GB2277090A - Fungicidal tetrahydropyrimidine and imidazoline derivatives - Google Patents

Abstract

Tetrahydropyrimidine and imidazoline derivatives of the general formula <IMAGE> or acid-addition salts thereof, in which m is 0 or 1; n is 0, 1, 2 or 3; R represents an optionally substituted alkyl, aryl or aralkyl group; R<1> represents an optionally substituted aryl group; and R<2> and R<3> independently represent a hydrogen atom or an optionally substituted alkyl group, are useful as plant fungicides.

Description

TETRAHYDROPYRIMIDINE DERIVATIVES This invention relates to certain tetrahydropyrimidine derivatives, a process for their preparation, compositions containing such compounds and their use as fungicides.

According to the present invention there is provided a compound of the general formula

or an acid-addition salt thereof, in which m is O or 1; n is O, 1, 2 or 3; R represents an optionally substituted alkyl, aryl or aralkyl group; R1 represents an optionally substituted aryl group; and R2 and R3 independently represent a hydrogen atom or an optionally substituted alkyl group.

When the compounds of this invention contain an alkyl substituent group, this may be linear or branched and may contain up to 12, preferably up to 6, and especially up to 4, carbon atoms.

An aryl group may be any aromatic hydrocarbon group, especially a phenyl or naphthyl group. An aralkyl group may be any alkyl group as defined above, preferably a C16 alkyl and especially a C14 alkyl group, substitued by an aryl group as defined above, especially a phenyl or naphthyl group. A benzyl group is a particularly preferred example of an aralkyl group.

When any of the foregoing substituents are designated as being optionally substituted, the substituent groups which are optionally present may be any one or more of those customarily employed in the development of pesticidal compounds and/or the modification of such compounds to influence their structure/activity, persistence, penetration or other property. Specific examples of such substituents include, for example, halogen atoms, nitro, cyano, hydroxyl, cycloalkyl, alkyl-cycloalkyl, alkyl, haloalkyl, alkoxy, haloalkoxy, amino, alkylamino, dialkylamino, formyl, alkoxycarbonyl, carboxyl, alkanoyl, alkylthio, alkylsulphinyl, alkylsulphonyl, carbamoyl, alkylamido, phenyl, phenoxy and halophenoxy groups. Typically, 0-3 substituents may be present.

When any of the foregoing substituents represents or contains an alkyl substituent group, this may be linear or branched and may contain up to 12, preferably up to 6, and especially up to 4, carbon atoms. A cycloalkyl substituent group may contain 3 to 8, preferably 3 to 6, carbon atoms. An aralkyl group may be substituted in the aryl and/or alkyl moiety.

It is preferred that R represents a C1-6 alkyl, phenyl or benzyl group, each group being optionally substituted by one or more substituents selected from halogen atoms, hydroxyl, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, C1-4 haloalkoxy, amino, C1-4 alkylamino, di-C1-4 alkylamino, C1-4 alkoxycarbonyl and carboxyl groups.

More preferably, R represents a C14 alkyl group optionally substituted by one or more substituents selected from halogen atoms, hydroxyl, C1-4 alkoxy, C1-4 haloalkoxy and amino groups.

It is also preferred that R1 represents a phenyl group optionally substituted by one or more substituents selected from halogen atoms, hydroxyl, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, C1-4 haloalkoxy, amino, C1-4 alkylamino, di-C1-4 alkylamino, C1-4 alkoxycarbonyl, carboxyl, phenyl, C3-6 cycloalkyl and C1-4 alkyl-substituted C3-6 cycloalkyl groups.

More preferably, R represents a phenyl group optionally substituted by one or more substituents selected from halogen atoms, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, C1-4 haloalkoxy, C3-6 cycloalkyl and C1-4 alkyl-substituted C3-6 cycloalkyl groups.

Preferably, R2 and R3 independently represent a hydrogen atom or a C1-6 alkyl group optionally substituted by one or more substituents selected from halogen atoms, hydroxyl, C1-4 alkoxy, C1-4 haloalkoxy, amino, C1-4 alkylamino, di-C1-4 alkylamino, formyl, C1 4 alkoxycarbonyl, carboxyl, phenyl, halophenyl and C1 4 alkylphenyl groups.

