DE2119211A1 - Organophosphates - active against insects and nematodes - Google Patents

Abstract

Cpds. of formula (I) (where R is lower alkyl or is phenyl or benzyl opt. substd. by halogen or lower alkyl), which are active against insects, spider-mites and soli nematodes, are prepd. by reacting a salt of formula (II) (where M is NH4 or a metal atom) with halogen -CH2-S-R pref. in a solvent or diluent at 0-100 degrees C.

Description

Insecticidal Agent The present invention relates to organic ones Phosphoric acid esters and their use for combating harmful insects and other pests.

In particular, the present invention relates to an insecticide which contains, as an active ingredient, an organic phosphoric acid ester represented by the following general formula (I), wherein R is a lower alkyl radical, a phenyl or benzyl radical substituted by a halogen atom or a lower alkyl radical, or an unsubstituted phenyl or benzyl radical.

In Japanese rice growing, the damage caused by larvae means the Insects of the genus Lepidoptera, such as the rice stem borer, which breeds twice or three times and the mites cause a serious problem. So far there have been extensive Research is being carried out which will combat these harmful insects aimed at, but only a few of the insecticides available on the market are almost all of which are based on organic phosphorus compounds built up are suitable for this purpose. Also, the harmful insects have as these Insecticides have so far been used in large quantities, creating a certain resistance built against it.

From Japanese Patent Publication No. i6875 / 6, there is known a method for producing insecticidal compounds represented by general formula (II) shown below: where R and R1 are optionally alkyl groups and R2 is optionally an aliphatic, alicyclic or aromatic radical which can also be substituted.

However, the patent publication cited above does not teach against which insects the compounds prepared according to the formula given above are to be used or what effect they have.

It has surprisingly been found that among the compounds listed above the organic phosphoric acid esters in which, as can be seen from formula (I), the Alkyl group in.

the PO-alkyl chain is an ethyl group and the alkyl group in the PS-alkyl chain is a saturated, straight-chain propyl group of the formula given below is to have particularly excellent insecticidal effectiveness.

The compounds according to the invention: can therefore within a wide range Scope of application to combat harmful sucking and stinging insects, Plant parasites, unhealthy insects and those that contain stored grain infested, are used.

In particular, the compounds according to the invention are effective for combating from harmful insects that occur in agriculture, such as, S. of the genera Coleoptera, Lepidoptera, Hemiptera, Orthoptera, Isoptera and Diptera, the spider mites and harmful nematodes occurring in the soil and can also be used as pesticides can be used against these pests.

As can be seen from Table 2 below, the Compounds according to the invention are particularly strong compared to analogous compounds insecticidal activity against insects of the genus Lepidoptera, their control with conventional insecticides has proven difficult. Also own the compounds according to the invention have very strong insecticidal activity against insects, which have built up resistance to organic phosphorus insecticides. They are also extremely effective in combating the female-breeding rice stem borer and, in contrast to parathion and methyl parathion, have because of their use their direct and indirect strong toxic effects on the human body is prohibited, only low toxicity. Even so, the insecticidal effectiveness is the Compounds according to the invention comparable or superior to those of parathion, therefore, they can be safely used as agricultural chemicals.

The compounds of the general formula (I) according to the invention can be prepared by the process listed below.

wherein R is as defined above, M is a metal atom or an ammonium radical and Hal is a halogen atom.

In the above reaction formula, R means a lower one Alkyl radical such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec. Or tert-butyl, a phenyl or benzyl radical optionally substituted by chlorine and / or bromine or a phenyl substituted with the lower alkyl radicals listed above or benzyl radical. M is a metal atom such as sodium or potassium or the ammonium residue, Hal is chlorine or bromine.

As examples of the halides of the formula (IV), the following are given called: ethylthiomethyl-, n-butylthiomethyl-, phenylthiomethyl-, 4-chlorophenylthiomethyl-, 2,4-dichlorophenylthiomethyl, 4-methylphenylthiomethyl, benzyithiomethyl, 4-chlorobenzylthiomethyl, 2,4-dichlorobenzylthiomethyl chloride or bromide.

