JPS5837298B2 - Cyclopropanecarboxylic acid ester derivative, method for producing cyclopropanecarboxylic acid ester derivative, insecticide containing cyclopropanecarboxylic acid ester derivative゜ - Google Patents

Description

Detailed Description of the Invention The present invention is based on the general formula 2 (wherein A is O, NH, .S, and R1 is an alkyl group, an alkenyl group, a haloalkyl group, a haloalkenyl group,
Alkoxyalkyl group and general formula (■), (m), (■
), (V), (VI), (■), (VUt), (IX)
, (X) represents a group.

Here, 1 is an integer from 1 to 5, m is an integer from 2 to 6, and n is an integer from 1 to 6.
Integer of 3, X is 0, S, CH2, CH2-CH2
where R3 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxyl group, and R4 represents a hydrogen atom or a methyl group.

Further, R2 represents a hydrogen atom, a cyano group or an ethynyl group.

), its optical and geometrical isomers, its production method, and an insecticide characterized by containing this compound as an active ingredient.

Various alcohol components of cyclopropane carboxylic acid esters have been studied and put into practical use.
It is susceptible to oxidative decomposition due to light, which has limited its use outdoors.

Recently, research into acid components has become active, and a compound that is more stable to light than conventional pyrethroids by replacing the methyl group with a halogen atom has been discovered.

However, when considering issues such as environmental pollution and chronic toxicity, compounds with structures similar to naturally occurring organic compounds, mainly consisting of carbon, hydrogen, oxygen, and nitrogen, are considered to be advantageous as future insecticidal ingredients. .

As a result of repeated research, the present inventor has found that the compound represented by the above formula (I) has an extremely excellent insecticidal effect as an insecticidal ingredient against various sanitary pests and agricultural and horticultural pests, while having extremely low toxicity to warm-blooded animals. I learned that it is much more stable against light than conventional pyrethroids.

The present invention was completed based on the above findings.

The compound represented by the above formula (L.) used as an active ingredient in the present invention can be prepared using the general formula (wherein A is 0, NH, S, R1 is an alkyl group, an alkenyl group, Haloalkyl group, haloalkenyl group, alkoxyalkyl group and general formula (II), (II[
), (IV), (V), (VI), (■), (vIII
), (IX), and (X).

Here, 1 is an integer from 1 to 5, m is an integer from 2 to 6, and n is an integer from 1 to 6.
3 is an integer; Or represents a methyl group.

) or its reactive derivative represented by the general formula (where R2 represents a hydrogen atom, a cyan group or an ethynyl group).

) or a reactive derivative thereof.

Examples of reactive derivatives of carboxylic acids include acid halides,
Examples include acid anhydrides, lower alkyl esters, and alkali metal salts.

Examples of reactive derivatives of alcohol include chloride.

The reaction is carried out in a suitable solvent, optionally in the presence of an organic or inorganic base or acid as a deoxidizer or catalyst, and optionally with heating.

What is obtained by a conventional synthesis method is a mixture of optical isomers and geometric isomers, each of which is included in the present invention.

Representative examples of the compound represented by the above formula (I) (shown as a mixture of optical isomers and geometric isomers).

) are as follows, but the present invention is of course not limited to these.

The compound of the present invention is a new compound, is solid or liquid at room temperature, and is generally easily soluble in organic solvents.

Therefore, as an insecticide for spraying, it can be used as an emulsion, oil, powder, permanent agent, aerosol, etc. It can also be mixed with wood flour or other suitable base material and used as an insecticide for fumigation such as mosquito coils. I can do it.

Also, when used as a so-called electric mosquito repellent by dissolving this active ingredient in an appropriate organic solvent and soaking it in a mount, or dissolving it in an appropriate solvent and heating and evaporating it with an appropriate heating element, it is as effective as a mosquito coil. shows.

The compound of the present invention is more stable against light than conventional pyrethroids, and can also be used as an agricultural and horticultural insecticide.

