JPS5855406A - Insecticidal and acaricidal composition - Google Patents

Abstract

PURPOSE:The titled composition that contains a 2-arylethyl ether or thioether derivative, which has been unknown, and an organophosphate insecticide and acaricide, thus showing a wide range of insecticidal spectrum and synergycally increased insecticidal effect and developing quick action with low toxcity. CONSTITUTION:A compound of the formula (Ar is aryl; R1 is H, methyl, ethyl; R2 is 1-6 C alkyl; R3, R4 are H, halogen, alkyl, alkoxy; X is O, S), which has been unknown, such as 3-(4-fluorophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2- methylpropyl ether and an organophosphate insecticide and acaricide are mixed at a ratio of 1/9-1/1. The composition develops eminent effect against insect pests resistant to organophosphate insecticide and acaricide and prevents a variety of insect pests from becoming resistant.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel compound of the following general formula (1) [wherein, Ar is an aryl group, R1 is a hydrogen atom, a methyl group or an ethyl group, and 1'L2 is a carbon number 1 to 6 straight chain or branched alkyl groups, R3 is a hydrogen atom, a halogen atom,
R4 represents a lower alkyl group or a lower alkoxy group, and R4 represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, respectively. X represents an oxygen atom or a sulfur atom.

] and 8-(1
, 2-bis(ethoxycarbonyl)ethyl]dimethylphosphorothioate (Marathon), dimethyl-4-nitro m-tolylphosphorothioate (MEP), s-(
α-(Etquin carbonyl)benzyl codimethyl phosphorothioate (Pgp), dimethyl-4-methylt-ohm-tolyl phosphorothioate (MPP), diethyl-2,3-dihydro-3-oxo-2-phenyl-6
-Pyridazinyl phosphorothioate (pyridafenethio), diethyl-2-isopropyl-6-methy7le4-
Pyrimidyl-phosphorothioate (Diazinon), o
, t-dimethyl-N-acetylphosphoβ-roamidothioate (acephate), dipropyl-P
-Methylthio-phenyl-bosphate (propaphos)
, 2-chloro-1-(2,4,5-)dichlorophenyl)vinyl-dimethylphosphate (OVMP), dimethyl-5-(N-methylcarbamoylmethyl)phosphorothiolthioate (dimethoate), P-cyano-phenyl -dimethyl-phosphorothioate (0YAP)
, 5-(2-acetamidoethyl)dimethylphosphorothionerthioe-) (DAEP), diethyl-3-(
2-ethylthioethyl) phosphorothiol thioate (
Ethylthiometh/), Dimethyl-8-(2-(1-methylcarbamoylethylthio)ethyl)phosphorothioate (bamidothione), P-cyanophenyl-ethyl-phenylphosphorothiony) (OYP), 2-chloro-1
-(2,4-dichlorophenyl)vinyldiethylphosphate) (OVP), 2-methoxy-4H-1,3,
2-benzodioxaphosphorine-2-sulfide (salithion), 2,2-dichlorovinyl-dimethyl-phosphate (Dovp), 5-p-chlorophenyl-dimethyl-phosphorothioate (DMOPl), dimethyl-2゜2 , 2-) IJ chloro-1-hydroxyethylphosphonate) (DBP), dimethyl-3,5,
6-) Dichloro-2-pyridyl-phosphorothionate (
chlorpylphosmethyl), dimethyl-8-phthalimidomethyl-phosphorothioronate (DMP), ethyl-P
-nitrophenyl-phenylphosphonothionate (gp
8-(N-formyl -N-methylcarbamoyl-methyl)dimethylphosphorothionate (formothione), 5-(2-ethylthioethyl)dimethyl-phosphorothiolothionate (thiometone), S
-2-(isopropylthio)ethyl-dimethyl-phosphorothiorothionate (isothioate), S-[4,6
-Diami2 1.3.5-) riazin-2-ylmethylcudimethyl-phosphorothiolothionate' (menazone), 0-(2-diethylamino-6-methylpyrydin-4-yl)0. 〇-Dimethyl phosphorothioate (pirimiphos methyl), 2-diethylamine-6-methyl-
4-pyrimidinyl-diethylphosphorothionate (hirimi;'gsuethyl), 2,4-dichlorophenyl-ethyl-phenylphosphonothionate) (EPBP), 5
-(2-ethylsulfinyl-1-)f-ethyl)dimethyl-phosphorothiolate (BSP), S-[°α-(
ethoxycarbonyl)benzyl]dimethylphosphorothiolothione) (,PAP), S-[(2-methoxy-5-oxo-Δ2-1.3.4-thiadiazolin-
4-yl)methyl]dimethylphosphorothiolothione)
(DMTP), 0-(2,4-dichlorophenyl)
0-ethyl-6-propylphosphorodithioate (Prothiophos), 2-chloro-1-(2,4-dichlorophenyl)vinyldimethylphosphate (Zingard),
(4-promo2,5-dichlorophenyl)methylphenylphosphonothione)-(MBOP), 1,2-dibromo-2,2-dichloroethyl-dimethylphosphate (DBP), 2,4-dichlorophenyl-diethylphosphorothio nate (diclofenthio), 5-((6-
Chloro-2-oxo-6-benzoxyazolinyl)methyl]diethylphosphorothiorothionate (Rubidox), 0 indicates the common name.

It relates to an insecticidal and acaricidal composition containing one or more of organophosphorus insecticides and acaricides such as.

Conventionally, examples of agricultural and horticultural insecticides and epidemic prevention insecticides include
s-(1,2-bis(ethoxycarbonyl)ethylcdimethylphosphorothioate (Marathon), dimethyl-
4-nitro m-tolyl-phosphorothioate (ME
P ), diethyl-2,3-dihydro-3-oxo-2
-Phenyl-6-pyridazinyl phosphorothioate (pyridafenthione), diethyl-2-isopropyl-6
-Methyl-4-pyrimidyl-phosphorothioate (Diazinon), 0. Dimethyl-N-acetyl phosphoroamide thioate (acephate), dimethyl-5-(
N-methylcarbamoylmethyl) phosphorothiol thioate (dimethoate), etc.
Carbamate insecticides such as 1-naphthylmethylcarbamate (NAO), m-1lylmethylcarbamate (MTMO), and 2-dimethylamino-5,6-dimethylpyrimidin-4-yl-dimethylcarbamate (pyrimer) are has been used. Some of these insecticides and acaricides have excellent properties such as fast-acting, systemic transferability, and gas effect, but none of them are satisfactory in terms of insecticidal spectrum, residual effectiveness, toxicity to fish, and toxicity to humans and animals. It's not something I can do. Furthermore, as a result of the long-term use of these insecticides, pests that exhibit strong resistance to these insecticides have appeared in various places. Paddy rice pests such as planthoppers and leafhoppers, vegetable pests such as diamondback moths, sanitary pests such as houseflies, and mites that damage various crops have developed remarkable drug resistance. Organophosphorus insecticides and carbamate insecticides are losing their practicality. The growing soil,
Environmental pollution of rivers and other areas is also a problem, and control using low doses of chemicals is desired.

The novel compound represented by the general formula (1) of the present invention is:
Although these compounds satisfy these requirements and have insecticidal and acaricidal activity even when used alone, the present inventors have further conducted various studies to obtain excellent control effects and reduce the amount of use of these compounds in actual situations. As a result of repeated application of the compound represented by the general formula CI) and one or more types of organophosphorus insecticides and acaricides, the insecticidal rate was greater than when applied alone. The present invention was completed based on the discovery that the insecticidal activity is synergistically enhanced as the insecticidal activity increases.

Representative examples of the compounds included in the general formula (1) of the present invention and their physical properties are shown in Table 1 below.

The compound represented by the general formula CI] is a new compound, and its synthesis example is as follows (.The compound represented by the general formula [1,1 is the general formula CU] +41 2 The compound is represented by the general formula (1,) [In these formulas, A'', Arashi, R2, R3, - each represent the above meanings, and one group of group A and group B represents a halogen atom, and the other group represents a halogen atom and the other group represents a halogen atom. Compounds in which the group is an It is obtained by reacting with

Next, representative examples of the compounds of the present invention thus obtained are shown, but of course the compounds of the present invention are not limited to these examples.

