JP2943246B2 - Nitroethylene derivative, production method thereof and insecticide - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a nitroethylene derivative, a method for producing the same, and an insecticide containing the derivative as an active ingredient.

[Conventional technology]

Many years of research and development of pesticides, many drugs,
For example, organophosphorus pesticides such as parathion and malathion,
Carbamate insecticides such as carbaryl and mesomil have been developed and put into practical use. These insecticides have played an extremely important role in improving agricultural production.However, in recent years, some of these insecticides have been restricted in use due to problems such as residue and accumulated environmental pollution, and as a result of long-term use, resistant pests have been identified. What happened is coming out. Therefore, there is a demand for the development of a new drug that has excellent insecticidal properties against various pests including these resistant pests and can be used safely.

[Problems to be solved by the invention]

An object of the present invention is to provide an agricultural chemical which can be synthesized industrially advantageously, has a certain effect and can be used safely.

[Means for solving the problem]

The present invention relates to a compound represented by the general formula Wherein R ₁ is a substituted heterocyclic ring, X is an optionally substituted alkylene group, a heteroatom or a single bond, R ₂ is hydrogen,
An optionally substituted alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, cycloalkenyl group or an aryl group, -Y-R _5, or (Where Y is O, S (O) -CO _2- is 0, 1, 2, R ₅ is hydrogen, an optionally substituted alkyl group, alkenyl group, alkynyl group,
A cycloalkyl group, a cycloalkenyl group or an aryl group, R ₆ and R ₇ are the same or different, and hydrogen, an optionally substituted alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group or Indicates an aryl group. And X and R ₂ may together form a ring with or without a heteroatom.

R ₃ is an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group or aryl group, or Here, R ₈ is hydrogen, an optionally substituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group or aryl group, and R ₉ is an optionally substituted alkyl group, alkenyl group, alkynyl. group, a cycloalkyl group, cycloalkenyl group or or an aryl group, -Z _10, or And Z is O, S (O) m, Or -CO ₂ - and, m is a 0, 1, 2, R ₁₀ is hydrogen, optionally substituted alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group or an aryl group, R ₁₁ , R ₁₂ are the same or different and each represents a hydrogen, an optionally substituted alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group or an aryl group, and further R ₁₁ and R ₁₂ together Thus, a ring may be formed with or without a hetero atom. R ₄ is halogen or -SR ₁₃ (where R ₁₃ is an optionally substituted alkyl group, an alkenyl group, an alkynyl group,. Showing a cycloalkyl group or an aryl group) compound represented by showing a], a method of manufacturing the same And an insecticide containing the compound.

 The production of the compound of the present invention is performed as follows.

(1) When R ₄ is halogen: In the above formula, Hal represents a halogen, and R ₁ , R ₂ , R ₃ and X have the same meaning as described above.

The reaction is carried out in an inert organic solvent such as chloroform, dichloroethane, carbon tetrachloride or the like at room temperature or under heating.
Benzoyl peroxide (BPO) or the like may be used as a reaction initiator.

As the halogenating agent, when Hal is a chlorine atom or a bromine atom, N-chlorosuccinoimide (NCS),
When N-bromosuccinoimide (NBS) is Hal is a fluorine atom, N-fluoro-2,4,6-trimethylpyridinium triflate (hereinafter referred to as F-agent) can be used.

(2) When R ₄ is -SR ₁₃ : In the above formula, L is the formula Or halogen, and R ₁ , R ₂ , R ₃ , R ₁₃ and X have the same meaning as described above. The reaction is carried out in an inert organic solvent such as chloroform, dichloroethane, and tetrachlorinated carbon at room temperature to
It is performed under reflux. If necessary, triethylamine, pyridine or the like is used as a catalyst or a deoxidizing agent.

(3) When R ₂ is hydrogen: In the above formula, Hal ₁ and Hal ₂ represent the same or different halogens, and R ₁ , R ₈ , R ₉ and X have the same meaning as described above.

The production of the general formula [IV] from the general formula [IV] is carried out under the same reaction conditions as in (1) using 2 mol or more of a halogenating agent. When entering different halogen atoms into Hal ₁ and Hal ₂
It is produced by carrying out a reaction in two steps by appropriately combining NCS, NBS, F agent and the like.

The reaction of the general formulas [IV] to [I] is carried out in an inert organic solvent, preferably an alcohol such as methanol or ethanol, at room temperature or under heating.

(5) When R ₈ is hydrogen: In the above formula, R ₁ , R ₂ , R ₉ , Hal ₁ , Hal ₂ and X have the same meaning as described above.

The production of the general formula [V] from the general formula [VII] and the production of the general formula [I ⁴ '] from the general formula [V] are the same as in the case of (4).

After completion of the reaction, the desired product can be obtained by performing ordinary post-treatment. The structure of the compound of the present invention is IR, NMR, M
Determined from ASS etc.

In the compound of the present invention, when R ₂ is hydrogen, May exist.

Also, R ₃ And when R ₈ is hydrogen, Such tautomers may exist.

