JPS6128665B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel sulfinyl derivatives of oxime carbamates and insecticides containing the derivatives as active ingredients. Conventionally, certain carbamate compounds have been known to have strong insecticidal activity, and many of them have been put to practical use. Some of the oxime carbamate compounds related to the present invention have insecticidal activity, such as S-methyl-N-(N'-methylcarbamoyloxy)thioacetimidate (common name;
(methomyl), S-methyl-1-(dimethylcarbamoyl)-N-[(methylcarbamoyl)-oxy]thioformimidate (generic name: oxamyl), 2
-Methyl-2-(methylthio)-propionaldehyde-O-(methylcarbamoyl)oxime (common name: aldecarb) and the like are compounds that have been put into practical use. However, these oxime carbamates are known to have strong insecticidal activity as well as strong toxicity to warm-blooded animals, which poses problems in their use. For this reason, strict caution and restrictions on usage situations are required when using it. Considering these facts, it is very meaningful to maintain the insecticidal activity of oxime carbamates and reduce their toxicity to warm-blooded animals. In recent years, various oxime carbamate sulfenyl compounds have been synthesized for the above purpose, and have been shown to have insecticidal activity.
A relationship of toxicity to warm-blooded animals has been shown. For example, Belgian patent 848912 describes N,N'-bis[1-methylthioacetaldehyde-O-(N-methylcarbamyl)oxime] sulfide, and New Zealand patent 7508396 describes S-methyl-N-[N ′-Methylcarbamoyloxy-N′-
Trifluoromethylbenzenesulfonamidosulfenyl]thioacetimidate and the like are disclosed. However, these sulfenyl derivatives of oxime carbamates cannot be said to be compounds that 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 on compounds that satisfy these conditions, the present inventors have arrived at a compound represented by the following general formula [], thereby completing the present invention. (In the formula, R ₁ is a lower alkyl group that may have a lower alkylthio group as a substituent, or
R ₄ R ₅ NCO- group (R ₄ and R ₅ represent a lower alkyl group, R ₂ represents hydrogen or a lower alkylthio group, R ₃ represents a lower alkyl group, and X represents a lower alkylene group) The above general formula [] The sulfenyl derivative of oxime carbamate represented by is a new compound. The compounds of the present invention represented by the general formula [] are pests belonging to Hemiptera, Lepidoptera, Coleoptera, Diptera, Synoptera, Orthoptera, etc., agricultural, forestry, and sanitary pests such as mites and nematodes. It has excellent insecticidal activity and control effect against oxime carbamates, and its activity and effect are equal to or higher than those of oxime carbamates, which are conventionally considered to have strong insecticidal activity. Furthermore, the toxicity of the compound of the present invention represented by the general formula [] to warm-blooded animals was several tens to hundreds of times lower than that of conventional compounds. Furthermore, 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, forestry and sanitary pests, and therefore is effective against pests in the agricultural and forestry field. It can be effectively used for extermination or hygiene. In addition, the compound of the present invention represented by the general formula [] is easy to produce, and is also economical because it can be obtained in high yield and purity. Representative compounds of the present invention represented by the general formula [] are listed below. Γ O,S-bis[N-methyl(1-methylthioacetiminooxycarbonyl)aminosulfinyl]thioethanolΓ O,S-bis[1-dimethylcarbamoyl-
(1-methylthioformiminooxycarbonyl)-N-methylaminosulfinyl]thioethanol Γ O,S-bis[N-methyl(2-methyl-2
-Methylthiopropane-1-iminooxycarbonyl)aminosulfinyl]thioethanol Γ O,S-bis[N-methyl(1-methylthioacetiminooxycarbonyl)aminosulfinyl]thiopropanol Γ O,S-bis[ N-methyl(1-methylthioacetiminoxycarbonyl)aminosulfinyl]thiobutanol Γ O,S-bis[N-methyl(1-methylthioacetiminoxycarbonyl)aminosulfinyl]-1-methyl-2- Mercaptoethanol Compounds of the present invention represented by the general formula [ ] are, for example, (In the formula, R ₁ is a lower alkyl group that may have a lower alkylthio group as a substituent, or
An oxime carbamate represented by R ₄ R ₅ NCO- group (R ₄ and R ₅ represent a lower alkyl group, R ₂ represents hydrogen or a lower alkylthio group, and R ₃ represents a lower alkyl group) and thionyl chloride are reacted. and then generate the expression (wherein R ₁ , R ₂ and R ₃ are the same as above) and the sulfinyl chloride of oxime carbamate represented by the general formula HS-X-OH [ ] (wherein X represents a lower alkylene group) It is produced by reacting with mercaptoalkyl alcohols. The oxime carbamates of the general formula [] used as raw materials in the above include S-methyl N-(N'-methylcarbamoyloxy)thioacetimidate, S-methyl 1-(dimethylcarbamoyl)-N-[(methyl carbamoyl)-oxy]thioformimidate, 2-methyl-2-
(Methylthio)-propionaldehyde-O-(methylcarbamoyl)oxime and the like. Mercaptoalkyl alcohols represented by the general formula [] include mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptopentanol, mercaptohexanol, 1
-Methyl-2-mercaptoethanol, 1,2-
Dimethyl-2-mercaptoethanol, 1-methyl-3-mercaptopropanol, 2-methyl-
3-Mercaptopropanol, 3-methyl-3-
Mercaptopropanol, 1,2-dimethyl-3
