WO1995030639A1

WO1995030639A1 - NOVEL β-METHOXY ACRYLIC ACID DERIVATIVES, PREPARATION METHOD THEREFOR AND USE THEREOF AS PESTICIDES

Info

Publication number: WO1995030639A1
Application number: PCT/FR1995/000566
Authority: WO
Inventors: Marc Benoit; Jean-Louis Brayer; Sylvain Laugraud
Original assignee: Hoechst Schering Agrevo S.A.
Priority date: 1994-05-09
Filing date: 1995-05-02
Publication date: 1995-11-16
Also published as: FR2719583A1

Abstract

Compounds of formula (I), wherein Q is CH or N, L is NH or O, m is 0, 1, 2 or 3, X is Hal, alc, O-alc, S-alc, NO2 or NH2, A is (a), (b), (c), (d), a heterocyclic radical joined to the phenyl nucleus or (e) joined to the phenyl nucleus, and R is an alcohol residue.

Description

New derivatives of β-methoxy acrylic acid, their preparation process and their application as pesticides.

The present invention relates to new derivatives of β-methoxy acrylic acid, their preparation process and their application as pesticides.

The subject of the invention is the compounds of formula (I):

^ϋ in which:

Q represents a CH radical or a nitrogen atom, L represents an NH radical or an oxygen atom,

- m represents the number 0, 1, 2 or 3, - X represents a halogen atom, an alkyl, alkenyl, alkynyl, O-alkyl, O-alkynyl, S-alkyl, S-alkenyl or

S-alkynyl, optionally substituted by one or more halogen atoms and containing up to 11 carbon atoms,

a radical C≡N, N0 ₂ , NH ₂ alk ₂ and alk ₃

identical or different from each other, representing an alkyl radical containing up to 8 carbon atoms,

- A represents a radical:

in which Hal ₁ represents a halogen atom, a radical

a radical:

^Hal v \ in which Hal ₂ represents a halogen atom, a heterocyclic radical attached to the phenyl nucleus or a radical:

)not

attached to the phenyl ring, to form a naphthalene radical in which Y and n respectively have the same meaning as X and m and - R represents:. an alkyl radical containing up to 11 linear, branched or cyclic saturated or unsaturated carbon atoms, optionally substituted by one or more hydroxyl, cyano, nitro radicals, by one or more halogen atoms, optionally interrupted by one or more heteroatoms chosen from oxygen, nitrogen or sulfur atoms,. a radical:

R

/ (CH ₂ ) _p N _χ

R

in which p represents an integer equal to 0, 1, 2, 3, 4, 5 or 6, and R'-L and R ' ₂ identical or different represent a hydrogen atom, a linear or branched alkyl radical, containing up to 4 carbon atoms,. an aryl or aryloxy radical containing up to 18 carbon atoms optionally substituted on the aryl ring by one or more substituents chosen from halogen atoms, the radical N0 ₂ , the radical C≡N, the alkyl radicals, O-alkyl and S-alkyl, linear, branched or cyclic, saturated or unsaturated, containing up to 8 carbon atoms, optionally substituted by one or more halogen atoms, aryl or aryloxy radicals containing up to 16 carbon atoms , optionally substituted by one or more halogen atoms and the radicals:

"1

\

^E "2 in which R '^ and R" ₂ , identical or different from each other, represent a hydrogen atom, an alkyl radical containing up to 4 carbon atoms or an aryl radical containing up to 18 carbon atoms, optionally substituted by one or more halogen atoms,. an aryl or aryloxy radical containing up to 18 carbon atoms optionally substituted on two adjacent carbon atoms of the aryl ring by a methylene or ethylenedioxy group optionally substituted by one or two halogen atoms,. a 5- or 6-membered heterocyclic aryl radical containing 1, 2 or 3 heteroatoms chosen from oxygen, sulfur and nitrogen atoms, optionally substituted by one or more radicals chosen from the group consisting of hydroxyl radicals, N0 ₂ , C≡N, halogen atoms, alkyl, O-alkyl and S-alkyl radicals, containing up to 8 carbon atoms, linear, branched or cyclic, optionally substituted by one or more atoms of halogen, by one or more hydroxyl radicals and the radicals: - \

R "' ₂ in which R"' ^ and R '" _2, identical or different, represent a hydrogen atom or an alkyl radical containing up to 4 carbon atoms,.

Rc in which Ra, Rb and Rc, identical or different, represent a linear, branched or cyclic alkyl radical containing up to 4 carbon atoms, optionally substituted by one or more halogen atoms, an aryl radical optionally substituted by one or more halogen atoms, one or more hydroxyl radicals, one or more alkyl radicals, linear or branched, optionally substituted by one or more halogen atoms, one or more O-alkyl or S-alkyl radicals, optionally substituted by one or more halogen atoms, or R represents a radical:

CR 'in which a and b, identical or different, represent a hydrogen atom, a halogen atom, a hydroxyl radical, a linear or branched alkyl radical containing up to 6 carbon atoms optionally substituted by one or more halogen atoms or a linear or branched alkoxy radical containing up to 6 carbon atoms, or a and b form together with the carbon atom to which they are attached a cycloalkyl radical containing up to 6 carbon atoms.