In addition, the compound of the present invention has an asymmetric carbon when R and turtle are different groups in the general formula [1], and optical isomers exist, but mixtures of these optical isomers and these components It includes.

3-(4-fluorophenoxy)-4-fluorohensyl 2-(4-chlorophenylene/L/)-2~methylpropyl ether and thioether, 6-fluorobenzyl 2-phenyl-2-methylpropyl ether and Yohitioether, 6-phenoxy-
4-chlorobenzyl 2-(4-10lophenyl)-2-
Methylpropyl ether and thioether, 6-phenoxy-4-fluorobenzyl 2-(4-methoxyphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(
3,4-dimethylphenyl)-2-methylpropyl ether and onythyl, 5-(4-fluorophenoxy)-4-fluoropenzyl 2-(4-methoxyphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(
4-chlorophenyl)-2-ethylbutyl ether and thioether, ro-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-butyl ether and thioether, 3-phenoxy-/--6-chlorobenzyl 2-(4-chlorophenyl) -2-methylpropyl ether and hythioether, 6-phenoxy-4-
Fluorobenzyl 2-(4-chlorophenyl)-6-
Methylbutyl ether oyohithioether, 3-(4-
Fluorophenoxy)-4-fluorobenzyl 2-
(3,4-dichlorophenyl)-2-methylbutyl ether and thioether, 5-pheno-1-cy5-methoxybenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-(3-
chlorophenoxy)-4-fluorobenzyl 2-(4
-chlorophenyl)-2-methylpropyl ether and thioether, 5-(6-chlorophenoxy)-4-
Fluorobenzyl 2-(3,4-dimethyl)-2,3
-dimethylbutyl ether and thioether, 6-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-(2-fluorophenoxy)-4-fluorobenzyl 2-(3-chloro- 4-chlorophenoxy)
-2-methylpropyl ether, 3
-(2-fluorophenoxy)-4-fluorobenzyl 2-(4-10lofenyl)-2-methylpropyl ether and thioether, 3-(4-fluorophenoxy)-4-chlorobenzyl 2-(3,4-dimethoxy phenyl) -2-butylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl
2-(naphthalen-2-yl)-2-methylpropyl ether and thioether, 6-phenoxy-4-fluorobendi A/ 2-(4-methoxy-3,5-dimethylphenyl)-2-methylpropyl ether and thioether , 3-phenoxy-4-fluorobenzyl
2-(4-tert-7”tylphenyl)-2-methylpropyl ether and thioether, 5-(4-methoxyphenoxy)-4-fluorobenzyl 2-(4-
2-(3,4-dichlorophenyl)-2-methylpropyl ether and thioether, 3-(4-bromophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-
(4-impropenyl)-butyl ether, 6-phenoxy-4-fluorobenzyl 2-
(5-Trifluoromethylphenyl)-2-methyl ether and thioether, 6-phenoxy-4-fluorobenzyl, 2-(4-bromophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-methylbenzyl 2-(4-chlorophenyl)-
2-Propyl ether and thioether, phenoxy-4-fluorobenzyl 2-(4-7cetoxyphenyl)-2-methylbutyl ether and thioether, 6-phenoxy-4-fluorobenzyl 2-(3
-Methylphenyl)-2-methylpropyl ether and thioether, 6-phenoxy-5-fluorobenzyl 2- (3,4-diethylphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2- (1,2,3,4-tetrahydro)naphthalen-7-yl-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(indan-5-yl)-2-methylpropyl ether and thioether , 3-(3-
fluorophenoxy)-4-fluorobenzyl 2-(
3-Methoxy-4-methylphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4
-Fluorobenzyl 2-(5-ethoxy-4-bromophenyl) -2-71 Tylprobyl ether oyohithionityl, 6-phenoxy-4-fluorober 2-
(4-chlorophenyl)-2-methylbutyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(3,4-(difluoromethylenedioxy)
-phenyl]-2-methylpropyl ether and thioether, 6-phuninoxy 4-fluorobenzyl 2
-(~4-chlorophenyl) -2,3,3-trimethylbutyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(4-difluoromethoxyphenyl)-2-methylpropyl ether and thioether, 3-(3- methylphenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-(5-ri,
rolophenoxy)-5-fluorobenzyl 2-(3-
Nitro-4,5 dimethylphenyl)-2-methylpropyl ether and thioether, 3-(2-fluorophenoxy)-4-fluorobenzyl 2-(4-methylthiophenyl)-2-methylpropyl ether and thioether, 3- (3-Fluorophenoxy)-5-fluorobenzyl 2-(3-chloro-4-methoxyphenyl)-2-methylpropyl ether and thioether, 6-phe7noxy6-promobenzyl 2-(4
-methylphenyl)-2-methylpropyl ether and thioether, 6-(4-fluorophenoxy) -
4-fluorobenzyl 2(384ychlorophenyl)
-2-methylpropyl ether and thioether, 3
-(4-methylphenoxy)-5-fluorobenzyl
2-(4-Methylsulfoxyphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-
2-fluorobenzyl 2-phenyl-2-methylpropyl ether and thioether, 6-7 enoxy 4
-fluorobenzyl 2-(4-chlorophenyl)-2
, 3-dimethylbutyl ether and thioether, 3
-Phenoxy-6-bromobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, 3-(4-fluorophenoxy)-2-fluorobenzyl 2-phenyl-2-methylpropyl ether and thioether, 6- Phenoxy-4-fluorobenzyl 2-(4-methylthiophenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(4-methylphenyl)
-2-methylpropyl ether and thioether,
3-(4-fluorophenoxy)-5-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether and thioether, ro-phenoxy-4-fluorobenzyl 2-(4-fluorophenyl)-2-
Methylpropyl ether and thioether, 6-phenoxy-5-fluorope/sil 2-(4-ri.

