KR840000255B1 - Process for preparation phosphoric acid esters of pyrazols - Google Patents

Abstract

The title compds. [I; R1=alkyl, cycloalkyl, aralkyl, (substituted) Ph; R2=H, lower alkyl; R3=H, halogen, NO2, alkyl, esterified CO2H; R4=lower alkyl; R5=lower alkylthio; X=O, S were prepd. and tested for insecticidal and acaricidal activity (test data tabulated). Thus, l-isopropyl-3-hydroxy-4-methylpyrazol-Na salt reacted with o-ethyl-S-n-propylthio-phosphateCl in methylethyl ketone to give o-ethyl-S-n-propyl-o-(1-isopropyl-4-methylpyrazol-3-yl) thiolophosphoric acid ester.

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 an alkyl group, alral kilgi or a phenyl group optionally substituted by a halogen atom or a lower alkyl group, R ² is a hydrogen atom or a lower alkyl group containing a cycloalkyl group, R ³ is a hydrogen atom, a halogen atom, a nitro group , A lower alkyl group or a pyrazole type represented by a group represented by the formula -COOR (wherein R ⁶ is a lower alkyl group), R ⁴ is a lower alkyl group, R ⁵ is a lower alkylthio group, and X is an oxygen atom or a sulfur atom It relates to a method for producing phosphate ethers.

The inventors of the present invention can produce an industrially advantageous, almost no harmful to plants, and also for the purpose of developing insecticidal and acaricide compositions which can be used safely and with low toxicity to warm-blooded animals or fish. Various studies have been conducted such as the synthesis of organic compounds and biological tests. As a result, it has been found that the compound of the present invention represented by the general formula (I) has an excellent insecticidal and acaricidal effect against the harmful pests, the plant pests and the plant parasitic mites, and can be industrially advantageously obtained. It was.

In general formula (I), as an alkyl group which R <^1> represents, a C1-C10 linear, branched chain, and jade mean a cyclic alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso Butyl, sec-butyl, n-pentyl, isopentyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, decyl group, and the like, and the aralkyl group include benzyl group, phenethyl group and the like. Can be mentioned. R ¹ may be a lower alkyl group or a phenyl group substituted with a halogen atom. As such a lower alkyl group and the lower alkyl group represented by R ² , R ³ , R ⁴ , and R ⁶ , a C 1-4 linear or branched alkyl group means methyl, ethyl, n-propyl, isopropyl, n -Butyl, isobutyl, sec-butyl group, etc. are mentioned. Examples of the lower alkyl thi group represented by R ⁵ include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio group, and the like. -Propylthio group is preferred. The halogen atom in the substituted phenyl group represented by R ¹ and the halogen atom represented by R ³ are a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, among which fluorine, chlorine and bromine are preferable.

When there are a plurality of substituents of substituted phenyl represented by R ¹ , these substituents may be the same or different. Specific examples of such a substituted phenyl group include 2,4-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2,4,5-trichloro Phenyl, 2,4,6-trichlorophenyl, 2,4-dibromphenyl, 4-brom-2-chlorophenyl, 4-chloro-2-chlorophenyl, 2,3-dimethylphenyl, 2,4-dimethyl Phenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 3-chloro4-methylphenyl, 3-chloro- 2methylphenyl, 4-chloro-2-methylphenyl, 5-chloro-2-methylphenyl, 2-brom-4-methylphenyl, 4-brom-2-methylphenyl, 4-brom-2,6-dimethylphenyl, etc. are mentioned. .

Among the compounds of the present name, one group of particularly important compounds is a general formula (I) wherein R ₄ represents an ethyl group and R ⁶ represents a-n-propylthio group, and R ¹ , R ² , R ³ and X have the same meaning as described above. ) Compound. Among these compounds of particular interest, R ⁴ is an ethyl group, R ⁵ is an n-propylthio group, X is an oxygen atom, and R ¹ , R ² and R ³ have the same meaning as in the above general formula ( The compound of I) is mentioned.

Moreover, as one group of preferable compounds, R <^4> is ethyl group, R <^5> is n-propylthio group, X is oxygen atom, R <^1> is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s A butyl group, isobutyl group, cyclohexyl group, benzyl group, phenyl group, 4-chlorophenyl group, or 4-methylbutyl group, R ² is hydrogen atom, R ³ is hydrogen atom, methyl group, combustion atom or bromine atom The compound of general formula (I) which X represents an oxygen atom is mentioned.

