JPS6052144B2 - Cyclopropanecarboxylic acid ester and insecticides containing it as an active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel cyclopropanecarboxylic acid esters, 0, ○
′ [] R.

:’Acid ester.

2 types [01'゛○ R.

This invention relates to chill and insecticides containing it as an active ingredient.

゛Japanese Patent Publication No. 53-87337 and Japanese Patent Application Publication No. 54-2234
No. 4 contains 3-(2-halogeno-1-propenyl)-2
, m-phenoxybenzyl ester and m-phenoxy-α-cyanobenzyl ester of 2-dimethyl-1-cyclopropanecarboxylic acid, respectively, are also disclosed in JP-A-1988-1996-
5947 and JP-A-54-5948, 3-(2
,2-dichlorovinyl)-2,2-dimethyl-1-cyclocarboxylic acid (substituted phenoxy)-α-
Cyanobenzyl ester is known as an insecticide.
However, these compounds are highly toxic to fish, and there is a demand for compounds with even lower toxicity. In other words, contamination of environmental water by pesticides is caused by direct application to water systems such as rice fields, scattering during spraying, or floating in the atmosphere due to rainfall, runoff and erosion from agricultural land, or discharge from factories. contaminate. Therefore, in order to fundamentally prevent the harm caused to fish by compounds used as agricultural chemicals, it is desired to provide compounds that are themselves less toxic to fish. The present inventors have made the invention detailed below as a result of intensive research to develop a pyrethroid insecticide with lower toxicity.

The cyclopropane carboxylic acid ester of the present invention is represented by the following formula.

In the above formula, R1 represents a chlorine atom or a bromine atom.

R2 represents a hydrogen atom or a cyano group, with a cyano group being particularly preferred. R3 represents a halogen atom such as a chlorine atom or a bromine atom. In addition, the ester having the above formula (1) includes stereoisomers based on the three-dimensional structure of the cyclopropane ring,
Geometric isomers based on double bonds and optical isomers based on asymmetric carbon atoms exist, but it goes without saying that all of these isomers are included in the present invention, and trans isomers generally have superior insecticidal efficacy. There is.

The ester of formula (1) of the present invention is synthesized as follows.

(In the formula, R2 and R3?i have the same meanings as above,
X represents a hydroxyl group, a halogen atom, or a trialkylammonium ion and its counter ion in a quaternary ammonium salt produced by its reaction with an organic tertiary base), an alcohol, a halide, or a quaternary ammonium salt; A cyclopropanecarboxylic acid having the formula (wherein R1 has the same meaning as defined above) or a reactive derivative thereof, such as an acid halide, an acid anhydride, an alkali metal salt, or a salt with an organic tertiary base. , if necessary, by reacting in the presence of a suitable reaction aid.

2 Furthermore, the compound in which R2 is a cyano group in formula (1) is an aldehyde having the formula (wherein R3 has the same meaning as above) and the formula (wherein R1 has the same meaning as above). It can also be obtained by reacting an acid halide of cyclopropanecarboxylic acid having the following meaning and Y represents a halogen atom with an alkali metal cyanide.

In method 1 above, when the alcohol of formula () in which x is a hydroxyl group and the carboxylic acid of formula () are reacted, the reaction is achieved under dehydrating conditions.

For example, it is carried out in an inert solvent such as benzene in the presence of a dehydration condensation agent such as synchhexylcarbodiimide. When the alcohol of the formula () in which X is a hydroxyl group and the carboxylic acid halide of the formula () are reacted, a deoxidizing agent,
For example, the reaction is carried out in the presence of an organic tertiary base such as pyridine or triethylamine, and the reaction is usually carried out at room temperature in an inert solvent such as benzene or toluene.
When reacting an alcohol of formula () in which X is a hydroxyl group with an acid anhydride of a carboxylic acid of formula (), the reaction usually proceeds at room temperature, but heating or the use of a solvent is recommended to accelerate the reaction. Although they are convenient for smooth reaction, they are not essential. In method 1 above, when the benzyl halide of formula () in which X is a halogen atom is reacted with the alkali metal salt of monocarphonic acid or the salt of an organic tertiary base of formula (), if necessary, in the presence of a phase transfer catalyst such as benzyltriethylammonium bromide in a solvent such as benzene, toluene, or water to a temperature at or below the boiling point of the solvent. A heating reaction can be carried out.

In method 1 above, a quaternary ammonium salt of formula () in which x is trialkylammonium and its counter ion in a quaternary ammonium salt produced by reaction with an organic tertiary base; When reacting with an alkali metal salt of an acid, it can be carried out under the same reaction conditions as when using benzyl halide of the above formula ().

