JPS6049638B2 - Carbamate insecticide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel 2,3-dihydro-2,2-di5methylbenzofuran-7-yl N-(N-monosubstituted mono-N-alkoxycarbonylalkyleneaminosulfenyl)N-methylcarbamate. The present invention relates to a derivative, a method for producing the same, and an insecticide containing the derivative as an active ingredient.

9 Certain carbamate compounds have been known to have strong insecticidal activity, and many of them have been put to practical use.

However, these carbamate compounds often have the disadvantage of being highly toxic to warm-blooded animals. Among them, 2
,3-dihydro7-2,2-dimethylbenzofuran-7
-yl N-methylcarbamate (common name: carbofuran, hereinafter referred to as "carbofuran") is a useful compound with strong insecticidal activity, but its toxicity to warm-blooded animals is extremely high and there are problems in its use. Considering this, it is very meaningful to maintain the insecticidal activity of carbofuran and reduce its toxicity to warm blood movements. recent years,
Various carbofuran sulfenyl compounds have been synthesized for the above-mentioned purpose, and the relationship between insecticidal activity and toxicity to warm hemodynamics has been shown.

For example, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N,N-dibutylaminosulfenyl) N-methylcarbamate is disclosed in Belgian Patent No. 8175.
No. 17, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-methyl-N-benzenesulfonylaminosulfenyl) N-methylcarbamate is disclosed in West German Published Patent Application No. 22543. There is.

However, these carbofuran sulfenyl compounds cannot be said to be compounds that satisfy all conditions such as insecticidal activity, toxicity to warm blood movements, toxicity to fish, and economic efficiency in production. As a result of various studies in order to satisfy these conditions, the present inventors have found that the compound represented by the following general formula [1] is a satisfactory compound, and has now completed the present invention. [In the formula, R1 represents a -X-COOR3 group.

Here, x represents a C1-6 linear or branched alkylene group, and R3 represents a C1-6 alkyl group. R2 represents a C1-8 alkyl group, a C3-6 cycloalkyl group, a benzyl group, or a phenyl group. The benzyl group and phenyl group represented by R2 may be substituted with at least one group selected from the group consisting of a halogen atom, a C1-3 alkyl group, and a C1-3 alkoxy group. ]2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-monosubstituted-N-alkoxycarbonylalkyleneaminosulfenyl)N represented by the above general formula [1]
-Methylcarbamay, a derivative is a novel compound discovered by the present inventors for the first time and which has not been described in any literature.

The compound of the present invention represented by the general formula [1] is suitable for agricultural and forestry pests, mites, nematodes, etc. belonging to Hemiptera, Lepidoptera, Coleoptera, Diptera, Threadoptera, Orthoptera, etc. Excellent against industrial and sanitary pests. It has an insecticidal activity or a control effect, and its activity or effect is equal to or greater than that of carbofuran, which is conventionally considered to have the strongest insecticidal activity. Moreover, the toxicity of the compound of the present invention represented by the general formula [1] to warm hemodynamics is less than carpo. Approximately 11 compared to that of the franc
5-11100, which is extremely low. Further, the compound of the present invention represented by the general formula [1] can exhibit insecticidal activity or control effect against all growth stages or specific growth stages of the above-mentioned agricultural and forestry pests and sanitary pests, and is therefore useful in the agricultural and forestry field. It can be effectively used for exterminating pests or for sanitary reasons. In addition, the compound of the present invention represented by the general formula [1] is easy to produce and can be obtained in high yield and purity, so it is economically superior. Representative compounds of the present invention represented by general formula [1] are listed below.