The geometry of the double bond of the beta-methoxyacrylic part can be E, Z or a mixture E and Z. In the definition of the different substituents:

alkyl preferably represents a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl radical,

cycloalkyl preferably represents cyclopropyl, cyclobutyl, cyclopentyl,

- unsaturated alkyl preferably represents ethenyl, ethyl, propenyl, propynyl, butenyl, butynyl.

When the linear or branched alkyl radical is interrupted by one or more heteroatoms, it is preferably one or more oxygen, nitrogen or sulfur atoms.

When it is a cycloalkyl radical interrupted by one or more heteroatoms, it is preferably a nitrogen heterocycle linked by a nitrogen atom such as pyrrolidine, pyrazoline, piperidine, piperazine or morpholine,

- aryl preferably represents the phenyl radical,

- Heterocyclic aryl preferably represents a thiazolyl, oxazolyl, isothiazolyl, isoxazolyl, thiadiazolyl, oxadiazolyl (1,2,4) or (1,3,4), triazolyl, imidazolyl, pyridynyl, pyridinyl or pyrazolyl radical.

When A represents a heterocyclic radical attached to the phenyl ring, the compounds of formula (I) can correspond to formula (I):

with Z = 0, S, CH ₂ = N or CH

The subject of the invention is in particular: - the compounds corresponding to formula (I _A )

in which R, X, Y, m and n retain the same meaning as before,

- the compounds corresponding to the formula (I _β ):

0 in which R, X, m and Hal- ^ retain the same significance as before, and more particularly those in which Ha ^ is a fluorine atom, - the compounds corresponding to the formula (I _c ):

in which R, X, Y, m and n retain the same significance as before - and the compounds of formula (I _D ):

in which R, X, Y, m and n retain the same significance as before. A more particular subject of the invention is the compounds of formula (I _A ), (I _B ), (I _c ) and (I _D ) in which m represents the number 0, as well as those in which R represents a radical alkyl containing up to 8 carbon atoms and in particular those in which R is a terbutyl radical.

A more particular subject of the invention is the compounds of formula (I) the preparation of which is given below in the experimental part and very especially the compound of example 1 or of example 3. The compounds of formula (I ) have interesting properties that allow their use in the fight against parasites. It can be a question of combating plant parasites, be they soil or aerial parasites, parasites of premises and parasites of warm-blooded animals.

The compounds of formula (I) have insecticidal, acaricidal and fungicidal properties.

The products of formula (I) can also be used to fight against insects in premises, to fight in particular against flies, mosquitoes and cockroaches.

The products of formula (I) can also be used to fight against insects and other soil parasites. for example beetles, like Diabrotica, wireworms and white worms, myriapods like scutigeria and blaniules, and diptera like midge and lepidoptera like ground moths. The products of formula (I) also have excellent miticide activity as shown by the results of the biological tests given below.

The compounds of formula (I) can also be used to fight against parasitic mites of animals, to fight for example against ticks and in particular ticks of the genus Boophilus, those of the genus Hyalomnia, those of the genus Amblyomnia and those of the genus Rhipicephalus or to fight against all kinds of scabies, in particular sarcoptic scabies, psoroptic scabies and chorioptic scabies. The subject of the invention is also, the pesticidal compositions containing as active principle at least one compound of formula (I) as defined above and more particularly the insecticidal compositions and the fungicidal compositions containing as active principle at least one compound of formula (I) as defined above. A very particular subject of the invention is the pesticidal compositions containing as active principle at least one compound, the preparation of which is given below and very especially the compound of Example 1 or of Example 3.

In these compositions intended for agricultural use and for use in premises, the active ingredient (s) can optionally be added with one or more other pesticidal agents. These compositions can be in the form of powders, granules, suspensions, emulsions, solutions, solutions for aerosols, combustible strips, baits or other preparations conventionally used for the use of this type of compound.

In addition to the active principle, these compositions generally contain a vehicle and / or a non-ionic surfactant, ensuring, moreover, a uniform dispersion of the constituent substances of the mixture. The vehicle used can be a liquid, such as water, alcohol, hydrocarbons or other organic solvents, a mineral, animal or vegetable oil, a powder such as talc, clays, silicates, kieselguhr or a combustible solid.

The insecticidal compositions according to the invention preferably contain from 0.005% to 10% by weight of active material.

According to an advantageous procedure, for use in premises, the compositions according to the invention are used in the form of fumigant compositions. The compositions according to the invention can then advantageously consist, for the non-active part, of a combustible insecticide coil (or coil), or also of an incombustible fibrous substrate. In the latter case, the fumigant obtained after incorporation of the active material is placed on a heating device such as an electric emitter.

In the case where an insecticide coil is used, the inert support may be, for example, composed of pyrethrum marc, Tabu powder (or Machilus Thu bergii leaf powder), pyrethrum stem powder, leaf leaf powder cedar, wood powder (such as sawdust) starch and coconut shell powder.

