KR850000429B1 - Process for preparing phosphorous esters of alkyl cyclo alkyl-5-pyrimidinol - Google Patents

Abstract

Insecticidal and acaricidal esters I [R= alkylcycloalkyl, cycloalkylalkyl; R1 = H, alkyl, alkylthio; R2 = alkyl; R3 = alkyl, alkylthio, alkylamino, Ph; X = O,S were prepd. Thus, 1- methylcyclopropyl cyanide was treated with NH3 and the resulting amidine treated with Me2NCH:C(OEt)CH:NMe.HClO4 to give 5-ethoxy-2- (1methylcyclopropyl)pyrimidine, which was dealkylated and esterified with (MeO)2P(S)Cl to give I.

Description

Process for preparing phosphorus ester of alkylcycloalkyl-5-pyrimidinol

The present invention relates to a process for preparing the phosphorus ester of alkylcycloalkyl-5-pyrimidinol. In addition, the present invention is applied to the crop soil such as corn, sugar cane, cotton and beet when applying to the leaves of the crop to corn root larvae, black gingidae, European corn borer and nematodes, Chinese cabbage moth, beet matrix maggots Very useful pyrimidinyl phosphate, phosphorothioate, phosphoro amidothioate, phosphorothioate and phosphorodithioate, which are particularly effective insecticides for tobacco moths, thyme moths and cabbage loopers It relates to a novel pyrimidinol.

Very useful novel compounds of the present invention are compounds of the structure :

Wherein R is alkylcycloalkyl or cycloalkylalkyl having 4 to 6 carbon atoms, R 'is hydrogen, alkyl or alkylthio having 1 to 3 carbon atoms

R '' is alkyl having 1 to 4 carbons, X is oxygen or sulfur, and R '' 'is alkyl having 1 to 2 carbon atoms, alkoxy, alkylthio or monoalkylamino having 1 to 4 carbon atoms, or phenyl, respectively.

The novel 2-cycloalkylalkyl or alkylcycloalkyl pyrimidinols are very useful insecticides, particularly for the preparation of phosphate compounds which may be sprayed onto the crops or leaves of the tree, which is good for spraying on soil. In particular, it has excellent control effect on corn root larvae, black giant semi-semi, European corn borer and nematode. It is convenient to use this compound by granulating a composition containing an insecticide carrier such as an inert solvent or a finely divided inert solid. Effective dosages range from 0.1 to 5 pounds (0.112 to 5.6 kg / ha) per acre when soil spraying and 0.5 to 2,000 ppm when sprayed on leaves.

Phosphate ester compounds are very useful for insects, particularly corn root larvae, black snails, European corn cloth insects and nematodes, which are problematic when spraying soil. Compositions containing 0.05 to 20% by weight are useful for soil spraying and use different concentrations when sprayed on leaves and used for chewing and vampire insects. Concentrations containing 5 to 98% by weight of active ingredient are useful. Soil coverage is in the range of 0.1 to 2 pounds (0.112 to 2.24 kg / ha) of active ingredient per acre. When spraying on leaves, the composition should contain 0.5 to 2,000 ppm of active ingredient.

Phosphate ester compounds are mostly more viscous oils or solids with melting points up to 100 ° C. and are more readily soluble in conventional thin organic solvents such as xylene and acetone or petroleum distillates and have very low solubility in water. This compound is an effective insecticide as an active poison in the composition as corn root larvae, western spotted cucumber beetles, cicada larvae, cabbage moths, tobacco moths, sugar beet matrix maggots, larvae, cabbage loopers, black giants It is used in various insects such as cotton leaf larvae, pink worm moths, thorny worm moths, rice worms, aphids, fire worms, root-knot nematodes and beetle nematodes.

