FR2601010A1 - Sulphonylbenzimidazole derivatives, their preparation and their use as fungicides - Google Patents

Abstract

The present patent application relates to new sulphonylimidazole derivatives and to the preparation of these compounds. It also relates to the agricultural use as pesticides, especially fungicidal and acaricidal, of sulphonylimidazole derivatives. The compounds according to the invention are characterised in that they correspond to the general formula I: in which: R1 and R2, which are identical or different, represent a hydrogen atom or a lower alkyl radical; R3 represents a lower alkyl radical or an amino radical optionally substituted by one or two lower alkyl radicals; Z1, Z2, Z3 or Z4, which are identical or different, each represent a group chosen from =CH-, =CR- or =N-; X represents a sulphoxide group S=O or a hydroxyimino group.

Description

 The present patent application relates to novel sulfonylimidazole derivatives as well as the preparation of compacted ESCs. It also relates to the use in agriculture as a pesticide, especially antifungal and acaricide, of sulfonylimidazole derivatives. It also relates to pesticide compositions, in particular antifungal compositions, which can be used in agriculture, and containing as active ingredient one of these derivatives, as well as the pesticidal treatments and more particularly the antifungal or acaricidal treatments carried out using these compounds. Finally, it relates to various chemical compounds used in the preparation of the sulfonylimidazole derivatives according to the invention.

 An object of the present invention is to make available to agriculture antifungal agents with improved efficacy against fungal diseases causing serious damage such as downy mildew, especially downy mildew. tomato (Phytophthora infestans), downy mildew (Plasmopara viticola) and tobacco mildew (Peronospora tabacina).

 Another object of the invention is to provide antifungal agents for agriculture which furthermore have antifungal activity with respect to various other phytopathogenic fungi.

 Other objects of the invention will appear on reading this text.

dans laquelle
- R1 et R2 identiques ou différents, représentent l'atome d'hydrogène ou un radical alkyle inférieur, cycloalkyle inférieur, aryle (notamment phényle), araîkyle, alkoxy inférieur, alcanoyle inférieur, aroyle (notamment benzoyle), ces divers radicaux pouvant être éventuellement substitués (par exemple par un ou plusieurs atomes ou radicaux tels que les atomes d'halogène, les radicaux alkoxy inférieur, carboxyle, hydroxy), ou bien
- R1 ou R2 peuvent former ensemble un radical unique divalent hydrocarboné, comprenant de 2 à 6 atomes de carbones, l'un de ces atomes de carbone pouvant être remplacé par un atome d'oxygène ou d'azote, ledit radical unique divalent étant lui-même éventuellement substitué (par exemple par un ou plusieurs atomes d'halogène ou radicaux alkyle inférieur, alkoxy inférieur, hydroxy),
- R3 représente un radical alkyle inférieur éventuellement substitué (par exemple par un ou plusieurs atomes d'halogène) ; cycloalkyle éventuellement substitué (par exemple par un ou plusieurs atomes d'halogène) ; amino éventuellement substitué par un ou deux radicaux alkyle inférieur eux-mêmes éventuellement substitués (par exemple par un ou plusieurs atomes d'halogène ou radicaux alkoxy inférieurs), ce radical amino pouvant être constitué par un atome d'azote substitué par un radical unique divalent formant avec cet atome d'azote un hétérocycle comportant de 3 à 7 chainons, comprenant éventuellement un deuxième hétéroatome choisi parmi l'oxygène et l'azote, ledit hétérocycle étant lui-même éventuellement substitué (par exemple par un ou plusieurs atomes d'halogène ou radicaux alkyle inférieur, alkoxy inférieur, hydroxy)
- Z2, z2, z3, Z4 identiques ou différents représentent chacun un groupe choisi parmi =CH-, =CR- ou =N-, un ou deux de ces quatre groupes Z1, Z2, Z3'
Z4 pouvant représenter l'atome d'azote trivalent =N- et, lorsque plusieurs groupes =CR- sont présents, les substituants R pouvant être identiques ou différents,
- R représente l'atome dthalogelle ou un radical alkyle inférieur éventuellement substitué (par exemple par un ou plusieurs atomes d'halogène) ; alkoxy inférieur éventuellement substitué (par exemple par un ou plusieurs atomes d'halogène ou par le radical phényle) ; alkylthio inférieur éventuellement substitué (par exemple par un ou plusieurs atomes d'halogène) ; alcényle inférieur alcényloxy inférieur ; alcynyle inférieur ; alcynyloxy inférieur ; phénoxy éventuellement substitué (par exemple par un ou plusieurs atomes d'halogène ou radicaux trifluorométhyle) ; phénylthio ou phénylsulfinyle ou phénylsuSfonyle, ces radicaux étant éventuellement substitués (par exemple par un ou plusieurs sloe; d'halogène ou radicaux trifluorométhyle) ; amino éventuellement substitué par un ou plusieurs radicaux alkyle inférieurs identiques ou différents ; nitro, cyano, thiocyanato, isothiocyanato, alkylsulfonyle inférieur, sulfamoyle éventuellement substitué par un ou deux radicaux alkyle inférieurs identiques ou différents, acyle (par exemple alcanoyle inférieur) éventuellement substitué (par exemple halogéné) ou benzoyle éventuellement halogéné, alkoxycarbonyle inférieur.The compounds according to the invention are characterized in that the tools correspond to the general formula (I):

in which
R 1 and R 2, which are identical or different, represent the hydrogen atom or a lower alkyl, lower cycloalkyl, aryl (especially phenyl), alkyl, lower alkoxy, lower alkanoyl, aroyl (especially benzoyl) radical, these various radicals possibly being substituted (for example by one or more atoms or radicals such as halogen atoms, lower alkoxy, carboxyl or hydroxy radicals), or
R 1 or R 2 may together form a single divalent hydrocarbon radical comprising from 2 to 6 carbon atoms, one of these carbon atoms being capable of being replaced by an oxygen or nitrogen atom, the said divalent single radical being -also optionally substituted (for example by one or more halogen atoms or lower alkyl radicals, lower alkoxy, hydroxy),
- R3 represents an optionally substituted lower alkyl radical (for example by one or more halogen atoms); optionally substituted cycloalkyl (for example with one or more halogen atoms); amino optionally substituted by one or two lower alkyl radicals themselves optionally substituted (for example by one or more halogen atoms or lower alkoxy radicals), this amino radical possibly being constituted by a nitrogen atom substituted with a single divalent radical; forming with this nitrogen atom a heterocycle comprising from 3 to 7 chain members, optionally comprising a second heteroatom selected from oxygen and nitrogen, said heterocycle being itself optionally substituted (for example by one or more halogen atoms) or lower alkyl, lower alkoxy, hydroxy)
Z2, z2, z3, Z4, which are identical or different, each represent a group selected from = CH-, = CR- or = N-, one or two of these four groups Z1, Z2, Z3 '
Z4 may represent the trivalent nitrogen atom = N- and, when several groups = CR- are present, the substituents R may be identical or different,
R represents the halogel atom or an optionally substituted lower alkyl radical (for example by one or more halogen atoms); lower alkoxy optionally substituted (for example with one or more halogen atoms or with the phenyl radical); optionally substituted lower alkylthio (for example with one or more halogen atoms); lower alkenyloxy lower alkenyl; lower alkynyl; lower alkynyloxy; optionally substituted phenoxy (for example by one or more halogen atoms or trifluoromethyl radicals); phenylthio or phenylsulphinyl or phenylsulfonyl, these radicals being optionally substituted (for example by one or more halogen or trifluoromethyl radicals); amino optionally substituted with one or more identical or different lower alkyl radicals; nitro, cyano, thiocyanato, isothiocyanato, lower alkylsulfonyl, sulfamoyl optionally substituted with one or two identical or different lower alkyl radicals, optionally substituted acyl (for example lower alkanoyl) (for example halogenated) or optionally halogenated benzoyl, lower alkoxycarbonyl.

X represents a sulphoxide group (S = O) or an oxyimino group of formula N-O-R4 in which R 4 corresponds to a hydrogen atom or to a lower alkyl radical, lower cycloalkyl, aryl (in particular phenyl), ara-alkyl
(especially benzyl), lower alkenyl (mono- or polyunsaturated), lower alkinyl (mono- or polyunsaturated), lower alkanoyl, lower cycloalkanoyl, aroyl (such as benzoyl), aryloxycarbonyl (such as benzyloxycarbonyl), lower cycloalkoxycarbonyl, lower alkoxycarbonyl, alkanoyloxy lower, aroyloxy, lower cycloalkanoyloxy (in this case the carbonyl group is not taken into account in the term "lower"), carbamyl, N-arylcarbamyl, N-lower alkyl carbamyl,
N, N-dialkyl-lower carbamyl, N, N-diaryl carbamyl,
N-alkyl N-aryl carbamyl, lower alkyl sulphonyl,
arylsulfonyl, alkylsulfonyl, lower alkenyl
sulfonyl, lower alkinylsulfonyl, alkyl phosphate
lower, lower alkyl phosphonate, phosphinate
lower alkyl, all the aforementioned radicals being
optionally substituted with one or more atoms
halogen or trifluoromethyl radicals or radicals
lower alkyl carboxylate, aryl or aralkyl,
more, the aforementioned radicals comprising a group
cycloaliphatic or aromatic which may be optionally
substituted by one or more lower alkyl radicals.

The invention also includes acceptable salts
in agriculture compounds of formula (I), especially those
formed with mineral bases such as soda as well
that the salts and / or complexes formed with the metals of
transition such as mercury copper, zinc, cadmium, iron,
cobalt, nickel.

As an example, complexes with zinc
can be obtained by reacting the compound of
formula (I) with zinc chloride.

