FR2638454A1 - NOVEL HETEROCYCLIC COMPOUNDS, PROCESS FOR THEIR PRODUCTION AND THEIR USE AS FUNGICIDES AND PLANT GROWTH SUBSTANCES - Google Patents

Abstract

The invention relates to novel heterocyclic compounds, their acid addition salts and metal complexes, as well as their stereoisomers, and their preparation. The compounds of the invention correspond to the formula: (CF DRAWING IN BOPI) in which R is an optionally substituted phenyl radical; R ** 1, R ** 2, R ** 3 represent H, a halogen or an alkyl or trialkylsilyl radical; R ** 4 represents H or an alkyl group, with the proviso that R ** 1 to R ** 4 do not all represent H and that when R ** 1 and R ** 2 represent H, R ** 3 is not an alkyl group; and R ** 5 is hydrogen or an organic group. Application: fungicides and substances influencing plant growth.

Description

The present invention relates to triazole derivatives which are useful

  fungicides and as substances influencing plant growth, methods for obtaining them, fungicidal compositions containing them and a method for combating fungi, especially fungal infections in plants,

Plant.

  The present invention provides triazole derivatives having the general formula (I):

7R5 R1 R2 (I)

--- N- C H-C C C- R

I 1 * 4 A <

  and their stereoisomers, wherein R is phenyl optionally substituted with halogen, alkyl, alkoxy, haloalkyl, haloalkoxy,

  nitro, halomethylenedioxy, amino, mono- or di-alkylamino

  no, hydroxy, morpholino or alkoxycarbonyl, or phenyl, phenoxy, benzyl or benzyloxy, each optionally substituted with halogen; R1, R2 and R3 independently represent hydrogen, halogen, alkyl, trialkylsilyl; R4 is hydrogen or an alkyl group; R5 is hydrogen, optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl, benzyl or alkylcarbonyl (with the proviso that the carbon atom adjacent to the oxygen atom is not involved in any unsaturation); and their acid addition salts and metal complexes; provided that R1, R2, R3 and R4 are not all hydrogen and that when R1 and R2 are both hydrogen, R3 is then

not an alkyl group.

  The compounds of the invention may contain geometric isomers for the double bond in the general formula (I). Mixtures containing these isomers can be divided into individual isomers by operations known in the literature. These

  isomers and their mixtures in all con-

  part of the present invention.

  The compounds of the invention contain one or more centers of chirality. These compounds are in

  obtained in the form of racemic mixtures.

  However, these and other mixtures can be fractionated into individual isomers by methods known in the art. These isomers and their mixtures in all

  proportions form part of the present invention.

  tion. Alkyl groups and alkyl portions of

  mono- or dialkylamino groups, alkylcarbonyl, alkoxycar-

  bonyl, haloalkyl, haloalkoxy and alkoxy contain 1 to 6, preferably 1 to 4 carbon atoms and are straight chain or branched chain groups, for example methyl, ethyl, propyl (n-propyl or isopropyl), butyl (n butyl, sec-butyl, isobutyl or tert-butyl),

  pentyl (e.g. n-pentyl) and hexyl (e.g.

hexyl).

  The term halogen includes fluorine, chlorine, bromine and iodine, and is preferably chlorine

or bromine.

  An alkenyl group contains 3 to 6 atoms of

  carbon and is preferably the allyl group.

  An alkynyl group contains 3 to 6 carbon atoms

  carbon and is preferably the propargyl group.

  A cycloalkyl group contains 3 to 8, preferably 3 to 6 carbon atoms and is, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Examples of substituents carried by an optionally substituted benzyl group are

  halo, alkoxy and alkyl substituents.

  An example of a halogenomethylenedioxy group is

the difluoromethylenedioxy group.

  According to another of its aspects, the invention proposes triazole derivatives corresponding to the general formula (I):

OR5 R1 R2 (I)

N --- N - CH-C C3

  and their stereoisomers, wherein R is phenyl or phenyl substituted with halogen, C1-C5 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, nitro; , halomethylenedioxy, amino, mono- or di-C1-

  C4) amino, hydroxy, morpholino or (C1-C4 alkoxy) car-

  or R is phenyl substituted with phenyl, phenoxy, benzyl or benzyloxy, each of which may be substituted by halogen; R 1, R 2, R 3 are hydrogen, halogen, C 1 -C 6 alkyl, trialkylsilyl (wherein the alkyl chains may be straight or branched chains having 1 to 6 carbon atoms) or a straight chain alkyl group or branched chain having 1 to 6 carbon atoms; R4 is hydrogen or (C1-C6) alkyl with the proviso that not all of R1, R2, R3 and R4 are hydrogen and that when R1 and R2 are both hydrogen, R3 is not a straight-chained or branched chain alkyl group having 1 to 6 carbon atoms; R 5 is hydrogen, C 1 -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, optionally substituted benzyl or C 1 -C 4 alkylcarbonyl (with the proviso that the carbon atom adjacent to the oxygen atom is not involved in unsaturation); and their acid addition salts and

their metal complexes.

  According to another of its aspects, the invention provides triazole derivatives in which R is a phenyl group or a substituted phenyl group which is a

  2-, 3- or 4-chlorophenyl, 2,4- or 2,5-dichlorophenyl group

  nyl, 2-, 3- or 4-fluorophenyl, 2,4- or 2,6-difluorophenyl

  2-, 3- or 4-bromophenyl, 2-chloro-4-fluorophenyl, 2-

  fluoro-4-chlorophenyl, 2-chloro-6-fluorophenyl, 2-, 3- or

  4-methoxyphenyl, 2,3-dimethoxyphenyl, 2-, 3- or 4-

  ethoxyphenyl, 2-, 3- or 4-nitrophenyl, 2-chloro-4-

  nitrophenyl, 2-chloro-5-nitrophenyl, 2-, 3- or 4-

  trifluoromethoxyphenyl, 2-, 3- or 4- (1,2,2,2-tetrafluorophenyl)

  ethoxy) phenyl, 2-, 3- or 4-methylphenyl, 2,4-dimethyl-

  phenyl, 2-, 3- or 4-butylphenyl, 2,3- (difluoromethylene)

  dioxy) phenyl, 2-fluoro-4-methoxyphenyl, 2-methoxy-4-

  fluorophenyl, 2-methoxy-4-chlorophenyl, 2-chloro-4-

  methoxyphenyl, 2-, 3- or 4-phenoxyphenyl, 2-, 3- or 4-

  phenylphenyl, (2-, 3- or 4-biphenylyl), 2-, 3- or 4-

  benzylphenyl, 2-, 3- or 4-benzyloxyphenyl, 2-, 3- or 4-

  (4-chloro- or 4-fluorobenzyloxy) phenyl, 2-, 3- or 4-

  aminophenyl, 2-, 3- or 4- (N, N-dimethylamino) phenyl, 2-,

  3- or 4-hydroxyphenyl, 2-, 3- or 4- (methoxycarbonyl) phenyl

  nyl or 2-, 3- or 4-morpholinophenyl.

  According to yet another of its aspects, the invention

  The invention proposes triazole derivatives corresponding to general formula (I):

OR5 R1 R2

He I

N-N 'CH-- C' C, -'--- C

R4 R (I)

  and their stereoisomers, wherein R is phenyl optionally substituted with fluorine, chlorine, C1-C4 alkyl or C1-C4 alkoxy; R1, R2 and R3 independently represent chlorine, bromine, hydrogen, C1-C4 alkyl or trimethylsilyl; R4 is hydrogen or C1-C4 alkyl; R5 is hydrogen, C1-C4 alkyl (C1-C4 alkyl) carbonyl, allyl, propargyl or benzyl optionally substituted with chlorine; and their acid addition salts and metal complexes; provided that R1, R2, R3 and R4 are not all hydrogen and that when R1 and R2 are both

  hydrogen, R3 is not a C1-C4 alkyl group.

  According to another of its aspects, the invention proposes triazole derivatives of general formula (I):

OR5 R1 R2

N -N-CH C ,, R

I1 I

  (I) and their stereoisomers, wherein R is phenyl, 4-chlorophenyl or 2,4-dichlorophenyl; R1, R2 and R3 are, independently, hydrogen, chlorine, bromine, methyl or trimethylsilyl; R4 is hydrogen; R5 is hydrogen, methyl or acetyl; and their acid addition salts and metal complexes; provided that when R1 and R2 are hydrogen, R3 is not hydrogen or

methyl group.

  According to one of its aspects, the invention proposes the compounds:

OH CH3

N -N- CH2 "C H2

Ci i (Compound 6 of Table I)

OH CH3

N- N - CH2 C__C CH2

  lN Ci (Compound 5 of Table I) and their stereoisomers; and their addition salts

  of acids and their metal complexes.