The novel 2-alkylcycloalkyl- or cycloalkylalkyl-5-pyrimidinol intermediates can be prepared by the following route: Suitable alkylcycloalkyl or cycloalkylalkylnitriles can be prepared by Pinner (Org. Synth. Collect. Vol. I, page 5) to alkylcycloalkanecarboximide amide or cycloalkylalkane carboxymidamide, followed by N-3- (dimethylamino) -2-ethoxy-2-propenylidene in the presence of sodium methoxide. ) -N-methylmethaneaminimum perchlorate (Z. Arnold, 1973, Collect. Czech. Chem. Commun. 38, 1168-72). The resulting ethyl ether can be converted to 2-cycloalkylalkyl- or 2-alkylcycloalkyl-5-pyramidinol by heating with sodium ethylmercaptide in dimethylformamide (DMF). Else Vilsmeier reagents can be prepared in methylene chloride from DMF and phosgene. Then methoxyacetaldehyde dimethylacetal is added, refluxed for 12-20 hours, cooled to 0 ° C., then alkanecarboxymid is added in an appropriate cycle and sodium methoxide in methanol is slowly added. Reflux for 2 hours after removal of the methylene chloride gives the desired 2-alkylcyclo alkyl- or 2-cycloalkylalkyl-5-methoxypyrimidine. Methyl ether is cleaved of the corresponding pyrimidinol by various methods together with sodium ethyl mercaptide in DMF, sodium cyanide in dimethyl sulfoxide or potassium hydroxide in glycol.

To obtain cycloalkylalkyl- or alkylcycloalkyl-4-methyl-5-pyrimidinol, methyl methoxyacetate is condensed with potassium t-butoxide with the corresponding aceto acetic ester. Cycloalkyl- or alkylcycloalkane carboxymidamides are added and the mixture is heated to reflux. The resulting 2-alkylcycloalkyl- or cycloalkylalkyl-5-methoxy-6-methoxymethyl-4-pyrimidol was treated with phosphorus oxychloride to give 4-chloro derivatives, followed by 1N aqueous sodium hydroxide solution. Reduction with zinc gives 2-alkylcycloalkyl- or cycloalkylalkyl-5-methoxy-4-methylpyrimidine. Decomposition as described above yields 2-alkylcycloalkyl- or cycloalkyl-alkyl-4-methyl-5-pyrimidinol.

To prepare 4-alkylthio-2-alkylcycloalkyl or cycloalkylalkyl-5-pyrimidinone, methylmethoxy acetate is condensed with ethyl formate with the help of potassium tert-butoxide. Cycloalkylalkanes or alkyl-cycloalkancarboxymidamides are added to the product and the mixture is heated to reflux. 2-alkylcycloalkyl- or cycloalkylalkyl-5-methoxy-4-pyrimidinol is obtained with phosphorusoxy chloride 4-chloro-2-alkylcycloalkyl- or cycloalkylalkyl-5-methoxypyrimidine Convert 4-alkyl-mercapto-2-alkylcycloalkyl- or cycloalkylalkyl-5-methoxy pyrimidine produced after reacting a chlorine compound with sodium alkyl mercaptide is obtained by any of the methods described above. Decomposition with alkylthio-2-alkylcycloalkyl- or cycloalkylalkyl-5-pyrimidinol.

Phosphorus derivatives of pyrimidinol are prepared using potassium carbonate as the suitable phosphorus chloride hydrogen chloride acceptor and acetonitrile as the solvent. A phosphorus ester of alkylcycloalkyl-5-pyrimidinol of formula (I) is prepared by reacting a compound of formula (II) with a compound of formula (III).

In the above structural formula

R is alkylcycloalkyl or cycloalkylalkyl having 4 to 6 carbon atoms, R 'is hydrogen, alkyl or alkylthio having 1 to 3 carbon atoms, R' 'is alkyl having 1 to 4 carbon atoms, X is oxygen or sulfur , R '' 'is alkyl having 1 to 2 carbon atoms, alkoxy, alkylthio or monoalkylamino each having 1 to 4 carbon atoms, or phenyl.

This reaction is carried out by ethers such as benzel, toluene, xylten, chlorobenzene, petroleum ether, methylene chloride, chloroform, carbon tetrachloride, diethyl ether, dibutyl ether and dioxane, acetone, methyl ethyl ketone, methyl isopropyl ketone or It is convenient to carry out in an inert organic solution such as ketone such as methyl butobutyl ketone, nitrile such as acetonitrile and propionitrile. Alkali carbonates, alkali hydroxides and alcoholates such as sodium carbonate, potassium carbonate, sodium or potassium methylate or ethylate and aliphatic, aromatic or hetero, such as triethylamine, trimethylamine, dimethylaniline, dimethylbenzylamine and pyridine Acid binders or receptors selected from the amines of the ring are used.