For the purposes of this text, we mean that the adjective
lower, when it qualifies an organic radical,
means that this radical has at most six atoms of
carbon. This radical can be linear or branched.

dans laquelle Z5 et Z6 correspondent à un motif choisi parmi = C- ou = N-, étant entendu que si Z5 et/ou Z6 correspondent à un motif = C-, ils sont associés à un groupement R ou à un atome d'hydrogène et dans laquelle
R1, R2 R3, R, X et R4 ont la signification déjà indiquée dans la formule (I) et n est un nombre entier, positif ou nul, inférieur à 4, étant entendu que lorsque n est supérieur à 1, les divers substituants R peuvent être identiques ou différents.Among the compounds corresponding to formula (I),
the invention relates more particularly to the derivatives of
benzimidazole of formula (II):

in which Z5 and Z6 correspond to a unit chosen from = C- or = N-, it being understood that if Z5 and / or Z6 correspond to a unit = C-, they are associated with an R group or a hydrogen atom and in which
R 1, R 2, R 3, R, X and R 4 have the meaning already indicated in formula (I) and n is an integer, positive or nil, less than 4, it being understood that when n is greater than 1, the various substituents R may be the same or different.

Among the compounds of formulas (I) and (II), the invention preferably relates to the following variants taken alone or in combination:
R represents a fluorine, chlorine, bromine atom or a
trifluoromethyl radical, trifluoromethoxy,
trifluoromethylthio, propargyl, nitro, phenoxy
optionally substituted by one or more atoms
halogen or trifluoromethyl radicals,
R3 represents a lower dialkylamino radical,
preferably the dimethylamino or pyrrolidino radical or
piperidino or lower alkyl preferably substituted
isopropyl,
R1 and R2 correspond to the hydrogen atom n, in the formula (II), is preferably equal to zero, one,
two or three, the value n = 2 being particularly
preferred,
R4 is the hydrogen atom or a group
S02-R5 wherein R5 is a hydrogen atom
or
a lower alkyl radical, aryl, araikyl, alkenyl
lower, lower alkinyl, all radicals
mentioned above which may be substituted by a
or more halogen atoms or radicals
trifluoromethyl or alkyl carboxylate radicals
lower, aryl or aralkyl, the aforementioned radicals
having a cycloaliphatic or aromatic group
possibly being substituted by one or
several lower alkyl radicals.

Among the meanings of R4 one will prefer
again those where R4 is the hydrogen atom, or a
lower alkylsulphonyl radical, arylsulfonyl
(phenylsulfonyl), aralkylsulfonyl (benzylsulfonyl)
optionally substituted as indicated above.

In addition, the invention preferably relates to
compounds of formula (I) wherein X is a sulfoxide group (S = O).

The present invention furthermore relates to the process
for preparing the compounds of formula (I) and of course
those of formula (II) since these are included in the
compounds of formula (I). The formulas of the compounds are
indicated in the appendix of the description.

1 - Preparation of the compounds of formula (I) for which R1 and R2 represent both the atom
of hydrogen and X represents N-O-R4, R4 having the same
meaning than that indicated in the definition of
formula (I).

These compounds, when R4 corresponds to the atom
of hydrogen (compounds of formula (Ia)), may be
obtained by the action of hydroxylamine (NH 2 OH) on
compounds of formula (III) in which Z1 to Z4 and R3
have the same meaning as that indicated in the
definition of formula (I). The reaction of the compounds of
formula (III) with hydroxylamine is carried out
advantageously in a polar organic solvent medium at a
temperature between OOC and temperature
boiling solvent. As a solvent, we use
advantageously alcohols such as methanol or
isopropanol, amides such as N-methyl pyrrolidine, or
mixtures of these solvents with water provided that
the proportion of water by volume does not exceed 20%
of the total volume of the solvent. This list is not limiting.

Preferably, the molar ratio, composed of formula
(III): hydroxylamine is between 0.9 and 0.2.

 Hydroxylamine can be generated in situ by the action of an organic or inorganic base on hydroxylamine hydrochloride. According to a particularly advantageous embodiment, an excess of hydrochloride (1.2 to 2 equivalents) of hydroxylamine is treated with a solution or a suspension of the compound of formula (III) in one of the abovementioned solvents, and then an equivalent amount is added. a mineral base such as sodium hydroxide or aqueous potassium hydroxide, sodium or potassium carbonates, organic bases such as alkoxides, alkali metal salts of carboxylic acids are also suitable for releasing in situ the hydroxylamine of its hydrochloride.

The reaction is preferably carried out between 200 and 6000. The reaction time is generally between 1 and 6 hours, these limits being however absolutely not critical and are given only as an indication.

 When the reaction is complete, the product formed is generally separated from the reaction mixture, for example by filtration, and then washed with the aid of the solvent used previously. When the product formed is soluble in the solvent used, it can be isolated by conventional methods such as precipitation by addition of water or evaporation to dryness.

The compounds of formula (I) for which R1 and
R2 corresponds to the hydrogen atom and X corresponds to the N-OR4 unit with R4 other than H (compounds of formula (Ib)) are obtained by treating the compounds of formula (Ia) with an agent of formula R4Hal in which R4 is different from the hydrogen atom and Hal corresponds to a halogen atom. The reaction is preferably carried out in an organic solvent medium in the presence of a base which may be a mineral base such as potassium hydroxide, sodium hydroxide, alkali metal carbonates or an organic base such as a tertiary amine or an alkoxide. alkali metal at a temperature between OOC and the reflux of the solvent in a molar ratio, starting compound: R4Hal between 1.1 and 0.2.On can also initially prepare the alkali metal salt of the compounds of formula (I) for which R1 and R2 correspond to the hydrogen atom and X = NOH and then react in a solvent medium with R4Hal. To prepare the foregoing salt, bases such as alkali metal hydrides can be used. As the solvent, use is advantageously made of alcohols such as isopropanol, ketones such as acetone, ethers such as dioxane or other solvents such as pyridine or acetonitrile.

 When the reaction is complete, the product formed is generally separated from the reaction mixture, for example by filtration, and then isolated by any means known per se.

When the product formed is soluble in the solvent used, it can be isolated by conventional methods such as precipitation by addition of water or evaporation to dryness.

2 - Preparation of compounds according to formula (I) for which at least one of the groups R1 and R2 does not represent the hydrogen atom and X represents
NO-R4, R4 having the same meaning as given in the definition of formula (I).

These compounds are obtained in three stages to
R4 = H (compounds of formula (Ic)) and in four steps for R4 = H (compounds of formula (Id)).

1st step: The compounds of formula (IV) for which Z1 to Z4, R3 have the same meaning as that indicated for the definition of formula (I) can be obtained by the action of hydrogen sulfide on nitriles of formula (III ).

 The reaction is advantageously carried out at a temperature of between 0 and 50 ° C. in the presence of a suitable catalyst, in an inert organic solvent medium.

 The catalyst used is preferably ammonia or an aliphatic amine such as triethylamine or triethanolamine. It is also possible to use as catalysts the hydrogen sulfides or the carbonates of the alkali metals or of ammonium.

 As such, aromatic hydrocarbons such as toluene, halogenated hydrocarbons such as chloroform, alcohols such as isopropanol, ketones such as acetone, ethers such as dioxane, or other solvents are advantageously used. such as pyridine.

 According to a particularly advantageous embodiment, a solution or suspension of the nitrile of formula (III) in one of the abovementioned solvents is saturated with hydrogen sulphide in the presence of a suitable catalyst. The reaction is preferably carried out at room temperature (about 20 ° C. to 300 ° C.). If desired, it may be carried out under a pressure of sulfuric acid above atmospheric pressure, and generally below 5 bar. The reaction time is generally between 1 hour and 6 hours, these limits being however absolutely not critical and being given only as an indication, They usually depend on the amount of reagents used.

 When the reaction is complete, the product formed is generally separated from the reaction mixture, for example by filtration, and then isolated by any means known per se. It is thus possible to rinse with the aid of the solvent used previously, and finally to wash, for example with a hydrocarbon, in particular a saturated hydrocarbon such as pentane.

 When the product formed is soluble in the solvent used, it can be isolated by conventional methods such as precipitation by addition of water or dry evaporation.

2nd step: The compounds of formula (IVa) for which at least one of the substituents R 1 or R 2 is not the hydrogen atom can be obtained from the compounds of formula (IV) obtained in the 1st step, by exchange reaction with a primary or secondary amine of HNR1R2 in which R1 and R2 have the same
meaning than that indicated in the definition of
formula (I), at least one of these substituents being other
that the hydrogen atom preferably in the presence of a
organic solvent.

The reaction is preferably carried out by simple
heating at a temperature ranging from 5O0C to reflux of
solvent.

As a solvent, it is advantageous to use
alcohols such as methanol or ethanol, amides like
N-methylpyrrolidine or mixtures of these solvents with
the water. This list is not exhaustive. According to a mode of
very simple embodiment, the compound of formula
(I) for which X = S and R1 and R2 are the atom
of hydrogen in the presence of a primary aliphatic amine or
secondary compound in a molar ratio of formula (IV)
HNR1R2 between 1.1 and 0.2; within one of
aforementioned solvents. The reaction is carried out beyond 500C
preferably at reflux of the solvent. The reaction time
is usually between 5 minutes and 2 hours.

When the reaction is complete the product formed is isolated
by any means known per se, then purified by methods
chemical chromatography.

3rd step: The compound (IVa) thus obtained is reacted
with hydroxylamine under conditions similar to those
indicated for the synthesis of the compounds of formula (I)
R1 and R2 correspond to the hydrogen atom and X to
NO-R4. The compounds of formula (Ic) are thus obtained.

4th step: This compound Ic is then reacted with a
agent of formula R4Hal in which R4 is different
of the hydrogen atom and Hal corresponds to an atom
of halogen under the same experimental conditions as
those indicated previously for the synthesis of the compounds
of formula (Ib) in order to obtain the compounds of formula (Id).

 3- Preparation of the compounds of formula (I) for which R1 and R2 represent the hydrogen atom and X represents S O (compounds of formula If).

 These compounds are obtained by the action of an organic peroxide or hydrogen peroxide on the compounds of formula (IV) previously defined in a compound (IV) molar ratio: peroxide of between 0.8 and 1.5.

 The reaction is advantageously carried out at a temperature of between -200 ° C. and 600 ° C. in a polar solvent medium.

 As the solvent, use is advantageously made of alcohols such as methanol or isopropanol, amides such as N-methyl pyrrolidine, carboxylic acids such as acetic acid, ketones such as acetone or other solvents such as pyridine. This list is not exhaustive.