Among the compounds of the present invention, a group of particularly important compounds are those in which R ₄ is a methyl group and R ⁵ is an n-propylthio group, and this grouping is excellent for relatively warm-blooded animals while maintaining excellent insecticidal and acaricide activity. It is characterized by low oral acute toxicity. This low toxicity tendency is apparent in R ₁ in a phenyl group or a substituted phenyl group.

In addition, this group exhibits insecticidal action against many insects, but in particular, exhibits excellent control against insect pests and ticks. This action is also manifested by contacting the compound of the present invention with a direct insect, such as by spraying a pest parasitic plant or the like, but once the drug is absorbed into the plant from the root, leaf, stem or the like, the plant is absorbed by the pest, or It also appears to chew or touch it. Such permeable insecticidal action is apparent when R ¹ is an alkyl group.

The compound of the present invention may be produced by a method known per se. For example, general formula (II)

Wherein R ¹ , R ² , and R ³ are as defined above, the compound represented by General Formula (III)

In the formula, W represents OR ⁴ or Y, Y represents a halogen atom, and R ⁴ and R ⁵ can be produced by esterifying with a compound represented by the same meaning. It is preferable to perform reaction of esterification in presence of an acid binder.

Suitable acid binders include, in particular, tertiary amines such as trialkylamines, pyridines and γ-colliding or alkali metals and alkalis such as sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate Hydroxides, oxides, carbonates, bicarbonates and alkali metal alcoholates of earth metals are used.

As the salt of the 3-hydroxypyrazole compound of the general formula (II), a corresponding alkali metal salt is suitable, and sodium salt, potassium salt and the like are preferable. In general, the reaction is preferably carried out in a suitable inert solvent. For example, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as methylene chloride, chloroform, tetrachloride, ethyl ether, dioxane and tetra Ethers such as hydrofuran, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile, acid amides such as dimethylformamide, esters such as ethyl acetate, and slopoxides such as dimethyl sulfoxide Can be used.

The reaction temperature may suitably select a temperature at which the reaction proceeds in the range of -20 ° to 150 ° C, but generally 0 ° to 100 ° C is appropriate. The reaction is completed in 0.5 hours to 6 hours, but the end can be confirmed by caterpillar chromatography or the like.

After completion of the reaction, the reaction mixture can be obtained by the known means. For example, the reaction solution is washed with water, 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, the solvent is distilled off to obtain the compound of the present invention.

If desired, it may be purified again by means such as distillation, recrystallization, column chromatography, and the like.

The raw material compound used in the reaction of the present invention can be easily produced by a known method or a similar method.

Compound (I) of the present invention is effective for controlling hygiene pests, plant parasitic insects and mites.

In more detail, the inventive compounds and compositions containing them include, for example, Eurydema rugosa, Scotinophara lurida, Riptotus clavatus, Stefani nasi ( Stephanitis, Laodelphax stiatellus, Nephotettix cincticeps, Umaspis yanonensis, Apis glycines, Lipapis pschdobrasica Semi-blind pests such as Lipaphis pseudobrassica, Brevicoryne yner brassicae, Ashis gossy-pii, etc., for example Spodostera littura, Furutella makuripen Plutella maculipennis, Pieris rapa crueivora, Chiro suppressalis, Plusia nigrisi-gna, Helicobpa Asla Asult assulta assulte, Lencaania separata, Mamestra brassicae, Adoxophyes orana, Syllepte derogata, Napallocsis medinaris (asphata assulte) Human pests such as Cnaphalocrocis medinalis, Phthorimea operculella, etc., e.g. Epilachna vigintioctopunctata, Aulacophora femoralis Vegetation pests such as Phyllotreta striolata, Oulema orgzae, Echinocnemus squameus, for example Musca domestica vicina, Curex Bilateral pests such as culex pipiens pallens, tabanus trigonus, hylemya antiqua, hylemva platura, for example, rock custard mig Direct pests such as Locusta migratoria, Gryllotalpa africana, Cockroach pests such as Bratella germanica, Periplaneta fuliginosa, For example, Tetranychus urticae, Panonicus citri, Tetranychus Kanzawai, Tetranychus cinnabarinus, Pansnychus ulmi It is particularly effective for controlling leaf-derived species such as Aculus pelekassi, for example nematodes such as Aphelenchoides besseyi.

