WO1996029305A1

WO1996029305A1 - Fungicidal compounds

Info

Publication number: WO1996029305A1
Application number: PCT/GB1996/000657
Authority: WO
Inventors: Clive Leonard Cornell; Ian Christopher Richards; Geoffrey Gower Briggs; Jean-Louis Brayer; Jean-Pierre Demoute
Original assignee: Agrevo Uk Limited
Priority date: 1995-03-21
Filing date: 1996-03-19
Publication date: 1996-09-26
Also published as: EP0819115A1; IL117593A0; JPH11501912A; AU5115996A; ZA962317B; GB9505702D0

Abstract

Compounds of formula (I) wherein either a) Z is N, Y is O or NH and W is O, S, SO or SO2, or b) Z is CH, Y is O and W is S, SO or SO2; and R is alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, phenyl or heterocyclyl, each of which is optionally substituted, or is hydrogen, have pesticidal, especially fungicidal, activity.

Description

Funαicidal compounds

This invention relates to compounds having pesticidal, especially fungicidal, insecticidal and acaricidal, activity.

In EP 267734 there are claimed compounds of formula

wherein X and Y, which are the same or different, are hydrogen, halogen, optionally substituted alkyl, optionally substituted cycloalkyi, optionally substituted cycloalkylalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted alkoxy, optionally substituted aryloxy, optionally substituted heteroarγloxy, optionally substituted arylalkoxy, optionally substituted heteroarylalkoxγ, optionally substituted acyloxy, optionally substituted amino, acylamino, nitro cyano, -CO₂R³, -CONR R⁵, or -COR^β, except that X and Y are not both hydrogen; R¹ and R², which are the same or different, are alkyl or fluoroalkyl; and R³, R⁴, R⁵ and R^β, which are the same or different, are hydrogen, alkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted aralkyl, or cycloalkylalkyl.

We have now found that related compounds with different values of X or Y and/or where the CH of the acrylate group is replaced by N, have particularly valuable pesticidal, especially fungicidal, insecticidal and acaricidal, activity.

The invention provides compounds of formula I

wherein either a) Z is N, Y is 0 or NH and W is 0, S, SO or S0₂, or b) Z is CH, Y is O and W is S, SO or S0₂; and

R is alkyl, cycloalkyi, alkenyl, cycloalkenyl, alkynyl, phenyl or heterocyclyl, each of which is optionally substituted, or is hydrogen, and acid addition salts of any compounds which are basic and basic addition salts of any compounds which are acidic.

The R-W- group is preferably attached to the naphthyl at the 6 or 7 position and more preferably at the 7-position.

Substituents when present on any phenyl or heterocyclyl group include for example halogen, cyano or nitro, or the group D-(L)_m-, where m is 0 or 1 , L is 0, S, SO, S0₂, CO, 0-CO or CO-0 and D is has the same meaning as R (except hydrogen when m is 0) or is optionally substituted amino; or two adjacent groups on the ring together with the atoms to which they are attached can form an homo or hetero ring which may be similarly substituted as for phenyl.

The term heterocyclyl includes both aromatic and non-aromatic heterocyclyl groups. Heterocyclyl groups are generally 5, 6 or 7-membered rings containing up to 4 hetero atoms selected from nitrogen, oxygen and sulfur. Examples of heterocyclyl groups are furyl, thienyl, pyrrolyl, pyrrolinyl, pyrrolidinyi, imidazolyl, dioxolanyl, oxazolyl, thiazolγl, imidazolyl, imidazolinγl, imidazolidinyl, pγrazolγl, pyrazolinyl, pyrazolidinyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, pyranyl, pyridyl, piperidinγl, dioxanyl, morpholino, pγridazinyl, pyrimidinyl, pyrazinyl, piperazinyl, triazinyl, thiazolinyl, benzimidazolyl, tetrazolyl, benzoxazolyl, imidazopyridinyl, 1 ,3-benzoxazinyl, 1 ,3-benzothiazinyl, oxazolopyridinyl, benzofuranyl, quinolinyl, quinazolinyl, quinoxalinyl, sulfolanyl, dihydroquinazolinyl, benzothiazolyl, phthalimido, benzofuranyl, azepinyl, oxazepinyl, thiazepinyl, diazepinyl and benzodiazepinyl. Heterocyclyl groups may themselves be substituted for example as for phenyl.

