CS270216B2 - Immatocide and insecticide and method of their efficient substances production - Google Patents

Description

(57) A nematicidal composition comprising, as an active ingredient, a compound of formula I wherein n is 1 or 2, X is oxygen or sulfur, R is hydrogen or optionally halogenated C 1 -C 5 -alkyl, R 1, and R 2; are hydrogen NEB · C - C ^ - ^ lkyl and Y is halogen or a residue where R _f ÓSOÍR CjC. -alkyl or C ₁ alkyIreny -C.-1 or Her-Enantiomers or diaetereomer. There is further described a process for preparing those compounds of formula 1 wherein Y is halogen by reacting a compound of formula III with a halogenating agent introducing chlorine or bromine as defined by Y and optionally reacting the product with an alkali or alkaline earth fluoride or iodide .

270 216 (11) (13) B2 (51) Int. CL ⁴

A 01 N 43/08

A 01 N 43/10

A 01 N 43/16

A 01 N 43/18

/ I / III

CS 270 216 B2

The present invention provides nematicidal compositions, their use in plant protection, heterocyclic derivatives which can be used as active ingredients in these compositions, and a process for the manufacture of such active ingredients.

The aforementioned compositions contain as active ingredient at least one compound of the general formula (II).

formula I (CH ₂ ) 1 in (AND) in which n is whole Number 1 or 2

X represents an oxygen atom or a sulfur atom, the substituents R 1, which may be the same or different, are selected from the group consisting of hydrogen and optionally halogen alkyl radicals and 1 to 3 carbon atoms,

R ₁ and R ₂ ', which may be the same or different, each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms and

Y represents a halogen atom or an OSOgRR group wherein R 'represents an alkyl group having 1 to 4 carbon atoms or an alkylphenyl group having 1 to 4 carbon atoms in the alkyl moiety, or, if the compound contains an asymmetric carbon atom, one of its enantiomers or this compound contains more than one asymmetric carbon atom, one of its diastereomers or one of its corresponding enantiomers!

Those compounds containing one asymmetric carbon atom exist in two enantiomeric forms R and S. In this case, the above general formula is to be understood as also defining a mixture of the two, either in equivalent proportions (raoemate) or in such a proportion that one of these enantiomers predominates.

Compounds containing more than one asymmetric carbon atom exist in diastereomeric forms, wherein each dlastereomer generally exists in two enantiomeric forms. In such cases, the above general formula is to be understood as also defining a mixture of diastereomers and enantiomers, either in an equivalent ratio or in a ratio where one of the components predominates.

Preferred compositions according to the invention comprise as active ingredient at least one compound of the above formula I wherein n is an integer of 1 or 2,

X is an oxygen atom,

R ^ and R? each represents a hydrogen atom or a methyl group; and

Y represents a halogen atom.

In addition to the aforementioned compositions, the present invention also relates to a process for the preparation of active compounds of the formula I in which n, R 6, R 8, R 8 and X are as defined above and Y represents a halogen atom or enantiomers or, when these compounds contain more than one asymmetric carbon atom, their diastereomers or their corresponding enantiomers, provided that they cannot simultaneously

X represent an oxygen atom and

R, ^R 1 ^{and R} 2 is a hydrogen atom ^{гпагпепа,} characterized in that a compound of formula III

CS 270 216 B2

(III) in which η, X, R _x> R _x and ^{m is as} defined above, reacted with a halogenating agent such as a thionyl chloride, phosphorus pentachloride, phosphorus pentachloride, phosphorus pentachloride, phosphorus tribromide or phosphorus oxybromide, in the presence of an acid acceptor, such as a tertiary amine or pyridine, the compound of the formula I in which Y is chlorine or bromine is optionally reacted with an agent of the formula

Μ - Y in which

M is an alkali metal or alkaline earth metal atom; and

Y represents an iodine or fluorine atom, and the resulting product is isolated in the form of an individual enantiomer, diastereomer or a mixture thereof. This procedure is carried out by the methods mentioned above (see, inter alia, J, March, Advanced Organic Chemietry, 3rd Edition, ed. John Wiley and Son, 1985, pp. 381-334).