 According to a particularly advantageous embodiment, a solution or suspension of the thioamide of formula (I) in one of the abovementioned solvents is treated with a substantially stoichiometric amount of hydrogen peroxide. The reaction is preferably carried out between OC and 300C. The reaction time is generally between 1 hour and 6 hours, these limits being however absolutely not critical and given only as an indication. They usually depend on the amount of reagents used. When the reaction is complete, the product formed is generally separated from the reaction mixture, for example by filtration, and then isolated by any means known per se. It is thus possible to rinse with the aid of the solvent used previously, and finally to wash, for example with a hydrocarbon such as pentane.

 When the product formed is soluble in the solvent used, it can be isolated by conventional methods such as precipitation by addition of water or dry evaporation.

 4 - Preparation of the compounds of formula (I) for which at least one of the substituents R 1 and R 2 is not the hydrogen atom and X represents the group S = O.

 These compounds (formula (Ie)) are obtained by oxidation, preferably by reaction with hydrogen peroxide or an organic peroxide, of a compound of formula (IVa) previously defined under the same conditions as those indicated for the preparation of the compounds of formula If from the compounds of formula (IV).

The subject of the invention is also the compounds of formula (IV) and (IVa) for which the substituents Z1 to
Z4, R1 and R2 and R3 have the same meaning as given in the definition of formula (I). These compounds also have fungicidal and acaricidal properties.

 The preparation of the compounds of formula (III) for which Z1 to Z4 and R3 have the same meaning as that indicated above consists in reacting a cyanobenzimidazole of formula (V) in which the groups Z1 to Z4 have the same meaning as for the definition of formula (I) or an alkali metal or ammonium salt of this compound of formula (V) on a halide of formula (VI) XSO 2 R 3 in which R 3 has the same meaning as in formula (I) and X represents a halogen atom, preferably a chlorine atom. The reaction is advantageously carried out in the presence of an acid acceptor, in an anhydrous or non-anhydrous medium, in a solvent which is inert under the reaction conditions, generally at the boiling point of the solvent.

As acid acceptors, it is possible to mention mineral bases such as, for example, sodium hydroxide or potassium hydroxide, alkali metal or alkaline earth metal carbonates, nitrogenous bases such as triethylamine.

As solvents, aprotic polar solvents are advantageously used, for example dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetone, methyl ethyl ketone, acetonitrile,
N-methylpyrrolidone. If desired, this reaction can be carried out in the presence of a suitable catalyst. As a useful catalyst, there may be mentioned phase transfer catalysts, such as, for example, quaternary ammonium derivatives.

 The reaction of the alkali metal or ammonium salt of the compound of formula (V) with halide (VI) does not require the presence of an acid acceptor. It is advantageously carried out in a polar aprotic solvent which is inert under the reaction conditions, anhydrous or otherwise, generally at the boiling point of the solvent. The polar aprotic solvents mentioned above can be used in this reaction.

 If desired, this reaction can also be carried out in the presence of a suitable catalyst, such as, for example, a phase transfer catalyst (for example a quaternary ammonium derivative).

 The alkali metal or ammonium salt of the compound (V) is prepared in a preliminary operation, optionally carried out in situ, by the action of a suitable base (for example sodium hydroxide, potassium hydroxide, ammonia) or an alkali metal carbonate. , or an alkali metal alkoxide (for example sodium methoxide or sodium or potassium ethylate) on this compound (V).

 At the end of the reaction, whatever the method that may be used, the compound formed is isolated from the reaction medium by any means known per se, such as, for example, by distillation of the solvent, or by crystallization of the product in the reaction medium, or by filtration, and then if necessary, this compound is purified by usual methods such as recrystallization in a suitable solvent or liquid chromatography on a silica or alumina column.

 The compound of formula (V) serving as starting material in the preparation process according to the invention may be prepared by the action of ammonia, at a temperature of the order of 10 C, on trichloromethyl-2-benzimidazole of formula (VII) in which the groups Z1 to Z4 have the same meaning for the definition of formula (I).

 The compound of formula (VII) can be prepared by the action of methyl trichloroacetimidate of formula (Cl) 3 C - C = NH (OCH 3) in the presence of acetic acid on the compound of formula (VIII) in which Z1 to Z4 have the same meaning as that indicated in formula (I). Compounds of formula (VIII) are compounds well known to those skilled in the art.

 The present invention also relates to the use of the compounds of formula I as fungicides.

The compounds according to the invention can be used for the fight, both preventive and curative, against various classes of phytopathogenic fungi, in particular against those of the siphomycete, ascomycete, basidiomycete, myxomycete, and fungi imperfecti type, in particular against Phytophthora sp. potato late blight, late blight tomato), Peronospora sp. (including tobacco mildew),
Plasmopora viticola (downy mildew),
Pseudoperonospora sp. (including cucumber mildew and hops mildew), Pythium sp. (melting of seedlings), Albugo sp. (including white cruciferous rust), Fusarium sp. (Fusarium wilt, especially Fusarium wilt)
Rhizoctonia sp. (including rhizoctonia cereals),
Botrytis sp. (including gray rot of the vine),
Plasmodiophora sp. (especially cabbage hernia), and Polymyxa (beetroot rhizomania agent).

The compounds according to the invention also have an advantageous activity against gram-positive and gram-negative bacteria (in particular
Xanthomonas sp. and Corynebacterium) as well as an acaricidal activity of interest against some phytophagous mites, such as Tetranychus urticae.

 Corrosion according to the invention is preferably used for the control of fungal damage to plants mainly late blight Solanaceae and downy mildew. They have excellent selectivity towards crops.

 They are advantageously applied at doses of 0.01 to 5 kg / ha, and more specifically of 0.02 to 1 kg / ha.

 For their practical use, the compounds according to the invention are rarely used alone. Most often they are part of compositions. These compositions, usable for the protection of plants against fungal diseases, or in regulating coripositions of plant growth, contain as active ingredient a compound according to the invention as described above in association with inert solid or liquid carriers, acceptable in agriculture and / or surfactants compatible with the active ingredient, also acceptable in agriculture. In particular, the usual inert carriers and surfactants are usable.

 By the term "carrier" in the present specification means an organic or inorganic material, natural or synthetic, with which the active ingredient is associated to facilitate its application on the plant, on seeds or on the ground. This support is therefore generally inert and must be acceptable in agriculture, especially on the treated plant. The support may be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases , etc ...).

 The surfactant may be an emulsifying, dispersing or wetting agent of ionic or nonionic type. There may be mentioned, for example, salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines. substituted phenols (especially alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (especially alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols. The presence of at least one surfactant is generally indispensable when the active ingredient and / or the inert carrier are not soluble in water and the application agent is water.

 For their application, the compounds of formula (I) are therefore generally in the form of compositions These compositions according to the invention are themselves in various forms, liquid or solid.

 As forms of compositions which are liquid or intended to constitute liquid compositions during application, mention may be made of solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols and powders. wettable (or powder spray), pasta.

 As forms of solid compositions, mention may be made of dusting powders or dispersions with a content of compound of formula (I) of up to 100%) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation from a powder (the content of compound of formula (I) in these granules being between 1 and 80% for the latter cases).

 The emulsifiable or soluble concentrates most often comprise 10 to 80% of active material, the emulsions or solutions ready for application containing, for their part, 0.001 to 20% of active ingredient.

 These compositions may also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, sequestering agents, etc. other known active substances with pesticidal properties (in particular insecticides or fungicides) or with properties promoting the growth of plants (especially fertilizers) or with properties regulating the growth of plants. More generally, the compounds according to the invention can be combined with any solid or liquid additive corresponding to the usual techniques of formulation.

 For example, in addition to the solvent, the emulsifiable concentrates may contain, when necessary, 2 to 20% of appropriate additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes or adhesives previously mentioned.

 From these concentrates, emulsions of any desired concentration can be obtained by dilution with water, which are particularly suitable for application to crops.

 The concentrated suspensions, also applicable in spraying, are prepared in such a way as to obtain a stable fluid product which does not settle and usually contain from 10 to 75% of active substance, from 0.5 to 15% of surfactants, from 0 to 1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, such as antifoams, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as a carrier, water or an organic liquid in which the active ingredient is little or not soluble: some organic solids or mineral salts may be dissolved in the support to help prevent sedimentation or as antifreezes for water.

 Wettable powders (or spray powder) are usually prepared to contain from 20 to 95% active ingredient, and usually contain, in addition to the solid support, from 0 to 5% of a wetting agent, to 10% of a dispersing agent, and, when necessary, from 0 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, coloring agents, etc ...

As an example, here is the composition of some emulsifiable concentrates
Example F (Formulation) 1 - Active Ingredient 400 g / l - Alkaline Dodecylbenzene Sulfonate 24 g / l - Nonylphenol Oxyethylated to 10 Molecules
of ethylene oxide 16 g / l - cyclohexanone 200 g / l - aromatic solvent qs 1 liter
According to another formula of emulsifiable concentrate, it is used
Example F 2 - active ingredient 250 g - epoxidized vegetable oil 25 g - mixture of alkylaryl sulfonate and
of polyglycol ether and fatty alcohols 100 g - dimethylformamide 50 g - xylene 575 g
From these concentrates, emulsions of any desired concentration can be obtained by dilution with water, which are particularly suitable for application to the leaves.

By way of example, here are various compositions of wettable powders (or-powders for spraying)
Example F 3 - active ingredient (compound n 1) ....................... 50% - ethoxylated fatty alcohol (wetting agent) .O 2.5% - ethoxylated phenylethylphenol (dispersing agent) 5% - chalk (inert carrier) ............................. 42,5%
Example F 4 - Active Ingredient (Compound No. 1) ............................. 10% - oxo synthetic alcohol of branched type, in C13
ethoxylated with 8 to 10 ethylene oxide (
wetting) ........................................... 0,75% - neutral calcium lignosulfonate (dispersing agent
health ............................................ 12% - carbonate of calcium (inert load) .... qsp 100% EY-eple F 5: this wettable powder contains the same ingredients as in the previous example, in the following proportions - active ingredient * 75% - wetting agent ... ................................. 1.50% - dispersing agent .......... .......................... 8 8% - calcium carbonate (inert load) .... qsp 100%
Example F 6 - active ingredient (compound n 1) ...................... 90% - ethoxylated fatty alcohol (wetting agent ........ ...... 4% - ethoxylated phenylethylphenol - (dispersing agent) ... 6%
Example F 7 :: active ingredient (compound n 1) .............................. 50% - mixture of surfactants anionic and non-anionic
ionic (wetting agent) ..................... 2,5% - sodium lignosulfonate (dispersing agent) .... 5% - kaolin clay (inert carrier ) 42.5%
In order to obtain these sprayable powders or wettable powders, the active ingredients are intimately mixed in appropriate mixers with the additional substances and milled with suitable mills or other mills. Spray powders are thus obtained, the wettability and suspension of which are advantageous; they can be suspended with water at any desired concentration and these suspensions can be used very advantageously especially for application to the leaves of plants.