The reaction for making the compounds of the invention will preferably carried out in a solvent or diluent. To this end can be any inert solvent. be used.

The preferred solvents and diluents are water, aliphatic and aromatic hydrocarbons (which can also be halogenated), e.g. Methylene chloride, di-, tri- or tetra-chloroethylene, toluene, chloroform, carbon tetrachloride, Gasoline, benzene, chlorobenzene or xylene; Ether, e.g.

Diethyl ether, di-n-butyl ether, dioxane or tetrahydrofuran; low boiling aliphatic ketones or nitriles such as aliphatic ketones or nitriles such as acetone, Methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, acetonitrile or propionitrile; and low-boiling aliphatic alcohols such as methanol, ethanol or isopropanol used.

According to the above procedure, the reaction can take place within a can be carried out over a wide temperature range, but in general it is at Temperatures from -20 ° C to the boiling point of the reaction mixture, preferably at Temperatures between 0 and 100C carried out.

The reaction is preferably carried out under normal pressure, they however, it can also be carried out under increased or reduced pressure. The production of the compounds according to the invention which are used as active ingredients described in more detail using the experimental examples given below.

Experimental example 1: 60 g of O-ethyl-Sn-propyldithiophosphoric acid potassium salt is dissolved in 200 ml of acetone, 28 g of ethylthiomethyl chloride are added dropwise to this solution at a temperature of 20 ° C. The temperature is then gradually increased to 60 ° C., and the reaction is brought to completion at this temperature with stirring for one hour.

The acetonitrile is distilled off from the reaction mixture and the The remainder is dissolved in benzene, washed with water and 1% sodium carbonate and dried over anhydrous sodium sulfate. After the benzene has been distilled off 54 9 colorless, oily O-ethyl-S-n-propyl-S-ethylthiomethylphosphorodithiolate obtain. The product obtained has a boiling point of 131-1350C / 0.1 mm Hg and a refractive index n20 of 1.5391.

D Versushcbeisotel 2: 60 g of 0-ethyl-Sn-propyldithiophosphate potassium salt is dissolved in 200 ml of alcohol, and 43.5 g of 4-chlorophenyl-thiomethyl chloride are added to this solution at room temperature. This mixture is passed for some time at room temperature and then for one hour at 60 ° C. The alcohol is then distilled off from the reaction mixture and the residue is dissolved in benzene, washed with water and 1% sodium carbonate and dried over anhydrous sodium sulfate. After the benzene has been distilled off, 73 g of colorless, oily O-ethyl-Sn-propyl-S-4-chlorophenylthiomethylphosphorodithiolate are obtained. The product has a boiling point of 154-1570C / 0.1 mm Hg and a refractive index n20 of 1.5922.

Experiment example 3: 60 g of O-ethyl-Sn-propyldithiophosphoric acid potassium salt are dissolved in 200 ml of acetonitrile, then 53.5 g of 4-chlorobenzylthiomethyl chloride are added dropwise at room temperature. The reaction mixture is then passed at a temperature of 60 ° C. for 1 hour. The acetonitrile is distilled off from the reaction mixture and the remainder is dissolved in benzene, mi. Was0 er and 1% sodium carbonate and washed over anhydrous sodium sulfate. After distilling the benzene, 70 g of colorless, oily O-ethyl-Sn-propyl-S-4-chlorobenzylthiomethylphosphoedithiolate are obtained.

The product has a refractive index nD20 of 1.5867.

The compounds listed below can be made using analogous methods getting produced.