More preferably, R2 and R3 independently represent a hydrogen atom or a C1-4 alkyl group optionally substituted by one or more substituents selected from halogen atoms, hydroxyl, C1-4 alkoxy, C1 4 haloalkoxy and amino groups.

A particularly preferred sub-group of compounds of formula I is that in which n is O or 2; R represents a methyl group; R represents a dichlorophenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, trifluoromethylphenyl or methylcyclohexyl-phenyl group; R2 represents a hydrogen atom or a methyl group; and R3 represents a hydrogen atom.

The compounds of formula I may form acid-addition salts with a variety of acids. However, acid-addition salts with acids such as saccharin and mineral acids, particularly hydrochloric acid and hydriodic acid, are especially preferred.

It should also be appreciated that the compounds of formula I are capable of existing as geometric isomers. The present invention thus includes both the individual isomers and mixtures of such isomers.

The present invention also provides a process for the preparation of a compound of formula I as defined above, or an acid-addition salt thereof, which comprises reacting a compound of the general formula

or an acid-addition salt thereof, in which m, n, R and R3 are as defined above, with a compound of the general formula

in which R1 and R2 are as defined above.

The process is preferably carried out in the presence of a solvent. Suitable solvents include ethers, such as tetrahydrofuran, aromatic hydrocarbons, such as toluene, and alcohols, such as ethanol. The reaction is conveniently carried out at a temperature in the range from ambient temperature (about 15"C) to the reflux temperature of the reaction mixture, the preferred reaction temperature being from 50"C to the reflux temperature of the reaction mixture.

Compounds of formula II may be conveniently prepared by hydrogenating a compound of the general formula

or an acid-addition salt thereof, in which m, n, R and R3 are as defined above. Suitable hydrogenating agents include hydrogen with a metal catalyst, such as palladium on charcoal.

Compounds of formula IV may be prepared by conventional techniques, for example, those described in EP 0 019 450.

Compounds of formula III are known compounds or can be prepared by processes analogous to known processes.

The compounds of general formula I have been found to have fungicidal activity. Accordingly, the invention further provides a fungicidal composition which comprises a carrier and, as active ingredient, a compound of formula I or an acid-addition salt thereof as defined above. A method of making such a composition is also provided which comprises bringing a compound of formula I as defined above, or an acid-addition salt thereof, into association with at least one carrier. Such a composition may contain a single compound or a mixture of several compounds of the present invention.

A composition according to the invention preferably contains from 0.5 to 95% by weight of active ingredient.

A carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may for example be a plant, seed or soil, or to facilitate storage, transport or handling. A carrier may be a solid or a liquid, including a material which is normally gaseous but which has been compressed to form a liquid, and any of the carriers normally used in formulating fungicidal compositions may be used.

Suitable solid carriers include natural and synthetic clays and silicates, for example natural silicas such as diatomaceous earths; magnesium silicates, for example tales; magnesium aluminium silicates, for example attapulgites and vermiculites; aluminium silicates, for example kaolinites, montmorillonites and micas; calcium carbonate; calcium sulphate; ammonium sulphate; synthetic hydrated silicon oxides and synthetic calcium or aluminium silicates; elements, for example carbon and sulphur; natural and synthetic resins, for example coumarone resins, polyvinyl chloride, and styrene polymers and copolymers; solid polychlorophenols; bitumen; waxes, for example beeswax, paraffin wax, and chlorinated mineral waxes; and solid fertilisers, for example superphosphates.

Suitable liquid carriers include water; alcohols, for example isopropanol and glycols; ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic or araliphatic hydrocarbons, for example benzene, toluene and xylene; petroleum fractions, for example, kerosine and light mineral oils; chlorinated hydrocarbons, for example carbon tetrachloride, perchloroethylene and trichloroethane. Mixtures of different liquids are often suitable.

