BE882335A - GEOMETRIC ISOMER OF 1-TRIAZOLYL-STYRENES SUBSTITUTED IN POISITION 1, THEIR PREPARATION AND THEIR USE AS FUNGICIDES, HERBICIDES AND / OR PLANT GROWTH REGULATORS - Google Patents

Description

       

  "Geometric isomer of l-triazolyl-styrenes substituted in position 1, their preparation and their use as fungicides, herbicides and / or regulators of plant growth".

  
The present invention relates to one of the two isomers

  
  <EMI ID = 1.1>

  
below) of a triazole compound corresponding to formula (I)

  

  <EMI ID = 2.1>


  
  <EMI ID = 3.1>

  
alkyl containing 1 to 4 carbon atoms, an alkenyl group containing 3 or 4 carbon atoms or a 2-propynyl group,

  
  <EMI ID = 4.1>

  
different, represent a halogen atom, an alkyl group containing 1 to 4 carbon atoms, an alkyl group containing 1 to 3 carbon atoms and substituted by a halogen atom, an alkoxy group containing 1 to 4 carbon atoms, a phenoxy group, a phenyl group, a cyano group or a nitro group, n is an integer from 0 to 3, the expression “halogen atom” designating a chlorine atom, a bromine atom

  
or a fluorine atom; the invention also relates to

  
salts of this compound, their preparation, as well as fungicides, herbicides and / or plant growth regulators containing this compound as an active ingredient and intended for agriculture and horticulture.

  
Any triazole compound of formula (I) has two geometric isomeric forms, namely form Z and form E, which are represented by the formulas:

  

  <EMI ID = 5.1>


  
form Z form E

  
Currently, it cannot be clearly defined at

  
  <EMI ID = 6.1>

  
of the present invention and, therefore, the properties of these compounds can only be expressed conditionally. These two isomers can be distinguished from each other by their melting point, their nuclear magnetic resonance spectrum or their analysis by gas chromatography, but their difference can be characterized more generally and more clearly by their material. starting, namely a triazole compound of formula (II):

  

  <EMI ID = 7.1>


  
  <EMI ID = 8.1>

  
above.

  
The triazole compound of formula (I) is obtained by reduction of a triazole compound of formula (II) to obtain a triazole compound of formula (I) in which R. represents a hydrogen atom, then by etherifying the compound obtained:

  

  <EMI ID = 9.1>


  
  <EMI ID = 10.1>

  
In this regard, one of the two geometric isomers of the triazole compound (II) whose olefin proton appears at a magnetic field higher than the nuclear magnetic resonance spectrum in deuterochloroform, is called "isomer II-A", while the other whose olefinic proton appears at a magnetic field lower than the reso-

  
  <EMI ID = 11.1>

  
In addition, the compound (I) in which R. is a hydrogen atom and which is obtained by reduction of the isomer II-A, is called "isomer I'-A"; the compound (I) in which R. represents the defined substituents (other than a hydrogen atom) and which is obtained by etherification of

  
  <EMI ID = 12.1>

  
of the II-B isomer in the same manner as that described above are respectively called the L'-B isomer "," I-isomer "-B" and "I-B-isomer". The present invention

  
  <EMI ID = 13.1>

  
intermediate product for the I-A isomer,

  
Up to now, a large number of organosynthetic compounds have been developed which make a great contribution in the field of agricultural chemicals by ensuring stable agricultural and horticultural crops thanks to their activity against diseases and parasites which deteriorate these crops. However, it is clear that there are still many problems that need to be resolved. These problems are sometimes resolved, for example, by developing new, more desirable pesticides; similarly, we can consider that these problems are also solved

  
  <EMI ID = 14.1>

  
appropriate application of agricultural chemicals.

  
Organosynthetic compounds which can also be present in the form of geometric or optical isomers, are not uncommon. Indeed, there are many cases in which pesticides containing these isomers are used in practice as agricultural chemicals: Not only in the field of agricultural chemicals, but also in many other fields, we know that with many active ingredients having the isomeric forms, there is a difference in biological activity between the isomers. Recently, the problem of environmental pollution has become very serious in the field of agriculture and horticulture and it is important to alleviate this problem by using the isomer of a pair whose activity is more powerful.

   Likewise, it can be considered that this results in a more economical impact in the manufacture of these compounds, as well as during their practical application as agricultural chemicals.

  
Consequently, starting from this point of view, we can consider that the isomer exercising a more powerful activity makes a contribution in this field,

  
From there, the Applicant undertook further studies on compounds which it had already found [Japanese patent application (published, but not examined) n [deg.] 130661/1978, Belgian patent n [deg.] 870243 (patent application

  
  <EMI ID = 15.1>

  
a wider range of plant pathogens, as well as a higher herbicidal effect and a stronger action on the regulation of plant growth than

  
the compounds defined by the expression "I-B isomer", that is to say that, in other words, they have excellent properties as agricultural chemicals. This is how the Applicant has arrived at the present invention.

  
  <EMI ID = 16.1>

  
of Germany n [deg.] 2,610,022, 2,654,890 and 2,734,426, as well as in the patent of the United States of America n [deg.] 4,086,351. However, the characteristic of the present invention resides in the fact that the following new information has been discovered:
one of the two geometric isomers of the triazole compound (1), which is characterized in that its structure comprises both

  
(1) a double bond (benzylidene group) and (2) a hydroxy group or its ethers:

  

  <EMI ID = 17.1>


  
has, as an agricultural chemical, superior properties compared to that of the other geometric isomer. In this regard, the compounds of the present invention have a different structural characteristic from that of the well-known compounds mentioned above and, moreover, they have properties far superior to those of these well-known compounds. Consequently, the originality of the

  
  <EMI ID = 18.1>

  
could never have been imagined from the prior art,

  
Among the diseases against which the compounds of the present invention (isomer I-A) can exert

  
excellent protective activity, we can mention:
Pyricularia oryzae, Pellicularia sasakii, Valsa Mali, Sclerotinis Mali, Podosphaera leucotricha, Venturia inaequalis, Mycosphaerella pomi, Alternaria Mali, Alternaria kikuchiana, Phyllactinia pyri, Gymnosporan &#65533; ium haraeanum Venturia nashicola, Diaporthe citri, Elsinoe fawcetti, Penicillium digitatum,. Penicillium italicum, Sclerotinia cinerea,

  
  <EMI ID = 19.1>

  
Puccinia graminis, Puccinia recondita, Ustilago tritici, Tilletia caries, Septoria tritici, Septoria nodorum, Puccinia striiformis, Puccinia graminis, Erysiphe graminis, Sphaerotheca fuliginea, Botrytis cinerea, Mycosphaerella melonis, Colleris , Botrvtis cinerea, Verticillium albo-atrum &#65533; Erysiphe cichoracearum, Leveillula taurica, Botrytis cinerea, Sphaerotheca humuli, Alternaria longipes, Erysiphe cichoracearum, Cercospora beticola, Cercospora personata, Cercospora arachidicola and

  
  <EMI ID = 20.1>

  
It became clear that these compounds also exerted antimicrobial activity against the Trichophyton rubrw strain. It was therefore found that the compounds of the present invention could also be used as antimycotic agents for medical purposes,

  
In addition, the compounds of the present invention
(IA isomer) can also be used as plant growth regulators to control the growth of useful plants * For example, they can be used to prevent height growth of rice, wheat, grass, trees hedges and fruit trees:
as well as to dwarf horticultural plants such as

  
  <EMI ID = 21.1>

  
During the cultivation of rice and wheat, the latter are very often strongly cut down by a strong wind or by the application of a fertilizer beyond the required quantity. However, the application of the compounds of the present invention at the right time makes it possible to effectively control the height of the rice and of the wheat, while preventing them from being slaughtered. of the present invention makes it possible to usefully enhance its commercial value, since these compounds can reduce the height of the stem without any harmful effect on the flower,

  
  <EMI ID = 22.1>

  
have potent herbicidal activity against weeds in grassy fields, for example: Echinochloa raw-gall

  
  <EMI ID = 23.1>

  
charis acicularis. When the compounds of the present invention are applied to fields, they are also very superior in the following points: they exert a potent herbicidal activity against the main weeds of the fields; they exercise their activity by treating the soil before weed germination or by treating the leaves at the start of growth and, in addition, they can be applied reliably without damaging the main crops (for example, rice, soybeans , cotton, mats, peanuts, sunflowers and beets), as well as vegetables (e.g., lettuce, radishes and tomatoes), When the compounds of the present invention are applied to paddy fields (paddy = husked rice),

   they also exert a powerful herbicidal activity against the main weeds, either as a pre-emergence treatment, or by treatment of the leaves at the beginning of the growth and, moreover, they have a high reliability with respect to rice plants.

  
In addition, the compounds of the present invention are very useful as herbicides not only for paddy, but also for various crops, vegetables, orchards, lawns, pastures, tea plantations, blackberry farms, farms rubber, forest regions and uncultivated regions.

  
In addition, it has become clear that the compounds of the present invention offer very high safety with regard to mammals and fish and that, in addition,

  
they could be used in practice without damaging useful agricultural crops.

  
The triazole II-A compounds (intermediate products for the preparation of the IA compounds of the present invention) also exert fungicidal activity against various pathogenic organisms harmful to agriculture, as well as herbicidal activity and regulating activity on the growth of plants. However, it is also certain that the compounds I-A of the present invention exert, compared to the compounds II-A, a far more potent activity against a wider range of plant pathogenic organisms, as well as a herbicidal activity and an activity

  
  <EMI ID = 24.1>

  
health.

