium oxide, the solvent was distilled off, and the residue was separated using column chromatography (silica gel) to obtain 1-(3-phenoxy-4-fluorophenyl). 2.49 g of -4-(ethoxyphenyl)-4-methyl-1-pentene was obtained. n ^19.8 _D 1.5902 ν ^Neat _nax (cm ^-1 ); 1610, 1590, 1515, 1425, 1395
,
1370, 1295, 1275, 1255, 1215, 1185,
1120, 1050, 970, 825, 750, 690 δ ^CCl4 _TMS (ppm); 1.28 (s, 6H), 1.38 (t, J=
7
Hz, 3H), 2.36 (d, J=8Hz, 3H) 3.89
(q, J=7Hz, 2H), 5.54-6.25 (m, 2H),
6.57-7.32 (m, 12H) (3) 1-(3-phenoxy-4-fluorophenyl)-4-(4-ethoxyphenyl)-4-methylpentane Add 1-(3-phenoxy-4) to a 200 ml autoclave. -fluorophenyl)-4-(4-ethoxyphenyl)-4-methyl-1-pentene 2.0 g,
0.2 g of Pd-C (5%) and 40 ml of ethyl acetate were charged, pressurized to 10 Kg/cm ² G with hydrogen, and stirred at 80° C. for 3 hours. After cooling, the reaction mass was filtered, the solvent was distilled off from the filtrate, and the residue was purified by column chromatography (silica gel).
-phenoxy-4-fluorophenyl)-4-
(4-ethoxyphenyl)-4-methylpentane
1.7g was isolated. n ^20.0 _D 1.5578 The IR spectrum and NMR spectrum matched those obtained in Synthesis Example 3. Synthesis Example 11 Triphenylphosphine and a slight excess of 3-phenoxy-4-fluorobenzyl bromide are mixed in benzene at -10°C in a dense flask and left at room temperature overnight to precipitate crystals. The crystals were separated by filtration, washed with benzene, and then dried. Phenyl lithium 40m
40 mmol of the crystalline bromide obtained above was added to a solution of 150 ml of dry ether in a nitrogen stream, and the mixture was reacted with stirring for 3 hours. Purified lithium bromide was precipitated to obtain a solution. 3 obtained above in dry ether
-Phenoxy-4-fluorobenzylidenetriphenylphosphorane and equimolar amount of 3-(4-ethoxyphenyl)-3-methyl-butyraldehyde were added when cold, then the temperature was raised, and after distilling off the ether, for 3 hours, The reaction was heated to 65°C, then poured into water, extracted with benzene, the benzene layer was washed with water, the solvent was distilled off after drying, and the residue was separated and purified using column chromatography (silica gel). -(3-phenoxy-4-fluorophenyl)-4-(4-ethoxyphenyl)-4-methyl-1-pentene was obtained. n ^19.8 _D 1.5902 The IR spectrum and NMR spectrum matched those obtained in Synthesis Example 11-(2). Synthesis Example 12 2-(4-methylphenyl)-2-methyl-3-
Method for producing butanone After adding 9.0 g of metallic magnesium (shavings) and 100 mg of I ₂ as a catalyst to 50 ml of dry ether, 25 ml of iodomethane was gradually added dropwise. After the addition was complete, the reaction mass was refluxed for 30 minutes. Next, 200 ml of dry benzene was added to the reaction mass, heated until the internal temperature reached 80°C, and after distilling off the ether, a solution of 45.6 g of α,α-dimethyl-4-methylbenzylnitrile/50 ml of benzene was added dropwise. After refluxing for 3 hours, 150 ml of 6N-HCl was carefully added dropwise to the reaction mass while cooling it with ice water. After refluxing for 1 hour, the mixture was cooled to room temperature and the benzene layer was separated. The benzene solution was washed with water, dried over anhydrous sodium sulfate, and benzene was distilled off under reduced pressure to obtain 45.2 g of a residue. Then, distillation was carried out under reduced pressure to obtain purified 2-(4-methylphenyl)-2-methyl-
20.0 g (94-95°C/5 mmHg) of 3-butanone was obtained. δ ^CCl4 _TMS (ppm); 1.41 (s, 6H), 1.81 (s, 3H)
,
2.31 (s, 3H), 7.07 (s, 4H), Synthesis Example 13 2-(4-chlorophenyl)-2-methyl-3-