In addition, in method 2 above, the aldehyde of formula () and the acid halide and alkali metal cyanide of formula () are
When the reaction is carried out in a non-aqueous system in an inert solvent such as benzene or toluene, a crown ether is used as a catalyst, and when the reaction is carried out in a two-phase system of inert solvent and water, a phase transfer method such as benzyltriethylammonium chloride is used. Good results are obtained by using catalysts.

The cyclopropane carboxylic acid ester of formula (1) of the present invention has excellent insecticidal activity at low concentrations against sanitary pests such as flies, cockroaches, and agricultural pests such as beetles, leafhoppers, planthoppers, mites, and aphids. shows.

Furthermore, it has the characteristics of low toxicity to humans, especially fish, and is relatively stable against the effects of light. Therefore,
It can be suitably used in rice fields, swamps, etc., and does not pollute environmental water systems. To produce the insecticide of the present invention, the active ingredient can be dissolved in a suitable solvent or diluent, and a surfactant may be added to form an oil, emulsion, spray, aerosol, or other liquid preparation. It can also be made into powders, wettable powders, granules, mosquito coils, and other solid preparations together with an inert solid carrier and a diluent.

A synergist such as piperonyl butoxide or safroxane can be added to the formulation to obtain a synergistic effect, and the formulation can also be formulated in combination with other insecticides, fungicides, etc. Example 1 m-(p-chlorophenoxy)-benzyl 3-(2-chloro-1-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylate (trans form) m-(p-
In a solution of 0.26y of (chlorophenoxy)-benzyl alcohol and 0.15y of pyridine dissolved in 10ml of benzene, 3(2-chloro1-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylic acid chloride (trans form)0 A solution of .23y dissolved in 5 ml of benzene was added dropwise under ice cooling, and the mixture was allowed to react at room temperature overnight.

The reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The extract was washed successively with saturated brine and then dried over anhydrous magnesium sulfate. The residue obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography (n-hexane 4:3) to obtain 0.3y of the target product. IR, ν
ヰ(o-1:1730,1580,1490,1255
, 1170NMR (CDCl3) δ1.15 (S.CH
3), 1.26 (S.CH3), 1.53 (D, lH,
J=5.5Hz), 2.12(S.CH
3), 2.0. ~2.5 (M.lH), 5.10 (S.
2H), [5.21 (D, J = 8.0Hz) + 5.33
(D, J=8.0Hz)1H]7.1~7.6(M.8
H) Rf (n-hexane diacetate ethyl 0.64-0.6
7=185:15) In Examples 2 to 6, the following compounds were produced according to the method of Example 1.

Example 2 m-(p-chlorophenoxy)-benzyl 3-1(2-
Chloro 1-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylate (cis form) IR, ν♀1]-1: 1730, 1580, 1485, 1255, 1
1402, NMR (CDCl3) δ: 1.22 (S.6
H, 2CH3), 1.78 (D, lH, J=8.9Hz
), 2.12 (S.CH3), 2.0-2.4 (M.lH), 5.10 (S.2H), 5.36 (D.
lH, J=8.0Hz), 6.9-2.7.6 (M.8
ll) Rf (n-hexane diacetate 0.63, 0.70 ethyl di 85:15) Example 3 m-(p-chlorophenoxy)-benzyl 3-31 (2
-bromo-1-propenyl)-2,2-dimethyl-1-
Cyclopropane carboxylate (trans form) IR,
ν? λ冫 『1:1725,1610,1580,148
5,1255,1160,11103! NMR (CDC
l3) δ1.38-1.12 (M, 6H, 2CH3),
1.57 (D.J=5.0Hz, 1H), 1.92~2
．． 57 (M.lH), 2.30 (S.C.
H3), 5.15 (S● 2H), [5.
48(DJ=8.04CHZ)+5.65(DJ=8
．． 0Hz) 1H]6.85~7.60(
M. 8H) Rf (n-hexane diacetate ethyl di85:
15):0.62,0.67〈Example 4m-(p-chlorophenoxy)-benzyl 3-(2-bromo-1-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylate (cis form) IR , ν pass′:c! rl-1:1
730, 1610, 1580, 1485, 1255, 1
680,1635NMR(CDCl3)δ1.23(S
．． CH3), 1.20 (S.CH3), 1.74-2.
50 (M.2H), 2.28 (Br.S.
CH3), 5.11 (S.2H), 5.93-6.37
(M.lH), 6.85-7.55 (M.8l() Rf (n-hexane diacetate ethyl di 85:15): 0.63, 0.70
m-(p-bromophenoxy)-benzyl 3-(2-chloro-1-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylate (trans form) IR, νzen〉'1:1730,1580,1260, 1165NM
R(CDCl3)δ: 1.12-1.36 (M.6FI
,2× CH3), 1.15(D.lH,J
=5.6Hz), 2.12 (S.3FI, CH3),
2.31 (Q.lH, J=5.6, 8.0H
z), 5.10 (S.2FI), [5.21 (D, J=
8.0Hz) + 5.37 (D, J = 8.0Hz) 1H]
, 6.8 to 7.6 (M.8H) Rf (n-hexane diacetate ethyl di 85:15): 0.51, 0.54 Example 6
m-(p-bromophenoxy)-benzyl 3-(2-chloro-1-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylate (cis form) R, ν pass (0-
1:1730,1580,1260,1222,114
0NMR (CDCl3) δ: 1.23 (S.6H, 2×
CH3), 1.80 (D.lH, J=8.
0Hz), 2.12 (S.3H, CH3)
2.17 (D.d.lH, J=8.0Hz), 5.0(
S. 2HCH3), 5.76 (D.lH, J=8.0Hz), 6.75~
7.50 (M.8H)Rf (n-hexane diacetate ethyl di 85:15): 0.57 Example 7 m-(p-chlorophenoxy)-α-cyanobenzyl 3
-(2-chloro-1-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylate (trans form)
Sodium cyanide 0.078g, 15-crown-50
．． 024y and benzene 10mt, m-(p
A solution of 5 ml of benzene containing 0.24y of -chlorophenoxy)benzaldehyde and 0.22V of 3-(2-chloro1-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylic acid chloride (trans form) was added dropwise at room temperature, The reaction was stirred at room temperature all day and night.