  
More specific methods will be described below for the preparation of the compounds of the present invention: Method A: Reduction of the triazole compound II:

  

  <EMI ID = 25.1>
 

  
  <EMI ID = 26.1>

  
mother II-A in a suitable solvent with a complex of a metal hydride (for example, lithium aluminum hydride;

  
sodium borohydride) or an aluminum alkoxide (for example, aluminum isopropoxide). The II-A isomer to be reduced can be obtained in pure form, for example,

  
by applying fractionated crystallization or

  
  <EMI ID = 27.1>

  
of a triazole compound (II) obtained in accordance with the reaction equation below. The isomer II-A can also be obtained with good yield, for example, by subjecting the mixture to irradiation with ultraviolet rays in order to carry out a photo-isomerization. A more detailed explanation will be given below with reference to methods C and D.

  

  <EMI ID = 28.1>


  
  <EMI ID = 29.1>

  
Among the solvents used during reduction with a metal hydride complex are, for example, ethers (for example, diethyl ether and tetrahy-drofuran) and alcohols (for example, methanol, l ethanol and isopropanol). When sodium borohydride is used as the metal hydride complex, the

  
  <EMI ID = 30.1>

  
for example, ethers (for example, diethyl ether and tetrahydrofuran) and alcohols (for example, methanol, ethanol and isopropanol). When lithium aluminum hydride is used as the metal hydride complex, the reaction is carried out by dissolving the lithium aluminum hydride in a molar amount equal to 0.25-0.8 times that of the isomer II- A in a solvent and adding the solution obtained to a solution of the isomer in the same solvent.

  
  <EMI ID = 31.1>

  
example, diethyl ether and tetrahydrofuran). At the end of the reaction, water or a dilute aqueous acid is added to the reaction solution and, if necessary after neutralization with an alkali, the crystals deposited are collected by filtration or extracted with an organic solvent poorly soluble in l 'water. The subsequent treatment is carried out by conventional methods. When aluminum isopropoxide is used as the reducing agent, it is preferable to use solvents such as alcohols (for example isopropanol) or aromatic hydrocarbons (for example, benzene). It is common practice to allow one mole of the II-A isomer to react with 1 to 2 moles of aluminum isopropoxide at a temperature ranging from

  
  <EMI ID = 32.1> with dilute sulfuric acid or an aqueous solution of sodium hydroxide, followed by extraction with an organic solvent sparingly soluble in water. The subsequent treatment is carried out by conventional methods.

  
  <EMI ID = 33.1>

  
physiologically acceptable acids with regard to plants, for example, halogenated hydracids (for example, hydrobromic acid, hydrochloric acid and hydroiodic acid), carboxylic acids (for example, acetic acid, trichloroacetic acid, maleic acid and succinic acid), sulfonic acids (e.g. p-toluenesulfonic acid and nethanesulfonic acid), nitric acid, sulfuric acid and Phosphoric acid. If necessary, these salts are prepared by conventional methods.

  
  <EMI ID = 34.1>

  

  <EMI ID = 35.1>


  
  <EMI ID = 36.1>

  
reagent having an alkyl group containing 1 to 4 carbon atoms, an alkenyl group containing 3 or 4 carbon atoms

  
  <EMI ID = 37.1> (e.g. methyl iodide, allyl bromide and

  
propargyl bromide), sulphate compounds (for example, dimethyl sulphate and diethyl sulphate), as well as sulphonate compounds (for example, p-toluenesulphonates and naphthalene sulphonates). Among the solvents there are, for example, inert organic solvents in general such as diethyl ether, tetrahydrofuran, dioxane, benzene, toluene, xylene and dimethylformamide. This reaction can be carried out in the presence of water using a phase transfer catalyst known as a reaction accelerator (for example, triethyl benzyl ammonium chloride and trimethyl benzyl bromide).

  
  <EMI ID = 38.1>

  
  <EMI ID = 39.1>

  
alkalines such as sodium hydride, as well as alkali metal amides such as sodium amide), carbonates (for example, sodium carbonate and potassium carbonate), as well as hydroxides of alkali metals (for example, potassium hydroxide and sodium hydroxide).

  
This reaction is carried out by mixing the isomer

  
  <EMI ID = 40.1>

  
1 to 4 carbon atoms, an alkenyl group containing 3 or 4 carbon atoms or a 2-propynyl group, as well as a base, preferably, in an equimolar ratio, in an appropriate solvent. The reaction is carried out at a temperature

  
  <EMI ID = 41.1>

  
of alkali metals and hard alkali metals) in an inert solvent, to then react the alkali metal salt obtained with a reactive derivative comprising an alkyl group containing 1 to 4 carbon atoms, an alkenyl group containing 3 or 4 atoms carbon or a 2-propynyl group.

  
In certain cases, in order to isolate the compounds I "-A of the present invention, it is desirable to adopt the following method: the reaction mixture is freed from the solvent by evaporation, water and a little organic solvent are added soluble in water at the residue, the organic layer is separated after extraction, then a purification is carried out by the usual methods,

  
The salts of the I "-A isomer are those obtained with physiologically acceptable acids such as halogenated hydracids (for example, hydrobromic acid, hydrochloric acid and hydroiodic acid), carboxylic acids (for example, acetic acid, trichloroacetic acid, maleic acid and succinic acid), sulfonic acids
(for example, p-toluene sulfonic acid and methanesulfonic acid), nitric acid, sulfuric acid and phosphoric acid. If necessary, these salts are prepared by the usual methods.

  
The present invention will be illustrated in more detail by the following examples. Unless otherwise indicated, in these examples, the magnetic resonance spectrum

  
  <EMI ID = 42.1>

  
chloroform as solvent and tetramethylsilane as internal standard.

Example 1

  
  <EMI ID = 43.1>

  
process A.

  
  <EMI ID = 44.1>

  
with ice. The reaction mixture is kept at 20 ° C. for 3 hours, then it is decomposed by the addition of 100 ml

  
  <EMI ID = 45.1>

  
organic with 100 ml of ethyl acetate and the extract is washed with 50 ml of a 5% aqueous solution of sodium hydrogencarbonate, then dried over anhydrous sodium sulfate.

  
Then, the solvent is removed under reduced pressure and the residue is recrystallized from isopropanol to obtain

  
  <EMI ID = 46.1>

  
be silent, as well as the nuclear magnetic resonance spectrum:
of the compound.

  
Elementary analysis:

  

  <EMI ID = 47.1>


  
Nuclear magnetic resonance spectrum:
8.52 (1H, s, triazole proton)

  
  <EMI ID = 48.1>

  
7.30 (4H, s, phenyl proton)

  
6.91 (1H, s, olefinic proton)

  
4.56 (2H, broad singlet, hydroxy proton and methine proton

  
containing an OH group)

  
0.66 (9H, s, butyl proton).

  
Comparative example 1

  
  <EMI ID = 49.1>

  
l16-117 [deg.] C) of compound n [deg.] 1. The elementary analysis and the nuclear magnetic resonance spectrum of the compound will be given below,

  
Elementary analysis:

  

  <EMI ID = 50.1>


  
Nuclear magnetic resonance spectrum:
7.92 (1H, s, triazole proton)

  
  <EMI ID = 51.1>

  
0.80 (9H, s, butyl proton) e

Example 2

  
  <EMI ID = 52.1>

  
n [deg.] 30) by method A.

  
2.9 g (0.01 mole) of the l'-isomer is dissolved
(melting point: 89-92 [deg.] C) of 3- (4-chlorophenyl) -l- (l-

  
  <EMI ID = 53.1>

  
(compound n [deg.] 29 ') characterized by the nuclear magnetic resonance spectrum described below in 50 ml of methanol.

  
0.38 g (0.01 mole) of sodium borohydride is added thereto.

  
  <EMI ID = 54.1>

  
the organic layer with 100 ml of chloroform and the extract is washed with 50 ml of a 5% aqueous solution of sodium hydrogencarbonate, then dried over anhydrous magnesium sulfate. Then, the solvent is removed under reduced pressure and the residue obtained is crystallized from 5 ml of a 1: 1 mixture of carbon tetrachloride and n-hexane to obtain 2.4 g (yield: 85%) of the title compound .

  
The nuclear magnetic resonance spectrum of the starting material, namely the isomer, will be given below.

  
  <EMI ID = 55.1>

  
8.28 (1H, s, proton triazole)

  
8.07 (1H, s, triazole proton)

  
  <EMI ID = 56.1>

  
7.19 (1H, s, olefinic proton)

  
1.45 - 1.15 (2H, m, methylene proton of the cyclopropyl group) 1.25 (3H, s, methyl proton)

  
0.99 - 0.75 (2H, m, methylene proton of the cyclopropyl group).

  
Comparative example 2

  
  <EMI ID = 57.1>

  
triazol-l-yl) -2-propen-l-one (compound n [deg.] 29 ') characterized by the nuclear magnetic resonance spectrum described below with 0.27 g (0.007 saw) of sodium borohydride in 50 ml of methanol. In this way, 1.7 g (yield: 85%) of the title compound are obtained.

  
The nuclear magnetic resonance spectrum of the starting material, namely the isomer, will be given below.

  
  <EMI ID = 58.1>

  
8.12 (1H, s, proton triazole)

  
8.03 (1H, s, proton triazole)

  
  <EMI ID = 59.1>

  
6.81 (2H, d, phenyl proton, J = 8Hz)

  
1.50 - 1.25 (2H, m, methylene proton of the cyclopropyl group) 1.28 (3H, s, methyl proton)

  
  <EMI ID = 60.1>

Example 3

  
  <EMI ID = 61.1>

  
3-methoxy-2- (1,2,4-triazol-1-yl) -1-pentene (compound n [deg.] 35) by method B.

