JPS6259710B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel gamma-pyranone (thiono)-phosphonic acid esters and their use for killing arthropods, particularly insects and mites, and more particularly to [In the formula, R is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 1 to 6 carbon atoms, a phenyl group, a cycloalkyl group, or a phenyl alkyl group , R ₁ represents a hydrogen atom or a halogenated lower alkyl group,
R ₂ is the same or different and represents a linear or branched alkyl group having 1 to 6 carbon atoms or a phenyl group,
Y represents an oxygen atom or a sulfur atom] A novel compound represented by: general formula [In the formula, R ₂ has the same meaning as above, and X represents a halogen atom] A (thiono)phosphoric acid (phosphonic acid) ester halide represented by the formula [In the formula, R and R ₁ represent the same meanings as above,
M represents a hydrogen atom, an alkali metal or an alkaline earth metal] A γ-pyranone (characterized in that it is reacted with a γ-pyrone derivative represented by The present invention relates to a method for producing a thione-phosphoric acid ester and an arthropod killer containing the phosphonic ester. The γ-pyranone (thione)-phosphate (phosphonic acid) ester of the present invention is a new compound that has not been described in any literature and was discovered for the first time by the present inventor. The present inventor also discovered that it has insecticidal and acaricidal properties, and has low toxicity, which is the most desirable characteristic for future pesticide development, so it is of great interest to the pesticide industry. seems to bring benefits. (thiono) used as starting material in the present invention
Phosphoric acid ester halide is a known compound and an industrially easily available raw material.
These raw materials include the following. o,o-dimethyl phosphate ester halide,
o,o-diethyl phosphate ester halide, o,
o-di-n-propyl phosphate ester halide,
o,o-di-iso-propyl phosphate ester halide, o,o-di-n-butyl phosphate ester halide, o,o-di-iso-butyl phosphate ester halide, o,o-diamyl phosphate ester halide, o , o-di-hexyl phosphate ester halide, o,o-diphenyl phosphate ester halide, o-methyl-o-ethyl phosphate ester halide, o-methyl-on-propyl phosphate ester halide, o-methyl-o- Iso-propyl-phosphate ester halide, o-methyl-o-
n-butyl phosphate ester halide, o-methyl-o-iso-butyl phosphate ester halide, o
-methyl-o-amyl phosphate ester halide,
o-methyl-o-hexyl phosphate ester halide, o-methyl-o-phenyl phosphate ester halide, o-ethyl-on-propyl phosphate ester halide, o-ethyl-o-iso-propyl phosphate ester halide, o-ethyl-on
-Butyl phosphate ester halide, o-ethyl-
o-iso-butyl phosphate ester halide, o-
Ethyl-o-amyl phosphate ester halide, o
-ethyl-o-hexyl phosphate ester halide, o-ethyl-o-phenyl phosphate ester halide, o-n-propyl-o-iso-propyl phosphate ester halide, o-n-propyl-o
-iso-butyl phosphate ester halide, o-n
-propyl-o-amyl phosphate ester halide, on-propyl-o-hexyl phosphate ester halide, on-propyl-o-phenyl phosphate ester halide, o-iso-propyl-
o-n-butyl phosphate ester halide, o-iso-propyl-o-iso-butyl phosphate ester halide, o-iso-propyl-on-butyl phosphate ester halide, o-iso-propyl-
o-amyl phosphate ester halide, o-iso-
Propyl-o-phenyl phosphate ester halide, on-butyl-o-iso-butyl phosphate ester halide, on-butyl-o-amyl phosphate ester halide, on-butyl-o-hexyl phosphate ester halide, o-n-butyl-o-phenyl phosphate halide, o-iso-butyl-o-amyl phosphate halide, o-iso-butyl-o-hexyl phosphate halide, o-iso-butyl-o-benzyl phosphate Ester halide, o-iso-butyl-o
- phenyl phosphate ester halide, o-amyl-o-hexyl phosphate ester halide, o-amyl-o-phenyl phosphate ester halide, o
-hexyl-o-phenyl phosphoric acid ester halides, and their corresponding thiono homologs can also be mentioned. On the other hand, the γ-pyrone compound represented by the general formula to be reacted with this is 3-hydroxy-
γ-pyrone, 2-methyl-3-hydroxy-γ-
Pyrone, 2-ethyl-3-hydroxy-γ-pyrone, 2-isopropyl-3-hydroxy-γ-pyrone, 2-n-butyl-3-hydroxy-γ-pyrone, 2-isobutyl-3-hydroxy-γ-pyrone Pyrone, 2-amyl-3-hydroxy-γ-pyrone, 2-hexyl-3-hydroxy-γ-pyrone, 2-cyclohexyl-3-hydroxy-γ-
Pyrone, 2-benzyl-3-hydroxy-γ-pyrone, 2-phenyl-3-hydroxy-γ-pyrone, 2-vinyl-3-hydroxy-γ-pyrone,
2-allyl-3-hydroxy-γ-pyrone, 2-
hexenyl-3-hydroxy-γ-pyrone, 3-
Hydroxy-6-chloromethyl-γ-pyrone, 3
-hydroxy-6-bromomethyl-γ-pyrone,
2-Methyl-3-hydroxy-6-chromiummethyl-γ-pyrone, 2-methyl-3-hydroxy-6
-bromomethyl-γ-pyrone, 2-ethyl-3-
Hydroxy-6-chloromethyl-γ-pyrone, 2
