CA1329612C - Compounds containing triazole or imidazole groups and tetrahydrofuran, use of these as fungicides and processes for the preparation thereof - Google Patents

Abstract

ABSTRACT
The invention relates to compounds of formula:

Description

- 1 - 13296~2 The present invention relates to new compounds for use in plant protection, to processes for their preparation and to intermediates useful in such processes. It also relates to the use of the new compounds as fungicides, to fungicidal compositions containing them and to use of the compounds for the control of fungal diseases of crops.
Numerous compounds, especially fungicides, containing triazole groups are already known, in particular, from European Patent Application No. 151,084 which describes compounds of the formula shown at the end of the description and their use as fungicides. The compounds of the present invention are novel and are not described in European Patent Application No.
151,084.
There is a continuing need for new compounds which have improved properties in the treatment of fungal diseases or which have an improved spectrum of activity and the applicants have discovered that certain new compounds represent, in some aspects of their activities, such an improvement.
The present invention accordingly provides compounds of formula (I) depicted hereinafter, wherein:
A represents a group (Y) n Ph-tCH2~ m ~ in which Ph a phenyl ring and m is 0 or 1, preferably o, Y is a halogen atom or a cyano or nitro group, or an optionally halogenated alkyl or alkoxy group, n is a positive integer 1, 2, 3, 4 or 5, or zero, the JJ:lcd -2- 132~612 groups Y being identical or different when n is greater than 1, Tr represents a 1,2,4-triazol-1-yl group and Im a 1,3-imidazol-1-yl group, Rl, R2, R3, R4 and Rs~ which may be identical or different, represent a hydrogen atom or a lower alkyl, lower cycloalkyl, aryl (preferably phenyl), aralkyl (preferably benzyl), lower alkoxy, lower alkanoyl or aroyl (preferably benzoyl) radical, these radicals being optionally substituted (for example, with one or more atoms or radicals such as halogen atoms and lower alkoxy radicals), Xl and X2, which may be identical or different,each represent a hydrogen atom; a halogen atom; a lower alkyl, lower cycloalkyl, aryl (preferably phenyl) or aralkyl (preferably benzyl) radical, these radicals being optionally substituted as hereinbefore defined for R1 to R5;
a Q-R6 group in which Q represents 0 or S, and R6 represents the hydrogen atom or a lower alkyl, lower cycloalkyl, aryl (preferably phenyl), aralkyl (preferably benzyl), acyl, aroyl or thioacyl (preferably acetyl, thioacetyl, propionyl, thiopropionyl or benzoyl) alkoxythioyl, aryloxythioyl or aralkyloxythioyl ithe term thioyl corresponds to C = S(S)] radical these radicals being optionally substituted as hereinbefore defined for Rl to Rs and _3_ 132~612 being identical or different when xl and x2 each represent CR6 or SR6;
an -NRt R9 group in which R8 and R3, which may be identical or different, represent the hydrogen atom or a lower alkyl, lower cycloalkyl, aryl (preferably phenyl) or aralkyl (preferably benzyl) radical, these radicals being optionally substituted as hereinbefore defined for R
to Rs~ or R8 and Rg may together form a divalent hydrocarbon radical, containing from 2 to 6 carbon atoms, one of the carbon atoms being optionally replaced by an oxygen, sulphur or nitrogen atom, the divalent hydrocarbon radical itself being optionally substituted (for example with one or more halogen atoms or optionally halogenated lower alkyl or lower alkoxy radicals or a hydroxy radical);
an N3 group, provided that X~ and X2 do not both represent N3;
or Xl and X2 togethex represent ~0 a group of formula -Q-~-Q- wherein Q is as hereinbefore defined and in which R~ is a divalent hydrocarbon radical, containing from 2 to 6 carbon atoms, one of the carbon atoms which is not attached directly to Q being optionally replaced by an oxygen or nitrogen atom, the divalent hydrocarbon radical being optionally substitute~ (for example, with one or more halogen atoms or lower alkyl, lower alkoxy or hydroxy radicals);

_ 4 _ 1 3 2 9 6 1 2 or Xl and X2 together represent an =N-RIo group in which Rlo represents a lower alkyl, lower cycloalkyl, aryl (preferably phenyl) or aralkyl (preferably benzyl) radical, or a group of formula ORIl in which Rll is a lower alkyl, aralkyl or aryl radical, these radicals being optionally substituted as hereinbefore defined for Rl to R5, or Rlo represents hydroxy; or Xl and X2 together represent = O or = S;
and with the proviso that if Xl is chosen from the group consisting of hydrogen, a lower alkyl radical, a lower cycloalkyl radical, an aryl radical or an aralkyl radical, X2 does not represent an atom or radical chosen from that group;
salts thereof and addition complexes thereof with metal salts.
More particularly, the present invention provides a compound according to the formula:

(Y)n ~ ~ R1 5 ~R3 Hall (Ia) W ~

in which the Rl-R5 groups correspond to a hydrogen atom, or to a cycloalkyl (C3-C6) or alkyl (Cl-C6) group, Hal corresponds to a bromine or chlorine atom, n is 1, 2 or 3, Y is a halogen JJ:lcd - 4a - 1329612 atom, a cyano group, a nitro group, alkyl (Cl-C6), alkoxy (C1-C6), haloalkyl (C1-C6) or haloalkoxy (C1-C6), W is a nitrogen atom, and X1 is selected from the group consisting of hydrogen, halogen, alkyl (cl-c6), cycloalkyl (C3-c6), phenyl, benzyl, halophenyl, halobenzyl, a Q-R~ group in which Q represents O or S and R~ represents hydrogen, alkyl (Cl-C6), cycloalkyl (C3-C6), phenyl, benzyl, halophenyl, halobenzyl, acetyl, thioacetyl, propionyl or thiopropionyl or an NR8 R9 group in which R8 and Rg may be identical or different, represents hydrogen, alkyl (C1-C6), cycloalkyl (C3-C6), phenyl or benzyl.
The salts according to the invention are preferably acceptable in agriculture and include the hydrochloride, sulphate, oxalate, nitrate or arylsulphonate; the addition complexes of the compounds of the invention with metal salts are preferably with iron, chromium, copper, manganese, zinc, cobalt, tin, magnesium and aluminum salts. The complexes may be prepared by known methods; for example, zinc complexes may be obtained by reacting a compound of formula I with zinc chloride.
In this specification and the accompanying claims it is to be understood that the adjective lower, when it qualifies an organic radical, means that the radical contains no more than six carbon atoms. Alkyl and alkoxy JJ:lcd 1329~2 radicals or moieties in this specification may be straight or branched-chain.
The compounds of formula I and compounds which may, if desired, be used as intermediates in the processes for their preparation, and which are described hereinafter, may exist in one or more isomeric forms depending on the number of asymmetric centres in the molecule. The invention relates to all the optical isomers as well as to their mixtures, in particular racemic mixtures, and to the corresponding diastereoisomers. The separation of the diastereoisomers and/or the optical isomers may be carried out according to methods known per se.
Preferred fungicidal compounds of the invention 15 are those of formula I in which Y is a halogen atom and n is 1, 2 or 3.
Compounds of formula I in which n is 1 or 2, and Y
is a halogen atom in the ortho and/or para position are especially preferred.
More preferably still, n is 2 and Y is halogen, advantageously chlorine, in the ortho and para positions.
Preferred compounds of the invention include those of formula I wherein Xz represents a halogen atom, such compounds being depicted in formula II in which Hal 25 represents a halogen atom, and those of formula I wherein X2 represents a group -QRs~ such compounds being depicted in formula III.

