JPS6187687A - Insecticide and acaricide containing organosilicon aromatic alkane derivative and their production - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (R1 and R2 are H, halogen, 1-4C alkyl, halomethyl, methoxy, ethoxy, difluoromethoxy, or R1 and R2 are linked to form methylenedioxy; X is O, or methyl; A is O, methylene, amino, or methylamino; R3 is H, or F; R4 is H, halogen, or methyl). EXAMPLE:Dimethyl(4-ethoxyphenyl){3-(3-pheoxy)phenylpropyl silane} shown by the formula II. USE:An insecticide and an acaricide. PREPARATION:An organosilicon aromatic compound shown by the formula III [M is metal atom (Na, K, Li, etc.)] is reacted with a compound shown by the formula IV (Y is halogen, or reactive derivative of OH).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (wherein lumis are the same or different, hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, halomethyl group, methoxy group, ethoxy group, difluoro A methoxy group or 9 represents a methylenedioxy group.

or an oxygen atom or a methylene group, A is an oxygen atom,
Represents a methylene group, an amino group, a methylamine group, or a formylamine group.

- represents a hydrogen atom or a fluorine atom, RIFi represents a hydrogen atom, a halogen atom, or a methyl group. The present invention relates to an insecticide and acaricide characterized by containing an organosilicon-based aromatic alkane derivative represented by () as an active ingredient, and a method for producing the same.

In recent years, research has been widely conducted on analogues of pyrethrin, a natural insecticidal ingredient, with modified chemical structures. High insecticidal activity has been found in a compound that contains the following compounds (Japanese Unexamined Patent Publication No. v858-201737).

Although these compounds are being widely developed as pesticides to replace conventional organic phosphorus agents and carbamate agents, they are unable to adequately deal with the problem of pyrethroid resistance that will arise in the future.

■Poor penetration into the plant body. ■In particular, the problems inherent to pyrethroids, such as high toxicity to fish, have not been sufficiently improved for compounds of type (5)).

The present inventors continued their intensive research to find even more useful insecticidal and acaricidal ingredients, and as a result, they found that by introducing silicon element, which is an alternative element to carbon element, the above disadvantages ①, ②, and ③ were significantly improved. On the other hand, the present invention was completed based on the knowledge that the insecticidal efficacy was enhanced compared to the original compound, and the toxicity to warm-blooded animals was further reduced. Although there are still many unknown points as to why the introduction of silicon element is effective, it is presumed that it is due to empty 3d orbitals existing in the outer shell of silicon atoms.

The compound represented by the above formula (I) used as an active ingredient in the present invention has the general formula (II) CH=.

(In the formula, R1 and R1 are the same or different, hydrogen atom, halogen atom, alkyl group having 1 to 4 carbon atoms, halomethyl group, methoxy group, ethoxy group, difluorometh9oxy group, or - and methylene Represents a dioxy group.Also, M
represents a metal atom (Ha, Ni, LL, etc.). ) and the general formula (in the formula, or an oxygen atom or a methylene atom, A represents an oxygen atom, a methylene group, an amino group, a methylamino group, or a formylamino group; R is a hydrogen atom) Alternatively, it can be prepared by reacting a fluorine atom with a compound represented by (R represents a hydrogen atom, a halogen atom, or a methyl group; Y represents a halogen or a reactive derivative of a hydroxyl group). The reaction is carried out in a suitable solvent, optionally in the presence of a catalyst, and optionally with heating. The above formula (I)
Representative examples of compounds represented by are as follows,
Of course, the present invention is not limited to these.

