JPH04149184A - Controller of acarids and acaricidal silane compound - Google Patents

Abstract

PURPOSE:To obtain a controller of acarids showing excellent nit killing activity, larva killing activity and young acarid killing activity over acarids living in plants, especially at stages of nits, larvae and young imagoes of acarid, comprising a specific silane compound as an active ingredient. CONSTITUTION:The objective controller of acarids comprising a compound shown by formula I (X is H, F or Cl; Y and Z are H, F, Cl, Br, lower alkyl, lower alkoxy or fluoroalkoxy; R is 1-10C straight-chain, cyclic alkyl, alkenyl or alkynyl) as an active ingredient. A monofluoromethylsilane compound shown by formula II wherein the group X is F is a new substance and is produced by reacting a monochloromethylsilane with metal magnesium to give a corresponding Grignard reagent and then electrophilically reacting the reagent with a fluorinating reagent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel mite control agent, a novel silane compound having acaricidal properties, and a method for producing the silane compound.

[Prior Art and Problems] Various compounds including organic phosphorus compounds, dinitrobenzene compounds, thiocarbamate compounds, etc. are used to control mites. However, in recent years, mites that are resistant to these drugs have appeared, and for the purpose of controlling them, there has been a desire to develop a new type of mite agent with a structure different from that of conventional drugs.

[Means for Solving the Problem] The present inventors have focused on organosilicon compounds and have conducted extensive research with the aim of developing effective, economical, and safe mite control agents from among these compounds. Ta. As a result, the general formula 1 (wherein, or represents a fluoroalkoxy group, and R represents a linear or cyclic alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms. The present invention was completed by the discovery, synthesis of surrounding compounds, and investigation of their activity.

That is, the present invention provides 1, general formula 1 (wherein, Represents a lower alkoxy group or a fluoroalkoxy group, and R represents a linear straddled cyclic alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms. A mite control agent characterized by containing it as an active ingredient.

2, General Formula 2 (However, in the formula, Y and 2 each represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a lower alkyl group, a lower alkoxy group, or a fluoroalkoxy group, and R has 1 to 10 carbon atoms. A monofluoromethylsilane compound represented by a linear or cyclic alkyl group, alkenyl group, or alkynyl group.

3. Represented by the general formula 2, which is characterized in that monochloromethylsilane in which X is a chlorine atom is reacted with metallic magnesium to obtain a corresponding Grignard reagent, which is then reacted with an electrophilic fluorinating reagent. A method for producing a monofluoromethylsilane compound.

4. A method for producing a monofluoromethylsilane compound represented by the general formula 2, which comprises reacting monochloromethylsilane in which X in the general formula 1 is a chlorine atom with a fluorine anion reagent in the presence of a crown ether.

It is related to.

The present invention will be explained in detail below.

The compound of the present invention is effective against various plant-parasitic spider mites, such as the two-spotted spider mite and the orange spider mite, and has particularly excellent ovicidal, larvicidal, and nymphicidal powers against the egg and nymph stages of various mites. It shows. The acarids that can actually be controlled by this drug include Boophilus m1croplus Canes.
triniPo], yphagtarsonemus
1atus Banks Panonychus cit
ri McGregorTetranycus cin
nabarinus BoisduvalTetran
ycus urticae EachRhizogl,
Yphus echinophus Fumouze
et Robin Red spider mite Tea dust mite Citrus spider mite False red spider mite Red spider mite Bull tick Broad m1te
Citrus red m1te Carmine
5pider mite Two-spotted 5
Examples include pider m1te and bulb m1te.

These drugs have low toxicity to warm-blooded animals and are highly safe when used for pest control.

The synthesis of these compounds is carried out as follows using methyltrichlorosilane or chloromethyltrichlorosilane as a raw material.

