KR860000083B1 - Process for the preparation of pyrazol-4-yl phosphates - Google Patents

Abstract

New pyrazoyl phosphate esters (I) [R1 = alkyl; R2 = alkoxy or alkylthio; R3 = H or alkoxycarbonyl; X = O or S; Y = alkyl, alkoxy, alkylthio, halo, NO2 or CF3 ; n = 0-3, except for the case of n = 0, where R1 = OEt, R2 = n-propylthio, and R3 = H were prepd. by esterification of the compds. (II) with R2(OR1)p(X)Z[Z =halo . Thus, 2.0g triethylamine were added to a soln. of 3.9g 1-(4-chlorophenyl)- 4-hydroxypyrazol in 60ml acetnitryl and reacted with 4g 0-ethyl-s-n- propylthiophosphate chloride at 50≰C for 3hr., followed by purifying the reaction mixt. using the column chromatography method to give 5.2g of 0-ethyl-0-(1-4-chlorophenylpyrazol -4-yl)-s-n- propylthiophosphate ester. I are useful as insecticides and acaricides.

Description

Manufacturing method of pyrazole type phosphate esters

The present invention relates to a method for producing novel pyrazole-based phosphate esters. More specifically, the present invention is formula (I)

[Wherein R ¹ is a lower alkyl group, R ² is a lower alkoxy group or a lower alkylthio group, R ³ is a hydrogen atom or a lower alkoxycarbonyl group, X is an oxygen atom or a sulfur atom, Y is a lower alkyl group or a lower alkoxy group , A lower alkylthio group, a halogen atom, a nitro group or a trifluoromethyl group, and n represents an integer of 0, 1, 2 or 3. Provided that n is 0, R ¹ is ethyl, R ² is n-propylthio, and R ³ is a hydrogen atom.

The inventors of the present invention have a number of organic compounds for the purpose of developing insecticides which can be produced industrially advantageously, and furthermore, there is no harm to plants and low toxicity to warm-blooded animals and fish and can be used safely. Various studies have been conducted, such as synthesis and biological tests. As a result, the compound of the present invention represented by the general formula (I) has an excellent insecticidal effect against hygienic pests including plant insect pests, plant parasitic mites, animal parasitic mites, and the like. It has been found that it is advantageously obtained.

In general formula (I), the lower alkyl group represented by R < ¹ > means a C1-C4 linear or branched alkyl group, for example, methyl, ethyl n-propyl, isopropyl, n-butyl, Isobutyl, sec-butyl and the like are used. The lower alkoxy group represented by R ² means an alkoxy group having 1 to 4 carbon atoms, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy group, and the like. The lower alkylthio group used means an alkylthio group having 1 to 4 carbon atoms, for example, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butyl tea. Ogi etc. are used. As the lower alkoxy carbonyl group represented by R ³ , for example, a C 2-5 alkoxycarbonyl group such as methoxycarbonyl or ethoxycarbonyl is used. Of the groups represented by Y, the lower alkyl group, the lower alkoxy group and the lower alkylthio group have the same meaning as the respective groups defined by R ¹ and R ² , but in addition to the phase, t-butyl is also used. As the halogen atom, fluorine, chlorine and bromine iodine atoms are used. n- represents the number of the substituent groups Y, and when it has two or more Y, these substituents may be same or different. Moreover, when group represented by Y is a lower alkoxy group, and n is 2, when two alkoxy groups are combined and it forms an alkiridenedioxy group, such as methylenedioxy and isopropylidenedioxy, this invention is also this invention. It is included in the range of.

Among the compounds of the present invention, ^one group of particularly important compounds is a compound of formula (I) wherein R ¹ represents an ethyl group and R ² represents a -propylthio group. Also important is the group of compounds in which R ³ represents a hydrogen atom.

The compound of the present invention has a strong insecticidal action against many insects and ticks, and also has an excellent feature of relatively low oral acute toxicity to warm-blooded animals while maintaining such excellent action. Among the compounds of the present invention, a group of compounds in which R ^{1, which} is an especially important compound, has an ethyl group and R ² having an n-propylthio group bond, exhibits excellent control effects, in particular, against insect pests and ticks, and moreover, warm-blooded animals Low oral acute toxicity to This action is also manifested by contacting the compound of the present invention with insects, such as by directly spraying a pest parasitic plant or the like, but once the drug is absorbed into the plant from the root, leaf, stem, etc., the plant is sucked by the pest. It can also be seen by eating, chewing, or touching it.