-- 1329~12 The triazole compounds of formula II in wh~-h Rl, R2, R3, R~ and Rs~ which may be the same or different, each represent a hydrogen atom or a lower cycloalkyl or alkyl group, Hal represents a halogen atom, preferably chlorine or bromine and Xl represents a halogen, preferably chlorine or bromine,or hydrogen atom,anc advantageously a hydrogen atom, are especiallv prer~red fungicidal compounds of the invention.
The triazole compounds of formula III in which Rl, R2, R3, R~ and Rs represent a hydrogen atom or a lower cycloalkyl or alkyl group, Y, n and m are as hereinbefore defined, Xl represents a hydrogen atom or an optionally substituted lower cycloal~yl or alkyl group, R6 represents a hydrogen atom or an optionally substituted lower cycloalkyl or alkyl group and the other symbols are as hereinbefore defined, are also preferred fungicidal compounds of the invention.
Preferred triazole compounds of for~ula II are those in which Rl, R2, Rl, R4 and Rs represent a hydrogen atom and the halogen atom(s~ within the definitions of Hal, X~ and X2 are the bromine or the chlorine atom.
Preferred triazole compounds of formu;a III are those wherein Rl, R2, R3, R~ and ~5 represent a hyd-oc,en atom, X1 represent a hydrogen atom or lower cycloal.'~yl or alkyl, ~6 represents an optionally substituted lo~e-cycloalkyl or alkyl group and preferably Q re-!eser.~s 0.
According to a feature o' the present in~er.;~on, compounds of formula Ia or II are prepared by a E`

-7~ 1 ~ 2 96 12 process which comprises: .
(a) reacting a haloketone of formula IIa (which may be obtained by a known process) wherein A and Rs are as hereinbefore defined and Z represents a halogen atom, with an organometallic compound of formula IIb, wherein M
represents an alkali metal or a magnesium-containing group (MgHal) or a zinc-containing group (ZnHal) in which Hal represents a halogen atom, to obtain a compound of formula IIc wherein the various symbols are as hereinbefore defined;
(b) reacting the compound of formula IIc with an unsubstituted triazole or imidazole in the presence of an organic or inorganic base, for example pyridine, triethylamine, sodium hydroxide, potassium hydro:-ide, carbonates and bicarbonates of alkali or alkaline earth metals, and in a solvent such as, for example, an alcohol, ketone, amide, nitrile or optionally halogenated aromatic hydrocarbon to obtain a compound of formula IId wherei the various symbols are as hereinbefore defined;
(c) reacting the compound of formula IId with a halogen or a mixed halogen preferably mole for mole, in an inert solvent such as a saturated hydrocarbon or an optionally halogenated aromatic hydrocarbon, to obtain a compound of formula IIe, wherein the various symbols are as hereinbefore defined;
(d) cyclization of the compound of formula IIe in the presence of an organic or inorganic base preferably at ambient temperature to obtain the compound of formula II or Ia.
To prepare compounds of formula Ia, precursor IIa is selected from compounds where m = 0 tsee definition of A) and a triazole is selected in step (b), above. To prepare compounds of formula II, precursors are selected such that m = 0 or 1 in compound IIa and a triazole or an imidazole may be used in step (b).
Step (a) is generally carried out in a solvent, preferably an ether such as diethyl ether or tetrahydrofuran, aliphatic, alicyclic or aromatic hydrocarbon such as hexane or toluene at a temperature from -50C to the reflux temperature of the reaction mixture and in a molar ratio of IIa:IIb which is preferably from 1.1 to 0.2. The reaction leads to the compound of formula IIc after neutralization of the reaction medium.
Step (b) is preferably carried out at a temperature of from 80C to the reflux temperature of the reaction mixture and in a molar ratio of IIc:imidazole or triazole which is preferably from 1.1 to 0.2, to obtain the compound of formula IId. The reaction generally passes through an epoxide intermediate of formula IIh which may, if desired, be isolated or prepared separately by known methods.
In step (d) the organic or inorganic base is, for example, a base listed in step b in a molar ratio of compound II:base which is preferably from 1.1 to 0.66: the reaction may be carried out in a protic or aprotic solvent (eg. water, JJ:
F

, ~ .

sa 1~3612 alcohol, ketone, nitrile, ester, saturated or optionally halogenated aromatic hydrocarbon, dimethyl sulphoxide or amide such as dimethylformamide).
A modification of the process described above for JJ:
F

-9- 13~9612 the preparation of the compounds of formula I wherein X2 represents a halogen comprises carrying out stage ~b) after stage (d), using the same reaction conditions for the different stages. Thus, the compound of formula IIc is reacted with a halogen or halogen halide (mixed halogenJ in an inert solvent to obtain a compound of formula IIf, the compound of formula IIf is then cyclized in the presence of an organic or inorganic base to obtain the compound of formula IIg, and the compound of formula IIg is then reacted with an unsubstituted triazole or imidazole group to obtain the compound of formula II.
According to a further feature of the invention compounds of formula I wherein X2 represents QR6, and X1 is other than Hal (compounds of formula III), are prepared by the reaction of a compound of formula II or IIg with a heteroatomic nucleophile of formula R6-Q-E, in which R6 and Q are as hereinbefore defined and E is a cation, for example an alkali or alkaline earth metal or a quaternary ammonium cation in the presence of a base and, optionally, a phase transfer catalyst and, when a compound of formula IIg is used as starting material, reaction of the compound of formula IIIa obtained with an unsubstituted triazole or imidazole. The reaction is generally carried out in a suitable solvent and at reaction temperatures which are generally from -30C to the reflux temperature of the reaction mixture and in a molar ratio III:R6QE which is preferably from 1.2 to 0.1.

-lo- ~329612 According to a further feature of the invention compounds of formula III wherein R6 is an optionally mono-or polyhaloqenated lower alkyl group, are prepared by reacting a compound of formula III or IIIa wherein R6 represents a hydrogen atom with an alkyl halide containing one or more halogen atoms in the presence of an organic or inorganic base and, when a compound of formula IIIa is used as starting material, by reaction of the compound obtained with an unsubstituted triazole or imidazole. A
molar ratio of III or IIIa:halide from 1.1 to 0.2 is generally used.
According to a further feature of the invention compounds of formula I wherein X2 represents a hydroxy group (i.e. compounds of formula III in which Q represents the oxygen atom and R6 the hydrogen atom), are prepared by the reaction of a compound of formula II or IIg with a metal (preferably an alkali metal or alkaline earth metal) hydroperoxide, hydroxide, oxide or superoxide. The reaction with the metal compound is generally carried out in the presence of an inert organic solvent, at a temperature from -30 to the reflux temperature of the reaction mixture, in a molar ratio which is preferably from 1.1 to 0.2.
According to a feature of the invention compounds Of formula I wherein X2 represents N3, are prepared by the reaction of a compound of formula II or IIg with an alkali metal or ammonium azide, preferably in a molar ratio of - ' 132g612 from 1.1 to 0.2, preferably in an aprotic solvent, at a temperature of from -30 to the reflux temperature of the reaction mixture and, when a compound of formula IIg is used, reaction of the compound thus obtained with an unsubstituted imidazole or triazole. When X2 in formula I
represents an alkoxythioyl, aryloxythioyl or aralkyloxythioyl group, the compounds of formula IIg or II
are reacted with an alkali metal or ammonium xanthate and, when a compound of formula IIg is used, the compound thus obtained is reacted with an unsubstituted triazole or imidazole.
According to a further feature of the invention compounds of formula I wherein X2 represents a hydroxy group, are prepared by the reaction of a compound of formula IIc or IId with a peroxide to obtain, respectively, an epoxide of formula IIIb or IIIc, hydrating the epoxides to obtain, respectively, the triols of formula IIId or IIIe, cyclising the triols in the presence of a dehydrating agent such as hydrochloric, hydrobromic, sulphuric or sulphonic acids, to obtain, respectively, the compounds of formula IIIa or III and reacting the compound of formula IIIa with an unsubstituted triazole or imidazole. The dehydration is carried out, if appropriate in a protic or aprotic solvent. Optionally, if necessary, the alcohol group may be protected in a manner known per se for compounds of formula IIId and IIIe.