That is, among the compounds of general formula 1, the compound in which X is hydrogen or chlorine atom is a conventionally known compound, and is disclosed in Japanese Patent Publication No. 62-535.
15, using methyltrichlorosilane or chloromethyltrichlorosilane as a raw material, and adding an organometallic compound such as a Grignard reagent or a lithium reagent derived from a substituted aromatic halide to these, It can be synthesized by sequentially reacting to yield diarylchloromethylchlorosilane, which is further reacted with an alkyl metal reagent represented by RM.

Furthermore, a general method for synthesizing compounds in which X is fluorine has not been known so far, and only a very limited number of compounds with simple structures have been synthesized. Some examples include:

l) Method using molecular fluorine References lN0RG, CHEM, 21524 (198
2) J, ORGANOMET, CHEM, 145167
(1978) 2) Method using antimony pentafluoride References J, ORGANOMETAL, CHEM, 1
92347 (1980) 3) Insertion reaction of fluorobromomethylcarbene produced by thermal decomposition of phenyl(fluorodibromomethyl)mercury into a silicon-hydrogen bond;
Subsequently (Method by reductive deodorization reaction with tributyltin hydride Reference J, ORGANOMET, C) IEM, 51
77 (1973) However, these methods use very harsh reaction conditions, making it difficult to control the reaction, and the product is a mixture of monofluoromethylsilane, difluoromethylsilane, and trifluoromethylsilane. They have drawbacks such as an unavoidable drop in yield, difficulty in separating them from each other, and a very complicated reaction method.

The methods known so far have low yields,
Isolation of the target component was also difficult and impractical.

The present inventors have developed a method for selectively producing monofluoromethylsilane under mild conditions using monochloromethylsilane as a raw material, and have synthesized various compounds using this method.

The first method is to react monochloromethylsilane with metallic magnesium to form the corresponding Grignard reagent, which is then reacted with an electrophilic fluorinating reagent such as fluoropyridinium salts. Since the reaction produces only fluoromethylsilane,
It is characterized in that the product can be easily separated and purified, and monofluoromethylsilanes having arbitrary substituents can be easily synthesized in high yield.

Conversion of monochloromethylsilane to a Grignard reagent is carried out under conventional Grignard reaction conditions. That is, it is carried out by reacting with metallic magnesium in the presence of an ether solvent such as ethyl ether, butyl ether, or tetrahydrofuran, and the Grignard reagent is obtained as a solution in these solvents.

Next, the fluoropyridinium salts used to react with the Grignard reagent synthesized by the above reaction include fluoropyridinium trifluoromethanesulfonate, fluoro-3,5-dichloropyridinium trifluoromethanesulfonate, fluoro-2,4,
6-trimethylpyridinium trifluoromethanesulfonate, etc., which can be prepared by solution in a suitable organic solvent, e.g., tetrahydrofuran, acetonitrile solution M
Then, to the Grignard reagent solution obtained in the above reaction, -
The reaction is carried out dropwise at a temperature of 20 to 50°C, preferably 0 to 10°C.

The monofluoromethylsilanes synthesized in this manner are isolated from the reaction solution by conventional operations. That is, water, dilute hydrochloric acid, ammonium chloride aqueous solution, etc. are added to the reaction solution, and this is extracted with an organic solvent that is immiscible with water, such as ethyl acetate or ethyl ether. After stripping the solvent, the residue is distilled under reduced pressure as necessary. It is isolated by separation and purification using methods such as chromatography.

According to the method described herein, if a monochloromethylsilane compound can be converted into its corresponding Grignard reagent, it can be easily converted into a corresponding monofluoromethylsilane compound.

The second method is to react monochloromethylsilane synthesized in the above reaction with a fluorine anion reagent in the presence of a suitable reaction aid. In carbon compounds, a method for synthesizing fluoroalkylsilanes by substituting a halogen group, hydroxyl group, or substituted hydroxyl group with a fluorine anion has already been known.

However, in silicon compounds, since the affinity between silicon atoms and fluorine atoms is extremely high, it was expected that such a slow reaction would cause cleavage of silicon-carbon bonds. As a result of intensive investigation of reaction conditions, we discovered that it is also possible to synthesize fluoromethylsilane compounds by reacting chloromethylsilane with a reagent that generates fluoride ions in the presence of crown ether. .