-mercaptopropanol, 1-methyl-4-mercaptobutanol, 1,4-dimethyl-4-mercaptobutanol, and the like. The reaction between the compound of formula [] and thionyl chloride is carried out without a solvent or in an appropriate 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. The ratio of the compound of formula [] and thionyl chloride to be used 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 mole, preferably 1 to 1.2 times by mole. Good to use. The reaction between the compound of formula [] and thionyl chloride 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 such a basic compound to be used may be any amount that can capture the hydrogen chloride by-produced by the above reaction, but it is usually 1 to 1 for the compound of formula [].
It is preferable to use 2 times the molar amount, preferably 1 to 1.5 times the molar amount. The reaction proceeds either under cooling, at room temperature, or under heating, but usually at -30°C to 50°C.
Preferably it is carried out at -10°C to 30°C. The reaction time is generally about 2 to 5 hours, and the compound of formula [] is thus 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 mercaptoalkyl alcohol of formula [] is carried out without a solvent or in a suitable solvent. As the solvent, any solvent used in the reaction between the compound of the above formula [] and thionyl chloride can be used. The ratio of the compound of formula [] to the mercaptoalkyl alcohol of 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 0.5 to 0.
It is good to use about 1 times the mole, preferably 0.5 to 0.7 times the mole. The reaction between the compound of formula [] and the compound of 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 thionyl chloride can be used.
The amount of the basic compound to be used may be any amount that can capture the hydrogen chloride by-produced by the reaction, but it is usually 1 to 2 times the molar amount of the compound of formula [], preferably 1 to 1.5 times the molar amount. It is better to use twice the molar amount. The reaction proceeds either under cooling, at room temperature, or under heating, but usually at -30°C to 50°C, preferably at -10°C.
Performed at ~30°C. The reaction time is generally about 10 to 15 hours. The compounds of the present invention are generally purified by known means such as extraction, concentration, distillation, column chromatography, and recrystallization. The present invention will be explained in more detail with reference to Examples below. Example 1 Production of O,S-bis[N-methyl(1-methylthioacetiminoxycarbonyl)aminosulfinyl]thioethanol 6.5 g of S-methyl N-(N'-methylcarbamoyloxy)thioacetimidate ( 0.04 mol) in 30 ml of chloroform and 3.8 g of pyridine.
(0.048 mol) was added and cooled to 0°C. 4.6 g (0.042 mol) of thionyl chloride was added dropwise under cooling, and after the addition, the mixture was stirred at room temperature for 30 minutes. Cool again at 0°C and add 1.6 g (0.02 mol) of mercaptoethanol and 3.8 g of pyridine.
A solution of g (0.048 mol) dissolved in 10 ml of chloroform was added dropwise. After dropping, stir at room temperature for 2 hours,
I left it overnight. Add 60ml of ether to the reaction solution,
After washing with water, the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. 7.8 g (yield 78.8%) of a slightly impure oil component was obtained. In order to confirm the target product, an oily substance was partially purified by silica gel column chromatography. (Solvent: hexane: ethyl acetate = 3:2) NMR and elemental analysis values of the purified oil were as follows. NMR (in deuterated chloroform, δ, ppm) 2.32 (6H, s) 2.44 (6H, s) 2.98 (2H,
t) 3.05 (6H, s) 4.27 (2H, t) Elemental analysis value (as C ₁₂ H ₂₂ N ₄ O ₇ S ₅ ) Analysis value (%) C28.98 H4.39 N11.65 Calculated value (%) C29 .14 H4.48 N11.33 The oily substance obtained from the above results is It was confirmed that Example 2 O,S-bis[1-dimethylcarbamoyl-
Production of (1-methylthioformiminooxycarbonyl)-N-(methylaminosulfinyl)thioethanol S-methyl 1-(dimethylcarbamoyl)-N-
4.4 g (0.02 mol) of [(methylcarbamoyl)-oxy]thioformimidate was suspended in 100 ml of tetrahydrofuran, and 2 g (0.025 mol) of pyridine was suspended in 100 ml of tetrahydrofuran.
was added and cooled to 5°C. Thionyl under salt under cooling
2.5 g (0.021 mol) was added dropwise, and after the dropwise addition, the mixture was stirred at room temperature for 5 hours. Cool again and add 0.8 g (0.01 mol) of mercaptoethanol and 2 g (0.025 mol) of pyridine at 5°C.
A solution of mol) dissolved in 10 ml of tetrahydrofuran was added dropwise. After stirring overnight at room temperature, 100 ml of ethyl acetate was added to the reaction mixture, washed with water, and the organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. 4.2 g (68.8% yield) of a slightly impure oil component was obtained.
In order to confirm the target product, a portion was purified by silica gel column chromatography to obtain an oily substance.
(Solvent: hexane: ethyl acetate = 1:1) NMR and elemental analysis values of the purified oil were as follows. NMR (in deuterated chloroform, δ, ppm) 2.35 (6H, s) 2.97 (2H, t) 3.06 (12H,
s) 3.13 (6H, s) 4.28 (2H, t) Elemental analysis value (as C ₁₆ H ₂₈ N ₆ O ₉ S ₅ ) Analysis value (%) C30.95 H4.59 N13.95 Calculated value (%) C31 .57 H4.64 N13.81 The oily substance obtained from the above results is It was confirmed that Example 3 Production of O,S-bis[N-methyl(1-methylthioacetiminooxycarbonylaminosulfinyl]thiopropanol) Using 1.9 g (0.02 mol) of mercaptopropanol in place of mercaptoethanol in Example 1,