 In place of the wettable powders, pasta can be made. The conditions and methods of production and use of these pastes are similar to those of wettable powders or powders to be sprayed.

 As already mentioned, the aqueous dispersions and emulsions, for example the compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included in the general scope of the present invention. The emulsions may be of the water-in-oil or oil-in-water type and may have a thick consistency such as that of a "mayonnaise".

 The compounds according to the invention may advantageously be formulated in the form of water-dispersible granules also included in the scope of the invention.

 These dispersible granules, with an apparent density generally of between approximately 0.3 and 0.6, have a particle size generally of between approximately 150 and 2000 and preferably between 300 and 1500 microns.

 The active ingredient content of these granules is generally between about 1% and 90%, and preferably between 25% and 90%.

 The rest of the granule is essentially composed of a solid filler and optionally surfactant adjuvants conferring on the granule properties of dispersibility in water. These granules can be essentially of two distinct types depending on whether the charge retained is soluble or not in water. When the filler is water soluble, it may be inorganic or, preferably, organic. Excellent results have been obtained with urea. In the case of an insoluble filler, it is preferably mineral, such as for example kaolin or bentonite. It is then advantageously accompanied by surfactants <at a rate of 2 to 20% by weight of the granule) of which more than half is, for example, at least one dispersing agent, essentially anionic, such as an alkaline or alkaline earth polynaphthalene sulfonate or an alkaline or alkaline earth lignosulfonate, the remainder being nonionic wetting agents or anionic compounds such as an alkaline or alkaline earth alkyl naphthalene sulphonate.

 On the other hand, although not essential, other adjuvants such as antifoam agents may be added.

 The granulate according to the invention can be prepared by the necessary ingredients and then granulation according to several techniques known per se (dredger, fluid bed, atomizer, extrusion, etc.). It is generally finished by crushing followed by sieving at the particle size chosen within the limits mentioned above.

 Preferably, it is obtained by extrusion, operating as indicated in the examples below.

Example F 8: Dispersible granules
In a mixer, 90% by weight of active ingredient (compound No. 1) and 10% of pearl urea are mixed. The mixture is then milled in a pin mill. A powder is obtained which is moistened with about 8% by weight of water. The wet powder is extruded in a perforated roll extruder. A granule is obtained which is dried, then crushed and sieved so as to keep only the granules with a size of between 150 and 2000 microns respectively.

Example F 9: Dispersible granules
In a mixer, the following constituents are mixed: active ingredient (compound n 1) 75%
wetting agent (alkylnaphthalene sulphonate
sodium ............................................ 2%
dispersant (polynaphthalene sulphonate
sodium) .................................. 8%
- inert load insoluble in water (kaolin) ..... 15%
This mixture is granulated in a fluid bed, in the presence
water, then dried, crushed and sieved to obtain
granules of dimension between 0.15 and 0.80 mm.

These granules can be used alone, in
solution or dispersion in water so as to obtain
the desired dose. They can also be used to
prepare associations with other active ingredients,
including fungicides, the latter being in the form of
wettable powders, or granules or aqueous suspensions.

The compounds of formula (I) may still be
used in the form of dusting powders; we can
also use a composition comprising 50 g of material
active and 950 g of talc; we can also use a
composition comprising 20 g of active ingredient, 10 g of
finely divided silica and 970 g of talc; we mix and
grind these constituents and apply the mixture by
powdering.

With regard to compositions adapted to
storage and transport, they contain more
advantageously from 0.5 to 95% (by weight) of substance
active.

Thus, the compositions for agricultural use according to
the invention may contain the active ingredients according to
invention in very wide limits, ranging from
5.10 5% to 95% (by weight). Their agent content
surfactant is advantageously between 5% and 40%
in weight.

Doses of use in the case of a use
as fungicides of the compounds according to the invention can
vary within wide limits, especially depending on the virulence of the fungi and climatic conditions.

 In general, compositions containing 5000 to 5000 ppm of active substance are suitable; these values are indicated for ready-to-use compositions. Ppm means "part by million". The zone from 0.5 to 5000 ppm corresponds to a zone of 5 × 10 5 to 0.5% (percentages by weight).

 The invention further relates to a method of treating plants against phytopathogenic fungi.

 This method is characterized in that it consists in applying to these plants an effective amount of a composition containing as active ingredient a compound according to formula (I). By "effective amount" is meant an amount sufficient to allow the control and destruction of fungi present on these plants. The doses of use may, however, vary within wide limits depending on the fungus to be combated, the type of culture, the climatic conditions, and the compound used.

 In practice doses ranging from 1 g / hl to 500 g / hl corresponding substantially to doses of active ingredient per hectare of 10 g / ha to about 5000 g / ha generally give good results. These doses are preferably between 20 and 1000 g / ha.

Example 1
Preparation of 2-carbothioamid-S-oxide 4-chloro-1-dimethylsulfamoyl 6-trifluoromethylbenzimidazole (Compound No. 1) of Formula

 2.5 g of anhydrous sodium acetate, 30 ml of acetic acid and 1.93 g (0.005 mol) of 2-carbothioamide 4-chloro-dimethylsulfamoyl are introduced successively into a flask equipped with magnetic stirring. trifluoromethyl benzimidazole. By maintaining the temperature in the vicinity of 200 ° C., 0.57 ml (0.005 mol) of hydrogen peroxide are added gradually to 300 μl-1. After three hours, the reaction is complete, the suspension is treated with an excess of water; the light yellow precipitate is washed several times with water and then dried under reduced pressure. 1.84 g of 2-carbothioamide-S-oxide 4-chloro-dimethylsulfamoyl-6-trifluoromethylbenzimidazole are thus obtained in the form of a yellow solid. melting at 1500C with decomposition.

Yield 91%.

Preparation of 2-carbothioamide 4-chloro-dimethylsulfamoyl 6-trifluoromethylbenzimidazole
In a three-necked flask equipped with mechanical stirring, 21 g (0.06 mol) of 4-chloro-2-cyano-dimethylsulfamoyl-1-trifluoromethylbenzimidazole are suspended in 250 ml of isopropanol and 10 ml of triethanolamine.

Then, with stirring, a stream of gaseous hydrogen sulfide is bubbled into the suspension at room temperature (about 15 ° C. to 300 ° C.). The reaction mixture then gradually becomes lemon yellow.

 After 4 hours, it is verified by thin layer chromatography (TLC) that the reaction is complete, filtered, washed with 100 ml of isopropanol and then with 200 ml of pentane. 19.9 g of 2-carbothioamide 4-chloro-1-dimethylsulfamoyl-6-trifluoromethylbenzimidazole are thus obtained, melting at 2700C. Yield 86 X.

 The 4-chloro-2-cyano-dimethylsulfamoyl 6-trifluoromethylbenzimidazole used as starting material was prepared according to the method described in European Patent Application No. 0087375.

 Working according to the method of Example 1, starting from the appropriate starting materials, the compounds shown in Table I below were prepared.

The index attached to the letter A indicates the position of the substituent A on the uycle. In the case where A is not indicated, it is the hydrogen atom. This table also shows the corresponding carbothioamide compound which served as starting material.

 The names of these compounds are indicated below according to the French official nomenclature except that the position of the substituents is indicated before the substituent itself.

N 2 6-bromo 2-carbothioamide-S-oxide 1-dimethylsulfamoyl
4-trifluoromethyl benzimidazole.

3-carbothioamide-S-oxide 4-chloro-dimethylsulfamoyl
6-fluoro benzimidazole.

4-Bromo 2-carbothioamide-S-oxide 1-dimethylsulfamoyl
6-trifluoromethyl benzimidazole.

5-carbothioamide-S-oxide 4,6-dichloro
1-dimethylsulfamoyl benzimidazole.

6 4-bromo 2-carbothioamide-6-cyano S-oxide
1-dimethylsulfamoyl benzimidazole.

7 2-carbothioamide-S-oxide 4-iodo-1-isopropylsulfonyl
6-trifluoromethyl benzimidazole 8 2-carbothioamide-S-oxide 1-dimethylsulfamoyl 4-iodo
6-trifluoromethyl benzimidazole.

2-carbothioamide-S-oxide 4-chloro I- (N-pyrrolidino)
sulfonyl 6-trifluoromethyl benzimidazole.

2-carbothioamide-S-oxide 4-chloro 1- (N-morpholino)
sulfonyl 6-trifluoromethyl benzimidazole.

11 80/20 or 20/80 mixture 2-carbothioamide-S-oxide 5-chloro
1-isopropylsulfonyl 6-trifluoromethylbenzimidazole and
2-carbothioamide-S-oxide 6-chloro-1-isopropylsulfonyl
5-trifluoromethyl benzimidazole.

12 4-chloro-dimethylsulfamoyl 2- (N-morpholino)
thiocarbonyl-S-oxide 6-trifluoromethyl benzimidazole.

 Furthermore, in Table I below, as well as in Tables II and III, a mixture of two compounds is sometimes obtained. In this case, the relative proportion of the two compounds is given under the melting point, without attributing to each a specific proportion. For example, in the case of compound No. 12, it was not determined which of them was in proportion 80.