enoxy) phenylpropyl I silane n 201.5641 dibenzyloxymethyl) silane n 201.5653
enoxy-4-fluoro)phenylpropyl I siladimethyl (4-ethoxyphenyl) i3-(3-aN-1f
4-taloloanilino)phenyl Iprofluorophenoxy)-4-fluorobenzyloxy-[-(N-formyl-4-methylanilino)phenyl)propylcosilane n 1.5738-1nilino4-fluorobenzyloxymethyl)silane
n 201.579013-(4-bromobenzyl)phenyl)furobirxilane
n 201.5765 dimethylphenyl f3-(
3-phenoxy) dimethyl (4-methoxyphenyl J3
-(N-methylanilino)-4-fluorobenzyloxymethyl silane n201.56
92J D dimethyl (3-chloro-4-trifluoromethylphenyl) ~3
-(N-formyl-4-7fluoroanilino)-4-fluoropenzyloxymethylnosiladimethyl(3,4-dimethylphenyl)(3-J3-(4-fluoro7e/L
r)phenyl7propyl]silane
n 201.5586-(4-bromoanilino)
Benzyloxymethyl J silane
n 201.5833)(3-(3-benzyl-4
-]lheolophenyl)propyl silane
n 201.5725D dimethyl (3-methyl-4-fluorophenyl) f3-
(4-bromophenoxy)-4-fluoroben-methylanilino)benzyloxymethyl Isilanedimethyl(3-7'-4-bromofluoromethylphenyl)C
3-(3-(4-methylphenoxy)-4-fluorophenylJpropyl)silane n" 1.5794 -(4-iodobenzylbenzyloxymethyl)silane n201.5751dimethyl4-chlorophenyl)(3-( 3-(4-fluoroanilino)phenyl) furovir xilane (3-(N
-Formyl-4-chloroanilino)benzyloxymethylmisilane n 201.5740-(4-chlorophenoxy)-4-fluorobenzyloxymethyl 1silane n 201.5659dimethyl(4-chlorophenyl)43-(3-phenoxyphenyl) Propyl)silane n201.5592 Orophenoxy)benzyloxymethylmisilane n”
1.5605 The compound used as an active ingredient in the insecticide and acaricide of the present invention is a new compound, is solid or liquid at room temperature, and is generally easily soluble in organic solvents. Therefore, insecticides and acaricides for spraying can be used as emulsions, oils, powders, wettable powders, aerosols, etc. They can also be mixed with wood flour or other suitable base materials for fumigation such as mosquito coils. Can be used as an insecticide and acaricide.

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 good as a mosquito coil. Show effectiveness. The compound of the present invention is more stable to light than conventional pyrethroid traps, has a broader insecticidal and acaricidal spectrum, has low toxicity, has low toxicity to fish, and is inexpensive, making it easier to use than conventional organic phosphorus traps. It can be used as an agricultural and horticultural insecticide and acaricide in place of organochlorine insecticides.

The insecticides and acaricides of the present invention can be used against sanitary pests such as flies, mosquitoes, and cockroaches, as well as organophosphorus agent- and carbamate-resistant black leafhoppers, planthoppers, stink bugs, armyworm moths, diamondback moths, tapako moths, bean thrushes, It is extremely useful for controlling agricultural pests such as yam moths, cabbage moths, chestnut beetles, leaf beetles, aphids, and scale insects, grain storage pests such as black elephants, mites, and the like. Furthermore, the compound of the present invention has significantly reduced toxicity to fish compared to conventional pyrethroids, and has good permeability into plants, making it possible to apply it as an insecticide for paddy rice. In addition, the insecticides and acaricides of the present invention KN-octylbicyclohebutene dicarboximide (trade name MGK-264), a mixture of N-octylbicyclohebutene dicarboximide and aryl sulfonate (trade name MGK-s026) , cynevirin 500, octachlorodipropyl ether,
The insecticidal effect can be further enhanced by adding a synergist such as piperonyl ptoxide. In addition, other insecticides such as fenitrothion, D
DVP, diazinon, propafos, organic phosphorus agents such as pyridafenthione, NAC%M'['MO, BPMC
.

Carbamate agents such as PHC, conventional pyrethroid insecticides such as pyrethrin, allethrin, phenothrin, 7lametrin, phenothrin, permethrin, cypermethrin, decametrin, fenvalerate, fenpropanate, insecticides such as cartap, clo I lefenamidine, menmyl Or acaricides, fungicides, nematicides,
By mixing herbicides, plant growth regulators, fertilizers, and other agricultural chemicals, highly effective multipurpose compositions can be obtained, and labor savings and synergistic effects among the drugs can be fully expected.

Next, examples of synthesizing compounds used as active ingredients in the present invention will be shown.

The metal organosilicon aromatic compound represented by the general formula (II) is prepared by adding Na and K to chlorosilane according to FIG.

It is obtained by reacting a metal element such as Ll.

On the other hand, the compound of general formula (-) can be prepared according to FIG. 2 using the alcohol component constituting the pyrethroid.

Synthesis Example 1 0.4 g of metallic lithium was added to 50% of dry tetrahydrofuran under a nitrogen stream. The suspension was cooled to -50°C with dry ice-acetone, and a solution of 4.1 g of dimethyl(4-chlorophenyl)chlorosilane dissolved in 20% of dry tetrahydro-7ran was added dropwise to this suspension over 30 minutes. After reacting at this temperature for 1 hour, the liquid temperature was gradually raised to 0°C and stirred for an additional 1 hour to generate lithium silane. The reaction solution was cooled to -20°C and then heated under a nitrogen stream.
(3-phenoxy)phenylpropyl chloride 4.9
A solution prepared by dissolving 1.0 g of 1.0 g in 40 rne of dry tetrahydro 7ran was added dropwise over 1 hour. After further stirring at room temperature for 2 hours, water was carefully added dropwise to the reaction solution while cooling to decompose the weekly lithium. After extraction with benzene, the benzene solution was washed with saturated brine and dried over sulfur salt. The oil obtained by distilling off benzene under reduced pressure was purified by column chromatography using 100 g of silica gel to obtain 6.4 g of dimethyl (4-chlorophenyl) J, 3-(3-phenoxyphenyl)probylnosilane.

