JPH0148904B2 - - 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-
The present invention relates to a disubstituted aminosulfenyl) N-methylcarbamate derivative, 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 these compounds have been put into practical use. However, these carbamate compounds often have the disadvantage of being highly toxic to warm-blooded animals. Among them, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N
-Methyl carbamate (common name: carbofuran,
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 thought that maintaining the insecticidal activity of carbofuran,
Reducing toxicity to warm-blooded animals is of great significance. In recent years, various carbofuran sulfenyl compounds have been synthesized for the above purpose, and the relationship between insecticidal activity and toxicity to warm-blooded 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-yl -N-benzenesulfonylaminosulfenyl)
N-methyl carbamate received West German published patent no.
Disclosed in No. 2254359. However, these carbofuran sulfenyl compounds cannot be said to satisfy all conditions such as insecticidal activity, toxicity to warm-blooded animals, 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 a compound represented by the following general formula [] is a satisfactory compound, and has now completed the present invention. [In the formula, X represents -CN group or -COOR ² group,
R ² represents a lower alkyl group. n represents 1 or 2. Y represents a carbonyl group or a sulfonyl group,
R ¹ represents a lower alkoxy group, a phenoxy group, a lower alkyl group that may have a halogen atom as a substituent, or a phenyl group that may have a halogen atom or a lower alkyl group as a substituent. ] 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N represented by the above general formula []
-(N,N-disubstituted aminosulfenyl)N-methyl carbamate 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 [] is suitable for use in agriculture and forestry, such as pests, mites, and nematodes belonging to Hemiptera, Lepidoptera, Coleoptera, Diptera, Threadoptera, Orthoptera, etc. It has excellent insecticidal activity and control effect against pests 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. Moreover, the toxicity of the compound of the present invention represented by the general formula [] to warm-blooded animals is approximately 1/5 to 1/1 that of carbofuran.
00, which is extremely low. Further, the compound of the present invention represented by the general formula [] 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 therefore is useful in the field of agriculture and forestry. 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 [] is easy to produce, and can be produced in high yield.
Since it can be obtained with high purity, it is also economical. Representative compounds of the present invention represented by the general formula [] are listed below. ◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(acetyl)-
N-(ethoxycarbonylmethyl)aminosulfenyl]N-methylcarbamate◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(propionyl)-N-(ethoxycarbonylmethyl)amino Sulfenyl]N-methylcarbamate◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(benzoyl)
-N-(ethoxycarbonylmethyl)aminosulfenyl]N-methylcarbamate◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(acetyl)-
N-(ethoxycarbonylethyl)aminosulfenyl]N-methylcarbamate◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(benzoyl)
-N-(cyanomethyl)aminosulfenyl]
N-Methylcarbamate◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(acetyl)-
N-(cyanoethyl)aminosulfenyl]N
-Methylcarbamate◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(methylsulfonyl)-N-(ethoxycarbonylmethyl)aminosulfenyl]N-methylcarbamate◇ 2,3 -dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(tosyl)-N
-(Ethoxycarbonylmethyl)aminosulfenyl]N-methylcarbamate◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(ethoxycarbonyl)-N-(ethoxycarbonylmethyl)
Aminosulfenyl]N-methylcarbamate◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(methoxycarbonyl)-N-(cyanoethyl)aminosulfenyl]N-methylcarbamate ◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(chloroacetyl)-N-(ethoxycarbonylmethyl)aminosulfenyl] N-methylcarbamate ◇ 2,3-dihydro- 2,2-dimethylbenzofuran-7-yl N-[N-(phenoxycarbonyl)-N-(ethoxycarbonylmethyl)aminosulfenyl]N-methylcarbamate◇ 2,3-dihydro-2,2-dimethyl Benzofuran-7-yl N-[N-(ethoxycarbonyl)-N-(cyanoethyl)aminosulfenyl]N-methylcarbamate◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N -(4-chlorobenzoyl)-N-(ethoxycarbonylmethyl)aminosulfenyl]N-methylcarbamate◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(methoxycarbonyl) -N-(ethoxycarbonylmethyl)
Aminosulfenyl]N-methylcarbamate◇ 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(ethoxycarbonyl)-N-(ethoxycarbonylethyl)
Aminosulfenyl]N-methylcarbamate The compound of the present invention represented by the general formula [] is, for example, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate and sulfur dichloride are reacted, and the formula is then produced. 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(chlorosulfenyl)N-methylcarbamate and the general formula [In the formula, X, Y, R ¹ and n are 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, dibutyl ether, tetrahydrofuran,
Examples include ethers such as dioxane. 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 1 mol. It is best to use ~1.2 times the mole. 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 an equimolar amount. It is preferable to use ~1.5 times the molar amount. The reaction proceeds either under cooling, at room temperature, or under heating, but is usually carried out at -70 to 50°C, preferably at -10 to 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 in the above reaction may be isolated and purified from the reaction mixture and then subjected to the next reaction, or the reaction mixture obtained in 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 a suitable solvent.The solvent used in the reaction between the compound of formula [] and sulfur dichloride can be used as the solvent. Both can be used. Compounds of formula [] and general formula []