Compound (I) of the present invention can be produced by a method known per se.

For example, general formula (II)

Wherein R ³ , Y and n are of the same meaning as described above, the compound represented by General Formula (III)

In the formula, Hal represents a halogen atom, and R ¹ , R ² and X can be prepared by esterifying with a compound represented by the above meaning. The reaction of esterification is preferably carried out in the presence of an acid binder.

Suitable acid binders include, in particular, tertiary amines such as trialkylamines, pyridine r-clidines or alkyllithium metals such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate and alkyls. Lithium metal hydroxides, carbonates, bicarbonates and alkali metal alcoholates are used. As the salt of the 4-hydroxypyrazole compound of the general formula (II), a corresponding alkali metal salt is suitable, and sodium salt, potassium salt and the like are preferable. It is preferable that reaction is generally performed in a suitable solvent, For example, water, methanol, ethanol, n-propanol, isopropane, alcohols, such as n-butanol and t-butanol, benzene, toluene, xylene, etc. Halogenated hydrocarbons such as aromatic hydrocarbons, methylene chloride and chloroform tetrachloride, ethers such as ethyl ether and dioxane tetrahydropolan, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile, dimethylformamide and the like Acid amides, esters such as ethyl acetate, and soxides such as dimethyl sulfoxide can be used.

Although reaction temperature can select suitably the temperature which reaction advances in the range of -20 degrees-150 degreeC, generally 0 degrees-100 degreeC is suitable. The reaction is completed in 0.5 hours to 10 hours, but the end can be confirmed by thin layer chromatography or the like.

After completion of the reaction, the reaction mixture can be pasted to its own known means to obtain the target product. For example, the reaction solution is washed with water as it is, or the solvent is removed, followed by extraction with an organic solvent such as toluene and washing with water. After drying this with anhydrous sodium sulfate etc., a solvent is distilled off and the compound of this invention is obtained. As needed, you may refine | purify again by means, such as distillation, recrystallization, column chromatography.

In addition, the compound (I) of the present invention represents a compound of the general formula (II) or a salt thereof in the general formula (IV).

Wherein R ² , X and Hal are the same compounds as described above, and are esterified in the same manner as in the reaction of the compound of the general formula (II) with the compound of the general formula (III).

Wherein R ² , R ³ , X, Y, Hal and n are of the same meaning as described above, and then react with this compound represented by R ¹ OH (R ¹ is of the same meaning). It can manufacture by making it. In the compound represented by the general formula (I), in particular, X is an oxygen atom, and R ² is a lower alkylthio group.

[Wherein, R ¹ , R ³ , Y and n are as defined above and R ⁵ represents a lower alkyl group. Except that n is 0, R ¹ is ethyl R ⁵ is n-propyl, and R ³ is a hydrogen atom.

0-lower alkyl-0- (1-phenylpyrazol-4-yl) thio represented by [wherein R ¹ , R ³ , Y and n are the same as defined above, M represents a metal atom or an ammonium group] Phosphates and General Formulas

In the formula, Hal represents a halogen atom, and R ⁵ can be produced by reacting a commonly used alkylating agent such as represented by the above. As the lower alkyl group represented by R ⁵ , methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl group and the like are used.

The reaction can be carried out under the same conditions as the reaction of the compound of the general formula (II) and the compound of the general formula (III), but when the branched lower alkylhalogen compound is used, the reaction is generally lengthened slightly longer. Can advantageously be derived. Further, the raw material compound represented by the general formula (Ⅶ) is generally known to be executed method, that is, a compound represented by the general formula (Ⅴ), X is a sulfur atom, R ² is a lower alkoxy group, which Hal is a chlorine atom A method of reacting alkali hydroxide with 0-lower alkyl 0- (1-phenylpyrazol-4-yl) thiophosphoric acid chloride, or a compound represented by formula (I), wherein X is a sulfur atom, R Sodium hydrosulfide, sodium alkyl mercaptide, sodium xanthogenate in anhydrous alcohol to 0, 0-di- lower alkyl-0- (1-phenylpyrazol-4-yl) thiophosphate ester which is a ^divalent lower alkoxy group, or It is manufactured by making potassium xanthogenate and the like react.

