JPH031302B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel sulfenyl carbamate derivative, a method for producing the same, and an insecticide containing the derivative as an active ingredient. It is known that certain carbamate compounds have strong insecticidal effects, and many compounds have already been put into practical use. However, these carbamate compounds generally have the drawback of being highly toxic to warm-blooded animals. Among them, 2-methyl-2-
(Methylthio)-propionaldehyde O-(methylcarbamoyl)oxime (generic name: aldecarb, hereinafter referred to as "aldecarb"), S-methyl 1-(dimethylcarbamoyl)-N-[(methylcarbamoyl)oxy]thioforme Imidate (generic name: oxamyl, hereinafter referred to as "oxamyl"), 3,3-dimethyl-1-(methylthio)-2
-Butanone O-(methylcarbamoyl)oxime (generic name: thiophanox, hereinafter referred to as ``thiophanox'') is a useful compound with strong insecticidal activity, but it is highly toxic to warm-blooded animals and poses problems in use. be. Therefore, it is of great significance to maintain the insecticidal activity of these carbamate agents while reducing their toxicity to warm-blooded animals. In recent years, various aldecarb sulfenyl compounds, oxamyl sulfenyl compounds, and thiophanox sulfenyl compounds have been synthesized for the above-mentioned purposes, and the relationship between insecticidal activity and toxicity to warm-blooded animals has been disclosed. For example, in JP-A-52-68104, N,N'-bis[2-methyl-2-(methylthio)propionaldehyde O-(methylcarbamoyl)oxime] sulfide, N,N'-bis[S-methyl -1-(dimethylcarbamoyl)-
N-[(methylcarbamoyl)oxy]thioformimidate]] sulfide and N,N'-bis[3,3-dimethyl-1-(methylthio)-2-butanone O-(methylcarbamoyl)oxime]
Sulfides are disclosed. However, these aldecarb sulfenyl compounds, oxamyl sulfenyl compounds, and thiophanox sulfenyl compounds all satisfy all conditions such as insecticidal activity, toxicity to warm-blooded animals, toxicity to fish, and economic efficiency in manufacturing. It is hard to say that it is a compound that does this. As a result of various studies in order to satisfy these conditions, the present inventors have discovered that the compound represented by the following general formula [] is a compound that satisfies these conditions, and has completed the present invention. [In the formula, R is

