JPS6051452B2 - Substituted isovaleric acids and their esters - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to substituted isovaleric acids or esters thereof, and more particularly to substituted isovaleric acids or esters thereof, and more particularly those having the general formula:
-COOZI(I)Cl' 11.

However, in the above general formula (I), R'' and Z'' are each a hydrogen atom or a lower alkyl group such as a methyl group, an ethyl group, an n-propyl group, or an iso-butyl group.General formula (I) of the present invention The compound represented by is useful as an intermediate for insecticides, acaricides, and aquatic pest control agents.

Since the discovery of BHC or DDT, the development of phosphorus, carbamate, and pyrethroid insecticides has been remarkable. Among these, pyrethroid insecticides have a Ξ-membered ring structure; for example, esters of primary chrysanthemum acid are used as household insecticides.
Additionally, permethrin [2,2-dimethyl-3-(2',2'-dichlorovinyl)cyclopropanecarboxylic acid 3'-phenoxybenzyl ester], which has been developed in recent years, is useful as an agricultural chemical. This pyrethroid insecticide is fast-acting against insect pests and is difficult to develop resistance to. Furthermore, it is highly safe because it decomposes very quickly in the body and is excreted from the body in a short period of time. However, these cannot necessarily be said to be perfect insecticides when considering stability, insecticidal spectrum, manufacturing process, price, etc. Through the research of the present inventors, the following general formula [wherein R1 has the same meaning as in general formula (1), l is the general formula (■), (■), (■) or (■)] represents a group shown as

Here, R2 represents a hydrogen atom, an allyl group, a propargyl group, a benzyl group, a thienylmethyl group, a furylmethyl group, a phenoxyl group, a halobinyloxy group, or a phenylthio group, and R3 represents a hydrogen atom, a methyl group, a trifluoromethyl group, or It represents a halogen atom, and cases in which R2 and R3 are bonded together at the ends to form a trimethylene or tetramethylene chain are also included.

R4 represents a hydrogen atom, an ethynyl group, a thioamide group or a nitrile group. n represents an integer of 1 to 2, and A represents an oxygen atom, a sulfur atom, or a (-CH=CH-) group. R5 represents a phthalimide group, a thiophthalimide group, a di- or tetrahydrophthalimide group, or a dialkylmaleimide group. R6 represents an allyl group, a propargyl group, a benzyl group or an alkadienyl group. R7
represents a hydrogen atom or a methyl group. R8 represents a phenyl group, thienyl group or furyl group, B is a hydrogen atom,
Represents a methyl group or a halogen atom. ]Although the substituted isovaleric acid ester group represented by the above group has a structure fundamentally different from that of conventional pyrethroid insecticides having a three-membered ring, it has an activity very similar to that of conventional pyrethroid insecticides. It was also found that it has much higher stability against light and oxygen than conventional pyrethroid insecticides, and has a wider insecticidal spectrum.

Therefore, the substituted isovalerate group (■) [hereinafter referred to as the active compound of the substituted isovalerate group (■)]
is an agricultural and horticultural insecticide that is required to have a residual effect for epidemic prevention and household use, such as leafhoppers, planthoppers, Japanese armyworms, armyworms, diamondback moths, nocturnal moths, cabbage moths, chestnut beetles, leafhoppers, aphids, scale insects, etc. It is highly effective as an insecticide for agricultural pests, such as grain storage pests such as the brown elephant, as well as an acaricide and aquatic pest control agent. Furthermore, like conventional pyrethroid insecticides, it has low toxicity to warm-blooded animals. The active compounds can also be used in combination with conventional pyrethroid insecticides such as allethrin, phthalthrin, resmethrin, flamethrin, permethrin, phenothrin, etc. to obtain even more effective insecticides.

Further, the insecticidal effect can be further enhanced by adding a synergist such as N-octylpicycloheptenedicarboximide, octachlordipropyl ether or piperonyl butoxide. Typical active compounds are listed below.