  The invention is illustrated by the particular compounds shown in the following Table I. They correspond to the general formula (I):

R4 OR5 R1 R2

I I t

N- N CH - C C - R3

  In Table I, the abbreviations have the following definitions: Me represents the methyl group Et represents the ethyl group npr represents the normal propyl group nBu represents the normal butyl group

  tBu represents the tert-butyl group.

BOARD]

  RN [duR12 R3 4Serochemistry P.F. Oc.

  Compound RRRRR R5 of the olefin 1 Ci Br Br HHH Cis 162-164 -C 1 2 Cl Br Br 1 1 11 11 trans 138-141 3 ci Cl Ci H is 159-162 4 ci Ci Cl Il Hl H ## STR2 ## wherein R 2 R 3 R 4 is a stereochemical compound of the formula ## STR4 ## ## STR3 ## of the Ster6ochi-PF C compound R R1 R2 R3 R4 R5 R5 of the Olefin 9 Ci Me Me HH - 111-114 8 C H H Me Me HH 105-106 Co im TARLFAU I (cont. Hl HH is: trans oil Q4s: Me Me Me HHH cls: trans oil:. 2 mixture of oil 11 cis Me HH cis: trans cis: trans 12 Me HHHH 84-86 or TABLE I (cont.) N of Stereo-PF OC compound R R1 R2 R3 R4 R5 chemistry of olefin 13 Cl Me Si HHHH trans 112-115 o

14 Cl Me H H H Me - semi

  solid Cl Me H H H - 111-113 C-Me o! TABLE I (cont.) N of 2 Stereochi.P.C. Compound R R R2R R of Olefin

16 Ci And H H H H -

  17 C and H H H H 18 Cl nPr H i H H 19 Cl nPr H Il H H Co

G _ .. '

  VI TABLE I (continued) Ndlu Stereochi-P.F. C compound R1 R2 R3 R4 R5 mole of olefin

Cl nBuH H H H -

Cl _CM

21 Ci nBuH H H H -

  22 Cl Me and trans HHH and CiH and HHH trans Co> J TABLE I (contd.) N of R2 - - R5 Stereo-PF C compound RR R2 R3 R4 R5 chemistry of olefin 24 Cl Me And C H H H cis cis and C H H H cis cis 26 C H N H H H trans 27 Cl He nPr HHH trans S TABLE I (cont.) N of Stereochi PF C compound R R1 R2 R3 R4 R5 mie of olefin 28 Ci Me Pr H H H cis C! 1 29 Cl Me nPr HHH Cis

C Me Me Me H H -

31 Ci Me Me Me H H -

  e01 TABLFEAU I (following () N of I 2 3 4 5 Stereochi-PF C composes RRRRRR mie of the olefin 32 Ci Me Me And it is 33 Ci Me Me Me HH cis 34 C i H And Me HH trans C1 Cl H Me And HH trans Co _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ co4 TABLE I (cont.) N of 1 2 34 Stereochi-PF C compound RRRRR R5 half of olefin 36 Ci H And And HH

37 Ci H And And H H -

  38 C And And Me HH cis 39 Ci And And Me HH trans Co U4N _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ COV TABILEAU T ( after)

NO of Stereo- P.F.

  Compound R 2 R 3 R 5 R 5 O 5 C 1 O 6 O 1 HCl and ClCl 2 O and HH and H 2 CH 2 Cl 2 CCH 2 Cl 2 CH 2 Cl 2 CH 2 Cl 2 TABLE I (after)

  fNO of RR1 R2 R3 R4 R5 Stereo- P.F.

  compound R chemistry of OC 1 'olefin 44 CI Me H H H CH2C-Cl-1 C H H H CH2CH ---- CH2 Cl 46 Cl MeSi H H H H2 33c, c 7 CI Me3Si H H il il TABLE I (continued)

No. of 3 4 5 Stereo-P.F.

  Compound RR R of C] 'ol & fine i 48 C It Me Me3SiH. he

49 MeO Me H H HI H -

CH3Me It i H H

51 CH O E H H H H -

  CH3 Ett Co IP. --- cH3 i. ,,, .. U TABLE I (continued)

N from Stereochi-P.F.

  Compound R 2 R 3 R 4 R 5 R 1 of olefin 52 H 3 npr H 1 H H 1 OCH 3

53 And Me H H H H -

  54 C Me Me HHH e _jLX C 1 Me Me HHH iu TABIEAU I (cont'd) N0 of 4 2 .. Sté rfoch i- P cN d RRRRRR mr C olefin 56 And Me Me HHH 57 And Me Me H H 58 nPr Me Me It HH n Co%; 1 TABLE I (continued)

cNIR Rdu 2 3 4 5 Stereochi-, P.F.

  The compounds of the general formula (I) can be prepared by reacting a compound of the general formula (II) with a compound of the general formula (II), or (III):

O R1 R2

CH C C C R

I l or

R4 R (II)

OH R1 R2

X - CH C C C R

He

R4 R (III)

  R, R1, R2, R3 and R4 are as defined above, R5 is hydrogen and X is a halogen atom (preferably

  a chlorine atom or a bromine atom) with 1,2,4-

  triazole, in the presence of an acid acceptor or in the form of one of its alkali metal salts, in a suitable solvent. The compound of general formula (II) or (III) is advantageously reacted at 20100 C with the sodium salt of 1,2,4-triazole (the salt may be prepared by addition of sodium hydride or methylate of 1,2,4-triazole sodium) in a suitable solvent such as acetonitrile, methanol, ethanol, isopropanol or N, N-dimethylformamide. The product can be isolated by pouring the reaction mixture into water and extracting it with ethyl acetate. After dehydration with a suitable agent such as magnesium sulfate or sodium sulfate and chromatography on silica gel, the solid or gum obtained can be (re) crystallized in

a suitable solvent.

  The compounds of general formulas (II) and (III) can be prepared by reaction of a compound of general formula (IVa) or (IVb)

R1 R2 O0

It t 1I

X = CH _CC C - R3 X- CH - C -R

I 14

R4 R4

  (IVa) (IVb) wherein R, R1, R2, R3 and R4 are as defined above and X is a halogen atom, with, respectively, a Grignard compound of the general formula (Va) or (Vb)

R1 R2

_I 1

Y-Mg 2 R Y Mg C-C-R 3 (Va) (Vb)

  wherein R, R 1, R 2 and R 3 are as defined above.

  Y is a halogen (preferably chlorine, bromine or iodine) in a suitable solvent such as ether

  of diethyl or tetrahydrofuran. We get general-

  a mixture of the compounds of general formulas (II) and

(III).

  Compounds of general formulas (IV) and (V) may be prepared by methods described in the literature. The compounds of general formula (II) in which R, R 1, R 2 and R 3 are as defined above may also be prepared by reaction of the appropriate ketone compound of general formula (VI):

O R1 R2

C - C C R.3 (VI)

I. R

  wherein R, R 1, R 2 and R 3 are as defined above.

  above, with dimethylsulfonium methylide or diphenylethylsulfonium methylide (Corey and Chaykovsky, J. Am Chem Soc., 1962, 84, 3782) using methods described in the literature. Compounds of general formula (VIII):

OH X X

r I

N N - CH - C - C - CH

kN R R

(VIII)

  wherein R and R4 are as defined above and X is halogen, which are examples of compounds of general formula (I) wherein R1 and R2 are halogen and R3 and R5 are hydrogen, may be produced by reacting a compound of the general formula

(VII):

OH

N-CH CH

  wherein R 4 and R 4 are as defined above, the preparation of which is described in EP 97 426 (U.S. Patent No. 4,634,466) with a halogen such as chlorine or bromine, in the presence of light, in a suitable solvent such as chloroform, at a temperature of 20 to 100 ° C, but preferably at room temperature. This procedure normally gives

  a mixture of geometric isomers.

  Compounds of general formula (XI):

OH H H

N.-N-CH & & R3

  (XI) wherein R 3 is a trialkylsilyl group and R 4 and R 4 are as defined above, may be prepared by reacting a compound of the general formula (IX): ## STR2 ## IX)

-N / R4 R

  in which R and R4 have the definitions given below.

  above, with a suitable base of the lithium-lithium type such as methyllithium or n-butyllithium, in a suitable solvent such as tetrahydrofuran, at a suitable temperature, for example -78 ° C, followed by treatment with a chlorotrialkylsilane to form a compound of the general formula (X): OH N N-CH 3cC (

N, - '4 to

  wherein R and R4 are as defined above and R3 is a trialkylsilyl group. Compounds of formula

  (X) can be reduced to trans-

  olefins (XI) using a reducing agent con-

  for example a toluene solution of sodium hydride and bis (2-methoxyethoxy) aluminum in a solvent

  such as tetrahydrofuran, and at a temperature of

  suitably, for example in the range of -10 ° C to

C, preferably at 0OC.

