CS236651B2 - Insecticide nematicide and acaricide agents and production method of efficient compound - Google Patents

Description

The invention relates to insecticidal, nematicidal and acaricidal compositions which contain, as active ingredient, the novel pyrimidinyl phosphates of the following general formula I. Further, the invention relates to a process for the preparation of these novel pyrimidinyl phosphates of the general formula I.

The insecticidal, nematicidal and acaricidal compositions according to the invention are characterized in that they contain at least one pyrimidinyl phosphate of the formula I as active ingredient.

in which

R 1 and R 2 may be the same or different from each other and are optionally branched alkyl of 1 to 5 carbon atoms,

R3 represents an optionally branched alkyl group having 1 to 6 carbon atoms,

R a is an optionally branched alkyl group having 1 to 5 carbon atoms,

Q is oxygen or sulfur,

Y is oxygen or sulfur; and

Z is oxygen or -NH, together with the carriers and excipients customary in such formulations.

The compounds of the formula I are prepared according to the invention by reacting them with a compound of the formula II

OM

(UJ in which

R 3, R 4 and Y are as defined above,

M is hydrogen or a cation, such as sodium or potassium, with a compound of formula III

O ORi

Itz x — p \

ZRz (ΠΙ) in which

R 1, R a, O and Z are as defined above and

X represents a halogen atom.

The reaction may be carried out, for example, to a compound of formula II in which M is preferably sodium, in a solvent inert under the reaction conditions, for example an ester such as ethyl acetate, an amide such as dimethylformamide, an aromatic hydrocarbon such as toluene , xylene, etc., in a halogenated hydrocarbon such as chlorobenzene, chloroform, etc., in an ether such as dioxane, tetrahydrofuran, or an interior such as acetonitrile at temperatures from 0 to 120 ° C, preferably at a temperature of A compound of formula III is added in which X is preferably chlorine, optionally in the above solvent, which is inert under the reaction conditions. When M in formula II is hydrogen, it is recommended to add an acid-binding agent such as triethylamine or optionally potassium carbonate.

A preferred embodiment of the reaction is to treat the sodium salt of the compound of formula II immediately after its preparation in dimethylformamide as a solvent with a compound of formula III wherein X is chlorine, for example in toluene as a solvent. It is also preferred that the entire process is carried out in toluene.

The reaction mixture is stirred for some time, for about 1 to 6 hours, optionally at an elevated temperature, for example at 40 to 120 ° C, after which it is allowed to stand for some time and then worked up in the usual manner. Pure compounds of the formula I are obtained in the form of colorless oils or crystalline products which can be characterized, for example, by an Rf value or a melting point. These compounds are soluble in organic solvents and are readily emulsified in water.

The compounds of the formula II required as starting materials can be prepared, for example, by reaction of a compound of the formula IV

in which

R 4 is as defined above, with an alkoxide and optionally a thioalkoxide of formula V

Me-Y-R ₃ (V) wherein j

ř j

j 'í' A

 □

238331

III and Υ are as defined above, and

Me is hydrogen or potassium, and when M in formula II is a cation, by conversion to these salts.

2-alkyl-4-chloro-6-hydroxypyrimidines of formula IV and compounds of formula III have already been described in the literature.

The compounds of formula I have potent insecticidal and some also nematicidal properties. They have both an excellent action against voracious and 1 against absorbent insects. Similar chemical structures predominate over the known compounds in terms of their action against pests and thus constitute a true enrichment of the prior art.

In addition to the above-mentioned excellent action against insects and, in part, also against nematodes, the compounds according to the invention have at the same time only a slight warm-blooded toxicity. The novel compounds can therefore be used as agents for controlling pests in living rooms, cellars, stables and the like, as well as for protecting living organisms of the plant and animal kingdoms at their various stages of development against harmful insects.

The control of the pests is carried out by conventional methods, for example by the action of the active substances or of the compositions containing the active substances on the objects to be protected.

For use as plant protection or pest control agents, the compounds of the invention may be formulated as liquid spray compositions, wettable powders, dusts, granules, scatters, pastes, aerosols and the like.

