DE2951350A1 - Controlling soil insects with organo:phosphorus derivs. - contg. 2-cyclopropyl-pyrimidyl gp. - Google Patents

Abstract

Compsn. for controlling soil insects contains as active ingredient a pyrimidine cpd. of formula (I), (X is oxygen or sulphur, R is alkyl, R1 is alkyl, alkoxy, alkylthio, alkylamino or phenyl. R2 is alkoxy, alkoxyalkyl or alkylthio- alkyl or when R1 is alkyl or phenyl, it can also be alkyl. R3 is H, alkyl or halo). (I), which are known cpds., are more effective against soil insects than other structurally similar cpds. They are well tolerated by plants and have low toxicity for warm-blooded animals. In an example, the cpd. (Ia) was incorporated into soil at 2.5 ppm, then 24 hr. later maggots of Phorbia antiqua introduced. After a further 2-7 days, kill of the insects was 100%, compared with 0% kill for the cpd. with cyclopropyl replaced by isopropyl. (Ia) was also 100% effective at 10 ppm against Tenebrio molitor larvae.

Description

2-Cyclopropyl-pyrimidin-4-yl (thiono) (thiol) -phosphor-

Agent for combating (phosphonic) acid esters or ester amides of insects in the soil The invention relates to the use of known 2-cyclopropyl-pyrimidin-4-yl (thiono) (thiol) phosphorus (phosphonic) acid esters or esteramides in agents for combating insects in the soil.

It has already become known that certain 2-alkylpyrimidin-4-yl-thionophosphoric acid esters, such as O, O-diethyl-0- (2-isopropyl-6-methoxy-pyrimidin-4-yl) -thionophosphoric acid ester, have insecticidal properties (see US Pat. No. 3,862,188). The effect of these compounds is, however, especially at low concentrations and application rates, not always satisfactory.

It has also become known that certain 2-cyclopropylpyrimidin-4-yl-thionophosphoric acid esters, such as O, O-diethyl-0- (2-cyclopropyl-6-methoxypyrimidin-4-yl) -thionophosphoric acid ester, 0,0-diethyl-0- (2-cyclopropyl-6- ethoxy-pyrimidin-4-yl) thionophosphoric acid ester and 0, O-diethyl-0- (2-cyclopropyl-6-isopropoxypyrimidin-4-yl) -thionophosphoric acid ester are very effective insecticidal (cf. DE-OS 2 737 401). About the possibility of a Application of these compounds in the ground, including because of the requirements regarding Penetration and persistence are only a small part of the known insecticides is suitable, nothing has become known so far.

It has now been found that the known 2-cyclopropylpyrimidin-4-yl (thiono) (thiol) phosphorus (phosphonic acid esters or ester amides of the formula I. in which X stands for oxygen or sulfur, R stands for alkyl, R1 stands for alkyl, alkoxy, alkylthio, alkylamino or phenyl, R2 for alkoxy, alkoxyalkyl, alkylthioalkyl or, if R1 stands for alkyl or phenyl, also for alkyl is, and R3 is hydrogen, alkyl or halogen, are very suitable as active ingredient components in agents for combating insects in the soil.

The term "insects in the soil" includes all those found in the soil Stages of insects.

Surprisingly, the compounds to be used according to the invention show of formula (I) significantly higher action against insects in the ground than from the state compounds known in the art-analogous constitution and the same direction of action. The use according to the invention of these compounds is thus a valuable one Enrichment of technology.

The 2-cyclopropylpyrimidin-4-yl (thiono) to be used according to the invention (Thiol) phosphorus (phosphonic) acid esters or ester amides are defined by formula (I) and already known (cf. DE-OS '2 737 401, 2 831 165 and 2 830 766).

