WO1998003464A1

WO1998003464A1 - Pesticides

Info

Publication number: WO1998003464A1
Application number: PCT/EP1997/003968
Authority: WO
Inventors: Jean-Louis Brayer; Nicole Reinier; Bernard Roisil; Sylvain Laugraud
Original assignee: Hoechst Schering Agrevo S.A.; LAUGRAUD, Pierre; LAUGRAUD, Rolande; LAUGRAUD, Philippe; LAUGRAUD, Bruno; SOLLOSSI, Martine
Priority date: 1996-07-24
Filing date: 1997-07-22
Publication date: 1998-01-29
Also published as: FR2751642B1; ZA976536B; AU3940697A; FR2751642A1

Abstract

Compounds of formula (I) in which R1, R2 and R3 are a) alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy or alkanoyloxy, each of which is straight, branched or cyclic, comprising up to 8 carbon atoms, optionally substituted by one or more halogen atoms and optionally interrupted by one or more oxygen atoms; b) phenyl or phenoxy, optionally substituted by one or more halogen atoms, one or more hydroxy radicals, one or more alkyl radicals which are linear or branched and are optionally substituted by one or more halogen atoms, one or more alkoxy or alkylthio radicals, which are optionally substituted by one or more halogen atoms, one or more hydroxy radicals (which may be esterified), or one or more cyano radicals; c) R1 and R2 can together with the carbon atom to which they are attached form a double carbon bond; d) R1 and R2 can together with the carbon to which they are attached form a ring comprising up to 8 chain atoms and which can comprise one or more hetero atoms selected from oxygen, sulfur and nitrogen; R4 is halogen, or an alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio or alkynylthio radical, each of which is optionally substituted by one or more halogen atoms and comprises up to 11 carbon atoms, a phenyl radical optionally substituted as defined under (b), CN, NO2, NH2, N(alk1)alk2, CO2alk3, where alk1, alk2 and alk3, which are the same or different from each other, are alkyl comprising up to 8 carbon atoms, X has the same meaning as R4 or can be hydrogen, or X and R4 together with atoms to which they are attached, can form a ring optionally containing one or more hetero atoms selected from oxygen, nitrogen and sulfur, have pesticidal, especially fungicidal or acaricidal, activity.

Description

Pesticides

The present invention relates to new derivatives of β-methoxyacrylic acid, process for their preparation and their application as pesticides

In EP 21 2859 there are claimed compounds of formula

C0₂ ¹ wherein V is an oxygen or a sulfur atom; X and Y, which may be the same or different, are hydrogen or halogen atoms, or optionally substituted alkyl, optionally substituted alkenyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkynyl, haloalkyl, alkoxy, haloalkoxy, optionally substituted aryloxy, optionally substituted arylalkoxy, optionally substituted acyloxy, optionally substituted ammo, acylamino, nitro, nitrile, -CO2 ³, -C0ιMR⁴R5, or COR^ groups; or the groups X and Y, when they are in adjacent positions on the phenyl ring, may join to form a fused ring, either aromatic or aliphatic, optionally containing one or more heteroatoms; and Z is optionally substituted methylene optionally substituted ammo, oxygen or sulfur and when Z is a substituted methylene group, the substituent may join the 2-posιtion of the phenyl ring to form a non-aromatic fused ring; R ¹ and R^ are alkyl groups containing from one to four carbon atoms, optionally substituted with one or more halogen atoms; and R^, R⁴, R5 and R*\ which may be the same or different, are hydrogen atoms or optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, or cycloalkylalkyl groups, and metal complexes thereof.

Of the 1 62 compounds specifically disclosed, there are only 5 where X and Y are both not hydrogen. In these compounds Z is -N(Me)-. There are no compounds where Z is 0 and the phenyl group is disubstituted. Nor are there any compounds where X or Y is an optionally substituted alkynyl group. We have now found that related compounds where Z is oxygen, X are specified alkynyl groups in the 5-posιtιon and Y are specified groups in the 2-posιtιon have particularly valuable properties.