Some of the compounds of formula III are known and some are new

Rp R ^, R *, X and n are as defined above except that they do not simultaneously represent n or 1, X is oxygen or sulfur and R ^, Rg and ^R _x are hydrogen atoms;

Those compounds of formula (I) wherein Y is halogen may also be prepared by reacting a compound of formula (IV)

/ IV / »where η, X, R, R, R ₂ and R 'has the above defined meaning, in a known manner (see previous citation, p. 382) responding ee salts of the formula

M - hal in which hal represents a halogen atom and

M represents an alkali metal or alkaline earth metal atom, in particular lithium, sodium or potassium.

Compounds of formula IV are novel, with the exception of 2- (hydroxymethyl) tetrahydropyranosylate. These substances can be prepared by reacting compounds of formula V r'so ₂ C / V / wherein

R 'is as defined above,

A compound of formula III in the presence of an acid acceptor, as a suitable base, for example a tertiary amine or pyridine (see in particular J. March, Advanced Organic Chemistry,

3rd edition, ed. John Wiley and Sons, 1985, pp. 357-358).

Another method of production of the active substances of general formula 1 is the subject of our related Czechoslovak patent specification No. 27O 225.

The following non-limiting examples illustrate the preparation of some of the compounds of the present invention and the nematicidal properties of the compositions containing them as active ingredients.

The structures of the resulting products were confirmed by NMR spectroscopy and / or δδ spectrography and / or mass spectrography and / or microanalysis.

Example l

Preparation of 2- (bromomethyl) tetrahydropyran (Compound 1)

A 250 ml round bottom flask was charged with 120 ml of toluene, 62 g of phosphorus tribromide and 11.5 g of pyridine, cooled to below 0 ° C and 80 g of 2- (hydroxymethyl) tetrahydropyran was added with stirring. and 4.6 g of pyridine. The temperature is kept below 0 ° C during the addition. Stirring was continued for one hour at the above temperature, then the mixture was allowed to warm to room temperature and allowed to stand overnight. The reaction mixture was filtered, washed with toluene and evaporated to dryness. The orange-yellow liquid residue afforded 35.5 g of a colorless liquid at boiling point of 74 ° C / 2.4 kPa, consisting of 2-bromomethyltetrahydropyran of the formula:

Example 2

Preparation of 2- (bromomethyl) tetrahydrofuran (compound 2)

The reaction is carried out in an analogous manner to that of Example 1 except that 2- (hydroxymethyl) tetrahydropyran is replaced by 2- (hydroxymethyl) tetrahydrofuran. 60.0 g of a colorless liquid 2- (bromomethyl) tetrahydrofuran are obtained at a boiling point of 70 ° C / 2.4 kPa corresponding to the formula

Example 3

Preparation of bis (2,6-bromomethyl) tetrahydropyran (compound 3)

The procedure is analogous to Example 1, using 5.0 g of cis-bis (2,6-hydroxymethyl) tetrahydropyran, 6.1 g of phosphorus tribromide, 1.3 g of pyridine and 30 ml of toluene. 0.7 g of white powdered cis-biв (2,? -Bromomethyl) tetrahydropyran is obtained, m.p.

Example 4

Preparation of 2- (1-bromoethyl) tetrahydropyran (compound 4)

The reaction was carried out in a manner analogous to Example 1 except that 2- (1-hydroxyethyl) tetrahydropyran was used in place of 2- (hydroxymethyl) tetrahydropyran. 23 g are obtained

CS 270 216 B2 colorless liquids with a refractive index Пр = 1.4855. This product consists of 2- (1-bromoethyl) tetrahydropyran of formula

in the form of a 55:45 mixture of two diaethereomers.