【formula】

【formula】 or

Represents [formula]. R ₁ and R ₂ are the same or different -X-COOR ₃ or -Y-CN
, X and Y each represent a C _1-6 alkylene group, and R ₃ represents a C _1-8 alkyl group or a C _3-6 cycloalkyl group. Furthermore, R ₂ is a C _1-8 alkyl group,
C _3-6 cycloalkyl group, C _3-8 alkoxyalkyl group, phenyl group that may have a halogen atom, C _1-3 alkyl group or C _1-3 alkoxy group as a substituent; halogen atom,
A benzyl group that may have a C _1-3 alkyl group or a C _1-3 alkoxy group, or a -Z-R ₄ group (wherein Z represents a carbonyl group or a sulfonyl group, and R ₄ is a C _1-3 (represents an alkyl group having _{1 to} 3 carbon atoms, a C1-3 alkoxy group, a phenoxy group, or a phenyl group that may have a lower alkyl group as a substituent). ] The sulfenyl carbamate derivative represented by the above general formula [ ] is a novel compound discovered for the first time by the present inventors 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 higher than those of aldecarb, oxamyl, and thiophanox, which are conventionally considered to have strong insecticidal activity. Moreover, the toxicity of the compound of the present invention represented by the general formula [] to warm-blooded animals is about 1/5 to 1/20 lower than that of aldecarb, oxamyl, and thiophanox. Furthermore, the compound of the present invention represented by the general formula [] exhibits 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 effective against pests in the agricultural and forestry field. It can be effectively used to exterminate or for hygiene reasons. In addition, the compound of the present invention represented by the general formula [] is easily produced 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 the general formula [] are listed below. Γ 2-Methyl-2-(methylthio)propionaldehyde O-[N-methyl-N-[N,N-
Bis(methoxycarbonylmethyl)aminosulfenyl]carbamoyl]oxime Γ 2-methyl-2-(methylthio)propionaldehyde O-[N-methyl-N-[N,N-
Bis(ethoxycarbonylethyl)aminosulfenyl]carbamoyl]oxime Γ 2-methyl-2-(methylthio))propionaldehyde O-[N-methyl-N-[N,N-
Bis(cyanoethyl)aminosulfenyl]carbamoyl]oxime Γ 2-methyl-2-(methylthio)propionaldehyde O-[N-methyl-N-(N-phenyl-N-ethoxycarbonylethylaminosulfenyl)carbamoyl] Oxime Γ 2-methyl-2-(methylthio)propionaldehyde O-[N-methyl-N-(N-butyl-N-ethoxycarbonylethylaminosulfenyl)carbamoyl]oxime Γ S-methyl 1-(dimethylcarbamoyl) −
N-[{N-methyl-N-(N-isopropyl-
N-ethoxycarbonylethylaminosulfenyl)carbamoyl}oxy]thioformimidate Γ S-methyl 1-(dimethylcarbamoyl)-
N-[{N-methyl-N-(N-benzyl-N-
ethoxycarbonylmethylaminosulfenyl)carbamoyl}oxy]thioformimidate Γ S-methyl 1-(dimethylcarbamoyl)-
N-[{N-methyl-N-(N-acetyl-N-
ethoxycarbonylethylaminosulfenyl)carbamoyl}oxy]thioformimidate Γ S-methyl 1-(dimethylcarbamoyl)-
N-[{N-methyl-N-(N-ethoxycarbonyl-N-ethoxycarbonylethylaminosulfenyl)carbamoyl}oxy]thioformimidate Γ 3,3-dimethyl-1-(methylthio)-2-
Butanone O-(N-methyl-N-(N-methyl-N-methoxycarbonylmethylaminosulfenyl)carbamoyl]oxime Γ 3,3-dimethyl-1-(methylthio)-2-
Butanone O-[N-methyl-N-{N-(4-
methylphenyl)-N-ethoxycarbonylethylaminosulfenyl}carbamoyl]oxime Γ 3,3-dimethyl-1-(methylthio)-2-
Butanone O-[N-methyl-N-(N-phenylsulfonyl-N-ethoxycarbonylethylaminosulfenyl)carbamoyl]oxime Γ 3,3-dimethyl-1-(methylthio)-2-
Butanone O-[N-methyl-N-(N-cyclohexyl-N-ethoxycarbonylethylaminosulfenyl)carbamoyl]oxime Γ 3,3-dimethyl-1-(methylthio)-2-
Butanone O-[N-methyl(N-isobutyl-N-ethoxycarbonylethylaminosulfenyl)carbamoyl]oxime The compound of the present invention represented by the general formula [] is, for example, or Carbamate and general formula shown as [In the formula, R ₁ and R ₂ are the same as above] It is produced by reacting with an aminosulfenyl chloride derivative represented by the following formula. Compounds of formula [], [] or [] and formula []