  Compounds of the general formula (I) wherein R5 is other than hydrogen and alkylcarbonyl may be prepared by treating the compound of the general formula (I) wherein R5 is hydrogen with a suitable base such as sodium hydride, in a suitable solvent such as tetrahydrofuran, with a compound of formula (XII):

R5-L (XII)

  in which R5 has the definition given above but is not hydrogen, and L is a halogen (for example chlorine or bromine) or a sulfonate group (for example a

  mesylate, tosylate or benzenesulfonate group).

  Compounds of general formula (I) in which R 5 is alkylcarbonyl can be prepared by treatment of compounds of general formula (I) wherein R 5 is hydrogen, with a suitable base, for example sodium hydride, in a suitable solvent, for example tetrahydrofuran, with a compound of formula (XIII): embedded image

  wherein L is bromine or chlorine.

  Compounds of general formula (I) in which R5 represents other than hydrogen may also be prepared by etherification or esterification of compounds of general formula (I) wherein R5 is hydrogen, by well-known conventional techniques

in the litterature.

  The salts and metal complexes of the compounds of general formula (I) can be prepared by standard techniques well known in the literature. For example, the complexes can be formed by reacting the non-complex compound with a metal salt in a suitable solvent. The compounds of the general formula (I) are generally prepared by the above reactions in the form of racemic mixtures. The splitting of these mixtures into the constituent enantiomers can be carried out by methods known in the art. Examples of these processes are given below: (1) formation of the diastereoisomeric salts or esters of the compound of the general formula (1) with an optically active acid (for example camphosulphonic acid), separation of the isomeric salts or esters and converting the separated isomeric salts or esters to the enantiomers of the compound of the general formula (I). (2) Formation of diastereoisomeric carbamates of the compound of general formula (I) by reaction

  haloformate (for example chloro

  formate) of this compound with an amine

  optically active (eg alpha-

  methylbenzylamine), separation of the isomeric carbamates and transformation of the separated isomeric carbamates into the enantiomers of the

compound of general formula (I).

  (3) Formation of the hemiphthalic ester of the compound

  of general formula (I), reaction of the hemi-

  phthalate with an optically active amine (for example alphamethylbenzylamine) to obtain a salt of the hemiphthalate, separation of the isomeric salts and conversion of the separated salts to the enantiomers of the compound of the general formula (I) or (4) splitting of the mixtures of using

  enantio-selective crystallisation techniques

  (Leigh, Chemistry and Industry (London), 1970, 1016-1017 and ibid., 1977, 36) The separation of the diastereoisomeric salts, esters and carbamates can be carried out, for example, by crystallization techniques or by chromatography. The compounds and their acid addition salts, their metal complexes and their N-oxides are active fungicides, in particular against the following pathogens: Puccinia recondita, Puccinia striiformis and other rust attacking agents. wheat, Puccinia hordei, Puccinia striiformis and other rust attacking barley, and rust developing on other hosts, eg coffee, apple, vegetables and ornamentals Ervsiphe qraminis (white) developing on barley and wheat and other whites developing on various hosts, such as Sphaerotheca fuliginea attacking cucurbits (eg cucumber), Podosphaera leucotricha developing on the pom first and

  Uncinula necator growing on the vine.

  Helminthosporium spp., For example Pyrenophora teres, Rnchosporium spp., Pseudocercosporella herpotrichoides, Septoria spp. and Rhizoctonia spp. developing on cereals. Cercospora arachidicola developing on peanut and other species of the genus Cercospora developing for example on sugar beet, banana and soybean, Botrvtis cinerea (gray mold) growing on

  tomatoes, strawberries, grapes and other hosts.

  Venturia inaequalis (scab) growing on the apple tree. Some of the compounds have also shown a broad field of activity against fungi in vitro. They are endowed with activity against various diseases developing on fruits after harvest (eg Penicillium diQatatum and Italicum growing on oranges, GloeosDorium musarum growing on bananas and Botrvtis cinerea developing on grapes). In addition, some of the compounds are active for seed disinfection against: Fusarium spp., Septoria spp., Tilletia spp. (ie caries, a disease transmitted by wheat kernels), Ustilacro spp., Helinthosporium spp. and Pseudocercosporella herDotrichoides developing on cereals, Rhizoctonia solani developing on the

cotton.

  The compounds are also useful for the treatment of candidiasis and infections due to

dermatophytes in human medicine.

  The compounds are capable of acropetal movement in the plant. In addition, they may be sufficiently volatile to act in the vapor phase against

  fungi growing on the plant.

  They can also be useful as fungicides

  (as opposed to fungicides for agriculture).

  cultivation), for example to prevent a fungal attack of

  wood, skins, leather and especially paint films.

  Some of the compounds of the invention act by influencing the growth of plants and they can

  be used for this purpose at appropriate rates of

tion.

  The compounds can be used as such for fungicidal purposes or to influence plant growth, but are more conveniently formulated into compositions for such uses. The invention thus proposes a fungicidal composition or a composition influencing the growth of plants, comprising a compound of general formula (I) as defined above, an acid addition salt or a metal complex of this compound and, as

  optional, a carrier or a thinner.

  The invention also proposes a method for combating fungi or influencing the growth of plants, which method consists in applying to a plant, to its seeds or to the place occupied by the plant or the seed, a compound, an addition salt or acid or a metal complex of a compound as defined above. The compounds, their acid addition salts and metal complexes may be applied in various ways, for example they may be applied, formulated or unformulated, directly to the foliage of a plant, or they may also be be applied to shrubs and trees, seeds or other environment in which plants, shrubs or trees grow or are to be planted, or may be applied by spraying, dusting or in the form of a cream or paste formulation, or they may be applied in the vapor state, or slow release granules. The application can affect any part of the plant, shrub or tree, for example foliage, stems, branches or roots, or the soil surrounding the roots, or the seeds before they are sown; or the soil in general,

  water from rice fields or hydropower plants

  Picnic. The compounds of the invention, their acid addition salts or metal complexes can also be injected into plants or into trees, or

  can also spray them on the vegetable

  using electronic spraying techniques

  dynamic. The term "plant" used in this

  memory covers seedlings, shrubs and trees.

  In addition, the fungicidal method of the invention comprises a preventive, protective, prophylactic and eradicative treatment. The compounds, their acid addition salts and metal complexes are advantageously used for agricultural and horticultural purposes in the form of a composition. The type of composition used in each case depends on the particular purpose being considered. The compositions may be in the form of

  dusting or granulating powders

  active ingredient and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fulling earth, gypsum, earth Hewitt, diatomaceous earth and kaolinite. These granules may be preformed granules capable of being applied to the soil without further treatment. They can be prepared by impregnating charge pellets with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler. Seed disinfection compositions, for example, may include an agent (such as mineral oil) which facilitates adhesion of the composition to the seeds; alternatively, the active ingredient can be formulated for seed disinfection with an organic solvent (eg N-methylpyrrolidone).

or N, N-dimethylformamide).

  The compositions may also be in the form of powders, granules or dispersible grains comprising a wetting agent for facilitating dispersion in liquids, powder or grains, which may also contain fillers and blowing agents.

suspended.

  The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient (s) in an organic solvent optionally containing one or more wetting, dispersing or emulsifying agents, and then adding the mixture to water which may also contain one or more wetting, dispersing or emulsifying agents. Suitable organic solvents are ledichlorethylene, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylenes, trichlorethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and ethers. glycol (for example

  2-ethoxyethanol and 2-butoxyethanol).

  The compositions for use in spraying may also be in the form of aerosols, in which the formulation is contained in a pressure vessel containing a propellant, for example the

  fluorotrichloromethane or dichlorodifluoromethane.

  The compounds, their acid addition salts and their metal complexes can be mixed in the state

  dry with a pyrotechnic mixture to form a composi-

  able to generate smoke in confined spaces

containing the compounds.

  Alternatively, the compounds, their additive salts,

Acids and their metal complexes can be used in a microencapsulated form. They can also be formulated into biodegradable polymeric formulations in order to obtain a slow and regulated release of the

active substance.

  By the incorporation of suitable additives, for example additives to improve the distribution, the adhesion and the resistance to rain on treated surfaces, it is better to adapt the different

  compositions with various applications.

  The compounds can be used in the form of mixtures with fertilizers (for example fertilizers containing nitrogen, potassium or phosphorus). Compositions which comprise only fertilizer granules in which the compound is incorporated, for example in the form of a coating, are preferred. These granules advantageously contain up to 25% by weight of the compound. The invention thus also proposes a fertilizer composition comprising the compound of general formula (I) or

a salt of this compound.