Example 5

Preparation of 2- (chloromethyl) tetrahydropyran (compound 5)

To a solution of 30 g of 2- (hydroxymethyl) tetrahydropyran in 44 ml of pyridine was added 22 ml of thionyl chloride while maintaining the temperature of the reaction mixture at about 40-45 ° C. The mixture was heated to 45 ° C with stirring for 8 hours, the oily material was taken up in ether, the ether phase was washed with water, then with saturated sodium bicarbonate solution and finally with saturated sodium chloride solution, dried over sodium sulfate and concentrated. A liquid residue is obtained by distillation under a vacuum of 2 kPa of 20.2 g of a colorless liquid, b.p. 55 ° C / 2 kPa, diluted with 2- (chloromethyl) tetrahydropyran of the formula ## STR2 ##

1) and example

Preparation of 2- (iodomethyl) tetrahydropyran (compound 6)

In 50 ml of acetonitrile, 5.4 g of 2- (bremomethyl) tetrahydropyran (compound 4.5 g of sodium jedide) are added, the reaction mixture is heated under reflux for 14 hours, then allowed to cool to room temperature, the precipitated sodium bromide is filtered off. and the filtrate is evaporated to dryness to give a brown residue which is distilled under vacuum in a water pump (1.6 kPa) to give 3 g of a brown liquid product, b.p. 88 ° C / 1.6 kPa, consisting of 2 (i-methyl) tetrahydroxypyrate of formula

Example 7

Preparation of 2- (tosyloxymethyl) tetrahydropyran (compound 7)

To 60 ml of pyridine was added 35 g of 2- (hydroxymethyl) tetrahydrofuran, the mixture was cooled to 5 ° C with stirring and 69 g of tosyl chloride were added portionwise while maintaining the temperature below 10 ° C. After the addition was complete, stirring was continued at 5 ° C for one more hour, then the mixture was allowed to warm to room temperature, stirred for a further 2 hours, then allowed to melt overnight. The reaction mixture was poured onto ice and extracted with toluene. The toluene phase is washed with 10% hydrochloric acid and water, dried over sodium sulfate and concentrated. There are obtained 33 g of a white solid, m.p. 73 DEG C., consisting of 2- (tosyloxymethyl) tetrahydropyran of the formula:

Ό ’

CS 270 216 B2

Example 6

Preparation of 2- (fluoromethyl) tetrahydropyran (compound 8)

13.5 g of 2- (tosyloxymethyl) tetrahydropyran (compound 7) and 13.5 g of potassium fluoride are added to 60 ml of ethylene glycol, the reaction mixture is heated to 130 ° C with stirring for 3 hours, then cooled to room temperature, diluted. 200 ml of water and extracted twice with 100 ml of ether each time. The combined ether extracts were washed with water, dried over sodium sulfate and evaporated to dryness. The residue was distilled at atmospheric pressure 1.8 g colorless liquid boiling at atmospheric pressure at 110 C and ^G consisting of 2- (fluoromethyl) tetrahydropyran morning formula

Example 9

Preparation of 2- (mesyloxymethyl) tetrahydropyran (compound 9)

The reaction is carried out in a manner analogous to Example 7, except that methyl chloride is used instead of tosyl chloride. 22 g of a viscous oily 2- (mesyloxymethyl) tetrahydropyran corresponding to the formula are obtained

@ 1 H-NMR (62.90 MHz, CDCl3, .delta. Ppm in ppm over tetramethylsilane): 75.1, 72.4, 68.3, 37.5, 27.3, 25.5, 22.8.

In an analogous manner to the preceding Examples may also be prepared the following compounds 6 _F 6-dimethyl-2- (iodomethyl) tetrahydropyran (Compound 10) Formula

CH

boiling point 34 ° C / 2.7 Pa and refractive index η ^ θ _R 1,5110j

2- (N, N -dimethyl-o-bromomethyl) tetrahydropyran (compound 11) of the formula

69.0, 68.0, 30.7, 30.1, 26.9, 25.8, 23.5;

5,5-dimethyl-2- (bromomethyl) tetrahydropyran (compound 12) boiling at 48 ° C / 6.7 Pa, corresponding to the formula *

CH

and

CS 270 216 32 diastereomer A (compound 13) and diastereomer V (compound 14)

2-bromomethyl-6-methyltetrahydropyran of formula

@ 1 C-NMR (62.90 MHz, CDCl3, dd / v ppm vs. tetramethylsilane): isomer A; 77.1, 74.6, 35.6, 33.0, 29.5, 23.5, 21.6; .

isomer B: 7.0, 6, 67.9, 34.2, 31.1, 28.0, 19.4, 19.1.