Table I

<tb><SEP> Composes <SEP> ae <SEP> formula
<tb> I <SEP> (I) <SEP> {(il)
<tb> IN <SEP> I <SEP> R3 <SEP> 1 <SEP> A4 <SEP> 1 <SEP> As <SEP> 1 <SEP> A6 <SEP> 1 <SEP> A7 <SEP> I <SEP > pF <SEP> i <SEP> Yield <SEP> 1 <SEP> pF <SEP> I
<tb> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> l <SEP> I <SEP> dec.l <SEP> I <SEP> dec.l
<tb> I <SEP> li <SEP> NMe2 <SEP> I <SEP> Cl <SEP> 1 <SEP> - <SEP> 1 <SEP> CF3 <SEP> 1 <SEP> - <SEP> 11500CI <SEP > 91 <SEP>% <SEP> 12700CI
<tb> I! <SEP> I <SEP> i <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1 <SEP> 2! <SEP> NMe2 <SEP> I <SEP> CF3 <SEP> I <SEP> - <SEP> I <SEP> Br <SEP> I <SEP> | <SEP> - <SEP> 1l62 C1 <SEP> 89 <SEP>% <SEP> 11850CI
<tb> I <SEP> 1 <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> 31 <SEP> NMe2 <SEP> I <SEP> Cl <SEP> I <SEP> - <SEP> | <SEP> I <SEP> F <SEP> I <SEP> - <SEP> Il530C1 <SEP> 90 <SEP>% <SEP> 12170CI
<tb>! <SEP>;<SEP> I <SEP> i <SEP> 1 <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1 <SEP> 41 <SEP> NMe2 <SEP> I <SEP> Br <SEP> | <SEP> I <SEP> | <SEP> CF3 <SEP> 1 <SEP> - <SEP> 1l66 C1 <SEP> 94 <SEP>% <SEP> I2090CI
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1 <SEP> 51 <SEP> NMe2 <SEP> I <SEP> Cl <SEP> | <SEP> I <SEP> - <SEP> I <SEP> Cl <SEP> | <SEP> I <SEP> - <SEP> 1l320CI <SEP> 91 <SEP>% <SEP>) 2000CI
<tb> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1 <SEP> 61 <SEP> NMe2 <SEP> I <SEP> Br <SEP> | <SEP> I <SEP> | <SEP> CN <SEP> g <SEP> - <SEP> 1l59 cl <SEP> 69 <SEP>% <SE> 1209 C |
<tb> I <SEP> I <SEP> - <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> 7ICHMe2 <SEP> I <SEP> I <SEP> I <SEP> - <SEP> I <SEP> CF3 <SEP> 1 <SEP> - <SEP> 1l80 C1 <SEP> 65 <SEP>%<SEP> 12090CI
<tb> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> ì
<tb> 1 <SEP> 81 <SEP> NMe2 <SEP> I <SEP> I <SEP> I <SEP> - <SEP> I <SEP> CF3 <SEP> I <SEP> - <SEP> 11710CI <SEP > 74 <SEP>% <SEP> 12500CI
<tb> I <SEP> I <SEP> rs <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> l <SEP> l <SEP> I
<tb> 1 <SEP> 91 <SEP> NI <SEP> Cl <SEP> ≈ <SEP> - <SEP> | <SEP> I <SEP> | <SEP> CF3 <SEP> | <SEP> I <SEP> - <SEP> 11130CI <SEP> 71 <SEP>% <SEP> 12290Cl
<tb> I <SEP> II <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> llOI <SEP> Cl <SEP> ci <SEP> I <SEP> I <SEP> | <SEP> CF3 <SEP> I <SEP> - <SEQ> 11740CI <SEP> 76 <SEP>% <SEP> 12340Cl
<tb> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP>! <SEP> I <SEP> I
<tb> gillCHMe2 <SEP> I <SEP> - <SEP> I <SEP> Cl <SEP> I <SEP> CF3 <SEP> 1 <SEP> - <SEP> I <SEP> 890CI <SEP> 90 <SEP >% <SEP> 11720CI
<tb> l <SEP> l <SEP> I <SEP> I <SEP> CF3 <SEP> I <SEP> Cl <SEP> 1 <SEP> 180/201 <SEP> l <SEP> I
<tb> l <SEP> l <SEP> I <SEP> l <SEP> l
<tb> I <SEP> I <SEP> i <SEP> s = o <SEP>! <SEP> I <SEP> I <SEP> I
<tb> 1121 <SEP> NI <SEP> I <SEP> N <SEP> | <SEP> Il990CI <SEP> 64 <SEP>% <SEP> j1850CI
<tb> I <SEP> I <SEP> ~ <SEP> 3- <SEP> C <SEP> Nt <SEP>, 0 <SEP> I <SEP> I <SEP> I
<tb> I! <SEP> F3c <SEP> J <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I! <SEP> So2e2 <SEP> I <SEP> I <SEP> I <SEP> I
<tb>'Example XIII
Preparation of 2-carboxamide oxime 4-chloro
1-dimethylsulfamoyl 6-trifluoromethylbenzimidazole of formula

 17.65 g (0.05 mol) of 4-chloro-2-cyano-dimethylsulfamoyl-6-trifluoromethylbenzimidazole, 200 ml of methanol, 3.84 g (0.056 mol) are successively introduced into a flask fitted with magnetic stirring. ) of hydroxylamine hydrochloride in 15 ml of distilled water and finally 5.6 ml of 1N sodium hydroxide. The reaction mixture gradually warms up to 35 ° C. After one hour, the mixture is heated at 65 ° C. for 3 hours. After cooling, the reaction mixture is poured into 250 ml of water, the white solid which precipitates is separated, washed with water, drained and dried under vacuum. There is thus obtained 15.7 g of 2-carboxamide oxime 4-chloro-1-dimethylsulfamoyl 6-trifluoromethylbenzimidazole melting at 180 ° C. Yield 81.4%.

 Working according to the method of Example XIII, from the appropriate starting materials, the compounds shown in Table II below were prepared. The names of the compounds are indicated below according to the French official nomenclature except that the position of the substituents is indicated before the substituent itself.

NO 14 to 33 14 60/40 to 40/60 mixture of 2-carboxamide-oxime
1-dimethylsulfamoyl 5-trifluoromethylbenzimidazole and
2-carboxamide-oxime 1-dimethylsulfamoyl
6-trifluoromethyl benzimidazole.

50/50 mixture of 2-carboxamide-6-chloro oxime
1-dimethylsulfamoyl 5-trifluoromethylbenzimidazole and
2-carboxamide oxime 5-chloro-dimethylsulfamoyl
6-trifluoromethyl benzimidazole.

16 2-carboxamide oxime 4,6 dichloro-1-dimethylsulfamoyl
benzimidazole.

2-carboxamide oxime 1-dimethylsulfamoyl benzimidazole.

18 4-bromo 2-carboxamide oxime 1-dimethylsulfamoyl
6-trifluoromethyl benzimidazole.

19 6-Bromo 2-carboxamide oxime 1-dimethylsulfamoyl
4-trifluoromethyl benzimidazole.

50/50 mixture of 6-bromo-2-carboxamide oxime
1-isopropylsulfonyl 5-trifluoromethylbenzimidazole and
5-bromo-2-carboxamide-oxime 1-isopropylsulfonyl
6-trifluoromethyl benzimidazole.

2-carboxamide oxime 4-chloro-1-isopropylsulfonyl
6-trifluoromethyl benzimidazole.

22 4-bromo 2-carboxamide oxime 1-dimethylsulfamoyl
6-trifluoromethoxy benzimidazole.

23 4-bromo 2-carboxamide oxime 1-isopropylsulfonyl
6-trifluoromethoxy benzimidazole.

2- carboxamide oxime 4-chloro-1-isopropylsulfonyl
6-trifluoromethoxy benzimidazole.

2-carboxamide oxime 4-chloro-dimethylsulfamoyl
benzimidazole.

26 4-Bromo 2-carboxamide-oxime 6-cyano-dimethylsulfamoyl
benzimidazole.

2-carboxamide oxime 1-dimethylsulfamoyl 4-iodo
6-trifluoromethylbenzimidazole.

28-carboxamide oxime 4-iodo-1-isopropylsulfonyl
6-trifluoromethylbenzimidazole.

4-bromo 2,6-bis (carboxamide oxime) 1-dimethylsulfamoyl
benzimidazole.

4-bromo-2-carboxamide-oxime 6-cyano-1-isopropylsulfonyl
benzimidazole.

31 2-carboxamide oxime 4-chloro 6-cyano-dimethylsulfamoyl
benzimidazole.

2-carboxamide oxime 4-chloro 1- (N-morpholino) sulfonyl
6-trifluoromethylbenzimidazole.

33 50/50 mixture of 6-bromo-2-carboxamide-oxime
3-dimethylsulfamoylimidazoE4,5-b] pyridine and 6-bromo
2-carboxamide oxime 1-dimethylsulfamoylimidazo (4,5-b) pyridine.