Lophenyl)-2-methylpropyl ether, 6-phenoxy-2-fluorobenzyl 2
-(4-Trimethylphenyl)-2-methylpropyl ether and thioether, Ro-phenoxy-4-fluorobenzyl 2-(4-nitrophenyl)-2-methylpropyl ether and thioether, Ro-phenoxy-5-chlorobenzyl 2- (4-chlorophenyl)
-2-methylpropyl ether and thioether, 6
-Phenoxy-6-chlorobenzyl 2-(4-methylphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-6-fluorobenzyl 2-
(a-methylphenyl)-2-methylpropyl ether and thioether, 3-phenoxy-4-fluorobenzyl 2-(6,4-methylenedioxyphenyl)
-2-methylpropyl ether and thioether, 3
-(6-chlorophenoxy)-4-fluorobenzyl 2
-(4-chlorophenyl)-butyl ether and thioether, 3-phenoxybenzyl 2-(4-methylphenyl)-2-methylpropyl ether, ro-phenoxypenzyl 2-(4-promonoenyl)-2-ethylpropyl ether , 3-phenoxybenzyl 2-(
3-chloro-4-methylphenyl)-2-methylpropyl ether, 3-j enoxybenzyl 2-(3,4-
dibromophenyl)-2-methylpropyl ether, 3
-phenoxybenzyl 2-(4-chlorophenyl)-
2-ethylpropyl ether, 3-phenoxybenzyl 2- (4-1ert -phthylphenyl #)-2-methylpropyl ether, 6-phenoxybenzyl 2-
(4-fluorophenyl)-2-methylpropyl ether, 6-phenoxybenzyl 2-(3-7' lomo 4-
chlorophenyl) 2-ethylpropyl ether, 3-phenoxybenzyl 2-(3,t-dichlorophenyl)
-2-Methylpropyl ether, 3-phenoxybenzyl 2-(4-=bromophenyl)-2-methylpropyl ether, 6-phenoxybenzyl 2-(4-ethylphenyl)-2-methylpropyl ether, 6-phenoxybenzyl 2-(4-70lofenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-
(3chloroni4-70lophenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(4-ethylphenyl)-2-ethylpropyl ether, 3-phenoxypenzyl 2=(5,4-dichlorophenyl)-
2-ethylpropyl ether, 6-phenoxybenzyl 2-(4-chloro-6-methylphenyl)-2-methylpropyl ether, 6-phenoxybenzyl 2-(
4-tert-jtylphenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(3,4-
dimethylphenyl)-2-methylpropyl ether, 3
-Phenoxybenzyl 2-(3-chloro-4-71tylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3-bromo-4-chlorophenyl)-2-methylpropyl ether, 6-phenoxybenzyl 2- (3,4-dibromophenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(
4-chloro-3-methyl, phenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-chlorophenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,4-dimethylphenyl)
-2-ethylpropyl ether, 3-phenokyethylpropyl ether, 6-phenoxybenzyl 2-(3-
Chloro-4-70lophenyl) = 2-methylpropyl ether, 6-phenoxybenzyl 2-C3,4-dichlorophenyl)-2-methylglobyl ether, 3-phenoxybenzyl 2-(3,4-dichlorophenyl)
-2-ethylpropyl ether, 3-phenoxybenzyl 2-(6-bromo4-570lophenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(
3-bromo-4-fluorophenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(s-fluoro-4-7''romophenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-20 3
-chloro-phenyl)-2-methylpropyl ether,
6-phenoxybenzyl 2-(4-bromo6-chloro-phenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(4-70rho-3-methylphenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(3-70rho-4-methylphenyl)-
2-Methylpropyl ether, 3-phenoxybenzyl 2-(3-70rho4-methylphenyl)-2-ethylpropyl ether, 6-phenoxybenzyl 2-(
3-7'lomo4-methylphenyl)-2-meIF-
Rubropylether, 6-phenoxybenzyl 2-(
3-furomo4-methylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3,4-
-)ethyl-phenyl)-2-mer F-propyl ether, 6-phenoxybenzyl 2-(3,4-diethyl-phenyl)-2-ethylpropyl ether, 5-phenoxybenzyl 2-(4-i, sopropylphenyl)-2-methylpropyl ether, 6-phenoxybenzyl 2-(4-+isopropylphenyl)-2-ethylpropyl ether, 3-fairtugidibenzyl 2-
(3,4-diynepropylphenyl)-2-methylglobyl ether, 3-phenoxybenzyl 2-(3,4
-di-isopropylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3,4-di-
tert-butylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3,4-di-tert-butylphenyl)-2-ethylpropyl ether, 3-phenoxybenzyl 2-(3-ethyl-4- , 'tylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(3-ethyl-4-
methylphenyl)-2-ethylpropyl ether, 3-
Phenoxybenzyl 2-(4-ethyl-5-butylphenyl)-2-methylpropyl ether, 6-phenoxybenzyl 2-(4-ethyl-5-methylphenyl)
-2-ethylpropyl ether, 6-phenoxybenzyl 2-(4-tert-butyl-6-methylphenyl)-2-methylpropyl ether, 3-phenoxybenzyl 2-(4-tert-butyl-6-methylphenyl) -2-ethylpropyl ether, 6-phenoxybenzyl 2-(a-isopropyl-5-methyl-phenyl)-2-methylpropyl ether, phenoxybenzyl 2-(4-isopropyl-3-methylphenyl) -2-ethylpropyl ether, etc.

Next, the method for producing the compound represented by the general formula (1) of the present invention will be described in more detail by giving synthesis examples.

Synthesis Example 1 3-(4-7'romophenoxy)-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether Sodium hydride (60 ml) was added to 20 ml of dry acetonitrile.
qbInoil) 0.99 and then 2-(4
-chlorophenyl)-2-methylpropyl alcohol 2
．． 8g710ml acetonitrile solution was added dropwise at 5000ml.

After heating under reflux for 30 minutes, 5-(4-propeptaphenoxy)-4-fluorobenzyl bromide 6,6.9/
Add 1 ornl acetonitrile solution dropwise for 10 minutes,
Further, the mixture was heated under reflux for 1 hour. After cooling to room temperature, the mixture was poured into water and extracted with cold toluene. The toluene extract was washed with saturated saline and dried with Glauber's salt. The crude ether obtained by distilling toluene off under reduced pressure was purified by column chromatography on 150 g of silica gel (developing solvent: toluene/n-hexane 1:1) to obtain the desired ether 4.6
fl (theoretical yield: 65 cm) was obtained.

lID15806 i1m νmax1590.1490.1465.1295.1
225.1105.1020.830cm a0c14 1.29 (8,6H), 512 (S, 2
H), 4.32 (8, 211), 6.7-7.5 (m,
11H) Analysis result CvH2x8rO (lFO2 Calculated value (cE) 0 59.56H4,56Br17.2
30e 7.65 F 4.10 Actual measurement value (Rice 0 59.85 H4,64B, 17
．． 0101 7.77 F 4.00 Synthesis Example 2 5-phenoquine-4-fluorobenzyl 2-(4-methylphenyl)-2-methylpropyl ether Sodium hydride (60% in o
il) 0.639 was heated to reflux, and 2-(4-
methylphenyl)-2-methylpropylarnia -#
1.79/25% DMF-toluene 1o! iIl
The solution was added dropwise over 15 minutes. After continuing stirring for 3.10 minutes, 10 ml of a solution of 6-phenoxy-4-fluorobenzyl chloride (3.0.9/) toluene was added dropwise over 20 minutes. After further heating under reflux for 1.5 hours, the mixture was cooled to room temperature and drained into water.

After extracting with toluene and washing the toluene extract with water,
Dried with Glauber's salt. The crude ether obtained by distilling toluene off under reduced pressure was subjected to column chromatography on a 100 g silica gel column (developing solvent: toluene/n-hexane 1:
1) to obtain the desired pure ether 2.7.9 (theoretical yield 71%).

11 is also 01.5611 film νmax 1600, 1500, 1435.1290
, 1225.1105.825.695Cm"δ"' 1.30 (8, 6H), 2.27 (S, 3H
), 3.34 (S, 2H), 4.34 (S, 2H),
6.8-7.4 (rn.

12H) Analysis result 024H25FO2 Calculated value (@ 079.09 H6,91F 5.2
1 Actual value (@ 079.1115 H7,01F
5.42 Synthesis Example 3 3-Phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether 50% NaOH aqueous solution 20. ! ill, 2-(4-chloro7)-2-methylpropyl alcohol6
, Qy, 6-phenoxy-4-fluorobenzilb,
86 g of romide and 1.1 g of tetrabutylammonium bromide were added, and the mixture was heated and stirred at 80'O for 1 hour. After cooling to room temperature, water was added, extracted with toluene, and washed with water. After drying the toluene extract over Glauber's salt, the toluene was distilled off under reduced pressure, and the resulting crude ether was purified using silica gel 250.
g column chromatography (developing solvent: toluene/
The desired ether 10.117 (theoretical yield: 80%) was obtained by purification using n-hexane (1:1).

n901.5710 vA, lrn 1 s 8s, 1490.1425.1
280.1210°1095.1100.820.68
5cTn″δC(4a 1.26(S, 6H), 3
30 (S, 2H), 4.32 (S.

2H), 6.8-7.4 (m, 12H) Analysis result 0, H, Oj? FO2 calculated value @) 071.77 H5,760e 9.
21 F 4.94 actual value (@ 071.95
H5,55oe 9.31 ++' 5.02 Synthesis Example 4 6-phenoxy-4-fluorobenzyl 2-(3-methylphenyl)-2-methylpropylene ethertoluene 72 D m1Vc concentrated sulfuric acid 2 ml, 3-phenoxy- 4-fluorobenzyl alcohol/L' 2.79
．． 21 g of 2-(3-methylphenyl)-2-methylpropyl alcohol was added and heated under reflux for 6 hours (produced water was removed to the outside of the thread using a water separator). After cooling to room temperature, water was added, and the toluene layer was separated, washed with water, and dried. The crude ether obtained by distilling toluene off under reduced pressure was purified by silica gel ioogO column chromatography (developing solvent: toluene y/n-hex 71:i) to obtain 1.9 g of the desired ether (theoretical yield). A rate of 42 cm) was obtained.

09° 1.5582 1lrn νmaX 16oO115o5.1435.1290
11225.1130.71Qcm1 δCRa 1.30 (S, 6H), 2.29 (, %
3) (), 3.34 (S.