Similarly, compounds 15 to 17 corresponding to the general formula can be prepared as above

compound ^R 1 r ₂ ^R ί xl ^R x2 ^R x3 ^R A x4 in ^R x6 ^R x7 ^R x8 15 ¹ ) H H H . H H H H H CH 2 ch ₃ compound ^R 1 R ₂ R ... xl ^R x2 ^R ·> x 3 ^R x4 ^R x5 ^R x6 ^R x7 ^R x8 16 ²⁾ 173) H H H ^C 2 ^H 5 H H H H H H H H CH ₃ H H H H H H H

Legend: ^ liquid with refractive index η ^ θ = 1.4870;

kapal liquid with refractive index η ^ θ = 1.4855 (70:30 diastereomeric mixture);

Fluid of refractive index n = ⁰ · 1.4855 (55:45 mixture of diastereomers).

Example Ю

Preparation of 2- (bromomethyl) tetrahydrothiopyran (compound 37)

The reaction is carried out in an analogous manner to that of Example 1 except that 2- (hydroxymethyl) tetrahydropyran is replaced by 2- (hydroxymethyl) tetrahydrothiopyran. 109 g of a colorless liquid are obtained, boiling at 58 DEG C./6 mm Hg, consisting of 2- (bromomethyl) tetrahydrothiopyran of the formula:

Example 11

In vitro nematicidal activity test (ovicidal and larvicidal effect)

The roots of tomato plants, contaminated for 2.5 months, are washed and coarsely chopped. Meloidogyne incognita eggs were isolated from a fraction of roots using a 20 µm sieve. Prepare a suspension in distilled water containing about 4000 embryo-bearing eggs or 4000 larvae per milliliter.

The test compound is dissolved in acetone or a suspension is prepared from it under rain

CS 270 216 B2 as shown, to which 0.02% of the condensation product of ethylene oxide was added with sorbitol monooleate containing 20 moles of ethylene oxide. These preparations are then diluted with distilled water to obtain solutions or suspensions of different concentrations of the active ingredient.

1 ml of a solution or suspension of the test compound is mixed with 1 ml of Meloidogyne ineognita egg or larvae suspension in a hemolytic tube. After shaking, the mixture is applied to a 3-well microscope slide. For each concentration, the ee determination is performed five times.

These slides are placed on a support in a five dish dish with a damp filter paper at the bottom to prevent drying of the vehicle during the experiment. Five to eight days after the start of the experiment, each slide is examined under a magnifying glass and the percent mortality of the egg or larvae of the nematode is calculated. '

In the above-described experimental design, compounds 1 and 2 at 100 ppn were found to cause total resp. 50% mortality of eggs resp. larvae, and that Compound 1 at a dose of 200 ppm completely suppresses egg hatching. Even at a dose of 10 ppm, Compound 1 causes total mortality of Meloidogyne ineognita larvae.

A dose of 100 ppm corresponds to the activity of commercial comparators such as ethoprophos.

Example 12.

Nematocidal Efficacy Test for Meloidogyne ineognita (greenhouse experiment)

As in the previous experiment, ee from the infested roots of the tomato plants is obtained by using a sieve of the egg of the experimental riddle. They prepare an aqueous suspension containing about 1500 eggs in each milliliter of distilled water, of which at least 10 to 15% contain embryos. Prepare a mixture of equal parts of river sand, compost and soil, and mix the slurry eggs of the nematode in such a quantity that each liter of the resulting soil contains about 3000 eggs. *

The test compound is either dissolved in acetone, the solution is mixed with attapulgite and mixed after mixing into the contaminated soil, or dissolved in water and the resulting solution is directly incorporated into the contaminated soil.

The contaminated and treated soil is filled with pots (the experiment is repeated twice for each dose), which is placed in a humid chamber for two weeks (average temperature 20 ° C, average relative humidity 100%). Each pot is then planted with 2 easter eggs of Lycoperaicum esculentum, var. Marmande, about 1 month old. The soil in the pots is kept moist in regular watering.