β-(3●3-dichloro-2-propen-1-yl)isovaleric acid 3″-phenoxybenzyl ester β-(3·
3-dichloro-2-propen-1-yl)isovaleric acid 3
″-phenoxy α2-cyanopendyl ester β-(
3,3-dichloro-2-propen-1-yl)isovaleric acid 3′-phenoxy α2-ethynylbenzyl ester β-(3●3-dichloro-2-propen-1-yl)isovaleric acid 3″-phenoxy α″-thioamide Benzyl ester α-methyl-β-(3,3-dichloro-2-propen-1-yl)isovaleric acid 3″-phenoxy α″
-cyanobenzyl ester α-isopropyl β-(
3,3-dichloro-2-propen-1-yl)isovaleric acid 3″-phenoxy α5-cyanobenzyl ester β
-(3●3-dichloro-2-propene-1-yl)isovaleric acid 3″-(2I・2″″-dichlorovinyloxy)
Benzyl ester α-methyl-β-(3●3-dichloro-2-propen-1-yl)isovaleric acid 5'-benzy-3'-furyl methyl ester β-(3,3-dichloro-2-propen-1-yl) isokichi Grass acid 5″-benzyl-3″-furylmethyl ester β-(3,3-dichloro-2-propen-1-yl)isovaleric acid 5″-propargyl-7-furyl methyl ester β-(3◆3-dichloro-2-propene-1-yl) Isovaleric acid 2''-methyl-5''-purpargyl-3'-furyl methyl ester β-(3,3-dichloro-2-propen-1-yl)isovaleric acid 5''-propargyl-3-furyl methyl ester β-(3,3-dichloro-2-propen-1-yl) -dichloro-2-propen-1-yl)
Isovaleric acid 2″-aryl-3″-methyl-2″-cyclopentene-1″-one-4″-yl ester β-(3.
3-dichloro-2-propene-1-yl) 3″・4″・
5″/6″-tetrahydrophthalimide methyl ester β-(3,3-dichloro-2-propen-1-yl)isovaleric acid 3″/4″-dichloro-α″-ethynylbenzyl ester β-(3●3-dichloro-2-propene-1
-yl) isovaleric acid 4″-phenyl-3″-chloro-2
″-Butene-1″-yl ester β-(3◆3-dichloro-2-propen-1-yl)isovaleric acid 3″-trifluoromethyl-α″-ethynylbenzyl ester α-ethyl-β-(3,3-dichloro-2-propene- 1-yl)isovaleric acid 2″●6′-dimethyl-4′-allylbenzyl ester β-(3●3-dichloro-2-propen-1-yl)isovaleric acid 5-propargyl-α5-ethynyl-2′-furylmethyl ester β- (3●3-dichloro-2-propen-1-yl)isovaleric acid 5''-benzyl-3''-thienylmethyl ester β-(3,3-dichloro-2-propen-1-yl)isovaleric acid 5''-propargyl-2-thienyl Methyl ester β-(3●3
-dichloro-2-propen-1-yl)isovaleric acid dimethylmaleimide methyl ester β-(3●3-dichloro-2-propen-1-yl)isovaleric acid 3''-(2''''
・2''-Dichlorovinyloxy-α5-cyanobenzyl ester-Substituted isovaleric acid or its ester represented by the general formula (1) is an important intermediate raw material in the production of the above active compounds, and is a typical example thereof. Some examples are as follows.

β-(3,3-dichloro-2-propen-1-yl)isovalerate α-methyl-β-(3,3-dichloro-2-propen-1-yl)isovalerate α-isopropyl-β-(3,3-dichloro-2- Propen-1-yl)isovaleric acid β-(3,3-dichloro-2-propen-1-yl)isovaleric acid methyl ester β-(3●3-dichloro-2-propen-1-yl)isovaleric acid ethyl ester [In the formula, R1 has the same meaning as in general formula (1), and l represents a lower alkyl group.

