GB2265371A - Isoxazole compounds - Google Patents

Abstract

Compounds of general formula <IMAGE> or salts thereof, wherein X represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heteroaryl or aryl group, but not including a hydroxyphenyl group; R represents a hydrogen or halogen atom, or an alkyl, haloalkyl, hydroxy, nitro, cyano or alkoxy group; and Q represents an optionally substituted aryl or heteroaryl group, are fungicidal. New compounds have the above formula where Q is <IMAGE> wherein R3 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl group; x represents 0, 1 or 2; R<4> represents a substituent; n represents 0, 1 or 2. Precursors of these compounds have the formulae:- <IMAGE>

Description

FUNGICIDAL COMPOUND8 This invention relates to the use of certain 3,5 disubstituted isoxazoles as fungicides, to fungicidal compositions containing such compounds, to certain novel compounds of this type, and to the preparation of such novel compounds.

3,5-Disubstituted isoxazole compounds are known for a variety of uses. For example, US 4172079 (Texaco Inc) discloses 4-nitro-isoxazoles substituted at the 3-position by an alkyl, aryl, aroyl or alkanoyl group and at the 5position by an alkyl group. Such compounds are stated to be both antimicrobial and anticorrosion agents. US 3879532 (Shell Oil) discloses that endoparasitic nematodes may be controlled with isoxazoles, for example, 3-chloroor 3,4-dichloro-5-(phenyl or halophenyl)-isoxazoles. US 4229204 (Monsanto Co.) discloses 3-trifluoromethylphenyl5-carboxyphenyl isoxazole derivatives, stated to be useful as herbicides and plant growth regulators.

The compound 3-methyl 5-[p-(methylsulphonyl)phenyl]- 4-isoxazolecarboxylic acid is referred to in Chem.Abs., 60, 5475d, 1966. J. Indian Chemical Society, 50(3) pages 213-214, discloses the preparation of 3-(hydroxyphenyl)-5arylisoxazoles and claims that such compounds show fungicidal activity. When 3-(2-hydroxyphenyl) -5- phenylisoxazole, a compound in accordance with the J.

Indian Chemical Society disclosure, was synthesized and tested during research work from which the present invention arose, it was found to have no discernable fungicidal activity in a range of tests against commercially important plant pathogenic fungi.

The present invention is based upon the discovery of the activity of certain 3,5-disubstituted isoxazole compounds and derivatives thereof, many of which are new, in combating fungi, including plant pathogenic fungi.

According to a first aspect of the invention, there is provided a method of combating a fungus at a locus, the method comprising treating the locus with a compound of general formula

or with a salt of a compound of general formula I wherein: X represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heteroaryl or aryl group, but not including a hydroxyphenyl group; R represents a hydrogen or halogen atom, or alkyl, haloalkyl, hydroxy, nitro, cyano or alkoxy group; and Q represents an optionally substituted aryl or heteroaryl group.

Unless otherwise specified in this specification, an alkyl moiety may be linear or branched and suitably contains up to 10, preferably up to 6, and most preferably up to 4 carbon atoms. An alkenyl or alkynyl moiety suitably contains up to 10, preferably up to 6, carbon atoms. A preferred optionally substituted alkenyl group is optionally substituted allyl. A preferred optionally substituted alkynyl group is optionally substituted propynyl. A cycloalkyl or cycloalkenyl moiety suitably contains 3 to 8, most preferably 6, carbon atoms.

A preferred optionally substituted aryl group is optionally substituted phenyl. A preferred optionally substituted heteroaryl group is optionally substituted pyridyl or optionally substituted thienyl.

Unless otherwise stated in this specification a salt of said compound of general formula I preferably represents an addition salt thereof. Suitably, said addition salt is provided by addition of a compound to a heteroatom of an optionally substituted heteroaryl moiety of said compound of general formula I. Suitably, said optionally substituted heteroaryl moiety is represented by substituent X. In this case, suitably, X represents a Nalkyl halide salt of an optionally substituted pyridyl moiety. Preferably, X represents an N-methyl iodide salt of an optionally substituted pyridyl moiety.

Unless otherwise stated in this specification, when any groups are designated as being optionally substituted, the substituent groups which are optionally present may be any of those customarily employed in the development of biocidal compounds, and/or the modification of such compounds to influence their structure/activity, persistence, penetration or other property. In relation to an alkyl, alkyl, or alkynyl moiety, specific examples of such substituents may include halogen, especially fluorine, chlorine or bromine atoms, and phenyl, alkoxy, hydroxy, cyano and (alkyl)amino groups. In relation to an aryl or heteroaryl moiety, optional substituents may include halogen atoms, for example fluorine, chlorine, bromine and iodine atoms, and nitro, cyano, alkoxy, hydroxy, (alkyl)amino, alkyl and haloalkyl (especially CF3) groups.Typically, 0-3 substituents may be present, most commonly 0 or 1.

Preferably, X as an optionally substituted aryl (preferably phenyl) group is optionally substituted by an optionally substituted alkyl group, a halogen atom, a nitro group, a cyano group or by a group of general formula -OCH2Rt wherein R1 represents a hydrogen or nalogen atom, a nitrile group, an optionally substituted alkyl, alkenyl, alkynyl, aryl or heteroaryl group or a salt thereof. More preferably, X represents an unsubstituted phenyl group or a phenyl group substituted by an alkyl, especially methyl, group, or halogen, especially a chlorine atom, or a group of general formula -OCH2Rt where Rl represents a hydrogen atom, a nitrile group, an alkyl group, a haloalkyl group, a phenyl group, or an acid addition salt of a pyridyl group.

Preferably, X represents an optionally substituted pyridyl group or a N-atom addition salt thereof, an optionally substituted thienyl, alkyl or cycloalkyl group or a phenyl group optionally substituted by an alkyl group, a halogen atom or a group of general formula -OCH2RI wherein Rl is in accordance with any definition given above.

Where X represents a pyridyl moiety or a thienyl moiety, suitably said moiety is unsubstituted. Where X represents an optionally substituted phenyl group, X is preferably unsubstituted or monosubstituted in the 2- or 4- position.