After 3-4 weeks the plants are plucked and their roots are washed with water. The nematicidal activity is evaluated visually and is given as a percentage of the reduction in the number of rats on the roots of the plants grown in the treated soil relative to the rats on the roots of the plants grown in the untreated soil.

In the above experiment set-up, compound 1 was found to be 100% effective at 10 kg / ha and compounds 2 to 6 had 90% potency at 50 kg / ha. At the above dose, the compounds of the invention are not phytotoxic.

For comparative purposes, the test described in Example 12 was subjected to methyl isothiocyanato-2-pyran known from U.S. Pat. No. 2,946,720. At a dose of 50 kg / ha, this compound did not show any activity at all, whereas greater than 90%) efficiency.

The above examples clearly illustrate the excellent nematicidal properties of the compositions of the invention. Thus, said compositions can be used to combat nematodes parasitic on plants. The compositions described are preferably applied in doses ranging from 1.5 to 50 kg of active ingredient per hectare, in particular from 1 to 25 kg / ha. .

CS 270 216 B2

In practice, the compounds of the invention are rarely used alone, but most often form part of the compositions of the invention. These compositions, which can be used to protect plants against parasitic nematodes and insects, contain as active ingredient the compound of the invention described above in combination with a solid or liquid diluent and / or a surfactant useful in agriculture. In particular, conventional inert carriers and conventional surfactants are used.

The compositions of the invention may also contain all kinds of other auxiliaries. substances such as protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, complexing agents and the like, such as other known active substances in pesticidal properties (especially nematicides, insecticides or fungicides), plant growth aids (especially fertilizers) or plant growth regulators. In general, the compounds of the invention may be combined with any solid or liquid additive, as is conventional techniques used in the production of similar compositions.

The application rates can be varied within wide limits and depend in particular on the extent of the infestation and the weather conditions.

Compositions containing from 0.5 to 5000 ppm of active ingredient are generally considered to be very suitable (these values apply to compositions suitable for application). The range of 0.5 to 5000 ppm corresponds to the range of 5x10 4 to 0.5% by weight.

More preferably, the compositions for storage and transport contain from 0.5 to 95% by weight of the active ingredient.

The compositions of the present invention suitable for use in agriculture may therefore contain the active compounds of the present invention in a wide concentration range ranging from 5x10 5 to 95% by weight.

As already mentioned, the compounds of the invention are usually used in combination with carriers and optionally surfactants.

The term "carrier" as used herein refers to an organic or inorganic, natural or synthetic material with which the active ingredient is combined to facilitate application to the plants, to their seeds or to the soil or soil. Thus, this carrier is generally inert and must be acceptable in agriculture, especially for treated plants. The carrier may be solid (clays, natural or synthetic silicates, silica, chalk, resins, waxes, solid mineral fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc. .).

The surfactant may be an emulsifier, dispersant or wetting agent of the ionic or non-ionic type. Examples of suitable agents include salts of polyacrylic acids, salts of lignosulfonic acids and salts of phenolsulfonic and naphthalenesulfonic acids, polycondensate products of ethyleneexide in fatty acids, fatty alcohols, fatty amines or substituted phenols (especially in alkylphenols or arylphenols), sulfosuccinic acid selers, derivatives taurine (especially alkyl taurates) and phosphoric acid esters with ethylene oxide condensation products and alcohols or phenols. The presence of at least one surfactant is generally essential when the active ingredient and / or the inert carrier are not water-soluble and is intended to serve as water as the vehicle for the preparation of the dosage form.

The compositions of the invention may be manufactured in a wide variety of solid or liquid forms. Suitable formulations of solid compositions include dusts in which the active ingredient content is up to de $ 100.

Forms of liquid formulations or formulations which are formulated as liquid application preparations include solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, suspension concentrates, aerosols, wettable powders (or spray powders), granules and pastes.