Synthesis Example 2 0.0% of metallic potassium was added to 40% of dry ether under a stream of nitrogen.
9 g was added and the suspension was cooled to -40°C. A solution of 4.0 g of dimethyl(4-methoxyphenyl)chlorosilane dissolved in 20% of dry ether was added to the suspension.
It was dripped in minutes. After stirring at -40°C for 2 hours, the liquid temperature was gradually raised to 0°C and stirred for another 1 hour to complete the formation of caricum silane. The reaction solution was heated to -40°C again.
3-(N-methylanilino) under a nitrogen stream.
-4-fluorobenzyloxymethyl chloride 5.6
A solution prepared by dissolving 40 g of dry ether was added dropwise over 1 hour. After reacting for 1 hour at -40°C and overnight at room temperature, water was added.
The ether layer was separated. After distilling off the solvent, the resulting residue was purified by column chromatography using 100 g of silica gel to obtain the desired dimethyl (4-methoxyphenyl) (3
6.8 g of -(N-methylanilino)-4-fluorobenzyloxymethyl I silane was obtained.

Similarly, Sodicum dimethyl(3-methoxy-4-chloromethylphenyl)silane,! :3-(3-benzyl-4-fluorophenyl)furobyl bromide to dimethyl(3-methoxy-4-talolomethylphenyl)
'3-(3-benzyl-4-fluorophenyl)propyl (silane), lyticum dimethyl (3-fluoro-4-
propylphenyl)silant 3-(N-formyl-4-
p of chloroanilino)benzyloxymethyl alcohol
-Toluenesulfonic acid ester to obtain dimethyl(3-fluoro-4-propylphenyl)(3-(N-formyl-4-chloroanilino)benzyloxymethyl(silane).

Next, in order to make it clearer that the composition provided by the present invention is excellent, the results of testing the effectiveness will be shown.

Test example 1. Insecticidal test with grass cloth A 0.2% white light solution of the compound of the present invention (A), 0.2% and a white light solution of 0.8% Cynevirin 500 (B), 0.
The fall/upside-down rate of house flies was determined for a white light solution of 1% and 0.1% phthalthrine (C), and a white light solution of 0.2% each of 7 tarthrine and compound (A), and the relative effectiveness of the test drug was determined. was calculated, and the mortality rate after 24 hours was determined as follows.

This H3 (compound described in JP-A No. 1111355-2017378) Test Example 2. Insecticidal test by fumigation Mosquito coils containing 0.5% of the insecticidal ingredient were produced and tested for their effectiveness in making adult Culex mosquitoes 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 that of the active ingredient example above.

Test example 8. Insecticidal test by microdropping method Each of the control compound (A) and the compound of the present invention and ``ranibiperonyl ptoxide'' were added in twice the amount of the active ingredient, and a predetermined amount of agriculturally produced acetone solution was mixed in a micrometer. Apply to the thoracic dorsal plate of adult house flies with a syringe,
The relative insecticidal activity with respect to the control compound and the synergistic effect of biveronyl ptoxide were investigated based on the mortality rate after hours, and the results were as follows.

Comparative Compound (A1) Next, an example of formulation will be shown, but the formulation does not require any special conditions similar to general agricultural chemicals and can be prepared by a method that is well-understood by art technicians.

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 2 White kerosene was added to 0.2 parts of the compound of the present invention (4) and 0.8 parts of biperonyl ptoxide to make a total of 100 parts to obtain an oil agent.

Reference Example 8゜Compound of the present invention (7120 parts was added to Trupol 8M-200 (
10 parts of Toho Chemical (registered trademark) and 70 parts of Kijirole were added and stirred and dissolved to obtain a 20% emulsion.

Reference Example 4 0.4 parts of the present compound (9), 0.1 part of resmethrin, and 1.5 parts of octachlorodiprobyl ether I were dissolved in 28 parts of refined kerosene, filled into an aerosol container, and the pulp portion was dissolved. After installation, 70 parts of propellant (liquefied petroleum gas) is pressurized and filled through the pulp portion to obtain an aerosol.

Reference Example 5゜0.5 g of the present compound 0→0.5 g 1 BIT was added to a base material for mosquito coils such as pyrethrum extract lees powder, wood flour, starch powder, etc.99.
The mixture is uniformly mixed with Og and a mosquito coil is obtained by a known method.