1 F-1 -5i-CHzCl --si-cl (21" Reagents containing fluoride ions used in this reaction include, for example, cesium fluoride, potassium fluoride, sodium fluoride, tetra-n-butylammonium fluoride, Examples of reaction aids include dicyclohexano-24-crown-8, dicyclohexano-18-crown-6, dibenzo-30-crown-10, and dibenzo-crown-10.
24-crown-8, dibenzo-18-crown-6,
Crown ethers such as 18-crown-6,]]5-crown-, organic sulfonyl fluoride reagents such as p-toluenesulfonyl fluoride and methanesulfonyl fluoride, and reaction solvents include diethyl ether, tetrahydrofuran, and dioxane. ethers such as, hydrocarbons such as pentane, hexane, benzene, toluene, etc., aprotic polar solvents such as dimethyl sulfoxide, dimethylformamide, hexamethylphosphortriamide, etc. can be used, and two or more of these can be mixed. It can also be used as Furthermore, it is also possible to simultaneously use a molecular sieve in order to maintain the reaction system in a non-aqueous state.

In this reaction, there are no restrictions on the reaction substrate, and a wide range of monochloromethylsilane can be used.Also, since it is an extremely mild and highly selective reaction, the product can be easily separated and purified, so monofluoromethylsilane is used. The purpose of the present invention is to provide a method for easily synthesizing these compounds with high yield.

When actually applying the compound of the present invention, it can be used as it is without adding any other ingredients, but in order to make it easier to use as a pesticidal agent, a carrier is added to form a preparation, which can be diluted as necessary. Generally, it is applied by

The compound of the present invention does not require any special conditions and can be formulated into emulsions, wettable powders, powders, granules, fine granules, oils, aerosols, heat-smoking agents, etc. using known methods similar to general agricultural chemicals. Fumigants such as Foraking, non-heated fumigants,
Poison baits can be prepared in any series, and these can be used for various purposes depending on the purpose.

Furthermore, these compounds can be used in combination of two or more types to express superior acaricidal power, and can also be used as other insecticides, acaricides, fungicides, nematicides, herbicides, and plant growth agents. Regulators, fertilizers, BT agents, insect hormones,
By mixing it with other agricultural chemicals, it is possible to create a multipurpose composition with even greater efficacy, and a synergistic effect can also be expected.

It can also be used with various other synergists, thereby increasing its efficacy several times.

The compounds of the present invention have high stability against light, heat, oxidation, etc., but if necessary, antioxidants or ultraviolet absorbers may be added, such as 2,6-tert-butyl-4-methylphenol (BHT), butyl Hydroxyanisole (B
HA), phenol derivatives such as bisphenol derivatives, and also phenyl-α-naphthylamine, phenyl-
By adding an appropriate amount of arylamines such as β-naphthylamine, a condensate of phenetidine and acetone, or benzophenone compounds as a stabilizer, a composition with more stable effects can be obtained. The following compounds are exemplified as the compound represented by the general formula 1 according to the present invention.