The reaction temperature may be selected in the range of 0 to 100 ° C, preferably 20 to 60 ° C. The reaction is generally carried out under ambient atmospheric pressure. The amount of reagent used is indisputable and the desired product is obtained no matter what proportion the reactants are used. Excellent results are obtained when pyrimidinol and phosphorochloridate, phosphoro amidochloridothioate, phosphorochloridothioate or phosphorochlorido thioate are carried out in the preferred method using equimolar ratios. The reaction proceeds smoothly in the temperature range of 0 to 100 ° C. to produce chloride with the desired products and by-products. In order to conduct the reaction, the reactants are mixed and reacted together in a convenient manner, and the resulting mixture is maintained at the reaction temperature range to complete the reaction. After completion of the reaction, the reaction mixture is washed with water and distilled under reduced pressure to remove the organic reaction medium to obtain the desired product as a residue. The product can be further purified by conventional methods of washing with water and aqueous aqueous alkali metal hydroxide side, solvent extraction and recrystallization. Phosphoro Chloridate, Phosphoro Amidochloridothioate, Phosphoro Chlorido Thioate or Phosphoro Chlorido Thioate Used as Intermediate is prepared according to methods known in the art. Dithioate is reacted with PCl ₃ with the appropriate alkylsulphenyl chloride in the presence of sulfur dioxide to obtain S-alkyl phosphorodichlorido thioate followed by phosphorus pentasulphide to react with S-alkyl phosphorodichlorido dithioate. Can be prepared by several steps to obtain. The latter compound is reacted with ethanol in the presence of an acid acceptor such as triethylamine to give the desired product, 0-ethyl S-alkyl phosphorochloridodithioate, starting materials and by-products 0,0-diethyl S-alkyl phosphoro dithio A mixture of eights is produced and this mixture is decomposed. Preferably, the ammonium salt of 0,0-diethyl dithio phosphoric acid is alkylated with an appropriate alkyl bromide to give S-alkyl 0,0-diethyl phosphoro dithioate, followed by sodium hydrogen sulfide or ethyl group. Is decomposed and sodium salt is obtained. Reaction of the sodium salt with phosphorus pentachloride affords the desired 0-ethyl S-alkyl phosphorochloridodithioate.

The following examples further illustrate the invention.

Example 1

1-methyl cyclopropane-carboxymidamide, monohydro chloride

A mixture of 48.3 g of 1-methylcyclopropyl cyanide (D. Gotkis and JB Cloke, J. Am. Chem. Soc. 56, 2710-2712 (1934)) and 35 ml of absolute ethanol was cooled to 0 ° C. and approximately 30 g of hydrogen chloride Is introduced at a rate such that the temperature of the reaction mixture does not rise above 5 ° C. After the addition is complete the cooling bath is removed and the mixture is stirred overnight at room temperature. The reaction mixture is evacuated to remove excess hydrogen chloride as much as possible. 25 ml of anhydrous ethanol was added to the oily viscous residue, and then a solution of about 20 g of ammonia in 125 ml of ammonia in 125 ml of anhydrous methanol was added dropwise. The mixture is cooled down and kept below 20 ° C. The resulting mixture was stirred at room temperature for 3 hours, filtered to remove ammonia chloride and the filtrate was concentrated in vacuo. The solid residue is recrystallized from isopropanol / ether to give 66.7 g (83%) of white crystals having a melting point of 185 ° to 187 ° C.

Analysis _{value: C 5 H 10 N 2 ·} HCI

Found: C 44.13 H 8.06 N 20.80

Calculated Value: C 44.61 H 8.24 N 20.81

Example 2

5-ethoxy-2- (1-methylcyclopropyl) pyrimidine

60.3 g of 1-methyl-cyclopropane carboxymidamide monohydrochloride, N- (3- (dimethylamino) -2-ethoxy-2-propenylidene) -N-methylammonium perchlorate (Z. Arnold, Collect Czech.Chem.Commun. 38, 1168-1172 (1973)) and a solution of sodium methoxide prepared from 31 g of sodium and 600 ml of methanol were added dropwise to a stirred mixture of 100 ml of methanol. After the addition is complete the mixture is heated to reflux for 3 hours and then concentrated in vacuo. The residue is taken up in water and extracted twice with ether. The ether extract is dried over anhydrous sodium sulfate, the ether is removed in a rotary evaporator and the remaining oil is distilled in cougelor (bath temperature 65 ° C., pressure 0.2 mm) to give a colorless oil.

RI (25 °) = 1,5162 Yield 66.7 g (83%)

Analytical Values: C ₁₀ H ₁₄ N ₂ O

Found: C 67.24 H 8.00 N 15.74

Calculated Value: C 67.38 H 7.92 N 15.72

The 5-ethoxypyrimidines described in Table I below are also prepared by the same method.