The proportion of the amine to be used is not particularly limited and can be appropriately selected within a wide range, but it is usually about 1 to 2 times the mole of the former, preferably 1 to 1.2 times the mole of the latter. . 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 basic compound 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 the hydrogen chloride produced as a by-product of the reaction, but it is usually an equimolar to twice the molar amount, preferably an equimolar amount, relative to the compound of formula []. It is preferable to use ~1.5 times the molar amount. 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 15 hours. Examples of the amine represented by the general formula [ ] used as a raw material in this reaction include N-acetylglycine methyl ester, N-acetylglycine ethyl ester, N-acetylglycine propyl ester, N-propionylglycine ethyl ester, N- Butyrylglycine ethyl ester, N-benzoylglycine ethyl ester, N
-(2-chlorobenzoyl)glycine ethyl ester, N-(4-chlorobenzoyl)glycine ethyl ester, N-(4-methylbenzoyl)glycine ethyl ester, N-methylsulfonylglycine ethyl ester, N-benzenesulfonylglycine ethyl ester , N-tosylglycine ethyl ester, N-ethoxycarbonylglycine ethyl ester, N-methoxycarbonylaminopyrlopionitrile, N-acetyl-β-alanine ethyl ester, N-benzoyl-β-alanine ethyl ester, and the like. The thus obtained compound of the present invention represented by the general formula [] 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 Spray preparations, aerosol preparations,
It can be formulated into microcapsule preparations, preparations for impregnating natural or synthetic substances, preparations for fumigation, preparations for spraying in concentrated small quantities, etc. In producing these preparations, various surfactants can be used for emulsification, dispersion, suspension, and foaming, such as polyoxyethylene alkyl phenol ether as a nonionic surfactant.
Polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, Examples include alkylnaphthalene sulfonates and lignin sulfonates. 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, dimethyl formamide, dimethyl sulfoxide,
Mention may be made of acetonitrile, mineral oil fractions, water, and the like. Examples of aerosol propellants include propane, butane, halogenated hydrocarbons, nitrogen,
Examples include carbon dioxide. Examples of minerals include kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, tyoke, calcite, 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 [] is used in an amount of about 0.1 to 95% by weight when producing the above various preparations.
It is preferably prepared to contain 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-(propionyl)
-N-(Ethoxycarbonylmethyl)aminosulfenyl] Production of N-methylcarbamate 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate 11g
(0.05 mol) was dissolved in 70 ml of methylene chloride, 5.2 g (0.05 mol) of sulfur dichloride was added under cooling, and further 5 g (0.05 mol) of triethylamine was added dropwise at -10 to -5°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, a solution of 8 g (0.05 mol) of N-propionylglycine ethyl ester dissolved in 10 ml of methylene chloride was added dropwise.
Furthermore, 5 g (0.05 mol) of triethylamine was added dropwise. After stirring at 0°C for 2 hours, it 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. Although this oily substance contained a slight amount of impurities, it was almost a single component. Yield 14.3g (yield
69.8%) To confirm the target product, a portion was purified by silica gel column chromatography to obtain crystals. (Solvent benzene:ethyl acetate = 9:1) Melting point of crystal: 108-109°C NMR of the crystal in deuterated chloroform was shown as follows. δ1.14ppm (t, 3H), δ1.23ppm (t, 3H), δ1.49ppm (s, 6H), δ2.7~3.3ppm (m, 2H), δ3.02ppm (s, 2H), δ3. 48ppm (s, 3H), δ4.15ppm (q, 2H), δ4.50ppm (s, 2H), δ6.6~7.1ppm (m, 3H) Elemental analysis value (molecular weight C ₁₉ H ₂₆ N ₂ O ₆ S =410.499) Analysis value (%) C: 55.35 H: 6.41 N: 6.77 Calculated value (%) C: 55.59 H: 6.38 N: 6.82 From the above results It was confirmed. Example 2 Production of 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-[N-(ethoxycarbonyl)-N-(ethoxycarbonylmethyl)aminosulfenyl]N-methylcarbamate 2,3 -dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate 11g
(0.05 mol) was dissolved in 70 ml of methylene chloride, 5.2 g (0.05 mol) of sulfur dichloride was added under cooling, and further 5 g (0.05 mol) of triethylamine was added dropwise at -10 to -5°C. The mixture was stirred at 0° C. for 1 hour and then at room temperature for 2 hours. After cooling to -10~-5℃ again, 8.8g of N-ethoxycarbonylglycine ethyl ester
(0.05 mol) was added dropwise, and then 5 mol of triethylamine was added dropwise.
g (0.05 mol) was added dropwise. After stirring at 0°C for 2 hours, it was left at room temperature overnight. 100ml of methylene chloride after reaction
was added and 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 impurities, but was almost a single component. Yield 18.2g (yield 84.7
%) To confirm the target product, a portion was purified by silica gel column chromatography to obtain an oily substance. (Solvent benzene:ethyl acetate = 4:1) NMR of the oil in deuterated chloroform was shown as follows. δ1.17ppm (t, 6H), δ1.44ppm (s, 6H), δ2.94ppm (s, 2H), δ3.41ppm (s, 3H), δ4.05ppm (q, 2H), δ4.15ppm (q , 2H), δ4.41ppm (s, 2H), δ6.5~7.0ppm (m, 3H) Elemental analysis (molecular weight C ₁₉ H ₂₆ N ₂ O ₇ S = 426.499) Analysis value (%) C: 53.82 H: 6.19 N: 6.44 Calculated value (%) C: 53.51 H: 6.14 N: 6.57 From the above results It was confirmed. Examples 3 to 10 Compounds of Examples 3 to 10 were produced in the same manner as in Examples 1 and 2. Physical properties and NMR data first
Shown in the table.