Compounds of formula I wherein X2 represents a hydroxy group may be prepared by the reaction of a compound of formula II or IIg with an alkali metal or alkaline earth metal carboxylate, especially sodium benzoate, in the presence of a phase transfer catalyst and optionally in the presence of an aprotic polar inert solvent, if required in the presence of water, and at temperatures of from 0 to the reflux temperature of the reaction mixture and, when a compound of formula IIg is used, reaction of the compound thus obtained with an unsubstituted triazole or imidazole.
Compounds of formula I wherein X1 and X2 together represent -0 (compounds of formula IV wherein X1 represents the oxygen atom), are prepared by the oxidation of a compound of formula IIIa or III in which QR6 represents hydroxy and X1 represents hydrogen, to obtain a compound of formula IV or IVa and, when a compound of formula IIIa is used as starting material, reaction of the compound obtained with an unsubstituted triazole or imidazole. The gem-halogenated compounds (X1~X2-Hal) of formula I are prepared by reacting a phosphorus pentahalide with a corresponding ketone (a compound of formula IV or IVa in which X1 represents an oxygen atom), . optionally in the presence of an inert aprotic solvent and optionally in the presence of a quaternary ammonium halide, preferably at ambient temperature, and when the starting material is a compound of formula IVa, reaction of the compound obtained with an unsubstituted triazole or imidazole.
The compounds of formula T wherein Xl and X2 together represent -~ (compounds of formula IV wherein x represents the sulphur atom) are prepared by the thionation of a compound of formula IV or IVa wherein X
and Xz together represent ~0, for example, with H25 or P2S5 in a molar ratio which is preferably from 1.1 to 0.2, in the presence of an inert organic solvent (pyridine or hydrocarbon, for example) at a temperature of from 20 'o the reflux temperature and, when the starting material is a compound of formula IVa, reaction of the compound obtained with an unsubstituted triazole or imidazole.
The compounds of formula I wherein Xl and X2 simultaneously represent QR6 (ie. a compound of formula V) are prepared by the reaction of a compound of formula IV
or IVa in which Xl and X2 together represent ~0 or -S with a compound of formula HQR6 wherein Q is 0 or S in a molar ratio which is preferably from 1.1 to 0.2, in the presence of an acid catalyst and in a suitable solvent, which may be the alcohol or thiol itself, or an inert solvent such as hydrocarbons or alcohols and, when the starting material is a compound of formula IVa, reaction of the compound obtained with an unsubstituted triazole or imidazole.
Compoundc of formula I wherein Xl and X2 together represent -Q-R7-Q- and R7 is as hereinbefore defined may be prepared by the process described for the preparation of compounds of formula I wherein Xl and X2 simultaneously represent QR6 by using a compound HQ-R~-QH instead of HQR6 .
Compounds of formula I wherein X2 represents NR~Rg, are prepared by reacting a compound of formula II
or IIg with an amine of formula H-NR~Rg, generally in a molar ratio from 1.1 to q.2, optionally in the presence of another organic or inorganic base to obtain a compound of formula VI from the compound of formula II and a compound of formula VIa from the compound of formula IIg and, when a compound of formula IIg is used as starting material, reacting the compound obtained with an unsubstituted triazole or imidazole.
Compounds of formula I wherein Xl and X2 together represent - N-Rlo (ie. a compound of formula VII), are prepared by reacting a compound of formula IV or IVa with an amine of formula Rlo~NH2 or a salt thereof in a molar ratio which is preferably from 1.1 to 0.2, generally in an inert organic solvent and, when a compound of formula IVa is used as starting material, reacting the compound (of formula VIIa) thus obtained with an unsubstituted imidazole or triazole.
Compounds of formula I wherein Xl and Xz together represent =N-Rlo in which R~o represents a group ORll wherein Rll represents an optionally substituted aralkyl or lower alkyl radical are prepared by the reaction of a compound of formula VII in which R1o represents a hydroxy radical with an alkylating agent of formula R1,D in which R11 is an optionally substituted aralkyl or lower alkyl radicai and D represents, as a leaving group, a halogen, sulphonium, ammonium, sulphonate or sulphate group, in the presence of an organic or inorganic base, in order to obtain the oxime substituted on the oxygen.
The invention also relates to compounds which can be used as intermediates in the preparative processes described above: the compounds of formula II, IIc, IId, IIe, IIf, IIg, IIh, III, IIIa, IIIb, IIIc, IIId, IIIe, IV, IVa, V, Va, Vb, VI, VIa, VII and VIIa in which R1 to R6, Y, Tr, Im, m, n, Xl, X2, Q, Hal and Z are as hereinbefore defined are novel and as such constitute features of the invention.
The present invention also relates to the use of the compounds of formula I as fungicides.
The compounds according to the invention may be used for the preventive as well as curative control of fungi, especially of the basidiomycetes, ascomycetes, adelomycetes or fungi imperfecti, in particular rusts, mildew, cercosporella diseases, fusarium diseases, helminthosporium diseases, septoria diseases and rhizoctonia diseases of crops and of plants in general and, in particular, of cereals such as wheat, barley, rye, oats and their hybrids and also rice and maize. The compounds according to the invention are active, in particular, against fungi, especially of the basidiomycetes, ascomycetes, adelomycetes or fungi imperfecti type such as Botrytis cinerea, Erysiphe graminis, Puccinia recondita, Piricularia oryzae, Cercospora beticola, Puccinia striiformis, ~rysiphe cichoracearum, Fusarium oxysporum (melonis), Pyrenophora avenae, Septoria tritici, Venturia inaequaLis, Whetzelinia sclerotiorum, Monilia laxa, Myco-sphaerella fijiensis, Marssonina panettoniana, Alternaria soLani, Aspergillus niger, Cercospora arachidicola, Clado-sporium herbarum, Helm;nthosporium oryzae, Penicillium expansum, Pestalozzia sp., Phialophora c;nerescens, Phoma betae, Phoma foveata, Phoma lingam, Ustilago maydis, Verti-cillium dahliae, Ascochyta pisi, Guignardia bidwell;i, tO Corticium rolfs;i, Phomopsis viticola, Sclerotinia sclero-tiorum, Sclerotinia minor, Coryneum cardinale and Rhizoc-ton;a solani.
They also possess aCti Jity a~,~inst the following fungi: Acrostalagmus koningi, the Alternaria, t5 the ~olletotrichum, Corticium rolfsii, Diplodia natalensis, Gaeumannomyces graminis, Gibberella fujikuroi, Hormodendron cladosporioides, Lentinus degener or tigrinus, Lenzites quercina, Memnoniella echinata, Myrothecium verrucaria, Paecylomyces varioti, Pellicularia sasakii, Phellinus megaloporus, Polystictus sanguineus, Poria vaporaria, Sclerotium rolfsii, Stachybotris atra, the Stereum, Stilbum sp., Trametes trabea, Trichoderma pseudokoningi and Trichothecium roseum The compounds of the invention are of special in-terest because of their broad spectrum as regards cerea~diseases (milde~, rust, eyespot, net blotch, leaf spot and foot rot) They are also of special interest because of 132~612 their effectiveness against grey mould t~otrytis) and cercospora diseases and, because of this, they may be applied on crops as varied as grape vine, vegetable crops and tree crops and tropical crops such as peanut, banana, coffee, pecan nut and others.
In addition to the applications already described above, the products according to the invention additionally have an excellent biocidal activity with respect to many other kinds of microorganisms, among which there may be tO mentioned fungi such as those belonging to the genera:

Pullularia such as the species P. pullulans, Chaetomium such as the species C. globosum, Aspergillus such as the species Aspergillus niger, - Coniophora such as the species C. puteana.
O~ing to their biocidal activity, the products of the invent;on make it possible to control effectively microorganisms whose proliferation g;ves rise to numer-ous problems in the agricultural and industrial fields.
To this end, they are particularly well suited for the protection of plants or of industrial products such as wood, leather, paints, paper, ropes, plastics and indus-trial water circuits.
They are particularly well suited for the pro-tection of lignocellulose products and especially of wood,whether it is timber for furniture or construction, or timber which is exposed to bad weather such as timber for l ~2961~

fencing, vine stakes or railway sleepers.
The compounds according to the invention, used on their own or in the form of compositions as defined above in the treatment of wood, are generally employed with organic solvents and may, if desired, be used in combination with one or more known biocidal products such as pentachlorophenol, metal salts, especially copper, manganese, cobalt, chromium or zinc salts derived from inorganic or carboxylic acids (heptanoic, octanoic or naphthenic acids), organic complexes of tin, mercaptobenzothiazole, and insecticides such as pyrethroids or organochlorine compounds.
Finally, they have an excellent selectivity with respect to crops.

They are advantageously applied at doses of 0.005 to 5 kg/ha, and more specifically 0.01 to 0.5 kg/ha.
In practical use, the compounds according to the invention are rarely used alone. Most often they form part of compositions. The present invention provides compositions which may be used, inter alia to protect plants against fungal diseases, or in plant growth regulating compositions, which comprise, as active ingredient a compound of general formula I or a salt thereof or an addition complex thereof with a metal salt in association with an agriculturally acceptable carrier. The compositions generally also comprise an agriculturally acceptable sur~actant. Conventional inert carriers and conventional surfactants can be used.