  
  <EMI ID = 62.1>

  
methyl. After having allowed to stand at room temperature for 20 hours, the solvent is removed under reduced pressure and the residue obtained is extracted by adding 100 g of ice water and 100 cm 3 of chloroform. The organic layer is dried over anhydrous magnesium sulfate and the solvent is removed under reduced pressure. The crude oily product obtained is purified by column chromatography on silica gel (acetone:
n-hexane = 1:10) and subjected to additional recrystallization from a 1: 2 mixture of carbon tetrachloride and n-hexane to obtain 1.6 g of the title compound

  
  <EMI ID = 63.1>

  
(compound n [deg.] 1) in 20 cm3 of dimethylformamide and 0.26 g of sodium hydride at 65% is added thereto, After stirring at room temperature for one hour, the

  
  <EMI ID = 64.1> one hour, then allowed to stand at room temperature for 16 hours. Dimethylformamide is removed under reduced pressure and the residue is extracted by adding 100 g of ice water and 100 cm 3 of chloroform. The organic layer is dried over anhydrous magnesium sulfate and the solvent is removed under reduced pressure. We purify the product

  
crude obtained by column chromatography on silica gel (acetone: n-hexane = 1:10) to obtain 1 g of the title compound in the form of an oily product,

  
  <EMI ID = 65.1>

  
Elementary analysis:

  

  <EMI ID = 66.1>


  
  <EMI ID = 67.1>

  
obtained by methods A and B are listed in Table 1 below. By way of comparison, the data relating to the I-B isomer are also indicated. Unless otherwise indicated, in this table, the nuclear magnetic resonance spectrum

  
  <EMI ID = 68.1>

  
also used in the dressai examples described below
  <EMI ID = 69.1>
  <EMI ID = 70.1>
 
  <EMI ID = 71.1>
  <EMI ID = 72.1>
 
  <EMI ID = 73.1>
  <EMI ID = 74.1>
 
  <EMI ID = 75.1>
  <EMI ID = 76.1>
 
  <EMI ID = 77.1>
  <EMI ID = 78.1>
 
  <EMI ID = 79.1>
  <EMI ID = 80.1>
 
  <EMI ID = 81.1>
  <EMI ID = 82.1>
 
  <EMI ID = 83.1>
  <EMI ID = 84.1>
 
  <EMI ID = 85.1>
  <EMI ID = 86.1>
 
  <EMI ID = 87.1>
  <EMI ID = 88.1>
 
  <EMI ID = 89.1>
  <EMI ID = 90.1>
 
  <EMI ID = 91.1>
  <EMI ID = 92.1>
 
  <EMI ID = 93.1>
  <EMI ID = 94.1>
 
  <EMI ID = 95.1>
  <EMI ID = 96.1>
 
  <EMI ID = 97.1>
  <EMI ID = 98.1>
 
  <EMI ID = 99.1>
  <EMI ID = 100.1>
 
  <EMI ID = 101.1>
  <EMI ID = 102.1>
  <EMI ID = 103.1>
 
  <EMI ID = 104.1>
  <EMI ID = 105.1>
 A description will be given below of the preparation of the II-A isomer of the triazole compound (II) which is a

  
  <EMI ID = 106.1>

  
(1).

  
Process C: Isomerization of the II-B isomer or of a mixture

  
  <EMI ID = 107.1>

  

  <EMI ID = 108.1>


  
Isomer II-B or a mixture of Isomer II-A of isomers II-B and II-A

  
  <EMI ID = 109.1>

  
The II-A isomer can be prepared by subjecting the II-B isomer or a mixture of the II-B and II-A isomers to irradiation with rays emitted by ultraviolet lamps or xenon lamps or else experimentally with rays emitted by fluorescent lamps or the sun, in a solvent inert with respect to these rays. Among the solvents usually used, there may be mentioned, for example, alcohols (for example, methanol, ethanol and propanol), ethers (for example, tetrahydrofuran and dioxane), ketones (for example, l acetone, methyl ethyl ketone and methyl isobutyl ketone), aliphatic hydrocarbons (for example, hexane, cyclohexane and petroleum ether), as well as aromatic hydrocarbons (for example, benzene, toluene and xylene).

  
The reaction can be carried out at temperatures at which the usual photo-isomerization takes place but, in reality, temperatures ranging from 0 to 100 [deg.] C are preferred. Of course, the reaction can be carried out with the addition of a sensitizer used in the usual photoreactions, for example, phenyl ketones such as acetophenone

  
and propiophenone, but there are not particularly great benefits.

  
A process for the preparation of the triazole compound corresponding to formula (II) will be described below.

  
Method D: Preparation of a mixture of geometric isomers

  
the triazole compound (II) and each isomer
(II-B, II-A):

  

  <EMI ID = 110.1>


  
  <EMI ID = 111.1>

  
The triazole compound (II) is obtained by reacting 1 mole of a ketone of formula (IV) with 1-2 moles of a benzaldehyde of formula (III) in an appropriate solvent and in the presence of a basic catalyst. Among the basic catalysts there are, for example, hydroxides of alkali metals or alkaline earth metals (for example, sodium hydroxide, potassium hydroxide and calcium hydroxide), metal alcoholates alkaline (e.g. sodium methylate, sodium ethylate and methylate

  
potassium), carbonates (for example, sodium carbonate and potassium carbonate), acetates (for example, sodium acetate and potassium acetate), secondary amines (for example, diethylamine, dipropylamine, pyrrolidine, piperidine and morpholine), as well as tertiary amines (for example, triethylamine, tributylamine, pyridine, picoline and dimethylaniline); this catalyst is used in amounts ranging from 0.01 to 10 moles. Among the solvents there are, for example, alcohols (for example, methanol and ethanol), aromatic hydrocarbons (for example, benzene, toluene and xylene), ethers (for example, diethyl ether,

  
  <EMI ID = 112.1>

  
boiling point of the solvent.

  
When the basic catalyst is chosen from acetates (for example, sodium acetate and potassium acetate), carbonates (for example, sodium carbonate and potassium carbonate) or tertiary amines, it is also possible to use acetic anhydride or glacial acetic acid as the reaction solvent.

  
The triazole compound (II) thus obtained is a mixture of two geometric isomers, that is to say the isomer II-A and the isomer II-B, in general, and each isomer can be isolated by chromatography in column or by fractional crystallization. As a general rule, the mixture of geometric isomers contains the II-B isomer in a larger proportion than the II-A isomer. Of course, all the II-A isomers of the ketone compound are new compounds and, among the II-B isomers, those in which R2 is a group

  
  <EMI ID = 113.1>

  
Methods C and D will be described below in more detail with reference to the following examples.

Example 4

  
  <EMI ID = 114.1>

  
41 g of anhydrous potassium carbonate, 200 ml of acetic anhydride and 46.3 g of 4-chlorobenzaldehyde, then the mixture is heated to 90 ° C. for 12 hours while stirring. After cooling the reaction solution, the precipitates are removed by filtration. The filtrate is added dropwise to 500 ml of hot water at 60 [deg.] C in order to decompose the acetic anhydride, then potassium carbonate is added little by little in order to alkalinize the solution. The oily product obtained is extracted with 500 ml of ethyl acetate and the organic layer is dried over anhydrous sodium sulfate, then concentrated under reduced pressure. One drop of the residue is dissolved in acetone and the acetone solution is subjected to gas chromatography under the conditions described below.

   We then observe a peak corresponding to the II-A isomer with a retention time of 300 seconds and that corresponding to the II-B isomer, with a retention time of 360 seconds. The relationship between the two isomers

  
  <EMI ID = 115.1>

  
centering of each surface.

  
The conditions for gas chromatography are as follows:

  
device: "Nippon Denshi gas chromatography device

  
20K "equipped with a flame ionization detector. Glass column column with a length of 1 m

  
liquid phase: 5% "XE-60"

  
  <EMI ID = 116.1> Temperature (column): 200 [deg.] C

  
  <EMI ID = 117.1>

  
Support gas: nitrogen, 1 kg / cm2.

  
The residue is dissolved in 100 ml of benzene. The solution is passed through a column packed with

  
1.2 kg of 100-200 mesh silica gel and column chromatography is carried out with a 10: 1 mixture of n-hexane and acetone as developing solvent. The fraction corresponding to each isomer is recrystallized from carbon tetrachloride to obtain 36 g (yield: 41.6%) of a

  
  <EMI ID = 118.1>

  
ment: 11.5%) of a pure II-A isomer (melting point: 108-
109 [deg.] C). The development solvent is again passed
(10: 3 mixture of n-hexane and acetone) through the column

  
  <EMI ID = 119.1>

  
will give below the elementary analysis and the nuclear magnetic resonance spectrum of each isomer. The nuclear magnetic resonance spectrum is measured with deuterochloroform as solvent and the chemical change is expressed by values 0 with tetramethylsilane as internal standard.

  
Isomer II-A of 1- (4-chlorophenyl) -4,4-dimethyl-

  
  <EMI ID = 120.1>

  
Elementary analysis:

  

  <EMI ID = 121.1>


  
Nuclear magnetic resonance spectrum:
8.11 (1H, s, proton triazole)

  
7.90 (1H, s, proton triazole)

  
7.15 (4H, s, phenyl proton)

  
  <EMI ID = 122.1>

  
0.99 (9H, s, butyl proton).

  
  <EMI ID = 123.1> <EMI ID = 124.1>

  
Elementary analysis:

  

  <EMI ID = 125.1>


  
Nuclear magnetic resonance spectrum:

  
  <EMI ID = 126.1>

  
7.22 (2H, d, phenyl proton, J = 8Hz)

  
6.73 (2H, d, phenyl proton, J = 8Hz)

  
7.49 (1H, s, olefinic proton)

  
1.22 (9H, s, butyl proton).