  The compositions may also be in the form of liquid preparations for use in bathing or spraying, which are generally aqueous dispersions or emulsions containing the active ingredient, in the presence of one or more surfactants, by

  example, one or more wetting agents, dispersing agents

  agents, emulsifiers or suspending agents

  if we; or which are sprayable formulations of the type suitable for use in electrodynamic spraying techniques. The agents mentioned above may

  be cationic, anionic or nonionic agents.

  Suitable cationic agents are compounds

  quaternary ammonium compounds, such as cetyltrimen-

  thylammonium. Suitable anionic agents are soaps, salts of aliphatic monoesters of sulfuric acid (for example sodium lauryl sulphate) and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, lignosulphonate, sodium butylnaphthalenesulphonate, calcium or ammonium, and

  a mixture of diisopropyl- and triisopropylnaphthalenesul-

sodium fonates).

  Suitable nonionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkylphenols such as octylphenol.

  or nonylphenol and octylcresol. Other non-

  are partial esters derived from long-chain fatty acids and hexitol anhydrides,

  condensation of said partial esters with ethylene oxide.

  lene, and lecithins. Advantageous examples of suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and the sodium salt of carboxymethylcellulose) and vegetable gums (for example

  example gum arabic and gum tragacanth).

  The compositions for use in aqueous dispersions or emulsions are generally presented in the form of a concentrate containing a high proportion of one or more active ingredients, and the

  concentrate should be diluted with water before use.

  tion. These concentrates must often be able to withstand storage for extended periods of time and, after such storage, must be diluted with water to form aqueous preparations which remain homogeneous for a period of time sufficient to can apply them using conventional electrodynamic spray equipment. The concentrates may conveniently contain up to 95%, preferably 10 to 85%, for example 25 to 60% by weight of one or more active ingredients. These concentrates advantageously contain organic acids (for example alkylaryl arylsulphonic acids such as

  xylenesulphonic acid or dodecylbenzenesulphonic acid

  that), since the presence of these acids can increase the solubility of the ingredient or active ingredients in the polar solvents frequently used in the concentrates. These can advantageously also contain a high proportion of surfactants, so as to obtain sufficiently stable aqueous emulsions. After dilution to form aqueous preparations, these preparations may contain varying amounts of the active ingredient or ingredients, depending on the purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of one or more

  Active ingredients can be used.

  The compositions of the present invention may also comprise one or more other compounds having biological activity, for example compounds having a similar or complementary fungicidal activity or compounds exerting an influence on the growth of plants, having a herbicidal activity or insecticide. The other fungicidal compound may be, for example, a compound that is capable of controlling cereal (eg, wheat) ear diseases, such as diseases caused by Septoria, Gibberella and Helminthosporium spp., Transmitted diseases. by the seeds and by the soil, and the oidium and mildew of the vine, and the white and scab of the apple tree, & c. These fungicide mixtures may have a broader spectrum of activity than the compound of general formula (I) used alone; in addition, the other fungicide can exert a synergistic effect on the fungicidal activity of the compound of general formula (I). Examples of the other fungicidal compound

  include carbendazim, benomyl, thiophanate-

  methyl, thiabendazole, fubéridazole, etridazole, dichlofluanid, cymoxanil, oxadixyl, ofurace,

  metalaxyl, furalaxyl, benalaxyl, fosetyl alumina

  nium, fenarimol, iprodione, procymidione, vinclozolin, penconazole, myclobutanil, systan, S3308, pyrazophos, ethirimol, ditalimfos, tridemorph, triforine, nuarimol, triazbutyl, guazatine, propiconazole, prochloraz, flutriafol,

  triadimefon, triadimenol, diclobutrazol, hexacoben

  nazole, furconazole, cis-furconazole, bromoconazo

  cyproconazole, flusilazole, tebuconazole, dimethomorph, fenpropimorph, fenpropidin, chlorozolinate, diniconazol, imazalil, fenfuram,

  carboxin, oxycarboxin, methfuroxam, dodemo-

  phe, bitertanol, bupirimate, etaconazole,

  streptomycin, cypofuram, biloxazol, quinomethio-

  nate, dimethirimol, 1- (2-cyano-2-methoxyimino)

  acetyl) -3-ethylurea, 4-chloro-N- (cyano (ethoxy) methyl) -

  benzamide, fenaponil, tolclofos-methyl, pyroxyfur, polyram, maneb, mancozeb, captafol, chlorothalonil, anilazine, thiram, captan, folpet, zineb, propineb, sulfur, dinocap, binapacryl, nitrothalisopropyl, dodine, dithianon, fentin hydroxide, fentin acetate, tecnazene,

  quintozene, dichloran, tetraconazole,

  piclonil, difenoconazole, copper-containing compounds such as copper oxychloride,

  copper and Bordeaux mixture, and

  ganomercuriels. The compounds of general formula (I) and their acid addition salts and metal complexes may be mixed with soil, peat and other rooting media for the protection of plants against transmitted fungal diseases. by the seeds,

  transmitted by the soil or developing on the foliage.

  Suitable insecticides which may be included in the composition of the invention include pirimicarb, dimethoate, demeton-s-methyl, formothion, carbaryl, isoprocarb, XMC, BPMC, carbofuran, carbosulfan, diazinon, fenthion, fenitrothion, phenthoate, chlorpyrifos, isoxathion,

  propaphos, monocrotophos, buprofezin,

proxyfene and cycloprothrin.

  Plant growth influencing compounds which can be used in the compositions of the invention are compounds which destroy weeds or inhibit the formation of their seeds, or selectively limit the development of lesser plants.

  desirable (eg grasses).

  Examples of suitable compounds influencing

  plant growth that can be used with the compositions of the invention are gibberellins (eg GA3, GA4 or GA7), auxins (eg indole acetic acid, indolebutyric acid, acid

  naphthoxyacetic acid or naphthylacetic acid), cytokinetic

  nes (eg kinetin, diphenyluree, benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids (eg 2,4-D or MCPA), substituted benzoic acids (eg triiodobenzoic acid), morpholines (e.g. chlorofluorecol), maleic hydrazide, glyphosate, glyphosine, alcohols and

  long-chain fatty acids, dikegulac, paclobutra-

  zol, flurprimidol, fluoridamide, mefluidide,

  quaternary ammonium and phosphonium compounds

  (eg chloromequat, chlorphonium or chloride

  mepiquat), ethephon, carbetamide, 3,6-dichloro-

  methyl nisate, daminozide, asulam, acid

  abscisic, isopyrimil, 1- (4-chlorophenyl) -4,6-

  dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylic acid, hydroxybenzonitriles (eg bromoxynil),

  difenzoquat, benzoylprop-ethyl, 3,6-dichloro-

  colinic, fenpentezol, inabenfid, triapenthenol

and tecnazene.

  The following examples illustrate the invention; temperatures are given in degrees centigrade ('C') and reactions involving water-sensitive intermediates were conducted under a nitrogen atmosphere. In the Examples, selected proton magnetic resonance characteristics are indicated for certain compounds. When these characteristics are given, the chemical shifts are in ppm relative to tetramethylsilane, and deuterochloroform was used as the solvent. All resonance spectra

  nuclear magnetic data were measured at 270 MHz.

  The peak of the molecular ion from a chemical ionization mass spectrum is given for some compounds. In the Examples, the following abbreviations are used: s = singlet 1 = broad d = doublet dd = doublet of doublets q = quadruplet m = multiplet THF = tetrahydrofuran DMF = N, N-dimethylformamide HPLC = high-level liquid chromatography

performance.

  The terms "DISPERSOL", "TWEEN" and "RED AL"

  are trademarks or registered trademarks of

tion.

EXAMPLE 1

  This example illustrates the preparation of compounds 1 and 2 of Table I. The reaction can be illustrated by the following scheme:

OH C1

  Br 2 / CHCl 3 Cl - / C - C C H H H / light C C c C1 C CC

- I I /

CH2 CH2 Br Br

N-N I

  N_N Ni I N N Light = 100W tungsten lamp form cis form 'Z' (compound 1 of

Table I)

C1 OH Br Cil) C C-C CH CH2 Br

N N

  b) Transform form 'E' (compound 2 of

Table I)

  3-hydroxy-3- (2,4-dichlorophenyl) -4- (1,2,4-

  triazol-1-yl) but-1-yne (0.99 g), the preparation of which is described in EP 97 426, was suspended in chloroform (5 ml) and a few drops of bromine in chloroform. have been added. The mixture was irradiated with a 100 watt tungsten lamp. After 10 minutes, discoloration occurred. The remainder of the bromine in chloroform (total amount of 0.56 g of bromine in 5 ml of chloroform) was added and stirring and irradiation were continued for 1.5 hours. The mixture was then poured into a very dilute aqueous sodium hydroxide solution, shaken, and the aqueous phase discarded. The chloroform solution was dehydrated over magnesium sulfate and filtered. The filtrate was evaporated in vacuo to give a white foam (1.66 g). This crude product was then purified by HPLC using a mixture of tert-butyl ether and methyl and methanol (99: 1 by volume) as eluent to give the pure E isomer (0.756 g) and

the pure Z isomer (0.33 g).