Method for producing butanone 13.0 g of metallic magnesium (shavings) and a catalytic amount of I ₂ were added to 100 ml of dry ether, and then 66 g of iodomethane was carefully added dropwise. After the addition was complete, the reaction mass was refluxed for 1 hour. Next, 150 ml of dry benzene was added to the reaction mass and heated until the internal temperature reached 80°C to distill off the ether, replacing the ether with benzene. A solution of 45 g of α,α-dimethyl-4-chlorobenzylnitrile/30 ml of benzene was added dropwise to the benzene solution, and the mixture was refluxed for 3 hours. While cooling the reaction mass with ice water, 270 ml of 6H-HCl was carefully added dropwise. After the dropwise addition was completed, the mixture was refluxed for 8 hours, cooled to room temperature, and the benzene layer was separated. After washing the benzene solution with water and drying, the solvent was distilled off under reduced pressure to obtain 52 g of a residue. This residue was distilled under reduced pressure to obtain purified 2-(4-chlorophenyl)-2.
-Methyl-3-butanone 43.0g (104℃/5mm
Hg) was obtained. n ^20.0 _D 1.5254 ν ^Neat _nax (cm ^-1 ); 1730, 1500, 1380, 1370, 1140,
1115, 1020, 840, 690, δ ^CCl4 _TMS (ppm); 1.43 (s, 6H), 1.85 (s, 3H), 7.16 (d, J _AB = 9.1Hz, 2H) 7.28 (d, J _AB = 9.1Hz , 2H) ABtype Synthesis Example 14 2-(4-methoxyphenyl)-2-methyl-3
-Production method of butanone In the same manner as in Synthesis Example 12, purified 2-(4-methoxyphenyl)-2-methyl-3-
51.4 g of butanone (106-111°C/4 mmHg) was obtained. n ^20.1 _D 1.5230 ν ^Neat _nax (cm ^-1 ); 1705, 1610, 1515, 1465, 1355,
1305, 1250, 1185, 630 δ ^CCl4 _TMS (ppm); 1.38 (s, 6H), 1.80 (s, 3H), 3.69 (s, 3H) 7.6.78 (d, J _AB = 9.0Hz, 2H) 7.10 ( d, J _AB = 9.0Hz, 2H) ABtype Synthesis Example 15 2-(3,4-methylenedioxyphenyl)-2
-Production method of methyl-3-butanone α,α-dimethyl-3,4-methylenedioxybenzylnitrile 93
g, purified 2-(3,4-methylenedioxyphenyl)-2-methyl-3-butanone 83.2 g
(116-117°C/0.9mmHg) was obtained. n ^19.8 _D 1.5306 ν ^Neat _nax (cm ^-1 ); 1710, 1510, 1500, 1490, 1480,
1430, 1230, 1130, 1110, 1035, 930, 810,
680 δ ^CCl4 _TMS (ppm); 1.39 (s, 6H), 1.85 (s, 3H),
5.88
(s, 2H), 6.6-6.8 (m, 3H) Synthesis Example 16 2-(4-ethoxyphenyl)-2-methyl-3
-Production method of butanone In the same manner as in Synthesis Example 12, purified 2-(4-ethoxyphenyl)-2-methyl-3-butanone 44.0
g (115°C/4mmHg). n ^20.2 _D 1.5122 ν ^Neat _nax (cm ^-1 ); 1700, 1510, 1250, 1180 δ ^CCl4 _TMS (ppm); 1.3-1.5 (m, 9H), 1.82 (s, 3H), 2.97 (q,
J = 7.2Hz, 2H) 6.76 (d, J _AB = 8.7Hz, 2H) 7.08 (d, J _AB = 8.7Hz, 2H) ABtype Synthesis Example 17 2-(3-trifluoromethylphenyl)-2-
Method for producing methyl-3-butanone 10 g of α,α-dimethyl-3-trifluoromethylbenzyl nitrile was treated in the same manner as in Synthesis Example 13 to obtain 9.6 g of a residue. The residue was subjected to column chromatography (200 g of silica gel, developing solvent;
benzene) to produce purified 2-(3-trifluoromethylphenyl)-2-methyl-3-butanone.
4.3g was obtained. ν ^Neat _nax (cm ^-1 ); 1700, 1330, 1235, 1160, 1125,
1070, 800, 700 The compounds listed in Table 1 above, other than the target compounds shown in this synthesis example, were also synthesized according to the above synthesis examples. The first feature of the insecticidal/acaricidal composition of the present invention is:
It has a broader insecticidal spectrum and synergistically enhanced insecticidal efficacy than when the compounds listed in Table 1 are used alone or in combination. That is, the composition of the present invention not only protects against agricultural, horticultural and forest pests that damage paddy rice, field crops, fruit trees, and forests, but also pests that damage stored materials such as grains, beans, and lumber, as well as flies,
It shows high control effects at low doses against a wide range of pests, including sanitary pests such as mosquitoes and cockroaches, as well as pests that damage clothing. Specific examples of pests to which the composition of the present invention can be applied include black leafhopper,
Black-bellied planthopper, brown planthopper, brown planthopper, southern green stink bug, white stink bug, Japanese brown planthopper, Japanese brown planthopper, Japanese brown planthopper, apple treehopper,