In addition, the compounds of the present invention include N-octylpincloheptene dicarboximide (trade name MGK-264), a mixture of N-octylpincloheptenedicarboximide and an arylsulfonate salt (trade name MGK-5026),
The insecticidal effect can be further enhanced by adding a synergist such as octachlorodipropyl JIy A-7/L/ or piperonyl butoxide.

The compound of the present invention may also be used with other insecticides such as Sumithion, DD.
VP, organic phosphorus agents such as diazinon, carbamate agents such as -naphthyl-N-methyl carbamate, 3,4-dimethylphenyl-N-methyl carbamate, pyrethrin, allethrin, phthalthrin, flamethrin, phenothrin permethrin, cypermethrin, decamethrin , fuenvalerate, fuenpropanetna, and other conventional pyrethroid insecticides, as well as acaricides, fungicides, nematicides, herbicides, plant growth regulators, fertilizers, By mixing other pesticides, a multipurpose composition with excellent efficacy can be obtained, and labor savings and synergistic effects between the drugs can be expected. Next, the insecticidal test results of the compounds of the present invention will be shown.

Test Example 1 Insecticidal test by spraying A 0.2% white light solution of the 44 compounds of the present invention of the above compound examples, 0.2% and piperonyl butoxide 0.8% white light solution (B), o. 1% and Phthalthrin 0.1%
For white light solution*Q, allethrin, and phthalthrin (0.2% white light solution), the falling and turning rate of house flies was calculated, the relative effectiveness of the test agent was calculated, and the mortality rate after 24 hours was calculated. The result I found was as follows.

Test Example 2 Insecticidal Test by Fumigation Mosquito coils containing 0.5% of insecticidal ingredients were prepared and tested for their effectiveness in making adult Culex mosquitoes fall and roll over.

This experiment was published in Insect Control Science Vol. 16 (1951), p. 176.
The relative effectiveness of the incense sticks was calculated according to the method of Nagasawa, Katsuta et al. and was as follows.

The test drug number is the same as that of the effective aliquot above.

Examples of the present invention will be shown below.

Note that the compound name is It is the same as the active ingredient example listed above.

Example 1 3.81 liters of 2,2-dimethyl-3-isopropoxycyclopropanecarboxylic acid chloride was added to 15 wL of dry benzene.
To this was added a solution of 4.71 3-phenoxy α-cyanobenzyl alcohol dissolved in 20 rnl of dry benzene, and 3.0 rnl of dry pyridine was added as a condensation aid.
When I71l is added, crystals of pyridine hydrochloride are precipitated.

After sealing the cap and leaving it overnight at room temperature, the pyridine hydrochloride was removed from the house, the benzene solution was dried with sulfuric acid, and the benzene was distilled off under reduced pressure to give 3'-phenoxy-α'-cyanobenzyl 2,2-
Dimethyl-3-impropoxycyclopropanecarboxylate 7.11 was obtained.

Example 2 5.4f of 2,2-dimethyl-3-(2,5-epoxy3,4-dimethylcyclohexylmethylamino)-cyclopropanecarboxylic acid and 4.6L of 3-phenoxyα-1ethynylbenzyl alcohol? benzene 150TrLl
and add 5 rfLl of concentrated sulfuric acid while stirring the solution vigorously.

Heat to reflux while stirring and remove water produced by azeotropy using a dehydrating agent.

Benzene was replenished from time to time and the reaction was carried out for about 4 hours.

The reaction solution was then washed with aqueous sodium bicarbonate and brine, and the benzene was distilled off under reduced pressure to give 3'-phenoxyα'-ethynylbenzyl 2,2-dimethyl-3-(2,5-epoxy 3,4
-dimethylcyclohexylmethylamino) monochloropropanecarboxylate7. 8 1 I got it.