Fungicidal compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application. The presence of small amounts of a carrier which is a surface-active agent facilitates this process of dilution. Thus preferably at least one carrier in a composition according to the invention is a surface-active agent. For example the composition may contain at least two carriers, at least one of which is a surface-active agent.

A surface-active agent may be an emulsifying agent, a dispersing agent or a wetting agent; it may be nonionic or ionic.

Examples of suitable surface-active agents include the sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitol, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohol or alkyl phenols, for example -octylphenol or p-octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkali or alkaline earth metal salts, preferably sodium salts, of sulphuric or sulphonic acid esters containing at least 10 carbon atoms in the molecule, for example sodium lauryl sulphate, sodium secondary alkyl sulphates, sodium salts of sulphonated castor oil, and sodium alkylaryl sulphonates such as dodecylbenzene sulphonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

The compositions of the invention may for example be formulated as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols. Wettable powders usually contain 25, 50 or 75% w of active ingredient and usually contain in addition to solid inert carrier, 3-10% w of a dispersing agent and, where necessary, 0-10% w of stabiliser(s) and/or other additives such as penetrants or stickers. Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and may be diluted in the field with further solid carrier to give a composition usually containing h-10% w of active ingredient.Granules are usually prepared to have a size between 10 and 100 BS mesh (1.676 - 0.152 mm), and may be manufactured by agglomeration or impregnation techniques.

Generally, granules will contain -75% w active ingredient and 0-10% w of additives such as stabilisers, surfactants, slow release modifiers and binding agents. The so-called "dry flowable powders" consist of relatively small granules having a relatively high concentration of active ingredient. Emulsifiable concentrates usually contain, in addition to a solvent and, when necessary, co-solvent, 1-508 w/v active ingredient, 2-20% w/v emulsifiers and 0-20% w/v of other additives such as stabilisers, penetrants and corrosion inhibitors.Suspension concentrates are usually compounded so as to obtain a stable, non-sedimenting flowable product and usually contain 10-75% w active ingredient, 0.5-15% w of dispersing agents, 0.1-10% w of suspending agents such as protective colloids and thixotropic agents, 0-10% w of other additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation or as anti-freeze agents for water.

Aqueous dispersions and emulsions, for example compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the invention. The said emulsions may be of the water-in-oil or of the oil-in-water type, and may have a thick 'mayonnaise' like consistency.

The composition of the invention may also contain other ingredients, for example other compounds possessing herbicidal, insecticidal or fungicidal properties.

Of particular interest in enhancing the duration of the protective activity of the compounds of this invention is the use of a carrier which will provide a slow release of the fungicidal compounds into the environment of the plant which is to be protected. Such slow-release formulations could, for example, be inserted in the soil adjacent to the roots of a vine plant, or could include an adhesive component enabling them to be applied directly to the stem of a vine plant.

The invention still further provides the use as a fungicide of a compound of the general formula I as defined above or an acid-addition salt thereof or a composition as defined above, and a method for combating fungus at a locus, which comprises treating the locus, which may be for example plants subject to or subjected to fungal attack, seeds of such plants or the medium in which such plants are growing or are to be grown, with such a compound or composition.

The present invention is of wide applicability in the protection of crop plants against fungal attack. Typical crops which may be protected include potatoes, grain crops such as wheat and barley, rice, tomatoes, broad beans and apples. The duration of protection is normally dependent on the individual compound selected, and also a variety of external factors, such as climate, whose impact is normally mitigated by the use of a suitable formulation.

The invention is further illustrated by the following examples.

Example 1 Preparation of cis-4,6-dimethyl-2-(4-tert-butylbenzylidene hydrazino)-3,4,5,6-tetrahydropyrimidine hydrochloride (mcl; n-2; R-4-CH3, 6-CH; R1-4-tert-butylphenyl; R2-R3-H) (i) Preparation of cis-4,6-dimethyl-2-hydrazino-3,4,5,6 tetrahydropyrimidine hydrochloride A mixture of 4,6-dimethyl-2-hydrazinopyrimidine (11.9 g, 86 mmol), palladium on charcoal lOw/w% (3.0 g), concentrated hydrochloric acid (10 ml) and 90v/v% ethanol (190 ml) was hydrogenated in a Parr apparatus until hydrogen uptake ceased (50 C/483 KPa).Filtration and evaporation of the solvent gave cis-4,6-dimethyl-2-hydrazino-3,4,5,6-tetrahydropyrimidine hydrochloride (15.0 g) as a pale green foam which was used in the next step without further purification.