The dose of active ingredient can then be, for example, from 0.03 to 1% by weight. In the case where an incombusible fibrous support is used, the dose of active material can then be, for example, from 0.03 to 95% by weight.

The compositions according to the invention for use in premises can also be obtained by preparing a sprayable oil based on active principle, this oil soaking the wick of a lamp and then being subjected to combustion. The concentration of the active ingredient incorporated in the oil is preferably from 0.03 to 95% by weight.

The insecticide compositions according to the invention, like the acaricide and nematicide compositions, can optionally be added with one or more other pesticidal agents. The acaricide and nematicide compositions can be presented in particular in the form of powder, granules. suspensions, emulsions, solutions.

For acaricide use, wettable powders are preferably used for foliar spraying, containing from 1 to 80% by weight of active ingredient, or liquids for foliar spraying containing from 1 to 500 g / l of active principle. It is also possible to use powders for leaf dusting containing from 0.05 to 3% of active material.

For nematicidal use, liquids are preferably used for treating soils containing 300 to 500 g / l of active ingredient.

The compounds of formula (I) exhibit excellent fungicidal activity. They make it possible to fight against the fungi which have already penetrated inside the tissues of plants. This is particularly interesting in the case where it is no longer possible to control the diseases caused by the fungi once the contamination has already taken place. The activity spectrum of the compounds of formula (I) covers a large number of phytopathogenic fungi of various economic importance, for example Pyricularia oryzae, Venturia inaequalis, Cercospora beticola, Erysiphicaceae (Sp. Powdery mildew), Fusarium- , Drechslera- and Leptosphaeria-, Plasmopara viticola, Phytophtora infestans, Pseudoperonospora cubensis, various rusts, strains of Botrylis cinerea sensitive and resistant to BCM- and / or Dicarboximide-, Sclerotinia solerotiorum, strains of Pseudocercercorella and herpotrich Pellicu- laria sasakii.

A more specific subject of the invention is the fungicidal compositions containing from 0.001 to 1% by weight of compounds of formula (I).

In addition, the compounds of the invention can also be used in different industrial sectors, for example to protect wood or as a preservative for paints. The invention also extends to fungicidal compositions which contain, in addition to the compounds of formula (I), suitable formulation agents.

The compositions of the invention generally contain 1 to 95% by weight of active ingredient.

The possible formulations vary according to biological and physicochemical parameters. They can be, for example, wettable powders, emulsifiable concentrates, aqueous solutions, emulsions, spray solutions, dispersions in oil or in water, suspoemulsions, powders, treatment of seeds, of granules for example of microgranules, of granules to be sprayed, of granules coated, of absorption granules, of granules dispersible in water, of ULV formulation, of microcapsules, of waxes or of baits.

The invention also relates to a process for the preparation of the compounds of formula (I), characterized in that one esterifies a compound of formula (II):

0 in which A, Q, L, X, and m retain the same meaning as above. In a preferred embodiment, the esterification reaction is carried out using an iso urea, for example 2R-1,3-diisopropyl iso urea of formula:

H

OR CH

or terbutyl trichloroacetamidate of formula: , NH

C l, c - C _v

0 tBu or alternatively by the action of an alcohol on the acid or a derivative of this acid, for example a mixed anhydride or an acid chloride in the presence of dimethylaminopyridine and / or dicyochexylcarbodiimide.

In a variant of the process of the invention, the compounds of formula (I) naphthalenic can be prepared according to the reaction scheme:

The compounds of formula (II) are new products and are in themselves an object of the present invention.

Some examples of preparation of compounds of formula (II) are given below in the experimental part.

The compounds of formula (II _A ):

used at the start of the process leading to the products of formula (I _A ) can be prepared for example by the action of carbon monoxide under pressure, in the presence of a catalyst such as palladium acetate and of 1,3-bis ( diphenyl) phosphinopropane from the compounds of formula (III _A ) for example:

which can be prepared according to the process described in EP 538097, or from the products of formula (III _B ):

which can be prepared according to the process described in EP 480785.

The invention particularly relates to the products of formula (H _A ) as defined above.

The compounds of formula (IIg) used at the start of the process leading to the products of formula (Ig) can be prepared according to the following process:

14

The invention also particularly relates to the products of formula (II _B ) as defined above. The compounds of formula (II _Q ):

used at the start of the process leading to the products of formula (I _c ) can be prepared from the compounds of formula (III _C ):

as indicated above for the preparation of the compounds of formula (II _A ) from the compounds of formula (HI _A ) •

The invention particularly relates to the products of formula (II _C ) as defined above. The compounds of formula (II _D )

used at the start of the process leading to the products of formula (I _D ) can be prepared by amidification of the compounds of formula (II _C ) by means of an amine within an alcohol for example methylamine in ethanol or methanol. The invention also particularly relates to the products of formula (IIp) as defined above.

It is understood that this amidification reaction can be carried out on the products of formula (II _A ) or (II _B ) in order to obtain, if desired, the corresponding products of formula (II) in which the substituent L represents an atom of nitrogen.

A more particular subject of the invention is the compounds of formula (II), the preparation of which is given below in the experimental part. The following examples illustrate the invention.