1 4-Fluorophenyldimethylp
henylsilane2 4-Fluorophen
ylmethylphenyl, fluorometh
yl-1lane 3 4-Fluorophenylmethylphe
nylchloromethyl-1lane 4 bis(4-fluorophenyl)dia
+ethy1.5ilane5 bis(4-flu
orophenyl) methylfluoromet
hyl-1lane 6 bis(4-fluorophenyl)met
hylchloromethyl-si 1ane 7 bis(4-fluorophenyl)vin
y1methylsilane8 bis(4-fl
urophenyl)vinylfluoromet
hyl-1lane 9 bis(4-fluorophenyl)vin
ylchloromethyl-1lane bis (4-fl, uorophenyl) cycle
opropylchloro-methylsilan
e bis(4-fluorophenyl)cyclop
ropylmethyl-ilane bis(4-fluorophenyl)cyclop
ropyfluoro-methylsilane bis(4-fluorophenyl)-n-dec
ylchloromethyl-ilane bis(4-fluorophenyl)-n-dec
y1methylsilaneb3s(4-fluor
ophenyl)-n-decylfluoromet
hyl-1lane bis (4-chlorophenyl) chlo
romethylmethyl-si 1ane bis (4-chlorophenyl) fluo
romethylmethyl-1lane bis (4-chlorophenyl) dime
thylsi lanebis (4-chloroph
enyl)chloromethylvinyl-1l
ane bi,s(4-chlorobenyl)fluor
omethylvinyisilane bis(4-chlorophenyl)methyl
vinylsilanebis (4-chloroph
enyl) cyclopropylehloro-me
thylsilane bis(4-chlorophenyl)cyclop
ropyfluoro-methylsilane bis (4-chloropllenyl) cycle
opropylmethyl-silane bis(4-chlorophenyl)ethylc
chloromethyl-silane bis(4-chlorophenyl)-1-pro
pynylchloro-methylsilane bis(4-chlorophenyl)-3,3,3
-trifluoro-propylmethylsi
lanebjs(4-fluorophenyl)-3
,3,3-trifluoro-propylmeth
ylsilanebis (4-chloropheny
l) propylchloromethyl-sil
ane bis(4-chlorophenyl)butylc
chloromethyl-silane bis(4-chlorophenyl)-2-met
hylpropyl-chloromethylsil
anebis (4-chlorophenyl) pen
tylchlorornethyl-silane bis(4-chlorophenyl) isopro
penylchloro-methylsilane bis(4-methoxyphenyl)ethyl
chloromethyl-sj, ]ane bis(4-methoxyphenyl) vinyl
chloromethyl-silane bis(4-methoxyphenyl)cyclo
propylchloro-methylsilane bis(3-chlorophenyl) chrome
thylethylsilanebis (3-chlo
rophenyl) chloromethylvinyls
ilanebis(3-chlorophenyl)c
hlomethylcyelo-propylsila
ne bis(4-methylphenyl)ethylc
chloromethyl-silane bis(4-methylphenyl) vinylc
chloromethyl-silane bis(4-methylphenyl)cyclop
ropylchlororo-methylsilane bis(4-chlorophenyl)fluoro
methylethyl-silane bis(4-chlorophenyl)-1-pro
penylchloro-methylsilane bis(4-chlorophenyl) isopro
pylchloro-methylsilane bis (4-chlorophenyl)-(2-m
ethyl)-1-propenylchlorome
thylsilanebis (4-chlorophe
nyl)ethylmethylsilanebis(
4-chlorophenyl) isopropeny
lmethyl-silane bis(4-trifluoromethylphen)
yl) cyclopropyl-chlorometh
ylsilanebis (4-ethoxypheny
l) cyclopropylchlor.

Methylsilane bis(4-ethoxyphenyl) vinylc
hloromethyl-11ane bis(4-ethoxyphenyl)-(1-pr
openyl) chloro-(netylsila)
ne 53 bis(4-methoxyphenyl)-
(1-propenyl)chloro-met, hy
lsilane 54 bis(4-chlorophenyl)-(
1-methyl-1-pro-penyl)chloro
Examples of the present invention will now be described.

Synthesis Example 1 To a mixture of 243 w+g (10 mmol) magnesium in 5 ml T HF under a nitrogen atmosphere, 2.47 g (]Ommol) of chloromethylmethyldiphenylsilane was added
The Grignard reagent is synthesized by adding mlT HF solution dropwise for 30 minutes. After further aging under reflux for 1 hour, the mixture was cooled to 5°C in an ice-water bath, and a solution of 2.47 g (10 mmol) of N-fluoropyridinium triflate in 5 ml of acetonidonol was added to the mixture in such a way that the temperature of the reaction solution did not exceed 10°C.
Add dropwise over 30 minutes. After stirring for another 30 minutes at room temperature, under water cooling, 10% aqueous solution of ammonium chloride, 30 m
1 and extracted twice with 20 ml of ethyl acetate. The organic layer was washed twice with 5% copper sulfate aqueous solution 10I111, dried over anhydrous sodium sulfate, filtered, and evaporated to give a slightly colored oily residue (yield 27.1% GC).
. This product was confirmed to be diphenylfluoromethylmethylsilane from the following analysis results.