Table II

<tb> N <SEP> R3 <SEP> A4 <SEP> A5 <SEP> A6 <SEP> A7 <SEP> pF <SEP> Yield
<tb> 13 <SEP> NME2 <SEP> CL <SEP> - <SEP> CF3 <SEP> - <SEP> 181 C <SEP> 81.4%
<tb> 1131 <SEP> NMe2 <SEP> 1 <SEP> CL <SEP> I <SEP> - <SEP> I <SEP> CF3 <SEP> I <SEP> - <SEP> 181 C <SEP> 81, 4 <SEP>% B <SEP>
<tb> 14 <SEP> NMe2 <SEP> - <SEP> F3C <SEP> - <SEP> - <SEP> 158 C <SEP> 74 <SEP>%
<tb> 15 <SEP> NMe2 <SEP> - <SEP> F3C <SEP> Cl <SEP> - <SEP> 179 C <SEP> 86 <SEP>% <SEP> I
<tb> - <SEP><SEP> F3C <SEP> - <SEP><SEP> 150/50 <SEP>
<tb> 1161 <SEP> NMe2 <SEP> I <SEP> Cl <SEP> I <SEP> - <SEP> I <SEP> Cl <SEP> i <SEP> - <SEP> 169 C <SEP> 85 <SEP>%<SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP>
<tb> 17 <SEP> Nme2 <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 160 C <SEP> 85 <SEP>%
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1181 <SEP> NMe2 <SEP> I <SEP> Br <SEP> I <SEP> - <SEP> I <SEP> CF3 <SEP> I <SEP> - <SEP> 192 C <SEP> 63 <SEP>%<SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1191 <SEP> NMe2 <SEP> I <SEP> CF3 <SEP> I <SEP> - <SEP> I <SEP> Br <SEP> I <SEP> - <SEP> 1194 <SEP> 65 <SEP>%<SEP> I
<tb> 20 <SEP> CHMe2 <SEP> - <SEP> CF3 <SEP> Br <SEP> - <SEP> 160 C <SEP> 40 <SEP>%
<tb> - <SEP> Br <SEP> CF3 <SEP> - <SEP> 50/50
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP>
<tb> 21 <SEP> CHMe2 <SEP> I <SEP> Cl <SEP> I <SEP> - <SEP> I <SEP> CF3 <SEP> I <SEP> - <SEP> 12090C1 <SEP> 26 <SEP >% <SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP>
<tb> 22 <SEP> NMe2 <SEP> Br <SEP> - <SEP> OCF3 <SEP> - <SEP> 200 C <SEP> 89 <SEP>%
<tb> 23 <SEP> CHMe2 <SEP> Br <SEP> - <SEP> OCF3 <SEP> - <SEP> 179 C <SEP> 59 <SEP>%
<Tb>
Table II (continued)

## EQU1 ## > pF <SEP> I <SEP> Yr
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1241CHMe2 <SEP> ss <SEP> Cl <SEP> I <SEP> - <SEP> I <SEP> OCF3 <SEP> I <SEP> - <SEP> 11760CI <SEP> 40 <SEP>% <SEP > I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1251 <SEE> NMe2 <SEP> I <SEP> Cl <SEP> | <SEP> I <SEP> - <SEP> I <SEP> OCF3 <SEP> I <SEP> - <SEP> 1200001 <SE> 97 <SEP>%
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> i261 <SEP> NMe2 <SEP> 1 <SEP> Br <SEP> | <SEP> - <SEP> I <SEP> CN <SEP> | <SEP> I <SEP> - <SEP> 1l890C1 <SEP> 77 <SEP>%
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 271 <SEP> NMe2 <SEP> I <SEP> I <SEP> 1 <SEP> - <SEP> I <SEP> CF3 <SEP> I <SEP> - <SEP> 11820CI <SEP> 27 <SEP >%
<tb> It <SEP> l <SEP> I <SEP> I <SEP> I <SEP> I <SEP> l
<tb> 1281CHMe2 <SEP> I <SEP> I <SEP> I <SEP> - <SEP> I <SEP> CF3 <SEP> I <SEP> - <SEP> 12500CI <SEP> 34 <SEP>%
<tb> I <SEP> I <SEP> I <SEP> I <SEP> -I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> I <SEP> I <SEP> 1 <SEP> NOHI <SEP> I <SEP> I
<tb> 1291 <SEP> NMe2 <SEP> I <SEP> Br <SEP> I <SEP> - <SE> IC <SEP> I <SEP> - <SEP> 12220C1 <SE> 65 <SEP>
<tb> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1301CHMe2 <SEP> I <SEP> Br <SEP> | <SEP> I <SEP> - <SEP> I <SEP> CN <SEP> I <SEP> - <SEP> 11870CI <SEP> 15 <SEP>%
SEP> I <SEP>
<tb> 1311 <SEP> NMe2 <SEP> I <SEP> Cl <SEP> | <SEP> I <SEP> - <SEP> I <SEP> CN <SEP> I <SEP> - <SEP> 1l860CI <SEP> 79 <SEP>%
<tb> It <SEP> I <SEP> l <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1321 <SEP> N <SEP> I <SEP> Cl <SEP> I <SEP> Cl <SEP> | <SEP> - <SEP> | <SEP> CF3 <SEP> 1 <SEP> - <SEP> 1l880C1 <SEP> 100 <SEP>%
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1331 <SEP> í <SEP> I <SEP> I <SEP> I <SEP> 11720CI
<tb> He
<tb><SEP> S02NMe
<tb><SEP> B <SEP> w <SEP><,<SE> NOH <SEP> Br <SE> S, O2NMe?
<tb> W <SEP> c <SEP>) <SEP> \ <SEP> F <SEP> TNH2
<tb> I <SEP> I <SEP> I <SEP> 2 <SEP> N-OH
<tb> I <SEP> I <SEP> SO2NMe2
<Tb>
Example XXXVII
Preparation of 2-carboxamide benzoate oxime 4-chloro-1-dimethylfamoyl 6-trifluoromethylbenzimidazole of formula

 19.3 g (0.05 mol) of carboxamide-2-oxime-4-chloro-1-dimethylsulfamoyl-6-trifluoromethylbenzimidazole, 250 ml of pyridine are added to a flask equipped with magnetic stirring and then 6.1 ml is added little by little. (0.052 moles) benzoyl chloride. After stirring for four hours at room temperature, the mixture is heated at 500 ° C. for four hours. After cooling, poured into 1000 ml of distilled water, the white precipitate is filtered off and washed with water.

After drying, 19.8 g of 2-carboxamide oxime 4-chloro-1-dimethylsulfamoyl-6-trifluoromethylbenzimidazole benzoate, melting at 1750 ° C., are thus obtained. Yield 81%.

 Working according to the method of Example XXXVII, from the appropriate starting materials the compounds shown in Table III below were prepared. The names of the compounds are indicated below according to the French official nomenclature except that the position of the substituents is indicated before the substituent itself.

34 2-t0- (benzoyl) carboxamide oxime 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

2- [0- (3,5-dichlorophenylcarbamoyl) carboxamide oxime]
4-chloro-dimethylsulfamoyl 6-trifluoromethyl
benzimidazole.

36 2-t0-pivaloyl) carboxamide oxime] 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

2- [O- (methylcarbamoyl) carboxamide-oximel 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

38 2- [0- (acetyl) carboxamide oxime] 4-chloro
1-dimethylsulfonyl 6-trifluoromethyl benzimidazole.

2- [0- (ethoxycarbonyl) carboxamide oxime] 4-chloro
1-dimethylsulfonyl 6-trifluoromethyl benzimidazole.

2- [0- (carbamoyl) carboxamide oxime] 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

2- [0- (methylsulfonyl) carboxamide oxime] 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

2- [O- (methylethoxycarbonyl) carboxamide oxime] 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

2- [O- (bromophenylsulfonyl) carboxamide oxime] 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

2- [O- (3-methyl-2-butene-1-yl) carboxamide oxime) 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

45 2-t0- (benzyl) carboxamide oxime] 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

2- [O- (4-bromophenylsulfonyl) carboxamide oxime] 4-bromo
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

2- (O- (4-methylphenylsulfonyl) carboxamide oxime] 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

2- [O- (diethylphosphate) carboxamide oxime] 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

49 2- [O- (octylsulfonyl) carboxamide oxime] 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

2- [O- (phenylsulfonyl) carboxamide oxime] 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

2- [O- (4-chlorophenylsulfonyl) carboxamide oxime] 4-chloro
1-dimethylsulfamoyl 6-trifluoromethyl benzimidazole.

Table III

<tb> tN I <SEP> R3 <SEP> I <SEP> R6 <SEP> 1 <SEP> A4 <SEP> 1 <SEP> A5 <SEP> 1 <SEP> A6 <SEP> 1 <SEP> A7 <SEP> I <SEP> pF <SEP> g <SEP> Yr
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> 10 <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> I <SEP> It <SEP> I <SEP> I <SEP> I <SEP> 1 <SEP> I <SEP> I
<tb> 1341NMe2 <SEP> I <SEP> C-C6H5 <SEP> I <SEP> Cl <SEP> I <SEP> - <SEP> I <SEP> CF31 <SEP> - <SEP> 11750CR <SEP> 81 <SEP>%
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> 10 <SEP> I <SEP> I <SEP> 1 <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> I <SEP> It <SEP> Cl <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1351NMe 2 <SEP> I <SEP> CN <SEP><SEP> I <SEP> Cl <SEP> I <SEP> - <SEP> I <SEP> CF3i <SEP> - <SEP> 11870C1 <SEP > 96 <SEP>%
<tb> I <SEP> I <SEP> I <SEP> Cl <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> I <SEP> 0 <SEP> CH3 <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> I <SEP> II <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1361NMe2 <SEP> I <SEP> C <SEP> C <SEP> CH3 <SEP> I <SEP> C1 <SEP> I <SEP> - <SEP> I <SEP> CF31 <SEP> - <SEP > 11720CI <SEP> 90 <SEP>%
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> 10 <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> I <SEP> it <SEP> .1 <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1371NMe2 <SEP> I <SEP> C <SEP> - <SEP> NHCH3 <SEP> I <SEP> Cl <SEP> | <SEP> I <SEP> - <SEP> I <SEP> CF31 <SEP> - <SEP> 11800C1 <SEP> 95 <SEP>%
<tb> It <SEP> l <SEP> I <SEP> I <SEP> I <SEP> I <SEP> l <SEP> l
<tb> I <SEP> I <SEP> 10 <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> I <SEP> It <SEP> 1 <SEP> I <SEP> 1 <SEP> I <SEP> I <SEP> I
<tb> 1381NMe2 <SEP> I <SEP> C <SEP> - <SEP> CH3 <SEP> I <SEP> Cl- <SEP> I <SEP> - <SEP> I <SEP> | <SEP> CF31 <SEP> - <SEP> 11800CI <SEP> 93 <SEP>%
<tb> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> -I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> 10 <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> I <SEP> it <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1391NMe2 <SEP> I <SEP> C <SEP> - <SEP> OC2H5 <SEP> I <SEP> Cl <SEP> I <SEP> - <SEP> | <SEP> I <SEP> | <SEP> CF3i <SEP> - <SEP> 11620CI <SEP> 94 <SEP> X
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> 10 <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> I <SEP> I <SEP> II <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I4OINMe2 <SEP> | <SEP> I <SEP> C <SEP> - <SEP> NMe2 <SEP> I <SEP> Cl <SEP> I <SEP> - <SEP> | <SEP> I <SEP> | <SEP> CF31 <SEP> - <SEP> 11740CI <SEP> 81 <SEP>%
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> i41iNMe2 <SEP> I <SEP> S02CH3 <SEP> I <SEP> Cl <SEP> I <SEP> - <SEP> I <SEP> CF31 <SEP> - <SEP> I1580CI <SEP> 76 <SEP >%
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> l
## STR2 ## SEP>%
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<Tb>
Table III (continued)