So far the compounds of the formula (I) are not yet in the literature are described, they can be prepared analogously to known processes, for example, by adding (thiono) (thiol) phosphorus (phosphonic) acid ester chlorides or ester amide chlorides with 2-cyclopropyl-4-hydroxypyrimidines, optionally in the presence of acid acceptors, such as potassium carbonate, and using diluents such as acetonitrile, at temperatures between 0 and 1000C. The work-up and isolation of the Reaction products of the Formula (I) can be carried out by customary methods, for example, by diluting the reaction mixture with water, with a Water-immiscible organic solvents, such as toluene, extracted, the extracts were washed with water, dried, filtered and the solvent removed from the filtrate carefully distilled off under reduced pressure.

In formula (I), R is preferably C1-C5-alkyl, R1 is C1-C5-alkyl, C1-C5-alkoxy, C1-C5-alkylthio, C1-c5-alkylamino or phenyl, R2 for C1-C5-alkoxy, C1-C5-alkoxymethyl, C1-C5-alkylthio-methyl or in the event that R is alkyl or Phenyl also represents C1-C5-alkyl, R3 represents hydrogen, C1-C5-alkyl, chlorine or Bromine, and X for oxygen or sulfur.

The invention relates in particular to the use of compounds of the formula (I) in which R stands for C1-C3-alkyl, R1 for C1-C3-alkoxy, Cl -C3-alkylthio, C1-C3-alkylamino, C1-C3-alkyl or phenyl, R2 stands for C 1-C3-alkoxy, R3 represents hydrogen, methyl, chlorine or bromine, and X represents sulfur.

The compounds of the formula (I) to be used according to the invention are in the following examples resp.

Tables listed.

Production examples Example 1: A mixture of 16.6 g (0.1 mol) of 2-cyclopropyl-4-hydroxy-6-methoxypyrimidine, 20.7 g (0.15 mol) of potassium carbonate, 16 g (0.1 mol) of O, O Dimethylthionophosphoric acid diester chloride and 300 ml of acetonitrile are stirred for 4 hours at 50.degree. The batch is then cooled to room temperature and, after adding 400 ml of toluene, shakes it out twice with 300 ml of water each time. The organic phase is separated off, dried over sodium sulfate, freed from the solvent in vacuo and the residue is incipiently distilled. This gives 22.6 g (78% of theory) of 0,0-dimethyl-0- (2-cyclopropyl-6-methoxypyrimidin (4) yl) -thionophosphoric acid ester in the form of a yellow oil with the refractive index nD3: 1, 5441.

Analogously to Example 1, the following compounds of the formula be produced: Bei- Physikal. Data game (refractive index melting point ° C) No. R R¹ R² R³ X 2 CH3 CH3 OCH3 HS nD23 1.5310 3 C2H5 OC2H5 OCH3 HS nD24 1.5166 4 C2H5 SC3H7-n OCH3 HS nD27 1.5449 5 C2H5 CH3 OCH3 HS nD27 1.5343 6 C3H7-n OC2H5 OCH3 HS nD27 1.5127 7 C2H5 NH-C3H7-iso OCH3 HS 46 8 C2H5 OC2H5 OCH3 Br S nD23 1.5370 9 C2H5 OC2H5 OCH3 HO nD24 1.4886 10 C2H5 OC2H5 OCH3 CH3 S nD25 1.5170 11 C2H5 NH-C3H7-iso OCH3 HO 44 12 CH3 NH-CH3 OCH3 HS nD25 1.5402 At- physical. data game 1 2 03 expansion index No.R a1 R R3 X melting point OC) 13 CH3 OCH3 OC2H5 HS n2D5 1.5254 n25 1 5130 14 C2H5 OC2H5 OC2H5 HS 15 C2H5 OC2H5 OCH3 Cl S 16 C2H5 CF OCH3 HS n22 1.5783 17 C3H-iso CH3 OCH3 HS n23 1.5281 D. 18 C2H5 C2H5 OCH3 HS 22 1.5402 19 P C2H5 OC2H5 OCH3 C2H5 8 20 C2H5 OC2R5 OC2H5 C2H5 S 21 C2H5 OC2H5 OC3H7-n HS 22 C2H5 OC2H5 OC3-iso HS n24 1.5110 D. 23 CH3 OCH3 OC3H7-iso HS 24 CH3 IJXl-CH3 OC2Hs HS 69 25 C3H7-iso CH3 OC2R5 HS 54 26 cm e OC2H5 H 5 25 - 0c2H5 n25 1 5677 27 C3H7-n C2H5 OCH3 HS n2D3lS262 At- RR R1 R2 R3 X Physical. Data play- (Brenching index, no. Melting point ° C) 28 C2H5 CH3 OC3H7-iso HS nD21 1.5232 29 C2H5 C2H5 OC3H7-iso HS nD21 1.5252 30 C2H5 C2H5 OC2H5 HS n2D2 1.5328 31 C2H5 CH3 OC2H5 HS nD22 1 , 5305 32 C2H5 SC3H7-n OCH3 HO nD21 1.5247 33 C2H5 SC3H7-n OC2H5 HS nD25 1.5418 With good plant tolerance and favorable warm-blooded toxicity, the active ingredients are suitable for combating animal pests, especially insects that occur in agriculture. They are effective against normally sensitive and resistant species and against all or individual stages of development. The abovementioned pests include: From the order of the Isopoda, for example Oniscus asellus, Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, e.g. Blaniulus guttulatus.