(ii) Preparation of cis-4 , 6-dimethyl-2- (4-tert-butylbenzylidene- hydrazino)-3,4,5,6-tetrahydropyrimidine hydrochloride The crude cis-4,6-dimethyl-2-hydrazino-3,4,5,6-tetrahydro- pyrimidine hydrochloride (1.3 g, 7.9 mmol) prepared in (i) above and 4-tert-butylbenzaldehyde (1.29 g, 7.9 mmol) in ethanol (20 ml) were refluxed for 2 hours. The solvent was then evaporated in vacuo and the resulting residue was purified by flash column chromatography using 6:1 toluene:ethanol as eluant. Evaporation of the product-containing fractions gave cis-4,6-dimethyl-2-(4-tert butylbenzylidene-hydrazino) -3,4,5, 6-tetrahydropyrimidine hydrochloride (1.1 g) as a pale yellow solid, m.pt. 180-184C.

Examples 2 to 11 By processes similar to those described in Example 1 above, further compounds according to the invention were prepared as detailed in Table I below. In this table, the compounds are identified by reference to formula I. Melting point and C, H, N analysis data for the compounds of Examples 2 to 11 are given in Table IA below.

Table I Example m n R R1 R2 R3 No.

2(HI salt) 1 2 4-CH3,6-CH3 4-C(CH3)3Phenyl -H -H 3(HCl salt) 1 2 4-CH3,6-CH3 4-(1-CH3-cyclo- -H -H hexyl) Phenyl 4(HCl salt) 1 2 4-CH3,6-CH3 4-CF3 Phenyl -H -H 5(HCl salt) 1 2 4-CH3,6-CH3 2,4-C12 Phenyl -H -H 6(HCl salt) 1 2 4-CH3,6-CH3 4-CH(CH3)2 Phenyl -H -H 7(HCl salt) 1 2 4-CH3,6-CH3 4-C2H5 Phenyl -H -H 8(HCl salt) 1 2 4-CH3,6-CH3 2-CH3 Phenyl -CH3 -H 9(HI salt) 1 0 - 4-C(CH3)3 Phenyl -H -H 1O(HI salt) 0 O - 4-C(CH3)3 Phenyl -H -H 11(HCl salt) 1 2 4-CH3,6-CH3 4-CH3 Phenyl -H -H Table IA Ex. M.Pt. C,H,N Analysis (%) No. C Calc.Found 2 217-221 C:49.28 H:6.57 N:13.62 C:49.28 H:6.57 N:13.41 3 130-180 (amorph.) 4 224-227 5 266-270 6 193-202 7 224-227 (Dec.) 8 175-178 9 147-153 10 202-206 11 193-196 Example 12 The fungicidal activity of compounds of the invention was investigated by means of the following tests.

(a) Activity against tomato early blight (Alternaria solani; AS) The test is a direct prophylactic one using a foliar spray.

Tomato seedlings (cv Outdoor Girl), at the stage at which the second leaf is expanded, are sprayed with a solution of the test compound in 1:1 water/acetone containing 0.04% "TWEEN 20" (Trade mark: a polyoxyethylene sorbitan ester surfactant). Plants are sprayed using a track sprayer equipped with 2 air-atomising nozzles. The concentration of the compound is 600 ppm and the spray volume is 750 1/aha. After drying, the plants are kept for 24 hours in a glasshouse at 20"C and 40% relative humidity followed by inoculation of the leaf upper surfaces with an aqueous suspension of A. solani conidia containing 1 x 10 conidia/ml.After 4 days in a high humidity cabinet at 21"C, disease is assessed based on the percentage of leaf surface area covered by lesions when compared with control plants.