Example 3 2,2-dimethyl-3-(3-}lifluoromethyl-α
-Methylpendylthio)monocyclopropanecarboxylic acid sodium salt 6.61 and 3-phenoxybenzyl chloride 4.5P were dissolved in 50 TIll of benzene and reacted under reflux for 3 hours in a nitrogen atmosphere, and then the reaction solution was After cooling and separating the precipitated salt from each house, it was thoroughly washed with brine and dried with sulfuric acid, and the benzene was distilled off under reduced pressure to obtain 3-phenoxybenzyl 2,2-dimethyl-3-(3-)refluorinated methyl-α. 8.1' was obtained.

Example 4 Methyl ester of 2,2-dimethyl-3-(2,2-dichlorovinyloxy)monocyclopropanecarboxylic acid4.
8? and 4.61 g of 3-phenoxy α-ethynylbenzyl alcohol are heated to 150°C.

When the temperature reaches 150°C, sodium 0. 2 5
9 was added to start distilling off methanol.

Once methanol has stopped distilling off, add another 0.2 liters of sodium.
5? and increase the temperature to 150℃ until the stoichiometric amount of methanol is obtained.
Keep the temperature around ℃ and repeat the above operation.

The mixture was then cooled and dissolved in ether, and the ether solution was washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over nitric acid, and the ether was distilled off under reduced pressure to give 3'-phenoxyα'-monoethynylbenzyl 2.2- Dimethyl-3-(2.2-
cyclovinyloxy) monocyclofuropanecarboxylate 7.5♂ obtained.

Example 5 2.2-dimethyl-3-(4-methoxy-2cyclopentenylthio)monocyclopropane carbon e anhydride4.
7? and 3-phenoxy alpha-one anobenzyl alcohol (4.71 g) were mixed, 98% sulfuric acid 8Z was gradually added under stirring, the reaction was carried out at 80 to 100°C for 3 hours, and then dissolved in ether, and the ether solution was dissolved in sodium bicarbonate water, After thoroughly washing with brine and drying with salt water, the ether was distilled off under reduced pressure to obtain 3'-phenoxyα'-cyanobenzyl 2,2-dimethyl-3.
-(4-methoxy-2-cyclopentenylthio)-cyclopropanecarboxylate}6.6P was obtained.

Example 6 5.11 of 2,2-dimethyl-3-(4-chloromethylcyclohexylamino)-cyclohexylbencarboxylic acid was dissolved in 71 l of dimethylformamide 50I, and 3-
Add 5.4% of phenoxybenzyl bromide.

Add triethylamine 4rI'Ll while stirring and add 60~8
After reacting at 0°C for 3 hours, it was dissolved in ether, the ether solution was thoroughly washed with aqueous sodium bicarbonate and brine, dried over sodium chloride, and the ether was distilled off under reduced pressure to give 3'-phenoxybenzyl.
2,2-dimethyl-3-(4-chloromethylcyclohexylamino)-cyclopropanecarboxylate 7.8
Get S'.

Example 7 1.5 l of sodium metal is dissolved in 50 μl of absolute ethanol, and 100 mA' of anhydrous toluene is added thereto.

Remove ethanol and toluene under reduced pressure in a nitrogen stream,
100 rILl of 1,2-dimel-xyethane was added to the precipitated sodium ethoxide, and 12. Add CI to 12
Heat to reflux for an hour.

After the isomerization is completed, 1.2-dimethoxyethane is distilled off under reduced pressure, and 100 ru of water is added to the residue to perform ether extraction.

The ether solution was thoroughly washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and saline, dried over sulfur salt, and after distilling off the ether, dl −
Ethyl ester of trans-2,2-dimethyl-3-isotoxine chloropropanecarboxylic acid (boiling point 126~
130° C./28 Hg fraction) 9.4P was obtained.