Example 5

  
Synthesis of the II-A isomer of 1- (4-chlorophenyl) -4,4-

  
  <EMI ID = 127.1>

  
of a 500 W high pressure mercury vapor lamp. During the reaction, a trace of the reaction solution is taken a few times as a sample and the ratio of the isomers is measured (isomer II- B / isomer II-A) by gas chromatography under the same conditions as those described in Example 4. The following results are obtained:

  

  <EMI ID = 128.1>
 

  
  <EMI ID = 129.1>

  
tional in a 500 ml eggplant-shaped flask and acetone is removed under reduced pressure to obtain 7.9 g of crystals. These crystals are recrystallized from

  
  <EMI ID = 130.1>

  
of crystals with a melting point of 108-109 [deg.] C. This compound is dissolved in acetone and subjected to gas chromatography under the conditions described above, but no peak is observed corresponding to isomer II-B.

Example 6

  
Synthesis of the II-A isomer from a mixture of the isomers

  
  <EMI ID = 131.1>

  
10 g of the reaction mixture obtained in Example 4 and containing the isomers II-A and II-B in a ratio of 1: 3 are subjected to irradiation with ultraviolet rays under the same conditions as those described in Example 5 .

  
  <EMI ID = 132.1>

  
and isomer II-B by gas chromatography and it is found to be approximately 19: 1.

  
After removing the solvent by evaporation,

  
the crystals obtained are recrystallized from tetrachloride

  
  <EMI ID = 133.1>

Example 7

  
(A) Synthesis of 3- (4-chlorophenyl) -1- (1-methylcyclopropyl) 2- (1,2,4-triazol-1-yl) -2-propen-1-one (compound n [deg. ] 29 ') by method C.

  
10 g (0.06 mole) of l- (l-methylcyclo-) are mixed

  
  <EMI ID = 134.1>

  
anhydrous potassium and 100 ml of acetic anhydride, then the mixture is heated to 100 [deg.] C for 6 hours while stirring.

  
The precipitates formed in the reaction solution are removed by filtration and the filtrate is concentrated under reduced pressure to obtain an oily product. This oily product is extracted with 300 ml of chloroform and the extract is washed with

  
300 ml of a saturated aqueous hydrogen carbonate solution

  
sodium. The organic layer is dried over anhydrous sodium sulfate and concentrated under reduced pressure.

  
One drop of the residue is dissolved in acetone and the acetone solution is subjected to gas chromatography under the conditions described below. Then, a peak corresponding to the II-A isomer is observed after a retention time

  
of 250 seconds and that corresponding to the II-B isomer after a retention time of 300 seconds. The relationship between

  
  <EMI ID = 135.1>

  
based on the percentage of each area. The conditions for gas chromatography are as follows:

  
Apparatus: "Nippon gas chromatography apparatus

  
Denshi 20K "equipped with a flame ionization detector.

  
Column: glass column with a length of 1 m.

  
  <EMI ID = 136.1>

  
Support: "Chromosorb W"

  

  <EMI ID = 137.1>

The residue is dissolved in 100 ml of benzene.

  
The solution is passed through a column packed with
300 g of 100-200 mesh silica gel and subjected to column chromatography with a 10: 1 mixture of n-hexane and acetone as developing solvent. The fraction corresponding to each isomer is recrystallized from carbon tetrachloride in order to separate the two geometric isomers listed under the heading from one another. The nuclear magnetic resonance spectrum of each isomer is shown in Table 2.

  

  <EMI ID = 138.1>


  
(B) Synthesis of the starting material, namely l- (l-methyl- <EMI ID = 139.1>

  
For 4 hours, while stirring vigorously at a temperature of 40 to 50 [deg.] C, 28 g of bromine are added to a mixture of 28 g of methyl-1-methylcyclopropyl-ketone [compound

  
  <EMI ID = 140.1>

  
5.8 g of potassium chlorate and 70 ml of water, then the reaction solution is stirred at room temperature for 2 hours. Then, the reaction solution is extracted with two 200 ml portions of ether and the organic layer is dried over calcium chloride, then it is concentrated under reduced pressure to obtain 53 g of a crude product, namely l- (l-methylcyclopropyl) -2-bromethan-l-one.

  
For one hour, a mixture of 18.3 g of 1,2,4-triazole, 37 g of anhydrous potassium carbonate and 250 ml of acetonitrile is refluxed, then cooled to

  
  <EMI ID = 141.1>

  
cyclopropyl) -2-bromethan-l-one crude obtained above, then stirred. room temperature overnight. The precipitates are removed from the reaction solution by filtration and the filtrate is concentrated under reduced pressure. The residue obtained is extracted by adding 100 ml of water and 300 ml of chloroform, then the organic layer is dried over anhydrous magnesium sulphate and concentrated under reduced pressure. The oily residue is crystallized from 100 ml of ether

  
  <EMI ID = 142.1>

  
on methyl-1-methylcyclopropyl-ketone; Fusion point :

  
57-600 C)

Example 8

  
Synthesis of the II-A isomer of 3- (4-chlorophenyl) -1- (lmethylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen-1-one

  
  <EMI ID = 143.1>

  
phenyl) -1- (1-methylcyclopropyl) -2- (1,2,4-triazol-1-yl) -2propen-1-one obtained in Example 7 in 500 ml of acetone and

  
  <EMI ID = 144.1>

  
ultraviolet ray generator equipped with a high pressure mercury vapor lamp of 500 W. The ratio between the isomer II-A and the isomer II-B is measured by chromatography

  
  <EMI ID = 145.1>

  
the ratio is 81.2: 18.1. The reaction solution is concentrated under reduced pressure to obtain 3.9 g of crystals. These crystals are recrystallized from carbon tetrachloride to obtain 2.8 g (yield: 70%) of

  
  <EMI ID = 146.1>

Example 9

  
Synthesis of the 3- (4-chlorophenyl) -l- (l-meth) isomer II-A:
cyclopropyl) -2- (1,2,4-triazol-1-yl) -2-propen-1-one from a mixture of its geometric isomers.

  
For 1.5 hours, 3 g of the reaction mixture comprising the isomers II-A and II-B (II-A / II-B = 1/3 obtained in Example 7) are subjected to irradiation with ultraviolet rays in the same conditions as in example 8. Then,

  
  <EMI ID = 147.1>

  
by gas chromatography. We note that this ratio goes from 1/3 to 7/3. After having removed the solvent by evaporation, the crystals formed are recrystallized from carbon tetrachloride to obtain 1.5 g of the isomer II-A.

Example 10

  
  <EMI ID = 148.1>

  
mixture at 10 [deg.] C for 2 hours. 200 ml of water and 50 g of concentrated sulfuric acid are added thereto and, after having been stirred for 16 hours, 500 ml of water are added thereto. We transfer

  
  <EMI ID = 149.1>

  
extract with 500 ml of ether. The organic layer is washed with a 5% aqueous solution of potassium carbonate, then dried over calcium chloride. Then, the solvent is removed under reduced pressure to obtain 89 g of crude 1-bromo2-hexancne in the form of an oily product.

  
For one hour, a mixture of 35 g of triazole and 69 g of anhydrous potassium carbonate is heated at reflux.

  
  <EMI ID = 150.1>

  
obtained above with the mixture which is then stirred at room temperature for 16 hours. The precipitates are removed from the reaction solution by filtration, while the solvent is removed under reduced pressure. To the residue obtained, 200 ml of water and 200 ml of chloroform are added, then the mixture is transferred to a separation funnel and then extraction is carried out. The organic layer is dried over anhydrous magnesium sulfate and the solvent is removed under reduced pressure to obtain 77 g of crude 1- (1,2,4triazolyl) -2-hexanone in the form of an oily product.

  
20 g of the 1- (1,2,4-triazolyl) -2-hexanone obtained, 20 g of anhydrous potassium carbonate, 20 g are mixed

  
of p-chlorobenzaldehyde and 200 ml of acetic anhydride, then the mixture is heated to 90 ° C. for 5 hours. Then, the reaction mixture is concentrated under reduced pressure, then the residue is dissolved in 500 ml of ethyl acetate and the solution thus obtained is transferred to a separation funnel. The ethyl acetate solution is washed with 200 ml of a saturated aqueous potassium carbonate solution, then the organic layer is separated. The solvent is removed from the organic layer under reduced pressure and the residue is deposited in a column of silica gel (0.5 kg of silica gel at 100-200

  
  <EMI ID = 151.1>

  
a 10: 1 mixture of n-hexane and acetone as the developing solvent. In this way, 3.7 g of the isomer are obtained.

  
  <EMI ID = 152.1>

  
for 2 hours, then pour it into 500 ml of ice water.

  
The aqueous liquor is neutralized with potassium carbonate and extracted with 300 ml of ethyl acetate. The organic layer is dried over anhydrous magnesium sulfate and the solvent is removed by evaporation. The crystalline residue is recrystallized from a 1: 1 mixture of carbon tetrachloride and n-hexane to obtain 6 g of the isomer II-B

  
  <EMI ID = 153.1>

Example 11

  
Synthesis of the IA isomer of 1- (2,4-dichlorophenyl) -2- (1,2,4triazol-1-yl) -4,4-dimethyl-1-penten-3-ol (compound n [deg. ] 2). First stage (condensation) - process D <EMI ID = 154.1>

  
and 700 cm3 of acetic anhydride, then add 255 g

  
triethylamine. After maintaining the temperature at 70 ° C. for 7 hours, the acetic anhydride is removed under reduced pressure. 3 liters of water are added to the residue and the crystals formed are collected by filtration, washed with water and dried. The crude product obtained is recrystallized from 600 cm3 of ethanol to obtain 304 g of the isomer

  
  <EMI ID = 155.1>

  
dimethyl-1-penten-3-one (compound n [deg.] 2 ').

