DD262992A5 - NEMATICIDES AND INSECTICIDES COMPOSITION - Google Patents

Abstract

According to the invention, the novel nematicidal and insecticidal compositions contain as active ingredient at least one compound of the formula (I) with n1, 2 or 3; XO, S; RxH, optionally halogenated C1-6 alkyl; R1 and R2, same or different; H, halogen, optionally halogenated C 1-3 alkyl; Y is H, ammonium, sulfonium or phosphonium, halogen, XR with optionally halogenated alkyl, C (X) R, SO2R, NC (R3R4) with RC1-6 alkyl, optionally substituted phenyl; R3 and R4, the same or different, are H, C1-4 alkyl. Formula (I)

Description

Field of application of the invention

The invention relates to nematicidal and insecticidal compositions, their use in crop protection and heterocyclic compounds useful as active ingredients in these compositions.

Characteristic of the known state of the art

There is no information available on which compounds with nematicidal and insecticidal activity have hitherto been used as an active substance for plant protection.

Object of the invention

The aim of the invention is to provide novel compositions with strong nematicidal and insecticidal activity, which are suitable as crop protection agents.

Explanation of the essence of the invention

The invention has for its object to find new compounds with strong nematicidal and insecticidal activity, which are suitable as an active ingredient in the novel compositions.

According to the invention, the active ingredient in the novel compositions is at least one compound of the formula (I)

(CH ₂ ) _n .

I ^U 1 V

R ₂

applied, where:

- η 1,2 or 3,

X oxygen or sulfur,

R _{x is} identical or different, hydrogen or optionally halogenated C 1-4 -alkyl,

R ₁ and R ₂ , identical or different, denote hydrogen, halogen or optionally halogenated C 1-4 -alkyl,

- Y is halogen, optionally substituted ammonium, sulfonium or phosphonium, XR with R = optionally halogenated C ^ -alkyl, C (X) -R ', SO ₂ R' or -N = C (R ₃ R ₄ ) with R '= G | _6-alkyl, optionally with at least one Ci. and / or at least one halogen-substituted phenyl or XR ₃ or -N (R ₃ R ₄ ), where R ₃ and R ₄ , identical or different, are hydrogen or optionally substituted C 1-4 -alkyl, or, if the compound of the formula (I ) has one asymmetric carbon atom, one of its enantiomers or, if the compound of formula (I) has more than one asymmetric carbon atom, one of its diastereoisomers or one of its corresponding enantiomers as active ingredient.

The compounds of the invention having an asymmetric carbon atom are present in the two enantiomeric forms R or S. In this case, the formula (I) comprises the mixture of the two enantiomers both in equal amounts (racemate) and in one of the other predominant amount.

Compounds of formula (I) having more than one asymmetric carbon atom exist in several diastereoisomeric forms, each diastereoisomer having generally two enantiomeric forms. In this case, the formula (I) includes the mixture of the diastereoisomers and the enantiomers in either equal amounts or in a predominant amount over the other

 Preferred compositions according to the invention contain as active ingredient at least one compound of the formula (I) in which

- η 1 or 2,

X oxygen,

R _x , R ₁ and R _{2 are} hydrogen, methyl or halomethyl and

- Y is halogen.

The invention also relates to compounds of the formula (I)

(CH _n ): 1 ^ - ^{Κχ 3 + α}

where:

- η 1,2 or 3,

X oxygen or sulfur,

R _x , identical or different, is hydrogen, halogen or optionally halogenated C 1-4 -alkyl,

- Y is halogen, substituted ammonium, sulfonium or phosphonium, XR with R = optionally halogenated C-i

CXR ', SO ₂ R' or -N = C (R ₃ R ₄ ) with R '= C ₁ -S-AlkYl or optionally substituted with at least one Ci ^ t-alkyl and / or at least one halogen-substituted phenyl, or XR ₃ or -N (R ₃ R ₄ ) in which R ₃ and R ₄ , the same or different, are hydrogen or optionally substituted C 1-4 alkyl.

or, when the compound of formula (I) has an asymmetric carbon, one of its enantiomers, or when the compound of formula (I) has more than one asymmetric carbon atom, one of its diastereoisomers or one of its corresponding enantiomers, with the proviso that abovementioned substituents can not simultaneously have the following meanings:

- η 1 or 2,

X oxygen,

R _x , R ₁ and R _{2 are} hydrogen and

- Y halogen.