The raw material compound of the general formula (II) used in these reactions may be prepared by the method described in Annalen der Chemie Vol. 313, p. 12 (1900) or the like. Can be.

In addition, the present inventors studied a novel method for preparing a raw material compound of industrial formula (II) (wherein R ³ = H), which is industrially advantageous, and under general conditions, the general formula (II) (where The following root was obtained from which the compound of R ³ = H) was obtained. In other words, the present method is an industrial manufacturing process, which would be very valuable, most of the raw material compound represented by the general formula ^{(Ⅱ) (R 3 = H} ) of the present invention can be prepared according to this method.

This method is a method of reacting a 4-halo aceto acetic acid represented by the general formula (VII) with a diazonium salt represented by the general formula (VII) in the presence of a base to form a 3-halow pyruv represented by the general formula (XI). after obtaining the aldehyde phenylhydrazone jonryu, to this ring closure with a base to obtain a compound represented by the general formula ^{(ⅱ) (R 3 = H} ).

The reaction for obtaining 3-haloyl pyruvaldehyde phenylhydrazones represented by the general formula (XI) is generally carried out at a temperature of -10 ° to 30 ° C. Although water is suitable as a solvent, alcohols, such as methanol, ethanol, and propane, may be added in order to suppress the generated crystals from being flushed with the generation of carbon dioxide gas. Examples of the base include organic carbonates, carbonates and carbonates of alkali metals and alkaline earth metals such as sodium acetate, potassium acetate, sodium propionate, potassium propionate, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide and potassium hydroxide. Anti-inflammatory, hydroxide and the like are used.

Next, in the compound of the general formula (XI), the reaction for obtaining the compound of the general formula (II) (wherein R ³ = H) is performed in the presence of a base. Examples of the base include hydroxides, carbonates, hydrogen carbonates and alkali metal alcoholates of alkali metals and alkaline earth metals such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide, sodium methylate and sodium ethylate. Among them, strong bases such as sodium hydroxide, potassium hydroxide and alkali metal alcoholate are preferable. The amount of the base used for the reaction is preferably economically 1 to 3 molar amounts relative to the compound (XI), but there is no problem even if used too much.

It is preferable to perform reaction in a solvent, For example, alcohol, such as water, methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, ethers, such as ethyl ether, dioxane, tetrahydrofran , Ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile, acid amides such as dimetalformamide, and sulfoxides such as dimethyl sulfoxide. The reaction generally proceeds in the range of -20 ° to 100 ° C. However, when sodium hydroxide, potassium hydroxide, alkali metal alcoholate or the like is used as the base in the alcohol solvent, the reaction is easy even at a temperature of 0 ° C or less. Proceed to In addition, the present method is that the desired product is also ^{(Ⅱ) (R 3 = H} ) by reaction in succession without isolating the compound (XI) in the middle can be obtained with yield. Next, the synthesis example of the raw material compound by the said manufacturing method is shown.

Reference Example A

Synthesis of 1- (4-chlorophenyl) -4-hydroxypyrazole (Compound No.e).

4.0 g of sodium hydroxide is dissolved in 50 ml of methanol, and when 9.3 g of 3-chloropyruvaldehyde 4-chlorophenylhydrazone is added at room temperature, the solution is immediately dissolved and the liquid temperature rises to approximately 40 ° C. After stirring for 1 hour, methanol is distilled off, and 50 ml of water is added to the residue, and the insoluble substance is filtered off. Neutralize with concentrated hydrochloric acid and precipitated crystals are filtered, washed with water and dried. Recrystallization from toluene yields 6.4 g of the indicated compound of the needle bed bottom. Melting Point 127-128 ℃

Reference Example B

Synthesis of 1- (4-chlorophenyl) -4-hydroxypyrazole (Compound No.e).