02,3-dihydro2,2-dimethylbenzofuran-7-ylN-(N-methyl-N-ethoxycarbonylmethylaminosulfenyl)N-methylcarnokmade 0
2,3-dihydro 2,2-dimethylbenzofuran-7
-ylN-(N-ethyl-N-ethoxycarbonylmethylaminosulfenyl)N-methylcarbamate ○2,
3-dihydro 2,2-dimethylbenzofuran-7-yl N-(N-butyl-N-ethoxycarbonylmethylaminosulfenyl) N-methylcarbamate ○2,3-
Dihydro 2,2-dimethylbenzofuran-7-yl N
-(N-butyl-N-ethoxycarbonylethylaminosulfenyl)N-methylcarbamate 02,3-dihydro2,2-dimethylbenzofuran-7-ylN-(
2,3-dihydro 2,2-dimethylbenzofuran-7-yl N-[N
-(4-methylbenzyl)-N-ethoxycarbonylmethylaminosulfenyl]N-methylcarbamate 02
,3-dihydro2,2-dimethylbenzofuran-7-
yl N-(N-phenyl-N-ethoxycarbonylmethylaminosulfenyl) N-methylcarbamate ○2,
3-dihydro 2,2-dimethylbenzofuran-7-yl N-[N-(4-methylphenyl)-N-ethoxycarbonylmethylaminosulfenyl] N-methylcarbamate This invention represented by the general formula [1] For example, the compound represented by the formula 2,3-dihydro 2,2-dimethylbenzofuran-7-yl N-methylcarbamate is reacted with sulfur dichloride, and then the compound 2,
3-dihydro 2,2-dimethylbenzofuran-7-yl N-(chlorosulfenyl)N-methylcarbamate and the general formula [wherein R1 and R2 are the same as above.

] is produced by reacting with the N-monosubstituted amino acid ester. The reaction between the compound of formula [■] and sulfur dichloride is carried out without a solvent or in a suitable solvent.

Examples of solvents include halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride, diethyl ether,
Ethers such as dibutyl ether, tetrahydrofuran, and dioxane can be mentioned. The ratio of the compound of formula [■] and sulfur dichloride to be used is not particularly limited and can be appropriately selected within a wide range, but the ratio of the latter to the former is usually about 1 to 2 times the mol, preferably Equimolar ~
It is preferable to use 1.2 times the mole amount. The reaction between the compound of the formula [old] and sulfur dichloride is preferably carried out in the presence of a basic compound. Examples of the basic compounds used include tertiary amines such as triethylamine, tributylamine, dimethylaniline, ethylaniline, and ethylmorpholine, and pyridines. The amount of the basic compound to be used may be any amount that can capture the hydrogen chloride produced as a by-product in the above reaction, but it is usually equivalent to 2 times the mole of the compound of formula [■], preferably Equimolar ~
It is preferable to use 1.5 times the molar amount. The reaction proceeds either under cooling, at room temperature, or under heating, but usually -70 to 5
It is carried out at 0°C, preferably -10 to 30°C. The reaction time is generally about 2 to 5 hours, and thus the formula [■
) is produced. In the present invention, the compound of formula [■] produced in the above reaction may be isolated and purified from the reaction product and then subjected to the next reaction, or the reaction mixture obtained in the above reaction may be subjected to the next reaction. good.

The reaction between the compound of formula [■] and the compound of general formula [■] is carried out without a solvent or in a suitable solvent.

As the solvent, any solvent used in the reaction of the compound of the above formula [old] with sulfur dichloride can be used. formula〔
The ratio of the compound of formula [■] to the compound of general formula [■] is not particularly limited and can be appropriately selected within a wide range.
Usually, the latter is used in an amount of about 1 to 2 times the mole of the former, preferably 1 to 1.2 times the mole of the former. Expression〔■〕
The reaction between the compound and the compound of general formula [■] is preferably carried out in the presence of a basic compound. As the basic compound 5, any of the basic compounds used in the reaction between the compound of the above formula [former formula] and sulfur dichloride can be used. The amount of the basic compound to be used may be any amount that can capture the hydrogen chloride produced as a by-product of the reaction, but it is usually equivalent to 2 times the mole of the compound of formula [■]. It is preferable to use an equimolar to 1.5-fold molar amount.
The reaction proceeds either under cooling, at room temperature, or under heating, but usually -70 to 50°C, preferably -10 to 30°C.
It will be held at Reaction time is generally about 10 to 1 hour.
It is. The general formula used as a raw material in the reaction [
Examples of N-monosubstituted amino acid esters represented by -Butylglycine ethyl ester, N-butylglycine hexyl ester, N-
Methyl-β-alanine ethyl ester, N-butyl-β
-Alanine ethyl ester, N-benzylglycine ethyl ester, N-(4-methylbenzyl)glycine ethyl ester, N-(4-chlorobenzyl)glycine ethyl ester, N-phenylglycine ethyl ester, N-
-(4-methoxyphenyl)glycine ethyl ester and the like. The compound of the present invention represented by the general formula [1] thus obtained can be separated by conventional separation means such as solvent extraction,
It is easily isolated and purified from the reaction mixture by recrystallization, column chromatography, etc.