MASS m/e 230 (M”), 197 (bas
e) NMR (CsD6.δ, ppm) 0.48 (3H
, s), 4.68 (2H, d.

J=47.4. Hz), 7.17 (6H, m), 7
．． 49(4H,m) Synthesis Example 2 Synthesis Example 1 except that 2.90 g (10 mm ○ 1) of N-fluoro-2,4,6-trimethylpyridinium triflate was used instead of N-fluoropyridinium triflate. Diphenylfluoromethylmethylsilane was synthesized by performing the same reaction as in Synthesis Example 1. (Yield 59
．． 1%) Synthesis Example 3 A reaction was carried out in the same manner as in Synthesis Example 2 using bis(4-chlorophenyl)tetramethylvinylsilane in place of the raw material tetraromethylmethyldiphenylsilane to obtain a product. This product was confirmed to be bis(4-chlorophenyl)fluoromethylvinylsilane from the following analysis results.

MASS m/e 310 (M”), 277 (bas
e), 251NMR (C6D, δ, ppm) 4.5
9(2)1. d, J engineering 47.4Hz), 5.65 (IH
, m) , 6.10 f2H1m) , 7.13
f8H,m) Synthesis Example 4 A reaction was carried out in the same manner as in Synthesis Example 2 using bis(4-chlorophenyl)chloromethylcyclopropylsilane in place of the raw material chloromethylmethyldiphenylsilane to obtain a product. This product was confirmed to be bis(4-chlorophenyl)fluoromethylcyclopropylsilane from the following analysis results. (Yield 61%) MASS m/e 324 (M”), 29Nbase
), 251NMR (C6D6.δ, ppm) −0,
30 (IH, m), 0.20 (2H, m) 0.5
1 (2H, ml, 4.56 (2H, d, J = 47.4H
z).

7, 1.8 (8)1. m) Synthesis Examples 5 to 9 A reaction was carried out in the same manner as in Synthesis Example 2 using the corresponding compound in place of the raw material chloromethylmethyldiphenylsilane to obtain the products shown below.

bis(4-fluorophenyl)methy
lfluoromethyl-1lane bis (4-fluorophenyl)vinyl
fluoromethyl-1lane bis (4-fluorophenyl)cyclo
propylfluoro-methylsilane bis (4-chlorophenyl)fluor
omethylmethyl-sil, ane bis (4-chlorophenyl)fluor
Omethylethyl-1lane Synthesis Example 10 Under nitrogen atmosphere, 3.65 g of cesium fluoride (23,4
5 mmo1. ) and 7.5g molecular sieve 4
To a suspension of A in 15 ml T HF was added 18-crown-ether-6,1,55 g (5,85 mmol) under stirring at room temperature.
) of 5 ml THF solution. After stirring for a further hour, 1.15 g (11,7
5 mmol) to 3 ml of THF solution, then 1.45 g of chloromethylmethyldiphenylsilane (5.9 ml of
ol) was added dropwise for 5 minutes each, and the mixture was heated under reflux for 5 hours. After cooling, it is filtered and the residue is washed with a small amount of ethyl acetate. After evaporating the filtrate, add 100 m of ethyl acetate.
Dissolve in l and wash with water. The organic layer was dried over anhydrous sodium sulfate, filtered, and evaporated to give a reddish-brown oil. (Yield 43.2% GC). This product was confirmed to be fluoromethyldiphenylsilane from the following analysis results.

MASS m/e 230 (M”), ], 9Hbas
e) NMR (C6D, δ, ppm) 0.48 (3H
, s), 4y68 (2H, d.