4.0 g of sodium hydroxide is dissolved in 50 ml of water, and then 9.3 g of 3-chloropyruvaldehyde 4-chlorophenylhydrazone is suspended and stirred at 50 ° C. for 3 hours. The crystals are gradually dissolved to form a dark red uniform solution. After cooling, the insolubles are filtered off, and the crystals which have been neutralized with concentrated hydrochloric acid and precipitated are filtered, washed with water and dried. Recrystallization from toluene yields 5.7 g of the indicated compound. Melting Point 127-128 ℃

Reference Example C

Synthesis of 1- (2,4-dichlorophenyl) -4-hydroxypyrazole (Compound No.n) 27.0 g of 3-chloropyruvaldehyde 2,4-dichlorophenylhydrazone was suspended in 100 ml of ethanol, and 12 g of dissolved sodium hydroxide is added to 10 ml. After stirring for 2 hours, ethanol is distilled off and water is added to the residue to dissolve. The insoluble matter is filtered off, the filtrate is neutralized with glacial acetic acid, and the precipitated crystals are filtered, washed with water and dried. Recrystallization from toluene gave 17.3 g of the indicated compound. Yield 87%, exemplifies a compound having a melting point of 148~149 ℃ in Reference Example A~C next Therefore, formula ^{(Ⅱ) (R 3 = H} ) synthesized in the following table.

Reference Example D

Dissolve 128 g of parachloroaniline in 500 ml of a compound of 3-chloropyruvaldehyde 4-chlorophenylhydrazone (Compound No.F) and 250 ml of concentrated hydrochloric acid, and add 69 g of sodium acetate dissolved in 100 ml of water while maintaining the temperature at 0 ° C. . Next, 136.5 g of 4-chloroaceto acetic acid dissolved in 200 ml of water was added while maintaining at 0 to 5 ° C., and 164 g of sodium acetate dissolved in 300 ml of water were further added. Immediately yellow crystals precipitate and violently blow. After stirring at room temperature until generation of gas stops, the crystals are filtered, washed with water and dried to obtain 224 g of the indicated compound.

Yield 97%, Melting Point 190-192 ° C (Decomposition)

Next, raw materials of the general formula (XI) synthesized in the same manner as in the reference example are shown in the following table.

* No melting point

In addition, the phosphate chloride represented by general formula (III) or (IV) can be manufactured easily by a well-known method or a method similar to a well-known method.

Compound (I) of the present invention is a hygienic pest. It is effective in controlling plant parasitic insects and mites. More specifically, the compound of the present invention and the composition containing the same are, for example, Lugosa (Eurydema rugosa), Scotinophara lurida, Riptortus clavatus, Stephanitis nashi, Poor pendulum ( Laodelphax stiatellus, Nephotettix cincticeps, Janone pod aphid (Unaspis yanonensis), Bean aphid (Aphis glycines), Radish pseudobrassicae, Radish aphid (Brevicoryne brass gothic aphid) Half-timber pests such as Spodoptera litura, moth (Plutella xylostella), white butterfly (Pieris rape crucivora), chilo suppressalis, plusia nigrisigna, tobacco moth (Halicoverpa assulta) Examples of insect pests include chestnut moth (Leucania separata), Chinese cabbage night moth (Mamestra brassicae), leaf moth (Adoxophyes orana), Syllepte derogata, Cnaphalocrocis medi-nalis, and potato moth (Phthorimaea operculella) For example, plant insects such as Epilachna vigintioctopunctata, Aulacophora femoralis, Yellow leaf beetle (Phyllotreta striolata), Olema orgzae, Echinocnemus squameus, etc. Musky pests such as Musca domestica, Culexpipiens pallens, Tabanus trigonus, Hylimya antiqua, Hylemys platura, for example Locusta migratoria Direct insects such as Gryllotalpa africana, cockroach pests such as the brown cockroach (Blattella germ-anica) and black cockroach (Periplaneta fuliginosa), such as Tetranychus urticae, Pantannychus citri, Nematodes, such as the Tetranychus kanzawai, Tetranychus cinnabarinus, Pansnychus ulmi, and Aculops pelekassi, and nematodes, such as Aphelenchoides besseyi. , Xilidu (lxodidae) Of dongmulgi generated and is particularly effective in the control of mites, etc.

In the use of the compound (I) of the present invention as an insecticidal composition, one or two or more forms of general pesticides, that is, compounds (I) may be dissolved or dispersed in a suitable liquid carrier depending on the purpose of use. In addition, the mixture is adsorbed with a suitable solid carrier or adsorbed and used as a formulation such as an emulsion, an emulsion, a hydrating agent, a powder, a granule, a tablet, a spray, an ointment. If necessary, these agents may be added an emulsifier, a suspending agent, a progressing agent, a penetrating agent, a humectant, a manager, a stabilizer and the like, and can be prepared by a publicly known method.

