JPS6193176A - Cyclopropanecarboxylic acid ester derivative, preparation of cyclopropanecarboxylic acid ester derivative, and insecticide containing cyclopropanecarboxylic acid ester derivative - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R is alkyl, allyl, haloalkyl or haloalkenyl), and its optical and geometrical isomer. EXAMPLE:5'-Benzyl-3'-furylmethyl 2,2,3-trimethyl-3-methoxymethylcyclopropane carboxylate. USE:Insecticide for agricultural and horticultural use or for fumigation. PREPARATION:The compound of formula I can be prepared by reacting the cyclopropanecarboxylic acid of formula II or its reactive derivative with 5- benzyl-3-furylmethyl alcohol or its reactive derivative in a proper solvent, if necessary, in the presence of an acid acceptor or a catalyst consisting of an organic or inorganic base or acid.

Description

Detailed Description of the Invention (In the formula, R is an alkyl group having 1 to 4 carbon atoms, an allyl group,
Represents a haloalkyl group or haloalkenyl group having 1 or 2 carbon atoms. ), its optical and geometrical isomers, its production method, and an insecticide characterized by containing this compound as an active ingredient. Various alcohol components of chrysanthemum acid esters have been studied and put to practical use, but they are susceptible to oxidative decomposition by light, which has limited their use outdoors. Recently, research into acid components has been active, and a compound that is more stable to light than conventional pyrethroids has been discovered by replacing the methyl group with an atom of hydrogen. 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 inventor of the tree found that the compound represented by the above formula (Il) has an extremely excellent insecticidal effect on various sanitary pests and agricultural and horticultural pests as an insecticidal ingredient, while having extremely low toxicity to warm-blooded animals. I learned that it is very stable against light compared to conventional pyrethroids.In this way, the above formula (I
) is an excellent pest control composition that overcomes the drawback of conventional pyrethroids such as being unstable to light and has a broad insecticidal spectrum and low blueness. Propanecarboxylic acid can be easily obtained at low cost. The present invention was completed based on the above findings. The compound represented by the above formula (I) used as an active ingredient in the present invention is prepared according to the general method for producing esters using H3 (wherein R is an alkyl group having 1 to 4 carbon atoms, an allyl group,
It represents a haloalkyl group or a haloalknyl group having 1 to 2 carbon atoms. ) and 5-benzyl-3-furylmethyl alcohol or a reactive derivative thereof. Examples of reactive derivatives of carboxylic acids include acid halides, acid anhydrides, lower alkyl esters, and alkali metal salts. An example of a reactive derivative of alcohol is talolide. The reaction is carried out in a suitable solvent in the presence of a deoxidizing agent or an organic or inorganic base or acid as a catalyst, if necessary with heating. Representative examples of the compound represented by the above formula (I) are as follows, but the present invention is of course not limited to these.

5'-Benzyl-3'-furylmethyl 2,2.3-
) Dimethyl-3-methoxymethylcyclopropanecarpoki5'-benzyl-3'-furylmethyl 2,2.3-
Trimethyl-3-ethoxymethyldicyclopropane 5'-benzyl-3'-furylmethyl 2,2.3
-Trimethyl-3-n-butoxymethylcyclopropanecar5'-benzyl-3'-furylmethyl 2,2.3
-) Limethyl-3-n-propoxymethylcycloprobanca 5'-benzyl-3'-furylmethyl 2,2.3
- Trinotyl-3-(2,2-dichloroethoxymethyl)-cy5t-benzyl-3'-furylmethyl 2,2
．． 3-Triphthyl-3-impropoxymethylcyclopropane 5'-benzyl-3'-furylmethyl 2,2
．． 3-Triphthyl-3-thalolomethoxymethylcyclopropane rupoxylate n
1.55295'-benzyl-3'-furylmethyl
2,2,3-trimethyl-3-isobutoxymethylcyclopropanecar5'-benzyl-3'-furylmethyl
2,2.3-1-dimethyl-3-(2,2-dichlorovinyloxymethyl)51-benzyl-31-furylmethyl 2,2.3-)dimethyl-3-(1-methyl-n-
propoxymethyl) 5'-benzyl-3'-furylmethyl 2,2,3-) dimethyl-3-allyloxymethylcyclopropancaru The compound of the invention is a new compound, solid or liquid at room temperature, and organic solvent-free. It is generally easily soluble. Therefore, insecticides for spraying can be used as emulsions, oils, powders, wettable powders, aerosols, 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. 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 extremely stable to light compared to conventional pyrethroids and can be used as an agricultural and horticultural insecticide. ,2
,5-ditertiary-glutylhydroquinone (DBHQ
The stability can be further improved by adding antioxidants such as , ), etc. The compound of the present invention also includes ■-octylbicyclohebutene dicarboximide (trade name: MGK
-264), a mixture of N-octylbicyclohebutene dicarboximide and aryl sulfonate (trade name
The insecticidal effect can be further enhanced by adding synergists such as MGK-5026), octachlorodipropyrohyde/L/Nytyl, and piveronyl ptoxide fx. The compounds of the present invention may also be used with other insecticides such as Sumithion, DDVP.
, organic phosphorus agents such as diazinon, 1-naphthyl-N-
Carbamate agents such as methyl carbamate and 3,4-dimethyl-N-methyl carbamate, conventional pyrethroid insecticides such as pyrethrin, allethrin, phthalthrin, flamethrin, and phenothrin, pagun, galefron,
Insecticides such as rannate, acaricides, fungicides,
By mixing nematicides, herbicides, plant growth regulators, fertilizers, and other agricultural chemicals, a multipurpose composition with excellent efficacy can be obtained, and labor savings and synergistic effects among the drugs can be expected. It is. Next, the insecticidal test results of the compounds of the present invention will be shown.