<tb> INol <SEP> R3 <SEP> I <SEP> R6 <SEP> I <SEP> A4 <SEP> I <SEP> As <SEP> l <SEP> A6 <SEP> I <SEP> A7 <SEP > I <SEP> pF <SEP> I <SEP> Yr
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> l <SEP> l <SEP> l <SEP> / 7 <SEP> l <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 1431NMe 2 <SEP> I <SEP> S 2 <SEP> + <SEP> bu <SEP> I <SEP> Cl <SEP> I <SEP> - <SEP> I <SEP> CF31 <SEP> - <SEP> 1l440C1 <SEP> 50 <SEP>%
<tb> I <SEP> i <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 144 :: NMe2 <SEP> I <SEP> CH2CH = C (CH3) 2 <SEP> 1 <SEP> 61 <SEP> 1 <SEP> Cl <SEP> I <SEP> | <SEP> CF31 <SEP> - <SEP> 1l66 C1 <SEP> 60 <SEP>%
<tb> i <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> l
<tb> 45jNMe2 <SEP> I <SEP> CH2 <SEP> - <SEP> C6H5 <SEP> I <SEP> Cl <SEP> I <SEP> - <SEP> | <SEP> I <SEP> | <SEP> CF3 | <SEP> - <SEP>) 1850CI <SEP> 15 <SEP>%
## EQU1 ##
<tb> l <SEP> l <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> I <SEP> l <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> j461NMe2 <SEP> | <SEP> I <SEP> SE <SE>>SEP>SEP> SEP > 28 <SEP>%
<tb> l <SEP> l <SEP> l <SEP> l <SEP> l <SEP> l
<tb><SEP> I <SEP> I <SEP> l <SEP> I <SEP> I <SEP> 1 <SEP> I
<tb> d47jNMe2 <SEP> li <SEP> 502 <SEP><<SEP> CH3 <SEP> i <SEP> Cl <SEP> I <SEP> - <SEP> I <SEP> CF31 <SEP> - <SEP > 11480CI <SEP> 28 <SEP>%
<tb> l <SEP> I <SEP> I <SEP> I <SEP> l <SEP> l <SEP> O <SEP> i <SEP> i
<tb> I <SEP> I <SEP> 1 <SEP> !! <SEP> I <SEP> 1 <SEP> I <SEP> I <SEP> I <SEP> I
<tb> 481NMe2 <SEP> IP (0C2H5) 2 <SEP> i <SEP> Cl <SEP> I <SEP> - <SEP> I <SEP> CF3i <SEP> - <SEP> 111620C1 <SEP> 39 <SEP >%
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> J491NMe2 <SEP> I <SEP> 502C8H17 <SEP> I <SEP> Cl <SEP> I <SEP> - <SEP> i <SEP> CF3i <SEP> - <SEP> 1490CI <SEP> 30 <SEP>%
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> SOINMe2 <SEP> I <SEP> S 2C6H5 <SEP> I <SEP> Cl <SEP> I <SEP> - <SEP> I <SEP> CF31 <SEP> - <SEP> 1l590C1 <SEP> 46 <SEP>%
<tb> I! <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> It <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> It <SEP> I <SEP> tii <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> li
<tb> i5ltNMe2 <SEP> li <SEP> S02 <SEP> Q <SEP> Cl <SEP> I <SEP> C1 <SEP> I <SEP> - <SEP> I <SEP> CF31 <SEP> - <SEP > 11510ci <SEP> 28 <SEP>%
<tb> t! <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<tb> l <SEP> l <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I <SEP> I
<Tb>
Biological tests
In vitro experimentation on soil phytopathogenic or aerial fungi
The action of the compounds according to the invention is observed on Phytophthora capsici and Pythium irregulare.

 For each test, the procedure is as follows: a nutrient medium consisting of a sterilized potato extract (83 g / l) and agar (20 g / l) (PDA) is supercooled in a series of Petri dishes (20 ml per box) after sterilization in autoclave at 1200C.

 During the filling of the dishes, an acetonic solution of the active substance is injected into the supercooled medium in order to obtain the desired final concentration.

 Petri dishes analogous to the preceding ones, in which similar amounts of a nutrient medium containing no active material are cast as a control.

 After 24 or 48 hours each dish is seeded by depositing a fragment of mycelium from a previous culture of the aforementioned mushrooms.

 The dishes are kept for 5 days (depending on the fungus tested) at 220 ° C. and the growth of the fungus in the dishes containing the active ingredient to be tested is compared with that of the same fungus in the can used as a control.

 Under these conditions, at the dose of 100 ppm (parts per million), the percentage inhibition of fungus development was as follows: in the case of Phytophthora capsici, the percentages of inhibition of the development of the fungus were greater than 80% for compounds 1 to 11, 14 to 16, 18 to 22, 24 to 26, 31, 33, 42, 43, 46-48, 50, 51.

in the case of Pythium irregulare, the inhibition percentages of fungus development were greater than 80% for compounds 1 to 9, 11, 12, 14 - 16, 18 - 21, 24, 25, 28, 31, 43 , 46, 47, 51-.

Exoérimentation in greenhouse on mildew of the vine (Plasmopara viticola)
Vine cuttings (Vitis vinifera), variety
Chardonnay, are grown in buckets. When these plants are 2 months old (stage 8 to 10 leaves, height 20 to 30 cm), they are sprayed with a suspension or aqueous solution of the test substance, at the desired concentration and containing a condensate. of sorbitan monooleate and 20 molecules of ethylene oxide to half the concentration of active ingredient. Each vine plant receives about 1 ml of the solution or dispersion. To check! Concentrate of active ingredient to be tested, the treatment is carried out on two plants. Plants used as controls are treated with a solution containing no active ingredient, but containing the same condensate of sorbitan monooleate and concentration of ethylene oxide. identical.

 After drying for 24 hours, each plant is contaminated by spraying with an aqueous suspension of Plasmopara Viticola spores, responsible for the downy mildew of the vine, at a rate of about 1 ml / plant (ie about 105 spores per plant).

 After this contamination, the vine plants are incubated for two days at about 18 ° C. in an atmosphere saturated with moisture and then for five days at about 20 ° -20 ° C. under 90-100% relative humidity.

 Seven days after the contamination, the results obtained in the case of the plants treated with the active ingredient to be tested are compared with those obtained in the case of the plants used as a control.

Under these conditions, it was observed that, at a dose of 100 ppm (0.1 g / l), compounds 1 to 8, 9, 11, 12 resulted in at least 80% inhibition of the development of the fungus.
at a dose of 1000 ppm (1 g / l) the compounds 13-16, 18-20, 22-26, 30, 31, 37, 38 to 43, 46, 47, 49, 51 result in at least 80% d inhibition of the development of the fungus.

Greenhouse experiment on late blight tomato (Phytophthora infestans)
Tomato plants (Lycopersicum esculentum), of Marmande variety, are grown in buckets. When these plants are one month old (5 to 6 leaf stage, 12 to 15 cm high), they are sprayed with a suspension or aqueous solution of the test material, at the desired concentration and containing a condensate of sorbitan monooleate and 20 molecules of ethylene oxide at half the concentration of active ingredient. Each tomato plant receives about 5 ml of the solution or dispersion. For each concentration of active ingredient to be tested, the treatment is carried out on two plants. Plants used as controls are treated with a solution containing no active ingredient, but containing the same condensate of sorbitan monooleate and ethylene oxide. at identical concentration.

 After drying for 24 hours, each plant is sprayed with an aqueous suspension of Phytophthora infestans spores, which is responsible for the tomato blight, at a rate of about 1 ml / plant (ie about 10 05 spores per plant).

 After this contamination, the tomato plants are incubated for two days at about 150 ° C. in an atmosphere saturated with moisture, then for five days at about 170 ° C. at 70% to 90% relative humidity.

 Seven days after the contamination, the results obtained in the case of the plants treated with the active ingredient to be tested are compared with those obtained in the case of plants used as controls.

Under these conditions, it was observed that at the dose of 100 ppm (0.1 g / l) compounds 1 to 8 resulted in at least 60% inhibition of the development of the fungus at a dose of 1000 ppm (1 g). / l) compounds 13 to 16, 18 to 20, 22, 24, 26 to 28, 31, 33, 35, 38, 39, 41, 43, 46 - 49, 51 result in at least 80% inhibition of development. mushroom.

Claims (22)