  
Second step (photo-isomerization) - process C

  
  <EMI ID = 156.1>

  
rator of ultraviolet rays equipped with a mercury vapor lamp under high pressure of 500 W. Then, the solvent is removed under reduced pressure to obtain 300 g of an oily product. On gas chromatography, it is found that this product consists of a mixture comprising 75% of

  
  <EMI ID = 157.1>

  
same compound. This product is transferred to the next step without separating each of the isomers.

  
Third step (reduction) - process A

  
We put 300 g of the mixture of geometric isomers

  
  <EMI ID = 158.1>

  
sion in 1 kg of methanol and 38 g of sodium borohydride are added thereto in portions while cooling the reaction mixture;

  
  <EMI ID = 159.1>

  
for one hour, the reaction solution is concentrated

  
under reduced pressure. The residue obtained is extracted by adding two liters of a 10% aqueous solution of acetic acid and

  
3 liters of ethyl acetate. The separated organic layer is washed with 1 liter of a 5% aqueous solution of potassium carbonate and dried over 100 g of anhydrous magnesium sulfate. After removing the drying agent by filtration, the solvent is removed under reduced pressure and

  
280 g of a crude product in the form of crystals. This product

  
consists of a mixture of the I-A and I-B isomers of the compound

  
  <EMI ID = 160.1>

  
280 g of the crude product in 600 cm 3 of carbon tetrachloride and 209 g of the title compound are obtained (isomer I-A of compound n [deg.] 2). The mother liquor of the recrystallization is concentrated to half its volume to obtain 25 g of the I-B isomer of compound n [deg.] 2 in the form of secondary crystals.

  
Table 2 below shows the isomers II-A

  
of the ketone compound (II) obtained by the processes

  
C and D, together with isomers II-B. Spectrum

  
of nuclear magnetic resonance of this table is indicated in the same form as in table 1.

  

  <EMI ID = 161.1>


  

  <EMI ID = 162.1>
 

  

  <EMI ID = 163.1>


  

  <EMI ID = 164.1>
 

  

  <EMI ID = 165.1>


  

  <EMI ID = 166.1>
 

  

  <EMI ID = 167.1>


  

  <EMI ID = 168.1>
 

  

  <EMI ID = 169.1>


  

  <EMI ID = 170.1>
 

  

  <EMI ID = 171.1>


  

  <EMI ID = 172.1>
 

  

  <EMI ID = 173.1>


  

  <EMI ID = 174.1>
 

  

  <EMI ID = 175.1>


  

  <EMI ID = 176.1>
 

  

  <EMI ID = 177.1>


  

  <EMI ID = 178.1>
 

  

  <EMI ID = 179.1>


  

  <EMI ID = 180.1>
 

  

  <EMI ID = 181.1>


  

  <EMI ID = 182.1>
 

  

  <EMI ID = 183.1>


  

  <EMI ID = 184.1>
 

  

  <EMI ID = 185.1>


  

  <EMI ID = 186.1>


  

  <EMI ID = 187.1>
 

  

  <EMI ID = 188.1>


  

  <EMI ID = 189.1>
 

  
During the practical application of the compounds thus obtained according to the present invention, these compounds can be used individually without other components or in a mixture with carriers in order to facilitate their use as fungicides, herbicides and regulators of plant growth. Among the forms of preparations usually used, there are, for example, powders for wetting powders, oily sprays, emulsifiable concentrates, tablets, granules, fine granules, aerosols and fluid preparations.

  
The above preparations generally contain 0.1 to 95% by weight of active ingredient (including other ingredients in mixture). A suitable amount of the active ingredient applied generally ranges from 2 to 500 g per 10 ares, while the concentration of the active ingredient

  
  <EMI ID = 190.1>

  
However, since the quantity and the concentration depend on the forms of preparation, the times, the techniques and the places of application, the diseases and the crops in question, they can be increased or reduced.

  
  <EMI ID = 191.1>

  
When formulating fungicides, herbicides and plant growth regulators according to the present invention, suitable solid or liquid carriers are mixed. Among the solid supports, mention may be made, for example, of inorganic substances (for example, clays such as those of the kaolinite group, of the montmorillonite group or of the attapulgite group, talc, mica, pyrophyllite, pumice, vermiculite, gypsum, calcium carbonate, dolomite, diatomaceous earth, magnesium, lime, apatite, zeolite, silicic acid anhydride and silicate synthetic calcium), organic plant substances (e.g. soybean powder, tobacco powder, nut powder, flour, wood powder, starch and crystalline cellulose),

   synthetic or natural high molecular weight compounds (e.g. coumarone resins, petroleum resin, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gum, copal gum and dammar gum), as well as waxes (for example, carnauba wax and beeswax) and urea.

  
Among the liquid carriers, mention may be made, for example, of paraffinic or naphthenic hydrocarbons

  
  <EMI ID = 192.1>

  
and white oil), aromatic hydrocarbons (e.g. benzene, toluene, xylene, ethylbenzene, cumene

  
and methylnaphthalene), halogenated hydrocarbons (for example, carbon tetrachloride, chloroform, trichlorethylene, monochlorobenzene and o-chlorotoluene), ethers (for example, dioxane and tetrahydrofuran), ketones (for example, acetone, methyl ethyl ketone,

  
diisobutyl ketone, cyclohexanone, acetophenone and isophorone), esters (e.g. ethyl acetate, amyl acetate, ethylene glycol acetate, acetate

  
diethylene glycol, dibutyl maleate and succinate

  
diethyl), alcohols (for example, methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol and benzyl alcohol), ethers

  
(for example, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene ethyl ether-

  
  <EMI ID = 193.1> polar (for example, dimethylformamide and dimethyl sulfoxide) and water.

  
As surfactants used for emulsification, dispersion, wetting, spreading, fixing, disintegration regulation, stabilization of the active ingredient, improvement of flowability and inhibiting molds, any nonionic, anionic, cationic or amphoteric surfactant can be used, but, as a general rule, nonionic and / or anionic surfactants are used.

  
Among the suitable nonionic surfactants, there may be mentioned, for example, those obtained by polymerizing ethylene oxide and a higher alcohol (for example,

  
  <EMI ID = 194.1>

  
que), ethylene oxide and an alkylphenol (for example, isooctylphenol and nonylphenol), ethylene oxide

  
and an alkyl naphthol (for example, butyl-naphthol and octylnaphthol), ethylene oxide and a higher fatty acid (for example, palmitic acid, stearic acid and oleic acid), ethylene oxide and a monoalkyl phosphate

  
or dialkyl (for example, stearyl phosphate and dilauryl phosphate) or ethylene oxide and an amine
(e.g. dodecylamine and stearic acid amide), the higher fatty acid esters of a polyhydric alcohol
(for example, sorbitan) and those obtained by polymerizing these esters and ethylene oxide, as well as polymers of ethylene oxide / propylene oxide. As suitable anionic surfactants, there may be mentioned, for example, the salts of an alkyl sulphate (for example, sodium lauryl sulphate, the amino salts of oleyl sulphate), alkyl &#65533; sulfonates (for example, a sodium salt of dioctyl-sulfo-

  
  <EMI ID = 195.1> sodium succinate and 2-ethyl-hexene sulfonate) and aryl sulfonates (e.g., isopropyl-naphthalene sulfonate, methylene-bis-naphthalene sulfonate, sodium lignosulfonate sodium and sodium dodecyl-benzene-sulfonate).

  
In addition, the preparations of the compounds of the present invention may contain high molecular weight compounds and other adjuvants in order to improve their yield and their biological activity. Among the high molecular weight compounds are, for example, casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and polyvinyl alcohol.

  
The above supports and adjuvants are used judiciously individually or in combination according to the uses envisaged, taking into account the forms of preparation and the techniques of application.

  
The content of the active ingredient in powders

  
to be sprinkled generally ranges from 1 to 25 parts by weight, the rest consisting of a solid support.

  
With regard to wettable powders, the

  
  <EMI ID = 196.1>

  
parts by weight. The remainder consists of a solid support and a dispersing-wetting agent and, if necessary, a protective bond, a thixotropic agent and an anti-foaming agent are added thereto.

  
With regard to the granules, the content of the active ingredient generally ranges from 1 to 35 parts by weight, the remainder consisting, for the most part, of a solid support. The active ingredient is uniformly mixed with a solid support or fixed or adsorbed uniformly on the surface of the solid support. The particles have a diameter ranging from about 0.2 mm to about 1.5 mm.

  
With regard to emulsifiable concentrates, the content of the active ingredient generally ranges from 5 to 30 parts by weight, and the content of emulsifier represents approximately 5 to approximately 20 parts by weight, while the rest consists of a liquid support. If necessary, mold inhibitors are added.