Emulsifiable or soluble concentrates most often contain 10 to 80% of the active ingredient,

CS 270 216 B2 whereas emulsions or solutions suitable for direct application contain 0.001 to 20% of the active ingredient. In addition to the solvent and the active ingredient, the emulsifiable concentrates may contain, if desired, suitable cosolvent with 2 to 20% of suitable additives, for example stabilizers, surfactants, in particular emulsifiers, penetration agents, corrosion inhibitors, dyes and adhesives.

Emulsions of any desired concentration, which are particularly suitable for application to crops, can be obtained from these concentrates by dilution with water.

Suspension concentrates, which can also be applied by spraying, are formulated to form a stable, liquid, non-depositing product, and typically contain Ю to 75% active ingredient, 0.5 to 15% surfactants, 0.1 to 10% thixotropic agents, 0-10% of suitable additives such as antifoam additives, corrosion inhibitors, stabilizers, penetration agents and adhesives, and as a carrier water or an organic liquid in which the active ingredient is only slightly soluble or not soluble at all. Certain organic solids or mineral piglets may be dissolved in said carrier, which additives are intended to help prevent sedimentation or act as antifreeze agents.

By way of example, ee discloses the following compositions of several aqueous suspensions of the invention.

Example A

An aqueous suspension is prepared having the following composition:

Active substance (Compound 1) Wetting agents (polycondensate of ethylene oxide with synthetic 13 carbon atom) Dispersing agent (salt of the condensation product of ethylene oxide with polyarylphenol phosphate) Antifreeze agent (propylonglycol) Thickening agent (Polysaccharide) Biocidal agent Sodium 4- (hydroxymethyl) benzoate Water

In this way a liquid suspension concentrate is obtained.

Example В

Aqueous suspension

An aqueous suspension of the following composition is prepared: active ingredient (compound 1) wetting agent (polycondensate of ethylene oxide with alkylphenol) dispersing agent (sodium naphthalenesulfonate) antifreeze agent (propylonglycol) thickener (polysaccharide) biooid (formaldehyde) water

Example C

Aqueous suspension

An aqueous suspension is prepared having the following composition:

Active substance (Compound 1) Wetting agent (polycondensate of ethylene oxide ee with 13-carbon synthetic alcohol) Dispersing agent (sodium lignosulfonate) Antifreeze agent (urea)

500 g / liter g / liter g / liter

100 g / liter

1.6 g / liter

Fill 3.3 g / liter to 1 liter

100 g / liter g / liter g / liter

100 g / liter g / liter g / liter top up to 1 liter

250 g / liter

Ю g / liter g / liter g / liter

CS 270 216 B2 thickener (polysaccharide) 2.5 g / liter biocide (formaldehyde) ig / liter _{water make} up to 1 liter

Wettable powders (or spray powders) are usually formulated to contain 20 to 95% of the active ingredient and usually contain, in addition to a solid carrier, 0 to 5% of a wetting agent, 3 to Ю% of a dispersant and optionally 0 to 10% of one or more stabilizers; / and other additives such as penetration agents, adhesives, anti-caking agents, dyes, etc. ·

By way of example, the following compositions of several wettable powders are mentioned.

Example

50% wettable powder active substance (compound 1), ethylene oxide condensation product with fatty alcohol (wetting agent) ethylene oxide condensation product with styrylphenol (dispersant) chalk (inert carrier)

Example

10% wettable powder active substance (compound 1) branched synthetic 13-carbon oxoalcohol condensed with 8 to 10 mol equivalents of ethylene oxide (wetting agent) calcium neutral lignosulfonate (dispersant) calcium carbonate (inert filler)

Example

75% wettable powder

This wettable powder contains the same but in the following proportions: active ingredient wetting agent calcium carbonate dispersant (inert filler)

Example

90% wettable powder active ingredient (compound 1) ethylene oxide condensation product with fatty alcohol (wetting agent) ethylene oxide condensation product with styrylphenol (dispersant)

Example

50% wettable powder active substance (compound 1) mixture of anionic and nonionic surfactants (wetting agents)%

2.5%%

42.5%

В%

0,75%%

up to 100%

P components as a preparation in the previous example,%

1.50% to 100%

G%

%%

H%

2.5%

CS 270 216 B2 Neutral Ligno Sodium Sulphonate (Dispersant) 5% Kaolin Wedge (Inert Carrier) £ 42.5

To collect these spray powders or wettable powders, the active ingredient is thoroughly mixed with other substances in a suitable mixer and milled in mills or other suitable crushers to obtain spray powders with advantageous wettability and suspendability. These powders can be suspended in water at any desired concentration and the resulting suspension can be used very advantageously, especially for application to plant leaves.