Liquid spray compositions may contain conventional non-phytotoxic solvents and diluents such as alcohols, glycols, glycol ethers, aliphatic and aromatic hydrocarbons, especially xylene and alkylated naphthalenes and other petroleum distillates, ketones, especially cyclohexsone or iscforone, etc.

Emulsifiable concentrates also contain suitable surface-active agents such as wetting and emulsifying agents, for example polyglycol ethers, formed from high-molar alcohols, mercaptans or alkylphenols by addition of alkylene oxide and / or alkylbenzenesulfonates.

Solid formulations (dusts, dusts and wettable powders) are prepared using conventional inert mineral carriers such as diatomaceous earth, talc, kaolin, attapulgite, pyrophyllite, as well as synthetic minerals based on silicon dioxide and silicates, limestone , Glauber's salt and herbal substances such as nutshell meal. The process is carried out in a manner known per se. In the case of wettable powders which can be suspended in water, the formulations additionally contain suitable wetting and dispersing agents, such as sodium lauryl sulfate, sodium dodecylbenzene sulfonate, naphthalene sulfonate formaldehyde condensation products, polyglycol ethers, lignin derivatives (e.g. sulfite waste liquors).

Granules may be prepared by known methods by coating or impregnating granular carrier materials such as pumice, lime, attapulgite, kaolin, plant skin material and the like with the active ingredients, or solutions or mixtures of the active ingredients with other ingredients.

All compositions according to the invention may contain, in addition to the active ingredients, the aforementioned carriers and surfactants, other additives, such as stabilizers, deactivators (for solid compositions on active surface carriers), plant adhesion promoters, corrosion inhibitors, antifoams. agents, pigments, etc.

The active compounds according to the invention can be present in the compositions and in the spray suspensions in admixture with other known active compounds. The compositions generally comprise between 1 and 90 wt. % of active compound, preferably between 5 and 50%. Applicable suspensions generally contain between 0.02 and 90% by weight. % of active ingredient, preferably between 0.1 and 20%.

The compositions of the invention may be prepared in a known manner, for example:

a) 25 parts by weight. of the compound of formula I is mixed with 20 parts by weight. isooctylphenyl dececaglycol ether and 5 parts by weight. Alkyl aryl sulfonic acid calcium salt and 50 parts by weight. xylene to give a clear, water-emulsifiable, clear solution. The concentrate is diluted with water to the desired concentration.

bj 25 parts by weight of the compound of formula (I) is mixed with 25 parts by weight. isooctylphenyloctaglycol ether and 5 parts by weight. Alkylaryl sulfonic acid calcium salt and 45 parts by weight. aromatic fraction of kerosene, boiling point 210-280 ° C (hzo = 0.92). The concentrate is diluted with water to the desired concentration.

c) 25 parts by weight. % of the compound of formula (I), 2 parts by weight. lauryl sulfate, 3 parts wt. of sodium lignin sulphonate is mixed with 70 parts by weight. diatomaceous earth and the mixture is ground until an average grain size of 10 μΐη is reached.

The following application examples serve to illustrate the excellent insecticidal activity of the compounds of the invention. However, these examples do not limit the invention in any way.

Insecticidal effect on Indian insect (Carausius marasus) - feeding effect

The tradescence stems are immersed in an emulsion containing 0.0125% of the compound of formula I for 3 seconds. After the drug coating has dried, the treated tradescence stems are inserted into small glass tubes of water and the tubes are placed in a glass bowl236651 (s). 10 larvae (Stage 2) of the stick insect (Carausius morosus) and the dish is covered with a net, and after 5 days, counting the live and dead larvae, the percent mortality is as follows: 100 O / o means all stick insect larvae have been killed, 0% means that none of the larvae were killed, and the results are shown in the following table.