Hemipteran pests such as grape whitefly, citrus whitefly, whitefly, green peach aphid, radish aphid, cotton aphid, stone scale, and green scale insect; pear moth, citrus whitefly, small-bellied whitefly, lentil moth, white yam moth, corn borer moth, snail borer moth, and black borer moth Lepidopteran pests such as rice beetles, diamondback moths, green caterpillars, armyworms, Japanese armyworms, Japanese armyworms, turnip moths, American white moths, gypsy moths, and burrs;
Coleopteran pests such as the white beetle, the Japanese yellow beetle, the Japanese ladybug, the pine beetle, the grape beetle, the cucurbit beetle, the rice beetle, the rice beetle, the red bean weevil, the rice weevil, the rice water weevil, the brown beetle, the red bean beetle; Ka, Soybean pod fly, onion fly, seed fly, house fly,
Diptera pests such as the melon fly, rice fly, and rice leafminer; Orthoptera pests such as mole crickets, grasshoppers, and locusts; Reticulate pests such as the German cockroach and black cockroach; Japanese yellow thrips, southern yellow thrips, and black thrips, etc. Grossopteran pests such as human fleas, Cheops rat fleas, and dog fleas; Cervicopteran pests such as body lice, pubic lice, and cow lice; White spider mites, false red spider mites, citrus spider mites, apple spider mites, dust mites, dust mites, woolly spider mites, and dust mites, etc. Acar order pests; also nematodes such as sweet potato nematode, northern nematode, and rice nematode. The second feature of the composition of the present invention is that it can be used against pests that have already developed resistance to organophosphorus and carbamate insecticides and acaricides, which have played a central role among conventionally used insecticides. It also has remarkable efficacy against such resistant pests, and a sufficient effect can be obtained even with a low dose even against such resistant pests. In addition, the composition of the present invention has fast-acting properties not seen in general organophosphorus-based and carbamate-based insecticides and acaricides, and can exterminate many pests within a short time after application. It has excellent properties. When actually applying the composition of the present invention, it is sufficiently effective even if the composition itself is diluted.
In order to make it easier to use as a pesticidal agent, it is common to mix various carriers into a preparation, dilute it as necessary, and apply it. The composition of the present invention can be formulated into emulsions, wettable powders, powders, and fine granules by methods well known in the art in accordance with general agricultural chemicals and epidemic prevention drugs without any special conditions. , granules, oils, aerosols, heated fumigants (mosquito coils, electric mosquito repellents, etc.), fogging agents such as fogging, non-heated fumigants, poison baits, etc. can be adjusted to any desired dosage form, and various types are available depending on the purpose. It can be used for various purposes. The composition of the present invention has high stability against light, heat, oxidation, etc., but if necessary, antioxidants or ultraviolet absorbers, such as phenol derivatives such as BHT and BHA, bisphenol derivatives, phenyl α −
naphthylamine, phenyl β-naphthylamine,
A composition with stable effects can also be obtained by adding an appropriate amount of amyl amines such as a condensate of phenetidine and acetone or benzophenone compounds as a stabilizer. Furthermore, for the purpose of obtaining a multipurpose agricultural chemical, the composition of the present invention may be used by adding an attractant, a repellent, a fungicide, a herbicide, a plant growth regulator, a fertilizer, etc. The composition ratio of the compound of general formula () and the organophosphorus insecticide or acaricide in the composition of the present invention is 99:1 to 99:1.
The ratio is 1 to 99, preferably 1:9 to 1:1. When the composition of the present invention is formulated, the active ingredient concentration is 5 to 50% for emulsions, 0.1 to 3% for powders, 5 to 50% for wettable powders, and 0.3 to 5% for granules (all by weight). is preferred. Next, some examples of formulations in which the composition of the present invention is used as an agrochemical or an epidemic prevention drug will be shown, but the present invention is not limited to these. All "parts" indicate "parts by weight.""Organophosphorus insecticides and acaricides" in the formulation examples are
