KR790001063B1 - Process for preparing thionophosphoric(phosphonic)acid esters - Google Patents

Abstract

Benzisoxazolothiophosphoric (phosphonic) acid esters (I; R = C1-C6 alkyl, R1 = C1-C6 alkyl, C1-C6 alkoxy, or phenyl) useful as insecticides and acaricides, were prepd. by reacting 3-hydroxy-7-nitrobenzisoxazol (II) with halothiophosphono(phosphoro) esters III; Hal = halogen) in the presence of acid acceptor or treating alk. metal salts, alk. earth metal, and ammonium salts of II with III.

Description

Method for preparing chionophosphorine (phosphonine) esters

The present invention relates to a process for preparing chionophosphorin (phosphonic acid esters) as a vent isoxazole of the following structural formula (I) effective as an insecticide and acaricide.

In the above structural formula

R is C₁-C ₆ alkyl

R₁ is C₁-C6 alkyl, C ₁ -C ₆ alkoxy or phenyl.

Among these compounds, R 'is preferably linear or branched alkyl, alkoxy (C ₁ -C ₄ , in particular C ₁ -C ₃ ) or phenyl, and R is a compound which represents straight or branched C ₁ -C ₄ alkyl.

Already 0, 0-Diethyl-0- [5-nitro or 6-nitro-benz isoxazol (3) yl] -thiophosphoric acid ester or 0-ethyl-0- [5-nitro-benzisoxazole (3 It is known that benzisoxazoles, such as) yl] -ciono ethanephosphonic acid esters, have a pesticidal and acaricide action. (British patent specification 965, 997).

Surprisingly, however, the benz isoxazolozinocio-phosphorinic acid esters produced according to the present invention are actually much more potent insecticides than known benz isoxazolozinocio-phosphoric acid esters having similar structure and the same action. And was found to exhibit acaricide.

According to the present invention, the benz isoxazolozinothiophosphorin (phosphonine) ester of formula (I) can be prepared by reacting 3-hydroxy-7-nitro-benzisoxazole of formula (II) in the presence of an acid acceptor or It is prepared by reaction with a thionophosphorinic acid (phosphonine) ester halide of formula (III) in the form of an alkali metal salt, an alkaline earth metal salt or an ammonium salt.

Wherein R and R ₁ are the same as in formula (I) and Hal is halogen, preferably chlorine.

For example, when using 0, 0-diethylthiophosphoric acid ester chloride and 3-hydroxy-7-nitro-benzisoxazole as starting materials, the reaction scheme can be expressed as follows.

Chionophosphorine (phosphonine) acid esters used as starting materials can be prepared according to conventional methods as known compounds, such as 3-hydroxy-7-nitro-benzisoxazole (II).

Examples of the thionophosphorine (phosphonine) ester halides of formula (II) which can be used as starting materials are as follows. :

0, 0-dimethyl-, 0, 0-dimethyl-, 0, 0-di-n-propyl-, 0, 0-di-isopropyl-, 0-methyl-0ethyl-, 0-methyl-0 -Isopropyl-, 0-ethyl-0-isopropyl-, 0-methyl-0-n-butyl-, 0, 0-di-n-butyl-, 0, 0-di-isobutyl-, 0, 0 -Di-n-tert-butyl-, 0, 0-di-tert-butyl-, 0-n-butyl-0-ethyl-, 0-tert-butyl-0-ethyl-, or 0-n-butyl- 0-n-propyl-cionophosphoric acid diester, chloride, and 0-methyl-methane-, 0-methyl-ethane-, 0-methyl-n-propane-, 0-methyl-isopropane, 0-methyl- n-butane-, 0-methyl-butane-, 0-methyl-isobutane-, 0-methyl-tert-butane-, 0-methyl-phenyl-, 0-ethyl-methane-, 0-ethylethane- , 0-ethyl-n-propane-, 0-ethyl-isopropane-, 0-ethyl-n-butane-, 0-ethyl-isobutane-, 0-ethyl-3 tert-butane-, 0-ethyl-2 class Butane-, 0-n-propyl-methane-, 0-n-propyl-ethane-, 0-n-propyl-n-propane-, 0-n-propyl-isopropane-, 0-n-propyl-n- Butane-, 0-n-propyl-isobutane-, 0-n-propyl-tert-butane-, 0-n-propyl-tert-butane-, 0-di Propyl-methane-, 0-isopropyl-ethane-, 0-isopropyl-n-propane-, 0-isopropyl-isopropane-, 0-isopropyl-n-butane-, 0-isopropyl tert-butane -, 0-isopropyl-phenyl-, 0-n-butyl-methane-, 0-n-butyl-ethane-, 0-n-butyl-butane, on-butyl-phenyl-, 0-tertiary butyl Ethane-, 0-tert-butyl-n-propane- or 0-tert-butyl-phenyl-cionophosphonic acid ester chloride.