]β-(3,3-dichloro-2-propen-1-yl)
Isovaleric acid n-propyl ester β-(3,3-dichloro-2-propen-1-yl)isovaleric acid t-butyl ester α-monoethyl-β-(3,3-dichloro-2-propen-1-yl)isovaleric acid n- According to research conducted by the present inventors, the butyl ester compound represented by the general formula (1) can be easily produced by the following method.

That is, first, an orthocarboxylic acid ester (■) is added to 3-methyl-2-buten-1-ol in the presence of an acid catalyst such as propionic acid, butyric acid, valeric acid, valatoluenesulfonic acid, phenol, or hydroquinone at 120%
By reacting at a temperature ranging from ℃ to 160℃, γ・
δ-unsaturated carboxylic acid ester (■) can be obtained (JP-A-51-6571-inch and JP-A-51-8
(See 641 Gin Gazette).

Next, chloroform is added to the γ/δ monounsaturated carboxylic acid ester (■) in the presence of a catalyst, such as azobisisobutyronitrile, benzoyl peroxide, acetyl peroxide, di-t-butyl peroxide, t-peracetic acid. Butyl, t-perbenzoate
In the presence of a radical initiator such as butyl, t-butyl perphthalate, or t-butyl hydroperoxide, or in combination with ferric chloride hexahydrate and n-butylamine, or in combination with ferric chloride hexahydrate. Reaction at a temperature in the range of 600 to 150°C in the presence of a transition metal salt catalyst such as a combination of benzoin and diethylamine hydrochloride or a combination of triethylamine phosphite and ferric chloride and diethylamine hydrochloride. The addition product (■) can be obtained by The addition product (■) is then treated with a basic substance such as sodium methylate, sodium ethylate, sodium t-butyrate, potassium t-butylate, sodium isoamylate, 15-diazabicyclo[5.4.0]undecene-5( DBU), 1,5-diazabicyclo[3.4
．． 0] Basic substances such as nonene-5 (DBN), sodium hydroxide, potassium hydroxide, sodium amide, sodium hydride, butyl lithium, -700 to +150
Lower alkyl esters of substituted isovaleric acids (1-
a) can be obtained.

Further, the lower alkyl ester (1-
Free substituted isovaleric acid (
1-b) can be obtained. Moreover, the general formula (1
) The substituted isovaleric acid or its ester is easily derived from the active compound.

That is, free substituted isovaleric acid (1-b) is treated with a halogenating agent such as thionyl chloride, thionyl bromide, phosphorus trichloride, phosphorus tribromide, phosphorus oxychloride, or phosphorus pentachloride to form the corresponding carboxyl group. Acid halide (X) is obtained. Next, alcohol Z2OH (X[)[
Z2 has the same meaning as in general formula (H). ] in the presence of a tertiary amine such as pyridine or triethylamine to obtain the active compound. In addition, as a method for converting substituted isovaleric acid or its ester represented by general formula (1) into an active compound, in addition to the above-mentioned method, alcohol (X[ ), free substituted isovaleric acid (1-b)
An esterification method in which alcohol (X[) is reacted with dehydration condensation, 1XCX represents a halogen atom in a salt of an alkali metal, silver or organic tertiary base of free substituted isovaleric acid (1-b), 7 has the same meaning as in the general formula (■)] or its quaternary ammonium salt is reacted with the acid anhydride of free substituted isoisovaleric acid (1-b) and alcohol (X A known method such as an esterification method in which [) is reacted can be used. As described above, the active compound of the present invention derived from the substituted isovaleric acid represented by the general formula (1) or its ester is easily soluble in commonly used organic solvents.

Accordingly, the active compounds can be formulated by conventional means into emulsions, oils, powders, wettable powders, aerosols, etc. and used as insecticides for spraying, or they can be mixed with wood flour or other suitable substrates. It can be used as an insecticide for fumigation, such as mosquito coils. In addition, when this active compound is dissolved in an appropriate organic solvent and soaked in a mount, or dissolved in an appropriate solvent and used as an electric mosquito repellent, the active compound is heated and evaporated using an appropriate heating element, in the same way as mosquito coils. Shows excellent effects. The active compound is N-octylbicycloheptenedicarboximide (trade name M
When synergists such as GK-264), a mixture of N-octylbicycloheptenedicarboximide and alkylaryl sulfonate (trade name MGK-5026), octachlorodipropyl ether, and piperonyl butoxide are added, The insecticidal efficacy can be further increased.