Accordingly the invention provides compounds of formula (I)

in which: R -| , R2 and R3 which may be the same as or different from each other are a) alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy or alkanoyioxy, each of which is straight, branched or cyclic, comprising up 8 carbon atoms, optionally substituted by one or more halogen atoms and optionally interrupted by one or more oxygen atoms, b) phenyl or phenoxy, optionally substituted by one or more halogen atoms, one or more hydroxy radicals, one or more alkyl radicals which are linear or branched and are optionally substituted by one or more halogen atoms, one or more alkoxy or alkylthio radicals, which are optionally substituted by one or more halogen atoms, one or more hydroxy radicals, (which may be esteπfied), or one or more cyano radicals, c) R -] and R2 can together with the carbon atom to which they are attached form a double carbon bond, d) R -] and R2 can together with the carbon to which they are attached form a ring comprising up to 8 chain atoms and which can comprise one or more hetero atoms selected from oxygen, sulfur and nitrogen; R4 is halogen, or an alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio or alkynylthio radical, each of which is optionally substituted by one or more halogen atoms and comprise up to 1 1 carbon atoms, a phenyl radical optionally substituted as defined under (b), CN, O2, NH2, N(alk -ι )alk2- CU2alk3, where alk -j , alk2 and alk3, which are the same or different from each other, are alkyl comprising up to 8 carbon atoms, X has the same meaning as R4 or can be hydrogen, or

X and R4 together with atoms to which they are attached, can form a ring optionally containing one or more hetero atoms selected from oxygen, nitrogen and sulfur.

The geometry of the double bond of the β-methoxyacrylate part of the molecule can be Z, E or a mixture of E and Z, but is preferably Z.

In the definition of the various substituents: - alkyl is preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert- butyl,

- cycloalkyl is preferably cyciopropyl, cyclobutyl or cyclopentyl,

-alkenyl is preferably vinyl, propenyl or butenyl, and

-alkynyl is preferably acetylenyl, propynyl or butynyl.

Preferred compounds are those where: two of R -| , R2 and R3 are alkyl comprising up to 4 carbon atoms, and the other is alkyl comprising up to 4 carbon atoms or alkoxy comprising up to 8 carbon atoms, R4 is halogen, e.g. chloro, or alkyl comprising up to 4 carbon atoms, e.g. methyl, and

X is hydrogen.

The compounds of formula (I) have interesting properties which allow their use in the control of parasites. They can be active against plant pests which act through the soil or above the soil parts of the plant, are active against parasites of buildings and also against parasites of warm-blooded animals.

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

The products of formula (I) can also be used for combating insects in buildings and for combating particularly flies, mosquitoes and cockroaches. The products of formula (I) can also be used for combating insects and other soil parasites for example Coleoptera, such as Diabrotica, wire worms and cockchafer larvae, myπapods such as centipedes and millipedes, Diptera such as gall-gnats and Lepidoptera such as cut-worms.

The products of formula (I) also possess acaricidal activity as shown in the results of the biological tests described later.

The compounds of formula (I) can be used for combating parasitic acaπds of animals for combating for Example ticks and especially ticks of the genus

Boophilos, those of the genus Hyalomma, those of the genus Amblyomma and those of the genus Ripicephalus and for combating all sorts of mites and especially sarcoptic, psoroptic and choπoptic mites

In the compositions for agricultural use and for use in buildings, the active ιngredιent(s) can optionally include one or more other pesticides. These compositions can be in the form of powders, granules, suspensions, emulsions, solutions, solutions for aerosols, combustible coils, baits or other preparations conventionally used in this class of compounds.

Besides the active ingredient, the compositions contain in general a carrier and/or a non-ionic surface active agent to ensure a uniform dispersion of the constituent substances of the mixture The carrier 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, clay, a silicate, kieselguhr or a combustible solid.

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

According to one advantageous method of operating the invention to obtain a use in buildings, the compositions according to the invention are used in the form of fumigant composition.

The compositions according to the invention can thus be advantageously formed for the non-active part of a combustible insecticidal serpent (or coil) or further from an incombustible fibrous substrate. In the last case, the fumigant is obtained after incorporation of the active material is placed on a heating apparatus such as an electrical emanator.

In the case that one uses an insecticidal serpent, the inner support can be for example a compound of pyrethrum residue, tabu powder (or powder of the leaves of Machilus thumbergii), pyrethrum stalk powder, cedar leaf powder, wood powder, such as pine sawdust), starch and coconut husk powder.

The dose of the active ingredient can be for example from 0.03 to 1 % by weight.

In the case where an incombustible 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 buildings can also be obtained by preparing a pulveπsable oil based on the active principle, this oil containing the wick of a lamp and thus being capable of combustion.