Preferably, Rl represents a hydrogen atom, a nitrile group, a trihalomethyl (especially trifluoromethyl) group, a N-methyl halide (especially iodide) group. Suitably, said N-methyl halide pyridyl group comprises a 3-pyridyl moiety.

Preferably, X represents 3-pyridyl, N-methyliodide-3pyridyl, 3-thienyl, methyl, t-butyl, phenyl, 4methylphenyl, 4-chlorophenyl, cyclohexyl, 2-methoxyphenyl, a 2'-(2-trihaloethyloxy)phenyl (especially 2'-(2trifluoroethyloxy)phenyl), 2- (cyanomethyloxy) phenyl, or 2 (N-methyliodide-3-pyridyl methoxy) phenyl.

R preferably represents a hydrogen or halogen atom, or a methyl, halomethyl, hydroxy, nitro, cyano or methoxy group.

R suitably represents a hydrogen or halogen atom.

Preferably, R represents. a hydrogen atom. When R is a halogen atom, suitably R represents a bromine atom.

Where X represents an optionally substituted phenyl moiety as stated in any of the preceding statements, preferably X does not represent trifluoromethylphenyl or a phenyl moiety substituted by a group -COOR2 wherein R2 is an optional substituent.

Where Q represents an optionally substituted phenyl moiety as stated in any of the preceding statements, preferably Q does not represent trifluoromethylphenyl or a phenyl moiety substituted by a group -COOR2 wherein R2 is an optional substituent.

Q suitably represents an optionally substituted phenyl group. Q may suitably represent a phenyl group, or a halophenyl group or a nitrophenyl group. Preferably, however, Q represents a group of general formula

wherein R3 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl group; x represents 0, 1 or 2; R4 represents a substituent; and n represents Q, i or 2.

The symbol n may suitably represent 1 and R4 then preferably represents a halogen atom, suitably, a chlorine atom, preferably in the 4-position. Preferably, however, n represents 0.

Suitably, R3 represents an optionally substituted alkyl, alkenyl or alkynyl group. Suitably, R3 represents an optionally substituted alkyl group Preferably, R3 represents an unsubstituted alkyl group, most preferably an unsubstituted ethyl or methyl group.

Preferably, the group -S(O),R3 is in the 2- or 4position. When R4 represents a substituent in the 4position suitably the group -S (O) XR3 is in the 2-position.

Suitably, the group -S(O),R3 represents a methylthio, ethylthio, methylsulphinyl, ethylsulphinyl, methylsulphonyl or an ethylsulphonyl moiety.

In the method according to the invention, as described above, the locus may be an agricultural or horticultural locus, for example plants subject to attack, seeds of such plants or the medium in which plants are growing or are to be grown. Compounds of the present invention have been shown to exhibit activity against a range of important fungi, including vine downy mildew, vine grey mould, barley powdery mildew, tomato early blight, wheat eyespot, seedling wheat blight and wheat brown rust.

Preferably, the method is a method of combating an undesired fungus at a locus. The method may comprise combating a fungus already present at a locus and/or prophylactic treatment at a locus. Suitably, the fungus is selected from Plasmopara viticola, Botrytis cinerea, leptosphaeria nodorum, Erysiphe graminis f.s.p. hordei, Puccinia recondita, Pyricularia oryzae, Alternaria solani, Pseudocercosporella herpotrichoides and Fusarium species.

Preferably, the fungus is selected from Plasmopara viticola, Botrytis cinerea, Leptosphaeria nodorum, Erysiphe graminis f.s.p. hordei and Pseudocercosporella herpotr icho ides The locus may convieniently be treated with the compound I at an application rate in the range 0.05-4 kg/ha, preferably 0.1-1 kg/ha.

The invention also provides the use of a compound of general formula I as defined, as a fungicide.

Further in accordance with the invention there is provided a fungicidal composition which comprises at least two carriers and, as active ingredient, a compound of general formula I, as defined in any of the statements above.

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, 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 biocidal compositions may be used. Preferably compositions according to the invention contain 0.5 to 958 by weight of active ingredient.

Suitable solid carriers include natural and synthetic clays and silicates, for example natural silicas such as diatomaceous earths; magnesium silicates, for example talcs; magnesium aluminium silicates, for example attapulgites and vermiculites,o 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; 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 kerosene and light mineral oils; chlorinated hydrocarbons, for example carbon tetrachloride, perchloroethylene and trichloroethane.

Mixtures of different liquids are often suitable.

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 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 p-octylphenol or g-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 are diluted in the field with further solid carrier to give a composition usually containing 0.5-10% 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 0.5-75% 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, 10-50% 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.

The invention extends to any novel compounds of general formula I per se.

In accordance with a further aspect of the invention there is provided a compound of general formula I per se or a salt thereof Der se wherein X represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heteroaryl or aryl group; R is as described in any of the preceding statements; and Q represents a group of general formula II as described in any of the preceding statements.

X may be as defined in any of the preceding statements.

Preferably, said compound is not a salt of a compound of general formula I.

Preferably, in a novel compound of general formula I, X represents an optionally substituted alkyl, cycloalkyl heteroaryl or aryl group as described in any of the preceding statements. More preferably, X represents an optionally substituted alkyl, cyclohexyl, thienyl or phenyl group. Suitably, X represents methyl, t-butyl, cyclohexyl, phenyl, methylphenyl or halophenyl groups.

Preferably, a thienyl moiety is a 3-thienyl moiety.

Preferably, in a novel compound of general formula I, when X represents a substituted phenyl group suitably said phenyl group is monosubstituted, preferably in the 4position. Preferred substituents of said phenyl group are a methyl group and a chlorine atom.

Preferably, in a novel compound~of general formula I, R represents a hydrogen atom.

The invention extends to a fungicidal composition which comprises a carrier and, as active ingredient, a novel compound of general formula I.

In accordance with a further aspect of the invention, there is provided a process for the preparation of a compound of general formula I, wherein X and R are as described in any of the preceding statements and Q represents a moiety of general formula II as described in any of the preceding statements, the process comprising reacting a compound of general formula

wherein X is as described in any of the preceding statements, Q represents a moiety of general formula II as described in any of the preceding statements and t1 and/or L2 represent leaving groups, with hydroxylamine or an acid salt thereof.