The same operation as in Example 1 was performed to obtain 7.4 g (yield: 73.7%) of an oily substance. The NMR and elemental analysis values of the oily substance were as follows. NMR (in deuterated chloroform, δ, ppm) 1.97 (2H, m) 2.30 (6H, s) 2.41 (6H,
s) 2.96 (2H, t) 3.03 (6H, s) 4.07
(2H, t) Elemental analysis value (as C ₁₃ H ₂₄ N ₄ O ₇ S ₅ ) Analysis value (%) C29.85 H4.81 N10.94 Calculated value (%) C30.70 H4.76 N11.01 or more The oily substance obtained from the results of It was confirmed that Example 4 O,S-bis[N-methyl(2-methyl-2-
Production of methylthiopropane-1-iminooxycarbonyl)aminosulfinyl)thioethanol 2-Methyl-2-(methylthio)-propionaldehyde-O-(methylcarbamoyl)oxime
7.6 g (0.04 mol) was dissolved in 30 ml of chloroform, 3.8 g (0.048 mol) of pyridine was added, and the mixture was cooled to 0°C. While cooling, 4.6 g (0.042 mol) of thionyl chloride was added dropwise, and after the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Cool again and add 1.6 g of methicaptoethanol (0.02
A solution of 3.8 g (0.048 mol) of pyridine and pyridine dissolved in 10 ml of chloroform was added dropwise. After the dropwise addition, the mixture was stirred at room temperature for 2 hours and left overnight. After adding 60 ml of ether to the reaction solution and washing with water, the organic layer was separated, dried, and concentrated under reduced pressure. 8.3 g (yield 75.5%) of a slightly impure oil component was obtained. A portion was purified by silica gel column chromatography to obtain an oil. (Solvent n-hexane: ethyl acetate = 1:
1) The NMR and elemental analysis values of the purified oil were as follows. NMR (in deuterated chloroform, δppm) 1.47 (12H, s) 1.96 (6H, s) 2.97 (2H, t) 3.12 (6H, s) 4.31 (2H, t) 7.48 (2H, s) Elemental analysis (C ₁₆ H ₃₀ N ₄ O ₇ S ₅ ) C H N Analytical value (%) 34.70 5.53 10.52 Calculated value (%) 34.89 5.49 10.17 The oily substance obtained from the above results is It was confirmed that The compound of the present invention represented by the formula [] is an emulsion,
Wettable powders, aqueous solutions, suspensions, concentrated suspensions, granules, microgranules, granules, powders, wettable powders, liniments, foam spray preparations, aerosol preparations, microcapsule preparations, natural or synthetic It can be formulated into preparations for impregnating substances, preparations for fumigation, preparations for smoking, preparations for spraying in concentrated small quantities, etc. In producing these preparations, various surfactants can be used for emulsification, dispersion, suspension, and foaming. Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, Polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, anionic surfactant such as alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, alkylnaphthalene sulfonate, lignin sulfonate. etc. can be mentioned. In addition, as a compound solubilizer, diluent, and carrier,
Examples include various organic solvents, various aerosol propellants, various natural minerals and plants, and various synthetic compounds. Particularly preferred organic solvents are benzene, toluene, xylene, ethylbenzene, chlorobenzene, alkylnaphthalene, dichloromethane, chloroethylene, cyclohexane, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohols, dimethylformamide, dimethyl sulfoxide, acetonitrile, and mineral oil. Distillates, water, etc. may be mentioned. Examples of aerosol propellants include propane, butane, halogenated hydrocarbons, nitrogen, and 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 other binders 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 formula [] is prepared to contain about 0.1 to 95% by weight, preferably about 0.5 to 90% by weight when producing the various formulations mentioned above, and the formulation is adjusted according to the purpose. It can be used as it is or freely diluted with a carrier or water. Formulation examples and test examples are listed below. Formulation Example 1 (Wettable powder) Weight % Compound of Example 1 50.0 Kaolin 30.0 Talc 10.0 Emar 40 powder 5.5 Demol EP powder 4.5 The above components are mixed in a conventional manner to obtain a wettable powder. Formulation example 2 (granules) Weight % Compound of Example 2 20.0 Kaolin 50.0 Talc 30.0 After mixing the above components, add 2% carboxymethylcellulose aqueous solution to 100 parts by weight of this mixture.
After adding 15 parts by weight and thoroughly mixing, the mixture is granulated using a granulator. Formulation Example 3 (Emulsion) Weight % Compound of Example 3 20.0 Cyclohexanone 67.6 Polyoxyethylene tridecyl ether
2.4 Dialkyl sulfosuccinate 4.0 Styrenated cresol 3.4 Dodecylbenzenesulfonate 2.6 The above components are mixed and stirred in a conventional manner to obtain an emulsion. Test Example 1 Ten 3rd instar larvae of Spodoptera litura were placed on potted Chinese Orchid plants (one month old seedlings), and a diluted solution of a 20% emulsion at a predetermined concentration was sprayed until the leaf surface was sufficiently wet. 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 1. Similarly, methomyl, oxamyl, and aldecarb were used as control drugs.
A 20% emulsion was prepared and treated in the same manner. The results for the untreated plot are also shown.