, b47.4Hz), 7.17 (6H, m),
7.49 (4H,m) Synthesis Example 11 In Synthesis Example 1, bis(4-chlorophenyl)chloromethyl-
The reaction was carried out in exactly the same manner as in Synthesis Example 1 except that 1-decylsilane was used to obtain a product.

This product was confirmed to be bis(4-chlorophenyl)fluoromethyl-1-decylsilane from the following analysis results.

MASS role 392(M”), 359,25
9 (base) NMR (C6D6.δ, ppm) 0.
93 (3H, s), 1.04 (3H, m).

1.27 (18H, m), 4.66 (2H, d, J=4
7.4Hz).

6.85 (2H, t, J = 9.3Hz), 7.27 (2
H, dod.

J=8.3)1z, 5.9)1z) Test Example 1 Two-spot spider mites (English name two-spot
ted 5pider m1te, scientific name Terany
chusurticae Kach) adults 10-20
A leaf piece with a parasitic head is placed there, and after 24 hours, the leaf piece is removed, and then the chemical solution is sprayed at 100 μ per 10 ares using a tower sprayer, and the leaf piece is left in a constant temperature room at 25°C. The investigation will be conducted as follows. In the investigation of adult insects, the treated items are observed 24 hours later to determine the degree of survival. Next, for egg inspection, all solids other than eggs are removed after the adult inspection, and the degree of clustering is compared 6 days after removal. Finally, a larval survey is conducted to observe the degree of larval survival if no ovicidal effect is observed. The results thus obtained were judged according to the table below.

The results below are 500 each ppm of Expresses the effect at concentration, Dicol was used as a control. there was.

methylsilane CC CC CC CC CC CC CC CC CC CC CC CC CC AB AB AB AB AB AB AB AB AB AB AA AB AB AC AC AB AB AB AB AB AC AC AB AC AB AA bi s(4-chlorophenyl)+cethy
l-vinylsilane bis(4-chlorophenyl)cyclo-
propylchloromethylsilaneb
is(4-chlorophenyl)cyclo-p
ropylfluoromethylsilanebi
s(4-chlorophenyl)cyclo-pr
opylmethylsilanebis (4-chl
orophenyl)ethyl-chloromet
hylsilanebis (4-chlorophen
yl)-1-pro-pynylchlorometh
ylsilanebis (4-chlorophen
yl)-1-pro-peny], chloromet
hylsilanebis (4-chlorophen
yl) isopr.

pylchloromethylsilanebis (
4-methoxyphenyl)cyclo-pro
pylchloromethylsilanebj, s
(3-chlorophenyl)chlo-meth
ylethylsilane bjs(4-methoxyphenyl)-(1-p
(ropenyl) chloromethylsilan
icohl

Claims (1)

[Claims] 1. General formula 1 ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, X represents a hydrogen atom, a fluorine atom, or a chlorine atom, and Y and Z represent a hydrogen atom and a fluorine atom, respectively. , represents a chlorine atom, a bromine atom, a lower alkyl group, a lower alkoxy group, or a fluoroalkoxy group, and R represents a linear or cyclic alkyl group, alkenyl group, or alkynyl group having 1 to 10 carbon atoms.) A mite control agent characterized by containing one or more of the compounds shown above as an active ingredient. 2. General formula 2 (However, in the formula, Y and Z each represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a lower alkyl group, a lower alkoxy group, or a fluoroalkoxy group, and R has 1 to 10 carbon atoms. A monofluoromethylsilane compound represented by a linear or cyclic alkyl group, alkenyl group, or alkynyl group. 3. General formula 2 characterized in that monochloromethylsilane in which X in general formula 1 is a chlorine atom is reacted with metallic magnesium to produce a corresponding Grignard reagent, which is then reacted with an electrophilic fluorinating reagent ▲ Formula, There are chemical formulas, tables, etc. ▼ Manufacturing method of monofluoromethylsilane compound. 4. General formula 2 characterized by reacting monochloromethylsilane in which X in general formula 1 is a chlorine atom with a fluorine anion reagent in the presence of a crown ether ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Represented by A method for producing a monofluoromethylsilane compound.