JPS6049637B2 - Carbamate insecticide - Google Patents

Description

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

Conventionally, certain carbamate compounds have been known to have strong insecticidal activity, and many of them have been put into practical use.

However, these carbafmate compounds often have the disadvantage of being highly toxic to warm-blooded animals. Among them, 2,3-dihydro-2,2-dimethylbenzofuran-7
-yl N-methylcarbamate (common name: carbofuran, hereinafter referred to as "carbofuran") is a useful compound with strong insecticidal activity, but it is extremely toxic to warm-blooded animals and has problems in use. Considering this, it is very meaningful to maintain the insecticidal activity of carbofuran and reduce its toxicity to mixed-breed animals. j In recent years, various carbofuran sulfenyl compounds have been synthesized for the above purpose, and the relationship between insecticidal activity and toxicity to mixed-breed animals has been demonstrated. For example, 2,3-dihydro 2,2-
Dimethylbenzofuran-7-yl N-(N,N-dibutylaminosulfenyl) N-methylcarbamate is disclosed in Belgian Patent No. 817517 as 2,3-dihydro-2,
2-dimethylbenzofuran-7-ylN-(N-methyl-N-benzenesulfonylaminosulfenyl)N-
Methyl carbamates are disclosed in West German Published Patent Application No. 225435 Wani.

However, these carbofuran sulfenyl compounds cannot be said to satisfy all conditions such as insecticidal activity, toxicity to mixed-breed animals, toxicity to fish, and economic efficiency in production. As a result of various studies to satisfy these conditions, the present inventors discovered that the compound represented by the following general formula [1] is a satisfactory compound, and thus completed the present invention. . [In the formula, R1 is -X-COOR3 group or -X-
CN group, R2 is -Y-COOR3 group or -Y-C
Indicates N group.

Here, R3 represents a C1-6 alkyl group. X and Y each represent a C1-6 linear or branched alkylene group. However, this excludes the case where x and Y are both methylene groups. ] 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N,N
-disubstituted aminosulfenyl) N-methyl carbamate derivatives are novel compounds discovered by the present inventors for the first time and which have 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. It has excellent insecticidal activity and control effect against industrial and sanitary pests, and its activity and effect are equal to or greater than that of ``carbofuran'', which is conventionally considered to have the strongest insecticidal activity. The toxicity of the compound of the present invention represented by formula [1] to mixed-breed animals is about 115% higher than that of carbofuran.
~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. It can be effectively used for exterminating pests in the field or for sanitary purposes. In addition, the compound of the present invention represented by the general formula [1] is easy to manufacture and can be obtained in high yield and high purity, so it is also excellent in economic efficiency. Representative compounds of the present invention represented by general formula [1] are listed below.

02,3-dihydro2,2-dimethylbenzofuran-7-yl N-[N,N-bis(methoxycarbonylethyl)aminosulfenyl]N-methylcarbamate 02
,3-dihydro2,2-dimethylbenzofuran-7-
yl N-[N,N-bis(ethoxycarbonylethyl)
Aminosulfenyl] N-methyl carno maid 02,
3-dihydro 2,2-dimethylbenzofuran-7-yl N-[N,N-bis(cyanoethyl)aminosulfenyl] N-methylcarbamate 02,3-dihydro 2
,2-dimethylbenzofuran-7-ylN-[N-(ethoxycarbonylethyl)-N-(ethoxycarbonylmethyl)aminosulnylphenyl]N-methylcarnokmade○2,3-dihydro2,2-dimethylbenzofuran- 7-yl N-[N-(ethoxycarbonylpropyl)-N-(ethoxycarbonylmethyl)aminosulfenyl]N-methylcarbamate 02,3-dihydro 2,2-dimethylbenzofuran-7-yl N-[N, N
-bis(ethoxycarbonylpropyl)aminosulfenyl]N-methylcarbamate 02,3-dihydro 2
,2-dimethylbenzofuran-7-ylN-[N-(1
-ethoxycarbonylpropyl)-N-(ethoxycarbonylmethyl)aminosulfenyl]N-methylcano(Made 02,3-dihydro2,2-dimethylbenzofuran-7-ylN-[N-(ethoxycarbonylbutyl)-N -(Ethoxycarbonylmethyl)aminosulfenyl]N-methylcarbamate The compound of the present invention represented by the general formula [1] is, for example, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl represented by the formula N-methyl carbamate and sulfur dichloride are reacted, and then 2,3-dihydro 2,2-dimethylbenzofuran-7-yl N-(chlorosulfenyl) N-methyl carbamate and the general formula [In the formula, R1 and R2
is the same as above.