(b) Direct protectant activity against tomato late blight (Phytophthora infestans; PIP) The test is a direct protectant one using a foliar spray.

Tomato plants with two expanded leaves (cv. First in the Field) are sprayed with the test compound at a dosage of 600 ppm as described under (a). After drying, the plants are kept for 24 hours in a glasshouse at 200C and 40% relative humidity. The upper surfaces of the leaves are then inoculated with an aqueous suspension containing 2 x 10 zoosporangia/ml. The inoculated plants are kept for 24 hours at 180C in a high humidity cabinet and then for 5 days in a growth chamber at 15"C and 80% relative humidity with 14 hours light/day. The assessment is based on the percentage of diseased leaf area compared with that on control leaves.

(c) Direct protectant activity against broad bean grey mould (Botrytis cinerea; BCB) The test is a direct protectant one using a foliar spray.

Broad bean plants (cv The Sutton) with two leaf pairs are sprayed with the test compound at a dosage of 600 ppm as described under (a). After drying, the plants are kept for 24 hours in a glasshouse at 20"C and 40% relative humidity. The upper surface of the leaves are then inoculated with an aqueous suspension containing 1 x 106 conidia/ml. Plants are kept for 4 days at 220C in a high humidity cabinet. The assessment is based on the percentage of diseased leaf area compared with that on control leaves.

(d) Activity against barley powder mildew (Erysiphe graminis f.sp.

hordei: EG) The test is a direct therapeutic one using a foliar spray.

Leaves of barley seedlings (cv Golden Promise) at the single leaf stage are inoculated by dusting with mildew conidia and kept in the glasshouse at 18"C and 40 relative humidity for 24 hours. Plants are then sprayed with the test compound at a dosage of 600 ppm as described under (a). After drying, plants are returned to the glasshouse at 18"C and 40% relative humidity for up to 7 days.

Assessment is based on the percentage of leaf area covered by sporulation compared with that on leaves of control plants.

(e) Activity against wheat eyespot in-vitro (Pseudocercosporella herpotrichoides; PHI) This test measures the in vitro activity of compounds gainst the fungus causing wheat eyespot. The test compound is dissolved or suspended in acetone and is added into 4 ml aliquots of half strength Potato Dextrose Broth dispensed in 25-compartment petri dishes to give a final concentration of 10 ppm test compound and 0.825% acetone. The fungal inoculum consists of mycelial fragments of P. herpotrichoides grown in half strength Potato Dextrose Broth in shaken flasks and added to the broth to provide 5 x 10 mycelial fragments/ml broth. Petri dishes are incubated at 20"C for 10 days until the assessment of mycelial growth.

(f) Activity against Rhizoctonia in-vitro (Rhizoctonia solani: RSI) The test measures the in-vitro activity of compounds against Rhizoctonia solani that causes stem and root rots. The test compound is dissolved or suspended in acetone and added into 4ml aliquots of half strength Potato Dextrose Broth dispensed in 25-compartment petri dishes to give a final concentration of 10 ppm compound and 0.825% acetone. The fungal inoculum consists of mycelial fragments of R. solani grown in half strength Potato Dextrose Broth in shaken culture flasks and added to the broth to provide 5 x 104 fragments/ml broth. Petri dishes are incubated at 20"C for 10 days until the assessment of mycelial growth.

(g) Activity against apple scab in-vitro (Venturia inaequalis; VII) This test measures the in-vitro activity of compounds against Venturia inaequalis that causes apple scab. The test compound is dissolved or suspended in acetone and added into 4ml aliquots of half strength Potato Dextrose Broth dispensed in 25-compartment petri dishes to give a final concentration of lOppm compound and 0.825% acetone. The fungal inoculum consists of mycelial fragments and spores of V. inaequalis grown on malt agar and added to the broth to provide 5 x 104 propagules/ml broth. Petri dishes are incubated at 20"C for 10 days until the assessment of mycelial growth.