TABLE I

*) Distilled in Kugeloer. In the temperature of the atmospheric bath,

Example 5

2- (1-methylcyclopropyl) -5-pyrimidinol

A mixture of 64.2 g of 5-ethoxy-2- (1-methyl-cyclopropyl) pyrimidine, 67.5 g of sodium ethyl mercaptide, and 440 ml of dimethylformamide was stirred and heated, followed by stirring the resulting diethyl sulfide into stark crab. Remove it. Heated under reflux for 2 hours and then distilled under vacuum to remove dimethylform amide. The residue is taken up in water and the resulting solution is acidified with glacial acetic acid. The precipitated product was collected by filtration, washed with water, dried in air and recrystallized with ethyl acetate to obtain 45.6 g (84%) of white crystals having a melting point of 168 to 170 ° C.

Analytical Value: C ₈ H ₁₀ N ₂ O

Found: C 63.78 H 6.74 N 18.53

Calculated Value: C 63.98 H 6.71 N 18.65

The 5-pyrimidinols described in Table II below are prepared by the same method as described above.

TABLE II

Example 8

Phosphorothioic acid: 0,0-dimethyl 0- (2- (1-methyl-cyclopropyl) -5-pyrimidinyl) ester

A mixture of 7.5 g of 2- (1-methylpropyne) -5-pyrimidinol, 8.0 g of 0,0-dimethyl phosphorochloridothioate, 60 ml of acetonitrile and 10 g of potassium carbonate fine powder is stirred for 90 minutes. The salt is removed by filtration, the filtrate is concentrated in vacuo and the remaining fractions are taken up in ether and the resulting ether solution is washed once with 2% sodium hydroxide solution and dried over anhydrous sodium sulfate. The ether is removed in a rotary evaporator to yield 11.7 g (86%) of a colorless oil.

RI (25 °) = 1.5274

Analytical Value: C ₁₀ H ₁₅ N ₂ O ₃ PS

Found: C 43.52 H 5.62 N 10.18

Calculated Value: C 43.79 H 5.51 N 10.22

By the same method the following dimethyl esters are prepared:

TABLE III

Example 10

Phosphorothioic acid: 0,0-diethyl 0- (2- (1-methyl-cyclopropyl) -5-pyrimidinyl) ester

A mixture of 7.5 g of 2- (1-methylcyclopropyl) -5-pyrimidinol, 10 g of potassium carbonate fine powder, 60 ml of acetonitrile and 9.4 g of 0,0-diethyl phosphorochlorido thioate is stirred for 90 minutes. . The salt is filtered off to remove salt and then the filtrate is concentrated in vacuo. The remaining oil is taken up in ether and the ether solution is washed twice with 2% aqueous sodium hydroxide solution and once with saturated sodium chloride solution and dried over anhydrous sodium sulfate. The ether is removed in a rotary evaporator to give 13.8 g (92%) of a colorless oil.

RI (25 °) = 1.5150

Analytical Value: C ₁₂ H ₁₉ N ₂ O ₃ PS

Found: C 47.69 H 6.40 N 9.26

Calculated Value: C 47.67 H 6.33 N 9.27

By the same method, the following diethyl ester is produced.

TABLE IV

Example 13

Phosphorodithioic acid: 0-ethyl 0- (2- (1-methylcyclopropyl) -5-pyrimidinyl) S-propyl ester

A mixture of 5.0 g of 2- (1-methylcyclopropyl) -5-pyrimidinol, 7 g of potassium carbonate fine powder, 50 ml of acetonitrile and 7.2 g of 0-ethyl S-propyl phosphorochloridodithioate was added for about 90 minutes. Stir. The salt is filtered off to remove salt and then the filtrate is concentrated in vacuo. The remaining oil is dissolved in ether and the ether solution is washed twice with 2% aqueous sodium hydroxide solution and once with saturated sodium chloride solution and dried over anhydrous sodium sulfate. The ether is removed in a rotary evaporator to give 10.3 g (94%) of colorless oil.

RI (25 °) = 1.5485

Analytical Value: C ₁₃ H ₂₁ N ₂ O ₂ PS ₂

Found: C 47.07 H 6.32 N 8.57

Calculated Value: C 46.97 H 6.37 N 8.43

By the same method the following 0-ethyl S-propyl ester is prepared.