  Z isomer melting point 162-164 ° C; Proton magnetic resonance:, 01 (1H, d), 5.35 (1H, d),, 32 (1H, s), 6.92 (1H, s) 7.11 (1H, dd), 7.40 (1H, d) 7.52 (1H, dd), 7.81 (1H, s), 7.96 (1H, s) Isomer E melting point 138-141 ° C; Magnetic resonance of protons; 4.95 (1H, d), 4.98 (1H, s), 24 (1H, d), 6.80 (1H, s), 7.12 (1H, dd), 7.36 (1H, d), 7.40 (1H, d), 7.83 (1H, s), 7.87 (1H, s)

EXAMPLE 2

  This example illustrates the preparation of compounds 3 and 4 of Table I. The reaction can be schematically illustrated by the following equation:

C12 / CHC13 I]

ci = light ci C- C = -CH \ ci c

C1 II CH2

CH2 1

N-N

N -N KN

  N 'N' form cis form 'Z' (compound 3 of

Table I)

  + C1 OH Ci Light = tungsten lamp of 100 W c C - C CE 1 f CH 2 Cl NN N trans form 'E' (compound 4 of

Table I)

  3-hydroxy-3- (2,4-dichlorophenyl) -4- (1,2,4-

  triazol-1-yl) but-1-yne (0.99 g) was suspended in chloroform (5 ml), and a volume of about 1 ml of a solution of chlorine in chloroform was added the suspension with stirring. The mixture was irradiated with a 100 watt tungsten lamp. After 10 minutes, the remaining amount of chloroform solution in chloroform (the total representing 0.25 g of chlorine in ml of chloroform) was added and stirring and irradiation were continued. After 30 minutes,

  all of the solid matter was passed into solution.

  One hour later, the reaction mixture was poured into very dilute aqueous sodium hydroxide. The organic phase was extracted with ethyl acetate (20 ml) and discarded. The organic phases were combined, washed with water (10 ml), dried over magnesium sulphate and filtered. The filtrate was evaporated in vacuo to give a white foam (1.28 g). This crude product was then purified by HPLC eluting with a 99: 1 volume mixture of tert-butyl ether and methyl and methanol to give the pure Z isomer (0.53 g) and methanol. pure E isomer

(0.27 g).

  Z-Isomer melting point 159-162 C Proton Magnetic Resonance: 4.96 (1H, d), 5.35 (1H, d), 36 (1H, s), 6.40 (1H, s), 7 , 21 (1H, dd), 7.40 (1H, d), 7.53 (1H, d), 7.81 (1H, s),

7.95 (1H, s).

  Isomer E melting point 131-133C; Proton magnetic resonance: H 4, 90 (1H, d), 5.10 (1H, s),, 24 (1H, d), 6.40 (1H, s), 7.11 (1H, dd), 7.30 (1H, d), 7.36 (1H, dd), 7.81 (1H, s),

7.83 (1H, s).

EXAMPLE 3

  This example illustrates the preparation of the compound

of Table I.

  Operation 1 Preparation of Grignard Reagent A small amount of a solution of 2-bromoprop-1-ene (5 g) in anhydrous THF (40 ml) was added to a stirred mixture of magnesium turn (1.1 g) in anhydrous tetrahydrofuran (10 ml) to initiate the formation of the Grignard reagent. After the reaction was initiated, the remainder of the 2-bromoprop-1-ene solution in anhydrous THF was added dropwise. The reaction mixture was then heated at reflux for

30 minutes.

  Operation 2 Preparation of compounds:

OH CH3

Br - CH 2 C C - CH 2 Cl and

O I

CH2 C C -CH2

  4-Chlorophenacyl bromide (7.5 g) in anhydrous THF (50 ml) was added dropwise at 0-5 ° C. to the Grignard reagent produced in step 1. After stirring for 15 minutes at 0 ° C. C, the reaction mixture was quenched by addition of saturated aqueous sodium chloride solution to the reaction mixture and the pH was adjusted to 5 (pH paper) using an aqueous solution

  diluted with 2M hydrochloric acid. This mixture was quickly

  extracted with diethyl ether (3 x 100 ml) and the

  collected phases of ether extraction were dehydrated

  on sodium sulphate. Filtration followed by evaporation of the ether solution in vacuo gave a pale yellow mobile liquid. The nuclear magnetic resonance spectrum and the infrared spectrum

  indicated that the product was a mixture of chlorhydrin

  and epoxide both shown above. This

  mixture was used in step 3 without purification.

  OD 3 Preparation of the compound:

OH CH3

N ...- N CH2- C -C - -H2

  Sodium hydride (50% dispersion in oil, 3.5 g) was washed beforehand with hexane to remove the oil and then suspended in anhydrous DMF (100 ml). A solution of 1,2,4-triazole (5g) in anhydrous DMF (50ml) was added to the sodium hydride with stirring at 0 ° C and the mixture was stirred at room temperature for 1 hour once. the addition completed. To the reaction mixture was added a solution of the mixture of epoxide and bromohydrin (produced in step 2) in anhydrous DMF (50 ml) in 15 minutes. After the addition was complete, the reaction mixture was heated at C for 2 hours. The reaction mixture was poured into water (200 ml) and the pH of the solution was adjusted to

  6 (pH paper) with 2M hydrochloric acid.

  The aqueous mixture was extracted with acetate

  (3 x 200 ml) and the combined phases of extrac-

  The ethyl acetate was dried over sodium sulfate, filtered and evaporated in vacuo to give a brown gum. The gum was flash chromatographed on a silica column using a mixture of ethyl acetate and hexanes (9: 1 by volume) as eluent. The fractions containing the pure product were combined and evaporated under vacuum to give a gum which crystallized on standing. The material

  solid was recrystallized from a mixture of dichloromethane

  thane and hexane giving white crystals (point of

88-90 ° C melting) (2.1 g, 24.7%).

  Proton magnetic resonance: - 1.67 (3H, s), 4.61, 4.72 (2H, AB q, 8Hz) 5.05 (1H, s),, (1H, s), 4 , 2-5.3 (1H, 1), 7.3 (4H, complex), 7.85 (1H,

s), 7.89 (1H, s).

M / Z 263 (M +)

  The following compounds were prepared by a procedure analogous to that described in

Example 3

  i) Compound 6 of Table I, prepared using 2-bromoprop-1-ene (5 g), magnesium turn (0.9 g), 1,2,4-triazole (4.76 g) and sodium hydride (55%, 1.51 g). There was thus obtained 1.022 g of a solid which

melted at 112-115C.

  Proton magnetic resonance: 1.72 (3H, s), 4.70 (1H, d), 4.72 (1H, s), 4.97 (1H, s),, 14 (1H, s), 5.46 (1H, d), 7.13 (1H, dd), 7.32 (1H, dd),

7.78 (1H, s), 7.89 (1H, s).

M / Z 297 (M +)

  (ii) Compound N 7 of Table I. This is a

  solid having a melting point of 111-

114'C.

  Proton magnetic resonance: 1.46 (3H, s), 1.73 (3H, s), 3.8 (1H, s, OH) 4.2 (1H, d), 4.37 (1H, d) , 5.7 (1H, s), 7.33 (4H, AA ', BB'), 7.88 (1H, s),

7.91 (1H, s).

M / Z 277 (M +)

  iii) Compound N 8 of Table I was obtained as a pale green solid having

a melting point of 105-106 ° C.

  Proton magnetic resonance: 1.42 (3H, s), 1.72 (3H, s), 4.18 (1H, t s -OH, 5.68 (2H, AB q), 5.72 (1H, fs), 7.18 (1H, dd), 7.37 (1H, dd), 7, 71 (1H,

d), 7.83 (1H, s), 7.97 (1H, s).

M / Z 311 (M +)

  iv) Compounds Nos. 9 and 10 of Table I were obtained in the form of oils, both of which are

mixtures of isomers.

  Trans isomer Proton magnetic resonance: 1.47 (3H, d), 1.78 (3H, d), 4.30 (1H,), 4.60 and 4.72 (2H, AB q), 5.55 (1H, s), 7.24 (4H, AA 'BB'), 7.83 (1H, s),

7.87 (1H, s).

  Cis isomer Proton magnetic resonance: 1.52 (3H, d), 1.65 (3H, d), 4.30 (1H, t), 4.62 and 4.70 (2H, AB q), 5, 68 (1H, q), 7.24 (4H, AA 'BB'), 7.86 (1H, s), 7.90

(1H, s).

  v) Compound N 11 of Table I was obtained under

the shape of an oil.