Alkyl groups are preferably of 1 to 8, e.g. 1 to 6, carbon atoms. Alkenyl and alkynyl groups are generally of 3 to 6 carbon atoms. Cycloalkyi or cycloalkenyl groups are preferably of 3 to 8 carbon atoms. Substituents, when present on any alkyl, cycloalkyi, cycloalkenyl, alkenyl or alkynyl moiety include halogen, cyano, optionally substituted alkoxy, optionally substituted alkylthio, hydroxy, nitro, optionally substituted amino, acyl, acyloxγ, optionally substituted phenyl, optionally substituted heterocyclyl, optionally substituted phenoxy and optionally substituted heterocyclyloxy.

Cycloalkyi or cycloalkenyl groups may also be substituted by alkyl.

Amino groups may be substituted for example by one or two optionally substituted alkyl or acyl groups, or two substituents can form a ring, preferably a 5 to 7-membered ring, which may be substituted and may contain other hetero atoms, for example morpholine, thiomorpholine, or piperidine.

The term acyl includes the residue of sulfur and phosphorus-containing acids as well as carboxylic acids. Examples of acyl groups are thus -COR⁵, -COOR⁵, -CXNR⁵R^β, -CON(R⁵)OR^β, -COONRV, -CON(R⁵)NR⁶R⁷, -COSR⁵, -CSSR⁵, -S(0)_pR⁵, -S(0)₂OR⁵, -S(0)_pNR⁵R^β, -P( = X)(OR⁵)(OR^β), -CO-COOR⁵, where R⁵, R^β and R⁷ which may be the same or different, are hydrogen, optionally substituted alkyl, optionally substituted cycloalkyi, optionally substituted cycloalkenyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted phenyl or optionally substituted heterocyclyl or R^β and R⁷ together with the atom(s) to which they are attached can form a ring, p is 1 or 2 and X is 0 or S.

The compounds of the invention exist as the E and Z isomers and the invention includes individual isomers as well as mixtures of these, with the E-isomer being preferred.

A preferred group of compounds are those where R is alkyl, substituted by one or more alkoxy, aryloxy, heteroaryloxy or heterocyclyoxy groups, (all of which may be optionally substituted). A particularly preferred group of this type Y-0-(CH₂)_n-, where Y is optionally substituted aryl, heteroaryl, heterocyclyl and heteroaryl, and n = 1 -4, especially 2 A particularly preferred group of compounds are those where R is an optionally substituted CτC_β linear or branched chain alkyl group, preferably substituted by one or more halogen atoms, especially fluorine and/or chlorine and/or bromine atoms.

Examples of such preferred groups include CF₂H, CF₂Br, CF₂CF₂CI, CFCICF₂CI. CF₂CF₂H or CF₂CHCI₂.

W is preferably 0.

The compounds of the invention have activity as fungicides, especially against fungal diseases of plants, e.g. mildews and particularly barley powdery mildew {Erysiphe graminis) and vine downy mildew (Plasmopara viticola), rice blast (Pyricularia oryzae), cereal eyespot (Pseudocercosporella herpotrichoides) , rice sheath blight (Pellicularia sasakii), grey mould (Botrytis cinerea), damping off (Rhizoctonia solani), wheat brown rust (Puccinia recondita), late tomato or potato blight (Phytophthora infestans), apple scab (Ventυria inaequalis), glume blotch

(Leptosphaeria nodorum). Other fungi against which the compounds may be active include other powdery mildews, other rusts, and general pathogens of Deuteromycete, Ascomycete, Phycomycete and Basidomycete origin.

The compounds of the invention also have insecticidal, acaricidal and nematicidal activity and are particularly useful in combating a variety of economically important insects, acarids and plant nematodes, including animal ectoparasites and especially Diptera, such as sheep blow-fly, Lucilia sericata, and house-flies, Musca domestica; Lepidoptera, including Plutella xylostella, Spodoptera littoralis, Heliothis armigera and Pieris brassicae; Homoptera, including aphids such as Megoura viciae and Aphis craccivora Coleoptera, including corn rootworms {Diabrotica spp., e.g. Diabrotica undecimpunctata); and spider mites, such as Tetranychus spp..