The compound of the present invention represented by the general formula [1] can be used as an emulsion, a wettable powder, an aqueous solution, a suspending agent, a concentrated suspension, a granule, a fine granule, a granule, a powder, a wettable powder, a coating agent, It can be formulated into foam spray preparations, aerosol preparations, microcapsule preparations, preparations for impregnating natural or synthetic substances, preparations for fumigation, preparations for spraying in concentrated small quantities, and the like.

In producing these preparations, various surfactants can be used for emulsification, dispersion, suspension, and foaming. Examples of nonionic surfactants include polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ether, and polyoxyethylene alkyl ether. Oxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, anionic surfactants such as alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene dialkyl ether sulfate, alkylnaphthalene sulfonate, lignin sulfonate, etc. be able to.

Further, examples of solvents, diluents, and carriers for compounds include various organic solvents, various aerosol propellants, various natural minerals and plants, and various synthetic compounds. For example, particularly preferred organic solvents are benzene, toluene, xylene, and ethylbenzene. , chlorobenzene, alkylnaphthalene, dichloromethane, chlorethylene, cyclohexane, cyclohexanone, acetone, methyl ethyl ketone,
Methyl isobutyl ketone, alcohols, dimethylformamide, dimethyl sulfoxide, acetonitrile,
Mention may be made of mineral oil fractions, water, and the like. Examples of aerosol propellants include propane, butane, halogenated hydrocarbons, nitrogen, and carbon dioxide. Examples of minerals include kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, chalk, calcite,
Examples include pumice, sepiolite, and dolomite. Examples of plants include walnut shells, tobacco stems, sawdust, etc., and examples of synthetic compounds include alumina, silicates, sugar polymers, etc. Examples of the binder include carboxymethylcellulose, gum arabic, polyvinyl alcohol, and polyvinyl acetate.
These preparations can also be colored using organic or inorganic dyes. The compound of the present invention represented by the general formula [1] has a concentration of about 0.1 to 95% when used in the above various formulations.
It is prepared to contain % by weight, preferably about 0.5 to 90% by weight, and the preparation can be used as it is or freely diluted with a carrier or water depending on the purpose.

The present invention will be explained in more detail with reference to Examples below.

Example 1 2,3-dihydro 2,2-dimethylbenzofuran-7
-yl N-(N-butyl-N-ethoxycarbonylmethylaminosulfenyl) Production of N-methylcarbamate 2,3-dihydro 2,2-dimethylbenzofuran-7
-yl N-methylcarbamate 11y (a). 05 mol) was dissolved in 70 ml of methylene chloride, 5.2 f (0.05 mol) of sulfur dichloride was added under cooling, and the mixture was further heated to -10°C.
Triethylamine 5y (0.05 mol) was added dropwise at 5°C.

The mixture was stirred at 0° C. for 1 hour and then at room temperature for 2 hours.

After cooling again to -10°C to -5°C, N-butylglycine ethyl ester 8.0f1 (0.05 mol) was added dropwise, and triethylamine 5y (0.05 mol) was further added dropwise.
After stirring at 0°C for 2 hours, it was left at room temperature overnight.

After the reaction, 100 mt of methylene chloride was added, and the mixture was washed three times with 100 mt of water. After drying the methylene chloride layer, it was concentrated under reduced pressure to obtain an oil. This oil contained a slight amount of impurities, but was almost a single component. Yield 15.7y (yield 7
6.6%) In order to confirm the target product, a portion was purified by silica gel column chromatography to obtain an oily substance. (Solvent: hexane ethyl diacetate 4:1) NMR of the oil in deuterated chloroform was shown as follows.