Table

Active substance Mortality rate in% po 5 days O, O-dimethyl-O- (2-e, thyl-4-methoxy-6-pyrimidinyl) thioxofate 100 ALIGN! O, O-dimethyl-O- (2-ethyl-4-ethoxy-6-pyrimidinyl) thioxofate 100 ALIGN! O, O-dimethyl-O- (2-methyl-4-ethoxy-6-pyrimidinyl) thiooxophosphate 100 ALIGN! O, O-dimethyl-O- (2-isopropyl-4-methoxy-6-pyrimidinyl) thioxophosphate 100 ALIGN! O, O-dimethyl-Q- (2-n- -propyl-4-ethoxy-6-pyrimidine nyljthiofosfát 100 ALIGN! O-methyl-N-methyl-O- (2-n-propyl-4-methoxy-6-pyrimidinyl) -phosphoramidate 100 ALIGN! Insecticidal effect against the pier flour (Ephestia kuchniella) - contact effect

Inject 0.1-0.2 ml of an emulsion containing 0.05% active ingredient of the formula I (prepared by diluting the formulation) using a nozzle into a: 7 cm diameter petri dish, each containing 10 caterpillars of 10 to 12 millimeters in length. After drying of the active substance coating, the wafer is fed as feed and the dose is renewed after 5 days mortality is determined by counting the live and dead caterpillars in%: 100% means that they have been killed all caterpillars, 0 o / o means that no caterpillar has been killed.

Table Active substance Mortality rate in% po 5 days O, O-dimethyl-O- (2-ethyl-4-methoxy-6-pyrimidinyl) thioxophosphate 100 ALIGN! O, O-dimethyl-O- (2-ethyl-4-ethoxy-6-pyrimidinyl) thioxophosphate 100 ALIGN! O, O-dimethyl-O- (2-methyl-4-ethoxy-6-pyrimidinyl) thioxophosphate 100 ALIGN! O, O-dimethyl-O- (2-isopropyl-4-methoxy-6-pyrimidinyl) thioxophosphate 100 ALIGN! O, O-diethyl-O- (2-methyl-4-ethoxy-6-pyrimidinyl) phosphate 100 ALIGN! O, O-dimethyl-O- (2-n-propyl-4-ethoxy-6-pyrimidinyl) thioxophosphate 100 ALIGN! O-methyl-N-methyl-O- (2-n-propyl-4-methoxy-6-pyrimidinyl) phosphoramidate 100 ALIGN! O, O-dimethyl-O- (2-n-propyl-4-methoxy-6-pyrimidinyl) phosphate 100 ALIGN! O, O-dimethyl-O- (2-ethyl-4-ethoxy-6-pyrimidinyl) phosphate 100 ALIGN! O, O-dimethyl-O- (2-methyl-4-ethoxy-6-pyrimidinyl) phosphate 100 ALIGN! O, O-dimethyl-O- (2-isopropyl- -4-methoxy-6-pyrimidinyl phosphate 100 ALIGN! O, O-dimethyl-O- (2-isopropyl-4-ethoxy-6-pyrimidinyl) phosphate 100 ALIGN! O, O-dimethyl-O- (2-n-propyl-4-ethoxy-6-pyrimidinyl) phosphate 100 ALIGN! Insecticidal action against aphids poppy (Aphis fabae) - contact effect

Equine bean plants (Vicia faba) are sprayed with a suspension containing 0.0125% of the active ingredient (sprayed by dilution with water from a)] until wet. The percent mortality rate is then determined on a day-to-day basis: 100 percent means that all aphids have been killed, 0% means that no aphids have been killed The results are shown in the following table.