-isopropyl-3-hydroxy-6-chloromethyl-γ-pyrone, 2-isobutyl-3-hydroxy-6-chloromethyl-γ-pyrone, 2-amyl-3-hydroxy-6-chloromethyl-γ-pyrone, 2-cyclohexyl -3-hydroxy-6
-chloromethyl-γ-pyrone, 2-phenyl-3
-hydroxy-6-chloromethyl-γ-pyrone,
Representative examples include 2-vinyl-3-hydroxy-6-chloromethyl-γ-pyrone. The compound of the present invention can be obtained using the above raw materials according to the following reaction formula. [In the above, R, R ₁ , R ₂ , Y and M are the same as above] The above reaction can be carried out in a suitable solvent and in the presence of an acid acceptor. Suitable solvents used in this reaction include ethers such as dioxane, tetrahydrofuran and diethyl ether, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene and xylene, acetone, Examples include aliphatic ketones such as methyl ethyl ketone and methyl isobutyl ketone, aliphatic nitriles such as acetonitrile and propionitrile, acid amides such as dimethylformamide and dimethylacetamide, and sulfoxides such as dimethyl sulfoxide and sulfolane. can. As acid acceptors it is possible to use a wide variety of all common acid binders. Specific examples include alkali metal hydroxide compounds such as sodium hydroxide and potassium hydroxide, alkali metal carbonate salts of sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate, alcoholates such as sodium methylate and sodium ethylate, and triethylamine. , aliphatic such as dimethylamine, diethylaniline, pyridine,
Mention may be made of aromatic and heterocyclic amines.
The amount of these acid acceptor compounds to be used is preferably 0.5 to 3.0 times the weight of the starting material, preferably 1.0 to 1.5 times the weight of the starting material. Alternatively, this reaction can be carried out in good yield by reacting a salt of a γ-pyrone derivative, preferably the corresponding sodium salt and potassium salt of γ-pyrone, with a phosphate halide instead of carrying out this reaction in the presence of an acid acceptor compound. The desired γ-pyranone (thiono) phosphoric acid (phosphonic acid) esters ( ) can be obtained. The process of the present invention can be carried out over a wide temperature range and is generally carried out between -30°C and the boiling point temperature of the solvent, preferably between 0 and 100°C. The reaction time of the present invention varies depending on the starting materials used for the reaction, but the reaction time is 1 to 10 hours, preferably 3 to 5 hours. The compound obtained under such conditions can be easily isolated and purified by conventional separation methods such as solvent extraction, solvent dilution, distillation, recrystallization, column chromatography, etc., and the desired general formula () can be easily isolated and purified. γ-pyranone (thiono) phosphoric acid (phosphonic acid) ester represented by can be obtained with high purity. The compound () according to the present invention is characterized by having excellent insecticidal and acaricidal activities. In other words, the compound () exhibits particularly excellent activity against insect pests, mites, and sanitary pests that occur in agricultural crops, but it is resistant to plants and has activity only against insects and mites, so it can be used in all fields. It can be used to exterminate insects and mites that occur in Furthermore, the killing effect of the compound () according to the present invention is effectively exhibited in all growth stages of insects and mites. Arthropods to which the killing agent of the present invention can be effectively applied include the following. members of the order Isopoda, such as the vulgare; members of the order Psiformes, such as Lepsima satucarina; members of the order Vectinidae, such as the serpentine snail, Onythiurus almatus; members of the order Lice, such as human lice, woolly lice, furry lice, members of the order Lice, such as the common leaf lice, members of the order Physiformes, such as rice thrips, thrips clitoris, and porpoise; Fleas, long-tailed fleas, those of the direct order, such as the Japanese locust, the Japanese grasshopper, the Japanese cricket, the Japanese cockroach, and those of the half-order, such as the bean aphid, the yellow-spotted aphid, the orange black aphid, the rice black stink bug, the southern green stink bug, and the spiny stink bug. Stink bug, green eyelid bug, green eyelid bug, white mealybug, white mealybug, black-and-white mealybug, giant scale insect, horned beetle, ruby beetle, black-spotted beetle, brown planthopper, black-legged planthopper, brown planthopper, black leafhopper, phlegm leafhopper , green leafhopper, pear beetle, psyllium, citrus whitefly, psyllid beetle, psyllid beetle, green leafhopper, apple stink bug, psyllium beetle, Japanese stink bug, Zysdercus intermezius, Viesma quadrata, Rhodonius prolix, Triatoma, Arelarodes francae,