EXAMPLE 1: 7 - [(1,1-dimethyl) ethoxycarbony1] o- (methyl methoxy) 1-methyl naphthalene acetate

Stage A: 7- [hydroxycarbonyl] α- (methyl methoxymethylene) 1-naphthhalene acetate 15 g of 1- (E) 7-bromo- (methoxymethylene) 1-methyl naphthalene are introduced into a container. g of potassium acetate, 150 ml of dimethyl sulfoxide, 0.6 g of palladium acetate and 1.7 g of 1,3-bis- (diphenyl) phosphinopropane. Carbon monoxide is reacted at constant volume at 60 ° C under a pressure of 5.8 bars. Stirring is continued for 16 hours. Purification is carried out by chromatography on silica, eluting with a heptane-ethyl acetate-acetic acid mixture 7-3-0.1. It is dried under reduced pressure for 16 hours at 50 ° C. 12.2 g of sought product is obtained, melting at 188 ° C.

Stage B: 7- [(1,1-dimethyl) ethoxycarbony1] a- (methyl methoxymethylene) 1-naphthaleneacetate

3.5 g of 1,1-dimethylethyl ester of N, N'-bis (1-methylethyl) carbamimide acid are introduced into a mixture of 0.5 g of product prepared in stage A and 7 ml of acetate ethyl. The reaction mixture is kept under stirring for 21 hours. We filter and concentrate. 2 g of product are obtained which is purified in a hexane-isopro ether mixture. pylic 5-5. 490 mg of sought product is obtained. Mp 110 ° C.

EXAMPLE 2: (Z, E) 2- [2-fluoro 2-carbetoxy ethenyl] α- (methoxymethylene) benzene methyl acetate Stage A: (E, E) 2- [2-fluoro 2-carbetoxy ethenyl] α - (methoxy-methylene) benzene methyl acetate

4.6 ml of triethylamine in a solution containing 3.74 g of lithium bromide and 20 ml of tetrahydrofuran are added at -30 ° C. The medium is brought to -50 ° C. and 2.21 g of 2-formyl α- (methoxymethylene) benzene methyl acetate are added 2.43 g of (2-ethoxy 1-fluoro 2-oxo ethyl) diethyl phosphonate and 25 ml of tetrahydrofuran. The mixture is stirred for one hour at -50 ° C., poured onto a solution of IN hydrochloric acid and extracted with isopropyl ether. The ethereal phase is washed with water and dried over magnesium sulfate. The solvent is removed and 3.1 g of product are obtained, which product is used as it is in the following stage.

Stage B: (Z, E) 2- [2-fluoro 2-carbetoxy ethenyl] α- (methoxy-methylene) benzene methyl acetate A solution containing 3.02 g of product obtained in stage A and 10 ml of tetrachloride is irradiated of carbon. 1 ml of a bromine solution in carbon tetrachloride (5% by moles) is added. The reaction seems complete after 7 hours of stirring and irradiation. The solvent is evaporated and 3.13 g of crude product is obtained which is purified by chromatography on silica eluting with the heptane-ethyl acetate mixture (8-2). 1.57 g of sought product is thus obtained. Mp 57 ° C. EXAMPLE 3: (Z, E) 2- [2-fluoro 2- (1,1-dimethylcarbetoxy) ethenyl] α- (methoxymethylene) benzene methyl acetate Stage A: Acid (Z, E) 2- [2-fluoro 2 -carboxy ethenyl] α- (methoxymethylene) benzene methyl acetate

5 ml of water and 0.5 ml of a 2N sodium hydroxide solution are added to a solution containing 0.29 g of product of Example 2 and 7 ml of methanol. The reaction mixture is kept under stirring for 2 hours, diluted with methylene chloride, acidified and extracted. The organic phases are combined, dried and concentrated under reduced pressure. We 0.24 g of sought product is obtained.

Stage B: (Z, E) 2- [2-fluoro 2- (1,1-dimethylcarbetoxy) ethenyl] α- (methoxymethylene) benzene methyl acetate

By operating as in Example 1, starting with 1.68 g of the product prepared in stage A and 6 g of N, N'-bis- (1-methylethyl) carba imide 1,1-dimethylethyl ester, 3.1 g of the crude product are obtained which are purified by chromatography on silica eluting with the heptane-ethyl acetate mixture (8-2). 0.91 g of the sought product is thus obtained. ₃ ppm CDC1 NMR

1.55 (s) C0 ₂ tBu

H 7.20 (m) 1H 7.34 (m) 2H

7.92 (m) 1H.

By operating as above, the products of formula were obtained:

R Isome- ^x n ^Y n NMR NMR NMR F ° C rie BMA SH ₆ SH ₈ SW tBu ΔE HH 7.58 8.46 7.79 110 °

Me ΔE H H 8.05 8.5 7.83 135 °

And ΔE H H 8.05 8.5 7.82 107 ° iPr ΔE H H 8.04 8.49 7.82 88 ° tBu ΔE H 6-C1 - 8.13 7.79 156.8 °

Me ΔE H 5-OCH3 7.38 8.11 7.80 147 °

EXAMPLE 4: (E) 2- (7-benzyloxycarbonyl-1-naphthyl) 2- (methoxyimino) methyl acetate.