Test example 1. Insecticidal test by spraying 0.2% white light solution (A) of the 11 compounds of the present invention of the above compound examples, 0.2% and piveronyl ptoxide 0.8
% white lamp solution (B), 0.1% and 7 talsuline 0.1%
For white lamp solution (C) and 0.2% white lamp solution of allethrin and phthalthrin, 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 numbers in parentheses indicate the mortality rate after 24 hours.

Test example 2. Insecticidal test by burning vapor Mosquito coils containing 0.5% of the insecticidal ingredient were prepared and tested for their effectiveness in making Culex Culex adults fall and roll over. This experiment was carried out in accordance with the method of Insect Control Science Vol. 16 (1951), p. 176, Nagasha, Katsuta et al., and the relative effectiveness of the incense sticks was calculated as follows. The sample drug number is the same as the effective test example 3. Insecticidal test by microdropping method Allethrin and the compound of the present invention were added to each of biveronyl ptoxide in an amount twice the amount of the active ingredient,
An acetone solution with a predetermined concentration was applied to the thoracic dorsal plate of adult house flies using a microsyringe, and the relative insecticidal power against allethrin and the synergistic effect with piveronylgutokitide were determined from the dead insects 24 hours later. An example of the present invention is shown. The compound names are the same as those in the active ingredient examples above.

Example 1 5.4 g of 2.2.3-)limethyl-3-(2,2-dichlorovinyloxymethyl)-cyclopropanecarboxylic acid chloride was dissolved in dry benzene 15-.
- Add 3.8 g of benzyl-3-furyl methyl alcohol dissolved in 20-20% of dry benzene, and then add Klt1
When 3 ml of dry pyridine was added as a coagulant, pyridine hydrochloride crystals were precipitated. After sealing the cap and leaving it overnight at room temperature, the crystals of pyridine hydrochloride were separated by F, the benzene solution was dried with nitric acid, and the benzene was distilled off under reduced pressure to give 5'-benzyl-3'-furylmethyl 2, 2.3-)limethyl-3
-(2,2-dichlorovinyloxymethyl)-cyclopropanecarboxylate) 7.3 g was obtained.

Example & 2.2.3-) Dimethyl-3-n-butoxymethylcyclopropanecarboxylic acid 43 g (!: 5-hen'
;iv - 3.8 g of 3-furyl methyl alcohol was dissolved in 150 g of benzene, and concentrated sulfuric acid 5- was added 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. Then, the reaction solution was washed with aqueous sodium bicarbonate and brine, and benzene was distilled off under reduced pressure to give 5'-benzyl-3'-
Furyl methyl 2,2.3-)limethyl-3-n-poxymethylcyclopropane rupoxylate s, sgt
[Ta.

Example 3 41 g of sodium salt of 2.2.3-trimethyl-3-ethoxymethylcyclopropanecarboxylic acid and 41 g of 5-benzyl-3-7ylmethyl chloride were mixed with 50 g of benzene.
After dissolving in 1nl and reacting under reflux in a nitrogen stream for 3 hours, the reaction solution was cooled and the precipitated salt was separated, thoroughly washed with brine, dried over nitric acid, and benzene was distilled off under reduced pressure. and 5'-benzyl-3'-7lylmethyl 2,2.
3-) 6.7 g of riftyl-3-ethoxymethylcyclopropane rupoxylate was obtained.

2.2.3-) 43g of methyl ester of dimethyl-3-allyloxymethylcyclopropanecarboxylic acid and 5-
3.8 g of benzyl-3-furyl methyl alcohol to 15
Heat to 0°CK. When the temperature reaches 150'C, 0.25 g of sodium is added and methanol distillation begins.

When the distillation of methanol has stopped, add 0.0% sodium.
Add 25 g and increase the temperature to 1 until the theoretical amount of methanol is obtained.
Keep the temperature around 50'C 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 sulfuric acid, and the ether was distilled off under reduced pressure to give 5'-benzyl-3'-furylmethyl.
6.5 g of 2,2,3-)dimethyl-3-allyloxymethylcyclopropane rupoxylate was obtained.