Suitably, wherein R of a compound of general formula I represents a hydrogen atom, both L1 and L2 are leaving groups. Wherein R does not represent a hydrogen atom, suitably L2 represents a leaving group and L1 is the same as R.

Suitably, L1 and L2 are halogen atoms, preferably the same halogen atoms. L1 and L2 may be introduced as a compound of formula Ll-L2. Most preferably Ll-L2 represents bromine.

Suitably, the reaction takes place in an aqueous solvent, for example, water and/or an alcohol, for example, ethanol. Suitably, a base is added and the reactants maintained at an alkaline pH, suitably about pH 8-9. Suitably, said base is an alkali metal hydroxide base, for example, potassium hydroxide.

The reaction is suitably carried out at a temperature above ambient temperature, preferably in the range 501500C, suitably at about 70-800C.

The product I is suitably extracted using an organic solvent, for example, dichloromethane, and preferably dried over a drying agent, for example, magnesium sulphate. The product I may be purified using column chromatography.

A compound of general formula III may be prepared as follows:

wherein X, L1 and L2 are as described in any of the preceding statements and Q represents a moiety of general formula II as described in any of the preceding statements.

Reaction (A) is suitably carried out in the presence of an aprotic organic solvent, for example, carbon tetrachloride. Preferably, compound Ll-L2, in said aprotic organic solvent, is added dropwise to compound IV also in said aprotic organic solvent.

Preferably, reaction A is carried out at a temperature in the range 0-6 OOC , more preferably, at ambient temperature.

Compounds of general formula III may be isolated by standard techniques, as required for subsequent process steps.

Compounds of general formula III are believed to be new and they and their preparation constitute further aspects of the invention.

A compound of general formula IV may be prepared as follows:

wherein X, R3, R4, n and x are as described in any of the preceding statements.

Reaction (B) is suitably carried out under standard conditions to effect a condensation reaction of compound V with compound VI. The reaction is suitably carried out in an aqueous solvent, suitably water and/or ethanol.

Suitably, the reaction is carried out in the presence of added base, for example, an alkali metal hydroxide base, for example, sodium hydroxide.

Preferably, the reaction is carried out at a temperature in the range -20 C to 500C, more preferably in the range OOC to ambient temperature.

Compounds of general formula IV may be isolated by standard techniques, as required for subsequent process steps.

Compounds of general formula IV are believed to be new and they, and their preparation, constitute further aspects of the invention.

A compound of general formula VI wherein x represents 0 may be prepared as follows:

wherein L3 is a leaving group, suitably a halogen atom, preferably a fluorine atom, and M+ is a metal cation suitably an alkali metal cation, preferably a cation of sodium or potassium.

Suitably, in reaction C, compound VII, suitably one equivalent thereof, is added to a suspension of M+SR3 in a polar aprotic solvent, for example, in dimethyl formamide (DMF), hexamethylphosphoric triamide (HMPT) or dimethylpropylene urea (DMPH). The reaction is suitably carried out at temperature above OOC, preferably in the range 20-500C. After standard work-up, a compound of general formula VI may be isolated by column chromatography By suitable choice of compound VII, in particular, the position of leaving group L3, ortho- and parasubstituted compounds VI can be obtained, as required.

A compound of formula VI wherein x represents 1 may be prepared by reacting a compound of formula VI wherein x represents 0 with an oxidizing agent, for example, with about one equivalent of a peracid, for example, metachloroperbenzoic acid. Suitably, the reaction is carried out in an organic solvent and preferably is carried out at a temperature in the range -200C to 500C most preferably at ambient temperature.

A compound of formula VI wherein x represents 2 may be prepared by reacting a compound of formula VI wherein x represents 0 with an oxidizing agent, for example, with about two equivalents, suitably 2.1 equivalents, of said aforementioned peracid, under conditions as described in the preceding paragraph.

Compounds of general formula VI are believed to be new and constitute further aspects of the invention.

Compounds of general formula V and VII are known and/or commercially available.

In accordance with a further aspect of the invention, there is provided a process for the preparation of a compound of general formula I, the process comprising reacting a compound of general formula

with a compound of general formula

wherein X is as described in any of the preceding statements, Q represents a moiety of general formula II as described in any of the preceding statements and L4 is a leaving group.

Suitably, L4 is a halogen atom, preferably a chlorine atom.

Suitably, the reaction is carried out in the presence of added base, suitably an organic base, for example, triethylamine. Preferably, the reaction is carried out at a temperature in the range -50 C to 500C, more preferably the reaction is carried out, at least in part, at a temperature in the range -100C to 10 C. Suitably, the reaction is carried out in an organic solvent, suitably an ethereal solvent, preferably, diethyl ether.

Towards the end of the procedure, suitably the reactant mixture is acidified, preferably with a protic acid, for example, concentrated hydrochloric acid. After a period of time, the pH of the reactant mixture is preferably raised by adding a base, suitably an inorganic base, for example, an alkali metal carbonate base, to a pH of about 10 and the product extracted and purified by standard techniques.

Compounds of general formula IX are believed to be new and constitute further aspects of the invention.

Compounds of general formula VIII and IX are suitably prepared in accordance with procedures as described in Gazz. Chim. Ital 1546, 76, 148 and Acta. Chem. Scand.

1984, 38B, 49 respectively.

Thus, a compound of general formula IX may be prepared by reacting a compound of general formula

with morpholine. Suitably, prior to reaction with compound of general formula X, a solution of titanium tetrachloride in an organic solvent, for example, in hexane, is added to morpholine also in an organic solvent, for example, in hexane and preferably under an inert atmosphere, for example, a nitrogen atmosphere. The mixture is then added to compound of general formula X and preferably refluxes.

Compounds of general formula X may be isolated by standard techniques, as required for subsequent process steps.

In accordance with a further aspect of the invention, there is provided a process for the preparation of a compound of general formula I, wherein Q represents a moiety of general formula II as described in any of the preceding statements and wherein x represents 1 or 2, the process comprising reacting a compound of general formula I wherein Q represents a moiety of general formula II as described above and wherein x represents 0, with an oxidizing agent.