Stage A: (E + Z) 2- (7-carboxy-1-naphthyl) 2- (methoxyimino) methyl acetate. In a Berghof reactor, 11 g of (2, Z) 2- (7-bro o 1-naphthyl) 2- (methoxyimino) methyl acetate, 11.8 g of potassium acetate, 0.77 g of a mixture are mixed. palladium acetate, 1,3-bis (diphenylphosphino) propane in 200 ml of dimethyl sulfoxide. After purging with nitrogen, was added carbon monoxide under a pressure of 15 bar and then heated to 64 ^° C for 30 hours. The reaction medium is ventilated and cooled, poured into 200 ml of ice water containing 25 ml of hydrochloric acid, stirred for 1 hour at 20 ° C. and diluted in 1 liter of water. Extracted with dichloromethane, washed with of sodium hydroxide solution, drying and evaporating the solvent at 70 ^° C under reduced pressure (1 torr) to remove dimethyl sulfoxide the residue was purified by chromatography on silica (eluant: hexane). comprising 20 to 90% ethyl acetate and obtains the expected products in the form of isomer Z, F = 182-183.5 ° C. and the isomer E, F = 184.5-186.5 ° C. Preparation of (E , Z) 2- (7-bromo 1-naphthyl) 2- (methoxyimino) methyl acetate.

10 g of 2- (7-bromo 1-naphthyl) 2-methyl oxoacetate and 4.3 g of chloro are heated at reflux for 6 hours. methoxyamine hydrate in 250 ml of methanol. The solution is refred, the solvent is evaporated off under reduced pressure, the residue is extracted with ethyl acetate, washed with water, dried and evaporated under reduced pressure. The expected product is obtained in the form of a mixture of isomers which are chromographed on silica (eluent: hexane comprising 5 to 20% ethyl acetate). Obtained the Z-isomer melting at ≈ 89 ^° C and the E isomer, mp 147-149'C. Possible isomerization of the Z isomer to the E isomer. To a solution of (E, Z) 2- (7-bromo 1-naphthyl) 2-

(methyl methoxyimino) acetate in 1.5 l of dichloromethane, 77 ml of hydrochloric acid are added. Was stirred vigorously at 20 ^° C for 23 hours, 200 ml of water and the organic phase separated, washed with aqueous sodium bicarbonate, drying and evaporating the solvent under reduced pressure. The residue is taken up in ethyl ether, filtered and the E isomer is obtained.

The Z isomer remains in the filtrate which is treated again as indicated above to obtain its conversion into the E isomer.

Stage B: (E) 2- (7-benzyloxycarbonyl-1-naphthyl) 2- (methoxy¬ imino) methyl acetate.

A solution comprising 1.7 g of the E isomer obtained in Stage A, 5 mg of 4-dimethylamino-pyridine and 0.3 ml of benzyl alcohol in 25 ml of dichloroethane is cooled to 0 ° C. 1.2 g of dicyclohexylcarbodiimide in solution in 10 ml of dichloromethane. The mixture is stirred for 30 minutes at 0 ° C. and allowed to return to 20 "C. for 18 hours. The dicyclohexylurea is filtered, washed with dichloromethane, the solvent is evaporated under reduced pressure, the residue is chromatographed on silica (eluent: hexane comprising 20 to 50% d 'ethyl acetate) and obtains, after recrystallization, the expected product. F = 112-113 "C. EXAMPLE 5: (E) 2- [7- (2-isopropoxyethoxycarbonyl) 1-naphthyl] 2- (methyl methoxyimino) acetate.

A solution comprising 1.5 g of the E isomer obtained in stage A of Example 4, 0.032 g of 4-dimethylaminopyridine, 0.75 ml of triethylamine and 0.62 ml is cooled to + 4 ° C. isopropoxyethanol in 35 ml of dichloromethane. 0.63 ml of isopropyl chloroformate is added, the mixture is stirred for 1 hour at + 4 "C and allowed to return to 20" C for 18 hours. Extracted with dichloromethane, washed with water, dried and the solvent evaporated. The residue is purified on silica, the residue is chromatographed on silica and the expected product is obtained. F = 74-75'C. EXAMPLE 6: (E) 2- [7- (2-methoxyimino) 2- [7- (3-pyridyl-methoxyxarbonyl) -1-naphthyl) methyl acetate.

5 ml of thionyl chloride are added to 15 g of the isomer (E) obtained as in Stage A of Example 4 and then heated for 1 hour at 85 ° C. in the presence of a desiccant (calcium chloride). The excess thionyl chloride is evaporated and the expected acid chloride is thus obtained which is dissolved in 20 ml of dichloromethane at 20 ° C. then 0.01 g of dimethylaminopyridine and 0.6 ml of 3-pyridylmethanol are added. solution in 10 ml of dichloromethane, stirred for 18 hours in the presence of a desiccant (calcium chloride), evaporate the solvent under reduced pressure, add 30 ml of saturated aqueous sodium bicarbonate solution, extract with acetate ethyl, washed with water, dried and evaporated the solvent. After purification by chromatography on silica, the expected product is obtained. F = 95-96.5 "C.