1~296~2 _ 19 _ The term "carrier", in the present description, de-notes a natural or synthetic,organic or inorganic material, ~ith which the active substance is combined in order to facilitate its application to the plant, to seeds or to the soil. Therefore, this carrier is generally inert and it must be acceptable in agriculture, especially on the treated plant. The carrier may be solid (e,g, clays, natural or synthetic silicates, silica, resins, ~axes and solid fertilizers,) or liquid (e 5 water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons and liquefied gases) The surfactant may be an emulsif;er, dispersant or wetting agent of ionic or non-ionic type. For example, there may be mentioned poLyacrylic acid salts, t5 lignosulphonic acid salts, phenolsulphonic or naphthalene-sulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols tespecially alkylphenols or arylphenols), sulphosuccinic acid ester salts, taurine ZO derivatives (especially alkyltaurates), phosphoric esters of alcohols or of poLycondensates of ethylene oxide with phenols. The presence of at least one surfactant is gen-erally indispensable when the active substance and/or the inert carrier are insoluble in water and the vector agent for the application is water.
Therefore, for their application, the compounds of formula (I) are generally in the form of compositions;

~329612 these compositions according to the invention are them-selves in fairly diverse solid or liquid forms.
As solid forms of compositions, there may be men-tioned powders for dusting or scattering (~ith a content S of the compound of formula (I) up to 100,') and pellets, especially those obtained by extrusion, by com-pact;ng, by ;mpregnation of a granulated carrier, or by granulation starting from a powder (the content of the compound of formula (I) in these pellets being ~rom l to 80% in these latter cases).
As liquid forms of compositions, or forms intended to constitute liquid compositions when appl;ed, there may be mentioned solutions, especially water-soluble concen-trates, emulsifiable concentrates, emulsions, flo~ables, aerosals, wettable powders ~or powder for spraying) and pastes.
The emuls;fiable or soluble concentrates most fre-quently contain 10 to 80~ of active substance, whereas the emulsions or solutions ready for application contain, for their part, 0.01 to 20~ of active substance.
These compositions may also contain other'oypes of ingredients such as, for e~ample, protective colloids, adhesives, thickeners, thi~otropic agents, penetrants, stabili~ers and sequestering agents, as well as Z5 other knodn a;tive substances ~ith pesticidal properties (especially insecticidal or fungicidal properties) or properties ~hich promote plant gro~th (especially fertilizers) or plant growth regulating properties. More generally, the compounds according to the invention may be combined with solid or liquid additives which correspond to the usual techniques of formulation.
S for example, in addition to the solvent, the emulsifiable concentrates may conta;n, when necessary, 2 to 20% of suitable additives such as the stabilizers, sur-factants, penetrants, corrosion inhibitors, colouring agents or adhesives mentioned above.
In the case uhere the compounds according to the invention are used as fungicides, the doses to be used may vary ~ithin broad limits according, in particular, to the virulence of the fungi and the climatic conditions.
In general, compositions containing 0.5 to 5,000 ppm of active substance are very suitable; these values apply to the compositions ready for application.
Ppm denotes "parts per million". The range from 0.5 to 5,000 ppm corresponds to a range from S x 10 5 to 0.5X
(percentages by weight).
As regards compositions which are suitable for storage and transportation, they more advantageously con-tain from O.S to 95X (by weight) of active substance.
Thus, the compositions for agricultural use according to the invention may contain the aceive sub-stances according to the invention within very broad limits, ranging from 5.10 5X to 95X (by weight).
By way of example, the compositions of some ~329612 concentrates are given below: unless otherwise specified percentages are by weight, Example F (formulation) 1 Active substance 400 g/litre Alkali metal dodecyl benzenesulphonate 24 g/litre 10:1 ethylene oxide/nonylphenol condensate 16 g/litre Cyclohexanone 200 g/litre Aromatic solvent q.s. 1 litre According to another formula for an emulsifiable lO concentrate, the following are used:
Example F 2:
Active substance 250 9 Epoxide-treated vegetable oil 25 9 Mixture of alkylarylsulphonate, poly-15 glycol ether and fatty atcohols 100 9 Dimethylformamide 50 9 Xylene 575 9 From these concentrates, by dilution with water, it is possible to obtain emulsions of any desired concen-20tration, which are especially suitable for application onleaves.
Flowables, which can also be applied by spraying, are prepared so as to obtain 3 stable fluid product which does not settle; they usually contain from 10 to 75Y of 25active substance, from 0.5 to 15Y of surfactants, from 0.1 to 10% of thixo~ropic agents and from Q to 10% of suitable additives such as antifoams, corrosion inhibitors, stabi-lizers, penetrants 2nd adhesives, and, as a carrier, water - 23 - ~2~612 or an organic liquid in which the active substance is of low solubility or insoluble: solid organic substances or inorganic salts may be dissolved in the carrier to as-sist in preventing sedimentatisn, or as anti-freezes for S the ~ater.
The wettable powders (or powder for spraying) are usually prepared so as to contain 20 to 95~ of active sub-stance, and they usually contain, in addition to the solid carrier, from 0 to 5X of a ~etting agent, from 3 to 10% of tO a dispersant, and, when necessary, from 0 to 10% of one or more stabilizers and/or other additives such as penetrants, adhesives, anti-caking agents or colouring agents, ~ y way of example, various compositions of wet-table po~ders are given belov:
Example F 3:
Active substance Sû%
Calcium lignosulphonate (deflocculant~ SX
Isopropyl naphthalenesulphonate (anionic wetting agent) 1%
Z0 Anti-caking silica 5%
Kaolin (filler) 39X
Another composition of po~der for sPraying, at 70% strength, uses the following constituents:
Example F 4:
Active substance 700 9 Sodium dibutyl naphthalenesulphonate S0 9 Condensation product of naphthalenesul-- 24 - 1~29612 phonic acid, phenolsulphonic acid and formaldehyde in proportions 3:2:1 ~ 30 9 Kaolin 100 9 Whitener 120 9 Another composition of powder for spraying, at 40% strength, uses the following constituents:
ExampLe F S:
Active substance 400 9 Sodium lignosulphonate 50 9 Sodium dibutylnaphthalenesulphonate 10 9 Silica 540 9 Another composition of powder for spraying, at 25% strength, uses the following constituents:
Example F 6:
t5 Active substance 250 9 Calcium lignosulphonate 45 9 Mixture of whitener and hydroxyethyl-cellulose in equal parts by weight 19 9 Sodium dibutylnaphthalenesulphonate 15 9 Silica 1~5 9 Whitener 1gS g Kaolin 281 9 Another composition of powder for spraying, at 25X strength, uses the foilowing constituents:
Z5 Example F 7:
Active substance 250 9 Isooctylphenoxy-polyoxyethylene-ethanol 25 9 - ZS - 13296~

Mixture of whitener and hydroxyethyl-cellulose in equal parts by ~eight 17 g Sodium aluminosilicate 543 9 - Kieselguhr 165 9 Another composition of powder for spraying, at 10% strength, uses the following const;tuents:
Example F 8:
Active substance 100 9 Mixtur~ of sodium salts of sulphates ~a of saturated fatty acids 30 9 Condensation product of naphthalene-sulphonic acid and formaldehyde 50 9 Kaolin 820 9 To obtain these povders for spraying or wettable t5 powders; the active substances are intimately m;xed in su;table mixers with the add;tional substances, and the mixtures are ground in m;lls or other suitable grinders.
Powders for spraying are thereby obta;ned, the wettabil;ty and suspendability of which are advantageous; they may be suspended in vater at any desired concentration and these suspensions may be very advantageously used, es-pecially for application on plant leaves.
Instead of ~he wettable powders, pastes can be produced. The conditions and means of production and use ~5 of these pastes are similar to those for wettable povders or powders for spraying.
As already stated, the dispersions and aqueous - ~6 -emulsions, for example the compositions obtained ~Y dilut-ing uith water a wettable powder or an emulsifiable con-centrate according to the invention, are included within the general scope of the present invention. The emul-sions can be of the water-in-oil or oil-in-water type, and they may have a thick consistency like that of "mayon-na;se".
Gr~nulates intended for placing on the soil are usually prepared so as to be between 0.1 and 2 mm in size, la and they may be manufactured by agglomeration or impreg-nation. In general, the granulates contain 0,5 to 25% of active substance and 0 to 10~ of additives such as sta-bilizers, slo~-release modification agents, binders and solvents.
-According to an example of a.granulate composition, the following constituents are used:
E~ample F 9:
Active substance 5û 9 Epichlorohydrin 2.5 9 Cetyl polygLycol ether 2.5 9 Polyethylene glycol 35 9 Kaolin (particle size: 0.3 to 0.8 mm) 910 9.
In this particular case, the active substance is mixed with epichlorohydrin and dissolved in 60 9 of ace-tone; polyethylene glycol and cetyl polyglycol ether arethen added. The kaolin is wetted with the solution ob-tained and the acetone is then evaporated under vacuum.