  
In addition, the compounds of the present invention can be applied in admixture with other fungicides, herbicides and plant growth regulators without reducing the control effect exerted by each active ingredient in the mixture. Among the fungicides, we can

  
  <EMI ID = 197.1>

  
manganese, bis (N, N-dimethylthiocarbamoyl) disulfide, tetrachloroisophthalonitrile, 8-hydroxyquinoline,

  
  <EMI ID = 198.1>

  
oxathiine-3-carboxanilide, N'-dichlorofluoromethylthioN, N-dimethyl-N'-phenylsulfamide, l- (4-chlorophenoxy) -3,3dimethyl-l- (1,2,4-triazol-l-yl) - 2-butanone, 1,2-bis- (3methoxycarbonyl-2-thioureido) -benzene, methyl N- (2,6-dimethylphenyl) -N-methoxyacetyl-2-methylglycinate, aluminum ethylphosphite and the like . Among the herbicides, mention may be made of those of the phenoxy series such as 2,4-dichlorophenoxyacetic acid, 2-methyl-4chlorophenoxyacetic acid, 2-methyl-4-chlorophenoxybutyric acid and 2-methyl- acid. 4-chlorophenoxyacetic (including their esters and their salts), herbicides from

  
the diphenyl ether series such as 2,4-dichloro- ether

  
  <EMI ID = 199.1>

  
methoxycarbonyl-4'-nitrophenyl, the herbicides of

  
  <EMI ID = 200.1>

  
triazine and 2-methylthio-4,6-bisisopropylamino-1,3,5-triazine, urea series herbicides such as

  
  <EMI ID = 201.1>

  
benzyl) -3-p-tolylurea and 1- (2-benzothiazolyl) - 1,3-dimethylurea, herbicides of the carbamate series such as

  
  <EMI ID = 202.1>

  
methyl dichlorophenyl) -carbamate, herbicides of the thiocarbamate series such as S- (4-chlorobenzyl) N, N-diethylthiocarbamate and N, N-hexamethylene-S-ethyl thiocarbamate, herbicides of the acid anilides such as 3,4-dichloropropionanilide, 2-chloro-N-methoxymethyl-2 ', 6'-diethylacetanilide, 2-chloro-2', 6'-diethyl-N-

  
  <EMI ID = 203.1>

  
uracil series such as 5-bromo-3-sec-butyl-6-methyluracil and 3-cyclohexyl-5,6-trimethylene-uracil, herbicides of the pyridinium salt series such as

  
  <EMI ID = 204.1>

  
of the phosphorus series such as N- (phosphonomethyl) - glycine, N, N-bis (phosphonomethyl) glycine, O- (2-nitro-5-methylphenyl) -N-sec-butyl-phosphoroamidothioate O-ethyl,

  
  <EMI ID = 205.1>

  
N, N-dipropyl-p-toluidine, 5-tert-butyl-3- (2,4-dichloro-

  
j

  
  <EMI ID = 206.1>

  
3- (methoxycarbonylamino) phenyl carbamate, 4-amino-3methyl-6-phenyl-1,2,4-triazine and the like.

  
Likewise, the compounds of the present invention can be applied in a mixture with other insecticides without reducing the control effect of each active ingredient in the mixture. Among the insecticides, mention may be made of organophosphorus insecticides

  
  <EMI ID = 207.1>

  
O, O-dimethyl phosphorodithioate S- (l-ethoxycarbonyl-1-phenylmethyl), as well as the insecticides of the series

  
  <EMI ID = 208.1>

  
1 of α-cyano-3-phenoxybenzyl, 3-phenoxybenzyl 2,2-dimethyl-3- (2,2-dichloro-vinyl) cyclopropane-carboxylate and the

  
  <EMI ID = 209.1>

  
cyano-3-phenoxybenzyl. As a result, two or more types of disease and parasites can be fought simultaneously and, in addition, a synergistic effect can be expected due to the mixture.

  
The utility will be described more clearly below.

  
compounds of the present invention as fungicides, herbicides and plant growth regulators for agriculture and horticulture with reference to the following test and preparation examples.

Test example 1

  
  <EMI ID = 210.1>

  
By heating, a solution of a medium containing 5 g of polypeptone, 20 g of malt extract, 20 g of sucrose and 20 g of agar-agar per liter of water is formed. We add

  
  <EMI ID = 211.1>

  
each test compound so as to obtain a predetermined concentration of this test compound in the medium. After vigorously agitating the medium, it is poured into a glass Petri dish to form an agar-agar plate. After the agar has solidified, a mycelial disc or a suspension of spores of a test fungus are inoculated there. The name of the test mushroom and the culture period from inoculation to observation are indicated

  
  <EMI ID = 212.1>

  

  <EMI ID = 213.1>
 

  

  <EMI ID = 214.1>


  
Compound growth inhibition is evaluated

  
  <EMI ID = 215.1>

  

  <EMI ID = 216.1>


  
As indicated in Table 3, it can be seen that the I-A isomer of the present invention has a very broad antimicrobial spectrum, as well as a remarkable activity.

  
  <EMI ID = 217.1>

  

  <EMI ID = 218.1>


  

  <EMI ID = 219.1>
 

  

  <EMI ID = 220.1>


  

  <EMI ID = 221.1>
 

  

  <EMI ID = 222.1>


  

  <EMI ID = 223.1>
 

  

  <EMI ID = 224.1>


  

  <EMI ID = 225.1>
 

  

  <EMI ID = 226.1>


  

  <EMI ID = 227.1>
 

  

  <EMI ID = 228.1>


  

  <EMI ID = 229.1>
 

  

  <EMI ID = 230.1>


  

  <EMI ID = 231.1>
 

Test example 2

  
Protective activity against Cercospora arachidicola.

  
We fill a 150 ml plastic pot with sandy soil and sow peanuts (variety:
"Hanritsusei") at the rate of 1 seed / pot, then cultivated for 12 days in an air-conditioned greenhouse

  
  <EMI ID = 232.1>

  
third actual sheet. At this time, the diluted aqueous liquor of the emulsifiable concentrate of each test compound is sprayed onto the leaves at a rate of 10 ml / jar.

  
After air drying, Cercospora arachidicola is inoculated on the young plants, they are covered with a polyvinyl film to maintain the humidity, then they are placed in an air conditioning greenhouse maintained at

  
  <EMI ID = 233.1>

  
for another 10 days in the greenhouse in order to infect them sufficiently, then the appearance of the disease is observed on the leaves. The severity of the disease is calculated as follows: the percentage of infected area of the leaves is measured and then classified according to the relevant indices.

  
  <EMI ID = 234.1>

  
calculates the severity of the disease by the following equation:
Disease onset index

  
of

  
disease

  
0 No colony or infected area on the surface of

  
leaves.

  
0.5 Colony or area infected with less than 5%

  
on the surface of the leaves.

  
1 Colony or area infected with less than 20%

  
on the surface of the leaves.

  
2 Colony or area infected with less than 50%

  
on the surface of the leaves.

  
  <EMI ID = 235.1>

  
on the surface of the leaves,
  <EMI ID = 236.1>
 The disease control is then calculated by the following equation:

  

  <EMI ID = 237.1>


  
  <EMI ID = 238.1>

  
that the I-A isomer of the compounds of the present invention exerts a remarkably high protective activity compared to its I-B isomer.

  
TABLE 4
  <EMI ID = 239.1>
 TABLE 4 (continued)

  

  <EMI ID = 240.1>

Test example 3

  
Protective activity against Botrytis cinerea.

  
We fill a 150 ml plastic pot with sandy soil and sow cucumber (variety:
"Sagami-hanjiro") at the rate of 3 seeds / pot, then we cultivate

  
  <EMI ID = 241.1>

  
cotyledonous stage. At this time, the diluted aqueous liquor of the emulsifiable concentrate of each test compound is sprayed onto the leaves at a rate of 10 ml / jar. After air drying, Botrytis cinerea is inoculated on the young plants which are then placed in a humid chamber

  
  <EMI ID = 242.1>

  
days, the onset of cotyledon disease is observed.

  
The infection examination and the disease control calculation are carried out in the same manner as in test example 2.

  
  <EMI ID = 243.1>

  
that the I-A isomer of compound 1 exerts a remarkably high protective activity compared to its I-B isomer.

  
TABLE 5

  

  <EMI ID = 244.1>


  
Note: (1) Commercial fungicide.

Test example 4

  
Protective activity against Puccinia recondita
(curative effect) (test on young plants).

  
We fill a 150 ml plastic pot with sandy soil and sow wheat (variety:

  
  <EMI ID = 245.1>

  
first real leaf, then Puccinia recondita is inoculated to the young plants which are infected by placing them for 16 hours in a humid room kept at

  
  <EMI ID = 246.1> dilute aqueous of the emulsifiable concentrate of each test compound at a rate of 10 ml / jar. The young plants are grown for 10 days in a room at constant temperature (23 [deg.] C) under fluorescent light, then the appearance of the disease of the first real leaf is observed. The infection examination and the disease control calculation are carried out in the same manner as in test example 2.

  
Consequently, from Table 6, it can be seen that the I-A isomer of the compounds of the present invention exerts a clearly high protective activity compared to

  
  <EMI ID = 247.1>

  
well known compound.

  

  <EMI ID = 248.1>


  

  <EMI ID = 249.1>
 

  

  <EMI ID = 250.1>


  

  <EMI ID = 251.1>
 

  

  <EMI ID = 252.1>


  

  <EMI ID = 253.1>
 

  

  <EMI ID = 254.1>


  

  <EMI ID = 255.1>
 

  

  <EMI ID = 256.1>


  

  <EMI ID = 257.1>


  

  <EMI ID = 258.1>
 

  
Test compound 5

  
Protective activity against Puccina graminis (curative effect) (test on young plants).

  
Young seedlings of wheat are obtained (variety:
"Norin n [deg.] 61 <1> <1>) in the same way as in test example 4. Then, Puccinia graminis is inoculated on the young plants which are infected by placing them for 16 hours in a chamber

  
  <EMI ID = 259.1>

  
spray, on young plants, the dilute aqueous liquor of the emulsifiable concentrate of each test compound at a rate of 10 ml / jar. Young plants are grown for 10 days

  
  <EMI ID = 260.1>

  
the appearance of the disease is observed on the first real sheet. Examination of the infection and calculation of the

  
  <EMI ID = 261.1>

  
test 2.

  
Consequently, according to Table 7, we see

  
  <EMI ID = 262.1>

  
a clearly high protective activity compared not only to the I-B isomer, but also compared to the commercial fungicide and the well-known compound.

  
TABLE 7
  <EMI ID = 263.1>
 TABLE 7 (continued)

  

  <EMI ID = 264.1>


  
  <EMI ID = 265.1>

Test example 6

  
Protective activity against Erysiphe graminis by application to the leaves (test on young plants).