EXAMPLE 7: (E) 2- [7- (2-cyanobenzyloxycarbonyl) -1-naphthyl] 2- (methoxyimino) methyl acetate. 0.25 g of sodium hydride (60% in oil) is added at 20 ° C. to 1.5 g of the isomer (E) obtained as in Stage A of Example 4 dissolved in 30 ml of dimethylformamide, the mixture is stirred for 30 minutes until a clear solution is obtained, 1.02 g of α-bromo 2-toluonitrile is added and the reaction medium is stirred for 18 hours at 20 ° C. The reaction is stopped by adding 0.4 ml of methanol and the solvent is evaporated off under reduced pressure. The residue is extracted with ethyl acetate, washed with water, dried and the solvent evaporated. The residue is purified by chromatography on silica and the expected product is obtained. F = 137-138.5 ^* C.

EXAMPLE 8: (E) 2- (7-terbutoxycarbonyl-1-naphthyl) 2- (methoxy¬ imino) N-methylacetamide. Stage A: (E) 2- (7-carboxy 1-naphthyl) 2- (methoxyimino) N- methylacetamide.

Was heated 2 hours at 50 ^° C 2 g of the isomer (E) obtained as indicated in Stage A of Example 4 and 30 ml of a 30% solution of methylamine in methanol. Cool, evaporate the solvent, take up the residue in 50 ml of water, acidify to pH 4 with acetic acid, then extract the aqueous phase with ethyl acetate, wash with water. , dries and evaporates the solvent. The expected product is obtained. F = 212-214'C. Stage B: (E) 2- (7-terbutoxycarbonyl-1-naphthyl) 2- (methoxy¬ imino) N-methylacetamide.

2 ml of terbutyl 2,2,2-trichloroacetamidate are added to 1.6 g of the product obtained in the preceding stage, suspended in 10 ml of dichloromethane and 20 ml of cyclohexane. The mixture is cooled to -5 ° C. under a nitrogen atmosphere, 0.2 ml of a solution of trifluoroboride in ether is added and the mixture is stirred, allowing it to return to 20 ° C. for 1 hour and a half. The reaction medium is poured in 100 ml of water, stir 10 minutes, stir 200 ml of ethyl acetate, stir until completely dissolved, separate the organic phase and continue the extraction of the aqueous phase with ethyl acetate. combines the extracts, dries them, evaporates the solvate under reduced pressure After purification of the residue by chromatography on silica, the expected product is obtained. F = 100-104 "C.

EXAMPLE 9: (E) 2- (7-terbutoxycarbonyl-i-naphthyl) 2- (methoxy¬ imino) N-methylacetamide.

1.12 g of product obtained as in Stage A of Example 8, suspended in 60 ml of dichloromethane and 0.025 g of 4-dimethylaminopyridine in terbutanol, is cooled to 0 "/ ⁺ 4 ° C. 0.91 g of dicyclohexylcarbodiimide in 10 ml of dichloromethane, allowed to warm to 20 ^° C and stirred 18 hours. the mixture was refluxed for 6 hours, cooled, filtered to remove dicyclohexylurea, and the solvent is evaporated under reduced pressure. We chromatograph the residue on silica (eluent: hexane containing 40 to 80% ethyl acetate) The expected product is obtained, F = 100-104 ° C, then bis-8 anhydride - [(E) methoxyimino) methylcarbamoyl) ethyl] 2-naphthoic, F = 187-189 ^* C. 0.45 g of this anhydride and 0.3 g of potassium terboxide in tetrahydrofuran are heated to reflux for 8 hours. It is cooled, the solvent is evaporated off under reduced pressure, the residue is taken up in 50 ml of water, acidified with acetic acid and extracted with ethyl acetate. The extract is dried, the solvent is evaporated off with entrainment in toluene to remove the residual acetic acid, purified by chromatography on silica and the expected product is obtained, identical to that of Example 8. F = 100-104 ^* C.

By operating as indicated in the previous examples, the following compounds were prepared:

EXAMPLE 10: (E, Z) 2- (7-methoxycarbonyl-1-naphthyl) 2- (methoxyimino) methyl acetate. F = 108-113 "C.

EXAMPLE 11: (Z) 2- (7-terbutoxycarbonyl-1-naphthyl) 2-

(methyloxyimino) methyl acetate. rf = 0.23 (CH ₂ C1 ₂ -hexane 8-2).

EXAMPLE 12: (E) 2- (7-terbutoxycarbonyl-1-naphthyl) 2- (methyloxy ino) methyl acetate. F = 96 ^* C.

EXAMPLE 13: (Z) 2- (benzyloxycarbonyl-1-naphthyl) 2- (methoxy¬ imino) methyl acetate. F = 80-81.5'C. EXAMPLE 14: (E) 2- [(2,2-dimethyl 1,3-dioxolan-4yl) oxy-carbonyl) -1-naphthyl] 2- (methoxyimino) methyl acetate. F = 86.5-87.5'C.