Further, isomers (A) and (B) as shown below may exist, but their abundances differ depending on the measurement conditions of instrumental analysis.

[Example-Compound] Next, the compound of the present invention will be described in more detail with reference to examples.

Example 1 1-chloro-2- (N-methyl-N-2-chloropyridin-5-ylmethylamino) -2-methylamino-1-
Nitroethylene (Compound No. 48): 2.6 g of 2- (N-methyl-N-2-chloropyridin-5-ylmethylamino) -2-methylamino-1-nitroethylene is dissolved in 30 ml of chloroform, and 1.4 g of N-chlorosuccinoimide is added thereto. For 3 hours. After completion of the reaction, insolubles were filtered and chloroform was distilled off to obtain a crystalline substance. The crystalline substance was reconstituted with acetonitrile to obtain 2.5 g of the desired product. mp 109.5-111.5 ° C.

Example 2 1-chloro-2- (2-chloropyridin-5-ylmethylamino) -2-methylamino-1-nitroethylene (Compound No. 1): 2- (2-chloropyridin-5-ylmethylamino)
0.96 g of -2-methylamino-1-nitroethylene was dissolved in 30 ml of chloroform, and N-chlorosuccinoimide 1.
Add 2 g and stir at room temperature for 1 hour. After the reaction, wash with water,
After drying over magnesium sulfate, the solvent was distilled off to obtain a crystalline substance (D). The obtained crystalline compound (D) was further dissolved in 50 ml of methanol, 0.6 g of sodium borohydride was added, and the mixture was stirred at room temperature for 20 minutes. After completion of the reaction, the residue was decomposed with a small amount of water and the solvent was distilled off under reduced pressure. The obtained oily substance was separated and purified by column chromatography to obtain 0.96 g of the desired product. mp 117-118 ° C.

Example 3 1- (2-methylphenylthio) -2- (N-methyl-
N-2-chloropyridine-5-methylamino) -2-methylamino-1-nitroethylene (Compound No. 237): 1.3 g of 2- (N-methyl-N-2-chloropyridine-5-methylamine) -2-methylamino-1-nitroethylene, 1.2 g of N-2-methylphenylthiosuccinoimino in 20 ml of ethylene chloride, Add 1 ml of triethylamine and add 8
Reflux for hours. After completion of the reaction, the solvent was distilled off, and the obtained oily substance was separated and purified by column chromatography to obtain 0.8 g of the desired product. mp 60-63 ° C.

Table 1 shows the representative compounds of the present invention including the above examples.

The compound of the present invention has high insecticidal activity against various pests such as armyworm, moth, aphid, leafhopper and brown planthopper. In recent years, many insect pests such as moth, planthopper, leafhopper, aphid and the like have developed resistance to organophosphates and carbamates, causing a problem of insufficient efficacy of those agents. Is desired. The compound of the present invention is an agent having an excellent insecticidal effect not only on susceptible strains but also on insect pests which are resistant to organophosphates and carbamates.

[Means for solving the problem-insecticide]

The insecticide of the present invention contains the compound represented by the general formula [I] as an active ingredient, and the active ingredient compound can be used as it is as a pure product. , Wettable powders, water solvents, powders, emulsions, granules, flowables and the like. As an additive and a carrier, when a solid agent is intended, soybean flour, vegetable powder such as flour, diatomaceous earth, apatite, gypsum, talc, bentonite, mineral fine powder such as clay, sodium benzoate,
Organic and inorganic compounds such as urea and sodium sulfate are used.

When intended for liquid dosage forms, vegetable oil, mineral oil, kerosene, petroleum fractions such as xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, trichloroethylene, methyl isobutyl ketone, water, etc. as solvents use. In these formulations, a surfactant can be added if necessary to obtain a uniform and stable form. The wettable powder, emulsion, aqueous solution and flowable thus obtained are diluted with water to a predetermined concentration and used as a suspension or emulsion. Is done.

It goes without saying that the compound of the present invention alone is sufficiently effective, but it can also be used as a mixture with various insecticides, acaricides and fungicides.

Representative examples of miticides and insecticides that can be used by mixing with the compound of the present invention are shown below.

Acaricides (fungicides): chlorbenzylate, chlorpropylate, proclonol, phenisobromolate, dicofol, dinobutone, binapacryl, chlorphenamide, amidraz,
BPPS, PPPS, benzomate, hexithiaox, fenbutatin oxide, polynactin, quinomethionate, thioquinox, CPCBS, tetradiphone, kayaside, avermectin, lime polysulfide, clofendegin, flubenzmin, flufenoxuron, thiophanate methyl,
Benomyl, thiuram, IBP, EDDP, fusalide, probenazole, isoprothiolane, TPN, captan, polyoxin, blasticidin S, kasugamycin, validamycin, tricyclazole, pyroquilon, phenazine oxide, mepronil, flutranil, pencyclon, iprodione, himexazole, metalaxyl, triflumimil Zol, diclomedin, teclophthalam.

