JPS5936683A - Isoxazolopyrimidine derivative and acaricide - Google Patents

Abstract

NEW MATERIAL:A compound shown by the formula I (X is halogen, or alkyl; n is 1, or 2, and X may be the same or different when n is 2) and its acid addition salt. EXAMPLE:3-Methyl-4-[2-(4-n-butyl-2-methylphenoxy(ethylamino)]-isoxazol o[5,4-d] pyrimidine. USE:An acaricide. Showing improved activity against imagines and nits of Tetranychus, Panonychus ulmi, Panonychus citri, rust mite, etc. PROCESS:A compound shown by the formula II is reacted with a compound shown by the formula III in the presence of a base (e.g., triethylamine, sodium hydroxide, etc.) in a solvent such as benzene, tetrahydrofuran, etc. at room temperature - the boiling point of the solvent, to give a compound shown by the formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to isoxazolopyrimidine derivatives or acid addition salts thereof and acaricides containing them as active ingredients.

The isoxazolopyrimidine derivative of the present invention is represented by the following general formula.

(In the formula, X does not represent a halogen atom or an alkyl group. n
represents 1 or 2, and when n is 2, X may be the same or different. ) Acid addition salts of the above formula (1) are also effective.

The alkyl group of Mention may be made of t-butyl, n-pentyl, n-hexyl, n-hebutyl, n-octyl, n-nonyl or n-decyl. Examples of the halogen atom of X include chloro or bromine.

Preferred compounds in formula (1) are those in which n is 1 or 2, X is the same or different alkyl group, and at least one is substituted at the 2-position. especially,
Compounds in which n is 2 and X is substituted with a methyl group at the 2-position and a linear alkyl group having 1 to 7 carbon atoms at the 4-position are preferred.

Examples of acids that form acid addition salts of the compound of formula (I) include inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, and phosphoric acid, and carbon acids such as formic acid, oxalic acid, and trichloroacetic acid. Organic sulfonic acids such as carcinic acid, methanesulfonic acid and benzenesulfonic acid are preferred, among which hydrochloric acid is preferred.

Examples of the compound of formula (1) are as follows.

In addition, the compound name will be referred to in the following description.

AXnm・p・CC-) 1 2-(:H, 147-9 22-n-C3H, 101-3 32-1-C, H, 11B-20 43-CIf5127-8 5 4-CL 145-76 2
．． 3- (CH3)2174-67 2.4- (
(Jl,)2126-88 2-ck13-4-n
-C,11,73-692-OH,-4-n-'C4H
764-710 2-CH3-4-n-C5H1,
97-9112-CI, -4-n-C6H1575-7
122-CH, -4-Ct153-5 13 2-n-C,H, -4-CH398-100
142-C1-4-CH, 137-9 152-C1-4-c, H, nDl, 575016
2-C1-4-t-041(,64-7172-C
H3-5-toC,H7n 1.5570 The compound of formula (1) is easily produced, for example, by the following method known per se.

(wherein X and n are as defined above) The reaction is preferably carried out in a solvent in the presence of a base.

The solvent is not particularly limited as long as it does not participate in this reaction, and examples include benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride,
Chloroform, dichloroethane, trichlorethylene,
Chlorinated and non-chlorinated aromatic, aliphatic, and cycloaliphatic hydrocarbons such as cyclohexane, ethers such as diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, and ketones such as acetone and methyl ethyl ketone. , alcohols such as methanol, ethanol, and ethylene glycol or hydrated products thereof, and mixtures of the above-mentioned solvents.

As a base, triethylamine, pyridine, N, N-
Organic bases such as diethylaniline, sodium alkoxide, potassium alkoxide, ammonium acetate, acetic acid), sodium hydroxide, potassium hydroxide,
Inorganic bases include sodium carbonate, potassium carbonate, and sodium hydride.

Although the reaction temperature is not particularly limited, it is usually above room temperature and below the boiling point of the solvent used, and heating is preferably performed in order to shorten the reaction time.

After completion of the reaction, the obtained target product can be appropriately purified by known means such as recrystallization and various chromatography.

Acid addition salts can be easily obtained, for example, by introducing an acid into the reaction solution and then removing the solvent.