EXAMPLE 15: (E) 2- (α-cyanobenzyloxycarbonyl-1-naphthyl) 2- (methoxyimino) methyl acetate. F = 145-145.5'C.

STUDY OF THE ACTIVITY OF THE COMPOUNDS OF THE INVENTION

Study of the acaricide activity on Tetranychus ϋrticae Bean plants are used comprising 2 leaves infested with 30 females of Tetranychus Urticae per leaf and placed in an airy box under a bright ceiling in constant light. The plants are treated with a Fisher spray gun: 4 ml toxic solution per plant of an equal volume mixture of water and acetone. It is left to dry for 1/2 hour and then the infestation is carried out. Mortality checks are carried out after 3 days. Results: From the dose of 100 ppm, the products of the invention exhibit an interesting acaricidal activity. Activity in Plas opara viticola

6 weeks after sowing, vine plants of the Riesling Ehrenfelder variety are treated with an aqueous suspension of active principle until runoff.

Once the product has vaporized dry, the plants are inoculated with a suspension of zoosporangia of Plasmopara viticola and the wet plants placed in a chamber at 23 ° C. and at a relative atmospheric humidity of 80-90%. After 7 days of incubation, the plants are placed in a culture chamber to promote the development of fungi. The extent of the disease is then assessed.

The degree of efficacy of the products is evaluated in relation to an infested untreated control. At a concentration of less than 25 ppm, the products of Examples 1, 2 and 3 have an efficiency close to 100%. Activity in Pyrenophora teres

Barley plants of the Igri variety at the "2-leaf" stage are treated with an aqueous suspension of active principle until runoff.

Once the product has vaporized, the plants are inoculated with an aqueous suspension of Pyrenophora teres spores and incubated for 16 hours in a room at 100% relative atmospheric humidity. The infested plants are then left to develop in the greenhouse at 25% at a relative humidity of 80%.

One week after inoculation the extent of the disease is assessed. The degree of efficacy of the products is evaluated compared to an infested untreated control. At a concentration of less than 25 ppm of active principle, the products of Examples 1 and 3 have an efficiency close to 100%. Activity on Erysiphe graminis Barley plants at the "2 leaf" stage are inoculated with barley powdery mildew conidia (Erysiphe graminés p sp. Hordie) and placed in the greenhouse at 20 ° C at 50% relative humidity, one day after inoculation. The plants are then treated with an aqueous suspension of active ingredient. We are looking for symptoms of powdery mildew. The degree of effectiveness is evaluated in relation to the untreated infested control.

At a concentration of less than 25 ppm, the compounds of Examples 1, 2 and 3 have an efficiency close to 100%. Activity on Leptosphaeria nodorum

Wheat of the Jubilar variety wheat is treated with an aqueous suspension of active ingredient, at the "2 leaf" stage until runoff. Once the product has vaporized dry, the plants are inoculated with an aqueous suspension of Leptosphaperia nodorum picnospores, and incubated for several hours in a room with controlled environment, at a relative atmospheric humidity of 100%. Plants are allowed to grow in a greenhouse at 90% relative atmospheric humidity until symptoms appear. The degree of effectiveness is expressed relative to an infested untreated control.

At a concentration of less than 25 ppm, the compounds of Examples 1 and 3 have an efficiency of 100%. Activity on Phytophtora infestans (PI), Plas ora viticola (PV), Erysiphe graminis (EG), Pyricularia oryzae (PO), Batrytis cinerea (BC), Venturia inaequalis (VI) and Leptosphaeria nodorum (LN).

Aqueous solutions or suspensions of the compounds of the invention are applied to test plants, by spraying or by soaking the base of the stem, at appropriate concentrations, further comprising a wetting agent. The plants or parts of plants are then treated with the desired pathogenic agent and then stored in a controlled environment, under conditions which make it possible to maintain the growth of the plant and the development of the disease.

The degree of efficacy of the products is evaluated compared to an infested untreated control. At a concentration less than or equal to 500 ppm, the compounds of the invention exhibit very good activity.

Claims

1.- The compounds of formula (I)

wherein :

- m represents the number 0, 1, 2 or 3,

- X represents a halogen atom, an alkyl, alkenyl, alkynyl, O-alkyl, O-alkynyl, S-alkyl, S-alkenyl or S-alkynyl radical, optionally substituted by one or more halogen atoms and containing up to 11 carbon atoms,

a radical C≡N, N0 ₂ , NH ₂ , C0 ₂ alc ₃ , alc ₁ , alc ₂ and alc ₃

identical or different from each other, representing an alkyl radical containing up to 8 carbon atoms, - A represents a radical:

in which Ha ^ represents a halogen atom, a radical

a radical:

a radical

Hal _Δ in which Hal ₂ represents a halogen atom, a heterocyclic radical attached to the phenyl nucleus or a radical:

attached to the phenyl ring, to form a naphthalene radical in which Y and n have the same meaning as X and m respectively

- R represents:

. an alkyl radical containing up to 11 linear, branched or cyclic saturated or unsaturated carbon atoms, optionally substituted by one or more hydroxyl, cyano, nitro radicals, by one or more halogen atoms, optionally interrupted by one or more heteroatoms chosen from oxygen, nitrogen or sulfur atoms,