TABLE V

Example 15

Phosphoramidothio acids: (1-methylethyl), 0-ethyl 0- (2- (1-methylcyclopropyl) -5-pyrimidinyl) ester

5.0 g of 2- (1-methylcyclopropyl) -5-pyrimidinol, 7 g of potassium carbonate fine powder, 50 ml of acetonitrile and 6.7 g of phosphoramido chloridothioic acid: (1-methylethyl)-, 0- The mixture of ethyl esters is stirred for 90 minutes. The salt is filtered off to remove salt and then the filtrate is concentrated in vacuo. The remaining oil is dissolved in ether and the ether solution is washed twice with 2% aqueous sodium hydroxide solution and once with saturated sodium chloride solution to dry anhydrous sodium sulfate over. The ether is removed in a rotary evaporator to give a colorless oil.

RI (25 °) = 1.5274

Yield 7.6 g (73%)

Analytical Value: C ₁₃ H ₂₂ N ₃ O ₂ PS

Found: C 49.52 H 7.13 N 13.48

Calculated Value: C 49.51 H 7.03 N 13.32

By the same method, the following 0-ethyl N-isopropyl ester is prepared.

Table VI

Example 17

Phenylphosphonothioic acid: 0-methyl 0- (2- (1-methyl-cyclopropyl) -5-pyrimidinyl) ester

A mixture of 5.0 g of 2- (1-methylcyclopropyl) -5-pyrimidinol, 7 g of potassium carbonate fine powder, 50 ml of acetonitrile and 6.8 g of 0-methylphenyl phosphonoclodoidoate is stirred overnight. After removing the salt by filtration, the filtrate was concentrated in vacuo, and the remaining oil was dissolved in ether, and then the ether solution was washed twice with 2% aqueous sodium hydroxide solution and once with saturated sodium chloride solution and dried over anhydrous sodium sulfate. The ether is removed in a rotary evaporator to give a colorless oil.

RI (25 °) = 1.5811

Yield 7.55 g (75%)

Analytical Value: C ₁₅ H ₁₇ N ₂ O ₂ PS

Found: C 55.64 H 5.59 N 8.26

Calculated Value: C 56.23 H 5.35 N 8.75

Example 18

Ethyl phosphono thio acid: 0-ethyl 0- (2- (1-methylcyclopropyl) -5-pyrimidinyl) ester

A mixture of 5.3 g of 2- (1-methylcyclopropyl) -5-pyrimidinol, 5.9 g of potassium carbonate fine powder, 42 ml of acetonitrile, and 6.7 g of 0-ethylethyl phosphonoclodoidoate is stirred for 3 hours. . After filtration to remove salts, the filtrate is concentrated in vacuo, the remaining oil is taken up in ether, the ether solution is washed twice with 2% aqueous sodium hydroxide solution and once with saturated sodium chloride solution and dried over anhydrous sodium sulfate. The ether is removed in a rotary evaporator to yield 9.1 g (93.8%) of colorless oil.

RI (25 °) = 1.5316

Analytical Value: C ₁₂ H ₁₉ N ₂ O ₂ PS

Found: C 50.17 H 6.6.7 N 9.89

Calculated Value: C 50.33 H 6.69 N 9.79

The compounds of the present invention are useful as insecticides that act on chewing and vampire-type insects that invade critical crops during cultivation. Compounds that are mixed esters, i.e. compounds with S-alkyl groups on the phosphorus, have relatively low toxicity to mammals and are cultivated in crops and beet rows, cabbage loopers, tobacco moths, cotton leaf moths, pink worm moths, and spiny stalks. Suitable for spraying on leaves for moths, grape moths, cicada worms and rice worm insects. These compounds are also effective against western speckled cucumber beetle larvae, indicating that they work well against corn root larvae. These compounds are particularly effective in controlling cabbage moths.

This new compound is useful for most insects but is particularly suitable for soil spreading due to its excellent stability to the soil. These compounds have excellent effects on western speckled cucumber beetles and corn root larvae, and are also useful in soil spraying to control insects such as corn, cotton, sugar beetles and beetles.

Compositions containing one or a mixture of pyrimidinyl phosphate, thiophosphate, dithiophosphate, amidothiophosphate or thiophosphonate as active ingredients and various agricultural or pesticidal carriers, surfactants and other additives may be used as insects. Very useful for detoxification control. It is an advantage of the present invention that the amount required to control detoxification of a composition containing this compound can be applied to soil or growing plants without causing specific damage to the leaves of the plant.