Cotton whitefly, Trialeurodes vaporasoforme, Cryptomys livis, Doralis flabae, Doralis bomi, Red leafhopper, Pseudo kotsucus, Lepidoptera, such as green caterpillar, rice caterpillar, Azuki podium, Swallowtail moth,
Akebikonoha, Acaeguriba, Akebi, Konaha, Imokomo, Iraga, Himekuroiraga, Aoiraga, Usueguriba, Umekunga, Shrimp sparrow, Pine moth, Nashihosomo, Kakimath, Apple tree moth, Kurimimi moth, Plum beetle, Noctuid moths, such as Futaobikoyaga, Army armyworm, Rice armyworm, Japanese armyworm, Fall armyworm, gourd borer, cotton beetle, members of the order Thyophyllaceae, such as rice beetles, grape beetles, black beetles, locust beetles, lead beetles, spotted beetles, apple cuttlefish, yellow bark beetles, pine wood beetles, serpentine beetles, black beetles, members of the order Thymenoptera,
For example, the grasshopper sawfly, the Japanese sawfly, the soybean sawfly, the black stone bee, the Diptera, such as the yellow-bellied gumbo, the rice carabae fly, the soybean leafminer fly, the rice leafminer fly, the rice leafminer fly, the soybean leafminer fly, the soybean leafhopper fly, the soybean leafminer fly, the soybean leafminer fly, and the fruit fly. things such as rice black carabae, soybean leaf fly, house fly, spider mites, such as citrus spider mite, cedar spider mite, kanzawa spider mite, red mite, citrus rust mite, grape red spider mite, nematodes,
For example, there are Nekobu centiyu, Negusare centiyu, Soybean cyst centiyu, Ishiyuku centiyu, Cyst centiyu, and the like. A series of biologically active compounds represented by the general formula () of the present invention can be formulated into emulsions, wettable powders, aqueous solvents,
Suspensions, concentrated suspensions, granules, microgranules, granules, powders, wettable powders, liniments, formulations for foam sprays, aerosol formulations, microcapsule formulations, formulations for impregnating natural or synthetic substances, smoke Vapor preparations,
It can be used in smoke preparations and concentrated small-dose spray preparations. In producing these preparations, various surfactants are used for emulsification, dispersion, suspension, and foaming. For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester as a nonionic surfactant, alkylbenzene sulfonate as an anionic surfactant,
These are alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, allyl sulfonate, and lingnin sulfite. Examples of the solubilizing agent and diluent carrier for the compound () include various organic solvents, various aerosol propellants, various natural minerals and plants, and various synthetic compounds. For example, a wide range of organic solvents can be used, but particularly preferred are benzene, toluene, xylene, ethylbenzene, chlorobenzene, alkylnaphthalene, dichloromethane, chloroethylene, cyclohexane, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohols, dimethylformamide, These include dimethyl sulfoxide, acetonitrile, mineral oil fraction and water. Examples of aerosol propellants include propane, butane, halogenated hydrocarbons, nitrogen, carbon dioxide, and the like. Examples of minerals include kaolin, talc, bentonite, diatomaceous earth, various clays, tyoke, calcite, pumice, sepiolite, and dolomite. Examples of plants include walnut shells, tobacco stems, and rice scraps. Examples of synthetic polymer compounds include alumina, silicates, sugars, and polymers. Moreover, various adhesives can be used as required, and examples of the adhesives in this case include carboxymethyl cellulose, gum arabic, polyvinyl alcohol, and polyvinyl acetate. These preparations can also be colored using organic or inorganic dyes. The compound according to the present invention is prepared to contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight when producing the various formulations mentioned above, and the formulation can be used as is or diluted with a carrier or water. It can be diluted freely in the range of 0.00001 to 100% by weight depending on the purpose, but preferably 0.0001 to 10%.
Use diluted to contain % active substance by weight. A production example of the compound of the present invention will be described. Example 1 o,o-dimethyl-o-[γ-pyranone]thionophosphate ester