The compounds of the present invention have excellent acaricidal activity against adults and eggs of two-spotted spider mites (Tetranychus), apple spider mites, citrus spider mites (Panonychug), and rust mites that parasitize fruit trees, vegetables, and flowers. Also, aphids, diamondback moths, leafhoppers,
It is also active against various agricultural and horticultural pests such as brown planthoppers. It is also effective as a fungicide for layer horticultural crops and against candidiasis and athlete's foot.

In order to provide the compound of the present invention for the above-mentioned uses, it can be mixed with a carrier and other adjuvants as necessary to form a formulation commonly used as an agrochemical, such as a powder, an aqueous solution, an emulsion, or an aqueous or oily suspension. It is prepared and used in compositions such as aerosols.

The term carrier refers to a synthetic or natural carrier that is mixed into a pesticide to help the active ingredient reach the area to be treated, and to facilitate the storage, transportation, or handling of the active ingredient. means any inorganic or organic substance.

Suitable solid carriers include clays represented by kaolinite group, montmorillonite group, or athanolugite group, melkite, mica, phyllite, pumice, perminikyrite, gypsum, calcium carbonate, dolomite, diatomaceous earth. , inorganic substances such as magnesium lime, apatite, zeolite, anhydrous silicic acid, synthetic calcium silicate, etc., vegetable organic substances such as soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, crystalline cellulose, Synthetic or natural polymer compounds such as coumaron resin, petroleum resin, alkyd resin, polyvinyl chloride, I-realkylene glycol, ketone resin, ester gum, coal gum, and dammar gum, waxes such as carnauba wax and beeswax, or urea. etc. can be mentioned.

Suitable liquid carriers include paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene, carbon tetrachloride, chloroform, etc. , chlorinated hydrocarbons such as trichloroethylene, monochlorobenzene, and 0-chlorotoluene, ethers such as nooxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, noisoptyl ketone, cyclohexanone, acetophenone, and isophorone, ethyl acetate, and acetic acid. amyl, ethylene glycol acetate, diethylene glycol acetate,
Esters such as dibutyl maleate and diethyl succinate, alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanone, benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether,
Examples include ether alcohols such as diethylene glycol ethyl ether and diethylene glycol butyl ether, polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. Further, as the gas carrier, gases such as air, nitrogen, carbon dioxide gas, and freon are preferable, and a mixture of these gases can also be injected.

In addition, in order to improve properties such as dispersion, emulsification, spreading, penetration, and adhesion of drugs, six-layer surfactants, polymeric compounds, etc. are added as necessary to improve the basic properties of wetting, adhesion, and adsorption to animals and plants. 1
1Y, and the effect can be enhanced.

Surfactants used for purposes such as emulsification, dispersion, wetting, spreading, binding, disintegration control, active ingredient stabilization, fluidity improvement, and rust prevention are nonionic, anionic, cationic, and Although any zwitterionic one can be used, nonionic and/or anionic ones are usually used.

Suitable nonionic surfactants include those obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol, and those obtained by polymerizing and adding ethylene oxide to al-Q alcohols such as inoctylphenol and nonylphenol. products obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol, products obtained by polymerizing and adding ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, and oleic acid, stearic acid, and dilauryl phosphorus. Mono- or dialkyl phosphoric acid with 1 ethylene oxide added to it, dodecylamine, stearamide amine with 1 ethylene oxide added to it, higher fatty acid esters of polyhydric alcohols such as sorbitan, and ethylene oxide Examples include those obtained by polymerizing and adding ethylene oxide and propylene oxide. Suitable ionic surfactants include, for example, alkyl esters such as sodium lauryl sulfate and oleyl alcohol sulfate amine salts. i!
Ester salt, sodium sulfosuccinate dioctyl ester, sodium 2-ethylhexene sulfonate, alkyl sulfonate, sodium isozolobylnaphthalene sulfonate, sodium methylenebisnaphthalene sulfonate, sodium sulfonate, sodium dodecylbenzenesulfonate Examples include arylsulfonate salts such as.

Furthermore, the composition of the present invention contains casein, gelatin, albumin, etc., for the purpose of improving the properties of the preparation and increasing the biological effect.
Glue, sodium alginate, methylcellulose, methylcellulose, hydroxyethylcellulose,
Polymer compounds such as polyvinyl alcohol and other auxiliary agents can also be used in combination.