The practice of the present invention is to control pests by spraying pyrimidinyl phosphate, dithiophosphate, amidothiophosphate, or thiophosphonate insecticides on insects, their habitat or pre-feed food. However, the present invention also includes the use of solutions containing poisons, wet powders, powders or granular compositions. These compositions are sprayed on living plants or planted places thereof without damaging the leaves or other parts of the plants. In the preparation of toxic compositions, pyrimidinyl phosphate, thiophosphate, amidothiophosphate, thiophosphonate or dithiophosphate products may be added to an aromatic solvent, a petroleum distillate surfactant dispersant, a wet powder or a finely active solid in powder or granule form. It may be modified with one or more of the supplements included. Depending on the concentration of the active product composition, it can be sprayed onto insects, their habitats or prey and diluted with concentrates or inert carriers. For compositions used as concentrates the poison concentration is 5 to 98% by weight. It depends on the susceptibility of certain insects to pyrimidinyl phosphate, thiophosphate, dithiophosphate, amidothiophosphatethiophosphonate or dithiophosphate compounds used in the composition to be applied to insects, their habitat or food. Excellent results are obtained with a solution composition containing 0.5 to 2,000 ppm, preferably 1 to 400 ppm, of active poison by weight. Sometimes it is convenient to use a composition containing 90% by weight of the poison. Excellent results are obtained with powder and granular compositions containing from 0.05 to 50% by weight, more preferably from 1 to 20 by weight, most preferably from 2.5 to 15% by weight.

In preparing powder or granular compositions, pyrimidinyl phosphate, thiophosphate, dithiophosphate, amidothiophosphate or thiophosphonate compounds are mixed with any of finely divided solids such as pyrophyllite, diatomaceous earth, gypsum and the like. . During this operation, the finely divided carriers are powdered, mixed with the poisons, or moistened with a poison solution in a volatile organic solvent. Likewise, powder compositions containing one of these activating compounds can be mixed with solid surface active dispersants such as table photo, attapulgite, bentonite and other clays. Depending on the proportions of the components, these powder compositions may be used as concentrates or added with a solid surfactant dispersant or diluted with pyrophyllite, diatomaceous earth, gypsum, etc. so that the amount of active ingredient in the composition is suitable for controlling insects. These concentrated powder compositions are also dispersed in water with or without the aid of dispersants and wetting agents to make spray mixtures.

It is also mixed with surfactant dispersants, such as ionic and nonionic emulsions, to make one of the active compounds or a powder concentrate containing the compound. If the composition is a powder concentrate, when properly mixed together with emulsions and / or wetting agents as known in the art, they are wettable powders. These concentrates can be readily dispersed in the carrier solution to produce a nebulizer containing the desired amount of poison. The dispersant and its amount of use are determined by the activity of the dispersant to promote dispersion of the concentrate in the carrier solution to produce the desired spray composition.

Granulated solid carriers, such as cryconitic granules prepared from Momorylonitrile clays, although mixed compositions of active or stabilized finely divided soils and poisons such as montmorillonite clay can be granulated by known methods It is preferred to spray the required amount of the poison on granulated solid carriers containing small amounts of butyrolactone or stabilizer or to add a poison solution in a volatile solvent such as methylene chloride as in a mobile bed operation. The poison is absorbed into the granules. The solvent present is dried off. Preferred excess size is a large amount of 24 to 48 mesh (size of pores 0.7 to 0.295 mm).

The active compound is mixed with a suitable organic solution and surfactant dispersant, which cannot be mixed with water, to prepare an emulsion concentrate and then diluted with water to prepare an emulsion spray mixture of water vapor. Carriers in this composition include water soluble emulsions, ie mixtures of solvents, emulsions and water that cannot be mixed with water. Preferred dispersants used in these compositions are oil solubles and include nonionic emulsions such as polyoxyethylene derivatives of sorbitan esters, complex ether alcohols and the like. However, oil-soluble ionic emulsions such as mahogany soaps or alkylbenzenesulfonates such as dodecylbenzene sulfonate or alkyl naphthalinsulfonate may also be used. Suitable organic solutions used in the composition include petroleum oyl and distillate, toluene, xylene, halohydrocarbon solutions, ketones and synthetic oils. Telephone emulsions can be manufactured and used if desired.