The reaction mixture was poured into a saturated aqueous sodium bicarbonate solution and extracted with ethyl acetate. Thereafter, the same procedure as in Example 1 was carried out to obtain 0.3y of the target product. IR, ν? ! ．． α-1:174
0,1585,1485,1245,1135NMR(
CDCl3) δ: 1.1-1.4 (M.6H, 2CH3
), 1.57 (D.IH, J=5.1Hz
), 2.13 (S.CH3), 1.9-2
．． 15 (M.lH), [5.31 (D.J=6.9Hz
)+5.43 (D.J=6.9Hz) 1H
], 6.50 (S.lH), 6.9-7.6 (M.8H
) Rf (n-hexane diacetate ethyl chloride 85:15): 0.48, 0.53 In the following Examples 8 to 13, the following compounds were produced according to the method of Example 7.

Example 8 m-(p-chlorophenoxy)-α-cyanobenzyl 3
-(2-chloro-1-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylate (cis form) IR
,ν幇1)0-1:1740,1580,1485,1
245,1130NMR (CDCl3) δ: 1.1-1
．． 4 (M.6H, 2CH3), 1.81 (
D. lH, J=9.0Hz), 2.11(
S. CH3), 2.0-2.5 (M.lH), 5.73
(D.lH)J=8.0Hz), [6.3
5(S)+6.38(S)1H], 6.8~7.5(M
．． 8H) Rf (n-hexane diacetate ethyl di 85:15): 0.41, 0.43, 0.5
03 Example 9 m-(p-chlorophenoxy)-α-cyanobenzyl 3-(2-bromo-1-propenyl)-2,2
-dimethyl-1-cyclopropanecarboxylate (trans form) IR, νi) α-1:1740,1600,
1580, 1485, 1240, 1135, 1110N
MR (CDCl3) δ 1.13-1.38 (M.6H
,2CI(3),1.58(D.lH,J=
5.0Hz), 1.90-2.46 (M.lH), 2
．． 29 (Br.S, CH3), [5.49 (D.J=7
．． 5Hz) +5.63 (D.J=7.5
Hz) IH], 6.89-7.63 (M.
8H) Rf (n-hexane diacetate ethyl di85:15
): 0.50, 0.55 Example 10 m-(p-chlorophenoxy)-α-cyanobenzyl 3-(2-bromo 1
-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylate (cis form) IR, ν? ? G-1:1
740, 1580, 1480, 1245 NMR (CDC
l3) δ: 1.1 to 1.4 (M.6H, 2CH3),
1.5-2.1 (M.2H), 2.2-2.
4 (M.3H), [6.03 (D, J= 7
．． 5Hz) + 6.17 (D, J = 7.5Hz) 1H],
6.9-7.8 (M.8H) Rf (n-hexane diacetate ethyl di 85:15): 0.40, 0.43, 0.4
9. Example 11m-(p-bromophenoxy)-α-cyanobenzyl 3-(2-bromo-1-propenyl)-2,
2-dimethyl-1-cyclopropanecarboxylate (
Cis-trans mixture) IR, ν Pass RrXC77! -1
:1745,1600,1575,1480,1240
NMR (CDCl3) δ: 0.97-1.27 (M.6
H, 2× CH3), 1.37-2.33(
M. 2H), [2.11and2.18
(Br.S)3H], [5.39,5.
50 (Br.d, J=7.0Hz)+5.87,6.0
0 (Br.d, J = 7.0Hz), [
6.33, 6.37 (S) 1H], 6.
71-7.68 (M.8H)Rf (n-hexane diacetate ethyl di 85:15): 0.39 Example 12 m-(p-bromophenoxy)-α-cyanobenzyl 3
-(2-chloro-1-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylate (trans form)
IR, ν→↓τ礪−1:1745,1580,1480
, 1250, 1140NMR (CDCl3) δ: 1.0
~1.4 (M.6H, 2CH3), 1.
49 (D, lH, J=4.5Hz), 2
．． 05 (S.3H, CH3), 1.9~
2.5 (M.lH), [5.20 (D, J=6.5Hz
)+5.32(D,J=6.5Hz)1
H], 6.38 (S.lH), 6.7~
7.7 (M.8H)Rf (n-hexane diacetate ethyl di 85:15): 0.43, 0.46 Example 13m-(
p-bromophenoxy)-α-cyanobenzyl 3-(2
-chloro-1-propenyl)-2,2-dimethyl-1-
Cyclopropane carboxylate (cis form) IR, ν♀
? α-1:1745,1580,14801250,1
130NMR (CDCl3) δ: 1.1-1.3 (M.
6l(,2CH3), 1.73(D.l
H, J=9.0Hz), 2.08(S.3
H, CH3), 1.9-2.5 (M.lH
), [5.71(Br.d, J=8.5Hz)+5.8
5(Br.d, J=8.5Hz)1H], 6.33 (S.lH), 6.8~7.8(M.8H)Rf(n-
Ethyl hexane diacetate 85:15): 0.44,0
．． 49 Test Example 1 Fish Toxicity Test The test compound was prepared into a 10% wettable powder and diluted with water to a predetermined concentration.