The reaction with the compound is carried out without a solvent or in a suitable solvent. Examples of the solvent include halogenated hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; and ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane. formula〔〕,
The ratio of the compound [] or [] to the compound of formula () is not particularly limited and can be appropriately selected within a wide range, but usually the latter is about 1 to 1.5 times the former by molar equivalent. It is preferable to use equimolar to 1.1 times the molar amount. formula〔〕,〔〕
The reaction between the compound of formula [] and the compound of formula [] is preferably carried out in the presence of a basic compound. Examples of the basic compounds used here include tertiary amines such as triethylamine, tributylamine, dimethylaniline, diethylaniline, and ethylmorpholine; pyridine, picoline,
Pyridines such as lutidine can be mentioned.
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 5 times the molar amount of the compound of formula [], [] or [], Preferably, an equimolar to twice molar amount is used. This reaction proceeds either under cooling, at room temperature, or under heating, but usually -70 to 70
It is carried out at a temperature of preferably -10 to 30°C. The reaction time varies depending on the basic compound used, and is generally 1
~30 hours. The compound represented by the general formula [] produced in this reaction 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 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, and the like. In producing these preparations, various surfactants can be used for emulsifying, dispensing, suspending, and foaming. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, and sorbitan alkyl ester, and anionic surfactants. Examples include alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, alkylnaphthalene sulfonate, and lignin sulfonate. In addition, as a compound solubilizer and diluent carrier,
Examples include various organic solvents, various aerosol propellants, various natural minerals and plants, various synthetic compounds, binders, etc. Particularly preferred organic solvents include benzene, toluene, xylene, ethylbenzene, chlorobenzene, and alkylnaphthalene. , dichloromethane, chlorethylene,
Cyclohexane, cyclohexanone, acetone,
Methyl ethyl ketone, methyl isobutyl ketone,
Examples include alcohols, dimethylformamide, dimethylsulfoxide, acetonitrile, mineral oil fractions and water. Examples of aerosol propellants include propane, butane, halogenated hydrocarbons, nitrogen, and carbon dioxide. Examples of natural minerals include kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, tyoke, calcite, pumice, sepiolite, and dolomite. Examples of plants include walnut shells, tobacco stems, and sawdust, and examples of synthetic compounds include alumina, silicates, sugar polymers, and the like. 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 adjusted to have a content of about 0.1 to 95% by weight, preferably about 0.5 to 90% by weight when producing the various formulations mentioned above. This preparation is tailored to the purpose.
It can be used as it is or optionally diluted with a carrier or water. The present invention will be explained in more detail with reference to Examples below. Example 1 Production of 2-methyl-2-(methylthio)propionaldehyde O-[N-methyl-N-[N,N-bis(ethoxycarbonylethyl)aminosulfenyl]carbamoyl]oxime N,N-bis( 14.2 g (0.05 mol) of ethoxycarbonylethyl)aminosulfenyl chloride and 9.5 g of 2-methyl-2-(methylthio)propionaldehyde O-(methylcarbamoyl)oxime