The compounds of the invention having an asymmetric carbon atom are present in the two enantiomeric forms RundS. In this case, the formula (I) comprises the mixture of the two enantiomers in either equal amounts (racemate) or in a predominant amount over the other

 The compounds of the invention having more than one asymmetric carbon atom are in diastereoisomers

Forms, each diastereoisomer generally having two enantiomeric forms. In this case, the formula (I) comprises the mixture of the diastereoisomers and the enantiomers in either equal amounts or in a predominant amount over the other

 Compounds of the invention of the formula (I) in which Y is halogen can be prepared by reacting a compound of the formula (III)

(IN THE)

in which n, X, R _x , Ri and R _{2 have} the abovementioned meaning, with a halogenating agent such as SOCl ₂ , P (O) Cl ₃ , PCI ₃ , PCI ₅ , PBr ₃ or P (O) Br ₃ , in Presence of an acid acceptor, such as a tertiary amine or a pyridine in a conventional manner (see, inter alia, J. MARCH "Advanced Organic Chemistry", 3rd Edition, Ed John WILEY &SONS; 1985, pages 382-384).

Some of the compounds of formula (III) are known.

Others are new, ie, compounds of formula (III) in which R ₁ , R ₂ , R _x , X and η are as defined above, provided that at the same time η is not 1 or 2, X is not oxygen or sulfur and R ₁ , R ₂ and R _{x are} not hydrogen. These compounds are also part of the invention.

Compounds of the formula (I) in which Y is halogen may also be obtained by reacting a compound of the formula (IV)

IV

in which n, X, R _x , R ₁ , R ₂ and R 'have the abovementioned meaning, with a salt of the formula M-hal, halo in the hai and

M is an alkali metal or alkaline earth metal and in particular lithium, sodium or potassium, in a manner known per se (cf.

cited above, p.382).

The compounds of formula (IV) are novel with the exception of tetrahydropyran-2-oxymethyltosylate and are part of the invention. They can be prepared by reacting a compound of the formula (III) with a compound of the formula (V).

R'SO ₂ Cl

(V)

in which R 'is as defined above in the presence of an acid acceptor such as a base and especially a tertiary amine or a pyridine (see, in particular, J. MARCH Advanced Organic Chemistry, 3rd Ed., John WILEY & SONS, 1985 , Pages 357-358).

Compounds of the formula (I) according to the invention in which Y is fluorine or iodine can also be prepared by reacting a compound of the formula (VI) ₁

(Vl)

in which n, X, R ₁ , R ₂ and R _{x have} the abovementioned meaning and Y 'is bromine or chlorine, with a salt of the formula MY ", in which Y" is fluorine or iodine and M has the abovementioned meaning, in known manner (cf the citation above, page 381).

Compounds of the invention of the formula (I) in which Y is halogen and X is oxygen can also be prepared by cyclization of an alcohol of the formula (VII)

(VII)

in which η, R _x , R ₁ and R _{2 have} the abovementioned meaning, can be prepared in a manner known per se: For example with a halo-etherifying agent such as N-bromosuccinimide or tert-butyl hypobromite (cf., in particular, ML MIHAILOVIC, et al. Bull. Soc. Chim. Beograd, 1982, 47 [8], 407-415), or with lead tetraacetate / M-hal, where M and hai are as defined above (see in particular S. MOTOHASHI, et al., Heterocycles, 1985, 23 [8], 2035-2039).

For their practical application, the compounds of the invention are seldom used alone, but rather are part of compositions. These compositions, which are suitable for the protection of plants against nematodes and parasitic insects, contain as active ingredient at least one compound according to the invention in combination with solid or liquid, agriculturally acceptable carriers and also agriculturally permissible border-active agents. In particular, the usual inert carriers and surfactants are suitable.

The compositions of the invention may contain any other kind of additives, such as protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers or complexing agents, as well as other known pesticidal agents, and in particular nematicides, insecticides or fungicides, or plant growth promoting fertilizers or fertilizers regulating agents. In general, the compounds used according to the invention can be combined with all solid or liquid additives customary in the formulation.

In general, compositions according to the invention with 0.5 to 5000 ppm of active ingredient are suitable; These values relate to compositions ready for use (ppm "means parts per 1 million"). The range of 0.5 to 5,000 ppm corresponds to 5 χ 10 ^-5 bis0,5Ma .-%.

Compositions according to the invention which are to be stored or transported advantageously contain from 0.5 to 95% by weight of active ingredient.

Thus, compositions of this invention for agriculture active ingredients in a seihr large width, ie χ of 5 10 ^-5 to 95mA .-% contained.