  
We fill a 150 ml plastic pot with sandy soil and sow barley (variety:
"Goseshikoku") at a rate of 10-15 seeds / pot, then cultivate for 7 days in an air-conditioned greenhouse (18 to
23 [deg.] C) to obtain young plants at the first stage

  
  <EMI ID = 266.1>

  
the diluted aqueous liquor of the emulsifiable concentrate of each test compound at a rate of 10 ml / jar. After air drying, Erysiphe graminis is inoculated into young plants which are grown for 10 days in a room at room temperature.

  
  <EMI ID = 267.1>

  
the appearance of the disease is observed on the first real sheet. The severity of the disease is calculated as follows: the percentage of infected area of the leaves is measured and then classified according to the corresponding indices.

  
  <EMI ID = 268.1>

  
of the disease by the following equation:

  
Index of

  
disease onset of disease

  
0 No colony on the leaf surface.

  
0.5 Colony at a rate of less than 5% on the surface

  
leaves.

  
1 colony at a rate of less than 20% on the surface

  
leaves.

  
2 Colony less than 50% on the surface

  
leaves.

  
4 Colony at a rate of 50% minimum on the surface

  
leaves.

  

  <EMI ID = 269.1>
 

  
Then we calculate disease control by the following equation:

  

  <EMI ID = 270.1>


  
Consequently, from Table 8, it can be seen that the compounds of the present invention exert a

  
  <EMI ID = 271.1>

  
that this activity is equal to or greater than that of the reference compound.

  
TABLE 8
  <EMI ID = 272.1>
 TABLE 8 (continued)
  <EMI ID = 273.1>
 TABLE 8 (continued)
  <EMI ID = 274.1>
 TABLE 8 (continued)
  <EMI ID = 275.1>
 TABLE 8 (continued)

  

  <EMI ID = 276.1>
 

Test example

  
500 g of a soil mixture comprising sea sand, mountain soil and peat are placed in a flower pot with a diameter of 13 cm and a chrysanthemum is grown there (variety: "Snow Ridge") . Two weeks after planting, the chrysanthemum is pinched and grown in a three-stemmed form, then new buds grow. Two weeks after pinching, we apply

  
  <EMI ID = 277.1>

  
predetermined concentration of each test compound and,

  
42 days after application of the pesticide, the regulatory effect on the growth of the plant is examined. The results are shown in Table 9.

  
The effect exerted is evaluated as follows:
an increase in the height of the plant is calculated by the difference between its initial height at the time of application and the height it reached on the 42nd day after application, this difference being expressed by the height index, the value 100 being attributed to the corresponding difference obtained in untreated ground. The values shown in this table are average values of three replicas.

  
As a reference compound, the

  
  <EMI ID = 278.1>

  
TABLE 9

  
Dwarfism test for potted chrysanthemum
  <EMI ID = 279.1>
 TABLE 9 (continued)

  

  <EMI ID = 280.1>


  
* 1 Reference compound (commercial fungicide)

  

  <EMI ID = 281.1>

Test example 8

  
Herbicide activity test on field weeds.

  
Soil is mixed with Digi seeds

  
  <EMI ID = 282.1>

  
manually activated, the diluted aqueous liquor of the emulsifiable concentrate containing a predetermined quantity of active ingredient is applied to the surface of the soil. After the application, we transplant, in the Wagner jar, sugar beet plants (variety: "Monohil")

  
in the 5 leaf stage that we have grown in pots

  
in paper. Then, the young plants are grown in the greenhouse.
20 days after application, the herbicidal activity and the phytotoxicity are observed with regard to the crops. The results obtained are shown in Table 10. The herbicidal activity is expressed by figures ranging from 0 to 5 as indicated below, provided that the phytotoxicity vis-à-vis the crops is also expressed by the same standard,

  

  <EMI ID = 283.1>


  
As can be seen from Table 10, the I-A isomer of the compounds of the present invention exerts a far more potent herbicidal activity than that of the I-B isomer.

  
TABLE 10
  <EMI ID = 284.1>
 TABLE 10 (continued)
  <EMI ID = 285.1>
 TABLE 10 (continued)
  <EMI ID = 286.1>
 TABLE 10 (continued)
  <EMI ID = 287.1>
 TABLE 10 (continued)

  

  <EMI ID = 288.1>

Test example 9

  
Height-regulating effect on soybeans and barley.

  
We fill a plastic pot with

  
500 ml with sandy soil. Remove the soil from the top half of the pot, mix it well with
10 ml of the diluted aqueous liquor of the emulsifiable concentrate of each test compound, then the mixture obtained is again deposited in the jar. Then sow soybeans and barley in the treated soil at the rate of 3 seeds / pot and

  
5 seeds / pot respectively.

  
We grow soybeans and barley in a glasshouse

  
  <EMI ID = 289.1>

  
measures the height of each plant. The results obtained are shown in Table 11. The numerical values in the table denote the average height of two soybean plants and that of three barley plants, expressed as a percentage, the value 100 being assigned to the corresponding average height. damage in untreated ground.

  
Consequently, it is found that the I-A isomer of the compounds of the present invention exerts a very powerful effect on the regulation of the height compared to

  
  <EMI ID = 290.1>

  
with both the I-A isomer and the I-B isomer, there is no phytotoxicity such as chlorosis and necrosis and it is also found that the leaves take on a fairly intense green color.

  
TABLE 11
  <EMI ID = 291.1>
 TABLE 11 (continued)

  

  <EMI ID = 292.1>

Test example 10

  
Regulatory effect on the growth of the barley internode.

  
Barley is sown (variety: "Goseshikoku") in a field on November 20 and, the following year, the diluted aqueous liquor of the emulsifiable concentrate of the IA isomer of compound 1 is sprayed on the leaves once (the

  
April 4) and twice (April 4 and 24).

  
On May 28, barley is harvested from each plot of land and the length of the internode is measured.

  
30 barley stalks per plot. As shown in Table 12, mainly the length of the fourth and fifth internode is remarkably shortened in the treated plot compared to the untreated plot and, moreover, the total length of the stems is also shortened in the treated plot.

  
No phytotoxicity is observed such as yellowing and sterility.

  

  <EMI ID = 293.1>


  

  <EMI ID = 294.1>
 

Test example II

  
Effect of growth regulation on the lawn.

  
We fill a pot of Wagner of 1 / 5,000 are with a mixture of soil (3: 1 mixture of mountain soil and peat) then, on December 6, we transplant lawn grass "Korai" (Zoysia matrella L).

  
The lawn grass is cultivated in a greenhouse maintained at a temperature of 30 [deg.] C by carrying out several fertilizations and several mowing until the growth of the grass becomes uniform. Immediately after mowing on May 9, using a manual spray device, apply the dilute aqueous liquor of the emulsifiable concentrate of each test compound at the rate of 10 ml / jar.

  
On June 2, an increase in the height of the grass is measured in order to evaluate the growth regulation effect exerted by the test compound. The effect exerted is expressed by the height index, the value 100 being attributed to the corresponding increase in untreated land. The results are shown in Table 13.

  
  <EMI ID = 295.1>

  
This invention has a regulatory effect on the growth of lawn grass.

  
TABLE 13

  

  <EMI ID = 296.1>
 

Test example 12

  
Test of herbicidal activity on weeds of paddy fields (paddy = unhulled rice).

  
  <EMI ID = 297.1>

  
with 1.5 kg of paddy field soil and keep the pots under irrigation. Young rice plants are then transplanted to the 3-leaf stage and seeds of Echinochloa crus-galli and Scirpus juncoides, variety "Hotarui Ohwi" are sown there. Then, to the irrigated soil, the required amount of each test compound is applied.

  
25 days after application, the herbicidal activity exerted by the test compound on the sown weeds, as well as on the weeds, is examined.

  
  <EMI ID = 298.1>

  
sprouted spontaneously. The results obtained are shown in Table 14,

  
When applying the test compounds, a predetermined amount of each compound is formulated into a wettable powder which is applied at the rate of
10 cm3 / pot using a pipette. The herbicidal activity is expressed in figures ranging from 0 to 5.

  

  <EMI ID = 299.1>


  
None of the test compounds showed phytotoxicity to rice plants (for example, malformation, yellowing and chlorosis).

  
TABLE 14
  <EMI ID = 300.1>
 TABLE 14 (continued)

  

  <EMI ID = 301.1>

Test example 13

  
Protective activity test against Rhizoctonia solani for rice.

  
  <EMI ID = 302.1>

  
grown in pots in a greenhouse for about 2 months, the diluted aqueous liquor is sprayed with the emulsifiable concentrate of each test compound. After air drying,

  
Rhizoctonia solani is inoculated into the sheaths of the rice stalks by gluing the mycelial disc (diameter: 5 cm). After inoculation, the rice plants are infected in a humid chamber (28 [deg.] C) for 4 days and the appearance of the disease is examined.

  
The severity of the disease is calculated as follows: the percentage of infected area of the sheaths is measured, which is then classified according to the corresponding disease indices 0, 1, 2, 4, 8; we calculate the severity of the disease by the following equation:

  
&#65533;

  
Index of

  
disease onset of disease

  

  <EMI ID = 303.1>


  
Then we calculate the disease control by the following equation:

  

  <EMI ID = 304.1>


  
  <EMI ID = 305.1>

  
that the I-A isomer of the compounds of the present invention exerts a remarkably high protective activity compared to the I-B isomer and that the activity is equal to or greater than that of the reference compound.

  
TABLE 15

  

  <EMI ID = 306.1>


  
* 1 Reference compound (commercial fungicide). Preparation example 1: dusting powder.