The invention thus also provides a method of combating pests (i.e. fungi, insects, nematodes, acarids and weeds) at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound of formula I. The invention also provides an agricultural composition comprising a compound of formula I in admixture with an agriculturally acceptable diluent or carrier.

The composition of the invention may of course include more than one compound of the invention.

In addition the composition can comprise one or more additional active ingredients, for example compounds known to possess plant-growth regulant, herbicidal, fungicidal, insecticidal or acaricidal properties. Alternatively the compound of the invention can be used in sequence with the other active ingredient.

The diluent or carrier in the composition of the invention can be a solid or a liquid optionally in association with a surface-active agent, for example a dispersing agent, emulsifying agent or wetting agent. Suitable surface-active agents include anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid; an N-acylsarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters; fatty alcohol sulfates such as sodium dodecγl sulfate, sodium octadecyl sulfate or sodium cetγl sulfate; ethoxγlated fatty alcohol sulfates; ethoxylated alkγlphenol sulfates; lignin sulfonates; petroleum sulfonates; alkyl-aryl sulfonates such as alkγl-benzene sulfonates or lower alkylnaphthalene sulfonates, e.g. butyl-naphthalene sulfonate; salts of sulfonated naphthalene-formaldehyde condensates; salts of sulfonated phenol-formaldehyde condensates; or more complex sulfonates such as the amide sulfonates, e.g. the sulfonated condensation product of oleic acid and N-methγl taurine or the dialkyl sulfosuccinates, e.g. the sodium sulfonate of dioctyl succinate. Nonionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid amides or fatty-alkyl- or alkenyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers, e.g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, e.g. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, or ethoxylated acetylenic glycols. Examples of a cationic surface-active agent include, for instance, an aliphatic mono-, di-, or polyamine as an acetate, naphthenate or oleate; an oxygen-containing amine such as an amine oxide or polyoxyethylene alkylamine; an amide-linked amine prepared by the condensation of a carboxylic acid with a di or polyamine; or a quaternary ammonium salt.

The compositions of the invention can take any form known in the art for the formulation of agrochemicals, for example, a solution, a dispersion, an aqueous emulsion, a dusting powder, a seed dressing, a fumigant, a smoke, a dispersible powder, an emulsifiable concentrate or granules. Moreover it can be in a suitable form for direct application or as a concentrate or primary composition which requires dilution with a suitable quantity of water or other diluent before application.

An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscible solvent which is formed into an emulsion with water in the presence of an emulsifying agent.

A dusting powder comprises a compound of the invention intimately mixed and ground with a solid pulverulent diluent, for example, kaolin.

A granular solid comprises a compound of the invention associated with similar diluents to those which may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient absorbed or adsorbed on a pre-granular diluent, for example, Fuller's earth, attapulgite or limestone grit.

Wettable powders, granules or grains usually comprise the active ingredient in admixture with a suitable surfactant and an inert powder diluent such as china clay.

Another suitable concentrate is a flowable suspension concentrate which is formed by grinding the compound with water or other liquid, a wetting agent and a suspending agent. The concentration of the active ingredient in the composition of the present invention, as applied to plants is preferably within the range of 0.0001 to 1 .0 per cent by weight, especially 0.0001 to 0.01 per cent by weight. In a primary composition, the amount of active ingredient can vary widely and can be, for example, from 5 to 95 per cent by weight of the composition.

In the method of the invention the compound is generally applied to seeds, plants or their habitat. Thus, the compound can be applied directly to the soil before, at or after drilling so that the presence of active compound in the soil can control the growth of fungi which may attack seeds. When the soil is treated directly the active compound can be applied in any manner which allows it to be intimately mixed with the soil such as by spraying, by broadcasting a solid form of granules, or by applying the active ingredient at the same time as drilling by inserting it in the same drill as the seeds. A suitable application rate is within the range of from 5 to 1000 g per hectare, more preferably from 10 to 500 g per hectare.

Alternatively the active compound can be applied directly to the plant by, for example, spraying or dusting either at the time when the fungus has begun to appear on the plant or before the appearance of fungus as a protective measure. In both such cases the preferred mode of application is by foliar spraying. It is generally important to obtain good control of fungi in the early stages of plant growth as this is the time when the plant can be most severely damaged. The spray or dust can conveniently contain a pre- or post-emergence herbicide if this is thought necessary. Sometimes, it is practicable to treat the roots of a plant before or during planting, for example, by dipping the roots in a suitable liquid or solid composition. When the active compound is applied directly to the plant a suitable rate of application is from 0.001 to 1 kg per hectare, preferably from 0.05 to 0.5 kg per hectare.

The compound of the invention may be prepared, in known manner, in a variety of ways. Compounds where W is S can be prepared by reacting a compound of formula

wherein Q is a leaving group, preferably halogen and especially bromine with a compound of formula III R-S-M III where M is an organometallic radical or hydrogen.

When M is an organometallic radical the reaction is usually carried out in the presence of a palladium catalyst, such as tetrakis(triphenylphosphine)palladium. M is preferably a trialkyltin radical. The reaction is generally carried out under an inert atmosphere, in the presence of a solvent, e.g. an aromatic hydrocarbon at a temperature of 0 to 100°C, preferably at room temperature.

When M is hydrogen, the reaction is carried out under basic conditions e.g. in the presence an alkali metal carbonate, and also in the presence of a metal salt catalyst, such as cuprous iodide.

Compounds where W is SO or S0₂ can be obtained by oxidising a compound where W is S, with a suitable oxidising agent such as meta-chloroperbenzoic acid.

The compounds of formula II are known or can be prepared in known manner. For example, EP 538097 discloses compounds where Z is CH.

Compounds of formula II where Z is N and Y is 0 can be prepared by reacting compounds of formula IV

with methoxyamine hydrochloride, in known manner. These compounds are known, e.g. EP 538097, or can be prepared in known manner.

Compounds of formula II where Z is N and Y is NH can be prepared by reacting a compound of formula IVa

with methylamine in known manner.

Compounds of formula I where W is O, Z is N and Y is 0 can be prepared by reacting a compound of formula V

with methoxyamine hydrochloride, in known manner. The compounds of formula V can be prepared by the following reaction scheme:

(VII)

(VI)

(V)

(VIII) where Q is a leaving group, e.g. a halide or a sulfonate and THF is tetrahydrofuran.

Compounds of formula I where W is 0, Y is NH and Z is N can be prepared by reacting a compound of formula X

with methylamine in known manner.

Compounds of formula I where W is 0, Z is N and Y is 0 can be also prepared from compounds of formula VIII according to the following reaction scheme

(X)

where Q is a leaving group, e.g. a halide or a sulfonate, THF is tetrahydrofuran and DMF is dimethylformamide.

Compounds of formula VIII can be also prepared from compounds of formula IV according to the following reaction scheme

(VIII)

Other methods will be apparent to the chemist skilled in the art as will be the methods for preparing starting materials and intermediates. The Examples also make apparent various methods of preparing compounds of the invention as well as starting materials and intermediates.

The invention is illustrated in the following Examples. Structures of isolated novel compounds were confirmed by elemental and/or other appropriate analyses. Temperatures are in °C.

Example 1

Methyl (E) 2-r7-(2.5-dimethylbenzylthio)-1 -naphthvM-3-methoxyacrylate

To methyl (E)-2-(7-bromo-1 -naphthyl)-3-methoxyacrylate (3.21 g; EP 538097) and

2,5-dimethylbenzylthio-(trimethyl)tin (3.46 g) in dry toluene (40 ml) under nitrogen was added tetrakis(triphenylphosphine)palladium (0.5 g). The mixture was heated under reflux for 10 hours, evaporated to dryness and the residue purified by silica gel using light petroleum (b.p 60-80°)/ether (3:1 ) as eluent, to give a colourless oil which slowly crystallised. Recrystallisation from diisopropyl ether gave the title compound, as a white solid m.p. 1 19-120° (Compound 1 ) Example 2

Methyl ⁽E⁾-2-f7-(2.5-dimethylbenzylsulfinyl)-1 -na^phthyll-3-methoxyacrylate

A solution of 3-chloroperoxybenzoic acid (0.45 g) in dichloromethane (25 ml), was added dropwise with stirring to a solution of compound 1 (0.5 g) in dichloromethane (75 ml) cooled to 0°. The mixture was stirred for 1 5 minutes at room temperature, washed with acidified aqueous ferrous sulfate, dried over magnesium sulfate and worked up to give a yellow oil. This was purified by silica gel chromatography, using light petroleum (b.p 60-80°)/ethyl acetate (1 : 1 ) as eluent, to give a colourless oil which slowly crystallised. Recrystallisation from diisopropyl ether gave the title compound as a white solid, m.p. 135-136°.