The concentration of the active ingredient incorporating the oil is preferably from 0.03 to 95% by weight.

The acaricidal and nematicidal compositions can be present, notably in the form of a powder, granule, suspension, emulsion or solution.

For acaricidal use, wettabie powders are preferably used for foliar application containing from 1 to 80% of active material where the liquid for spraying the leaves contains from 1 to 500 grams per litre of the active ingredient. Foliar dusting powders can also be used containing from 0.05 to 3% of active agent.

For nematicidal use liquids for treating soils containing from 30 to 500 grams per litre of active ingredient are preferably used.

The compounds of the invention have activity against pathogens of Deuteromycete, Ascomycete, Phycomycete and Basidiomycete origin, especially against fungal diseases of plants, e.g. mildews and particularly cereal powdery mildew (Erysiphe gramims), cucumber powdery mildew [Erysiphe cichoracaerum), vine downy mildew [P/asmopara viticola) and vine powdery mildew {Uncinυ/a necator), rice blast (Pyriculaπa oryzae), cereal eyespot (Pseudocercosporella herpotrichoides) , rice sheath blight (Pellicularia sasakii), grey mould (Botrytis cinerea), wheat brown rust (Puccinia recondita), late tomato or potato blight (Phytophthora infestans), apple scab [Ventur/a inaequalis) and glume blotch (Leptosphaeria nodorum). Some compounds may be active against only a few pathogens whereas others may have a broader spectrum of activity.

Further, the compounds of the invention can also be used in various industrial sectors, for example for protecting wood and as a paint preservative.

The invention also extends to fungicidal compositions which comprise besides the compounds of formula I appropriate formulation agents.

The compositions of the invention in general comprise from 1 to 95% by weight of the active ingredient.

The possible formulations vary as a function of the biological and physicochemical parameters. They can be for example wettabie powders, emulsifiable concentrates, aqueous solutions, emulsions, vapoπsable solutions, dispersions in oil in or in water, suspo-emulsions, powders, seed treatment agents, granules for example microgranules, pulveπsable granules, coated granules, absorption granules, water-dispersible granules, ULV formulations, micro-capsules, waxes or baits.

The compositions according to the invention can in addition optionally contain one or more other pesticidal agents. The invention also includes a process characterised in that a compound of formula (ID

in which Hal represents a halogen atom, and X and R4 have the same meanings as above, is reacted with a compound of formula (III)

:C H

in which R -_j , R2 and R3 have the same meanings as above.

Compounds of formula (I), where R3 is alkoxy, alkenyloxy, alkynyloxy or alkanoyloxy, can be prepared from the corresponding compound of formula (!) in which R3 is hydroxy by alkylation etc. in known manner.

The compound of formula I in which R3 is hydroxy can be prepared in a similar manner to above using a compound of formula (II) in which R3 is hydroxy.

In the preferred method of carrying out the process of the invention, the reaction between the compound of formula (II) and the compound of formula (III) is carried out in an aprotic dipolar solvent, such as acetonitrile or DMF, in the presence of a tertiary amine, such as triethylamine, and in the presence of palladium, for example present as PdCl2(PPh3)2- or palladium metal supported on carbon, a tertiary phosphine, such as triphenylphosphiπe and a catalyst based on copper such as copper iodide. Hal preferably represents an atom of bromine or iodine. The compounds of formula (II) can be prepared as follows

The starting product can be prepared according to the following processes.

The compounds (III) are synthesised by methods described in the literature. The invention is illustrated in the following Examples. Structures of isolated novel compounds were confirmed by NMR and/or other appropriate analyses.

Example 1 A mixture, comprising methyl 2-[5-bromo-2-chlorophenoxy]-3-methoxy- 2-propenoate ( 1 .25 g), acetonitrile ( 1 2.5 ml), 3-butoxy-3-methyl-1 -pentyne ( 1 .1 5 g), PdCl2( θ3>2 (80 mg), copper iodide (30 mg), triphenyl phosphine ( 1 20 mg) and tπethylamine (3 ml), was heated under reflux for 5 hours, The mixture was added to N hydrochloric acid (50 ml) and ice, extracted with diethyl ether, dried and evaporated to dryness. The residue was purified by silica gel chromatography to give methyl 2-[2-chloro-5-(3-butoxy-3-methyl- 1 -pentynyl)phenoxy]-3-methoxy-2-propenoate, as an oil. (Compound 1 )