. a radical:

A * (CH ₂ ) _p N

* '2 in which p represents an integer equal to 0, 1, 2, 3, 4, 5 or 6, and R' and R ' ₂ identical or different represent a hydrogen atom, a linear alkyl radical or branched, containing up to 4 carbon atoms, . an aryl or aryloxy radical containing up to 18 carbon atoms optionally substituted on the aryl ring by one or more substituents chosen from halogen atoms, the radical N0 ₂ , the radical C≡N, the alkyl radicals, O-alkyl and S-alkyl, linear, branched or cyclic, saturated or unsaturated, containing up to 8 carbon atoms, optionally substituted by one or more halogen atoms, aryl or aryloxy radicals containing up to 16 carbon atoms , optionally substituted by one or more halogen atoms and the radicals:

R "/ 1

\ S ^" 2 in which R '^ and R" ₂ , identical or different from each other, represent a hydrogen atom, an alkyl radical containing up to 4 carbon atoms or an aryl radical containing up to with 18 carbon atoms, optionally substituted by one or more halogen atoms,

. an aryl or aryloxy radical containing up to 18 carbon atoms optionally substituted on two adjacent carbon atoms of the aryl ring by a methylene or ethylenedioxy group optionally substituted by one or two halogen atoms,. a 5- or 6-membered heterocyclic aryl radical containing 1, 2 or 3 heteroatoms chosen from oxygen, sulfur and nitrogen atoms, optionally substituted by one or more radicals chosen from the group consisting of hydroxyl radicals, N0 ₂ , C≡N, halogen atoms, alkyl, O-alkyl and S-alkyl radicals, containing up to 8 carbon atoms, linear, branched or cyclic, possibly substituted by one or more atoms of halogen, by one or more hydroxyl radicals and the radicals:

"'i

\

R "2 in which R "' ₁ and R"' ₂ identical or different, represent a hydrogen atom or an alkyl radical containing up to 4 carbon atoms,. a radical

/ '

in which a and b, identical or different, represent a hydrogen atom, a halogen atom, a hydroxyl radical, a linear or branched alkyl radical containing up to 6 carbon atoms optionally substituted by one or more atoms of halogen or a linear or branched alkoxy radical containing up to 6 carbon atoms, or a and b together with the carbon atom to which they are linked form a cycloalkyl radical containing up to 6 carbon atoms, the geometry of the double bond of the β-acrylic methoxy part can be E, Z or a mixture E and Z.

2.- The compounds defined in claim 1, corresponding to formula (I _A ):

wherein R, X, Y, m and n retain the same meaning as in claim 1.

3.- The compounds defined in claim 1, corresponding to formula (I _B ):

in which R, X, m and Ha ^ retain the same significance as in claim 1.

4.- The compounds of formula (I) as defined in claim 3 in which Hal- _^ is a fluorine atom.

5.- The compounds of formula (I) as defined in claim 1 and corresponding to formula (I _c ):

of ⁾

W

RO

in which R, X, Y, m and n retain the same significance as in claim 1.

6.- The compounds of formula (I) as defined in claim 1 and corresponding to formula (I _D ):

in which R, X, Y, m and n retain the same significance as in claim 1.

7.- The compounds of formula (I) as defined in any one of claims 2 to 6, in which m represents the number 0.

8.- The compounds of formula (I) as defined in any one of claims 2 to 6, in which R represents an alkyl radical containing up to 8 carbon atoms.

9.- The compounds of formula (I) as defined in claim 8, in which R is a terbutyl radical.

10.- The compounds of formula (I) as defined in claim 1, the names of which follow: - 7- [(1,1-dimethyl) ethoxycarbony1] α- (methyl methoxymethylene) 1-naphthaleneacetate,

- (Z, E) 2- [2-fluoro 2- (1,1-dimethylcarbetoxy) ethenyl] α- (methoxymethylene) benzene methyl acetate.

11.- A process for preparing the compounds of formula (I) as defined in claim 1, characterized in that a compound of formula (II) is subjected:

in which A, Q, L, X, and m retain the same meaning as in claim 1, to the action of an esterifying agent to obtain the corresponding compound of formula (I).

12.- As new chemicals, the compounds of formula (II):

as defined in claim 11.

13.- As a new chemical, the compounds as defined in claim 11, of formula

and

in which X, Y, m and n retain the meaning indicated in claim 1.

14.- As a new industrial product, the compounds as defined in claim 11 of formula:

and

in which X, Y, m and n retain the same meaning as claimed in claim 1.

15. The pesticidal compositions containing as active principle at least one compound of formula (I) as defined in any one of claims 1 to 9.

16. The insecticide compositions containing as active principle at least one compound of formula (I) as defined in any one of claims 1 to 9.

17. The fungicidal compositions containing as active principle at least one compound of formula (I) as defined in any one of claims 1 to 9.

18.- The pesticidal compositions as defined in any one of claims 15 to 17, containing as active principle at least one compound defined in claim 10.