The above-mentioned carriers and various auxiliary agents are used individually or in combination as appropriate depending on the purpose, taking into account the dosage form of the preparation, the application situation, etc.

Powders contain, for example, usually 25 parts by weight of the active ingredient compound, with the remainder being a solid carrier.

Hydrating agents usually contain 25 to 90% of the active ingredient compound, for example.
parts by weight, the remainder being a solid carrier, a dispersion wetting agent,
A protective colloid, a chicken trope, an antifoaming agent, etc. are added as necessary.

Emulsions, for example, usually contain 5 to 50 parts by weight of the active ingredient compound, this includes about 5 to 20 parts by weight of an emulsifier, and the remainder is a liquid carrier, with a rust preventive added if necessary. .

When the composition of the present invention prepared in various dosage forms in this way is sprayed on agricultural crops infested with spider mites in a field, for example, the active ingredient concentration is 100 to 100%.
It can be effectively controlled by applying 1,000 ppm to the leaves and foliage of agricultural crops.

It is preferable that other insecticides be added to the composition of the present invention in order to broaden the spectrum, and a synergistic effect can be expected in some cases. Examples of such other insecticides include, for example, 0.0-diethyl 0-(2-
0.0-diethyl 5-2-[(ethylthio)ethylphosphorodithionite; 0,0-dimethyl 0-(3-methyl-4-nitro phenyl)thiophosphate; 01O-dimethyl 8-(N-methylcarpamoylmethyl)phosphorodithiony); 0,0-dimethyk
8-(N-)f-N-hornlucarpamoylmethyl)phosphorodithioate; 0,0-dimethyl 8-2
-(ethylthio)ethylphosphorodithiony): O, O
-dimethyl 1-hydroxy-2,2,2-)lichloroethylphosphonate; o, o-? ) Ethyl 0-(5-
Phenyl-3-isoxazolyl) phosphorothioate;
o,o-dimethyl 0-(3-methyl-4-methylmercazotophenyl)thiophosphate; 0-4-thyl 0
-p-cyanophenyl phenylphosphonothiony):
O,O-dimethyl S-(1,2-nocarzaethoxyethyl)phosphorodithioate; 2-chloro-1-(2,
4,5-trichlorophenyl)vinyldimethylphosphate: 2-chloro-1-(2,4-dichlorophenyl)
Vinyl dimethyl phosphate): 0.0-dimethyl 0-
p-cyanophenyl phosphorothiony): 2.2-dichlorovinyl dimethyl phosphate; ethyl mercaptophenyl acetate 0.0-dimethyl phosphorothiony) SS-((6-chloro-2-oxo-3-benzoxazolinyl)methyl [0,0-Noethylphosphorodithioate; 4-methylthiophenyl ciflohir phosphate); 2-chloro-1-(2,4-dichlorophenyl)vinyl diethyl phosphate; 0,0-diethyl-〇-(3 0゜0-dimethyl 8-
Phthalimidomethyl phosphorodithimeate; dimethyl-methyl carpamoylethioethyl thiophosphorothiolet): 0, O-diethyl 5-(N-ethoxycarbonyl-N-methylcarpa-7ylmethyl) phosphorodithiony): O, O-dimethyl-8-[2-methoxy-1,3,4-thiadiazol-5(4H)-onyl-(4)-methyl]dithiophosphate; 2-methoxy-4H-1,3,2-penzodio Quizaphosphorine 2
-Sulfide; 0゜0-diethyl-〇 -(3,5,6
-Dolichloro2-pyridyl)phosphorothiony):
0,8-dimethyl-N-acetyl phosphoroamide thioney): O-2,4-dichlorophenyl 〇-ethyl S-probyl phosphoroxyf;A-:r--):
0.