  
While transforming them into powder, part of the I-A isomer of each of the

  
  <EMI ID = 307.1>

  
of clay and 10 parts of talc to obtain a dusting powder containing 1% of the active ingredient.

  
Preparation example 2: dusting powder.

  
While transforming them into powder, 3 parts of the IA isomer of each of the compounds (1) to (52) of the present invention, 67 parts of clay and 30 parts of talc are suitably mixed to obtain a dusting powder containing 3% of active ingredient.

  
Preparation example 3: wettable powder.

  
While transforming them into powder, 30 parts of the I-A isomer of each of the

  
  <EMI ID = 308.1>

  
diatomaceous earth, 20 parts of white carbon, 3 parts of a wetting agent (sodium lauryl sulphate) and 2 parts of a dispersing agent (calcium lignosulfonate) to obtain a wettable powder containing 30% of active ingredient ,

  
  <EMI ID = 309.1>

  
While transforming them into powder, 50 parts of the IA isomer of each of the compounds (1) to (52) of the present invention are suitably mixed, 45 parts of diatomaceous earth, 2.5 parts of a wetting agent (calcium alkylbenzene sulfonate) and 2.5 parts of a dispersing agent (calcium lignosulfonate) to obtain a wettable powder containing 50% of active ingredient, Preparation example 5: emulsifiable concentrate.

  
10 parts of the I-A isomer of each of the compounds (1) to (52) of the present invention are mixed,

  
80 parts of cyclohexanone and 10 parts of an emulsifier (polyoxyethylene alkylaryl ether) to obtain an emulsifiable concentrate containing 10% of active ingredient. Preparation example 6: granules,

  
While transforming them into powder, we mix

  
  <EMI ID = 310.1>

  
each of the compounds (1) to (52) of the present invention,
40 parts by weight of bentonite, 50 parts by weight of clay and 5 parts by weight of sodium lignosulfonate. The mixture is kneaded well with water, it is subjected to a granulation and it is dried to obtain granules, Preparation example 7: dusting powder.

  
While transforming them into powder, 2 parts of the II-A isomer of each of the

  
  <EMI ID = 311.1>

  
of clay and 10 parts of talc to obtain a dusting powder containing 2% of active ingredient,

  
Preparation example 8: dusting powder.

  
While transforming them into powder, 3 parts of the II-A isomer of each of the

  
  <EMI ID = 312.1>

  
of clay and 30 parts of talc to obtain a dusting powder containing 3% of active ingredient.

  
Preparation example 9: wettable powder.

  
While transforming them into powder, 30 parts of the II-A isomer of each of the

  
  <EMI ID = 313.1>

  
diatomaceous earth, 20 parts of white carbon, 3 parts of a wetting agent (sodium lauryl sulfate) and 2 parts of a dispersing agent (calcium lignosulfonate) in order to obtain a wettable powder containing 30% d active ingredient.

  
Preparation example 10: wettable powder,

  
While transforming them into powder, 50 parts of the II-A isomer of each of the

  
  <EMI ID = 314.1>

  
diatomaceous earth, 2.5 parts of a wetting agent
(calcium alkyl benzene sulfonate) and 2.5 parts of a dispersing agent (calcium lignosulfonate) to obtain a wettable powder containing 50% of active ingredient.

  
Preparation example 11: emulsifiable concentrate.

  
10 parts of the II-A isomer of each of the compounds (le) to (33 ′) of the present invention are mixed,
80 parts of cyclohexanone and 10 parts of an emulsifier (polyoxyethylene alkylaryl ether) to obtain an emulsifiable concentrate containing 10% of active ingredient Preparation example 12: granules.

  
While transforming them into powder, we mix

  
  <EMI ID = 315.1>

  
40 parts by weight of bentonite, 50 parts by weight of clay and 5 parts by weight of sodium lignosulfonate. Mix the mixture well with water,

  
  <EMI ID = 316.1>

  
granules containing 5% of active ingredient.

  
Preparation example 13: wettable powder.

  
While transforming them into powder, 80 parts of the I-A isomer of each of the

  
  <EMI ID = 317.1>

  
dispersing agent (calcium lignosulfonate) to obtain a wettable powder containing 80% of active ingredient.


    

Claims (1)

1. Geometric isomer of formula: <EMI ID = 318.1> in which R. represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms, an alkenyl group containing 3 or 4 carbon atoms or a 2-propynyl group, <EMI ID = 319.1> different, each represents a halogen atom, an alkyl group containing 1 to 4 carbon atoms, an alkyl group containing 1 to 3 carbon atoms and substituted by a halogen atom, an alkoxy group containing 1 to 4 carbon atoms, a phenoxy group, a phenyl group, a cyano group or a nitro group and n is an integer of 0 to 3, this isomer being obtained by reduction of one of the two isomers <EMI ID = 320.1> <EMI ID = 321.1> <EMI ID = 322.1> above, the olefin proton of this isomer appearing at a magnetic field greater than the nuclear magnetic resonance spectrum in deutero-chloroform, or by additional etherification of the reduced product obtained, or the salts of this geometric isomer. 2. Geometric isomer or its salts according to claim 1, characterized in that R. is a hydrogen atom and R2 is a tert-butyl group, 3. Geometric isomer or its salts according to claim 2, characterized in that n is equal to 1 and R3 represents a chlorine atom in position 4 * 4. Geometric isomer or its salts according to claim 2, characterized in that n is equal to 2, while the symbols R3 represent chlorine atoms occupying positions 2 and 4. <EMI ID = 323.1> halogen and n is 0, 1 or 2. 6. One of the two geometric isomers of a triazole compound corresponding to the formula: <EMI ID = 324.1> <EMI ID = 325.1> appearing at a magnetic field higher than the nuclear magnetic resonance spectrum in deuterochloroform, <EMI ID = 326.1> triazole compound corresponding to the formula: <EMI ID = 327.1> wherein R2 is a 1-methylcyclopropyl group, while R3 and n have the meanings defined in claim 1, the olefinic proton of this isomer appearing at a magnetic field lower than the nuclear magnetic resonance spectrum in deuterochloroform. 8. Process for the preparation of one of the two geometric isomers of a triazole compound spreading with the formula: <EMI ID = 328.1> <EMI ID = 329.1> in claim 1, the olefinic proton of this isomer appearing at a magnetic field higher than the spectrum nuclear magnetic resonance in deuterochloroformt characterized in that the other geometric isomer isomerized, the olefinic proton of which appears at a magnetic field lower than the nuclear magnetic resonance spectrum in deuterochloroform, by irradiation with rays. 9. Process for the preparation of one of the two geometric isomers of a triazole compound corresponding to the formula: <EMI ID = 330.1> <EMI ID = 331.1> in claim 1, the olefin proton of this isomer appearing at a magnetic field higher than the spectrum of <EMI ID = 332.1> characterized in that a mixture of the two geometric isojners of this compound is isomerized by irradiation with rays, 10. Process for the preparation of a geometric isomer of formula: <EMI ID = 333.1> <EMI ID = 334.1> in claim 1, characterized in that one of the two geometric isomers of a triazole compound corresponding to the formula is reduced: <EMI ID = 335.1> <EMI ID = 336.1> in claim 1, the olefinic proton of this isomer appearing at a magnetic field greater than the nuclear magnetic resonance spectrum in deuterochloroform. 11. Process for the preparation of a geometric isomer of formula: <EMI ID = 337.1> in which R. is an alkyl group containing 1 to 4 atoms <EMI ID = 338.1> have the meanings defined in claim 1, characterized in that it consists in reacting a geometric isomer of formula: <EMI ID = 339.1> <EMI ID = 340.1> tion of one of the two geometric isomers of a triazole compound corresponding to the formula <EMI ID = 341.1> <EMI ID = 342.1> in claim 1, the olefinic proton of this isomer appearing at a magnetic field higher than the nuclear magnetic resonance spectrum in deuterochloroform &#65533; <EMI ID = 343.1> <EMI ID = 344.1> alkyl group containing 1 to 4 carbon atoms, an alkenyl group containing 3 or 4 carbon atoms or a 2-propynyl group, in the presence of a base., or salts of this isomer. 12. Fungicide, herbicide and / or agent for regulating the growth of plants for agriculture and horticulture, characterized in that it contains, as active ingredient, a geometric isomer of formula: <EMI ID = 345.1> <EMI ID = 346.1> in claim 1, this fungicide, this herbicide and / or this agent for regulating plant growth being obtained by reduction of one of the two geometric isomers of a triazole compound corresponding to the formula: <EMI ID = 347.1> wherein R2, R3 and n have the meanings defined in claim 1, the olefinic proton of this isomer appearing at a magnetic field higher than the nuclear magnetic resonance spectrum in deutero-chloroform, or by etherification of the reduced product obtained, or salts of the aforementioned geometric isomer. 13. Fungicide for agriculture and horticulture, characterized in that it contains, as active ingredient, one of the two geometric isomers of a triazole compound corresponding to the formula: <EMI ID = 348.1> wherein R2, R3 and n have the meanings defined in claim 1, the olefinic proton of this isomer appearing at a magnetic field greater than the nuclear magnetic resonance spectrum in deutero-chloroform, or the salts of this isomer. <EMI ID = 349.1> <EMI ID = 350.1> The undersigned is aware that no document attached to the file of a patent for invention can be of a nature to bring, either to the description or to the drawings, substantive modifications and declares that the content of this note does not 'does not make such modifications and has no other object than to signal one or more material errors. It acknowledges that the content of this note cannot have the effect of rendering the patent application totally or partially valid if it was not <EMI ID = 351.1> not in whole or in part under the legislation currently in force. He authorizes the Administration to attach this note to the patent file and to issue a photocopy. Attached you will find, in fiscal stamps, the amount of tax required. Please accept, Sir, the assurance of our distinguished consideration.