Organic acids and carbamate insecticides (miticides): fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, bamidione, fentoate,
Dimethoate, Formothion, Marathon, Dipterex, Thiometon, Phosmet, Menazone, Dichlorvos, Acephate, EPBP, Diarihor, Methylparathion, Oxydimetone-methyl, Ethion, Aldicarp, Propoxur, Mesomemil, BPMC, Pyrethroid insecticides (miticidal agents) ): Permethrin, cypermethrin, decamerin, fenvalerate, fenpropasulin, pyrethrin, areresulin, tetramethrin, resmethrin, pasulin, dimethrin, propasulin, bifensulin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flusilinate, etofenbrox, cycloprothrin, Tralomethrin, benzoylureaphenyl and other insecticides: diflubenzuron, chlorflu Zuron, triflumuron, teflubenzuron, buprofezin, machine oil.

(Example-insecticide)

Examples of the following formulations are shown, but the carriers, surfactants and the like to be added are not limited to these examples.

Example 4 Emulsion 10 parts of the compound of the present invention 5 parts of alkylphenylpolyoxyethylene 5 parts of dimethylformamide 50 parts of xylene 35 parts or more are mixed and dissolved, diluted with water before use, and dispersed as an emulsion.

Example 5 wettable powder 20 parts of the compound of the present invention 5 parts of higher alcohol sulfate ester 70 parts of diatomaceous earth 5 parts of white carbon The above components are mixed and pulverized into fine powder, diluted with water and sprayed as a suspension before use.

Example 6 Powder 5 parts of the compound of the present invention 94.7 parts of talc 0.3 parts of silica The above components were mixed and pulverized.

Example 7 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctyl sulfosuccinate sodium salt 1 part Sodium phosphate 1 part The above is granulated and used as it is when used.

〔The invention's effect〕

Test Example 1 Efficacy against Cotton Aphid A cucumber seeded 10 days after germination in a 2 inch pot was inoculated with 30 to 50 cotton aphids per area using a small pen. After one day, the injured insects were removed and
A solution diluted with water was sprayed so that the compound concentration became 125 ppm in accordance with the emulsion formulation shown in (1). Temperature 25 ° C, Humidity 65
%, And after 7 days, the number of live insects was counted, and the control rate was determined by comparison with the untreated plot. The results are shown in Table 2.

Target compound A: Target compound B: Test Example 2 Efficacy against Leafhopper Leafhopper A rice seedling 7 days after germination was immersed for 30 seconds in a drug solution diluted with water to a compound concentration of 125 ppm according to the emulsion formulation shown in Example 4 of the drug. . After air-drying, the treated seedlings were placed in a tester, and inoculated with ten third-instar larvae of the leafhopper leafhopper, a strain resistant to organophosphates and carbamates. It was covered with gauze and placed in a thermostat at a temperature of 25 ° C. and a humidity of 65%, and the insecticidal rate was examined after 5 days. The results are shown in Table 3.

Target compound C:

────────────────────────────────────────────────── ─── Continued on front page (51) Int.Cl. ⁶ Identification code FI C07D 213/64 C07D 213/64 213/84 213/84 277/28 277/28 277/32 277/32 // C07D 233/64 105 233/64 105 237/08 237/08 237/12 237/12 239/26 239/26 241/12 241/12 241/16 241/16 261/08 261/08 261/10 261/10 263/32 263/32 263/34 263/34 307/52 307/52 (72) Inventor Tomio Yamada 345 Takada Yanagimachi, Odawara City, Kanagawa Prefecture Japan Inside Soda Co., Ltd.Odawara Research Laboratory (72) Inventor Renpei Hatano Takada, Odawara City, Kanagawa Prefecture Yanagimachi 345 Japan Soda Co., Ltd. Odawara Research Laboratory (72) Inventor Nobuo Takakusa 345 Odawara-shi, Odawara-shi, Kanagawa Japan Soda Co., Ltd. Odawara Research Laboratory (56) References JP-A-60-116676 (JP, A) JP-A-60-67473 (JP, A) JP-A-60-61561 (JP, A) (58) Field (Int.Cl. ^6, DB name) C07D 213/00 - 213/84 C07D 277/00 - 277/32 A01N 43/00 - 43/78 REGISTRY (STN) CA (STN)

Claims (2)

(57) [Claims] 1. A compound of the formula [I] In the formula, R ₁ represents a pyridyl group substituted with a halogen atom or a thiazolyl group substituted with a halogen atom, and X represents
Methylene or a single bond, R ₂ is hydrogen or a C _1-6 alkyl group, R ₃ is a C _1-6 alkyl group, a mono C _1-6 alkylamino group or a di C _1-6 alkylamino group, R ₄ Is a halogen atom or —S—R ₁₃ (where R ₁₃ is a C _1-6 alkyl group or
And a phenyl group which may be substituted with a halogen atom or a C _1-6 alkyl group. ). Compound represented by｝. 2. Formula (I) (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and X have the same meanings as described above). An insecticide comprising as an active ingredient at least one compound represented by the formula: .