In using the compound (I) of the present invention as an insecticidal or acaricide composition, one or two or more types of compounds (I) that can be taken by general pesticides can be dissolved in a suitable liquid carrier depending on the purpose of use. It is made to disperse | distribute, and mixed or adsorb | sucked with a suitable solid support | carrier, and it is used as a formulation of emulsion, emulsion, powder, tablet, spray, ointment, etc. If necessary, these agents may be added an emulsifier, a suspending agent, an electrodeposition agent, a penetrant, a humectant, a store agent, a stabilizer and the like, and can be prepared by a publicly known method.

The content ratio of the active ingredients in the insecticidal and acaricide composition differs depending on the purpose of use, but about 10 to 90% by weight of the emulsion and the hydrating agent are appropriate, and 0.1% to 10% by weight as the emulsion or powder. Although about% is suitable, about 1 to 20 weight% is suitable as a granulation, Depending on a use purpose, you may change these concentrations suitably. In addition, when using an emulsion, a hydrating agent, etc., it is good to spray by making it the red lime weight (for example, 100-100,000 times) with water etc.

As the liquid carrier to be used, for example, water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol, etc.), ketones (for example, acetone, methyl retyl ketone, etc.), ethers (for example dioxane) , Tetrahydrofuran, cellulose solution, etc., aliphatic hydrocarbons (e.g. gasoline, kerosene, kerosene, fuel oil machine oil, etc.), aromatic hydrocarbons (e.g. benzene, toluene, xylene, solvent, naphtha, methyl Naphthalene), halogenated hydrocarbons (e.g. chloroform, carbon tetrachloride, etc.), acid amides (e.g. dimethylformamide, etc.), esters (e.g. ethyl acetate, butyl acetate, glycerin esters of fatty acids, etc.) ), Nitriles (for example, acetonitrile and the like) are suitable, and one or a mixture of two or more thereof is used. Examples of solid carriers include plant powders (e.g. tobacco powder, wheat flour, wood powder, etc.), mineral powders (e.g., clays such as kaoring, bentonite, acidic clay, talc, diatomaceous earth, Alumina, sulfur powder, activated carbon and the like are also used, and one or a mixture of two or more thereof is used.

Moreover, as a raw material, polyhydric alcohol ester of higher fatty acids, such as polyethylene glycol, pectin, for example, monostearic acid glycerol ester, cellulose derivatives, such as methylcellulose, sodium alginate, bentonite, Higher alcohols, for example, polyhydric alcohols such as glycerin, waserine, white waserine, liquid paraffin, lard various vegetable oils, lanolin, dehydrated lanolin, cured oils, resins, and the like, or various interfaces thereof. The thing which added activator etc. can be selected suitably.

루, 다께모도 유지(주) 제), 알킬황산염류(예, 에마루 10

, 에마루 40

, 가오오아트라스(주) 제) 알킬슨폰산염류(예, 네오겐

, 네오겐 T

, 다이이찌고오교오(주)제 : 네오폐렉스

, 가오오라트라스(주)제), 폴리에틸렌글리코올에테르류(예, 노니포오루 85

, 노니포오루 100

, 노니포오루 160

, 산요가세이(주)제), 다가알코올에스테르류(예, 토우인 20

, 토우인 80

, 가오오아트라스(주)제)등이 사용된다. 또, 본 발명 화합물과 예를들면 다른 종류의 살충제(피레스린계 살충제) 유기인산계 살충제, 카르바메이트계 살충제, 천연살충제 등), 살비제, 살선충제, 제초제, 식물홀몬제, 식물발육조절물질, 살균제(예를들면 구리계 살균제, 유기염소계 살균제, 유기유황계 살균제, 페놀계 살균제등), 협력제, 유인제, 기피제, 색소, 비료 등을 배합하여, 혼합 사용하는 것도 가능하다.Moreover, as surfactant used as an emulsifier, an electrodeposition agent, a penetrant, a dispersing agent, etc., soaps, polyoxyalkylaryl esters (for example, Noda) as needed.