132~612 A microgranulate o~ this type is advantageously used to control soil fungi, The compounds of formula (I) may also be used in the form of po~ders for dusting; a composition containing 50 9 of active substanse and 950 9 of talc can also be used; a composition containing 20 9 of active substance, 10 9 of finely divided silica and 970 9 of talc may also be used; these constituents are mixed and ground, and the mixture is applied by dusting.
Examples I to VII illustrate particular methods of preparing the compounds according to the invention as well as the compounds themselves, Example I: Preparation of 1-t4-bromo-2-(2,4-dichloro-phenyl)tetrahydrofuran-2-ylmethyl~-1H-1,2,4-triazole.
Compounds Nos. 1a,1b and 1a ~ 1b Stage a) Preparation of 1-chloro-2-(2,4-dichlorophenyl) 4-penten-2-ol:
An organomagnes;um derivative is preoared by add-ing a solution of allyl bromide (110 cc) in ethyl ether (7û0 cc) and tetrahydrofuran (200 cc) vith magnesium (110 9), bet~een 15 and 20C, over three hours. The mi~-ture is refluxed for 30 min and decanted, and the residue is ~ashed ~ith ether.
A solution of alpha,2,4-trichloroacetophenone ~ ~

- Z8 - ~3296~2 (175 9) in tetrahydrofuran (250 9) at -30C i5 added to this organic phase and the mixture is neutralized with acetic acid. This is ~ashed with water, dried over sodium sulphate, concentrated and then distilled under vacuum. A
colourLess oil is obtained (205 9). B.p. (3~10 2mm Hg) =
140-142C.
Stage b) Preparation of 1-C2-(Z,4-dichlorophenyl)-2-hydroxypenten-4-yl]-1H-1,2,4-triazole A mixture of the product obtained in stage a) 10 (106 9), triazole (55 9) and potassium carbonate (160 9) is heated in dimethylformamide (600 cc) at 120 for four hours. The insoluble materials are filtered and ~ashed with dimethylformamide, and the reaction mixture is con-centrated under vacuum. The residue, dissolved in tS methylené chloride, is washed with water and then concen-trated. The product is obtained by crystallization in ethyl acetate after dilution with heptane. A pale pink solid, m.p. 101, is isolated (97 9).
Stage c) Preparat;on of the compounds No. 1a and No. 1b Z0 The compound obtained in stage b (35 9) in chloro-form (200 cc) is treated with bromine at 0. After de-colorizing, the solvent is evaporated and the residue re-dissolved in methanol. An aqueous solution of potassium hydroxide is then added until a basic pH is obtained.
Z5 After evaporating the medium under vacuum, the residue is extracted with ethyl acetate, washed with water and con-centrated. The oil obtained (40 9) consists of a mixture - Z9 ~ 9 6 1 2 of two diastereoisomers in substantially equal propor-tions. Using silica column chromatography, the least polar isomer No. 1a: white crystals m.p. 83, and then the most polar isomer No. 1b: white crystals m.p. 94, are isolated in sequence. After recrystallization, 1a, m.p. 96 and lb, m.p. 104, are obtained. The 50:50 mixture of 1a and 1b has a melting point of 74.
The following compounds were prepared in the same way, using the appropriate raw materials: 1-C4-bromo-2-(4-ta chlorophenyl)tetrahydrofuran-2-ylmethyl)-1H-1,2,4-triazole:
1c: m.p. 74; 1d: m.p. 78 and 1c+d: m.p. 69.
Examplé II - Preparation of 1-t2-t2,4-dichlorophenyl)-4-hydroxytetrahydrofuran-2-ylmethyl]-1H-1,2,4-triazole.
Compounds No. 2a and No. 2b.
~he isomer (10 9) 1a of Example I, which is the least polar isomer, dissolved in chlorobenzene (3û cc), is refluxed for 48 hj in the presence of sodium benzoate (20 9) in ~ater (30 cc), and the phase transfer cata-lyst "ADOÇEN 464" methyltrialkylammonium chloride t1g).
After diluting with ether, the organic phase is washed with water and reduced under vacuum. The residue is then treated with methanol (10û cc) in the presence of po-tassium hydroxide (7 9) at reflux temperature for 3 hours.
The mixture is cooled, diluted with water and extracted with ethyl acetate, and the product washed to neutrality and purified by chromatography, the crude product being ob-tained after concentration under vacuum. The alcohol 2a is _ 30 _ 1329~12 isolated in the form of a white powder (2.8 g)~, m.p. 193.
Operating in the same way, starting from the most polar isomer lb obtained according to Example I, the optically active alcohol 2b is obtained in the form of a white powder, m.p. 162C. The 50:50 mixture of 2a and 2b is an oil.
Example III - Preparation of 1-[2-(2.4-dichlorophenyl~-4-ethoxytetrahydrofuran-2-ylmethvl~-lH-1 2.4-triazole.
Compounds No. 3a and No. 3b.
The alcohol 2a (2.2 g) dissolved in dimethylsulphoxide (12 cc) is treated, in sequence, with 80%
strength sodium hydride (0.42 g) and then with ethyl iodide (1.15 cc). After 15 minutes, the medium is diluted with water and extracted with ethyl acetate. After washing with water, the solvent is evaporated and the residue is purified by silica column chromatography to obtain a colourless oil which is the isomer 3a which crystallizes on trituration with pentane m.p.
90; in the same way, starting with 2b, the isomer 3b, which is a white powder, m.p. 63, is obtained. The 50:50 mixture of 3a + 3b is an oil. The compounds of formula VIII listed in the following table were obtained in the same way, using the appropriate alkyl halide or acid:

~-~ JJ:lcd No. X1 X2 Melting 4a H O-C-~ (phenyl) 98 4bOC-~ (phenyl) H 140 5a H OCH3 oil 5b O-CH3 H oil 6a H O-n-Pr oil 6b O-n-Pr H oil Example IV - Preparation of 1-t2-(2,4-dichlorophenyl)-4-ethylthiotetrahydrofuran-2-ylmethyl]-1H-1,2,4-tr;azole.
Compounds No. 7a and No. 7b The bromide la t3.8 9) dissoLved in dimethyl sul-15 phoxide (38 cc) containing ~ater t2 cc) is treated ~;thsodium hydrogen sulphide t2.8 9) for 2 hours. Po~dered potassium hydroxide (3.3 g) is then added, follo~ed by - ethyl iodide (4 cc). After 10 minutes of stirring, the 0edium is diluted ~ith ~ater and extracted ~ith ether.
20 After drying and evaporation, the isomer 7a, ~hich is a yello~ oil (3.9 9), m.p. 88, is obtained.

Operating in the same ~ay, starting ~ith 1b, 7b is obtained in the form of a paLe yello~ powder, m.p. 64.
The mixture of isomers is an oiL. The compounds of formula 25 VIII listed in the follo~ing table ~ere obtained in the same ~ay, using the appropriate thiols:

- 3Z ~ I 3 2 9~ I2 No.~ ¦ X1 ¦ Xz Melting point 8a H S-CH3 96 8b 5-CH3 H oil 9a H S-n-Pr i110 9b S-n-Pr H oil 10a H j S-Z-ClEt ,127 10b S-Z-ClEt I H ioil 11a H S-i-~u 68 11b S-i-au H oil ta 12a H S-i-Pr 75 1Zb S-i-Pr H 65 -Example V - Preparation of 1-[8-(2,4-dichlorophenyl)-1,4,7-trioxaspiro [4.4] nonan-8-~lmethyl]-lH-1,2,4-triazole Compound ~o. 13 5 Stage a) Preparation of 1-chloro-Z-(Z,4-dichlorophenyl)-3,4,5-pentanetriol.
The chlorohydrin obtained in stage a) of Exampie I
(91 9) is epoxidized in 1,2-dichloroethane (125 cc) in the presence of vanadyL acetylacetonate (5 9) and 70~ strength tert-butyl peroxide (ZOO cc) by heating at the reflux tem-perature for 48 hours. The cooled medium is diluted ~ith ~ater, ~ashed several times wi~h a sodium bisulphite sol-ution and then concentrated. The residue is then converted ~ 33 ~ ~32~612 to triol by heating in water (Z00 cc) and dioxane (200 cc) in the presence of perchloric acid (5 cc) for 3 hours.
After dilution with water, the medium is extracted with toluene (300 cc) and then concentrated.
Stage b) Preparation of 2-(2,4-dichlorophenyl)-2-chloro-methyltetrahydrofuran-4-one The oily residue obtained in stage a) is then heated in toluene (100 cc) and butanol (200 cc) in the presence of paratoluenesulphonic acid (0.5 9), with the separation of the water formed. After evaporating the re-action medium, the residue is chromatographed on a silica column (40:60 ethyl acetate/heptane eluant) to obtain a colourless oil (14.5 9) corresponding to a mixture of alcohol diastereoisomers, namely 2-(2,4-dichlorophenyl)-4-hydroxy-2-chloromethyltetrahydrofuran. This product ;s d;rectly oxid;zed ~;th chrom;c anhydr;de ;n acetic acid to obtain, after purification by s;l;ca column chromatography, furanone ;n the form of wh;te crystals, m.p. 99C.
0 Stage c) Preparation of 7-chloromethyl-7-(2,4-dichloro-phenyl)-1,4,6-trioxaspiro[4.4]nonane.
The furanone obtained in stage b) (4.2 9), in toluene (S0 cc), is heated at reflux temperature in the presence of ethylene glycol (6.5 cc) and p-toluenesulphonic acid (0.1 9), ~ith the separation of the water formed, until the disappearance of the starting product.
The medium is washed with sodium hydroxide and - 34 - ~ ~29612 -then diluted with water, extracted ~ith ether and concen-trated. A white solid (5.1 g), m.p. 99, is obtained.
Stage d) Preparation of compound 13 The halide of stage c) (5 9) in dimethyl sulphoxide (20 cc) is heated to 170 in the presence of triazolyl sodium t2.75 9) for 6 hours. The medium is poured into water, extracted with ethyl acetate, concentrated and puri-fied by silica column chromatography. After recryst3lli-zation in an ethyl acetate/heptane mixture, pale yello~
tO crystals (3.6 9), m.p. 1Z3, are isolated.
Example VI - Preparation of 1-C4-chloro-2-t2,4-dichloro-phenyl)-tetrahydrofuran-2-ylmethyl]-1H-1,2,4-triazole.
Compounds No. 14a and No. 14b Stage a) Preparation of Z-(2,4-dichlorophenyl)-1,4,5-~5 trichloro-2-pentanol.
The chlorohydrin obta;ned in stage a) of Example I
dissolved in dichloromethane (150 cc) is treated ~ith gaseous chlorine (13.4 g) at -15. The medium is then treated with a 37Z strength sodium bisulphite solution (15 cc), ~ashed with ~ater, dried and then evaporated.
A crude product in the form of a colourless oil (49.7 9) containing approximately 70Z of the desired product in the form of a mixture of two diastereoisomers is obtained.
Stage b) Preparation of 1-(Z,4-dichlorophenyl)-1-(2,3-dichloro-1-propanyl)oxirane A first method consists in dissolving the crude chlorohydrin (10.3 9) obtained in stage a) above in 132~612 methanol ~30 cc) and treating it ~ith a solution of m~~h-anolic potassium hydroxide (12 cc) at a concentration of 2 55 x 103 moles/litre, at ambient temperature. The pre-cipitate is filtered and the methanolic solution is evapor-ated under vacuum. The residue is purified by silica columnchromatography. A colourless oil is obtained (7.4 g) A second method consists in dissolving the chlorohydrin (19.9 9) obtained in stage a) of Example I in methanol (75 cc), and treating it ~ith a potassium hydro-~ide (4.9 9) solution in methanol (20 cc) at ambient tem-perature. After the filtration of the insoluble material and evaporation, epo~ide (17.1 9) is obtained in the form of a yello~ oil. This epo~ide is treated ~ith chlorine until the yello~ colour (1û 1 9) persists at -15C The medium is then vashed ~ith a sodium bisulphite solution follo~ed by ~ater, and then evaporated under vacuum. A
yello~ oil (20.8 9) consisting of a mixture of t~o diastereoisomers in a ratio of 45:55 is obtained.
Stage c) Preparation of 1-~4-chloro-2-(Z,4-dichlorophenyl) Z0 tetrahydrofuran-2-ylmethyl]-1H-1,Z,4-triazole The epo~ide obtained in stage b) (61 7 9) in 1-butanol (0.5 litre) is heated at 90 ~or 6 hours in the presence of triazolyl sodium (18.6 9). The inorganic precipitate is filtered and the butanol is evaporated The ZS residue is purified by silica column chromatography (48X
ethyl acetate:48~ heptane:4X methanol eluant) to ootain, in sequence, the fir,t diastereoisomer 14a, m.p., 113, and - 36 - 1~2~612 then the second diastereoisomer 14b, m.p. 97. The 50:50 mixture of 14a + 14b has a melting point of 90.
Example VII
Preparation of 1-~4-oxo-2-(2,4-dichLorophenyl)tetrahydro-furan-2-ylmethyl]-1H-1,2,4-triazole. Compounds 15 2nd 20 The alcohol 2a (37.7 g) is added at -60C to a solution of dimethyl sulphoxide (17 cc), in dichloromethane (120 cc), treated at -60 with a solution of trifluoro-acetic anhydride (25.4 cc) in dichloromethane (60 cc).
1~ After maintaining at -60 for half an hour, the temperature is allowed to rise to ambient temperature and triethylamine (48 cc). The medium is poured into water, extracted with dichloromethane and evaporated. A white powder (m.p. 91) is isolated by crystallization in e~her.
A mixture of ketone 15 ~3.1 9), phosphorus penta-chloride (2.3 g) and dichloromethane (30 cc) containing triethylbenzylammonium chloride (0.25 9) is stirred for 2 hours at ambient temperature until the starting material disappears. The medium is evaporated, diluted with water Z0 (100 cc), neutralized with sodium bicarbonate and extracted with ether. After drying and evaporation, the oily residue is recrystallized in isopropyl ether (twice). A white powder (0.6 9), m.p. 138, is o5tained. 1-t4,4-dichloro-2-(2,4-dichlorophenyl)tetrahydrofuran-2-ylmethyl~-iH-1,2,4-triazole, compound No. 20.

_ 37 _ 132~2 Example VIII - Preparation of 1-[4-dimethylamino-Z-(2 _ dichlorophenyL)tetrahydrofuran-2-ylmethyL]-1H-1,2,4-triazoLe. Compound 16 The ketone of example III and then sodium cyano-borohydride (0.24 g) are successively added to a solutionof potassium hydroxide (0.24 9) and d1methylam;ne hydro-chloride (1.05 9) in methanol. After 15 hours, the medium is diluted with vater and extracted with ether. The desired product is then extracted from the organic phase with 6N
hydrochloride acid (3 x 20 ml). After neutralization, ex-traction and silica column chromatography, compound No. 5 (1.6 9) is isolated in the form of a pale yellow oiL (50:50 mixture of 2 isomers).
Example IX - Preparation of 1-~4-methoxyimino-2-(2,4-dichlorophenyl)tetrahydrofuran-Z-ylmethyl]-1H-1,2,4-tr;azole. Compound 17.
The ketone of example III (29) in ethanol (30 cc) is heated under reflux in the presence of methoxylamine hydrochloride (5.8 cc of a 25~ solution in water) for 2 hours. The medium is diluted vith water, extracted with dichloromethane and evaporated. The product is isoLated by crystaLLization -in a mixture of diisopropyL ether and heptane, in the form of a white powder, m.p. 108 (mixture of the two geometric isomers).
Z5 ExampLe X
The compounds in vhich R11 = H (4-hydroxyimino) m.p. = 195 18 R11 = - ~(S-isopropoxyimino) oil 19 were prepared in the same manner.
Example X and those which follow illustrate the fungicidal applications of the compounds according to the S invention.
In these examples, the sprayings of solutions or suspensions of active substances are carried out under conditions such that the spraying of a solution or suspension of concentration equal to 1 g/litre corresponds on average to the application of approximately Z micrograms of active substance per cm2 of leaf area of the plant.
Under the conditions of Example X and those which follow, the compounds illustrated showed no phytotoxicity.
In these Examples, a product is regarded as pro-v;ding complete protection against a fungal disease when the protection is at least 95~; the protection is regarded as good ~hen it is at least 80% (but less than 95%), as fairly good uhen it is at least 70% (but less than 80%) and as average when it is at least 50% (but less than 70%).
In the present specification, the percentages are except where otherwise indicated and except those relatin~
to yields, percentages by weight. In the case where the percentages are expressed relative to the stoichiometry, these are molar percentages. As regards concentrations, some of these are expressed in ppm (part per million) - which corresponds to mg/litre.

1~29612 Example XI - In vivo test on 3Otrytis cinerea on tomato An aqueous emulsion of the active substance to be tested, having the following composition, is prepared by fine grinding:
active substance under test: 60 mg Tween*80 (surfactant consisting of an oleate of a polycondensate of ethylene oxide w;th a sorbi-tan derivative) diluted to 10% strength in water:
0.3 cc the volume is made up to 60 cc with water.
This aqueous emulsion is then diluted with water to obtain the desired concentration.
30- to 40-day-old, greenhouse-cultivated tomatoes (variety Marmande) are treated by spraying with diluted aqueo~s e.~ulsions (called slurries) as defined ab~ve and 2~ v~rious concentra~io~s of the compound to be te~ted, The tri 21 is re~licated twice with each concentration, After 24 or 48 hours, the leaves are cut and placed in 2 Petri dishes (diameter 14 cm) the base of Z~ which has previously been provided with a disc of moist filter paper (5 leaflets per dish).
The inoculum is then applied by means of 3 syringe by depositing drops (3 drops per Leaflet) of 3 SDOre SUS-pension. This suspension of 8Otrytis cinerea spores was obtained from a 15-day-old culture, which was then suSQen-ded in a nutrient soLution (100,000 units/cc).
Verification is carried out 3 and 6 days after ,~,~j ~ ' * trade-~ark the inoculation by comparison ~ith an untreated control.
Under these conditions, at a dose of 1 g/litre, a good or total protection is observed with compounds 1a, 1b, 1a + 1b, 3b, 5b, 6b, 8b, 9b, 12b, 14a, 14b, 14a + 14b and 17.
Example XII - In vivo test on Erysiphe graminis on barley (barley m;lde~) ~ arley, in pots, so~n in plain soil, is treated at the 10 cm height stage by spraying ~ith an aqueous ta emulsion (called slurry) at the concentration indicated belo~. The trial is replicated twice. After 24 hours, the barley plants are dusted uith Erysiphe graminis spores, the dusting being carried out using diseased plants.
Readings are taken 8 to 14 days after ;noculation.
Under-these condit;ons, the follo~;ng results are observed: at a dose of 1 g/litre, good or total protection ~ith 1a, 1b, 1a + 1b, 2a, 2b, 3a, 3b, 3a + 3b, 4a, 4b, Sa, Sb, 6a, 6b, 7a + 7b, 8a~ 8b, 13, 14a 14b, 14a + 14b, 15, 17, 19.
Example XIII - In vivo test on "Puccinia recondita" respon-sible for ~heat rust ~ heat, sown in plain soil in pots, is ~reated at the 10 cm height stage by spraying with diluted aqueous emulsions of the same composition as that described in Example VIII and at various concentrations of the com-pound to be tested. The trial is replicated t~ite a~ each csncentration.