Although the content ratio of the active ingredient in the insecticidal composition is different depending on the purpose of use, about 10 to 90% by weight of the emulsion, wetting agent, etc. are suitable, and about 0.1% to 10% by weight of the emulsion, powder, etc. Is suitable, and about 1% to 20% by weight is suitable as granulation, but these concentrations may be appropriately changed depending on the purpose of use. In addition, an oil agent, a hydrating agent, etc., in use, it is good to spray by diluting with red dilution weight (for example, 100-100000 times) with water etc.

, 다께모도 유지사제), 알킬황산염류(예, 에멀 10

, 에멀 40

, 가오오아토라스사제), 알킬슬폰산염류(예, 네오겐

, 네오겐 T

, 다이이찌고오교오제약사 제), 네오페렉스

, 가오오아토라스사 제), 폴리에틸렌글리코올에테르류(예, 노니포올 85

, 노니포올 100

, 노니포올 160

, 산요오가세이사 제), 다가알코올 에스테르류(예, 토우인 20

, 토우인 80

, 가오오아토라스사 제)등이 사용된다. 또, 본 발명 화합물과 예를들면 타 종류의 살충제(피레트린계 살충제, 유기인산계 살충제, 카르바메이트계 살충제, 천연살충제 등) 살제비, 살선충제, 제초제, 식물홀몬제, 식물발육조절물질, 살균제(예를들면 구리계 살균제, 유기염소계 살균제, 유기유황계 살균제, 페놀계 살균제 등), 협력제, 유인제, 기피제, 색소, 비료 등을 배합하여, 혼합 사용하는 것도 가능한 것이다.As a liquid carrier to be used, for example, water, alcohols (eg, methyl, alcohol, ethyl alcohol, ethylene glycol, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.), ethers ( For example, dioxane, tetrahydrofuran, cellosolve, etc., aliphatic hydrocarbons (e.g. gasoline, petroleum, kerosene, fuel oil, base oil, etc.), aromatic hydrocarbons (e.g. benzene, toluene, Xylene, solvent naphtha, methylnaphthalene, etc.), halogenated hydrocarbons (e.g., chloroform, carbon tetrachloride, etc.), acid amides (e.g., dimethylformamide, etc.), esters (e.g., ethyl acetate) Solvents such as butyl acetate, glycerin esters of fatty acids, and the like, nitriles (for example, acetonitrile, etc.), and one or a mixture of two or more thereof is used. Examples of solid carriers include plant powders (e.g., soy flour, tobacco powder, wheat flour, wood flour), mineral powders (e.g., talc, such as kaolin, bentonite, acidic clay, talc powder, and talc powder, Silica, such as diatomaceous earth, mica powder, etc.) Alumina, sulfur powder, activated carbon, etc. are also used, 1 type, or 2 or more types of these are used. In addition, as the ointment agent, for example, polyethylene glycol, pecting, for example, polyhydric alcohol esters of higher fatty acids such as monostearic acid glycerin test, cellulose derivatives such as methyl cellulose, sodium alginate, bentonite , One or two or more kinds of higher alcohols, for example, polyhydric alcohols such as glycerin, waselin, white waselin, liquid paraffin, lard, various vegetable oils, lanolin, dehydrated lanolin, hydrogenated oil, resins, and various interfaces thereof. The thing which added activator etc. can be selected suitably. Moreover, as surfactant used as an emulsifier, an electrodeposition agent, a penetrant, a dispersing agent, etc., soaps, polyoxyalkylaryl esters (enonalal as needed)

, Kedodo oils and fats), alkyl sulfates (e.g. emulsion 10

, Emulsion 40

, Manufactured by Gao Attora Co., Ltd., alkyl sulfonates (e.g. neogen

, Neogen T

, Daiichi Gokyo Pharmaceutical Co., Ltd.), Neoperex

, Gao Atator's Co., Ltd., polyethylene glycol ethers (e.g., nonipool 85

, Nonipool 100

, Nonipool 160

, Sanyo Kasei Co., Ltd., polyhydric alcohol esters (e.g., toin 20

, Toin-in 80

, Gao Attoras Co.) are used. In addition, the compounds of the present invention and other types of insecticides (pyrethrin insecticides, organophosphate insecticides, carbamate insecticides, natural insecticides, etc.) insecticides, nematicides, herbicides, plant holmones, plant growth regulators , A fungicide (for example, a copper fungicide, an organochlorine fungicide, an organic sulfur fungicide, a phenol fungicide, etc.), a cooperative agent, an attractant, a repellent, a dye, a fertilizer, etc., may be mixed and used.

