JPH02295961A - Guanidine derivative, production thereof and insecticide and acaricide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I {R<1> is formula IV [R<5> is phenyl or thienyl; A is -O- or formula V (R<8> and R<9> are H, alkyl or alkoxy); R<6> and R<7> are alkyl or alkoxyalkyl]; R<2> is alkyl; R<3> is H, alkyl, alkenyl, benzyl, etc.; R4 is H or alkyl}. EXAMPLE:N-(4-Benzyl-2,6-diisopropylphenyl)-N'-tert. butyl-N''-hydroxyguanidine. USE:An insecticide and acaricide. PREPARATION:A compound expressed by formula II is reacted with an amine expressed by formula III and hydrochloride thereof as shown in the reaction formula to provide the compound expressed by formula I. The reaction is car ried out without solvent or in water or organic solvent at 0-120 deg.C, preferably at ambient temperature to boiling point of solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel guanidine derivative, a method for producing the same, and an insecticide/acaricide.

[Conventional technology]

Various compounds, including organophosphorus compounds, carbamate compounds, pyrethroid compounds, and dinitro compounds, are used to control harmful insects and mites, but in recent years, insect pests that are resistant to these drugs have been used. With the emergence of insects and mites, it has become difficult to control them, and new types of insecticides and acaricides are desired.

The following compounds are known as compounds having a skeleton similar to the compound of the present invention.

(East German patent 84530 and French patent 2098r, r
t: hydrogen, Cl-1 to alkyl, aryl, aralkyl, etc. rt rs: alkyl, halogen, nitro, alkoxy, alkylthio, amino, substituted amino; Both of these two patents indicate use as a herbicide.

[Ll that the invention tries to solve! ! An object of the present invention is to provide a drug that can be industrially advantageously synthesized, has reliable effects, and can be used safely.

[Means to solve the problem]

The present invention provides - Formula (1): hydrogen, an alkyl group optionally substituted with a halogen or an alkoxy group, an alkenyl group optionally substituted with a halogen, an alkyl group substituted with a halogen, an alkyl group, an alkoxycarbonyl group, or a cyano group. optionally substituted benzyl group, optionally substituted with halogen, Rs: substituted? A phenyl group or thienyl group that may have I) Rh R? , each independently an alkyl group or an alkoxyalkyl group; R2: an alkyl group; an alkyl group optionally substituted with an alkoxy group, a phenoxy group, (alkoxy(RI Cycloalkyl group or phenyl group)); R': Hydrogen or alkyl group) Compounds of the present invention, their production methods, and insecticides and acaricides 6. The compounds of the present invention can be used for armyworms, diamondback moths, aphids, leafhoppers, brown grasshoppers, etc. Insecticides such as organic phosphorus agents and carbamate agents frequently exhibit high insecticidal and acaricidal activity against various pests and insects such as two-spotted spider mites. However, resistance to acaricides has developed, resulting in the lack of efficacy of these drugs.Therefore, there is a desire for a drug that is effective against resistant strains of insect pests and mites. As well,
The method for producing the compound of the present invention, which is a drug having an excellent insecticidal effect on insect pests and mites resistant to organic phosphorus agents, carbamate agents, and various acaricides, is as follows.

(I+) (Ill) Here, RI
R1Rs Ra has the same meaning as above.

0 to 120°C, preferably from room temperature to 11°C, without solvent, in water, or in a solvent with IR. The amine of formula [1] can also be used as its hydrochloride, which is carried out up to the boiling point of the solvent.

As the solvent, alcohols, aromatic hydrocarbons such as toluene, etc. are used.

(IV) (V) R'R''R'R' has the same meaning as above, X represents a halogen atom, and an inorganic alkali such as potassium carbonate or a tertiary amine such as triethylamine is used as the deoxidizing agent. As the solvent, when an inorganic alkali is used, acetone, acetonitrile, etc. can be used, and when a tertiary amine is used, acetone, acetonitrile, halogenated hydrocarbon, aromatic hydrocarbon, etc. can be used.

The reaction is carried out at a temperature of 0 to 120"C, preferably from room temperature to the boiling point of various solvents. The compound (f) of the present invention can also be synthesized by the following method.

Z Z can be C1, Br, 5R1OR, etc. After the reaction is completed, the desired product can be obtained by performing a usual post-treatment.

The structure of the compound of the present invention was determined from IR, NMR, MASS, etc. The compound of the present invention has the following tautomers.

[Example] Next, the compound of the present invention will be explained in more detail with reference to Examples.

Example 1 N-(4-benzyl-2,6-diitubrobylphenyl)-N'-Lertbutyl-N'-hydroxyguanidine (compound number 1): When R' is hydrogen, the following There are tautomers.