Preparation of starting materials a) methyl 2-[5-bromo-2-chlorophenoxyl-3-methoxy-2-propenoate Stage A

At 0 °C, boron tπbromide (9 ml) was added portionwise to a solution of 5-bromo- 2-chloroanιsole (20 g) in methylene chloride (200 ml). The mixture was stirred for 10 minutes at 0°C, and then for 24 hours at 20°C and poured into a mixture of ice and water. The resulting suspension was stirred for 30 minutes, extracted with methylene chloride, saturated with sodium chloride, and extracted twice with methylene chloride. The combined organic phases were dried over magnesium sulfate and evaporated under reduced pressure to give 5-bromo-2-chlorophenol. m.p. 56°C.

Stage B

Potassium carbonate ( 12 g) was added to a solution of 9 g of the product prepared in stage A and methyl bromoacetate (4.3 ml) in anhydrous acetone (200 ml). The resulting suspension was heated under reflux under nitrogen for 3 hours, poured into water and extracted with methylene chloride. The combined organic phases were washed with a saturated solution of sodium chloride, dried over magnesium sulfate and evaporated under reduced pressure, to give methyl (5- bromo-2-chlorophenoxy)acetate, m.p. 72°C. Stage C

A suspension of 9 g of the product obtained in stage B in bιs(dιmethyiamιπo)te/ - butoxymethane (75 ml) was heated for 1 hour at 80°C. The temperature was allowed to return to 20 °C, the mixture poured into water and extracted with methylene chloride. The combined organic phases were dried over magnesium sulfate and evaporated under reduced pressure.

The residual oil was taken up in THF. To this solution cooled to 0°C, is slowly added 100 ml 2N hydrochloric acid. The reaction mixture is stirred for 1 hour at 20°C, the poured into a saturated aqueous solution of sodium chloride, and extracted with diethyl ether The combined organic phases are dried over magnesium sulfate and evaporated under reduced pressure.

The product was taken up in acetone (250 ml) and dimethyl sulfate (3 4 ml) and potassium carbonate (8.9 g) were added. The suspension was stirred under nitrogen for 20 hours, poured into water and extracted with methylene chloride. The combined organic phases were dried over magnesium sulfate and evaporated under reduced pressure. The residue was purified by silica gel chromatography to the title product.

b) 3-butoxy-3-methyl-1 -pentvne

3-Methyl-1 -pentyn-3-ol (98 %, 1 1 .9 ml) and dimethylformamide ( 1 5 ml) were added over 45 minutes to a suspension of sodium hydride (5 g) in dimethylformamide (50 ml) at 0°C The mixture was stirred for 1 5 minutes and dibutyl suifate (25 g) and dimethylformamide ( 1 5 ml) were added at 0 °C over 20 minute,. The temperature was allowed to return to 20°C and the mixture stirred for 1 6 hours. It was added to a mixture of 2N hydrochloric acid (100 ml) and ice- water (700 ml), extracted with pentane, the extract dried and evaporated to give the title product.

Example 2

In a similar manner to Example 1 , methyl 2-[2-chioro-5-ιodophenoxy]-3-methoxy-

2-propenoate was reacted with 3-hydroxy-3-methyl-1 -pentyne to give methyl

2-[2-methyl-5-(3-hydroxy-3-methyl-1 -butynyl)phenoxy]-3-methoxγ-2-propenoate. A solution comprising this compound (3.04 g), methyl iodide (3 ml) and dimethylformamide (25 ml) was stirred at 0-5°C whilst sodium hydride (60% in mineral oil) (0.44 g) was added portionwise over 30 minutes.

The mixture was stirred overnight then poured onto aqueous ammonium chloride, extracted with diethyl ether, dried and evaporated to dryness. The residue was purified by silica gel chromatography to give methyl 2-[2-methyl-5-(3-methoxy- 3-methyl-1 -butynyl)phenoxy]-3-methoxy-2-propenoate, m.p. 1 14°C. (Compound 2)

In a similar manner to the previous Examples, the following products of formula (la) were obtained.