  Proton magnetic resonance: 1.40 (3H, d), 1.95 (3H, s), 4.40 (1H, s), 4.84 (2H, dd),, 50 (1H, m), 7 , 05 (1H, m), 7.35 (2H, m), 7.75 (1H, s),

7.78 (1H, s).

  vi) Compound NI 12 of Table I was purified by crystallization (solvent mixture of diethyl ether and hexane) rather than column chromatography. The product

  crystalline had a melting point of 84-86 ° C.

  Proton magnetic resonance: 1.66 (3H, s), 4.45 (1H, es), 12, 4.67 and 4.75 (2H, AB q), 5.04 (1H, fs), , 12 (1H is), 7.2-7.42 (5H, complex), 7.83 (1H, s), 7.88 (1H, s)

M / Z 229 (M +).

EXAMPLE 4

  Preparation of compound N 13 of Table I: ## STR1 ##

  3-hydroxy-3- (2,4-dichlorophenyl) -4- (1,2,4-

  triazol-1-yl) but-1-yne (1.383 g) was dissolved in anhydrous THF (100 ml), the solution was kept under an anhydrous nitrogen atmosphere and cooled to -78 ° C. using a cooling bath consisting of solid carbon dioxide and acetone. N-Butyllithium (1.6M in hexanes, 6.13ml) was added to this solution dropwise at a rate selected so that the

  the temperature of the reaction mixture is maintained

  below -70'C. The reaction mixture was then stirred for 10 minutes. Undiluted trimethylsilyl chloride (1.4 mL, 1.17 g) was added dropwise to the reaction mixture and once the addition was complete, the cooling bath was removed and the reaction mixture allowed to warm up. at room temperature

  and stirred for a further 20 minutes.

  Dilute aqueous hydrochloric acid (2M, 10ml) and methanol (10ml) were added to the reaction mixture with stirring. The reaction mixture was chromatographed by thin layer chromatography (using a 3: 1 by volume ether: hexane mixture as eluant) until all the triazole material of higher Rf value (as determined by chloroplatinic acid spraying) has disappeared. The reaction mixture was poured rapidly into saturated sodium chloride solution and extracted with ethyl acetate (3 x 100 ml). The combined ethyl acetate phases were dehydrated over sodium sulfate, filtered, and the volatile solvents were distilled off under reduced pressure to leave an orange-colored oil. The oil was subjected to column chromatography on silica gel using a solvent mixture of diethyl ether and hexanes (3: 1 by volume) as eluent. Fractions containing triazolylsilylacetylene were pooled and evaporated in vacuo. The residue was crystallized from

  diethyl ether to give 1-trimethylsilyl-3-

  hydroxy-3- (2,4-dichlorophenyl) -4- (1,2,4-triazol-l-yl) but-

  1-yne (0.258 g) as a white solid having a melting point of 140-143 ° C. Starting material was recovered in the chromatography column using ethyl acetate used as eluent. Proton magnetic resonance: 0.13 (9H, s), 4.63 and 4.89 (2H, AB q), 4.6 (1H, s), 7.25 (1H, dd), 7.44 ( 1H, d), 7.78 (1H,

d), 7.93 (1H, s), 8.12 (1H, s).

M / Z 338 (M-Me) +.

  A solution of sodium hydride and bis (2-

  methoxyethoxy) aluminum in toluene (Red-Al sold by Aldrich Chemical Co. Ltd.) (3.4M, 0.86ml) was dissolved in anhydrous THF (100ml) and cooled to 0OC using a cooling bath containing ice with added salt. We added drop by drop a

  solution of 1-trimethylsilyl-3-hydroxy-3- (2,4-dichlorophenyl)

  nyl) -4- (1,2,4-triazol-1-yl) but-1-yne (0.258 g) in anhydrous THF (10 ml) with stirring under an anhydrous nitrogen atmosphere at 0 ° C. After the addition was complete, the cooling bath was removed and the reaction mixture was allowed to warm to room temperature. The reaction mixture was then stirred for a further 3 hours. It was then cautiously poured into the water (to avoid foaming too vigorously) and the products were extracted into ethyl acetate (3 x 100 ml). The combined ethyl acetate extracts were dried (Na 2 SO 4), filtered, and the filtrate evaporated under reduced pressure. The resulting gum was purified by column chromatography on silica gel using as eluent a mixture of ethyl acetate and

  hexanes (3: 1 by volume). Chromatographic fractions

  Vinyl silane-containing materials were collected and evaporated in vacuo. The resulting semi-solid material was crystallized using a solvent mixture of diethyl ether and hexane to give the

  trans-1-trimethylsilyl-3-hydroxy-3- (2,4-dichlorophenyl) -4-

  (1,2,4-triazol-1-yl) but-1-ene (0.138 g) as a crystalline solid having a melting point

112-115C.

  Proton magnetic resonance: 0.01 (9H, s), 4.53 (1H, es), 4.71 and 5, 17 (2H, AB q), 6.12 and 6.60 (2H, AB q, J 14 Hz), 7.23 (1H, dd), 7.40 (1H, d), 7.72 (1H, d), 7.89 (1H, s),

8.05 (1H, s).

M / Z 340 (M-Me +).

EXAMPLE 5

  Preparation of compound N 14 of Table I: OMe

J / CH3

  N-c CH 2 Cl Sodium hydride (50% dispersion in mineral oil, 0.176 g) was washed twice with anhydrous hexane to remove the mineral oil and was placed in water.

  suspension in anhydrous THF (50 ml). 2-methyl-3-

  hydroxy-3- (2,4-dichlorophenyl) -4- (1,2,4-triazol-1-yl) but-1-ene (0.8 g) (Compound No. 6 of Table I) was added slowly to the suspension of sodium hydride. There was effervescence during the addition. The mixture was stirred and heated at reflux for 30 minutes under an anhydrous inert atmosphere, cooled to room temperature and supplemented with methyl iodide (0.769 g). The mixture was stirred and refluxed in 30 minutes. It was refluxed for 3 hours under an anhydrous inert atmosphere. The reaction mixture was then cooled to room temperature, poured into water and extracted into ethyl acetate (3 x 100 ml). The combined ethyl acetate extracts were dried (Na 2 SO 4), filtered, and the filtrate evaporated in vacuo to leave an oil. This oil was subjected to column chromatography on silica gel with ethyl acetate as eluent. We got in the form

  of a yellow oil, 2-methyl-3-methoxy-3- (2,4-dichlorophenyl)

  nyl) -4- (1,2,4-triazol-1-yl) but-1-ene (0.412 g).

  Proton magnetic resonance: 1.50 (3H, s), 3.41 (3H, s), 4.88 and 5.27 (2H, AB q), 5.8 (1H, s), 5.43 ( 1H, s), 7.08 (1H, dd), 7.37 (1H, d), 7.40 (1H, d), 7.59 (1H, s), 7.70 (1H, s), M / Z 280 (M-OMe) +

EXAMPLE 6

  Preparation of Compound No. 15 of Table I

0 = -C -CH3

0 /

_ / CH3

N-N - CH2 - C

  kN; CH 2 Cl 2 Sodium hydride (55% dispersion, 0.11 g), washed with anhydrous hexane to remove the mineral oils, was suspended in anhydrous THF

  (50 ml). 2-methyl-3-hydroxy-3- (2,4-dichlorophenyl) -4-

  (1,2,4-triazol-1-yl) but-1-ene fine powder (0.5 g) (compound N 6 of Table I) was added with stirring with sodium hydride. There was effervescence during the addition. The mixture was heated under reflux for an hour under an anhydrous inert atmosphere and was cooled to room temperature. Acetyl chloride (0.267 g) in THF (5 ml) was added to the reaction mixture, and the reaction mixture was slowly heated to reflux temperature and refluxed for 3 hours. The reaction mixture was then poured into water and extracted with ethyl acetate (3 x 100 ml). The combined ethyl acetate extracts were dried (Na 2 SO 4), filtered, and the filtrate evaporated in vacuo to leave a brown gum. The brown gum was purified by HPLC using as eluent a

  mixture of ethyl acetate and hexane (3: 1 by volume).

  The desired fractions were evaporated in vacuo leaving a residue which was crystallized from a solvent mixture of diethyl ether and hexane.

  giving 2-methyl-3- (2,4-dichlorophenyl) acetate

  (1,2,4-triazol-1-yl) but-1-en-3-yl as a

  solid having a melting point of 111-113 ° C.

  Proton magnetic resonance: 1.60 (3H, s), 2.15 (3H, s), 5.03 (1H, s), 5.22 (1H, s),, 34 and 5.50 (2H, AB q), 7.22 (1H, dd), 7.38 (1H, d), 7.41 (1H, d), 7.77 (1H, s), 7.82;

(1H, s).