Suitably, said oxidizing agent is a per-acid, preferably metachloroperbenzoic acid. To prepare a compound of general formula I wherein x represents 1, suitably a compound of general formula I wherein x represents 0 and the oxidizing agent are reacted in substantially equivalent amounts. To prepare a compound of formula I wherein x represents 2, suitably about two, preferably about 2.1 equivalents of said oxidizing agent are provided for each equivalent of said compound of formula I where x represents 0.

Compounds of general formula I wherein R and Q are as described in any of the above statements and wherein X represents a phenyl group substituted by a group of general formula -OCH2Rt as described above may be prepared by reacting a 3-(hydroxyphenyl)-5-phenylisoxazole with an alkyling agent of general formula R1C112t5 wherein L5 is a leaving group. The reaction is suitably carried out in the presence of added base, for example, an inorganic base, for example, potassium carbonate in an organic solvent, for example dimethylformamide or acetone. The reaction is suitably carried out at ambient temperature and the products isolated by standard techniques.

A 3-(hydroxyphenyl)-5-phenylisoxazole, more particularly 3-(2' -hydroxyphenyl) -5-phenylisoxazole, may be prepared by reacting flavone and hydroxylamine hydrochloride together in pyridine and/or water, suitably at an elevated temperature, suitably under reflux. Upon cooling, the reactants may be added to water and/or glacial acetic acid and the precipitate isolated by standard techniques. The phenylisoxazole may then be alkylated as described above to provide compounds of general formula I.

Compounds of general formula I wherein Q is as described in any of the preceding statements, may be prepared according to any of the aforementioned process steps by substituting the reference therein to Q respecting a moiety of general formula III to a reference to Q respecting a moiety described in any of the preceding statements. Alternatively, compounds of general formula I may be prepared by known methods, for example, using processes analgous to those described in the documents cited in the prior art section of this specification, where applicable. The reader may additionally refer to "Chemistry of Heterocyclic Compounds" (Weissberger 1962) Chapter 62 entitled "Isoxazoles and Related Compounds".

The invention will now be further described with reference to the following examples.

Example 1 PreParation of 3-henvl-5-F4'-(methvlthio)henvli isoxazole.

[ X=phenyl; R=H; Q= -phenyl-s(o)xR wherein x=O and R3= methyl; -S(o)XR3 group is para- located i) Preparation of 1-oxo-3-[4'-(methylthiopheyl)prop-2- enylbenz ene To an ice-cold solution of sodium hydroxide (3g, 75mml) in water (20ml) and ethanol (20ml) was added a solution of acetophenone (6.9ml, 59.05 mmol) in ethanol (lOml) with vigorous stirring. After one minute a solution of 4-methylthiobenzaldehyde (7.8ml, 58.7 mmol) in ethanol (10ml) was added in one portion. The resulting mixture was stirred at 0 C for 2 hours, then at ambient temperature overnight. Water was added and the product was extracted into dichloromethane.The combined organic extracts were dried over magnesium sulphate and concentrated to give a yellow oil which was purified by column chromatography on silica eluting with dichloromethane: petroleum ether (1:1). The title compound was obtained as a fine yellow powder (13.8g, 92%) Melting point: 76-77 C Analysis Calc: C: 75.6; H: 5.5 % Found: C: 75.6; H: 5.5 % ii) Prenaration of 1-oxo-2,3-dibromo-3-[4'- (methvlthio 'ohenvl Propylbenzene.

A solution of bromine (1.2g, 7.5 mmol) in carbon tetrachloride (5ml) was added dropwise over a period of 20 minutes to a solution of l-oxo-3-[ (4'-(methylthio) phenyl)] prop-2-enylbenzene (1.75g, 6.89 mmol) prepared in i) in carbon tetrachloride (45ml). On completion of the addition, the reaction mixture was stirred for a further 2 hours before being partitioned between dichloromethane and aqueous sodium carbonate. The organic phase was separated, washed with water and brine and then dried over magnesium sulphate.

Concentration gave a sticky solid which was extracted with petroleum ether to give the title compound as a white solid (2.25g, 79%).

Melting point 143-1450C.

Analvsis Calc: C: 46.4; H: 3.4 % Found: H: 46.3; H: 3.4 % iii) Preparation of 3-phenyl-5-[4'-(methylthio)phenyl] isoxazole To a solution of hydroxylamine hydrochloride (0.6g, 8.63 mmol) in water (5ml) was added a solution of l-oxo-2, 3-dibromo-3-[4'-(methylthio)phenyl] propylbenzene (3.25g, 7.85 mmol) in ethanol (30 ml). 50% aqueous potassium hydroxide was added dropwise until the pH was about 9 and the mixture was heated at 70-800C for 4 hours. Potassium hydroxide solution was added periodically to maintain the pH at 8-9. The mixture was allowed to cool, poured into water and the product was extracted with dichloromethane.

The combined extracts were dried over magnesium sulphate and evaporated in vacuo to give a crude product which was purified by column chromatography on silica, eluting with dichloromethane: petroleum ether (2:1). The title compound was obtained as a white powder (0.88g, 42%).

Melting point 138-1400C.

Analysis Calc: C: 71.9; H: 4.9; N: 5.2 % Found: C: 71.9; H: 4.9; N: 5.7 % Example 2 Preparation of 3-phenyl-5-[2'-(methylthio)phenyl] isoxazole (X=phenyl; R=H; Q = -phenyl-S(O)xR wherein x=O and R3=methyl; -S(O)x R group is ortho-located) i) Preparation of 1-{1-[(2'-methylthio)phenyl] ethen-lyl} morpholine A solution of titanium tetrachloride (3.9ml, 35.56 mmol) in hexane (100ml) was added over a period of 20 mins to an ice-cooled solution of morpholine (25ml, 0.286 mol) in hexane (100 ml) under a nitrogen atmosphere. The resulting yellow mixture was stirred in ice for a further 10 minutes before a solution of 2-(methylthio) acetophenone (8.2g, 49.33 mmol) in benzene (40ml) was added in one portion. The mixture was ref fluxed for one and a half hours, cooled and filtered.Evaporation of the filtrate in vacuo gave the title compound as a yellow oil (1l.6g, 100%) which was pure by 300 MHz 'H nmr; M+ 235.

ii) Preparation of 3-Dhenvl-5- T2'- (methvlthiolhenvl 1 isoxazole A solution of triethylamine (7 ml, 50.2 mmol) in diethyl ether (50 ml) was added over a period of 1 hour to an ice - cooled solution of 1 - {1 - [(2' methylthio)phenyl)ethen-l-yl} morpholine (11.6g, 49.29 mmol) and chlorobenzaldoxime (7.3g, 46.9 mmol) in diethyl ether (200 ml). The resulting mixture was stirred at ambient temperature for 26 hours, poured into water and the product was extracted with diethyl ether. The combined ethereal extracts were dried over magnesium sulphate and evaporated to give a yellow solid (16g).