Table of active substance Mortality rate in% after 5 days

O, O-dimethyl-O- (2-ethyl-4-methoxy-6-pyrimidinyl) thioxophosphate 100

O, O-dimethyl-O- (2-ethyl-4-ethoxy-6-pyrimidinyl) thiophosphate 100

O, O-dimethyl-O- (2-methyl-4-ethoxy-6-pyrimidinyl) thioxophosphate 100

O.O-dimethyl-O- (2-isopropyl-4-methoxy-6-pyrimidinyl) thioxophosphate 100

O, O-Diethyl-O- (2-methyl-4-methoxy-8-pyrimidinyl) phosphate 100

O, O-dimethyl-O- (2-n-propyl-4-ethoxy-6-pyrimidinyl) thioxophosphate 100

O-methyl-N-methyl-O- (2-n-propyl-4-methoxy-8-pyrimidinyl) phosphoramidate 100

O, O-dimethyl-O- (2-n-propyl-ethoxy-6-pyrimidinyl) phosphate 100

O, O-dimethyl-O- (2-ethyl-4-ethoxy-6-pyrimidinyl) phosphate 100

O, O-dimethyl-O- (2-methyl-4-ethoxy-6-pyrimidinyl) phosphate 100

O, O-dimethyl-O- (2-isopropyl-4-methoxy-6-pyrimidinyl) phosphate 100

The nematicidal action against Panagrellus redivivus ml of an aqueous suspension of Panagrellus redivivus, containing about 120 animals, is dispersed in a small beaker of 5.5 cm diameter and 3.2 cm height containing 7 g of terralite. Thereafter, 1 ml of an emulsion of the active ingredient of formula I is mixed with said mixture. After 48 hours, the contents of the beaker are examined by the extraction method described by G. Baermann, Meded. Geneesk, Lab. Weltevreden 41-47, (1917) and a binocular magnifier is used to determine the number of live nematodes.The mortality rate is reported on a scale of 0 to 9 (9 = maximum effect, ie no live nematodes, 0 = no effect, over 100 live nematodes) The evaluation is shown in the following table.

Active substance

Concentration Nematocidal effect of the active substance in%

O, O-diethyl-O- (2-ethyl-4-methoxy-6-pyrimidinyl) thioxophosphate O, O-dimethyl-O- (2-isopropyl-4-methylthio-6-pyrimidinyl) thioxophosphate O, O- dimethyl O- (2-n-propyl-4-methoxy-6-pyrimidinyl) thioxophosphate O, O-dimethyl-O- (2-n-propyl-4-ethoxy-6-pyrimidinyl) thioxophosphate O, O- dimethyl O- (2-n-propyl-4-isopropoxy-6-pyrimidinyl) thioxophosphate O-methyl-N-methyl-O- (2-methyl-4-methoxy-6-pyrimidinyl) thioxophosphoramidate

O, O-dimethyl-O- (2-n-propyl-4-methoxy-6-pyrimidinyl) phosphate O, O-dimethyl-O- (2-n-propyl-4-ethoxy-6-pyrimidinyl) phosphate O, O-dimethyl-O- (2-ethyl-4-methoxy-6-pyrimidinyl) phosphate O, O-dimethyl-O- (2-methyl-4-ethoxy-6-pyrimidinyl) phosphate

Acaricidal effect against spider mite (Tetranychus telarius) - contact effect

Bean leaf segments (Phaseolus vulgaris) contaminated in each case 20 to 30 exem0,2 9

0,2 9

0,2 9

0.2 · 9

0,2 9

0,2 9

0,2 9

0,2 9

0,2 9

0.2 9 plaques of spider mite (larvae and adults) are immersed in a 0.0125% active substance suspension for 3 seconds and then the leaf segments are placed in a dish. Cover the dish with moistened filter paper to allow moderate ventilation. After 48 hours, the number of live and dead specimens was determined using a binocular magnifier. Mortality is given in% and is shown in the following table:

Table

Active substance Mortality in% after 48 hours

O, O-dimethyl-O- (2-ethyl-4-ethoxy-6-pyrimidinyl) phosphate 100

O, O-dimethyl-O- (2-n-propyl-4-ethoxy-6-pyrimidinyl) phosphate 100

The following examples serve to illustrate the preparation of the compounds of the invention. However, these examples do not limit the invention. Temperature data is in degrees Celsius.

Example 1

O, O-dimethyl-O- (2-methyl-4-methoxy-6-pyrimidinyl) thioxophosphate

To 14 g (0.1 mol) of 2-methyl-4-methoxy-6-hydroxypyrimidine in 300 ml of absolute dimethylformamide was added with vigorous stirring and exclusion of air humidity.

4.8 g (0.1 mol) of sodium hydride (50% in mineral oil). After stirring for about one hour at room temperature, the solids were quickly filtered off and 16 g (0.1 mol) of O, O-dimethylthioxophosphoric acid chloride in 100 ml of absolute toluene were added dropwise to the filtrate with stirring. The mixture was stirred at 45 ° C for 5 hours and then allowed to stand overnight at room temperature.