M / Z 339 (M +)

EXAMPLE 7

  An emulsifiable concentrate was prepared by mixing the ingredients and stirring the mixture until

  that all the constituents have dissolved.

  Compound of Example 1 10% Dichlorethylene 40% Calcium Dodecylbenzenesulfate 5% "Lubrol" L 10% "Aromasol" H 35%

EXAMPLE 8

  A composition in the form of easily dispersible grains in a liquid, for example water, was prepared by grinding the first three ingredients together in the presence of added water, and then mixing with sodium acetate. The resulting mixture was dried and sieved through N-series sieve 44-100.

  British Standard, giving grains of the desired diameter.

  Compound of Example 1 (Form E) 50% "Dispersol" T 25% "Lubrol" APN5 1, 5% Sodium Acetate 23.5%

EXAMPLE 9

  The ingredients were all ground together to produce a powder formulation easily

dispersible in liquids.

  Compound of Example 1 45% "Dispersol" T 5% "Lissapol" NX 0.5% "Cellofas" B600 2% Sodium acetate 47.5%

EXAMPLE 10

  The active ingredient was dissolved in a solvent and the resulting liquid was sprayed onto the kaolinite granules. The solvent was then allowed to evaporate to produce a

granular composition.

* Compound of Example 1 5% kaolinite granules 95%

EXAMPLE 11

  A composition suitable for use in the disinfection of seeds has been prepared by mixing the

three ingredients.

  Compound of Example 1 50% Mineral Oil 2% Kaolinite 48%

EXAMPLE 12

  A powder for dusting was prepared by

  mixing the active ingredient with talc.

  Compound of Example 1 5% Talc 95%

EXAMPLE 13

  A colloidal formulation was prepared by

  ball milling of the constituents indicated below.

  below then formation of an aqueous suspension of the mixture

crushed, with water.

  Compound of Example 1 40% "Dispersol" T 10% "Lubrol" APN5 1% Water

EXAMPLE 14

  A dispersible powder formulation was prepared by mixing the ingredients indicated below

  then grinding the mixture until homogeneous consistency.

  Compound of Example 1 25% "Aerosol" OT / B 2% "Dispersol" AC 5% Kaolinite 28% Silica 40%

EXAMPLE 15

  This example illustrates the preparation of a dispersible powder formulation. The ingredients were blended and then the mixture was ground in a spray apparatus. Compound of Example 1 25% "Perminal" BX 1% "Dispersol" T 5% Polyvinylpyrrolidone 10% Silica 25% Kaolinite 34%

EXAMPLE 16

  The ingredients listed below have been formulated into a dispersible powder by mixing and grinding

of these ingredients.

  Compound of Example 1 25% "Aerosol" OT / B 2% "Dispersol" AC 5% Kaolinite 68% In Examples 7 to 16, the proportions of

  mentioned ingredients are given by weight.

  The compounds shown in Table 1 and numbered 2 to 15 may be formulated from

  as described in particular in Examples 7 to 16.

  An explanation of the composi-

  tions or substances represented by the various

  trademarks mentioned above.

  LUBROL L condensation product of nonyl

  phenol (1 mole) with ethylene oxide (13 moles) AROMASOL H mixture of solvents formed of alkyl benzene DISPERSOL T and AC mixture of sodium sulfate and a

formaldehyde condensation product

  dehyde with sodium naphthalenesulphonate

  LUBROL APN5 condensation product of nonyl

  phenol (1 mole) with naphthalene oxide (5.5 moles)

  CELLOFAS B600 sodium salt of carboxymethyl

  cellulose used as thickening agent

  LISSAPOL NX condensation product of nonyl

  phenol (1 mole) with ethylene oxide (8 moles) AEROSOL OT / B sodium dioctylsulfosuccinate

  PERMINAL BX sodium alkylnaphthalenesulphonate.

EXAMPLE 17

  The compounds have been tested against various fungal diseases attacking the foliage of plants. The

  technique used was as follows.

  The plants were grown in John Innes jar compost (compost No. 1 or 2) in miniature pots 4 cm in diameter. The test compounds were formulated by bead milling with aqueous "Dispersol" T or as a solution in acetone or in an acetone / ethanol mixture which was diluted to the desired concentration immediately prior to use. use. For foliar diseases, formulations (at 100 ppm active ingredient) were applied by foliar spraying and applied to plant roots in the soil. Spraying was carried out to maximum retention and root watering was carried out to a final concentration equivalent to about 40 ppm of active ingredient based on dry soil. Tween 20 has been added in such quantity that its

  final concentration of 0.05% when the spraying is

  have been applied to cereals.

  For most tests, the compound has been

  applied to the soil (roots) and foliage (by spraying

  one or two days before inoculation of the pathogen with the plant. An exception was the Erysiphe graminis trial, in which plants were inoculated 24 hours before treatment. of the

  foliar pathogens were applied by pul-

  Verification in the form of suspensions of spores on the leaves of the test plants. After inoculation, the plants were placed in an appropriate environment to allow the infection to develop, and then incubated until the disease had developed to the point where Evaluation. The time elapsed between inoculation and evaluation varied from

  4 to 14 days depending on the pathogen and the environment

  is lying. Inhibition of the disease was assessed according to the following rating scale: 4 = no attack 3 = traces up to 5% attack of untreated plants 2 = 6 to 25% non-plant attack treated 1 = 26 to 59% attack of untreated plants

  0 = 60 to 100% attack of untreated plants.

  The results are shown in Table II.

EXAMPLE 18

  Some compounds in Table I have been submitted to

  an activity test on the growth of plants vis-à-

  of four species to estimate various effects in relation to

  with the regulation of plant growth.

  Methodology The plant species used in this selective test are presented in Table III which indicates the leaf development stage at which the plants were sprayed. Each chemical agent was applied at a rate of 4000 parts per million (4 kg / ha in a volume of 1000 liters per hectare of field) at

  medium of a rail-mounted sprayer.

  After spraying, the plants were grown in a greenhouse at temperatures of 25 ° C during the day and 22 ° C at night and additional lighting was provided if necessary (using mercury vapor lamps) to achieve photoperiod of 16 hours An exception was made for the temperature of cereals, wheat and barley, which were grown at temperatures of 16'C

the day and 13 C at night.

  After 2 to 6 weeks in the greenhouse, depending on the time of year, the plants were examined with the naked eye to assess their morphological characteristics. Blank formulations were used as controls for the evaluation of plants. The results are presented

in Table IV.

TABLE II

  No of PUCCINIA ERYSIPHE VENTURIA CERCOSPORA

  RECONDITA GRAMINIS COMPOUND INAEQUALIS ARACHIDICOLA

(BLE) (BARLEY) (POMMIER) (PEANUT)

1 4 4 4 4

2 4 4 4 4

3 4 4 4 4

4 4 4 '4 4

4 4 4 4

6 4 4 4

7 4 4 4 4

8 4 4 4 4

9 4 4 4 4

4 4 4 -

he 3 4 4 4

12 4 2 4 4

13 4 1 4 4

14 4 4 4 4

3 1 4 4

- No result

TABLE III

  VEGETABLE EQUIPMENT USED FOR SELECTIVE STUDY ON WHOLE PLANTS

  SPECIES CODE VARIETE STAGE OF NUMBER OF

GROWTH IN PLANTS BY

MOMENT OF THE 7.5 CM POT

TREATMENT

  Barley BR Atem 1-1.5 Sheets 3 * Wheat WW Rapier ** 1-1.5 Sheets 3 * But MZ Earliking 2 1/4 Sheets 1 Tomato TO Alisa Craig 2 1/2 Sheets 1

  * For compound 1, there were 4 plants per pot.

  ** For compound 1, the Timmo variety was used.

re en

TABLE IV

SPECSE BR WW MZ TO

EFFECT COMPOUND

1 Y 1 2 3 3

L 1 2 3 3

D 1 2 3 3

G i 1 2 R i

E 1 3

Q 3

2 Y 2 i D 1 i

B 2

G 2

E 1

Q 1 3 Y i

D 2

E 2

G 1 2

L 1

4 Y 1 2

D 1 2

L 2

E 3

G 3

B 2

Q 3

R i TABLE IV (continued)

SPECSE BR WW MZ TO

EFFECT COMPOUND

Y 1 1

L 2 1

E 1

R 2

G 1

s 1 1

6 R 1

Y 2 3

L 3 3

D 3

B 3

E 3

Q 3

S 2

G 1

9 Y 1

L 1

D 1

E 1

R 1

10 Y 1

L 1

E 1

R 2

  Key Y = delay of whole plant L = shorter internodes D = smaller leaf area G = darker green R = greater number of lateral shoots E = morphogenic effects (on leaves) Q = apical effects B = leaves less many S = reduced number of lateral shoots All effects were visually assessed on a scale of 1 to 3 in which

1 = 10 - 30%

2 = 31 - 60%

3 - 61 - 100%

  A blank means that the effect is less than 10% or that

the test was not performed.