By "carrier" is meant herein generally an organic or inorganic, natural or synthetic material with which the active ingredient is combined for ease of application to the plant, seeds or soil.The carrier is generally inert and must be agriculturally permissible, and in particular The carrier can be solid (for example clays, natural or synthetic silicates, silica, synthetic resins, waxes or solid fertilizers) or liquid (eg water, alcohols, ketones, petroleum fractions, aliphatic or aromatic) Hydrocarbons, chlorinated hydrocarbons or liquefied gases).

The surfactant used in the present invention may be an emulsifying, dispersing or wetting, ionic or nonionic agent such as polyacrylic acid salts, lignosulfonic acid salts, phenolsulfone or naphthalenesulfonic acid salts, ethylene oxide polycondensates with fatty alcohols, fatty acids or fatty amines, substituted phenols, and especially alkyl or. Arylphenols, Sulfonbernsteinsäureestersalze, taurine derivatives (and in particular alkyl taurates), phosphoric acid esters of alcohols or polyoxyethylated phenols. The presence of at least one surfactant is generally essential if the active ingredient and / or the inert carrier are insoluble in water and.

the application agent is water.

The compositions of the invention may be in various forms, solid or liquid.

As solid compositions, atomisable powders having an active substance content of up to 100% are suitable.

As liquid compositions or those prepared in use as liquid compositions, solutions and in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or sprayable powders), granules and pastes are suitable soluble concentrates generally contain from 10 to 80% active ingredient, the emulsions or solutions ready for use contain from 0.001 to 20% active ingredient. In addition to the active ingredient and the solvent, the emulsifiable concentrates may optionally contain a suitable cosolvent and from 2 to 20% of suitable additives such as stabilizers, surfactants and especially emulsifiers, penetrants, corrosion inhibitors, dyes and adhesives.

From these concentrates emulsions of any desired concentration can be prepared by dilution with water, which are particularly suitable for application to crops.

The concentrated suspensions, which may also be applied by spraying, are prepared to give a liquid, stable, non-depositing product and generally from 10 to 75% active ingredient, from 0.5 to 15% surfactant, from 0 , 1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, such as antifoaming agents, corrosion inhibitors, stabilizers, penetrating agents and adhesives, and containing as carrier water or an organic liquid in which the active ingredient is little or insoluble: some organic Solid or inorganic salts can be dissolved in the carrier to prevent sedimentation or to act as antifreeze for the water.

Moisturable powders (or sprayable powders) are generally prepared to contain from 20 to 95% active ingredient and, apart from the solid carrier, from 0 to 5% of a wetting agent, from 3 to 10% of a dispersant and optionally from 0 to 10% of at least one stabilizer and / or other additives such as penetrants, adhesives, anticaking agents or dyes.

To prepare these sprayable or wettable powders, the active ingredient and the additives are mixed in suitable mixers and ground in mills or other suitable milling equipment. In this way, atomisable powders are obtained whose wettability and suspensibility are favorable; they can be suspended in water in any desired concentration, this suspension is very suitable for application to the leaves of the plants.

However, the compositions according to the invention can also be formulated in the form of granules which can be dispersed in water.

These dispersible granules, whose relative density is generally from about 0.3 to 0.6, generally have a particle size of about 150 to 2000, and preferably from 300 to 1500 microns.

The active ingredient content of these granules is generally from about 1 to 90 and especially from 25 to 90%.

The remainder of the granules consists essentially of a solid filler and, if appropriate, surface-active auxiliaries which impart dispersibility in water to the granules. These granules can be classified into substantially two different types, depending on whether the filler is soluble in water or not. A water-soluble filler may be inorganic and preferably organic. Excellent results were obtained with urea. Is the filler

-5- Z6Z99Z

insoluble in water, it is preferably inorganic, such as kaolin or bentonite. It is then combined with surfactants in an amount of 2 to 20% by weight, based on the granules. More than half of these surfactants consist of at least one substantially anionic dispersant, such as an alkali or alkaline earth polynaphthalene sulfonate or an alkali or alkaline earth metal sulfinate, the remainder being nonionic or anionic humectants, such as alkali or alkaline earth alcylnaphthalenesulfonate.

In addition, although not strictly necessary, other adjuvants may be added, such as antifoaming agents.

The granules of the invention can be prepared by mixing the ingredients and granulating in a conventional manner (such as tabletting, fluidized bed, sputtering or extrusion). In general, the process is terminated with comminution and sieving to the desired particle size indicated above.

The granules according to the invention are preferably prepared by extrusion (as indicated in the examples).