R'NHCNHI(-N-(4-benzyl-2,6-diisopropylphenyl)-N'-terL butylcarbodiimide IO,Og
and 2.73 g of hydroxyamine hydrochloride were reacted in 5 ml of ethanol at room temperature for 24 hours.

The reaction solution was poured into an aqueous sodium hydrogen carbonate solution, and the resulting crystals were filtered and washed with water. Further, the crystals were washed with a mixture of n-hexane and ethyl acetate and dried to obtain the desired product. Yield Ji 7.86g, melting point J 81.0-1B
3.0°C.

Example 2 Separation with N-(4-benzyl-2,6-dibutylphenyl)-N'-Lertbutyl-N''-ethoxyguanidine (compound number 3) yielded 1.55 g of the target product. I got it.

m, p, 77.0-79.0°C0 Example 3 N-(4-benzyl-2,6-diitupropylphenyl)-N'-tertbutyl-N''=(3-chlorobenzyloxy) Guanidine (Compound No. 16) N-(4-benzyl-2,6-diitubrobylphenyl)-N'-tertbutylcarbodiimide 1.74 g
, 0.46 g of ethoxyamine was added to 10 d of ethanol and stirred at room temperature for 24 hours. The reaction solution was added to the aqueous layer and extracted with ethyl ether. After washing the ether layer with water and dehydrating it with anhydrous magnesium sulfate, the ether was distilled off and subjected to silica gel column chromatography (developing solvent: n-hexane:
Ethyl acetate N-(4-benzyl-2,6-diitubrobylphenyl)-N'-tertbutyl-N''-hydroxyguanidine 1. Og 3-chlorobenzyl chloride 0
．． 46g, potassium carbonate 0.36g acetonitrile 101! and heated under reflux for 7.5 hours.

After cooling, the reaction solution was poured into water and extracted with diethyl ether. The ether layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. After evaporating the ether under reduced pressure, the residual liquid was separated by silica gel column chromatography (developing solvent: n-1-xane:ethyl acetate = 2.1:1) to obtain 0.76 g of the desired product.

n 14°'1.5520 Representative examples of the compounds of the present invention, including the above examples, are shown in Table 1.

[Means for solving the problem - Insecticide/acaricide] The insecticide/acaricide of the present invention contains the compound represented by formula (1) as an active ingredient, and the active ingredient compound is Although it can be used as a pure product, it is usually used in the forms that common agricultural chemicals can take, such as wettable powders, aqueous solutions, powders, emulsions, granules, etc.
It is used in the form of a flowable product, etc. As additives and carriers, for solidifying agents, vegetable powders such as soybean flour and wheat flour, fine mineral powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, and clay, sodium benzoate, and urea are used. Organic and inorganic compounds such as mirabilite and the like are used.

If a liquid formulation is desired, petroleum distillates such as vegetable oil, petroleum oil, kerosene, xylene, and solvent naphtha,
Cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, trichlorethylene, methyl isobutyl ketone, water, etc. are used as the solvent. In these preparations, a surfactant may be added if necessary in order to obtain a uniform and stable form. The wettable powders, emulsions, water-solvents, flowables, etc. obtained in this way can be diluted with water to a predetermined concentration to form a suspension or emulsion, and powders and granules can be sprayed on plants as they are. used.

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

Representative examples of acaricides and insecticides that can be used in combination with the compound of the present invention are shown below.

11 Antibiotics (bactericides): BCPE, chlorbenzilate, chlorpropylate, proclonol, fenisobromolate, dicofol, zipton, pinabacryl, chlorzenamidine, amitraz, BPPS: PPP
S: benzomate, hexythiazox, cyhexatin, fenbutastin oxide, polynactin, chinomethionate, thioquinox, CPCBS, tetradifon, kayaside, avermectin, polysulfide coal, chlorintedin, flubentumin flufenoxuron, organophosphorus insecticide (acaricide): Fenthion, fenitrothion, diazinon, chlorpyrifos, ESP, vamidothion,
Phentoate, dimethoate, formothion, Marathon, dibuterex, thionton, phosmet, menazone, dichlorvos, acephate, EPBP, dialifor, methyl parathion, oxydimedone methyl, nithion, aldicarb, proboxur, pyrethroid insecticides (miticides): Vermethrin, Cypermethrin, Decamethrin, Fenvalerate, Fenpropathrin, Pyrethrin, Allethrin, Tetramethrin, Resmethrin, Parsulin, Dimethrin, Propathrin,
Bifenthrin, Prosulin, Fluparinate, Cyfluthrin, Dihalothrin, Fluparinate, Etofenbrox, Cycloprothrin, Tralomethrin, Machine oil.