The solvent was distilled off under vacuum and high vacuum as much as possible and the residue was taken up in ether. The ether solution was concentrated. The compound crystallized as colorless crystals, m.p. 66-67 ° C. The degree of purity was tested on a thin layer of silica gel using a fluorescent indicator and ether as the developing solvent. _Rf value = 0.75. Chromatographic purification can be performed on a silica gel column using ether as the eluent. Molecular Weight: 264,24

Analysis for CeHisN2CUPS calculated:

C, 36.4; H, 5.0; N, 10.6; P, 11.7; S, 12.1;

found:

C 36.8%, H 5.1%, N 10.7%, P 11.7%, S 12.1%.

Example 2

O, O-dimethyl-O- (2-methyl-4-ethoxy-6-pyrimidinyl) thioxophosphate

To 15.4 g (0.1 mol) of 2-methyl-4-ethoxy-6-hydroxypyrimidine in 300 ml of absolute dimethylformamide was added 4.8 g (0.1 mol) of sodium hydride (50 moles) while stirring vigorously. After stirring at room temperature for about 1 hour, the solids were rapidly filtered and 16 g (0.1 mol) of O-dimethylthioxophosphoric chloride in 100 ml of absolute toluene was added dropwise with stirring.

The mixture was stirred for an additional 5 hours at 45 ° C and then left to stand at room temperature. Preferably, the solvent is distilled off under vacuum and high vacuum. The residue is taken up in chloroform, washed four times with 100 ml of 1 N sodium hydroxide solution each, and then four times with 100 ml of water each at 8 ° C. The chloroform phase is dried over sodium sulfate and optionally treated with activated carbon.

After filtration, the filtrate is concentrated in vacuo. The compound remains as an almost colorless oil. The degree of purity is determined on a thin layer of silica gel using a fluororescence indicator and ether as the developing solvent. _Rf value amounts to 0.52. Chromatographic purification can be performed on a silica gel column using ether as the eluent. Molecular Weight: 278,3

Analysis for C9H15N2O4PS calculated:

38.8 ° O / o C, 5.4% H, 10.1% N, 11.1% P,

11.5% S;

found:

H, 5.8%; N, 10.0%; P, 10.9%.

11,5% S.

The following compounds of formula I can be obtained in an analogous manner to those described in Examples 1 and 2, wherein in Examples 3 to 51, Q is sulfur.

The compounds of Examples 3 to 51 are separated in the form of slightly colored or colorless oils.

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Example 52

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To 21 g (0.15 mol) of 2-methyl-4-methoxypyrimidine in 400 ml of absolute dimethylformamide was added, with vigorous stirring and excluding air humidity, 7.2 g (0.15 mol) of sodium hydride (50% suspension in mineral). oils). After stirring at room temperature for about 1 hour, the solids were rapidly filtered off, and 25.8 g (0.15 mol) of diethylphosphoric chloride in 100 ml of absolute toluene was added dropwise to the filtrate with stirring over about 30 minutes. The reaction mixture was then stirred at room temperature for about 4½ hours. The solids were filtered off and the filtrate was freed of solvent under vacuum and high vacuum. The residue was digested three times with 200 ml of ether each time and the ether solution was evaporated in vacuo. The crude product can then be directly purified, if possible, on a silica gel column using ether as the eluent. Obtained as a colorless oil. The purity grade is tested on a thin layer of silica gel using a fluorescent indicator and ether as the developing solvent. R _f = 0.23.

Analysis for C 10 H 17 N 2 O 5 P molecular weight: 276.2 calculated:

C: 43.5%, H: 6.2 ° / o, N: 10.1%, P: 11.2%, found:

C: 43.0%, H: 6.4% N: 10.0%, P: 10.8%.