Lu, Tadomodo oils and fats), alkyl sulfates (for example, Emaru 10)

, Emaru 40

, Gao Atlas Co., Ltd. alkylsononates (e.g. neogen

, Neogen T

Daiichi Gokyo Co., Ltd.: Neo-Frex

, Gao Latras Co., Ltd., polyethyleneglycol ethers (e.g., noniporu 85

, Nonipooru 100

, Nonipooru 160

, Sanyosei Co., Ltd., polyhydric alcohol esters (e.g., Toin 20

, Toin-in 80

, Gao Atlas Co., Ltd.) are used. In addition, the compounds of the present invention and other types of insecticides (pyresrin insecticides) organophosphate insecticides, carbamate insecticides, natural insecticides, etc.), acaricides, nematicides, herbicides, plant hormones, plant growth regulators, It is also possible to mix and use 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 and the like.

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

Example 1

0-Ethyl-S-n-propyl-0- (1-isopropyl-4-methylpyrazol-3-yl) thiophosphate ester (Compound No. 13)

3.2 g (0.02 mol) of sodium salt of 1-isopropyl-3-hydroxy-4-methylpyrazole were suspended in 60 ml of methyl ethyl ketone, and 4.0 g (0.02 of 0-ethyl-Sn-propylthiophosphate) was added thereto. Mole) is added and stirred at room temperature for 3 hours. After completion of the reaction, methyl ethyl ketone is distilled off, toluene is added to the residue, and the toluene layer is washed with water and dried over anhydrous sodium sulfate. Toluene was distilled off and the residue was purified by silica gel-chromatography (developing solvent: chloroform) to obtain 4.3 g of a colorless transparent oily substance.

Example 2

0-Ethyl-S-n-propyl-0- (1-phenyl-4-chloropyrazol-3-yl) thiophosphate ester (Compound No. 30)

4.3 g (0.02 mol) of 1-phenyl-3-hydroxy-4-chloropyrazole sodium salt were suspended in 100 ml of acetone, and 4.0 g (0.02 mol) of 0-ethyl-Sn-propylthiophosphate was added thereto at room temperature. Stir for 3 hours. After completion of the reaction, acetone is distilled off. The following operations were performed in the same manner as in Example 1 to obtain 5.4 g of a colorless transparent oily substance.

Next, the compound formed by the method similar to Example 1, 2 is described in a 1st table including the compound obtained in Examples 1, 2.

TABLE 1

Example 3 Emulsion

Compound no. 30 20% by weight

Xylene 75 wt%

Polyoxyethylene glycol ether

) 5중량%(Nonipooru 85

5% by weight

Oil agent containing (The said component was mixed and manufactured.).

Example 4 Hydration

Compound no. 29 30% by weight

5% by weight of lignin sulfonate

Polyoxyethylene glycol ether

) 5중량%(Nonipooru 85

5% by weight

60% by weight clay

Hydrating agent containing (The above components were mixed and manufactured.).

Example 5 Powder

Compound no. 38 3% by weight

96.6% by weight of clay

0.3% of silicon

Polyethylene Glycol Ether

) 0.1중량%(Nonipooru 85

0.1% by weight

Powder containing (The said component was mixed and manufactured.).

Example 6 granulation

Compound no. 13 10% by weight

5% by weight of lignin sulfonate

Bentonite 85% by weight

Granulated granulated by adding water to the mixture of the mixture.

Example 7

Test Example 1 Effect on Laodelphax striatellus

a) The test compound was diluted with water as an emulsion according to the formulation of Example 3, and a 40 p.p.m treatment solution was prepared. 2.5 ml of this treatment solution was placed in a test tube (1.7 cm in diameter and 4 cm in depth), 3 seedlings (day 7 after germination) were erected, and the roots were soaked for 2 hours. Was transferred to a test tube containing 10 ten layers of perilla oil. The test tube was placed indoors (28 ° C.) for 24 hours and the number of deceased extinctions was examined. The test was repeated twice, and the test results are shown in Table 2 as mortality rates.

TABLE 2

The compound number of Table 2 is a number corresponding to the compound number of Table 1. Test Example 2 Effect on spodoptera littura

3000배 첨가) 20ml를 아이스크림컵으로 수경한 대두의 실생묘(발아후 10일)에 분무실내에서 분무기(분무압 1㎏/㎝²)를 사용해서 살포하였다.a) 500 p.pm water dilution of electrode compound (Example 3 prescription emulsion)

20 ml was sprayed using the sprayer (spray pressure 1 kg / cm <^2> ) in the spray room in the seedlings (10 days after germination) of the soybeans hardened by the ice cream cup.