Reference Example 6゜Compound θ of the present invention 0.4g, MGK-50261.0g
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: 0.3 parts of the compound of the present invention @1) and 99.7 parts of clay are ground and mixed to obtain a 0.3% powder.

Reference example 8゜40 parts of the compound of the present invention, 35 parts of diatomaceous earth, 20 parts of clay
1 part, 3 parts of lacryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder.

Test Example 4 Compounds of the present invention (3), (7), (1O), (I) of the emulsion obtained in Reference Example 3 were applied to a radish field at the 5-6 leaf stage where a large number of green peach aphids were infested. A 1000-fold dilution with water of each emulsion containing the ring, (sha) and side was made into 1
001! /Scattered per counter. A parasitism survey conducted two days later showed that the parasitism density had decreased to less than 1/10 of the pre-spraying density in each ward.

Test Example 5 Among the emulsions obtained in Reference Example 3, compounds of the present invention (2), (
4), (7 in (river, (151, C1η and (231(
7) Fresh leaves were immersed in a 2000-fold diluted solution for about 5 seconds, and after drying the solution, 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 immersion in the fresh leaves and 5 days later, and the mortality rate 24 hours later was determined.

Test Example 6: Approximately 200 aphids were infested on each tree one day before applying the insecticidal ingredient to potted fava beans. Reference example 8
(2), (6), (9) of the hydratactic agents obtained by
A 4000-fold diluted solution of 241 was sprayed on leaves infested with insects using a compressed air spray method per LM/pot, and the degree of damage was observed after 2 days. However, no increase in the degree of damage was observed.

Test Example 7゜ (1), (5), (8), Q obtained by Reference Example 7
Each of the powders of odor, αη and @0 was uniformly sprinkled on the bottom of a waist-high glass petri dish with a diameter of 14a at a rate of 2g1rd,
Apply the tree to the wall, leaving the bottom part 1c*. Adult German cockroaches were released into it, 10 in each group, and 30
If the cockroaches were left in contact for a minute and transferred to a new container, more than 80% of the cockroaches could be killed three days later with either powder.

Test Example 8: Four leaves of potted green beans 5 days after sowing are infested with 10 female adult mites per leaf and stored in a constant temperature room at 27°C. After 6 days, the emulsion obtained in Reference Example 3 (
4), (7), 100p100pp of the active ingredients were diluted with water, and IO+m' was applied to each pot on a turntable. After 10 days, the number of parasitic mites was determined by a plant specialist. investigated. As a result, all of the insecticides and acaricides of the present invention were used as control agents for the test example 9゜ carp, and were tested according to the agricultural policy notification No. B% 2735 (
(November 25, 1940) Toxicity tests on fish were carried out according to the Wk method, and compounds of the present invention (2), (8), (11
), (1 o'clock and @phantom TLm48 (ppm) were determined to be 20 or more in both cases.

Procedural amendment (voluntary) LL month L5, 1988 1.Display of the incident 1981 Patent Application No. 2099751 3. Person who makes corrections 4. Agent 5. Date of amendment order 7. Subject of correction Full statement 8. Contents of amendment As per attached sheet

Claims (2)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(I) (In the formula, R_1 and R_2 are the same or different, hydrogen atom, halogen atom, alkyl having 1 to 4 carbon atoms) group, halomethyl group, methoxy group, ethoxy group, difluoromethoxy group, or R_1 and R_2 represent a methylenedioxy group. X is an oxygen atom or a methylene group, A is an oxygen atom,
Represents a methylene group, an amino group, a methylamino group, or a formylamino group. R_3 represents a hydrogen atom or a fluorine atom, and R_4 represents a hydrogen atom, a halogen atom, or a methyl group. ) An insecticide and acaricide characterized by containing an organosilicon aromatic alkane derivative represented by: (2) General formula ▲ Numerical formula, chemical formula, table, etc. ▼・・・・・・(II) (In the formula, R_1 and R_2 are the same or different, hydrogen atom, halogen atom, alkyl having 1 to 4 carbon atoms) group, halomethyl group, methoxy group, ethoxy group, difluoromethoxy group, or R_1 and R_2 represent a methylenedioxy group. Also, M represents a metal atom (Na, K, Li, etc.). Group compounds and general formulas▲Mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(III) (In the formula, X is an oxygen atom or a methylene atom, and A is an oxygen atom, methylene group, amino group, methylamino or formylamino group.R_3 represents a hydrogen atom or a fluorine atom, R_4 represents a hydrogen atom, a halogen atom, or a methyl group.Y represents a halogen atom or a reactive derivative of a hydroxyl group). General formulas obtained by reacting ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (I) (Here, R_1, R_2, R_3, R_4, X, and A have the same meanings as above.) 1. A method for producing an insecticide or acaricide containing an organosilicon aromatic alkane derivative represented by: