The present invention relates to novel N-naphthylcarbamates, having use as pesticides, especially fungicides.

In EP 398,396 and WO 931 5046, there are disclosed oΛtΛo-substituted phenylcarbamates having fungicidal activity. We have now found that certain naphthylcarbamates have pesticidal, especially fungicidal activity

The invention provides compounds of formula I

in which:

X is hydrogen, halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio or alkynylthio group, comprising up to twelve carbon atoms optionally substituted by one or more halogen atoms, or X is O2.

CN or

/

in which R _a and R _D are the same or different and are hydrogen or alkyl comprising up to four carbon atoms or R _a and R^ together with the nitrogen to which they are attached form a heterocyclic radical comprising optionally another hetero atom chosen from oxygen, sulfur and nitrogen, saturated or unsaturated, mono or bi-cyclic, aromatic or non-aromatic, Y in position 6 or 7 is either an alkyl, alkenyl or alkynyl radical comprising up to twelve carbon atoms, optionally substituted by one or more halogen atoms or by an alkoxy, alkenyloxy or alkynyloxy radical which is linear, branched or cyclic

comprising up to twelve carbon atoms or substituted by an alkylthio, alkenylthio or alkynylthio radical which is linear, branched or cyclic comprising up to twelve carbon atoms or by nitro, cyano or by a radical:

\

in which R _c and R^ are the same or different and are hydrogen atom, an alkyl radical which is linear or branched and comprises up to four carbon atoms, or by a radical

/

\

in which R _e , Rf and Rg are the same or different and are an alkyl radical which is linear, branched or cyclic comprising up to four carbon atoms, optionally substituted by one or more halogen atoms, OI an aryl radical optionally substituted by one or more of the same or different groups selected from halogen, hydroxy, alkyl, alkenyl, alkynyl, aryl or heteroaryl which are optionally substituted by one or more halogen atoms, one or more alkoxy or alkylthio radicals each of which optionally substituted by one or more halogen atoms, one or more of CN NO2. or CO2R . in which R' is an alkyl radical comprising up to eight carbon atoms, or. an alkoxy, alkenyloxy or alkynyloxy radical which is linear branched or cyclic comprising up to twelve carbon atoms, optionally substituted by one or more of the substituents mentioned above for Y when Y is an alkyl radical

OI a radical, R _n CO or R,OCO in which Rf-, and R, represent a hydrogen atom or an optionally substituted alkyl radical of up to twelve carbon atoms, m a radical

in which R|< and R| which are the same or different, are hydrogen atom, alkyl, alkenyl or alkynyl comprising up to twelve carbon atoms and which are each optionally substituted, aryl or heteroaryl radical, Z is alkyl, R is hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio, or alkynylthio, comprising up to twelve carbon atoms, optionally substituted by one or more halogen atoms by CN or by alkoxy comprising up to eight carbon atoms and all possible isomeric forms as well as mixtures thereof

In the definition of the substituents:

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

- alkenyl is preferably a vinyl, allyl or 1 , 1 -dιmethylallyl radical, - alkynyl is preferably an ethynyl or propynyl radical,

- aryl is preferably a phenyl or naphthyl radical,

- the heterocyclic radical is preferably a thiazolyl, oxazolyl, isothiazolyl, isoxazolyl, thiadiazolyl or oxadiazolyl ( 1 , 2,4 or 1 ,3,4) , tπazolyl, imidazolyl, pyrazolyl, morpholinyl or pyrrolidinyl , - halogen is preferably a bromo. fluoro or chloro atom

Preferred compounds of the invention are those in which X is hydrogen, Y is in the position 7 on the naphthyl ring and especially those in which Y is an alkynyl radical comprising up to eight carbon atoms optionally substituted, e.g. a radical

CH,

H ₃ C-

CH, or

CH,

CH ₃

Preferred compounds of the invention are those in which R is hydrogen, an alkyl radical comprising up to four carbon atoms such as for example methyl or ethyl, an alkynyl radical comprising of six carbon atoms such as for example a radical

-CH ₂ -C-≡CH or an alkenyl radical comprising up to four carbon atoms such as for example allyl.

Among the preferred compounds of the invention are those in which Z is methyl or ethyl, preferably methyl.

The compounds of formula I can be prepared in a variety of methods. For example a compound of formula II

OOZ in which the OH group is in position 6 or 7 on the naphthyl ring and Z has the meaning given above, is reacted with a compound susceptible of substituting the OH with an easily cleavable group L to obtain the compound of formula III

and if one so desires, treating the compound with a compound capable of introducing the radical X -\ on the naphthyl ring to obtain a compound of formula IV

in which X -) has the same meaning as X except hydrogen and L and Z have the meaning given above, and then submitting the compound of formula III or IV to the action of an organometallic coupling agent capable of introducing the radical Y to obtain the compound of formula l :

Z

in which X, Y and Z have the meaning given above, and if desired submitting the compound 1 A to the action of a compound of formula (V)

R, Hal (V) in which Hal is a halogen atom and R - _j has the same meaning as R with the exception of hydrogen, in order to obtain the corresponding compound of formula

in which X, Y, R -| and Z have the meaning given above.

In the preferred method of carrying out the process: - the easily cleavable group is preferably a triflate, mesylate or a tosylate,

- the reactant capable of introducing the cleavable group is an anhydride for example tπfluoromethylsulfonic acid anhydride and the reaction is preferably carried out in the presence of a base, for example an amine such as triethylamine or pyridine, -the radical X -| can be introduced by means of N-chlorosuccinimide or N- bromosuccinimide when X -| is a chlorine or bromine atom and the reaction is generally carried out in an organic acid medium such as acetic acid

- the reaction with the compound of formula III or IV and the organometallic coupling agent is carried out in a dipolar aprotic solvent medium such as acetonitrile or dimethylformamide, in the presence of a tertiary amine such as triethylamine, with a catalyst of palladium such as (Ph3P)PdCl2 and a copper catalyst such as copper iodide using Heck's reaction.

-the reaction of compound of formula 1 ^ with a compound of formula IV is preferably carried out in the presence of a base such as sodium hydride in DMF or in the presence of LDA in THF.

Alternatively a compound of formula V:

in which Hal^ is a halogen atom is treated with a reducing agent to obtain the compound of formula VII

which is then treated with a compound of formula VIII

ZOHal _B (Vim in which Z has the meaning given above and Halg is a halogen atom, to obtain a compound of formula IX

and then treating the compound of formula IX to the action of a compound of formula X:

Hal _c R' (X) in which R' is an alkyl radical and Hair _, is a halogen atom to obtain a compound of formula ( 1 Q ) :

and then if desired, treating the compound 1 with an organometallic coupling agent capable of introducing the radical Y -| , in which Y -| is all the values of Y except halogen, to obtain the compound of formula 1 p:

in which Y-| , Z and R' have the meanings given above.

Compounds of formula I in which Y is an alkoxy, alkenyloxy or alkynyloxy radical and Z is an alkoxy radical comprising up to two carbon atoms, for example a methoxy radical can be made by the treatment of a compound of formula Ila:

with two equivalents of a compound of formula CICOZ in the presence of a base such as pyridine to give a compound of formula lib:

The compound of formula lib may be alkylated, e.g with an alkyl halide in the presence of a base, e.g . sodium hydride and preferably in a polar aprotic solvent such as dimethylformamide to give a compound of formula lie:

Selective deprotection of the carbonate group in formula He under mild basic conditions, e.g. with potassium carbonate in methanol gives compounds of formulc lid:

Alkylation of a compound of formula lid with an alkyl halide, alkenyl halide e.g. allyl bromide or an alkynyl halide, e.g. propargyl bromide, gives compounds of the invention of formula I where X = hydrogen. If desired, this compound can be treated with a reagent capable of introducing the radical X on the former naphthyl ring to give the desired compounds of formula I.

In a preferred method of carrying out the invention:

- the reduction of compound of formula VI is preferably with hydrazine in the presence of rhodium on carbon.

- the reaction between compound VII and VIII is generally in a mixture of dichloromethane and water in the presence of sodium bicarbonate or an equivalent base.

- the alkylation of compound IX is generally carried out using an alkyl iodide in the presence of a strong base such as sodium hydride in tetrahydrofuran

- The reaction of compound 1 r _, with the organometallic coupling agent is carried out in the same preferred conditions as those used for compound III or IV The compounds used as starting materials for the preparation of the products of the invention are known compounds or can be obtained in known manner

The invention also includes as new chemical products the compounds of formulae III, IV, VII and IX.

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 acaπcidal properties as well as fungicidal properties. They 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 Boophilus, those of the genus Hyalomma, those of the genus Amblyomma and those of the genus Rhiptcephalus and for combating all sorts of mites and especially sarcoptic, psoroptic and choπoptic mites.

The invention also includes pesticidal compositions for combating warm-blooded animals, parasites of buildings and plants characterised in that it comprises at least one of the compounds of formula I defined above The invention is especially applicable to insecticidal compositions as the active ingredients at least one of the products defined above as well as the acaricidal compositions comprising as active ingredients at least one of the products defined above

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 composed 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 insecticide compositions according to the invention such as the acaricidal and nematicidal compositions can in addition optionally contain one or more other pesticidal agents. The acaricidal and nematicidal compositions can be present, notably in the form of a powder, granule, suspension, emulsion or solution.

For acaricidal use, wettable 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 5 litre of active ingredient are preferably used.

The compounds of formula I show excellent fungicidal activity. They enable the control of fungi which have penetrated the interior of the tissues of the vegetation. This is particularly interesting in the case where it is no longer possible to control 0 disease caused by fungi which have already contaminated the plant. The spectrum of activity of the compounds of formula I covers a large number of phytopathogenic fungi of diverse economic importance, for example Pyriculana oryzae, Venturia inaequalis, Cercospora beticola, Erysiphicaceae (Sp. powdery mildew), Fusarium-, Drechslera- et Leptosphae a-, Plasmopara viticola, 5 Phytophthora infestans, Pseudoperonospora cubensis, Rhizoctonia solani, various rusts, Botrytis cinerea, sensitive and resistant to MBC and/or dicarboximides, Sclerotinia solerotiorum, Pseudocercosporelia herpotrichoides resistant to MBC and Pellicularia sasakii.

0 The invention particularly includes fungicidal compositions containing as active ingredient a compound defined above.

The fungicidal compositions according to the invention preferably comprise from 0.001 to 20% by weight of the compound of the formula I.

:-)

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

The invention also extends to fungicidal compositions which comprise besides the 0 compounds of formula I appropriate formulation agents.

The possible formulations vary as a function of the biological and physicochemical parameters. They can be for example wettable powders, emulsifiable concentrates, aqueous solutions, emulsions, vaporisable solutions, dispersions in 5 oil in or in water, suspo-emulsions, powders, seed treatment agents, granules for

example microgranuies, pulveπsable granules, coated granules, absorption granules, water-dispersible granules, ULV formulations, microcapsules, waxes or baits.

The invention is illustrated in the following Examples. Structures of isolated novel compounds were confirmed by NMR and/or other appropriate analyses.

EXAMPLE 1

Methyl 7-(3.3-dimethyl-1 -butynyl)-1 -naphthylcarbamate. Stage A:

Methyl 7- ⁽ trιfluoromethvlsulfonvloxv ⁾ -1 -na ^p hthylcarbamate.

A mixture of 2.2 g methyl 7-hydroxy-1 -naphthylcarbamate and 60 ml of methylene chloride was stirred at a temperature below 10°C under nitrogen. A small amount of triethylamine was added and then portionwise 1 .65 ml tπfluoromethylsulfonic anhydride. The mixture was stirred for one hour, poured into water and extracted three times with diethyl ether. The organic phases are washed with water, dried over sodium sulfate and the solvent evaporated under reduced pressure. The residue was chromotographed on silica using a mixture of heptane-ethyl acetate (8- 2) as eluent, to give the title compound. m.p. : 1 03.1 °C

Rf = 0.55 (heptane-ethyl acetate 8-2)

NMR (CDCI ₃ )

3.84 (S, 3H, OMe) - 6.84 (large 1 H NHCO) IR (CDCI ₃ ) 3427 cm ¹ NH 1 749 cm ¹ CO

S_ias≤_B:

Methvl 7-(3.3-dιmethvl-1 -butvnvl)-1 -naphthylcarbamate A mixture of 30 g of the product obtained from the previous stage, 60 ml dimethylformamide and 40 ml triethylamine was stirred at 0 °C under nitrogen. 25 ml of 3,3-dιmethyl- 1 -butyne, 1 .2 g tπphenylphosphinepalladium chloride and 0.4 g copper iodide was added. The reaction mixture was stirred at 20 °C for 1 8 hours. It was then poured into water and extracted with ether. The combined organic phases are washed with water, dried and the solvent evaporated. The

residue was chromatographed on silica, using heptane-ethyl acetate (8-2) as eluent. 22 g of research product was obtained. Rf = 0.43 (heptane-ethyl acetate 8-2) m.p. = 1 27 °C. NMR (CDCI ₃ )

1 .36 (s) H of tert. -butyl; 3.83 (s) H of C0 ₂ Me.

EXAMPLE 2

Methyl (7-(3,3-dimethyl- 1 -butynyl)- 1 -naphthyl(methyl)carbamate A solution comprising 1 .1 24 g of the product of Example 1 at the preceding stage and 1 0 ml dimethylformamide was stirred at 0°C under an atmosphere of nitrogen. 0.1 9 g sodium hydride as a 50 % oil was added, stirring was continued for 30 minutes before adding 0.3 ml methyl iodide and continuing stirring for 3 hours. The reaction mixture was poured into water and extracted with ether. The combined organic phases were washed with water, dried with magnesium sulfate and solvent evaporated under reduced pressure. The residue was chromatographed on silica, using heptane-ethyl acetate (8-2) as eluent, to give the title compound. Rf = 0.5 (ethyl acetate-heptane 1 - 1 ) m.p. = 1 23.8 °C. NMR (CDCI ₃ )

1 .37 (9H,s) tBu , 3.37 (3H,s) Me-N ; 3.59 (s) and 3.89 (m large) OMe.

EXAMPLE 3

Methyl 7-{3,3-dimethyl- 1 -butynyl)- . -naphthyl(2-propynyl)carbarnate 0.4 g sodium hydride (50% in oil) was added with stirring at 0°/ + 5 °C to a solution comprising 2 g of the product obtained in stage B of Example 1 and 20 ml dimethylformamide. The temperature was allowed to rise to ambient with stirring over 30 minutes. An 80% toluene solution of 1 .6 ml propargyl bromide was then added at a temperature below 30°C. The mixture was stirred for 1 8 hours at room temperature, treated with water and extracted with diisopropyl ether. It was washed with a saturated solution of sodium chloride, dried over sodium sulfate and evaporated to dryness. 2.31 g of crude research product was obtained which was chromatographed on silica, using a mixture of methylene chloride-heptane 70/30, as eluent to give the title product. m.p. = 1 39 °C.

Rf = 0.55 (CH ₂ CI ₂ ). nmr (CDCI ₃ )

1 .36 (9H,s) tBu ; 3.63 (si) ; 3.92 C0 ₂ Me ; 4, 1 1 (dd), 4,88 (dl) NCH ₂ ; 2.27 (t) -C≡CH. IR (CDCI ₃ )

1 701 cm ^{' 1} = C0 ; 3308 cm ^{' 1} ≡CH ; 2248-2218 cm ^'1 C≡C.

EXAMPLE 4 : Methyl 7-(3,3-dimethyl- 1 -butynyl)-1 -naphthyl|ethyl)carbamate

In a similar manner to Example 2 or 3, starting from 5 g of the product obtained in stage B of Example 1 , and with 2.7 ml ethyl bromide, there was obtained 4.75 g of the desired compound product, m.p. 47 °C. NMR (CDCI ₃ )

1 .36 (s) tBu ; 3.58 (si) and 3.85 (large) C0 ₂ Me ; 1 .1 8 (t), NCH ₂ CH ₂ ; 3.47 (m) and 4, 10 (m) NC-H2CH ₃ . IR

1 691 cm ¹ CO ; 2223 cm ^{' 1} C≡C.

EXAMPLE 5

Methyl 7-bromo-1 -naphthyKmethoxy (carbamate Stage A

7-bromo-N-hydroxy- 1 -naohthylamine

A solution comprising 2.0 g 7-bromo- 1 -nιtronaphthalene in 40 ml tetrahydrofuran was stirred under an atmosphere of nitrogen at a temperature below 10°C .0.1 6 g rhodium on carbon was added. 0.96 ml hydrazine hydrate was added dropwise. The mixture was stirred for 30 minutes at a temperature below 10°C and the temperature allowed to rise to ambient temperature. After one hour at ambient temperature, the mixture was filtered. It was extracted with diethyl ether and the combined organic phases washed with water, dried over sodium sulfate and the solvent evaporated, to give the title product which was used in the next stage.

Stage B

Methyl 7-bromo-1 -naphthyl(hvdroxy)carbamate

A mixture of 1 .9 g of product obtained in stage A, 80 ml of methylene dichloride,

10 ml water and 1 .6 g of sodium hydrogen carbonate was stirred at a temperature below 10°C. 2.1 ml methyl chloroformate was added over 5 minutes. The reaction

mixture was stirred for 1 .5 hour at room temperature. The reaction mixture was poured into water and 20 ml N hydrochloric acid added. The mixture was extracted with diethyl ether and the combined organic phases washed with water, dried over sodium sulfate and the solvent evaporated under reduced pressure, to give the title which was used in the next stage.

Stage C

Methyl 7-bromo-1 -naphthylimethoxyicarbamate

A mixture of 2.2 g of product obtained from the preceding stage and 40 ml tetrahydrofuran was stirred under an atmosphere of nitrogen at a temperature below 1 0°C. 0.37 g sodium hydride (50 % in oil) was added and the mixture stirred for 1 5 minutes, 0.8 ml methyl iodide was added and the reaction mixture agitated over 30 minutes. The mixture was poured into water and extracted with diethyl ether. The organic phases are washed with water, dried over magnesium sodium sulfate and the solvent evaporated under reduced pressure, the residue was chromatographed on silica using a mixture of heptane-ethyl acetate (9- 1 ) as eluent to give the title product

Rf = 0.5 (ethyl acetate-heptane 1 - 1 ) m.p. = 1 29.1 °C. NMR (CDCI ₃ )

3.80 (6H,s) 2 x OMe

IR (CDCI ₃ )

1 730 cm ^{' 1} CO

EXAMPLE 6

Methyl 7-(3,3-dimethyl-1 -butynyl)-1 -naphthyl(methoxy)carbamate

A solution comprising 1 .2 g of the product of Example 5, 5 ml triethylamine and 1 0 ml dimethylformamide was stirred. With stirring at 0°C, 0.8 ml 3,3-dιmethyl-1 - butyne, 0.1 2 g tπphenylphosphinepalladium chloride and 0.04 g copper iodide was added. The mixture was stirred for 18 hours at 20°C. The reaction mixture was poured into water and extracted with diethyl ether. The combined organic phases are washed with water, dried over magnesium sulfate and the solvent evaporated. The residue was chromatographed on silica using a mixture of heptane-ethyl acetate (9-1 ) as eluent, to give the title product m.p. = 98.4°C

Rf = 0.5 (heptane-ethyl acetate 1 -1 )

NMR (CDCI ₃ )

1 .35 (9H,s) tBu ; 3.78 (3H,s) OMe ; 3.80 (3H,s) OMe.

EXAMPLE 7

Methyl 7-[2-(trimethylsilyl)ethynyll-1 -naphthyl(2-propynyl)carbamate

A solution of 0.61 ml diisopropylamine in 1 5 ml tetrahydrofuran was stirred under an atmosphere of nitrogen at -60°C. 3 ml butyllithium (1 .6 M) was added. The temperature was allowed to rise to -20°C, the mixture cooled again to -60°C and a solution comprising 1 .32 g of the product of Example 1 3 (see later) in 1 0 ml tetrahydrofuran was added. The temperature was allowed to rise to -30°C and maintained at this temperature for 30 minutes. The mixture was cooled again to -60°C, the 0.50 ml propargyl bromide in 80% toluene solution introduced The mixture was stirred at room temperature for 18 hours, added to water and extracted with diethyl ether. The combined organic phases are washed with water, dried over sodium sulfate and the solvent evaporated. 2.0 g solid was obtained which was chromatographed on silica using a mixture of methylene chloride- toluene (50-50) as eluent, to give the title product, m.p. 1 38.1 °C. Rf : 0,25, CH ₂ CI ₂ -toluene (50-50) .

NMR (CDCI ₃ )

0,29 (9H,s) , Me ₃ Sι ; 2.27 ( 1 H,t) H-C--C-, 4, 1 3 ( 1 H,dl), 4,86 ( 1 H,dl) -CH N-CO , 3 63 (si), 3.70 (large) C0 ₂ Me IR (CHCI ₃ ) 3308 cm ¹ H-C≡C

21 53 c ¹ C≡C

1 701 cm ¹ C = 0

EXAMPLE 8 8-(methoxycarbonylamino)naphthalene-2-carboxylic acid

In an autoclave under a pressure of 10 bars of carbon dioxide, was placed a mixture of 40 g of the product obtained from stage A of Example 1 , 1 .2 g palladium diacetate, 3.5 g 1 ,3 bιs(dιphenyl)phosphιnopropane, 55 g potassium acetate and 400 ml dimethyl sulfoxide. The mixture was stirred for 24 hours at 20-25 °C. The reaction mixture was poured into 1 litre of water, 20 ml of aqueous

sodium hydroxide (400 g/l) was added and a litre methylene chloride. The organic phases were extracted with aqueous sodium hydroxide. The aqueous phases were acidified to pH = 1 with hydrochloric acid. The precipitate was air dried and washed with water. It was dried at 50°C to give the title product. m.p. = 230°C.

EXAMPLE 9

1 , 1 -dimethylethyl 8-(methoxycarbonylamino)naphthalene-2-carboxylate

2 g of the acid prepared in the last Example was added to 30 ml ethyl acetate at 20°C. 9.5 ml 0-tert-butyl-N,N-dιιsopropylurea was added portionwise with stirring over about one hour. The mixture was stirred for 1 7 hours at 20-25 °C, filtered and washed with ethyl acetate. The filtrate was left to dry and chromatographed on silica, using methylene chloride as eluent, to give the title product as a resin NMR (CDCI ₃ )

1 .65 (9H,s) ; 3.84 (3H,s).

Microanalysis:

H % N %

Calculated 6.35 4.65

Found 6.3 4.25

EXAMPLE 10

Methyl 7-[3-(4-trifluoromethylphenyl)-1 ,2,4-oxadιazol-5-yl] naphthylcarbamate

5 g of the product of Example 8 was added to 100 ml methylene chloride at 20°C I drop of dimethylformamide was added and then a suspension comprising 2 ml oxalyl chloride and 10 ml methylene chloride was added dropwise. The mixture was stirred over 2 hours and left to dry. It was taken up in toluene and 4.3 g 4-trιfluoromethylbenzamιdoxιme and 3.5 ml triethylamine added. The mixture was stirred for 2 hours at 20°C and heated under reflux for 1 7 hours. The residue was left to dry, taken up in methanol, and the crystals obtained dried and washed. After drying, the title product was obtained, m.p. 240°C.

EXAMPLE 1 1

Methyl 7-methoxy-1 -naphthyl(propargyl)carbamate

To a stirred suspension of sodium hydride (0.1 3 g) in dry dimethylformamide ( 1 5 ml) was added a solution of methyl 7-hydroxy-1 -naphthyl(propargyl)carbamate

(0.85 g) in dry dimethylformamide (25 ml). The mixture was stirred at room temperature for half an hour and then treated with a solution of methyl iodide (0.5 g) in dry dimethylformamide ( 10 ml). The mixture was stirred at room temperature for one hour, poured into ice water and extracted with ethyl acetate. The extract was washed, dried, filtered and solvent evaporated in the residue purified by silica gel column chromatography to give an oil which slowly crystallised. This was recrystalhsed from light petroleum (b.p. 60-80°C) to give the title product, m.p. 105-6°C.

Preparation of the starting material:

Methyl 7-hydroxy-1 -naphthyKpropargyllcarbamate

Methyl chloroformate (30 g) was added dropwise to a stirred solution of 7-hydroxy- 1 -naphthylamine (26.7 g) and pyridine (27 g) in dichloromethane (500 ml) . The mixture was stirred at room temperature for two hours, washed with water, dried, filtered and the solvent evaporated. The residue was purified by silica gel column chromatography to give methyl 7-methoxycarbonyloxy- 1 -naphthylcarbamate. A solution of this compound (27 5 g) in dry dimethylformamide ( 1 50 ml) was added to a suspension of sodium hydride (4 4g) in dry dimethylformamide ( 100 ml) with stirring The mixture was stirred at room temperature for one hour A solution of propargyl bromide ( 1 3 g) in dimethylformamide (50 ml) was added dropwise and the mixture stirred at room temperature for one hour, poured into ice water and extracted with ethyl acetate. The extract was washed with water, dried, filtered and the solvent evaporated The residue was purified by silica gel column chromatography and the product recrystalhsed from diisopropyl ether to give methyl 7-methoxycarbonyloxy- 1 -naphthyKpropargyllcarbamate, m.p. 1 84-5 °C.

A mixture of this product (1 5.65 g) and potassium carbonate (7.5 g) in methanol (500 ml) was stirred at room temperature for one hour. The solvent was evaporated, water added and the mixture extracted with ethyl acetate. The extract was washed, dried, filtered and the solvent evaporated. The residue was purified by silica gel column chromatography to give the desired starting material, m.p. 1 21 -2°C.

Example 1 2 onwards

In a similar manner to one of the previous examples the following compounds were obtained.

Ex Y X R m.p. (°C)

47 MeO-C(Me2>-C≡C- H CH=C-CH ₂ - 83

48 MeO-C(Me ₂ )-C≡C- H H 117

49 CH≡C-CH ₂ -0- H CH=C-CH ₂ - 84-5

50 EtCH(Me)-0- H CH≡C-CH ₂ - 113-4

51 Et ₂ CH-0- H CH≡C-CH ₂ - 82-3

52 HCF ₂ -0- H CH≡C-CH ₂ - 135-6

53 CH ₂ =CH-CH ₂ -0- H CH-EC-CH ₂ - 86-7

54 Pr'-O- H CH--C-CH ₂ - 144-5

55 BrCH ₂ -CH ₂ -0- H CH≡C-CH ₂ - 91-2

56 BrCF ₂ -CF ₂ -0- H CHsC-CH ₂ - 79-80

57 CH≡C-CH ₂ -0- 4-Cl CH≡C-CH ₂ - 171-2

Study of the Activity of the Compounds of the Invention

a) Study of the acaricidal activity against Tetranychus urticae.

Bean plants comprising two leaves infested with 30 female Tetranychus urticae per leaf were put under an aerated hood under an illuminated ceiling under constant light conditions. The plants were treated with a Fisher gun: 4 ml of toxic solution per plant of a mixture of water and acetone. The plants were allowed to dry over half an hour and then the infestation was allowed to proceed. The control of mortality was estimated at the end of 3 days.

Results: At a dose of 100 ppm or less, the following compounds of the invention show activity against Tetranychus urticae: 1 -3, 6, 7, 1 2-1 6, 24, 37, 40-4 and 47

Study of Fungicide Activity

Compounds are assessed for activity against one or more of the following: Phytophthora infestans: late tomato blight Plasmopara viticola: vine downy mildew Erysiphe grammis: f sp. horde/; barley powdery mildew Erysiphe graminis f. sp. tritici, wheat powdery mildew

Pyricularia oryzae: rice blast

Botrytis cinerea: grey mould

Venturia inaequalis: apple scab

Leptosphaeria nodorum: glume blotch Pellicuiaria sasakii: rice sheath blight

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 infestans 1 -4, 7, 24

P/asmoeara vitico/a

1 -7, 14, 17, 24-6, 31 , 35-6, 43, 45, 47, 57

Ervsiohe graminis: f sp. hordei 1 -4, 6, 7, 1 2- 14

Ervsiphe αraminis f. sp. tritici

3, 6, 1 6-1 9, 22-3, 26, 28-9, 31 -8, 40-2, 44-7

Pyricularia orvzae 2-4, 6, 7, 1 2-14, 1 7, 1 9, 21 -5, 32, 35, 39, 42-5, 47

Rntrytis cinerea

1 3, 25, 28, 31 -2, 36, 46

Venturia inaequalis

1-4, 6, 7, 15, 19, 23, 25, 31, 36, 44, 57

Leptosphaeria nodorum 22-3, 25-9, 31, 37, 47-8

Pellicularia sasakii

3, 6, 7, 13, 17-19, 21-3, 26, 28, 36, 42-4, 47, 52