After 2 hours of spraying, two pieces of the main leaves of soybeans are cut out, 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, and the cup is indoors (25 ° C). In addition, the number of dead worms after 48 hours was examined. The test was repeated twice, and the test results are shown in Table 3 (I) as mortality rates.

b) 100 mg of the granules prepared according to the prescription of Example 6 were mixed in the soil of the soybean wheat glutinous planted in a pot (9 cm in diameter), and the treatment pot was placed in a glass chamber (28 ° C.), and 5 days after the treatment. Two leaves were cut out, and each one was placed in an ice cream cup, 10 larvae of larvae were placed therein, and the cup was placed indoors (25 ° C.) for 48 hours, and the dead larvae were examined. The test was repeated twice, and the test results are shown in Table 3 (II) as mortality rates.

[Test Example 3] Effect on the Unopened Layer (Unaspis yanonensis)

3000배 첨가)로 희석하 여, 500p.p.m의 물 현탁액을 조정하였다. 이 물 현탁액 20ml를 포트(직경 9㎝)에 심은 탱자나무의 실생묘(발아후 22개월)에 기생시킨 개각충의 2령 암유충(기생두수 10~50마리)에 살포하였다. 살포후의 포트를 온실(25~30℃)내에 옮겨, 살포후 20일째에 성충으로 생육된 개체수를 조사하였다. 시험은 2회 반복으로, 시험결과는 사망율로 표 4에 표시하였다. 사망율(%)은 다음식에 의해서 산출하였다.In accordance with the formulation of Example 4, the disclosed compound was used as a hydrating agent,

Diluted to 3000-fold) to adjust a water suspension of 500 p.pm. 20 ml of this water suspension was sprayed on the second-largest female larvae (10-50 parasitic heads) of the larvae parasitic on the seedlings (22 months after germination) of the tangerine trees planted in pots (9 cm in diameter). The pots after spraying were moved into a greenhouse (25-30 ° C), and the number of adults grown at 20 days after spraying was examined. The test was repeated twice, and the test results are shown in Table 4 as mortality. The mortality rate (%) was calculated by the following equation.

TABLE 3

The compound numbers in Table 3 correspond to the compound numbers in Table 1.

TABLE 4

3000배 첨가)로 희석해서 500p.p.m.의 수용액을 조정하였다. 아이스크림컵에 수경한 강남콩의 실생묘에 진드기의 암성충 10마리를 접종하여, 24시간 유리실(28℃)에 두고, 수용액 20ml를 강남콩에 살포하였다. 살포후 컵을 유리실 내에 되돌려서, 살포후 2일 및 7일째 잎위에 생식하고 있는 유성충수를 조사하였다. 시험은 2회 반복 행하였으며, 시험결과는 감소율을 다음식에 의해 구하여, 효력단계에 따라서 표 5에 표시하였다.The compound number of Table 4 is a number corresponding to the compound number of Table 1. Experimental Example 4. Effect on Tite (Tetranychus urticae) The disclosed compound was emulsified in the formulation of Example 3, and water (electrode dye dynein)

Diluted 3000 times) to adjust an aqueous solution of 500 p.pm. Ten adult female insects of ticks were inoculated into the seedlings of hydroponic gangnam beans in the ice-cream cup, placed in a glass chamber (28 ° C) for 24 hours, and 20 ml of aqueous solution was sprayed on the gangnam beans. After spraying, the cups were returned to the glass chamber, and oily reptiles on leaves were examined on days 2 and 7 after spraying. The test was repeated twice, and the test results were obtained by the following equation, and are shown in Table 5 according to the validity stages.

TABLE 5

The compound number of Table 5 is a number corresponding to the compound number of Table 1.

Claims (1)

(1) General formula (II)

[Wherein, R ¹ is a phenyl group which may be substituted with an alkyl group, an alalkyl group or a halogen atom or a lower alkyl group, R ² is a hydrogen atom or a lower alkyl group, R ³ is a hydrogen atom, a halogen atom, a nitro group, a lower alkyl group or a formula Or a salt thereof represented by -COOR ⁶ (wherein R ⁶ represents a lower alkyl group).

Wherein R ⁴ is a lower alkyl group, R ⁵ is a lower alkylthio group, X is an oxygen atom or a sulfur atom, and Y is a halogen atom. )

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and X are of the same meaning as in the above definition).