Example 5゜2.2.3-) 43 g of dimethyl-3-ingtoxymethylcyclopropanecarboxylic acid was mixed with 5 g of dimethylformamide.
Dissolve in 0W11 and add 41 g of 5-benzyl-3-7ylmethyl chloride. Triethylamine 41R1 was added under stirring and reacted with 60 to 80'Cf for 3 hours, then dissolved in ether. The ether solution was thoroughly washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over nitric acid, and the ether was distilled off under reduced pressure. 5'-benzyl-3'-7lylmethyl 2,
2.3-) 7.0 g of dimethyl-3-isoptoxymethylcycloprobancarboxylate was obtained.

Reference Example 1゜ White kerosene was added to 0.2 parts of the compound of the present invention (1) to obtain a 0.2% oil solution, making the total 100 parts.

Reference Example & White kerosene is added to 0.2 parts of the compound of the present invention (2) and 0.8 parts of piveronyl ptoxide to obtain an oil solution, with the total amount being 10 parts.

Reference Example 3 20 parts of the compound of the present invention (4) and Tsurupol 5M-200
(Toho Chemical registered trademark) and 70 parts of Kijirole were added and mixed and dissolved with stirring to obtain a 20% emulsion.

To the reference example, the compound of the present invention (510.4 parts, resmethrin 0.1 @
',, Dissolve 1.5 parts of octachlorodipropyl ether in 28 parts of refined kerosene, fill it into an aerosol container, attach the pulp part, and then pressurize and fill 70 parts of propellant (liquefied petroleum gas) through the pulp part. and get an aerosol.

Reference Example 5 0.5 g of the compound (6) of the present invention and 0.5 g of BHT were added to a substrate for mosquito coils such as pyrethrum extract lees powder, wood flour, starch powder, etc.99. O
g to obtain a mosquito coil by a known method.

Reference example 6゜Compound (8) of the present invention 0.4g1MGK-50261,0
6 was uniformly mixed with 98.6 g of a mosquito coil base material to obtain a mosquito coil by a known method.

Reference Example 7 3 parts of the compound (9) of the present invention and 97 parts of clay were thoroughly ground and mixed to obtain a 3% powder.

Reference Example 8 40 parts of the compound of the present invention (l(2), 35 parts of diatomaceous earth, 20 parts of clay, 3 m of lacryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder.

Test Example Compounds (3), (4), (8) and (11) of the present invention from the emulsion obtained in Reference Example 3 were applied to a field of radish at the 5th to 6th leaf stage in which the melon peach aphid was abundantly infested. A 1000-fold diluted solution of each emulsion contained in water was sprayed on 10017 strips. A parasitic rate survey after 2 days showed that the density was 1/10 of the pre-spraying density.
The number decreased in each ward as follows.

Test Example 5 Approximately 200 aphids were infested on one day before applying the insecticidal active ingredient to potted fava beans. Among the hydrating agents obtained in Reference Example 8, (2), (7), (
9) and (spray the 4000-fold diluted solution of the field on the leaves infested with compressed air using the compressed air stripe method,
The degree of damage was observed after several days. As a result, no increase in the degree of damage was observed in either case.

Test Example 6゜Among the emulsions obtained in Reference Example 3, compounds of the present invention (1), (
Fresh leaves of 2000-fold diluted solution K of (6) and (lt) were immersed in the chemical solution for about 5 seconds, and after the chemical solution was dried, they were placed in a petri dish and 10 healthy larvae of armyworm were released. The test insects were released twice, once on the day of soaking the fresh leaves and 5 days later, and after 24 hours dead insects were obtained according to Example 7 and Reference Example 7 (2), (5), (9). Each of the powders of (10) and (10) is uniformly sprinkled on the bottom of a tall glass Petri dish with a diameter of 14 CII+ at a rate of 2g1rd, and the bottom 1c+++ is coated with Bac- on the wall surface. Adult German cockroaches were released into it, 10 in each group, and 30
After 3 days of contact with the powder for a minute and transferring the cockroaches to a new container, more than 80% of the cockroaches could be killed by either powder.

Claims (4)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼... (I) (In the formula, R is an alkyl group having 1 to 4 carbon atoms, an allyl group,
It shows a haloalkyl group and a haloalkenyl group having 1 to 2 carbon atoms. ) and its optical and geometric isomers. (2) General formula▲ Numerical formulas, chemical formulas, tables, etc.▼・・・・・・(II) (In the formula, R is an alkyl group having 1 to 4 carbon atoms, an allyl group,
It shows a haloalkyl group and a haloalkenyl group having 1 to 2 carbon atoms. ) is a general formula characterized by reacting cyclopropanecarboxylic acid or its reactive derivative with 5-benzyl-3-furylmethyl alcohol or its reactive derivative ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼・...(I) A method for producing a cyclopropane carboxylic acid ester derivative represented by (R here has the same meaning as above). (3) General formula ▲ Numerical formula, chemical formula, table, etc. ▼... (I) (In the formula, R is an alkyl group having 1 to 4 carbon atoms, an allyl group,
It represents a haloalkyl group or a haloalkenyl group having 1 to 2 carbon atoms. ) An insecticide characterized by containing a cyclopropanecarboxylic acid ester derivative represented by: (4) The insecticide according to claim (3), which contains a pyrethroid synergist as an adjuvant.