Those compounds in the previous Examples for which melting points are not quoted have the following characteristic nmr data

compound 24

1.45(3H,s,CH₃), 3.58{2H,t,OCH₂), 3.73(3H,s,OMe), 3.99(3H,s,OMe),

6.82(1H,d,ArH), 7.01 (1H,dd,ArH), 7.3(1H,d,ArH), 7.37(1 H,s, =CH)

compound 4 1.54(6H,s,2xCH₃), 3.74(3H,s,OMe), 3.9(3H,s,OMe), 6.82(1 H,d,ArH),

7.0(1H,dd,ArH), 7.29(1 H,d,ArH), 7.37(1 H,s, = CH)

compound 31

0.99(6H,dd,2xCH(CH₃)₂), 1.47(3H,s,CCH₃), 1.66(2H,m,CH₂CH),

1.94(1H,m,CH(CH₃)₂), 3.56(2H,m,OCH₂), 3.73(3H,s,OMe), 3.89(3H,s,OMe),

6.81(1H,d,ArH), 6.99(1H,dd,ArH), 7.3(1 H,d,ArH), 7.36(1 H,s, =CH)

compound 32

1.0(6H,dd,2xCH(CH₃)₂), 1.47(3H,s,CCH₃), 1.66(2H,m,CH₂CH), 1.94(1H,m,CH(CH₃)₂), 2.33(3H,s,ArCH₃), 3.57(2H,m,OCH₂), 3.71 (3H,s, OMe), 3.88(3H,s,OMe), 6.73(1 H,d,ArH), 6.96(1 H,dd,ArH), 7.08(1 H,d,ArH), 7.33(1H,s,=CH) compound 34

1.53(6H,s,2xCH₃), 3.58(2H,m,OCH₂), 3.73(3H,s,OMe), 3.89(3H,s,OMe),

6.82(1H,d,ArH), 7.0(1 H,dd,ArH), 7.3(1 H,d,ArH), 7.36(1 H,s, = CH)

compound 37

1.45(3H,s,CH₃), 1.76(2H,m,CH₂CH₃), 2.33(3H,s,ArCH₃), 3.58(2H,m,OCH₂),

3.79(3H,s,0Me), 3.88(3H,s,OMe), 6.75(1 H,d,ArH), 7.0(1 H,dd,ArH), 7.07(1H,d,ArH), 7.33(1 H,s, = CH)

compound 54

1.77(3H,s,CH₃), 3.25(3H,s,OMe), 3.75(3H,s,OMe), 3.91 (3H,s, OMe),

6.91(1H,d,ArH), 7.11 (1 H,dd,ArH), 7.4(1 H,s, =CH)

compound 55 3.74(3H,s,OMe), 3.9 (3H,s,OMe), 5.96(1 H,d, = CH), 6.13(1H,d, =CH), 6.89(1H,d,ArH), 7.08(1 H,dd,ArH), 7.36(1 H,d,ArH), 7.38(1 H,s, = CH)

compound 60

1.74(6H,s,2xCH₃), 2.32(3H,s,ArCH₃), 3.71(3H,s,OMe), 3.9 (3H,s,OMe), 6.74(1H,s,ArH), 7.32(1 H,s, = CH)

compound 63

1.65(3H,s,CH₃), 2.35{3H,s,ArCH₃), 3.72(3H,s,OMe), 3.75(2H,m,OCH₂),

3.89(3H,s,OMe), 6.77(1 H,d,ArH), 7.05(1 H,dd,ArH), 7.1 (1 H,d,ArH), 7.35(1H,s,=CH)

compound 64

1.66(3H,s,CH₃), 2.35(3H,s,ArCH₃), 3.72(3H,m,OMe), 3.75(2H,s,OCH₂),

3.89(3H,s,OMe), 6.77(1H,d,ArH), 7.05(1 H,dd,ArH), 7.1 (1 H,d,ArH), 7.35(1H,s, = CH) compound 72