The compositions of the invention may also be in the form of organic solutions in capsules, such as polyurea- or urea-polyamide-based capsules, with polymer walls obtained by interfacial polymerization. These capsules are in the form of an aqueous concentrated dispersion which can be diluted to the desired atomization slurry when used.

The aqueous dispersions and emulsions of the present invention, for example, compositions which can be prepared by dilution with water of a wettable powder or emulsifiable concentrate, may include water-in-oil.

or oil-in-water emulsions and have the texture of a mayonnaise.

The invention also relates to the use of the compositions according to the invention for the treatment of plants against nematodes and phytopathogenic insects.

In this case, an effective amount of a composition according to the invention which contains at least one active ingredient of the formula (I) is applied to the culture site of these plants. The term "effective amount" is understood to mean an amount sufficient to control and destroy the nematodes and insects present on the plants, but the dose of application may vary widely, depending on the parasites, crop species, climatic conditions and conditions to be controlled the active ingredient used.

In practice, good results are generally obtained with doses of 1 to 500 g / hl, which corresponds essentially to doses of active substance of 10 to 5000 g / ha.

embodiment

The invention is illustrated by the examples. The structure of the compounds is confirmed by MNR, and / or IR and / or mass spectroscopy and / or microanalysis.

Example 1: Preparation of 2-bromomethyltetrahydropyran (Compound 1)

120 ml of toluene, 62 g of phosphorus tribromide and 11.5 g of pyridine are introduced into a 250 ml flask. The mixture is stirred and cooled to ⁰ ° C., then 80 g of 2-hydroxymethyltetrahydropyran and 4,6 g of pyridine are added. The temperature is kept while stirring under O ⁰ C while Zugbe the reactants, the mixture is stirred at the same temperature for 1 additional hour. The mixture warms to room temperature and is allowed to stand overnight, then filtered, washed with toluene and evaporated to dryness. The resulting yellow-orange liquid residue is distilled with a water jet pump (24mbar, 18mm Hg) to give 2-bromomethyltetrahydropyran of the following formula. Yield: 35.5 g of a colorless liquid, bp. 74 ° C / 24mbar (18mm Hg):

Cl-UB r

Example 2: Preparation of 2-bromomethyltetrahydrofuran (Compound 2)

The procedure according to Example 1, the 2-hydroxymethyltetrahydropyran is replaced by 2-hydroxymethyltetrahydrofuran. There are 60.0 g of 2-Brommethyltetrahydrofuran the following formula as a colorless liquid with a boiling point of 70 ⁰ C (24mbar, 18mm Hg) was obtained.:

Example 3: Preparation of bis (2,6-bromomethyl) -tetrahydropyran (Compound 3)

According to Example 1, 5.0 g of bis (2,6-hydroxymethyl) -cis-tetrahydropyran, 6.1 g of phosphorus tribromide, 1.3 g of pyridine and 30 ml of toluene are reacted, while 0.7 g of (2,6-bromomethyl) -cis Tetrahydropyran the following formula as a white powder with a mp. Of 37 ⁰ C obtained:

-6- zöz asz

br

Example 4: Preparation of 2- (1-bromoethyl) tetrahydropyran (Compound 4)

The procedure of Example 1 is repeated with 2- (1-hydroxyethyl) -tetrahydropyran instead of 2-hydroxymethyltetrahydropyran. There are obtained 23 g of 2- (1-bromoethyl) -tetrahydropyran of the following formula as a colorless liquid (no °: 1.4855) as a mixture of 2 diastereoisomers in a ratio of 55:45:

br

Examples: Preparation of 2-chloromethyltetrahydropyran (Compound 5)

To a solution of 30g 2-hydroxymethyltetrahydropyran in 44cm ^{3 of} pyridine 22cm ³ thionyl chloride are added so that the temperature of the reaction mixture at 40 to 45 ° C. remains. The mixture is then heated to 45 ° C with stirring for 8 hours. The remaining oil is taken up in ether, the ether phase is washed with water, a saturated. Washed sodium bicarbonate solution and a saturated sodium chloride solution, dried over sodium sulfate and concentrated. A colorless residue is obtained, which is distilled at 20 mbar (15 mm Hg). 20.2 g of 2-chloromethyltetrahydropyran of the following formula are obtained as a colorless liquid having a boiling point of 55 ° C. (20 mbar, 15 mm Hg):

Examples: Preparation of 2-iodomethyltetrahydropyran (Compound 6)

5.4 g of 2-bromomethyltetrahydropyran (Compound 1 (and 4.5 g of sodium iodide are placed in 50 ml of acetonitrile, stirred and heated under reflux for 14 hours.) The mixture is cooled to room temperature, the precipitated sodium bromide is filtered off and the solution becomes dry . evaporated case a brown residue is obtained, which with a water jet pump (16 mbar, 12 mm Hg) is distilled case (, 16 mbar 12mm Hg) caused 3g 2-Jodmethyltetrahydropyran the following formula as a brown liquid with a Kp von88 ^c C..:

Example 7: '.