] is produced by reacting with the amine shown below. 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,
Examples include ethers such as dibutyl ether, tetrahydrofuran, and dioxane. Formula [The ratio of the old compound and sulfur dichloride to be used is not particularly limited and can be appropriately selected within a wide range, but usually the latter is about 1 to 2 times the former by mole, preferably about 1 mole. ~
It is preferable to use 1.2 times the mole amount. The reaction between the compound of formula [■] and sulfur dichloride is preferably carried out in the presence of a basic compound. Examples of the basic compound used include tertiary amines such as triethylamine, tributylamine, dimethylaniline, diethylaniline, and ethylmorpholine, and pyridine. 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 an equimolar to twice the molar amount of the compound of formula [■], preferably is preferably used in an equimolar to 1.5 times molar amount. The reaction proceeds either under cooling, at room temperature, or under heating, but usually at -70
It is carried out at ~50°C, preferably -10~30°C.
The reaction time is generally about 2 to 5 hours. In this way, a compound of formula [■] is produced. In the present invention, the compound of formula [■] produced by the above reaction may be isolated and purified from the reaction mixture and then subjected to the next reaction, or the reaction mixture obtained from the above reaction may be subjected to the next reaction. . The reaction between the compound of formula [■] and the amine of general formula [■] is carried out in the absence of a solvent or in an appropriate solution.

As the solvent, any solvent used in the reaction between the compound of the above formula [■] and sulfur dichloride can be used. The ratio of the compound of the formula [■] and the amine of the general formula [■] 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 mole of the former. It is preferable to use equimolar to 1.2 times the molar amount. Expression〔■
] The reaction between the compound of formula [■] and the compound of general formula [■] is preferably carried out in the presence of a basic compound. As the basic compound, any of the basic compounds used in the reaction between the compound of the above formula [■] and sulfur dichloride can be used. The amount of the basic compound to be used may be any amount that can capture hydrogen chloride produced as a by-product of the reaction.
It is usually used in an equimolar to 2-fold molar amount, preferably in an equimolar to 1.5-fold molar amount, relative to the compound of formula [■].
The reaction proceeds either under cooling, at room temperature, or under heating, but is usually carried out at -20 to 50°C, preferably at 0 to 30°C. The reaction time is generally about 10 to specific hours. General formula [■] used as a raw material in the reaction
Examples of the amines include methyl iminodipropionate, ethyl iminodipropionate, iminodipropionitrile, ethyl iminodibutyrate, N-ethoxycarbonylmethyl-N-ethoxycarbonylpropylamine, N-ethoxycarbonylmethyl-N -Ethoxycarbonylbutylamine, N-ethoxycarbonylpropyl-N-ethoxycarbonylbutylamine, N-ethoxycarbonylmethyl-N-ethoxycarbonylhexylamine, N-(1-ethoxycarbonyl)propyl-N-ethoxycarbonylmethylamine, etc. .
The compound of the present invention represented by the general formula [1] thus obtained can be easily isolated and purified from the reaction mixture by conventional separation means such as solvent extraction, 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, 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, alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, alkylnaphthalene sulfonate, lignin sulfonate, etc. as anionic surfactants. can be mentioned.

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 include benzene, toluene, xylene, 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, tane, halogenated hydrocarbons, nitrogen, and carbon dioxide. Examples of minerals include kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, chalk, calcite, pumice, sepiolite, and dolomite. Examples of plants include walnut shells, tobacco stems, sawdust, etc.
Examples of synthetic compounds include alumina, silicates, sugar polymers, and the like. Examples of binders include carboxymethyl cellulose, gum arabic,
Examples include 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] is used in the production of the various preparations mentioned above.
It is prepared to contain 1 to 95% 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
-ylN-[N,N-bis(ethoxycarbonylethyl)aminosulfenyl]Production of N-methylcarbamate 2,3-dihydro 2,2-dimethylbenzofuran-1
-yl N-methylcarbamate 11y (0.05 mol)
was dissolved in 70 ml of methylene chloride, and 5.2 y (0.05 mol) of sulfur dichloride was added under cooling.
Triethylamine 5y (0.05 mol) was added dropwise at °C.

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

After cooling to −10 to −5° C. again, 10.9 q (0.05 mol) of diethyl iminonipropionate was added dropwise, followed by 5 q (0.05 mol) of triethylamine. 2 at 0℃
After stirring for an hour, the mixture was left at room temperature overnight.

After the reaction, 100 ml of methylene chloride was added, and the mixture was washed three times with 100 ml of water. The methylene chloride layer was dried and concentrated under reduced pressure to obtain an oil. This oil contained a slight amount of impurity, but was essentially one component. Yield 16.9y (yield 72.2
%) To confirm the desired product, a portion was purified by silica gel column chromatography to obtain an oily substance.

(Solvent benzene ethyl diacetate 5:1) NMR of the oil in deuterated chloroform was shown as follows.

δ1.21ppm (T., 6H), δ1.44ppm (
Sl6ll), δ2.67ppm (Tl4H), δ2,
97ppm (Sl2ll), δ3.37ppm (S..
3ll), δ3.42ppm (Tl4H), δ4.04
ppm (Ql4H), δ6.5-7.2ppm (Ml3
H) Elemental analysis value (molecular weight C2.

H3. N2O7S=468.58) Analysis value (%) C: 5
6.26H: 6.91N: 5.52a Calculated value (%) C:
56.39H: 6.88N: 5.98 or higher results were confirmed.