Also, 2●6-di-t-butyl-4-methyl''phenol (
The stability of the active compound can be further increased by adding phenolic or amine antioxidants such as BHT), 2●6-di-t-butylphenol, etc. Moreover, by blending other insecticides with the active compound, an insecticide with high saw layer effect can be obtained.

Other insecticides include DDT, . Organic chlorine agents such as BHCl methoxychlor; 1-naphthyl N-methyl carbamate, 3,4-dimethylphenyl N-methyl carbamate, 3,5-dimethylphenyl N-methyl carbamate, 2-isopropoxyphenyl N-methyl carbamate, etc. Carbamate agent; O-0-dimethyl-0-(3-
Methyl-4-nitrophenyl) phosphorothioate, D
DVPCO●O-dimethyl-0-(2,2-dichlorovinyl)phosphate], diazinon, fenthion,
O●0-dimethyl-0-4-cyanophenyl phosphorothioate, 0●0-dimethyl-S-[α-(ethoxycarbonyl)benzyl]phosphorodithioate, 2-methoxylated mono-1,3,2-benzodioxaphospho Rin-2
- Organic phosphorus agents such as sulfide, 0-ethyl-0-4-cyanophenyl phenylphosphonothioate: pyrethrin, arsulin, N-(3,4,5,6-tetrahydrophthalimide)methylchrysansemate (tetramethrin), 5-benzy-3-furylmethylchrysanthemate (resmethrin), 5-propargylfurfurylmethylchrysanthemate (flamethrin), 5-propargyl-2-methyl-3-furylmethylchrysanthemate (proparthrin), 3-phenox Cybenzyl chrysanthemate (phenothrin), 3-phenoxy alpha-ethynylbenzyl chrysanthemate, 3-phenoxybenzyl 2'●2''-dimethyl-3''-(25'●2''-dichlorvinyl)cyclopropanecarboxylate (permethrin) , 3-phenoxy α-ethynylbenzyl 2″
◆2″-dimethyl-3″-(2!5●275-dichlorovinyl)cyclopropanecarboxylate, 3-phenoxy α-cyanobenzyl 2″・2″-dimethyl-3″
- Cyclopropanecarboxylic acid ester agents such as (2″・2″-dichlorovinyl)cyclopropanecarboxylate; 3-phenoxy α-cyanobenzyl α5-isopropyl-4″-chlorophenylacetate, 3-phenoxy α-ethynylbenzyl α5 -isopropyl 4″
Examples include substituted acetate ester agents such as -chlorophenylacetate. Examples, synthesis reference examples, test examples, formulation examples, and effect reference examples of the present invention are shown below.

In addition, in the formulation examples and effect reference examples, 1 part means part by weight. The compound numbers are the active compounds (1) to (23) described above.
). Example 1 Ethyl 3,3-dimethyl-4-pentenoate 20.0f1
Chloroform 200f and t-butyl perbenzoate 1.
After 0 g of the mixture was placed in a pressure tube and the tube was tightly stoppered, it was heated at a temperature of 120° C. for 2 hours.