1 -Naphthyl N-methylcarbamate; S-methyl-N-[(methylcarpamoyl)oxy]thioacetimidate: 2-sec-butylphenyl-N-methylcarbamate): 2-4sopropoxyphenyl-N-methylcarpamate -): 1,3-bis(carpamoylthio)-2-(N,N-dimethylamino)gulonone hydrochloride; 2-tumethylamino-5,6
-Simethylpyrimidin-4-yl Carbamate insecticides such as dimethyl carbamate, nicotine sulfate; Milbemycin D; 6-methyl-2,3-quinoxaline dithiocyclic S,S-dithiocargenate; 2.4--
/Nitro 6-butylphenyl dimethyl acrylate; 1,1-bis(p-chlorophenyl) 2,2.
2-) IJ dichlorotanol; azoxybenzene;
Di-Cp-10lophenyl)-cyclopropyl carbinol; isozolobyl-4,4-dichlorobenzilate; ethyl-4゜4'-dichlorobenzilate; ethyl
0-Benzoyl-3-chloro-2,6-simethoxybenzohydrocimate; Isopropyl 4,41-zopromopendylate; Tricyclohexyltin hydroxide; Hexakis (β, β-zomethylphenethyl) distanoxane: 2 -(4-t-butylphenoxy)cyclohexylzolobinyl sulfide; 3-methyl-1,5-bis(2,
4-xylyl)-1,3,5-)reazaventer 1,4
-diene; 2゜4.5.4'-f) 910 diphenyl sulfone: hexachlorhexahydromethanobenzodioxachepinoxai P; 5-dimethylamino-1
, 2,3-) lithian-hydrogen oxalate; insecticides such as machine oil, etc., but are not limited to these.

The composition of the present invention can also be used in combination with the following fungicides.

3.3'-Ethylenebis(tetrahydro-4,6-tumethyl-2H-1,3,5-thiazoazine-2-thione; ethylenebisdithiocarbamate zinc salt or manganese salt; bis(dimethyldithiocarpamoyl)disulfide ; Propylene pith dithiocarbamate zinc salt;
Methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate; 1,2-bis(3-methoxycarbonyl-2-thioureido)benzene; Carbamate fungicides such as bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarpamate, N -) dichloromethylthio 4-cyclohexene-1,2-dicarboximide;
N-tetrachloroethylthio-4-cyclohexene-1
゜Dicarboximide fungicides such as 2-dicarzaximide, oxanone fungicides such as 5,6-dihydro-2-methyl-1,4-oxazine-3-carboxalide-4,4-dioxide,2. Naphthoquinone fungicides such as 3-dichloro-1,4-naphthoquinone, 3-hydroxy-5-
Methylisoxa/-/l/: 5-! ) xy-3-)dichloromethyl-1,2,4-thiadiazole;2,4-dichloro-6-(0-chloroanilino)-
1,3,5-triazine; 2,3-dicyano-1,4-
Dithioanthraquinone; 8-oxyquinoline copper; polyoxin; validamycin; tetrachloroisophthalonitrile: 2-(1-methylglobil)-4,6-sinitrophenyl β,β-tumethylacrylate; l.
Riphenyltine hydroxide; humanmycin; dinitromethylhebutylphenylcrotonate; 5-butyl-2-dimethylamino-6-methylpyrimidine-4-
ol; 6-(3,5-dichloro-4-methylphenyl)-3(2H)-pyridazinone; 6-(3-bromophenyl)-3(2H)-pyridazinone; N-(2,6-dimethylphenyl)- Bactericidal agents such as N-methoxyacetyl)-alanine methyl ester; bis(8-guazinooctyl)amine acetate.

Example 4 - Cyano-5-ethoxymethyleneamino-3-methylisoxazole 3.67f ethanol 5 (l ml
2-(4-n-butyl-2-methylphenoxy-2-methylphenoxy)ethylamine 4.1
y-f (added and heated under reflux for 3 hours. Next, an ethanol solution of sodium ethoxide prepared by dissolving 0.1 ml of sodium in 10 m of ethanol was added to the reaction solution, and the mixture was refluxed for 2 hours. was distilled off, water was added, and the separated oil was extracted with toluene. The extract was washed with water and dried, then the toluene was distilled off, and the crystals were extracted with toluene.
Recrystallized from n-hexane, 3-methyl-4-(2-(4-n-butyl-2-methylphenoxy)ethylamine)-isoxazolo[5 , 4-d] Virimison 50f was obtained.

Examples of formulations of the composition of the present invention are given below. In the text, all references to parts mean parts by weight.

Formulation example 1. Powder Compound No. 8 compound 5 parts, talc 50 parts, kaolin 4
Five parts were uniformly mixed to obtain a powder.