~ 41 ~ 13296~2 - After Z4 hours, an aqueous suspension of spores (50,000 sp/cc) is sprayed onto the ~heat; this suspension was obtained from contaminated plants. The wheat is then pLaced for 48 hours in an incubation cell at approximately S 18C and at 10û% relative humidity.
After these 2 days, the relative humidity is louered to 60%. The condition of the plants is verified bet~een the 11th and the 15th days, after inoculation, by comparison with the untreated control.
At a dose of 1 g/litre, good or total protection ~ith compounds 1a, 1b, 1a + 1b, 3a, 3b, 3a + 3b, Sb, 6b, 7a, 7a + 7b, 8b, 12b, 13, 14a, 14b, 14a + 14b, 17 and 19.
Example XIV - In vivo test on "Piricularia oryzae"
-responsible for rice blast -Rice,-in pots, so~n in a 50:50 mixture of enriched peat and pozzolana, is treated at the 10 cm height stage by spraying ~ith an aqueous emulsion defined above at the concentration indicated below, The trial is repeated t~ice. After 48 hours, treatment is Zû carried out by applying on the leaves a suspension of spores obtained in pure culture.
Verification is carried out 8 days after inocula-tion. Under these conditions, the follo~ing results are observed: at a dose of 1 g/litre, good or tc~tal protec-tion ~ith compounds 1a, 1b, 1a + 1b, 3a, 3b, 6a, 8a, 8b,9a, 9b, 10b, 11a, 11b, 12a, 12b, 14a, 14b, 14a + 14~ and 15 ~

- 42 ~ 13296~2 Example XV - In vitro test on seed fungi and soil 'ungi The action of the compounds according to the invention is studied on the folLowing fungi responsible for diseases of cereals and other plants:
1) Pyrenophorae avenae 2) Septoria nodorum 3) Helminthosporium teres 4) Fusarium roseum 5). Fusar;um nivale 6) Fusarium culmorum 7) Rhizoctonia cerealis 8) Septoria tritici 9) Botrytis cinerea sensitive to carbendazime and to cyclic imides 10) Botrytis c-inerea resistant to carbendazime and to cyclic imides 11) Pseudocercosporella herpotrichoides 1Z) Fusarium oxysporum F. sp. melonis 13) Rhizoctonia solani 14) Helminthosporium gramineum The numbers ~hich appear before the names ~ill be used to represent these fungi in Table ( II) .
For each trial, the procedure is as follows: a nutrient medium consisting of potato, glucose and agar (PDA medium) is introduced suPercooled into a series of Petri dishes (Z0 cc per dish) after sterilizing in an autoclave at 120C.

In the course of filling the dishes, an acetone solution of the active substance is injected into the supercooled medium, to obtain the desired final concen-tration.
Petri dishes similar to the above, into which are poured similar quantities of a nutrient med;um which does not contain the active substance, are taken as control.
After Z4 or 48 h each dish is seeded by depositing a fragment of mycelium originating from a previous culture of the same fungus.
The dishes are stored for 2 to 10 days (depending on the fungus being tested) at 22C, and the growth of the fungus in the dishes containing the active substance to be tested ;s compared with that of the same fungus in the tS dish used as the control.
For each compound tested, the degree of ;nh;bition of the fungus considered, at a dose of 30 ppm, is thus determined. The results are given in the following table 44_ 132~612 -Compound ~ Fung i No. 1 1 1 2 ¦ 3 ¦ 4 ¦ 5 ¦ 6 ¦ 7 la I 100 1 lO0 1 100 1 95 1 100 ¦ 100 ¦ 95 1 b ¦ 100 ¦ 90 ¦ 100 ¦ 100 ¦ 100 ¦ 100 ¦ 90 1 la + lb ¦ 100 ¦ 95 ¦ 100 ¦ 95 ¦ 100 ¦ 100 ¦ 90 ¦
2a 1 50 1 95 1 80 150 1 80 1 100 1 80 1 2b ¦ 80 ¦ 110 ¦ 80 ¦50 ¦ 90 ¦ 90 ¦ 80 ¦
3a ¦ 95 1 ~ 90 1 100 1 50 1 80 1 80 1 90 1 3b 1 95 1 95 ¦ 100 ¦80 ¦ 90 ¦ 100 ¦ 90 ¦
3a +3b ¦80 1 0 1 80 1 0 180 180 1 80 4a 1 90 1 0 1 90 1 80 180 ¦90 1 90 4b ¦ 95 ¦ 80 ¦ 95 ¦ 80 180 ¦100 ¦ 90 5a 1 50 1 90 1 50 1 50 150 150 1 50 5b 1100 1100 !100 1 90 195 1100 1 95 6a 1 50 1 90 1 50 1 50 150 150 1 50 1 6b ¦100 ¦ 95 ¦ 95 ¦ 80 190 190 1 90 1 7a 1 -95 ¦95 1 95 ¦ 0 1 0 10 1 50 1 7b ¦ 95 1 90 ¦ 95 1 0 ¦ 0 10 1 50 ¦
7a + 7b ¦ 50 ¦ 95 ¦ 50 1 0 ~0 ¦ 0 ¦ 50 ¦
8a 1 95 180 1 95 180 150 1100 1 80 1 8b ¦ 100 ¦90 ¦ 95 ¦80 180 190 1 80 1 9a ¦ 95 ¦90 ¦ 95 180 180 190 1 80 1 9b ¦ 80 195 1 95 10 1 0 180 1 80 1 lOa I 80 1 0 1 80 150 190 195 ¦ 80 1 lOb ¦ 90 ¦80 ¦ 90 ¦0 ¦ 0 ¦50 ¦ 80 1 lla I 90 ¦ 50 ¦ 95 ¦ 0 ¦ 0 ¦0 ¦ 80 ¦
llb ¦ 90 ¦ 80 1 95 ¦ 0 ¦ 0 ¦0 ¦ 80 12a ¦ 90 ¦ 80 ¦ 95 1 0 180 180 1 80 1 12b ¦ 95 ¦90 ¦ 95 ¦80 180 190 1 80 ¦

1329~12 _ 4~ _ ..