【table】

[Table] Next, formulation examples of the present invention are 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 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 Wettable powder 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 Emulsion Compound of Example 2 50.0% Xylene 30.0 Cyclohexanone 10.0 Tween80 6.5 Span80 3.5 Formulation Example 3 Granule Wettable powder of Formulation Example 1 40.0% Dolomite 60.0 In the case of a wettable powder, each component is mixed and ground,
In the case of an emulsion, these can be obtained by mixing and dissolving each component. In the case of granules, each component is mixed uniformly, 15 parts by weight of a 2% carboxymethylcellulose aqueous solution is added to 100 parts by weight of this mixture, thoroughly kneaded, granulated using a granulator, and then finely cut. It is made into granules, dried and granulated. Next, test examples of the present invention will be shown. Test Example 1 Ten 3rd instar larvae of Spodoptera litura were placed on pot-planted 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.

[Table] Chilcarbamate Test Example 2 A diluted solution of a 50% hydrating powder at a predetermined concentration was sprayed on potted rice (one-month old seedlings) until the leaf surface was sufficiently wet. After air drying, the cage was covered with a net cage and 10 adult leafhoppers (Nephotettix cincticeps) were placed there.
The test was conducted in two consecutive days, and the determination of life and death was made after three days.
The mortality rate is shown in Table 3. For comparison, a control chemical-sprayed plot and an untreated plot were created, and their mortality rates were also recorded.

[Table] Test Example 3 A predetermined amount of 20% granules was mixed into soil contaminated with Meloidogyne incognita, and tomato seedlings were immediately transplanted. One month later, the degree of root nodule growth was observed.
The test area was 2 x 2 m ² and each test was repeated twice, 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

[Table] Test Example 4 An acute oral toxicity test was conducted on mice (〓). The LD ₅₀ value was determined from the mortality rate after 7 days by the Litchfield-Wilcoxon method and is shown in Table 5.

【table】

【table】

Claims (1)

[Claims] 1. General formula [In the formula, X represents -CN group or -COOR ² group,
R ² represents a lower alkyl group. n represents 1 or 2. Y represents a carbonyl group or a sulfonyl group,
R ¹ represents a lower alkoxy group, a phenoxy group, a lower alkyl group that may have a halogen atom as a substituent, or a phenyl group that may have a halogen atom or a lower alkyl group as a substituent. ] 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N,N-disubstituted aminosulfenyl) N-methylcarbamate derivative. 2 formulas 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate and sulfur dichloride are reacted, and the formula is then produced. 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(chlorosulfenyl)N-methylcarbamate and the general formula [In the formula, X represents -CN group or -COOR ² group,
R ² represents a lower alkyl group. n represents 1 or 2. Y represents a carbonyl group or a sulfonyl group,
R ¹ represents a lower alkoxy group, a phenoxy group, a lower alkyl group that may have a halogen atom as a substituent, or a phenyl group that may have a halogen atom or a lower alkyl group as a substituent. ] A general formula characterized by reacting with an amine represented by [In the formula, X, Y, R ¹ and n 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 [In the formula, X represents -CN group or -COOR ² group,
R ² represents a lower alkyl group. n represents 1 or 2. Y represents a carbonyl group or a sulfonyl group,
R ¹ represents a lower alkoxy group, a phenoxy group, a lower alkyl group that may have a halogen atom as a substituent, or a phenyl group that may have a halogen atom or a lower alkyl group as a substituent. ] characterized by containing a 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-(N,N-disubstituted aminosulfenyl) N-methylcarbamate derivative as an active ingredient. Insecticide.