Next, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

Example 1

Preparation of 0-ethyl-0- [1-4-chlorophenyl) pyrazol-4-yl] -s-n-propylthiophosphate ester (Compound No. 14). 3.9 g of 1- (4-chlorophenyl) -4-hydroxypyrazole is dissolved in 60 ml of acetonitrile, and 2.0 g of triethylamine is added. Next, 4.0 g of 0-ethyl-s-n-propylthiophosphate chloride is added, and it stirred at 50 degreeC for 3 hours. After completion of the reaction, acetonitrile is distilled off.

1.5604The residue was purified by silica gel column and chromatography (developing solvent, chloroform) to give 5.2 g of the title compound as pale yellow oil.

1.5604

Example 2

Preparation of 0-ethyl-0- [1- (3,4-dichlorophenyl) pyrazol-4-yl] -s-n-propylthiophosphate ester (Compound No. 29)

1.57374.6 g of 1- (3,4-dichlorophenyl) -4-hydroxypyrazole was dissolved in 60 ml of methyl ethyl ketone, and 2.8 g of potassium carbonate and 4.0 g of 0-ethyl-sn-propylthiophosphate were added thereto. Stir at C for 2 hours. Purification according to the following Example 1 yields 5.9 g of the title compound as pale yellow oil.

1.5737

Example 3

Preparation of 0-ethyl-0- [1- (4-chlorophenyl) pyrazol-4-yl] -s-n-propylthiophosphate ester (Compound No. 14)

1.5604To 60 ml of ethanol, 6.8 g of 0-ethyl-0- [1- (4-chlorophenyl) pyrazol-4-yl] thiophosphate and 2.7 g of n-propyl bromide were added, followed by stirring at 70 ° C. for 8 hours. The resulting inorganic salt is filtered off to remove ethanol, toluene is added to the residue, and the toluene layer is washed with water and dried. When prepared according to Example 1 below, 5.0 g of the title compound in the form of a pale yellow oil was obtained.

1.5604

Next, the compound synthesize | combined by the method similar to Examples 1-3 is shown in Table 1 including the compound obtained by Examples 1-3.

TABLE 1

Example 4 Emulsion

Compound no. 14 20% by weight

Xylene 75 wt%

) 5중량%인 성분을 혼합해서 제조한 유제.Polyoxyethylene glycol ether (nonipool 85

) An emulsion prepared by mixing 5% by weight of components.

Example 5 Hydration

Compound no. 17 30% by weight

5% by weight of lignin sulfonate

) 5중량%Polyoxyethylene Glycool Ether (Nonipool 85

5% by weight

30% by weight of white carbon

30% by weight clay

Hydrating agent prepared by mixing phosphorus component.

Example 6 Powder

Compound no. 29 3% by weight

White carbon 3% by weight

94% by weight of clay

Powder prepared by mixing phosphorus component.

Example 7 granulation

Compound no. 7 10% by weight

5% by weight of lignin sulfonate

85% by weight clay

Granulated granules by mixing phosphorus ingredients.

Example 8

Test Example 1 Effect on Laodelphax striatellus

a) A test compound was prepared into an emulsion according to the formulation of Example 4, diluted with water to prepare a 40 ppm treatment solution. 2.5 ml of this treatment solution was placed in a test tube (1.7 cm in diameter and 4 cm in depth), three sprouted tombs (day 7 after germination) were placed, and the roots were soaked for 2 hours. The test tube was placed in 1 ml of water, and 10 larvae of larvae were added. The test tube was placed indoors (28 ° C.) for 24 hours, and the number of death was examined. The test was repeated twice and the test results are shown in Table 2 (I) as mortality rates.

b) A powder was prepared according to the formulation of Example 6, and 500 mg of the powder was dumped into rice planted in a pot (1 / 5,000a) to apply the duster method. After the flesh was cut, the leaves of rice (15 cm long) were cut, placed in a test tube with 1 ml of water at the bottom, and 10 adult adults of the sluggish were placed therein. Test tubes were placed indoors (28 ° C.) to examine the number of deaths after 24 hours of insect repellent. The test was repeated twice, and the test results are shown in Table 2 (II) as mortality rates.