Com~oundl Fungi ,~1 - I 1 I Z 1 3 1 4 15 1 6 1 7 13a ¦ -- ¦ 9 0 514a ¦ 95 ¦95 ¦100 ¦ 95 ¦100 ¦100 ¦ 90 14b ¦ 95 ¦90 ¦100 ¦ 9û ¦95 ¦100 ¦ 90 14a+14b ¦ 100 ¦95 ¦100 1 100 1100 ¦100 ¦ 95 1 o 195 180 1 0 10 150 1 _ _ _ Compoun~ Fungi ¦ 8 1 9 ¦10 ~ 12 1 13 ¦ 14 ¦
.
la ¦ 100 ¦ 100 1 100 ¦ 100 ¦ 100 ¦ 80 1 100 ¦
lb I - I 95 1 95 ¦ 100 ¦ 100 1 80 ¦ 1001 la +lb i100 ¦ 95 ¦ 95 ¦ 100 ¦ 100 ¦ 90 ¦ 951 2a ¦ 0 1 95 1 95 ¦ 100 ¦ 0 ¦ ¦ 80 ¦
2b ¦ 0 ¦ 80 ¦50 1100 ¦80 ¦ 0 1 801 3a ¦ 95 1 90 190 ¦95 10 ¦ 0 1 901 I0 3b ¦100 ¦ 95 ¦100 ¦95 ¦80 ¦ 80 ¦ 95 3a +3b ¦0 ¦ 80 ¦95 ¦0 ¦ 0 ¦ 0 j 80 ¦
4a 1 0 ¦ 95 ¦95 ¦0 ¦ 0 ¦ 0 ¦ 90 ¦
4b ¦ 0 ¦ 95 ¦95 ¦ 90 ¦ - 95 ¦ 0 ¦ 95 ¦
5a 1 0 ¦ 0 ¦0 ¦ 100 ¦ 0 ¦ 0 ¦ 501 5b ¦ 0 ¦95 ¦90 ¦100 ¦ 95 ¦90 1901 6a ¦ 0 ¦50 150 ¦100 ¦ 0 ¦ 0 ¦50 ¦
6b ¦ 50 ¦95 ¦95 ¦100 ¦ 80 ¦80 ¦95 ¦
7a 1 0 195 ¦95 ¦95 ¦ 0 ¦80 1801 7b ¦ 0 ¦90 ¦95 190 1 0 150 1501 20 7a +7b ¦ - ¦95 ¦95 1100 ¦ 50 ¦80 ¦50 ¦
8a ¦ 0 ¦80 ¦80 ¦80 ¦ 80 ¦80 ¦95 ¦
8b 1 0 ¦95 ¦95 190 ¦ 80 ¦80 ¦95 ¦
9a 1 0 190 190 ¦90 ¦ 80 ¦80 ¦951 9b ¦ 0 ¦95 ¦90 ¦100 ¦ 80 ¦80 ¦50 ¦
2'5 lOa I 50 180 1 0 I g 1 0 1 0 101 lOb ¦ 0 ¦90 ¦95 ¦80 ¦ 50 ¦50 ¦90 ¦
lla I 0 10 180 150 1 50 150 1951 llb ¦ 0 ¦80 ¦80 ¦80 ¦ 80 ¦80 ¦9S ¦
12a ¦ 0 ¦50 ¦80 ¦80 ¦ ¦80 ¦901 12b 1 0 195 ¦95 ¦90 ¦ 80 ¦80 ¦100 ¦
13a 1 _ 10 ¦ ¦100 ¦ 50 ¦ 0 1 _ 13296~2 --Compound I Fung i 1 8 19 110 ~ 12 113 ¦14 ¦
14a 1 - I100 1100 1100 1100 180 1100 14b ¦ 0 ¦95 ¦95 ¦100 ¦80 ¦80 ¦100 ¦
14a+14b ¦ 50 ¦95 ¦95 ¦100 ¦100 ¦80 ¦951 18 1 l l l l l l l 20 10 180 190 1lO0 150 180 1 90 1~29612 O ~ Rl EP 151084 A ¦ l ~ Tr or Im R~ X2 A ~ I\R4R3 (I) ~L Tr or Im _ 49 _ 1 3 2 9 6 ~ 2 Z >~ Rl IIa ~ R3R4 R2 IIb .

IIc R5 ~ R2 A~ X

R5~ ~ _I 5 ~/I

¦' R2 Im IIg R5 ~ R5 or Im ~Rl L/

II R5--~R )~<3 or Im 132961~

IIIa~

OH Xl R

~ ~ Rl 5 ~ ~`
z R3 R4 IIIc orTImR3 4 OH X R

S ~ ~R OH IIIe IIId or Im IVa ~1~ ~ 11 R5 or Im 2 R5 ~6 R2 R5~ 17-Rlo R5 ~ ~ ~ Q~R 7 Tr R / R3 A ol~R

VII~ 5 R5 Y~xl ` / ~ X

Claims (18)

1. A compound according to the formula:
(Ia) in which the R1-R5 groups correspond to a hydrogen atom, or to a cycloalkyl (C3-C6) or alkyl (C1-C6) group, Hal corresponds to a bromine or chlorine atom, n is 1, 2 or 3, Y is a halogen atom. a cyano group, a nitro group, alkyl (C1-C6), alkoxy (C1-C6), haloalkyl (C1-C6) or haloalkoxy (C1-C6), W is a nitrogen atom, and X1 is selected from the group consisting of hydrogen, halogen, alkyl (C1-C6), cycloalkyl (C3-C6), phenyl, benzyl, halophenyl, halobenzyl, a Q-R6 group in which Q represents O or S and R6 represents hydrogen, alkyl (C1-C6), cycloalkyl (C3-C6), phenyl, benzyl, halophenyl, halobenzyl, acetyl, thioacetyl. propionyl or thiopropionyl, or an NR8 R9 group in which R8 and R9 may be identical or different, represent hydrogen, alkyl (C1-C6), cycloalkyl (C3-C6), phenyl or benzyl.

2. A compound according to claim 1, in which Y is a halogen atom and n = 1, 2 or 3.

3. A compound according to claim 2, in which n = 1 or 2 and Y is a halogen atom placed in the ortho and/or para position.

4. A compound according to claim 3, in which Y is a chlorine atom.

5. The compound 1-[4-bromo-2-(2,4-dichlorophenyl)tetrahydrofuran-2-ylmethyl]-1H-1,2,4-triazole.

6. The compound 1-[4-chloro-2-(2,4-dichlorophenyl)tetrahydrofuran-2-ylmethyl]-1H-1,2,4-triazole.

7. A fungicidal composition which comprises, as active ingredient, a compound according to any one of claims 1 to 6 or an agriculturally acceptable salt thereof or an agriculturally acceptable addition complex thereof with a metal salt in association with an agriculturally acceptable carrier.

8. A fungicidal composition which comprises, 0.5 to 95 weight percent as active ingredient, a compound according to any one of claims 1 to 6 or an agriculturally acceptable salt thereof or an agriculturally acceptable addition complex thereof with a metal salt in association with an agriculturally acceptable carrier.

9. A method for the control of fungal diseases at a locus which comprises the application of an effective amount of compound according to claim 1 or a salt thereof or an addition complex thereof with a metal salt.

10. A method according to claim 9 for the control of fungal diseases of plants at a locus.

11. A method according to claim 10 which comprises the application of the active ingredient at a rate of 0.005 to 5 kg/ha.

12. A method according to claim 9 which comprises the application of the active ingredient at an application rate of 0.01 to 0.5 kg/ha.

13. A method for the control of fungal diseases of plants at a locus which comprises the application of an effective amount of compound according to any one of claims 2 to 6 or a salt thereof or an addition complex thereof with a metal salt.

14. A process for the preparation of the compound of Claim 1 comprising the steps of:
(a) reacting a haloketone of the formula:
IIa wherein Z represents a halogen atom;
with an organometallic compound of the formula:
IIb wherein M represents an alkali metal or a magnesium-containing group MgHal or a zinc-containing group ZnHal wherein Hal represents a halogen atom;

Claim 14 Cont'd.

to obtain a compound of the formula:

IIc (b) reacting the compound of formula IIc with 1,2,4-triazole in the presence of an organic or an inorganic base, in a solvent, to obtain a compound of the formula:
IId (c) reacting the compound of formula IId with a halogen or a mixed halogen in an inert solvent to obtain a compound of the formula:

IIe and (d) cyclization of the compound of formula IIe in the presence of an organic or an inorganic base to obtain the compound of Claim 1, wherein R1, R2, R3, R4, R5, Hal, X1, Y and n are as defined in Claim 1.

15. A method for the preparation of the compound of Claim 1 comprising the steps of:
(a) reacting a haloketone of the formula:
IIa wherein Z represents a halogen atom;

Claim 15 Cont'd.

with an organometallic compound of the formula:
IIb wherein M represents an alkali metal or a magnesium-containing group MgHal or a zinc-containing group ZnHal wherein Hal represents a halogen atom;

to obtain a compound of the formula:
IIc Claim 15 Cont'd.

(b) reacting the compound of formula IIc with a halogen or a mixed halogen in an inert solvent to obtain a compound of the formula:
IIf (c) cyclization of the compound of formula IIf in the presence of an organic or an inorganic base to obtain a compound of the formula:

IIg and (d) reacting the compound of formula IIg with 1,2,4-triazole in the presence of an organic or an inorganic base, in a solvent, to obtain the compound of Claim 1, wherein R1, R2, R3, R4, R5, Hal, X1, Y and n are as defined in Claim 1.

16. A compound of the formula:

IId wherein R1, R2, R3, R4, R5, X1, Y and n are as defined in Claim 1.

17. A compound of the formula:
IIe wherein R1, R2 R3, R4, R5, Hal, X1, Y and n are as defined in Claim 1.

18. A compound of the formula:

IIg wherein R1, R2, R3, R4, R5, Hal, X1, Y, Z and n are as defined in Claim 1.