(compound 2)

Example 3

Methyl (E)-2-f7-(2.5-dimethylbenzylsulfonyl)-1 -naphthyll-3-methoxyacrylate In a similar manner to Example 2, compound 2 was treated with 2.2 equivalent of 3-chloroperoxybenzoic acid to give the title compound, as a white solid m.p. 182- 1 83°. (compound 3)

Example 4 Methyl (E)- and (Z)-2-(methoxyimino)-2-(7-methoxy-1 -naphthyl)acetate

Methoxyamine hydrochloride (0.1 1 g) was added to a solution of methyl 2-{7- methoxy-1 -naphthyl)-2-oxoacetate (0.30 g) in methanol (3 ml) The mixture was heated under reflux for 8 hours. The solvent was removed in vacuo and the residue partitioned between dilute hydrochloric acid and dichloromethane. The organic layer was worked up and the residue purified by silica gel chromatography light petroleum (b.p 60-80°)/ethyl acetate (1 : 1 ) as eluent, to give methyl (Z)-2- (methoxyimino)-2-(7-methoxy-1 -naphthyl)-acetate as a white solid, m.p. 90-96°, (compound 4a); and methyl (E)-2-(methoxyimino)-2-(7-methoxy-1 -naphthyl)- acetate, as a white solid, m.p. 88-92°, (compound 4b). Example 5

(E)-2-(methoxyimino⁾-N-methyl-2-(7-^pro^poxy-1 -naphthyl)acetamide

Methyl (E)-2-(methoxyimino)-N-methyl-2-(7-propoxy-1 -naphthyl)acetate (1 .43 g) was dissolved in 23% w/v methylamine in methaπol (10 ml) and methanol and allowed to stand at room temperature for 24 hours. The precipitated solid was filtered and triturated with 20% ethyl acetate in hexane to give (E)-2-

(methoxyimino)-N-methyl-2-(7-propoxy-1 -naphthyl)acetamide, m.p. 142.5-144°.

(Compound 61 )

Example 6

Methyl (E)-2-(methoxyimino)-2-(7-propoxy-1 -naohthvPacetate Methyl (E)-2-(methoxyimino)-2-(7-hydroxy-1 -naphthyl)acetate (1.5 g) was dissolved in dry DMF (25 ml). Sodium hydride (60% in mineral oil, 350 mg) was added and the solution stirred for 10 minutes before adding n-propyl iodide (0.72 ml). The solution was stirred for 56 hours, then poured onto water and acidified with acetic acid. Extraction with ethyl acetate followed by flash column chromatography on silica gel using a gradient of 1 5-30% ethyl acetate in light petroleum (b.p.40-60°). Crystallisation of the product from 40% ethyl acetate in hexane gave methyl (E)-2-(methoxyimino)-2-(7-propoxy-1 -naphthyl)acetate, m.p. 82.5-83.5°. (Compound 59 -see also in table later)

Preparation of starting materials a) 2-(7-Hvdroxy-1 -naphthyl)-2-oxoacetic acid 2-(7-Methoxy-1 -naphthyl)-2-oxoacetic acid (25.63 g) (prepared according to the method of Gottlieb, Kellner and Loewenthal; Synth. Comm. (1 989) 2987-2997) in dry dichloromethane (800 ml) was added over 30 minutes to a stirred suspension of aluminium trichloride (59.5 g) in dry dichloromethane (500 ml). Sodium iodide (67 g) was added in one portion with stirring and the mixture was stirred at room temperature for 1 8 hours. It was poured into water (2 litres) containing concentrated hydrochloric acid (300 ml) and the solid broken up. Eventually an orange solid was deposited. This was filtered and washed with water to give the desired product as an orange powder, m.p. 220-3° (dec).

b) Methyl 2-(7-hvdroxy-1 -naphthyl)-2-oxoacetate 2-(7-Hydroxy-1 -naphthyl)-2-oxoacetic acid (2.40 g) and methanol (50 ml) containing cone, sulfuric acid (5 drops) were heated under reflux for 1 hour. The solvent was removed in vacuo and the residue dissolved in ethyl acetate. The solution was washed with aqueous sodium bicarbonate, dried over magnesium sulfate and worked up to give a brown solid. This was purified by silica gel chromatography using hexane:ethyl acetate ( 1 : 1 ) as eluent. to give the title product as a yellow solid), m.p. 126-8°.

c) Methyl (E)-2-(methoxyimino)-2-(7-hvdroxy-1 -naohthvDacetate Methyl-(7-hydroxy-1 -naphthyl)-2-oxoacetate (23 g), O-methyl- hydroxylamine hydrochloride (9.2 g) and methanol (500 ml) were refluxed for 24 hours. The solvent was removed to near dryness and water (500 ml) added. The product was filtered and re-dissolved in dichloromethane (300 ml), concentrated hydrochloric acid (5 ml) was added and the mixture stirred for 72 hours to equilibrate the isomer ratio in favour of the (E) isomer. The solvent was then removed and water added. The product was filtered, washed with water, triturated with ice cold methanol and finally washed with ether. This gave methyl (E)-2-(methoxyimino)- 2-(7-hydroxy-1 -naphthyl) acetate, m.p. 240°, which was used without further purification. Example 7

Methyl (E)-2-r7-(tert.-butylthio)-1 -naphthyll-3-methoxyacrylate

A mixture of methyl (E)-2-(7-bromo-1 -naphthyl)-3-methoxyacrylate (0.93 mmoles), tert. -butyl mβrcaptan (18.6 mmoles), potassium carbonate (2,4 g) and cuprous iodide (100 mg) was heated at 1 70° for 5 hours, under nitrogen. The mixture was cooled and water and dichloromethane added. The organic extract was worked up to give the title product, as an oil (Compound 5)

Example 8 Methyl (E)-2-(methoxyimino)-2-[7-(2-chloro-1 .2.2-tetrafluoroethoxy)-1 -naohthyll-

_________

To a solution containing methyl (E)-2-(methoxyimino)-2-(7-hydroxy-1 -naphthyl)- acetate (3.0 g) in dry DMF (80 ml) was added sodium hydride (0.70 g). The mixture was stirred at room temperature for 30 minutes before adding 1 ,2- dichlorotetrafluoroethane (9.3 g). After 56 hours the reaction mixture was poured into brine and acidified with acetic acid. Extraction with ethyl acetate gave an oil that was further purified by gradient elution flash chromatography on silica gel using 1 5 to 40% ethyl acetate in light petroleum (b.p. 40-60°). Isolation and re- crystallisation from hexane gave the tittle product, m.p. 92-3 ° (Compound 66).

Example 9

(E)-2-(methoxyimino)-2-f7-(2-chloro-1 .1 .2.2-tetrafluoroethoxy)-1 -naphthyllacetate Methyl (E)-2-(methoxyimino)-2-[7-(2-chloro-1 ,1 ,2,2-tetra fluoroethoxy)-1 - naphthyllacetate (1 .05 g) was dissolved in methanol (50 ml). To this was added 20% w/v methylamine in methanol (10 ml) and the mixture was stirred for 4 hours as room temperature. Evaporation of the solvent followed by trituration with hexane and ethyl acetate gave the title product, m.p. 144-5 °. (Compound 69). In a similar manner to the previous Examples, the following compounds of formula

I were obtained:

Cpd R Position W Z Y EZ m.p. (°) of R-W-

6 MeOCOCH₂ 7 S CH 0 E 90-1

7 EtOCH₂CH₂ 7 s CH 0 E 94-5

8 2,5-Me₂-PhCH₂ 7 s N 0 E 108-9

9 2,5-Me₂-PhCH₂ 7 so N 0 E 125-6

10 2,5-Me₂-PhCH₂ 7 so₂ N 0 E 160-1

11 4-MeO-PhCH₂ 7 s CH 0 E 97-8

12 pyridin-2-yl 7 s CH 0 E 103-4

13 PhCH₂ 7 s CH 0 E 115-6

14 4,6-Me₂-pyrimidin-2-yl 7 s CH 0 E 169-70

15 4-CI-PhCH₂ 7 s CH 0 E 129-30

16 6-CI-pyrimidin-2-yl 7 0 N 0 E/Z 146-8

17 3-Ph-1,2,4-thiadiazol-5-yl 7 0 N 0 E/Z 179-83

18 2-benzothiazolyl 7 0 N 0 E/Z 175-8

19 2-benzoxazolyl 7 0 N 0 E/Z 165-7.5

20 1 -Ph-tetrazol-5-yl 7 0 N 0 E 166-9

21 quinazolin-4-yl 7 0 N 0 E 165-7

22 "butyl 7 s CH 0 E

.23 benzyl 7 0 N 0 E Oil

24 3-<2-CF₃-C_βH₄-)- 7 0 N 0 E 106-8 1,2,4-thiadiazol-5-yl

25 benzyl 7 0 N 0 Z Oil

26 3-(4-CF₃-C_βH₄-)- 1,2,4- 7 0 N 0 E 150-4 thiadiazol-5-yl Cpd R Position W z Y E/Z m.p. (°) of R-W-

27 6-CI-quinazolin-4-yl 7 O N O E 189-90

28 3-methylbut-2-en-1 -yl 7 0 N 0 E 73

29 4,6-{MeO)₂-pyrimidin-2-yl 7 0 N 0 E 1 70

30 6-MeO-pyrimidin-4-yl 7 O N O E 236-9

31 4,6-(MeO)₂-pyrimidin-2-yl 7 O N NH E 1 85-8

32 'butyl 7 0 N O E 1 14

33 'butyl 7 0 N NH E 135

34 6-(2-CN-C_βH₄0)- 7 0 N 0 E 140-5 pyrimidin-4-yl

35 isopropyl 7 0 N NH E 182-4

36 PhCH(Me)- 7 0 N NH E 1 32-3

37 3-CF₃-C_βH₄-CH(Me)- 7 0 N 0 E 1 1 9-20

38 3-CF₃-C_βH₄-CH(Me)- 7 0 N NH E 1 14-5

39 isopropyl 7 0 N 0 E 70-3

40 NCCH(Me)- 7 0 N 0 E 131 -2

41 CH ~ CHCH - 7 0 N O E 103-4

42 CH₂ ⁼ CHCH - 7 0 N NH E 139-40

43 5-Br-pyrimidin-4-yl 7 0 N 0 E 1 85-6

44 Me 7 0 N NH E 1 62-4.5

45 HC=C-CH₂- 7 0 N O E 1 36.5-7.5

46 HCF₂- 7 0 N 0 E 106-7.5

47 sec-butyl 7 0 N 0 E Oil

48 1 -ethylpropyl 7 0 N O E 89-91 .5

49 (2,4,6-CI₃C_βH₂0)CH₂CH₂ 7 0 N 0 E 126-7.5

50 2-methylprop-2-en-1 -yl 7 0 N 0 E 77.5-9.5

51 PhOCH₂CH₂- 7 0 N O E 1 52-4

52 HCF₂- 7 0 N NH E 1 10.5-2

53 prop-2-yn-1 -yl 7 0 N NH E 1 82.5-4

54 sec-butyl 7 0 N NH E 125.5-6.5

55 1 -ethylpropyl 7 0 N NH E 107-8

56 (2,4,6-CI₃-C_βH₂0)CH₂CH₂- 7 0 N NH E 147-8

Ol

Those compounds in the above table which do not have discrete melting points have the following characteristic nmr data

Compound 23 ¹HNMR(CDCI₃)

3.84(3H,s,OCH₃), 3.98(3H,s,OCH₃), 5.1 2(2 H,s,CH₂), 6.90(1 H,s,aryl), 7.25-7.56(8H,m,aryl), 7.87(2H,m,aryl)

Compound 25 ¹HNMR(CDCI₃)

3.85 (3H,s,OCH₃), 4.08(3H,s,0CH₃), 5.20 (2H,s,CH₂), 7.22-7.58(8H,m,aryl), 7.74-7.88 2H,m,aryl), 7.22(1 H,s,aryl)

Compound 47 ^NMRfCDCIa)