Table 1 Connect- physical dunq no. structure characteristics 0 1 C2H50 0 Kp 131-1350C / 0.1 mm Hg PS-CH2-S-C2W5 nD mg n-C3H7S / 20 2 C, H, O \ n-C3HrS / 3 0 20 n-C3H75 / 2 <3 nD 1. 5885 4 CH5O O C2H50 \ Kp. L4l57OC / 0.1 mm Hg n-C3H7S and 20 1.5922 C1 5 C2H5 0 20 C23-150P-s-CH, -SI n-C3H75 / 2 to 1 n20 1. C2''taO9CH, CH3 n C3F17Sz 2 7 C2H5 oO n20 1. 5810 'PS-CH, -S- @ H D. 0 20 C2Ha8% ,, 20 nD 1.5867 C1 9 C2P150 \ 0 n C3H7S 2 When the compounds according to the invention are used as insecticides, these are either applied directly diluted with water or, as required, with solvents or auxiliaries or various inert gaseous, liquid or solid diluents and / or carriers, optionally with other auxiliaries such as surface-active agents , Emulsifiers, dispersants, spreaders and adhesives mixed and used in the various forms common in the preparation of agricultural chemicals.

Examples of gaseous diluents and / or carriers are Freon and other propellants for aerosols that are gaseous under normal conditions are called. Liquid diluents and / or carriers are water and organic Solvents such as aromatic hydrocarbons, e.g.

Xylene, toluene, benzene, dimethylnaphthalene or aromatic petroleum fractions, chlorinated aromatic or aliphatic hydrocarbons such as chlorobenzene, Chloromethylene, chloroethylene or carbon tetrachloride; aliphatic hydrocarbons, e.g. gasoline, cyclohexane or paraffin, alcohols, e.g. methanol, propanol or butanol, Ketones, e.g.

Acetone, methylethy, leon or cyclohexanone, polar solvents, e.g. Called acetonitrile, dimethylformamide and dimethyl sulfoxide. As examples of solid Diluents and / or carriers id the powders of natural mineral substances such as attapulgite, clay, chalk, talc, kaolin, montmorillonite, kieselguhr and calcium carbonate and the powders of synthetic mineral substances such as highly dispersed silica, Mention aluminum oxides and silicates. Examples of auxiliaries are non-ionic or anionic surface-active agents or emulsifiers such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, alkylaryl polyglycol ethers, alkyl sulfonates and aryl sulfonates and dispersants such as lignin, sulfite waste liquors and methyl cellulose. As required The compounds according to the invention can also be used together with other agricultural compounds Chemicals such as insecticides, nematocides, fungicides (including antibiotics), Herbicides, plant growth regulators, Fertilizers and fertilizers be used.

The insecticides according to the invention contain 0.1-95% by weight, preferably 0.5 ° 90% by weight of the above-mentioned active ingredient. The active ingredient content can vary depending on o the form of preparation, process, object, time and place of application and the degree of infestation can be varied.

The insecticides according to the invention can either only consist of the active ingredient However, they can also exist in any other in the field of agricultural Chemicals in the usual form of preparation, e.g. as a liquid preparation, emulsifiable Liquid, concentrated emulsion, wettable powder, soluble powder, oily Preparation, aerosol, paste, smokers, dust, particles, encrusted Use particles, tablets, granules and meal.

The insecticides according to the invention can either directly affect the habitat of harmful insects applied or using devices after each any method of spraying, scattering, atomizing, misting, scattering of powder, scattering of particles, mixing, smoking, injecting or Covering with powder can be used. The insecticides according to the invention can can also be used according to the so-called §'Ultra-Low-Volume "procedure, which Concentrations of active ingredient between 95 and 100% permitted.

In actual use, the active ingredient content may be in the ready-to-use Preparations for the same reason that applies to the preparation form itself, can be varied within a wide range. The content is preferably of active ingredient, however, generally 0.0001-20% by weight, in particular 0.001-5.0% by weight. The application amount of the invention Insecticide amounts about 15-1000 g / 10 a, preferably 40-600 g / 10 a, based on the active ingredient.

However, these quantities can be exceeded or undercut as required.

The present invention therefore relates to an insecticidal agent, which as an active ingredient is a compound of the formula (I) given above, a solid or liquid diluent and / or carrier and, if necessary, an auxiliary Contains J-substance.

The present invention relates to a method of combating Insects, which consists in that on the habitat of harmful insects a compound of the above formula (I) alone or blurred with one solid or liquid diluents and / or carriers, as required with an auxiliary, is applied.

The present invention is made based on the following Examples which are, however, nlc.t restrictive, explained in more detail.