g (0.05 mol) was dissolved in 50 ml of dichloroethane and cooled. Triethylamine below 10℃
10.1 g (0.1 mol) was added dropwise and reacted at the same temperature for 2 hours. After the reaction, the reaction solution was washed with water, diluted sulfuric acid, and water, and the dichloroethane layer was dried and concentrated to obtain an oily substance.
18.4g (yield 84.1%) was obtained. A part of the oil was purified by silica gel column chromatography to obtain an oil. NMR of the oil in deuterated chloroform was shown as follows. δ = 1.23ppm (t, 6H), 1.43ppm (s, 6H) 1.95ppm (s, 3H), 2.63ppm (t, 4H) 3.30ppm (s, 3H), 3.0~3.7ppm (m,
4H) 4.08ppm (q, 4H), 7.49ppm (s, 1H) The elemental analysis values of the oily substance were shown as follows. Elemental analysis value (C ₁₇ H ₃₁ N ₃ O ₆ S ₂ = 437.591) Actual value (%) C: 46.72 H: 7.19 N: 9.23 Calculated value (%) C: 46.66 H: 7.14 N: 9.60 From the above results It was confirmed. Example 2 S-methyl-1-(dimethylcarbamoyl)-N
-[{N-methyl-N-(N-isopropyl-N-
ethoxycarbonylethylaminosulfenyl)
Production of carbamoyl}oxy]thioformimidate 11.3 g (0.05 mol) of N-isopropyl-N-ethoxycarbonylethylaminosulfenyl chloride and S-methyl 1-(dimethylcarbamoyl)
11 g (0.05 mol) of -N-[(methylcarbamoyl)oxy]thioformimidate was dissolved in 50 ml of dichloromethane and cooled. 10.1 g (0.1 mol) of triethylamine was added dropwise at 10° C. or below, and the mixture was reacted at the same temperature for 2 hours. After the reaction, wash the reaction solution with water,
After washing with dilute sulfuric acid and water, the dichloromethane layer was dried and concentrated to obtain 16.7 g (yield: 81.9%) of an oily substance. A part of the oil was purified by silica gel column chromatography to obtain an oil. Its NMR in deuterated chloroform was shown as follows. δ = 1.14ppm (d, 6H), 1.19ppm (t, 3H) 2.26ppm (s, 3H), 2.68ppm (t, 2H) 2.96ppm (s, 3H), 3.03ppm (s, 3H) 3.25ppm ( s, 3H), 3.0-3.8ppm (m,
3H) 4.04ppm (q, 2H), and the elemental analysis value of the oily substance was shown as follows. Elemental analysis value (C ₁₅ H ₂₈ N ₄ O ₅ S ₂ = 408.553) Actual value (%) C: 43.95 H: 6.88 N: 13.54 Calculated value (%) C: 44.10 H: 6.91 N: 13.71 From the above results It was confirmed. Example 3 Preparation of 3,3-dimethyl-1-(methylthio)-2-butanone O-[N-methyl-N-(N-isopropyl-N-ethoxycarbonylethylaminosulfenyl)carbamoyl]oxime. 11.3 g (0.05 mol) of N-isopropyl-N-ethoxycarbonylethylaminosulfenyl chloride and 3,3-dimethyl-1-(methylthio)-
10.9 g (0.05 mol) of 2-butanone O-(methylcarbamoyl)oxime was dissolved in 50 ml of dichloroethane and cooled. 10.1 g (0.1 mol) of triethylamine was added dropwise at 10° C. or below, and the mixture was reacted at the same temperature for 2 hours. After the reaction, the reaction solution was washed with water, diluted sulfuric acid, and water, and the dichloroethane layer was dried and concentrated to obtain 16.5 g (yield: 81.0%) of an oily substance. A portion of the oil was purified by silica gel column chromatography to obtain an oil. Its NMR in deuterated chloroform was shown as follows. δ = 1.16ppm (d, 6H), 1.20ppm (t, 3H) 1.24ppm (s, 9H), 2.13ppm (s, 3H) 2.70ppm (t, 2H), 3.30ppm (s, 3H) 3.1 to 3.8 ppm (m, 3H), 3.37ppm (s,
2H) 4.06ppm (q, 2H) The elemental analysis value of the oily substance was shown as follows. Elemental analysis value (C ₁₇ H ₃₃ N ₃ O ₄ S ₂ = 407.607) Actual value (%) C: 51.15 H: 8.33 N: 10.11 Calculated value (%) C: 50.09 H: 8.16 N: 10.31 From the above results It was confirmed. Examples 4 to 34 The same operations as in Examples 1 to 3 were performed to obtain Examples 4 to 34.
The compound was prepared. The physical properties and NMR data are shown in Table 1.