TABLE 2

Test Example 2 Effect on Spodoptera lifura

3,000배 첨가) 200ml를 아이스크림 컵으로 수경한 대두의 실생묘(발아 후 10일)에 분무실 내에서 분무기(분출압력 1kg/cm²)를 사용해서 살포하였다. 살포 2시간 후에 대두의 본잎 2매를 짤라내서, 각각 1매씩 아이스크림 컵(직경 6㎝, 깊이 4㎝)속에 수용하여, 야도충의 2령유충 10마리를 넣고, 방출 후 컵을 실내(25℃)에 두어서, 48시간 후의 사망충수를 조사하였다. 시험은 2회 반복 행하여 시험 결과는 사망율로 표 3에 표시하였다.a) 500 ppm water dilution of the test compound (Example 4 prescription emulsion) electrodeposition dyne

200 ml of 3,000 times) was sprayed on the seedlings (10 days after germination) of the soybeans sown with an ice cream cup using an atomizer (injection pressure 1 kg / cm ² ) in a spray chamber. After 2 hours of spraying, the two leaves of the soybeans are cut, and each one is placed in an ice cream cup (6 cm in diameter and 4 cm in depth), and 10 larvae of larvae are placed. The death toll after 48 hours was examined. The test was repeated twice and the test results are shown in Table 3 as mortality.

TABLE 3

3,000배 첨가)로 희석하여, 500ppm의 물 현탁액을 조정하였다. 이물 현탁액 20ml를 포트(직경 9㎝)에 심은 탱자의 실생묘(발아 후 2개월)에 기생시킨 야노네깍지진딧물의 2령암유충(기생두수 1-~50마리)에 살포하였다. 살포 후의 포트를 온실(25~30℃)속에 옮기고, 살포 후 20일째에 성충으로 생육한 개체수를 조사하였다. 시험은 2회 반복 행하여, 시험결과는 사망율로 표 4에 표시하였다. 사망율(%)은 다음식에 의해서 산출하였다.Test Example 3 Effect on Yanapes aphid (Unaspis yanonensis) The disclosed compound was prepared as a hydrate according to the formulation of Example 5, and water (electrode dye)

3,000-fold addition) to adjust 500 ppm of water suspension. 20 ml of the alien suspension was sprayed on the second-larvae cancer larvae (1-50 parasitic heads) of Janoneca aphids parasitic on the seedlings (2 months after germination) of a tanza planted in a pot (9 cm in diameter). The pot after spraying was moved into a greenhouse (25-30 degreeC), and the number of the adult grown on the 20th day after spraying was examined. The test was repeated twice, and the test results are shown in Table 4 as mortality rates. The mortality rate (%) was calculated by the following equation.

TABLE 4

Test Example 4 Effect on Tetranychus urticae The test compound was emulsified in the formulation of Example 4, diluted with water (3,000 times of electrodeposition dyne), and the aqueous solution of 500 ppm was adjusted. Ten female larvae of leaf mites were inoculated into the seedlings of Gangnam beans, which were hydroponicly treated with ice cream cups, placed in a glass chamber (28 ° C) for 24 hours, and 20 ml of aqueous solution was sprayed on the beans. After spraying, the cups were returned to the glass chamber, and the oily reptiles growing on the leaves were examined on days 2 and 7 after spraying. The test was repeated five times, and the test result was calculated by the following equation, and is shown in Table 5 according to the validity stage.

TABLE 5

Reference Example Toxicity Test

Venus oral toxicity values for 5 week old ddY-SLC strains (♂) are indicated.

Claims (1)

General formula (Ⅱ)

[Wherein, R ³ represents a hydrogen atom or a lower alkoxy carbonyl group, Y represents a lower alkyl group, a lower alkoxy group, a lower alkylthio group, a halogen atom, a nitro group or a trifluoromethyl group, and n represents 0.1, 2, or 3 The integer of which is represented by the following formula; or its salt is represented by a formula (III)

Wherein R ¹ represents a lower alkyl group, R ² represents a lower alkoxy group or a lower alkylthio group, X represents an oxygen atom or a sulfur atom, and Hal represents a halogen atom. General formula (Ⅰ)

[Wherein R ¹ , R ² , R ³ , X, Y and n are of the same meaning as above, provided that n is O, R ¹ is ethyl, R ² is n-propylthio, and R ³ is a hydrogen atom Manufacturing method of the compound