Add 4.81 of this ethyl ester to 20 ml of acetic acid and 35%
The resulting carboxylic acid 4.21 was hydrolyzed in 20ml of an aqueous solution of hydrobromic acid, and the resulting carboxylic acid 4.21 was reacted with 3-phenoxy α-cyanobenzyl alcohol 4.71 according to the method of Example 1 to give 3'-phenoxy-α'-cyano. benzyl dl −
7.2-dimethyl 3-isobutoxine chloropropanecarboxylate 7.5P was obtained.

Example 8 Ethyl ester of d1-cis, I.Lance 2,2-dimethyl-3-methoxychloropropanecarboxylic acid 15.
Repeat precision distillation for 0P, dl-trans-
Ethyl ester of 2,2-dimethyl-3-methoxycyclopropane carboxylic acid (boiling point 74°C/17 mrI
Lng fraction) 6.4f and ethyl ester of d1-cis-2,2-dimethyl-3-methoxycyclopropanecarboxylic acid (boiling point 78°C/13mmHg fraction) 1.8
I got P.

The latter ethyl ester was treated in the same manner as in Example 7.
-Phenoxy-α'-cyanobenzyl d]-cis-2
-2-dimethyl-3-methoxycyclopropanecarboxylate was obtained.

Hereinafter, the symbol A will be added after the compound number to indicate that the acid moiety is the dl-trans form, and the symbol B will be added to indicate that the acid moiety is the d1-cis form.

Example 9 dl-4 lansu 2,2 dimethyl-3-isobutoxine clopropanecarboxylic acid 4.1 obtained in Example 7
Dissolve the male in 50 ml of methanol at 50°C, and add 1-
A solution of 5.22 of (4-}lyl)-2-7enethylamine dissolved in 25 r/L of methanol is added to form a salt.

Cool to room temperature and leave for 2 hours, and collect precipitated crystals.

These crystals are further re-crystallized with methanol to obtain 3.4♂ crystals.

After suspending the crystals by adding 20rfLl of 10% caustic soda aqueous solution, l-(4-}lyl) was extracted with ether.
1-2-Phenethylamine is recovered.

The aqueous layer was acidified with hydrochloric acid, extracted with methylene chloride, and the solvent was distilled off to obtain 1.5f of l-}lansu 2,2-dimethyl-3-isobutoxycyclopropanecarboxylic acid.

[α) 2,S1 4 9° (Chloroform) Optical purity 92% 1.21 of this carboxylic acid was converted into 3-
3'-phenoxy α'-cyanopenzyl by reacting with phenoxy α-cyanobenzyl bromide 1.41
1.8 grams of l-trans-2.2-dimethyl-3-isoptoxycyclopropanecarboxylate were obtained.

Note that this compound exhibited approximately twice the insecticidal activity as compared to the dl-}trans ester.

Hereinafter, the symbol C will be added after the compound number to indicate that the acid moiety is the 1-trans form.

Example 10 d1-cis-2,2-dimethyl-3 obtained in Example 8
- 3.5 r of methoxycyclopropanecarboxylic acid is dissolved in 40 ml of methanol at 50°C, and a solution of 5.1 tiI of d-(4-tolyl)-2-7enethylamine dissolved in 251 rLl of methanol is added thereto.

The precipitated salt was subjected to the same operation as in Example 9 to obtain d-cis-2,2-dimethyl-3-methoxychloropropanecarboxylic acid 1.11.

Reference Example 1 White kerosene was added to 0.2 parts of the compound (1) of the present invention, and the total amount was 1 part.
0.2% oil solution is obtained as 00 parts.

Reference Example 2 White kerosene is added to 0.2 parts of the compound (2) of the present invention and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil agent.

Reference Example 3 To 20 parts of the compound (4) of the present invention, 10 parts of Solpol SM200 (registered trademark of Toho Chemical) and 70 parts of xylol were added and mixed and dissolved with stirring to obtain a 20% emulsion.