After that, by distilling off low-boiling substances from the reaction solution and performing vacuum distillation, β-(3, 3, 3-
trichloropropyl) ethyl isovalerate (6◆6●6-
trichloro-ethyl 3,3-dimethylhexanoate) 2
7.2y was obtained (yield 77%). Boiling point: 90-97! 'C
/0.6TwtHgNMR spectrum (60MHz) δ
7 Hei 13: 1.07 (s), 1.26 (T..J=7H
z)9H:1.67-2.03(m)2H;2.24(
s) 21 (; 2.60-2.95 (m) 211; 4.1
7 (Q..J=7Hz) 2H then metallic sodium 2.5
Prepare a solution of V dissolved in 50 f of ethyl alcohol,
To this solution was added 20.0 f of the above ethyl β-(3●3.3-trichloropropyl)isovalerate, and the mixture was heated under reflux for 8 hours. Thereafter, the reaction solution was neutralized by adding anhydrous ethyl alcohol solution of hydrogen chloride, concentrated to a volume of about 1120 y, and then 100 y of ice water was added and extracted with diethyl ether. After drying the ether layer with anhydrous magnesium sulfate, the low boiling point substances were distilled off to obtain the following NIV
Ethyl β-(3,3-dichloro-2-propen-1-yl)isovalerate (ethyl 6,6-dichloro-3,3-dimethyl-5-hexenoate) with R spectrum was 13
．． 7y was obtained (yield 79%). NMR spectrum (60M
Hz) δ part S: 0.99 (s) 6F [, 1.20 (TN
J=7.5Hz)3H12.09~2.35(m)4H
14.07(Q,,J=7.5Hz)2H15.94(
T. ．． J=7.5Hz) 1H sodium hydroxide 2.2g
10 of the above ethyl β-(3,3-dichloro-2-propen-1-yl)isovalerate was dissolved in 15 V of water.
．． 0q and 20y of ethyl alcohol were added, and the mixture was heated under reflux for 4 hours.

After this, ethyl alcohol was distilled off from the reaction solution, then hydrochloric acid water was added until it became acidic, extracted with diethyl ether, the ether layer was dried over anhydrous magnesium sulfate, and low boiling point substances were distilled off. β-(3,3-dichloro-2-propene-1) with an NMR spectrum of
8.2 f of isovaleric acid (6,6-dichloro-3,3-dimethyl-5-hexenoic acid) was obtained (yield 93%).
. NMR spectrum (60MHz) δ part S: 1.04 (
s) 6H12.14-2.34 (m) 4H15.94 (
T. ．． J=7.5Hz) 1H synthesis reference example 1 β-(3◆3-dichloro-2-propen-1-yl)isovaleric acid 2.1y, thionyl chloride 3.0y and benzene 1
0y was added and the mixture was heated under reflux for 5 hours.

After this, β-
(3,3-dichloro-2-propen-1-yl)isovaleric acid chloride was obtained. Next, the β-(3●3-dichloro-2-propen-1-yl)isovaleric acid chloride was dissolved in 30 y of anhydrous benzene, 2.0 y of 3-phenoxybenzyl alcohol was added to this solution, and then 1.6 y of pyridine was added.
After adding q dropwise, the mixture was stirred at room temperature overnight. Thereafter, the reaction solution was diluted with diethyl ether, washed with diluted hydrochloric acid and water, then dried over anhydrous magnesium sulfate, and low-boiling substances were distilled off to obtain an oily product. The oily product was purified by column chromatography, and β-(3,3-dichloro-2-propen-1-yl)isovaleric acid 3''-phenoxybenzyl ester having the following properties was purified at 2.8V.
[Yield 71% from β-(3,3-dichloro-2-propen-1-yl)isovaleric acid]. NMR spectrum (
60MHz) δ+P: 0.93 (s) 61112.03
~2.23(m)4H14.98(s)21115.8
8 (T..J=7.5Hz) 1H16.76~7.50
(m) 911 elemental analysis value (calculated value in brackets) C%64.08 (64.13) H%5.60 (5.64
) Synthesis Reference Examples 2 to 7 In Synthesis Reference Example 1, instead of 2.0y of 3-phenoxybenzyl alcohol, 2.2g of 3-phenoxy α-cyanobenzyl alcohol, and 2.29,5 g of 3-phenoxyα-monethynylbenzyl alcohol were used. -benzy-3-furyl methyl alcohol 1.9y15-
Propargyl-2-furyl methyl alcohol 1.4y1
3-(2″·2″-dichlorovinyloxy)benzyl alcohol 2.2y or 3-(2″●2″-dichlorovinyloxy)-α-cyanobenzyl alcohol 2.5y
Follow the same method as Synthesis Reference Example 1 except for using y,
The corresponding esters of β-(3●3-dichloro-2-propen-1-yl)isovaleric acid were obtained.