211), 4.53 (S, 2H), 6. B ~74
(m, 12H) Analysis result 02<HzsFOz Calculated value (4) 079.09 H6,91F 5.21
Actual value (hook 079.31 H7,02F 5.01 Synthesis Example 5 3-phenoxy-4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl-ethyl 4-chloroneophyl chloride-8, 55 g, 5-phenoxy-4-fluorobenzyl alcohol 8.72.
9. 45% NaOH 3,9 and dimethyl sulfoxide 48.9 were heated and stirred at 140°0 for 3 hours.

1.8 fl of 45% NaOH was added, and the mixture was further extracted with benzene at the same temperature for 4 hours. After washing the benzene extract with water, it was dried using Glauber's Salt Q. The crude ether obtained by distilling off benzene under reduced pressure was separated and purified using 250 g of silica gel column chromatography (developing solvent: toluene/n-hexane 1:1) to obtain the desired ether 7.279 (theoretical yield). A ratio of 77% to consumed 4-chlorneophyl chloride was obtained.

n901.5710 The infrared spectrum and NMR spectrum were consistent with the ether obtained in Synthesis Example 3.

Synthesis Example 6 Lorophenoxy-6-chlorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether 2-(4-Jlorophenyl)-2-)fluprobyl alcohol 2.0 g, 5-phenoxy-6- A 50 ml separable flask was charged with 3.5 g of chlorobenzyl bromide, 20 g of 50% NaOH, and 0.4 g of toluethylbenzylammonium bromide, and stirred at 500C for 2 hours. After cooling to room temperature, water and benzene were added and stirred while cooling with ice water. After separation, the benzene layer was washed with water and dried with sodium sulfate. The crude ether obtained by distilling off benzene under reduced pressure was purified by column chromatography on silica gel 150I (developing solvent: toluene-hexane 1:1) to obtain 3.8 g of the desired ether (87% of theoretical yield). I got it.

n1Q' 1.5854, fllln 1500.1480, '275.126
0.1215, ax 1110.1020.83 ocm- δ0014 1.29 (S, 6H), 3.44 (S
, 2H), 449(S, 2H), 6.7-7.5 (
m, 12H) Synthesis Example 7 3-phenoxy-4-fluorobenzyl 2-(4
-chlorophenyl) -2,3-dimethylbutyl ether Toluene 20me and sodium hydride (60% 1noi
l ) r3.6 [Add 1 g and heat to reflux, add 2
-(4-chlorophenyl)-2-isopropyl alcohol 2.09/40% DMF-) toluene ioml solution was added dropwise over 20 minutes. Continue stirring for 10 minutes.
fl and 5-phenoxy-4-fluorobenzyl bromide were added dropwise. After further heating under reflux for 1 hour, the mixture was cooled to room temperature and drained into water. Extraction was carried out with toluene, and the toludiene-extracted product was washed with water and dried with Glauber's salt. The crude ether obtained by distilling off toluene under reduced pressure was subjected to column chromatography on 120 g of silica gel (developing solvent: toluene-hexane 1:
1) to obtain 28 g of the desired ether (72% of theoretical yield).

1 layer 91.5656 i1m vmax 1610, 1530, 1510114
5011300.

1230, 1140, 1120, 103 parts m-1δ”0
′? 4 o62 (d, 3H, J=6.8H2),
0.85 (d.

3H,J268Hz), 1.19(S,
3H), 1,9-2.3(m, IH), 4,30(S,2H), 6.7-7.4(m, 1
2H) The production method will be explained below in detail with reference to synthesis examples.

Synthesis Example 8 (R)rTl It was synthesized according to the following order.

(1) arylacetonitrile 10i, θH2D
(J11120 20 g, ) Methyl iodide (1.2 molar ratio to arylacetonitrile) was added dropwise to 2J of ethylpendylammonium bromide over 1 to 2 hours while maintaining the temperature at 80°C to 90°C. Then KOH
lop,) ethylbenzylammonium bromide 2
At the same temperature, add 1 g of the desired alkyl halide (1.2 molar ratio to ryoryl acetonitrile).
The mixture was added dropwise over a period of ~4 hours, and after cooling to room temperature, the mixture was extracted with toluene. The desired dialkyl form of arylacetonitrile was obtained from the toluene layer.

(2) Hydrolyze the dialkyl form of arylacetonitrile synthesized in (1) with 50% HzSO4 or water-soluble diethylene glyco, -KOH at 160 to 150°C to obtain 2-aryl-2-alkylpropionic acid. Ta.

(rt)mFL.

Representative compounds are shown below.

(R)m R,mp l(01(3-75~76.5°C 6pe(! OH366,5~67.5°C3,4 to e2 0H393,5~94.5°0'-C1430H
380~81.5°04-Oe 02H5-59~
61.5°C 4th edition OH3ClI2- 82.5-84
°0(3) The 2-aryl-2-alkylpropionic acid synthesized in (2) is reduced with lithium aluminum hydride in tetrahydrofuran to obtain the desired 2-aryl-2-
Obtain alkylpropyl alcohol.

Synthesis Example 9 2-(4-chlorophenyl)-2-methylpropyl alcohol Synthesized according to the following sequence.

(1) After adding 1.5 g of ferric chloride to 169 g of chlorobenzene, hydrochloric acid gas was blown in for 10 minutes. Then, 46 g of tertiary-butyl chloride was added dropwise at 30°C (1 hour) and kept at 30'O for an additional 2 hours. After washing with an aqueous sodium carbonate solution and water, distillation was performed under reduced pressure to obtain 25p of 4-tert-butylchlorobenzene (113°C! /
2 B mmHg) was obtained.

(2) After adding 25 g of 4-tert-butylchlorobenzene synthesized in (1), 20 g of sulfuryl chloride, and a catalytic amount of benzoyl peroxide, the temperature was raised to 10
After keeping at 0°C for 1 hour, distillation L2-(4-
chlorophenyl)-2"-71f/l/-1-chloro-propa717.0.9 (121-123°0/10
I got a scream g).

(3) Dry tetrahydrofuran 100W+/! Magnesium (tur+tings) 27 jj, a small amount of iodine as a catalyst was added, and 2-(4-chlorophenyl)-2-methyl-1-chloropropane 20.3 was heated under reflux.
．． 9 was added dropwise over 60 minutes, and heating and refluxing was continued for 10 hours.

After cooling to room temperature, oxygen gas was blown in for 1 hour. Next, 7J11 of a saturated aqueous ammonium chloride solution was added, and most of the tetrahydrofuran was distilled off under reduced pressure, followed by extraction with toluene. Toluene was distilled off under reduced pressure to obtain crude alcohol.

Next, 163 g of 2-(4-chlorophenyl)-2-methylpropyl alcohol for the purpose of recrystallization was obtained from cold hexane.

mp4/, ~48°C Analysis result 0+oHx30j? 0 Calculated value (vaginus c 65.04 H7,10og 19.
2Q actual value (@064.18 H6, 95C119,
16 Synthesis Example 10 2-(3,4-methylenedioxyphenyl)-2methylglobyl alcohol was synthesized according to the following sequence.

(1) Magnesilla A (turni) in 100ml of dry ether
ngs) 27,9. A small amount of iodine was added as a catalyst, and 17 g of methyl iodide was slowly added dropwise. After finishing dropping 3
Heating and refluxing was continued for 0 minutes. Next, while increasing the temperature, ioml of benzene was added dropwise to replace the ether with benzene.

While heating under reflux, raw material nitrile 18.9.9 was added dropwise.

Furthermore, after heating under reflux for 3 hours, 6N-HB 2 was added under cooling.
oml was added dropwise over 30 minutes. Then, the temperature was raised and the mixture was heated under reflux for 7 hours. After cooling to room temperature, the benzene layer was separated, washed with water, and dried with Glauber's salt. Benzene was distilled off under reduced pressure to obtain the desired 2-(3,-4-methylenedioxyphenyl)-
192 g of 2-methyl-3-butanone was obtained.

(2) 12.8 g of bromine in 7.4 g of sodium hydroxide, 35 ml of water and 10 +++ l of dioxane at below 20°C.
was dripped.

Then, the temperature was raised to 90°C, and 1.0 g of 2-(4-methylenedioxyphenyl)-2-methyl-6-ptanone was slowly added dropwise, followed by heating and stirring at 90-95°C for 2 hours.