The extent of disease control in all the above tests is expressed as a rating compared with either an untreated control or a diluent-sprayed-control, according to the criteria: 0 - less than 50% disease control 1 - 50-80% disease control 2 - greater than 80% disease control The results of these tests are set out in Table II below: Table II Example Fungicidal Activity No. AS PIP BCB EG PHI RSI VII 1 2 1 2 2 2 1* 1* 2* 3 2 2 1 2 2 2 4 2 2 1 5 2 6 2 1 7 1 2 8 1 9 2 10 2 11 2 2 2 * signifies concentration of test compound - 30 ppm

Claims (14)

1. CLAIMS 1. A compound of the general formula

   or an acid-addition salt thereof, in which m is O or 1; n is 0, 1, 2 or 3; R represents an optionally substituted alkyl, aryl or aralkyl group; R1 represents an optionally substituted aryl group; and R2 and R3 independently represent a hydrogen atom or an optionally substituted alkyl group.
2. 2. A compound according to claim 1 in which R represents a C16 alkyl, phenyl or benzyl group, each group being optionally substituted by one or more substituents selected from halogen atoms, hydroxyl, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, C1-4 haloalkoxy, amino, C1-4 alkylamino, di-C1-4 alkylamino, C1-4 alkoxycarbonyl and carboxyl groups.
3. 3. A compound according to claim 1 or claim 2 in which R represents a phenyl group optionally substituted by one or more substituents selected from halogen atoms, hydroxyl, C1-4 alkyl, C1-4 haloalkyl, C1-4 alkoxy, C1-4 haloalkoxy, amino, C1-4 alkylamino, di.C1-4 alkylamino, C1-4 alkoxycarbonyl, carboxyl, phenyl, C3-6 cycloalkyl and C1-4 alkyl-substituted C3-6 cycloalkyl groups.
4. 4. A compound according to any one of the preceding claims in which R2 and R3 independently represent a hydrogen atom or a C1-6 alkyl group optionally substituted by one or more substituents selected from halogen atoms, hydroxyl, C1-4 alkoxy, C1-4 haloalkoxy, amino, C1-4 alkylamino, di-C1-4 alkylamino, formyl, C1-4 alkoxycarbonyl, carboxyl, phenyl, halophenyl and C14 alkylphenyl groups.
5. 5. A compound according to any one of the preceding claims in which n is O or 2; R represents a methyl group; R represents a dichlorophenyl, methylphenyl, ethylphenyl, propylphenyl, butylphenyl, trifluoromethylphenyl or methylcyclohexyl-phenyl group; R2 represents a hydrogen atom or a methyl group; and R3 represents a hydrogen atom.
6. 6. A compound according to claim 1 as named in any one of Examples 1 to 11.
7. 7. A process for the preparation of a compound of formula I as defined in any one of the preceding claims, or an acid-addition salt thereof, which comprises reacting a compound of the general formula

   or an acid-addition salt thereof, in which m, n, R and R3 are as defined in any one of the preceding claims, with a compound of the general formula

   in which R1 and R2 are as defined in any one of the preceding claims.
8. 8. A process according to claim 7 substantially as hereinbefore described and with reference to Example 1.
9. 9. A compound of formula I whenever prepared by a process according to claim 7 or claim 8.
10. 10. A fungicidal composition which comprises a carrier and, as active ingredient, a compound of formula I or an acid-addition salt thereof as defined in any one of claims 1 to 6 or 9.
11. 11. A composition according to claim 10 which comprises at least two carriers, at least one of which is a surface-active agent.
12. 12. A method of combating fungus at a locus which comprises treating the locus with a compound of formula I or an acid-addition salt thereof as defined in any one of claims 1 to 6 or 9 or with a composition as defined in claim 10 or claim 11.
13. 13. A method according to claim 12 in which the locus comprises plants subject to or subjected to fungal attack, seeds of such plants or the medium in which such plants are growing or are to be grown.
14. 14. The use as a fungicide of a compound of formula I or an acid-addition salt thereof as defined in any one of claims 1 to 6 or 9 or with a composition as defined in claim 10 or claim 11.