The yield and elemental analysis values of each ester are summarized in Table 1. Example 2 A mixture of 20.0 y of ethyl 3.3-trimethyl-4-pentenoate, 200 y of chloroform, and 1.0 y of benzoyl peroxide was placed in a pressure-resistant tube, sealed tightly, and then heated at a temperature of 120° C. for 2 hours.

After that, excess chloroform was distilled off from the reaction solution, and vacuum distillation was performed to recover 16.2y of ethyl 2●3,3-trimethyl-4-pentenoate, and then α-methyl-β-(3●3●3 5.4y of ethyl isovalerate (6,6,6-trichloro-2,3,3-trimethylhexanoate) was obtained (reacted 2●3
●Yield 8 based on ethyl 3-trimethyl-4-pentenoate
4%). Next, 5.0 y of ethyl α-methyl-β-(3●3·3-trichloropropyl)isovalerate was added in the same manner as in Example 1, and a solution of 0.6 f of metallic sodium dissolved in 15 y of ethyl alcohol was added. was treated to give ethyl α-methyl-β-(3,3-dichloro-2-propen-1-yl)isovalerate (ethyl 6●6-dichloro-2●3●3-trimethyl-5-hexenoate), and then diluted with water and ethyl alcohol. Sodium hydroxide in a mixed solvent 1.
4f and further neutralized with hydrochloric acid water to obtain α-methyl-β-(3,3-dichloro-2-propyl-1-yl).
2.7y of isovaleric acid was obtained [α-methyl-β-(3.3
・Yield 69% from ethyl 3-trichloropropyl)isovalerate].

Synthesis of 2.2y of α-methyl-β-(3,3-dichloro-2-propen-1-yl)isovaleric acid Following the same method as in Reference Example 1, 3.6g of thionyl chloride was prepared in a benzene solvent.
to give α-methyl-β-(3●3-dichloro-2-propen-1-yl)isovaleric acid chloride, and then reacted with 2.0y of 3-phenoxybenzyl alcohol in the presence of 2.4y of pyridine in an anhydrous benzene solvent. 2.9 f of α-methyl-β-(3,3-dichloro-2-propen-1-yl)isovaleric acid 3″-phenoxybenzyl ester having the following properties [α-methyl-β-(
3●Yield 71% from 3-dichloro-2-propen-1-yl)isovaleric acid].

NMR spectrum (60MHz) δF Gl3: 0.94
(s), 1.12 (D..J=7Hz) 9H; 2.06
~2.57(m)3H;5.12(s)2H;5.94
(T.sJ=7.5Hz) 1H; 6.90-7.57 (
m) 9H elemental analysis value (calculated value in brackets) C% 64.7
2 (64.87) H% 5.92 (5.94) Example 3 Methyl 3,3-dimethyl-4-pentenoate 18 instead of ethyl 3,3-dimethyl-4-pentenoate 20.0V in Example 1 24.5y of methyl β-(3.3.3-trichloropropyl)isovalerate was obtained in the same manner as in Example 1 except that .2y was used (yield: 73%).

Next, add 1.79 y of metallic sodium to 25 y of methyl alcohol.
13.1y of the above methyl β-(3,3,3-trichloropropyl)isovalerate was added to the solution dissolved in 8.5 g of methyl isovalerate (
yield 75%). Synthesis Reference Example 8 5.3f of β-(3,3-dichloro-2-propen-1-yl)isovaleric acid and 4.5y of 3,4,5,6-tetrahydrophthalimidomethyl alcohol were dissolved in 50y of anhydrous benzene, and then dicyclohexyl 8.2y of carbodiimide was added and left overnight.