Preparation of 2-tosyloxymethyltetrahydropyran (Compound 7)

35 g of 2-hydroxymethyltetrahydropyran are introduced into 60 ml of pyridine, stirred and cooled to 5 ° C. The mixture is added 69 g of tosyl chloride portionsweisejmit, wherein the temperature is maintained below 10 ⁰ C. At the end of the addition, it is stirred for 1 hour at 5 ° C, then warmed to room temperature, stirred for 2 hours and allowed to stand overnight. The mixture is poured onto ice and extracted with toluene. The toluene phase is washed with 10% hydrochloric acid and water, dried over sodium sulfate and concentrated. 33 g of 2-tosyloxymethyltetrahydropyran of the following formula are obtained as a white solid (mp 73 ° C.):

CH ₂ -O-SO ₂ -

Example 8: Preparation of 2-fluoromethyltetrahydropyran (Compound 8)

13.5 g of 2-tosyloxymethyltetrahydropyran (compound 7) and 13.5 g of potassium fluoride are introduced into 60 ml of ethylene glycol. The mixture is stirred and heated to 13O ⁰ C for 3 hours. It is then cooled to room temperature, diluted with 200 ml of water and extracted twice with 100 ml of ether. The combined ether extracts are washed with water, dried over sodium sulfate and evaporated to dryness. A residue is obtained which is distilled under atmospheric pressure to 1.8 g of 2-fluoromethyltetrahydropyran of the following formula as a colorless liquid (bp 110 ° C./1.090 mbar, 760 mm Hg):

Example 9: Preparation of 2-methanesulfonyltetrahydropyran (Compound 9)

The procedure of Example 7, but instead of tosyl chloride methanesulfonyl chloride was used. There were obtained 22 g of a yellow viscous oil of 2-methanesulfonyltetrahydropyran of the following formula:

CH ₉ -O-SO ₂ -CH-

¹³ C, 62, 90 MHz; L ^CDC1 3 (ppm): 75.1 / 72 ^:, 4 /. . ·

TMS

  6.8.3 / 37.5 / 27.3 / 25.5 / 22.8.

Example 10: Preparation of 6,6-dimethyl-2-iodomethyltetrahydropyran (Compound 10)

A solution of 44.3 g of lead tetraacetate in 200 ml of 1,2-dimethoxyethane is added with stirring at 0 ° C. to a solution of 7.2 g of 2-methyl-6-hepten-2-ol in 100 ml of 1,2-dimethoxyethane. Then a solution of 15 g of sodium iodide in 200 ml of 1,2-dimethoxyethane is added, the mixture is stirred for a further 30 minutes at 0 ⁰ C, poured into a solution of 1 500ml of ice water and 500 ml of 10% hydrochloric acid and extracted with ether. The ether phase is washed successively with a saturated sodium bicarbonate solution, a 10% sodium thiosuifate solution, a saturated sodium chloride solution previously dried over sodium sulfate, and evaporated to dryness. This gives a yellow residue which at 0.0267 mbar (0.02 mm Hg) to 4 g of a yellow liquid (bp 34 ° C / 0.0267 mbar, 0.02 mm Hg; ng ⁰ = 1.5110) of 6,6-dimethyl-2-iodomethyltetrahydropyran of the following formula is distilled:

Example 11: Preparation of 2- (a, a'-dimethylbromomethyl) tetrahydropyran (compound 11) and 5,5-dimethyl-2

bromomethyltetrahydropyran (compound 12)

In 75 ml of carbon tetrachloride, 12.8 g of 6-methyl-5-hepten-.1-ol and 19 g of N-bromosuccinimide are introduced and stirred at room temperature for 8 hours. The reaction mixture is filtered and washed with a 10% solution of Na ₂ S ₂ O ₃ and water, dried over sodium sulfate and evaporated to dryness. The residue is chromatographed on a silica gel column with heptane / ethyl acetate in a ratio of 98: 2. Here, 1.5 g of 2- (a, a'-dimethyl-2-bromomethyl) -tetrahydropyran (compound 11) of the following formula is obtained as a colorless liquid:

? ^K 3

;, 90 MHz rS ⁰¹ ^ ^(p ? ^M):

TMS 85.0 / 69.0 / 68.0 / 30.7 / 30.1 / 26.9 / 25.8 / 23.5.