Example 1: 15 parts of compound no. 4 according to the invention, 80 parts a mixture of kieselguhr and kaolin and 5 parts of the emulsifier "RUNNOX" (product the Toho Kagaku Kogyo Kabushiki Kaisha) were ground and made into a wettable Mixed powder, which was applied diluted with water.

Example 2: 30 parts of compound no. 1 according to the invention, 30 parts Xylene, 30 parts '| KAWAKASOI.' (Product of the Kavrasaki Kasei Kogyo Kabushiki Kaisha) and 10 parts of the emulsifier SORPOL11 (product of Toho Kagaku Kogyo Kabushiki Kaisha) were converted into an emulsifiable preparation with stirring, which was applied diluted with water.

Example 3: 10 parts of compound no. 2 according to the invention, 10 parts Bentonite, 78 parts of zeeklite and 2 parts of lignosulfonate were mixed and then mixed intimately mixed with 25 parts of water. The mixture was injected with granules processed into fine particles of 375-750 / u diameter (20-40 mesh) and then. dried at a temperature of 40-50 0C.

Example 4: 2 parts of compound nos. 8 and 98 according to the invention Parts of a mixture of talc and clay were ground together and made into dusts mixed.

Compared to known compounds of analogous structure and connections The compounds according to the invention are of similar biological effectiveness significantly improved effectiveness and very low toxicity compared to warm-blooded Animals and therefore of great usefulness.

The unexpectedly great effect and the advantages of the invention Compounds are made from the results of tests for effectiveness against various harmful insects of the genus Lepidoptera can be seen.

Test 1 Test for effectiveness against the twice-breeding rice stem borer: preparation of the test chemicals: Solvent: 3 parts by weight of dimethylformamide Emulsifier: 0.1 Parts by weight of alkylaryl polyglycol ether To convert the active ingredient into a suitable preparation transferred, 1 part by weight of active ingredient with the above amount of solvent, which contained the above-mentioned amount of emulsifier, mixed, the resulting Mixture was mixed with water to the prescribed concentration before use Active ingredient diluted.

Test method: Water rice seedlings were placed in a pot with a volume of 12 cm Planted diameter and the egg soaks of the double roasting rice auger upset. 7 days after the insects hatched, the was on the prescribed Amount of active ingredient diluted, emulsifiable liquid in amounts of 40 ml per pot sprayed on and the chemical-treated pot lant in a glass neck for 3 days held. The stems of the rice plants treated in this way were examined individually4, to determine the number of live and dead insects and the kill rate to be calculated Test 2 Test for effectiveness against the larvae of the tobacco seed owl: Test method: Sweet potato leaves were diluted in a, emulsifiable liquid that contained the contained the prescribed amount of compound according to the invention and as in test 1 was prepared, immersed, air dried and placed in a petri dish laid with a diameter of 9 cm. Then 10 larvae of the tobacco seed owl were im 3. Development stage placed in the bowl and this in a Thermostatic chamber held at 28 ° C for 24 hours. After expiration During this period, the number of dead insects and the kill rate were determined calculated.

Test 3 Test for effectiveness against almond moths: Test procedure o 20 fully developed almond moth larvae were placed in a container made of fine mesh wire 7 cm in diameter and 0.9 cm in height, the container was 10 seconds long in a liquid diluted with water containing the prescribed amount of the invention Contained active substance and was prepared in the same way as described in test 1, submerged, the container then left in a thermostatic chamber for 24 hours. Then the number of dead insects was determined and the kill rate was calculated.