Indicates the compound described herein. Similarly, “1st
"Compounds in Table" is any one of the compounds listed in Table 1.
Indicates the species. Formulation example 1 Compounds shown in Table 1 (compound number 1 to
69, hereinafter the same) 10 parts, organophosphorus insecticides and acaricides
10 parts, Solbol SM-200 (Toho Chemical brand name)
10 parts of xylene and 70 parts of xylene are stirred and mixed to form an emulsion. Formulation Example 2 Dissolve 1 part of the compound shown in Table 1 and 3 parts of an organophosphorus insecticide/acaricide in acerone, add 96 parts of powder clay, stir, and evaporate the acetone to make a powder. . Formulation Example 3 10 parts of the compounds shown in Table 1 and organic phosphorus insecticides
Add 20 parts of acaricide, add 5 parts of Solbol 355TLL (Toho Chemical brand name), stir well, and add 300 parts of acaricide.
Add 65 parts of diatomaceous earth from Metshiyu and thoroughly stir and mix in a Raikai machine to prepare a wettable powder. Formulation Example 4 3 parts of the compounds shown in Table 1 plus organophosphorus insecticides.
Added 5 parts of acaricide, 88 parts of clay, and Toyolignin.
Add 4 parts of CT (Tobo registered trade name) and mix well.
After adding water and stirring, the mixture is granulated using a granulator.
Dry to make granules. Formulation Example 5 One part of the compounds shown in Table 1 and an organophosphorus insecticide.
Add 5 parts of acaricide and dissolve in white kerosene etc.
100 parts as oil solution. Formulation Example 6 Add 0.2 g of the compound shown in Table 1, 0.2 g of an organophosphorus insecticide/acaricide, 0.9 g of a synergist, and 0.3 g of BHT, dissolve in 20 ml of methanol, and prepare each carrier for mosquito coils (Tab powder, Mix 99.4g of lees powder and wood flour in the ratio of 3:5:1), evaporate the methanol, add 150ml of water, mix well, mold and dry to make mosquito coils. do. Formulation Example 7 Add 0.1 g of the compound shown in Table 1, 0.1 g of organophosphorus insecticide/acaricide, 1.0 g of synergist, and 0.2 g of BHT, dissolve in chloroform, and adsorb onto a 0.3 cm thick filter paper. The fiber fumigation composition is heated on an electric heating plate. Formulation example 8 0.1 part of the compound shown in Table 1, 0.1 part of organophosphorus insecticide/acaricide, 0.3 part of synergist, xylol 7
1 part and 7.5 parts of deodorized kerosene are mixed and dissolved. Fill this into an aerosol container and attach the valve. 80 parts of propellant (liquefied petroleum gas) is pressurized and filled through the valve part to form an aerosol. Production Example 9 0.1 part of the compound shown in Table 1, 0.1 part of organophosphorus insecticide/acaricide, 0.3 part of synergist, 11.5 parts of deodorized kerosene
1 part of the emulsifier Atmos 300 (registered trade name of Atlas Chemical Co.), and add 50 parts of pure water to emulsify it. Fill it to make a water-based aerosol. Next, the insecticidal and acaricidal effects of the composition of the present invention will be specifically explained using test examples. Test Example 1 Effect on green peach aphid Each test drug obtained by the method shown in Formulation Example 1, 20 parts of each test compound, Sorbol
A 20,000 times diluted emulsion obtained by stirring and mixing 10 parts of SM-200 and 70 parts of xylene was sprayed at a rate of 30 ml per pot to potted eggplant seedlings (4-5 leaf stage) infested with green peach aphid. . After air-drying, the seedlings were left standing in a greenhouse, and the number of insects infesting the seedlings was investigated immediately before and 3 days after the treatment. The test was conducted in triplicate, and the results are shown in Table 2 as a value of (number of insects after 3 days/number of insects before treatment) x 100.