Put 200ml of this chemical solution into a 300ml beaker,
Place 8 gutspies (3 week old larvae) in each beaker and
The number of deaths of a total of 16 animals was determined after 4S1 at 25°C using two beakers for each concentration, and the TLm value was calculated. The results are shown in Table 1. The comparative compounds are as follows.

Comparative compound A: m-phenoxybenzyl 3-(2-chloro-1-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylate (trans form) Comparative compound B: m-phenoxybenzyl 3-(2-bromo-1- Comparative compound C: m-
Phenoxybenzyl 3-(2-bromo-1-propenyl)-2,2-dimethyl-1-cyclopropanecarboxylate (cis form) Comparative compound D: m-phenoxy α
-cyanobenzyl 3-(2-chloro-1-propenyl)
1-2,2-dimethyl-1-cyclopropanecarboxylate (trans form) Comparison compound E: m-phenoxy α
-cyanobenzyl 3-(2-bromo-1-propenyl)
-2,2-dimethyl-1-cyclopropanecarboxylate (trans form) Comparative compound F: m-phenoxy α
-cyanobenzyl 3-(2-bromo-1-propenyl)
-2,2-dimethyl-1-cyclopropanecarboxylate (cis form) Comparative compound G: m-(p-chlorophenoxy)-α-cyanobenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-1 - Cyclopropane carboxylate (cis/trans mixture) comparative compound H:
m-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethyl-1-cyclopropanecarboxylate (cis-trans mixture = permethrin) From the test results in Table 1, the TLm value of the compound of the present invention is Also 10
showed a value larger than ppm and 10% higher than that of the comparative compound.
It can be seen that there is only ~10 safety.

Test Example 2 American Cockroach Insect Killing Test A predetermined amount of acetone solution of the test compound was placed in a glass bottle with a diameter of 2 cm and a height of 5 d, and after air drying, 10 American cockroaches (1st instar larvae) were placed in the bottle and the bottle was stoppered. The number of dead insects was determined after 24 hours.

The results are shown in Table 2. In addition, each numerical value is expressed as follows.

6: 100% mortality at 1 µy 5: 100% mortality at 10 µy Test Example 3 Insecticidal test on flies After anesthetizing successive-bred domesticated house flies (adult females on the 4th day after emergence) with carbon dioxide gas, A 1 μ' solution of each test compound in acetone was dropped onto the back plate using a microsyringe, and 30 animals each were placed in a waist-high shear dish. After 2 hours at 25°C, the number of dead insects was determined. Table 3 shows the number of dead insects. It is expressed as the concentration of compound at which the ratio reaches 50% (LD5O).

Test Example 4 Insecticidal test against black-and-white fly: A plastic pot with an inner diameter and height of about 10 cm was filled with soil and water to create a paddy field with a water depth of 2 cm.

Claims (1)

[Claims] 1 Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_1 represents a chlorine atom or a bromine atom, R_2
represents a hydrogen atom or a cyano group, R_3 represents a halogen atom) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 represents a chlorine atom or a bromine atom, R_2 represents a hydrogen atom or Indicates a cyano group,
An insecticide whose active ingredient is a cyclopropanecarboxylic acid ester (R_3 represents a halogen atom).