Example 53

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To a solution of 15.4 g (0.1 mol) of 2-ethyl-4-methoxy-6-hydroxypyrimidine in 250 ml of ethyl acetate was added 20.0 g (0.145 mol) of potassium carbonate and then at room temperature over a period of 5 minutes. 1.0 g (0.1 mol) of O-methyl-N-methylthiophosphoramidochloridate. The reaction mixture was further stirred for 1 hour at room temperature and then refluxed for 5 hours at a bath temperature of 80-90 ° C. After cooling, the precipitate was filtered off and the reaction solution was concentrated in vacuo. O-methyl-N-methyl-O- (2-ethyl-4-methoxy-6-pyrimidinyl) thiophosphoramidate is obtained in the form of a crystalline mass which can be recrystallized from ethyl acetate to give colorless crystals having a melting point of 51-53.5 °. C.

Analysis for C9H16N3O31PS molecular weight 277.3 calculated:

C: 39.0%, P: 11.6 '% H: 5.8%, S: 11.2% N: 15.2% found: C: 38.7%, H: 5.9%, N: 15.1% P: 11.5% S: 11.2%. Example 54

O-methyl-N-methyl-O- (2-isopropyl-4-methoxy-6-pyrimidinyl) phosphoramidate o-p.

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To a solution of 19.0 g (0.1 mol) of sodium 2-isopropyl-4-methoxy-6-hydroxypyridine in 100 ml of absolute toluene is added dropwise a solution of 14.35 g (0.1 mol) of O-methyl-N- over 15 minutes. of methylphosphoramidochloridate in 300 ml of toluene, the reaction mixture is stirred at room temperature for 1 hour and then heated at 50 ° C for 8 hours. The reaction solution was cooled, washed three times with 200 ml of water each time until the wash water was pH 7, the toluene phase was dried over sodium sulfate and the toluene was evaporated in a rotary evaporator. There was thus obtained O-methyl-N-methyl-O- (2-isopropyl-4-methoxy-6-pyrimidinyl) phosphoramidate as a yellow oil.

Analysis for C10H18N3O4P MW: 275.2 calculated:

C: 43.6%, H: 6.6%, N: 15.3%, P: 11.3%, found:

C: 43.9%, H: 6.7%, N: 15.3%, P: 11.1%.

The degree of purity of the compounds produced according to the invention can be determined by thin layer chromatography (silica gel plates, developing solvent: ether).

The sodium salt of 2-isopropyl-4-methoxy-6-hydroxypyrimidine can be prepared, for example, by reacting hydroxypyrimidine with sodium methoxide in methanol and evaporating the solvent.

In a manner analogous to that described in Examples 53 and 54, the following compounds of formula I can be obtained, wherein Z in Examples 55 to 103 is in each case -NH.

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Example 104

O-methyl-N-dimethyl-O- (2-ethyl-4-ethoxy-6-pyrimidinyl) thioxophosphonamidate

Slightly yellowish oil.

Molecular Weight: 305,3

Analysis for C11H20N3O3PS calculated:

43.3 O / o C, 6.6% H, 13.8% N, 10.5% S,

10.1% P;

found:

43.6% C, 6.7% H, 13.5% N, 10.8% S, 9.8 Ό / ο P.

Example 105

O-methyl-N-dimethyl-O- (2-ethyl-4-ethoxy-6-pyrimidinyl) phosphoramidate

Oil.

Molecular Weight: 289,3

Analysis for C11H20N3O4P calculated:

C, 45.7; H, 7.0; N, 14.5; P, 10.7; ηΗΐθΖΘΠΟ *

% C, 46.0;% H, 7.2%; N, 14.7%;

The following examples can be used to prepare the starting materials of formula (II).

Example 106

2-methyl-4-ethoxy-6-hydroxypyrimidine

To a still warm solution of 9.2 g of sodium metal in 140 ml of absolute ethanol was added with stirring 28.8 g [0.2 mol) of 2-methyl-4-chloro-6-hydroxypyrimidine. Wait until a clear solution is formed and transferred to a heatable autoclave. After heating in an autoclave at 130 ° C for 96 hours, the mixture was allowed to cool and the solvent was evaporated. The residue was dissolved in about 200 mL of water. The pH is then adjusted to 6 with glacial acetic acid with vigorous stirring. The mixture is cooled to about 4 ° C and the crystals formed are filtered off after about 10 minutes. The crystals may be washed with a small amount of ice water. Colorless needle crystals can be recrystallized from water.

Melting point: 193-194 ° C.