The results of the tests for effectiveness against harmful insects of the genus Lepidoptera such as the double-brooding rice stem borer and the larvae of the tobacco seed owl and the almond moth are shown in Table 2, which also shows the results of comparative tests with analogous compounds. Table 2 Malicious insects twice-breeding the Reisstogel- Active ingredient concentration tobacco seed owl larvae almond moth borer Connection 0.1% 0.03% 0.01% 0.1% 0.03% 0.01% 0.03% C2H5O O ## PS-CH2-S-C2H5 50 0 0 0 0 0 0 # C2H5S Connection according to Pat. Publ. Sho 32-7520 C2H5O O ## PS-CH2CH2-S-C2H5 70 0 0 0 0 0 0 # C2H5S Connection according to Pat. Publ. Sho 38-16875 C2H5O O ## PS-CH2-S-C2H5 100 100 100 100 100 100 100 # C2H5S Connection No. 1 according to the present invention continuation Table 2 (Continuation) Harmful insects twice-breeding the Reisstogel- Active ingredient concentration tobacco seed owl larvae almond moth borer Connection 0.1% 0.03% 0.01% 0.1% 0.03% 0.01% 0.03% C2H5O O ## PS-CH2-S-C2H5 90 15 0 75 0 0 20 # n-C4H9S C2H5O O ## PS-CH2-S - # - Cl 25 0 0 0 0 0 0 # C2H5S Connection according to Pat. Publ. Sho 44-25348 C2H5O O ## PS-CH2-S - # - Cl 100 100 100 100 100 100 100 # n-C3H7S Compound no. 4 according to of the present invention C2H5O O ## PS-CH2-S-C2H5 90 50 0 80 0 0 15 # n-C4H9S continuation Table 2 (Continuation) Harmful insects twice-breeding the Reisstogel- Active ingredient concentration tobacco seed owl larvae almond moth borer Connection 0.1% 0.03% 0.01% 0.1% 0.03% 0.01% 0.03% C2H5O O ## PS-CH2-S-CH2 - # - Cl 65 0 0 0 0 0 0 # C2H5S C2H5O O ## PS-CH2-S-CH2 - # - Cl 100 100 100 100 100 100 100 # n-C3H7S Compound no. 8 according to of the present invention C2H5O O ## PS-CH2-S-CH2 - # - Cl 95 0 0 90 0 0 40 # n-C4H9S It can be seen from the results given in Table 2 that the compounds according to the invention show excellent activity against harmful insects of the genus Lepidoptera compared to analogous compounds.

The following are the results of tests with the inventive Listed compounds against various harmful insects.

Test for effectiveness against the tobacco seed: Test method: The test was carried out in the same manner as Test 2, the results are from Table 3 can be seen.

Table 3 Results of the efficacy tests on the tobacco seed Compound no. Degree of destruction (%) 300 ppm 100 ppm 1 100 100 2 where. 100 3 100 100 4 100 100 5 100 100 6- 100 100 7 100 50 8 100 100 9 100 100 Sumithion (commercial equivalent product) 80 20 Comments: 1.) The compound numbers correspond to those in Table 1 2.) Sumithio: Dimethyl (3-methyl-4-nitrophenyl) thiopho spha t Test for effectiveness against house flies: Test method: 1 ml of a liquid diluted with water, which contains the active ingredient in A prescribed amount and prepared as described in Test 1 was dropped onto a filter paper in a Petri dish 9 cm in diameter. Then 10 female, fully developed house flies were placed in the dish and the dish was kept in a thermostatic chamber at a temperature of 280 ° C. for 24 hours. At the end of this period, the dead insects were counted and the number of dead insects was counted. calculated.

The results are shown in Table 4.

Table 4 Results of the tests for effectiveness against house flies: Compound @ degree of destruction (%) No. 1000 ppm 100 ppm 1: 100 100 2 100 100 3 100 100 4 100 100 5 100 70 6 100 70 7 100 80 8 100 70 9 100 90 Continuation of Table 4 (continued) Connection degree of destruction (%) ~~~~~~~~~~~~~~~~~~~~~~~ ppm ~ C2Hs0 \? 1 PS-CH -s / \ Cl O 0 2 - n-C4H9S (comparison)) ~~. ,. * C2H50 0 \ II PS-CH2-S-C2H5 100 0 n-C4Hg / (compare) Test for effectiveness against the Brown Springer Corner: Test method: A liquid diluted with water, which contained the prescribed amount of active ingredient and was prepared as described in test 1, was in amounts of 10 ml per pot to 10 cm high, in pots of 12 Rice seedlings planted in a diameter of cm are sprayed on. After the liquid had dried, the pots were covered with cylindrical wire nets 7 cm in diameter and 14 cm in height, in which 30 female, fully developed brown jumpers were located. The pots were kept in a thermostatic chamber for 24 hours, after which time the number of dead insects was determined and the kill rate was calculated.