After cooling to room temperature, add a specified amount of sodium bisulfite,
Extracted with toluene. The aqueous layer was acidified with concentrated hydrochloric acid and extracted with toluene. This toluene layer was washed with water, dried with Glauber's salt, and the toluene was distilled off under reduced pressure to obtain the desired 2-(3
, 4-methylenedioxyphenyl)-2-methyl-propionic acid 7.5, F was obtained.

(3) The 2-(3,4-methylenedioxyphenyl)-2-methyl-propionic acid synthesized in (2) above was crushed with lithium aluminum hydride in tetrahydrofuran to reconstitute the desired 2-(3 ,4-methylenedioxyphenyl)
-2-Methylpropyl alcohol was obtained.

jkn'roJ-35390,1495.1235.1040
cr+″δ00′?41.25 (S, 75H), 3.
39 (S, 2) 1), 5.87 (8, 2H), 6.
+S ~6.9 (m13H) Synthesis Example 11 2-(4-difluoromethoxyphenyl)-2-methylpropyl alcohol Synthesized according to the following sequence.

(1) 2.4-bis(4-hydroxyphenyl)-
After dissolving 18.09 g of 4-methyl-2-pentene in 100 ml acetonitrile, 1 Cg of 5oINaO++ was added dropwise. Then, blowing of difluoromethane (Freon-22) was started at a temperature of 60-70°C. When about 60 g of the required amount for the reaction had been blown into the reactor (about 20 minutes later), 10 g of 50% KOH was added and the blowing was continued. Blowing was stopped when 15 times the amount of difluorochloromethane required for the reaction was blown into the reactor.

After cooling to room temperature, it was poured into 5 DD ml of water and extracted with toluene. After washing the toluene layer with water, it was dried with Glauber's salt, the toluene was distilled off under reduced pressure, and the resulting crude ether was washed with silica.
Column chromatography using 200 g of gel (developing solvent:
2,4-bis(4-
1q, 29 of difluoromethoxyphenyl)-4-methyl-2-pentene was obtained. Yield: 77 cm.

n”” 1.5285 (2) 2.4-bis(4-difluoromethoxyphenyl)-4-methyl-2-pentene 8.09 in acetone 100ml! 450 g of KMnO dissolved in 30°C
added. After stirring at 3000 for 10 hours, excess KMn
To decompose O4, add 20 r of ethyl alcohol under cooling.
nl was added dropwise. After continuing to stir for 1 hour, the manganese produced from 1 to 2 was filtered and thoroughly washed with water and acetone. Acetone was distilled off under reduced pressure, diluted hydrochloric acid aqueous solution was added, and the mixture was extracted with toluene. Dilute NaOH in toluene layer
An aqueous solution was added, and the mixture was separated after shaking with RyoX. The resulting aqueous layer was diluted with concentrated hydrochloric acid, extracted with toluene, washed with water, and dried.

When toluene is distilled off under reduced pressure, the desired 2-(4-difluoromethoxyphenyl)-2-methylpropion B
4.2 g was obtained.

(mp, 68; 5-695°0). Yield 84%.

accll+ 1.58(,9,6H), 6.42(
t, IH, J=75H2) 11.76 (broads
, it()ppm(3) Tetrahydrofuran 20ml
, 0.5% of lithium aluminum hydride, 1u11 of 2-(4-difluoromethoxyphenyl)-2-methylpropyl/acid/2.09% of tetrahydrofuran to a mixture of j7
1 solution was added dropwise at 4°0C. After dropping, raise the temperature 3
Refluxed for 0 minutes.

After cooling to room temperature, excess aqueous lithium aluminum was decomposed by dropping ethanol, and water was further added to completely decompose it. The formed precipitate was removed by filtration, and tetrahydrofuran was distilled off under reduced pressure.

Extraction was performed with benzene, and the benzene layer was washed with water and then dried over anhydrous sodium sulfate.

Benzene was distilled off under reduced pressure to obtain the desired 2-(4-difluoromethoxyphenyl)-2-methylpropyl alcohol 1.
8g was obtained. Yield: 96 cm.

i 1m νmax 3360, 1510, 1380, 1220
, 1185.1160.1040.855Cm'' Synthesis Example 12 2-(4-fluorophenyl)-2-methylbutyl alcohol was synthesized according to the following sequence.

(1) 4-fluorotoluene 166g%Nn530.0
．． 0.5 g of 91 benzoyl peroxide and 150 ml of carbon tetrachloride were placed in a 500 ml flask and refluxed for 2.0 hours. After cooling to room temperature, the resulting precipitate was removed by filtration, and the acg4 solution was washed with dilute alkali and water in that order, and dried with sodium sulfate. Carbon chloride was distilled off under reduced pressure, and crude 4-fluorobenzyl was blown away. Id28. -8 g was obtained.

In NaON 8.89 and 90 g of water, the crude powder obtained above was added.
Might 28. F39/xri)-#30ml solution from 70~
It was dropped at 80t (60 minutes). Then at 80°C
After being kept for 0 hours, it was cooled to room temperature and drained into water. Add celite and benzene to this, stir, and remove by filtration through celite. After separation, the benzene layer was washed with water and dried over anhydrous sodium sulfate. Benzene was distilled off under reduced pressure to obtain 15.29 pieces of crude 4-fluorobenzyl cyanide.

ibn νmax 2270.1615.1520.1430
．． 1240°1170.825Cm (2) 12Bg of crude 4-fluorobenzyl cyanide obtained in (1), 50% NaOH4[19], and 2.9g of triethylbenzylammonium bromide were placed in a flask and 14g of methyl iodide was added dropwise with stirring. (70°G
, 15 minutes).

After further holding at 70°C for 60 minutes, the mixture was cooled to room temperature and discharged into I7 water. Extraction was performed with benzene, and the benzene layer was washed with water and dried over Glauber's salt. Under reduced pressure 1. Benzene S/ was distilled off 5. α-
134 g of methyl-4-fluorobenzyl cyanoide was obtained.

α-Methyl-4-fluorobenzyl cyanite 7,0
fj, KOH15,9,02010'J, Tory 1-F
- Rubenzylammonium Proma (2.0) was placed in a flask, and 810ml of ethyl bromide was added dropwise at 80°C for 11 hours while stirring.Then, the same temperature was maintained for 2 hours.The subsequent operations were as described above. .

79 g of crude α-ethyl-α-methyl-4-fluorobenzyl cyanide was obtained.

7.6 g of crude α-ethyl-α-methyl-4-fluorobenzyl cyanide (202 (3me, concentrated sulfuric acid 20me)
was placed in a flask and heated under reflux at 134-137°0 for 5.5 hours. It was cooled to room temperature and extracted with benzene.

The benzene layer was extracted with dilute alkali, and the resulting dilute alkali layer was adjusted to pH 7.5 with concentrated hydrochloric acid, and extracted with benzene to remove impurities. Next, the aqueous layer was adjusted to pH 4.6 with concentrated hydrochloric acid and extracted with benzene. The benzene layer was washed with water and dried with Glauber's salt. Benzene was distilled off under reduced pressure to obtain 3.8 fi of the desired 2-(4-fluorophenyl)-2-methylbutyric acid.

δ0DOe3 0.85 (t, 3H, J=7H2),
1.55 (3,3H), 1.8-2. ! l (m, 2
H), 7. G ~7.6 (m, 4H), 113 (bro
ad S, IH) (3) Tetrahydrofuran 20ml
, 2 to a mixture of 0.5 g of lithium aluminum hydride
-(4-fluorophenyl)-2-methylbutyric acid'10
, i9 / Te) 40ml of 10ml solution of lahydrofuran
It was added dropwise at °C. After the dropping was completed, the temperature was raised and refluxed for 60 minutes. After cooling to room temperature, excess lithium aluminum hydride was decomposed by dropping ethanol, and water was further added to completely decompose it. The generated precipitate was removed by filtration, and tetrahydrofuran was distilled off under reduced pressure. Extraction was performed with benzene, and the benzene layer was washed with water and dried over Glauber's salt.