δ0.65ppm to δ1.85ppm (Ml7H), δ
1.22ppm (T..3H), δ1.44ppm (S
l6H), δ3.30ppm (S, .2H), δ3.3
0ppm (Tl2FI), 7 δ3.4? Pm(S,,
3H), δ4.14ppm (Sl2H), δ4.13p
pm (Q..2H), δ6.9ppm (M..3H) elemental analysis (molecular weight C2OH3ON2O5S = 410.54
) Analysis value (%) C: 58.39H: 7.41N: 6.7
5 Calculated value (%) C: 58.51H: 7.37N: 6.8
2 or more results were confirmed.

Example 2 2,3-dihydro 2,2-dimethylbenzofuran-7
-yl N-(N-phenyl-N-ethoxycarbonylmethylaminosulfenyl) Preparation of N-methylcarbamate 2,3-dihydro 2,2-dimethylbenzofuran-7-yl N-methylcarbamate 11f(4). 05 mol) was dissolved in 70 ml of methylene chloride, 5.2 y (0.05 mol) of sulfur dichloride was added under cooling, and further 5 g (0.05 mol) of triethylamine was added dropwise at -10C to 5°C.

The mixture was stirred at 0° C. for 1 hour and then at room temperature for 2 hours.

After cooling again to -10'C to -5C, N-phenylglycine ethyl ester 9y (0.05 mol) was added dropwise, and further 5 g (0.05 mol) of triethylamine was added dropwise. 0
After stirring at °C for 2 hours, it was left at room temperature overnight.

After the reaction, 100ml of methylene chloride was added and the mixture was washed three times with 100ml of water. The methylene chloride layer was dried and concentrated under reduced pressure to obtain an oil. Add benzene-hexane (
1:1) was added, and crystals were precipitated and filtered. The mother liquor was concentrated to give an oil. This oily substance was cooled to obtain crystals. The crystals were recrystallized from ether to give 13.4 f white crystals (yield: 6
2.3%). NMR of the crystals with a melting point of 92 to 93° C. in deuterated chloroform was shown as follows. δ1.15pp
m (T..3H), δ1.46ppm (Sl6l(),
δ3.00(S,,2H), δ3.32ppm(S.,
3H), δ4.12(q1:;;I:([),
δ4.76PPm(S1:;11:([), δ6.5
~7.5ppm (M..8H) elemental analysis (molecular weight C2.

H26N2O5S=430.53) Analysis value (%) C: 6
1.11H: 6.15N: 6.49 Calculated value (%) C: 6
The following results were confirmed: 1.38H: 6.09N: 6.51.

Examples 3 to 12 The compounds of Examples 3 to 12 were produced in the same manner as in Examples 1 and 2.

Physical properties and NMR data are shown in Table 1.

Next, examples of formulations of the present invention will be shown.

The following formulation can be applied to all of the above compounds, and a suitable formulation is used depending on the usage situation.

The formulation example described here is just one example, and the ratio of the active ingredient, organic solvent, surfactant, carrier, etc. can be changed each time, and in some cases, the types of organic solvent, surfactant, carrier, etc. can be changed. You can also do that. All percentages shown are by weight. Formulation example 1 Hydrating agent 1? 1 Compound of Example 1 50.0% Kaolin 30.0 Talc 10.0 Emal 40 Powder 5.5 Demol EP Powder 3.5 Alkyl Phosphate 1.0 Formulation Example 2 Compound of Emulsion Example 2 50.0 %Xylene 30.0 Cyclohexanone 10.0 Tween8
06.5Span803.5 Formulation Example 3 Wettable powder of Granule Formulation 1 40.

0% clay 60.
In the case of a wettable powder, the components can be mixed and ground, and in the case of forming an emulsion, the components can be mixed and dissolved.

In the case of granules, each component is mixed uniformly, and this mixture
2% carboxymethylcellulose aqueous solution 1 part to weighing part
After adding 5 parts by weight and sufficiently kneading, the mixture is granulated using a granulator, then finely cut into granules, dried, and granulated. Next, test examples of the present invention will be shown. Test Example 1 Spodoptera spodoptera (SpOdOpteralltura)
Ten 3rd instar larvae were placed on pot-planted Chinese Orchid plants (one-month old seedlings), and a diluted solution of a 50% emulsion at a predetermined concentration was sprayed on the leaves until the leaves were sufficiently leaked.