The compounds of the invention are preferably formulated into pellets which are dispersible in water and are also within the scope of the invention. *

These dispersible poles having a bulk density of between about 0.3 and 0.6 usually have a particle size of between about 150 and 200 µm, preferably between 300 and 1500 µm.

The active ingredient content of these palms is generally between approximately 1% and 90%, preferably between 25% and 90%.

The remainder of the pellet (roep · granulo) is mainly composed of a solid filler and optionally surfactants which impart dispersibility in the water to the granule. The aforementioned granules may be essentially of two types, depending on whether or not the filler contained therein is water-soluble. The water-soluble filler may be inorganic, but preferably is organo-organic. Excellent results are obtained with urea. The insoluble filler is preferably an inorganic substance, for example kaolin or bonton! The filler in the granulate is accompanied by surface-active agents (in an amount of from 2 to 20% by weight, based on the weight of the granulate), of which at least one-half is at least one substantially anionic dispersant, such as alkali metal the earth or alkali metal lignosulfonate or alkaline earth metal, and the remainder are nonionic or anionic surfactants, such as alkali metal alkylnaphthalene sulfonates or alkali earth metal alkylnaphthalenesulfonates.

Other adjuvants such as antifoams may also be added, although the presence of such adjuvants is not necessarily required.

The granulate according to the invention may be prepared by mixing the required ingredients and the subsequent granulation, which may be carried out by several different techniques known in the art (for example, in a drum granulation apparatus, in fluid power, in an atomizer, extrusion, etc.). The aforementioned preparation is then generally terminated by roughing and sieving to the scale size within the above limits.

The granulate is preferably produced by extrusion, using the procedure described in the following examples.

Example I

Bispergible granules containing 90 active ingredients

In the mixer, 90% by weight of the active compound (compound 1) is mixed with 10 µl of bead-shaped urea • The mixture is then ground in a roller crusher. and the obtained powder is moistened with about 8% by weight of water. The wet powder is extruded on a cylindrical extruder, the resulting granules are dried, crushed and sieved so that only granules between 150 and 2000 µm are isolated.

Example J

Dispersible granules contain up to 75% active ingredient

The following components are mixed in the mixer:

Active substance (Compound 1) 75%

CS 2-0 216 B2 wetting agent (sodium alkylnaphthalene sulfonate) 2% dispersant (sodium polynaphthalene sulfonate) 8% water-insoluble inert filler (kaolin) 15%

This mixture is granulated in a fluidized bed in the presence of water, the granulate is dried, crushed and sieved. The granules having a size between Q, 16 and 0.40 mm are isolated.

These granules may be used as such or dissolved or dispersed in water in an amount appropriate to the desired dosage. The granules may also be used for the preparation of mixtures with other active substances, in particular β fungicides, which are in the form of a wettable powder, granules or an aqueous suspension.

Granules suitable for application by shoveling have a size between 0.1 and 2 mm and can be produced by agglomeration or impregnation. These granules generally contain 0.5 to 25% of active ingredient and 0 to 10% of additives such as stabilizers, agents used to delay the release of the active ingredient, binders and solvents. *

Two examples of the composition of such a granulate are given below. Examples K1 and K2 K1 K2 active substance 50 g 200 g propylene glycol 50 g 50 g cetyl polyglycol ether 2.5 8 2,5 g polyethylene glycol 35 g 35 g kaolin (particle size 0, , 3-0.8 mm) 910 g 760 g

The compounds of the invention may also be formulated into encapsulated organic solutions, in particular by interfacial polymerization, or on a polymer coated band, for example based on a polyamide-polyurea or polyamide-urea combination. These capsules are in the form of a concentrated aqueous dispersion which can be diluted to the spray mixture at the time of application.