1 .04 (3H,t,CH₃), 1 .35(3H,d,CH₃), 1 .68-1 .80

(2H,m,CH₂), 3.9(3H,s,OCH₃),

4.04 (3H,s,OCH₃), 4.41 (1 H,m,CH), 6.82-7.84

(6H,m,aromatics)

Test Examples

1 Fungicidal Activity

Compounds are assessed for activity against one or more of the following:

Phytophthora infestans: late tomato blight (PI)

Plasmopara viticola: vine downy mildew (PV)

Erysiphe graminis: barley powdery mildew (E.G)

Pyricularia oryzae: rice blast (PO)

Pellicularia sasakii: rice sheath blight (PS

Botrytis cinerea: grey mould (BC)

Venturia inaequalis: apple scab (VI)

Leptosphaeria nodorum: glume blotch (LN) 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 were considered active if they gave greater than 50% control of the disease at a concentration of 500 ppm (w/v) or less.

Activities are shown in the following table ( + = active against this species)

Cpd PI PV EG PO PS BC VI LN

1 +

2 +

3 +

4a +

4b + +

5 + + +

7 + + +

9 +

10 +

1 1 + + 3 + 4 + Cpd I V EG PO PS BC VI LN

15 + + + + +

16 + +

18 +

20 + + + +

21 + + +

23 + + + +

24 + + 5 + + 6 + + 7 + + + + + + 8 + 9 + 0 + 1 + + + 2 + + 3 + + 4 + + 5 + + + + + 6 + + 7 + + + + 8 + + + + 9 + + + + + 0 + + 1 + + + + 2 + + + + 3 + 4 + 5 + 6 + 7 + 8 + 9 + + Cpd PI PV EG PO PS BC VI LN

50 + +

51 + +

52 + +

53 + +

54 + + +

55 + +

56 + + + +

57 + + + +

58 + 9 + + 0 + + + 1 + + 2 + + + + + 3 + + + + 4 + + + + 5 + + + + 6 + + +

2 Insecticidal/acaricidal

• Aphis craccivora

Bean plants are treated by dipping the leaves in an aqueos acetone solution of active ingredient (50% acetone, 50% water) then dried under a ventilated hood. The leaves are then infested with 20 adult Aphis craccivora females per leaf and kept at 22° under a intense light conditions. Mortality checks are carried out after 48 hours. Compounds were considered active if they gave greater than 75% mortality of the insects at a concentration of 300 ppm(W/v) or less. Compound 96 was active against this species.

• Tetranychus urticae

Haricot bean plants are used comprising 2 leaves infested with 30 Tetranychus urticae females per leaf and put under a ventilated hood under a luminous ceiling with constant illumination. The plants are treated with a 4 ml of an aqueous acetone solution of active ingredient per plant. The leaves are left to dry for 30 minutes. Mortality checks are carried out after 72 hours. Compounds were considered active if they gave greater than 75% mortality of the insects at a concentration of 300 ppm(W/v) or less. Compound 96 was active against this species.

Claims

1 ) A compound of formula I

wherein either a) Z is N, Y is 0 or NH and W is O, S, SO or S0₂, or b) Z is CH, Y is O and W is S, SO or S0₂; and

2) The E isomer of the compound of claim 1 .

3) A compound according to claim 1 or 2 in which W is 0

4) A compound according to any one of claims 1 to 3 wherein the RW- group is attached to the naphthalene ring in the 7-position.

5) A compound according to any one of the preceding claims, wherein R is an optionally substituted C-|-C_β linear or branched chain alkyl group.

6) A compound according to claim 5, wherein R is optionally substituted by one or more halogen atoms.

7) A compound according to claim 6, wherein R is optionally substituted by one or more fluorine and/or chlorine and/or bromine atoms.

8) A compound according to claim 7 wherein R is CF₂H, CF₂Br, CF₂CF₂CI, CFCICF₂CI, CF₂CF₂H or CF₂CHCI₂. 9). Pesticidal, especially fungicidal, compositions which comprise a compound as claimed in any one of the preceding claims in admixture with an agriculturally acceptable diluent or carrier.

10). A method of combating pests, especially phytopathogenic fungi, at a locus infested or liable to be infested therewith, which comprises applying to the locus a compound as claimed in any one of claims 1 to 9.