The results are shown in Table 5.

Table 5 Results of tests for efficacy against the brown spring insect Connection no. Degree of destruction (%) Active ingredient concentration 0.05% 1 100 2 100 3 96.7 7 93.3 Malathion (commercially available 60.5 Comparison product) Note: The connection numbers correspond to those in Table 1.

Test 6 Test for effectiveness against the green rice jumping insect.

Test Procedure: This test was performed as described in Test 5 with 30 female green spring knuckles carried out.

The results are shown in Table 6.

Table 6 Results of the tests for effectiveness against the green rice shrimp Connection no. Degree of destruction (%) Active ingredient concentration 0.05% 1 100 2 100 3 89.7 7 100 Note: The connection numbers correspond to those in Table 1.

Test 7 Test of effectiveness against fully developed mosquito larvae.

Test method: 100 ml of a liquid diluted with water, which contained the prescribed amount of active ingredient and prepared as described in test 1 were poured into a petri dish 9 cm in diameter and 6 cm in depth. Then 25 fully developed mosquito larvae were placed in the Srhale and these 24 Held in a thermostatic chamber for hours.

After the lapse of this period, the number of dead insects and the mortality rate was calculated.

The results are shown in Table 7.

Table 7 Results of the tests for effectiveness against fully developed mosquito larvae Connection no. Degree of destruction (%) Active ingredient concentration 0.1 ppm 1 100 2 100 4 100 8 100 Note: The connection numbers correspond to those in Table 1.

Test 8 Test for action against the red spider mite: Testvejfahren: Kidney bean seedlings at the two-leaf stage were placed in a 6 cm diameter pot planted and infected with 50-100 adults and nymphs of the red spider mite. 2 days after infection, a lye diluted with water was used, which contained the active ingredient e contained the prescribed amount and prepared as described in Test 1 was sprayed onto the pots in amounts of 40 ml per pot. The pots were Maintained in a glass house for 10 Taoe, after which time the control effect became effective rated. The evaluation was carried out according to the index corresponding to the following scale: Index: 3: No liver adults, nymphs or eggs 2: Less than 5% live Adults, nymphs and eggs compared to the untreated control area 1: 5 - 50% live adults, nymphs and eggs compared to the untreated control area 0: more than 50% live adults, nymphs and eggs compared to untreated Control area The results are shown in Table 8.

Table 8 Results of the tests for effectiveness against the red spider mite Compound drug concentration 0.1% 0.03% 0.01% 0.003% No. 1 3 3 3 3 2 3 3 3 3 4 33 3 3 8 3 3 5 2 9 3 3 3 2 Sappiran 3 2 0 0 Notes: 1) the compound numbers correspond to those in Table 1 2) Sappiran: chlorophenyl chlorobenzene sulfonate.

Claims (6)

Sponsorship claims: 2) Organic phosphonic acid esters of the general formula where R is a lower alkyl radical, a phenyl or benzyl radical substituted with a halogen atom or a lower alkyl radical, or an unsubstituted phenyl or benzyl radical. 2) Process for the preparation of organic phosphoric acid esters, characterized in that one O-ethyl-S-n-propyl-dithiophosphoric acid metal or ammonium salts of the general formula with likylating captomethyl halides of the formula Hal -CH2- S - lt:, where in the above formulas R has the meaning given in claim 1, while M is a metal atom or the ammonium group and Hal is a halogen atom. 3) insecticidal, acaricidal and nematicidal agents characterized by a content of compounds according to claim 1. 4) method Lur control of insects, mites and nematodes, thereby characterized in that compounds according to claim 1 are obtained from the pests mentioned or lets its habitat act. 5) Use of compounds according to claim 1 for combating of insects, mites and nematodes. 6) experienced in the manufacture of insecticidal, acaricidal and nematicidal Agents, characterized in that compounds according to Claim 1 are mixed with extenders and / or mixes surfactants.