As already mentioned, aqueous dispersions and emulsions, for example compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, are also within the scope of the invention. The emulsions thus obtained may be of the water-in-oil or oil-in-water type and may also have a thick consistency, such as mayonnaise.

The invention also provides a method of treating useful plants to protect them against phytopathogenic nematodes and insects.

The method consists in applying, instead of or in the course of production, an effective amount of a composition comprising as an active ingredient a compound of formula I. An effective amount means an amount sufficient to suppress and destroy nematodes and insects present on such crops. plants. These dosages, however, can be varied within wide limits, depending on the pest to be controlled, the species of the crop, the climatic conditions and the compound employed.

In practice, in general, good results are obtained with formulations containing the active ingredient in a concentration of 1 g / hl to 500 g / hl, which basically corresponds to the doses of active substance per unit area ranging from about 10 g / ha to 5000 g / ha.

SUBJECT OF THE INVENTION

Claims (6)

1. A nematocidal agent for the protection of plants against nematodes, characterized in that it contains at least one compound of the formula I as active substance. In which * n is an integer of 1 or 2, X represents an oxygen atom or a sulfur atom,. . . The ub _χ eubotituents, which may be stand-alone or different, are selected from the group consisting of hydrogen and optionally halogenated C 1 -C 3 alkyl radicals, R 1 and B ₂ , which may be stand-alone or different, are each hydrogen or alkyl. a group having 1 to 3 carbon atoms; and. X represents a halogen atom or an OSOgR group, wherein R 'represents a C1-C4 alkyl group or a C1-C4 alkylphenyl group, or, if the compound contains an asymmetric carbon atom, one of its enantiomers, if the compound contains more than one asymmetric carbon atom, one of its diastereomers or one of the corresponding onantiomers. 2. A composition according to claim 1, wherein the active ingredient is a compound of formula (I), in which the number is 1 or 2; X is an oxygen atom, Β _χ , R 1 and B ₂ are each hydrogen or methyl and X represents a halogen atom. 3. A composition according to claim 1, characterized in that it comprises as active ingredient at least one compound of the formula I, wherein η, X, R, R ₂ а X are as defined in claim 1 and substituonty _Β χ which may be selected from the group consisting of hydrogen and alkyl radicals of 1 to 3 carbon atoms; or, if the compound contains an asymmetric carbon atom, one of its enantiomer or, if the compound contains more than one asymmetric carbon atom, one of its diastoreomers or one of the corresponding onantiomers. 4. A composition according to claim 3, wherein the active ingredient is 2- [(bromomethyl) tetrahydropyran]. 5. A method for producing the active compounds ebooného pattern according to claim 1, wherein n, R p R _2, R _x а X are as defined in claim 1 а X is halogen, or, if these compounds contain an asymmetric carbon atom. Their onantiomers or, if these compounds contain more than one asymmetric carbon atom, their diastereomers or their corresponding enantiomers, except that they cannot simultaneously X represent an oxygen atom and R _x , R j. and R ₂ is hydrogen, is further characterized in that a compound of formula IIX CS 270 216 B2 r ₂ · (ni) wherein η, X, R _x, R and R ₂ have the above meanings, · reacting 8 with a halogenating agent such as β Thionyl chloride, phosphorus oxychloride, phosphorus trichloride or phosphorus tribromide in in the presence of an acid acceptor, the compound of formula I in which Y is chlorine or bromine is optionally reacted with a β reagent of formula M - Y in which M is an alkali metal or alkaline earth metal atom; and Y represents an iodine or fluorine atom, and the resulting product is isolated in the form of the individual enantiomers, diatereomers C or mixtures thereof · 6. A method according to claim 5, characterized in that the application of the corresponding starting materials, to give compounds of the formula I wherein n, R, R _2, R а X are defined as in point 3, and Y represents halogen or, if these compounds contain an asymmetric carbon atom, their enantiomers or, if these compounds contain more than one asymmetric carbon atom, their diastereomers or their corresponding enantiomers, with the limitation that they cannot simultaneously X represent an oxygen atom and