1.66(3H,s,CH₃), 3.75(2H,m,OCH₂), ), 3.75(3H,s,OMe), 3.91 (3H,s, OMe),

6.86(1H,d,ArH), 7.06(1 H,dd,ArH), 7.35(1 H,d,ArH), 7.39(1 H,s, = CH)

compound 77

1.56(6H,s,2xCH₃), 1.77(3H,s,CH₃), 2.34(3H,s,ArCH₃), 3.72(3H,s,OMe),

3.89(3H,s,OMe), 4.05(2H,s,OCH₂), 4.87(1 H,bs, = CH), 5.02(1 H,bs, =CH),

6.74(1H,d,ArH), 7.0 (1H,dd,ArH), 7.08(1 H,d,ArH), 7.34(1 H,s, = CH)

compound 81

1.55(6H,s,2xCH₃), 3.73(3H,s,OMe), 3.89(3H,s,OMe), 4.1 (2H,s,OCH₂), 5.39(1H,d,=CH), 6.63(1 H,d,ArH), 7.02(1 H,dd,ArH), 7.3(1 H,d,ArH), 7.36(1H,s, = CH)

compound 84

1.68(6H,s,2xCH₃), 2.34(3H,s,ArCH₃), 3.71 (3H,s, OMe), 3.88(3H,s,OMe),

4.17(2H,s,OCH ), 6.76(1 H,d,ArH), 6.99(1 H,dd,ArH), 7.08(1 H,d,ArH),

7.33(1H,s, = CH)

compound 86

0.94(3H,t,CH₃CH₂), 1.35(9H,s,tBu), 1.38(3H,s,CH₃), 1.7(2H,m,CH₂CH₃), 3.52(2H,m,OCH₂), 3.64(3H,s,OMe), 3.78(3H,s,OMe), 6.68(1 H,d,ArH), 6.9(1H,dd,ArH), 7.19(1H,d,ArH), 7.29(1H,s, = CH)

compound 87

1.58(3H,s,CH₃), 2.28(3H,s,ArCH₃), 3.65(2H,m,OCH₂), 3.66(3H,s,OMe), 3.82(3H,s,0Me), 6.7 (1H,d,ArH), 6.97(1 H,dd,ArH), 7.04(1 H,d,ArH), 7.28(1H,s, = CH)

compound 91

1.04(3H,t,CH₃CH₂), 1.49(3H,s,CH₃), 1.82(2H,m,CH₂CH₃), 3.74(3H,s,OMe), 3.9(3H,s,OMe), 4.13(2H,m,OCH₂), 5.15(1 H,bd, = CH), 5.32(1 H,bd, = CH), 6.82(1H,d,ArH), 7.02(1H,dd,ArH), 7.31 (1 H,d,ArH), 7.38(1H,s, = CH) compound 93

1 .45(3H,s,CH₃), 1 .76(2H,m,CH₂CH₃) , 3.57(2H,m,OCH₂) , 3.74(3H,s,OMe),

3.89(3H,s,OMe), 6.87( 1 H,dd,ArH), 7.02(2H,m,2xArH), 7.34(1 H,s, = CH)

compound 99

1 .55(6H,s,2xCH₃), 2.33(3H,s,ArCH₃), 3.66(3H,s,OMe), 3.71 (3H,s, OMe),

4.1 4( 1 H,dd,0CH) , 4.38( 1 H,dd,OCH), 6.75( 1 H ,d,ArH) , 6.99( 1 H,dd,ArH) , 7.07(1 H,s, = CH) , 7.33(1 H,d ,ArH)

compound 1 02

1 .64(6H,s,2xCH₃) , 3.73(3H,s,OMe), 3.89(3H,s,OMe), 7.37( 1 H ,s, = CH),

Test Example a) Fungicide tests Compounds are assessed for activity against one or more of the following:

Phytophthora mfestans; late tomato or potato blight

Plasmopara viticoia: vine downy mildew

Erysφhe gramiπis f. sp. triticr. wheat powdery mildew

Pyricularia oryzae: rice blast Pelliculana sasakn- rice sheath blight .

Botrytis cmerea: grey mould

Ventuna inaequalis: apple scab

Leptosphaena nodorum: glume blotch

Aqueous solutions or dispersions of the compounds at the desired concentration, including a wetting agent, were applied by spray or by drenching the stem base of the test plants, as appropriate. Plants or plant parts were then inoculated with appropriate test pathogens and kept under controlled environment conditions suitable for maintaining plant growth and development of the disease. After an appropriate time, the degree of infection of the affected part of the plant was visually estimated. Compounds are assessed on a score of 1 to 3 where 1 is little or no control, 2 is moderate control and 3 is good to total control. At a concentration of 500 ppm (w/v) or less, the following compounds scored 2 or more against the fungi specified Phytophthora infestaπs 104-9 and 111-3

Plasmopara viticoia 4, 5, 7, 12, 13, 65, 69, 70, 71, 74, 76, 77, 81-3, 85, 103-9 and 111-113