Reference Example 4 Compound (8) of the present invention 0. Part 4, Resmethrin 0.1
After dissolving 1.5 parts of octachlorodiprobyl ether in 28 parts of refined kerosene and filling it into an aerosol container and attaching a valve part, 70 parts of a propellant (liquefied petroleum gas) was pressurized and filled through the valve part. Get an aerosol.

Reference Example 5 The compound of the present invention (1.5 g, BHT0.5'iI) was added to a substrate for mosquito coils such as pyrethrum extract lees powder, wood flour, starch powder, etc.99.
0'? to obtain a mosquito coil by a known method.

Reference Example 6 Compound of the present invention α'j)0.4? , MGK-50261.
0P base material for mosquito coils 98.6ti! to obtain a mosquito coil by a known method.

Reference Example 7 3 parts of the compound (24) of the present invention and 97 parts of clay are thoroughly ground and mixed to obtain a 3% powder.

Reference example 8 40 parts of the present compound (30), 35 parts of diatomaceous earth, clay 2
0 parts of lauryl sulfonate, 3 parts of lauryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a permanent agent.

Test row 3 Among the emulsions obtained in Reference Example 3, compounds of the present invention (1), (
3), (4), (7), (9), (13), (16)
,01),(26),(self),(33),(rug(40)
), Sir, (2)-A, (17>-C, (30)-B,
A crude drug was immersed in a 2000-fold dilution of (44)-A for about 5 seconds, and after drying, the drug was placed in a petri dish and 10 healthy armyworm larvae were released.

The test insects were released twice, once on the day of immersion in the fresh leaves and 5 days later, and the mortality rate after 24 hours was determined.

Test Example 4 Compounds of the present invention (2), (4), (6), (IL (14 ), (
18), (2 stations (27), (31), (36). (3
A 1000-fold diluted solution of each of the emulsions containing (8), (4υ and (44)) with water was sprayed at 100 liters per square.

A parasitic rate survey two days later showed that the density had decreased to less than 1/10 of the pre-spraying density in each plot.

Test Example 5 One day before applying the insecticidal active ingredient to potted fava beans, a tree was infested with approximately 200 Aphrodites.

Among the permanent agents obtained in Reference Example 8, (1) and (5)
, (8), 0υ, 0, (19), (22), (2
4), (28), (35), (39), (42),
(4)-B, (12)-C, (25)-C and (3
7) A 4,000-fold diluted solution was sprayed on leaves infested with pests using a compressed air spray method at 10 TIll/pot, and the degree of damage was observed 2 days later.

As a result, no increase in damage was observed in either case.

Claims (1)