The crude isoxazolidine (16g, 45.14 mmol) was suspended in methanol (200 ml) and concentrated hydrochloric acid (35 ml) was added dropwise with efficient stirring at 0 C. After stirring for 3.5 hours at ice-temperature, the methanol was removed and water was added to the residue. Solid sodium carbonate was cautiously added to adjust the pH to 10 and the product was extracted into diethyl ether. The combined extracts were dried over magnesium sulphate and concentrated to give an orange solid which was purified by chromatography on silica eluting with dichloromethane:hexane (1:1). The title compound was obtained as a white solid (9.72g, 81%).

Melting point 68-70 C.

Analvsis Calc: C: 71.9; H: 4.9; N: 5.2 % Found: C: 71.8; H: 5.0, N: 5.5 % Example 3 Preparation of 3 - phenyl - 5 - ( 2' methylsulphinylphenvl)isoxazole [X=phenyl; R=H; Q= -phenyl-S(O)xR3 wherein x=1 and R3=methyl; S(O)xR3 group is ortho-located] 3-phenyl-5-[2'-(methylthio)phenyl]isoxazole prepared in Example 2 was dissolved in dichloromethane (DCM). One equivalent of metachloroperbenzoic acid (MCPBA) was added and the reactants stirred at ambient temperature overnight. The reactants were purified by column chromatography on silica gel, eluting with trichloromethane to give the title compound.

Melting point 110 -1120C Analvsis Calc: C: 67.8; H: 4.6: N: 5.2% Found: C: 67.7; H: 4.5; N: 5.0 % Example 4 Preparation of 3 - phenyl - 5 - ( 2' methylsulphonylphenyl)isoxazole [X=phenyl; R=H; Q= -phenyl-S(O)R3 wherein x=2 and R3=methyl; -S(O),R3 group is ortho-located] 3-phenyl-5-[2'-(methylthio)phenyl]isoxzole prepared in Example 2 was dissolved in dichloromethane. 2.1 equivalents of metachloroperbenzoic acid (MCPBA) was added and the reaction carried out as described in Example 3.

Melting point 112-114 Analvsis Calc: C: 64.2; H: 4.4; N: 4.7% Found: C: 64.3: H: 4.4; N: 4:9 % Examples 5 to 39 By processes similar to those described in Examples 1 to 4 above, further compounds according to the invention were prepared as noted in Tables 1 and 2.

Elemental analysis data and melting point data (where appropriate) for the compounds of Examples 5 to 39 are given in Table 4 below.

Examples 40 to 43 By processes analgous to those described below, further compounds according to the invention were prepared as noted in Table 3. Elemental analysis data and melting point data (where appropriate) for the compounds of Examples 40 to 43 are given in Table 4 below.

Example 40 Preparation of 3-[2'-(alkyloxy)phenyl]-5-phenylisoxazole i) PreDaration of 3-(2'-HvdroxYphenyl)-5-shenvlisoxazole A solution of flavone (log, 44.55 mmol) and hydroxylamine hydrochloride (15g, 0.216 mol) in pyridine (80 ml) and water (40 ml) was refluxed for 21 hours. The solution was cooled and poured into water (500 ml) and glacial acetic acid (500 ml). The precipitated solid was filtered, washed with a small quantity of acetone and dried in vacuo at 500C to give the title compound as a white solid (8.22g, 78 %).

Melting point 232-233"C Analvsis Calc: C: 75.9; H: 4.7; N: 5.9 % Found: C: 74.2; H: 4.6; N: 6.8 % ii) General procedure for alkvlation of hvdroxvhenvl isoxazoles.

The alkylating agent (including optionally substituted and unsaturated alkylating agents) (1.1 equivalents) was added to a mixture of the hydroxyphenylisoxazole (1 equivalent) prepared in i) and potassium carbonate (2 equivalents) in dimethylformamide (or acetone) and the resulting mixture was stirred at room temperature for the approximate time (usually 3-15 hours).

Water was added to the mixture and the product was extracted with diethyl ether. The combined ethereal extracts were washed with brine, dried over magnesium sulphate and evaporated to give the crude products. All the isoxazoles were obtained as solids which could be purified by recrystallization or column chromatography with dichloromethane eluent.

TABLE 1

Example Q X R Number # (R4)n X R Position of -S(O)xR 1 - 0 methyl para- phenyl H 2 - 0 " ortho- " " 3 - 1 " " " " 4 - 2 " " " " 5 - 0 " " 3-pyridyl " 6 - 0 " " 3(N-methyliodide)-pyridyl " 7 - 1 " " phenyl BR 8 - 1 " para- " H 9 - 0 ethyl ortho " " 10 - 1 " " " " 11 - 2 " " " " TABLE 1 (continued)

Example Q X R Number as above (R4)n X R Position of -S(O)xR 12 - 1 ethyl ortho 4-chlorophenyl H 13 - 2 " " " " 14 - 1 methyl " " " 15 - 2 " " " " 16 - 0 " " 4-methylphenyl " 17 - 2 " " " " 18 - 0 " " methyl " 19 - 1 " " " " 20 - 2 " " " " 21 - 1 " " t-butyl " 22 - 2 " " " " 23 - 0 enthy " 4-methylphenyl " TABLE 1 (continued)

Example Q X R Number as above (R4)n X R3 Position of -S(O)R 24 - 1 ethyl ortho 4-methylphenyl H 25 - 2 " " " " 26 - 1 " " methyl " 27 - 2 " " " " 28 - 0 " " t-butyl " 29 - 1 " " " " 30 - 2 " " " " 31 4-chloro 0 methyl " phenyl " 32 " 1 " " " " 33 - 0 " " cyclohexyl " 34 - 1 " " " " 35 - 0 " " 3-thienyl " 36 - 1 " " " " 37 - 2 " " " " TABLE 2

Example No. Q X R 38 2-nitrophenyl phenyl H 39 2-bromophenyl phenyl H TABLE 3

Example No. Q X=2-OCH2R- R phenyl R 40 phenyl H H 41 " trifluoromethyl H 42 " nitrile H 43 " 3-(N methyliodide) H pyridyl TABLE 4

Example No. M.Pt. Analysis % C C H Found N Calc. Found Calc. Calc. Found 5 72-74 67.1 67.3 4.5 4.6 10.4 10.6 6 241-244 46.8 46.6 3.7 3.7 6.8 6.7 7 135-137 53.05 53.7 3.3 3.3 3.9 3.8 8 182-183 67.8 66.5 4.6 4.6 4.9 4.9 9 iol - - - - - 10 115 68.7 67.6 5.1 4.8 4.7 5.0 11 120.2 65.1 64.6 4.8 4.6 4.5 4.6 12 - 61.6 61.7 4.3 4.4 4.2 4.7 13 117.6 58.7 58.6 4.1 4.0 4.0 4.3 14 148 60.7 59.4 3.8 3.8 4.4 4.6 15 159 57.6 57.3 3.6 3.6 4.2 4.5 16 90.3 72.6 72.5 5.4 5.6 5.0 5.1 17 151 65.2 65.1 4.8 4.7 4.5 4.6 18 iol 64.4 65.0 5.4 5.8 6.8 7.4 19 75.6 59.7 59.7 5.0 5.0 6.3 6.2 20 90.3 55.7 55.8 4.7 4.7 4.9 5.8 21 106.7 63.8 64.0 6.5 6.5 5.3 5.7 TABLE 4 (continued)

Example No. M.Pt. Analysis % C C H N Calc. Found Calc. Found Calc. Found 22 131.9 60.2 59.6 6.1 6.0 5.0 4.8 23 70.8 73.2 74.0 5.8 6.0 4.7 5.4 24 128.5 69.4 69.2 5.5 5.2 4.5 5.0 25 87.8 66.0 66.3 5.2 5.0 4.3 4.7 26 iol 61.3 62.1 5.6 6.0 6.0 6.7 27 96.3 57.4 57.3 5.2 4.8 5.6 5.7 28 iol 68.9 69.4 7.3 7.5 5.4 6.0 29 iol 65.4 64.1 6.9 6.6 5.1 5.5 30 iol 61.4 62.2 6.5 6.3 4.8 5.8 31 92.3 63.6 64.0 4.0 4.2 4.6 5.0 32 142.2 60.5 60.0 3.8 3.9 4.4 4.7 33 iol 70.3 71.3 7.0 7.5 5.1 4.5 34 iol - - - - - 35 77.1 61.5 61.6 4.1 4.2 5.1 5.7 36 121.6 - - - - - 37 - - - - - - 38 84 67.6 68.2 3.8 3.8 10.5 10.8 39 60.7 60.0 60.4 3.4 3.7 4.7 4.9 TABLE 4 (continued)

Example No. M. Pt. Analysis % C C H N Calc. Found Calc. Found Calc. Found 40 56-57 76.5 76.7 5.2 5.2 5.6 5.9 41 157-159 63.95 63.9 3.8 4.0 4.4 5.1 42 117-119 73.9 73.9 4.4 4.5 10.1 10.4 43 162-165 56.2 56.5 4.1 4.1 6.0 6.4 Example 44 The fungicidal activity of compounds of the invention was investigated by means of the following tests.

(a) Antisporulant activity against vine downy mildew (PlasmoDara viticola: Pva) The test is a direct antisporulant one using a foliar spray. The lower surface of leaves of whole vine plants (cv Cabernet Sauvignon) are inoculated by spraying with an aqueous suspension containing 104 zoosporangia/ml 2 days prior to treatment with the test compound. The inoculated plants are kept for 24 hours in a high humidity compartment, then 24 hours at glasshouse ambient temperature and humidity. Infected leaves are sprayed on their lower surfaces with a solution of active material in 1:1 water/acetone containing 0.04% "TWEEN 20" (Trade Mark; a polyoxyethylene sorbitan ester surfactant). The spraying is carried out with a moving track sprayer giving an application rate of 1Kg/ha.After spraying, the plants are returned to normal glasshouse conditions for 96 hours and are then transferred to the high humidity compartment for 24 hours to induce sporulation, prior to assessment.

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

(b) Direct protectant activity against vine downy mildew (Plasmopara viticola; Pvp) This test is a direct protectant one using a foliar spray. The lower surfaces of leaves of whole vine plants (cv Cabernet Sauvignon) are sprayed with the test compound at a dosage of 1 kilogram of active material per hectare using a track sprayer as described under (a), and after a subsequent 24 hours under normal glasshouse conditions the lower surfaces of the leaves are inoculated by spraying with an aqueous solution containing 104 zoosporangia/ml.

The inoculated plants are kept for 24 hours in a high humidity compartment, 5 days under normal glasshouse conditions and then returned for a further 24 hours to high humidity. Assessment is based on the percentage of leaf area covered by sporulation compared with that on control leaves.

(c) Direct protectant activity against vine prey mould (Botrytis cinerea: Bcp) The test is a direct protectant one using a foliar spray. The lower surfaces of detached vine leaves (cv Cabernet Sauvignon) are sprayed with the test compound at a dosage of 1Kg/ha using a track sprayer as in (a). 24 Hours after spraying the leaves are inoculated with droplets of aqueous suspension containing 105 conidia/ml.

After a further 5 days in high humidity the percentage of leaf area covered by disease is assessed.