Preparation of [Formula]. Add 3 g of anhydrous potassium carbonate to a mixed solution of 2.24 g of 3-hydroxy-γ-pyrone and 50 ml of acetonitrile.
Add and stir. To this solution, 3.22 g of o,o-dimethylthiophosphoric acid ester chloride was added dropwise over 10 minutes. After the completion of the dropwise addition, the reaction was carried out at 40 to 50°C for 5 hours with stirring, then cooled to room temperature, and the precipitated crystals were filtered. The liquid was concentrated under reduced pressure to obtain 4.6 g of o,o-dimethyl-o-[γ-pyranone]thionolinate as a yellow oil. Yield 97%. Analysis value IR (Neat); 1642, 1585 (C=C), 2820 (-
CCH ₃ ), 1660 (C=O), 805, 610 cm ^-1
(P=S) NMR (CCl ₄ ); δ3.75, 3.95 (S, 6H, CH ₃ O
−) 6.38 (d, 1H, CH-O), 7.78 (d,
1H, CH=C), 7.94 (d, 1H, CH=C,
CH ₃ O-) Example 2 o,o-diethyl-o-[2-methyl-γ-pyranone] phosphate ester

Preparation of 2-methyl-3-hydroxy-γ-pyrone
Put 2.52 g into a mixed solution of 20 ml of 5% aqueous sodium hydroxide solution and 40 ml of benzene, and add 16 ml of 50% aqueous tetrabutylammonium chlorsulfate solution dropwise while stirring. Add o, o to this mixture while stirring.
Gradually add 3.46 g of diethyl phosphate chloride dropwise. After the dropwise reaction was carried out at room temperature for 3 hours, the benzene layer was separated and washed with saturated saline.
The benzene layer was then dried over anhydrous magnesium sulfate, and after removing the magnesium sulfate, the benzene was concentrated under reduced pressure to yield o,o-diethyl-o-[2-methyl-γ-pyranone] phosphate as a yellow oil. 4.75g obtained. Yield 90.3%. Analysis value IR (Neat); 1640, 1580 (C=C), 1666 (C=
O), 1270cm ^-1 (P=O) NMR (CCl ₄ ); δ1.40 (t, 6H, CH ₃ -C),
2.32 (S, 3H, CH ₃ -C), 4.30 (m,
4H, −CH ₂ CH ₃ ), 6.28 (d, 1H, CH=
C), 7.68 (d, 1H, CH=C) Example 3 oo-diethyl-o-[2-cyclohexyl-γ
-Pyranone]thionophosphate ester