Ervsiohe graminis

2, 7, 8, 13-17, 19, 26, 36, 41, 43, 49, 52, 62, 79-85, 88-91, 98, 101, 104, 107-9 and 111-113

Py cularia oryzae

5, 12, 62, 76, 77, 80, 81, 83, 85, 86, 89-91, 98, 104, 107, 108, 111 and 112

Pellicularia sasakii 1, 5, 7, 8, 14-17, 19-23, 25, 27, 28, 30, 34-37, 39-41, 43-45, 47, 54, 59, 63, 65, 67, 80, 82, 83, 85, 88-91, 102-9, 111 and 112

Botrvtis cinerea 10 and 108

Venturia inaeσualis

7, 8, 12, 13 and 104-109

Leptosphaeήa nodorum 5, 7, 14, 16, 17, 19, 43, 59, 62, 81, 83, 85, 88-91, 98, 102, 104, 106-9 and 113

b) Study of the acaricidal activity against Tetranychus υrticae.

Bean plants comprising two leaves infested with 30 female υrticae per leaf were put under an aerated hood under an illuminated ceiling under constant light conditions. The plants were treated using a Fisher gun with an aqueous acetone solution of test compound at various concentrations.4 ml of test solution were applied to each plant. The plants were allowed to dry over half an hour and then the infestation was allowed to proceed. The degree of control of the Tetranychus was determined at the end of 3 days. Results: At a dose of 100 ppm or less, the following compounds gave at least 50% control of the acaπds:

Compounds 2, 5, 7, 8, 11-26, 28-47, 50, 51, 54, 56, 58-60, 62-67, 69-74, 78, 80, 83, 87-91, 93, 94, 98, 99, 101 and 103-113

Claims

1 ) Compounds of formula (I)

in which. R -] , R2 and 3 which may be the same as or different from each other are a) alkyl, alkoxy, alkenyl, alkenyloxy, alkynyl, alkynyloxy or alkanoyloxy, each of which is straight, branched or cyclic, comprising up 8 carbon atoms, optionally substituted by one or more halogen atoms and optionally interrupted by one or more oxygen atoms, b) phenyl or phenoxy, optionally substituted by one or more halogen atoms, one or more hydroxy radicals, one or more alkyl radicals which are linear or branched and are optionally substituted by one or more halogen atoms, one or more alkoxy or alkylthio radicals, which are optionally substituted by one or more halogen atoms, one or more hydroxy radicals, (which may be esteπfied) , or one or more cyano radicals, c) R -_| and R₂ can together with the carbon atom to which they are attached form a double carbon bond, d) R -_| and R2 can together with the carbon to which they are attached form a ring comprising up to 8 chain atoms and which can comprise one or more hetero atoms selected from oxygen, sulfur and nitrogen;

R4 is halogen, or an alkyl, alkenyl, alkynyl , alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio or alkynylthio radical, each of which is optionally substituted by one or more halogen atoms and comprise up to 1 1 carbon atoms, a phenyl radical optionally substituted as defined under (b), CN, NO2. NH2, N(alk -| )alk2, Cθ2alk3, where alk _{1 #} all<2 and all<3_# which are the same or different from each other, are alkyl comprising up to 8 carbon atoms, X has the same meaning as R4 or can be hydrogen, or X and R4 together with atoms to which they are attached , can form a ring optionally containing one or more hetero atoms selected from oxygen, nitrogen and sulfur.

2) Compounds according to claim 1 , in which the geometry of the exo double bond (enol ether) is Z.

3) Compounds according to claim 1 or 2, in which at least two of R -_j , R2 and R3 are alkyl comprising up to 4 carbon atoms.

4) Compounds according to claim 1 , 2 or 3, in which one of R i , R2 and R3 is alkoxy comprising up to 8 carbon atoms.

5) Compounds according to any one of the preceding claims, in which R4 is halogen.

6) Compounds according to any one of claims 1 to 4, in which R4 is alkyl comprising up to 4 carbon atoms.

7) Compounds according to any one of claims 6, in which R4 is methyl.

8) Compounds according to any one of the preceding claims, in which X is hydrogen.

9) Pesticidal compositions comprising as active ingredient at least one compound claimed in any one of the preceding claims, in admixture with an agriculturally acceptable diluent or carrier.