(d) Activity against wheat leaf spot (leDtosphAeria nodorum; Ln.) The test is a direct therapeutic one, using a foliar spray. Leaves of wheat plants (cv Mardler), at the single leaf stage, ate inoculated by spraying with an aqueous suspension containing 1 x 106 spores/ml. The inoculated plants are kept for 24 hours in a high humidity compartment prior to treatment. The plants are sprayed with a solution of the test compound at a dosage of 1 kilogram of active material per hectare using a track sprayer as described under (a). After drying, the plants are kept for 6-8 days at 20-250C and moderate humidity, followed by assessment. Assessment is based on the density of lesions per leaf compared with that on leaves of control plants.

(e) Activity against barlev powdery mildew (Erysiphe graminis f.s. hordei= Ea) The test is a direct therapeutic one, using a foliar spray. Leaves of barley seedlings, (cv Golden Promise) are inoculated by dusting with mildew condia one day prior to treatment with the test compound. The inoculated plants are kept overnight at glasshouse ambient temperature and humidity prior to treatment. The plants are sprayed with the test compound at a dosage of 1 kilogram of active material per hectare using a track sprayer as described under (a). After drying, plants are returned to a compartment at 20-25 C and moderate humidity for up to 7 days, followed by assessment.Assessment is based on the percentage of leaf area covered by sporulation compared with that on leaves of control plants (f) Activity against wheat brown rust (Puccinia recondita; Pr) The test is a direct protectant one using a foliar spray. Wheat seedlings (cv Brigand) are grown to the 1-1 leaf stage. The plants are then sprayed with the test compound at a dosage of 1Kg/ha using a track sprayer as described under (a). Test compounds are applied as solutions or suspensions in a mixture of acetone and water (50:50 v/v) containing 0.04% surfactant ("TWEEN 20" Trade Mark).

18-24 hours after treatment, the seedlings are inoculated by spraying the plants from all sides with an aqueous spore suspension containing about 105 spores/ml.

For 18 hours after inoculation, the plants are kept in high humidity conditions at a temperature of 20-22"C.

Thereafter, the plants are kept in ambient glasshouse conditions, that is, in moderate relative humidity and at a temperature of 20"C.

The disease is assessed 10 days after inoculation on the basis of the percentage of the plant covered by sporulating pustules compared with that on the control plants.

(g) Activity against rice leaf blast (Pyricularia orvzae: Po) The test is a direct therapeutic one using a foliar spray. The leaves of rice seedlings (about 30 seedlings per pot) are sprayed with an aqueous suspension containing 105 spores/ml 20-24 hours prior to treatment with the test compound. The inoculated plants are kept overnight in high humidity and then allowed to dry before spraying with the test compound at a dosage of 1 kilogram of active material per hectare using a track sprayer as described under (a). After treatment the plants are kept in a rice compartment at 25-300C and high humidity. Assessments are made 4-5 days after treatment and are based on the density of necrotic lesions per leaf when compared with control plants.

(h) Activity against tomato early blight (Alternaria solani: As) This test measures the contact prophylactic activity of test compounds applied as a foliar spray.

Tomato seedlings (cv Outdoor Girl) are grown to the stage at which the second true leaf is expanded. The plants are treated using a track sprayer as described under (a). Test compounds are applied as solutions or suspensions in a mixture of acetone and water (50:50, v/v) containing 0.04% surfactant ("TWEEN 20" - Trade Mark).

One day after treatment the seedlings are inoculated by spraying the leaf upper surfaces with a suspension of A. solani conidia containing 104 spores/ml For 3 days after inoculation plants are kept moist in a glasshouse compartment at or near 100% RH and 210C. Thereafter plants are kept under humid, but not saturated, conditions.

Disease is assessed 7 days after inoculation, based on the density and spread of lesions.

(i) Activity against wheat eyespot in-vitro 1Pseudocercosporella herDotrichoides PhI) This test measures the in vitro activity of compounds against the fungus causing wheat eyespot.

The test compound is dissolved or suspended in acetone and is added to molten half strength Potato Dextrose Agar to give a final concentration of 100 ppm compound and 3.5% acetone. After the agar has set, plates are inoculated with 6mm diameter plugs of agar/mycelium taken from 14 day old culture of P. hertotrichoides.

Plates are incubated at 200C for 12 days and radial growth from the inoculation plug is measured.

(j) Activity against Fusarium in-vitro (Fusarium species= FsI) This test measures the in vitro activity of compounds against a species of Fusarium that causes stem and root rots.

Compound is dissolved or suspended in acetone and added to molten half strength Potato Dextrose Agar to give a final concentration of 100 ppm compound and 3.5% acetone. After the agar has set, plates are inoculated with 6 mm diameter plugs of agar and mycelium taken from a 7 day old culture of Fusarium sp.

Plates are incubated at 20"C for 5 days and radial growth from the plug is measured.

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: - = test not carried out 0 = less than 50% disease 1 = about 50-80% disease control 2 = greater than 80% disease control The results of these tests are set out in Table 5 below: - TABLE 5

Fungicidal Activity Compound Pva Pvp Bcp Ln Eg Pr Po As PhI FsI Example No.

1 0 0 2 - 0 0 - - - 0 2 1 1 0 2 2 2 - 1 - 0 3 0 2 0 0 1 1 0 0 0 0 4 0 1 0 2 1 1 0 0 2 1 5 0 0 - 1 2 1 0 0 1 1 6 0 1 1 0 2 1 0 1 0 0 7 0 2 0 1 1 1 0 1 0 1 8 0 0 2 - 0 0 - - - 0 9 0 1 - 0 0 0 0 0 0 0 10 0 1 - 2 0 0 0 0 0 1 11 0 2 - 1 0 0 0 0 0 0 12 0 2 - 2 0 0 1 0 0 0 13 0 1 - - 0 0 0 0 0 0 14 0 0 - 2 0 0 0 0 0 0 15 0 0 - 0 0 0 0 0 0 1 16 0 0 - 1 0 0 0 0 0 0 TABLE 5 (continued)

Compound Pva Pvp Bcp Ln Eg Pr Po As PhI FsI Example No.