1) Compounds, characterized in that they have the formula

 in which  R.sub.1 and R.sub.2 represent a hydrogen atom or a lower alkyl, lower cycloalkyl, aryl, arylalkyl, lower alkoxy, lower alkanoyl, aroyl radical, these various radicals may be optionally substituted, or else  R 1 and R 2 together form a single divalent hydrocarbon radical comprising from 2 to 6 carbon atoms, one of these atoms possibly being replaced by an oxygen or nitrogen atom, and which may be optionally substituted,  R3 represents a lower alkyl, cycloalkyl or amino radical, these radicals being optionally substituted,  Z1, Z2 Z3 Z4, which may be identical or different, each represent a group chosen from = CH-, = Crou = N-, one or two of these four groups Z1, Z2, Z3, Z4 may represent the trivalent nitrogen atom = N- and, when several groups = CR- are present, the substituents R may be identical or different,  R represents the halogen atom or an optionally substituted lower alkyl radical (for example by one or more halogen atoms); lower alkoxy optionally substituted (for example with one or more halogen atoms or with the phenyl radical); lower alkylthio optionally substituted (for example with one or more halogen atoms) lower alkenyl; lower alkenyloxy; lower alkynyl; lower alkynyloxy; phenoxy optionally substituted for example by one or more halogen atoms or trifluoromethyl radicals); phenylthio or phenylsulfinyl or phenylsulfonyl, these radicals being optionally substituted (for example by one or more halogen atoms or trifluoromethyl radicals); amino optionally substituted with one or more identical or different lower alkyl radicals; nitro, cyano, thiocyanato, isothiocyanato, lower alkylsulfonyl, sulfamoyl optionally substituted with one or lower identical or different lower alkyl radicals, optionally substituted acyl (for example lower alkanoyl) (for example halogenated) or optionally halogenated benzoyl, lower alkoxycarbonyl.  X represents a sulphoxide group (S = O) or an oxyimino group of formula NO-R4 in which R4 corresponds to a hydrogen atom or a lower alkyl, lower cycloalkyl, aryl (especially phenyl), araikyl (in particular benzyl) radical, lower alkenyl (mono- or polyunsaturated), lower e-lcinyl (mono- or polyunsaturated), lower alkanoyl, lower cycloalkanoyl, aroyl (such as benzoyl), aryloxycarbonyl (such as benzyloxycarbonyl), lower cycloalkoxycarbonyl, alkoxycarbonyl, lower alkanoyloxy, aroyloxy, lower cycloalkanoyloxy (in this case the carbonyl group is not taken into account in the term "lower"), carbamyl, N-arylcarbamyl, N-lower alkylcarbamyl, N, N-diacetyl-carbamoyl, N, N-diaryl carbamoyl, N-alkyl N-aryl carbamyl, lower alkylsulphonyl, arylsulphonyl, alkenylsulphonyl, lower alkenylsulphonyl, loweralkylsulphonyl, lower alkyl phosphate, phosphonate  lower alkyl, lower alkyl phosphinate,  all the aforementioned radicals possibly being  substituted by one or more halogen atoms or  trifluoromethyl radicals or carboxylate radicals  of lower alkyl, aryl or aralkyl, moreover,  aforementioned radicals having a cycloaliphatic group  or aromatic that can be optionally substituted  by one or more lower alkyl radicals.  as well as the agriculturally acceptable salts of these  compounds of formula (IY. 2) Compounds according to claim 1, characterized in that  that they have for formula

 in which Z5 and Z6 correspond to a pattern  chosen from = C- or = N-, provided that if Z5 and  or Z6 correspond to a pattern = C-, they are  associated with an R group or a hydrogen atom and  wherein R1, R2, R3, R, X and R4 have the  meaning already indicated in the formula (I) and n  is an integer, positive or zero, less than 4,  it being understood that when n is greater than 1, the  various substituents R may be identical or  different. 3) Compounds according to one of claims 1 or 2  characterized in that the groups R1 and R2  correspond to the hydrogen atom. 4) Compounds according to claim 3 characterized in that  that the grouping R3 is chosen from the groupings  following: isopropyl, piperidino, pyrrolidino,  dimethylamino. 5) Compounds according to one of claims 1 to 4  characterized in that when X is N-O-R4,  R4 corresponds to the hydrogen atom or to a group  S02-R5 wherein R5 is a hydrogen atom  or a lower alkyl, aryl, aralkyl radical,  lower alkenyl, lower alkinyl. 6) Process for preparing the compounds of formula (I)  according to one of claims 1 to 5 in the case where X  corresponds to N-O-R4 and R1, R2 correspond to  the hydrogen atom characterizes in that it consists  in the following steps  Step a - a compound of formula (III) in which  Z to Z, R have the same meaning as in the  Claim 1 is reacted with hydroxylamine  of formula H2NOH to yield the compound of formula  (la) in which R3, Z1 to Z4 have the same  meaning as in claim 1  Step b - the compound obtained is then reacted  step a) with an agent of formula R4Hal in  which R4 has the same meaning as in the  claim 1 except the hydrogen atom and Hal  corresponds to a halogen atom in order to obtain the  compound of formula (Ib) in which Z1 to Z4, R3  have the same meaning as that indicated in  claim, R1 and R2 correspond to the atom  of hydrogen and R4 is different from the atom  hydrogen.  7.) Process for the preparation of the compounds of formula (I)  according to one of claims 1, 2 or 5 in the case where  X is N-O-R4, at least one of the groupings  R1 or R2 being different from the hydrogen atom  characterized in that it consists in the steps  following  Step a - a compound of formula (IV) in which Z1  at Z4, R3 have the same meaning as in the  claim 1 is reacted with a mono amine  or di-substituted of formula HNR1R2 in which  at least one of the groups R1 or R2 is  different from the hydrogen atom in order to get a  compound of formula (IVa) in which Z1 to Z4,  R3 have the same meaning as in the  claim 1 and at least one of the groups R1  or R2 are different from the hydrogen atom  Step b - the compound obtained in step a) is set  react with the hydroxylamine of formula NH20H to  to the compound of formula (Ic) in which Z1  at Z4, R3 have the same meaning as in the  claim 1, wherein at least one of the  R1 or R2 groups are different from the atom  of hydrogen and R4 corresponds to the hydrogen atom  Step c - the compound obtained in step b) is set  react with an agent of formula R4Hal in which  R4 has the same meaning as in the claim  2 except the hydrogen atom and Hal is an atom  halogen to obtain the compound of formula (Id)  in which Z1 to Z4, R3 have the same  meaning as that indicated in claim 1,  and wherein at least one of the groups R1 or  R2 do not correspond to the hydrogen atom and R4  is different from the hydrogen atom. 8) Method according to claim 7, characterized in that  the reaction with the mono- or di-substituted amine  HNR1R2 formula in which at least one of the  R1 or R2 groups are different from the atom  hydrogen is carried out in an organic solvent medium at  a temperature between 500C and the reflux of  solvent in a molar ratio compound of formula  (IV): amine HNR1R2 between 1.1 and 0.2. 9) Method according to one of claims 6 or 7  characterized in that the reaction of the compounds of  formula (III) or (IVa) with hydroxylamine NH20H is  carried out in a polar organic solvent medium  possibly mixed with water, provided  that the proportion of water by volume is not  greater than 20% of the total volume of the solvent, at a  temperature between OOC and solvent reflux  and in that the molar ratio compounds (III) or  (IVa): hydroxylamine is between 0.9 and 0.2. 10) Method according to one of claims 6 or 7  characterized in that the reaction with the R4Hal agent  in which R4 does not correspond to the atom  of hydrogen and Hal is a halogen atom is  carried out in an organic solvent medium, in the presence  of an organic or mineral base, at a temperature  between OOC and the reflux of the solvent and in a  molar ratio starting compound: R4Hal included  between 1.1 and 0.2. 11) Process for preparing the compounds of formula (I)  according to claim 1 or 2 in the case where X  corresponds to S = O and at least one of the groups R1  or R2 does not correspond to the hydrogen atom  characterized in that it consists in the steps  following  Step a - a compound of formula (IV) in which Z1  at Z4, R3 have the same meaning as in the  claim 1 and R1, R2 correspond to the atom  hydrogen is reacted with a mono- or  di-substituted formula of formula HNR1R2 in which one  at least one group R1 or R2 is different from  the hydrogen atom to obtain a compound of  formula (IVa) in which Z1 to Z4, R3 have the  same meaning as in claim 1 and one  at least one group R1 or R2 is different from  the hydrogen atom;  Step b - the compound of formula (IVa) obtained in step  a) is subjected to oxidation so as to obtain the  compound of formula (Ie). 12) Process for preparing the compounds of formula (I)  according to one of claims 1 to 4 in the case where X  corresponds to S = O and the groups R1 and R2  correspond to the hydrogen atom characterized in that  that the compound of formula (IVa) in which Z1 to  Z4, R3 have the same meaning as in the  claim 1 is subjected to oxidation so as to  obtain the compound of formula (If). 13) Method according to claim 11 characterized in that  the reaction with the mono- or di-substituted amine  HNR1R2 formula in which at least one of the  R1 or R2 groups are different from the atom  hydrogen is carried out in an organic solvent medium at  a temperature between 500C and the reflux of  solvent in a molar ratio composed of the formula  (IV): amine HNR1R2 between 1.1 and 0.2. 14) Process for preparing the compounds of formula (I)  according to one of claims 11 or 11, characterized in  that the oxidation is carried out by means of a peroxide  organic or hydrogen peroxide, at a temperature  between -200C and 600C, in a polar solvent medium, in a  molar ratio compound (IV) or (IVa) peroxide included  between 1 and 1.5. 15) Compounds of formula (IV) or (IVa) in which the  groups Z1 to Z4, R3 have the same meaning  that in claim 1, at least one of the  groups R1 or R2 etan.t different from the atom  hydrogen. 16) Process for preparing the compounds of formula (IV)  according to claim 15 wherein Z1 to Z4,  R3 have the same meaning as in the  claim 1 characterized in that a reaction is  compound of formula (III) in which Z1 to Z4,  R3 have the same meaning as in the  claim 1 with hydrogen sulfide. 17) Method according to claim 16 characterized in that  the reaction is carried out at a temperature between  O and 800C in the presence of a suitable catalyst, in  inert solvent medium, in an amount greater than the  stoichiometry for hydrogen sulfide.  18, Preparation of compounds of formula (IVa>  according to claim 15 characterized in that  consists of the following steps  Step a - a compound of formula (III) is subjected to  the action of hydrogen sulphide to obtain the  compounds of formula (IV)  Step b - the compounds of formula (IV) are set  react with a mono- or di-substituted amine of formula  HNR1R2 in which at least one of the groupings  R1 or R2 is different from the hydrogen atom so  to obtain the compound of formula (IVa). 19) Method according to claim 18 characterized in that  step b) is carried out in an organic solvent medium at  a temperature between 500C and the reflux of  solvent in a molar ratio compound of formula  (IV) = amine HNR1R2 between 1.1 and 0.2. 20) Use of the compounds according to one of  Claims 1 to 5 as a fungicide. 21) Fungicidal compositions, characterized in that  they contain as active ingredient a compound  according to one of claims 1 to 5, this material  active being in association with at least one support  inert, acceptable in agriculture. 22) Compositions according to claim 17, characterized  they contain 0.5 to 95% of active ingredient. 23) Method for controlling fungal diseases  descultures, characterized in that a dose is applied  of an active ingredient according to one of the  Claims 1 to 5. 24) Method for controlling fungal diseases of  cultures according to claim 23, characterized in. this  that the active ingredient is applied at the rate of 0.01 to  5 kg / ha, preferably 0.02 to 1 kg / ha.