Preparation of [Formula] 2.24 g of 2-cyclohexyl-3-hydroxy-γ-pyrone is dissolved in 50 ml of acetone, and 4 g of anhydrous potassium carbonate is added to this solution. While stirring this mixed solution, 2.2 g of o,o-diethylthiophosphoric acid ester chloride was gradually added dropwise. After completion of the dropwise addition, 0.1 g of potassium iodide was added, and after refluxing for 6 hours, the mixture was cooled to room temperature and the precipitated crystals were filtered. When the liquid is concentrated under reduced pressure, a yellow oily o,o-diethyl-
3.05 g of o-[2-cyclohexyl-γ-pyranone]thionolinate is obtained. Yield 82.4%. Analysis value IR (Neat); 1642, 1580 (C=C), 1668 (C=
O), 806, 612 cm ^-1 (P=S) NMR (CCl ₄ ); δ1.38 (t, 6H, CH ₃ -C), 1.2
−2.05(broad11H,

[Formula]), 4.28 (m, 4H, CH ₂ −C), 6.28 (d, 1H, CH=
C), 7.68 (d, 1H, CH=C) Example 4 o,o-dimethyl-o-[6-chloromethyl-
γ-pyranone] phosphate ester

Preparation of [Formula] Dissolve 3.2 g of 3-hydroxy-6-chloromethyl-γ-pyrone in 20 ml of dimethylformamide,
Add 1 g of sodium hydride and stir at room temperature for 1 hour. 3.2 g of o,o-dimethylphosphoric acid ester chloride is gradually added dropwise to this solution while stirring. After completion of the dropwise addition, the mixture was stirred at 40 to 50°C for 1 hour, cooled to below 10°C, and 1 ml of acetic acid was added. Next, the precipitated salt is filtered off, the solvent is concentrated under reduced pressure, and the residue is extracted with benzene, washed with 5% sodium bicarbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. After the dried benzene solution was passed through a silica gel column, the solvent was concentrated under reduced pressure to form a yellow oil.
3.87 g of o-dimel-o-[6-chloromethyl-γ-pyranone] phosphate ester is obtained. Yield 72%. Analysis value IR (Neat); 1642, 1600 (C=C), 2824
(OCH ₃ ), 1664 (C=O), 1268cm ^-1 (P=
O) NMR (CCl ₄ ); δ3.72, 3.94 (δ, 6H, CH ₃ O),
4.72 (d, 2H, CH ₂ −Cl), 6.52 (δ,
1H, CH=C), 7.98 (d, 1H, CH=C) Examples 5 to 22 Using the same conditions as in Example 1, various compounds shown in Table 1 below were synthesized. The analysis data is shown in the second section below.
Shown in the table.

【table】

【table】

【table】

【table】

【table】

【table】

[Table] The biological test results for each compound obtained in the Examples of the present invention are shown below. However, this test also showed the case where either of the following two types of known comparison compounds A and B were used. Example 23 Prodenia Litura Test Two parts by weight of the specified test compounds shown in Table 3 below are dissolved in 98 parts by weight of acetone. This is diluted to a predetermined concentration using an aqueous solution containing 0.04% spreading agent (Nihon Nohyaku Co., Ltd., using Shin Rino). The solution prepared as described above is sprayed onto cabbage leaves (Brassica Oleracea) until it drips, and after air-drying, 3rd instar larvae of Spodoptera sinensis are inoculated, and the mortality rate after 2 days is determined. However, mortality rate = number of dead insects/total number of tested insects x 100 The test compound, the test concentration, and the mortality rate after 2 days are shown in Table 3 below. In the table, 100% means all cases of death of all test insects, and 0% means all cases of survival of all test insects. However, the number of the test compound indicates the example number.