【table】

[Table] Test Example 2 Effect on resistant black leafhopper Four-leaf stage paddy rice seedlings planted in pots are treated with a 20,000-fold dilution of each test chemical obtained in Formulation Example 1 by spraying 10 ml per pot in the same manner as in Test Example 1. . After air-drying, the seedlings were covered with a wire mesh cylinder, and 10 adult female resistant black leafhoppers (native to Nakagawa) were released and left in the greenhouse. After 48 hours, the number of dead insects was counted. The test was conducted in triplicate and the results are shown in Tables 3 and 4.

【table】

【table】

[Table] Test Example 3 Effect on Spodoptera spp. In the same manner as Test Examples 1 and 2, sweet potato leaves were sufficiently immersed in a 20,000-fold diluted solution of each test drug obtained in Formulation Example 1. After air-drying, the treated leaves were placed in a plastic cup with a diameter of about 10 cm and a depth of about 5 cm, and 10 3rd instar larvae of Spodoptera were released and left in a room at 25°C. After 72 hours, the number of dead insects was counted. The reagents were run in duplicate and the results are shown in Table 5.

【table】

〔Effect of the invention〕

General formula () which is a new compound related to the present invention
By applying the compound represented by and one or more of the organophosphorus insecticides and acaricides according to the present invention in combination, the insecticidal spectrum is not only expanded compared to when applied alone, but also the insecticidal effect is increased. can increase synergistically to improve pest control efficiency. At the same time, since it is possible to reduce the amount of application in actual use, the danger to the environment, humans, livestock, crops, etc. can be further reduced.

Claims (1)

[Claims] 1 General formula () [Wherein, Ar is unsubstituted or a halogen atom, lower alkyl group, lower haloalkyl group, lower alkoxy group, lower haloalkoxy group, lower alkylthio group, lower haloalkylthio group, lower alkenyl group, lower haloalkenyl group, lower alkoxy lower Alkyl group, lower haloalkenyloxy group, lower alkynyloxy group, lower alkoxy lower alkoxy group, lower alkoxycarbonyl group, lower haloalkoxycarbonyl group, lower cycloalkoxy group, phenyl group, phenoxy group, cyano group or methylenedioxy group It represents a substituted phenyl group, and when it has a plurality of substituents, these groups may be the same or different. R ¹ and R ² represent a methyl group, R ³ represents a group (), (In the formula, R represents a hydrogen atom or a fluorine atom.)] and 0-(2,2-dichlorovinyl)0,0-dimethylphosphate (DDVP). ), 0-(4-methylthiophenyl)0,0-di-
(n-propyl) phosphate (propaphos), 0,0-dimethyl 0-(3-methyl-4-methylthiophenyl) phosphorothioate (MPP), 0,0-dimethyl 0-(3-methyl-4-nitrophenyl) phosphorothioate (MEP), 0-(3,5,6-trichloro-2-pyridine)
0,0-diethyl phosphorothioate (chlorpyrifos), 0,0-diethyl 0-(2-isopropyl-6
-Methyl-4-pyrimidinyl) phosphorothioate (diazinon), 0,0-diethyl 2,3-dihydro-3-oxo-2-phenyl-6-pyridazinyl phosphorothioate (pyridafenethione), 0-(4- Bromo-2-chlorophenyl)0-
Ethyl S-(n-propyl)phosphorothiolate (prophenofos), 0,0-dimethyl S-(N-methylcarbamoylmethyl)phosphorodithioate (dimethoate), S-(N-formyl-N-methylcarbamoyl) Methyl 0,0-dimethylphosphorodithioate (formothion), 0-(2,4-dichlorophenyl)0-ethyl-S-propylphosphorodithioate (prothiophos), 0,S-dimethyl N-acetylphosphoramidothio acephate or 0,0-dimethyl 2,2,2-trichlor-1
An insecticidal/acaricidal composition containing one or more of -hydroxyethylphosphonate (DEP).