Example 2 Preparation of 2,3-dihydro 2,2-dimethylbenzofuran-7-yl N-[N,N-bis(cyanoethyl)aminosulfenyl]N-methylcarbamate 2,3-dihydro 2,2- Dimethylbenzofuran-7-yl N-
Methyl carbamate 11f (a). 05 mol) was dissolved in 50 ml of chloroform, and 5.2 mol of sulfur dichloride was dissolved under cooling.
fI (0.05 mol) was added, and further triethylamine 5y (0.05 mol) was added dropwise at -10 to -5°C.

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

After cooling to -10 to -5°C again, iminopropionitrile 6.2f (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 ml of chloroform was added and the mixture was washed three times with 100 ml of water. The chloroform layer was dried and concentrated under reduced pressure to obtain an oil.

This oil contained a slight amount of impurities, but was almost a single component. Yield 12.2q (yield 65.2%) To confirm the target product, a portion was purified by silica gel column chromatography to obtain an oily product.

(Solvent benzene ethyl diacetate 4:1) NMR of the oil in deuterated chloroform was shown as follows.

δ1.43ppm (S..6H), δ2.73ppm (
Tl4H), δ2.97ppm (Ss2H), δ3.3
7ppm (Sl3H), δ3.43ppm (T..4H
), δ6.5-7.2ppm (Ml3H) elemental analysis (molecular weight Cl8H22N4O3S=374.47) analysis value (
%) C: 57.91H: 5.79N: 15.04 Calculated value (%) C: 57.73H: 5.92N: 14.96 From the above results, it was confirmed.

Examples 3 to 6 The compounds of Examples 3 to 6 were produced in the same manner as in Examples 1 and 2.

Physical properties and NMR data are shown in Table 1. Next, formulation examples of the present invention will be described.

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

The two formulation examples described here are just examples, and the ratios of active ingredients, organic solvents, surfactants, and carriers can be changed, and in some cases, the types of organic solvents, surfactants, carriers, etc. can be changed. You can also change it. All percentages shown are by weight. Formulation Example 1 Wettable powder Compound of Example 1 50.0% Kaolin 30.0 Talc
10.0 Emar 40 Powder 5.5 Demol E
P 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 Example 1 40.0% Clay 60.0
In the case of a wettable powder, the components can be mixed and ground, and in the case of an emulsion, the components can be mixed and dissolved.

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

The test was conducted in two consecutive series, and after 3 days, the animals were judged to be alive or dead, and the mortality rate is shown in Table 2. For comparison, a control chemical-sprayed area and an untreated area were created, and their mortality rates were also recorded. 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 leaf surfaces were sufficiently wet.

After air-drying, cover with a net basket to remove the black leafhopper (NephO).
tettjxcincticeps) were provided. The test was conducted in duplicate, and after 3 days, the test was conducted to determine whether the animals were 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. Test Example 3 Sweet Potato Kub Centipede (MelOldOgyTl)
A predetermined amount of 20% granules was mixed into the contaminated soil, and tomato seedlings were immediately transplanted.

One month later, the degree of root nodule growth was observed.

The test plot was repeated twice with 2 x 2 squares 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 0% 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 knot adhesion 0% 1... 〃 1-24% 2... 〃 25-49 3... 〃 50-74 14... 〃 75-100 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 -X-COOR^3 group or -X-CN group, and R^2 represents -Y-COOR ^3 groups or -Y-CN
Indicates the group. Here, R^3 represents an alkyl group of C_1_ to_6. X
and Y each represent a C_1_ to_6 linear or branched alkylene group. However, this excludes the case where both X and Y are methylene groups. ] 2,3-dihydro-2
,2-dimethylbenzofuran-7-yl N-(N,N-
(disubstituted aminosulfenyl) N-methylcarbamate derivatives. 2 Formula ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl, N-mercarbamate, and sulfur dichloride are reacted, and then the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(chlorosulfenyl) N-methylcarbamate and the general formula ▲ Mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents -X-COOR^3 group or -X-CN group, and R^2 represents -Y-COOR^3 group or -Y-CN
Indicates the group. Here, R^3 represents an alkyl group of C_1_ to_6. X
and Y each represent a C_1_ to_6 linear or branched alkylene group. However, this excludes the case where both X and Y are methylene groups. ] There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ that are characterized by reacting with amines shown in [In the formula, R^1 and R^2 are the same as above. ] A method for producing a 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N,N-disubstituted aminosulfenyl) N-methylcarbamate derivative. 3 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents -X-COOR^3 group or -X-CN group, and R^2 represents -Y-COOR^3 group or -Y -CN
Indicates the group. Here, R^3 represents an alkyl group of C_1_ to_6. X
and Y each represent a C_1_ to_6 linear or branched alkylene group. However, this excludes the case where both X and Y are methylene groups. ] 2,3-dihydro-2
,2-dimethylbenzofuran-7-yl N-(N,N-
An insecticide characterized by containing a (disubstituted aminosulfenyl) N-methyl carbamate derivative as an active ingredient.