The next day, the mixture was heated under reflux for 4 hours, and after cooling, the precipitated solid was separated, the benzene was distilled off, and the resulting product was purified by column chromatography to obtain β-(3. 3-dichloro-2-propen-1-yl)
5.3 f of isovaleric acid 3″, 4″, 5″, 6″-tetrahydrophthalimide methyl ester was obtained (yield 57%).
. Elemental analysis value (calculated value in brackets) C%54.38 (5
4.56) H%5.59 (5.66) Synthesis Reference Example 9β-
5.8 y of sodium salt of (3,3-dichloro-2-propen-1-yl)isovaleric acid and 3.9 y of 5-propargyl-2-furylmethyl chloride were added to 50 y of benzene, and the mixture was heated under reflux for 3 hours under a nitrogen atmosphere.

Thereafter, the reaction solution was cooled and diluted with diethyl ether, the precipitated sodium chloride was separated, and then washed well with water and dried over anhydrous magnesium sulfate to distill off low-boiling substances to obtain an oily product. Ta. The oily product was purified by column chromatography to obtain β-(3,3-dichloro-2-propen-1-yl)isovaleric acid 5''-propargyl-7.
-5.3y of furyl methyl ester was obtained (yield?%).
Test Example 1 Insecticidal test against house flies by microdropping test A predetermined amount of the sample was accurately weighed, and 1% and 0.1% acetone solutions were prepared.

House flies anesthetized with ether (MllSCadOmes
ticavicirla Denken Colony) 1 μe of the above prepared solution was dropped on the dorsal pronotum of each female adult, placed in a waist-high shear dish with food, covered with a wire mesh lid, and stored at a temperature of 25°C. Table 2 shows the results of observing the mortality rate after 2 h.

Thirty test insects were used in each concentration area. Test Example 2 Compounds (2) and (3) were each accurately weighed as specimens for insecticidal test against black leafhopper by microdropping test, and 0.1% acetone solutions were prepared for each.

An adult female leafhopper, which is resistant to organophosphorus insecticides, was anesthetized with carbon dioxide gas, and 0.5 μ' of the above prepared solution was dropped onto the abdominal surface of its thorax. Thereafter, the test insects were fed rice seedlings and stored at a temperature of 25°C. 15 test insects were used in each area. 24T1! Afterwards, the test insects were observed to see if they were alive or dead, and the mortality rate was determined to be 90% or more for all compounds.

Formulation Example 1 Prepare 0.1 part each of compounds (1) to (20) and (23), add 0.1 part of resmethrin to each, then add white kerosene to bring the total to 100 parts, stir, and prepare each of the compounds. An oil solution was obtained.

Formulation Example 2 Prepare 0.2 parts each of compounds (1) to (3) and (9), add 0.8 parts of piperonyl butoxide to each, and then add white kerosene to bring the total to 100 parts. Each oil solution was obtained by stirring.

Formulation example 3 Compounds (1) to (4), (7) to (9), (16) to (
Prepare parts of (20) and (23), and add Xylol 5 and surfactant Solpol SM-2 to each of them.
00 (registered trademark of Toho Chemical Co., Ltd.) 2 was added thereto, and these were mixed and dissolved with thorough stirring to obtain a 30% emulsion.

Formulation Example 4 Compounds (1) to (4), (7), (9), 01
Prepare 1 part each of 1(16), (20) and (23), add 5 parts of piperonyl butoxide to each, dissolve in 2 parts of acetone, add 94 parts of 300 mesh diatomaceous earth, and shake. After thorough stirring and mixing in a container, acetone was removed by evaporation to obtain each powder.

7 Formulation Example 5 Compounds (1) to (4), (6), (7), (9), (1
0, (13), (15) to (18) and (23) were prepared, and the surfactant Solpol S was added to each of them.
Mix well 5 parts of M-200 (Toho Chemical registered trademark name),
Each wettable powder was obtained by adding 75 parts of 300 mesh talc and thoroughly stirring and mixing in a shaker.