[Example - Insecticide/acaricide]

Next, examples of formulations will be shown, but the carriers, surfactants, etc. to be added are not limited to these examples.

Example 4 Emulsion Compound of the present invention 10 parts Alkylphenylpolyoxyethylene 5 parts Dimethylformamide 50 parts Xylene
Mix and dissolve 35 parts or more, dilute with water before use, and spray as an emulsion.

Example 5 Wettable powder Compound of the present invention 20 parts Higher alcohol sulfate ester 5 parts Diatomaceous earth
70 parts silica
Mix 5 or more parts, grind into a fine powder, dilute with water and spray as a suspension before use.

Example 6 Powder Compound of the present invention 5 parts Talc
94.6 parts silica
0.3 parts Alkylphenylpolyoxyethylene 0.1 parts or more are mixed and pulverized, and sprinkled as is before use.

〔Effect of the invention〕

Test Example 1 Efficacy against fall armyworm The compound of the present invention was diluted with water according to the formulation of the wettable powder shown in Example 5 so that the compound concentration was 125 ppm. Corn leaves were soaked in the chemical solution for 30 seconds, air-dried, placed in a petri dish with a lid, and inoculated with 5 3rd instar armyworm larvae. The petri dish has a temperature of 25'C and a humidity of 65'C.
% in a constant temperature room, and the insect killing rate was examined after 5 days. The results are shown in Table 2.

Table 2 Test Example 2 Efficacy against cotton aphids Cucumbers that had been sown in two sizes and 10 sips old after germination were inoculated with cotton aphids using a small brush at 30 to 50 heads per section. After one day, the injured pests were removed, and a chemical solution diluted with water to a compound concentration of 125 PPm was sprayed on the area according to the emulsion formulation shown in Example 4 of the above-mentioned drug. 1 degree 25°C 5 humidity 6
The plants were placed in a 5% constant temperature room, the number of live insects was counted after 7 days, and the control rate was calculated from a comparison with the untreated area. The results are shown in Table 3.

Table 1 Test Example 3 Efficacy against two-spotted spider mites Thirty female adults of organic phosphorus-resistant two-spotted spider mites were inoculated onto the first true leaves of green beans that had been sown in two sizes for 7 to 10 days after germination. According to the emulsion formulation shown in Example 4, the compound was diluted with water to a compound concentration of 125 ppm and sprayed. Three days after spraying, the survival of adult insects was investigated to determine the acaricidal rate. The results are shown in Table 4.

Control compound B (Birimi Curve) Control compound

Claims (5)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] {In the formula, R^1: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R^5: Even if it has a substituent Good phenyl group or thienyl group A: -O- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼(R
^8, R^9 are each independently hydrogen, an alkyl group, or an alkoxy group) R^6, R^7: Each independently is an alkyl group or an alkoxyalkyl group; R^2: an alkyl group; R^3: Alkyl group optionally substituted with hydrogen, halogen or alkoxy group, alkenyl group optionally substituted with halogen, benzyl group optionally substituted with halogen, alkyl group, alkoxycarbonyl group or cyano group, substituted with halogen There is a pyridylmethyl group that may be
: Halogen, alkoxy group, alkyl group which may be substituted with phenoxy group, (alkoxyiminoalkyl group,) phenyl group which may be substituted with halogen, or ▲Mathematical formula, chemical formula, table, etc.▼ (R＾ 1^1, R^1^2: each independently hydrogen, alkyl group, cycloalkyl group, or phenyl group)]; R^4: hydrogen or alkyl group). (2) Compounds represented by R^1N=C=NR^2 [II] (R^1 and R^2 have the same meanings as above) and general formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. There is a general formula [I] characterized by reacting the compound represented by ▼ [III] (R^3 and R^4 have the same meanings as above).
] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (R^1, R^2, R^3, R^4 have the same meanings as above.) A method for producing a compound represented by. (3) General formula [IV] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [IV] (R^1, R^2, R^4 have the same meanings as above.)
A general formula characterized by reacting a compound represented by the general formula [V] with a compound represented by the general formula [V] [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (R^1, R^2, R^3, R^4 have the same meanings as above.) A method for producing a compound represented by. (4) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (R^1, R^2, R^3, R^4 have the same meanings as above.) Compounds represented by An insecticide characterized by containing one or more of the following as active ingredients. (5) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (R^1, R^2, R^3, R^4 have the same meanings as above) Compounds represented by An acaricide characterized by containing one or more of the following as active ingredients.