The crude reaction is preferably carried out in the presence of a suitable solvent or diluent. Virtually all inert organic solvents may be used, in particular aliphatic and aromatic, optionally chlorine substituted hydrocarbons such as benzene, toluene, xylene, benzine, methylene chloride, chloroform, carbon tetrachloride and chlorobenzene; Ethers such as diethyl ether, dibutyl ether and dioxane; Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; And nitriles such as acetonitrile and propionitrile.

All conventional acid binders can be used as acid acceptors, like sodium thorium carbonate, potassium carbonate, sodium as well as aliphatic, aromatic or heterocyclic amines such as triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine. Alkali metal carbonates and alkali metal alcoholates such as methacrylate and methacrylate and potassium methacrylate and acrylate are proved to be particularly suitable.

The reaction temperature range is wide but generally 0-120 ° C., preferably 40-60 ° C. It also usually occurs under atmospheric pressure.

In this reaction, it is preferable to use benzisoxazole in an excess of 10-20%. The reaction is preferably directed at one solvent in the presence of an acid acceptor in most cases at slightly elevated temperatures. After the reaction is completed, the reaction mixture is cooled, poured into water, extracted by shaking with an organic solvent. The organic phase is washed, dried and the solvent is vacuum laminar.

The novel compounds prepared according to the invention are usually obtained in the oil phase and are mostly decomposed when distilled, thus releasing them from the final volatiles by so-called "slight distillation". This undistillation is a method of continuing to refine | purify to the temperature raised slightly under reduced pressure. Therefore, the compound can be specified by the rate of refraction. Compounds obtained in crystalline form are characterized by melting point.

As already described, the benz isoxazoles obtained according to the present invention, chionophosphorinic (phosphonine) acid esters have excellent insecticidal and acaricide activity. These compounds are not only effective against plant pests, sanitary pests and stockpile pests, but also for veterinary applications against animal parasites (parasitic worms) such as parasite larvae. They not only show excellent action against insects, insects and mite, but also have a weakening effect. Some compounds also have bactericidal action.

Economically important pests in agriculture and forestry, along with stored and sanitary pests, include:

Conformal such as Oniscus asellus, Armadillidium vulgare and porcellio Scaber; Blaniulus guttulatus as Diplolopoda; Chilopoda, including Geophillus carpophagus and Scutigera; Scutigerelia immaculata as Symphyla; Arachnida as Scorpio maurus and Latrodectus mactans; The mites are Acarus siro, Argas reflexus, Ornithodoros moubata, Dermanyssus gallinae, Eriphyes ribis, Philokop Phyllocoptuta oleivora, Boophilus microplus, Rhipicephalus evertsi, Sarcoptes Scabiei, Tarsonemus, Clover Ngae , Tangerine mite, apple mite Tetranychus tumidus and spotted mite; Lepisma saccharina; Onychiurus armatus as a popping tree; Locust wheels, flywheels, dysentery wheels, Leucophaea maderae, wheels, Acheta domesticus, ground puppy, Fulchi, Melanoplus differentialis And Chistocerca gregaria; Forficula auricularia as the herb beetle; Isoptera, Reticulitermes; At a glance Phylloxera vastatrix, Pemphigus; And Pediculus humanus corporis, Hercinothrips femoralis and shellfish larvae as coleoptera; Euphorbia is a genus of Euphorgaster, Dysdercus intermedius, Pisma quadrata, bedbugs, Rhodnius prolixus, and Triatoma ; Alliumoids are Aleurodes brassicae, Bemisia tabaci, cotton aphids, cabbage, aphids, crow aphids, Doraris fabae, Doralis pomi (Doralis) pomi) Lecanium corni, Saissetia oleae, Laodelphax striatellus, Creeper, Aonidiella aurantii, Apidiotus he Aspidiotus hederae, Pseudococcus and Psylla; Lepidoptera, cotton tarnamo, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, apple moth, cabbage moth, tent moth, pattern moth , Lymanthria, Bucalatrix thurberiella, Mandarin moth, Cockroach, Euxoa, Feltia, Erias insulana, Helio Helithis, Laphygma exigua, Mamestra brassicae, Panolis flammea, Tobacco coax, Spodoptera, Tri-flu Trioplussia, Carpocapsa pomonella, Pieris, chilio, light moth, Ephestia kuhniella, galleria mellonella Cacaocia Poda Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, and totrix Tortrix viridana, Anoblum punctatum as coleoptera, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus , Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleriae, Diabrotica, Psylliodes chrysocephala, Epilachna varivestis, Atomaria, Sawdust Captain, Antonomus, Sitophilus us, Otiorrhynchus sulcatus, Cosmoplites sordidus, Ceuthorrhynchus assimilis, Hyperapostica, Dermestes ), Trogoderma, Anthranus, Athenus, Lyctus, Meligthes aeneus, Ptinus , Niptus hololeucus, Gibbium psylloides, Tribolium, Brown rice, Agripeas, Agriotes, Conoderus, Melonta Melo Melolontha melolontha, Amphimalus solstitialis, and Costelitra Zealandica; By felling Diprion, Holocampa, Lasius, Monomorium pharaonis and Vespa; Flies with Aedes, Anopheles, Culex, Drosophila, Housefly, Fannia, Chimpanzee, Hypoderma, Vibio Hortulans Bibie hortulans, Oscinella frit, Phormia, Spinach chisels, Camallifora erythrocephala, Lucilia, Chrysomyia, Ceratis Caratitis capitata, Dacus oleae and tipula paludosa; Xenopsylla cheopis in Siphonaptera.

The active compounds prepared according to the invention can be made into conventional preparations, for example solutions, emulsions, suspensions, powders, pasta preparations and granules. Such formulations are prepared according to conventional methods, for example obtained by mixing an extender, i.e. a liquid, solid or liquefied gas diluent or carrier, with an active compound, optionally with surfactants such as emulsifiers and dispersants and / or blowing agents. When water is used as an extender, an organic solvent can be used as an adjuvant.

As a liquid diluent or carrier, aromatic hydrocarbons such as xylene, toluene, benzene or alkylnaphthylenes, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, chloroethylene or methylene chloride, cyclohexane or mineral oil fractions Aliphatic hydrocarbons such as paraffins, alcohols such as butanol or glycol, or ethers and esters thereof, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, dimethyl in addition to water Preference is given to solvents such as formamide, dimethylsulfoxide or acetonitrile.

Liquefied gas diluent or carrier means a liquid that is a gas at atmospheric pressure and room temperature, such as chlorinated hydrocarbons such as freon.

The solid diluent or carrier is preferably a natural mineral such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth or a synthetic mineral such as highly dispersed silicic acid, alumina or silicate.

Preferred emulsifiers and blowing agents include nonionic and anionic emulsifiers such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, alkylsulfonates, alkylsulfates, arylsulfonates, albumin hydrolysates, and dispersants as lignin , Sulfite waste and methylcellulose.

The active compounds according to the invention can be used in admixture with other active compounds.

Generally, the effective compound content of the formulation is 0.1-95% (weight), preferably 0.5-90%.

This active compound may be used as it is or as a preparation. The method of use is according to the usual methods such as spraying, fumigation, and smearing.

The range of effective compound concentrations in the ready-to-use formulations is wide, but is generally 0.0001-10%, preferably 0.01-1% (weight).

In addition, the result is good when used as a ULV method, and 95% or even the effective compound (100%) can be used as it is.