Formulation Example 6 Prepare 0.4 parts each of compounds (1) to (3), (5), (8) to [phase] and (13), and add 0.1 part of resmerin and octachlordi to each of them. Propyl ether 1.
5 parts of refined kerosene and 28 parts of refined kerosene were added and dissolved, each was filled into an aerosol container, a valve part was attached, and 7 parts of a propellant (liquefied petroleum gas) was filled under pressure through the valve part to obtain an aerosol.

``Formulation Example 7 Prepare 0.5 parts each of compounds (1) to (3), (5), (7) to (14), and (18), and add BH to each of them.
T.O. 5 parts, 99 parts of a base material for mosquito coils such as pyrethrum extracted lees powder, wood flour, and starch powder were added and mixed uniformly to prepare each mosquito coil by a known method.

Formulation Example 8 Compounds (1) to (4), (7) to (9), (13), (
19) and (23) were prepared, and O.0-dimethyl-0-4-cyanophenyl phosphorothioate [Cyanox (registered trademark name of Sumitomo Chemical)] was added to each of them.
2 Osaka surfactant Solpol SM-200 (registered trademark of Toho Chemical Co., Ltd.) and 40 parts of xylene were added, and these were thoroughly stirred and mixed to dissolve each emulsion to obtain each emulsion.

Formulation Example 9 15 parts each of compounds (1) to (4), (6), (7), (9), [phase], (13), (15) to (18) and (23) were prepared. , 15 parts each of 1-naphthyl-N-methylcarbamate, and the surfactant Solpol SM-
Mix 5 parts of 200 (registered trademark name of Toho Chemical) well, and add 30 parts of
Each wettable powder was obtained by adding 65 parts of 0 mesh talc and sufficiently stirring and mixing in a shaker.

Formulation example 10 Compounds (1) to (4), (6) to (11), (13),
Prepare 01 parts each of (19) and (23), add 02 parts of 2-isopropoxyphenyl N-methylcarbamate and 5 parts of xylol to each, and dissolve in white kerosene to make a total of 100 parts. Each oil solution was obtained.

Formulation example 11 Compounds (1) to (4), (6), (7), (9), (1
Prepare 0.3 parts each of 0), (12) to (14), (19) and (23), and add DDVPO. Add 3 parts and dissolve in a 1:1 mixture of xylene and refined kerosene to make a total of 15 parts, and fill each into an aerosol container.
After the valve part was attached, 85 parts of a propellant (liquefied petroleum gas) was pressurized and filled through the valve part to obtain each aerosol.

Formulation example 12 Compounds (1), (7), [phase], (12), (13),
Prepare 0.05y of each of
．． 15f1BHT0.1y was added and dissolved in an appropriate amount of chloroform.

This solution is 2.5C77! ×1ゐα Each heated fiber fumigation insecticide on a hot plate was obtained by adsorbing it evenly onto the surface of asbestos having a thickness of 0.3 gourd, and pasting asbestos of the same size on top of it. Effect Reference Example 1 Each of the emulsions of compounds (2) and (3) obtained in Formulation Example 3 was diluted with water to 30 μl.

Next, each of these diluted solutions was sprayed at 10 ml/pot on rice plants planted in pots on the 25th day after sowing, covered with a wire mesh cylinder, and 15 leafhoppers were released into the cylinder.
After 1 hour, the animals were observed to be alive or dead. Both compounds (2) and (3) showed a mortality rate of 87% or more. Effect Reference Example 2 Compounds (1), (2), (3) obtained by Formulation Example 2
) and (9) were used to perform an insecticidal test against house flies according to the spray drop method.

2? As a result of observing whether the house flies were alive or dead after the test, a mortality rate of 901% or more was observed in all cases.

Effect Reference Example 3 Compounds (1), (2), (3) obtained by Formulation Example 1
) and (9) were used to perform an insecticidal test against house flies according to the spray drop method.

As a result of observing the life and death of the house flies after 24 hours, the mortality rate was over 90% in all cases.

Claims (1)

[Claims] 1. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (in the formula, R
^1 and Z^1 each represent a hydrogen atom or a lower alkyl group. ).