Molecular Weight: 154,2.

Analysis calculated for C7H1 & N2O2:

H, 6.5; N, 18.2.

% C, 54.7%;% H; 6.5%;% N 18.2%.

The following compounds of formula II can also be prepared in an analogous manner to that described for 2-methyl-4-ethoxy-6-hydroxyipyrimidine in Example 106:

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236951

Example 124

2-Isopropyl-4-methylthio-6-hydroxypyrimidine

170 g (3.4 mol) of methyl mercaptan are introduced into the pure solution of 76 g of sodium metal in 1500 ml of methanol, which is kept at 0 DEG C. by cooling. The mixture was stirred for Ϋ2 hours with cooling and the excess methyl mercaptan was evaporated on a rotary evaporator. In a pressure autoclave, 258 g (1.5 mol) of 2-isopropyl-4-chloro-6-hydroxypyrimidine was added to a methanolic sodium thiomethoxide solution along with 100 ml of methanol. The well-closed autoclave was then heated to 100 ° C for 24 hours. After this time, it was allowed to cool to room temperature and the solvent was evaporated in vacuo. The residue was dissolved in 300 ml of water and the product was precipitated by the addition of glacial acetic acid. The product was then filtered off at 5 ° C. Crystallized from alcohol / water (6: 4) and dried at 80 ° C under vacuum. Colorless crystals having a melting point of 205 to 206 ° C are obtained. Molecular Weight: 184,2.

Analysis for CaHizNaOS calculated:

H, 6.6; N, 15.2; S, 17.4; found:

52.2% C, 6.6% H, 15,2 _0/0 N, 17.7% S

In an analogous manner to ipopsane for 2-isopropyl-4-methylthio-6-hydroxypyrimidine (Example 124), the following compounds of Formula II can also be prepared:

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Example 132

Ο, Ο-dimethyl-O- (2-isopropyl-4-methoxy-6-pyrimidinyl) phosphate

To a still hot solution of 3.45 g of sodium metal in 100 mL of absolute methanol was added 25.2 g (0.15 mol) of 2-isopropyl-4-methoxy-6-hydroxypyrimidine, and the solution was stirred at 60 ° C for 30 min. exclusion of moisture. Then the methanol is removed in vacuo and the salt is dried under high vacuum for 2 hours (at 50 ° C).

The sodium salt was suspended in 150 ml of absolute acetonitrile and 23.0 g (0.16 mol) of dimethylphosphoric chloride was added dropwise over 30 minutes with good stirring. When the reaction temperature reaches 30 ° C, the reaction mixture is cooled. The reaction mixture was stirred at room temperature for 3 hours. The reaction mixture is then introduced, together with 500 ml of benzene, into a separatory funnel and washed 3 times with 150 ml of ice-cold 2 N sodium hydroxide solution and then with 3 times 150 ml of cold water, the last washing liquid being neutral.

The organic phase is dried over sodium sulphate, optionally clarified by the addition of activated carbon, filtered and the solvent is removed in vacuo. After drying, under high vacuum, the product can be purified by molecular distillation.

A colorless oil is obtained at 70 DEG C. in a distillation flask under a vacuum of 0.0133 Pa.

In a solvent system of chloroform, acetone, methanol, 25% aqueous ammonia (80: 60: 5: 2.5) in a saturated chamber, Rf = 0.68 was found on thin layers of silica gel using a fluorescent indicator.

Analysis for C10H17N2O5P (MW 276.2)

Calculated:

C: 43.5%, H: 6.2%, N: 10.1%, P: 11.2%.

Found:

C: 43.4%, H: 6.8%, N: 9.8%, P: 11.3%.