The test was conducted in duplicate, and after 3 days, the animals were determined to be alive or dead, and the mortality rates are shown in Table 2. For comparison, a control chemical-sprayed area and an untreated area were created, and their mortality rates were also recorded. (1)
Control drug: 1-naphthyl-N-methylcarbame
Test Example 2 A diluted solution of a 50% hydrating powder at a predetermined concentration was sprayed on rice plants (1 month old seedlings) planted in pots until the leaves leaked sufficiently.

After air-drying, cover with a net basket to remove the black leafhopper (NephO).
tettixcincticeps) were provided. The test was conducted in duplicate, and after 3 days, the animals were judged to be alive or dead, and the mortality rates are shown in Table 3. For comparison, a control chemical-sprayed plot and an untreated plot were created, and their mortality rates were also recorded. (support)
Control drug: 2-isopropoxyphenyl-N-
Methyl Carbamate) Test Example 3 Sweet Potato Kub Centennial (MelOldOgyrl
A predetermined amount of 20% granules was mixed into the contaminated soil, and tomato fungi were immediately transplanted.

One month later, the degree of root nodules that had grown on the roots was observed.

The test plot was repeated twice with 2×2d as one test, and the degree of root nodule settlement is shown in Table 4 according to the evaluation criteria below. For comparison, a group mixed with 20% granules of the control drug and an untreated group were prepared, and the results are also listed in Table 4. The evaluation criteria are as follows. 0... Root nodule growth 0% 1... 〃 1-24% 2... 〃 25-49 3... 〃 50-74 4... 〃 75-100 (1) Control drug: Bis(2-chloro-1-methylethyl)ether Test Example 4 An acute oral toxicity test was conducted on mice (including mice).

The LD5O value was determined from the mortality rate after 7 days by the Litchfield-Wilcoxon method (Litchfield-WilcOxOn method) and is shown in Table 5.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R^1 represents a -X-COOR^3 group. Here, X represents a linear or branched alkylene group of C_1_ to_6, and R^3 represents an alkyl group of C_1_ to_6. R^2 is an alkyl group of C_1_-_8, C_3
It represents a cycloalkyl group, a benzyl group, or a phenyl group of ___ to ___6. The benzyl group and phenyl group represented by R^2 include a halogen atom, an alkyl group of C_1_ to_3, and a C
It may be substituted with at least one group selected from the group consisting of alkoxy groups of _1_ to _3. ] 2,3 indicated by
-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-substituted-N-alkoxycarbonylalkyleneaminosulfenyl) N-methylcarbamate derivative. 2 Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ The formula that is produced when 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate and sulfur dichloride are reacted and then produced ▲ Mathematical formula , chemical formulas, tables, etc. ▼ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(chlorosulfenyl) N-methylcarbamate and the general formula ▲ Numerical formulas, chemical formulas, tables, etc. Yes▼ [In the formula, R^1 represents -X-COOR^3 group. Here, X represents a linear or branched alkylene group of C_1_ to_6, and R^3 represents an alkyl group of C_1_ to_6. R^2 is an alkyl group of C_1_-_8, C_3
It represents a cycloalkyl group, a benzyl group, or a phenyl group of ___ to ___6. The benzyl group and phenyl group represented by R^2 include a halogen atom, an alkyl group of C_1_ to_3, and a C
It may be substituted with at least one group selected from the group consisting of alkoxy groups of _1_ to _3. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ that are characterized by reacting with the N-substituted amino acid ester shown by [In the formula, R^1 and R^2 are the same as above. ] 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N-substituted-N-alkoxycarbonylalkyleneaminosulfenyl) N-methylcarbamate derivative. 3 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents -X-COOR^3 group. Here, X represents a linear or branched alkylene group of C_1_ to_6, and R^3 represents an alkyl group of C_1_ to_6. R^2 is an alkyl group of C_1_-_8, C_3
It represents a cycloalkyl group, a benzyl group, or a phenyl group of ___ to ___6. The benzyl group and phenyl group represented by R^2 include a halogen atom, an alkyl group of C_1_ to_3, and a C
It may be substituted with at least one group selected from the group consisting of alkoxy groups of _1_ to _3. ] 2,3 indicated by
-Dihydro-2,2-dimethylbenzofuran-7-yl N-(N-substituted-N-alkoxycarbonylalkyleneaminosulfenyl) N-methylcarbamate derivative as an active ingredient.