【table】

[Table] Test example 2 Meloidogyne
incognita) Mix a predetermined amount of 20% granules into contaminated soil,
Tomato seedlings were immediately transplanted. One month later, the degree of root nodule growth was observed. The test area is 2×
One test plot of 2 m ² was repeated three times, and the degree of root nodule adhesion was judged according to the evaluation criteria below. The results are shown in Table 2 as the average value of the three replicates. As control drugs, 20% granules of methomyl, oxamyl, and aldecarb were similarly prepared and treated in the same manner. The results for the untreated plot are also listed. The evaluation criteria are as follows. Root nodule growth 0% …1 〃 ~ 25% …2 〃 ~ 50% …3 〃 ~ 75% …4 〃 ~100% …5

【table】

[Table] Test Example 3 An acute oral toxicity test was conducted on male mice. Based on the mortality rate after 7 days, the Litchfield-Wilcoxon method was used.
The _LD50 value was determined. The results are as follows.

【table】

Claims (1)

[Claims] 1. General formula (In the formula, R ₁ is a lower alkyl group that may have a lower alkylthio group as a substituent, or
R ₄ R ₅ NCO- group (R ₄ and R ₅ represent a lower alkyl group), R ₂ is hydrogen or a lower alkylthio group, R ₃ is a lower alkyl group, and X is a lower alkylene group) sulfinyl derivatives of. 2 General formula (In the formula, R ₁ is a lower alkyl group that may have a lower alkylthio group as a substituent, or
R ₄ R ₅ NCO- group (R ₄ and R ₅ represent a lower alkyl group), R ₂ is hydrogen or a lower alkylthio group, R ₃ is a lower alkyl group, and X is a lower alkylene group) An insecticide containing a sulfinyl derivative as an active ingredient.