The following compounds of Formula I can be obtained in an analogous manner to that described in Example 132:

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236851

Claims (12)

SUBJECT Insecticidal, nematicidal and acaricidal compositions, characterized in that they contain, as active ingredient, at least one pyrimidinyl phosphate of the general formula I in which iR 1 and R 2 are the same or different from each other and are optionally branched C 1 -C 5 alkyl, R3 represents an optionally branched alkyl group having 1 to 6 carbon atoms, R 4 represents an optionally branched alkyl group having 1 to 5 carbon atoms, Q is oxygen or sulfur, Y is oxygen or sulfur; and Z is oxygen or -NH, together with carriers and excipients. 2. Compositions according to claim 1, characterized in that they contain at least one pyrimidinylthionophosphate of the general formula IA (1A) in which: R1 and R2 are the same or different from each other and are optionally branched alkyl of 1 to 5 carbon atoms, R3 represents an optionally branched alkyl group having 1 to 6 carbon atoms, R 1 represents an optionally branched alkyl group having 1 to 5 carbon atoms, and Y is oxygen or sulfur, together with carriers and excipients. 3. A composition according to claim 1, wherein the active ingredient comprises at least one pyrimidinyl ester phosphoric acid of the formula IB. OF THE INVENTION in which R1 and R2 are the same or different from each other and are optionally branched alkyl of 1 to 5 carbon atoms, R3 represents an optionally branched alkyl group having 1 to 6 carbon atoms, R 1 represents an optionally branched alkyl group having 1 to 5 carbon atoms, and Q and Y are oxygen or sulfur, together with carriers and excipients. 4. Compositions as claimed in claim 1, characterized in that they contain, as active ingredient, O, O-dimethyl O- (2-ethyl-4-ethoxy-pyrimidin-6-yl) -thionophosphate together with carriers and excipients. 5. Compositions as claimed in claim 1, characterized in that they contain, as active ingredient, O, O-dimethyl-O- (2-isopropyl-4-methoxypyrimidin-6-yl) thionophosphate, together with carriers and excipients. 6. Compositions as claimed in claim 1, characterized in that they contain, as active ingredient, O, O-dimethyl O- (2-isopropyl-4-ethoxy-pyrimidin-6-yl) -thionophosphate together with carriers and excipients. 7. A process for the preparation of an active ingredient of the formula I as claimed in claim 1, which process comprises the preparation of a compound of the formula II OM in which R 3, R 1 and Y have the meanings given in 1 a M is hydrogen or a cation, such as sodium or potassium, with a compound of formula III ORi liz x — p Z zr ₂ (III), Her in which R1, R2, Q and Z have the meanings given in 1 a X represents a halogen atom. 8. A process for the preparation of an active ingredient of the formula (IA) according to claim 2, which comprises: in which R 3, R 6 and Y are as defined in point 2 a Z ‘represents hydrogen or a cation, such as sodium or potassium, with a compound of formula IIIA S ORi 11 / x — p \ 0R2 (IIIA) in which: R1 and R2 are as defined in 2 a X represents a halogen atom, preferably chlorine. 9. A process for the preparation of an active ingredient of the formula (IB) as claimed in claim 3, wherein the compound is of the formula (IB) IIB in which R 3, R 4 and Y are as defined in 3a Z ‘represents hydrogen or a cation, such as potassium or sodium, with a compound of formula IIIB O ORi 1 / x — p \ NHR 2 (IIIB) wherein R 1, R 2 and Q are as defined in 3a X represents a halogen atom. 10. A process for the preparation of O, O-dimethyl-O- (2-ethyl-4-ethoxypyrimidin-6-yl) thionophosphate as active ingredient according to item 4, characterized in that it is converted to 2-ethyl-4-ethoxy-6. The hydroxypyrimidine or its sodium or potassium salt is treated with thionophosphoric acid O, O-dimethyl ester. 11. A process for the preparation of O, O-dimethyl-O- (2-isopropyl-4-methoxypyrimidin-6-yl) thionophosphate as active ingredient according to claim 5, characterized in that it is converted to 2-isopropyl-4-methoxy. The 6-hydroxypyrimidine or its sodium or potassium salt is treated with thionophosphoric acid O, O-dimethyl ester chloride. 12. A process for the preparation of O, O-dimethyl-O- (2-isopropyl-4-ethoxypyrimidin-6-yl) thionophosphate as an active ingredient according to item 6, characterized in that it is converted to 2-isopropyl-4-ethoxy-6. The hydroxypyrimidine or its sodium or potassium salt is treated with thionophosphoric acid O, O-dimethyl ester chloride.