By the same procedure of 14.2g of 2,2-dimethyl-5-hexene-1-ol and 21 g of N-bromosuccinimide in 150g carbon tetrachloride 8.8 g of 5,5-dimethyl-2-bromomethyltetrahydropyran (compound 12) of the following formula a boiling point of 48 ° C / 0,067mbar (0,05mm Hg):

V ^CH 3 CH ₃

O CH ₂ Br

Example 12:.

Preparation of the two diastereoisomers of 2-bromomethyl-6-methyltetrahydropyran (compound 13 and 14)

The procedure of Example 11, instead of 6-methyl-5-hepten-1-ol, 6-hepten-2-ol is used. By chromatography

- 5g of a colorless liquid of the diastereoisomer A and

1 g of a colorless liquid of diastereoisomer B of 2-bromomethyl-6-methyltetrahydropyran of the following formula:

RMN ¹³ C at 62.90 MH =: ^ ^COC \ (ppn):

TMS ^J

Isomer A: 77.1 / 74.6 / 35, 6/33, 0/29, 5 / 23.5 / 21.6.

Isomer B: 70.6 / 67.9 / 34.2 / 31.1 / 28.0 / 19.4 / 18.1

Example 13: Preparation of compounds 15 to

According to the procedure of Examples 10 and 11, starting from the corresponding alcohols, compounds 15 to 36 of the following formula are obtained:

Rx ς

Rx 6

n ° | R X

l · --- I l

C-Br

₁ L | Rx IRx, RxJr ^: IRxJrx | Rx | Rx ₀ Z '% J. ZI J 4 OO / O

I i

HI I H I H I H I HI IcH ₃ I ¹ CH ₃ I H-I HI I H I ! H I ₃ I I H I H I H I H I H ! cn

"15 I H ;. I H I ₃ I ₃ I IH 161 H. H- IHIH 17 j H _H ihihih 18 |;! HI I ₃ HLHLH IH HI f H | _H" HVI IH hihihihih ICH ₃ I Hl H | H Hi ηΙηΙηΙηΙηΙηΊ H-IcH ₃ I η

211 H 1 "CH ₃ ICH ₃ ICH ₃ I HlHlHl Η --- ΜΗ-Ί H 22 | H

[CH ₃ IHIH I ₃ I ₃ IHI 'H-- I, H> ^: KH

23 | H I ₃ IHIHIHIH ME ₃ 1CH ₃ T Ή '^; | H 24 H CH.

HlHlHlHl H ^; I ₃ -ICH ₃

25 | H I ₃ I ₃ IHIHIHIHIHIHIH

26 | H I ₃ IHIH I ₃ IHIHIHIHIH

27! H I ₃ IHIHIHIH I ₃ IHIHIH

28 | H-I ₃ IHIHIHIHIHIH I ₃ IH

291 CH ₃ I CH ₃ 1 CH ₃ ICH ₃ IH

H I H I H I H I H

301 CH ₃ I CH ₃ IHIHI CH ₃ I CH ₃ IH iH · '! -H f H 31ICH ₃ I ₃ IHIH 32ICH ₃ I ₃ IHIH

H ICH ₃ IiCH ₃ I

H I H

HIHIH | i H ICH ₃ IiCH ₃

331.CH ₃ IcH ₃ IcH ₃ I η I η I η I η Γ η Γη Y- ε

35 I CH ₃ I CH ₃ I 361 CH ₃ I CH ₃ I

H H

H I ₃

H H

H H

H I H

H I H

rf -'P-H I-H

H Γ H I H

HIH I ₃ IH

Example 14: Preparation of 2-bromomethyltetrahydrothiopyran (Compound 37)

The procedure is as in Example 1, but the 2-hydroxymethyltetrahydropyran is replaced by 2-hydroxymethyltetrahydrothiopyran. 109 g of a colorless liquid (bp 58 ° C./0.67 mbar, 0.5 mm Hg) of 2-bromomethyltetrahydrothiopyran of the following formula are obtained:

br

Example 15: Nematicidal in vitro (ovicidal and larvicidal action)

Tomato plant roots that have been infested for about 2 and a half months are washed and coarsely ground. The eggs are separated from the Wurzeltrümmem by screening (mesh: 20μηι). Then, a liquid suspension is prepared with about 4,000 fertilized eggs or 4,000 larvae per ml of distilled water. The compound to be tested is dissolved in acetone or with a Pottermuhle in distilled water, the 0.02%

-10- Ze * 99Z

oxyethylated sorbitan monooleate was added with 20 moles of ethylene oxide. For dilution series, dilute with distilled water.