17 0 0 - 1 0 0 0 0 0 0 18 0 1 - - 0 0 0 0 0 1 19 0 0 - - 0 0 0 1 0 0 20 0 2 - - 0 0 0 1 1 0 21 1 1 - - 0 0 0 0 0 0 22 1 0 - - 0 0 0 0 0 0 23 0 1 - 0 0 0 0 1 0 0 24 2 2 - 1 0 0 0 1 0 0 25 0 2 - 0 0 0 0 0 0 0 26 0 0 - 0 0 0 0 1 0 0 27 0 0 - 0 0 0 0 1 0 0 28 0 1 - 0 0 0 0 0 2 0 29 0 0 - 0 1 0 0 0 0 0 30 1 0 - 1 0 0 0 0 0 0 31 0 0 - 1 0 0 0 1 0 0 32 0 1 - 2 0 0 0 1 0 0 33 0 0 - 0 1 0 0 0 0 0 TABLE 5 (continued)

Compound Pva Pvp Bcp Ln Eg Pr Po As PhI FsI Example No.

34 0 2 - 0 0 0 1 0 1 1 35 0 0 - 0 1 0 0 1 0 0 36 0 1 - 1 1 0 1 0 2 1 37 1 0 - 0 0 0 0 0 1 2 38 - - - - - 1 - - - 39 - 1 - - - - - - - 40 1 1 0 - 1 0 - - - 0 41 0 0 - - 1 0 - - - 0 42 0 1 - 0 0 0 0 0 0 0 43 0 2 - 0 0 0 0 2 0 0

Claims (23)

1. CLAIM8 1. A method of combating a fungus at a locus, the method comprising treating the locus with a compound of general formula

   or with a salt of a compound of general formula I wherein: X represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heteroaryl or aryl group, but not including a hydroxyphenyl group; R represents a hydrogen or halogen atom, or an alkyl, haloalkyl, hydroxy, nitro, cyano or alkoxy group; and Q represents an optionally substituted aryl or heteroaryl group.
2. 2. A method according to Claim 1, wherein X represents an optionally substituted pyridyl group or a N-atom addition salt thereof, an optionally substituted thienyl, alkyl or cycloalkyl group or a phenyl group optionally substituted by an alkyl group, a halogen atom or a group of general formula -OCH2Rt wherein Rl represents a hydrogen atom, a nitrile group, an alkyl group, a haloalkyl group, an alkynyl group, a phenyl or halophenyl group, or a pyridyl group or salt thereof 0
3. 3. A method according to Claim 1 or Claim 2, wherein R represents a hydrogen or halogen atom.
4. 4. A method according to any of the preceding Claims, wherein Q represents an optionally substituted phenyl group.
5. 5 A method according to any of the preceding Claims wherein Q represents a group of general formula

   wherein R3 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl group; x represents 0, 1 or 2; R4 represents a substituent; n represents 0, 1 or 2.
6. 6. A method according to Claim 5, wherein R3 represents an unsubstituted alkyl group.
7. 7. A method according to any of the preceding Claims, wherein said method is a method of combating an undesired fungus at a locus.
8. 8. Use of a compound of general formula I as defined in any of Claims 1 to 6, as a fungicide.
9. 9. A fungicidal composition which comprises at least two carriers and, as active ingredient, a compound of general formula I, as defined in any of Claims 1 to 7.
10. 10. A compound of general formula I per se wherein X represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, heteroaryl or aryl group; R represents a hydrogen or halogen atom, or an alkyl, haloalkyl, hydroxy, nitro, cyano or alkoxy group; and Q represents a group of general formula II as defined in Claim 5 or Claim 6.
11. 11. A process for the preparation of a compound of general formula I, wherein X, R and Q are as defined in Claim 10, the process comprising a) reacting a compound of general formula

    wherein X and Q are as defined in Claim 10 and Lt and/or L2 represent leaving groups, with hydroxylamine or an acid salt thereof; or b) reacting a compound of general formula

    with a compound of general formula

    wherein X and Q are as described in Claim 10 and L4 is a leaving group; or c) reacting an optionally substituted 3-(hydroxyphenyl)5-phenylisoxazole with an alkylating agent; or d) wherein Q represents a moiety of general formula II according to Claim 10 and wherein x represents 1 or 2, the process comprising reacting a compound of general formula I as described in Claim 10 and wherein x represents 0, with an oxidizing agent.
12. 12. A compound of general formula I as claimed in Claim 10, when prepared by a process as claimed in Claim 11.
13. 13. A fungicidal composition which comprises a carrier and, as active ingredient, a compound of general formula I as defined in Claim 10.
14. 14. Use as a fungicide of a compound of general formula I as defined in Ciaim 10 or Claim 12 or a composition as claimed in Claim 13.
15. 15. A compound of general formula III as defined in Claim 11 rer se.
16. 16. A process for the preparation of a compound of general formula III as defined in Claim 11, the process comprising reacting a compound of general formula

    with Ll-L2, wherein X, Q, L1 and L2 are as defined in claim 11.
17. 17. A compound of general formula rV as defined in claim 16 per se.
18. 18. A process for the preparation of a compound of general formula IV as defined in Claim 17, the process comprising reacting a compound of general formula

    with a compound of general formula

    wherein X is as defined in claim 1 and x, n, R3, R4 are as defined in claim 5.
19. 19. A compound of general formula VI as defined in claim 18 ner se.
20. 20. A process for the preparation of a compound of general formula VI as defined in Claim 19 wherein x=O, the process comprising reacting a compound of general formula

    with M±SR3, wherein R3, R4 and n are as defined in claim 18 and M+ is a metal cation.
21. 21. A compound of general formula IX as defined in claim 11 Per se.
22. 22. A process for the preparation of a compound of general formula IX, as defined in claim 21, the process comprising reacting a compound of general formula

    wherein Q is as defined in claim 5, with morpholine.
23. 23. A novel compound of general formula I, as defined or named herein; or a process for the preparation of such a compound; or a fungicidal composition comprising a compound of formula I; or a fungicidal method or use; or any novel intermediate or preparation thereof; any such aspect being substantially as herein described with reference to the examples.