When used against hygienic pests and stored pests, the active compounds not only have good retention in wood and clay, but also have good stability against alkalis on lime matrix.

The following biological tests describe the pesticidal and acaricide activities of the compounds prepared according to the present invention. Here, a part shows a weight part.

[Test Example 1]

Tatranicus test (resistant)

Solvent: 3 parts Acetone

Emulsifier: 1 part alkylaryl polyglycol ether

One part of the active compound was mixed with the solvent of the amount containing the amount of emulsifier and diluted with water to the desired concentration.

Soybeans (Pazeolus vulgaris) about 10-30 cm tall were treated with this agent and heavily infected with spotts of all metamorphic stages. After a certain period of time, the killing effect was expressed in%. 100% indicates that all mites are dead and 0% are not dead. Effective compounds, effective compound concentrations, measurement times and results are shown in the following table.

TABLE 1

[Test Example 2]

Flutella test

Solvent: 3 parts Acetone

Emulsifier: 1 part alkylaryl polyglycol ether

In order to make a suitable active compound formulation, one part of the active compound was mixed with the amount of solvent containing this amount of emulsifier and diluted to the desired concentration.

Cabbage leaves (Brassica oleracea) were sufficiently sprayed with the above active compound formulations before infecting some cabbage moths.

After a certain period of time, the results showing the percentage of pesticides are as follows.

TABLE 2

[Test Example 3]

Peden Larva Test

Solvent: 3 parts Acetone

Emulsifier: 1 part alkylaryl polyglycol ether

One part of the active compound was mixed with a solvent of this amount containing this amount of emulsifier and diluted to molar to the desired concentration.

Cabbage leaves (Brassica oleracea) were sufficiently treated with the active compound preparations and then infected with Peden Coclearia.

After a certain time, the percentage of insecticide is expressed in the following table.

TABLE 3

[Test Example 4]

Parasitic Fly Larva Test

Solvent: 35 parts ethylene polyglycol monomethyl ether

Emulsifier: 35 parts norylphenol polyglycol ether

30 parts of the active compound were mixed with the above amount of solvent containing the above amount of emulsifier and diluted with water to the desired concentration.

About 20 fly larvae (Lucilia cuprina) were placed in a test tube containing about 2 cm ³ of horse breeding and 0.5 ml of the drug was treated to horse breeding. After 24 hours, the percentage of insecticide is shown in the following table.

TABLE 4

The following examples are specific examples of the present invention.

Example 1

A mixture of 65 g (0.36 mole) 3-hydroxy-7-nitro-benzisoxazole and 54 g (0.39 mole) potassium carbonate in 450 ml acetone was stirred at 50 ° C. for 30 minutes. 56.5 g (0.3 mole) of 0-ethyl-0-isopropyl-thiophosphoric acid diester chloride was added dropwise at 50 ° C followed by addition of 50 ml of water. The reaction mixture was warmed to 50 ° C. for 6 hours, cooled and poured into water. The separated oil was taken up in toluene and the organic phase was shaken with water and then shaken and extracted twice with 2N sodium hydroxide solution and washed with water until alkali was removed. After drying over sodium thorium sulfate, the solvent was distilled off under reduced pressure. 76 g (77% of theory) of 0-ethyl-0-isopropyl-0- [7-nitrobenzisoxazol (3) yl] -cionophosphorinic acid ester purified by chromatography were obtained. Refractive Index n _D ²¹ = 1, 5183

According to a method similar to Example 1, the compound of formula (I) was prepared.

Claims (1)

The 3-hydroxy-7-nitro-benz isoxazole of the following formula (II) is substituted with a thionophosphorin (phosphonine) ester of formula (III) in the presence of an acid acceptor or in the presence of an alkali metal salt, alkaline earth metal salt or ammonium form thereof. Reacting with a halide to produce the benzisoxazolo-cionophosphorine (phosphonine) ester of formula (I).

In the above structural formula R is C₁-C ₆ alkyl, R 'is C₁-C ₆ alkyl, C ₁ -C ₆ alkoxy or phenyl and Hal represents halogen.