[Claims] 1 - General formula (wherein A is 01 and S, R1 is an alkyl group, an alkenyl group, a haloalkyl group, a haloalkenyl group, an alkoxyalkyl group, and the general formula ), (EV)
, (V), (VI), (■), (Vll), (IX),
Indicates a group represented by (X). Here, 1 is an integer from 1 to 5, m is an integer from 2 to 6, n is an integer from 1 to 3, and X is 0, S, CH2, CH2-CH
2, R3 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a haloalkyl group, or an alkoxynyl group, and R4 represents a hydrogen atom or a methyl group. Further, R2 represents a hydrogen atom, an ano group or an ethynyl group. ) and its optical and geometric isomers. 2 General formula (wherein R1 is an alkyl group, an alkenyl group, a haloalkyl group, a haloalkenyl group, an alkoxyalkyl group and a general formula ([), (III), (IIV), (V), (V
It shows groups represented by I), (■), (vMI), (■), and (X). Here, 1 is an integer from 1 to 5, m is an integer from 2 to 6, and n is an integer from 1 to 6.
3 is an integer, X is O1S1CH2, CH2-CH2, R3 is a hydrogen atom, lower alkyl group, lower alkenyl group, halogen atom, haloalkyl group, alkoxyl group, R. 4 represents a hydrogen atom or a methyl group. Further, R2 represents a hydrogen atom, a cyano group or an ethynyl group. ), the cyclopropanecarboxylic acid ester derivative according to claim 1, and its optical system and geometric isomer. The cyclopropanecarboxylic acid ester derivative according to claim 2, which is a compound represented by formula 3, and its optical and geometric isomers. The cyclopropanecarboxylic acid ester derivative according to claim 2, which is a compound represented by formula 4, and its optical and geometric isomers. The cyclopropanecarboxylic acid ester derivative according to claim 2, which is a compound represented by formula 5, and its optical and geometric isomers. Cyclopropanecarboxylic acid ester derivatives and optical and geometric isomers thereof according to claim 2, which are compounds represented by: 7. The cyclopropanecarboxylic acid ester derivative and optical and geometrical isomers thereof according to claim 2, which are compounds represented by formula 7. The cyclopropanecarboxylic acid ester derivative according to claim 2, which is a compound represented by formula 8, and its optical and geometric isomers. The cyclopropanecarboxylic acid 1 ester derivative and optical and geometric isomers thereof according to claim 2, which are compounds represented by formula 9. The cyclopropanecarboxylic acid ester derivative and optical and geometrical isomers thereof according to claim 2, which are compounds represented by formula 10. 11 General formula (wherein A is O, NH, S, R1 is an alkyl group,
Alkenyl groups, haloalkyl groups, haloalkenyl groups, alkoxyalkyl groups and general formulas (■), (III), (
IV), (V), (VI), (■), (vi), (IX
), (X) represents a group. Here, 1 is an integer from 1 to 5, m is an integer from 2 to 6, and n is an integer from 1 to 6.
3 is an integer; represent. ) or a reactive derivative thereof, and an alcohol represented by the general formula (where R2 represents a hydrogen atom, a cyano group, or an ethynyl group) or a reactive derivative thereof. General formula (where A, R1, and R2 have the same meanings as above)
A method for producing a cyclopropanecarboxylic acid ester derivative and its optical and geometric isomers. (m)
(IV), (V), (VI), (■), (%II), (
IX), represents a group represented by (X). In particular, 1 is an integer from 1 to 5, m is an integer from 2 to 6, and n is an integer from 1 to 6.
3 is an integer, X is 01S, CH2, CH2-CH2, R3 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halokene atom, a haloalkyl group, or an alkoxyl group, and R4 represents a hydrogen atom or a methyl group. Further, R2 represents a hydrogen atom, a cyano group or an ethynyl group. ) and its optical and geometric isomers. 13 General formula (in the formula, R1 and R2 represent the same meanings as in item 12 above)
The insecticide according to claim 1, which contains a cyclopropanecarboxylic acid ester derivative represented by: and its optical and geometric isomers. 14. The insecticide according to claim 13, which contains the cyclopropanecarboxylic acid ester derivative represented by formula 14 and its optical and geometric isomers. 14. The insecticide according to claim 13, which contains a cyclopropanecarboxylic acid ester derivative represented by formula 15 and its optical and geometric isomers. 14. The insecticide according to claim 13, which contains a cyclopropanecarboxylic acid ester derivative represented by formula 16 and its optical and geometric isomers. 14. The insecticide according to claim 13, which contains a cyclopropanecarboxylic acid ester derivative represented by formula 17 and its optical and geometric isomers. 14. The insecticide according to claim 13, which contains a cyclopropane carboxylic acid ester derivative represented by formula 18 and its optical and geometric isomers. The insecticide according to claim 13, which contains a cyclopropane carboxylic acid ester derivative represented by formula 19 and its optical and geometric isomers. **Insecticide according to claim 13, characterized in that it contains a cyclopropanecarboxylic acid ester derivative represented by formula 20 and its optical and geometric isomers. 14. The insecticide according to claim 13, which contains a cyclopropanecarboxylic acid ester derivative represented by Formula 21 and its optical and geometric isomers. 22 Contains a pyrethroid synergist as an adjuvant.■
The first insecticide of claim 1, which is characterized by the fact that the insecticide is harmful to the skin.