Benzene was distilled off under reduced pressure to obtain 2.6 g of the desired 2-(4-fluorophenyl)-2-methulfthyl alcohol.

n is also 3 1.5035 i1m νmax ””60.1610.1520.1240
．． 1175.1040.840 Cm Synthesis Example 13 2-(4-71 methylthiophenyl)-2-methylpropyl alcohol (1) Synthesis of 4-methylthiobenzyl chloride Methisil 18.2! ! 1.2-dichloroethane 200ml
! While cooling with water, 61.49 g of silver aluminum chloride was added. To this, 24.8 g of thioaesol was added dropwise at room temperature, and acid was added thereto for 6 hours to dissolve the solids, followed by extraction with benzene, and the extract was washed with water, cooled aqueous sodium hydrogen oxide, and then water. After that, after drying with Glauber's salt, the solvent was removed 1. 607 g of oily residue was obtained.

(2) Synthesis of (4-methylthiophene A-)-acetonitrile Dissolve 105 g of soda in 12 g of water and heat to 60°C. This was dissolved in 55 ml of ethanol (
The oily substance 607I obtained in 1) was added dropwise and reacted by refluxing for 4 hours. After post-treatment in a conventional manner, separation was carried out by column chromatography using benzene as a developing agent.
4.7 J of (4-methylthiophenyl)-acetonitrile (oil) was obtained.

δ0(″?4 2.57(S, 3H), s, 56(s
, 2H), 716 (S, 4H) (3) Synthesis of 1-(4-methylthiophenyl)-1,1-dimethylacetonitrile In the same manner as in Synthesis Example 10 (1) (4-methylthiophenyl) - Acetonitrile 13.1g to 139
g target product was obtained.

IJc0e4 1,66 (S, 6H), 2.45 (
S, 3H), 7.2 to '7.6 (m, 411) (4) Synthesis of 1-(4-methylthiophenyl)-1-methylpropionic acid 50 g of caustic potash, 5 g of water, 20 g of diethylene glycol
Add 3.8 g of 1-(4-methylthiophenyl)-1,1-dimethylacetoni) to m1,
The reaction was carried out at 0°0 for 7 hours. After the reaction was completed, the mixture was cooled, poured into water, and extracted with benzene. When the aqueous layer was acidified with concentrated hydrochloric acid, a precipitate was deposited. This was extracted with ether, washed with saturated brine, dried with Glauber's salt to remove the solvent, and the solid 1-(4
-methylthiophenyl)-1-methylpropionic acid 1
I got 9g.

δ Acetone d6 1.54 (S, <SH), 2
．． 43 (S, 3H), 7.0-7.5 (m, 4H) (5) Synthesis of 2-(4-methylthiophenyl)-1-methylpropyl alcohol Reduction with lithium aluminum dihydride as usual. 1-(
4-Methylthiophenyl)-1-methylpropionic acid 1
．． The target alcohol 1,5y was obtained from 9g.

δccg41.26 (S, 6H), 2.39 (S,
3H), 338 (S, 2H), 7.0-7.4 (InS
4H) Synthesis Example 14 Synthesis of 2-(4-chlorophenyl)-2-methylglobylthiol Synthesis was performed according to the following sequence.

(1) Synthesis of 1-note 2-(4-chlorophenyl)-2-methylglobin To 10.0 g of 2-(4-chlorophenyl)-2-methylpropyl alcohol -) Add 20 ml of pyridine to 108 g of luenesulfonyl chloride. , 50~55°C
The reaction was carried out for 1 hour. The reaction product was drained into 100 I ice water, acidified with dilute hydrochloric acid, and taken out from a furnace. The benzene layer was washed with saturated brine, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 193 g of white solid solution. Melting point 69-71580+5c''4 1.31 (S,
<SH), 2.44 (S, 3'11), 38
9 (S, 2H), 7.13 (S, 4H), 718-Z6
0 [m, 4H (ABType)) ν thought 1595.1480.1655.1175.97
0.825Cm″ (2) Bis-(2-(4-chlorophenyl)-2-
13.0 g of tosylate obtained in synthesis (1) of methylpropyl disulfide and 20.0 g of sodium hydrogen sulfide! i'(
70% product) and 90% and 90% ethanol 100
+nl was stirred and reacted for 6 hours under reflux. The reaction product was discharged into water, extracted with benzene, and the benzene layer was washed with water and then dried with Glauber's salt. Benzene was distilled off under reduced pressure to obtain a liquid residue Z911. This was separated by silica gel column chromatography using a mixed solvent of benzene-hexane (1:3) to obtain 56 g (oil) of the target product.

ν! See% 2950.1500.1410.1395
．． 1ro801.1120.1105.1D20.830
．． 755cm-1, 5CCe4 1.31 (S, 6H)
, 2.81 (S, 2Ij), 7.18” (d, A1
1) Elemental analysis Calculated value % 6017 6.01 16.0617.76 Measured value % 59,06 6.07 16.55 17.5
6(3) Synthesis of 2-(4-chlorophenyl)-2-methylpropylthiol 0.0959 lithium aluminum hydride was suspended in 25 ml of dry needle, and 101 nl of ether-dissolved bis-(2-( 1.0 y of 4-chlorophenyl)-2-methylpropylthiol was added dropwise and allowed to react under reflux for 2 hours. After the reaction was complete, the reaction product was poured into water, 1.15 y of diluted sulfuric acid was added, and benzene was added. Extracted.

The benzene layer was washed with saturated brine, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 1.0 g of a liquid residue.

i1m sirr1a82965.257o, 1495.14o5
．． 13kai○, 1370.11o5.1020.851C
J'δ(Q: la o, 8o(t, IH), t66(
s, 6H), 2.68 (d, 2H), y, 23(s
, 4n) Compounds in Table 1 above other than the target compounds shown in this synthesis example can also be synthesized according to the above synthesis examples.

The first feature of the insecticidal and acaricidal composition of the present invention is that
It has a broader insecticidal spectrum and synergistically enhanced insecticidal efficacy than when the compounds shown in the table are applied alone. That is, the composition of the present invention is effective against agricultural, horticultural, and forest pests that cause damage to paddy rice, field crops, fruit trees, forests, etc. (e.g., black leafhoppers, planthoppers, beetles, rice beetles, rice weevils, rice weevils, stink bugs, aphids, Green caterpillars, armyworms, mealybugs, cutworms, seed flies, sink beetles, scale insects,
It is effective against a wide range of pests, including storage pests such as spider mites, spider mites, white wigeon, gypsy moths, bark beetles, nematodes, and thurilapsidae, as well as storage pests such as brown weevils and snail moths, and sanitary pests such as flies, spider mites, and cockroaches. However, it has a control effect at low concentrations.

The second feature of the composition of the present invention is that it is an organophosphorus insecticide.

It has remarkable insecticidal and acaricidal effects even against pests that have already developed resistance to acaricides and/or carbamate-based insecticides and acaricides, and is drug-resistant against various pests. It means having a personality that is difficult to criticize.

In addition, the third feature of the composition of the present invention is that it has fast-acting properties that are not found in general organophosphorus insecticides, acaricides, and carbamate insecticides and acaricides, and can be used within a short period of time after spraying. It is possible for a pest to fall.

Furthermore, the fourth feature is that it has low toxicity to fish and warm-blooded animals and has no risk of causing environmental pollution, making it an extremely ideal insecticide and acaricide.

When the composition of the present invention is actually applied, it is sufficiently effective even if the composition itself is diluted, but in order to make it easier to use as a pesticidal agent, various carriers are mixed into the formulation.
It is common to dilute this product as necessary before applying. The formulation of the composition of the present invention does not require any special conditions, and can be formulated into emulsions, water concentrators,
Can be adjusted to any dosage form such as powder, fine granules, granules, oil, aerosol, heated fumigants (mosquito coils, electric mosquito repellents, etc.), fogging agents, non-heated fumigants, poison baits, etc. , can be used for various purposes depending on the purpose.

Although the composition of the present invention has high stability against light, heat, oxidation, etc., it is necessary to add antioxidants or ultraviolet absorbers, such as phenyl derivatives such as BHT and BHA, bisphenol derivatives, phenyl α A composition with stable effects can also be obtained by adding an appropriate amount of amyl aminos or benzophenone compounds such as -naphthylamine, phenyl β-naphthylamine, and a condensate of phenetidine and acetone as a stabilizer.

Additionally, 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.