When operated in accordance with the present invention, one or a mixture of the active compounds is fed to insects, to soil-containing habitats or to their food in a convenient manner, for example by feeding or by mixing with food or by using a manual sprayer or sprayer. Spray. It is convenient to spray from the leaves of the plant with a powder sprayer, a sprayer. On large scale operations, powder and low volume sprays are sprayed by air. Soil spraying is convenient to use sprayers such as straight sprayers and continue to harrow the soil. In addition, the soil spraying is conveniently sprayed between the seeded gyrus with the composition as a powder or granules during the seeding plant, and preferably the granules are sprayed on the heat of mixing the seeds and soil.

When spraying soil, it is effective to spread the composition containing the active toxin from 0.1 to 5 pounds per acre (0.112 to 5.6 kg / ha), preferably in the range of 0.1 to 2 pounds per acre (0.112 to 2.24 kg / ha). to be. The most active poison among the new compounds is that spraying about 1.0 pounds per acre is effective without damaging the growing crop.

Methods of controlling insects by administering the novel active compounds are described in the following examples.

Example 19

By separate operation, a water-soluble composition of pyrimidinyl phosphate, thiophosphate, dithiophosphate, amidothiophosphate or thiophosphonate poison compound is prepared as follows.

4 parts by weight of each toxic compound, 0.08 parts of sorbitan trioleate (span ^* 85) and 0.02 parts of sorbitan monolaurate polyoxyethylene derivative (Twon ^* 80) in 40 ml of acetone, which can be dispersed in water The concentrated composition is prepared into a phase. The concentrated composition is dispersed in water to obtain a water-soluble composition containing various amounts of poisons. In addition, a toxic compound is mixed with alkyl arylsulfonate (Nacconol ^* NR) and substituted benzoide alkyl sulfonic acid (Daxad ^* No. 27) in water to prepare a water-soluble composition. Each material was ball milled to prepare a composition containing various amounts of one of the poisons, 300 parts by weight of Nacconol ^* NR and 300 parts by weight of Daxad NO.27.

The water-soluble compositions prepared as described above have desirable wettability and, in particular, are sprayed on pests, such as aphids, mites and insects, or on their habitat and food to control pests.

Example 20

The composition is prepared according to the Span ^* 85 method of Example 19 containing 400 ppm of poison. In each case, 75 g of the air-dried soil is treated with a sufficient amount of the test composition, about 5 ml, so that the poison in the soil is 25 ppm after air drying for 25 hours. The treated soil is agitated and split until well mixed and then placed in two vials infected with 50 to 100 wild-spotted cucumber beetles (Diabroica Undecimpunctata Undecimpunctata). Corn grains are planted in each vial and water is added to the vials and incubated in a warm damp place. After 12 days, count the damaged corn trees and observe for larvae. If no larvae are present in the vial, it is 100% controlled.

Full control was observed in the test with the compound of Examples 8-13.

Example 21

Example 20 was repeated at concentrations of toxic compositions in air dried soils of 6.25 and 1.5 ppm to observe that various compounds of the present invention achieved complete control at concentrations of toxic compositions of 1.5 ppm or less.

Each compound contains 2,000 ppm, more typically 400 ppm or less, e.g. 0.5 to 1.5 ppm, for each pest described above, or 5 pounds per acre (5.6 kg / ha), more typically 2 per acre Effectiveness has been observed by spraying less than pounds (2.24 kg / ha), for example 0.25 to 0.5 pounds (0.28 to 0.56 kg / ha) per acre. The compound acts as a systemic contact poison on insects. The compound has good soil mobility and does not need to be sprayed on growing plants or adjacent areas to protect against pests.

The 0,0-diethyl phosphorothioate compound having 4 to 5 carbon atoms in the cycloalkylalkyl group has excellent soil stability for the control of black giant, European corn insects, western speckled cucumber beetles and corn root larvae. It is composed of a preferred group which has sufficient residue and increases the fruit in the treated corn.

Compounds with other preferred groups where R ¹ is hydrogen showed excellent action against western speckled cucumber beetles, tarmac spider mites and greenhouse dusts.

Claims (1)

A process for preparing a phosphorus ester of formula (I) alkyl-cycloalkyl-5-pyrimidinol, characterized by reacting a compound of formula (II) with a compound of formula (III).

R '' is alkyl having 1 to 4 carbon atoms, R '' 'is alkyl having 1 to 2 carbon atoms, alkoxy, alkylthio or monoalkylamino having 1 to 4 carbon atoms, or phenyl, respectively.