[Table] Example 24 Tetranyohus Telarius test 2 parts by weight of the test compounds shown in Table 4 below are dissolved in 98 parts by weight of acetone. This was diluted to a predetermined concentration using an aqueous solution containing 0.04% spreading agent (Nihon Nohyaku Co., Ltd. Shin Rino) to prepare a solution. Potted green beans (Phaseolus vulgaris) are inoculated with adult spider mites and then sprayed with the solution prepared as described above until it drips. The insect mortality rate after a certain period of time was measured, and the results shown in Table 4 below were obtained.

[Table] Example 25 Laodelphax Striatellus test Two parts by weight of the specified test compounds shown in Table 5 below are dissolved in 98 parts by weight of methanol. This is diluted to a predetermined concentration using an aqueous solution containing 0.04% spreading agent. The solution prepared as described above was sprayed on potted rice (Orysa Sativa) until it dripped gently, and after air-drying, the planthopper was grown. Calculate the mortality rate after a certain period of time.

【table】

[Table] Example 26 Adzuki bean weevil (Callasobruchus Chineneis)
Test Two parts of the given test compound listed in Table 6 below are dissolved in 98 parts by weight of acetone. This is diluted with acetone to prepare a solution with a predetermined concentration. Add 0.5 of the acetone solution prepared above to a mini-shear.
ml injected, air-dried, and then provided with adzuki bean weevil adults. The insect mortality rate after a certain period of time is shown in Table 6 below.

[Table] Example 27 House fly test Two parts by weight of the specified test compounds shown in Table 7 below are dissolved in 98 parts by weight of acetone. This is diluted with acetone to adjust to a predetermined concentration. An adult house fly is anesthetized with ether, and 1 μl of the acetone solution prepared as described above is dropped onto the dorsal thorax, and the mortality rate is determined after a certain period of time.

[Table] Example 28 German Cockroach Test Two parts by weight of the specified test compounds listed in Table 8 below are dissolved in 98 parts by weight of acetone. This is diluted with acetone to adjust to a predetermined concentration. 1 ml of the acetone solution prepared as above was applied to the entire surface of a 9 cm diameter paper, and after air drying, a plastic ring 9 cm in diameter and 5 cm in height was placed on the paper, and an adult German cockroach was introduced into the ring. Calculate the mortality rate after a certain period of time.

【table】

【table】

Claims (1)

[Claims] 1. General formula [However, in the formula, R is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 1 to 6 carbon atoms, a phenyl group, a cycloalkyl group, or a phenylalkyl group. R ₁ represents a hydrogen atom or a halogenated lower alkyl group, R ₂ is the same or different and represents a straight or branched alkyl group having 1 to 6 carbon atoms or a phenyl group, Y is an oxygen atom Or represents a sulfur atom. ] γ-pyranone (thiono)-phosphoric acid (phosphonic acid) ester represented by: 2 General formula below [However, in the formula, R is a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkenyl group having 1 to 6 carbon atoms, a phenyl group, a cycloalkyl group, or a phenylalkyl group. R ₁ represents a hydrogen atom or a halogenated lower alkyl group, R ₂ is the same or different and represents a straight or branched alkyl group having 1 to 6 carbon atoms or a phenyl group, Y is an oxygen atom Or represents a sulfur atom. ] An arthropod killer characterized by containing a γ-pyranone (thiono)-phosphate (phosphonic acid) ester represented by the following as an active ingredient. 3. The arthropod killer according to claim 2, wherein the arthropod is an insect or a mite.