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【table】

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[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 examples listed here are only examples, 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 it. All percentages in the formulations below are percentages by weight. Formulation example 1 Wettable powder Compound of Example 1 50.0% Kaolin 30.0 Talc 10.0 Emal 40 powder 5.5 Demir powder 3.5 Alkyl phosphate 1.0 Formulation example 2 Emulsion Compound of Example 2 50.0% Xylene 30.0 Cyclohexanone 10.0% Tween 80 6.5 Span 80 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, and in the case of an emulsion, each component is mixed and dissolved. You can get it. 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 with a granulator, and then finely mixed. It is cut into granules, dried and granulated. Next, test examples of the present invention will be shown. Test Example 1 Ten wingless adults of the green green peach aphid (Myzus Persicae) were placed on potted Japanese orchid plants (one-month old seedlings), and one day later, 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 duplicate, and the determination of life or death was made after 3 days. 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】

[Table] 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 duplicate, and the determination of life or death was made 3 days later. 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】

[Table] Test example 3 Meloidogyne
incognita) Mix a predetermined amount of 20% granules into contaminated soil,
Tomato fungi were immediately transplanted. One month later, the degree of root nodule growth was observed. The test area is 2×
The test was repeated twice with 2 m ² 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%

【table】

[Table] Test Example 4 An acute oral toxicity test was conducted on mice (〓). Litchfield-Wilcoxon based on mortality rate after 7 days
Table 5 shows the results of determining the LD ₅₀ value using the method.

【table】

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Claims (1)

[Claims] 1. General formula [In the formula, R represents [formula] [formula] or [formula]. R ₁ and R ₂ are the same or different -X-COOR ₃ or -Y-
represents CN, X and Y each represent a _C1-6 alkylene group, and _R3 represents a _C1-8 alkyl group or a _C3-6 cycloalkyl group. Furthermore, R ₂ is a C _1-8 alkyl group, a C _3-6 cycloalkyl group, a C _3-8 alkoxyalkyl group, a halogen atom as a substituent, a C _1-3
a phenyl group which may have an alkyl group or a _C1-3 alkoxy group, a benzyl group which may have a halogen atom, a _C1-3 alkyl group or a _C1-3 alkoxy group as a substituent, or - Z-
R ₄ group (Z in the group represents a carbonyl group or sulfonyl group, R ₄ is a C _1-3 alkyl group, a C _1-3 alkoxy group, a phenoxy group, or a phenyl group that may have a lower alkyl group as a substituent) (representing a group). ] A sulfenyl carbamate derivative represented by. 2 General formula [In the formula, R represents [formula] [formula] or [formula]. ] A carbamate derivative represented by and the general formula [In the formula, R ₁ and R ₂ are the same or different -X-
COOR ₃ or -Y-CN, X and Y each represent a C _1-6 alkylene group, and R ₃ represents a C _1-8 alkyl group or a C _3-6 cycloalkyl group. Furthermore
R ₂ is a C _1-8 alkyl group, a C _3-6 cycloalkyl group, a C _3-8 alkoxyalkyl group, a halogen atom, a C _1-3 alkyl group, or a C _1-3 alkoxy group as a substituent. a phenyl group which may have a halogen atom, a C _1-3 alkyl group or a C _1-3 alkoxy group as a substituent, or a -Z-R ₄ group (Z in the group is carbonyl or a sulfonyl group, and R ₄ may be a C _1-3 alkoxy group, a phenoxy group, or a phenyl group which may have a lower alkyl group as a substituent). ] A general formula characterized by reacting with an aminosulfenyl chloride derivative represented by [In the formula, R, R ₁ and R ₂ are the same as above. ] A method for producing a sulfenyl carbamate derivative represented by 3 General formula [In the formula, R represents [formula] [formula] or [formula]. R ₁ and R ₂ are the same or different -X-COOR ₃ or -Y-CN
, X and Y each represent a C _1-6 alkylene group, and R ₃ represents a C _1-8 alkyl group or a C _3-6 cycloalkyl group. Furthermore, R ₂ is a C _1-8 alkyl group,
C _3-6 cycloalkyl group, C _3-8 alkoxyalkyl group, phenyl group that may have a halogen atom, C _1-3 alkyl group or C _1-3 alkoxy group as a substituent; halogen atom,
A benzyl group that may have a C _1-3 alkyl group or a C _1-3 alkoxy group, or a -Z-R ₄ group (wherein Z represents a carbonyl group or a sulfonyl group, and R ₄ is a C _1-3 (represents an alkyl group having _{1 to} 3 carbon atoms, a C1-3 alkoxy group, a phenoxy group, or a phenyl group that may have a lower alkyl group as a substituent). ] An insecticide characterized by containing a sulfenyl carbamate derivative represented by the following as an active ingredient.