Formulation example 2. 50 parts of irrigation agent compound number 9, 29 parts of clay, 1 part of gravel soil
0 parts of white car, 75 parts of white car, 3 parts of sodium lignin sulfonate, = 2 parts of Nykol 11 (16 (trade name of Nippon Nyukazai Co., Ltd.) and 1 part of polyvinyl alcohol were mixed uniformly in a mixer, and 3 parts of sodium lignin sulfonate were mixed in a mixer, and 3 parts of sodium lignin sulfonate were mixed uniformly in a mixer, and 3 parts of sodium lignin sulfonate were mixed uniformly in a mixer. It was crushed twice to obtain an irrigation agent.

Formulation example 3. Emulsion 20 parts of the compound 11 of the present invention and Rupol 8M-2
(10 (Toho Chemical registered song title) 10 parts and Kijiroru 70
% and mix well with stirring to obtain an emulsion.

Test examples of the composition of the present invention prepared in this way are given below. The test drug in the test example was the active ingredient compound of the present invention produced in accordance with Formulation Example 2 above.
An irrigation agent containing 50% was used.

Test example 1. Two-spotted spider mite control test (adult) Contains 30 (i ppm) of the compound of the present invention, and 0.01 ppm of a spreading agent.
A chemical solution with a 4-year period was used. Saza) IA leaves infested with adult Nummy mites were immersed in this chemical solution for 10 seconds, air-dried, and left in a constant temperature room at 25°C. After 72 hours, the mite killing rate was 10.
Those in the 0th category are shown as 4, those in the 99-80th category are shown as 3. Those in the 39th category or less are shown as 0. The average number of adult spider mites tested was 50 in each treatment area. The results are shown in Table 1.

Table 1 Test Example 2. Two-spotted spider mite control test (eggs) Same as test example 1 (prepared a 300 ppm chemical solution, added two-spotted spider mite eggs that had been laid on the leaves of the bamboo grass in advance)
Dip for 10 seconds, air dry, and leave in a constant temperature room at 25°C. After 2 weeks, the egg killing rate was displayed as 100 parts, 4.99 to 80 parts, and 3.39 parts or less as 0. .

The results are shown in Table 2.

Table 2 Patent Applicant Sankyo Co., Ltd. Ube Industries Co., Ltd. Agent Patent Attorney Detected Pressure Oil 23- Procedural Amendment (Voluntary) September 2J, 1981 1, Indication of Case Patent Application No. 131286 1988 2, Name of the invention: Isoxazolopyrimidine derivatives and acaricides 3; Relationship with the person making the amendment Patent applicant address: 6 Name, 3-1 Nihonbashi Honmachi, Chuo-ku, Tokyo 103 (185) Sankyo Co., Ltd. (Other 1) Name) Representative: Director and President Kikure Kawamura 4; Agent residence: 6 Sankyo Co., Ltd., 1-2-58 Hiromachi, Honbunagawa-ku, Tokyo 140; Subject of amendment: Column 7 for detailed description of the invention; Contents of amendment. As shown in the attached sheet = 24-1, Meiji M, page 7, line 14 [Two-spotted spider mites (Tetr
anychus) J is corrected as "two-spotted spider mite".

2, page 7, line 15 [1] Citrus spider mite (Panon
ychus) Correct J to 1 tangerine spider mite.

3, page 22, lines 8 to 9 t-j, "When mixed, an emulsion was obtained." was changed to "I" to obtain an emulsion. ” he corrected.

4. At the end of page 22, the phrase "72 hours later" is corrected to "the acaricidal effect after 72 hours."

5. On the bottom of page 23, line 64, ``after 2 weeks'' should be corrected to ``the ovicidal effect after 12 weeks''.

that's all

Claims (1)

[Claims] 1. An isoxazolopyrimidine derivative having the formula or an acid addition salt thereof. (In the above formula, X represents a halogen atom or an alkyl group. n represents 1 or 2, and when n is 2, X may be the same or different.) 2. , X are the same or different alkyl groups, and at least one is substituted at the 2-position. 3.%WF where n is 2 and X is substituted with a methyl group at the 2nd position and a linear alkyl group having 1 to 7 carbon atoms at the 4th position
A compound according to claim 2. An isoxazolopyrimidine derivative having the following formula: or an acaricide containing its acid addition salt as an active ingredient.