In a hemolysis tube, 1 ml of the solution or suspension of the compound to be tested is mixed with 1 ml of the egg or larvae suspension of Meloidogyne incognita. After manual shaking, this mixture is applied to three-cuvette microscope slides. Each concentration is examined 5 times.

These platelets are placed on a support in a Petri dish, the bottom of which is lined with a moist filter paper to prevent the medium from drying out during the test period.

After 5 to 8 days, the platelets are examined with the magnifying glass and the percentage mortality of the nematode larvae is calculated.

Under these conditions 100% of the eggs and 50% of the larvae die with the compounds 1 and 2 at a dose of 100 ppm, at a dose of 200 ppm the compound 1 completely prevents hatching of the eggs. At 100 ppm, a 100% mortality of the larvae of Meloidogyne incognita is achieved.

Example 16:

Nematicidal experiment in the greenhouse with Meloidogyne incognita

According to Example 14 are obtained from infected tomato plant roots by sieving nematode eggs and suspended to an aqueous suspension with about 1 500 eggs, of which at least 10 to 15% are fertilized suspended per ml of water. From river sand, garden soil and potting soil, a mixture is prepared in equal proportions, into which the egg suspension is mixed in a concentration of about 3,000 eggs per liter of soil

 The compound to be examined is dissolved either

- In acetone, then mixed with aluminum silicate (Attagel), the mixture is mixed after homogenization in the contaminated soil or

- in water, the solution is then introduced directly into the contaminated soil.

The treated and contaminated soil is divided into pots (2 repetitions per dose) which are kept moist for 2 weeks (at 20 ^° C. and 100% relative humidity).

In each pot about 1 month old tomato plantlets (Lycopersicum esculentum), variety Marmande, are planted; the soil is kept moist by regular watering.

After 3 to 4 weeks, the plants are ripped off, the roots are washed with water.

The nematicidal activity is visually determined and reported in percent reduction in bumps that occur on the roots of plants growing in treated soil compared to bivalves that appear on roots of plants growing in untreated soil.

Under these conditions compound 1 has a 100% effect at this dose of 10 kg / ha and compounds 2 to 6 have a complete effect (> 90%) at a dose of 50 kg / ha. In addition, no plant toxicity is found at this dose.

These examples clearly demonstrate the excellent nematicidal properties of the compounds according to the invention, which are thus suitable for controlling parasitic plant nematodes. Conveniently, they are applied in doses of 0.5 to 50 kg of active ingredient per ha and preferably from 1 to 25 kg / ha, these doses can vary within wide limits, in particular they depend on the virulence of the infestation and the climatic conditions.

The following is the composition of some aqueous suspensions according to the invention:

Example A: -

An aqueous suspension is prepared from the following constituents:

ad g / i 11 Active substance (compound 1) 500 Humectant (synthetic polyethoxylated 10 C ₁₃ -alkyl) Dispersant (ethoxylated 50 Polyarylphenolphosphat) Antifreeze (propylene glycol) 100 Thickener (polysaccharide) 1.6 Bioeid (sodium 4-hydroxymethylbenzoate) 3.3 water

In this way, a concentrated liquid suspension is obtained.

Example B:

An aqueous suspension is prepared from the following constituents:

g / l

- Active substance (compound 1) 100

Moistening agent (polyethoxylated alkylphenol) 5

Dispersant (sodium naphthalenesulfonate) 10

- Antifreeze (propylene glycol) 100

Thickener (polysaccharide) 3

- Bioeid (formaldehyde), 1

- Water ad 1Γ

Examples:

An aqueous suspension is prepared from the following constituents:

ad 1.9 - active substance (compoundi) 250 - Moistening agent (polyethoxylated synthetic C ₁₃ -Alcohol) 10 Dispersant (sodium lignosulfonate) 15 - antifreeze (urea) 50 - thickener (polysaccharide) 2.5 - Bioeid (formaldehyde) 1 - Water 11

The following is the composition of some wettable powders:

Example D: ·

- Active substance (compound 1)