In the composition of the present invention, the composition ratio of the compound of general formula [ ] to the organophosphorus insecticide or acaricide is 99:1 to 1:99, preferably 1:9 to 1:1.

When the composition of the present invention is formulated, the concentration of the active ingredient is 5 to 50 qb for emulsions, 0.3 to 3 qb for granules, 5 to 50 qb for irrigation agents, and 0.5 to 5 qb for granules (all by weight). %)
is desirable.

Next, some examples of formulations in which the composition of the present invention is used as an agrochemical or an epidemic prevention drug are shown below, but the present invention is not limited to these. All "parts" indicate "parts by weight."

[Organophosphorus insecticide and acaricide] in the formulation example refers to the above-mentioned compound described in the present specification. Same (“Compound in Table 1” refers to any one of the compounds listed in Table 1.

Formulation example-1 5 parts of the compound shown in Table 1, 15 parts of organic insecticide and acaricide
Emulsifier Tsurupol 5M-200 (Toho Chemical brand name)
10 parts of xylene and 70 parts of xylene were stirred and mixed to obtain milk.

Formulation Example-2 Dissolve 3 parts of the agent in acetone, add 96 parts of clay for powder, stir, and evaporate the acetone to obtain a powder.

Formulation Example-6 5 parts of the compounds in Table 1 and 15 parts of an organophosphorus insecticide and acaricide
1 part, 5 parts of emulsifier Tsurupol 355TLL (trade name of Toho Chemical Co., Ltd.) are added, stirred thoroughly, 600 mesh of Ku1 Sou 175 parts are added, and the mixture is sufficiently stirred and mixed in a laikai machine to prepare an irrigation agent.

Formulation Example-4 Add 5 parts of an organophosphorus insecticide and acaricide to 6 parts of the compound in Table 1, add 88 parts of clay, and 4 parts of Toyolignin OT (trade name of Toho Chemical), mix well, and then add water and stir. After mixing,
The mixture is granulated using a granulator and dried to form granules.

Formulation Example-5 Add 5 parts of an organophosphorus insecticide or acaricide to 1 part of the compound shown in Table 1, dissolve in white kerosene, etc., and make an oil solution to make 100 parts.

Formulation Example-76 0.2g of the compounds in Table 1 and 0 organophosphorus insecticides and acaricides
2g and synergist 0.9,9. Add 3 g of BHT O, dissolve in 2 aml of methanol, and stir and mix uniformly with 99.4 g of carrier for mosquito coils (Tab flour, lees flour, wood flour mixed at a ratio of 5:5:10). After evaporating the methanol, add 150ml of water and mix well.
molded and dried to make mosquito coils).

Formulation Example-7 01 g of the compound shown in Table 1, 0.0 g of organic insecticide, 0.
Add 2 g of BHTo to 1 g of synergist 1.0.9, dissolve in chloroform, and adsorb onto a piece of paper with a thickness of 0.3 cm to obtain a fiber fumigation composition heated on an electric heating board.

Formulation Example-8 0.1 part of the compounds in Table 1, 0 organophosphorus insecticides, 0 acaricides
1 part of the synergist, 03 parts of the synergist, 7 parts of Kijirole, and 75 parts of deodorized kerosene are mixed and dissolved. Fill this into an aerosol container and attach the pulp. 80 parts of a propellant (liquefied petroleum gas) is injected under pressure through the pulp portion to form an aerosol.

Formulation Example-9 0.1 part of the compound shown in Table 1, 0.1 part of acaricide, 0.1 part of acaricide, 0.6 part of synergist, 11.5 parts of deodorized kerosene, 00 part of emulsifier Atmos (Atlas Chemical Co., Ltd.) (registered product name) and 50 parts of pure water to emulsify. This is filled into an aerosol container with 37 parts of a 3:1 mixture of furin bromide and deodorized propane to form a water-based aerosol.

Next, specific insect pest groups to which the insecticide and acaricide of the present invention can be applied are listed. [Scientific name - (Japanese name)].

1. Hem1ptera (Hemiptera) Nepho
tettix cin4sticeps Uhler
(Black-spotted Japanese Warbler 2) sogatella furcifera Horva
tb (White-tailed Planthopper) Nilaparvata l
ugens 5tsI ()Laode
lphax 5triatellus B'allen
(Hifu 1 flying cormorant/force) Burydema rugos
Cooperation Motschulsky (Nagame) Eysarc
oril parvus uhler () Halyomorpha m1sta Uhler (
Lagynotomus elong
atus Dallas (Rice Cameum 7) N◆zar
a viridula Linne C1ctus trigonus Thunbe
rg (Himehari stink bug) S tephan mountain s n
ashi Esaki et Takeya Slcphanitis pyrioides 5co
tt (Tsutsujigunbai) psilla pyris
uga P6rstcr (Pyrus psyllid) Psyl
lamali schmidberier (apple psyllium) Aleurolobus taonabae
Kuwana (grape whitefly) pialeu
rodes citri Ashmead (Mikan no Kona) Rami) Trialeurodes vap den raiorum
Westvvod (ontic whitefly) Aphisg, tssypii Glover (r7
Brevicoryne brassi
cae Linn; (radish aphid) Myzus persicae 5ulzer (peach aphid) + 1hopalosiphum ma
idis Fitch rcerya purchasi Maskell
(Iseriya citri Ashi) Planococcus citri R, 1sso
(Ocitan mealbug) trnaspis yanonensis Ktr, v
ana (Yanoneka f.) 2, Lepidoptera (Lepidoptera) aan
ephora asiatica slaudinge
r (Minoga) Spulerina astaurcta
Aleyrjck (Nashihosoga) Plutell
a xylostella Linne (:7 Naga) promalactis inopisema Bu
tler (r) Tamiga)Adoxophyes o
rana Fischer von BBslerst
amm (:l Hakumonhamaki) Bactra furfurana Havnrth
(Igusasinmushiga) T, eguminivora
glycinivorella Matsumura
(-rMeshinkuiga) Onaphalocrcismedinalis G
uenee (:7 Bunomeiga) Etiella zinccnella Treat
schke (Ostrinia furnacalis Guene)
e (Pleuroptya der)
ogalApabricjus (wa, tanomeiga)
++yphantria cunea Drury (
Abralxas m1rand
a Bu-mouth Lymantria dispar japonica
Motschulsky (gypsy moth) Phalera fiavescens Bremer
et Gray (monk black killer whale) Agrotis 9egetum Denis et
Schiffermuller (Kaburayaga) Hel jcoverpa armigera H'+
51)ner (bolltail moth) 1)seudale
tia 5eparata Walker Mamestra brassicae Lin
n'e (Spider moth) P 1usia nigris
igna Walker (Tamanaginwaba) Spn
doptera l1tura F'ablicius
(Hasfuunyoto) Parnara guttat
a Bremer et Gray Pieris rapac crucivora Bo
isduval Chilo 5uppressalisWalker
(=Kameiga)'s, 0nleoptera
(Coleoptera) Melanotus fortnumia a
and5ze (-q Rukubikushikometsuki) Anthrenus verbasci Linne
(Hi7memarkatsopsimushi) Tencbroides mauri1a+1icus
Linne (-y Knust) Lyctus bru
nneus 5tephens
Henoscpilacbr+a vigintioc
monochamus alternatus Hop
e (-q ツ) Mapp-ra-)) Mikiri) xylotrechus pyrrhoderus l
3ates (grape beetle) Aulacnphora femoralis MOt
schulsky (Uri beetle) ulema oryzae xuwayama (
Phyllotreta 5tri
olata Fablicius (allosobruchus chinensis)
L+nne (adzuki bean weevil) Hchinocnep+1is sqt+ameus
BBllber (rice weevil, Order S ophi Iu)
soryzae Linne (-y-z whale)
Apoderus erythrogaster Vo
llenhoven (Himekuro 1st Shibumi) Tthynchites ht:rns 1Loelo
fs (-E-chokkirin-nushi) Anomala cuprea Hope (Douganepuipui) Popillia japonica N
ewman 4, Hynenop
tera (membrane 1) Ajh; mountain a rosae
japonensis Rolranr (Kabrahaba) Arge 51mlis Vollenhoven
(/l/rithu range) Arge pagana
Panger σEurenge Pachi) 5, Dip
tera (Diptera) T 1pula aino A
lexander Oulex
pipiens fatigans Wiedeman
n (Aedes aegypti) Acdes aegypti Linn; (Aedes aegypti) ASphOnd) lIl, 3Sp, (Aedes aegypti) nylemya antiqua Mci
gen (onion fly) Hylemya plat
ura Meigen (seed fly) htusca d
omestica vicina Macqtlart
(Housefly) Dacus cucurbitac
0oquillett Ohloro
ps oryzae Matsumura (Rice fly)Agromyza oryzae Munak
ata (rice leafminer) 6, 8iphona
ptera (Cryptera) Pulex 1rriLan
s Linne (human flea) xenopsylla
cheopisaothschild Otenocephal 1des canis c3
urtis (I, Nunomi) 7, T11ysa!
+optera (Tonoptera) Scirtothrip
s dorsalis Hood (Chanokiiro 7
Thrips tabaci l1nden]an
(Negia thrips) Ohloetllips ory
zae wil I iams (rice thrips)
8. Anoplura Pedic
+1 anus corporis D
e Geer (: IO Mouse) Phlbirus pubis T, 1nue (Popular louse) Haematopinus euryster
nus N i tzsh (Ujishijimi) 9,
Psocoptcra Trogi
um pulsatsrium Linne (:I
Nachi-1 Liposcelis bostry
chophilus Badonoel (Hiratachi V vertical) 10, 0 rthhoptera (Orthoptera) ory
llotalpa arricana palisot
de Beauvnis (kera)t,ocust
a migratoria danica linne
Oxya yezoensis 5hiraki () Oxya yezoensis 5hiraki (
D 1ctyoptera) 11, D 1ctyoptera
(Opiptera)]+1aHella germanica
1,1nne (German cockroach) peripl
aneta fuliginosa 5erville
(black cockroach) 12, Acarina (
acarinae) noophilus m1croplus c
anestrini Polypb
agotarsonemus 1atus Banks
(Chano dust mite) Panonychus citri Mc orego
r (citrus spider mite) Tetranychus ci
Tetranychus urticae Koch
(Two-spotted spider mite) ahizoglyphus echi
nophus pumouze et uobin
(Mites) Next, the effects of the composition of the present invention as an insecticide and acaricide will be explained in detail by giving test examples.