Claims (12)

  1. Derivatives of triazole and their stereo-   isomers, characterized in that they correspond to the general formula (I): OR5 R1 R2 (I) NN N-CH - C 'R3    Wherein R is phenyl optionally substituted with halogen, alkyl, alkoxy,   haloalkyl, haloalkoxy, nitro, halomethylenedio-   xy, amino, mono- or di-alkylamino, hydroxy, morpholino or alkoxycarbonyl, or phenyl, phenoxy, benzyl or benzyloxy, each optionally substituted with halogen; R1, R2 and R3 represent independently   hydrogen, a halogen, an alkyl group or trialkyl-   silyl; R4 is hydrogen or an alkyl group; R5 is hydrogen, alkyl, cycloalkyl, alkenyl,   alkynyl, optionally substituted benzyl or alkylcar-   bonyle (provided that the carbon atom adjacent to   the oxygen atom is not involved in any   saturation); and their acid addition salts and metal complexes; provided that R1, R2, R3 and R4 are not all hydrogen and that when R1 and R2 are both hydrogen then R3 is not alkyl group.   2. Triazole derivatives and their stereo-   isomers, characterized in that they correspond to the general formula (I): OR5 R1 R2 - N - CH C C C R 3   N R i and their stereoisomers wherein R is phenyl or phenyl substituted with halogen, C1-C5 alkyl, C1-C4 alkoxy, haloalkyl   C1 to C4, C1-C4 haloalkoxy, nitro, halomethyl-   ethyldioxy, amino, mono- or di- (C1-C4) alkylamino, hydroxy, morpholino or (C1-C4) alkoxycarbonyl, or R is phenyl substituted with phenyl, phenoxy, benzyl or benzyloxy, each of which may be substituted by a halogen; R1, R2, R3 represent hydrogen, halogen, C1-C6 alkyl, trialkylsilyl (where the alkyl chains may be straight or branched chains having 1 to 6 carbon atoms) or a straight-chained alkyl group or branched chain having 1 to 6 carbon atoms; R4 is hydrogen or (C1-C6) alkyl with the proviso that not all of R1, R2, R3 and R4 are hydrogen and that when R1 and R2 are both hydrogen, R3 is not a straight or branched chain alkyl group having 1 to 6 carbon atoms; R5 is hydrogen, C1-C6 alkyl, C3-C6 alkenyl, C3-C6 alkynyl, optionally substituted benzyl or (C1-C4) alkylcarbonyl (with the proviso that the carbon atom adjacent to the oxygen atom is not involved in unsaturation); and their acid addition salts and their metal complexes.   3. Derivatives of triazole according to any   than the preceding claims, characterized in that   R is a phenyl group or a substituted phenyl group which   is a 2-, 3- or 4-chlorophenyl group, 2,4- or 2,5-   dichlorophenyl, 2-, 3- or 4-fluorophenyl, 2,4- or 2,6-   difluorophenyl, 2-, 3- or 4-bromophenyl, 2-chloro-4-   fluorophenyl, 2-fluoro-4-chlorophenyl, 2-chloro-6-   fluorophenyl, 2-, 3- or 4-methoxyphenyl, 2,3-dimethoxy-   phenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-nitro-   phenyl, 2-chloro-4-nitrophenyl, 2-chloro-5-nitrophenyl,   2-, 3- or 4-trifluoromethoxyphenyl, 2-, 3- or 4- (1,2,2,2-   tetrafluoroethoxy) phenyl, 2-, 3- or 4-methylphenyl, 2,4-   dimethylphenyl, 2-, 3- or 4-butylphenyl, 2,3- (difluoro-   methylenedioxy) phenyl, 2-fluoro-4-methoxyphenyl, 2-   methoxy-4-fluorophenyl, 2-methoxy-4-chlorophenyl, 2-   chloro-4-methoxyphenyl, 2-, 3- or 4-phenoxyphenyl, 2-, 3-   or 4-phenylphenyl, (2-, 3- or 4-biphenylyl), 2-, 3- or   4-benzylphenyl, 2-, 3- or 4-benzyloxyphenyl, 2-, 3- or 4-   (4-chloro- or 4-fluorobenzyloxy) phenyl, 2-, 3- or 4-   aminophenyl, 2-, 3- or 4- (N, N-dimethylamino) phenyl, 2-,   3- or 4-hydroxyphenyl, 2-, 3- or 4- (methoxycarbonyl) phenyl   nyl or 2-, 3- or 4-morpholinophenyl.   4. Triazole derivatives and their stereo-   isomers according to any one of the claims   preceding, characterized in that they correspond to the general formula (I): OR5 R1 R2 N-N- CH - C - C C R3 N. R4 R (I)   wherein R is an optional phenyl group   substituted with fluorine, chlorine, C1-C4 alkyl or C1-C4 alkoxy; R1, R2 and R3 independently represent chlorine, bromine, hydrogen, C1-C4 alkyl or trimethylsilyl; R4 is hydrogen or C1-C4 alkyl; R5 is hydrogen, C1-C4 alkyl (C1-C4 alkyl) -carbonyl, allyl, propargyl or benzyl optionally substituted with chlorine; and their acid addition salts and metal complexes; provided that R1, R2, R3 and R4 are not all hydrogen and that when R1 and R2 are both hydrogen, R3 is not a group C1 to C4 alkyl.   5. Triazole derivatives and their stereo-   isomers according to any one of the claims   preceding, characterized in that they correspond to the general formula (I): OR5 R1 R2 R3 N-N CH C R   (I) wherein R is phenyl, 4-chlorophenyl or   2,4-dichlorophenyl; R1, R2 and R3 independently represent   hydrogen, chlorine, bromine, methyl or trimethylsilyl; R4 is hydrogen; R5 is hydrogen, methyl or acetyl; and their acid addition salts and metal complexes, provided that when R1 and R2 are hydrogen, R3 is neither hydrogen or a methyl group. 6. The compounds of formulas: OH CH3 N N - CH2 - C 2   (Compound 6 of Table I) ## STR2 ## N ... CH2. C-C CH2   CH 2 C (Compound 5 of Table I) and their stereoisomers; as well as their acid addition salts and their metal complexes according to the claim 1.   7. Process for the preparation of the derivatives of   triazole according to any one of claims 1 to 6,   characterized in that it consists in reacting a compound of general formula (II) or (III): ## STR2 ## CH- C h C R3 X -CH2-C C- 4 R (II) (III)   wherein R, R 1, R 2, R 3 and R 4 are as defined in claim 1 and X is a halogen (preferably a chlorine or bromine atom), with 1,2,4-triazole in the presence of a acid acceptor or in the form of one of   its alkali metal salts in a suitable solvent.   8. Process for preparing triazole derivatives of general formula (VIII): OH R1 R2 N-N-C - C - C -H 11 <1 1 \ N R4 R (VIII)   in which R and R4 have the definition given in claim 1, and R1 and R2 represent the same halogen atom, characterized in that it consists in reacting a compound of general formula (VII): OH N-N - CH - C-C-CH X'NV <R4 R   (VIi) with a halogen (preferably chlorine or bromine) in   presence of light in a suitable solvent.   9. Process for the preparation of triazole derivatives of general formula: OH H H I <NS R4 A ( NN -CHC   in which R and R4 have the definition given in claim 1 and R3 is a tri (C1-C6) alkyl silyl group, characterized in that it consists in reacting a compound of general formula (IX): OH N- N CH- C C - C-H   Wherein R4 and R are as defined in claim 1, with an alkyl lithium (preferably methyl lithium or n-butyllithium) in a suitable anhydrous solvent of the type d. an ether, and then treat with a trialkylsilyl halide to obtain a compound of the general formula (X): OH N-N-CH-C-CR3 (X) I - 'R4 R   wherein R and R4 are as defined in claim 1 and R3 is a tri (C1-C6) alkyl silyl group, which is then reduced with a reducing agent of the type of an aluminum hydride (preferably sodium hydride and bis (2-methoxyethoxy) aluminum) in a suitable solvent.   10. Composition with fungicidal or regulatory effect   plant, characterized in that it comprises as active ingredient a compound according to claim 1 or a stereoisomer, an acid addition salt or a metal complex thereof and,   an appropriate support or diluent.   Method for combating fungi, characterized in that it consists in applying to a plant, to its seeds or in the place of the plant or seed, a compound according to claim 1 or a stereoisomer, a salt of acid addition or a metal complex of this   compound, or a composition according to claim 10.   12. A method for influencing plant growth, characterized in that it consists in applying to a plant, to its seeds or to the place of the plant or plant.   seed, a compound according to claim 1 or a steroid   isomer, an acid addition salt or a metal complex thereof, or a composition according to claim 10.