Ethoxylated fatty alcohol (humectant) 2.5

Ethoxylated styrylphenol (dispersing agent)

- Chalk (inert carrier) 42.5

Example E: Moisturizing powder with 10% active ingredient

- Active substance (compound!) ^X

- Synthetic, ethoxylated, branched C ^ -alcohol

with 8 to 10 moles of ethylene oxide (humectant) 0.75

- Neutral calcium lignin sulfate (dispersing agent)

Calcium carbonate (inert filler) ^ ad 100

Example F: Moisturizing powder with 75% active ingredient

From the components specified in Example E, a wettable powder is prepared in the following amounts:

- Active substance 75

- Moisturizer 1.50

- Dispersant

- Calcium carbonate (inert filler). ad

Example G: Moisturizing powder with 90% active ingredient

- Active substance (compound 1) 90 -

Ethoxylated fatty alcohol (humectant)

Ethoxylated styrylphenol (dispersing agent) 6 '

Example H: Moisturizing powder with 50% active ingredient

- Active substance (compound 1)

Mixture of anionic and nonionic surfactants (humectant) 2,5

Neutral sodium lignosulfonate (dispersing agent)

- Kaolin clay (inert support) 42.5

The following is the preparation of some granules according to the invention:

Example I: Dispersible granules with 90% active ingredient

In a mixer, 90% by weight of active compound (compound 1) and 10% of urea are mixed in bead form. The mixture is ground in a spindle mill to give a powder which is moistened with about 8% water by weight. The wet powder is extruded in a perforated roll extruder to produce granules which are dried, crushed and sieved to leave only particles having a particle size between 150 and 2000 microns.

Example J: Dispersible granules with 75% active ingredient

In a mixer, the following components are mixed:

- Active substance (compound!) 75

- Humectant (sodium alkylnaphthalenesulfonate) 2

Dispersant (sodium polynaphthalenesulfonate) 8

- Insoluble inert filler (kaolin) 15

This mixture is granulated in a fluidized bed in the presence of water, dried, crushed and sieved to obtain granules having a particle size of 0.16 to 0.40 mm.

These granules may be used alone or as aqueous solutions or dispersions of the desired dose. However, they can also be used for the preparation of combinations with other active substances and in particular fungicides, these combinations then being able to be in the form of wettable powders, granules or aqueous suspensions.

Scattering granules have a particle size of 0.1 to 2 mm and can be prepared by agglomeration or impregnation. In general, the granules contain 0.5 to 25% active ingredient and 0 to 10% additives such as stabilizers, slower release agents, binders and solvents.

Two examples of granule compositions are given below:

Examples K1 and K2:

G 50 G active substance 50 200 propylene glycol 2.5 50 Polyglycol cetyl ether 35 2.5 polyethylene glycol 910 35 Kaolin (particle size: 0.3 to 0.8 mm) 760

Claims (4)

claims: 1. Nematicidal and insecticidal compositions for the protection of plants against nematodes and phytophagous insects, characterized by at least one compound of the formula (I) < ^CH 2> n ^. ^(R x> 3 ^R 2 where: - η 1,2 or 3, -X oxygen or sulfur R _{x is} identical or different, hydrogen or optionally halogenated CWAlkyl, - Ri and R ₂ , identical or different, are hydrogen, halogen or optionally halogenated --Y halogen, optionally substituted ammonium, sulfonium or phosphonium, XR with R = optionally halogenated Ci_6-alkyl, C (X) -R ', SO ₂ R' or -N = C (R ₃ R ₄ ) with R '= C ₁ H ₃ alkyl, _{phenyl optionally} substituted by at least one C 1 -C 4 alkyl and / or at least one halogen or XR ₃ or N (R ₃ R ₄ ), wherein R ₃ and R ₄ , the same or different, represent hydrogen or optionally substituted C ₁ ^ - are alkyl, or, when the compound of formula (I) has an asymmetric carbon atom, one of its enantiomers or, if the compound of formula (I) has more than one asymmetric carbon atom, one of its diastereoisomers or one of its corresponding enantiomers as active ingredient. in addition to usual aids and additives. 2. Composition according to claim 1, characterized by a compound of formula (I) in which η is 1 or 2, X oxygen, R _x , R ₁ and R _{2 are} hydrogen, methyl or halomethyl and Y is halogen. 3. Composition according to claim 1 or 2, characterized by 2-bromomethyltetrahydropyran as active ingredient. 4. Use of the compositions according to one of claims 1 to 3, characterized in that they are used to protect the plants against nematodes and phytophagous insects at the site of culture.