Test example-1 Effect on German cockroaches Diameter 9cm,
A solution of the compound shown in Table 1 at a specified concentration in acetone was dropped onto the bottom of a 5 cm tall Petri dish and air-dried to form a dry film. On the other hand, the compounds shown in Table 1 and organophosphorus insecticides were treated in the same manner.

A solution of acetone with a predetermined concentration containing acaricides mixed at a ratio of 1:3 was dropped and air-dried to form a dry film of the compound.

Apply butter to the inner wall of a waist-high dish 1/-, release 10 female adult German cockroaches per dish, and calculate the mortality rate after 24 hours. LD-50 when mixed with acaricides
I found the value.

In the case of any compound, it is more effective when treated alone, but when mixed with organophosphorus insecticides and acaricides,
A more than two-fold increase in activity was observed.

Test Example-2 Effect on Spodoptera spp. Tm Diameter 1 o
cm Put 3rd instar larvae of Spodoptera sinensis in an ethylene cup, and prepare an emulsion of the compound shown in Table 1 alone or mixed with an organophosphorus insecticide or acaricide according to Formulation Example 1. , diluted with water to a specified concentration, and sprayed 2 ml per cup directly onto the larvae using a spray tower. 1. Immediately gave artificial feed. After 24 hours, the mortality rate of each was determined and the LO-50 value was calculated. did.

Organophosphorus insecticide compared to each compound alone.

2 in any combination when acaricides are mixed.
A more than double increase in efficacy was observed.

Test Example 3 Effect on spider mites Adult two-spotted spider mites were released onto a green bean leaf disk with a diameter of 15 mm, the same emulsion as in Test Example 2 was sprayed, and each L.
When we calculated the O-50 value and compared the effects, we found that the LO-50 value for the compounds shown in Table 1 alone and the LO-50 value for the addition of good insecticides and acaricides were 1 for the latter. /2 or less, indicating a high synergistic effect.

Test Example 4: Effect on sensitive brown planthopper Rice seedlings (2 to 3 true leaves) were hydroponically cultivated in pots with a diameter of 5 cm, and 20 ppm concentration of each test chemical was obtained by the method shown in Formulation Example 1. Each drug solution was treated using a sprayer at a rate of 5 ml/pot.

After air-drying, the seedlings were covered with a wire mesh cylinder, and 10 male adults of the susceptible brown planthopper (from Chigasaki) were released per pot.
00 room. 24 hours after treatment, the number of live and dead insects was investigated, and the mortality rate was calculated. The results are shown in Table 2 as the average value of three runs.

Table 2 1 10 100 100 1004
0 80 100 10010 30
100 100 1L)+)16 5
0 100 1(h) 1+1021
70 100 100 1jl129
10 90 100 10030 0
80 100 10033 10
95 100 10039 0 B
5 100 10041 1 100
100 111:, 142 5L1
100 10+'l
l0I344 0 90 IQl+
101) 48 20 100
100 10051
20 100 100
10054 0 8rl
10i]101358 0
90 11] 1] 1
006ro o so
ic+o io.

72 10 85 10
0 10078 50 1
00 100 10079
50 100 100
10081 10 95
100 10084 10
95 100 1
0087 30 100
100 100'91 50
100 100 100/U As shown in Table 2, using organic insecticides and acaricides alone or the compounds in Table 1 alone have a mortality rate of 0 to 70, which is small, but By applying the compound in combination with organophosphorus insecticides and acaricides, a mortality rate of 100% was achieved, and an excellent synergistic effect was observed.

Test Example-5 Effect on resistant black leafhopper Young paddy rice seedlings (2 to 3 leaves) were hydroponically cultivated in pots with a diameter of 5 cm, and 10 ppm of each test chemical was obtained by the method shown in Formulation Example 1. Each sample was treated with a concentrated chemical solution using a sprayer at a rate of 3 ml/pot.

After air-drying, the seedlings were covered with a wire mesh cylinder, and 10 male adult resistant leafhoppers (native to intercultivation) were released per pot.
It was left standing in a room at 5°C. 24 hours after the treatment, the number of live and dead animals was investigated and the mortality rate was calculated.

The results are shown in Table 6 as three consecutive average values.

Table 3 1 30 0 100 10 1004 3
0 (39010100 1050010010100 164001001010LI 213oo100101o.

29 70 Q 100 10 1003
0 60 0 100 10 10+J55
40 0 100 10 10p39 5,
]0 100 10 10041 40 0
100 10 10042 50 0
100 10 10044 600 100
10 10048 40 0 100 1,
．． 10 10051 70 13
10 [11010054201J 90
10 10058 3fJ
0 100 10 1006
3 5 on 100
10 10°72 20
D 100 10 1007
8 713 0 100
10 10079 80 0
100 10 10[1814
0D 100 10 10
084- 50 0 100 16
10087 20 0 100
10 10091 40
[11D[l 10 1
As seen in the 006 table, the organic phosphorus agent alone is 0 to 10
H. The compounds in Table 1 also have a mortality rate of 20 to 70 h, and are not very effective when used alone, but by mixing the two,
The mortality rate was 0.00%, and an excellent synergistic effect was observed.

Test % '1.2.3.4.5) k, the combination of organophosphorus insecticides and acaricides other than dimethoate, diazinon, and pyridafenthione described herein with the compounds listed in Table 1 above. As a result of testing the mixture, Test Example 1.
2.3.4.5 Insecticidal and acaricidal effects similar to those of 2.3.4.5 were obtained.

Claims (1)

[Claims] [In the formula, Ar represents an aryl group, R represents a hydrogen atom, a methyl group or an ethyl group, R2 represents a straight chain or branched alkyl group having 1 to 6 carbon atoms, and 'FL3 represents a hydrogen atom. :f-, halogen atom, lower alkyl group or lower alkoxy group,
k represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, respectively. X represents an oxygen atom or a sulfur atom. ] or 2-arylethyl ether or thioether derivatives represented by
゛An insecticidal or acaricidal composition comprising one or more types of organophosphorus insecticides and acaricides.