From the order of the Chilopoda, e.g. Geophilus carpophaus and Scutigera spec.

From the order of the Symphyla, e.g. Scutigerella immaculata.

From the order of the Collembola, e.g. Onychirus armatus.

From the order of the Orthoptera, e.g. Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera, e.g. Forficula auricularia.

From the order of the Isoptera, e.g. Reticulitermes spp ..

From the order of the Anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Linognathus spp.

From the order of the Lepidoptera, for example Agrotis spp., Euxoa spp., Feltia spp Earias insulana, Prodenia litura, Spodoptera spp., Chilo spp., Pyrausta nubilalis, From the order of the Coleoptera, e.g. Diabrotica spp., Psylliodes chrysocephala, Atomaria spp., Sitophilus spp., Otiorrhynchus sulaatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

From the order of the Diptera e.g. Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Tipula paludosa.

The active ingredients can be converted into the usual formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, soluble Powder, granules, bait suspension-emulsion concentrates, seed powder, active ingredient-impregnated Natural and synthetic materials, finest encapsulation in polymer materials and in Enveloping compounds for seeds.

These formulations are prepared in a known manner, for example by Mixing the active ingredients with extenders, i.e. liquid solvents, under Liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, i.e. emulsifiers and / or dispersants and / or foam-generating agents. In the case of using water as an extender For example, organic solvents can also be used as auxiliary solvents. The following liquid solvents are essentially: aromatics, such as xylene, Toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic Hydrocarbons, such as cyclohexane or paraffins, e.g. petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, such as water; with liquefied gaseous Extenders or carriers are liquids that are meant to be used in normal Temperature and under normal pressure are gaseous, e.g. aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; come as solid carriers in question: e.g. natural rock flour, such as kaolins, clays, talc, chalk, Quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates; as solid carriers for granulates are possible: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules made from inorganic and organic flours as well as granules made of organic material such as sawdust, coconut shells, Corn on the cob and tobacco stalks; come as emulsifying and / or foam-producing agents in question: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolysates; come as a dispersant in question: e.g. lignin sulphite waste liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-like polymers are used such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g.

Iron oxide, titanium oxide, ferrocyan blue and organic color fabrics, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention are used in the form of them commercial formulations and / or those prepared from these formulations Application forms.

The active ingredient content of the prepared from the commercially available formulations Application forms can vary within wide ranges. The active ingredient concentration the use forms can range from 0.0000001 to 100% by weight of active ingredient, preferably are between 0.0001 and 10% by weight.

They are used in a customary manner adapted to the use forms Way, usually by spraying, scattering or dusting on or in the ground or but by administration in bait, which is scattered when pests appear will.

Example limit concentration test / soil insect test insect: Phorbia antiqua maggots in the soil solvent: 3 parts by weight acetone emulsifier: 1 part by weight Alkylaryl polyglycol ethers For the production of an expedient active ingredient preparation mixing 1 part by weight of active ingredient with the specified amount of solvent, add the specified amount of emulsifier and dilute the concentrate with water the desired concentration.

The active ingredient preparation is intimately mixed with the soil. Included does the concentration of the active ingredient in the preparation play practically no role, The only decisive factor is the amount of active substance by weight per unit volume of soil, which is given in ppm (mg / l). The bottom is filled into pots and these are left at room temperature stand.

After 24 hours, the test animals are placed in the treated soil and after another 2 to 7 days, the effectiveness of the active ingredient is determined by counting of the dead and living test insects determined in%. The efficiency is 100% when all test insects have been killed, it is O * if there are just as many test insects live like in the untreated control.

Active ingredients, application rates and results are shown in the table below: Table Soil insecticides Phorbia antiqua maggots in the soil Active ingredient kill rate at% in (Constitution) active ingredient concentration in 2.5 5 OP (OC2H5) 2 -1 iso CH30 C3H7 iso (known) 5 OP (OC2H5) 2 P 100% CH3O 100% v 5 OP (OC2H5) 2 C2H50 NV 100% 5 OP (OC2H5) 2 in 100% iso C3H70 N Example limit concentration test / soil insects Test insect: Tenebrio molitor larvae in the soil Solvent: 3 parts by weight acetone Emulsifier: 1 part by weight alkylaryl polyglycol ether To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified amount of solvent, the specified amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil. Dahei the concentration of the active ingredient in the preparation is practically irrelevant, The only decisive factor is the weight of the active ingredient per unit volume of soil, which is given in ppm (= mg / l). You fill the bottom in pots and leave them at Stand room temperature.

After 24 hours, the test animals are placed in the treated soil and after another 2 to 7 days, the effectiveness of the active ingredient is determined by counting of the dead and living test insects determined in%. The efficiency is 100% when all test insects have been killed; it is O% if there are just as many test insects live like in the untreated control.

Active ingredients, application rates and results are shown in the table below: Table of soil insecticides Tenebrio molitor larvae in the soil Active substance kill rate in% (Constitution) Active ingredient concentration in 10 ppm 5 0-P (0C2H5) 2 t; O% CH3O C3H7 iso 0% (known) S. (OC2H5) 2 N t NS 100% CH3O N 5 OP (OC2H5) 2 iW 100% C 2H50 19 5 OP (OC2H5) 2 iso C3H70 100%

Claims (4)

Claims 1. Agent for combating insects in the soil, characterized by a content of 2-cyclopropyl-pyrimidin-4-yl (thiono) (thiol) phosphorus (phosphonic) acid esters or ester amides of the formula I. in which X stands for oxygen or sulfur, R stands for alkyl, R1 stands for alkyl, alkoxy, alkylthio, alkylamino or phenyl, R2 for alkoxy, alkoxyalkyl, alkylthioalkyl or, if R1 stands for alkyl or phenyl, also for alkyl and R3 is hydrogen, alkyl or halogen. 2. Use of 2-cyclopropyl-pyrimiden-4-yl (thiono) (thiol) phosphorus (phosphonic) acid esters or ester amides of the formula I for combating insects in the soil. 3. A method of combating insects in the soil, characterized in that that 2-cyclopropyl-pyrimidin-4-yl (thiono) (thiol) -phosphorus (phosphonic) acid esters respectively. -esteramiden of the formula I on soil insects and / or their habitat can act. 4. A process for the production of soil insecticidal agents, characterized in that that 2-cyclopropylpyrimidin-4-yl (thiono) (thiol) phosphorus (phosphonic) acid esters or ester amides of the formula I with extenders and / or surface-active agents mixed.